Hidrocarbonetos e esterois como indicadores de fontes e destino de matéria orgânica em sedimentos da Baía de Sepetiba, Rio de Janeiro

The inputs of organic matter derived from natural and anthropogenic sources to Sepetiba Bay were investigated by using aliphatic hydrocarbons and sterols in superficial sediments. Concentrations ranged from 0.26 to 2.65 μg g-1, <0.01 to 17.41 μg g-1 and 0.77 and 9.24 μg g-1 for n-alkanes, UCM (unresolved complex mixture) and total sterols, respectively. The selected markers and ratios among individual compounds showed the major contribution of terrestrial sources to the total pool of sedimentary organic matter in the bay, but the accumulation of autochthonous organic matter increased with distance from the shoreline. The input of petroleum hydrocarbons and sewage (coprostanol in the range 0.01 to 0.43 μg g-1) were also detected, especially in the more urbanized regions of the bay, but at lower levels of contamination when compared to estuaries in other Brazilian coastal regions.

Avaliação de solventes de extração por ultrassom usando-se cromatografia líquida de alta eficiência para a determinação de hidrocarbonetos policíclicos aromáticos em solos contaminados

A method using ultrasonication extraction for the determination of 17 polycyclic aromatic hydrocarbons (PAHs), selected by the USEPA and NIOSH as "consent decree" priority pollutants, in soil by High Performance Liquid Chromatography (HPLC) was studied. Separation and detection were completed in 20 min with a C18 columm, acetonitrile-water gradient elution and ultraviolet absorption and fluorescence detections. The detection limits, for a 10 µL of solution injection, were less than 9,917 ng/g in UV detection and less than 1,866 ng/g in fluorescence detection. Several organic solvents were tested for extraction of the 17 PAHs from soils. Acetone was the best solvent among the three solvents tested, and the order of the extraction efficiencies was: acetone>methanol>acetonitrile. Ultrasonication using acetone as solvent extraction was used to evaluate the biodegradation of those compounds in contaminated soil during a vermicomposting process.

Salinidade em petróleo bruto: otimização de metodologia e proposta de um novo método para extração de sais em petróleo

The quantity of salts in the crude oils depends on the origin and of the wells production and these salts cause several problems during the transport and the process of refine as corrosions, incrustations and deactivation of the employed catalysts in the refineries. In this study were implemented changes for improvements in the execution of ASTM D 6470 method and has also developed a new methodology of extraction system of salts using process of mechanical agitation without heating. The results of the optimization produce larger efficiency and safety to the process compared to the traditional ASTM method.

Análise de compostos sulfurados em efluentes gasosos de refinaria de petróleo

This work discusses an analytical procedure for analysis of sulfur compounds in treated petroleum refinery gaseous effluents using a sulfur chemiluminescence detector with dual plasma burner (SCD-DP). Calibration was accomplished by using standards and gaseous streams of known concentration of sulfur compounds. The response factors agree with the calibration table of ASTM standard D 5504 (2008). The detection range for sulfur compounds is in μg m-3. The analytical procedure allowed the construction of a chromatographic chart of sulfur compounds present in several refinery gaseous effluents. SO2 was the most difficult compound to be determined because of its high reactivity.

Determinação do coeficiente de atividade em diluição infinita de hidrocarbonetos em furfural a 298,15 K por SPME-GC/FID

In this work a new method (SPME-GC/FID) was developed to analyze the activity of binary liquid mixtures. The purpose is to demonstrate that SPME is capable to be used to determinate activity coefficients at infinite dilution knowing the fiber properties, with a lower cost than the conventional methods encountered in literature such as GLC. The activity coefficients at infinite dilution in furfural for n-hexane, n-heptane and cyclohexane at 298.15 K was determined using SPME and deviations of literature data was about 7%.

Avaliação geoquímica de óleos brasileiros com ênfase nos hidrocarbonetos aromáticos

Aromatic compounds are still poorly evaluated in geochemical studies of Brazilian oil samples. For this reason, the objective of this work was to analyze and evaluate 26 oil samples from four Brazilian sedimentary basins. Aromatic hydrocarbon fractions have been analyzed by gas chromatography coupled to mass spectrometry. The results were also compared with previously evaluated saturated hydrocarbon data. Maturation parameters obtained using the 4- and 1-methyl-dibenzothiophenes and trimethyl-dibenzothiophenes led to the best results because a better grouping was observed. For this correlation, the samples were grouped by maturity degree enabling the routine use of these parameters to evaluate oil maturity levels.

