Search Results (216)

Understanding the microscopic occurrence states of shale oil—particularly the distribution between adsorbed and free phases—is essential for optimizing the development of unconventional reservoirs. In this study, we propose an integrated methodology that combines experimental techniques with molecular dynamics simulations to investigate shale oil behavior within kerogen nanopores. Specifically, pyrolysis–gas chromatography–mass spectrometry (PY-GC-MS), solid-state ¹³C nuclear magnetic resonance (¹³C NMR), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) were performed to construct a representative kerogen molecular model based on shale samples from the Lianggaoshan Formation in the Sichuan Basin. Grand Canonical Monte Carlo (GCMC) simulations and a theoretical occurrence model were applied to quantify the adsorption characteristics of n-dodecane under varying pore sizes, temperatures, and pressure. The results show that temperature exerts a stronger influence than pore diameter on adsorption capacity, with adsorption decreasing by over 50% at higher temperatures, and pressure has a limited effect on the adsorption amount of dodecane molecules. This study offers a robust workflow for evaluating shale oil occurrence states in complex pore systems and provides guidance for thermal stimulation strategies in tight oil reservoirs. Full article

The Northern Tibetan Plateau Basin is the most extensive and least explored Mesozoic marine basin in China and shows considerable potential for oil and gas exploration. This study systematically analyzed the abundance, type, hydrocarbon generation potential, and conversion rate of organic matter within three Jurassic drill core samples from the Biloucuo area of the Northern Tibetan Plateau Basin. The total organic carbon (TOC) content of these Jurassic source rocks was >4%, on average, permitting their classification as excellent source rocks. The average contents of sapropelinite, exinite, vitrinite, and inertinite in kerogen were 74%, 4%, 18%, and 4%, respectively. The H/C and O/C ratios of the kerogen mainly ranged from 0.8 to 1.3 and 0.06 to 0.11, respectively, indicative of type II₁ kerogen. The average S₁ + S₂ content was 15.0 mg/g rock, indicating a high hydrocarbon generation potential. On the basis of the relationship between the quantity of soluble hydrocarbons remaining in the strata and the S₂ and TOC contents, it can be inferred that the hydrocarbon generation conversion rate of these Jurassic source rocks was between 25% and 50%, and partial hydrocarbon expulsion has taken place. It is estimated that the maximum oil generation potential of the formation will reach 20 kg/t rock at a greater depth, which equates to good exploration potential. Full article

The study presents the results of investigations into various types of anhydrous pyrolysis aimed at determining the kinetic parameters of hydrocarbon generation processes from source rocks. Surface outcrop samples from the Silesian, Dukla, and Skole units, characterized by a low level of thermal maturity, were used as experimental material. The samples predominantly represented the Menilite Beds from the aforementioned three units, but also included Istebna, Lgota, Verovice, and Spas beds, which exhibit significantly lower parameters that describe generation properties. The anhydrous pyrolysis experiments provided information on the rate of organic matter decomposition (TG/DSC), the degree of conversion (Rock-Eval), the quality of the obtained products (Py/GC), and the isotopic composition of the gaseous products (Py/GC/IRMS). Chromatographic analyses confirmed the oil-prone nature of kerogen contained in the Menilites from the Dukla Unit (Tylawa area), the Silesian Unit (Iwonicz fold), and the Skole Unit, revealing an equal share of all hydrocarbon fractions: C₁–C₉, C₁₀–C₁₅, and C₁₅₊. Through the integration of pyrolytic studies conducted on potential source rocks in the polish Outer Carpathians, a new type of information was obtained regarding the rate of organic matter decomposition, as well as the fractional and isotopic composition of the pyrolysis products. The set of obtained results was used to estimate the activation energy and characterize the potential source levels. The innovative aspect of this approach involved the isotopic characterization of gaseous products generated during thermal degradation of the source rocks. These data were subsequently used to establish genetic correlations with natural gases accumulated in hydrocarbon reservoirs of the Carpathian region. It has been demonstrated that pyrolysis using PY-GC-IRMS can yield results comparable to those obtained through generation in natural geological conditions. Full article

