Este trabalho teve como objetivo principal a utilização de duas variantes da técnica analítica de fluorescência de raios X, dispersiva em energia - EDXRF e reflexão total TXRF, na determinação de Pb em amostras de águas superficiais e subterrâneas, e em sedimentos em suspensão e de fundo. Cinco amostras de cada matriz foram coletadas em uma área contaminada, nas proximidades da desativada fábrica de baterias Indústria Acumuladores Ajax Ltda., localizada no km 229 da rodovia Jaú-Ipaussu, em Bauru, SP. As variantes EDXRF com pré-concentração com APDC e medida direta por TXRF mostraram resultados satisfatórios na determinação de Pb em soluções-padrão e amostra certificada de água natural SRM1640, produzida pelo NIST, obtendo-se concentrações compatíveis com os valores esperados. A primeira técnica resultou em limite de detecção da ordem de 0,70 mg L-1, com tempo de análise de 300 s, melhor que a segunda técnica (4,46 mg L-1), em 200 s. Estas duas variantes também foram utilizadas para outros elementos químicos, como o Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn e Br, onde a EDXRF mostrou também melhores limites de detecção para todos os elementos. Para Ni, Cu e Zn, importantes na indústria de baterias, foram encontrados os limites de 0,34 - 0,27 e 0,24 mg L-1, respectivamente, enquanto que por TXRF foram encontrados os valores ao redor de 1 mg L-1. Na validação destas duas metodologias para análise de água, a EDXRF mostrou resultados mais próximos aos valores esperados, enquanto que por TXRF foram superestimados na maioria das vezes, com exceção para As, Se e Pb. Este erro foi devido a uma interferência espectral ocasionada provavelmente pela presença dos elementos Ti ao Zn nos componentes metálicos do arranjo experimental, ausentes no suporte refletor de quartzo, colimador do detector ou solução do padrão interno. Sem a eliminação dessa interferência, os resultados obtidos por TXRF para estes elementos, com exceção para As, Se e Pb, só podem ser utilizados como qualitativos. Para análise de sedimentos em suspensão foi utilizada a técnica de EDXRF, assumindo a amostra como filme fino, atingindo limite de detecção da ordem de 2 mg g-1 para Pb, enquanto que para o Cu e Zn o limite de detecção foi da ordem de 5 mg g-1, em 300 s. Para sedimento de fundo foi utilizada a mesma técnica, mas admitindo a amostra como espessa, corrigindo-se o efeito matriz através do fator de absorção, validando-a pela análise de amostras certificadas de sedimento (SRM1646a/NIST) e solo (SRM2711/NIST). O limite de detecção para Pb ficou em torno de 2 mg g-1, e para outros elementos os limites foram de 3,07 mg g-1 para Ni, 2,12 mg g-1 para Cu e 1,50 mg g-1 para Zn, em 500 s. Com base nos valores máximos permitidos para Pb, estabelecidos pela Portaria 1469/00 e Resolução 20/1986 CONAMA, duas amostras de água mostraram-se contaminadas pelos resultados obtidos pela variante EDXRF, e quatro pelos resultados da TXRF. Para os outros elementos, apesar da interferência na TXRF, por esta técnica uma amostra de água ultrapassou o limite permissível para Cu e todas as cinco para Zn, e pela EDXRF uma amostra para Ni e Cu em água, e três para Zn. Na legislação brasileira não há limite máximo permitido para Pb e outros elementos em solos e sedimentos, e portanto foram adotados os limites TEL (Threshold Effect Level, nível limiar do efeito) e PEL (Probable Effect Level, nível provável do efeito), utilizados pela Agência Ambiental Canadense. As amostras de sedimento em suspensão mostraram concentrações de Pb menores que o limite de detecção, e das cinco amostras de sedimento de fundo, uma amostra apresentou valor acima do limite TEL, e outra, coletada num ponto bem ao lado da fábrica, acima do limite PEL. Para os outros elementos Ni, Cu e Zn, nenhuma das amostras de sedimento em suspensão ou de fundo não ultrapassaram os limites TEL. / This study had as main objective the use of two variants of the analytical technique of X-ray fluorescence, energy dispersive - EDXRF and total reflection - TXRF, for the determination of Pb in superficial and underground water and in suspended and bottom sediment samples. Five samples of each matrix were collected in a contaminated area near the closed battery plant, Indústria de Acumuladores Ajax Ltd., located on km 229 of the Jaú-Ipaussu highway, near the city of Bauru in São Paulo State, Brazil. The two variants – EDXRF with preconcentration with APDC and TXRF direct measurement – had shown satisfactory results in the determination of Pb in standard solutions and certified natural water sample SRM1640/NIST, obtaining compatible concentrations with the expected values. The first technique resulted in a 0.70 mg L-1 limit of detention, with 300 s analysis time, and the second one 4.46 mg L-1 in 200 s. These two variants were also used for other chemical elements, such as Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn and Br. EDXRF also showed better limits of detection for all the elements. For Ni, Cu and Zn, important in the industry of batteries, the limits of 0.34, 0.27 and 0.24 mg L-1, respectively, were found, while with TXRF the values of around 1 mg L-1 were achieved. In the validation of these two methodologies for water analysis, the EDXRF showed results nearer to the expected values, while with TXRF the results were overestimated most of the times, with the exceptions of As, Se and Pb. This error was due to a spectral interference caused probably by the presence of the elements Ti to Zn in