Organic Geochemical Characteristics and Organic Matter Enrichment of the Upper Permian Longtan Formation Black Shale in Southern Anhui Province, South China.

Although previous studies have yielded valuable insights into shale gas reservoirs, a comprehensive understanding of the organic geochemical characteristics and organic matter enrichment of marine-continental transitional shale has yet to be achieved. The Longtan Formation transitional shales were extensively deposited in Southern Anhui Province, South China, during the Late Permian. Our analysis of twenty-two rock samples from one core (Gangdi-1 well) and two outcrops (Daoshanchong outcrop and Changqiao outcrop) revealed that the Longtan Formation shale extracts exhibit a wide range of C11-C35n-alkanes and acyclic isoprenoids, with unimodal, bimodal, and multimodal distributions. The carbon peak ranges from nC15 to nC24, with high quantities of medium-chain n-alkanes (nC22-nC25), indicating that the organic matter in Longtan Formation shale originates from a mixed source of higher plant debris and lower aquatic organisms. Our conclusion is supported by the ternary diagram of C27-C28-C29 regular steranes and the variations of the δ13C values of C15-C32n-alkanes, which is higher than the corresponding value (<1.6‰) of n-alkanes from a single source. Furthermore, thermal maturity proxies based on organic petrography (Ro and Tmax) and biomarkers, such as the ratios of C31 22S/(22S + 22R), C29 20S/(20S + 20R), and C29 ßß/(αα + ßß), suggest that organic matter is in a mature stage of hydrocarbon generation. By analyzing the Pr/Ph ratio and pyrite morphology combined with a plot of total organic carbon (TOC) versus total sulfur (TS) and the Pr/nC17-Ph/nC18 diagram, we speculate that the Longtan Formation shales were chiefly developed in a dysoxic-to-oxic water environment. Finally, we establish depositional models of organic matter enrichment in deltaic and tidal flat-lagoon environments, emphasizing that the abundant mixed-sourced organic matter can significantly enhance primary productivity, and a higher sedimentation rate can distinctly shorten organic matter exposure time in the oxidized water environment, thereby promoting organic matter accumulation in such a setting.

Nanoscale Pore Fractal Characteristics of Permian Shale and Its Impact on Methane-Bearing Capacity: A Case Study from Southern North China Basin, Central China.

Fractal dimension is closely related to the nanoscale pore structure of shale, and it also has an important influence on the gas content of shale. To investigate the correlation between the fractal dimension and the methane (CH4) bearing features of shale, seven Permian shale samples were analyzed with field emission scanning electron microscopy (FE-SEM), low temperature nitrogen (N2), carbon dioxide (CO2) and CH4 adsorption and on-site gas desorption experiments. Based on the N2 adsorption and desorption data, we proposed a new method to better determine the gas adsorption stage at different relative pressure (P/P0) points in the multilayer adsorption or capillary condensation stage. On this basis, two fractal dimensions, D1 (representing the surface roughness) and D2 (representing pore irregularity), were obtained. By correlating the fractal dimensions and nanoscale pore structure parameters, we found that D1 does not correlate with the pore structure parameters except for the micropore volume. Influenced by the aggregation of porous and nonporous materials, D2 has a positive linear relationship with the specific surface area (SSA) and micropore volume but has a negative linear correlation with the average diameter of pores. D1 is negatively correlated with water saturation and positively correlated with free CH4 content. The CH4 adsorption content is positively correlated with D2. By fitting the on-site desorption data, the positive correlation between the total desorbed CH4 content and the desorbed CH4 content in stage 2 and D2 was also confirmed. D2 better reflects the CH4 adsorption capacity of organic-rich shale than D1. However, D1 can be used to reflect the influence of shale surface properties on water saturation and to indirectly reflect the free CH4 content in shale. The fractal dimension (D1 and D2) is a clear indicator of the total free and adsorbed CH4 content, but cannot indicate the desorbed CH4 content at different stages.

Characteristics of three organic matter pore types in the Wufeng-Longmaxi Shale of the Sichuan Basin, Southwest China.

A consensus has been reached through previous studies that organic matter (OM) pores are crucial to porosity in many shale gas reservoirs; however, their origins and types remain controversial. Here, we report the OM pore types hosted in algae, bitumen, graptolite and other fossil fragments in the Wufeng-Longmaxi Formations of the Sichuan Basin, Southwest China. Algae types mainly include multicellular algae, unicellular algae, etc. The OM pores in multicellular algae usually exhibit irregular, bubble-like, spherical and/or elliptical profiles, and their diameters vary between 300 and 800 nm. The shapes of the OM pores in unicellular algae are either irregular or oval, and the pores are hundreds of nanometres in size. The pores associated with solid bitumen are sporadic, isolated and variable in size, ranging from 500 nm to 3 µm. The pores in the graptolite, sponge spicule, radiolarian and other fossil fragments are much smaller and fewer. The pores may only have developed in the surface of the graptolite and bitumen by filling in the biological cavity of the sponge spicule. These new findings provide stronger evidence that multicellular algae are the main hydrocarbon generating organisms of OM pores development.