This diploma thesis deals about determination of hazardous elements and their mobility in soils from Brno and Ostrava. For extraction of soil samples was used sequential extraction by Tessier and BCR sequential extraction. Extraction by nitric acid was also used. Mercury was determinated by the advanced mercury analyser AMA 254. Lead, copper and zinc were determinated by the flame atomic absorption spectrometry. Cadmium and vanadium were determinated by the electrotermic atomic absorption.

The mercury occurs in the environment in a variety of forms. Mercury compounds can be found in the soil, atmosphere, water and living organisms. Although some of the mercury substances are very toxic, they are often used in various sectors of industry, agriculture and medicine. Mercury compounds differ in their toxicity, so it is necessary to do speciation analysis. The aim of this diploma thesis was to develop and validate a new analytical method for the determination of mercury compounds in different samples. This method involves the combination of high performance liquid chromatography, UV-photochemical cold vapor mercury generation and atomic absorption spectrometry. Effective separation of mercury(II), methylmercury(I), ethylmercury(I) and phenylmercury(I) ions and subsequent comparable efficient of mercury cold vapor generation from all of forms was achieved using these techniques. The reached detection limits were 8 µg l-1 , 31 µg l-1 , 16 µg l-1 and 38 µg l-1 . At the end of experimental work, the proposed method of RP-HPLC-UV-CVG- QTAAS was used for the determination of mercury compounds in real samples (fish tissue and water samples: Labe, Vltava and tap water) and in certified reference materials (DORM-3 and DOLT-4). Several methods for extraction of mercury species from solid samples...

Rhenium complexes coordinated with suitable organic ligand gain increased interest in radiopharmaceutical medicine. Besides suitable radiological properties given by a metal ion itself, detailed knowledge of overall chemical properties of formed complexes, namely their exact structures, chemical stabilities and possible degradation pathways are essential pre-requisites for their clinical application. Selected rhenium complexes with pyrogallol 2,3-dihydroxynaphthalene and catechol as strongly bound ligands were prepared by a reaction of tetrabutylammonium tetrachlorooxorhenate with twofold molar excess of ligand in presence of various amount of triethylamine. The structures of formed complexes and their consequent reaction products were estimated by means of mass spectrometry with electrospray ionization. The kinetics of reactions in course of complex formation and consequent decomposition were primarily followed by UV- Vis absorption spectra measurement, complemented by single or continuous electrospray mass spectrometry analyses. Optimized HPLC and CZE procedures were utilized for monitoring of the composition of reaction mixtures in course of Re complex formation and for purity check of prepared complexes. Semi-preparative HPLC mode was succesfully utilized for isolation and final purification of...

The presented thesis deals with UV-photochemical generation of volatile compounds of Se and Te from various species. The aim of the project was to expand the current state of knowledge by the application of photocatalytic reduction of higher oxidation states of Se and Te for the speciation analysis based on UV-photochemical generation of volatile compounds. The first step of the study was the assembly of the apparatus for the photocatalysed UV-photochemical generation of volatile compounds. The material of reactor and the whole experimental set-up were based on literature survey and previous research done in our research group. Experiments were directed towards finding the optimum conditions for generation of volatile compounds of selected model elements Se and Te. Se was studied as the element most commonly determined by the UV-photochemical generation of volatile compounds. Conversely, Te was selected as a model analyte representing elements forming less stable volatile compounds. The second part was the application of the optimised method of photocatalysed UV- photochemical generation of volatile Se compound to the determination of Se in water matrices, liquid certified reference materials and also samples of dietary supplements. TiO2/UV-photochemical generation was also successfully modified to...

Atomization conditions for tin hydride in the planar dielectric barrier discharge (DBD) plasma atomizer were optimized with detection by atomic absorption spectrometry (AAS). The effects of apparatus arrangement such as the shape of a waveform function of the high voltage power supply source, DBD atomizer design as well as presence of a dryer tube filled with NaOH pellets to prevent residual aerosol and moisture transport into the DBD were investigated in detail. The optimal experimental setup consisted of a square wave high voltage power supply source coupled to a DBD with vapor-deposited electrodes in the presence of NaOH dryer upstream the DBD atomizer. Argon was found as the best discharge gas under a flow rate of 120 mL min-1 while the DBD optimum high voltage supply rate was 7 kV. A sensitivity of 0.05 s ng-1 Sn and a limit of detection of 1.1 ng mL-1 Sn were reached under optimized conditions. Optimization of the whole experimental setup resulted in 7-fold improvement of sensitivity compared to the original arrangement consisting of a sinusoidal source coupled to a DBD atomizer with glued electrodes in absence of the dryer. Keywords atomic absorption spectrometry, hydride generation, hydride atomization, quart tube atomizer, dielectric barrier discharge (DBD)

