O mesilato de imatinibe é um importante fármaco pertencente à classe dos inibidores da tirosina-quinase, desenvolvido e utilizado atualmente no tratamento da Leucemia Mielóide Crônica. No histórico da utilização deste medicamento, casos de resistência tem sido relatados cujos mecanismos envolvidos, além dos mecanismos celulares, podem estar relacionados ao metabolismo aumentado deste fármaco. O imatinibe é metabolizado principalmente pelo CYP 3A4, cuja atividade enzimática apresenta grande variabilidade interindividual e é suscetível a indução ou inibição por inúmeras co-medicações, constituintes ambientais e dietéticos. Sendo assim uma dose do medicamento pode resultar em concentrações plasmáticas muito diferentes entre pacientes. A maior parte dos métodos existentes para a determinação do imatinibe em amostras biológicas utiliza a cromatografia líquida de alta eficiência. Entretanto, o método desenvolvido e validado neste trabalho propôs a utilização da eletroforese capilar para a análise deste fármaco em plasma. Para isto foi utilizado um capilar de sílica fundida (46,5 cm de comprimento total, 38 cm de comprimento efetivo e 50 µm de diâmetro interno), tampão fosfato de sódio 50 mmol/L, pH 2,5 como eletrólito de corrida, injeção hidrodinâmica por 20 s a pressão de 50 mbar, tensão de 30 kV, temperatura de 35 °C e detecção em 200 nm. O procedimento de preparo das amostras foi baseado na extração líquido-líquido com o éter metil-terc-butílico como solvente extrator. Os parâmetros de desempenho analítico, linearidade, precisão, exatidão, recuperação, limite de quantificação, seletividade e estabilidade, avaliados na validação do método, cumpriram os requisitos preconizados na legislação vigente e o método desenvolvido foi validado com sucesso. Além disso, sua aplicação foi demonstrada na análise de amostras de plasma de pacientes portadores de Leucemia Mielóide Crônica. / Imatinib mesylate is an important tyrosine kinase inhibitor that has been used for the treatment of Chronic Myeloid Leukemia (CML). Despite the efficacy of imatinib therap, some cases of treatment resistance have been described. A number of mechanisms of resistance have been identified, which include innate or acquired mutations in the BCR-ABL gene, imatinib binding to 1- acid glycoprotein and altered imatinib pharmacokinetics. Imatinib is mainly metabolized by CYP 3A4, whose enzymatic activity presents a large inter-individual variability and is susceptible to induction or inhibition by numerous co-medications, environmental and dietary constituents. Therefore a given dose can yield very different circulating concentrations between patients. The major of methods available for the determination of imatinib in biological samples apply high performance liquid chromatography as analytical technique. However, in this work, we developed and validated a method by capillary electrophoresis for the determination of this drug in human plasma. The analysis was performed using a fused silica capillary (50 µm internal diameter x 46.5 cm total length, 38.0 cm effective length), a 50 mmol/L sodium phosphate buffer pH 2,5 as background electrolyte, hydrodynamic injection time of 20s (50 mbar), voltage of 30 kV, capillary temperature of 35°C and detection at 200 nm. Plasma samples pre-treatment involved liquid-liquid extraction with methyl-terc-butyl ether as extractor solvent. The analytical parameters investigated, linearity, precision, accuracy, recovery, limit of quantification, selectivity and stability, presented in accordance with the confidence criteria established in the literature. Furthermore the application of the method was performed in the analysis of plasma samples from CML patients undergoing treatment with imatinib.

