Simulation study has shown oil production is accelerated when propane is used as an additive during steam injection. To better understand this phenomenon, distillation experiments were performed using San Ardo crude oil (12oAPI). For comparison purposes, three distillation processes were investigated: dry-, steam-, and steam-propanedistillation, the latter at the propane-to-steam mass ratio of 0.05 at steam injection rate 0.5 g/min. Two sets of the distillation experiments were carried out. In the first set of experiments, the distillation temperatures ranged from 115ºC to 300ºC. Distillation pressures ranged from 0 psig to 998 psig for steam- and steam-propane distillation. The temperature-pressure combination used represented 15ºC superheated steam conditions. In the second set of experiments, the distillation temperatures ranged from 220oC to 300oC at 260 psig. The temperature pressure combination used represented field conditions for crude oil. For both conditions, the cell was kept at each temperature plateau (cut) until no increase occurs in distillation yields. Distillation yields were collected at each cut, and the volume and weight of water and hydrocarbon measured. Based on these experiments, a thermodynamic modeling framework was developed that describes distillation effect and oil production for steam distillation experiments. The model is based on composition of crude oil, molecular weight of heavy fraction. The analytical model results are compared against the experimental data for synthetic crude and crude oil to verify the validity of the model. Main results of the study may be summarized as follows. The yields for steam distillation for saturated conditions of Tsat+15 o C and Psat is 10 % and with addition of 5% of propane to steam no significant increase occurs in distillation yields. The yields for steam distillation for field conditions of 260 psig and temperature range (220 ~300oC) is 18 % and with addition of 5% of propane to steam no significant increase in distillation yields. The results indicate that propane has minimal distillation effect on the heavy oil. This occurs possibly because of lesser amount of light fractions in the heavy oil that enhance the separation of components in the oil caused by the concentration gradient.

Recent experimental and simulation studies -conducted at the Department of Petroleum Engineering at Texas A&M University - confirm oil production is accelerated when propane is used as an additive during steam injection. To better understand this phenomenon, distillation experiments were performed using seven-component synthetic oil consisting of equal weights of the following alkanes: n-C5, n-C6, n-C7, n-C8, n-C9, nC10, and n-C15. For comparison purposes, three distillation processes were investigated: dry-, steam-, and steam-propane-distillation, the latter at a propane:steam mass ratio of 0.05. The injection rate of nitrogen during dry-and steam-distillation was the same as that of propane during steam-propane distillation, 0.025 g/min, with steam injection rate kept at 0.5 g/min. The distillation temperatures ranged from 115°C to 300°C and were increased in steps of 10°C. The cell was kept at each temperature plateau (cut) for 30 minutes. Distillation pressures ranged from 0 psig for dry distillation to 998 psig for steam-and steam-propane distillation. The temperature-pressure combination used represented 15°C superheated steam conditions. Distillate samples were collected at each cut, and the volume and weight of water and hydrocarbon measured. In addition, the composition of the hydrocarbon distillate was measured using a gas chromatograph. Main results of the study may be summarized as follows. First, the hydrocarbon yield at 125°C is highest with steam-propane distillation (74 wt%) compared to steam distillation (58 wt%), and lowest with dry distillation (36 wt%). This explains in part the oil production acceleration observed in steam-propane displacement experiments. Second, the final hydrocarbon yield at 300°C however is the same for the three distillation processes. This observation is in line with the fact that oil recoveries were very similar in steam- and steam-propane displacement experiments. Third, based on the yields of individual hydrocarbon components, steam-propane distillation lowers the apparent boiling points of the hydrocarbons significantly. This phenomenon may be the most fundamental effect of propane on hydrocarbon distillation, which results in a higher yield during steam-propane distillation and oil production acceleration during steam-propane displacement. Fourth, experimental K-values are higher in distillations with steam-propane for the components n-hexane, n-heptane, n-octane, and n-nonane. Fifth, vapor fugacity coefficients for each component are higher in distillations with steam-propane than with steam. Finally, Gibbs excess energy is overall lower in distillations with steam-propane than with steam. The experimental results clearly indicate the importance of distillation on oil recovery during steam-or steam-propane injection. The experimental procedure and method of analysis developed in this study (for synthetic oil) will be beneficial to future researchers in understanding the effect of propane as steam additive on actual crude oils.

