A poluição dos corpos d\'água é de grande preocupação mundial, pois a maioria da população utiliza a água doce de reservatórios, represas ou rios como principal fonte de água potável. A presença no Brasil de florações de cianobactérias capazes de produzir anatoxina-a, revela a necessidade de métodos simples e rápidos que permitam sua detecção e monitoramento. Neste trabalho foram desenvolvidos, otimizados e validados dois métodos analíticos por GC/MS para identificação e quantificação de anatoxina-a em amostras de água e florações, respectivamente. A norcocaína foi usada como padrão interno em ambos os métodos. Os íons escolhidos para serem monitorados foram (íons quantificadores sublinhados): anatoxina-a: 191,164, 293 e norcocaína: 195, 136, 168. As curvas de calibração dos métodos mostraram-se lineares nas faixas de 2.5-200 ng.mL-1 e 13-250 ng.mg-1. Os limites de detecção obtidos foram 2 ng.mL-1 e 10 ng.mg-1. Os métodos demonstraram sensibilidade e especificidade adequada para seu uso no monitoramento ambiental da anatoxina-a. / The water pollution is a big concern around the world, since the most of cities use freshwater reservoirs, dams or rivers as the main drinking water suppliers. Cyanobacterial blooms capable to produce anatoxin-a are regularly present in Brazilian waters. Therefore, there is a necessity of simple and rapid analytical methods to monitor this cyanotoxin. In the present work, two analytical methods by GC/MS for identification and quantification of anatoxin-a in water and algae bloom samples were developed, optimized and validated. Norcocaine was used as internal standard in both methods. The ions chosen to be monitorated were (quantification ions underlined): anatoxin-a 191, 164, 293 and norcocaine: 195, 136, 168. Both method calibration curves showed linearity in the ranges of: 2.5-200 ng.mL-1 and 13-250 ng.mg-1. The obtained limit of detection were: 2 ng.mL-1 and 10 ng.mg-1. The methods showed sensitivity and specificity enough to be used routinely as a tool for anatoxin-a monitoring.

Waste plastic treatment was a global issue currently. A sustainable recycling process was required to recovery the monomer units from the polymer, thus avoiding environmental impacts due to disposal and enhancing the economic benefit from the recovered products. Pyrolysis was one of the promising process and previous MQP group has studied the pyrolysis with molten salts. In this work, a standardized and optimized pyrolysis reaction process of polystyrene was developed, based on the previous work on molten salt pyrolysis 5. The literature of pyrolysis mechanism and catalytic effects were reviewed as a guide process design. The orientation of the reactor was standardized to be consistent with literature record of preceding work. The positioning of the flow tube for the carrier gas and thermocouple were standardized in locations to provide mixing process of the reactant, the removal of products, and the accurate measurement of reaction temperature. The product collection system was also investigated and optimized to maximize collection efficiency while avoiding excessively low temperatures. The experiment results with standardized reaction configuration showed an improved styrene yield, 65%, compared with a previous yield of 44%. Then with the standardized reaction configuration, the catalytic effects of molten salt were studied at 400℃ pyrolysis temperature. Quantitative analysis indicated that the molten salt improved the styrene selectivity of the monomer compared to the dimer. Analysis of product composition and mass balance indicated formation of heavy non-GC detectable species in the liquid products. Gas phase secondary reaction during pyrolysis, and re-polymerization inside the liquid products, were discussed to explain the different styrene yield and the existence of heavy species. Based on the current results, recommendations for the pyrolysis temperature, initial reactants loading, and condenser temperature and analysis strategies were provided for further study of the molten salt pyrolysis of polystyrene.