the metallic parts of the experimental arrangement, absent in the quartz reflecting support, detector collimator or internal standard solution. Without the elimination of this interference, the results for TXRF for these elements, with the exceptions of As, Se and Pb, can only be used as qualitative results. For analysis of suspended sediments, the EDXRF technique was used, assuming the sample as thin film, the limit of detection of around 2 mg g-1 for Pb was reached, while that for Cu and Zn was around 5 mg g-1, in 300 s. For bottom sediments the same technique was used, but admitting the sample as thick, the matrix effect through the absorption factor was corrected, validating it for the analysis of certified samples of sediment (SRM1646a/NIST) and soil (SRM2711/NIST). The limit of detention for Pb was around 2 mg g-1 and for other elements the limits were 3.07, 2.12 and 1.50 mg g-1 for Ni, Cu and Zn, respectively, in 500 s. On the basis of the Brazilian allowed maximum values for Pb, established by Decree 1469/00 and Resolution 20/1986 CONAMA, two water samples were shown to be contaminated by the results gotten with variant EDXRF, and four by the results of TXRF. For the other elements from the TXRF results (despite the interference) one water sample exceeded the permissible limit for Cu and all the five for Zn, and for the EDXRF results one sample for Ni and Cu and three for Zn. In the Brazilian legislation there is no maximum limit allowed for Pb and other elements in soils and sediments; therefore, TEL (Threshold Effect Level) and PEL (Probable Effect Level) limits from the Canadian Environment Agency were adopted. The suspended sediment samples showed Pb concentrations lesser than the limit of detection. From the five bottom sediment samples, one sample presented a value above the TEL limit, and another one, collected in a point very close to the plant, above the PEL limit. For the other elements, Ni, Cu and Zn, none of the suspended or bottom sediment samples exceeded the TEL limits.

La connaissance des processus de mobilisation et de migration de l’uranium dans les milieux souterrains est un enjeu majeur pour évaluer les risques environnementaux associés aux activités anciennes ou actuelles d'installations nucléaires en vue d'anticiper et gérer tout impact environnemental. La mobilisation et la migration sont habituellement décrites comme fortement contrôlées par les réactions d'adsorption, la présence de ligands, notamment sous forme colloïdale, étant susceptible de l'augmenter considérablement. La capacité des entités colloïdales à transporter l'uranium sur de longues distances va dépendre de leur origine, de leur composition, de leur structure, de leur stabilité et de leur réactivité, ainsi que de leur capacité à complexer l'uranium de manière forte et irréversible. Cependant, les faibles concentrations colloïdales dans les eaux souterraines s’avèrent parfois être un verrou analytique à la détection et à la caractérisation de la mobilisation et du transport colloïdaux de polluant(s) dans les eaux souterraines. Les protocoles d'extraction des phases colloïdales depuis les sols ou les méthodes destinées à concentrer les colloïdes depuis un échantillon d'eau souterraine ne sont pas toujours optimisés pour à la fois assurer un rendement d'extraction satisfaisant et respecter l'intégrité physiques et chimiques des entités colloïdales.Dans ce contexte, deux axes de recherche ont été définis dans ce travail de thèse afin 1) d’appréhender l’impact de l’utilisation de méthodes de préconcentration sur la phase colloïdale et 2) d’améliorer notre compréhension de la dynamique de mobilisation de l’uranium au sein d’un sol podzolisé et ainsi améliorer les modèles prédictifs du transport colloïdal de l’uranium dans les eaux souterraines.Les méthodes de séparation membranaires permettent de préconcentrer la phase colloïdale des eaux souterraines tout en assurant un recouvrement supérieur à 80%. Elles engendrent néanmoins des modifications des paramètres intrinsèques des entités colloïdales avec en particulier un décalage vers les grandes tailles de la distribution en taille de ces entités ainsi qu’une modification de la distribution des espèces entre phases dissoute et colloïdale. Ces modifications peuvent mener à une mauvaise appréciation non seulement des concentrations colloïdales mais aussi des mécanismes de complexation/sorption impliquant la surface des entités colloïdales et de leur stabilité dans les eaux souterraines. La matière organique constitutive des eaux du sol d’étude a été identifiée comme étant le vecteur principal de la remobilisation de l’uranium dans les eaux de sol, sans toutefois avoir un contrôle total de ce processus. Elle est constituée majoritairement d’acides fulviques et humiques de petite taille qui tendent à s’agglomérer au cours du temps, lors de la lixiviation du sol. La composition moléculaire de la matière organique varie de manière temporelle à la fois à l’échelle de l’horizon superficiel mais aussi le long du profil de sol. Divers processus (réduction, dénitrification…) interviennent durant la migration de la matière organique vers les horizons plus profonds et pourraient modifier ainsi sa nature. A l’échelle de l’horizon superficiel, les mécanismes de mobilisation diffèrent selon l’élément considéré. L’uranium en particulier est mobilisé rapidement mais de manière limitée (<2% du sol considéré), tandis que la matière organique est générée en continu et de manière