Determinação de benzeno, tolueno, etilbenzeno e xilenos em gasolina comercializada nos postos do estado do Piauí

Automotive gasoline consists of a complex mixture of flammable and volatile hydrocarbons derived from crude oil with carbon numbers within the range of 4-12 and boiling points range of 30-225 ºC. Its composition varies with the kind of crude oil and the type of refinery process that they undergone. Aromatics hydrocarbons, in particular benzene, toluene, ethylbenzene and isomeric xylenes (BTEX) are the toxic group constituents presents. GC-FID was employed to quantify these hydrocarbons in 50 commercial gasoline samples from Piauí state. Statistical analysis techniques, such as PCA and HCA were used to analyze the data. Moreover, several validation parameters were evaluated.

Solarização em microcosmo: efeito de materiais vegetais na sobrevivência de fitopatógenos de solo e na produção de voláteis

Além das brassicaceas associadas à solarização do solo, novos materiais vegetais como a mandioca e a mamona têm apresentado potencial no controle de fitopatógenos de solo. Assim, objetivou-se verificar os efeitos da incorporação e decomposição de parte aérea de brócolis, mamona e mandioca brava e mansa, associadas à solarização, em conjuntos de microcosmos, sob condições de ambiente controlado, na sobrevivência das estruturas de resistência de Fusarium oxysporum f. sp. lycopersici Raça 2, Macrophomina phaseolina, Rhizoctonia solani AG-4 HGI e Sclerotium rolfsii; e identificar e apontar o(s) volátil(eis) emanado(s) pela decomposição dos materiais, que poderia(m) estar correlacionado(s) com a inativação dos fitopatógenos. Quanto à sobrevivência dos patógenos, quatro ensaios idênticos foram instalados nos microcosmos, com quatro períodos de exposição independentes (7, 14, 21 e 28 dias). A identificação dos voláteis contou com ensaios realizados sob as mesmas condições da sobrevivência, mas em frascos âmbar e com cromatografia gasosa com detectores por espectrometria de massas (GC-MS) e por ionização em chama (GC-FID), utilizando a técnica de Microextração em Fase Sólida - SPME. Os tratamentos solo+materiais vegetais, ao longo dos períodos testados, reduziram a sobrevivência das estruturas de resistência de todos os fungos. No geral, destacaram-se o brócolis e a mandioca brava, além da mandioca mansa para S. rolfsii. Os voláteis identificados foram oriundos da decomposição de brócolis, mamona e mandioca mansa. Foram identificados 26, 37 e 29 compostos voláteis para brócolis, mamona e mandioca mansa, respectivamente. Correlações positivas e negativas foram observadas entre alguns voláteis e a média dos compostos com a sobrevivência das estruturas de resistência dos fitopatogênicos.

Développement de méthodes d’analyse directe de polluants organiques volatils à l’état de traces dans l’air et les biogaz