Este trabalho aborda a modelagem matemática do processo de extração de óleos essenciais por arraste a vapor e a otimização deste processo em escala industrial. Utilizouse dados experimentais de óleos essenciais de alecrim e citronela obtidos em uma unidade industrial de extração por arraste a vapor. O modelo é constituído de um sistema de equações diferenciais parciais, que representam o balanço de massa unidimensional nas fases vapor e sólido. Para resolver o modelo desenvolvido, utilizouse o método das linhas com o uso da técnica de diferenças finitas para discretizar a coordenada espacial e suas derivadas, resultando em um sistema de equações diferenciais ordinárias implementado no simulador EMSO. Os parâmetros do modelo foram estimados pelo método dos poliedros flexíveis, utilizando dois conjuntos de dados experimentais e um terceiro para sua validação. O modelo ajustou-se bem aos dados experimentais industriais, resultando, para duas condições ambientais e geográficas das plantas aromáticas de alecrim, em coeficiente global de transferência de massa de 8,64 x 10 -4 s -1 e 9,10 x 10 -4 s -1, e a constante de equilíbrio de 2,72 x 10 -4 m3=kg e 1,07 x 10 -2m3/kg. Enquanto que para a citronela obteve-se coeficiente global de transferência de massa de 8,29 x 10 -4s -1 e 1,23 x 10 -3 s -1, e constante de equilíbrio de 1,25 x 10 -2 m3/kg e 1,52 x 10 -3 m3/kg. Foi proposto também um problema de otimização para determinar o tempo ótimo de extração e o número de bateladas por dia. Os resultados da otimização do processo indicam que se pode reduzir o tempo de extração, permitindo que outras extrações sejam realizadas por dia, maximizando o volume de óleo extraído ao fim do dia. / This work has as objective the development of a mathematical model of essential oils extraction by steam distillation and the optimization of this process on an industrial scale. We used experimental data obtained from rosemary and citronella in an industrial steam distillation unit. The model consists a system of partial differential equations, which represent the one-dimensional mass balance in steam and solid phases. To solve the developed model, we used the method of lines with the finite differences technique to discretize the spatial coordinate and its derivatives, resulting in a system of ordinary differential equations implemented in the EMSO simulator. The model parameters were estimated by the method of flexible polyhedra, using two experimental runs and a third experimental run to test the model. The model fitted to the experimental data industry, resulting, for two environmental and geographical conditions of rosemary, in mass transfer coefficients of 8,64 x 10 -4 s -1 and 9,10 x 10 -4 s -1, and the equilibrium constant of 2,72 x 10 -4 m3/kg and 1,07 x 10 -2m3/kg. For citronella, the obtained mass transfer coefficient of 8,29 x 10 -4 s -1 and 1,23 x 10 -3 s -1 and equilibrium constant of 1,25 x 10 -2 m3/kg and 1,52 x 10 -3 m3/kg. It was also proposed an optimization problem to determine the optimum extraction time and number of batches per day. The optimization results indicate that the process can reduce the extraction time, allowing other extractions are performed each day, maximizing the essential oil volume extracted in the day.

