O presente estudo teve como objetivo selecionar procedimentos de purificação de óleos vegetais, com enfoque na desacidificação, comparando a eficiência de métodos de refino alternativos (adsorção e extração liquido-liquido) com o convencional (alcalino). Para tanto, foram utilizados óleos com baixo impacto na cadeia alimentícia, como óleo de andíroba e óleo de macaúba, visando contribuir para a ampliação de matérias-primas lipídicas na produção de biodiesel. A triagem do método de purificação mais adequado foi baseada na redução de ácidos graxos livres, na quantidade recuperada de matéria-prima após o refino e na qualidade do biodiesel gerado. Adotando óleos com diferentes teores de ácidos graxos livres, óleo de andíroba (17,7%) e óleo de macaúba (7,9%) a desacidificação por adsorção, empregando diferentes adsorventes foi excluída com base nos baixos valores de desacidificação (<34,1%) e de recuperação em massa de óleo (22,2-43,1%). A acidez mais elevada do óleo de andíroba se mostrou como um fator limitante adicional, portanto, o uso deste óleo foi eliminado para as etapas posteriores de triagem. Em contrapartida, o refino por extração liquido-liquido (ELL) usando etanol como solvente forneceu valores mais elevados de recuperação mássica (>75,9%) e de redução de ácidos graxos livres (>48,8%). Buscou-se por meio da utilização de um método estatístico determinar as condições adequadas de refino por ELL usando etanol hidratado. Esta etapa foi realizada por meio de uma matriz de planejamento fatorial composto de face centrada 22, avaliando simultaneamente a influência da porcentagem mássica de agua no solvente alcoólico (2, 4 e 6%) e da razão mássica solvente/óleo (1:1, 1,5:1, 2:1). De acordo com a análise estatística foi possível estabelecer que a adição de 5,3% de agua no etanol e razão mássica etanol/óleo de 1,79:1 maximizaram a remoção de ácidos graxos livres (64,4%) sem ocasionar elevadas perdas de óleo refinado (93,9%). Adotando as condições otimizadas de ELL, o óleo de macaúba foi refinado em único e duplo estagio. Constatou-se que o teor de ácidos graxos livres em relação ao óleo bruto (7,9%) foi reduzido expressivamente em ambos os casos para valores de 2,9% (refino em único estagio) e de 1,0% (refino em duplo estagio), com a vantagem de não promover oxidação do material lipídico. Entretanto, a recuperação mássica de óleo refinado obtida na ELL em duplo estagio foi menor, da ordem de 78,5%. Para validar a metodologia de purificação, foram realizadas reações de etanólise das amostras de óleo refinado por ELL em único e duplo estagio, óleo bruto e óleo refinado por via alcalina utilizando como catalisador oxido nióbio impregnado com sódio. Enquanto a acidez do óleo bruto inibiu o catalisador, os produtos originados pelas amostras de óleo refinadas por ELL em único e duplo estagio contiveram teores em ésteres etílicos (97,4% e 97,8%, respectivamente) que atenderam as especificações recomendadas pela Agencia Nacional de Petróleo, Gás Natural e Biocombustível para uso como combustível. Esses valores foram similares a conversão alcançada na reação conduzida com o óleo refinado por via alcalina (99,0%), que teve desvantagens como recuperação mássica de 80,1% e aumento do índice de peroxido, indicando que a extração liquido-liquido tem potencial para desenvolvimento e aplicação em processos de refino de óleos vegetais para posterior utilização na síntese de biodiesel. / This study aimed at comparing the purification of non-edible vegetable oils by two different types of refining (adsorption and liquid-liquid extraction) with conventional alkali refining, contributing to the expansion of lipid feedstocks for biodiesel production. The use of non-edible vegetable oils is related to the final cost of biodiesel by increasing product competitiveness. The screening of the purification methods for vegetable oils (andiroba oil and macaw palm oil) was based on the reduction of free fatty acids content, oil mass recovery after the refining and the quality of biodiesel. Adopting oils with different levels of free fatty acids, andiroba oil (17.7%) and macaw palm oil (7.9%), the deacidification by adsorption, employing different adsorbents was excluded on the basis of the low deacidification values (<34.1%) and the oil mass recovered (22.2-43.1%). The higher acidity of andiroba oil was found to be an addition drawback and therefore, this oil was disqualified for further testing. On the other hand, the purification by liquid-liquid extraction (LLE) of macaw palm oil using ethanol as solvent gave higher values for oil mass recovery (>75.9%) and reduction of free fatty acids (>48.8). To determine the suitable conditions for oil refining by LLE using hydrated ethanol as solvent a statistical method was proposed. For this a 22 central composite face-centered experimental design was adopted to simultaneously evaluate the influence of the water percentage in the alcoholic solvent (2, 4, and 6%), and mass ratio of solvent-to-oil (1:1, 1.5:1 and 2:1). According to the statistical analysis it was possible to establish that the addition of 5.3% of water in the ethanol and mass ratio of ethanol to oil of 1.79:1 maximizes the removal of free fatty acids (64.4%) resulting in high refined oil recovered (93.9%). Adopting the optimized LLE conditions, the macaw palm oil was refined in single and double-stage. It was noted that the level of free fatty acids in relation to crude oil (7.9%) was significantly reduced in both cases for values of 2.9% (refining in single stage) and 1.0% (refining in double-stage), with the advantage of not promoting lipid oxidation. However, the percentage of the recovered refined oil obtained in LLE double-stage was slightly lower, in the order of 78.5%. To validate the purification methodology, ethanolysis reactions catalyzed by niobium oxide impregnated with sodium were performed using samples refined by LLE (single and double-stage), oil refined by alkali neutralization and crude oil. The obtained dataset demonstrated that the catalyst was inhibited by the high acidity level of the crude oil, while refined oil by LLE (single-stage and double-stage) gave levels of ethyl esters contents of 97.4% and 97.8%, respectively that meet the criteria established by the Brazilian National Agency of Petroleum, Natural Gas and Biofuels to be used as a fuel. These values were similar to that attained in the reaction using refined oil by alkaline protocol (99.0%), which had disadvantages such as oil mass recovered of 80.1% and oil oxidation (increased peroxide value), indicating that the liquid-liquid extraction has the potential for development and application in vegetable oils refining processes for further using as feedstocks in the biodiesel synthesis.

Thesis (M.Sc. (Chemistry)) --University of Limpopo, 2017 / The presence of polycyclic aromatic hydrocarbons (PAHs) in the environment is of major concern since these compounds are highly persistent, toxic and wide spread pollutants. The aim of this study was to evaluate the levels of PAHs in water and sediment samples collected from Blood and Mokolo Rivers in Limpopo Province, South Africa. Liquid-liquid extraction (LLE) was used for the extraction of PAHs from water, whereas PAHs in sediments were extracted using optimised microwaveassisted extraction (MAE). Furthermore, ultrasonication and a combination of ultrasonication and mechanical agitation were used for the extraction of PAHs from sediments samples. The quantification of sixteen (16) PAHs in water and sediment was carried out using gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring (SIM) mode and by GC-flame ionisation detector (GC-FID). Concentrations of PAHs in sediments were higher than in water. The highest concentrations of PAHs were obtained in Mokolo River sediments, with the concentration ranging between 0.044 and 51.9 mg/kg. The levels of PAHs recorded in Blood River sediments were lower than those obtained in Mokolo River with concentrations ranging between 0.014 and 3.10 mg/kg. In water samples, higher levels of PAHs were observed in Mokolo River (between 0.0219 and 1.53 µg/L) while lower concentrations were recorded in Blood River (between 0.0121 and 0.433 µg/L). In water and sediment samples from both Rivers, higher molecular weight (HMW) PAH compounds (4-6 rings) were found at greater concentration levels than lower molecular weight (LMW) PAHs (2-3 rings), and this can be attributed to pyrogenic activities in the study areas. The efficiencies and accuracy of the methods for the extraction of PAHs were determined by assessing the recoveries of samples spiked with known amount of standards (for water samples), while a certified reference material (CRM) was used for sediments. Percentage recoveries ranged from 67.6 to 115% for LLE and 83.8 to 125% for MAE for both sample types. Diagnostic ratio was used for the source identification of PAHs in sediment samples. Several PAHs ratios indicated that both pyrogenic and petrogenic could be the sources of these compounds in both rivers. Toxic equivalency factors (TEFs) and benzo(a)pyrene equivalent (BaPE) were used to quantitatively estimate the PAHs potential human health risk. The assessment of ecotoxicological risk indicated that the v sediment samples collected from Mokolo River are at high toxicity risk while sediments from Blood River are at low sediment toxicity risk. / Water Research Commission (WRC), National Research Foundation (NRF) and Sasol Inzalo Foundation