This master's thesis deals with the optimization of conditions of chemical hydride generation (HG) of bismuth, its atomization and detection by atomic absorption spectrometry (AAS) and atomic fluorescence spectrometry (AFS). Two types of atomizers were used for atomization of volatile species, a miniature diffusion flame for AAS as well as for AFS and a flame-in-gas-shield atomizer for AFS. At first, the parameters of HG in a flow injection mode were optimized - the concentration of hydrochloric acid, the concentration of sodium borohydride and the volume of the reaction coil. Subsequently, the atomization conditions were optimized using both atomizers. The parameters optimized were hydrogen fraction, total gas flow rate and observation height. Due to the more complicated construction of the FIGS atomizer, more parameters were studied, such as the oxygen flow rate through the capillary and the flow rate of shielding argon required for shielding the free atoms. A special part of the thesis dealt with the optimization of the optical path of the atomic fluorescence spectrometer, the selection of an interference filter and the optimization of a power supply of an electrodeless discharge lamp. It was found that under optimum conditions of generation, atomization and detection excellent detection limits...

Объектами исследования служили лекарственные препараты активированного угля, аскорбиновой кислоты, инсулина, ацетилцистеина и подсластителя, в основе которого лежит шестиатомный спирт – сорбитол. Целью работы является разработка методик определения микропримесей тяжелых металлов в готовых фармацевтических препаратах методом атомной абсорбции. В литературном обзоре рассмотрены вопросы влияния микропримесей тяжелых металлов на стабильность лекарственного средства и степень его лечебного воздействия на организм человека. Показано, что контроль содержания тяжелых металлов является важной задачей фармацевтического анализа. Анализ литературных источников позволяет заключить, что атомно-абсорбционная спектрометрия является наиболее распространенным методом, используемым в фармакопейном анализе для определения тяжелых металлов. В ходе экспериментальной части были апробированы методики определения микропримесей тяжелых металлов в субстанциях и готовых лекарственных препаратах, представленных в Государственной Фармакопее Российской Федерации ; внесены корректировки в процедуру анализа с учетом особенностей состава присутствующих добавок в лекарственных препаратах; правильность полученных результатов определения микропримесей тяжелых металлов в образцах активированного угля методом ААС оценена путем сравнения с независимым методом инверсионной вольтамперометрии. / The objects of the study were activated charcoal, ascorbic acid, insulin, acetylcysteine and a sweetener, which is based on six-atom alcohol – sorbitol. The aim of the work is to develop methods for the determination of trace amounts of heavy metals in finished pharmaceutical preparations by atomic absorption. In a literature review, the issues of the influence of trace metals of heavy metals on the stability of the drug and the degree of its therapeutic effect on the human body are considered. It is shown that control of the content of heavy metals is an important task of pharmaceutical analysis. An analysis of literary sources allows us to conclude that atomic absorption spectrometry is the most common method used in pharmacopoeia analysis to determine heavy metals. During the experimental part, methods were tested for determining microimpurities of heavy metals in substances and finished medicinal products presented in the State Pharmacopoeia of the Russian Federation; adjustments were made to the analysis procedure taking into account the characteristics of the composition of the additives present in the drugs; the correctness of the results of determination of microimpurities of heavy metals in activated carbon samples by the AAS method was evaluated by comparison with the independent method of inversion voltammetry.

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.