Este trabalho aborda a modelagem matemática do processo de extração de óleos essenciais por arraste a vapor e a otimização deste processo em escala industrial. Utilizouse dados experimentais de óleos essenciais de alecrim e citronela obtidos em uma unidade industrial de extração por arraste a vapor. O modelo é constituído de um sistema de equações diferenciais parciais, que representam o balanço de massa unidimensional nas fases vapor e sólido. Para resolver o modelo desenvolvido, utilizouse o método das linhas com o uso da técnica de diferenças finitas para discretizar a coordenada espacial e suas derivadas, resultando em um sistema de equações diferenciais ordinárias implementado no simulador EMSO. Os parâmetros do modelo foram estimados pelo método dos poliedros flexíveis, utilizando dois conjuntos de dados experimentais e um terceiro para sua validação. O modelo ajustou-se bem aos dados experimentais industriais, resultando, para duas condições ambientais e geográficas das plantas aromáticas de alecrim, em coeficiente global de transferência de massa de 8,64 x 10 -4 s -1 e 9,10 x 10 -4 s -1, e a constante de equilíbrio de 2,72 x 10 -4 m3=kg e 1,07 x 10 -2m3/kg. Enquanto que para a citronela obteve-se coeficiente global de transferência de massa de 8,29 x 10 -4s -1 e 1,23 x 10 -3 s -1, e constante de equilíbrio de 1,25 x 10 -2 m3/kg e 1,52 x 10 -3 m3/kg. Foi proposto também um problema de otimização para determinar o tempo ótimo de extração e o número de bateladas por dia. Os resultados da otimização do processo indicam que se pode reduzir o tempo de extração, permitindo que outras extrações sejam realizadas por dia, maximizando o volume de óleo extraído ao fim do dia. / This work has as objective the development of a mathematical model of essential oils extraction by steam distillation and the optimization of this process on an industrial scale. We used experimental data obtained from rosemary and citronella in an industrial steam distillation unit. The model consists a system of partial differential equations, which represent the one-dimensional mass balance in steam and solid phases. To solve the developed model, we used the method of lines with the finite differences technique to discretize the spatial coordinate and its derivatives, resulting in a system of ordinary differential equations implemented in the EMSO simulator. The model parameters were estimated by the method of flexible polyhedra, using two experimental runs and a third experimental run to test the model. The model fitted to the experimental data industry, resulting, for two environmental and geographical conditions of rosemary, in mass transfer coefficients of 8,64 x 10 -4 s -1 and 9,10 x 10 -4 s -1, and the equilibrium constant of 2,72 x 10 -4 m3/kg and 1,07 x 10 -2m3/kg. For citronella, the obtained mass transfer coefficient of 8,29 x 10 -4 s -1 and 1,23 x 10 -3 s -1 and equilibrium constant of 1,25 x 10 -2 m3/kg and 1,52 x 10 -3 m3/kg. It was also proposed an optimization problem to determine the optimum extraction time and number of batches per day. The optimization results indicate that the process can reduce the extraction time, allowing other extractions are performed each day, maximizing the essential oil volume extracted in the day.

Este trabalho aborda a modelagem matemática do processo de extração de óleos essenciais por arraste a vapor e a otimização deste processo em escala industrial. Utilizouse dados experimentais de óleos essenciais de alecrim e citronela obtidos em uma unidade industrial de extração por arraste a vapor. O modelo é constituído de um sistema de equações diferenciais parciais, que representam o balanço de massa unidimensional nas fases vapor e sólido. Para resolver o modelo desenvolvido, utilizouse o método das linhas com o uso da técnica de diferenças finitas para discretizar a coordenada espacial e suas derivadas, resultando em um sistema de equações diferenciais ordinárias implementado no simulador EMSO. Os parâmetros do modelo foram estimados pelo método dos poliedros flexíveis, utilizando dois conjuntos de dados experimentais e um terceiro para sua validação. O modelo ajustou-se bem aos dados experimentais industriais, resultando, para duas condições ambientais e geográficas das plantas aromáticas de alecrim, em coeficiente global de transferência de massa de 8,64 x 10 -4 s -1 e 9,10 x 10 -4 s -1, e a constante de equilíbrio de 2,72 x 10 -4 m3=kg e 1,07 x 10 -2m3/kg. Enquanto que para a citronela obteve-se coeficiente global de transferência de massa de 8,29 x 10 -4s -1 e 1,23 x 10 -3 s -1, e constante de equilíbrio de 1,25 x 10 -2 m3/kg e 1,52 x 10 -3 m3/kg. Foi proposto também um problema de otimização para determinar o tempo ótimo de extração e o número de bateladas por dia. Os resultados da otimização do processo indicam que se pode reduzir o tempo de extração, permitindo que outras extrações sejam realizadas por dia, maximizando o volume de óleo extraído ao fim do dia. / This work has as objective the development of a mathematical model of essential oils extraction by steam distillation and the optimization of this process on an industrial scale. We used experimental data obtained from rosemary and citronella in an industrial steam distillation unit. The model consists a system of partial differential equations, which represent the one-dimensional mass balance in steam and solid phases. To solve the developed model, we used the method of lines with the finite differences technique to discretize the spatial coordinate and its derivatives, resulting in a system of ordinary differential equations implemented in the EMSO simulator. The model parameters were estimated by the method of flexible polyhedra, using two experimental runs and a third experimental run to test the model. The model fitted to the experimental data industry, resulting, for two environmental and geographical conditions of rosemary, in mass transfer coefficients of 8,64 x 10 -4 s -1 and 9,10 x 10 -4 s -1, and the equilibrium constant of 2,72 x 10 -4 m3/kg and 1,07 x 10 -2m3/kg. For citronella, the obtained mass transfer coefficient of 8,29 x 10 -4 s -1 and 1,23 x 10 -3 s -1 and equilibrium constant of 1,25 x 10 -2 m3/kg and 1,52 x 10 -3 m3/kg. It was also proposed an optimization problem to determine the optimum extraction time and number of batches per day. The optimization results indicate that the process can reduce the extraction time, allowing other extractions are performed each day, maximizing the essential oil volume extracted in the day.