pseudo-linéaire. / Knowledge of the processes of mobilization and migration of uranium in underground environments is a major challenge to assess the environmental risks associated with ancient or current activities of nuclear facilities in order to anticipate and manage any environmental impact. Mobilization and migration are usually described as strongly controlled by adsorption reactions, the presence of ligands, especially in colloidal form, being able to increase considerably. The ability of colloidal entities to transport uranium over long distances will depend on their origin, composition, structure, stability and reactivity, as well as their ability to complex uranium in a significant and irreversible manner. However, low colloidal concentrations in groundwater sometimes prove to be an analytical lock on the detection and characterization of colloidal mobilization and transport of pollutant(s) in groundwater. Protocols for extracting colloidal phases from soils or methods for concentrating colloids from a groundwater sample are not always optimized to both ensure satisfactory extraction yield and respect physical and chemical integrity colloidal entities.In this context, two lines of research have been defined in this thesis work to 1) to understand the impact of the use of preconcentration methods on the colloidal phase and 2) to improve our understanding of mobilization dynamics of uranium within a podzolized soil and thus improve predictive models of colloidal uranium transport in groundwater.The membrane separation methods make it possible to preconcentrate the colloidal phase of the groundwater while ensuring a recovery greater than 80%. Nevertheless, they cause modifications of the intrinsic parameters of the colloidal entities with, in particular, a shift towards the large sizes of the size distribution of these entities as well as a modification of the species distribution between dissolved and colloidal phases. These modifications may lead to an inaccurate appreciation not only of colloidal concentrations but also of complexation/sorption mechanisms involving the surface of colloidal entities and their stability in groundwater. The constituent organic matter of the study soil waters has been identified as the main vector for the remobilization of uranium in the soil water, without having a complete control of this process. It consists mainly of small fulvic and humic acids that tend to agglomerate over time, during leaching of the soil. The molecular composition of organic matter varies temporally both at the level of the superficial horizon and also along the soil profile. Various processes (reduction, denitrification ...) occur during the migration of organic matter to deeper horizons and could thus change its nature. At the level of the superficial horizon, mobilization mechanisms differ according to the element considered. Uranium in particular is mobilized quickly but in a limited way (<2% of the considered soil), while organic matter is generated continuously and in a pseudo-linear way.

Les charges à l'interface liquide/solide sont un élément originel majeur des phénomènes électrocinétiques observés en micro/nanofluidique. Elles sont donc la colonne vertébrale de mon manuscrit de thèse, qui se décompose en trois parties : Dans la première partie, un rappel des concepts de base sur les interfaces liquides/solides est proposé au lecteur. Il est suivi d'une description des différentes méthodes expérimentales permettant de mesurer le potentiel zeta de couples solide/électrolyte, puis d'une présentation des travaux de la littérature exploitant les charges aux interfaces pour la préconcentration de molécules biologiques dans des systèmes Micro-Nano-Micro (MNM) fluidiques. Ensuite, une deuxième partie est consacrée à la mesure du potentiel zeta par la méthode des courants d'écoulement. Nous y présentons l'amélioration du banc expérimental issu des travaux antérieurs à ma thèse, ainsi que le développement de nouveaux protocoles de préparation des surfaces permettant de rationaliser et de stabiliser les mesures. Une application à un détecteur original de molécules biologiques clos cette deuxième partie. Enfin, la troisième et dernière partie s'intéresse à la préconcentration de molécules biologiques. Une méthode originale de fabrication des dispositifs MNM et les résultats de préconcentration obtenus, très encourageants, sont décrits. Des premiers modèles numériques et phénoménologiques sont proposés, qui mettent en avant l'originalité de notre travail / The charges at liquid/solid interfaces are a key element for both understanding and exploiting the electrokinetic phenomena in micro/nanofluidics. The manuscript of my Ph.D thesis is dedicated to these phenomena, which is divided into three main parts: Above all, a simple overview of charges at the liquid/solid interface is proposed. Then, several common methods for measuring the zeta potential at the liquid/solid interface are described. Next, various effective methods to preconcentrate the biological molecules is presented with the help of the surface charges. Secondly, the streaming current, which is a standard method to measure the zeta potential in our laboratory, is detailed. It contains the upgrade of the experimental setup from the previous version and the development of new protocols, which improve dramatically the stabilization and the reproducibility of the measurements. In addition, an original biological sensor is briefly presented based on these advancements. Lastly, in the final part, we describe a method which is primitively utilised in the fabrication of Micro-Nano-Micro fluidic system. Based on this system, some favorable preconcentration results is obtained. Moreover, numerical simulations are presented to prove the originality of our work