Spent nuclear fuel (SNF) resultant from the generation of nuclear power is a chemically and radiologically diverse system which is advantageous to chemically process prior to geologic disposal. Hydrometallurgy is the primary technology for chemical processing for light water reactor spent fuels, where spent fuel is dissolved in an acid for liquid based separations. The primary means for recovery of desired metals from the SNF solution is liquid-liquid extraction which is based on distribution (partitioning) of the metal ions between two immiscible phases based on thermodynamic favorability. One of the means of increasing this favorability is by designing extractant molecules to be either "harder" or "softer" bases, which will more preferentially extract harder or softer metal ions respectively. This technique is used in designing extractant molecules for targeted extraction as actinides are slightly softer than lanthanides, and precious metals produced in significant quantities from the fission process are especially soft metals. The work performed in this thesis involved the synthesis of a novel soft electron donor organic extractant molecule for testing of targeted soft metal extraction. The molecule synthesized was bis-dibutanethiolthiophosphinato-methane, or S6, a bidentate neutral extractant molecule with significant thiolysis for a softer electron environment. The synthesis technique was refined and the molecule composition and structure was confirmed by ¹H NMR, ³¹P NMR, and elemental analysis. Two metal groups, f-elements (actinides and lanthanides) and soft transition metals were tested for their extractability from nitric acid solutions into an S6 solution in n-dodecane. Aqueous solutions of nitric acid and n-dodecane as an organic diluent are typical liquid-liquid extraction conditions in spent nuclear fuel reprocessing. As extraction experiments were performed with radiotracers, for the soft metal extraction experiment, a mixture of the selected metals was neutron-activated in the OSU TRIGA reactor, as was europium to create a lanthanide radiotracer. Actinides and lanthanides were not seen to effectively extract into the organic or form a precipitate at all, making their partitioning with this extractant seemingly ineffective. Through gamma spectroscopy of an irradiated metal solution post-extraction, it is seen that only silver and palladium preferentially complex in the mixed metal samples into an insoluble organic ligand, dropping out of solution. This effect was more pronounced at higher acid concentrations, but silver was seen to slightly extract to the organic phase at all acid concentrations as well. This testing has shown that the S6 extractant can be used to recover silver and palladium from a mixed metal aqueous solution, such as one resultant from advanced spent nuclear fuel reprocessing operations. This result shows promise for future development of sulfur based organophosphate ligands for targeted extraction of precious metals from solutions. / Graduation date: 2013

This research investigate the matrix effect, operation time, cost and solvent comsumption for triarylmethanes and corresponding metabolites in different aquaculture products by different extraction methods. Triarylmethane was determined by LC-ESI-MS/MS in positive mode. The analytical method validation were followed the regulation of 2002/657/EC. HPLC separation was conducted with the RP-18 column. The mobile phases consisted of 0.5 mM ammonium acetate buffer (pH 3.8, adjusted with acetic acid) ¡V acetonitrile (contained 0.1% formic acid) solution. The ratios of standard deviation to average residual time for all compounds are less than 0.05. The ion ratio is stable and allowed by the regulation of 2002/657/EC. The regression constant of calibration curve is in the range from 0.998 to 0.999. The CC£\ for MG, LMG, CV, LCV are 0.09 ¡Ó 0.05, 0.19 ¡Ó 0.14, 0.15 ¡Ó 0.13, 0.15 ¡Ó 0.10 £ggkg-1, respectively. The CC£] for MG, LMG, CV, LCV are 0.09 ¡Ó 0.05, 0.19 ¡Ó 0.14, 0.15 ¡Ó 0.13, 0.15 ¡Ó0.10 £ggkg-1, respectively. The results for SPE and liquid-liquid extraction are not significantly different; the liquid-liquid extraction have shorter operation time, cheaper cost and less solvent consumption in comparison with SPE.

