Thiadiamondoids and diamondoidthiols are orders of magnitude more abundant in oil altered by thermochemical sulfate reduction (TSR) than they are in nonaltered oil. This suggests that thiadiamondoids and diarriondoidthiols form during TSR. In order to prove this hypothesis, we perform laboratory TSR experiments on diverse organic compounds using sodium sulfate as an oxidant in the presence of elemental sulfur and deionized water at 200 and 350 ??C for 48 and 96 h under acidic conditions (pH = 4). Our results show that thiadiamondoids and diamondoidthiols can e created from non-sulfur-containing diamondoids by TSR. It seems likely that diamondoid species are organic precursors of thiadiamondoids and diamondoidthiols. In addition, thiocholesterol yields trace quantities of dimethyl-2-thiaadamaintanes when heated with montmorillonite at 200 ??C, suggesting that these diamondoid derivatives may partly originate by molecular rearrangement of polycyclic sulfides and thiols in the presence of acidic clay minerals since they also exist in crude oil that has not undergone TSR. The present study of these heteroatomic cage compounds improves understanding of TSR and can be used to reduce risk in petroleum exploration. ?? 2007 American Chemical Society.
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Origins of thiadiamondoids and diamondoidthiols in petroleum