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Development of Diffusive Gradients in Thin Films Technique for Determination of Mercury in Aquatic Systems
Szkandera, Roman ; Chýlková, Jaromíra (referee) ; Čelechovská, Olga (referee) ; Řehůřková, Irena (referee) ; Dočekalová, Hana (advisor)
The theoretical part of this doctoral thesis deals with determination of mercury and its species in aquatic systems. Special attention is paid to the use in situ sampling technique diffusive gradients in thin films technique (DGT) and its development. Current resin gels used for determination of mercury by DGT technique Duolite GT-73, Chelex-100 and Spheron-Thiol are described. Moreover, new types of resin gels including Iontosorb AV modified by imidazole or 6-mercaptopurine and commercially available titanium dioxide. Preparations of resin gels and their basic tests in model solution according to DGT Research are described. Mercury accumulation in relation to time and basic recovery test were tested and capacity of resins was determined. All tested resins meet the requirements of basic DGT Research tests and relative standard deviations of mercury in recovery tests were lower than 10 %. The sorption capacity of resins varied from 1,5 to 6 µmol.l-1 and decreased in following order: Duolite GT-73 > ISAV-IM > Chelex-100 > Spheron-Thiol > TiO2 > ISAV-MP. Mercury sorption on resins was investigated under conditions similar to those in natural waters. It was found that the ionic strength commonly occurring in natural waters does not affect the determination of mercury. The presence of chlorides significantly affects the determination of mercury using DGT with titanium dioxide and therefore this sorbent can not be recommended for the determination of mercury in sea waters. The accumulated amount of mercury, depending on the pH shows that all the sorbents can be used in natural waters with pH in the range form 4 to 8. Mercury sorption is most affected by the presence of humic acids, especially at ion-exchange resins containing other than thiol functional groups. The exception is titanium dioxide for which physical sorption of humic acid metal complexes is typical. Cadmium and copper in model solutions in the molar balance of the excess mostly influenced the sorption of mercury on Chelex-100 and Spheron-Thiol resins. After laboratory tests, the DGT units with studied sorbents were used for the determination of mercury in natural waters of South Moravia (Svratka, Jihlava and Svitava river). Mercury concentration determined using DGT units containing Duolite GT-73 resin was comparable to the total dissolved concentration of mercury in river water provided by direct determination using AAS technique. Order of magnitude smaller concentrations than the total dissolved mercury concentration were found using DGT containing Spheron-Thiol and ISAV-MP resins. These sorbents are probably able to capture only mercury present in the form of labile complexes. This can be used for speciation analysis if more DGT units with different resins are deployed together. Subtracting the measured DGT Spheron-Thiol or ISAV-MP concentrations from the DGT Duolite GT-73 concentration, information about the amount of mercury present in the form of stabile complexes can be obtained. The amount of mercury determined after application of DGT units containing ISAV-IM, Chelex 100 or TiO2 can probably represent the mercury fraction bound in even weaker complexes than fraction determined by Spheron-Thiol and ISAV-MP DGT.
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Analysis of Organic Markers for Identification of Sources of Atmospheric Aerosols
Křůmal, Kamil ; Chýlková, Jaromíra (referee) ; Vávrová, Milada (referee) ; Smolík,, Jiří (referee) ; Večeřa, Zbyněk (advisor)
In this work the organic markers that serve for identification of sources of aerosols are monitored. Theoretic part deals with detailed survey of organic markers emitted from the most significant sources of atmospheric aerosols (biomass combustion, combustion of fossil fuels and traffic) as well as with sampling of aerosols and analysis of organic markers by analytical techniques. Monosaccharide anhydrides (emissions from biomass combustion) and polyaromatic hydrocarbons (emissions from traffic and incomplete combustion) were observed especially. Hopanes and steranes (traffic, coal combustion) and fatty acids (cooking) were next groups of monitored organic markers. Markers were studied mainly in size fraction PM1 because this fraction of aerosols is the most harmful to human health. Aerosols were sampled in two seasons (winter and summer) in two towns in 2009. Higher concentrations of aerosols and organic compounds were found in winter season, which resulted from increased combustion of biomass, coal and other organic material while traffic was the most significant source of aerosols in summer.
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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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Controlled Drug Release from Biodegradable Hydrogels.