Pour augmenter les performances de nos composants électroniques, les fabricants ont recourt à de nouveaux matériaux tels que les terres rares. Malgré leur nom, les terres rares sont présentes en quantité sur le globe terrestre mais de façon diluée dans les minerais extraits. L’extraction de ces éléments est peu effectuée en Europe mais majoritairement en Asie où les procédés chimiques de séparations employés sont parfois peu respectueux de l’environnement. De plus les industriels européens sont contraints économiquement par le marché asiatique pour l’achat de ces matières premières. En revanche l’Europe dispose d’une grande quantité de déchets électroniques contenant les éléments d’intérêts. Les procédés de recyclage sont donc primordiaux pour réduire notre dépendance économique et répondre aux besoins d’une économie circulaire. Des procédés de recyclage comme par exemple, l’extraction liquide-liquide existent déjà, mais la diversité des déchets présents nécessite d’adapter le procédé en fonction du lot de déchets afin d’améliorer le rendement. Mais l’optimisation d’un procédé nécessite des expérimentations qui peuvent prendre plusieurs années. L’objectif de la thèse est de trouver des moyens innovants pour réduire le temps nécessaire à l’étude d’un système d’extraction liquide-liquide de quelques années à quelques semaines. Pour cela le domaine a besoin d’une instrumentation dédiée pouvant analyser de façon automatique et rapide les procédés. Les travaux de cette thèse ont donc porté sur le développement d’un dispositif microfluidique d’extraction liquide-liquide associé à deux techniques principales d’analyses en ligne. La première technique d’analyse est basée sur une méthode de fluorescence des rayons X (XRF) pour déterminer la performance d’extraction. La seconde méthode est basée sur de la spectrométrie infrarouge à transformée de Fourrier (FTIR) afin d’étudier l’activité des solvants (aqueux et organiques), informant sur les mécanismes d’extraction. / To increase the performance of our electronic components, manufacturers are using new materials such as rare earth elements (REE). Despite their name, the REE are present in quantity on Earth but in a diluted way in the ores extracted. The extraction of these elements is little carried out in Europe but mainly in Asia where the chemical processes of separations employed are sometimes not very respectful of the environment. Moreover European manufacturers are economically constrained by the Asian market for the purchase of these raw materials. On the other hand, Europe has a large quantity of electronic waste containing the elements of interest. Recycling processes are therefore essential to reduce our economic dependence and meet the needs of a circular economy. Recycling processes such as, for example, liquid-liquid extraction already exist, but the diversity of the present waste requires to adapt the process according to the batch of waste in order to improve the yield. But the optimization of a process requires experiments that can take several years. The aim of the thesis is to find innovative ways to reduce the time needed to study a liquid-liquid extraction system from a few years to a few weeks. For this the domain needs a dedicated instrumentation that can analyse processes automatically and quickly. The work of this thesis is focused on the development of a microfluidic liquid-liquid extraction device associated with two main online analysis techniques. The first analytical technique is based on an X-ray fluorescence (XRF) method to determine the extraction performance. The second method is based on Fourier transform infrared spectrometry (FTIR) in order to study the activity of solvents (aqueous and organic), informing about extraction mechanisms.

O emprego de solventes no processo de obtenção de óleos de sementes oleaginosas é um processo amplamente empregado, sendo o hexano o solvente tradicionalmente adotado. O objetivo principal desta dissertação de mestrado foi avaliar a viabilidade da substituição do hexano por etanol no processo de extração de óleo de soja. A utilização de etanol apresenta vantagens bastante atrativas como: menor toxicidade, boa seguridade operacional além deste ser obtido de fonte biorenovável. A produção de etanol em larga escala no Brasil torna, ainda, o processo vantajoso do ponto de vista econômico, além de ser um solvente facilmente recuperado para posterior reutilização no processo devido às suas características físico-químicas. Desta forma, neste trabalho foram realizados experimentos de cinética de extração e experimentos de extração sólido-líquido na condição de equilíbrio, nos quais foram avaliadas as variáveis: temperatura (40 a 90 °C) e