Nuclear power waste contains radioactive isotopes with long half lives and the problem lies in the fact that the lanthanides and actinides must be separated before the nuclear waste can be reprocessed. Transuranic Extraction (TRUEX), a liquid-liquid extraction method, has been developed but fails to separate the lanthanide and actinides and creates large volumes of liquid waste. It has been shown that attaching three CMPO (carbamoyl phosphine oxide) ligands used in the TRUEX process to a calixarene increases the separation and extraction efficiency of the system. The research goal is to attach the CMPO ligand to a polymer to make a membrane to be used in nuclear waste remediation. The triblock polymer system has been designed to have a cross-linking group to create the membrane structure, a solubilizing group to improve the flow of aqueous media through the membrane, and the CMPO ligand to chelate actinides. This paper describes the design of the polymer, its synthesis, and my research data. / text

Aujourd’hui, une large part des métaux utilisés par l’industrie provient généralement des mines. Certains, dits stratégiques, pourraient présenter un risque d’approvisionnement voire d’épuisement des ressources naturelles. Ces métaux sont généralement utilisés dans des processus dispersifs, et se retrouvent répartis de façon inégale, avec d’autres métaux, dans des matrices toujours plus complexes, ce qui rend leur récupération couteuse en termes de procédés et d’énergie. Que ce soit pour des raisons stratégiques, économiques ou sociétales, il apparait que le recyclage des métaux est amené à devenir une activité importante dans le futur. L’approche hydrométallurgique, et en particulier l’extraction-séparation liquide-liquide, est une technique adaptée et éprouvée à ce jour pour répondre au recyclage des métaux. Ce travail de thèse s’intéresse au développement et l’étude de systèmes moléculaires fluorés pour l’extraction et la séparation de métaux par une approche liquide-liquide. La modularité de la partie fluorée de ce type de système moléculaire permet l’étude des diverses interactions (complexations, supramoléculaires) importantes d’un point du vue fondamental dans l’extraction liquide-liquide de métaux. De plus, leurs propriétés physico-chimiques (miscibilité,…) permettent d’envisager le design de procédés innovants dans le domaine de la séparation liquide-liquide, comme la mise en œuvre de systèmes tri-phasiques. Pour cela, deux séries de malonamides fluorés avec des espaceurs de taille variable, entre la tête complexante et le groupement perfluoré, ont été synthétisés. La modulation par l’espaceur de l’effet inductif des chaines perfluorées sur les propriétés physico-chimiques des extractants et sur la complexation d’un métal a été étudiée. De même, l’influence de certains paramètres d’extraction comme la charge en extractant, en acide et l’influence du diluant ont été caractérisés. La comparaison avec les ligands homologues hydrogénés a été effectuée, et les limites des différents systèmes établies. Une série de phosphates de trialkyles a également été étudiée et appliquée à un système tri-phasique d’extraction liquide-liquide. Des résultats préliminaires valident de manière encourageante l’approche choisie. / A large part of the metals used by the industry is still coming from mines. Some metals, called strategic metals, may encounter a supply risk or even a total depletion of natural resources. They are usually used in dispersive way which make their recovery complicated, costly and energy intensive since they are in unequal amount, with other metal, in ever more complex matrices. Whether for strategic, economic or societal reason, the metal recycling is about to become an important industry in a near future. Hydrometallurgical processes, and liquid-liquid extraction in particular, are a robust technic giving answer to some of the recycling challenge. Our aim was to develop and study some fluorinated system for the extraction and the separation of metal through liquid-liquid approach. The tenability of the fluorinated part of these system allow the study of multiple interaction (complexation or supramolecular ordering) important in a fundamental point of view in liquid-liquid extraction. Physical and chemical properties such as their miscibility allow the development of new processes in the solvent extraction field such as triphasic liquid extraction system. To this end, two series of fluorinated malonamides with various spacer length between the complexing head and the fluorinated moiety were synthetized. The modulation, through the spacer, of the inductive effect of the fluorinated chain on the physical and chemical properties of the extractant and the complexation of the metal was studied. The influence of various extraction parameters such as the concentration in extractant, the acid and the diluent were characterized. The comparison of these malonamides with their hydrogenated homologues was done and the limits of these systems established. A family of trialkylphosphate was developed and apply to a triphasic extraction system. Preliminary results confirm the approach.

