Um estudo sistemático a respeito da utilização de padrão interno em determinações multielementares por espectrometria de absorção atômica (ETAAS) foi desenvolvido. O objetivo principal do presente trabalho foi verificar a possibilidade de melhorar a precisão e a exatidão dos resultados analíticos, que são obtidos na análise de fluidos biológicos. O pré-tratamento dessas amostras foi simplificado e reduzido a uma única etapa de diluição com surfactante (Triton X-100) e ácido (HNO3). Conseqüentemente, a complexidade da solução diluída de amostra, a ser introduzida no tubo de grafite, apresenta uma elevada quantidade de concomitantes que podem provocar interferências químicas. A seleção preliminar dos elementos a serem testados como padrão interno considerou a semelhança de parâmetros físico-químicos relacionados com o processo de atomização. Desta forma, Ag, Bi, In e Tl foram testados como padrão interno para a determinação simultânea de Cd/Pb em sangue e urina, enquanto Bi, Ge, In, Sb, Sn e Te foram os elementos selecionados para a determinação de Mn/Ni/Se em soro sangüíneo. A melhoria da qualidade dos resultados analíticos obtidos na determinação simultânea de Cd e Pb em sangue foi observada quando Ag foi utilizada como padrão interno, na presença de NH4H2PO4 como modificador químico. Verificou-se uma melhoria na exatidão dos resultados obtidos para Cd e Pb, após a correção com padrão interno. Por outro lado, os resultados obtidos na análise de urina não foram corrigidos por nenhum dos elementos testados. Os melhores resultados para a determinação simultânea de Mn, Ni e Se foram obtidos com a utilização de Bi, Sn e Te como padrão interno. Entretanto, verificou-se que a correção de todos os resultados não seria viável com o uso de um único padrão interno. O melhor desempenho nos testes realizados na presença de soro sangüíneo foi obtido com Bi, que melhorou discretamente a precisão dos resultados obtidos para Se. Desta forma, a padronização interna visando a determinação simultânea de Mn, Ni e Se não foi eficiente. A padronização interna em ETAAS, com a finalidade de melhorar a precisão e a exatidão dos resultados analíticos, é uma estratégia tão complexa, quanto os efeitos interferentes que se pretende corrigir: são necessários mais estudos para compreender melhor como a utilização de uma condição de compromisso afeta os processos de atomização, bem como mais informações a respeito das interferências físicas e químicas causadas por amostras complexas, analisadas por ETAAS após uma simples etapa de diluição. Deve-se considerar com especial atenção o modificador químico e as temperaturas das etapas de pirólise e de atomização empregadas, que são parâmetros críticos para o desempenho de um elemento como padrão interno. / A systematic study involving the use of internal standard for multielement determinations by electrothermal atomic absorption spectrometry was developed. The main objective of this work was evaluate the possibility of improving precision and accuracy of the analytical results for biological fluids. The sample pre-treatment was reduced to a single dilution step with surfactant (Triton X-100) and acid (HNO3), increasing the amount of concomitant introduced into the atomizer. The preliminary selection of the elements to be tested as internal standard considered the resemblance of physico-chemical parameters related with the atomization process. Thus, Ag, Bi, In and Tl were tested as internal standard for the simultaneous determination of Cd/Pb in blood and urine, and Bi, Ge, In, Sb, Sn and Te were the selected elements for the determination of Mn/Ni/Se in blood serum. The correction of the results obtained for the simultaneous determination of Cd and Pb in blood was achieved when Ag was used as internal standard, in presence of NH4H2PO4 as chemical modifier. An improvement for the accuracy of the results was observed for both analytes after their correction with the internal standard. On the other hand, the results obtained for the urine analysis were not corrected by using the tested elements. The best results for the simultaneous determination of Mn, Ni and Se were observed when Bi, Sn and Te were used as internal standard. However, the correction for the results for all analytes was not possible by using only one internal standard. The best performance in presence of the serum was obtained for Bi, which improves slightly the precision for the Se results. Thus, the internal standardization for the simultaneous determination of Mn, Ni and Se was not efficient. The internal standardization in ETAAS, aiming the improvement of precision and accuracy of the analytical results, is a strategy as complex as the interference effects to be corrected: more studies are required in order to better understand how the adoption of a compromised condition disturbs the atomization processes, as well as to get more information about the physical and chemical interference caused by complex samples, analyzed by ETAAS after a single dilution step. The chemical modifier and the selected temperatures for the pyrolysis and atomization steps are critical parameters for the performace of an internal standard and they should be carefully considered.