Ácidos naftênicos no petróleo

Brazilian petroleum is known by its high acidity due to the presence of acidic constituents, especially naphthenic acids (NA). The total characterization of the NA in petrochemical samples has been receiving special attention in research and comprises an analytical challenge, mainly due to the complexity of their mixtures. Gas chromatography with mass detector (GC/MS) is the technique of analysis more used, but recently comprehensive two-dimensional gas chromatography (GC × GC) has been used, due to its high resolution, peak capacity and sensitivity. The goal of this article is to discuss the techniques for sample preparation and analysis of NA in petroleum.

Processos naturais de biodegradação do petróleo em reservatórios

Petroleum biodegradation in reservoirs is a process caused by different microorganisms affecting many oil deposits which modifies the oil composition in a quasi-stepwise process starting from n-alkanes and isoprenoids through to diasteranes. This causes oil souring and increased viscosity, sulfur and metal content, having a direct impact on oil production and refining costs.

Determinação de compostos carbonilados e carboxilados em derivados de petróleo

Although metals and nitrogen/sulfur compounds have been the main concern of the petroleum industry, issues concerning the harmful effects on catalysts poisoning and product contamination by other contaminants such as oxygen-containing compounds have been raised. Trace amounts of carbonyl and carboxyl compounds in petroleum products can lead to catalyst poisoning. Additionally, oxygenates may be present in final polyethylene and polypropylene resins, affecting the quality of food packaging. In this work, we reviewed potential analytical approaches for oxygenates determination in petroleum products and report the features of each potential technique.

PCA: uma ferramenta para identificação de traçadores químicos para água de formação e água de injeção associadas à produção de petróleo

This study describes the use of Principal Component Analysis to evaluate the chemical composition of water produced from eight oil wells in three different production areas. A total of 609 samples of produced water, and a reference sample of seawater, were characterized according to their levels of salinity, calcium, magnesium, strontium, barium and sulphate (mg L-1) contents, and analyzed by using PCA with autoscaled data. The method allowed the identification of variables salinity, calcium and strontium as tracers for formation water, and variables magnesium and sulphate as tracers for seawater.

Terpanos pentacíclicos como indicadores de heterogeneidades composicionais em reservatório de petróleo biodegradado

Reservoir geochemistry has been effectively used to evaluate compositional heterogeneity in petroleum reservoirs by employing oil fingerprinting technique to assess reservoir continuity, primarily in paraffin oil accumulations. In-reservoir biodegradation has resulted in vast deposits of heavy oils globally; therefore, the application of reservoir geochemistry to such accumulations becomes necessary. We recommend the use of pentacyclic terpanes instead of lower molecular compounds, which are less resistant to biodegradation. Using oil fingerprinting technique in this novel way enabled the differentiation of oil composition among sedimentary facies of tar sands (Pirambóia Formation, Paraná Basin).

ANÁLISE EXPLORATÓRIA DAS CONCENTRAÇÕES DOS METAIS NA, CA, MG, SR E FE EM EXTRATO AQUOSO DE PETRÓLEO, DETERMINADOS POR ICP OES, APÓS OTIMIZAÇÃO EMPREGANDO PLANEJAMENTO DE EXPERIMENTOS

AbstractThe purpose of this study was to evaluate the best operating conditions of ICP OES for the determination of Na, Ca, Mg, Sr and Fe in aqueous extract of crude oil obtained after hot extraction with organic solvents (ASTM D 6470-99 modified). Thus, the full factorial design and central composite design were used to optimize the best conditions for the flow of nebulization gas, the flow of auxiliary gas, and radio frequency power. After optimization of variables, a study to obtain correct classification of the 18 samples of aqueous extract of crude oils (E1 to E18) from three production and refining fields was carried out. Exploratory analysis of these extracts was performed by principal component analysis (PCA), hierarchical cluster analysis (HCA) and linear discriminant analysis (LDA), using the original variables as the concentration of the metals Na, Ca, Mg, Sr and Fe determined by ICP OES.

