Iodine is an important element essential for higher animals. A large part of the global human population suffers from a lack of iodine; elucidation of transfer and mobility of this element in the environment, water, soil, air and in organisms is thus very important. The aim of this work was the elaboration and optimisation of the method for determination of very low concentrations of iodine in the waters. The mass spectrometry with inductively coupled plasma (ICP-MS) technique was used. It has been shown that using of different filter types during sample preparation had no significant effect on the content of impurities in the filtered sample. Antimony was recommended as an internal standard, despite commonly used elements (indium or tellurium). Samples were not preserved because nitric acid caused volatilization of iodine from the sample and the addition of aqueous ammonia had no significant effect. The optimised method was tested on several groups of water samples, including precipitation, surface water and lysimetric waters. From autumn 2009 to summer 2010, a part of the Blanice River (Šumava Mountains, South Bohemia) was sampled. The average content of iodine in samples ranged from 1.48 ? 0.30 ?g?dm-3 (April 2010) to 3.05 ? 0.38 ?g?dm-3 (July 2010). The average content of iodine in samples from all tributaries of the Blanice River ranged between 2.52 ? 1.63 ?g?dm-3 (March 2010) and 3.67 ? 1.37 ?g?dm-3 (July 2010). The concentration of iodine in the monitored surface waters did not change significantly along the flow of the river. The other two streams were sampled near Rapotín village (Jeseníky Mountains, north Moravia). The average contents of iodine were as follow: Annov (upper stream) 1.60 ? 0.65 ?g?dm-3, Annov (lower stream) 1.88 ? 1.18 ?g?dm-3, Salaš (upper stream) 1.77 ? 0.92 ?g?dm-3, Salaš (lower stream) 1.42 ? 0.58 ?g?dm-3. Generally, the data showed that considering iodine, the area of Šumava had slightly higher levels than those observed in the Jeseníky Mountains. Precipitation collected in the South Bohemia (Arnoštov village and city of České Budějovice) and in Jeseníky (Rapotín) contained less iodine compared to surface waters, and rarely exceeded 3 micrograms per liter of water. The situation has changed in the spring of 2010, because of the occurrence of volcanic dust and ash over the Czech Republic. This volcanic cloud came from the sudden activity of the Eyjafjallajökull Volcano (Iceland). In the mentioned period, the contents of iodine in precipitation were increased several times at all sample collection sites. This is an indirect evidence that iodine could be released during volcanic eruptions and transferred over long distances through the atmosphere. It turned out that the wastewater treatment plant can eliminate iodine in wastewater only partially. However, the wastewater treatment plants in the monitored region were too small to evaluate the overall impact on the environment. The maximum iodine content at the outlet of the wastewater treatment plant Prachatice town (South Bohemia) was 28.5 ?g?dm-3, which is several times higher than natural levels in the Živný stream, to which the treated water flows. Lysimetric water samples were collected from lysimeters installed in three nearby plots in Arnoštov village (Šumava, South Bohemia). The highest concentrations of iodine were found on plot where cattle were grazed. These values were significantly higher (average 4.38 ? 1.74 ?g?dm-3) than those obtained from a site used as hay meadow (average 2.69 ? 1.19 ?g?dm-3) or an untreated meadow (average 2.25 ? 1.39 ?g?dm-3). Iodine therefore probably originated from the urine and feces of grazed cattle. This thesis contributes to the total knowledge of iodine, particularly to the part concerning determination of iodine in the hydrosphere.