<p>Different sample preparation steps prior to a detection method are often essential in analytical chemistry. In this thesis, both static extractions and on-line coupled solid-phase extractions have been studied in combination with different detection techniques. Aspects of performing sample preparations in miniaturized analytical devices and the development of poly(dimethylsiloxane) (PDMS) microchips are discussed. Polypyrrole was also evaluated as an electrochemically controllable stationary phase for solid-phase microextraction (SPME) and solid-phase extraction (SPE).</p><p>The first part of this thesis describes the extraction of an organic compound from a very complex solid matrix utilizing the pressurized-fluid extraction (PFE) technique. The presented results show that PFE is easily optimized and enables rapid extractions and extracts relatively free from interferences.</p><p>An integrated three-electrode device, which enabled electrochemical (EC) SPME under potential control, was developed. With this device, both anions and cations could be extracted employing two types of polypyrrole films. Planar micro band electrodes positioned at the end of a capillary were also used to electrochemically extract and detect anions in a miniaturized flow system. Different analyte concentrations and preconcentration times were examined, and good linear correlations were found between the extraction time and the detection response. The on-line coupling of a thin layer EC cell, with a polypyrrole coated working electrode, to different mass spectrometric (MS) techniques is also described and evaluated. The results show that EC-SPE, employing polypyrrole as stationary phase, can be used as a preconcentration step prior to detection.</p><p>In addition, this thesis describes the development and on-line coupling of a microelectrode array equipped PDMS microchip with an integrated graphite electrospray emitter to electrospray ionization (ESI) MS. The system enabled short transfer times and an EC conversion efficiency of 30% at a flow rate of 0.5 μL/min. The on-line EC/ESI-MS experiments were significantly simplified using a wireless Bluetooth battery-powered EC instrument.</p>

Different sample preparation steps prior to a detection method are often essential in analytical chemistry. In this thesis, both static extractions and on-line coupled solid-phase extractions have been studied in combination with different detection techniques. Aspects of performing sample preparations in miniaturized analytical devices and the development of poly(dimethylsiloxane) (PDMS) microchips are discussed. Polypyrrole was also evaluated as an electrochemically controllable stationary phase for solid-phase microextraction (SPME) and solid-phase extraction (SPE). The first part of this thesis describes the extraction of an organic compound from a very complex solid matrix utilizing the pressurized-fluid extraction (PFE) technique. The presented results show that PFE is easily optimized and enables rapid extractions and extracts relatively free from interferences. An integrated three-electrode device, which enabled electrochemical (EC) SPME under potential control, was developed. With this device, both anions and cations could be extracted employing two types of polypyrrole films. Planar micro band electrodes positioned at the end of a capillary were also used to electrochemically extract and detect anions in a miniaturized flow system. Different analyte concentrations and preconcentration times were examined, and good linear correlations were found between the extraction time and the detection response. The on-line coupling of a thin layer EC cell, with a polypyrrole coated working electrode, to different mass spectrometric (MS) techniques is also described and evaluated. The results show that EC-SPE, employing polypyrrole as stationary phase, can be used as a preconcentration step prior to detection. In addition, this thesis describes the development and on-line coupling of a microelectrode array equipped PDMS microchip with an integrated graphite electrospray emitter to electrospray ionization (ESI) MS. The system enabled short transfer times and an EC conversion efficiency of 30% at a flow rate of 0.5 μL/min. The on-line EC/ESI-MS experiments were significantly simplified using a wireless Bluetooth battery-powered EC instrument.

Obsidian has been a center of interest both for geologists and archaeologists. Geologists have studied on physical and chemical properties of obsidian where archaeologists have worked on this material as a common artifact found in excavations. In this study, obsidian samples from &Ccedil / atalh&ouml / y&uuml / k excavations are examined using their rare earth element (REE) concentrations. Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES) have been used for this purpose. A mixture (4:1) of lithium metaborate and lithium tetraborate was used for fusion of samples. Because of the low concentrations of REEs, a preconcentration step is needed. Successful recovery results have been achieved with Amberlite IR-120. The developed method is tested using the standard reference material SARM-1.