Neste estudo determinou-se o nonilfenol - um composto xenobiótico utilizados na fabricação de antioxidantes, aditivos para óleos lubrificantes e produção de surfactantes etoxilados - e o bisfenol A - um composto químico utilizado na produção de diversos produtos, como, plásticos policarbonatos, resinas epóxi e retardantes de chama. Ambos exibem atividade estrogênica em concentrações abaixo de 1ng L-1 - em cinco pontos de coleta na cidade de Americana, SP. Devido à ampla utilização, esses compostos estão presentes em esgoto industrial em quantidades substanciais. A primeira etapa deste estudo foi a validação dos método analítico seguindo o Método 8270D da United States Environmental Protection Agency (USEPA) que descreve o procedimento de validação para os compostos semivoláteis analisados por cromatografia gasosa acoplada a espectrometria de massas (GC/MS). Os limites de detecção e de quantificação do método para a determinação do nonilfenol foram, respectivamente, 1 e 5 µg L-1. O coeficiente de determinação (R2) e a recuperação média para o nonilfenol foram, respectivamente, 0,99 e 99,04%. Os limites de detecção e de quantificação do método para o bisfenol A foram, respetivamente, 1 e 5 µg L-1. O coeficiente de determinação (R2) e a recuperação média para o bisfenol A foram, respectivamente, 0,99 e 91,55%. Na segunda etapa desta pesquisa analisaram-se amostras de água coletadas na cidade de Americana para a determinação do nonilfenol e do bisfenol A. Como método de extração dos compostos, usou-se a extração em fase sólida (SPE) e como técnica analítica a cromatografia gasosa acoplada a espectrometria de massas (GC/MS). Os resultados indicaram a presença desses compostos em alguns pontos de amostragem sendo que a concentração do nonilfenol a variou de 5,028 a 10,524 µg L-1 e para o bisfenol A a concentração variou de 5,645 a 295,255 µg L-1. Foram feitos também testes ecotoxicólogicos utilizando como organismo teste o microcrustáceo Daphnia similis, porém o nonilfenol e o bisfenol A, na concentração testada que variou de 0,05 a 500 µg L-1 não apresentaram toxicidade aguda. / In this study it was determined nonylphenol - a xenobiotic compound used in the manufacture of antioxidants, additives for lubricating oils and production of ethoxylated surfactant - and bisphenol A - a chemical compound used in production of various products, such as polycarbonate plastic, epoxy resins and flame retardants. Both exhibit estrogenic activity at concentrations lower than 1 ng L-1 - in five sampling points in the city of Americana, SP. Due to the widespread use of these compounds, they are present in substantial quantities in industrial sewage. The first step of this study was to validate the analytical method following the Method 8270D of the United States Environmental Protection Agency (USEPA) that describes the validation procedure for semi-volatile compounds analized by gas chromatography-mass spectrometry (GC/MS). The limits of detection and quantification for determining the nonylphenol were, respectively, 1 and 5 µg L-1. The coefficient ofdetermination (R2) and recovery for nonylphenol were respectively 0.99 and 99.04%. The limits of detection and quantification for the bisphenol A were, respectively, 1 and 5 µg L-1. The coefficient of determination (R2) and recovery for bisphenol A were respectively 0.99 and 91.55%. In the second step of this study were analized in water samples of Americana city for the determination of nonylphenol and bisphenol A. As a method of extraction of the compounds it was used solid-phase extraction (SPE) and as analytical technique GC/MS. The results indicated the presence of such compounds in some sampling points and the concentration of nonylphenol ranged from 5.028 to 10.524 µg L-1 and bisphenol A concentration ranged from 5.645 to 295.255 µg L-1. Ecotoxicological tests were also performed using as test organism microcrustaceans Daphnia similis, but nonylphenol and bisphenol A, tested at concentration ranging from 0,05 to 500 µg L-1 showed no acute toxicity.