Neste trabalho, a decomposição por via úmida em sistema fechado assistida por radiação micro-ondas (MW-AD) e a decomposição por via úmida em sistema fechado assistida por radiação micro-ondas e ultravioleta (MW-UV) foram avaliadas para amostras comerciais de biodiesel para posterior determinação de Ba, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sr, V e Zn por espectrometria de massa com setor eletromagnético com plasma indutivamente acoplado (SF-ICP-MS). A MW-AD empregando ácido diluído foi primeiramente avaliada sendo possível a decomposição de até 700 mg de biodiesel com HNO3 7 mol L-1 e 2 mL de H2O2 30% (m/m). As soluções finais apresentaram teor de carbono residual (RCC) de 8,7% e acidez residual (RA) de 4%. Posteriormente, com o objetivo de obter maior eficiência de decomposição, o método MW-UV foi avaliado para a decomposição de biodiesel. Com o emprego deste método até 950 mg de amostra foram decompostas com HNO3 7 mol L-1 e soluções finais com RCC de 17,4% e RA de 19,3% foram obtidas. As soluções finais, para ambos os métodos, foram adequadas para a determinação de elementos traço por SF-ICP-MS. Possíveis interferências na etapa de determinação dos analitos, causadas pela presença de carbono residual, foram estudadas através do emprego de padrão interno 115In e de ensaios de recuperação de analito para monitorar a formação de espécies poliatômicas no plasma. Os resultados obtidos mostraram a necessidade da utilização de padrão interno, sendo o instrumento operado no modo de baixa resolução para a determinação da maioria dos analitos, com exceção de 52Cr, para o qual o instrumento foi operado no modo de média resolução. A exatidão dos métodos propostos foi avaliada mediante a análise de material de referência certificado, obtendo-se resultados concordantes, com nível de confiança de 95% (teste t-student), com os valores certificados para a maioria dos elementos. Ensaios de adição de analito também foram feitos para a avaliação da exatidão e recuperações de 92 à 109% foram obtidas. Os limites de detecção (LD) obtidos para o método MW-UV foram inferiores aos obtidos para MW-AD, na faixa de 0,08 a 6,9 ng g-1 e 1,0 a 14 ng g-1, respectivamente. / In this work, the microwave-assisted digestion (MW-AD) and microwave-assisted ultraviolet digestion (MW-UV) were evaluated for commercial biodiesel samples for subsequent determination of Ba, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sr, V and Zn by sector field inductively coupled plasma mass spectrometry (SF-ICP-MS). Using the MW-AD method with diluted acid up to 700 mg of biodiesel were digested with 7 mol L-1 HNO3 and 2 mL of 30% (w/w) H2O2. Final solutions presented residual carbon content (RCC) of 8.7% and residual acidity (RA) of 4%. In order to improve the digestion efficiency, the MW-UV method was evaluated for biodiesel digestion. Using MW-UV method up to 950 mg of sample were digested with 7 mol L-1 HNO3 and the final solutions with RCC of 17.4% and RA of 19.3% were obtained. The final solutions obtained for both methods were suitable for the determination of trace elements by SF-ICP-MS. Interferences in the determination step were studied using 115In as internal standard and analyte recovery to monitor the formation of polyatomic species in the plasma. The low resolution mode was used for the determination of almost of the analytes with the exception of 52Cr that was determine using medium resolution mode. Accuracy of the investigated methods were evaluated by analysis of certified reference material and the values obtained were in agreement with 95% confidence level (t-student test) with the certified values for all elements. Analyte recovery was also performed to evaluate the accuracy and recoveries of 92 to 109% were obtained. The limits of detection (LOD) obtained by the MW-UV method were lower than MW-AD method and are in the range of 0.08 to 6.9 ng g -1 and 1.0 to 14 ng g -1, respectively.

