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Metals Transport in the System Soil/Plant. Comparison of the Active and Passive Sampling Method (The Diffusive Gradients in Thin Films Technique)
Trávníčková, Jana ; Janoš, Pavel (referee) ; Chýlková, Jaromíra (referee) ; Čelechovská, Olga (referee) ; Dočekalová, Hana (advisor)
The doctoral thesis deals with comparison between copper uptake by radish (Raphanus sativus L.) and concentration of copper measured by a DGT-device and concentration of copper obtained by extraction with generally used extraction agents (HNO3, NaNO3 and water). Plants were cultivated in pot experiments on a tested non-treated and gradually spiked soil. The amount of copper was determined in various part of radish (whole plant, above- and below-ground part) after mineralization in the APION mineralizer by ET – AAS. The highest concentration was in belowground part, especially in root tissues and sheel of root bulb. It confirms copper is associated with cell walls. The amount of copper taken by radish up does not pass beyond sanitary standards not even in spiked soils and consummation of radish is not unhealthy. Good correlations were found between copper concentration in radish and the amount of copper extracted with HNO3, NaNO3 and water and the amount found in soil solution. Results of extraction with HNO3 confirmed the amount of copper was stable in spiked soils during the pot experiments. The DGT experiments have shown that the rate of resupply from the solid phase to soil solution is constant during the deployment time. Whereas the release of copper decreases after 24 hours in natural soil. Copper added to soil in form of cupric ions is present in the different form after one month-equilibration than copper present in unspiked soils. The results obtained by DGT measurements were approximately up to two orders of magnitude lower than copper concentration obtained by leaching with sodium nitrate. The extraction with sodium nitrate does not provide true reflection of metal availability to plant root system and soil microorganism. High values of correlation coefficients (R2 > 0,9) were found between concentration of copper in radish plant and the concentration of copper in soil solution measured by DGT technique. Concentration of copper in soil solution was three times higher than concentration measured by DGT technique. Soil solution contains species of copper that are not measured by DGT technique and available to plants. Concentration of metals obtained by DGT measurements is more closely to real concentration of bioavailable forms of metal in soil. Therefore it is possible to recommend the DGT technique as a technique for determination of bioavailable forms of copper in soils.
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Non-energy Applications of Lignite
Majzlíková, Petra ; Maršálek, Roman (referee) ; Janoš, Pavel (referee) ; Pekař, Miloslav (advisor)
This thesis deals with various physical-chemical aspects of agricultural and environmental applications of the South Moravian lignite. The main attention was paid to the behavior of lignite in an aqueous environment and the application potential of lignite as a cheap, effective and universal sorbent. In the experimental part of the thesis, aqueous extracts of lignite were characterized in detail (by measurement of pH, conductivity, and by the qualitative and quantitative determination of inorganic constituents). The high sorption affinity towards polar (cationic dyes) and nonpolar compounds (petroleum products) was confirmed experimentally. At last, simple methods of the laboratory preparation of lignite granules was designed and optimized. The main aim of this part was to combine the unusual sorption properties of lignite with an improvement of the end-use properties of the product (user-friendly handling, controlled release of the lignite into the aqueous environment, etc.). The thesis represents a complex compilation of the results of pilot experiments which represent the starting point of detailed future works focused on the non-energetic application of this valuable natural material.
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Investigation of Miniature Devices for Collection of Hydride Forming Elements in Atomic Spectrometry Methods
Krejčí, Pavel ; Čelechovská, Olga (referee) ; Janoš, Pavel (referee) ; Otruba, Vítězslav (referee) ; Dočekal, Bohumil (advisor)
Capability of a prototype of miniature collection device based on a strip of the molybdenum foil for collecting hydride forming elements (As, Se, Sb and Bi) was studied. The device was combined with a miniature hydrogen diffusion flame for detection by atomic absorption spectrometry. The conditions for trapping and subsequent vaporization of analytes of interest were optimized. A twin-channel hydride generation system was used for study of mutual interference effects of co-generated hydride forming elements. The influence of modification of the molybdenum surface with noble metals - Rh, Pt and Ir on trapping and vaporization processes was also studied and changes of microstructure of the foil surface after modification were investigated using scanning electron microscope equipped with energy dispersive x-ray analyzer and electron backscattered diffraction system. Complementary radiotracer and radiography experiments were performed in order to determine trapping efficiency and to assess the spatial distribution of collected analytes within the device. Practical application of the method was demonstrated on determination of antimony in water samples at trace level. Possibility of multi-element analysis was demonstrated by combining the collection device with atomization and excitation of the analyte in microwave induced plasma and with detection by atomic emission spectrometry method. The results of the experiments proved that tested miniature collection device is capable of trapping analytes that form volatile hydrides. This device can be coupled to various types of atomizers, typically used in spectrometry methods. Thus, very sensitive and specific detection of hydride forming elements can be performed.