O tensoativo anfotérico cocoamidopropil betaína (CAPB) é largamente utilizado na indústria de cosméticos, e é considerado um insumo essencial para a formulação de sabonetes líquidos, shampoos e géis de limpeza facial. A síntese deste tensoativo se dá por meio da reação entre ácido graxo de coco e dimetilaminopropilamina (DMAPA) e, posterior reação com o ácido monocloroacético (AMCA). O excesso de DMAPA considerado impureza, precisa ser monitorado devido a sua irritabilidade no contato com a pele, olhos e mucosas podendo em alguns casos provocar dermatite. Atualmente, o método adotado pela empresa Clariant S/A utiliza para a determinação desta substância, cromatografia líquida de alta eficiência (HPLC), entretanto, esta metodologia apresenta elevado tempo de análise e consumo de solventes, comprometendo a produtividade na indústria, por manter os reatores inoperantes na espera do resultado da análise. Existe uma demanda crescente na indústria de cosméticos para utilização de metodologias que abordem critérios de tempo e custo na determinação de impurezas, para assegurar a qualidade dos produtos finais. Assim, com o intuito de aumentar a eficiência no processo de produção, este trabalho tem como objetivo propor um método rápido e confiável por eletroforese capilar para determinar o teor de DMAPA durante a produção (controles de processo) e no produto final do tensoativo CAPB. Neste trabalho foram abordadas diversas técnicas de preparo de amostra e condições instrumentais, para se alcançar um limite de quantificação (LOQ) 10 mg kg-1 (especificação exigida pelo cliente no produto final). O DMAPA foi analisado como cátion, utilizando um eletrólito de corrida com imidazol e HIBA (ácido alpha hidroxibutírico), ambos com concentração de 0,01 mol L-1e pH acertado para 4,0 utilizando uma solução de HCl 1,0 mol L-1. Foi realizada inicialmente, uma tentativa de analisar o CAPB diluindo-o diretamente em água, porém, mesmo após tentativas de pré-concentração on-line como o Stacking (plug de água antes da injeção da amostra) e injeção de amostra no modo eletrocinético, os subprodutos presentes na amostra, interferiram, prejudicando a detectabilidade do método. Então, foi proposta uma alternativa de preparo de amostra por meio da destilação por arraste de vapor, que permitiu isolar o DMAPA de sua matriz, diminuindo o limite de detecção (LOD) e LOQ do método proposto. Posteriormente foi construída uma curva analítica processada (em CAPB) e o método proposto apresentou boa precisão (%CV < 5) e linearidade (R2=0,9955 faixa linear de 2,0 a 20 mg kg-1), com LOD e LOQ de 0,03 mg kg-1 e 0,1 mg kg-1, respectivamente. O método proposto nesta dissertação alcançou o objetivo desejado, uma vez que apresentou um LOQ para o DMAPA abaixo da especificação exigida pelos clientes no produto final, e significativamente mais rápido do que o método atualmente utilizado pela Clariant S/A. / The amphoteric surfactant cocoamidopropyl betaine (CAPB) is widely used in pharmaceuticals and cosmetics industries, and is considered an essential input for the formulation of liquid soaps, shampoos and facial cleansing gels. Its synthesis is based on the reaction between fatty acid and coconut dimethylaminopropylamine (DMAPA) and subsequent reaction with monocloroacetic acid (MCA). The excess of DMAPA, regarded as an impurity, needs to be monitored because of its skin, eyes and mucous membranes irritability and in some cases, it causes dermatitis. Currently, the method adopted by Clariant S/A Industry for the determination of this substance is based on high performance liquid chromatography (HPLC). However, this method has a high analysis time and solvent consumption, compromising the productivity because of the inactive reactors which cannot be operated without the results of DMAPA analysis. There is a growing demand in the cosmetics industry to use methodologies which use time and cost criteria for determination of impurities to ensure the end products quality. Thus, in order to increase efficiency in the production process, this paper aims to propose a fast and reliable method for capillary electrophoresis to determine the DMAPA content during production (process control) and in the end product (CAPB surfactant). In this study, we addressed several sample preparation techniques and instrumental conditions to achieve an LOQ (limit of quantification) 10 mg kg-1 (specification required by the customer in the final product). The DMAPA was