El glifosat, N-(fosfonometil) glicina, és un dels herbicides més utilitzats arreu del món a causa de la seva baixa toxicitat i al seu ampli espectre d'aplicació. A conseqüència del gran ús que se'n fa, és necessari monitoritzar aquest compost i el seu principal metabòlit, l'àcid aminometilfosfònic (AMPA), en el medi ambient. S'han descrit diversos mètodes instrumentals basats en cromatografia de gasos (GC) i de líquids (HPLC), sent aquesta darrera l'opció més favorable a causa del caràcter polar dels anàlits. Per assolir nivells de concentració baixos cal, però, la preconcentració dels anàlits.En aquest treball s'estudien diferents alternatives amb aquest objectiu. S'ha avaluat la tècnica de membrana líquida suportada (SLM) on la membrana consisteix en una dissolució orgànica, que conté un transportador (en el nostre cas, un bescanviador d'anions comercial, Aliquat 336), que impregna un suport polimèric microporós que se situa entre dues solucions aquoses: la de càrrega, que conté els anàlits inicialment, i la receptora, on es retenen els anàlits després del seu transport a través de la membrana. Les condicions d'extracció més adequades s'obtenen treballant en medi bàsic amb NaOH on els anàlits estan en forma aniònica i les majors recuperacions s'obtenen amb HCl 0,1 M o NaCl 0,5 M, la qual cosa indica que l'ió clorur és la força impulsora del transport.Un cop dissenyat el sistema, es duen a terme experiments de preconcentració amb dues geometries diferents: un sistema de membrana laminar (LSLM) on recircula la fase receptora i un sistema de fibra buida (HFSLM). Els millors resultats s'obtenen amb el mòdul de fibra buida, amb factors de concentració de 25 i 3 per a glifosat i AMPA, respectivament, fent recircular durant 24 hores 100 ml de solució de càrrega i 4 ml de solució receptora. També s'aplica una tècnica més selectiva, la cromatografia d'afinitat amb ió metàl·lic immobilitzat (IMAC), basada en la interacció entre els anàlits i un metall immobilitzat en una resina a través d'un grup funcional d'aquesta. En aquest estudi s'immobilitza pal·ladi al grup funcional 8-hidroxiquinoleïna de la resina amb matriu acrílica Spheron Oxine 1000 i s'avalua per a l'extracció i preconcentració de glifosat i AMPA. Per a ambdós anàlits l'adsorció és del 100 % i les recuperacions són superiors al 80 % i al 60 % per a glifosat i AMPA, respectivament, utilitzant HCl 0,1 M + NaCl 1 M com a eluent. Aquests resultats es comparen amb els obtinguts amb dues resines més, també carregades amb pal·ladi: Iontosorb Oxin 100, que té el mateix grup funcional però matriu de cel·lulosa, i Spheron Thiol 1000, on el grup funcional és un tiol i la matriu també és acrílica. Per al glifosat els resultats són similars amb totes les resines, però per a l'AMPA la resina Spheron Thiol és la única que proporciona recuperacions superiors al 93 %.Finalment, una altra opció estudiada és l'acoblament de dues columnes de cromatografia líquida (LC-LC). En l'estudi l'objectiu és millorar el mètode existent per a glifosat i AMPA en aigües naturals on el LOD era de 0,25 ug/l. El mètode consisteix en la derivatització precolumna amb el reactiu fluorescent FMOC i l'anàlisi amb l'acoblament LC-LC-fluorescència. Variant lleugerament les condicions de derivatització s'aconsegueix quantificar 0,1 ug/l de glifosat i AMPA. Es fortifiquen aigües naturals amb 0,1, 1 i 10 ug/l dels anàlits per validar el mètode. S'obtenen recuperacions d'entre el 85 % i el 100 %, amb desviacions estàndard relatives inferiors al 8 %. Aplicant una tècnica de preconcentració prèvia a la derivatització i anàlisi utilitzant una resina de bescanvi aniònic, Amberlite IRA-900, es millora la sensibilitat del mètode i s'assoleix un LOD per al glifosat de 0,02 ug/l. / Glyphosate, N-(phosphonomethyl)glycine, is one of the most widely used herbicides in the world due to its low mammal toxicity. Therefore, there is a great interest in the monitoring of this compound and its major metabolite aminomethylphosphonic acid (AMPA), in environmental matrices. A great variety of methods based on gas chromatography (GC) and liquid chromatography (HPLC) have been applied for their determination. HPLC is the most popular option due to the polar nature of both compounds. However, the analysis of these compounds at residue levels requires the use of preconcentration techniques.In this work we have studied different alternatives to this aim. We have evaluated the supported liquid membrane (SLM) technique where the membrane consists of an organic solution, which contains the carrier (in this case a commercial anion exchanger extractant, Aliquat 336), that impregnates a microporous polymeric support placed between two aqueous solutions: the feed solution, which initially contains the analytes, and the stripping solution, where the analytes are retained after their transport through the membrane. The best conditions were achieved with NaOH as feed solution, where the analytes are present in their anionic form and 0.1 M HCl or 0.5 M NaCl as stripping solutions indicating that the chloride ion is the responsible for the transport.Under these chemical conditions some preconcentration experiments