Lymphatic filariasis (LF) is an incapacitating disease caused by three filarial nematodes belonging to the family Onchocercidae, namely Brugia timori, Wuchereria bancrofti and Brugia timori. An estimated 90% of lymphatic filariasis cases globally are caused by Wuchereria bancrofti. To evaluate the success of the Global Program to eliminate Lymphatic Filariasis it is essential to monitor the frequency of larval infection in the mosquito vector. Molecular methods to detect Wuchereria bancrofti DNA in mosquitoes have been in existence since 1996. However these methods have not been widely adopted due to the high cost associated with them and the inability of these assays to distinguish between immature and infectious stages in the mosquito vector. The overall aim of this project was to modify, as previously described in literature, the Laney real time PCR assay to permit it to be used in an end point Reverse Transcriptase (RT)-PCR ELISA format. The endpoint PCR-ELISA uses inexpensive conventional thermocyclers and inexpensive reagents and probes. To accomplish this overall goal the specific objectives were to produce a positive control RNAs for Wb-cut-1.2 L3 specific RT-PCR and Wb-TPH RT-PCR that detects any stage of the parasite, and to adapt the detection of both transcripts to a PCR-ELISA format. Positive RNA controls were prepared and purified using template cDNA made available through FR3, subsequent development and optimization of the RT PCR ELISA was achieved through the adaptation of the Onchocerca volvulus O150 PCR ELISA protocol. We found a 16-fold difference in the limit of detection between the ELISA assay and conventional end point RT-PCR when we did a 2-fold dilution series of PCR products for both Wb-Cut-1.2 and Wb-TPH. This indicates that our assay was 16 times more sensitive than the use of regular agarose gel electrophoresis to analyze PCR products. The limit of detection with ELISA and gel analysis were comparable when a 10-fold dilution series of the positive control RNA template was done. The RT-PCR ELISA takes a day to complete and up to three 96 well plates a day can be processed compared to the limited number of samples that can be analyzed by gel electrophoresis a day. It is anticipated that our assay will be used in the molecular xenomonitoring of Wuchereria bancrofti providing earlier time-point assessments of LF infection in endemic areas. In areas that were once endemic, our diagnostic tool will play a pivotal role in monitoring LF resurgence.

O objetivo desta tese foi o desenvolvimento de um equipamento compacto para o tratamento de águas subterrâneas contaminadas por BTEX e TPH em postos de combustíveis. Esta questão ambiental é uma preocupação mundial devido ao nível de contaminação e a quantidade de vazamentos existentes, toxicidade dos poluentes e a necessidade de uso de aquíferos para consumo humano. O equipamento é composto por unidades que contemplam as seguintes etapas: (a) sucção e volatilização de compostos orgânicos voláteis; (b) injeção de ar (“air sparging”) para remoção de substâncias orgânicas voláteis; e (c) filtro de adsorção com recheio composto por mistura de 50% de carvão ativado e 50% de cinza de casca de arroz para a remoção de TPH. A parte experimental envolveu a caracterização de águas subterrâneas contaminadas e estudos em escala piloto e real. Os resultados obtidos demostraram que o equipamento de remediação desenvolvido é altamente eficiente para o tratamento de águas subterrâneas contaminadas. Com um tempo de detenção de 8 horas, obtiveram-se decréscimos superiores a 96% de BTEX e TPH. Nesta situação, a água contaminada tratada alcança valores que atendem aos critérios de lançamento estabelecidos pelas legislação nacional vigente. / This study describes the development of a compact device to treat groundwater contaminated with BTEX and TPH in gas stations. This environmental issue raises concerns worldwide, due to the level of contamination, the high occurrence of leaks, the toxicity of contaminants, and the importance of aquifers for human consumption. The equipment was formed by: a) a suction and treatment stage using vacuum and aeration with injectors (to replace the suction system based on a conventional vacuum pump and the air stripping and/or air sparging system); b) small-scale surface aerators (to replace the air stripping and/or air sparging system); c) an adsorption filter using a mixture of activated carbon (50%) and rice husk ash (50%) (to replace the activated carbon system). The experiment was conducted in four stages: a) characterization of groundwaters; b) presentation of the adsorbents used in the filter; c) pilot test (under controlled conditions to measure the efficiency to remove BTEX and TPH); and d) the full-scale tests (observation and confirmation of equipment efficiency). The results show that the remediation equipment developed is highly efficient to treat contaminated groundwater. An 8-h retention time afforded to reduce BTEX and TPH levels by over 96%. In this scenario, the treated water parameters meet the current legal requirements for discharge.

