Les interactions plasma-paroi représentent l'un des principaux problèmes à résoudre pour avancer dans la recherche sur la fusion contrôlée. Ce travail de thèse a pour objectif de développer une source d'hydrogène atomique à basse pression (< Torr) dans un réacteur à configuration hélicon en mélange H2/Ar pour étudier la gravure chimique du graphite et de composites à fibres de carbone utilisés dans le tokamak Tore Supra. Selon les conditions expérimentales, le réacteur peut générer les modes de couplages capacitif, inductif, Trivelpiece-Gould et hélicon à bas champ. Leur caractérisation a montré que le mode inductif est, dans ce cas, celui présentant le plus grand intérêt pour la source d'hydrogène atomique. Les études en mode inductif ont révélé un phénomène de décroissance de la densité relative de deux niveaux métastables de l'ion Ar+ et d'un niveau métastable de l'argon neutre lors de l'augmentation du champ magnétique de confinement. Un modèle simple a confirmé que ces niveaux métastables sont détruits par collisions électroniques vers des niveaux de plus grande énergie. La gravure du graphite par la source d'hydrogène atomique est relativement efficace (jusqu'à 3 µm/h) à 10 mTorr et diminue avec la pression. Une analyse qualitative de la cinétique de l'hydrogène atomique a permis de conclure que cette baisse de la vitesse de gravure est due au flux d'hydrogène atomique arrivant sur l'échantillon qui décroît lorsque la pression augmente. Les premières observations de la surface après gravure ont mis en évidence la présence de structures carbonées (agglomérats de nanoparticules et dépôts). Ces structures ressemblent à celles observées dans différents tokamaks / Plasma-wall interactions are one of the main issues in fusion research and must be thoroughly studied to progress in this topic. The objective of this work is to develop an atomic hydrogen source at low pressure (< Torr) in a helicon configuration reactor working in H2/Ar gas mixture. This source is then used to study the chemical etching of graphite and carbon fiber composites composing the limiter of the Tore Supra tokamak. Depending on the experimental conditions, the RF power coupling of the reactor can be in capacitive, inductive, Trivelpiece-Gould or low field helicon mode. The characterization of these modes determined that in this case the inductive one presents the greatest interest for the atomic hydrogen source. Further studies in inductive mode showed that increasing the confinement magnetic field leads to a decrease of measured relative densities of two metastable levels of argon ion and one metastable state of neutral argon. A simple model simulating neutral metastable state behavior confirmed that these levels are destroyed by electronic collisions towards upper levels. The chemical etching of graphite exposed to the atomic hydrogen source is relatively efficient (up to 3 µm/h) at 10 mTorr and drops with the pressure. A qualitative analysis of atomic hydrogen kinetics concluded that this behavior is due to the decrease of atomic hydrogen flux on the sample with increasing pressure. Finally, first observations of the etched surface underlined different structures (nanoparticles clusters and deposits). These can be compared to the ones observed in different tokamaks

Boron element plays an important role for our country since approximately 70% of the world&rsquo / s reserves are in Turkey. It is widely used in different areas of industry. Besides being vital for the plants, it is important also for human health. It has been shown that high boron exposure does not affect fertility negatively and also with an increasing boron exposure, risk of prostate and cervical cancers decreases. There are different opinions regarding health effects of boron. There are both positive and negative findings. Therefore, determination of boron in body fluids such as urine and blood is necessary to monitor exposed concentration level and its relation with diseases. Furthermore, these studies may contribute to define a reference value for safe maximum daily boron intake. In this study, a method previously developed by our research group was applied for the determination of boron in urine samples. Urine and blood samples were collected from human subjects living or working in different regions of Balikesir where boron reserves are located. While urine analysis was done by using Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES), due to lower concentrations of boron in blood, Inductively Coupled Plasma Mass Spectrometry (ICP-MS) was used for blood analysis. A sensitive method was developed using ICP-MS. Samples were digested in microwave oven by applying optimized digestion procedures. Indium (In) and Beryllium (Be) internal standards were spiked into the urine and blood samples, respectively. A sample introduction system containing no glass or silica surfaces was used in ICP-MS to eliminate boron memory effect. Two isotopes of the boron, 10B and 11B, were monitored during the study. Space charge effect due to Na+ ion and carbon interference on B and Be signals was investigated in detail. Limit of Detection was 0.021 mg/L for ICP-OES and it was 2.2 &micro / g/L for ICP-MS. The accuracies of the methods were checked by using NIST 1573a Tomato Leaves and BCR Human Hair certified reference materials for urine and blood, respectively.

