Simultaneous determination of neutral nitrogen compounds in gasoline and diesel by differential pulse voltammetry

The presence of trace neutral organonitrogen compounds as carbazole and indole in derivative petroleum fuels plays an important role in the car's engine maintenance. In addition, these substances contribute to the environmental contamination and their control is necessary because most of them are potentially carcinogenic and mutagenic. For those reasons, a reliable and sensitive method was proposed for the determination of neutral nitrogen compounds in fuel samples, such as gasoline and diesel using preconcentration with modified silica gel (Merck 70-230 mesh ASTM) followed by differential pulse voltammetry (DPV) technique on a glassy carbon electrode. The electrochemical behavior of carbazole and indole studied by cyclic voltammetry (CV) suggests that their reduction occurs via a reversible electron transfer followed by an irreversible chemical reaction. Very well resolved diffusion controlled voltammetric peaks were obtained in dimethylformamide (DMF) with tetrabutylammonium tetrafluoroborate (TBAF(4) 0.1 mol L-1) for indole (-2.27 V) and carbazole (-2.67 V) versus Ag vertical bar AgCl vertical bar KClsat reference electrode. The proposed DPV method showed a good linear response range from 0.10 to 300 mg L-1 and a limit of detection (L.O.D) of 7.48 and 2.66 mu g L-1 for indole and carbazole, respectively. The results showed that simultaneous determination of indole and carbazole presents in spiked gasoline samples were 15.8 +/- 0.3 and 64.6 +/- 0.9 mg L-1 and in spiked diesel samples were 9.29 +/- 1 and 142 +/- 1 mg L-1, respectively. The recovery was evaluated and the results shown the values of 88.9 +/- 0.4 and 90.2 +/- 0.8% for carbazole and indole in fuel determinations. The proposed method was also compared with UV-vis spectrophotometric measures and the results obtained for the two methods were in good agreement according to the F and t Student's tests. (C) 2007 Elsevier B.V. All rights reserved.

Screening Brazilian automotive gasoline quality through quantification of saturated hydrocarbons and anhydrous ethanol by gas chromatography and exploratory data analysis

In this paper a set of Brazilian commercial gasoline representative samples from São Paulo State, selected by HCA, plus six samples obtained directly from refineries were analysed by a high-sensitive gas chromatographic (GC) method ASTM D6733. The levels of saturated hydrocarbons and anhydrous ethanol obtained by GC were correlated with the quality obtained from Brazilian Government Petroleum, Natural Gas and Biofuels Agency (ANP) specifications through exploratory analysis (HCA and PCA). This correlation showed that the GC method, together with HCA and PCA, could be employed as a screening technique to determine compliance with the prescribed legal standards of Brazilian gasoline.

Screening Brazilian C gasoline quality: Application of the SIMCA chemometric method to gas chromatographic data

A total of 2400 samples of commercial Brazilian C gasoline were collected over a 6-month period from different gas stations in the São Paulo state, Brazil, and analysed with respect to 12 physicochemical parameters according to regulation 309 of the Brazilian Government Petroleum, Natural Gas and Biofuels Agency (ANP). The percentages (v/v) of hydrocarbons (olefins, aromatics and saturated) were also determined. Hierarchical cluster analysis (HCA) was employed to select 150 representative samples that exhibited least similarity on the basis of their physicochemical parameters and hydrocarbon compositions. The chromatographic profiles of the selected samples were measured by gas chromatography with flame ionisation detection and analysed using soft independent modelling of class analogy (SIMCA) method in order to create a classification scheme to identify conform gasolines according to ANP 309 regulation. Following the optimisation of the SIMCA algorithm, it was possible to classify correctly 96% of the commercial gasoline samples present in the training set of 100. In order to check the quality of the model, an external group of 50 gasoline samples (the prediction set) were analysed and the developed SIMCA model classified 94% of these correctly. The developed chemometric method is recommended for screening commercial gasoline quality and detection of potential adulteration. (c) 2007 Elsevier B.V. All rights reserved.

Determination of saturates, aromatics and ethanol in Brazilian commercial gasoline with low olefin content using 1 H NMR spectroscopy

In this work, a Hydrogen Nuclear Magnetic Resonance (1H NMR) method has been developed to determine aromatics and ethanol in Brazilian commercial gasoline with low olefin content. The proposed method involves subdividing an 1H NMR spectrum into regions, each of which is assumed to be associated with a specific type of structural group (OH, CH, CH2 and CH3). The method is based on the assignment of overlapping regions of 1H NMR spectra due to the signals of naphthene (N), iso and normal paraffins (P) and ethanol (E). Each 1H NMR spectrum was divided into 8 regions and the integration was correlated to the percentage of the substances to be determined. The results of the analysis by 1H NMR were compared with analysis of GC-FID obtained with the PONA system. The proposed technique of 1H NMR was shown to be an appropriate method for this sample type.