Compostos butílicos de estanho (BTs) estão na lista dos contaminantes impactantes relacionados ao ambiente marinho. Sua ampla distribuição associada à elevada toxicidade faz com que o monitoramento desses compostos no ambiente costeiro seja de fundamental importância. A ocorrência de BTs foi verificada em sedimentos superficiais, material particulado em suspensão e nos tecidos (fígado e brânquias) de três espécies de bagres estuarinos: Cathorops spixii, Aspistor luniscutis e Genidens genidens; amostrados em 8 estuários da região sul e sudeste brasileira. As análises foram realizadas através de GC-PFPD, seguindo padrões de controle de qualidade analítico e onde foi constatada a ocorrência de efeito matriz sobre o sistema analítico a partir da quantificação das amostras de tecido. Dentre os estuários amostrados, verificou-se um maior impacto dos BTs sobre os sistemas estuarinos de Paranaguá e Itajaí, em decorrência da presença destes compostos em todos os compartimentos ambientais analisados. As três espécies investigadas puderam ser consideradas como biomonitoras da presença de BTs no ambiente, uma vez que são passíveis de assimilação destes compostos, mesmo em organismos amostrados em regiões distantes de potencias fontes de entrada. Os efeitos sobre a fisiologia de C. spixii amostrado em Paranaguá também foi investigada a partir do uso de biomarcadores no fígado desses organismos, constatando um impacto associado à presença destes contaminantes no sistema. / Butyltin compounds (BTs) are in the list of related contaminants striking marine environment. Their widespread distribution associated with high toxicity causes the monitoring of fundamental importance. The occurrence of BTs were checked through superficial sediments, suspended particulate matter and tissues (liver and gill) analysis on three estuarine catfishes: Cathorops spixii, Aspistor luniscutis e Genidens genidens; sampled in eight estuaries from Brazilian south and southeast coast. Analysis were carried by GC-PFPD, following quality control procedures, where was verified the presence of matrix effect over the system from tissues quantification. Among estuaries, the major impact was found in Paranaguá-PR and Itajaí-SC, due the presence of these compounds in all investigated compartments. These three catfish species have shown good biomonitors of BTs presence once were liable of uptake, even in groups sampled far from potential BTs sources. The effects over C. spixii physiology were also checked in Paranaguá from the use of biomarkers on liver of these organisms, noting the impact related with the presence of these compounds on the system.

The biggest limitation to conventional gas chromatography (GC) is limited peak capacity, making the analysis of complex mixtures a difficult or even impossible task. Comprehensive two-dimensional gas chromatography (GC×GC) significantly increases peak capacity and resolution, improves sensitivity and generates structured 3D chromatograms. This is achieved by connecting two columns coated with different stationary phases through a special interface (modulator). The interface samples the first column effluent and periodically injects fractions of this material, as narrow injection pulses, onto the second column for further separation. Commercial instruments achieve this with cryogenic agents. Since this expensive approach permits only in-laboratory analysis, the development of simple, economical and field-capable GC×GC systems is in demand. This report summarizes the fundamentals governing GC×GC separations and a brief history of technological advances in the field. It also documents the construction of a simple interface, devoid of moving parts and cryogenic consumables, and hence highly suitable for field analysis and monitoring applications. Evaluation of the interface suggests on-par performance with more complicated cryogenic modulators. GC×GC separations of technical mixtures of fatty acid methyl esters (FAMEs), common environmental pollutants (EPA 8270), polychlorinated biphenyls (PCBs), pesticides (toxaphene), as well as selected essential oils and major distillation fractions of crude oil indicate very good performance. Most notably, the interface prototype was applied for the first ever time-resolved on-site analysis of the semivolatile organic fraction of urban air particulate matter (PM2.5).