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Modification of Diffusive Gradient in Thin Films Technique for Characterization of Environmental Systems
Gregušová, Michaela ; Sommer, Lumír (referee) ; Janoš, Pavel (referee) ; Dočekal, Bohumil (advisor)
Diffusive gradient in thin film technique (DGT) represents a relatively new approach for in situ determinations of labile metal-species in aquatic systems. The DGT device passively accumulates labile species from the solution while deployed in situ, and therefore contamination problems associated with conventional collection and filtration procedures are eliminated. This study deals with a possible modification of DGT technique. The key of using DGT technique for speciation analysis of metals is to find out suitable binding phase and diffusion layer. The new resin gel based on Spheron Oxin (5 sulphophenyl-azo-8-hydroxyquinoline) ion exchanger with a higher selectivity to trace metals than Chelex 100 could potentially provide more information on metals speciation in aquatic systems. The performance of this new binding phase was tested for the determination of Cd, Cu, Ni, Pb and U under laboratory conditions. The hydrogel layer based on poly(2-hydroxyethyl methacrylate) was synthesized and tested as a new diffusion gel for application in DGT technique.
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Development of Gel Techniques for in situ Measurement of Bioavailable Metals in Soils and Sediments
Kovaříková, Vladěna ; Sommer, Lumír (referee) ; Janoš, Pavel (referee) ; Dočekalová, Hana (advisor)
The doctoral thesis deals with usage of gel techniques for in situ measurement of bioavailable metals in soils and sediments. The DGT technique was applied to soil samples from the localities of Zlín, Tuřany and Chrlice for estimation of bioavailable metals in soils. These soils were amended by sewage sludges in years 1980-1987. The experiment using diffusive gels with different pore size, APA and RG gels, has shown that the DGT can be used for assessment of trace metal soil complexes - small inorganic and larger organic. The results obtained by DGT measurements were approximately up to two orders of magnitude lower than metal concentrations obtained by leaching with sodium nitrate. The leaching with sodium nitrate does not provide true reflection of metal availability to plant root system and soil microorganisms and the DGT technique seems to be a better predictor of metal bioavailability. Only small differences between undisturbed and homogenized soil samples were found out by application of DGT to soil samples from localities of Veverská Bítýška and Ostrovačice. The undisturbed soil is not homogenous and the DGT unit gives information only about the part of the soil which is in direct contact with the unit. The procedure with soil slurry can be recommended for the characterization of large soil areas and estimation of bioavailable metals in soils. Gel techniques were also used for the study of processes occuring in sediments. Mercury species and other metals were analysed in surface water, pore water and sediments collected from two sampling sites in the Dele River in northern France. This river had been polluted during the last century by the activity of Métaleurop factory, which dealt with metal ore treatment. The application of DGT technique using two specific ion-exchange resins, Chelex-100 and Duolite GT-73, provided assessment of mercury in sediment pore water. DGT and DET techniques together with centrifugation provided also high resolution depth profiles of Fe, Mn, Zn, Pb, Cr and Cd in pore water. It is not possible to determine which sampling site was more contaminated. Only small differences in mercury species and metal content were observed between sampling sites. The Dele River can be classified as contaminated river according to total mercury content in sediments and as slightly contaminated river from the point of view of methylmercury content. Correlations between mercury species and sulphide content confirm that total mercury and sulphide content count among factors influencing the mercury release to pore water and controlling processes of methylation and demethylation. Only low toxicity of sediment slurries was found out by the bioluminiscence test with Vibrio fischeri. The results of doctoral thesis demonstrate gel techniques as a very good tool in environmental analysis.