Influence of gasoline inhalation on the enantioselective pharmacokinetics of fluoxetine in rats

Fluoxetine is used clinically as a racemic mixture of (+)-(S) and (-)-(R) enantiomers for the treatment of depression. CYP2D6 catalyzes the metabolism of both fluoxetine enantiomers. We aimed to evaluate whether exposure to gasoline results in CYP2D inhibition. Male Wistar rats exposed to filtered air (n = 36; control group) or to 600 ppm of gasoline (n = 36) in a nose-only inhalation exposure chamber for 6 weeks (6 h/day, 5 days/week) received a single oral 10-mg/kg dose of racemic fluoxetine. Fluoxetine enantiomers in plasma samples were analyzed by a validated analytical method using LC-MS/MS. The separation of fluoxetine enantiomers was performed in a Chirobiotic V column using as the mobile phase a mixture of ethanol:ammonium acetate 15 mM. Higher plasma concentrations of the (+)-(S)-fluoxetine enantiomer were found in the control group (enantiomeric ratio AUC(+)-(S)/(-)-(R) = 1.68). In animals exposed to gasoline, we observed an increase in AUC0-∞ for both enantiomers, with a sharper increase seen for the (-)-(R)-fluoxetine enantiomer (enantiomeric ratio AUC(+)-(S)/(-)-(R) = 1.07), resulting in a loss of enantioselectivity. Exposure to gasoline was found to result in the loss of enantioselectivity of fluoxetine, with the predominant reduction occurring in the clearance of the (-)-(R)-fluoxetine enantiomer (55% vs. 30%). Chirality 25:206-210, 2013. © 2013 Wiley Periodicals, Inc. Copyright © 2013 Wiley Periodicals, Inc.

Simple, Direct and Simultaneous Stripping Voltammetric Determination of Lead and Copper in Gasoline Using an In Situ Mercury Film Electrode

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Segurança das condições de aplicação de herbicidas com aerobarco em plantas daninhas aquáticas no lago da Hidrelétrica de Jupiá

Os objetivos deste trabalho foram quantificar as exposições dérmicas (EDs) e respiratórias (ERs) proporcionadas ao piloto e ao seu ajudante nas aplicações de herbicidas para o controle de plantas daninhas aquáticas com aerobarco; classificar essas condições de trabalho em seguras ou inseguras; e calcular a necessidade de controle das exposições (NCE) e o tempo de trabalho seguro (TTS). O aerobarco utilizado tinha casco de alumínio (4,85 x 2,42 m) e acionamento por hélice acoplada a motor a gasolina de 350 HP. O equipamento de pulverização era composto por bomba de diafragma com fluxo máximo de 49,69 L min-1, pressão máxima de 25 kg cm-2, acionada por motor a gasolina de 4 HP, e tanque de calda de 189 L. A barra de pulverização de alumínio era composta de duas seções laterais de 3 m, posicionadas na linha entre o encosto do banco do piloto e o início da estrutura protetora da hélice. Cada seção da barra tinha seis bicos com pontas de jato plano com indução de ar AI 100 03, espaçados de 0,5 m, e uma ponta OC 20 fixada em cada extremidade. O conjunto de pontas pulverizava faixas de 6 m de largura e aplicava o volume de calda de 200 L ha-1. O sistema tinha gerenciador de fluxo, controlado por central eletrônica acoplada a DGPS (com precisão submétrica), para corrigir automaticamente a vazão em função de alterações na velocidade real da embarcação. As EDs e ERs aos herbicidas foram calculadas com os dados substitutos das exposições às caldas, avaliadas com os traçadores cobre e manganês adicionados às caldas. As exposições foram extrapoladas para uma jornada de trabalho de seis horas. A segurança das condições de trabalho foi determinada com o cálculo da margem de segurança (MS), utilizando-se a fórmula MS = (NOEL x 70)/(QAE x 10), em que QAE = quantidade absorvível da exposição. As condições de trabalho foram classificadas em seguras, se MS>1, ou inseguras, se MS<1. As exposições proporcionadas pelas condições de trabalho foram de 10,65 mL de calda por dia para o piloto e de 16,80 mL por dia para o ajudante, que fica sentado em uma cadeira a 2,0 m à frente do piloto e da barra de pulverização. Classificaram-se como seguras as aplicações dos herbicidas glyphosate (Rodeo, 6 L ha-1), 2,4D (DMA 806 BR, 8 L ha-1) e fluridone (Sonar AQ, 0,4 L ha-1), para o piloto e o seu ajudante. Classificou-se como insegura a aplicação do herbicida diquat (Reward, 4,0 L ha-1) para as duas condições de trabalho, cujas necessidades de controle das exposições calculadas foram de 65% para o piloto e de 78% para o ajudante do piloto.

