Submitted by MARCOS HENRIQUE PEREIRA WONDRACEK null (marcoswondracek@ufgd.edu.br) on 2017-10-29T05:42:20Z No. of bitstreams: 1 TESE - versão final.pdf: 3488966 bytes, checksum: 44030b3422f6b77b9ba441eb0905cb23 (MD5) / Approved for entry into archive by LUIZA DE MENEZES ROMANETTO (luizamenezes@reitoria.unesp.br) on 2017-11-09T13:58:32Z (GMT) No. of bitstreams: 1 wondracek_mhp_dr_araiq.pdf: 3488966 bytes, checksum: 44030b3422f6b77b9ba441eb0905cb23 (MD5) / Made available in DSpace on 2017-11-09T13:58:32Z (GMT). No. of bitstreams: 1 wondracek_mhp_dr_araiq.pdf: 3488966 bytes, checksum: 44030b3422f6b77b9ba441eb0905cb23 (MD5) Previous issue date: 2017-10-05 / Item merged in doublecheck by Monique Sasaki (sayumi_sasaki@hotmail.com) on 2017-12-07T17:59:08Z Item was identical to item(s): 153113, 153193 at handle(s): http://hdl.handle.net/11449/152063, http://hdl.handle.net/11449/152164 / Este trabalho relata o desenvolvido de métodos analíticos que visa à determinação de algumas espécies tóxicas e potencialmente tóxicas de metais e metalóides em níveis ultra-traço em amostra de água naturais, utilizando uma técnica analítica menos sensível, como a espectrometria de absorção atômica em chama (FAAS). Essa técnica foi escolhida por ser relativamente simples e possuir baixo custo operacional. A técnica de extração em fase sólida (EFS), utilizando um novo material sorvente, foi utilizada para separar e pré-concentrar os analitos. Este estudo demonstra o procedimento de uma nova rota sintética via co-condensação visando à produção de uma sílica mesoporosa organofuncionalizada com o ligante 4-amino-3-hidrazino-5-mercapto-1,2,4-triazole e, sua utilização como sorvente para pré-concentração/análise de especiação de íons metálicos em amostras de água. O material produzido foi caracterizado por espectroscopia na região do infravermelho (FTIR), BET, ressonância magnética nuclear (RMN) de 29Si e 13C, dentre outras. As características adsortivas desse material foram estabelecidas em estudos de batelada, onde se estudou o efeito do pH, cinética de adsorção e capacidade máxima de adsorção. A otimização multivariada foi utilizada para obtenção das melhores condições químicas e de fluxo no sistema de pré-concentração, permitindo avaliar as interações principais e secundárias entre os fatores. Por meio da análise dos espectros obtidos por FTIR foi possível observar bandas de estiramento C–H, C–Cl e (NH2) oriundos da fração orgânica do material. A área superficial foi de 369,84 m2 g-1com diâmetro médio de poros em 7,1 nm, relacionados a materiais mesoporosos. Os resultados obtidos por RMN de 29Si comprovam a formação do material híbrido, sintetizado por co-condensação, e o RMN de 13C confirma o ancoramento do ligante na matriz. O pH que favorece a adsorção dos íons foi 5,0 para Cu(II) e 3,0 para Cd(II) e As(V). O modelo cinético de pseudo segunda ordem apresentou melhor ajuste aos dados experimentais, indicando adsorção química. Os dados de sorção desses íons metálicos mostraram bom ajuste ao modelo de Langmuir, com capacidade máxima de adsorção próxima aos valores obtidos experimentalmente, 0,057, 0,018 e 0,060 mmol g-1 para Cu(II), Cd(II) e As(V), respectivamente, indicando que a sorção ocorre em monocamada. Os parâmetros analíticos encontrados para o Cu(II) foram: fator de pré-concentração de 18,1; intervalo linear de 10,0 – 200,0 µg L-1 (R = 0,999) e LD de 1,45 µg L-1. Para o Cd(II): fator de pré-concentração de 15,8; intervalo linear de 2,0 – 100,0 µg L-1 (R = 0,999) e LD de 0,38 µg L-1. Para o As(V): fator de pré-concentração de 5,0; intervalo linear de 0,25 – 2,5 µg L-1 (R = 0,999) e LD de 0,039 µg L-1. A exatidão foi checada pelo método de adição e recuperação e/ou método comparativo com GFAAS ou ICP OES. As recuperações variaram de 97 – 106% (Cu), 100 – 105% (Cd), 88 – 103% (As(V)) e 