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Interferences in determination of antimony by UV-photochemical generation of volatile compounds and atomic fluorescence spectrometry
Kračmarová, Aneta ; Červený, Václav (advisor) ; Hraníček, Jakub (referee)
This work is focused on the study of interferents of selected elements during UV-photochemical generation of volatile antimony compounds. The interferents included transition metals, halides, hydride-forming elements and salts of mineral acids. Detection was performed by atomic fluorescence spectrometry. Some of the tested added substances proved to be potential reaction modifiers; in their presence, an increase in responses was observed. The best results were obtained using Fe3+ for the determination of Sb3+ and SO4 2- had the best results for the determination of Sb5+ . The largest interferent, i.e. the substance causing the most significant decrease in signal, was for both antimony ions Se4+ .
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UV-photochemical generation of volatile compounds of selenium and tellurium
Nováková, Eliška
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...
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Study of properties of UV-photochemical generation of volatile compounds od antimony
Adámková, Dominika ; Červený, Václav (advisor) ; Hraníček, Jakub (referee)
The master thesis deals with comparison of atomic fluorescence spektrometry and high resolution continuum source atomic absorption spektrometry for three methods generation of volatile compounds Antimony. In both methods of atomic antimony detection, it compares the most common chemical generation of volatile compounds (hydrides) with two alternative methods - electrochemical and UV - photochemical. The values of performance parameters for the determination of Sb(III) and Sb(V) were determined for all the above combinations. In the case of chemical generation, a surprisingly almost four times higher limit of detection of Sb(III) was found in connection with AFS detection than AAS detection. The final part was devoted to UV - photochemical vapor generation, with AAS detection for Sb(III) reaching limit of detection 4,96 ppb, for Sb(V) 8,63 ppb. Although UV - photochemical generation of volatile antimony compounds did not reach such performance parameters as chemical or electrochemical generation, it was observed that the sensitivity of antimony determination increased greatly when introducing oxygen into the apparatus. The interference study also found a significant positive effect of Fe(II) on the generation efficiency, and this modification partially persisted without further introduction of these...
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Determination of Te(IV) by photochemical generation of volatile compounds with atomic spectrometric detection
Ruxová, Helena ; Hraníček, Jakub (advisor) ; Šíma, Jan (referee)
This thesis deals with the development of a method suitable for determination Te(IV) by UV-photochemical generation of volatile compounds (UV-PVG) in liquid samples. Atomic absorption spectrometry (AAS) and atomic fluorescent spectrometry (AFS) were used as detection methods. The basis of the apparatus for UV-PVG was a mercury lamp wrapped by PTFE capillary. Firstly, the experimental parameters were optimized for both methods. The optimized parameters were the type, concentration, pH and flow rate of the reaction medium, the length of the PTFE reaction coil, carrier gas flow rate (argon), supportive gas flow rate (hydrogen) and atomization temperature. The figures of merit with both detection methods were determined and compared after the method was optimized. Detection limits achieved for these two detection methods were 6,0 µg dm-3 for AFS and 1,50 µg dm-3 for AAS. Performed interference study confirmed a significant effect of many cations of transition metals and hydride forming elements on tellurium determination. The influence of nitric acid in the sample was studied separately. The suitability of the method for tellurium determination was confirmed by using a spiked certified reference material.
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Hydride generation of bismuth for atomic absorption and fluorescence spectrometry.
Kolrosová, Marta ; Musil, Stanislav (advisor) ; Nováková, Eliška (referee)
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...
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UV-photochemical generation of cadmium volatile compounds with atomic spectrometric detection
Horová, Kateřina ; Nováková, Eliška (advisor) ; Červený, Václav (referee)
The aim of this master's thesis has been to develop and optimize the method of UV- photochemical vapor generation of cadmium volatile compounds for atomic fluorescence spectrometry. Two configurations with different materials wrapped around the low-pressure mercury vapor lamp were tested. I experimentally determined optimal conditions for both systems; the optimalized parametres included selection of photochemical reagent and its concentration, flow rate of liquids and gases, and the lenghth of the reaction coil. After finding the optimal parametres I determined the figures of merit of the method. I found from the measured data that UV-photoreactor with the quartz capillary provided lower limits of detection and thus was more suitable for generation of cadmium volatile compounds. With this arrangement and using the ferrous sulphate heptahydrate as the chemical modifier I obtained limit of detection 2,0 µg·l-1 , limit of determination 7,0 µg·l-1 , linear dynamic rate LOD-50 µg·l-1 and repeatibility 0,35 %. I also carried out the interference study in my thesis and determined the generation effeciency of cadmium volatile compounds. The interference study shows the influence of mineral acids (HCl, H2SO4, HNO3), their salts (NaNO2, NaNO3) and transition metals (Co, Ni, Cu). Based on literature review I also...
