An experimental comparison of gas generation from three oil fractions: Implications for the chemical and stable carbon isotopic signatures of oil cracking gas

Although oil cracking has been documented as one of the important sources of gas in many overmature marine sedimentary basins, the chemical and carbon isotopic signatures of gases of this origin are still open to question. In this study a Cambrian crude oil from the central Tarim basin, along with its main separated fractions (saturates, aromatics and asphaltenes), were pyrolyzed in sealed gold tubes to investigate how generated gases vary in chemical and carbon isotopic composition and how this variation would influence the genetic interpretation of oil cracking gas. The results indicate that the gases from cracking of aromatics and asphaltenes are much drier and more enriched in C-13 than the gases from the cracking of saturates and crude oil at the same level of thermal maturity. In the experimental run of 20 degrees C/h, the dryness index of the gases (defined as the volume percentage of C-1 in C1-5) from the cracking of saturates ranges from 26.2-90.6% with the methane carbon isotope change ranging from -54.8 parts per thousand to -35.5 parts per thousand, whereas the dryness index is never lower than 60.6% for the gases from the cracking of aromatics with methane carbon isotope ranging from -39.9 parts per thousand to -32.2 parts per thousand. Correspondingly, experimental data for the four samples plot in different areas in diagrams designed to distinguish oil cracking gas from kerogen cracking gas, such as ln(C-2/C-3) vs. delta C-13(2)-delta C-13(3) and delta C-13(1) vs. delta C-13(2)-delta C-13(3), indicating compositional variability of crude oil could assert an important influence in these diagrams. Therefore it is prudent to bring other geological constraints into consideration to avoid misinterpretation. The kinetic parameters for the bulk generation of C1-5 gas and the methane carbon isotope fractionation extrapolated to geological conditions of 2 degrees C/Ma and an initial temperature of 50 degrees C show that the temperatures of C1-5 gas generation from the aromatics and asphaltenes are lower than those from the saturates and crude oil due to their lower activation energies and frequency factors. Generation of C1-5 gases from the aromatics is modeled to be initiated about 122 degrees C whereas the initiation temperature for the saturates sample is 176 degrees C. Below 189 degrees C (EasyRo = 1.8%), the yields of C1-5 gases follow the order: aromatics > asphaltenes > crude oil > saturates. At similar thermal maturity levels, the methane carbon isotopic compositions are significantly different for the four samples, with an order of C-13 enrichment: aromatics > asphaltenes > crude oil > saturates, however the difference in methane carbon isotopes becomes smaller with increasing temperature. This indicates that methane carbon isotopic values can be significantly different for gases cracked from oils that are compositionally diverse, especially in the early stage of methane generation. (C) 2012 Elsevier Ltd. All rights reserved.