were run using two different geometries of the membrane: a laminar membrane system (LSLM) where the stripping solution can be recirculated and a hollow fiber liquid membrane (HFSLM). The best results were obtained for the liquid membrane system in HF configuration, with concentration factors of 25 and 3 for glyphosate and AMPA, respectively, after recirculation during 24 hours of 100 ml of feed solution and 4 ml of stripping solution.A more selective technique is also studied, immobilised metal ion affinity chromatography (IMAC), which is based on the interaction between the analytes and a metal immobilised in a resin through a functional group. In this work we have immobilised palladium through the chelating group 8-hydroxyquinoline of the acrylic resin Spheron Oxine and it has been evaluated for the preconcentration of glyphosate and AMPA. 100 % adsorption has been obtained for both analytes and the recoveries are higher than 80 % and 60 % for glyphosate and AMPA, respectively, using 0.1 M HCl + 1 M NaCl as eluent. These results are compared with the results obtained working with two different resins also charged with palladium: Iontosorb Oxin, which has the same functional group but cellulose matrix, and Spheron Thiol, which a thiol functional group and acrylic matrix. The results for glyphosate are similar with all the resins tested, but for AMPA the best results are obtained with Spheron Thiol with recoveries higher than 93 %.Finally, another option studied is the coupling of two liquid chromatographic columns (LC-LC). In this work the objective is to improve the existing method for the analysis of glyphosate and AMPA in natural waters which had a LOD of 0.25 mg/l. The method consists of the pre-column derivatization with the fluorescent reagent FMOC and the analysis by LC-LC-fluorescence detection. The derivatization step has been slightly modified with the aim of decreasing the limits of quantification of glyphosate and AMPA down to 0.1 mg/l. Different water samples spiked at three concentration levels (0.1, 1, 10 mg/l) were analysed by the improved method yielding recoveries between 85-100 % with relative standard deviations lower than 8 %.Additionally, the potential of an anion-exchange resin, Amberlite&#61650; IRA-900, for preconcentration of glyphosate, previously to the derivatization step, has been investigated. In this way the LOD of the parent compound has been lowered to 0.02 mg/l.

The use of slotted quartz tube (SQT) as an atom trap in atomic absorption spectrometry (AAS) provides a more stable chemical environment for atomization / the technique is simple and easily applicable in any laboratory. This thesis study involves application of SQT together with some other approaches to thallium determination by AAS. The first stages involve the efforts to improve nebulization efficiency of conventional flame atomic absorption spectrometry (FAAS) with and without the use of SQT. This is achieved by mixing 100 &micro / L of propanol with 500 &micro / L of Tl standard solution using the optimum conditions. By this method, Propanol-SQT-FAAS, 4.49 times enhancement in sensitivity has been obtained with respect to conventional FAAS, method in which the characteristic concentration was calculated as 894 ng/mL. The second stage of investigation is about the use of SQT as an atom trap, AT, preconcentration device for thallium determination. The similar technique has been successfully applied to some other analytes such as Pb, Cd, Bi and Au / detection limits at the level of ng/mL were obtained in the previous studies. In the present work, the analyte atoms are trapped on the inner surface of SQT in the presence of a lean air-acetylene flame for few minutes. After this collection step, a volume of methyl isobutyl ketone, MIBK, amounting to 10-50 microliters is introduced via conventional nebulization / this causes a momentary alteration in the flame composition and thus results in the release of trapped analyte atoms from the quartz surface. This revolatilization step is followed by a rapid atomization and transient signal was obtained. In addition to this method, a novel approach has been investigated where the inner surface of SQT was modified by using a metal coating with low volatility. For this purpose, eight different coating materials which were tungsten, palladium, molybdenum, gold, tantalum, zirconium, titanium and osmium, have been applied to the inner surface of SQT and as osmium was found to be most appropriate one, the rest of the study was continued with Os-Coated-SQT. This modification provided a better surface than quartz alone so that analyte atoms are trapped more efficiently and also released easily. Although the working principle of the Coated-SQT-AT-FAAS method is same with SQT-AT-FAAS, the conditions for SQT-AT-FAAS and Os-Coated-SQT-AT-FAAS methods were optimized seperately. Limit of detections, 3s/m, has been found to be 38 ng/mL and 3.5 ng/mL for these cases, respectively. While the SQT-AT-FAAS method has provided 92 fold enhancement, the Os-Coated-SQT-AT-FAAS method has provided a 319 fold sensitivity improvement with respect to conventional FAAS method.