Os hidrocarbonetos policíclicos aromáticos (HPA) representam hoje grande preocupação à comunidade científica devido a sua comprovada ação cancerígena e mutagênica, assim tornam-se necessárias metodologias mais eficientes para suas determinações. O presente trabalho desenvolveu a técnica de extração por líquido pressurizado com a etapa de clean-up simultânea a extração, com sílica e alumina como adsorventes dentro da cela do equipamento ASE-350. A metodologia desenvolvida foi comparada com a tradicional extração por Sohxlet através de material de referência certificado. A extração por Soxhlet, apesar de eficiente, mostrou-se dispendiosa pelo gasto enorme de tempo, solvente e adsorventes quando comparada a extração por líquido pressurizado. De maneira geral a extração por líquido pressurizado apresentou-se mais vantajosa que a tradicional extração por Soxhlet. A eficiência da metodologia desenvolvida também foi testada através de quatro diferentes tipos de solos brasileiros fortificados com solução padrão de HPA. Os solos utilizados foram dos seguintes locais: Nova Lima MG, Lavras MG, Casimiro de Abreu RJ e Luiz Eduardo Magalhães BA. Todos possuíam características granulométricas e químicas diferentes entre si. Dois solos foram classificados em latossolos vermelhos, um em vermelho-amarelo e um em planossolo. Houve diferença significativa na eficiência de recuperação de alguns HPA quando comparados os quatro tipos de solos, já para outros HPA não evidenciou-se influência da tipologia do solo / Polycyclic aromatic hydrocarbons (PAH) are now a great concern to the scientific community due to its proven carcinogenic and mutagenic action. Therefore more efficient methodologies become necessary for its determinations. This research developed the technique of extraction by pressurized liquid with the clean-up step simultaneous to the extraction, i.e., the soil sample is extracted as the clean-up occurs. For this silica and alumina adsorbents was used in the ASE-350 equipment cell. For the study four different types of Brazilian soils with their well-defined characterizations were used. The soils used were from the following locations: Nova Lima - MG, Lavras - MG, Casimiro de Abreu - RJ and Luiz Eduardo Magalhães - BA. All of them had different soil gradation and chemical characteristics. The soils were classified as red oxisols, red-yellowish oxisols and planosols. There was significant difference between the recovery efficiency of some PAH in the four soil types, as for other HPA showed up no influence of soil type. The developed methodology was compared to traditional Sohxlet extraction by certified reference material (CRM). The Soxhlet extraction, although effective, has proved costly for large expenditure of time, adsorbents and solvent when compared to pressurized liquid extraction. In general the pressurized liquid extraction was more advantageous than traditional Soxhlet extraction. The developed methodology efficiency was also tested through four different Brazilian soil types spiked with standard PAH solution. The soils used were from the following locations: Nova Lima - MG, Lavras - MG, Casimiro de Abreu - RJ and Luiz Eduardo Magalhães - BA. All of them had different soil gradation and chemical characteristics among themselves. Two soils were classified as red oxisols, one as red-yellowish oxisol and one as planosol. There was significant difference among the recovery efficiency of some PAHs when the four soil types were compared; as for other HPA showed up no evidence of soil type influence

Face à une croissance effrénée de la demande en indium et aux enjeux à la fois socio-économiques et politiques potentiels qu'il représente, le recyclage de l'indium contenu dans les équipements en fin de vie reste la seule alternative pour remédier à des risques de pénuries. Au-delà des aspects économique et stratégique, le recyclage de l'indium peut permettre de préserver l'environnement en évitant l'exploitation à grande échelle des gisements de minerais contenant l'indium. Par ailleurs, la toxicité de l'indium justifie à elle seule le développement de procédés de traitement de déchets en contenant. Pourtant, la récupération de l'indium à partir de déchets électroniques est actuellement assez peu développée, mis à part au Japon, où plusieurs procédés existent à l'échelle industrielle. Ces procédés