The origin, migration pathways, as well as the influence of secondary processes of oil and natural gas accumulated in lower Cretaceous to lower Miocene strata of the western part of the Polish Outer Carpathians (between Kraków and Pilzno towns) based on results of organic geochemical analyses are investigated in this paper. Oil and thermogenic hydrocarbon gases were generated mainly from type II kerogen, and type II and III kerogen mixed in various proportions. These kerogens mainly occur in the Oligocene Menilite beds of the Silesian and Dukla nappes. Oils were generated from early to late “oil window”. Secondary cracking was recorded in oils from Dukla nappe, other secondary processes including biodegradation, water washing and evaporative fractionation were also developed to a various extent in many oils. The most biodegraded oils occur in seep S-Li, and the most extensive water washing is observed in the oil from seep S-Sa/1. The evaporative fractionation processes most significantly occur in the selected deepest parts of the multi-horizontal Biecz field. Hydrocarbon gases originated during both microbial and thermogenic processes of organic matter transformation. Natural gas has not been subjected to biodegradation processes. Carbon dioxide is derived from both microbial and thermogenic decomposition processes of organic matter and was generated together with hydrocarbon gases.
Twenty-seven gases and sixteen rock wastes from the thermal active Rymer coal waste dump were collected. The composition and origin of gaseous, liquid, and solid pollutants emitted during the self-heating process and the development of these processes with time were established. Gases were subjected to determination of molecular and stable isotope (δ13C and δ2H) composition. Rock-Eval pyrolysis and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) were applied for evaluation of the quantity and molecular composition of pyrolysates released during the heating of rocks in temperatures from 100 to 650 °C. The main products of Py-GC-MS are released between 350 and 650 °C, namely alkanes, aromatic hydrocarbons, and aromatic alcohols. These components were also recorded in Py-GC-MS products of samples collected from the dump surface. Besides the high-molecular-weight organic compounds, in emitted gases CO2, CO, gaseous hydrocarbons, and S-compounds were recorded. The stable isotope data indicated that methane was generated mainly during the low-temperature thermogenic process, but a share of the microbial-originated gas was visible. The source of the CO2 was the oxidation of organic matter. The gaseous S-compounds were products of high-temperature decomposition of sulphides and organic S-compounds. The hydrocarbon and CO contents of the emitted gases proved to be good indicators for tracking of the self-heating processes.
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