hidratação do solvente (0 a 12%). Através da execução destes experimentos e a avaliação estatística dos resultados foi possível determinar os rendimentos de óleo e proteína, monitorar o comportamento dos compostos minoritários (ácidos graxos livres) e da água presente na matéria-prima, avaliar a qualidade da fração proteica resultante do processo de extração, além da composição química dos óleos obtidos. Assim, os resultados mostraram que o aumento do teor de água no etanol suprimiu fortemente a extração de óleo enquanto que a elevação da temperatura favoreceu a extração. Já a proteína exibiu um comportamento contrário ao óleo, sendo que o aumento da hidratação do solvente elevou a extração destes compostos e o aumento da temperatura diminuiu o teor de proteínas na fase extrato. Quanto à hidratação da fase extrato, pôde-se notar que esta foi independente da temperatura e que existe um equilíbrio entre a umidade do sólido e o nível de hidratação do etanol. A elevação da temperatura também aumentou a extração de ácidos graxos livres e a avaliação do perfil químico e da composição em AGL dos óleos obtidos via etanol mostrou que estes apresentaram composição típica de óleo de soja, independente da condição adotada. A qualidade da fração proteica resultante da extração do óleo, avaliada na forma de solubilidade de nitrogênio e análise térmica (DSC), mostrou que a proteína também foi fortemente influenciada pela presença da água no solvente e pelo aumento da temperatura, apresentando menores valores de solubilidade conforme o aumento do teor de água no etanol e da temperatura do processo. Diante dos resultados, pode-se inferir que é viável tecnicamente a utilização de etanol no processo de extração de óleo de soja, no entanto as condições de hidratação do solvente e temperatura devem ser consideradas devido à influência destas sobre as características da fração proteica do farelo desengordurado. / The use of solvents in the extraction of oil from oilseeds is a widely employed process and the hexane is the solvent traditionally adopted. The aim of this work was to evaluate the feasibility of replacing hexane by ethanol in the soybean oil extraction process. The use of ethanol has very attractive advantages such as: low toxicity, good operational security, as well as being obtained from a biorenewable source. The large scale production of ethanol in Brazil also makes the process advantageous from the economics point of view, besides being a solvent easily recovered for reuse in the process due to its physicochemical characteristics. Thus, in this work were performed experiments of kinetics of extraction and experiments of solid-liquid extraction in equilibrium condition in which the variables evaluated were: temperature (ranging from 40 to 90 °C) and solvent hydration (0 to 12% of water). The accomplishment of these experiments and the statistical evaluation of the results made possible to determine the yields of oil and protein, monitor the behavior of minor compounds (free fatty acids) and of the water present in raw material, evaluate the quality of the protein fraction resulting from oil extraction process, and the chemical composition of the extracted oils. Then, the results showed that increasing in water content of ethanol suppresses strongly the extraction of oil while the increase of temperature increases the extraction. About protein, it exhibits an opposite behavior to the oil, with the rise in water content of the solvent increasing the extraction of such compounds and the rise of temperature decreases in the protein content of extract phase. Regarding the hydration of the extract phase, it can be seen that this is temperature independent and that there is equilibrium between the solid matrix and the moisture level of the solvent ethanol. The increase in temperature also increases the extraction of free fatty acids and the evaluation of the chemical profile and composition in FFA of oils obtained via ethanol showed that they had typical composition of soybean oil, regardless the condition adopted. The quality of the protein fraction resulting from oil extraction evaluated as nitrogen solubility and thermal analysis (DSC) showed that the protein is also strongly influenced by the presence of water in the solvent and by increasing the temperature, with lower values of solubility with increasing water content in the ethanol and the process temperature. From the results, it can be inferred that it is technically feasible to use ethanol in the soybean oil extraction process, however hydration conditions of the solvent and temperature must be considered due to the influence of these on the protein fraction characteristics of the defatted meal.

