Abstract Biosurfactants and waterflooding have been widely reported thus far for enhancing oil production. Nevertheless, there is a lack of literature to explore enhanced oil recovered methods effects on its chemical composition. The aim of this work is to investigate the effects of a biosurfactant produced by Bacillus safensis and brine injection on the recovered petroleum composition, and their implications for geochemical interpretation. Original and oils recovered from displacement tests were analyzed by gas chromatography and ultra-high-resolution mass spectrometry, emphasizing saturated and aromatic biomarkers and basic and acidic polar compounds. Geochemical parameters based on some saturated compounds were subtly affected by the recovery methods, showing their reliable applicability in geochemical studies. Contrarily, parameters based on some aromatic compounds were more affected by biosurfactant flooding, mostly the low molecular weight compounds. Thus, these aromatic parameters should be applied with caution after such methods. The distribution of basic and acidic polar compounds can also be modified affecting the geochemical interpretation. In the case of the basic ones, the biosurfactant greatly influenced the N class species with favorable loss of lower aromaticity compounds. In addition to water solubilization, the compositional changes described in this study can be related to fractionation due to adsorption on reservoir rocks.

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.

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.