Bodenkontaminationen durch Mineralölkohlenwasserstoffe sind ein weltweites Umweltproblem. Die Kontaminatiosquellen stehen im Zusammenhang mit Förderung, Lagerung, Transport, Verteilung und Endlagerung von Erdöl und Erdölprodukten. Brasilien beginnt zurzeit einen Prozess der Altlastenerfassung und –erkundung und in Konsequenz dessen auch die Suche nach geeigneten Sanierungstechniken. Biologische Prozesse spielen eine immer stärkere Rolle insbesondere bei der Sanierung von Bodenkontaminationen mit organischen Substanzen. Diese Prozesse gelten als “ökologisch korrekter” und sind im Vergleich mit anderen Techniken mit geringeren Kosten und technischen Aufwand durchführbar. Ziel dieser Arbeit war es, die Anwendungsmöglichkeiten der biologischen Bodensanierung mittels des Terraferm® Verfahrens unter den Umweltbedingungen des Bundesstaates São Paulo, Brasilien zu überprüfen. Zu diesem Zweck wurde der Boden einer MKW-kontaminierte Fläche (Mina de Argila) in der Raffinerie REPLAN der PETROBRÁS S/A in Paulínia -SP ausgekoffert. Es wurden zehn Bodenproben in Bezug auf ihre physikalisch-chemischen Eigenschaften MKW, PAK, BTEX, Metalle (Cr, Zn, Pb, Ni, Cu, Cd, As, Hg, Fe, Ta), Wassergehalt, pH, Korngröße analysiert. Drei Proben mit durchschnittlichen MKW-gehalten wurden zur Überprüfung der biologischen Sanierbarkeit und der Bestimmung der Kontrollparameter für den später Sanierungsdurchführung Säulenversuchen unterzogen. Insgesamt wurden 72.384t kontaminierten Bodens ausgekoffert, wovon 21.050t der Abfallklasse II (nach NBR 10004) zugeordnet wurden und direkt auf eine Mülldeponie verbracht wurden. Es wurden 51.334t der Abfallklasse 1 in die Bodenreinigungsanlage der Firmen SAPOTEC/ESTRE in Paulínia - SP mittels des Terraferm® Verfahrens behandelt. Dieses Verfahren ist darauf ausgelegt, alle für den biologischen Abbau nötigen Prozessparameter im Optimum zu halten. Die Behandlung erfolgt in Hallen auf versiegeltem Untergrund und die dabei freigesetzten Schad- und Geruchsstoffe werden gefasst und einer Abluftreinigung zugeführt. Nach der Vorbehandlung (Aussortierung von Störstoffen, Zugabe von Strukturmaterial, Durchmischung) mittels speziellem Aufbereitungsaggregat wurden insgesamt elf Behandlungsmieten aufgesetzt. Der Sauerstoffgehalt, Bodenfeuchte und Nährstoffgehalte wurden im Optimalbereich gehalten. Die Analysen und die Säulenversuche bestätigten die biologische Sanierbarkeit des Bodens. Die Abbauraten in den Säulenversuchen lagenzwischen 70,2% und 88,6% in 14 Tagen. Diese hohen Abbauraten lassen sich durch die Zusammensetzung der MKW begründen, die sich hauptsächlich aus gut abbaubaren n-Alkanen und iso-Alkanen bestehen. Die durchschnittliche Abbaurate bei den elf Behandlungsmieten lag bei 80,88%, wobei die niedrigste bei 54,71% und die höchste Abbaurate bei 97,97% lagen. Die statistische Auswertung ergab, dass sich die Mittelwerte der MKW-gehalte während der Behandlung signifikant voneinander unterscheiden (<0,01). Die im Rahmen dieser Arbeit durchgeführten Versuche bestätigen den erfolgreichen Einsatz des Terraferm® Verfahrens unter Umweltbedingungen des Bundesstaates São Paulo, Brasilien. Die starke Variabilität der Abbauraten in den Behandlungsmieten deutet aber auf einen weiteren Forschungsbedarf, insbesondere hinsichtlich des Temperatur-einflusses, hin. / Contaminações de solos com hidrocarbonetos de petróleo são um problema ambiental com abrangência mundial devido à alta demanda de produtos refinados de petróleo. As fontes são múltiplas e estão relacionadas à exploração, produção, armazenamento, transporte, distribuição e à destinação final de petróleo e seus derivados. Hoje o Brasil está iniciando um processo de avaliação e cadastramento de suas áreas contaminadas e, conseqüentemente, está procurando alternativas para a remediação das mesmas. Processos biológicos estão ganhando cada vez mais importância no tratamento, especialmente de solos contaminados com compostos orgânicos. Estes métodos são favorecidos por serem mais limpos, com custos baixos e de mais fácil aplicação em escala industrial. Assim, com o objetivo de verificar a aplicabilidade da biorremediação através do processo Terraferm® às condições ambientais do Estado de São Paulo, Brasil, foi realizada a remediação ex situ de uma área contaminada com TPH, chamada Mina de Argila na Refinaria de Paulínia – REPLAN da PETROBRÁS S/A, em Paulínia - SP. Foram analisadas dez amostras de solo contaminado em relação aos parâmetros físico-químicos TPH, PAH, BTEX, metais (Cr, Zn, Pb, Ni, Cu, Cd, As, Hg, Fe, Ta), umidade, pH, oxigênio e granulometria. Três amostras com valores médios de TPH foram submetidas a ensaios de coluna para verificação da biotratabilidade do material e para definição de parâmetros de controle do processo em escala industrial. Foram removidos um total de 72.384t de material contaminado. Deste total, 21.050t foram classificadas como resíduo classe II segundo a NBR 10004 e encaminhadas para um aterro sanitário, e 51.334t foram classificadas como resíduo classe I, sendo destinadas à estação de biorremediação das empresas SAPOTEC/ESTRE, em Paulínia - SP. O solo contaminado foi tratado com o processo Terraferm®, que visa à otimização dos parâmetros que influenciam diretamente a atividade microbiana necessária para a biodegradação. O tratamento é feito em galpões com piso impermeabilizado e com um sistema de captação e tratamento das emissões geradas durante o processo de biodegradação. Após o pré-tratamento em máquina especial, que consiste na separação dos materiais não-tratáveis, na homogeneização e na adição de material estrutural, o solo contaminado foi colocado em onze pilhas de tratamento. Os fatores chave como o teor de oxigênio, a umidade e os nutrientes foram mantidos nas faixas consideradas ótimas. A caracterização química e o ensaio de coluna comprovaram a biotratabilidade do solo. Noensaio em coluna, obteve-se taxas de degradação entre 70,2% e 88,6% em 14 dias. Essas taxas altas são explicadas pela composição do TPH que consiste, neste caso, basicamente de n-alcanos e iso-alcanos considerados de fácil degradação biológica. A taxa média de degradação obtida no tratamento das onze pilhas foi de 80,88%, sendo a menor de 54,71% e a maior de 97,97%. Na análise estatística, verificou-se que as médias das concentrações de TPH durante cada período de tratamento diferem significativamente (<0,01). O trabalho conclui que o processo Terraferm® foi aplicado com sucesso nas condições ambientais do Estado de São Paulo, Brasil. Entretanto, os resultados do tratamento mostram uma alta variabilidade das taxas de degradação nas pilhas, que indica a necessidade de novas pesquisas, especialmente sobre a influência da temperatura no processo. / Soil