A series of pottery samples provided from the survey investigations and excavations from Degirmentepe Mound (Malatya), belonging to Chalcolithic (Ubaid), Early Bronze and Iron Ages, were investigated by petrographic and X-ray diffraction (XRD) analyses to determine their textures, mineralogical compositions and microstructures. The sample microstructures and chemical (semiquantitative) compositions were also studied by scanning electron microscope with energy dispersive X-ray spectrometry (SEM - EDX). The chemical analyses of some samples were further investigated by inductively coupled plasma &ndash / optical emission spectrometry (ICP-OES). Almost all samples were observed to consist of rock fragments, originating from metamorphic and igneous rocks, although larger grain sizes and higher grain to matrix ratios are recorded for Chalcolithic Age samples compared to those samples belonging to Iron Age. XRD investigations on representative samples of the three periods, revealed high abundances of quartz, feldspar, and pyroxene group minerals in all samples, while the presence of hematite and mica minerals were observed both in Chalcolithic and Iron Age samples, but underlying the use of micaceous raw materials mostly in Iron Age. In the XRD traces of the investigated sherds of Chalcolithic and Iron Ages, the absence of clay fractions both in the bulk and oriented samples, supports a minimum firing temperature of around 800- 850 &deg / C, while the presence of mullite phase both in XRD and SEM &ndash / EDX results showed the possible use of high firing temperatures, in the range of 950&ndash / 1050&deg / C, starting from Chalcolithic Age. Chemical compositions of major oxides obtained ICP &ndash / OES analyses exhibit similar compositions both for Chalcolithic and Iron Age samples. Few exceptions observed may indicate possible use of different raw material and/or different manufacturing technique.

Investigations on pulsed reactive magnetron sputtering processes for the deposition of thin oxide films are presented by means of time-resolved and time-integrated measurements. The pulsed process can be successfully described in terms of a model of Berg et al. for reactive sputtering processes. Time-resolved Langmuir double probe measurements are confirmed using time-resolved optical emission spectroscopy. Combining the results leads to an insight into elementary processes governing the discharge. / Mit Hilfe zeitlaufgelöster und zeitlich mittelnder Methoden wird eine gepulste Magnetronentladung zur reaktiven Abscheidung von Oxidschichten untersucht. Das Modell von Berg et al. zur Beschreibung des Abscheideprozesses lässt sich dabei erfolgreich auf die reaktive Abscheidung mit einem gepulsten Prozess anwenden. Mittels zeitaufgelöster optischer Emissionsspektroskopie können die Ergebnisse zeitaufgelöster Langmuir-Doppelsondenmessungen bestätigt werden. In Kombination ermöglichen diese Verfahren die Untersuchung von Elementarprozessen in der Entladung.

