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Lamellar calcite veins are prevalent in carbonate-rich, lacustrine dark shale. The formation mechanisms of these veins have been extensively debated, focusing on factors such as timing, depth, material source, and driving forces. This paper examines dark lacustrine shale lamellar calcite veins in the Paleogene strata of Dongying Depression, using various analytical techniques: petrography, isotope geochemistry, cathodoluminescence, inclusion thermometry, and electron probe micro-analysis. Two distinct types of calcite veins have been identified: granular calcite veins and sparry calcite veins. These two types differ significantly in color, grain structure, morphology, and inclusions. Through further investigation, it was observed that vein generation occurred from the shallow burial period to the maturation of organic matter, with a transition from granular calcite veins to sparry calcite veins. The granular calcite veins exhibit characteristics associated with the shallow burial period, including plastically deformed laminae and veins, the development of strawberry pyrite, the absence of oil and gas, weak fractionation in oxygen isotopes, and their contact relationship with sparry calcite veins. These granular calcite veins were likely influenced by the reduction of sulfate bacteria. On the other hand, sparry calcite veins with fibrous grains are antitaxial and closely linked to the evolution and maturation of organic matter. They contain oil and gas inclusions and show a distribution range of homogenization temperature between 90 °C and 120 °C and strong fractionation in oxygen isotopes, indicating formation during the hydrocarbon expulsion period. The carbon isotope analysis of the surrounding rocks and veins suggests that the material for vein formation originates from the shale itself, specifically authigenic micritic calcite modified by the action of methanogens. The opening of horizontal fractures and vein formation is likely driven by fluid overpressure resulting from undercompaction and hydrocarbon expulsion. Veins may form rapidly or through multi-stage composite processes. Early veins are predominantly formed in situ, while late veins are a result of continuous fluid migration and convergence. Furthermore, the veins continue to undergo modification even after formation. This study emphasizes that the formation of lamellar calcite veins in shale is a complex diagenetic process influenced by multiple factors: biology, organic matter, and inorganic processes, all operating at various stages throughout the shale's diagenetic history. [ABSTRACT FROM AUTHOR]

From core observations of shales of the Niutitang formation in the northern part of Guizhou Province, China, calcite was often found to act as a natural fracture filler and affect the extension of fractures in hydraulic fracturing. Therefore, it is crucial to understand the tensile mechanical behavior of shales by calcite veins. In this paper, by computed tomography scanning of shales containing calcite veins of different dip angles from the Niutitang formation, a three‐dimensional numerical model reflecting the internal fine structure of the shale was constructed. Direct tensile numerical simulations were carried out to investigate the effect of calcite veins at different angles on the fine‐scale damage process and mechanical properties of shale. The experimental results show that the tensile capacity of the shale increases with the increase in calcite veins. Depending on the dip angle of the calcite vein, the damage pattern of the shale is divided into three types of damage: pull‐off damage along the calcite vein, jagged damage, and horizontal damage perpendicular to the loading method. At high dip angles, the shale damage is more intense and the fracture network more complex. The temporal and spatial characteristics of the acoustic emissions provide a good indication of the microscopic behavior of the shale specimens during the damage process. The box dimension method was used to calculate the fractal dimension of the shale specimens at the final damage, and it was found that the damage was more intense and the fracture network was more complex at high dip angles, and there was an angular threshold. [ABSTRACT FROM AUTHOR]

The preservation of natural gas can be easily dismissed by late crustal deformations, which are often concealed by fracture-filling calcite vein networks. This study introduces a novel approach to confine the timeframe of natural gas-leakage processes by employing coupled in situ U–Pb dating and clumped isotope (Δ 47) analysis of late-fracture calcite veins associated with brittle deformation in caprock/unconventional reservoirs during basin uplift. Specifically, Δ 47 and U–Pb data were acquired for fracture calcite veins that formed in high-angle or vertical fractures within the early Silurian shale reservoirs of the Southeastern Sichuan Basin in China. Absolute U–Pb ages revealed two distinct calcite precipitation events at 6.89 ± 0.18 and 3.55 ± 0.11 Ma, respectively. The primary mechanism for shale gas escape from early Silurian shale reservoirs was the leakage of natural gas through activated high-angle faults that had remained unsealed since at least 6.89 Ma. At approximately 3.55 Ma, the overlying weathered layer was lifted to the surface of the Earth, facilitating the connection between meteoric water and shale reservoirs through activated fractures. Natural gas leakage occurred concurrently with meteoric water infiltration, and a non-linear mixing effect between methanogenesis and meteoric water, as well as intense ventilation along the water-bearing fracture surface, is identified as the cause of delayed late-fracture calcite precipitation, leading to an abnormal δ13C of calcite vein (up to +22.1‰). This approach holds significant implications for assessing natural-gas preservation in uplifted basins worldwide. • Late crustal movements can mask natural gas risks, challenging preservation assessments. • Combined U–Pb dating and clumped isotope analysis on calcite veins show timing of natural gas leakage events at 6.89 Ma and 3.55 Ma. • Lifting of weathered layer connected meteoric water to shale reservoirs, causing natural gas leakage and abnormal calcite precipitation. [ABSTRACT FROM AUTHOR]