96 – 106% (As(total)). Os resultados para Cu(II) determinados com os métodos propostos foram concordantes com os obtidos com o método comparativo. Conclui-se que o material produzido apresenta bom potencial para ser aplicado na extração/pré-concentração de cobre, cádmio e análise de especiação inorgânica de arsênio. Provou-se também que baixos limites de detecção e quantificação podem ser obtidos mesmo utilizando uma técnica menos sensível como a FAAS. / This paper reports on the development of analytical methods for the determination of some toxic and potentially toxic species in ultra - trace levels in natural water samples using a less sensitive analytical technique such as flame atomic absorpti on spectrometry (FAAS). This technique was chosen because it is relatively simple and has a low operating cost. The solid phase extraction technique (SPE) using a new sorbent material was used to separate and preconcentrate the analyte. This study demonstr ates the procedure of a new synthetic route using the technique of the co - condensation for the production of a mesoporous organo - functionalised silica with the 4 - amino - 3 - hydrazino - 5 - mercapto - 1,2,4 - triazole ligant and its use as a sorbent for preconcentrati on/ analysis of metal ion s speciation in water samples. The material produced was characterized by infra - red spectroscopy (FTIR), BET, 29 Si and 13 C nuclear magnetic resonance (NMR), among others. The adsorptive characteristics of this material were establis hed in batch studies, where the effect of pH, adsorption kinetics and maximum adsorption capacity were studied. Multivariate optimization was used to obtain the best chemical and flow conditions in the preconcentration system, allowing the evaluation of th e main and secondary interactions among the factors. By means of the analysis of the spectra obtained by FTIR, it was possible to observe C - H, C - Cl and (NH 2 ) stretch bands from the organic fraction of the material. The surface area was 369.84 m 2 g - 1 with a verage pore diameter at 7.1 nm related to mesoporous materials. The results obtained by 29 Si NMR prove the formation of the hybrid material, synthesized by co - condensation, and the 13 C NMR confirms the anchoring of the ligan t in the matrix. The pH 5.0 it w as favors the adsorption of the ions Cu (II), the pH 3.0 it was favors the adsorption of the Cd (II) and As (V). The kinetic model of pseudo second order showed better adjustment to the experimental data, indicating chemical adsorption. The adsorption data of Cu (II), Cd (II), and As (V) were similar to those of the Langmuir model, with a maximum adsorption capacity of 0.057, 0.018 and 0.060 mmol g - 1 for Cu (II), Cd(III) and As(V) , respectively, indicating that the sorption occurs in monolayer. The analyt ical parameters for Cu (II) were: preconcentration factor of 18.1; linear range of 10.0 - 200.0 μg L - 1 (R = 0.999) and LD of 1.45 μg L - 1 . For Cd (II): preconcentration factor of 15.8; linear range of 2.0 - 100.0 μg L - 1 (R = 0.999) and LD of 0.38 μg L - 1 . Fo r As (V): preconcentration factor of 5.0; linear range of 0.25 - 2.5 μg L - 1 (R = 0.999) and LD of 0.039 μg L - 1 . Accuracy was checked by addi tion and recovery method of the standard and/ or comparative method with GFAAS or ICP OES. The recovery ranged from 97 - 106% Cu(II), 100 - 105% Cd (II), 88 - 103% As (V) and 96 - 106% As (total)). The results for Cu (II) determined with the proposed methods were concordant with those obtained with the comparative. It is concluded that the material produced can be successfully applied in the extraction / preconcentration of copper, cadmium and analysis of inorganic speciation of arsenic and low limits of detection and quantification can be obtained even using a less sensitive technique such as FAAS.