Ceramic metal composites, or cermets, currently have widespread applications in the chemical, automotive and oil and gas sectors, due to their combination of high wear resistance, and aqueous corrosion resistance. In the present study, a family of novel titanium carbide (TiC)-stainless steel cermets has been produced as potential materials for use as erosion and corrosion resistant materials. The development of the TiC-stainless steel cermets is based on a simple melt infiltration technique, with the stainless steel “binder” contents varied from 5 to 30 vol.%, using the austenitic grades 304L and 316L, and the martensitic grade 410L. These materials have subsequently been evaluated for their wear and corrosion response, as well as characterisation of their basic mechanical properties and microstructure. Results from wear and corrosion studies show an improvement in wear and corrosion resistance of the cermets at lower steel binder content . / The original abstract from thesis is below. Ceramic metal composites, or cermets, currently have widespread applications in the chemical, automotive and oil and gas sectors, due to their combination of high wear resistance, and aqueous corrosion resistance. In the present study, a family of novel titanium carbide (TiC)-stainless steel cermets has been produced as potential materials for use as erosion and corrosion resistant materials. The development of the TiC-stainless steel cermets is based on a simple melt infiltration technique, with the stainless steel “binder” contents varied from 5 to 30 vol.%, using the austenitic grades 304L and 316L, and the martensitic grade 410L. These materials have subsequently been evaluated for their wear and corrosion response, as well as characterisation of their basic mechanical properties and microstructure. Reciprocating wear tests involved a ball-on-flat geometry (using a WC-Co counter face sphere), with loads varied from 20 to 80 N, for up to 120 minutes. The wear tracks were assessed using a high-resolution optical profilometer, in order to determine the wear volume. The specific wear rate of the cermets was found to increase with both the applied load and the steel binder content. To investigate the morphology of worn surfaces, scanning electron microscopy (SEM), and associated energy dispersive x-ray spectroscopy (EDS) were used, in order to fully understand the operative wear mechanisms. A transition from two- to three-body abrasive wear was observed, together with the formation of a oxygen-rich tribolayer, indicating that adhesive wear was also occurring on the cermets. In order to assess the electrochemical behaviour of the cermets in a simulated seawater environment, the samples were evaluated using potentiodynamic, cyclic and potentiostatic polarisation tests, with basic corrosion parameters and rates subsequently determined through Tafel extrapolation and weight loss measurement. Each stage of electrochemical assessment was then evaluated by characterising the corroded surfaces and solution using SEM, EDS and inductively coupled plasma optical emission spectrometry. Microstructural observations using SEM images revealed significant degradation of the samples, with steel binder preferentially dissolved while TiC remained relatively unaffected. The corrosion rate of the cermets increases with steel binder content, which is attributed to the preferential dissolution of the binder.

Pathological processes in the alveolar and facial bones can lead to bone loss that may not heal with complete regeneration. Biomaterials can be used to facilitate the healing process and/or as a bone substitute, but the mechanisms are not fully understood. Persistent leakage of bacteria/bacterial toxins, after root canal treatment, may lead to a residual bone defect. The healing is dependent on a placed dental biomaterial providing a tight seal. The composition of the filling material may also influence the healing process. The general aim of this study is to investigate surface properties and biological interactions of biomaterials used in dento-alveolar surgery. A dental biomaterial, a bonded compomer (DAP) containing a corroding glass filler, was used as a root end filling material, promoting a new operation