The lack of effective paleogeothermometers restricts the study of the thermal history of carbonate strata. Carbonate clumped isotope thermometry and in-situ U–Pb dating are appropriate for reconstructing the thermal history of carbonate strata. Herein, this study analyzed clumped isotope compositions and U–Pb ages of calcite fabrics, including micrite matrix and veins, from Permian carbonate strata in the eastern Sichuan Basin. U–Pb dating of the micrite matrix was performed to rule out the influence of recrystallization and determine the diagenetic age of the samples. Clumped isotope temperatures of the four micrite matrix samples ranged from 102 °C to 137 °C. The maximum paleotemperature derived from a solid-state reordering model was between 210 °C and 220 °C. From all four samples, three calcite veins yielded crystallization temperatures corresponding to 160 ± 10 °C, 60 ± 10 °C, and 29 ± 4 °C, as determined by clumped isotope and solid-state reordering model analyses. In-situ U–Pb dating provided corresponding crystallization ages of 159 ± 17 Ma, 256.6 ± 5.5 Ma, and 17.86 ± 0.8 Ma. The crystallization ages and temperatures of the three calcite veins align well with the thermal history of the Permian strata, indicating a high degree of accuracy. This study introduces a new strategy for reconstructing the thermal history of carbonate strata. The thermal history can be quantified using the constraints of the crystallization ages and temperatures from different stages of calcite veins or cements. This approach is suitable for determining the maturation progress of the source rock and conducting oil and gas exploration in petroliferous basins. • Permian strata's maximum paleotemperature simulated by clumped isotope is 210–220 °C. • Solid-state reordering model can get the calcite vein's crystallization temperature. • Calcite veins are essential to reconstructing the thermal history of carbonate strata. [ABSTRACT FROM AUTHOR]

The continent is the second largest carbon sink on Earth's surface. With the diversification of vascular land plants in the late Paleozoic, terrestrial organic carbon burial is represented by massive coal formation, while the development of soil profiles would account for both organic and inorganic carbon burial. As compared with soil organic carbon, inorganic carbon burial, collectively known as the soil carbonate, would have a greater impact on the long-term carbon cycle. Soil carbonate would have multiple carbon sources, including dissolution of host calcareous rocks, dissolved inorganic carbon from freshwater, and oxidation of organic matter, but the host calcareous rock dissolution would not cause atmospheric CO2 drawdown. Thus, to evaluate the potential effect of soil carbonate formation on the atmospheric pCO2 level, different carbon sources of soil carbonate should be quantitatively differentiated. In this study, we analyzed the carbon and magnesium isotopes of pedogenic calcite veins developed in a heavily weathered outcrop, consisting of limestone of the early Paleogene Guanzhuang Group in North China. Based on the C and Mg isotope data, we developed a numerical model to quantify the carbon source of calcite veins. The modeling results indicate that 4–37 wt% of carbon in these calcite veins was derived from atmospheric CO2. The low contribution from atmospheric CO2 might be attributed to the host limestone that might have diluted the atmospheric CO2 sink. Nevertheless, taking this value into consideration, it is estimated that soil carbonate formation would lower 1 ppm atmospheric CO2 within 2000 years, i.e., soil carbonate alone would sequester all atmospheric CO2 within 1 million years. Finally, our study suggests the C–Mg isotope system might be a better tool in quantifying the carbon source of soil carbonate. [ABSTRACT FROM AUTHOR]

Abstract The dissolution of marine shales and its influence on reservoir physical properties was revealed based on shale samples from the Ordovician-Silurian Wufeng and Longmaxi Formations in the southeast of the Sichuan Basin, China. Three kinds of gas storage spaces were formed by dissolution, including intergranular dissolution (InterD) pores, intragranular dissolution (IntraD) pores and dissolution microfractures (DmF). The diameters of the InterD and IntraD are 10.2–72.4 μm and 0.13–1.52 μm, respectively. The apertures of the DmF are between 0.5 and 11.2 μm. The dissolution effect resulted in a diagenetic environment for quartz cementation and a material basis for calcite veins. The main controlling factors of the dissolution effect are the mineral constituent content in the matrix, the amount of organic matter and the strata burial rate. Dissolution pores and fractures play important roles in shale gas enrichment and migration. The porosity of shale reservoirs with DmF is twice the porosity of reservoirs without DmF, and the spaces formed by dissolution pores and fractures are well connected. A new model for shale gas flow in shale reservoirs was proposed, which provides a new understanding for the connection between organic material pores, and the results can be used for shale reservoirs worldwide. Highlights • Calcite veins are effective channels for shale flow. • Dissolution pores and dissolution fractures play an important role in the transfusion of shale gas. • Three main controlling factors of dissolution in shale reservoirs are given. • A new model for shale gas flow in shale reservoirs is proposed. [ABSTRACT FROM AUTHOR]