Investigation on Oil Physical States of Hybrid Shale Oil System: A Case Study on Cretaceous Second White Speckled Shale Formation from Highwood River Outcrop, Southern Alberta

Nine samples collected from the Upper Cretaceous Second White Speckled Shale Formation at the Highwood River outcrop in southern Alberta were geochemically characterized for their oil contents, physical states, and chemical compositions. Cold extraction was performed on 8-10 mm and 2-5 mm chips sequentially to obtain the first and second extractable organic matter (EOM-1 and EOM-2), while Soxhlet extraction was performed on powder from previously extracted chips to obtain the third extract (EOM-3). EOM-1 can be roughly regarded as free oil and EOM-2 is weakly adsorbed on mineral surfaces, while EOM-3 may represent the oil strongly adsorbed on kerogen. While both extraction yields and Rock-Eval pyrolysates differed from their original values due to the evaporative loss during outcropping, there was a generally positive correlation between the total EOM and total oil derived from Rock-Eval pyrolysis. EOM-1 was linearly correlated with Rock-Eval S-1, while the extractable S-2 content was well correlated with the loss of TOC, suggesting that TOC content was the main constraint for adsorbed oils. A bulk composition analysis illustrated that EOM-1 contained more saturated hydrocarbons, while EOM-3 was enriched in resins and asphaltenes. More detailed fractionation between the free and adsorbed oils was demonstrated by molecular compositions of each extract using quantitative GC-MS analysis. Lower-molecular-weight n-alkanes and smaller-ring-number aromatic compounds were preferentially concentrated in EOM-1 as compared to their higher-molecular or greater-ring-number counterparts and vice versa for EOM-3. Fractionation between isoprenoids and adjacent eluted n-alkanes, isomers of steranes, hopanes, alkylnaphthalenes, alkylphenanthrenes and alkyldibenzothiophenes was insignificant, suggesting no allogenic charge from deep strata. Strong chemical fractionation between saturated and aromatic hydrocarbon fractions was observed with EOM-1 apparently enriched in n-alkanes, while EOM-3 retained more aromatic hydrocarbons. However, the difference between free and adsorbed state oils was less dramatic than the variation from shales and siltstones. Lithological heterogeneities controlled both the amount and composition of retained fluids. Oil that resided in shales (source rock) behaved more similar to the EOM-3, with diffusive expulsion leading to the release of discrete molecules from a more adsorbed or occluded phase to a more free phase in siltstones with more connected pores and/or fractures (reservoir). Under current technical conditions, only the free oil can flow and will be the recoverable resource. Therefore, the highest potential can be expected from intervals adjacent to organic-rich beds. The compositional variations due to expulsion and primary migration from source rocks to reservoirs illustrated in the present study will contribute to a better understanding of the distribution of hydrocarbons generated and stored within the shale plays.