technique. The healing (assessed according to Molven´s x-ray criteria) demonstrates a significant improvement in healing results for the compomer group, compared to a commonly used technique. The surface properties and biological interactions of DAP were analyzed. ICP-OES of DAP cell culture medium extract demonstrated a significant release of Sr, Si and F from the dental biomaterial. Human periodontal ligament (PDL) cells grew on and around DAP specimens without any sign of toxic reactions. DAP extract stimulated proliferation of PDL cells, but caused an inhibition of osteoblastic gene expression in mouse bone marrow cells. The surface properties of the glass containing compomer may contribute to improved healing of the periapical lesions. A bovine inorganic bone graft substitute (BO) is commonly used as a treatment option in dento-alveolar surgery with new bone formation in immediate close contact with BO material. ICP-OES dissolution analysis of cell culture media, after incubation with BO particles, demonstrated a dosedependent release of Si and a decrease of Ca and P. An uptake of Ca from the medium to the BO particle was demonstrated with calcium-45 labeling. The Si dissolution varied between different batches, possibly reflecting a variation in food intake in the animals. Stimulated osteogenic response was seen in close contact to the BO particles in cell cultures. Furthermore, it was clearly demonstrated that the study design is a critical factor for correctly understanding biomaterials’ biological interactions. The surface properties of three bone graft substitutes reported to have good results in dento-alveolar surgery were investigated, in order to establish whether or not dissolution-precipitation reactions could contribute to the bone healing. Dissolution-precipitation extracts of BO, bioactive glass 45S5 (BG) and a marine algae hydroxyl apatite (AP) in cell culture media were analyzed. Dissolution of Si at significant levels was detected for BO and 45S5 over time. Significant uptake levels of Ca and P from the culture were seen for both 45S5, BO and AP but at different times. Surface analysis of the biomaterials with SEM/EDAX, before and after immersion in cell culture media, revealed a smoothing of the surface morphology for 45S5 over time. No obvious alterations for BO and AP were detected. Ca/P ratio decreased significantly for 45S5, but no major changes were detected by XPS for BO or AP. XPS further demonstrated a surface charge for BO, changing from negatively to positively charged when exposed to serum. 45S5 and AP had positive surface charges, both in the absence and the presence of serum. These demonstrated surface changes in biomaterials could contribute to adherence of cells and subsequently affect bone healing. Conclusion: Biomaterials used in dento-alveolar surgery interact with biological surroundings through surface and dissolution-precipitation reactions which may have implications for bone healing.

137 f. / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-03-27T16:17:33Z No. of bitstreams: 1 TESE_Daniele_V FINAL.pdf: 3318748 bytes, checksum: 5c34e1db8db6c739cde7c6d8b715fac2 (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-06-05T15:40:50Z (GMT) No. of bitstreams: 1 TESE_Daniele_V FINAL.pdf: 3318748 bytes, checksum: 5c34e1db8db6c739cde7c6d8b715fac2 (MD5) / Made available in DSpace on 2013-06-05T15:40:50Z (GMT). No. of bitstreams: 1 TESE_Daniele_V FINAL.pdf: 3318748 bytes, checksum: 5c34e1db8db6c739cde7c6d8b715fac2 (MD5) Previous issue date: 2012 / CNPq / Neste trabalho foram desenvolvidos métodos espectrométricos para a determinação de ozônio em águas e elementos traço em leite de coco. A primeira etapa foi desenvolvida, no âmbito de um projeto de doutorado sanduíche, na Faculdade de Farmácia da Universidade do Porto em Portugal e a segunda no Instituto de Química da Universidade Federal da Bahia, Brasil. Na primeira parte do trabalho foi proposto um sistema de análise por injeção sequencial para determinação de O3 em água baseado na quimiluminescência deste com luminol sem a presença de catalisadores. Parâmetros físico-químicos foram estudados para obter o melhor desempenho analítico. O ciclo analítico desenvolvido permitiu a