sont toutefois peu respectueux de l'environnement et fortement énergivores. Dans ce travail de doctorat, le recyclage de l'indium par extraction liquide/liquide dans un liquide ionique suivie de son électrodéposition in situ nous est apparu comme un procédé prometteur, permettant de s'affranchir de l'étape souvent difficile de dés-extraction du cation métallique. Parmi les liquides ioniques que nous avons synthétisés et caractérisés, en termes de structure et de propriétés physico-chimiques, le bis(trifluorométhylsulfonyl) amidure de 1-butyl-1-éthylpipéridinium (BEPipNTf2) s'est avéré le plus adapté du fait de sa bonne stabilité cathodique, de sa faible viscosité, de son caractère hydrophobe et peu hygroscopique. Nous avons montré qu'en synergie avec l'oxyde de trioctylphosphine (TOPO) comme extractant, il est possible d'extraire plus de 90% de l'indium contenu dans une phase aqueuse 10-2 M en HCl. Le système électrochimique In(III)/In(0) dans le BEPipNTf2 a alors été étudié en présence de chlorures, d'eau, d'oxygène et de TOPO, espèces présentes à l'issue de l'étape d'extraction liquide/liquide de l'In(III). Une étude détaillée de l'influence des ions chlorures a notamment été réalisée, mettant en évidence la formation de chlorocomplexes d'indium lors de l'application d'un potentiel cathodique de réduction de l'In(III), ce qui modifie considérablement les caractéristiques électrochimiques du système In(III)/In(0). Les résultats obtenus montrent qu'il est possible d'électrodéposer de l'In(III) sous sa forme métallique dans le domaine de stabilité électrochimique du liquide ionique, et ceci de façon non réversible en présence de TOPO, dont l'électroactivité dans le domaine de potentiel correspondant porte néanmoins à croire que la réduction pourrait entraîner la présence d'impuretés organiques dans le dépôt d'indium et limiter la quantité de métal déposée. / Faced with explosive growth in demand for indium and, faced with challenges to both socio-economic and political potential it represents, the recycling of indium content in the equipments of end of life remains the only alternative to address risk of shortages. Beyond the economic and strategic aspects, recycling of indium can help preserving the environment by preventing large-scale exploitation of mineral ores containing indium. In addition, the toxicity of indium alone justifies the development of methods for treating waste containing indium. However, the recovery of indium from electronic waste is currently fairly limited, except in Japan where there are several processes at an industrial scale. However, these processes are not environmentally friendly and are energy-intensive In this PhD work, recycling of indium by liquid / liquid extraction in an ionic liquid followed by its electrodeposition in situ appeared to us as a promising process, to overcome the often difficult step of de-extraction of the metal cation. Among the ionic liquids that we have synthesized and characterized in terms of structure and of physicochemical properties, 1-butyl-1-ethylpiperidinium bis(trifluoromethylsulfonyl) imide (BEPipNTf2) has been shown most suitable because of its cathodic stability, its low viscosity, its hydrophobic and weakly hygroscopic character. We have shown that in synergy with the trioctylphosphine oxide (TOPO) as extractant, it is possible to extract more than 90% of the indium contained in a 10-2 M HCl aqueous phase. The electrochemical system In(III)/In(0) in the BEPipNTf2 was then studied in the presence of chlorides, of water, of oxygen and of TOPO, which are the species present after the liquid/liquid extraction step of the In(IIII). A detailed study of the influence of chloride ions has been particularly carried out, highlighting the formation of chlorocomplexes of indium when applying a cathodic potential of reduction of In(III), which significantly changes the electrochemical characteristics of the system In(III)/In(0), The results obtained show that indium (III) can be electrodeposited in its metallic form in the range of electrochemical stability of the ionic liquid and that this is non-reversible in presence of TOPO, whose electroactivity in the corresponding potential range suggests that the reduction could result in the presence of organic impurities in the deposition of indium and could limit the amount of metal deposited.