Origin of oil in the Wilmington field in California

No presente trabalho, o autor trata da formação de campo petrolífero que se teria formado às expensas de organismos planctónicos, misturados com areia das dunas, material esse que teria sido transportado pelo vento. Refere-se, assim, o autor, ao campo petrolífero de "Wilmington", situado na Ilha Terminal, ao sul de Los Angeles, California. Esse campo, que já fora descrito, em 1943, por GILLULY & GRANT, faz parte do Mioceno e do Plioceno inferior, achando-se separado dos schistos Jurássicos metamórficos, por uma discordância localizada a 6.000 pés de profundidade. O conjunto das camadas petrolíferas alcança espessura de 1 .500 pés, sendo cada uma delas separada das outras por estratos do "siltstone" (siltito). O tamanho dos grãos, nos dois tipos de rochas, é o de depósitos eólicos, mas, ao contrário do que acontece em depósitos sub-aéreos, esses grãos são angulosos ou sub-angulosos. De acordo com MCNAUGHTON , esses depósitos se teriam formado em profundidade crescente, de 200 a 5.000 pés; esse fato, relacionado com as dimensões dos grãos, leva a crer que o material tenha sido transportado pelo vento. A sedimentação deu-se longe da costa, de maneira muito lenta, provavelmente em consequência de tempestades de excepcional intensidade. O petróleo teria sido produzido por organismos planctónicos que se teriam misturado com areia das dunas, sendo a velocidade da sedimentação desta, muito menor. Os cálculos indicam que foram armazenados somente 23% dos hidrocarbonetos que caíram sobre a areia de sedimentação, sob a forma de organismos mortos. M. V.

Hidrocarbonetos aromáticos policíclicos em margarina, creme vegetal e maionese

Hidrocarbonetos aromáticos policíclicos (HAPs) são um grupo de compostos que têm sido objeto de muitas pesquisas devido ao seu potencial tóxico. Neste estudo, margarinas, cremes vegetais e maioneses disponíveis no mercado brasileiro foram analisadas quanto ao teor de pireno, fluoranteno, benzo(a)antraceno, criseno, benzo(b)fluoranteno, benzo(k)fluoranteno, benzo(a)pireno e dibenzo(a,h)antraceno. A metodologia analítica envolveu extração líquido-líquido, limpeza em coluna de sílica gel e determinação por cromatografia líquida de alta eficiência com detector de fluorescência. Níveis variáveis de contaminação foram encontrados em marcas diferentes do mesmo produto e em lotes diferentes da mesma marca. O teor médio de HAPs totais encontrados esteve na faixa de 4,1 a 7,1mig/kg em cremes vegetais, de 1,7 a 3,9mig/kg em margarinas e de 1,0 a 21,7mig/kg em maioneses. Em geral, os produtos que declaravam conter óleo de milho em sua formulação mostraram os maiores níveis de contaminação. Com base nestes resultados e na importância de gorduras, óleos e produtos derivados como fonte de ingestão de HAPs, recomenda-se aos produtores de margarinas, cremes vegetais e maioneses que iniciem o controle da contaminação dos óleos vegetais utilizados na elaboração destes produtos, de forma a reduzir a exposição do consumidor à quantidades excessivas de compostos potencialmente carcinogênicos.

Chá-mate e café como fontes de hidrocarbonetos policíclicos aromáticos (HPAs) na dieta da população de Campinas

Com o objetivo de determinar os níveis dos contaminantes hidrocarbonetos policíclicos aromáticos (HPAs) em chá-mate e café e avaliar a contribuição desses produtos como fonte de HPAs na dieta da população de Campinas, três marcas com três diferentes lotes de chá-mate e café em pó, totalizando 18 amostras, foram analisadas. Os dados de consumo de chá-mate e café foram obtidos de uma pesquisa de hábitos alimentares feita no ano de 1993 junto à população local, através do método de freqüência de alimentos. A determinação de HPAs foi conduzida por cromatografia líquida de alta eficiência com detecção por fluorescência. A presença de diferentes hidrocarbonetos foi observada em todas as amostras de café analisadas, em níveis variando tanto entre as marcas quanto em função da técnica de preparo da bebida. A quantidade média de HPAs totais encontrada no café (bebida pronta para consumo) foi de 10,12mig/kg, enquanto que o chá-mate apresentou um nível de contaminantes significativamente menor (sigma=0,70mig/kg). Considerando-se a estimativa de consumo diário médio per capita de 69,79g de chá-mate e de 86,77g de café, pode-se considerar que o chá-mate e o café aportam diariamente cerca de 0, 05mig e 0, 88mig de HPAs totais, respectivamente, na dieta da população estudada (n=600 indivíduos).