Um dos principais setores do sistema agroindustrial brasileiro é composto pelo processamento de oleaginosas. Sua importância não se deve apenas ao seu produto principal, o óleo, mas também à fração desengordurada, composta por proteínas. Tradicionalmente, hexano é o solvente empregado na extração de óleos vegetais e, por esta razão, os objetivos principais deste trabalho foram estudar a viabilidade de substituição deste solvente por solventes alcoólicos na extração do óleo de farelo de arroz e, neste sentido, avaliar o impacto desta mudança nas características do óleo e da fração proteica. Foram realizados experimentos de extração sólido-líquido na condição de equilíbrio com a finalidade de avaliar a influência das variáveis de processo, tipo de solvente (etanol ou isopropanol), teor de água no solvente (0, 6 ou 12%) e temperatura (50 a 80 °C), na extração do óleo de farelo de arroz. Através dos experimentos de extração foi possível caracterizar os extratos obtidos e o farelo desengordurado em termos de rendimento de extração de compostos lipídicos, proteicos e minoritários, além da caracterização da fração proteica presente no rafinado, em termos de solubilidade e análise térmica. De maneira geral, os resultados mostraram influência da água no solvente no sentido da supressão da extração de óleo e, por outro lado, observou-se que o aumento da temperatura favoreceu o processo de extração lipídica. No caso do conteúdo proteico presente no extrato, observou-se que a hidratação do solvente e a temperatura favoreceram a extração de proteínas. A elevação da temperatura de processo favoreceu também, a extração de γ-orizanol, porém o aumento da água no solvente diminuiu a extração deste composto minoritário. A água também exerceu forte influência na quantidade de acilgliceróis e ácidos graxos livres transferidos para o extrato, porém, para o teor de fosfolipídeos, essa influência foi menor. As condições de processo não afetaram significativamente a composição do óleo, que se mostrou típica de óleo de farelo de arroz. Com relação à fração proteica, a solubilidade e propriedades térmicas, que definem o grau de desnaturação proteica, sofreram forte influência do grau de hidratação do solvente e da temperatura de processo, uma vez que à medida que a quantidade de água no solvente e a temperatura foram aumentados, notou-se uma diminuição no índice de solubilidade de nitrogênio. A partir dos resultados obtidos pode-se inferir que a extração de óleo de farelo de arroz com solventes alternativos, etanol e isopropanol, é possível, porém, as condições de processo devem ser muito bem avaliadas de maneira que este seja viável e os produtos oriundos, tanto o óleo de farelo de arroz quanto a fração proteica, possuam qualidade adequada para serem destinados à fins alimentícios. / One of the main areas of the Brazilian agroindustrial system is composed by the processing of oilseeds. Its importance is not only due to its main product, the oil, but also to the defatted fraction, composed of proteins. The hexane is the solvent traditionally used in vegetable oils extraction and, for that matter, the main objectives of this paper were to study the feasibility of substitution of t his solvent for alcoholic solvents on the rice bran oil extraction and also evaluate the impact of this change on the oil characteristics and the protein fraction. Some solid-liquid extraction experiments on balance condition were made to evaluate the variables on the process, such as the solvent type (ethanol or isopropanol), solvent water content (0, 6 or 12%) and temperature (50 to 80 °C) in the rice bran oil extraction. This way, the results show water influence on the solvent suppressing the oil extraction, and, on the other hand, the temperature increase benefits the process. Through extraction experiments, it was possible to characterize the obtained extracts and the defatted bran in terms of lipid, protein and minorities compound extraction, besides the characterization of the protein fraction present on the raffinated in terms of solubility and thermal analysis. In general, the results showed the water solvent influence in order to suppress the oil extraction and, on the other hand, it has been observed that the temperature increase benefited the lipid extraction process. Related to the protein content present in the extract, it was observed that the solvent hydration and temperature benefited the protein extraction. The temperature increase on the process also benefited the the γ-oryzanol extraction, however, the water solvent increase decreased the extraction of this minority compound. The water also has a strong influence on the amount of acylglycerol and free fatty acid transferred to the extract, however, for the phospholipids content, there is a decreasing influence. The process conditions did not have a significant affection on the oil composition, which is typical on rice bran oil. Regarding the protein fraction, solubility and thermal properties, which define the protein denaturing degree, there was a strong influence of the solvent hydration degree and the processing temperature, once the amount of water in the solvent and temperature are increased, it was noticed the decrease on the nitrogen solubility index. Based on the results it is possible to infer that the rice bran oil extraction with alternative solvents, ethanol and isopropanol, is possible, however, the process conditions must be well evaluated in order to be viable and the originated products, as well the rice bran oil as the protein fraction, have the proper quality for food purposes.