O chumbo é um metal muito tóxico e que tem ampla distribuição pela sua grande utilidade. Mesmo a exposição a baixos níveis (que não causam sintomas de intoxicação aguda) de chumbo é associada a desordens cognitivas e neurológicas. O osso é considerado o melhor marcador de exposição a chumbo. No tecido ósseo, vários elementos estão presentes, e alguns deles poderiam ter sua concentração modificada pela exposição a chumbo. Testou-se a hipótese de que haja variações nos elementos Zn e Mg nas tíbias de animais expostos a chumbo (por técnica de química analítica convencional). Testou-se também se variações em microelementos poderiam ser detectadas por técnicas semiquantitativas nas tíbias de controles e animais expostos a chumbo. O objetivo deste projeto foi caracterizar em animais expostos ao chumbo desde a gestação e controles as concentrações deste elemento no osso (tíbia) de animais de 28 e 60 dias. Além do chumbo, investigamos também a concentração de 2 outros microelementos no osso: zinco e magnésio. As medidas quantitativas de chumbo foram feitas no sangue total coletado ao final dos períodos. As medidas quantitativas de chumbo, cálcio, zinco e magnésio foram realizadas a partir de soluções ácidas obtidas pela dissolução total do osso, sendo estas utilizadas para quantificar por Espectrometria de Absorção Atômica no modo chama ou com Forno e Grafite. Mandíbulas foram análisadas em Microscopia Eletrônica de Varredura e utilizando os acessórios Eletron Dispersive Spectroscopy para os elementos mais abundantes e Wavelenght dispersive Spectroscopy para investigar por análise semiquantitativa os mais abundantes elementos inorgânicos no osso destes animais, como forma de verificar se há variações nestes microelementos nos animais expostos a chumbo em comparação com controles. Como o chumbo se concentra na superfície do esmalte, também analisou-se o esmalte de primeiros molares inferiores, a fim de verificar se era visto o sinal do elemento chumbo nestes dentes. Foram usados ratos Wistar machos de 28 e 60 dias divididos em 2 grupos: C 28D (n=5) e Pb 28D (n=5) e, C 60D (n=12) e Pb 60D (n=17). Em todas as medidas de chumbo dos grupos controle as concentrações obtidas foram próximas ao limite de detecção, e houve sempre diferença estatisticamente significante (P<0.0001) quando os controles foram comparados aos grupos expostos a chumbo. As concentrações de chumbo obtidas no sangue de animais do grupo Pb 28D foi de 8,0 ug/dl (± 1.1) e no grupo Pb 60D foi de 7,2 ug/dl (± 0.89). Houve diferença estatisticamente significante entre as massas das tíbias (aferidas em balança e também a partir da quantidade de cálcio dissolvida em solução) do grupo C 60D (0,86 g ± 0,13) e Pb 60D (0,61 g ±0,11)(p=0.0004). As concentrações de chumbo detectadas nos ossos do grupo Pb 28D foi 8,02 (± 1,12) e no grupo Pb 60D foi de 43,3ug/g (± 13,26). Concentração de zinco no osso do grupo C 60D foi 0,22 mg/g e no grupo Pb 60D foi 0,22 mg/g (p>0.05). A concentração de magnésio no osso do grupo C 60D foi de 4,89 mg/g ± 0,74 e no grupo Pb 60D foi de 4,98mg/g ±0,79 (p>0.05). Os microelementos mais abundantes detectados nas tíbias contralaterais por Microscopia Eletrônica de varredura por EDS/WDS foram cálcio, fósforo, carbono, oxigênio, magnésio, sódio e potássio, não tendo sido detectadas variações nestes elementos entre os grupos controle e expostos a chumbo de 60 dias. O chumbo foi detectado apenas na região cervical dos dentes molares por MEV-EDS, e, nesta posição, apenas na forma de óxido de chumbo (deposição extrínseca) que pode ser útil para fins forenses ou de determinação de contaminação desconhecida. As conclusões deste estudo são: Houve diferença estatisticamente significante entre as massas de osso do grupo Pb 60D e C 60D. Mesmo não havendo diferença entre as concentrações de chumbo no sangue total de animais de 28 e 60 dias, houve quantidade de chumbo 5 vezes maior nos animais Pb 60D. Não houve diferenças nas concentrações de zinco e magnésio entre controles e animais expostos a chumbo. Os microelementos mais abundantes detectados nas tibias contralaterais por Microscopia Eletrônica de varredura por EDS/WDS foram cálcio, fósforo, carbono, oxigênio, magnésio, sódio