Oborná, Jana ; Chýlková, Jaromíra (referee) ; Kráčmar, Stanislav (referee) ; Kučerík, Jiří (referee) ; Vávrová, Milada (advisor)
This dissertation is focused on the controlled release of drugs from a biodegradable amphiphilic hydrogel based on hydrophobic poly(lactic acid), poly(glycolic acid) and hydrophilic poly(ethylene glycol) (PLGA-PEG-PLGA, ABA) and its modification with itaconic anhydride (ITA). The resulting ,-itaconyl(PLGA-PEG-PLGA) copolymer is referred to as ITA/PLGA-PEG-PLGA/ITA or ITA/ABA/ITA. Itaconic acid provides reactive double bonds and a functional carboxyl group at the ends of the PLGA-PEG-PLGA copolymer chain, thereby rendering the modified ITA/ABA/ITA copolymer less hydrophobic and offering the possibility of forming a carrier for hydrophilic drug substances. These functional copolymers are thermosensitive and change in the external environment (e.g. temperature) causes a sol-gel phase transition due to the formation of micellar structure. The bioactive substances can thus be mixed with a copolymer which is in a low viscous phase (sol phase) and subsequently the mixture can be injected into patient's body at the target site where it forms a gel at 37 °C. This hydrogel becomes a drug depot, which gradually releases the active substance. Prediction of the substance’s release profile from the hydrogel is an effective tool to determine the frequency of administration, potentially enhancing efficacy, and assessment of side effects associated with dosing. The analgesic paracetamol and the sulfonamide antibiotic sulfathiazole were used as model drugs, representing hydrophilic and hydrophobic substances, respectively. The active substances had a significant effect on the resulting hydrogel stiffness. Type of solvent, incubation medium and nanohydroxyapatite also influenced on the gel stiffness and subsequent stability of the hydrogel-drug system. Controlled release of drugs took place in simulated conditions of the human body. Verification of Korsmeyer-Peppas (KP) drug-release model is also discussed in this thesis. The KP model was found suitable for simulating the release of sulfathiazole from ABA and ITA/ABA/ITA hydrogels. On the contrary, the performance of KP model was not suitable for describing the release of paracetamol from the ABA hydrogels. Therefore, a new regression model suitable for both buffered simulated media and water has been proposed. The proposed model fitted better the release of both sulfathiazole and paracetamol from composite material prepared from ABA hydrogel and nanohydroxyapatite.
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Study of the influence of fires of municipal and industrial waste landfills on the enviromental contamination, the combustion products of rubber and halogenated polymers
Sikora, Henryk ; Hroch, Martin (referee) ; Chýlková, Jaromíra (referee) ; Vávrová, Milada (referee) ; Čáslavský, Josef (advisor)
This thesis deals with the issue of fires of municipal and industrial wastes, particularly of rubber and halogenated polymers. When these materials burn, significant amount of harmful substances liberate into environmental compartments. Analysis of samples subjected to thermal decomposition in laboratory conditions explored formation of characteristic compounds in dependence on conditions of combustion. Samples of air, water and soil taken from real fires that occurred between the years 2007 – 2011 in the region of Western Bohemia monitored spreading of these substances into the environment. Majority of these samples were analysed by the means of gas chromatography with mass spectrometric detection. Additionally the effect of extinguishing methods and use of fire extinguishers on formation and spreading of combustion products was studied, especially in soil and in water sources.
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The Use of Liquid Chromatography for Determination of Drug Residues
Dvořáková, Petra ; Hajšlová, Jana (referee) ; Chýlková, Jaromíra (referee) ; Sokol, Jozef (referee) ; Vávrová, Milada (advisor)
This work is based on the occurrence of drug residues in the environment. This study is focused on the development and optimization methods for determination of selected drugs in the surface water, aquatic sediment and sewage sludge from waste water treatment plant. From the group of drugs were chosen antibiotics. Antibiotics presented in the environment can cause adverse effects including toxic effects, immunity disorders and indirect bioalteration effects. Sulfonamide antibiotics, which are used in the treatment of urinary and respiratory tract infections as well as in the treatment of other infectious diseases, were chosen as a target compounds. Three optimized analytical methods for determination of sulfonamide antibiotics were developed. For the optimization of extraction were tested: solid phase extraction, pressurized solvent extraction, microwave extraction and ultrasonic extraction. For the final analysis was used liquid chromatography with two detectors - diode array detector and mass spectrometer. These optimized methods were applied for the analysis of real samples. The surface water and sediment samples were collected from two Moravian rivers (the Svratka river and the Svitava river). Samples of sewage sludge were collected from waste water treatment plant Brno-Modřice. Fish samples from the Svratka river were also collected. It was observed that all the selected sulfonamide antibiotics are present in real sediment samples (ug.kg-1). Simultaneously presence of some target analytes in real surface water (ug.l-1) and in sewage sludge (ug.kg-1) samples has been confirmed. In samples of surface water from the Svitava river and in fish samples sulfonamide antibiotics were not detected or their concentrations were below the limit of detection.
