The diploma thesis is dealing with monitoring of arsenic in foodstuffs. The aim of this thesis is the determination of arsenic in samples of fish and rice and the study of forms, in which arsenic occurs, using speciation analysis. Arsenic is known as a toxic element, but its measure of toxicity depends on the chemical form it occurs in. Arsenic is present in the environment naturally or it gets in the environment by human activities. Complete characterization of arsenic compounds is necessary to understand intake, accumulation, transport, detoxification and activation of this element in the natural environment and living systems. The field of arsenic speciation analysis has grown rapidly in recent years, because determination of the total element content is not sufficient in the case of arsenic. Speciation method was done using separation by high performance liquid chromatography and detection by atomic fluorescence spectrometry with hydride generation. Extractable arsenic was present in the form of nontoxic arsenobetaine in all analysed samples of fish. In samples of rice there was confirmed the presence of toxic inorganic species of arsenic, esspecially As (III), but their concentration was at low level.

This diploma thesis deals with a potential contamination of hazardous metals of soil and sediments. The metals cadmium, copper, lead and mercury were chosen, their specification, limited concentration and methods of determination are also described in thesis. City Jihlava and its surroundings were chosen for evaluating pollution of the soil and sediments in this area. In collected samples of the soil and sediments presence of copper, cadmium, lead and mercury were detected via atomic absorption spectrometry (F-AAS, ET-AAS, AMA 254). The metal pollution of soils and sediments by hazardous elements in Jihlava River and in Jihlava region was evaluated.

The theoretical part of this master’s thesis is mainly focused on the physical and chemical properties of chromium, its toxicity and possibility of entering of various forms of chromium into the environment. There are also described the most common analytical methods for determination of chromium in water, including ways of modification and preconcentration water samples. The aim of experimental part is the optimalization and assessing the conditions spectrophotometric determination of Cr(III) by selected organic reagents (chromazurol S, eriochromcyanine R, 4-(2-thiazolylazo)resorcinol) and their comparison with the determination of total chromium, as Cr(III), using atomic absorption spectrometry with electrothermic atomization. The analytical procedure for spectrophotometric determination of chromium with chromazurol S, which was found to be most suitable and ET-AAS, were applied to real water samples.

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...

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.