Comparisons of pyrolysis parameters between source rocks and their clay-sized fractions: Implication for source material of hydrocarbon generation

In natural environments, organic-clay interactions are strong and cause organo-clay composites (a combination between organic matter [OM] and clay minerals) to be one of the predominant forms for OM occurrence, and their interactions greatly influence the hydrocarbon (HC) generation of OM within source rocks. However, despite occurring in nature, dominating the OM occurrence, and having unique HC generation ways, organo-clay composites have rarely been investigated as stand-alone petroleum precursors. To improve this understanding, we have compared the Rock-Eval pyrolysis parameters derived from more than 100 source rocks and their corresponding <2 μm clay-sized fractions (representing organo-clay composites). The results show that all of the Rock-Eval pyrolysis parameters in bulk rocks are closely positively correlated with those in their clay-sized fractions, but in clay-sized fractions the quality of OM for HC generation is poorer, in that the pyrolysable organic carbon levels and hydrogen index values are lower, whereas the residual organic carbon levels are higher than those in bulk rocks. Being integrated with the effects of organic-clay interactions on OM occurrence and HC generation, our results suggest that organo-clay composites are stand-alone petroleum precursors for HC generation occurring in source rocks, even if the source rocks exist in great varieties in their attributes. Our source material for HC generation comprehensively integrates the original OM occurrence and HC generation behavior in natural environments, which differs from kerogen and is much closer to the actual source material of HC generation in source rocks, and it calls for further focus on organic-mineral interactions in studies of petroleum systems.

Hydrocarbon source rock assessment of the shale and coal bearing horizons of the Early Paleocene Hangu Formation in Kala-Chitta Range, Northwest Pakistan

The present study aims to investigate the origin, type, thermal maturity and hydrocarbon generation potential of organic matter and paleo-depositional environment of the Early Paleocene (Danian) Hangu Formation outcropped in the Kala-Chitta Range of Northwest Pakistan, Eastern Tethys. Organic-rich shale and coal intervals were utilized for geochemical analyses including TOC (total organic carbon) and Rock–Eval pyrolysis coupled with carbon (δ13Corg) and nitrogen (δ15Norg) stable isotopes. The organic geochemical results showed that the kerogen Type II (oil/gas prone) and Type III (gas prone) dominate the investigated rock units. The TOC (wt%) and S2 yield indicate that the rock unit quantifies sufficient organic matter (OM) to act as potential source rock. However, the thermal maturity Tmax°C marks the over maturation of the OM, which may be possibly linked with the effect attained from nearby tectonically active Himalayan Foreland Fold-and-Thrust Belt system and associated metamorphosed sequences. The organic geochemical analyses deciphered indigenous nature of the OM and resultant hydrocarbons. The δ13Corg and δ15Norg stable isotopic signatures illustrated enrichment of the OM from both marine and terrestrial sources accumulated into the Hangu Formation. The Paleo-depositional model established using organic geochemical and stable isotopic data for the formation supports its deposition in a shallow marine proximal inner shelf environment with prevalence of sub-oxic to anoxic conditions, a scenario that could enhance the OM preservation. Overall, the formation holds promising coal and shale intervals in terms of organic richness, but due to relatively over thermal maturation, it cannot act as an effective source rock for liquid hydrocarbon generation and only minor amount of dry gas can be expected. In implication, the results of this study suggest least prospects of liquid hydrocarbon generation potential within Hangu Formation at studied sections.

Depositional Setting and Enrichment Mechanism of Organic Matter of Lower Cretaceous Shale in Ri-Qing-Wei Basin in the Central Sulu Orogenic Belt

A suite of source rock consists of mudstone and shale, with great thickness and continuous deposition was found in the well LK-1 in Lingshan island in Ri-Qing-Wei basin. In order to evaluate the hydrocarbon generation prospects of these source rock and find the mechanism of organic matter enrichment, shale samples were selected from the core for TOC (total organic carbon) and element geochemistry analysis. The results show that organic matter abundance of the source rocks are generally high with average TOC content of 1.26 wt%, suggesting they are good source rocks. The geochemical features show that the sedimentary environment is mostly anoxic brackish water to salt water environment with arid to semiarid climate condition. The enrichment mechanism of organic matter varied with the evolution of the basin, which was divided into three stages according to the sedimentary characteristics. In the initial-middle period of rifting evolution (stage 1 and early stage 2), paleoproductivity is the major factor of OM-enrichment reflecting by high positive correlation between the TOC contents and paleoproductivity proxies. While with the evolution of the rift basin, redox condition and terrigenous clastic input became more and more important until they became the major factor of OM enrichment in the middle stage of rift evolution (stage 2). In the later stage of rift evolution (latest stage 2 and stage 3), besides terrigenous clastic input, the effect of paleoclimate on OM-enrichment increased gradually from a minor factor to a major factor.