determinação de ozônio em 20 segundos com um consumo de 200 μL de amostra e 200 μL de luminol. O método apresentou boa precisão (RSD < 2,9%) bons limites de detecção e quantificação foram 0,04 e 0,13 mg L-1, respectivamente e a taxa de amostragem foi de cerca de 140 determinações/h. O método desenvolvido foi aplicado para a determinação de ozônio residual em águas e os resultados concordam a 95% de confiança com os fornecidos pelo procedimento de referência, a espectrofotometria no UV-Vis e o teor de ozônio nas diferentes amostras variou entre 0,21 - 1,36 mg L-1. O método analítico proposto representou uma alternativa vantajosa, pois requer um baixo consumo de reagentes e produz um volume reduzido de resíduos. A segunda parte consistiu no desenvolvimento de estratégias para a determinação de constituintes inorgânicos em amostras de leite de coco comercializadas na cidade de Salvador, Bahia. Para a avaliação multielementar foram propostos dois procedimentos de decomposição: em bloco digestor e assistido radiação por micro-ondas. Também foi proposto um procedimento de extração assistida por energia ultrassônica (US). As técnicas espectrométricas empregadas para determinação dos analitos foram: espectrometria de emissão óptica com plasma indutivamente acoplado (ICP OES) e espectrometria de massas com plasma indutivamente acoplado (ICP-MS). A eficiência de decomposição foi avaliada considerando os parâmetros acidez e teor de carbono residual. Ferramentas estatísticas, PCA e HCA, evidenciaram que há diferença entre três fornecedores de leite de coco em relação aos analitos determinados após decomposição em forno de micro-ondas, bem como o tipo de embalagem. Para avaliação do US, foram aplicados planejamentos fatorial e Doehlert. A exatidão das metodologias propostas foi verificada com materiais de referência certificados (NIST SRM 8435 e 1549) e teste de adição e recuperação. As faixas de concentração, em μg g-1, para os analitos foram: Ca (10 - 138); Cu (0,15 – 1,7); Fe (0,9 – 4,9); K (97 - 1773); Mg (23 - 206); Mn (0,3 – 3,2); P (116 – 701); Zn (0,4 – 2,2); Cr (0,185 – 0,211), Na (59-1186); Ni (0,113 – 0,133) e Pb (0,0220 - 0,0296). As concentrações dos elementos As, Cd e Co estavam abaixo do limite de quantificação. Os teores dos macro e micronutrientes foram comparados com os valores apresentados na Tabela Brasileira de Composição de Alimentos (TACO) e foi possível perceber que as amostras analisadas apresentam composições diferentes, o que pode ser creditado aos diferentes tipos de solo e processamento. A concentração dos contaminantes estava abaixo do valor máximo permitido pela Agência Nacional de Vigilância Sanitária (ANVISA) / Salvador

109 f. / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-04-03T13:32:48Z No. of bitstreams: 2 Pag_Iniciais.doc: 792576 bytes, checksum: 12dfaef31d9159988f77ea8619fd118e (MD5) Cap. I - V.doc: 4237312 bytes, checksum: be8dd2f149baada6ca89d1396f98bbb5 (MD5) / Rejected by Ana Hilda Fonseca(anahilda@ufba.br), reason: Solicito o envio em arquivo único. Transformar o arquivo em pdf sem senha. on 2013-04-18T16:41:59Z (GMT) / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-05-20T15:50:31Z No. of bitstreams: 1 Tese Luiz Souza Carvalho.pdf: 2954132 bytes, checksum: 0bd3a51a7e2edab66b3681ac3f94951f (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-05-20T15:51:43Z (GMT) No. of bitstreams: 1 Tese Luiz Souza Carvalho.pdf: 2954132 bytes, checksum: 0bd3a51a7e2edab66b3681ac3f94951f (MD5) / Made available in DSpace on 2013-05-20T15:51:43Z (GMT). No. of bitstreams: 1 Tese Luiz Souza Carvalho.pdf: 2954132 bytes, checksum: 0bd3a51a7e2edab66b3681ac3f94951f (MD5) Previous issue date: 2008 / CAPES / Os metais traço e os hidrocarbonetos policíclicos aromáticos particulados transportados por via aérea são considerados como um risco á saúde e ao ambiente, pois podem ser absorvido pelo tecido do pulmão humano durante a respiração. A queima de combustível fóssil e da madeira, assim como a incineração de dejetos e processos industriais, são as principais fontes antrópicas de metais e hidrocarbonetos policíclicos aromáticos (PAH) á atmosfera.. Este trabalho tem a finalidade de determinar as concentrações em suspensão (TSP e PM10 de metais, assim como as