The Permian Kupferschiefer shale, a key stratigraphic unit within the Zechstein sequence of the Fore-Sudetic Monocline, represents both a metal-rich lithofacies and a potential source rock for hydrocarbon generation. This study presents a comprehensive geochemical characterization of selected Kupferschiefer samples obtained from the Legnica–Głogów Copper District (LGOM) and exploratory boreholes. Analytical methods included Rock-Eval pyrolysis, Py-GC/FID, elemental analysis, TG-FTIR, biomarker profiling, and stable carbon isotope measurements. Results indicate that the shales contain significant amounts of Type II and mixed Type II/III kerogen, derived primarily from marine organic matter with minor terrestrial input. The organic matter maturity, expressed by T_max, places most samples within the oil window. Rock-Eval S2 values exceed 60 mg HC/g rock in some samples, confirming excellent generative potential. Py-GC/FID data further support high hydrocarbon yields, particularly in samples from the CG-4 borehole and LGOM mines. The thermal decomposition of kerogen reveals multiple degradation phases, with evolved gas analysis identifying sulfur-containing compounds and hydrocarbons indicative of sapropelic origin. Isotopic compositions of bitumen and kerogen suggest syngenetic relationships and marine depositional settings, with samples from a North Poland borehole showing isotopic enrichment consistent with post-depositional oxidation. Kinetic parameters calculated using the Kissinger–Akahira–Sunose method demonstrate variable activation energies (107–341 kJ/mol), correlating with differences in organic matter composition and mineral matrix. The observed variability in geochemical properties highlights both regional and facies-dependent influences on the shale’s generative capacity. The study concludes that the Kupferschiefer in southwestern and northern Poland exhibits substantial hydrocarbon generation potential. This potential has been previously underestimated due to the unit’s thinness, but localized zones with high TOC, favorable kerogen type, and low activation energy could be viable exploration targets for natural gas. Full article

The Baorao Trough of the Jiergalangtu Sag, located in the central Erlian Basin, is rich in petroleum resources. However, due to a lack of systematic geochemical characterization and comparative studies with other source rocks, the hydrocarbon generation potential of its Jurassic strata remains unclear. In this study, 125 samples from the Baorao Trough were analyzed to evaluate their hydrocarbon generation potential, identify organic matter sources and depositional environments, and characterize hydrocarbon generation and expulsion. Results show that source rocks from the first member of the Tengge’er (K₁bt₁) Formation and the Aershan (K₁ba) Formation have high organic matter content, favorable kerogen types, and have reached low to medium maturity. In contrast, Jurassic source rocks are predominantly Type III kerogen and highly mature. K₁bt₁ was deposited in a weakly oxidizing to reducing, brackish environment, while K₁ba formed under weakly reducing, saline conditions. Jurassic source rocks also developed in weakly reducing, brackish to saline settings. Notably, saline and reducing environments promote the development of high-quality source rocks. The lower total organic carbon (TOC) threshold for effective source rocks in the study area is 0.8%, and the hydrocarbon expulsion threshold for vitrinite reflectance ratio (R_o) is approximately 0.8%. Accordingly, K₁bt₁ and K₁ba have undergone partial hydrocarbon expulsion but remain within the oil-generating window, indicating strong oil-generating potential. Jurassic source rocks likely experienced early thermal cracking of Type III kerogen, with generated oil migrating or escaping during early geological activity. However, some gas-generating potential remains. These findings provide significant evidence for assessing resource potential, predicting the distribution of high-quality source rocks and favorable exploration areas. Full article