contaminations with petroleum hydrocarbons are a worldwide environmental problem due to the high demand for refined petroleum products. Contamination sources are multiple and related to the exploration, production, storage, transportation, distribution, and final disposal of petroleum and its derivatives. Nowadays Brazil is starting to assess and record its contaminated areas and consequently search for alternatives for their remediation. Biological processes are gaining more and more importance, specially in the treatment of soils contaminated by organic compounds. These methods are favored for being cleaner, with lower costs, and more easily applicable to industrial scale. Therefore, with the objective of verifying the applicability of bioremediation to the environmental conditions of São Paulo State, Brazil, the ex situ remediation of a contaminated area by TPH was carried out by using the Terraferm® process. The area called Mina de Argila was located in the Paulínia Refinery – REPLAN, which belongs to PETROBRÁS S/A (the country's leader in the exploration, production, and distribution of petroleum products). Ten samples of contaminated soil were analyzed in relation to the physical-chemical parameters TPH, PAH, BTEX, metals (Cr, Zn, Pb, Ni, Cu, Cd, As, Hg, Fe, Ta), humidity, pH, oxygen and texture. Three samples with average values of TPH were submitted to column tests in order to assess the material biotreatability and define the control parameters of the process on industrial scale. A total of 72,384t of contaminated soil were removed. From this total, 21,050t were classified as class II waste according to NBR 10004 and sent to a landfill, and 51,334t were classified as class I waste and sent to the bioremediation plant of the companies SAPOTEC/ESTRE, in Paulínia – São Paulo State. The contaminated soil was treated with the Terraferm® process whose purpose is to optimize the parameters which directly influence the microbial activity necessary for biodegradation. The treatment was carried out in sheds with waterproof floor and a collection and treatment system for the emissions generated in the biodegradation process. After the treatment in a special machine, which consists in separating non-treatable materials, homogenizing, and adding structural material, the soil was placed into eleven treatment piles. The oxygen content, humidity, and nutrients were kept within a range considered optimum. The chemical characterization and the column test proved the soil biotreatability. In the column test, the degradation rates were between 70.2% and 88.6% in 14 days. These high rates are due to the TPHcomposition, which in this case basically consists in n-alkenes and iso-alkenes of easy biological degradation. The average degradation rate verified in the treatment of the eleven piles was of 80.88%, the lowest being 54.71% and the highest 97.97%. In the statistical analysis, it was verified that the average concentrations of TPH during each treatment period differ significantly (<0.01). The conclusion of this work is that the Terraferm® process was successfully applied to the environmental conditions of São Paulo State. However, the treatment results show a high variability in the degradation rates of the piles, which indicates the need for further research, specially on the influence of temperature on the process.

Bodenkontaminationen durch Mineralölkohlenwasserstoffe sind ein weltweites Umweltproblem. Die Kontaminatiosquellen stehen im Zusammenhang mit Förderung, Lagerung, Transport, Verteilung und Endlagerung von Erdöl und Erdölprodukten. Brasilien beginnt zurzeit einen Prozess der Altlastenerfassung und –erkundung und in Konsequenz dessen auch die Suche nach geeigneten Sanierungstechniken. Biologische Prozesse spielen eine immer stärkere Rolle insbesondere bei der Sanierung von Bodenkontaminationen mit organischen Substanzen. Diese Prozesse gelten als “ökologisch korrekter” und sind im Vergleich mit anderen Techniken mit geringeren Kosten und technischen Aufwand durchführbar. Ziel dieser Arbeit war es, die Anwendungsmöglichkeiten der biologischen Bodensanierung mittels des Terraferm® Verfahrens unter den Umweltbedingungen des Bundesstaates São Paulo, Brasilien zu überprüfen. Zu diesem Zweck wurde der Boden einer MKW-kontaminierte Fläche (Mina de Argila) in der Raffinerie REPLAN der PETROBRÁS S/A in Paulínia -SP ausgekoffert. Es wurden zehn Bodenproben in Bezug auf ihre physikalisch-chemischen Eigenschaften MKW, PAK, BTEX, Metalle (Cr, Zn, Pb, Ni, Cu, Cd, As, Hg, Fe, Ta), Wassergehalt, pH, Korngröße analysiert. Drei Proben mit durchschnittlichen MKW-gehalten wurden zur Überprüfung der biologischen Sanierbarkeit und der Bestimmung der Kontrollparameter für den später Sanierungsdurchführung Säulenversuchen unterzogen. Insgesamt wurden 72.384t kontaminierten Bodens ausgekoffert, wovon 21.050t der Abfallklasse II (nach NBR 10004) zugeordnet wurden und direkt auf eine Mülldeponie verbracht wurden. Es wurden 51.334t der Abfallklasse 1 in die Bodenreinigungsanlage der Firmen SAPOTEC/ESTRE in Paulínia - SP mittels des Terraferm® Verfahrens behandelt. Dieses Verfahren ist darauf ausgelegt, alle für den biologischen Abbau nötigen Prozessparameter im Optimum zu halten. Die Behandlung erfolgt in Hallen auf versiegeltem Untergrund und die dabei freigesetzten Schad- und Geruchsstoffe werden gefasst und einer Abluftreinigung zugeführt. Nach der Vorbehandlung (Aussortierung von Störstoffen, Zugabe von Strukturmaterial, Durchmischung) mittels speziellem Aufbereitungsaggregat wurden insgesamt elf Behandlungsmieten aufgesetzt. Der Sauerstoffgehalt, Bodenfeuchte und Nährstoffgehalte wurden im Optimalbereich gehalten. Die Analysen und die Säulenversuche bestätigten die biologische Sanierbarkeit des Bodens. Die Abbauraten in den Säulenversuchen lagenzwischen 70,2% und 88,6% in 14 Tagen. Diese hohen Abbauraten lassen sich durch die Zusammensetzung der MKW begründen, die sich hauptsächlich aus gut abbaubaren n-Alkanen und iso-Alkanen bestehen. Die durchschnittliche Abbaurate bei den elf Behandlungsmieten lag bei 80,88%, wobei die niedrigste bei 54,71% und die höchste Abbaurate bei 97,97% lagen. Die statistische Auswertung ergab, dass sich die Mittelwerte der MKW-gehalte während der Behandlung signifikant voneinander unterscheiden (<0,01). Die im Rahmen dieser Arbeit durchgeführten Versuche bestätigen den erfolgreichen Einsatz des Terraferm® Verfahrens unter Umweltbedingungen des Bundesstaates São Paulo, Brasilien. Die starke Variabilität der Abbauraten in den Behandlungsmieten deutet aber auf einen weiteren Forschungsbedarf, insbesondere hinsichtlich des Temperatur-einflusses, hin. / Contaminações de solos com hidrocarbonetos de petróleo