analyzed as cation, using a running buffer with imidazole and HIBA (a-hydroxybutyric acid), both with concentration of 0.01 mol L-1, and pH adjusted to 4.0 using a solution of HCl 1.0 mol L-1. First, CAPB was diluted directly in water. However, even after online preconcentration as Stacking (water plug before sample injection) and sample injection using the electrokinetic mode, the by-products present in the sample interfered in the method detectability. Thus, it was proposed an alternative sample preparation by steam distillation, allowing the isolation of the DMAPA from its matrix, lowering the limit of detection (LOD) and LOQ. Subsequently a processed calibration curve was constructed (in CAPB) and the proposed had good precision (CV% <5) and linearity (R2 = 0.9955, linear range from 2.0 to 20 mg kg-1), with LOD and LOQ of 0.03 mg kg-1 and 0.1 mg kg-1, respectively. The developed method in this thesis has achieved its purpose, since it presented an LOQ for the DMAPA below the required specification by customers in the final product, and significantly faster than the method currently used by Clariant S/A.

O tensoativo anfotérico cocoamidopropil betaína (CAPB) é largamente utilizado na indústria de cosméticos, e é considerado um insumo essencial para a formulação de sabonetes líquidos, shampoos e géis de limpeza facial. A síntese deste tensoativo se dá por meio da reação entre ácido graxo de coco e dimetilaminopropilamina (DMAPA) e, posterior reação com o ácido monocloroacético (AMCA). O excesso de DMAPA considerado impureza, precisa ser monitorado devido a sua irritabilidade no contato com a pele, olhos e mucosas podendo em alguns casos provocar dermatite. Atualmente, o método adotado pela empresa Clariant S/A utiliza para a determinação desta substância, cromatografia líquida de alta eficiência (HPLC), entretanto, esta metodologia apresenta elevado tempo de análise e consumo de solventes, comprometendo a produtividade na indústria, por manter os reatores inoperantes na espera do resultado da análise. Existe uma demanda crescente na indústria de cosméticos para utilização de metodologias que abordem critérios de tempo e custo na determinação de impurezas, para assegurar a qualidade dos produtos finais. Assim, com o intuito de aumentar a eficiência no processo de produção, este trabalho tem como objetivo propor um método rápido e confiável por eletroforese capilar para determinar o teor de DMAPA durante a produção (controles de processo) e no produto final do tensoativo CAPB. Neste trabalho foram abordadas diversas técnicas de preparo de amostra e condições instrumentais, para se alcançar um limite de quantificação (LOQ) 10 mg kg-1 (especificação exigida pelo cliente no produto final). O DMAPA foi analisado como cátion, utilizando um eletrólito de corrida com imidazol e HIBA (ácido alpha hidroxibutírico), ambos com concentração de 0,01 mol L-1e pH acertado para 4,0 utilizando uma solução de HCl 1,0 mol L-1. Foi realizada inicialmente, uma tentativa de analisar o CAPB diluindo-o diretamente em água, porém, mesmo após tentativas de pré-concentração on-line como o Stacking (plug de água antes da injeção da amostra) e injeção de amostra no modo eletrocinético, os subprodutos presentes na amostra, interferiram, prejudicando a detectabilidade do método. Então, foi proposta uma alternativa de preparo de amostra por meio da destilação por arraste de vapor, que permitiu isolar o DMAPA de sua matriz, diminuindo o limite de detecção (LOD) e LOQ do método proposto. Posteriormente foi construída uma curva analítica processada (em CAPB) e o método proposto apresentou boa precisão (%CV < 5) e linearidade (R2=0,9955 faixa linear de 2,0 a 20 mg kg-1), com LOD e LOQ de 0,03 mg kg-1 e 0,1 mg kg-1, respectivamente. O método proposto nesta dissertação alcançou o objetivo desejado, uma vez que apresentou um LOQ para o DMAPA abaixo da especificação exigida pelos clientes no produto final, e significativamente mais rápido do que o método atualmente utilizado pela Clariant S/A. / The amphoteric surfactant cocoamidopropyl betaine (CAPB) is widely used in pharmaceuticals and cosmetics industries, and is considered an essential input for the formulation of liquid soaps, shampoos and facial cleansing gels. Its synthesis is based on the reaction between fatty acid and coconut dimethylaminopropylamine (DMAPA) and subsequent reaction with monocloroacetic acid (MCA). The excess of DMAPA, regarded as an impurity, needs to