Os hidrocarbonetos policíclicos aromáticos (HPA) representam hoje grande preocupação à comunidade científica devido a sua comprovada ação cancerígena e mutagênica, assim tornam-se necessárias metodologias mais eficientes para suas determinações. O presente trabalho desenvolveu a técnica de extração por líquido pressurizado com a etapa de clean-up simultânea a extração, com sílica e alumina como adsorventes dentro da cela do equipamento ASE-350. A metodologia desenvolvida foi comparada com a tradicional extração por Sohxlet através de material de referência certificado. A extração por Soxhlet, apesar de eficiente, mostrou-se dispendiosa pelo gasto enorme de tempo, solvente e adsorventes quando comparada a extração por líquido pressurizado. De maneira geral a extração por líquido pressurizado apresentou-se mais vantajosa que a tradicional extração por Soxhlet. A eficiência da metodologia desenvolvida também foi testada através de quatro diferentes tipos de solos brasileiros fortificados com solução padrão de HPA. Os solos utilizados foram dos seguintes locais: Nova Lima MG, Lavras MG, Casimiro de Abreu RJ e Luiz Eduardo Magalhães BA. Todos possuíam características granulométricas e químicas diferentes entre si. Dois solos foram classificados em latossolos vermelhos, um em vermelho-amarelo e um em planossolo. Houve diferença significativa na eficiência de recuperação de alguns HPA quando comparados os quatro tipos de solos, já para outros HPA não evidenciou-se influência da tipologia do solo / Polycyclic aromatic hydrocarbons (PAH) are now a great concern to the scientific community due to its proven carcinogenic and mutagenic action. Therefore more efficient methodologies become necessary for its determinations. This research developed the technique of extraction by pressurized liquid with the clean-up step simultaneous to the extraction, i.e., the soil sample is extracted as the clean-up occurs. For this silica and alumina adsorbents was used in the ASE-350 equipment cell. For the study four different types of Brazilian soils with their well-defined characterizations were used. The soils used were from the following locations: Nova Lima - MG, Lavras - MG, Casimiro de Abreu - RJ and Luiz Eduardo Magalhães - BA. All of them had different soil gradation and chemical characteristics. The soils were classified as red oxisols, red-yellowish oxisols and planosols. There was significant difference between the recovery efficiency of some PAH in the four soil types, as for other HPA showed up no influence of soil type. The developed methodology was compared to traditional Sohxlet extraction by certified reference material (CRM). The Soxhlet extraction, although effective, has proved costly for large expenditure of time, adsorbents and solvent when compared to pressurized liquid extraction. In general the pressurized liquid extraction was more advantageous than traditional Soxhlet extraction. The developed methodology efficiency was also tested through four different Brazilian soil types spiked with standard PAH solution. The soils used were from the following locations: Nova Lima - MG, Lavras - MG, Casimiro de Abreu - RJ and Luiz Eduardo Magalhães - BA. All of them had different soil gradation and chemical characteristics among themselves. Two soils were classified as red oxisols, one as red-yellowish oxisol and one as planosol. There was significant difference among the recovery efficiency of some PAHs when the four soil types were compared; as for other HPA showed up no evidence of soil type influence