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Humic Substances Characterization Employing High Resolution Ultrasonic Spectroscopy
Drastík, Martin ; Franců, Juraj (referee) ; Janoš, Pavel (referee) ; Pekař, Miloslav (advisor)
Předkládaná dizertační práce se zabývá využitím techniky vysoce rozlišovací ultrazvukové spektroskopie (HRUS) při analýze huminových látek, za účelem získání hlubšího vhledu do problematiky vztahu mezi jejich primárními charakteristikami (elementární složení a rozložení uhlíku ve funkčních skupinách) a agregačními vlastnostmi. V literární rešerši jsou shrnuty nejnovější poznatky z oblasti studia huminových látek a představeny základní principy HRUS. Dále jsou uvedeny základní informace z oblasti fraktální analýzy a její aplikace na data získaná pomocí různých metod při studiu huminových látek. První úkol experimentální části je zaměřen na výhodné využití HRUS pro výzkum huminových látek, zde reprezentovaných standardy Mezinárodní společnosti pro huminové látky (IHSS) a to sodnými solemi huminových a fulvinových kyselin. Fulvinové kyseliny v jejich protonované formě byly taktéž zkoumány a to z důvodu objasnění vlivu sodného kationu. Pro popis chování vzorků byla použita mocninná funkce, jejíž empirické parametry byly korelovány s primárními charakteristikami. Byla vytvořena metoda fraktální analýzy a následně byla aplikována na data získána ultrazvukovou spektroskopií. Data získaná pomocí ultrazvukové spektroskopie byla zpracována i alternativní metodou. Ta spočívala v globálním pohledu na závislost ultrazvukové rychlosti na koncentraci a využití lineární regrese. Druhým z cílů práce je získání informací o vlivu teploty na stabilitu agregátů HS (IHSS standardy). Byl zkoumán vliv teplotních gradientů na chování agregátů při čtyřech různých koncentracích. V třetí části práce pak byly zkoumány koncentrační závislosti u vzorků pocházejících především z lokalit příliš nezasažených lidskou činností. HRUS data byla proložena mocninnou funkcí a zkoumána pomocí fraktální analýzy. Takto získané parametry byly korelovány s primárními vlastnostmi. Ze znalosti hustoty při dané koncentraci mohly být stanoveny velikosti hydratačních obálek. Jak se v současné době ukazuje, informace o agregačním chování huminových biomolekul mohou být v budoucnu velmi důležité pro navrhování průmyslových aplikací huminových látek, zejména v zemědělství a v ochraně životního prostředí, ale také například v medicíně.
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Determination of methanol derivatives in drying oils
Horká, Hana ; Hraníček, Jakub (advisor) ; Janoš, Pavel (referee)
The formation of metal carboxylates is a major problem for historical and contemporary paintings, and therefore understanding the mechanism of their formation is a crucial step for developing appropriate conservation strategies and preserving the world's cultural heritage. The determination of reactive components in drying oils is an important step towards understanding the reaction mechanism. This work is aimed at developing a simple and rapid methodology for HPLC-DAD determination of low molecular weight degradation products of traditional drying oils, namely methanol, formaldehyde and formic acid. In this work, QuEChERS conditions for the extraction of methanol, formaldehyde and formic acid from various oil samples (olive, walnut, poppy and linseed oils) were optimized followed by purification of the samples from the oil matrix using a commercial d-SPE sorbent (Z-Sep/C18) and two nanostructured sorbents, CeO2 and ZrO2.
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Non-energy Applications of Lignite
Majzlíková, Petra ; Maršálek, Roman (referee) ; Janoš, Pavel (referee) ; Pekař, Miloslav (advisor)
This thesis deals with various physical-chemical aspects of agricultural and environmental applications of the South Moravian lignite. The main attention was paid to the behavior of lignite in an aqueous environment and the application potential of lignite as a cheap, effective and universal sorbent. In the experimental part of the thesis, aqueous extracts of lignite were characterized in detail (by measurement of pH, conductivity, and by the qualitative and quantitative determination of inorganic constituents). The high sorption affinity towards polar (cationic dyes) and nonpolar compounds (petroleum products) was confirmed experimentally. At last, simple methods of the laboratory preparation of lignite granules was designed and optimized. The main aim of this part was to combine the unusual sorption properties of lignite with an improvement of the end-use properties of the product (user-friendly handling, controlled release of the lignite into the aqueous environment, etc.). The thesis represents a complex compilation of the results of pilot experiments which represent the starting point of detailed future works focused on the non-energetic application of this valuable natural material.