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UV-photochemical generation of volatile compounds of selenium and tellurium
Nováková, Eliška
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...
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Miniature plasma DBD atomizer for AAS and AFS
Straka, Marek ; Kratzer, Jan (advisor) ; Hrdlička, Aleš (referee)
Five designs of dielectric barrier discharge (DBD) atomizers have been constructed and optimized employing arsane as a model analyte. The individual DBD designs differed from each other in the style of electrode attachment, electrode shape and area. An externally heated quartz tube atomizer and another DBD atomizer design that have been studied before were used as reference. All the atomizer designs studied including the reference atomizers were found compatible with detection by atomic absorption spectrometry (AAS) giving comparable sensitivity of 0.44 s ng-1 As and detection limit around 0.2 ng ml-1 As under optimum atomization conditions. However, significant differences in optimum operation conditions were found among the DBD designs in terms of the applied voltage depending strongly on the style of electrode attachment. The design with metal strip electrodes glued to a quartz body requires more than 14 kV to be operated. The design with sputtered electrodes of the same shape can reach the same sensitivity with 8.5 kV. Selected DBD designs have been proven to be compatible also with other spectrometric detectors such as atomic fluorescence spectrometry (AFS) reaching detection limit 0.05 ng ml-1 As or atomic emission spectrometry (AES) with detection limit of 30 ng ml-1 As showing the...
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Comparison of various approaches to determination of antimony by atomic fluorescence spectrometry
Adámková, Dominika ; Červený, Václav (advisor) ; Hraníček, Jakub (referee)
Bakalářská práce se zabývá porovnáním tří způsobů generování těkavých sloučenin pro stanovení antimonitých a antimoničných iontů pomocí atomové fluorescenční spektrometrie. Pro porovnání jednotlivých stanovení byly vždy nejprve nalezeny nejvhodnější experimentální podmínky. Protože je chemické generování považováno za nejúčinnější v porovnání s ostatními typy generování a je také nejčastěji používáno, bylo charakterizováno jako první. Bylo dosaženo limitu detekce 0,12 ppb pro Sb3+ a 0,28 ppb pro Sb5+ . Ovšem nejvyšší citlivosti a nejnižšího limitu detekce bylo dosaženo pro elektrochemické generování hydridu antimonu. Metoda EcHG byla přibližně 4×citlivější než technika CHG. Dosaženo bylo limitu detekce 9 ppt pro Sb3+ a 45 ppt pro Sb5+ . Nejnižší citlivost byla získána podle předpokladu při UV - fotochemickém generování, a to přibližně 9×nižší oproti elektrochemickému generování. Celkově stanovení antimonitých iontů bylo nejméně 4×citlivější než stanovení antimoničných iontů. Podle tvaru píku usuzuji, že tvorba těkavé sloučeniny probíhala u všech způsobů generování v případě Sb5+ pomaleji než u Sb3+ . Klíčová slova Atomová fluorescenční spektrometrie, antimon, generování těkavých sloučenin, chemické generování těkavých sloučenin, UV - fotochemické generování těkavých sloučenin, elektrochemické...
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Development of Instrumentation and Methodology for Elemental and Speciation Analysis of Arsenic Based on Hydride Generation and on Atomic Fluorescence Spectrometric Detection
Marschner, Karel ; Dědina, Jiří (advisor) ; Kanický, Viktor (referee) ; Spěváčková, Věra (referee)
(EN) The presented dissertation is devoted to hydride generation from arsenic species and its application for speciation analysis based on atomic fluorescence detection. Hydride generation from toxicologically relevant arsenic species was optimized in order to achieve a 100% efficiency. The resulted experimental setup was subsequently used for speciation analysis of arsenic in human urine by high performance liquid chromatography with detection by atomic fluorescence spectrometry. The accuracy of the developed method was verified by comparative analyses of human urine samples collected from five individuals with an independent reference method. The cleavage of As-C bond during the reaction of methylated arsenic species with tetrahydridoborate(1-) (THB) in acidic media was studied in detail. Pronounced demethylation of methylated arsenic species was found during the reaction of THB with HCl, H2SO4, and HClO4 while hydride generation from CH3COOH or TRIS buffer after prereduction with L- cysteine resulted in the exclusive formation of the corresponding hydrides. Firstly, this phenomenon can endanger the accuracy of arsenic speciation which is based on hydride generation of substituted arsanes. Secondly, the more complex arsenic species can be converted to the hydride. That was demonstrated on hydride...
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