são um problema ambiental com abrangência mundial devido à alta demanda de produtos refinados de petróleo. As fontes são múltiplas e estão relacionadas à exploração, produção, armazenamento, transporte, distribuição e à destinação final de petróleo e seus derivados. Hoje o Brasil está iniciando um processo de avaliação e cadastramento de suas áreas contaminadas e, conseqüentemente, está procurando alternativas para a remediação das mesmas. Processos biológicos estão ganhando cada vez mais importância no tratamento, especialmente de solos contaminados com compostos orgânicos. Estes métodos são favorecidos por serem mais limpos, com custos baixos e de mais fácil aplicação em escala industrial. Assim, com o objetivo de verificar a aplicabilidade da biorremediação através do processo Terraferm® às condições ambientais do Estado de São Paulo, Brasil, foi realizada a remediação ex situ de uma área contaminada com TPH, chamada Mina de Argila na Refinaria de Paulínia – REPLAN da PETROBRÁS S/A, em Paulínia - SP. Foram analisadas dez amostras de solo contaminado em relação aos parâmetros físico-químicos TPH, PAH, BTEX, metais (Cr, Zn, Pb, Ni, Cu, Cd, As, Hg, Fe, Ta), umidade, pH, oxigênio e granulometria. Três amostras com valores médios de TPH foram submetidas a ensaios de coluna para verificação da biotratabilidade do material e para definição de parâmetros de controle do processo em escala industrial. Foram removidos um total de 72.384t de material contaminado. Deste total, 21.050t foram classificadas como resíduo classe II segundo a NBR 10004 e encaminhadas para um aterro sanitário, e 51.334t foram classificadas como resíduo classe I, sendo destinadas à estação de biorremediação das empresas SAPOTEC/ESTRE, em Paulínia - SP. O solo contaminado foi tratado com o processo Terraferm®, que visa à otimização dos parâmetros que influenciam diretamente a atividade microbiana necessária para a biodegradação. O tratamento é feito em galpões com piso impermeabilizado e com um sistema de captação e tratamento das emissões geradas durante o processo de biodegradação. Após o pré-tratamento em máquina especial, que consiste na separação dos materiais não-tratáveis, na homogeneização e na adição de material estrutural, o solo contaminado foi colocado em onze pilhas de tratamento. Os fatores chave como o teor de oxigênio, a umidade e os nutrientes foram mantidos nas faixas consideradas ótimas. A caracterização química e o ensaio de coluna comprovaram a biotratabilidade do solo. Noensaio em coluna, obteve-se taxas de degradação entre 70,2% e 88,6% em 14 dias. Essas taxas altas são explicadas pela composição do TPH que consiste, neste caso, basicamente de n-alcanos e iso-alcanos considerados de fácil degradação biológica. A taxa média de degradação obtida no tratamento das onze pilhas foi de 80,88%, sendo a menor de 54,71% e a maior de 97,97%. Na análise estatística, verificou-se que as médias das concentrações de TPH durante cada período de tratamento diferem significativamente (<0,01). O trabalho conclui que o processo Terraferm® foi aplicado com sucesso nas condições ambientais do Estado de São Paulo, Brasil. Entretanto, os resultados do tratamento mostram uma alta variabilidade das taxas de degradação nas pilhas, que indica a necessidade de novas pesquisas, especialmente sobre a influência da temperatura no processo. / Soil contaminations with petroleum hydrocarbons are a worldwide environmental problem due to the high demand for refined petroleum products. Contamination sources are multiple and related to the exploration, production, storage, transportation, distribution, and final disposal of petroleum and its derivatives. Nowadays Brazil is starting to assess and record its contaminated areas and consequently search for alternatives for their remediation. Biological processes are gaining more and more importance, specially in the treatment of soils contaminated by organic compounds. These methods are favored for being cleaner, with lower costs, and more easily applicable to industrial scale. Therefore, with the objective of verifying the applicability of bioremediation to the environmental conditions of São Paulo State, Brazil, the ex situ remediation of a contaminated area by TPH was carried out by using the Terraferm® process. The area called Mina de Argila was located in the Paulínia Refinery – REPLAN, which belongs to PETROBRÁS S/A (the country's leader in the exploration, production, and distribution of petroleum products). Ten samples of contaminated soil were analyzed in relation to the physical-chemical parameters TPH, PAH, BTEX, metals (Cr, Zn, Pb, Ni, Cu, Cd, As, Hg, Fe, Ta), humidity, pH, oxygen and texture. Three samples with average values of TPH were submitted to column tests in order to assess the material biotreatability and define the control parameters of the process on industrial scale. A total of 72,384t of contaminated soil were removed. From this total, 21,050t were classified as class II waste according to NBR 10004 and sent to a landfill, and 51,334t were classified as class I waste and sent to the bioremediation plant of the companies SAPOTEC/ESTRE, in Paulínia – São Paulo State. The contaminated soil was treated with the Terraferm® process whose purpose is to optimize the parameters which directly influence the microbial activity necessary for biodegradation. The treatment was carried out in sheds with waterproof floor and a collection and treatment system for the emissions generated in the biodegradation process. After the treatment in a special machine, which consists in separating non-treatable materials, homogenizing, and adding structural material, the soil was placed into eleven treatment piles. The oxygen content, humidity, and nutrients were kept within a range considered optimum. The chemical characterization and the column test proved the soil biotreatability. In the column test, the degradation rates were between 70.2% and 88.6% in 14 days. These high rates are due to the TPHcomposition, which in this case basically consists in n-alkenes and iso-alkenes of easy biological degradation. The average degradation rate verified in the treatment of the eleven piles was of 80.88%, the lowest being 54.71% and the highest 97.97%. In the statistical analysis, it was verified that the average concentrations of TPH during each treatment period differ significantly (<0.01). The conclusion of this work is that the Terraferm® process was successfully applied to the environmental conditions of São Paulo State. However, the treatment results show a high variability in the degradation rates of the piles, which indicates the need for further research, specially on the influence of temperature on the process.