O estágio pós-colisional Neoproterozoico no sul do Brasil é marcado por intenso magmatismo granítico controlado por zonas de cisalhamento transcorrentes, relacionadas ao Cinturão de Cisalhamento Sul-brasileiro (CCSb). O CCSb controlou a ascensão e o posicionamento de magmas crustais e mantélicos. Neste contexto, O Granito Corre-mar (GCM) representa uma pequena intrusão posicionado em uma zona de baixa deformação localizada entre dois importantes segmentos do CCSb: as Zonas de Cisalhamento Major Gercino e Itajaí- Perimbó. O GCM possui um diagnóstico par de foliações subevetical que forma um par S-C sinistral, presente em todas as intrusões, independentemente do tamanho, e foi posicionado em um sistema conjugado, onde um cisalhamento sinistral de direção NNE, e uma extensão na direção NW-SE, gerando espaço ao longo da direção NE. Deformação de estado sólido associada ao cisalhamento NNE é atestado por microestruturas como recristalização de feldspatos e caudas de recristalização assimétricas. A abertura é atribuída à dinâmica regional destral transcorrente das zonas de cisalhamento Major Gercino e Itajaí-Perimbó, sendo que o posicionamento foi controlado essencialmente pela componente de estensão NW-SE. A idade de cristalização em zircão U-Pb LAMC- ICP-MS do GCM de 615 ± 4 Ma, muito próxima a outros granitos regionais, como as idades de 611 Ma do Granito Serra dos Macacos (GSM) e de 620 Ma do Granito Rio Pequeno (GRP) sugere que esses três corpos graníticos são sincrônicos. As fortes feições de deformação presents no GCM, diferentemente dos granitos Neoproterozoicos próximos, demonstra que o espaço, mais do que o tempo, pode explicar a diferença dos padrões estruturais identificados no GCM. Assinaturas geoquímicas e de isótopos de Sr-Nd, como caráter levemente peraluminoso, altos conteúdos de K, altas razões de ETRL/ETRP, moderados conteúdos de Rb, Nb, Zr e ETR em relação à SiO2, juntamente com baixas razões de 86Sr/87Sri e valores de εNdt fortemente negativos, indicam que o GCM é derivado de fontes crustais antigas, possivelmente relacionadas à rochas quartzofeldspáticas ortognáissicas Paleoproterozoicas do Complexo Camboriú. A relaçãodas das idades das heranças Arqueanas a Paleoproterozoicas do GCM com as idades dos eventos de migmatização identificados no Complexo Camboriú, além da relação das idades de cristalização de ~615-611 Ma dos granitos crustais da área com o último evento de migmatização em 640-610, reforça a conexão genética entre eles. As idades TDM paleoproterozoicas, as assinaturas geoquímicas e isotópicas, a cristalização e as idades de heranças do GCM e do GSM atestam que eles representam pulsos graníticos contemporâneos e comagmáticos, com uma conexão genética com o evento de migmatização Neoproterozoico do Complexo Camboriú. / The Neoproterozoic post-collisional stage in south Brazil is marked by intense granitic magmatism controlled by transcurrent shear zones all related to the Southern Brazilian Shear Belt (SBSB). The SBSB controls the ascent and emplacement of crustal and mantle magmas. In such scenario, the Corre-mar Granite (CMG), represent a small intrusion emplaced in a low strain zone located between two important segments of the SBSB: the Major Gercino and Itajaí-Perimbó Shear Zones. The CMG have a diagnostic subvertical foliation pair that form a sinistral S-C pair, present in all intrusions regardless of their size, and was emplaced within a conjugate system, where sinistral NNE shearing and NW-SE extension were both active, generating space along the NE direction. Solid state deformation associated to the NNE shearing is attested by microstructures as feldspar recrystallization and asymmetric recrystallization tails. The opening is attributed to the regional dextral transcurrent dynamics of the Major Gercino and Itajaí-Perimbó shear zones and magma emplacement was essentially conditioned by the NW extension component. The zircon U-Pb LA-MC-ICP-MS crystallization age of CMG at 615 ± 4 Ma, very close to other regional granites, as the 611 Ma Serra dos Macacos (SMG) and 620 Ma Rio Pequeno Granite (RPG) points these three granitic bodies as quite synchronous. The strong deformation features present in the CMG, as opposed to the other nearby Neoproterozoic granites (RPG and SMG) demonstrate that space, rather than time, must be called upon to explain the difference in the structural patterns identified in the CMG. Geochemical and Sr-Nd isotopic signatures, as slight peraluminous character, high-K contents, high LREE/HREE ratios, moderate Rb, Nb, Zr, and REE contents to regular SiO2, together with low 86Sr/87Sri and the strongly negative εNdt values indicate that the CMG is derived from old crustal sources possibly related to the Paleoproterozoic Camboriú Complex quartz-feldspatic orto-gneissic rocks. The match of the Archean to Paleoproterozoic inheritance ages of the CMG with the migmatization event ages identified in the Camboriú Complex and moreover the match of the crystallization ages of ~615-611 Ma of the crustalderived granites with the last migmatization event at 640-610 Ma reinforces the genetic link between them. The Paleoproterozoic TDM ages, the geochemical and isotopic signatures, the crystallization and inheritance ages resemblance of the CMG and the SMG attest that they represent comagmatic and contemporaneous granitic pulses with a genetic connection with the Neoproterozoic migmatization event in the Camboriu Complex.