No description available.

This master thesis deals with the development, optimization and validation of an analytical method for determination of neurotoxin -N-methylamino-L-alanine in pond water and cyanobacteria using LC/MS. Firstly, basic parameters of the analytical method developed within authors´s bachelor thesis were verified. Following parameters were selected for verification: selection of suitable MRM transitions, voltage applied to S-lens and F-lens and standardized collision energy. Secondly, the system suitability testing was performed. Thirdly, the analytical method was successfully validated. Then, the testing and optimization of solid phase extraction for analysis of water samples were carried out. The pH of sample solution and composition of elution solution were chosen for the optimization. In addition, the trichloroacetic acid extraction with acid hydrolysis for cyanobacterial samples was carried out too. Finally, both solid phase extraction and trichloroacetic acid extraction were evaluated and applied to the analysis of real samples.

Submitted by ANA KARLA PEREIRA RODRIGUES (anakarla_@hotmail.com) on 2017-07-31T12:10:23Z No. of bitstreams: 1 arquivototal.pdf: 5468289 bytes, checksum: dc45efa53e8cc6251d00164b611309f9 (MD5) / Made available in DSpace on 2017-07-31T12:10:23Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 5468289 bytes, checksum: dc45efa53e8cc6251d00164b611309f9 (MD5) Previous issue date: 2016-05-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / In the last decade, the extraction magnetic solid phase (MSPE) has been intense study target in Analytical Chemistry, mainly because of its potential application in sample preparation. Recently, with the development motivation automatic analytical methods, this technique has been combined with flow systems. However, the synergistic integration of MSPE with these systems is still a challenge, especially when it involves the handling of viscous matrices. In this perspective, this thesis proposes the development of an effective automated method to perform the MSPE in aqueous and oily matrices. For be applied as magnetic adsorbent nanoparticles of Fe3O4 coated with alumina and functionalized with sodium dodecyl sulfate (SDS) and 1-(2-pyridylazo)-2-naphthol (PAN) were synthesized. The nanoparticles were characterized by diffraction analysis X-ray and scanning electron microscopy, where it was confirmed that the method used to obtain the particles was adequate. Secondly, the automatic system to run the MSPE was developed. To this end an extraction chamber was made of Teflon with a quartz window on the side, where all steps of MSPE was performed without the need for any auxiliary apparatus for immobilizing the adsorbent. For generating the magnetic field in the extraction chamber, a robotic device has been developed. After these steps, the applicability of the method was demonstrated in the extraction and preconcentration of Cd and Pb in drinking water samples and Cd in edible oils, using as detection atomic absorption spectrometry graphite furnace. Factors affecting MSPE, such as pH, the amount of adsorbent, the type and concentration of the eluent and the elution time were studied. In the best experimental conditions to the sample water, the detection limit was 0.004, and 0.043 ug L-1 for Cd and Pb, respectively. Even in this array, relative standard deviations less than 3.5% were achieved with a 15-fold enrichment factor for both analytes. In the case of determination of Cd in edible oils, detection limit (0.006 ug L-1) and standard deviation (< 3.3%) was obtained satisfactorily with a 9-fold enrichment factor. Interfering studies have been performed successfully for the two determinations, not revealing significant percentage interference in determinations. The developed automatic method is simple and robust since it does not require immobilization of the adsorbent, and was successfully applied in the determination of Cd and Pb in drinking water samples and Cd in edible oils. / Na última década, a extração em fase sólida magnética (MSPE) tem sido alvo de intenso estudo na Química Analítica, principalmente em virtude do seu potencial de aplicação no preparo de amostras. Recentemente, tendo como motivação o desenvolvimento de métodos analíticos automáticos, essa técnica vem sendo combinada aos sistemas em fluxo. Contudo, a integração sinérgica da MSPE com esses sistemas ainda é um desafio, principalmente quando envolve a manipulação de matrizes viscosas. Nessa perspectiva, a presente tese propõe o desenvolvimento de um eficiente método automático para realização da MSPE em matrizes aquosas e oleosas. Para serem aplicadas como adsorvente magnético foram sintetizadas nanopartículas de Fe3O4 revestidas com alumina e funcionalizadas com dodecil sulfato de sódio (SDS) e 1-(2-piridilazo)-2-naftol (PAN). As nanopartículas foram caracterizadas através da análise de difratometria de raios-X e da microscopia eletrônica de varredura, onde confirmou-se que o método empregado para obtenção das partículas foi adequado. Num segundo momento, o sistema automático para executar a MSPE foi desenvolvido. Para isso, uma câmara de extração foi confeccionada em Teflon, com uma janela de quartzo na lateral, onde todos os passos da MSPE foram realizados sem a necessidade de qualquer aparato auxiliar para imobilizar o adsorvente. Para geração do campo magnético, na câmara de extração, um dispositivo robótico foi desenvolvido. Depois de estabelecida essas etapas, a aplicabilidade do método foi demonstrada na extração e preconcentração de Cd e Pb em amostras de água de abastecimento e de Cd em óleos comestíveis, empregando como detecção a espectrometria de absorção atômica em forno de grafite. Fatores que afetam a MSPE, tais como o pH, a quantidade de adsorvente, o tipo e a concentração do eluente e o tempo de eluição foram estudados. Nas melhores condições experimentais, para a amostra água, o limite de detecção foi 0,004 e 0,043 μg L-1 para o Cd e o Pb, respectivamente. Ainda nessa matriz, desvios padrão relativos menores que 3,5 % foram alcançados com um fator de enriquecimento de 15 vezes para ambos os analitos. No caso da determinação de Cd em óleos comestíveis, limite de detecção (0,006 μg L-1) e desvio padrão relativo (< 3,3 %) satisfatório foi obtido com um fator de enriquecimento de 9 vezes. Os estudos de interferentes foram realizados com êxito para as duas determinações, não revelando interferência percentual significativa nas determinações. O método automático desenvolvido é simples e robusto, uma vez que não requer a imobilização do adsorvente, e foi aplicado com sucesso na determinação de Cd e Pb em amostras de água de abastecimento e de Cd em óleos comestíveis.