be monitored because of its skin, eyes and mucous membranes irritability and in some cases, it causes dermatitis. Currently, the method adopted by Clariant S/A Industry for the determination of this substance is based on high performance liquid chromatography (HPLC). However, this method has a high analysis time and solvent consumption, compromising the productivity because of the inactive reactors which cannot be operated without the results of DMAPA analysis. There is a growing demand in the cosmetics industry to use methodologies which use time and cost criteria for determination of impurities to ensure the end products quality. Thus, in order to increase efficiency in the production process, this paper aims to propose a fast and reliable method for capillary electrophoresis to determine the DMAPA content during production (process control) and in the end product (CAPB surfactant). In this study, we addressed several sample preparation techniques and instrumental conditions to achieve an LOQ (limit of quantification) 10 mg kg-1 (specification required by the customer in the final product). The DMAPA was analyzed as cation, using a running buffer with imidazole and HIBA (a-hydroxybutyric acid), both with concentration of 0.01 mol L-1, and pH adjusted to 4.0 using a solution of HCl 1.0 mol L-1. First, CAPB was diluted directly in water. However, even after online preconcentration as Stacking (water plug before sample injection) and sample injection using the electrokinetic mode, the by-products present in the sample interfered in the method detectability. Thus, it was proposed an alternative sample preparation by steam distillation, allowing the isolation of the DMAPA from its matrix, lowering the limit of detection (LOD) and LOQ. Subsequently a processed calibration curve was constructed (in CAPB) and the proposed had good precision (CV% <5) and linearity (R2 = 0.9955, linear range from 2.0 to 20 mg kg-1), with LOD and LOQ of 0.03 mg kg-1 and 0.1 mg kg-1, respectively. The developed method in this thesis has achieved its purpose, since it presented an LOQ for the DMAPA below the required specification by customers in the final product, and significantly faster than the method currently used by Clariant S/A.

Thermal recovery methods are frequently used to enhance the production of heavy crude oils. Steam-based processes are the most economically popular and effective methods for heavy oil recovery for several decades. In general, there are various mechanisms over steam injection to enhance and have additional oil recovery. However, among these mechanisms, steam distillation plays pivotal role in the recovery of crude oil during thermal recovery process. In this study, an experimental investigation was carried out to investigate the role of various minerals present in both sandstone and carbonate formations as well as the effect of steam temperature on steam distillation process. Two different types of dead-heavy crude oils were tested in a batch autoclave reactor with 30 % water and the content of the reactor (crude oil, 10 % rock and mineral). The results were compared as the changes in the density, viscosity and chemical composition (SARA and TPH analyses) of heavy crude oil. Five different mineral types (bentonite, sepiolite, kaolinite, illite and zeolite) were added into the original crude oil and reservoir rocks to observe their effects on the rheological and compositional changes during steam distillation process. Analysis of the results of experiments with Camurlu and Bati Raman heavy crude oils in the presence of different minerals such as Bentonite, Zeolite, Illite, Sepiolite, and Kaolinite in both sandstone and limestone reservoir rocks indicate that steam distillation produces light end condensates which can be considered as solvent or condensate bank during steam flooding operation. It was also illustrated that minerals in reservoir formations perform the function of producing distilled light oil compounds, resulting in enhancement of heavy crude oils recovery in steam flooding. Measurements showed that the remaining oil after steam distillation has higher viscosity and density. On the other hand, the effect of steam distillation is more pronounced in limestone reservoirs compared to sandstone reservoirs for the given heavy crude oil and steam temperature. Among the five different minerals tested, kaolinite found to be the most effective mineral in terms of steam distillation.