Il est reconnu que le benzène, le toluène, l’éthylbenzène et les isomères du xylène, composés organiques volatils (COVs) communément désignés BTEX, produisent des effets nocifs sur la santé humaine et sur les végétaux dépendamment de la durée et des niveaux d’exposition. Le benzène en particulier est classé cancérogène et une exposition à des concentrations supérieures à 64 g/m3 de benzène peut être fatale en 5–10 minutes. Par conséquent, la mesure en temps réel des BTEX dans l’air ambiant est essentielle pour détecter rapidement un danger associé à leur émission dans l’air et pour estimer les risques potentiels pour les êtres vivants et pour l’environnement. Dans cette thèse, une méthode d’analyse en temps réel des BTEX dans l’air ambiant a été développée et validée. La méthode est basée sur la technique d’échantillonnage direct de l’air couplée avec la spectrométrie de masse en tandem utilisant une source d’ionisation chimique à pression atmosphérique (APCI-MS/MS directe). La validation analytique a démontré la sensibilité (limite de détection LDM 1–2 μg/m3), la précision (coefficient de variation CV < 10%), l’exactitude (exactitude > 95%) et la sélectivité de la méthode. Des échantillons d’air ambiant provenant d’un site d’enfouissement de déchets industriels et de divers garages d’entretien automobile ont été analysés par la méthode développée. La comparaison des résultats avec ceux obtenus par la technique de chromatographie gazeuse on-line couplée avec un détecteur à ionisation de flamme (GC-FID) a donné des résultats similaires. La capacité de la méthode pour l’évaluation rapide des risques potentiels associés à une exposition aux BTEX a été prouvée à travers une étude de terrain avec analyse de risque pour la santé des travailleurs dans trois garages d’entretien automobile et par des expériences sous atmosphères simulées. Les concentrations mesurées dans l’air ambiant des garages étaient de 8,9–25 µg/m3 pour le benzène, 119–1156 µg/m3 pour le toluène, 9–70 µg/m3 pour l’éthylbenzène et 45–347 µg/m3 pour les xylènes. Une dose quotidienne environnementale totale entre 1,46 10-3 et 2,52 10-3 mg/kg/jour a été déterminée pour le benzène. Le risque de cancer lié à l’exposition environnementale totale au benzène estimé pour les travailleurs étudiés se situait entre 1,1 10-5 et 1,8 10-5. Une nouvelle méthode APCI-MS/MS a été également développée et validée pour l’analyse directe de l’octaméthylcyclotétrasiloxane (D4) et le décaméthylcyclopentasiloxane (D5) dans l’air et les biogaz. Le D4 et le D5 sont des siloxanes cycliques volatils largement utilisés comme solvants dans les processus industriels et les produits de consommation à la place des COVs précurseurs d’ozone troposphérique tels que les BTEX. Leur présence ubiquitaire dans les échantillons d’air ambiant, due à l’utilisation massive, suscite un besoin d’études de toxicité. De telles études requièrent des analyses qualitatives et quantitatives de traces de ces composés. Par ailleurs, la présence de traces de ces substances dans un biogaz entrave son utilisation comme source d’énergie renouvelable en causant des dommages coûteux à l’équipement. L’analyse des siloxanes dans un biogaz s’avère donc essentielle pour déterminer si le biogaz nécessite une purification avant son utilisation pour la production d’énergie. La méthode développée dans cette étude possède une bonne sensibilité (LDM 4–6 μg/m3), une bonne précision (CV < 10%), une bonne exactitude (> 93%) et une grande sélectivité. Il a été également démontré qu’en utilisant cette méthode avec l’hexaméthyl-d18-disiloxane comme étalon interne, la détection et la quantification du D4 et du D5 dans des échantillons réels de biogaz peuvent être accomplies avec une meilleure sensibilité (LDM ~ 2 μg/m3), une grande précision (CV < 5%) et une grande exactitude (> 97%). Une variété d’échantillons de biogaz prélevés au site d’enfouissement sanitaire du Complexe Environnemental de Saint-Michel à Montréal a été analysée avec succès par cette nouvelle méthode. Les concentrations mesurées étaient de 131–1275 µg/m3 pour le D4 et 250–6226 µg/m3 pour le D5. Ces résultats représentent les premières données rapportées dans la littérature sur la concentration des siloxanes D4 et D5 dans les biogaz d’enfouissement en fonction de l’âge des déchets.

Catalytic ethanolysis of soybean oil with immobilized lipase from Candida antarctica and (1)H NMR and GC quantification of the ethyl esters (biodiesel) produced

The catalytic ethanolysis of soybean oil with commercial immobilized lipase type B from Candida antarctica to yield ethyl esters (biodiesel) has been investigated. Transesterification was monitored with respect to the following parameters: quantity of biocatalyst, reaction time, amount of water added and turnover of lipase. The highest yields of biodiesel (87% by (1)H NMR; 82.9% by GC) were obtained after a reaction time of 24 h at 32 degrees C in the presence of lipase equivalent to 5.0% (w/w) of the amount of soybean oil present. The production of ethyl esters by enzymatic ethanolysis was not influenced by the addition of water up to 4.0% (v/v) of the alcohol indicating that it is possible to use hydrated ethanol in the production of biodiesel catalyzed by lipase. The immobilized enzyme showed high stability under moderate reaction conditions and retained its activity after five production cycles. The (1)H NMR methodology elaborated for the quantification of biodiesel in unpurified reaction mixtures showed good correlations between the signal areas of peaks associated with the alpha-methylene groups of the ethyl esters and those of the triacyl-glycerides in residual soybean oil. Monoacylglycerides, diacylglycerides and triglycerides could also be detected and quantified in the crude biodiesel using (1)H NMR spectroscopic and GC-FID chromatographic methods. The biodiesel production by enzymatic catalysis was promising. In this case, was produced a low concentration of glycerol (0.74%) and easily removed by water extraction. (C) 2010 Elsevier B.V. All rights reserved.