This thesis describes two different sample preparation strategies for inductively coupled plasma atomic emission spectrometry (ICP-AES), and their ability regarding multi element quantification in complex samples. Sensitivity, repeatability, reproducibility and accuracy were investigated. The aim was to increase the over all efficiency, the speed of analysis, and/or the sensitivity of the analytical method. The intention was to measure analytes with concentrations ranging from ng/g to mg/g simultaneously. The aim was additionally to study chemical and physical processes occurring during the sample preparation, the sample transport to the plasma, and the atomization therein. In the first sample preparation strategy, a hydrophilic highly cross-linked iminodiacetate-agarose adsorbent, IDA-Novarose, was used for preconcentration of metal ions, and matrix elimination in natural water samples. The sorbent was synthesized with different binding capacities. The effect of the capacity on preconcentration, matrix elimination, and uptake capability at high flow rates was studied. For a high capacity IDA-Novarose (≥ 45 µmole/ml) quantitative uptake was seen even at high flow rates (100 ml/min) for Cu2+ with a high affinity to the adsorbent, and for Cd2+ with a moderate affinity. For lower capacities the uptake of Cd2+ was affected by the sample matrix and the flow rate. A method based on the determination of the conditional stability constant of the metal sorbent complex was suggested for the prediction of the sorbent capacity needed to obtain quantitative recovery and optimal matrix elimination. The sorbent was used in a flow system with online buffering for the analysis of a certified riverine water (SLRS-3), tap water and lake water. With few exceptions the results obtained by ICP-AES after preconcentration agreed well with the certified concentrations and results obtained by ICP-MS. The other sample preparation strategy discussed is a method for non digested biological samples from different animal organs for the multi element analysis by ICP-AES. This “mix and measure method” consists of a simple homogenization of the sample with a mixing rod in a small amount of neutral media, followed by dilution and direct measurement with ICP-AES. The total time of analysis is only a few minutes. The ability of this fast method to accurately quantify some elements of toxic, environmental, and/or physiological concern with the lowest possible sample dilution and the highest possible plasma load was evaluated. In 10 % liver slurry Cd, Co, and Sr, at concentration levels around 0.05 µg/g were quantified simultaneously with P and K around 2000 µg/g and with several other elements in between (Al, Ca, Cu, Fe, Mg, Mn, Pb, and Zn). The relative standard deviation of repeated measurements of samples was around 5 - 6 % for regardless of the concentration of the element. The method was also used for fast screening of the elemental distribution in mice organs (brain, heart, kidney, liver, lung and spleen).

Um estudo sistemático a respeito da utilização de padrão interno em determinações multielementares por espectrometria de absorção atômica (ETAAS) foi desenvolvido. O objetivo principal do presente trabalho foi verificar a possibilidade de melhorar a precisão e a exatidão dos resultados analíticos, que são obtidos na análise de fluidos biológicos. O pré-tratamento dessas amostras foi simplificado e reduzido a uma única etapa de diluição com surfactante (Triton X-100) e ácido (HNO3). Conseqüentemente, a complexidade da solução diluída de amostra, a ser introduzida no tubo de grafite, apresenta uma elevada quantidade de concomitantes que podem provocar interferências químicas. A seleção preliminar dos elementos a serem testados como padrão interno considerou a semelhança de parâmetros físico-químicos relacionados com o processo de atomização. Desta forma, Ag, Bi, In e Tl foram testados como padrão interno para a determinação simultânea de Cd/Pb em sangue e urina, enquanto Bi, Ge, In, Sb, Sn e Te foram os elementos selecionados para a determinação de Mn/Ni/Se em soro sangüíneo. A melhoria