e potássio, não tendo sido detectadas variações semi-quantitativas nestes elementos. O chumbo não foi detectado nem nos grupos controle ou expostos por MEV, e nos molares só foi detectada no grupo exposto como uma deposição extrínseca. / Lead is a highly toxic metal that is ubiquitous do to its great usefulness. Exposure to even low levels of lead (which do not cause symptoms of acute poisoning) is associated with cognitive and neurological disorders. Bone is considered the best marker of exposure to lead. Several chemical elements are found in bone, and some of them may have a different concentration or distribution due to exposure to lead. We tested the hypothesis that there are variations in the elements zinc and magnesium in the tibia of animals exposed to lead (being those elements determined by a conventional analytic chemistry technique). It was also tested whether variations in microelements could be detected by semiquantitative microanalysis in tibias of controls and animals exposed to lead. The objective of this project was to determine the concentration of lead in bone (tibia) of animals exposed to lead from pregnancy to day 28 and day 60. Besides lead, zinc and magnesium were also determined. Lead was also determined in whole blood collected at the end of the 2 time points. Quantitative measurements of lead, calcium, zinc and magnesium have been made in solutions obtained by dissolution of the bone by Atomic Absorption Spectrometry using flame or Graphite Furnace. Tibias were analyzed by scanning electron microscopy using the accessories Electron Dispersive Spectroscopy and Wavelength dispersive Spectroscopy for semiquantitative analysis of inorganic elements in the bone and molars of these animals. Lower molars were also analyzed by these means. Male Wistar rats aged 28 and 60 days were used in these study. In both these ages there were animals in the control (C 28D, n = 5 and C 60D, n=12) and lead exposed group (Pb 28D, n = 5 and Pb 60D, n = 17). Lead concentrations found in control groups were close to the detection limit, and there was always statistically significant differences (P <0.0001) when control groups were compared with those exposed to lead. Blood lead of groups Pb 28D and Pb 60D was 8.0 ug/dl (± 1.1) and 7.2 ug/dl (± 0.89), respectively. There was a statistically significant difference between the masses of the tibia (measured in balance and also from the amount of calcium dissolved in solution): C 60D showing 0.86 g (± 0.13 g) and 0.61 g (± 0, 11) of the Pb 60D group (p = 0.0004). Lead concentrations increased five times when the Pb 28D group was compared with the Pb 60D (8.02 and 43.3 ug/g)(p<0.0001). Zinc concentrations were not different in the C 60D (0.22 mg/g) and in the Pb 60D group (0.22 mg/g)(p>0.05). Magnesium concentrations were 4.89 mg/g in the C 60D and 4.98 mg/g in the Pb 60D (p>0.05). The most abundant trace elements detected in the contralateral tibiae by SEM-EDS/WDS were calcium, phosphorus, carbon, oxygen, magnesium, sodium and potassium and no variations in these elements were detected between the control and lead exposed groups. Lead was detected only in the cervical region of molar teeth of the lead exposed groups by SEM-EDS. This finding revealed lead in the lead oxide (extrinsic deposition) which may be useful for forensic purposes or for determining unknown contaminations. Conclusions: There was a statistically significant difference between the bone masses of the Pb 60D and C 60D groups. While there is no difference between lead concentrations in whole blood of animals 28 and 60 days, the amount of lead was 5 times higher in animals Pb 60D. There were no differences in the concentrations of zinc and magnesium between controls and lead exposed animals. The most abundant trace elements detected in the contralateral tibiae by SEM-EDS/WDS were calcium, phosphorus, carbon, oxygen, magnesium, sodium and potassium, and no semi-quantitative variations in these elements were detected in relation to exposure to lead. Lead was not detected either in control or exposed groups by SEM, and in molars it was only detected in the exposed group as an extrinsic deposition.