Bodenkontaminationen durch Mineralölkohlenwasserstoffe sind ein weltweites Umweltproblem. Die Kontaminatiosquellen stehen im Zusammenhang mit Förderung, Lagerung, Transport, Verteilung und Endlagerung von Erdöl und Erdölprodukten. Brasilien beginnt zurzeit einen Prozess der Altlastenerfassung und –erkundung und in Konsequenz dessen auch die Suche nach geeigneten Sanierungstechniken. Biologische Prozesse spielen eine immer stärkere Rolle insbesondere bei der Sanierung von Bodenkontaminationen mit organischen Substanzen. Diese Prozesse gelten als “ökologisch korrekter” und sind im Vergleich mit anderen Techniken mit geringeren Kosten und technischen Aufwand durchführbar. Ziel dieser Arbeit war es, die Anwendungsmöglichkeiten der biologischen Bodensanierung mittels des Terraferm® Verfahrens unter den Umweltbedingungen des Bundesstaates São Paulo, Brasilien zu überprüfen. Zu diesem Zweck wurde der Boden einer MKW-kontaminierte Fläche (Mina de Argila) in der Raffinerie REPLAN der PETROBRÁS S/A in Paulínia -SP ausgekoffert. Es wurden zehn Bodenproben in Bezug auf ihre physikalisch-chemischen Eigenschaften MKW, PAK, BTEX, Metalle (Cr, Zn, Pb, Ni, Cu, Cd, As, Hg, Fe, Ta), Wassergehalt, pH, Korngröße analysiert. Drei Proben mit durchschnittlichen MKW-gehalten wurden zur Überprüfung der biologischen Sanierbarkeit und der Bestimmung der Kontrollparameter für den später Sanierungsdurchführung Säulenversuchen unterzogen. Insgesamt wurden 72.384t kontaminierten Bodens ausgekoffert, wovon 21.050t der Abfallklasse II (nach NBR 10004) zugeordnet wurden und direkt auf eine Mülldeponie verbracht wurden. Es wurden 51.334t der Abfallklasse 1 in die Bodenreinigungsanlage der Firmen SAPOTEC/ESTRE in Paulínia - SP mittels des Terraferm® Verfahrens behandelt. Dieses Verfahren ist darauf ausgelegt, alle für den biologischen Abbau nötigen Prozessparameter im Optimum zu halten. Die Behandlung erfolgt in Hallen auf versiegeltem Untergrund und die dabei freigesetzten Schad- und Geruchsstoffe werden gefasst und einer Abluftreinigung zugeführt. Nach der Vorbehandlung (Aussortierung von Störstoffen, Zugabe von Strukturmaterial, Durchmischung) mittels speziellem Aufbereitungsaggregat wurden insgesamt elf Behandlungsmieten aufgesetzt. Der Sauerstoffgehalt, Bodenfeuchte und Nährstoffgehalte wurden im Optimalbereich gehalten. Die Analysen und die Säulenversuche bestätigten die biologische Sanierbarkeit des Bodens. Die Abbauraten in den Säulenversuchen lagenzwischen 70,2% und 88,6% in 14 Tagen. Diese hohen Abbauraten lassen sich durch die Zusammensetzung der MKW begründen, die sich hauptsächlich aus gut abbaubaren n-Alkanen und iso-Alkanen bestehen. Die durchschnittliche Abbaurate bei den elf Behandlungsmieten lag bei 80,88%, wobei die niedrigste bei 54,71% und die höchste Abbaurate bei 97,97% lagen. Die statistische Auswertung ergab, dass sich die Mittelwerte der MKW-gehalte während der Behandlung signifikant voneinander unterscheiden (<0,01). Die im Rahmen dieser Arbeit durchgeführten Versuche bestätigen den erfolgreichen Einsatz des Terraferm® Verfahrens unter Umweltbedingungen des Bundesstaates São Paulo, Brasilien. Die starke Variabilität der Abbauraten in den Behandlungsmieten deutet aber auf einen weiteren Forschungsbedarf, insbesondere hinsichtlich des Temperatur-einflusses, hin. / Contaminações de solos com hidrocarbonetos de petróleo são um problema ambiental com abrangência mundial devido à alta demanda de produtos refinados de petróleo. As fontes são múltiplas e estão relacionadas à exploração, produção, armazenamento, transporte, distribuição e à destinação final de petróleo e seus derivados. Hoje o Brasil está iniciando um processo de avaliação e cadastramento de suas áreas contaminadas e, conseqüentemente, está procurando alternativas para a remediação das mesmas. Processos biológicos estão ganhando cada vez mais importância no tratamento, especialmente de solos contaminados com compostos orgânicos. Estes métodos são favorecidos por serem mais limpos, com custos baixos e de mais fácil aplicação em escala industrial. Assim, com o objetivo de verificar a aplicabilidade da biorremediação através do processo Terraferm® às condições ambientais do Estado de São Paulo, Brasil, foi realizada a remediação ex situ de uma área contaminada com TPH, chamada Mina de Argila na Refinaria de Paulínia – REPLAN da PETROBRÁS S/A, em Paulínia - SP. Foram analisadas dez amostras de solo contaminado em relação aos parâmetros físico-químicos TPH, PAH, BTEX, metais (Cr, Zn, Pb, Ni, Cu, Cd, As, Hg, Fe, Ta), umidade, pH, oxigênio e granulometria. Três amostras com valores médios de TPH foram submetidas a ensaios de coluna para verificação da biotratabilidade do material e para definição de parâmetros de controle do processo em escala industrial. Foram removidos um total de 72.384t de material contaminado. Deste total, 21.050t foram classificadas como resíduo classe II segundo a NBR 10004 e encaminhadas para um aterro sanitário, e 51.334t foram classificadas como resíduo classe I, sendo destinadas à estação de biorremediação das empresas SAPOTEC/ESTRE, em Paulínia - SP. O solo contaminado foi tratado com o processo Terraferm®, que visa à otimização dos parâmetros que influenciam diretamente