Dans le cadre du développement de nouveaux procédés par extraction liquide-liquide pour le recyclage du combustible nucléaire usé, de nouvelles molécules extractantes sont à l’étude. Les molécules à fonction amide (monoamide, malonamide ou diglycolamide) sont particulièrement étudiées. Les objectifs de cette thèse sont d’étudier la spéciation moléculaire et supramoléculaire de solutions organiques représentatives des différents procédés en cours de développement. Cette spéciation a été réalisée en couplant des études expérimentales et théoriques. Après extraction de solutés, la composition des solutions organiques est déterminée expérimentalement. Des boites de simulation par dynamique moléculaire ayant la même composition que les solutions expérimentales sont ensuite construites. Après simulation, les trajectoires de dynamique moléculaire permettent de calculer les masses volumiques et les intensités diffusées aux petits angles théoriques des solutions simulées. Dès lors que les données calculées et les données expérimentales sont en accord, on estime que les simulations sont représentatives des solutions réelles. Ces simulations couplées à des caractérisations expérimentales supplémentaires (spectroscopie infra-rouge – IR – et spectrométrie de masse à ionisation par électrospray – ESI-MS –) permettent de décrire les structures en solution à la fois à l’échelle moléculaire et supramoléculaire. Cette méthodologie a été appliquée à l’extraction d’eau et de nitrate d’uranyle par les monoamides DEHBA et par le malonamide DMDOHEMA ainsi qu’à l’extraction d’eau et de nitrate de néodyme par des solutions à base de TODGA.L’extraction d’eau en phase organique est dépendante de l’organisation de la solution : les solutions de monoamides essentiellement constituées de monomères et dimères solubilisent peu d’eau contrairement aux solutions de DMDOHEMA ou de TODGA majoritairement constituées d’agrégats. L’extraction de nitrate d’uranyle a mis en évidence différents comportements dépendant de la structure de la molécule ou de la concentration d’uranyle. Des complexes UO2(NO3)2L2 sont observés à faible concentration d’uranium après extraction par les monoamides. Lorsque la concentration d’uranium augmente, des espèces polymétalliques sont observées et deviennent majoritaire en solution. Dans le cas du DMDOHEMA, des complexes monométalliques sont majoritaires mais n’ont pas une stœchiométrie unique. L’uranyle peut être coordiné à 1 ou 2 malonamides (monodenté ou bidenté), 2 nitrates et parfois une molécule d’eau. Le néodyme est extrait par le TODGA dans l’heptane sous forme de petits agrégats contenant 2 ou 3 cations liés par des nitrates pontants. Une augmentation de la concentration de néodyme entraine une augmentation de l’agrégation jusqu’à l’apparition d’une démixtion de phase. La présence d’octanol (0,3 mol/L) permet d’extraire une plus forte concentration de Nd sans séparation de phase. Les simulations ont montré que l’octanol se place dans la 1ère sphère de coordination du néodyme à la place des molécules d’eau ou de TODGA améliorant ainsi la solubilité des complexes et agrégats dans la phase organique. L’ajout de 0,5 mol/L de DMDOHEMA à une solution de TODGA permet également d’éviter la démixtion en structurant la solution. En présence de malonamide des agrégats plus petits sont observés.Pour les deux systèmes étudiés (mono et diamides), les phases obtenues après démixtion de la phase organique (phénomène de formation de 3ème phase) ont également été caractérisées.Ces travaux ont permis de déterminer l’organisation moléculaire et supramoléculaire dans des solutions d’extraction par l’utilisation d’une méthode couplant études expérimentales et simulations par dynamique moléculaire. / In the framework of development of new processes for spent nuclear fuel reprocessing, new extractant molecules are studied.The goals of this thesis are to study the molecular and supramolecular speciation of representative organic solutions. The speciation was determined by coupling experimental and theoretical study. After solute extraction, the composition of the organic solutions is experimentally determined. Simulations boxes with the same composition than experimental solutions are build. After simulation, trajectories are used to calculate small angle scattered intensities. The representativeness of the simulations is checked by comparison of experimental and calculated scattered intensities. The use of the simulation, ESI-MS spectrometry and IR spectroscopy provides the description of the structures in organic solution at the molecular and supramolecular scale. This methodology was applied on water and uranyl nitrate extraction by the monoamide DEHBA and MOEHA and by the malonamide DMDOHEMA as well as the extraction of water and neodymium nitrate by TODGA solutions.The extraction of water is dependent of the organization of the solution: monoamide solution made of monomer and dimer solubilize few amount of water in comparison with DMDOHEMA or TODGA solutions.The extraction of uranyl nitrate showed different behavior. UO2(NO3)2L2 complexes are observed at low uranium concentration after extraction by the monoamides. Polymetallic species are observed with the increase of uranium concentration. In the case of DMDOHEMA, monometallic complexes are majority but without a unique stoichiometry. The uranyl can be linked to 1 o 2 malonamides, 2 nitrates and sometimes to a water molecule. Neodymium is extracted by TODGA within small aggregates made of 2 or 3 cations liked by bridging nitrates. The increase of the concentration of neodymium leads to a phase separation. The presence of octanol provides the extraction of higher concentration of neodymium nitrate. Simulations showed the replacement of water and TODGA molecules and the first coordination sphere of the cation with octanol molecule. This increases the solubility of the aggregates. The presence of DMDOHEMA prevents also the phase separation by structuring the solution. With malonamide, smaller aggregates are observed.For both systems, phases after demixing (third phase formation) were characterized.This work provides the study of the molecular and supramolecular organization of organic solutions by combining experimental studies and molecular dynamic simulations.