Aufgrund der höheren elektrischen Leitfähigkeit und des größeren Widerstandes gegen Elektromigration im Vergleich zum Aluminium wird seit einigen Jahren Kupfer als Leitbahnmaterial in der Mikroelektronik eingesetzt. Da Kupfer jedoch eine hohe Beweglichkeit in den für die Halbleitertechnologie relevanten Werkstoffen aufweist, sind zur Verhinderung einer Diffusion effektive Barrieren notwendig. Dabei muss die u. a. geforderte hohe thermische Stabilität der Barrierematerialien auch im Zuge der fortschreitenden Miniaturisierung der mikroelektronischen Bauelemente und damit der Reduzierung der Barriereschichtdicken sichergestellt sein. Im Rahmen der Arbeit wurden mittels Magnetron-Sputtern neben Ta- und TaN-Einfachschichten sowie Ta-TaN-Mehrfachschichten auch Ta-Si-N-Einfachschichten jeweils mit und ohne Cu-Metallisierung sowohl auf blanke als auch auf thermisch oxidierte Si-Scheiben abgeschieden. Die Dicken der Barriereeinzelschichten und die der Cu-Schichten betrugen 10 nm bzw. 50 nm. Die Beurteilung der Barrierestabilität sowie die Charakterisierung der Ausfallmechanismen erfolgten nach Wärmebehandlungen durch den kombinierten Einsatz von Röntgenstreumethoden, spektroskopischen sowie mikroskopischen Analyseverfahren. In Abhängigkeit von ihrer Zusammensetzung und damit von der Mikrostruktur im Ausgangszustand finden für die zwischen Kupfer und SiO2 abgeschiedenen Diffusionsbarrieren unterschiedliche Prozesse während thermischer Belastungen statt. Bei den mehrstufigen Ta-TaN-Barrieren setzt bereits bei T = 300 °C eine Umverteilung von Stickstoff ein, die bei T = 500 °C in der Bildung von Ta2N-Kristalliten resultiert. Im Fall der Ta-Si-N-Barrieren führt die vorhandene Cu-Metallisierung zu einer an der Cu/Barriere-Grenzfläche beginnenden Kristallisation. Dabei hängen sowohl deren Einsatzzeitpunkt während einer bei konstanter Temperatur durchgeführten Wärmebehandlung als auch das entstehende Kristallisationsprodukt von der Barrierezusammensetzung ab. Im Zuge der Kristallisation erfolgt die vollständige Zerstörung der ursprünglichen Schichtintegrität, so dass Kupfer in unmittelbaren Kontakt zum SiO2-Substrat gelangt. Der sensitive Nachweis einer Cu-Diffusion durch die Barriere erfolgte einerseits durch die Charakterisierung von Cu/Barriere/SiO2/Si-Systemen mit Hilfe spurenanalytischer Methoden und andererseits durch die Untersuchung von Proben mit geändertem Aufbau. Durch Abscheidung der Barrieren zwischen Kupfer und Silizium ist mittels Röntgenbeugung die nach Diffusion von Cu-Atomen ins Substrat einsetzende Bildung von Cu3Si detektierbar. Mit den kritischen Temperaturen für die Bildung dieses Kupfersilizids erfolgte die vergleichende Bewertung der thermischen Stabilitäten der Barrieren. Werden die dünnen Ta-basierten Schichten zusätzlich bezüglich ihres spezifischen elektrischen Widerstandes beurteilt, so stellt sich eine Ta56Si19N25-Diffusionsbarriere als am geeignetsten für den Einsatz in Cu-Metallisierungssystemen heraus. Die mikrostrukturellen Untersuchungen gestatten Aussagen zu den Versagensmechanismen der einzelnen Barrieren. Für die Ta-TaN-Mehrfachschichten wird durch die einsetzende Stickstoffumverteilung und die sich anschließende Ta2N-Bildung bereits frühzeitig die stabile Mikrostruktur der TaN-Schicht zerstört. Während für Ta-Si-N-Schichten mit einem N-Gehalt von bis zu 25 at.% eine Cu-Diffusion ins Substrat erst nach vorzeitiger Barrierekristallisation beobachtet wird, erfolgt sie im Fall der stickstoffreichen Ta-Si-N-Barrieren in einem Zustand, für den mittels Röntgenbeugung eine Kristallisation noch nicht nachweisbar ist. Die Untersuchung der Abhängigkeit der sich während des Cu-Schichtwachstums bzw. einer nachträglichen Wärmebehandlung ausbildenden Cu-Texturkomponenten von der chemischen Zusammensetzung der Unterlage erfolgte mittels röntgenographischer Texturanalyse. Zur Diskussion der beobachteten Vorzugsorientierungen wurde das Modell des zweidimensionalen Kornwachstums in dünnen Schichten herangezogen.