a atividade microbiana necessária para a biodegradação. O tratamento é feito em galpões com piso impermeabilizado e com um sistema de captação e tratamento das emissões geradas durante o processo de biodegradação. Após o pré-tratamento em máquina especial, que consiste na separação dos materiais não-tratáveis, na homogeneização e na adição de material estrutural, o solo contaminado foi colocado em onze pilhas de tratamento. Os fatores chave como o teor de oxigênio, a umidade e os nutrientes foram mantidos nas faixas consideradas ótimas. A caracterização química e o ensaio de coluna comprovaram a biotratabilidade do solo. Noensaio em coluna, obteve-se taxas de degradação entre 70,2% e 88,6% em 14 dias. Essas taxas altas são explicadas pela composição do TPH que consiste, neste caso, basicamente de n-alcanos e iso-alcanos considerados de fácil degradação biológica. A taxa média de degradação obtida no tratamento das onze pilhas foi de 80,88%, sendo a menor de 54,71% e a maior de 97,97%. Na análise estatística, verificou-se que as médias das concentrações de TPH durante cada período de tratamento diferem significativamente (<0,01). O trabalho conclui que o processo Terraferm® foi aplicado com sucesso nas condições ambientais do Estado de São Paulo, Brasil. Entretanto, os resultados do tratamento mostram uma alta variabilidade das taxas de degradação nas pilhas, que indica a necessidade de novas pesquisas, especialmente sobre a influência da temperatura no processo. / Soil contaminations with petroleum hydrocarbons are a worldwide environmental problem due to the high demand for refined petroleum products. Contamination sources are multiple and related to the exploration, production, storage, transportation, distribution, and final disposal of petroleum and its derivatives. Nowadays Brazil is starting to assess and record its contaminated areas and consequently search for alternatives for their remediation. Biological processes are gaining more and more importance, specially in the treatment of soils contaminated by organic compounds. These methods are favored for being cleaner, with lower costs, and more easily applicable to industrial scale. Therefore, with the objective of verifying the applicability of bioremediation to the environmental conditions of São Paulo State, Brazil, the ex situ remediation of a contaminated area by TPH was carried out by using the Terraferm® process. The area called Mina de Argila was located in the Paulínia Refinery – REPLAN, which belongs to PETROBRÁS S/A (the country's leader in the exploration, production, and distribution of petroleum products). Ten samples of contaminated soil were analyzed in relation to the physical-chemical parameters TPH, PAH, BTEX, metals (Cr, Zn, Pb, Ni, Cu, Cd, As, Hg, Fe, Ta), humidity, pH, oxygen and texture. Three samples with average values of TPH were submitted to column tests in order to assess the material biotreatability and define the control parameters of the process on industrial scale. A total of 72,384t of contaminated soil were removed. From this total, 21,050t were classified as class II waste according to NBR 10004 and sent to a landfill, and 51,334t were classified as class I waste and sent to the bioremediation plant of the companies SAPOTEC/ESTRE, in Paulínia – São Paulo State. The contaminated soil was treated with the Terraferm® process whose purpose is to optimize the parameters which directly influence the microbial activity necessary for biodegradation. The treatment was carried out in sheds with waterproof floor and a collection and treatment system for the emissions generated in the biodegradation process. After the treatment in a special machine, which consists in separating non-treatable materials, homogenizing, and adding structural material, the soil was placed into eleven treatment piles. The oxygen content, humidity, and nutrients were kept within a range considered optimum. The chemical characterization and the column test proved the soil biotreatability. In the column test, the degradation rates were between 70.2% and 88.6% in 14 days. These high rates are due to the TPHcomposition, which in this case basically consists in n-alkenes and iso-alkenes of easy biological degradation. The average degradation rate verified in the treatment of the eleven piles was of 80.88%, the lowest being 54.71% and the highest 97.97%. In the statistical analysis, it was verified that the average concentrations of TPH during each treatment period differ significantly (<0.01). The conclusion of this work is that the Terraferm® process was successfully applied to the environmental conditions of São Paulo State. However, the treatment results show a high variability in the degradation rates of the piles, which indicates the need for further research, specially on the influence of temperature on the process.