O rio Corumbataí, principal tributário do rio Piracicaba, e fonte de abastecimento da cidade de Piracicaba, vêm sofrendo degradação desde a sua nascente, na cidade de Analândia até sua foz, no rio Piracicaba. Entre 2005 e 2006, foram determinados os teores dos elementos: Be, Al, Na, Mg, Ca, K, V, Mn, Fe, Cr, Co, Ni, Cu, Zn, As, Se, Ag, Cd, Sb, Ba, Hg, Pb, Th, Tl, U por Espectrofotometria de massas com fonte de plasma induzido (ICP-MS) e as propriedades físicas, químicas e microbiológicas, na água e sedimento do rio Corumbataí. As coletas foram realizadas em setembro e dezembro de 2005 e em março, junho e setembro de 2006. Na água, os elementos foram determinados na fração dissolvida, filtrando-se a amostra em campo e preservando-se com HNO3 e na fração total, utilizando-se o método de extração aberta com o uso de HNO3 e HCl. No sedimento, os elementos foram determinados na fração trocável, agitando-se por 12 horas em HCl 1 mol L-1 e na fração total, com a extração em forno microonda. Nas amostras de água, foi calculado o Índice de qualidade da água (IQA), o que demonstrou uma diminuição na qualidade ao longo dos anos, principalmente nos pontos localizados na região à jusante de Rio Claro (RJ) e Piracicaba (PI). O Fósforo Total, Turbidez, pH, OD, Clorofila-a, Escherichia Coli, DBO e os metais Fe e Al dissolvido, Mn, Cd e Hg total, apresentaram concentrações acima do Conama 357/2005 para rios classe 2 em diversos pontos e épocas de coleta, ao longo do rio. No sedimento, os metais Cr, Ni, Cu, As, Cd, Hg, Pb não apresentaram valores acima dos preconizados pela Companhia de Tecnologia de Saneamento - CETESB como causadores de efeitos tóxicos. Os outros metais não possuem valores máximos de referência na legislação brasileira. Os elementos que apresentaram fração trocável maior que 50% em todos os pontos de coleta foram: Na, Ca, Mn, Tl, Co, Cu, Be, Pb. A análise estatística multivariada de componentes principais e a análise de agrupamento indica os pontos RJ e PI, como os mais comprometidos e demonstra que o IQA é um bom indicador da qualidade ao longo da bacia hidrográfica. / The Corumbataí River, main tributary of the Piracicaba river and source of water supply to the city of Piracicaba has been suffering degradation from its waterhead in the city of Analândia to its mouth in the Piracicaba river. In 2005 and 2006 were determined the concentration of the elements, Be, Al, Na, Mg, Ca, K, V, Mn, Fe, Cr, Co, Ni, Cu, Zn, As, Se, Ag, Cd, Sb, Ba, Hg, Pb, Th, Tl, U by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS), as well as physicochemical and microbiological proprieties, in the water and sediments of the Corumbataí River. The collections were carried out in September and December of 2005 and March, June and September of 2006. In the water, the elements in the dissolved fraction were determined by filtering the sample in field and preserving themselves with HNO3, and in the total fraction, by using the method of open extration using HNO3 and HCl. In the sediment, the elements were determined in the exchangeable fraction, by agitating for 12 hours in HCl 1 mol L-1 and in the total fraction, with the extration in microwave. In the samples of water, the water quality Index (WQI) was calculated, and the results showed a reduction in the quality throughout the years, mainly in the points located in the region downstream regions of Rio Claro, (RJ), and Piracicaba, (PI). The Total Phosphorus, Turbidity, pH, Dissolved Oxygen, Chlorophyill-a, Escherichia Coli, BOD and the dissolved metals Al and Fe, and total Hg, Mn, Cd presented concentrations above Conama 357/2005 for rivers class 2 in several points and periods of collection, along the river. In the sediment, the Cr, Ni, Cu, As, Cd, Hg, Pb did not present values above the recommended ones by Companhia de Tecnologia de Saneamento - CETESB as responsible for toxic effect. Reference values for the the other metals are not indicated in the Brazilian legislation. The elements that presented bigger exchangeable fraction than 50% in all the collection points were: Na, Ca, Mn, Tl, Co, Cu, Be, Pb. The multivaried statistical analysis of main components and the Hierarchical Cluster Analysis indicated RJ and PI points, as the most damaged and showed that the WQI is a good indicative of quality along the hydrographic basin.