The biggest limitation to conventional gas chromatography (GC) is limited peak capacity, making the analysis of complex mixtures a difficult or even impossible task. Comprehensive two-dimensional gas chromatography (GC×GC) significantly increases peak capacity and resolution, improves sensitivity and generates structured 3D chromatograms. This is achieved by connecting two columns coated with different stationary phases through a special interface (modulator). The interface samples the first column effluent and periodically injects fractions of this material, as narrow injection pulses, onto the second column for further separation. Commercial instruments achieve this with cryogenic agents. Since this expensive approach permits only in-laboratory analysis, the development of simple, economical and field-capable GC×GC systems is in demand. This report summarizes the fundamentals governing GC×GC separations and a brief history of technological advances in the field. It also documents the construction of a simple interface, devoid of moving parts and cryogenic consumables, and hence highly suitable for field analysis and monitoring applications. Evaluation of the interface suggests on-par performance with more complicated cryogenic modulators. GC×GC separations of technical mixtures of fatty acid methyl esters (FAMEs), common environmental pollutants (EPA 8270), polychlorinated biphenyls (PCBs), pesticides (toxaphene), as well as selected essential oils and major distillation fractions of crude oil indicate very good performance. Most notably, the interface prototype was applied for the first ever time-resolved on-site analysis of the semivolatile organic fraction of urban air particulate matter (PM2.5).

No description available.

Submitted by Reginaldo Soares de Freitas (reginaldo.freitas@ufv.br) on 2016-09-27T12:30:49Z No. of bitstreams: 1 texto completo.pdf: 357938 bytes, checksum: f975d715fb6efe1c76a16c8780062ffc (MD5) / Made available in DSpace on 2016-09-27T12:30:50Z (GMT). No. of bitstreams: 1 texto completo.pdf: 357938 bytes, checksum: f975d715fb6efe1c76a16c8780062ffc (MD5) Previous issue date: 2001-04-06 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Foi obtido o tempo de retenção (tr) e o espectro de massas em cromatografia gasosa acoplado a espectrometria de massas de 76 acetatos lineares monoinsaturados (19 dodecenila, 23 tetradecenila, 22 hexadecenila e 12 octadecenila) em três colunas capilares de fases estacionárias diferentes [DB-1 (apolar), Supelcowax-10 (polar) e SP 2340 (altamente polar)]. Os dados obtidos foram utilizados na construção de um banco de dados no software do CG-EM, de modo a verificar a presença dos acetatos monoinsaturados em extratos bruto de glândulas de E. lignosellus e P. sequax. A cromatografia gasosa-espectrometria de massas (“CG-EM”) foi utilizada para a identificação dos acetatos, e cromatografia gasosa-eletroantenografia (“CG-DEA”) para identificar as substâncias ativas, onde foi possível identificar o acetato de (Z)-hexadec-11-enila pela “CG-EM” e acetatos de (Z)-tetradec-9-enila e (Z)-hexadec-11-enila pela “CG-DEA” que se mostraram ativos a antenas de E. lignosellus. / The retention times (tr) and the mass spectrum in gas chromatography coupled to mass spectrometry were obtained for 76 linear monounsaturated acetates (19 dodecenyl, 23 tetradecenyl, 22 hexadecenyl and 12 octadecenyl) with three capillary columns of different stationary phases [DB-1 (non-polar), Supelcowax-10 (polar) and SP 2340 (highly polar)]. The obtained data were used in the construction of a database in the software of the GC-MS, in way to verify the presence of monounsaturated acetates in rude extracts of glands of E. lignosellus and P. sequax. The gas chromatography-mass spectrometry (GC-MS) was used for the identification of the acetates, and gas chromatography- eletroantenography (GC-EAD) to identify the active substances, where was possible to identify the (Z)-hexadec-11-enyl acetate by GC-MS, the (Z)-tetradec- 9-enyl and (Z)-hexadec-11-enyl acetates by CG-DEA, that were shown to be active to antennas of E. lignosellus.