Made available in DSpace on 2015-05-14T13:21:34Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 2349929 bytes, checksum: 3d3e0699d877063cdd3b4736536785b4 (MD5) Previous issue date: 2014-03-21 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / A simple and rapid method for determination of furfural in yeast-distilled beverages from sugar cane by liquid-liquid extraction (LLE) is proposed. The techniques of extraction and / or preconcentration allows analytes can be determined by separation of sample components due, mainly, the solubility differences that allows the separation of one or more matrix components by contact and mechanical stirring of a solvent immiscible or slightly miscible in the matrix. The component to be separated (analyte) must be soluble in this solvent. In the proposed method equal amounts of standard sample and chloroform are mixed, the mixture is stirred mechanically for about 2 minutes, forming an emulsion. After this, it´s expected one minute to complete phase separation. Once the analyte is in the extractor solvent (chloroform) it was separated from the mixture and subjected to spectrophotometric analysis in the UV region (279 nm). The stability of the standard solution of furfural and waste disposal were evaluated. The viability of the LLE method was evaluated in the determination of furfural in samples of sugar cane spirits. The proposed method was compared with the reference method based on gas chromatography with flame ionization detector (FID) (GC-FID), no statistical difference between the results was observed. The LLE method was sensitive, accurate and precise with recoveries in the range 102-109%, linear range of 0,2 to 8 mg 100 ml-1, limits of detection and quantification of 0,0118 mg 100 mL-1 and 0,0203 mg 100 ml-1, respectively, repeatability factor of 0,026. The LLE methodology was validated and successfully applied to the analysis of eight cachaças samples demonstrating the feasibility and reliability of the method. The levels of furfural, in the analyzed cachaças was between 0,4 to 1,1 mg 100 mL-1 and is therefore, beverages analyzed, within the limit of 5 mg 100 mL-1, established by legislation. / Um método simples e rápido para determinação de furfural em cachaças por extração líquidolíquido (LLE) é proposto. As técnicas de extração e/ou pré-concentração permitem que analitos sejam determinados por meio da separação de componentes da amostra devido, principalmente, às diferenças de solubilidade que possibilitam a separação de um ou mais componentes da matriz por meio do contato e agitação mecânica de um solvente imiscível ou pouco miscível na matriz. O componente a ser separado (analito) deve solúvel neste solvente. No método proposto, são misturadas quantidades iguais de amostra/padrão e de clorofórmio, esta mistura é agitada mecanicamente por cerca de 2 minutos, formando uma emulsão. Após isto, espera-se mais um minuto para haver a completa separação de fases. Uma vez que o analito encontra-se no solvente extrator (clorofórmio), este foi separado da mistura e submetido à análise espectrofotométrica na região do UV (em 279 nm). A estabilidade da solução padrão de furfural e o descarte dos resíduos foram avaliados. A viabilidade do método LLE foi avaliada na determinação de furfural em amostras de cachaça. O método proposto foi comparado com o método baseado na cromatografia gasosa com detector de ionização de chama (GC-FID), nenhuma diferença estatística entre os resultados foi observada. O método LLE mostrou-se sensível, exato e preciso com recuperações na faixa de 102 a 109%, faixa linear de 0,2 a 8 mg 100 mL-1, limites de detecção e quantificação de 0,0118 mg 100mL-1 e 0,0203 mg 100mL-1, respectivamente, fator de repetitividade de 0,026. A metodologia de LLE foi validada e aplicada com sucesso na análise de oito amostras de cachaças demonstrando assim, a viabilidade e confiabilidade do método. Os teores de furfural, nas cachaças analisadas, variaram de 0,4 a 1,1 mg 100 mL-1, estando pois, as bebidas analisadas, dentro do limite, de 5 mg 100 mL-1, estabelecido pela legislação.