Genotoxicidade e composição do material particulado emitido pela queima de Biomassa: um estudo de caso em Tangará da Serra, Região da Amazônia Brasileira

Tangara da Serra is located on southwestern Mato Grosso and is found to be on the route of pollutants dispersion originated in the Legal Amazon s deforestation area. This region has also a wide area of sugarcane culture, setting this site quite exposed to atmospheric pollutants. The objective of this work was to evaluate the genotoxicity of three different concentrations of organic particulate matter which was collected from August through December / 2008 in Tangara da Serra, using micronucleus test in Tradescantia pallida (Trad-MCN). The levels of particulate matter less than 10μm (MP10) and black carbon (BC) collected on the Teflon and polycarbonate filters were determined as well. Also, the alkanes and polycyclic aromatic hydrocarbons (PAHs) were identified and quantified on the samples from the burning period by gas chromatography detector with flame ionization detection (GC-FID). The results from the analyzing of alkanes indicate an antropic influence. Among the PAHs, the retene was the one found on the higher quantity and it is an indicator of biomass burning. The compounds indene(1,2,3-cd)pyrene and benzo(k)fluoranthene were identified on the samples and are considered to be potentially mutagenic and carcinogenic. By using Trad-MCN, it was observed a significant increase on the micronucleus frequency during the burning period, and this fact can be related to the mutagenic PAHs which were found on such extracts. When the period of less burnings is analyzed and compared to the negative control group, it was noted that there was no significant difference on the micronuclei rate. On the other hand, when the higher burning period is analyzed, statistically significant differences were evident. This study showed that the Trad-MCN was sensible and efficient on evaluating the genotoxicity potencial of organic matter from biomass burning, and also, emphasizes the importance of performing a chemical composition analysis in order to achieve a complete diagnosis on environmental risk control

Dessulfurização oxidativa em diesel utilizando catalisadores à base de vanádio ou manganês

The oxidative desulfurization process (ODS) of a commercial diesel fuel was performed under mild conditions in the presence of catalysts based on vanadium or manganese, supported on alumina, clays (commercial, natural and pillared) and zeolites (NaX, NaY, beta, mordenite and ZSM-5). The catalysts were synthesized by wet impregnation and characterized by X-ray diffraction, textural analysis by N2 adsorption and scanning electron microscopy. The dibenzothiophene (DBT) was used as sulfur compound in catalytic evaluation. The reactions were performed using acetonitrile as solvent and the hydrogen peroxide as oxidant at 55°C. The reaction products were analized by gas chromatography (GC-FID). In the studied conditions, the process was efficient due to the DBT was converted to its corresponding sulfone. Both DBT and corresponding sulfone were extracted by the solvent. Removals and oxidations up to 100% of sulfur compound were achieved. The catalysts supported on ZSM-5 zeolite showed are more effective for oxidation reaction of sulfur compound, presenting the best results. It was observed for oxidation reaction, that vanadium catalysts were more effective and manganese catalysts showed best results for removal of sulfur compounds

Caracterização de resíduo sólido formado em biodiesel de sebo bovino

Biodiesel production has increased over the last decade because of the benefits associated with this fuel, including renewability, domestic feedstock, lower toxicity, and biodegradability. From 2008, the use of beef tallow as a feedstock for biodiesel production in Brazil has increased in significance, representing the second largest source of biodiesel, after soybeans. However, the performance of biodiesel in cold weather conditions is worse than diesel because of deposition of insoluble at low temperatures, accelerating the plugging of fuel filters and injectors of the vehicle engine. Studies have been conducted on beef tallow biodiesel, mostly related to the properties of thermal and oxidative stability. However, few studies have described the nature of the precipitate formed and its influence on product quality. Research suggests that the cause of deposition is related to the nature of saturated esters and monoacylglycerols as inducing agents. This study monitored the levels of mono-, diand triacylglycerols, the oxidation stability and the cold filter plugging point (CFPP) in beef tallow biodiesel samples from two commercial producers in Brazil for a period of twelve months. Filtered precipitates were analyzed by comparative techniques of GCFID, HPLC-UV/VIS, HPLC-MS-IT-TOF and TG to verify the nature, using monopalmitin and monostearin as reference standards. The formation of precipitate reduced the levels of monoacylglycerols in the beef tallow biodiesel. GC-FID and LCMS- IT-TOF results confirmed the nature of the deposit as saturated monoacylglycerols, predominantly monostearin and monopalmitin as the second major component. Moreover the TG analysis of the residue indicated similar thermal decomposition of the reference standards. The precipitate did not affect the oxidation stability of beef tallow biodiesel and the CFPP characteristic of blends up B60. However, the presence of iron reduced significantly the oxidation stability of biodiesel

