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Construction of miniature flow-through cells for electrochemical generation of volatile compounds
Hraníček, Jakub ; Rychlovský, Petr (advisor) ; Spěváčková, Věra (referee) ; Komárek, Josef (referee)
(EN) The presented dissertation thesis summarizes the new results of electrochemical generation of volatile compounds usable in atomic spectral methods. The main aim of this work is to develop and to characterize new types of electrolytic flow-through cells and to examine their possibilities of determination of arsenic, selenium and antimony by using the electrochemical hydride generation technique coupled with atomic absorption spectrometry with a quartz tube atomizer. Individual electrolytic cells were designed and constructed to comply with two important requirements. The cathode chamber of the electrolytic cell should have a minimal volume and a high efficiency of analyte conversion to the volatile hydride. Constructed electrolytic cells are divided into the construction groups and described in the experimental part. Selenium was chosen as the first analyte. The relevant working parameters (such as type, concentration and flow rate of electrolytes, generation current and carrier gas flow rate) were optimized for each newly constructed electrolytic cell. Under the optimal working parameters, the basic characteristics of selenium determination were found out by using electrochemical hydride generation. The electrolytic cells were compared to each other and with the classical electrolytic cell...
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Speciation analysis of selected mercury compounds using combined technique HPCL-EcMCVG-QFAAS
Leštinová, Veronika ; Červený, Václav (advisor) ; Spěváčková, Věra (referee)
Today, the information about total mercury content in a sample is not enough to know because of different toxicity of various species like inorganic forms such as Hg+ , Hg+II and organic bonded mercury in Methyl-mercury, Ethyl-mercury or Phenyl-mercury. Therefore a speciation analysis is needed to do. The aim of this diploma thesis was to develop and validate a new method for speciation determination of selected mercury compounds. This method comprises a connection of high performance liquid chromatography, electrochemical mercury cold vapor generation as a postcolumn derivatization technique and atomic absorption spectrometer. Using this on-line connection of mentioned techniques, an efficient separation of Hg+II and methylmercury was achieved. Reached limits of detection were 0.3 µgml-1 and 0.5 µgml-1 for Hg+II and methylmercury, respectively. At the end of experimental work, proposed hyphenated technique HPLC- EcMCVG-QFAAS was used for determination of these two mercury compounds in six real tap water samples (Bílý potok, Bílina, Labe, Vltava, Botič, pond Kovošrot). In Bílý potok, inorganic mercury (Hg+II ) was identified on the base of identical of retention time compared to standard. Standard addition method was used in both FIA and HPLC arrangements and determined content of Hg+II was (0.4...
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Contributions to Volatile Compound Generation of Arsenic, Silver and Gold by Tetrahydroborate Reaction for Atomic Absorption Spectrometry
Musil, Stanislav ; Rychlovský, Petr (advisor) ; Kanický, Viktor (referee) ; Spěváčková, Věra (referee)
(EN) The presented dissertation thesis summarizes the results contained in five original research papers that were published in prestigious international scientific journals in the field of analytical chemistry and atomic spectrometry. It is devoted to the method of generation of volatile compounds using a tetrahydroborate reaction and detection in a quartz multiatomizer by atomic absorption spectrometry. The thesis can be divided into two thematic parts - speciation analysis of arsenic based on hydride generation technique with collection and separation in a cryogenic trap and generation of volatile species of transition metals. In the first thematic part pre-reduction of pentavalent inorganic and methylated arsenicals has been studied. A simple setup for on-line pre-reduction employing thioglycolic acid as a fast pre-reductant has been developed, connected with a current hydride generator and applied/verified to oxidation state specific arsenic speciation analysis of human urine samples. In the same method the possibility of drying the gaseous phase from water vapor has been investigated to avoid incidental blocking the cryogenic trap by frozen water and to decrease fluctuations of signal baseline. Pronounced losses of methylated species have been discovered on Nafion tube dryer currently used in...
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Digestion methods for speciation analysis of toxicologically important forms of arsenic in tissue by hydride generation with cryotrapping and atomic absorption spectrometry
Taurková, Petra ; Rychlovský, Petr (advisor) ; Spěváčková, Věra (referee)
This diploma thesis develops methodology of arsenic speciation analysis by selective hydride generation with cryotrapping and atomic absorption spectrometry. Using this technique it is possible to determine toxicologically important forms of arsenic, i.e arsenites, arsenates and their mono-, di-, and trimethylated forms at concentration levels below 0,1 ng.ml-1 . The first part of the thesis is focused on testing tubular membrane gas dryers with nafion membrane for drying gaseous phase containing generated hydrides. The suitability for arsenic speciation analysis was investigated and transport losses of individual arsenic species were found. The second part describes mild digestion procedures suitable for arsenic speciation analysis in tissues. Two procedures were compared, acid digestion in phosphoric acid and more recent alkalic digestion by tetramethylammonium hydroxide. Digestion procedures were tested on certified reference material DOLT - 4 (Dogfish Liver) and chicken liver matrix. Key words: Tubular nafion membrane dryers, Arsenic speciation analysis, Digestion, Phosphoric acid, Tetramethylammonium hydroxide, Chicken liver, CRM DOLT - 4, Hydride generation, Atomic absorption spectrometry
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Novel Approaches to the Application of Electrochemical Volatile Compounds Generation in Spectrometric Methods
Červený, Václav ; Rychlovský, Petr (advisor) ; Spěváčková, Věra (referee) ; Komárek, Josef (referee)
Various possibilities for the use of electrochemical generation of volatile compounds for the determination of trace and ultratrace quantities of elements using atomic absorption spectrometry and optical emission spectrometry, respectively, were studied in this work. The Thesis is divided into four thematic sections. Electrochemical cold mercury vapor generation is common to the first two parts. The third part is devoted to electrochemical generation of the volatile form of cadmium and the last part deals with the use of the electrochemical hydride generator as a derivatization unit for speciation analysis of arsenic compounds. The optimization of each individual determination was carried out including, for example, various designs of the generator of volatile compounds (forms) of the analyte, the changes in the design of the gas-liquid separator, optimization of the concentration and the flow rate of all the solutions and the carrier gas. However, the value of the electric current employed was the most important parameter. In the first section, the in-situ trapping system of the cold mercury vapor generated in the graphite furnace (with the inner surface covered with a gold foil) of the atomic absorption spectrometer was also designed and optimized. The absolute limit of detection, 80 pg, was...
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Preconcentration of Hydride Forming Elements in Quartz Atomizers for Atomic Absorption Spectrometry
Kratzer, Jan ; Dědina, Jiří (advisor) ; Komárek, Josef (referee) ; Spěváčková, Věra (referee)
CHARLES UNIVERSITY IN PRAGUE FACULTY OF SCIENCE Department of Analytical Chemistry PRECONCENTRATION OF HYDRIDE FORMING ELEMENTS IN QUARTZ ATOMIZERS FOR ATOMIC ABSORPTION SPECTROMETRY Synopsis of the PhD Thesis Prague 2008 RNDr. Jan Kratzer 2 CONTENTS CONTENTS................................................................................................................... 2 CURRICULUM VITAE............................................................................................... 4 LIST OF PUBLICATIONS ......................................................................................... 6 ABSTRACT................................................................................................................... 9 1 ULTRATRACE ANALYSIS OF HYDRIDE FORMING ELEMENTS ....... 11 2 OBJECTIVES OF THE THESIS ...................................................................... 13 3 EXPERIMENTAL .............................................................................................. 15 3.1 Apparatus ....................................................................................................... 15 3.2 Procedure........................................................................................................ 16 3.3 Detection by atomic absorption spectrometry...
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