Steroids are widely used in geochemical studies. They are common in living organisms, sediments and petroleum, and the diagenetic pathways of steroidal compounds in the subsurface are reasonably well understood. However, there are still some questions concerning their thermal evolution (i.e., isomerization, aromatization, and cracking), such as the rates of formation and alteration of various steroidal compounds and the effects of catalysis on these processes, specifically the possible influence of sulfur-containing species. To address these questions, cholesterol and a mixture of cholesterol and elemental sulfur were reacted to simulate the thermal evolution pathways of steroids in the laboratory. Anhydrous pyrolysis experiments were conducted in sealed gold tubes at temperatures ranging from 150 °C to 600 °C using heating rates of 2 °C/h and 20 °C/h, and the products were analyzed by gas chromatography and gas chromatography-mass spectrometry. For the pure cholesterol experiments, the formation of sterenes, steranes and monoaroamtic steroids, and finally triaromatic steroids occurred at EasyRo ~ 0.42%, 0.73%, and 1.36%, respectively. All species were converted into smaller moieties such as phenanthrenes, pyrenes, etc., at EasyRo > 1.69%. The presence of elemental sulfur in the pyrolysis experiments significantly increased the rate of the thermal evolution of steroids, with an earlier onset of the generation of smaller moieties such as methylphenanthrenes and dimethylphenanthrenes at EasyRo 0.86%. Diasterenes and diasteranes were not observed in either the pure cholesterol or the cholesterol with elemental sulfur experiments. The aromatization path starting from the C-ring of steroids was not observed in the experiments using pure cholesterol but occurred in the sulfur-containing series. The presence of sulfur significantly increased the rate of isomerization and aromatization of steranes, especially sterane ring isomerization, and increased the equilibrium values of isomerization parameters by 0.1–0.2 compared to that of the pure cholesterol series. These findings indicate that the presence of sulfur-containing species has important implications for the thermal evolution of steroids.
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