da qualidade dos resultados analíticos obtidos na determinação simultânea de Cd e Pb em sangue foi observada quando Ag foi utilizada como padrão interno, na presença de NH4H2PO4 como modificador químico. Verificou-se uma melhoria na exatidão dos resultados obtidos para Cd e Pb, após a correção com padrão interno. Por outro lado, os resultados obtidos na análise de urina não foram corrigidos por nenhum dos elementos testados. Os melhores resultados para a determinação simultânea de Mn, Ni e Se foram obtidos com a utilização de Bi, Sn e Te como padrão interno. Entretanto, verificou-se que a correção de todos os resultados não seria viável com o uso de um único padrão interno. O melhor desempenho nos testes realizados na presença de soro sangüíneo foi obtido com Bi, que melhorou discretamente a precisão dos resultados obtidos para Se. Desta forma, a padronização interna visando a determinação simultânea de Mn, Ni e Se não foi eficiente. A padronização interna em ETAAS, com a finalidade de melhorar a precisão e a exatidão dos resultados analíticos, é uma estratégia tão complexa, quanto os efeitos interferentes que se pretende corrigir: são necessários mais estudos para compreender melhor como a utilização de uma condição de compromisso afeta os processos de atomização, bem como mais informações a respeito das interferências físicas e químicas causadas por amostras complexas, analisadas por ETAAS após uma simples etapa de diluição. Deve-se considerar com especial atenção o modificador químico e as temperaturas das etapas de pirólise e de atomização empregadas, que são parâmetros críticos para o desempenho de um elemento como padrão interno. / A systematic study involving the use of internal standard for multielement determinations by electrothermal atomic absorption spectrometry was developed. The main objective of this work was evaluate the possibility of improving precision and accuracy of the analytical results for biological fluids. The sample pre-treatment was reduced to a single dilution step with surfactant (Triton X-100) and acid (HNO3), increasing the amount of concomitant introduced into the atomizer. The preliminary selection of the elements to be tested as internal standard considered the resemblance of physico-chemical parameters related with the atomization process. Thus, Ag, Bi, In and Tl were tested as internal standard for the simultaneous determination of Cd/Pb in blood and urine, and Bi, Ge, In, Sb, Sn and Te were the selected elements for the determination of Mn/Ni/Se in blood serum. The correction of the results obtained for the simultaneous determination of Cd and Pb in blood was achieved when Ag was used as internal standard, in presence of NH4H2PO4 as chemical modifier. An improvement for the accuracy of the results was observed for both analytes after their correction with the internal standard. On the other hand, the results obtained for the urine analysis were not corrected by using the tested elements. The best results for the simultaneous determination of Mn, Ni and Se were observed when Bi, Sn and Te were used as internal standard. However, the correction for the results for all analytes was not possible by using only one internal standard. The best performance in presence of the serum was obtained for Bi, which improves slightly the precision for the Se results. Thus, the internal standardization for the simultaneous determination of Mn, Ni and Se was not efficient. The internal standardization in ETAAS, aiming the improvement of precision and accuracy of the analytical results, is a strategy as complex as the interference effects to be corrected: more studies are required in order to better understand how the adoption of a compromised condition disturbs the atomization processes, as well as to get more information about the physical and chemical interference caused by complex samples, analyzed by ETAAS after a single dilution step. The chemical modifier and the selected temperatures for the pyrolysis and atomization steps are critical parameters for the performace of an internal standard and they should be carefully considered.

