This study examined the molecular and isotopic compositions of gases generated from different kerogen types (i.e., Types I/II, II, IIS and III) in Menilite Shales by sequential hydrous pyrolysis experiments. The experiments were designed to simulate gas generation from source rocks at pre-oil-cracking thermal maturities. Initially, rock samples were heated in the presence of liquid water at 330 ??C for 72 h to simulate early gas generation dominated by the overall reaction of kerogen decomposition to bitumen. Generated gas and oil were quantitatively collected at the completion of the experiments and the reactor with its rock and water was resealed and heated at 355 ??C for 72 h. This condition simulates late petroleum generation in which the dominant overall reaction is bitumen decomposition to oil. This final heating equates to a cumulative thermal maturity of 1.6% Rr, which represents pre-oil-cracking conditions. In addition to the generated gases from these two experiments being characterized individually, they are also summed to characterize a cumulative gas product. These results are compared with natural gases produced from sandstone reservoirs within or directly overlying the Menilite Shales. The experimentally generated gases show no molecular compositions that are distinct for the different kerogen types, but on a total organic carbon (TOC) basis, oil prone kerogens (i.e., Types I/II, II and IIS) generate more hydrocarbon gas than gas prone Type III kerogen. Although the proportionality of methane to ethane in the experimental gases is lower than that observed in the natural gases, the proportionality of ethane to propane and i-butane to n-butane are similar to those observed for the natural gases. ??13C values of the experimentally generated methane, ethane and propane show distinctions among the kerogen types. This distinction is related to the ??13C of the original kerogen, with 13C enriched kerogen generating more 13C enriched hydrocarbon gases than kerogen less enriched in 13C. The typically assumed linear trend for ??13C of methane, ethane and propane versus their reciprocal carbon number for a single sourced natural gas is not observed in the experimental gases. Instead, the so-called "dogleg" trend, exemplified by relatively 13C depleted methane and enriched propane as compared to ethane, is observed for all the kerogen types and at both experimental conditions. Three of the natural gases from the same thrust unit had similar "dogleg" trends indicative of Menilite source rocks with Type III kerogen. These natural gases also contained varying amounts of a microbial gas component that was approximated using the ????13C for methane and propane determined from the experiments. These approximations gave microbial methane components that ranged from 13-84%. The high input of microbial gas was reflected in the higher gas:oil ratios for Outer Carpathian production (115-1568 Nm3/t) compared with those determined from the experiments (65-302 Nm3/t). Two natural gas samples in the far western part of the study area had more linear trends that suggest a different organic facies of the Menilite Shales or a completely different source. This situation emphasizes the importance of conducting hydrous pyrolysis on samples representing the complete stratigraphic and lateral extent of potential source rocks in determining specific genetic gas correlations. ?? 2009 Elsevier Ltd.
Additional publication details
Comparison of natural gases accumulated in Oligocene strata with hydrous pyrolysis gases from Menilite Shales of the Polish Outer Carpathians