O estágio pós-colisional Neoproterozoico no sul do Brasil é marcado por intenso magmatismo granítico controlado por zonas de cisalhamento transcorrentes, relacionadas ao Cinturão de Cisalhamento Sul-brasileiro (CCSb). O CCSb controlou a ascensão e o posicionamento de magmas crustais e mantélicos. Neste contexto, O Granito Corre-mar (GCM) representa uma pequena intrusão posicionado em uma zona de baixa deformação localizada entre dois importantes segmentos do CCSb: as Zonas de Cisalhamento Major Gercino e Itajaí- Perimbó. O GCM possui um diagnóstico par de foliações subevetical que forma um par S-C sinistral, presente em todas as intrusões, independentemente do tamanho, e foi posicionado em um sistema conjugado, onde um cisalhamento sinistral de direção NNE, e uma extensão na direção NW-SE, gerando espaço ao longo da direção NE. Deformação de estado sólido associada ao cisalhamento NNE é atestado por microestruturas como recristalização de feldspatos e caudas de recristalização assimétricas. A abertura é atribuída à dinâmica regional destral transcorrente das zonas de cisalhamento Major Gercino e Itajaí-Perimbó, sendo que o posicionamento foi controlado essencialmente pela componente de estensão NW-SE. A idade de cristalização em zircão U-Pb LAMC- ICP-MS do GCM de 615 ± 4 Ma, muito próxima a outros granitos regionais, como as idades de 611 Ma do Granito Serra dos Macacos (GSM) e de 620 Ma do Granito Rio Pequeno (GRP) sugere que esses três corpos graníticos são sincrônicos. As fortes feições de deformação presents no GCM, diferentemente dos granitos Neoproterozoicos próximos, demonstra que o espaço, mais do que o tempo, pode explicar a diferença dos padrões estruturais identificados no GCM. Assinaturas geoquímicas e de isótopos de Sr-Nd, como caráter levemente peraluminoso, altos conteúdos de K, altas razões de ETRL/ETRP, moderados conteúdos de Rb, Nb, Zr e ETR em relação à SiO2, juntamente com baixas razões de 86Sr/87Sri e valores de εNdt fortemente negativos, indicam que o GCM é derivado de fontes crustais antigas, possivelmente relacionadas à rochas quartzofeldspáticas ortognáissicas Paleoproterozoicas do Complexo Camboriú. A relaçãodas das idades das heranças Arqueanas a Paleoproterozoicas do GCM com as idades dos eventos de migmatização identificados no Complexo Camboriú, além da relação das idades de cristalização de ~615-611 Ma dos granitos crustais da área com o último evento de migmatização em 640-610, reforça a conexão genética entre eles. As idades TDM paleoproterozoicas, as assinaturas geoquímicas e isotópicas, a cristalização e as idades de heranças do GCM e do GSM atestam que eles representam pulsos graníticos contemporâneos e comagmáticos, com uma conexão genética com o evento de migmatização Neoproterozoico do Complexo Camboriú. / The Neoproterozoic post-collisional stage in south Brazil is marked by intense granitic magmatism controlled by transcurrent shear zones all related to the Southern Brazilian Shear Belt (SBSB). The SBSB controls the ascent and emplacement of crustal and mantle magmas. In such scenario, the Corre-mar Granite (CMG), represent a small intrusion emplaced in a low strain zone located between two important segments of the SBSB: the Major Gercino and Itajaí-Perimbó Shear Zones. The CMG have a diagnostic subvertical foliation pair that form a sinistral S-C pair, present in all intrusions regardless of their size, and was emplaced within a conjugate system, where sinistral NNE shearing and NW-SE extension were both active, generating space along the NE direction. Solid state deformation associated to the NNE shearing is attested by microstructures as feldspar recrystallization and asymmetric recrystallization tails. The opening is attributed to the regional dextral transcurrent dynamics of the Major Gercino and Itajaí-Perimbó shear zones and magma emplacement was essentially conditioned by the NW extension component. The zircon U-Pb LA-MC-ICP-MS crystallization age of CMG at 615 ± 4 Ma, very close to other regional granites, as the 611 Ma Serra dos Macacos (SMG) and 620 Ma Rio Pequeno Granite (RPG) points these three granitic bodies as quite synchronous. The strong deformation features present in the CMG, as opposed to the other nearby Neoproterozoic granites (RPG and SMG) demonstrate that space, rather than time, must be called upon to explain the difference in the structural patterns identified in the CMG. Geochemical and Sr-Nd isotopic signatures, as slight peraluminous character, high-K contents, high LREE/HREE ratios, moderate Rb, Nb, Zr, and REE contents to regular SiO2, together