concentrações e os perfis dos 16 PAH prioritários para estudos ambientais segundo a U.S. EPA), que estão agregados ao material particulado. Os metais: Fe, Mn, Cu e Zn determinados por ICP-OES, e os PAH foram separados por cromatografia gasosa, identificados e quantificados por GC-MS. A amostragem foi feita em três sítios em Salvador-BA: i) Estação de ônibus da Lapa, ii) Porto de Aratu, iii) Vila de Bananeira,,na ilha de Maré próximo ao Porto de Aratu. Os dados experimentais foram analisados usando o programa (STATISTICA 6 Stat Soft). Para os metais: Fe apresentou as concentrações mais elevadas (variou de 26,8 a 328µgm-3) na maioria dos sítios, exceto bananeiras, onde o Zn predominou (variou de 1,83 a 145µgm-3). Para os hidrocarbonetos policíclicos aromáticos: BbF apresentou maiores concentrações na maioria dos sítios (variou de 0,130 a 6850ng m-3), exceto na estação da Lapa, predominou CRY(variou de 0,075 a 6,85µgm-3). Os metais e PAH, são principalmente de fonte antrópica, e podem originar sérios problemas de saúde / Salvador

Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2016-05-02T15:47:06Z No. of bitstreams: 1 Dissertação_Larissa_corrigidaII.pdf: 1019512 bytes, checksum: edf232cf9ac3bc5e1e6b995c18e3398e (MD5) / Approved for entry into archive by Ana Hilda Fonseca (anahilda@ufba.br) on 2016-05-13T14:13:08Z (GMT) No. of bitstreams: 1 Dissertação_Larissa_corrigidaII.pdf: 1019512 bytes, checksum: edf232cf9ac3bc5e1e6b995c18e3398e (MD5) / Made available in DSpace on 2016-05-13T14:13:08Z (GMT). No. of bitstreams: 1 Dissertação_Larissa_corrigidaII.pdf: 1019512 bytes, checksum: edf232cf9ac3bc5e1e6b995c18e3398e (MD5) / CNPq / Alimentos industrializados, tais como misturas de condimento e sopas instantâneas, geralmente possuem alto teor salino em sua composição, o que torna mais difícil a quantificação dos micro elementos por espectrometria de emissão óptica com plasma indutivamente acoplado (ICP OES). Nesse contexto, o presente trabalho teve como objetivo o estudo de estratégias para a determinação de elementos essenciais e não essenciais em matrizes alimentícias com alto teor salino por ICP OES. O estudo das variáveis potência de radiofrequência (PR) e vazão de gás de nebulização (VGN) foi realizado utilizando planejamento fatorial completo 22e matriz Doehlert. A partir da avaliação dos gráficos de superfície e dos perfis de desejabilidade, foi possível estabelecer uma condição operacional ótima de potência e vazão de 1250 We 1,0 L min-1, respectivamente. Foi também realizada a avaliação dos elementos Be, Ga, In, Sc e Y como candidatos a padrão interno. Esse estudo foi feito a partir da comparação dos coeficientes angulares de curvas analíticas preparadas na ausência, na presença da matriz, sem e com adição do padrão interno.Os candidatos recomendados foram Sc e Y. As amostras adquiridas em supermercados da cidade de Salvador, Bahia, foram submetidas ao procedimento de decomposição ácida assistida por radiação micro-ondas, cujas condições foram selecionadas com base no teor de carbono residual, na acidez residual e nas concentrações dos elementos de interesse. Os parâmetros de desempenho do método proposto foram estabelecidos com base nos limites de detecção e quantificação, teste de adição e recuperação, precisão e exatidão. A exatidão do método foi avaliada a partir da análise do material de referência certificado NIST 1570a (Trace Elements in Spinach Leaves) e foram obtidos percentuais de recuperação na faixa entre 84,4 a 104,4%. O método proposto foi aplicado em amostras com diferentes sabores de misturas de condimento e de sopas instantâneas. As faixas de concentração para os elementos determinados, em µg g-1, foram: Ba (0,312 – 1,865), Ca (348 - 3909); Cu (0,530 – 1,315); Fe (6,1 – 44,8); K (405 - 16403); Mg (97 - 504); Mn (0,504 – 8,416); P (332 – 2921), Sr (0,98 – 20,47), Zn (0,439 – 19,47) e em % m m-1 Na (2,84 – 10,21). Um estudo de acessibilidade “in vitro” nas amostras de sopas instantâneas foi realizado por meio do método in vitro SBET (Simple Bioaccessibility Extraction Test) e foi encontrada uma faixa de 7,5 – 87,1%, sendo a maior porcentagem para o elemento K. A contribuição deste trabalho está relacionada a proposta de novas estratégias que viabilizaram