Evaluating Re-Os systematics in organic-rich sedimentary rocks in response to petroleum generation using hydrous pyrolysis experiments
Successful application of the 187 Re– 187 Os geochronometer has enabled the determination of accurate and precise depositional ages for organic-rich sedimentary rocks (ORS) as well as establishing timing constraints of petroleum generation. However, we do not fully understand the systematics and transfer behaviour of Re and Os between ORS and petroleum products (e.g., bitumen and oil). To more fully understand the behaviour of Re–Os systematics in both source rocks and petroleum products we apply hydrous pyrolysis to two immature hydrocarbon source rocks: the Permian Phosphoria Formation (TOC = 17.4%; Type II-S kerogen) and the Jurassic Staffin Formation (TOC = 2.5%; Type III kerogen). The laboratory-based hydrous pyrolysis experiments were carried out for 72 h at 250, 300, 325 and 350 °C. These experiments provided us with whole rock, extracted rock and bitumen and in some cases expelled oil and asphaltene for evaluation of Re–Os isotopic and elemental abundance. The data from these experiments demonstrate that the majority (>95%) of Re and Os are housed within extracted rock and that thermal maturation does not result in significant transfer of Re or Os from the extracted rock into organic phases. Based on existing thermodynamic data our findings suggest that organic chelating sites have a greater affinity for the quadravalent states of Re and Os than sulphides. Across the temperature range of the hydrous pyrolysis experiments both whole rock and extracted rock 187 Re/ 188 Os ratios show small variations (3.3% and 4.7%, for Staffin, respectively and 6.3% and 4.9% for Phosphoria, respectively). Similarly, the 187 Os/ 188 Os ratios show only minor variations for the Staffin and Phosphoria whole rock and extracted rock samples (0.6% and 1.4% and 1.3% and 2.2%). These isotopic data strongly suggest that crude oil generation through hydrous pyrolysis experiments does not disturb the Re–Os systematics in ORS as supported by various studies on natural systems. The elemental abundance data reveal limited transfer of Re and Os into the bitumen from a Type III kerogen in comparison to Type II-S kerogen (0.02% vs. 3.7%), suggesting that these metals are very tightly bound in Type III kerogen structure. The 187 Os/ 188 Os data from the pyrolysis generated Phosphoria bitumens display minor variation (4%) across the experimental temperatures, with values similar to that of the source rock. This indicates that the isotopic composition of the bitumen reflects the isotopic composition of the source rock at the time of petroleum generation. These data further support the premise that the Os isotopic composition of oils and bitumens can be used to fingerprint petroleum deposits to specific source rocks. Oil generated through the hydrous pyrolysis experiments does not contain appreciable quantities of Re or Os (~120 and ~3 ppt, respectively), in contrast to natural oils (2–50 ppb and 34–288 ppt for Re and Os, respectively), which may suggest that kinetic parameters are fundamental to the transfer of Re and Os from source rocks to oils. From this we hypothesise that, at the temperatures employed in hydrous pyrolysis, Re and Os are assimilated into the extracted rock as a result of cross-linking reactions.