with low 86Sr/87Sri and the strongly negative εNdt values indicate that the CMG is derived from old crustal sources possibly related to the Paleoproterozoic Camboriú Complex quartz-feldspatic orto-gneissic rocks. The match of the Archean to Paleoproterozoic inheritance ages of the CMG with the migmatization event ages identified in the Camboriú Complex and moreover the match of the crystallization ages of ~615-611 Ma of the crustalderived granites with the last migmatization event at 640-610 Ma reinforces the genetic link between them. The Paleoproterozoic TDM ages, the geochemical and isotopic signatures, the crystallization and inheritance ages resemblance of the CMG and the SMG attest that they represent comagmatic and contemporaneous granitic pulses with a genetic connection with the Neoproterozoic migmatization event in the Camboriu Complex.

Les déchets solides générés par notre société sont nombreux. Les cendres volantes sont des déchets solides produits lors de la combustion de déchets domestiques ou industriels dans des incinérateurs. Les cendres volantes sont également produites par la combustion du charbon dans les centrales à charbon. Les cendres volantes sont des résultats de ces combustions et représentent importante quantité de déchets produits chaque année par notre société. Les possibilités de recyclage de ces déchets sont nombreuses : dans la construction, l'industrie routière. Elles sont également stockées pour une utilisation ultérieure. Les origines différentes des charbons et déchets incinérés conduisent à une minéralogie et une composition élémentaire complexe. En tant que sous-produit le devenir des cendres volantes est important à déterminer, aussi la détermination de la composition élémentaire de ces cendres volantes est-elle indispensable.Les méthodes classiques de préparation des échantillons solides sont la minéralisation acide ou la fusion alcaline. Ces procédures prennent du temps et supposent l’utilisation de réactif, de plus la digestion complète n'est pas toujours assurée. Le risque de contamination par les réactifs employés est important au cours de ces méthodes classiques de préparation. Au cours de la dernière décennie, le développement d’analyse directe d'échantillons solides en utilisant des méthodes d'ablation laser a été important en raison de la nécessité de réduire le temps d'analyse et de réduire aussi la consommation de réactifs. Dans ce travail, deux méthodes basées sur l'ablation par laser seront étudiées pour l'analyse des cendres: Laser Induced Breakdown Spectroscopy (LIBS) et Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). La spectrométrie LIBS sera étudiée pour la détermination quantitative des éléments majeurs dans les échantillons de cendres alors que le couplage ablation laser ICP / MS sera employé pour détermination des éléments traces. L'optimisation de la sensibilité et les stratégies d'étalonnage sont les principaux problèmes traités dans ce travail. La préparation des échantillons et l’optimisation ont été effectuées pour déterminer les éléments tels que Al, As, Ba, Ca, Cr, Cu, Fe, Mg, Mn, Pb, Sr, V et Zn par les deux méthodes.Les performances analytiques telles que les limites de détection, justesse ont été obtenus à la suite d'optimisations appropriées des liants et de la sélection de l’étalon interne approprié. En conclusion, l’analyse directe de solides en utilisant les techniques basées sur l’ablation laser développées dans ce travail conduisent à une justesse acceptable pour la détermination des éléments majeurs et traces dans les cendres volantes / Solid waste generated by our society are numerous, fly ashes are produced during the combustion of domestic or industrial waste in incinerators. Fly ashes are also produced through coal combustion in coal fired power plants. Fly ashes are results of these combustions and represent important quantity of waste produced every year by our society. They have variable use – in construction, road industry, or they can be stocked for further use. As they are result of different origin, they have complex mineral and elemental composition. As a by-product or as a recycled product fly ashes fate is important to determine. In this view the determination of the elemental composition of fly ashes is the aim of this work.Conventional methods of sample preparation are acid digestion or alkali fusion. These procedures are time and reagent consuming and complete digestion is not assured. The potential contamination of the reagents employed is important during these classical sample preparation methods. During