a avaliação da composição em termos de elementos essenciais em alimentos com alto teor salino. Além disso, informações inéditas foram obtidas sobre a acessibilidade para as amostras de sopas instantâneas. / Processed foods, such as seasonings mixtures and instant soups, usually have high salt levels in their composing which makes it more difficult quantification of microelements by inductively coupled plasma optical emission spectrometry (ICP OES). In this context, the present work had as objective the study of strategies for the determination of essential and non-essential elements in food matrices with high saline content by ICP OES. The study of radiofrequency power variables and nebulizer gas flow had performed using full 22 factorial design and Doehlert matrix. From the evaluation of surface charts and desirability profiles, it was possible to establish a suitable operating condition of 1250 W and 1.0 L min-1 for radiofrequency power and nebulizer gas flow, respectively. It was also performed the assessment of the elements Be, Ga, In, Sc and Y as candidates for internal standardization. This study was done from the comparison of the slope of analytical curves prepared in the absence, in the presence of the matrix, with and without addition of internal standard. The recommended candidates were Sc and Y. Samples purchased at supermarkets in the city of Salvador, Bahia, underwent the procedure of microwave-assisted acid decomposition, whose conditions were selected based on the residual carbon content, on residual acidity and on the concentrations of the elements of interest. The performance parameters of the proposed method were established based on limits of detection and quantification, addition and recovery testing, precision and accuracy. The accuracy of the method was evaluated from the analysis of certified reference material NIST 1570a (Trace elements in spinach leaves) and the recovery percentages were in the range between 84.4 to 104.4%. The proposed method was applied to samples with different flavors of seasoning mixtures and instant soups and the concentration ranges for certain elements, in µg g-1 were: Ba (0.312 – 1.865), Ca (348 – 3909); Cu (0.530 –1.315); Fe (6.1 –44.8); K (405 – 16403); Mg (97 – 504); Mn (0.504 – 8.416); P (332 –2921), Sr (0.98 – 20.47), Zn (0.439 – 19.47) and in% m m- 1Na (2.84 – 10.21). A study of accessibility in the samples of instant soups was done through the in vitro SBET method (Simple Bioaccessibility Extraction Test) and was found a range of 7.5 – 87.1%, being the largest value for the element K. The contribution of this work is related to proposed new strategies that enable the assessment of the composition in terms of essential elements in foods with high salt content. In addition, unpublished information was obtained about the accessibility for samples of instant soup

Made available in DSpace on 2016-06-02T20:35:09Z (GMT). No. of bitstreams: 1 TeseMCS.pdf: 2092312 bytes, checksum: 9994cc8bab5cc486586caf4f13ce51cf (MD5) Previous issue date: 2006-03-03 / Universidade Federal de Minas Gerais / The main goal of this thesis was the investigation of alternative procedures for chemical analysis of refractory materials and clays using an inductively coupled plasma optical emission spectrometry (ICP OES) with axial view by direct analysis of slurries and microwave-assisted alkaline digestion. The preliminary experiments of this work focused the introduction of slurries into the ICP OES with axial view and evaluated the effects caused by the particle size distribution on the intensities emission signals. Afterwards, a grinding method in which solid samples were ground together with chemical modifiers was developed. The chemical modifiers studied were LiBO2 and Na2CO3, since they are frequently used as fluxes in fusion procedures, and NH4Cl, ascorbic acid, and graphite. The effects of the chemical modification on the intensities of emission signals and the grinding time required for obtaining greater intensities emission signals were evaluated. The chemical modification procedure was implemented in order to promote the formation of new compounds with thermal properties different of the original materials. The synthesis of less