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Study of Exposure PBDE and Perfluorinated Compounds into Aquatic Ecosystem
Vondráčková, Ilona ; Chýlková, Jaromíra (referee) ; Hroch, Martin (referee) ; Kráčmar, Stanislav (referee) ; Vávrová, Milada (advisor)
In the presented PhD. thesis, problems covering occurrence of polybrominated diphenyl ethers (PBDE) and perfluorinated compounds in the environment were solved. The study was focused on identification and further verification of optimal methods in order to determine PBDEs and perfluorinated compounds sampled from the aquatic ecosystem. Polybrominated diphenyl ethers belong to persistent compounds classified as main pollutants; within the environmental constituents, they have been observed particularly in the last decade. For these studies, there were selected surface water matrices and sediments taken in various localities within the river Svratka basin. The analyses were to demonstrate whether they accumulate and remain in these specific matrices for longer time. There we assessed the congeners of polybrominated diphenyl ethers as follows: BDE-28, 47, 66, 85, 99, 100, 153, 154 and 183. In order to isolate them from matrices, various extraction techniques were used, i.e., ultrasonic extraction, microwave extraction, and pressure solvent extraction. Gas chromatography method with electron capture detection (GC/ECD) was selected for determination. The accomplished studies also assessed basic chemical, physical and environmental characteristics of diphenyl ethers in the environmental constituents. The attention was also paid to perfluorooctanoic compounds (PFOA), (PFOS) and (FOSA); physico-chemical properties of these organic pollutants were characterised and their toxicological and environmental aspects were evaluated. Usability of extraction techniques (ultrasonic extraction, pressure solvent extraction, solid phase extraction) applied to PFCs isolation from sediments samples was assessed. Identification and quantification of these analytes were performed using a high performance liquid chromatography/mass spectrometry method (HPLC/MS). After that, the optimized methods applied to real samples. Surface water and sediments were sampled within the river Svratka basin, in particular, from 19 sampling localities. PBDE occurrence was confirmed in sediments samples from the Svratka river (g.kg-1), PBDE were not detected in the surface water samples, their concentrations were below the detection limit, resp.; perfluorinated compounds were not detected in sediments and water samples at all.
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The Use of Separation Methods for the Study of Selected Drugs and Pesticides in Water
Burešová, Jitka ; Hajšlová, Jana (referee) ; Chýlková, Jaromíra (referee) ; Kráčmar, Stanislav (referee) ; Vávrová, Milada (advisor)
This work is focused on the study of penetration of pesticides and pharmaceuticals in the aquatic environment. The aim was to develop and verify the optimal method for long-term monitoring of the occurrence of selected pesticides and pharmaceuticals in surface waters. Two frequently used analgesics ibuprofen and diclofenac, and carbamazepine that is used to treat epilepsy, were chosen from the group of drugs. A group of 41 pesticides were selected for monitoring too. The attention was focused on a group of urea pesticides and phenoxyacetic acids, as well as on selected pesticides falling to the group of priority substances or identified as environmental quality standards. Some of pesticides were selected because their consumption in the Czech Republic exceeds 30 tons a year. Liquid chromatography with tandem mass spectrometry (LC / MS / MS) was used for the determination of selected analytes in surface waters. Two optimized analytical method were developed. Ten analytes were determined in negative ion mode and 34 analytes in positive ion mode. Solid phase extraction (SPE) was used for purification and concentration of the samples. Developed methodology was validated and used for monitoring of selected compounds in samples of surface waters from the Morava River basin. Samples were collected on the rivers Morava and Svratka monthly for two years. Samples from the river Blata and stream Nivnička were collected for one year. Surface water samples were also collected from the river Litava. Four samples were taken throughout the length of the flow during one day. Smaller streams were chosen for monitoring because of the probability of occurrence of pesticides. They flow abundantly agriculturally cultivated areas. Drugs ibuprofen and diclofenac were detected in all taken samples, carbamazepine mostly. Among the most commonly occurring pesticides were bentazon, diuron, isoproturon, carbendazim, MCPA, MCPP, propiconazole, tebuconazole and 2,4-D.