the past decade, development of direct solid sampling using laser ablation methods was important due to the need of reducing analysis time and also reducing reagent consumption. In this work, two methods based on laser ablation will be studied for fly ash analysis: Laser Induced Breakdown Spectroscopy (LIBS) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). LIBS will be studied for quantitative determination of major elements in fly ash samples while Laser ablation / ICP MS will be employed for trace element determination.The sensitivity optimization and different calibration strategies are key problems of laser sampling methods. Sample preparation and condition optimisation were performed to determine major, minor and trace elements such as Al, As, Ba, Ca, Cr, Cu, Fe, Mg, Mn, Pb, Sr, V and Zn by both methods – LIBS for major elements and LA-ICP-MS for minor and trace elements.Analytical properties such as detection limits, accuracy and analytical working curves were obtained following suitable optimisation of binders and internal standards. Compromise binder and analytical conditions were selected to determine the elements in fly ash samples.In conclusion, direct solid sampling using laser ablation followed by LIBS or for solid introduction into ICP was found to determine major, minor and trace elements in fly ashes, improving pellets mechanical stability, high samples sensitivity and acceptable accuracy and detection limits.

No description available.

Sulphur stable isotope ratios are useful tracers in geological and environmental studies. They can for example be used to trace the origin of atmospheric sulphate aerosols, because anthropogenic sulphate and natural sulphate have distinguishable δ34S-values (δ34S value of approximately +0 to +8 ‰ for anthropogenic and approximately +12 to +19 ‰ for natural). This is useful for climate modelling research, due to the net cooling effect of aerosol sulphate. In the present study a Nu Plasma II (Nu Instruments) multi collector inductively coupled plasma mass spectrometer (MC-ICP-MS) method for measuring stable sulphur isotope ratios in low sulphur content samples, such as sulphate aerosols, was developed. The method was then applied to a sulphate aerosol sample collected in the Maldives.Most of the measurements were performed at high resolution, due to the interferences on 33S. Heated spray chamber coupled to a desolvating membrane, Aridus II (Cetac), increased the sensitivity and reduced interferences notably compared to wet plasma mode. Aridus II gave more stable measurements than DSN-100 (Nu Instruments). Determinations of δ34S for IAEA S1, S3, and S4 were accurate and the determined δ34S-value of the CIT #39 seawater standard (21.05 ± 0.36 ‰, 2SD, n=42) was comparable with published data. In general, Si internal standardization correction increased precision ~2.5 times compared to non-corrected values. The δ34S-value for the sulphate aerosol sample was determined to 3.82 ±0.41 ‰ (2SD, n=40). Repeatability of ~62 nmol introduced sulphur (2 μg/mL) was generally 0.15 ‰ (2SD, n=5) for the SW and 0.19 ‰ (2SD, n=5) for the sulphate aerosol sample. Comparable results for the SW (20.61±0.09 ‰, 2SD, n=4) and sulphate aersosol sample (3.77 ± 0.08 ‰, 2SD, n=8) were obtained with the method applied to Neptune Plus (Thermo Fischer Scientific) MC-ICP-MS in a different laboratory. The determined aerosol sulphate δ34S-value indicated that the sampled sulphate aerosol originated from anthropogenic sources.

Hair is an excellent matrix for monitoring trace elements and minerals in the body. To long-term changes in concentration of elements in the body are reflected in their value in her hair, so the assessment of the organism from the mineral analysis of hair is a very suitable method. This method is widely used in toxicological testing and forensics. This work deals with the analysis of Mg, K, Fe, Zn, Mn, Se, As, Cd and Pb in 100 samples by ICP-MS. It is a male hair samples with the age range 19 – 74 years. Analysis of hair revealed that concentrations of individual elements are moving in a narrow range of values. Values of older age category are in some case significantly deflective.

The aim of this thesis is the actual elaboration literature search concerning the issue of platinum group metals in the environment, determination of platinum and palladium in great urban agglomerations. It includes chemical and physical properties, occurrence and platinum and palladium cycle in the environment. It also contains methods for extraction and determination of platinum and palladium.