Study on Hydrocarbon Accumulation Periods Based on Fluid Inclusions and Diagenetic Sequence of the Subsalt Carbonate Reservoirs in the Amu Darya Right Bank Block

In order to provide paleofluid evidence of hydrocarbon accumulation periods in the Amu Darya Right Bank Block, microexperiments and simulations related to the Middle-Upper Jurassic Callovian-Oxfordian carbonate reservoirs were performed. On the basis of petrographic observation, the diagenetic stages were divided by cathodoluminescence, and the entrapment stages of fluid inclusions were divided by laser Raman experiment and UV epifluorescence. The hydrocarbon generation (expulsion) curve and burial (thermal) history curve of source rocks were simulated by using real drilling data coupled with geochemical parameters of source rocks, such as total organic carbon (TOC) and vitrinite reflectance ( R o ). The above results were integrated with microthermometry of fluid inclusions by inference the timing of hydrocarbon migration into the carbonate reservoirs. The horizon-flattening technique was used to process the measured seismic profile and restore the structural evolution profile. Four diagenetic periods and three hydrocarbon accumulation periods were identified. (i) For Syntaxial stage, the fluid captured by the overgrowing cement around particles is mainly seawater; (ii) for (Early) Mesogenetic burial stage, the calcite cements began to capture hydrocarbon fluids and show yellow fluorescence under UV illumination; (iii) for (Late) Mesogenetic burial stage, two sets of cleavage fissures developed in massive calcite cements, and oil inclusions with green fluorescence were entrapped in the crystal; (iv) for Telogenetic burial stage, blue fluorescent inclusions along with hydrocarbon gas inclusions developed in dully luminescent calcite veins. Based on the accurate division of hydrocarbon migration and charging stages, combined with the structural evolution history of the traps, the hydrocarbon accumulation model was established. Because two of the three sets of source rocks are of marine origin, resulting in the lack of vitrinite in the kerogen of those source rocks, there may be some deviation between the measured value of R o and the real value. Some systematic errors may occur in the thermal history and hydrocarbon generation (expulsion) history of the two sets of source rocks. Due to the limitations of seismic horizon-flattening technique—such as the inability to accurately recover the inclined strata thickness and horizontal expansion of strata—the final shape of the evolution process of structural profile may also deviate from the real state in geological history. The accumulation model established in this study was based upon the fluid inclusion experiments, which can effectively characterize the forming process of large condensate gas reservoirs in the Amu Darya Right Bank Block and quantify the timing of hydrocarbon charging. However, the hydrocarbon migration and accumulation model does not take the oil-source correlation into account, but only the relationship between the mature state of source rocks and the timing of hydrocarbon charging into the reservoirs. Subsequent research needs to conduct refined oil-source correlation to reveal the relationship between gas, condensate, source rocks, and recently discovered crude oil and more strictly constrain and modify the accumulation model, so as to finally disclose the origin of the crude oil and oil reservoir forming process in the Amu Darya Right Bank Block, evaluate the future exploration potential, and point out the direction of various hydrocarbon resources (condensate gas and crude oil).

Accessibility of Pores to Methane in New Albany Shale Samples of Varying Maturity Determined Using SANS and USANS

The accessibility of pores to methane has been investigated in Devonian New Albany Shale Formation early-mature (Ro = 0.50%) to post-mature (Ro = 1.40%) samples. A Marcellus Shale Formation sample was included to expand the maturation range to Ro 2.50%. These are organic matter-rich rocks with total organic carbon (TOC) values of 3.4 to 14.4% and porosity values of 2.19 to 6.88%. Contrast matching small-angle neutron scattering (SANS) and ultra-small angle neutron scattering (USANS) techniques were used to generate porosity-related data before and after pressure cycling under hydrostatic (in a vacuum and at 500 bar of deuterated methane) and uniaxial stress (0 to ca. 350 bar) conditions. Our results showed that the accessible porosity was small for the samples studied, ranging from zero to 2.9%. No correlation between the accessible porosity and TOC or mineralogical composition was revealed, and the most likely explanation for porosity variation was related to the thermal transformation of organic matter and hydrocarbon generation. Pressure caused improvements in accessible porosity for most samples, except the oil window sample (Ro = 0.84%). Our data show that densification of methane occurs in nanopores, generally starting at diameters smaller than 20 nm, and that the distribution of methane density is affected by pressure cycling.