L’application de la biosorption à l’analyse inorganique est un sujet en plein essor. Dans cette étude, un support à base de cellules de boulanger Saccharomyces cerevisiae a été développé pour la spéciation et la préconcentration des espèces inorganiques de l’antimoine Sb(III) et Sb(V). Nous avons tout d’abord montré qu’il était possible de fixer de manière sélective Sb(III) en présence de Sb(V) sur les cellules dans une large gamme de pH (5-9) et de force ionique (0-0,1M). Un prétraitement thermique de la biomasse (80°C, 30min) permet d’augmenter significativement la cinétique de fixation de Sb(III) sans nuire à la séparation. L’élution de Sb(III) par l’acide thioglycolique à pH 10 est rapide et quantitative, permettant d’obtenir un facteur de préconcentration proche de 9. Nous avons mis en évidence que la rétention de Sb(V) observée à bas pH était due à des complexation avec les groupements sulfhydryle de la paroi cellulaire. La modélisation des isotherme de sorption de Sb(III) (qmax = 450µg.g-1) ont permis de définir 3 types de sites d’affinité et de coordination différentes. Parmi les matrices testées pour l’immobilisation des cellules, le polysulfone s’avère être le plus performant, alliant perméabilité, faible affinité vis-à-vis de l’antimoine et préservation des sites de fixation. Des colonnes remplies de levures immobilisées ont été couplées à un spectromètre ICP-AES et appliquées avec succès à la spéciation de l’antimoine dans l’eau minérale dopée à faible concentration. Les limites de quantification de Sb(III) ont été améliorées d’un facteur 5 par préconcentration / The application of biosorption to inorganic analysis is an expanding research area. In this study, an analytical support based on baker’s yeast Saccharomyces cerevisiae was developed for the speciation and the preconcentration of inorganic antimony species Sb(III) and Sb(V). It was shown that Sb(III) can be retained selectively by the cells in the presence of Sb(V) in a wide range of pH (5-9) and ionic strength (0-0,1M). Heat pretreatment of the biomass (80°C, 30min) significantly increased the kinetics of Sb(III) uptake without degrading the separation. The elution of Sb(III) by thioglycolic acid at pH 10 was rapid and quantitative, allowing to achieve a preconcentration factor close to 9. Interactions between Sb(V) and the cells, as observed at lower pH, were found to be purely electrostatic, while Sb(III) retention was attributed to the complexation of the species with sulfhydryl groups of the cell walls. Three kinds of sites with different affinities and coordinations were identified by modeling Sb(III) sorption isotherms (qmax = 450µg.g-1). Among the different materials tested, polysulfone was found to be the most suitable matrix for yeast immobilization, combining a good permeability to a low affinity for antimony species and preservation of the sorption sites. Columns filled with immobilized cells were coupled with ICP-AES and successfully applied to antimony speciation in mineral waters samples spiked at low concentration level. The limit of quantification was improved by a factor of 5 by preconcentration

Fundação de Amparo a Pesquisa do Estado de Minas Gerais / Industrial process have been historically an important factor of environmental degradation. The disposal of industrial wastes, mainly containing toxic metals, in water sources represents a problem of great concern not only in relation to biota in receiving environment but also to humans. In this work, the adsorptive capacity of the crushed seeds of Moringa oleifera Lam. was evaluated in order to quest alternative materials for removal and preconcentration of silver ions. The first chapter describes the results of removal of Ag(I) ions in contaminated aqueous systems utilizing moringa seeds. Preliminary tests were carried out using the seeds of moringa as: non-shelled, shelled seeds and husks were tested for their adsorption potential for ions Ag(I). The results showed greater efficiency for non-shelled seeds. The parameters evaluated were: particle size, pH and agitation time, concentration and volume of solution, adsorbent mass. Silver was quantified before and after treatment, by Flame Atomic Absorption Spectrometry. The optimum conditions were: particle size &#8804; 500 &#956;m, pH = 6.5, agitation time = 20 minutes, adsorbente mass = 2.0 g, concentration of Ag(I) = 25 mg L-1 and volume = 100 mL. In these conditions, the removal of ions Ag(I) was 98%. The proposed methodology was applied to the treatment of the following samples: residue of experimental classes of Analytical Chemistry and analysis of chemical oxygen demand, generated at the university, and waste photographic material from local industries. The values obtained for the removal of Ag(I) were 92%, 82% and 91% respectively, using the non-shelled seeds of moringa as adsorbent. Also, it was studied the possible interference of other metals in proposed method, namely Cd(II), Co(II), Cu(II) e Pb(II). The value of the maximum adsorptive capacity for ions Ag(I) was 25.56 mg g-1 obtained through of the adsorption isotherm. Characterization