The theoretical part of this diploma thesis consists of current matters regarding the presence of perfluorinated organic compounds in living environment elements. The attention has been focused on perfluoroktanoic acid (PFOA), (PFOS), and (FOSA). Physical-chemical characteristics of these organic pollutants and their toxicological and environmental aspects have been described. Possible ways of the pollutants analytical determination have been specified. The experimental part has explored effects of extraction techniques (sonication, pressurized solvent extraction, solid-phase extraction) used for PFAS separation from seats of fire soil sample. Identification of the analytes have been achieved by liquid chromatography/mass spektrometry.

Nonsteroidal anti-inflammatory substances became a very frequently used and constantly evolved group of the drugs, particularly in a human medicine. The risk of their penetration into the environment, especially to the water environment, is rising during the recent years. The diploma thesis is focused on a selection of appropriate separation method and optimization of analytical procedure for the identification and determination of the non-steroidal anti-inflammatory drugs in sewage and surface waters. Salicylic acid, ketoprofen, diclofenac and ibuprofen were chosen from the wide range of NSAIDs as the most widespread agents of this drugs group in the medical practice. The method was optimized and elaborated using the model water samples. This method was used for determination of the analytes contained in the real water samples. Waste water samples were taken from the large-scale wastewater treatment plant in Brno-Modřice and surface water samples were taken from the Highlands river Křetínka. Solid phase extraction (SPE) was used for the real samples treatment and preconcentration, the determination was performed using the high performance liquid chromatography with mass spectroscopy method (LC-MS).

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.

This work is based on the current issue of increasing concentrations of pharmaceutical residues in various components of the environment. These new environmental contaminants continuously enter the environment. The most affected environmental component is the aquatic environment. This study is focused on the development and optimization of reliable analytical method, which can determine selected drugs in the aquatic environment (waste waters and surface waters) qualitatively and quantitatively. The target compounds were selected mainly from the group of non-steroidal anti-inflammatory drugs (NSAID): salicylic acid, acetylsalicylic acid, clofibric acid, ibuprofen, acetaminophen, caffeine, naproxen, mefenamic acid, ketoprofen and diclofenac. NSAIDs are one of the most used drugs in Czech Republic. For the final analysis of this study was used the comprehensive two-dimensional gas chromatography with mass spectrometric detection Time-of-Flight (GCxGC-TOF MS). It is a very sensitive and reliable analytical method for trace and ultra-trace analysis. Simultaneously, solid phase extraction (SPE) and derivatization are optimized in this work. Optimized analytical method including SPE, derivatization with MSTFA (N-methyl-N-(trimethylsilyl) trifluoroacetamide) and final analysis by GCxGC-TOF MS were applied successfully for the analysis of real samples. Samples of waste water were collected from the waste water treatment plant in Brno – Modřice and samples of surface water were collected from two river streams Svratka and Svitava in Moravian region. The range of concentrations of selected drug residues varied from one to tens of g/L in wastewater and from tens to hundreds of ng/L in surface waters. The degree of wastewater and surface waters contamination by drug residues is assessed in conclusions of the work. Simultaneously, spontaneous degradation of selected drugs in water and removal efficiency of the wastewater treatment plant is assessed in conclusions of the work. The developed method is usable for monitoring and environmental analysis of water ecosystems. It is usable not only for selected drugs, but even for other organic compounds with similar properties.

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.

Modern separation and spectrometric techniques for biological sample lipidom investigation Due recent progress in field of mass spectrometry the lipidomics, part of metabolomics, is increasing its importance for broad fields of biological study. The aim of this study is to test the lipid extraction techniques and to optimize the preseparation and separation of lipids suitable for mass spectrometry detection. The fragmentation patterns of four, the most abundant lipid classes of glycerolipids (PC, PE, TG, DG), were acquired for the proposed system. These patterns were compared with literature. The most appropriate method for extraction was declared technique according Folch based on methanol and chloroform solution. The preseparation due SPE method is very useful tool for lipid determination. The optimized were focused to reach higher recovery especially in polar lipid fraction. Proposed HPLC system is based on methanol with ammonium buffer, water and isopropanol. The testing was done on three columns with different type of sorbents (Gemini, Syncronis and Kinetex). The separation was evaluated according mass spectrometer response, shape and wide of particular analytes peaks. Composition contains 20% of water was determinate as the best and also the best separation was achieved by Kinetex column. The proposed...