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2016-04-13T15:18:33Z No. of bitstreams: 1 Mestrado Manuel Moreira.pdf: 7413069 bytes, checksum: 0f15055b235c438ffd4fac6dde85f099 (MD5) / Made available in DSpace on 2016-04-13T15:18:33Z (GMT). No. of bitstreams: 1 Mestrado Manuel Moreira.pdf: 7413069 bytes, checksum: 0f15055b235c438ffd4fac6dde85f099 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Fundação de Amparo à Pesquisa do Estado do Rio de Janeiro / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências-Geoquímica. Niterói, RJ / Elementos-tarços são freqüentemente utilizados como indicadores das condições redox e da paleoprodutividade marinha, que podem afetar a distribuição e o fracionamento geoquímico destes elementos. O potencial efeito do ciclo re-oxidativo da pirita sedimentar sobre o grau de piritização destes indicadores (degree of trace metal pyritization – DTMP) não tem sido anteriormente avaliado. Esta avaliação foi realizada em testemunhos sedimentares da plataforma continental sob influência do Sistema de Ressurgência de Cabo Frio (RJ). A relação do DTMP com a assinatura isotópica do S na pirita (δ34S), que se torna mais leve em resposta ao ciclo re-oxidativo da pirita na área de estudo, sugere que a influência pode ser alta (para Pb, As, Cd e Mn), baixa (para Zn e Cu) ou desprezível (para Cr e Ni), dependendo do elemento considerado. Sedimentos mais antigos e ricos em pirita possibilitaram a identificação de um aparente limiar para o efeito da re-oxidação, após o qual os elementos Pb, As, Cd, Mn e Zn apresentaram maior piritização. Um testemunho em posição intermediária na plataforma apresentou correlações negativas das concentrações reativas de Mn, Cu, Ni e Pb com as concentrações de Fe na pirita, assim como outros dois testemunhos apresentaram em relação a Mn e Pb. Isto sugere um consumo de óxidos de Mn (e metais associados) em reação com a pirita, contribuindo para explicar o alto DTMP apresentado pelo Pb, que discorda das predições termodinâmicas e de cinética de incorporação deste metal pela pirita. As assinaturas isotópicas da pirita na área de estudo (que apresenta condições óxicas), foram semelhantes às de ambientes sedimentares anóxicos e euxínicos reportadas na literatura, sugerindo que o ciclo re-oxidativo pode afetar a susceptibilidade de incorporação e a preservação dos elementos na pirita em uma ampla variedade de condições sedimentares. A abordagem metodológica proposta pode subsidiar a melhor interpretação do processo de piritização e suas aplicações para a indicação de condições paleo-redox e de paleo-produtividade / Potential effects of sedimentary pyrite re-oxidative cycling on the degree of trace metals pyritization (DTMP) were evaluated in four sediment cores from the continental shelf under the influence of a tropical upwelling system (Cabo Frio, Brazil). The DTMP relation with stable isotope signals (δ34S) of chromium reducible sulfur, which became lighter in response to intense pyrite re-oxidative cycling in the study area, suggests high (Pb, As, Cd and Mn), low (Zn and Cu) or negligible (Cr and Ni) re-oxidation influences. Oldest pyrite-richer sediments provide an apparent threshold for intense pyrite re-oxidation, after which most trace elements (Pb, As, Cd, Mn and Zn) presented more accentuated DTMP. A middle shelf core presented negative correlations of reactive Mn, Cu, Ni and Pb with pyrite iron, suggesting Mn oxide (and associated metals) depletion in reaction with pyrite. This contributes to explain the observed high degree of Pb pyritization in disagreement with predictions derived from both thermodynamics and water exchange reaction kinetics. Pyrite δ34S signatures under the oxic bottom water from the study area were similar to those from euxinic sedimentary environments, suggesting that pyrite re-oxidative cycling can affect trace element susceptibility to be incorporated and preserved into pyrite in a wide range of sedimentary conditions

L’enjeu actuel autour de la gestion des MIDND est de valoriser, dans la mesure du possible, les mâchefers sur les chantiers routiers à maîtrise d’ouvrage publique ou privée, tout en tenant compte de la réglementation en vigueur et en réalisant un suivi rigoureux dès l’élaboration jusqu’à leur mise en place. Un des freins de la valorisation des MIDND est relatif aux critères de qualité de plus en plus contraignants. Parmi les polluants potentiels qui peuvent entrainer des restrictions environnementales d’utilisation, les éléments trace métalliques (ETM), dont le comportement en fonction des paramètres que sont la maturation et la granulométrie reste peu connu, sont des plus préoccupants. Dans cette thèse, l’approche développée