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are two structurally related groups of chemicals, generally referred to as `dioxins´. These are of great concern due to their high toxicity and global spread. Other groups of compounds with similar chemical structure and toxicity mechanisms are the brominated analogues polybrominated dibenzo-p-dioxins (PBDDs) and polybrominated dibenzofurans (PBDFs), and the dioxin-like polychlorinated biphenyls (PCBs). Numerous studies have been undertaken to investigate sources and transport routes of dioxins. However, much remains to be done, including analytical, inventories of dioxin-like compounds, such as PBDD/Fs, and the development of more convenient analytical methods. The currently standard procedure for analyzing dioxins (and dioxin-like compounds) is to use Soxhlet extraction followed by multi-step clean-up and gas chromatography - high resolution mass spectrometry (GC- HRMS) for detection. Unfortunately, this method is very solvent, labor and time-consuming, making it very expensive. The main aim of the studies this thesis was to develop pressurized liquid extraction (PLE) with integrated clean up techniques for fast, convenient preparation of dioxin samples. PLE with integrated clean-up has previously been used for extracting dioxins from biological samples, but in these studies the possibility of extending its use to abiotic samples was explored. The results show that PLE with an integrated carbon trap is suitable for analyzing dioxins in various types of soil samples, sediment and flue gas samples. The results also showed that it has potential for analyzing dioxins in fly ash. The thesis focuses on developments of the methodology for dioxin analysis, but also includes results obtained from PBDDs and dioxin-like PCB analyses. In addition, the possibility of using various other kinds of detection techniques rather than GC-HRMS, such as enzyme-linked immunosorbent assays (ELISAs) or two-dimensional gas chromatography with micro electron capture detection (GCxGC-µECD) was explored. The results indicate that ELISA and GCxGC-µECD could serve as complementary detection systems in some cases. However, it is not yet possible to fully replace GC-HRMS. A further refinement of the PLE with in-cell clean-up technique is the modular approach developed in these studies. With this technique it is possible to include various steps for both clean-up and fractionation. For example, sulphuric acid impregnated silica could be combined with active carbon for the simultaneous removal of lipids (along with other interferences) and fractionation of PCBs and PCDD/Fs. It was shown that the method could provide data that agreed reasonably well with both reference values and values obtained using traditional methods. In general PLE proved to have high extraction efficiency and to yield very similar congener profiles to the reference method. In addition, it was shown that it allowed one-step extraction and clean-up of a salmon sample. Such single-step procedures are the ultimate goals for any extraction technique, and it would be highly desirable to develop one-step methods that could be extended to other types of samples. For the rest of the matrices tested (soil, sediment, mussel and crab tissue and flue gas) the method was successful, however a final polishing step is currently required, involving either dilution or clean-up using miniaturized multilayer silica columns, to obtain extracts that are pure enough for GC-HRMS analysis. Using the developed modular-PLE system substantial costs could be saved. It was estimated that the method could reduce the cost of preparing samples by up to 90%, which would greatly facilitate large-scale inventories.