refractory compounds would favor the process of atomization-excitation of the chemically modified materials in the direct analysis of slurries, and it would also facilitate the digestion of these materials. The effects of the chemical modification were also evaluated by using X-ray diffraction and thermogravimetric analysis. The direct analysis of chemically modified materials by ICP OES required the investigation of several calibration methods based on different approaches: use of aqueous reference solutions, calibration with slurries prepared using certified reference materials, and calibration using the generalized standard addition method. The calibration is the most critical aspect in the direct analysis of slurries by ICP OES, because is critically dependent on the particle sizes and of the thermal behavior of the several mineralogical phases of each material. On the other hand, microwave -assisted digestion was investigated in two alkaline media: KOH and NaOH. Applying a paired t-test it was shown that results were in agreement at 95% confidence level with those obtained by microwave-assisted acid digestion. The values of the detection limits and signal-to-background ratio obtained for the two microwave -assisted procedures were compared, and the alkaline digestion has shown adequate performance for the digestion of the chemically modified materials. / A proposta desta tese foi investigar procedimentos alternativos para análise química de materiais refratários e argilas por espectrometria de emissão óptica com plasma acoplado indutivamente (ICP OES) com configuração axial pela análise direta de suspensões e digestão assistida por radiação microondas empregando meio alcalino. A primeira etapa do trabalho foi avaliar a introdução de suspensões em ICP OES com configuração axial e os efeitos causados pela distribuição de tamanho de partículas sobre as intensidades dos sinais, sendo que o desempenho desse arranjo foi avaliado para suspensões de materiais refratários e argilas com diferentes tamanhos de partículas. A segunda etapa foi o desenvolvimento de um método de moagem das amostras sólidas juntamente com modificadores químicos. Dentre os modificadores químicos estudados encontram-se o LiBO2 e o Na2CO3, que são utilizados como fundentes em procedimentos de decomposição por fusão, NH4Cl, ácido ascórbico e grafite. Foram avaliados os efeitos da modificação química sobre as intensidades dos sinais de emissão dos analitos em suspensões dos materiais cerâmicos quimicamente modificados e o tempo de modificação necessário para obtenção de maiores valores de intensidades dos sinais de emissão. Esse procedimento de modificação química foi implementado a fim de promover a formação de novos compostos com propriedades térmicas diferentes dos materiais originais, ou seja, compostos menos refratários. Isso favoreceria o processo de atomização-excitação dos materiais quimicamente modificados na análise direta de suspensões e também facilitaria a digestão desses materiais. Os efeitos da modificação química também foram avaliados por estudos de difração de raios-X e análise ermogravimétrica. Na análise direta de suspensões dos materiais quimicamente modificados foram avaliados diversos meios que pudessem viabilizar a calibração do ICP OES com soluções de referência preparadas em meio aquoso, calibração com materiais de referência certificados e calibração empregando o método generalizado das adições do analito. Cabe ressaltar que o aspecto mais crítico da análise direta de suspensões por ICP OES é o procedimento de calibração, que é criticamente dependente do tamanho de partículas nas suspensões e da refratariedade das várias fases mineralógicas de cada material. Nos procedimentos assistidos por radiação microondas em meio alcalino, foram avaliadas dois reagentes: KOH e NaOH. Aplicando-se o teste t com 95% de confiança conclui-se que os resultados são concordantes com aqueles obtidos por procedimentos de digestão ácida assistido por radiação microondas. Para comparar os dois meios foram avaliados os valores de limite de detecção e razões sinal analítico-sinal de fundo para os dois meios, sendo que o meio alcalino se mostrou adequado para a digestão das amostras quimicamente modificadas.