Representative tar balls collected in two distinct years (2012 and 2014) in a beach along the State of Bahia, northeastern Brazil, were geochemically characterized in order to identify correlations between them and investigate potential sources. Terpanes and steranes biomarkers (detected by gas chromatography coupled to mass spectrometry, GC-MS), carbon stable isotope ratio (δ13C), Ni and V ratios and polar compounds by Fourier transform ion cyclotron resonance mass spectrometry using electrospray ionization in negative mode (ESI(-) FT-ICR MS) were evaluated. Three Brazilian oil samples from distinct sources were assessed as possible spill sources, comparing their results with the tar ball samples. Using chemometric techniques, it was verified correlation between the two set of tar ball samples, suggesting same source. However, no correlation with the oil samples was observed, with different geochemical profile among them. The heteroatom class distribution displayed severe degradation levels for tar balls and its seems that photo-oxidation and biodegradation processes were further relevant. Tar ball samples show multiple classes, most oxygenated, and with one sample showing considerable relative abundance of N1 class, suggesting it is from a more recent oil spill. In brief, our results suggest that the region, with very sensitive ecosystem, is possibly subjected to frequent spills from the same source.
Abstract The presence of acidic compounds as naphthenic acids in crude oil causes several problems for the petroleum industry, including corrosion in both upstream and downstream production processes. Based on this scenario, the main objective of this work was to investigate the removal of the acidic compound from two Brazilian heavy oils by adsorption processes using six potential adsorbents: powdered shale, activated carbon, bentonite, silica gel, powdered sandstone and powdered wood. These raw materials were previously characterized by conventional and surface analysis techniques, which show that they offer a good surface area and thermal stability. To evaluate the removal efficiency at the molecular level, the crude oil samples and the filtered oils were analyzed by negative electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry [ESI (-) FTICR MS]. The O2 class, which is related to the relatively high acidity of the samples, was the most abundant in both crude oil samples, moreover, this class was more retained by adsorbents. Silica gel, activated carbon and bentonite were the best adsorbents of acidic compounds from the tested oils, in agreement with their markedly higher surface area and porous volume. Additionally, a chromatographic analysis was performed and showed no changes in the oil profile.
Abstract In offshore oil wells it is very common to perform seawater injection through injection wells for hydrocarbon recovery. When seawater, rich in sulfate ion, mixes with formation water, whose composition can contain divalent cations such as barium and calcium, it often leads to sulfate salts formation due to their chemical incompatibility. These salts can cause serious damage in production wells. The barium sulfate (BaSO4) is the most problematic scale and may cause many complications. In order to solve this issue, polycarboxylic acids, such as diethylene triamine pentaacetic acid, are used. Thus, the primary focus of this work was to develop an experimental procedure to study the BaSO4 dissolution. Initially, through static tests to understand the relationship between dissolver concentration, temperature and dissolution time, and then through dynamic tests in sandstone reservoirs. Based on the results obtained, in the static tests the best condition for barite to dissolve was at high temperatures (80 ºC) and contact time of 48 hours, since from 50 °C there is an increase in dissolution rate, associated with a long contact time between dissolver and barite. In the dynamic tests, after scale formation, barite could be removed, but the high DTPA concentration should be avoided.
A set of eight tar sand samples with identical source, from sedimentary facies of the Pirambóia Formation, Paraná Basin, provides an interesting opportunity to assess the biodegradation extent of bitumens using high-resolution mass spectrometry with Orbitrap mass analyzer. The results suggest that acidic compounds have been degraded by microorganisms, since the O2 and O3 classes were lower to bitumens from dry interdune facies, the most biodegraded. It was also proposed a new parameter to evaluate biodegradation, DBE ratio (ratio between acidic species with the same number of double bond equivalent), that was used together with the already proposed A/C ratio (acyclic to cyclic naphthenic acids), both obtained from O2 class distribution. The bitumens from dry interdune facies presented the highest DBE ratios and lowest A/C ratios, which suggested that these parameters can be used to assess the extent of bitumen biodegradation in which the DBE ratios increase and the A/C ratios decrease with increasing biodegradation.
The growing global concern about the environment associated with academic and government efforts are enabling a number of alternatives for sustainable development. Within this perspective one can include the search for value-added products using waste from renewable energy sources, such as those from the production of biodiesel. The rapid development of biodiesel production in Brazil directly affected the supply of glycerin and therefore the sector is seeking a market that can absorb this waste. Thus, with the increasing search for environmentally friendly products, formulation of a drilling fluid using a co-product of biodiesel production to replace the n-paraffin is of great importance to the oil industry for meeting the requirement of environmental regulation and, in addition, considerably reducing the cost of raw materials. In this context, the aim of this study was to characterize different glycerins to evaluate their potential as basis for drilling fluids for oil wells and gas. The glycerins were stable under the conditions evaluated without phase separation and precipitation of solids, exhibited good rheological profile and low value of interface tension. The results indicate a strong possibility of use of these glycerins as basis for drilling fluids and applicability by the oil industry.
Microbial consortia recuperated of crude oil samples from the Pampo Sul field, Campos Basin, RJ, produced biosurfactants in mineral media containing glucose and 9,10-dihydrophenantrene, n-nonadecane, nonadecanoic acid, slightly biodegraded crude oil (P1) or heavily biodegraded crude oil (P2) as carbon sources. The production of exopolimeric substances (EPS) and petroleum biodegradation do not necessarily occur simultaneously. The EPS analyses by infrared and eletronspray ionization mass spectrometry (ESI-MS) revealed a mixture of surfactine isoforms. The biosurfactants reduced the surface tension of water and Zinder medium from 72.4 and 55.7 to 28.6 mN m"1. Additionally, this surfactant emulsified different oils in water with performances similar to or better than of a conventional surfactant, Tween 80.
Durante o monitoramento de ensaios de biodegradação com consórcios microbianos recuperados de amostras de petróleo do campo Pampo Sul, Bacia de Campos, RJ, observou-se a produção de substâncias exopoliméricas (EPS) a qual ocorria independentemente do processo de biodegradação. Para potencializar essa produção utilizou-se um meio mineral enriquecido com glicose e 9,10-di-hidrofenantreno, n-nonadecano, ácido nonadecanóico, petróleo levemente biodegradado (P1) e petróleo severamente biodegradado (P2) como fontes de carbono. A análise dos EPS por infravermelho e espectrometria de massas com ionização por electrospray (MS-ESI) revelou uma mistura de isoformas de surfactina, que reduziu a tensão superficial da água e do meio Zinder de 72,4 e 55,7 para 28,6 mN m"1. Além disso, demonstraram capacidade de formar emulsões de diferentes óleos em água, com resultados até melhores que de surfactantes comerciais, como Tween 80. A produção dos EPS não foi inibida por nenhum dos substratos testados.