Naphthenic acids (NAs) are toxic organic acid compounds released during the caustic hot-water extraction of crude oil from oil sands in north-eastern Alberta, Canada. NAs subsequently accumulate in the large volume of oil sands process water (OSPW) produced daily by oil sands operations. The complexity of dealing with a mixture of over 200 individual NA compounds, combined with their acute aquatic toxicity and large volume of production has made them an emerging pollutant of concern for western Canada. The following thesis outlines a variety of experiments designed to determine the potential to use wetland plants to enhance the dissipation of NAs from OSPW (phytoremediation). <p>Investigations were carried out with three native emergent macrophyte species cattail (<i>Typha latifolia</i>), common reed (<i>Phragmites australis </i>subsp. <i>americanus</i>), and hard-stem bulrush (<i>Scirpus acutus</i>) to see if they enhanced the dissipation of NAs from a hydroponic system. Dissipation of NAs (at 30 mg L-1 and 60 mg L-1) was investigated with both a commercially available NA mixture as well as with a NA mixture extracted from the OSPW. Dissipation of NAs was also investigated under the different ionized forms of NAs (ionized, pH = 7.8; and non-ionized, pH = 5.0) to better elucidate the mechanisms of NA uptake and toxicity in plants. Phytotoxicity of NAs was investigated in hydroponic experiments through fresh weight gain and evapotranspiration was monitored throughout the experiment by water uptake. Commercially available NA mixture was more phytotoxic than oil sands NAs mixture. As well, NAs were found to be more phytotoxic in their non-ionized form therefore indicating that they may be taken up through an ion-trap‟ mechanism. However despite this, no significant dissipation of total NAs was observed from planted hydroponic systems. Nevertheless there was a significant change in the distribution (percent abundance) of individual NA families of certain size. These changes were related to the one- and two-ring NA compounds (Z = -2 and Z = -4). Despite not detecting any dissipation of total NAs from the systems, plants were able to reduce the toxicity of a NA system over 30 days by 45% as determined by Daphnia magna acute toxicity bioassays; a 11% greater reduction than unplanted systems.<p> Studies were also conducted investigating the microbial community inhabiting cattail roots exposed to NAs. It was observed that the rhizosphere community changed with NA exposure, with a general increase in potentially pathogenic bacteria and a decrease in bacteria previously found to be beneficial to plant growth. The observed microbial community change could be an indirect effect of the Phytotoxicity experienced by aquatic macrophytes exposed to NAs. Synchrotron-sourced, fourier transform microspectroscopy analysis of root cross sections revealed that there were significant physiological changes to those roots exposed to NAs. These changes were identified as being cell death in the plant root epidermis as well as a change in the chemistry of parenchyma cells in the root pith. It is not known if these changes are a direct effect of NAs to the plant or due to changes of the associated rhizosphere community in the roots or some combination of both these factors.

Naphthenic acids (NAs) are toxic organic acid compounds released during the caustic hot-water extraction of crude oil from oil sands in north-eastern Alberta, Canada. NAs subsequently accumulate in the large volume of oil sands process water (OSPW) produced daily by oil sands operations. The complexity of dealing with a mixture of over 200 individual NA compounds, combined with their acute aquatic toxicity and large volume of production has made them an emerging pollutant of concern for western Canada. The following thesis outlines a variety of experiments designed to determine the potential to use wetland plants to enhance the dissipation of NAs from OSPW (phytoremediation). <p>Investigations were carried out with three native emergent macrophyte species cattail (<i>Typha latifolia</i>), common reed (<i>Phragmites australis </i>subsp. <i>americanus</i>), and hard-stem bulrush (<i>Scirpus acutus</i>) to see if they enhanced the dissipation of NAs from a hydroponic system. Dissipation of NAs (at 30 mg L-1 and 60 mg L-1) was investigated with both a commercially available NA mixture as well as with a NA mixture extracted from the OSPW. Dissipation of NAs was also investigated under the different ionized forms of NAs (ionized, pH = 7.8; and non-ionized, pH = 5.0) to better elucidate the mechanisms of NA uptake and toxicity in plants. Phytotoxicity of NAs was investigated in hydroponic experiments through fresh weight gain and evapotranspiration was monitored throughout the experiment by water uptake. Commercially available NA mixture was more phytotoxic than oil sands NAs mixture. As well, NAs were found to be more phytotoxic in their non-ionized form therefore indicating that they may be taken up through an ion-trap‟ mechanism. However despite this, no significant dissipation of total NAs was observed from planted hydroponic systems. Nevertheless there was a significant change in the distribution (percent abundance) of individual NA families of certain size. These changes were related to the one- and two-ring NA compounds (Z = -2 and Z = -4). Despite not detecting any dissipation of total NAs from the systems, plants were able to reduce the toxicity of a NA system over 30 days by 45% as determined by Daphnia magna acute toxicity bioassays; a 11% greater reduction than unplanted systems.<p> Studies were also conducted investigating the microbial community inhabiting cattail roots exposed to NAs. It was observed that the rhizosphere community changed with NA exposure, with a general increase in potentially pathogenic bacteria and a decrease in bacteria previously found to be beneficial to plant growth. The observed microbial community change could be an indirect effect of the Phytotoxicity experienced by aquatic macrophytes exposed to NAs. Synchrotron-sourced, fourier transform microspectroscopy analysis of root cross sections revealed that there were significant physiological changes to those roots exposed to NAs. These changes were identified as being cell death in the plant root epidermis as well as a change in the chemistry of parenchyma cells in the root pith. It is not known if these changes are a direct effect of NAs to the plant or due to changes of the associated rhizosphere community in the roots or some combination of both these factors.