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Metals Transport in the System Soil/Plant. Comparison of the Active and Passive Sampling Method (The Diffusive Gradients in Thin Films Technique)
Trávníčková, Jana ; Janoš, Pavel (referee) ; Chýlková, Jaromíra (referee) ; Čelechovská, Olga (referee) ; Dočekalová, Hana (advisor)
The doctoral thesis deals with comparison between copper uptake by radish (Raphanus sativus L.) and concentration of copper measured by a DGT-device and concentration of copper obtained by extraction with generally used extraction agents (HNO3, NaNO3 and water). Plants were cultivated in pot experiments on a tested non-treated and gradually spiked soil. The amount of copper was determined in various part of radish (whole plant, above- and below-ground part) after mineralization in the APION mineralizer by ET – AAS. The highest concentration was in belowground part, especially in root tissues and sheel of root bulb. It confirms copper is associated with cell walls. The amount of copper taken by radish up does not pass beyond sanitary standards not even in spiked soils and consummation of radish is not unhealthy. Good correlations were found between copper concentration in radish and the amount of copper extracted with HNO3, NaNO3 and water and the amount found in soil solution. Results of extraction with HNO3 confirmed the amount of copper was stable in spiked soils during the pot experiments. The DGT experiments have shown that the rate of resupply from the solid phase to soil solution is constant during the deployment time. Whereas the release of copper decreases after 24 hours in natural soil. Copper added to soil in form of cupric ions is present in the different form after one month-equilibration than copper present in unspiked soils. The results obtained by DGT measurements were approximately up to two orders of magnitude lower than copper concentration obtained by leaching with sodium nitrate. The extraction with sodium nitrate does not provide true reflection of metal availability to plant root system and soil microorganism. High values of correlation coefficients (R2 > 0,9) were found between concentration of copper in radish plant and the concentration of copper in soil solution measured by DGT technique. Concentration of copper in soil solution was three times higher than concentration measured by DGT technique. Soil solution contains species of copper that are not measured by DGT technique and available to plants. Concentration of metals obtained by DGT measurements is more closely to real concentration of bioavailable forms of metal in soil. Therefore it is possible to recommend the DGT technique as a technique for determination of bioavailable forms of copper in soils.
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Investigation of Miniature Devices for Collection of Hydride Forming Elements in Atomic Spectrometry Methods
Krejčí, Pavel ; Čelechovská, Olga (referee) ; Janoš, Pavel (referee) ; Otruba, Vítězslav (referee) ; Dočekal, Bohumil (advisor)
Capability of a prototype of miniature collection device based on a strip of the molybdenum foil for collecting hydride forming elements (As, Se, Sb and Bi) was studied. The device was combined with a miniature hydrogen diffusion flame for detection by atomic absorption spectrometry. The conditions for trapping and subsequent vaporization of analytes of interest were optimized. A twin-channel hydride generation system was used for study of mutual interference effects of co-generated hydride forming elements. The influence of modification of the molybdenum surface with noble metals - Rh, Pt and Ir on trapping and vaporization processes was also studied and changes of microstructure of the foil surface after modification were investigated using scanning electron microscope equipped with energy dispersive x-ray analyzer and electron backscattered diffraction system. Complementary radiotracer and radiography experiments were performed in order to determine trapping efficiency and to assess the spatial distribution of collected analytes within the device. Practical application of the method was demonstrated on determination of antimony in water samples at trace level. Possibility of multi-element analysis was demonstrated by combining the collection device with atomization and excitation of the analyte in microwave induced plasma and with detection by atomic emission spectrometry method. The results of the experiments proved that tested miniature collection device is capable of trapping analytes that form volatile hydrides. This device can be coupled to various types of atomizers, typically used in spectrometry methods. Thus, very sensitive and specific detection of hydride forming elements can be performed.
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