Methods were developed for the determination of methylmercury in natural waters and sediments based on steam distillation and aqueous phase ethylation followed by gas chromatography-atomic fluorescence spectrometry. The methods were shown to be free from measurable artefactual methylation of inorganic mercury and offered improved sample throughput over existing methods. Improvements were made to existing methods for the determination of total mercury in biota, sediments and natural waters and dissolved mercury species in natural waters. These methods were applied to the study of mercury cycling in two remote field sites. The cycling of mercury species was studied in Lake Murray in Western Province, Papua New Guinea, which has been historically noted as a region of high mercury concentrations in fish. Concentrations of methylmercury and total mercury in the water column were found to be variable and consistent with non-contaminated lake systems. Concentrations of methylmercury and total mercury in the sediments were also found to be low, except for in the south of the lake, which was influenced by an intermittent supply of water and sediments with elevated mercury concentrations from the Strickland River. Methylmercury concentrations in the sediments were generally higher in the backwater areas due to littoral processes. The low concentrations of methylmercury in the sediments and waters were inconsistent with other systems previously studied in the northern hemisphere, showing a link between high mercury concentrations in fish and high concentrations of methylmercury in waters or sediments. Therefore, the biota of Lake Murray were studied in order to account for the differences between this and other systems. A study was conducted of the stable isotope ratios of carbon and nitrogen in biota from Lake Murray to elucidate key food-web interactions. This study revealed that the dominant carbon source for fish in the lake is plankton, although algae and macrophytes may also be involved in the food-web. The methylmercury bioaccumulation factors between trophic levels were similar to those measured in temperate systems of the northern hemisphere. The high concentrations of methylmercury, observed in piscivorous fish, were shown to be a consequence of the complex food-web and the number of trophic levels in the food-chains. The cycling of mercury species was studied in Lake Gordon and Lake Pedder in southwest Tasmania, which has recently been identified as being in a region of high mercury concentrations in trout and eels. The concentrations of total mercury were found to be reasonably uniform in the waters of both lakes, spatially and temporally. The concentrations of methylmercury in the waters were seasonally variable, and were consistently lower in Lake Pedder than in Lake Gordon. Dilution of methylmercury concentrations by precipitation direct to the lake surface, probably accounts for the most of the difference in methylmercury concentrations between the lakes. Owing to the long residence time of water in Lake Gordon, this reservoir mixes inputs of water with varying methylmercury concentrations. Concentrations of total mercury and methylmercury in submerged soils were low and depth profiles of mercury species in the water column did not show evidence of a gradient of mercury concentrations due to releases from the sediments. The concentrations of methylmercury observed in the water column are consistent with the concentrations observed in the fish. A budget of the mercury inputs and outputs to Lake Gordon showed that in-lake processes and sources in the catchment areas both contributed significantly to the concentrations of methylmercury in the lake. The methylation of mercury in Lake Gordon appeared to mainly occur in the surface waters (< 10 m) and was not consistent with processes leading to the methylation of mercury at the oxic/anoxic boundary observed in seepage lakes in Wisconsin. The concentrations of total mercury and methylmercury in bogs in the catchment areas of Lakes Gordon and Pedder, were high and governed by the concentration of organic matter in the sediments. The processes involved in the supply of mercury species from the Lake Gordon and Lake Pedder catchments appear to be similar to those in drainage lakes in the temperate and boreal regions of the northern hemisphere. The formation of the Lake Gordon and Lake Pedder reservoirs appears to have had little impact on the mean annual concentrations of methylmercury released to the downstream environment.

Orientador: Maria Angela de Almeida Meireles / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-16T15:05:33Z (GMT). No. of bitstreams: 1 NavarroDiaz_HelmutJoel_M.pdf: 20602791 bytes, checksum: 810d1333271b6db64857c64c3c2a7904 (MD5) Previous issue date: 2010 / Resumo: O resumo poderá ser visualizado no texto completo da tese digital / Abstract: The abstract is available with the full electronic document / Mestrado / Mestre em Engenharia de Alimentos