techniques, including infrared spectrometry, X-ray diffraction, thermogravimetric analysis and scanning electron microscopy were used to assess physical and chemical proprieties of nonshelled seeds of moringa. The second chapter was presented a method for preconcentration of v ions using flow system and non-shelled seeds of Moringa oleifera Lam. as adsorbent material. The preconcentration system was coupled to FAAS. The following experimental conditions carried out: for 4 minutes leachate solution of Ag(I) 0.01 mg L-1, about of ground seeds of moringa packaged in a mini-column flow of. The elution was performed with of HNO3 0.5 mol L-1. The concentration factor was 35, resulting in detection limit of 0.22 &#956;gL-1 e quantification limit of 0.73 &#956;gL-1. Accuracy of the method was cheked by using certified reference material for water APS-1071 (Alpha Resources 3090 Johnson RD, Stevensville, USA). The proposed method has advantages such as low cost of sorbent, high efficiency and minimization of chemical sludge. The moringa is an alternative material for chemical remediation and is economically and environmentally friendly. / Processos industriais tem sido historicamente um importante fator de degradação ambiental. A disposição inadequada de resíduos industriais contendo metais tóxicos em fontes de águas representa um grande problema, que concerne não somente à biota, mas também para humanos. Neste trabalho, foi avaliada a capacidade adsortiva das sementes trituradas de Moringa oleifera Lam. como um material alternativo para remoção e pré-concentração de íons Ag(I) em águas. No primeiro capítulo foi avaliada a capacidade das sementes de moringa para remoção de íons Ag(I) em sistemas aquosos contaminados por este íon metálico. Antes da otimização dos parâmetros foram realizados testes preliminares com a moringa envolvendo a casca da semente, polpa da semente e a semente integral para avaliar a parte da semente que apresentava maior capacidade de remoção, e como espécie analítica de interesse, utilizou-se íons Ag(I). Os resultados mostram maior eficiência usando as sementes integrais. Os parâmetros de otimização avaliados para o adsorvente nos ensaios de remoção foram: granulometria, pH e tempo de agitação, volume de solução, concentração e massa do adsorvente. A quantificação do teor de prata, antes e após o tratamento, foi realizada por Espectrometria de Absorção Atômica por Chama (FAAS). As condições otimizadas foram: Granulometria &#8804; 500 &#956;m; pH = 6,5; Tempo de Agitação = 20 minutos; Massa = 2,0 g; concentração de Ag(I) = 25 mg L-1 e volume = 100 mL. Observou-se uma remoção de íons Ag(I) de 98% quando se utiliza a Moringa oleifera Lam. como adsorvente. A metodologia proposta foi aplicada para o tratamento das seguintes amostras: resíduo de aulas práticas de Química Analítica e de análise de DQO, gerados nesta Instituição de Ensino; de material fotorrevelador e resíduo de material gráfico, ambos obtidos em indústrias locais. Os valores obtidos para a remoção de Ag(I) foram de 92%, 82% e 91% respectivamente, utilizando as sementes trituradas de moringa como adsorvente, sendo que para o resíduo do material gráfico não foi detectado a presença do metal de interesse. Foi estudada a possível interferência de outros metais nesta análise, a saber: Cd(II), Co(II), Cu(II) e Pb(II). O valor da capacidade máxima adsortiva (CMA) de íons Ag(I) pelo adsorvente 25,56 mg g-1 de semente de moringa seca, foi obtido com a construção da isoterma de adsorção, determinando-se graficamente a quantidade máxima (mg) do adsorvato que pode ser adsorvido numa dada massa de adsorvente (g). Técnicas de caracterização incluindo espectrometria por infravermelho, difração de raios-X, análise termogravimétrica e microscopia eletrônica de varredura foram utilizadas na avaliação físico-química das sementes trituradas de moringa. No segundo capítulo foi apresentado um método de pré-concentração de íons Ag(I) utilizando análise em fluxo com o emprego de sementes trituradas de Moringa oleifera Lam., como material adsorvente. O sistema de pré-concentração acoplado ao FAAS foi executado com o referido adsorvente percolando durante 4 minutos solução de Ag(I) 0,01 mg L-1, na mini-coluna recheada com 35 mg de sementes trituradas de moringa a uma vazão de 5,5 mL min-1. A eluição foi realizada com 100 &#956;L de HNO3 0,5 mol L-1. Foi obtido um fator de préconcentração igual a 35; limite de detecção (LD) igual a 0,22 mg L-1 e limite de quantificação (LQ) igual a 0,73 mg L-1. A exatidão do método foi atestada com o uso de padrão certificado para águas APS-1071 (Alpha Resources 3090 Johnson RD, Stevensville, USA). Diante dos resultados obtidos, conclui-se que o material apresentou alta capacidade de remoção para íons Ag(I). O método desenvolvido mostrou-se satisfatório para a pré-concentração e determinação de íons prata em águas dada a sua simplicidade, eficiência, baixo custo e pouca influência dos contaminantes estudados. Avalia-se que a utilização da Moringa oleifera Lam. como material alternativo para a pré-concentração de prata é viável. / Doutor em Química