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Κατά τις τελευταίες δεκαετίες παρατηρείται συνεχής αύξηση της έντασης του φαινομένου του θερμοκηπίου γεγονός που προκαλεί σημαντικές συνέπειες στο περιβάλλον και στη ζωή μας γενικότερα. Συνεπώς, είναι απαραίτητη η μείωση της ανθρωπογενούς εκπομπής των αερίων που συμβάλλουν στην αύξηση του φαινομένου αυτού. Η εκμετάλλευση και χρήση των δύο πιο σημαντικών θερμοκηπικών αερίων, του μεθανίου και του διοξειδίου του άνθρακα, μπορεί να επιτευχθεί με την αναμόρφωση του CH4 με CO2 ή αλλιώς ξηρή αναμόρφωση του μεθανίου (Dry Reforming of Methane-DRM). Με τη διεργασία DRM τα δύο συγκεκριμένα αέρια μετατρέπονται σε αέριο σύνθεσης (synthesis gas), το οποίο χρησιμοποιείται είτε για τη σύνθεση πληθώρας οργανικών ενώσεων, είτε για την παραγωγή Η2 για ενεργειακούς σκοπούς. Η DRM παρουσιάζει σημαντικά πλεονεκτήματα: δεν απαιτείται η χρήση ύδατος, φθηνό σχετικά κόστος εγκαταστάσεων, χρησιμοποιείται σε χημικά συστήματα μεταφοράς ενέργειας, ενώ και το αέριο σύνθεσης που παράγεται έχει ακόμα κατάλληλη αναλογία για συνθέσεις Fischer–Tropsch. Παρόλα αυτά η DRM δεν έχει εκτεταμένη βιομηχανική εφαρμογή επειδή αντιμετωπίζει ένα σημαντικό μειονέκτημα: ο καταλύτης μετά από κάποιο χρόνο λειτουργίας απενεργοποιείται λόγω του άνθρακα που αποτίθεται πάνω του. Στην παρούσα εργασία μελετήθηκε ο state of the art καταλύτης Ni/Al2O3, τον οποίο τροποποιήσαμε με βόριο σε διάφορους λόγους [Β/(B+Νi)] με κύριο στόχο τη μείωση των ανθρακούχων αποθέσεων. Οι τροποποιημένοι καταλύτες συντέθηκαν με τη μέθοδο του υγρού συνεμποτισμού και χαρακτηρίστηκαν φυσικοχημικά με διάφορες τεχνικές, ώστε να μελετήσουμε την επίδραση του βορίου στην υφή τους (ΒΕΤ, porosimetry, SEM, TEM), στη δομή τους (XRD, UV-Vis DRS) και στην αναγωγιμότητά τους (H2-TPR). Η καταλυτική συμπεριφορά τους για την αντίδραση της ξηρής αναμόρφωσης του μεθανίου αξιολογήθηκε σε αντιδραστήρα σταθερής κλίνης, για 24h, σε συνθήκες: 973Κ, 1 atm, τροφοδοσία 50%CH4-50%CO2. Ο άνθρακας που αποτέθηκε στους χρησιμοποιημένους καταλύτες μετρήθηκε με τη μέθοδο της θερμοπρογραμματισμένης υδρογόνωσης (TPH). Τα ανηγμένα και χρησιμοποιημένα στην DRM καταλυτικά δείγματα μελετήθηκαν επίσης με ηλεκτρονικό μικροσκόπιο σάρωσης (SEM με αναλυτή EDS) και ηλεκτρονικό μικροσκόπιο διαπερατότητας (ΤΕΜ). Βρέθηκε ότι η παρουσία του Β μειώνει σημαντικά την ποσότητα του αποτιθέμενου άνθρακα στους καταλύτες Ni/Al2O3, σε ποσοστό έως και 86%, χωρίς να επηρεάζει ιδιαίτερα τη δραστικότητα και την εκλεκτικότητα των καταλυτών. Σημαντικό ρόλο παίζει το ποσοστό του Β στον καταλύτη, με τον καταλύτη με λόγο Β/(B+Νi) = 0,5 να εμφανίζει τη βέλτιστη συμπεριφορά. Τα αποτελέσματα μας έδειξαν ότι η ιδιαίτερη θετική επίδραση του βορίου οφείλεται κυρίως στο γεγονός ότι ευνοεί τη διασπορά του μεταλλικού νικελίου. Τροποποίηση με βόριο, σε κατάλληλη περιοχή φορτίσεων, του καταλύτη Ni/Al2O3 μεγιστοποιεί το πλήθος των νανοσωματιδίων νικελίου με μέση διάσταση < 6.0 nm, τα οποία, ως γνωστόν, ελαχιστοποιούν την απόθεση άνθρακα. / The intensity of the greenhouse effect is constantly increasing in the last few decades with an adverse effect both on the environment and the humanity. In order to decrease the effect, human-caused emissions should be minimized. The two most important greenhouse gases, methane and carbon dioxide, can be used in the DRM (Dry Reforming of Methane) process. With this process the above mentioned gases are converted to synthesis gas, which is then used for the synthesis of a great number of organic compounds and synthetic fuels (through the Fisher-Tropsch syntheses) or for the production hydrogen to be used as a fuel (energy purposes). The DRM process presents a number of advantages, namely: no water is required, relatively low cost of process plants,it can be used as a Chemical Energy Transfer System and, finally, the produced synthesis gas has adequate CO/H2 ratio for Fisher-Tropsch syntheses. Although DRM is a promising process, its industrial application is hindered by a major drawback: the catalysts are rapidly deactivating due to coking. In the current study, the state of the art catalyst Ni/Al2O3 was studied and modified with boron, using different ratios of Β/(B+Νi). Our primary objective was to reduce coking. The modified catalysts were synthesized by wet co-impregnation and physicochemically characterized in their oxidic, reduced and used forms, using various techniques, in order to investigate the influence of boron on the texture (BET, Porosimetry, SEM, TEM), structure (XRD, UV-Vis DRS) and reducibility (H2-TPR) of the catalysts. The catalytic performance for the DRM process was studied under stable conditions (973Κ, 1 atm and 50%CH4-50%CO2 undiluted feed), for 24h, using a fixed bed reactor. Carbonaceous deposits on the used catalysts were determined by Temperature Programmed Hydrogenation (TPH). Scanning Electron Microscopy (SEM) with EDS analyser and Transmission Electron Microscopy (TEM) were also used in the study of reduced and used catalytic samples. Modifying Ni/Al2O3 catalysts with boron results in a great decrease of the deposited coke (up to 86%), without any significantly influence on the activity and selectivity of the catalysts. A major factor influencing the catalyst is the B loading, with the ratio Β/(B+Νi)=0,5 giving the best results. Boron’s positive effect was mainly attributed to its ability to increase Ni dispersion. Modification of Ni/Al2O3 catalysts, by using the appropriate boron loading, resulted to an increase of the amount of nickel nanoparticles with an average dimension under 6.0 nm, which are known to minimize coke deposition.