Woven textile fabrics were designed and constructed from hydrophilic and hydrophobic spun yarns to give planar substrates containing amphiphilic microchannels with defined orientations and locations. Polypropylene fibers were spun to give hydrophobic yarns, and the hydrophilic yarns were spun from a poly(ethylene terephthalate) copolyester. Water wicking rates into the fabrics were measured by video microscopy and longitudinal wicking tests from single drops and from reservoirs. Intra-yarn microchannels in the hydrophilic polyester yarns were shown to selectively transport aqueous fluids, with the flow path governed by the placement of the hydrophilic yarns in the fabric. Simultaneous wicking of an aqueous and hydrocarbon fluid into the hydrophilic and hydrophobic microchannels of an amphiphilic fabric was successfully demonstrated. The high degree of interfacial contact and micron-scale diffusion lengths of such co-flowing immiscible fluid streams inside amphiphilic fabrics suggest potential applications as highly scalable and affordable microcontactors for industrial liquid-liquid extractions. The efficiency of liquid-liquid extractions carried out with the amphiphilic fabrics was evaluated. Solvent extraction efficiencies were shown to reach up to ~98%.

Die Effektivität der Reaktivextraktion als Verfahren zur Stoffabtrennung aus wässrigen Lösungen mit organischen Lösungsmitteln lässt sich durch den Zusatz weiterer Stoffe deutlich steigern. Das können Co-Ionen, Lösungsvermittler und Stoffe sein, die die Phasengrenzfläche beeinflussen. Wichtigste Vertreter der letzteren Gruppe sind Tenside, die die Grenzflächenspannung zwischen den Phasen verringern. Sie werden in der industriellen Technik bereits seit Jahrzehnten mit gleich bleibendem Erfolg angewandt. Dabei sind die Vorgänge an der Phasengrenze, die durch die Tenside beeinflusst werden, noch nicht vollständig geklärt. In diesem Umfeld ist auch die vorliegende Arbeit entstanden. Sie soll bereits am Lehrstuhl vorliegende Arbeiten ergänzen. Gegenstand der Untersuchungen ist der Einfluss von Tensiden auf die Extraktion von Schwermetallionen im elektrischen Feld, hier untersucht an dem kationischen Tensid Hexadecyltrimethylammoniumbromid (CTAB). Als Untersuchungsmethode wird die Polarographie verwendet. Der Ladungsdurchtritt durch die Grenzfläche Wasser/Quecksilber und deren Beeinflussung durch das Tensid werden für die Metallionen von Zink, Cadmium, Blei und Chrom bei unterschiedlichen pH-Werten untersucht. Es zeigt sich, dass die Modifizierung der Grenzfläche nur einen Teil der Beeinflussung ausmacht, weitere entstehen durch die chemische Modifizierung der vorhandenen Spezies. Weiterhin kann abgeleitet werden, dass trotz chemischer Verwandtschaft der eingesetzten Systeme eine klare Vorhersage der Beeinflussung nur begrenzt möglich ist. Der grundlegende Trend von Systemen mit chemisch ähnlicher Zusammensetzung ist zwar der gleiche, jedes System reagiert jedoch individuell in Abhängigkeit der genauen stofflichen Zusammensetzung und der Versuchsbedingungen, so dass stets konkrete Voruntersuchungen notwendig erscheinen.