Molecular and isotopic compositions of bitumens in Silurian tar sands from the Tarim Basin,NW China: Characterizing biodegradation and hydrocarbon charging in an old composite basin

Biodegradation and oil mixing in Silurian sandstone reservoirs of the Tarim Basin, one of the largest composite basins in China, were investigated by analyzing the molecular characteristics and stable carbon isotopic signatures of low-molecular-weight (LMW) saturated hydrocarbons and high-molecular-weight (HMW) asphaltenes. Detection of 25-norhopanes and 17-nortricyclic terpanes in most Silurian tar sands from the Tabei Uplift in the Tarim Basin suggests a much greater degree of biodegradation here than in the Tazhong Uplift. This explains the relatively more abundant tricyclic terpanes, gammacerane, pregnane and diasteranes in tar sands from the Tabei Uplift than in those from the Tazhong Uplift. Hence, care must be taken when assigning oil source correlations using biomarkers in tar sands because of the biodegradation and mixing of oils derived from multiple sources in such an old composite basin. Asphaltenes in the tar sands seem to be part of the oil charge before biodegradation, depending on the relative anti-biodegradation characteristics of asphaltenes, the similarity in carbon isotopic signatures for asphaltenes and their pyrolysates, and the consistent product distribution for flash pyrolysis and for regular steranes in asphaltene pyrolysates, regardless of whether the tar sands were charged with fresh oil. According to the relative distributions of regular steranes and the relatively abundant 1,2,3,4-tetramethylbenzene significantly enriched in ¹³C, the oil sources for asphaltenes in the tar sands might be related to lower Paleozoic marine source rocks formed in euxinic conditions. Nevertheless, the relatively low abundance of gammacerane and C₂₈ regular steranes observed in asphaltene pyrolysates and residual hydrocarbons, within limited samples investigated in this work, made a direct correlation of oils originally charged into Silurian tar sands with those Cambrian source rocks, reported so far, seem not to be possible. Comparison of carbon isotopic signatures of n-alkanes in asphaltene pyrolysates with those of LMW saturated hydrocarbons is helpful in determining if the abundant n-alkanes in tar sands are derived from fresh oil charges after biodegradation. The limited carbon isotopic data for n-alkanes in LMW saturated hydrocarbons from the tar sands can be used to classify oils charged after biodegradation in the composite basin into four distinct groups.     

Studies of the formation process of water-in-oil emulsions

This paper summarizes studies to determine the formation process of water-in-oil emulsions and the stability of such emulsions formed in the laboratory and in a large test tank. These studies have confirmed that water-in-oil mixtures can be grouped into four states: stable emulsions, unstable water-in-oil mixtures, mesostable emulsions, and entrained water. These states are differentiated by rheological properties as well as by differences in visual appearance. The viscosity of a stable emulsion at a shear rate of one reciprocal second is about three orders of magnitude greater than that of the starting oil. An unstable emulsion usually has a viscosity no more than about 20 times greater than that of the starting oil. A stable emulsion has a significant elasticity, whereas an unstable emulsion does not. A mesostable emulsion has properties between stable and unstable, but breaks down within a few days of standing. The usual situation is that emulsions are either obviously stable, mesostable, or unstable. Entrained water, water suspended in oil by viscous forces alone, is also evident. Very few emulsions have questionable stability. Analytical techniques were developed to test these observations.

The type of emulsion produced is determined primarily by the properties of the starting oil. The most important of these properties are the asphaltene and resin content and the viscosity of the oil. The composition and property ranges of the starting oil that would be required to form each of the water-in-oil states are discussed in this paper.     

Tmax of asphaltenes: a parameter for oil maturity assessment

A new maturity parameter determined on both oil and bitumen samples, the asphaltene T_max, is proposed and discussed. This parameter could be very useful to address the maturity of the source rock. The asphaltene T_max is measured by programmed Rock-Eval pyrolysis, using a modified temperature program. Some phases of the experimental procedure, such as the asphaltene preparation and the Rock-Eval measurement substratum choice, are crucial in order to achieve reliable data. Laboratory simulations were carried out in order to assess the possible effects of both primary and secondary migration on asphaltene T_maxin the expelled oil: the original value of the asphaltene T_max in the bitumen is not substantially modified and it is very close to that measured on kerogen. Examples of the determination of asphaltene T_max on many samples, collected from different areas and with different organic matter composition, are given. Results show that T_max values from oil asphaltenes are reasonable indicators of source rock maturity.     

Evaluation of the petroleum composition and quality with increasing thermal maturity as simulated by hydrous pyrolysis: A case study using a Brazilian source rock with Type I kerogen

Hydrous pyrolysis (HP) experiments were used to investigate the petroleum composition and quality of petroleum generated from a Brazilian lacustrine source rock containing Type I kerogen with increasing thermal maturity. The tested sample was of Aptian age from the Araripe Basin (NE-Brazil). The temperatures (280–360 °C) and times (12–132 h) employed in the experiments simulated petroleum generation and expulsion (i.e., oil window) prior to secondary gas generation from the cracking of oil. Results show that similar to other oil prone source rocks, kerogen initially decomposes in part to a polar rich bitumen, which decomposes in part to hydrocarbon rich oil. These two overall reactions overlap with one another and have been recognized in oil shale retorting and natural petroleum generation. During bitumen decomposition to oil, some of the bitumen is converted to pyrobitumen, which results in an increase in the apparent kerogen (i.e., insoluble carbon) content with increasing maturation.The petroleum composition and its quality (i.e., API gravity, gas/oil ratio, C₁₅₊ fractions, alkane distribution, and sulfur content) are affected by thermal maturation within the oil window. API gravity, C₁₅₊ fractions and gas/oil ratios generated by HP are similar to those of natural petroleum considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous age. API gravity of the HP expelled oils shows a complex relationship with increasing thermal maturation that is most influenced by the expulsion of asphaltenes. C₁₅₊ fractions (i.e., saturates, aromatics, resins and asphaltenes) show that expelled oils and bitumen are compositionally separate organic phases with no overlap in composition. Gas/oil ratios (GOR) initially decrease from 508–131 m³/m³ during bitumen generation and remain essentially constant (81–84 m³/m³) to the end of oil generation. This constancy in GOR is different from the continuous increase through the oil window observed in anhydrous pyrolysis experiments. Alkane distributions of the HP expelled oils are similar to those of natural crude oils considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous age. Isoprenoid and n-alkane ratios (i.e., pristane/n-C₁₇ and phytane/n-C₁₈) decrease with increasing thermal maturity as observed in natural crude oils. Pristane/phytane ratios remain constant with increasing thermal maturity through the oil window, with ratios being slightly higher in the expelled oils relative to those in the bitumen. Generated hydrocarbon gases are similar to natural gases associated with crude oils considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous, with the exception of elevated ethane contents. The general overall agreement in composition of natural and hydrous pyrolysis petroleum of lacustrine source rocks observed in this study supports the utility of HP to better characterize petroleum systems and the effects of maturation and expulsion on petroleum composition and quality.     

Recognizing and compensating for interference from the sediment’s background organic matter and biodegradation during interpretation of biomarker data from seafloor hydrocarbon seeps: An example from the Marco Polo area seeps,Gulf of Mexico,USA

A suite of seep samples from the vicinity of the Marco Polo field in the Green Canyon area of the Gulf of Mexico provides an exceptional opportunity to study the impact of interference from sediment background organic matter and alteration by biodegradation on thermogenic hydrocarbons from seafloor seeps. These seep samples contain a range in both the concentration of seeped hydrocarbons present and level of biodegradation experienced. In addition, the subsurface oil that sources the seepage was available for comparison.