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Removal of organic pollution using advanced oxidation processes
Přibilová, Petra ; Kučerík, Jiří (referee) ; Chýlková, Jaromíra (referee) ; Opatřilová, Radka (advisor)
The presented doctoral thesis deals with the use of advanced oxidation processes combining hydrodynamic cavitation (HC) to produce hydroxyl and sulfur-based radicals. The investigated micropollutants are selected natural estrogens estrone (E1), 17-estradiol (E2), estriol (E3) and synthetic 17-ethinylestradiol (EE2). The theoretical section includes information on the properties of estrogens, their occurrence and effects in the environment on non-target organisms across trophic levels; and list of options for their removal from wastewater. The advanced oxidation processes themselves are also discussed and current knowledge in this area is summarised. In the research section, used analytical methods (LC-MS/MS and spectrophotometry), designs of individual experiments and results of tested processes are described. In addition monitoring the efficiency of different combinations of hydrodynamic cavitation and other agent and the suitability of the materials used on the experimental unit were also investigated. The sorption/desorption onto the surface of selected plastic materials (SBR, EPDM, PTFE, Tygon S3TM, PVDF and PVC) was also evaluated. Based on the results, the material for the unit - on which the degradation experiments were carried out - was selected. The methods chosen for the removal of estrogens from water were HC/H2 O2 , HC/O3, HC/percarbonate, HC/persulfate, hydrodynamic cavitation alone, and H2O2 alone. The design of the experiments was created to minimize the time required to treat the water, ideally one cycle per unit (4 seconds), which corresponds to the flow-through arrangement of the system.
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Controlled Drug Release from Biodegradable Hydrogels.
Oborná, Jana ; Chýlková, Jaromíra (referee) ; Kráčmar, Stanislav (referee) ; Kučerík, Jiří (referee) ; Vávrová, Milada (advisor)
This dissertation is focused on the controlled release of drugs from a biodegradable amphiphilic hydrogel based on hydrophobic poly(lactic acid), poly(glycolic acid) and hydrophilic poly(ethylene glycol) (PLGA-PEG-PLGA, ABA) and its modification with itaconic anhydride (ITA). The resulting ,-itaconyl(PLGA-PEG-PLGA) copolymer is referred to as ITA/PLGA-PEG-PLGA/ITA or ITA/ABA/ITA. Itaconic acid provides reactive double bonds and a functional carboxyl group at the ends of the PLGA-PEG-PLGA copolymer chain, thereby rendering the modified ITA/ABA/ITA copolymer less hydrophobic and offering the possibility of forming a carrier for hydrophilic drug substances. These functional copolymers are thermosensitive and change in the external environment (e.g. temperature) causes a sol-gel phase transition due to the formation of micellar structure. The bioactive substances can thus be mixed with a copolymer which is in a low viscous phase (sol phase) and subsequently the mixture can be injected into patient's body at the target site where it forms a gel at 37 °C. This hydrogel becomes a drug depot, which gradually releases the active substance. Prediction of the substance’s release profile from the hydrogel is an effective tool to determine the frequency of administration, potentially enhancing efficacy, and assessment of side effects associated with dosing. The analgesic paracetamol and the sulfonamide antibiotic sulfathiazole were used as model drugs, representing hydrophilic and hydrophobic substances, respectively. The active substances had a significant effect on the resulting hydrogel stiffness. Type of solvent, incubation medium and nanohydroxyapatite also influenced on the gel stiffness and subsequent stability of the hydrogel-drug system. Controlled release of drugs took place in simulated conditions of the human body. Verification of Korsmeyer-Peppas (KP) drug-release model is also discussed in this thesis. The KP model was found suitable for simulating the release of sulfathiazole from ABA and ITA/ABA/ITA hydrogels. On the contrary, the performance of KP model was not suitable for describing the release of paracetamol from the ABA hydrogels. Therefore, a new regression model suitable for both buffered simulated media and water has been proposed. The proposed model fitted better the release of both sulfathiazole and paracetamol from composite material prepared from ABA hydrogel and nanohydroxyapatite.
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