a permis de définir les conditions favorables au relargage des ETM suivants : Cu, Cr, Pb, Sb, Ni et Zn. La démarche scientifique s’articule autour de trois grands axes : Le premier axe concerne le développement d’une méthode de caractérisation pertinente des MIDND (notamment de la fraction organique et de la fraction minérale polluante) afin de pouvoir mieux juger de leurs qualités. La matrice initiale d’étude prélevée sur un site industriel ainsi que ses fractions granulométriques, ont été finement analysée, tant d’un point de vue physico-chimique qu’en ce qui concerne leur comportement environnemental. La modélisation géochimique basée sur ces données physicochimiques et de lixiviation permet d’identifier des phases majoritaires et de simuler le comportement du matériau dans la perspective de prévoir l’évolution du MIDND en conditions spécifiques de stockage ou de valorisation. Le deuxième axe décrit l’impact des conditions de maturation, et du fractionnement granulométrique sur l’évolution de la qualité des MIDND. Trois différentes conditions de maturation (naturelle sur plate-forme; accélérée sur petit tas; forcée) ont été étudiées. Les résultats montrent que les changements dans la composition chimique et minéralogique des MIDND étudiés et de leurs fractions granulométriques sont plus significatifs lorsque la maturation progresse. La maturation naturelle accélérée et la carbonatation forcée limite la lixiviation du Cu, du Pb et du Zn. Au contraire, la lixiviation du Cr, de Sb, des Cl- et des SO42- augmente lorsque le pH diminue. Le troisième axe est dédié à l’étude de l’utilisation des MIDND comme matière première secondaire dans un scénario de valorisation alternatif aux utilisations en sous-couches routières classiquement pratiquées. Le scénario consiste à incorporer les MIDND dans un coulis auto-compactant utilisable pour l’élargissement de chaussées ou le comblement de fossés. Une formulation a pu être définie. La conformité des performances mécaniques, géotechniques et environnementales aux spécifications d’usage normalisées, est encourageante pour les potentiels utilisateurs des MIDND en technique routière. / Current challenge of Municipal Solid waste Incineration (MSWI) bottom ash management lays in its valorization, mainly to be used in road construction projects. The process must take into account environmental regulations and conduct rigorous monitoring from production to utilization. One constraint in the assessment of MSWI bottom ash is related to quality criteria which is becoming more restrictive. Among potential pollutants that can cause environmental use restrictions are metal trace elements (MTE), whose behavior based on weathering and grain size is not yet well known and represent one of greatest concern. In this thesis, the developed research approach defined the favorable conditions for Cu, Cr, Pb, Sb, Ni and Zn release. The aforementioned approach is based on three pillars: The first pillar focuses on the development of a pertinent characterization method for bottom ash (including the polluting organic and mineral fraction) aiming at a better assessment of its properties. The initial study matrix, taken from an industrial site, was carefully analyzed from both, physico-chemical and environmental performances. Geochemical modeling based on physico-chemical and leaching data, allowed to identify the main mineral phases and to simulate material behavior with the purpose of predicting the evolution of MSWI bottom ash in specific storage or valorization conditions. The second pillar describes the impact of weathering conditions and size partitioning on MSWI bottom ash quality evolution. Three different weathering conditions (natural on industrial scale heap; accelerated on small heap; and forced) were studied. The results showed that changes in the chemical and mineralogical composition of MSWI bottom ash as well as in its size fractions are more significant when the weathering proceed. The natural accelerated weathering and the forced carbonation limited the leaching of Cu, Pb and Zn, whereas, the leaching of Cr, Sb, Cl and the SO42- increased as pH decreased. The third pillar focuses on the study of MSWI bottom ash alternative utilization as secondary raw material for the typically practiced road sub-layers construction. It consisted of incorporating MSWI bottom ash in a self-compacting material used for pavement sub-layer or coated road shoulders structures. A formulated material was obtained by mixing MSWI bottom ash, water and cement as a hydraulic binder. The results of the mechanical, geotechnical and environmental assessment are promising for MISWI bottom ash potential use in road construction.