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2016-05-02T17:58:54Z No. of bitstreams: 1 GALLOTTA_30_06_14.pdf: 62695484 bytes, checksum: 33335ee3affc2bcffb11fc10caf9ae3f (MD5) / Made available in DSpace on 2016-05-02T17:58:54Z (GMT). No. of bitstreams: 1 GALLOTTA_30_06_14.pdf: 62695484 bytes, checksum: 33335ee3affc2bcffb11fc10caf9ae3f (MD5) / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências-Geoquímica. Niterói, RJ / Os hidrocarbonetos presentes no ambiente consistem em misturas complexas de compostos derivados de múltiplas fontes. Os combustíveis fósseis representam a principal contribuição, devido à taxa e escala espacial, em que o petróleo tem sido usado como fonte de energia e matéria-prima para a indústria química. O objetivo deste estudo foi avaliar os níveis de concentração e identificar fontes de hidrocarbonetos na Bacia do Alto Iguaçu e, em especial, na área de influência da Refinaria Presidente Getúlio Vargas (REPAR). Além dos fatores de poluição crônica, a área de estudo foi alvo de um derrame acidental de petróleo em julho de 2000. Diversos indicadores em diferentes compartimentos ambientais (água superficial, sedimento, solo e água subterrânea) foram avaliados na fase pós-derrame e no monitoramento ambiental ao longo de várias campanhas por mais de uma década. Os esforços de avaliação foram concentrados nos seguintes indicadores: os nalcanos, os alcanos isoprenoides, os hidrocarbonetos policíclicos aromáticos (HPA), os biomarcadores de petróleo e ainda o total de hidrocarbonetos de petróleo (THP). Os resultados identificaram como principal aporte de matéria orgânica para as águas superficiais dos rios Barigüi e Iguaçu, os fluxos materiais originados em região a montante do acidente, refletindo a contribuição antropogênica crônica da cidade de Curitiba. Em 2007 e 2008, as concentrações de THP e HPA nas águas superficiais e sedimentos dos rios Barigüi e Iguaçu refletem uma expressiva melhoria nas condições desses rios em relação a 2000. Na área interna da refinaria (Ponto Zero), observou-se uma nítida diminuição (atenuação) natural das concentrações de THP no solo em todas as profundidades dos perfis amostrados ao longo do tempo nos Banhados 1 e 4 e, em particular, uma diminuição importante das concentrações entre 2004 e 2007. Para a identificação das fontes de hidrocarbonetos foram utilizadas razões diagnósticas e quimiometria. As razões diagnósticas calculadas a partir de concentrações de HPA sugeriram que, na maioria dos sedimentos dos Rios Barigüi e Iguaçu coletados nas campanhas de 2000 e 2001, a fonte petrogênica é a principal. Somente na estação a montante do acidente no Rio Barigüi, a fonte pirolítica predominou nestas duas campanhas. As razões diagnósticas que apresentaram maior eficiência na identificação de fontes de hidrocarbonetos nos sedimentos dos rios Barigüi e Iguaçu foram: ΣC1-Fenantrenos/Fenantreno; e (ΣHPA parentais de 3-6 anéis)/(Σ5 séries de HPA alquilados). A identificação de fontes através de razões diagnósticas calculadas a partir de áreas e alturas de picos cromatográficos demonstrou sua aplicabilidade verificando a relação entre os compostos encontrados em amostras de solo da área interna da refinaria com a amostra de petróleo derramado no acidente, após quase uma década da ocorrência do vazamento. A identificação de fontes através método de quimiométrico baseado na análise de componentes principais (ACP) de seções pré-processadas e combinadas dos Cromatogramas de Íons Selecionados (CIS) mostrou que as amostras mais contaminadas estão na área interna da refinaria. Essas amostras apresentam um padrão de distribuição petrogênica e diferentes graus de intemperismo. As amostras da área externa à refinaria (Guajuvira, General Lúcio e Balsa Nova) são menos ou não contaminadas e/ou contém uma mistura de contribuições diagenéticas, pirolíticas e petrogênicas onde predominam diferentes proporções. Os locais mais distantes da atividade industrial (Balsa Nova) contem, como esperado, os níveis mais baixos de contaminação por HPA. Os resultados de biomarcadores demonstraram que não há evidências para concluir que as amostras da área externa à refinaria e o óleo Cusiana vazado tenham a mesma origem. Os resultados ao longo dos rios Barigüi e Iguaçu e do Ponto Zero demonstraram que as ações de emergência para a contenção do óleo foram adequadas para os rios, e que a contaminação decorrente do derrame ficou predominantemente contida no Ponto Zero e diminuiu significativamente após uma década. / Hydrocarbons present in the environment consist of complex mixtures of compounds derived from multiple sources. The main contribution lies on fossil fuel inputs due to the rate and spatial scale by which petroleum has been used as an energy source and chemical feedstock. The aim of this study was to assess the concentration levels and identify sources of hydrocarbons in the Upper Iguaçu Watershed and, in particular, in the area of influence of the President Getulio Vargas Refinery (REPAR). In addition to the factors of chronic pollution, the study area was the scenario of an acute accidental oil spill in July 2000. Numerous indicators in different environmental compartments (surface water, sediment, soil and groundwater) were assessed in the post spill phase and during the environmental monitoring programs over the course of several campaigns for more than a decade. Assessment efforts were concentrated on the following indicators: n-alkanes, alkanes isoprenoids, polycyclic aromatic hydrocarbons (PAH), petroleum biomarkers and total petroleum hydrocarbons (TPH). The results identified as the main contribution of organic matter to surface waters of the Barigüi and Iguaçu Rivers the materials flows originated in the region upstream of the accident, reflecting chronic anthropogenic contribution of the city of Curitiba. In 2007 and 2008, the TPH and PAH concentrations in surface waters and sediments of the Barigüi and Iguaçu Rivers revealed a significant improvement in the conditions of these rivers when compared with 2000. Inside the refinery area (Point Zero), it was observed a clear natural decrease (attenuation) of the concentrations of TPH in the soil at all depths sampled over time in Marshes 1 and 4 and, in particular, an important decrease of concentrations between 2004 and 2007. Diagnostic ratios and chemometrics were used to identity hydrocarbon sources. The diagnostic ratios calculated from the concentrations of PAH suggested that, in the majority of sediments from the Barigüi and Iguaçu Rivers collected in 2000 and 2001 campaigns, the main source is petrogenic. Only in the station upstream the accident in the Barigüi River, the pyrolytic source predominated in these two campaigns. The diagnostic ratios that presented higher efficiency in identifying sources of hydrocarbons in sediments of the Barigüi and Iguaçu Rivers were: ΣC1- Phenantrenes/Phenanthrene; and (Σ3-6 rings parental PAH)/(Σ5 alkylated PAH series). The source identification through diagnostic ratios calculated from heights and areas of chromatographic peaks demonstrated its applicability establishing a relationship between the compounds found in soil samples of the internal area of the refinery and the sample of the oil spilled in the accident, after nearly a decade of occurrence of the spillage. The source identification through chemometric method based on principal components analysis (PCA) of preprocessed and combined sections of Selected Ion Chromatograms (SIC) showed that the most contaminated samples are inside the refinery area. These samples present a petrogenic pattern and different weathering degrees. Samples from outside the refinery area (Guajuvira, General Lúcio e Balsa Nova) are either less or not contaminated, and/or contain mixtures of diagenetic, pyrogenic and petrogenic inputs where different proportions predominate. The locations farthest away from industrial activity (Balsa Nova) contain, as expected, the lowest levels of PAH contamination. The biomarkers results do not show any evidences to conclude positive matches between the samples from outside the refinery area and the spilled Cusiana oil. The results along Barigüi and Iguaçu rivers and Point Zero demonstrated that emergency actions to contain the oil were appropriate for the rivers, and that the contamination resulting from the spill was mostly contained in the Point Zero and decreased significantly after one decade