The increasing need for sustainable valorization of fossil-based and waste-derived materials has gained interest in converting complex organic matrices such as kerogen into valuable chemicals. This study explores a two-step oxidative strategy to decompose and valorize kerogen-rich oil shale, aiming to develop a locally based source of aliphatic dicarboxylic acids (DCAs). The method combines air oxidation with subsequent nitric acid treatment to enable selective breakdown of the organic structure under milder conditions. Air oxidation was conducted at 165–175 °C using 1% KOH as an alkaline promoter and 40 bar oxygen pressure (or alternatively 185 °C at 30 bar), targeting 30–40% carbon conversion. The resulting material was then subjected to nitric acid oxidation using an 8% HNO₃ solution. This approach yielded up to 23% DCAs, with pre-oxidation allowing a twofold reduction in acid dosage while maintaining efficiency. However, two-step oxidation was still accompanied by substantial degradation of the structure, resulting in elevated CO₂ formation, highlighting the need to balance conversion and carbon retention. The process offers a possible route for transforming solid fossil residues into useful chemical precursors and supports the advancement of regionally sourced, sustainable DCA production from unconventional raw materials. Full article

The Silurian marine shale in the Sichuan Basin is currently the main reservoir for shale gas reserves and production in China. This study investigates the reservoir evolution of the Silurian marine shale based on fractal dimension, quantifying the complexity and heterogeneity of the shale’s pore structure. Physical simulation experiments were conducted on field-collected shale samples, revealing the evolution of total organic carbon, mineral composition, porosity, and micro-fractures. The fractal dimension of shale pore was characterized using the Frenkel–Halsey–Hill and capillary bundle models. The relationships among shale components, porosity, and fractal dimensions were investigated through a correlation analysis and a principal component analysis. A comprehensive evolution model for porosity and micro-fractures was established. The evolution of mineral composition indicates a gradual increase in quartz content, accompanied by a decline in clay, feldspar, and carbonate minerals. The thermal evolution of organic matter is characterized by the formation of organic pores and shrinkage fractures on the surface of kerogen. Retained hydrocarbons undergo cracking in the late stages of thermal evolution, resulting in the formation of numerous nanometer-scale organic pores. The evolution of inorganic minerals is represented by compaction, dissolution, and the transformation of clay minerals. Throughout the simulation, porosity evolution exhibited distinct stages of rapid decline, notable increase, and relative stabilization. Both pore volume and specific surface area exhibit a trend of decreasing initially and then increasing during thermal evolution. However, pore volume slowly decreases after reaching its peak in the late overmature stage. Fractal dimensions derived from the Frenkel–Halsey–Hill model indicate that the surface roughness of pores (D1) in organic-rich shale is generally lower than the complexity of their internal structures (D2) across different maturity levels. Additionally, the average fractal dimension calculated based on the capillary bundle model is higher, suggesting that larger pores exhibit more complex structures. The correlation matrix indicates a co-evolution relationship between shale components and pore structure. Principal component analysis results show a close relationship between the porosity of inorganic pores, microfractures, and fractal dimension D2. The porosity of organic pores, the pore volume and specific surface area of the main pore size are closely related to fractal dimension D1. D1 serves as an indicator of pore development extent and characterizes the changes in components that are “consumed” or “generated” during the evolution process. Based on mineral composition, fractal dimensions, and pore structure evolution, a comprehensive model describing the evolution of pores and fractal dimensions in organic-rich shale was established. Full article

Fossil resins from the area of Gulf of Gdańsk, Lublin area, Denmark, Bitterfeld, Lusatia and Ukraine, often grouped under the collective term ‘Baltic amber’, are complex organic mineraloids that have undergone various post-depositional transformations. Despite their role in paleontology as a source of for biological inclusions, fossil resins themselves are rarely analyzed as taphonomic objects. In this work, a new geochemical approach to fossil resin taphonomy is presented. Applying the van Krevelen diagram—traditionally used for kerogen classification—allows the diagenetic and catagenetic changes of fossilized resin maturation to be evaluated. Based on literature-derived elemental composition data of C, H, and O contents of ‘Baltic amber’, the diagram is interpreted as an organic matter transformation framework of fossil resins. The results suggest that the so-called ‘Baltic amber’ deposits represent a composite taphocoenoses of resins with different burial histories and maturation scenarios. This approach integrates petrological classification, geochemical maturation, and taphonomic analyses, offering a new way of “tracking” fossil resins maturation changes. Full article