Caracterização de resíduo sólido formado em biodiesel de sebo bovino

Biodiesel production has increased over the last decade because of the benefits associated with this fuel, including renewability, domestic feedstock, lower toxicity, and biodegradability. From 2008, the use of beef tallow as a feedstock for biodiesel production in Brazil has increased in significance, representing the second largest source of biodiesel, after soybeans. However, the performance of biodiesel in cold weather conditions is worse than diesel because of deposition of insoluble at low temperatures, accelerating the plugging of fuel filters and injectors of the vehicle engine. Studies have been conducted on beef tallow biodiesel, mostly related to the properties of thermal and oxidative stability. However, few studies have described the nature of the precipitate formed and its influence on product quality. Research suggests that the cause of deposition is related to the nature of saturated esters and monoacylglycerols as inducing agents. This study monitored the levels of mono-, diand triacylglycerols, the oxidation stability and the cold filter plugging point (CFPP) in beef tallow biodiesel samples from two commercial producers in Brazil for a period of twelve months. Filtered precipitates were analyzed by comparative techniques of GCFID, HPLC-UV/VIS, HPLC-MS-IT-TOF and TG to verify the nature, using monopalmitin and monostearin as reference standards. The formation of precipitate reduced the levels of monoacylglycerols in the beef tallow biodiesel. GC-FID and LCMS- IT-TOF results confirmed the nature of the deposit as saturated monoacylglycerols, predominantly monostearin and monopalmitin as the second major component. Moreover the TG analysis of the residue indicated similar thermal decomposition of the reference standards. The precipitate did not affect the oxidation stability of beef tallow biodiesel and the CFPP characteristic of blends up B60. However, the presence of iron reduced significantly the oxidation stability of biodiesel

Solarização em microcosmo: efeito de materiais vegetais na sobrevivência de fitopatógenos de solo e na produção de voláteis

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Pollination Biology of Jacaranda oxyphylla with an Emphasis on Staminode Function

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Multivariate calibrations in gas chromatographic profiles for prediction of several physicochemical parameters of Brazilian commercial gasoline

Several Brazilian commercial gasoline physicochemical parameters, such as relative density, distillation curve (temperatures related to 10%, 50% and 90% of distilled volume, final boiling point and residue), octane numbers (motor and research octane number and anti-knock index), hydrocarbon compositions (olefins, aromatics and saturates) and anhydrous ethanol and benzene content was predicted from chromatographic profiles obtained by flame ionization detection (GC-FID) and using partial least square regression (PLS). GC-FID is a technique intensively used for fuel quality control due to its convenience, speed, accuracy and simplicity and its profiles are much easier to interpret and understand than results produced by other techniques. Another advantage is that it permits association with multivariate methods of analysis, such as PLS. The chromatogram profiles were recorded and used to deploy PLS models for each property. The standard error of prediction (SEP) has been the main parameter considered to select the "best model". Most of GC-FID-PLS results, when compared to those obtained by the Brazilian Government Petroleum, Natural Gas and Biofuels Agency - ANP Regulation 309 specification methods, were very good. In general, all PLS models developed in these work provide unbiased predictions with lows standard error of prediction and percentage average relative error (below 11.5 and 5.0, respectively). (C) 2007 Elsevier B.V. All rights reserved.

Determinação de benzeno, tolueno, etilbenzeno e xilenos em gasolina comercializada nos postos do estado do Piauí

Automotive gasoline consists of a complex mixture of flammable and volatile hydrocarbons derived from crude oil with carbon numbers within the range of 4-12 and boiling points range of 30-225 ºC. Its composition varies with the kind of crude oil and the type of refinery process that they undergone. Aromatics hydrocarbons, in particular benzene, toluene, ethylbenzene and isomeric xylenes (BTEX) are the toxic group constituents presents. GC-FID was employed to quantify these hydrocarbons in 50 commercial gasoline samples from Piauí state. Statistical analysis techniques, such as PCA and HCA were used to analyze the data. Moreover, several validation parameters were evaluated.

Rapid determination of furanocoumarins in creams and pomades using SPE and GC

A solid-phase extraction and chromatography-flame ionization detection (GC-FID) method has been developed for the routine analysis of psoralen, bergapten, isopimpinellin and pimpinellin in creams and pomades employed in Brazil for the treatment of vitiligo. The calibration curve for psoralen was linear in the range 10-100 mu g ml(-1), for bergapten 5-90 mu g ml(-1), for pimpinellin 10-90 mu g ml(-1) and for isopimpinellin 5-100 mu g ml(-1). The best recoveries of the furanocoumarins in the creams analysed were 94-97%, whereas in the pomades, recoveries were 94-96%. The R.S.D. of the quantitative analysis of the furanocoumarins in the products analyses were within 5%. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Otimização da modificação de cadeia do PHB com anidrido maleico e estudo de comportamento térmico

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Desenvolvimento, aperfeiçoamento e validação de método cromatográfico para previsão da qualidade e propriedades físico-químicas do óleo diesel tipo B

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)