Search

The Paleozoic Wufeng-Longmaxi shale is one of the main horizons for shale gas exploration in Sichuan Basin. Outcrop, core and thin section observations, X-ray diffraction analysis, trace element geochemistry and other methods have been used to understand the sedimentary characteristics and identify hydrocarbon source rocks in suitable sedimentary paleoenvironments in the Wufeng-Longmaxi shale in northern Guizhou Province. The thickness of the Wufeng-Longmaxi Formation ranges from 20 to 200 m and it was mainly deposited on a deep-water shelf. The TOC content is high, up to 5.75%. The main non-organic minerals are detrital quartz and clay minerals, with a little plagioclase feldspar, potassium feldspar, calcite, dolomite and pyrite. There is also biogenic microcrystalline quartz. Six lithofacies have been identified: siliceous shale, clay shale, calcareous shale, silty shale, carbonaceous shale, and muddy siltstone. Using biological Ba, V/(V+Ni), TOC, V/Cr, B, Sr/Ba and other indicators, we estimate primary productivity, redox conditions and paleosalinity and show that the early stage of Wufeng-Longmaxi deposition occurred under strong anoxic conditions, high paleosalinity and yielded a high TOC content and an excellent potential shale gas source. The anoxic environment was destroyed at the late stages of Wufeng-Longmaxi deposition, the TOC content decreased, so that it is likely to be a high quality source rock. Organic pores acted as the key reservoir space in the shales, and the pores are mainly mesopose, with most pore diameters less than 20 nm. The siliceous shale has high TOC content and brittle mineral (quartz) content making it an important exploration target for shale oil and gas exploration. [ABSTRACT FROM AUTHOR]

Although the annual production of shale gas in China was 13 × 10 8 m 3 in 2014, a systematic study on geochemical and isotopic characteristics of these unconventional gases has not been well addressed. In the present study, almost all shale gas samples available in China, including marine shale gas from the Wufeng-Longmaxi Formation in the Sichuan Basin (O 3 w–S 1 l) and terrestrial shale gas from Chang 7 Member (T 3 y 7 ) in the Ordos Basin, were collected and analyzed for their geochemical and isotopic compositions. The shale gas from the Wufeng-Longmaxi Shale is dry gas with an average methane content of 98.38% and records a highest content of CH 4 in the world (99.59%), which is consistent with the very high thermal maturity levels of the gas shales that have equivalent vitrinite reflectance (EqVRo) values between 2.4 and 3.6%. The δ 13 C 1 values are correspondingly heavy and record a heaviest δ 13 C 1 values (−26.7‰) for the shale gases found in the world as well. The average values of δ 13 C 1 , δ 13 C 2 and δ 13 C 3 for the Wufeng-Longmaxi shale gas are −31.3‰, −35.6‰, and −47.2‰, respectively, displaying a complete carbon isotopic reversal (i.e., δ 13 C 1 > δ 13 C 2 > δ 13 C 3 ). δ 2 H CH4 and δ 2 H C2H6 has an average value of −148‰ and −173‰, respectively, also yielding a hydrogen isotopic reversal (i.e., δ 2 H CH4 > δ 2 H C2H6 ). The Chang 7 shale has an average TOC content of 13.81% with vitrinite reflectance (VRo) values between 0.7 and 1.2%. The Chang 7 shale gas is wet gas with an average methane content of 84.90% and is rich in heavy gaseous hydrocarbons (C 2 –C 5 ). The respective values of δ 13 C 1 , δ 13 C 2 and δ 13 C 3 are −48.7‰, −36.4‰ and −31.3‰, displaying a positive carbon isotopic distribution pattern (i.e., δ 13 C 1 < δ 13 C 2 < δ 13 C 3 ). The average δ 2 H CH4 , δ 2 H C2H6 and δ 2 H C3H8 values are −256‰, −244‰ and −188‰, respectively, and are characterized by a positive distribution pattern (i.e., δ 2 H CH4 < δ 2 H C2H6 < δ 2 H C3H8 ). The differences in gas wetness and carbon and hydrogen isotopic distribution patterns between the shale gases from the Wufeng-Longmaxi and Chang 7 shale are attributed to variations in thermal maturity levels. CO 2 is present in low content in both the Wufeng-Longmaxi and Chang 7 shale gases, mostly less than 1%. δ 13 C values for the CO 2 in the Wufeng-Longmaxi Formation are between 8.9 and −9.2‰, indicating an inorganic origin from the cracking of carbonate mineral in the shales under high temperatures. In contrast, δ 13 C values of the CO 2 in the Chang 7 shale gas range from −8.2 to −22.7‰, indicating an organic origin from the thermal degradation of organic matter. Helium in both the Wufeng-Longmaxi and Chang 7 shale gases is dominantly of curst origin in terms of their R/Ra ratios that vary from 0.01 to 0.08. Positive carbon isotopic distribution pattern is typical of primitive thermogenic gas. However, it can be converted into complete or partial carbon isotopic reversal patterns due to secondary alteration. The causes that yield carbon isotopic reversal include (1) mixing of gases with the same source but different thermal maturity levels; (2) secondary cracking of oil or wet gas; (3) formation water-involved reactions; (4) gas diffusion; and (5) carbon isotope exchange between alkane gases at high temperature. Among them, carbon isotopic exchange between alkane gases at high temperature is a key factor. Nine plots have been drawn based on the shale gases from China, USA and Canada. Among them, the plot of δ 13 C 2 versus wetness demonstrates a “lying-S” shape with two inflection points on the gas wetness axis. The wetness value of 1.4% represents a critical point from pyrolytic gas (primary cracking gas) to cracking gas (secondary cracking gas) and whereas the wetness value of 6% marks the end of oil generation. On the diagram of wetness versus δ 13 C, shale gases with wetness values greater than 1.6% are characterized by positive carbon isotopic distribution pattern, whereas a complete or partial carbon isotopic reversals are observed for shale gases with wetness values less than 1.6%. [ABSTRACT FROM AUTHOR]

The Lower Cambrian organic-rich marine shale, which is a significant source of China’s shale gas, is widely distributed in southern China. An integrated characterization of the Niutitang shale is provided in this study in terms of organic geochemistry, mineralogy, pore characterization, methane sorption capacity, rock mechanical properties, fractures and gas content based on samples from three wells. The results indicate that the Lower Cambrian Niutitang shale is thermally over-mature and has rich shale gas resources, with a total organic carbon content (TOC) between 0.51% and 10.49% and a high quartz content between 35.3% and 78.5%. Compared to the major gas-producing shales in the U.S. and China, most of the organic matter (OM)-hosted pores in the Niutitang shale are generally smaller than 5 nm, significantly affecting the methane sorption capacity. The inter-particle and intra-particle pores and fractures are the primary sources of storage space, especially for free gas. For samples with TOC values less than 6.5%, TOC is positively correlated with the total porosity, total pore volume, brittleness (Young’s modulus), core fracture density, free gas content and Langmuir pressure; however, for samples with TOC values greater than 6.5%, the positive correlations become negative. These characteristics are due to the ductility and low hydrocarbon generation potential of organic matter in high thermal maturity shales that are vulnerable to compaction. Thus, TOC has a significant impact on the macroscopic (e.g., brittleness) and microscopic (e.g., pore structure and sorption capacity) properties of shale reservoirs, potentially controlling the enrichment and productivity of shale gas. These results can be used to optimize drilling and fracturing stimulation intervals during shale gas exploration and development. [ABSTRACT FROM AUTHOR]