Compostos butílicos de estanho (BTs) estão na lista dos contaminantes impactantes relacionados ao ambiente marinho. Sua ampla distribuição associada à elevada toxicidade faz com que o monitoramento desses compostos no ambiente costeiro seja de fundamental importância. A ocorrência de BTs foi verificada em sedimentos superficiais, material particulado em suspensão e nos tecidos (fígado e brânquias) de três espécies de bagres estuarinos: Cathorops spixii, Aspistor luniscutis e Genidens genidens; amostrados em 8 estuários da região sul e sudeste brasileira. As análises foram realizadas através de GC-PFPD, seguindo padrões de controle de qualidade analítico e onde foi constatada a ocorrência de efeito matriz sobre o sistema analítico a partir da quantificação das amostras de tecido. Dentre os estuários amostrados, verificou-se um maior impacto dos BTs sobre os sistemas estuarinos de Paranaguá e Itajaí, em decorrência da presença destes compostos em todos os compartimentos ambientais analisados. As três espécies investigadas puderam ser consideradas como biomonitoras da presença de BTs no ambiente, uma vez que são passíveis de assimilação destes compostos, mesmo em organismos amostrados em regiões distantes de potencias fontes de entrada. Os efeitos sobre a fisiologia de C. spixii amostrado em Paranaguá também foi investigada a partir do uso de biomarcadores no fígado desses organismos, constatando um impacto associado à presença destes contaminantes no sistema. / Butyltin compounds (BTs) are in the list of related contaminants striking marine environment. Their widespread distribution associated with high toxicity causes the monitoring of fundamental importance. The occurrence of BTs were checked through superficial sediments, suspended particulate matter and tissues (liver and gill) analysis on three estuarine catfishes: Cathorops spixii, Aspistor luniscutis e Genidens genidens; sampled in eight estuaries from Brazilian south and southeast coast. Analysis were carried by GC-PFPD, following quality control procedures, where was verified the presence of matrix effect over the system from tissues quantification. Among estuaries, the major impact was found in Paranaguá-PR and Itajaí-SC, due the presence of these compounds in all investigated compartments. These three catfish species have shown good biomonitors of BTs presence once were liable of uptake, even in groups sampled far from potential BTs sources. The effects over C. spixii physiology were also checked in Paranaguá from the use of biomarkers on liver of these organisms, noting the impact related with the presence of these compounds on the system.

Neste trabalho foi desenvolvida, otimizada, e validada, uma metodologia para análise de 15 pesticidas organoclorados em sedimento através de HS/SPME-GC/MS. Esta metodologia foi aplicada para análise de amostras reais visando à realização de um diagnóstico da contaminação por pesticidas organoclorados do Rio Atibaia, principalmente em sua região próxima a contaminação oriunda da empresa Shell Brasil S.A. unidade de Paulínia. Para realização deste diagnóstico, também foi desenvolvida uma metodologia padronizada para diagnóstico ambiental de áreas contaminadas, embasada principalmente em conceitos de Gestão de Qualidade e Meio Ambiente abordadas nas normas ISO 17025, ISO 14001 e GLP. Finalmente, aplicando a metodologia analítica validada, e a metodologia para realização de um diagnóstico ambiental, foi realizado o diagnóstico da presença de pesticidas organoclorados no Rio Atibaia, indicando a existência de diferentes pesticidas organoclorados em sedimento, com destaque para os compostos DDE e BHC que se encontraram em valores acima dos recomendados pela legislação canadense. Os resultados encontrados também demonstraram que as metodologias desenvolvidas foram adequadas para análise de uma contaminação real. / In this work a methodology was developed, optimized and validated for the analysis of 15 organochlorine pesticides in sediment through HS/SPME-GC/MS. This methodology was applied to the analysis of real samples for diagnosis of the organochlorine pesticides contamination of the Atibaia River, mainly in its region close the contamination from company Shell Brasil S.A. site of Paulínia. For accomplishment of this diagnosis, also a standard methodology for environmental diagnosis of contaminated areas was developed, mainly based in concepts of Quality Management and Environmental Management find in standards like ISO 17025, ISO 14001 and GLP. Finally, applying the validated analytical methodology and the methodology proposed for environmental diagnosis, the diagnosis of the organoclhorine pesticide presence in the Atibaia River was performed, indicating different organoclorine pesticides in sediment, mainly DDE and yBHC, which were found in values above of those recommended by the Canadian legislation. The results also demonstrated that the developed methodologies are adequate for analysis of a real contamination.