Structural and Electric-Optical Properties of Zinc Phthalocyanine Evaporated Thin Films: Temperature and Thickness Effects

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

Ecological impacts from syngas burning in internal combustion engine: Technical and economic aspects

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Determination of ecological efficiency in internal combustion engines: The use of biodiesel

This paper evaluates and quantifies the environmental impact from the use of some renewable fuels and fossils fuels in internal combustion engines. The following fuels are evaluated: gasoline blended with anhydrous ethyl alcohol (anhydrous ethanol), conventional diesel fuel, biodiesel in pure form and blended with diesel fuel, and natural gas. For the case of biodiesel, its complete life cycle and the closed carbon cycle (photosynthesis) were considered. The ecological efficiency concept depends on the environmental impact caused by CO(2), SO(2), NO(x) and particulate material (PM) emissions. The exhaust gases from internal combustion engines, in the case of the gasoline (blended with alcohol), biodiesel and biodiesel blended with conventional diesel, are the less polluting; on the other hand, the most polluting are those related to conventional diesel. They can cause serious problems to the environment because of their dangerous components for the human, animal and vegetable life. The resultant pollution of each one of the mentioned fuels are analyzed, considering separately CO(2), SO(2), NO(x) and particulate material (PM) emissions. As conclusion, it is possible to calculate an environmental factor that represents, qualitatively and quantitative, the emissions in internal combustion engines that are mostly used in urban transport. Biodiesel in pure form (B100) and blended with conventional diesel as fuel for engines pollute less than conventional diesel fuel. The ecological efficiency for pure biodiesel (B100) is 86.75%: for biodiesel blended with conventional diesel fuel (B20, 20% biodiesel and 80% diesel), it is 78.79%. Finally, the ecological efficiency for conventional diesel, when used in engines, is 77.34%; for gasoline, it is 82.52%, and for natural gas, it is 91.95%. All these figures considered a thermal efficiency of 30% for the internal combustion engine. Crown Copyright (C) 2008 Published by Elsevier Ltd. All rights reserved.

Biodiesel CO2 emissions: A comparison with the main fuels in the Brazilian market

The use of biodiesel is increasing as an attractive fuel due to the depleting fossil fuel resources and environmental degradation. This paper presents results of an investigation on the potentials of biodiesel as an alternative fuel and main substitute of diesel oil, comparing the CO2 emissions of the main fuels in the Brazilian market with those of biodiesel, in pure form or blended in different proportions with diesel oil (2%, 5%, and 20%, called B2, B5, and B20, respectively). The results of the study are shown in ton CO2 per m(3) and ton CO2 per year of fuel. The fuels were analyzed considering their chemical composition, stoichiometric combustion parameters and mean consumption for a single vehicle. The fuels studied were: gasoline, diesel oil, anhydrous ethyl alcohol (anhydrous ethanol), and biodiesel from used frying oil and from soybean oil. For the case of biodiesel, its complete life cycle and the closed carbon cycle (photosynthesis) were considered. With data provided by the Brazilian Association of Automotive Vehicle Manufacturers (ANFAVEA) for the number of vehicles produced in Brazil, the emissions of CO2 for the national fleet in 2007 were obtained per type of fuel. With data provided by the Brazilian Department of Transit (DENATRAN) concerning the number of diesel vehicles in the last five years in Brazil, the total CO2 emissions and the percentage that they would decrease in the case of use of pure biodiesel, B100, or several mixtures, B2, B5 and B20, were calculated. Estimates of CO2 emissions for a future scenario considering the mixtures B5 and B20 are also included in this article. Crown Copyright (C) 2008 Published by Elsevier B.V. All rights reserved.

Aplicação da resistividade e cargabilidade em estudos de contaminação de sedimentos por derivados de hidrocarbonetos

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

Atmospheric particulate polycyclic aromatic hydrocarbons from road transport in southeast Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Contribution of sugar-cane harvesting season to atmospheric contamination by polycyclic aromatic hydrocarbons (PAHs) in Araraquara city, Southeast Brazil

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