MENVSC / Department of Hydrology and Water Resources / ABSTRACT Siloam and Tshipise Springs are scalding geothermal springs geologically located within the Soutpansberg Group in the Limpopo Province of South Africa. These geothermal springs are associated with faults and impermeable dykes and are assumed to be of meteoric origin. The optimal use of a geothermal spring largely depends upon its physical and chemical properties as well as the geological controls at source and surrounding pathway to the surface. This study aimed at investigating trace element concentrations in these geothermal springs in order to quantify their impacts on neighbouring soil and vegetation. Impact on vegetation was assessed by incorporating seasonal variations of the trace element mobility from the geothermal springs to the vegetation (Mangifera indica at Siloam and Acacia robusta at Tshipise) via soil. The geothermal spring water, soil and vegetation samples at both sites were collected from May – July (winter) and September – November (summer), 2014. The soil samples were collected at 5 m intervals up to 20 m away from the geothermal spring in each of the sites. The bark and leaf parts of the vegetation were sampled. The control samples for water, soil and vegetation were obtained from Riverside residence at University of Venda, Thohoyandou, Limpopo Province, where there is non-geothermal source of water. The temperature, electrical conductivity (EC), pH and total dissolved solid (TDS) of the geothermal spring water and control samples were determined in situ and in the laboratory. The water samples were acidified for major cations and trace elements determination. There were also non-acidified water samples for major anion analyses. The soil and vegetation samples were digested using microwave and hot block methods, respectively. Concentrations of arsenic (As), antimony (Sb), barium (Ba), beryllium (Be), boron (B), cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), mercury (Hg), lanthanum (La), lead (Pb), lithium (Li), manganese (Mn), molybdenum (Mo), nickel (Ni), selenium (Se), tin (Sn), strontium (Sr), tellurium (Te), thallium (Tl), titanium (Ti), tungsten (W), vanadium (V), and zinc (Zn) were determined by inductively coupled plasma – mass spectrometry (ICP-MS) (Agilent 7700 series). Concentrations of calcium (Ca), magnesium (Mg), sodium (Na) and potassium (K) were analysed using inductively coupled plasma – optical emission spectrometry (ICP-OES) (X – Series 2) whereas the concentrations of chloride (Cl-), fluoride (F-), nitrate (NO3-), phosphate (PO42-), bicarbonate (HCO3-) and sulphate (SO42-) were determined by ion chromatography (IC) (Dionex Model DX 500). Results from this study revealed that the geothermal springs were rich in trace elements compared to that from non-geothermal source of water. The mineral elements present were vii mainly due to rock-water interaction in the deep aquifer at both sites. The geothermal spring water is not fit for drinking because it is particularly high in fluoride (F) having 6.66 and 5.97 mg/L at Siloam ; 6.72 and 7.28 mg/L at Tshipise for winter and summer, respectively. Also, high Nickel (Ni) with 462 µg/L and 868 µg/L: Lead (Pb) with 652 µg/L and 211 µg/L at Siloam and Tshipise respectively, for summer season. In addition, it is not suitable for irrigation owing to high sodium absorption ratio (SAR) values which were above the standard guidelines (˂1) by South African Bureau of Standards (SABS) and World Health Organization (WHO) at both sites. In summer season, there were higher trace elements concentrations than in the winter season. The higher concentration values could be attributed to rainfall, which aids in the dissociation of rock particles, resulting in higher concentrations of these elements. Siloam spring water was more mineralised than Tshipise spring water, hence its neighbouring soils and vegetation possess more trace elements concentrations than the latter. Owing to their high mineral elements content, the geothermal spring water flows across the soil, making it vulnerable to sorption of the trace elements. The trace elements present in the surrounding soil of the geothermal spring were as a result of geothermal water and soil pedogenesis. The geothermal water contaminates the surrounding soil with substantial quantity of trace elements, which decreases with the distance from the geothermal spring, making far distanced soil less-contaminated. High levels of Cr, Co, Ni, Cu, Zn and Pb at Siloam soil can be attributed to more minerals present in the spring, therefore making absorption by Mangifera indica inevitable. Soils at Tshipise are moderately concentrated owing to moderate trace elements concentrations from the geothermal spring water. Generally, seasonal variations were observed in the parameters analysed in the geothermal spring water, surrounding soil and vegetation to ascertain the most favourable season in terms of the trace elements concentrations. There were higher concentrations of trace elements in the geothermal spring, particularly during the summer season, compared to the winter season; this leads to more contamination of the surrounding soils and vegetation. This study showed that geothermal spring has potential to enrich the neighbouring soils and vegetation with trace elements, which could result in contamination. It can be concluded that geothermal spring, despite its benefits to humans, also contaminates the surrounding surface soils with toxic trace elements. Soils are a platform for vegetation. Therefore, if the soil is contaminated by toxic elements, there are high possibilities that these trace elements are absorbed by the neighbouring vegetation, which is likely to affect human beings adversely.