Surfactants can be utilized to improve oil recovery by changing the performance of reservoirs in rock pores. Kerogen is the primary organic matter in shale; however, high temperatures will affect the overall performance of this surfactant, resulting in a decrease in its activity or even failure. The effect of surfactants on kerogen pyrolysis has rarely been researched. Therefore, this study synthesized a polymeric surfactant (PS) with high temperature resistance and investigated its effect on kerogen pyrolysis under the friction of drill bits or pipes via molecular dynamics. The infrared spectra and thermogravimetric and molecular weight curves of the PS were researched, along with its surface tension, contact angle, and oil saturation measurements. The results showed that PS had a low molecular weight, with an MW value of 124,634, and good thermal stability, with a main degradation temperature of more than 300 °C. It could drop the surface tension of water to less than 25 mN·m⁻¹ at 25–150 °C, and the use of slats enhanced its surface activity. The PS also changed the contact angles from 127.96° to 57.59° on the surface of shale cores and reversed to a water-wet state. Additionally, PS reduced the saturated oil content of the shale core by half and promoted oil desorption, indicating a good cleaning effect on the shale oil reservoir. The kerogen molecules gradually broke down into smaller molecules and produced the final products, including methane and shale oil. The main reaction area in the system was the interface between kerogen and the surfactant, and the small molecules produced on the interface diffused to both ends. The kinetics of the reaction were controlled by two processes, namely, the step-by-step cleavage process of macromolecules and the side chain cleavage to produce smaller molecules in advance. PS could not only desorb oil in the core but also promote the pyrolysis of kerogen, suggesting that it has good potential for application in shale oil exploration and development. Full article

The Jurassic Tamulangou Formation in the Hongqi Depression has favorable hydrocarbon generation conditions and great resource potential. This study systematically analyzes the geochemical characteristics and thermal evolution history of the source rocks using data from multiple key wells. The dark mudstone of the Tamulangou Formation has a thickness ranging from 50 to 200 m, with an average total organic carbon (TOC) content of 0.14–2.91%, an average chloroform bitumen “A” content of 0.168%, and an average hydrocarbon generation potential of 0.13–3.71 mg/g. The organic matter is primarily Type II and Type III kerogen, with an average vitrinite reflectance of 0.71–1.36%, indicating that the source rocks have generally reached the mature hydrocarbon generation stage and are classified as medium-quality source rocks. Thermal history simulation results show that the source rocks have undergone two major thermal evolution stages: a rapid heating phase from the Late Jurassic to Early Cretaceous and a slow cooling phase from the Late Cretaceous to the present. There are differences in the thermal evolution history of different parts of the Hongqi Depression. In the southern part, the Tamulangou Formation entered the hydrocarbon generation threshold at 138 Ma, reached the hydrocarbon generation peak at approximately 119 Ma, and is currently in a highly mature hydrocarbon generation stage. In contrast, the central part entered the hydrocarbon generation threshold at 128 Ma, reached a moderately mature stage around 74 Ma, and has remained at this stage to the present. Thermal history simulations indicate that the Hongqi Depression reached its maximum paleotemperature at 100 Ma in the Late Early Cretaceous. The temperature evolution pattern is characterized by an initial increase followed by a gradual decrease. During the Late Jurassic to Early Cretaceous, the Hongqi Depression experienced significant fault-controlled subsidence and sedimentation, with a maximum sedimentation rate of 340 m/Ma, accompanied by intense volcanic activity that created a high-temperature geothermal gradient of 40–65 °C/km, with paleotemperatures exceeding 140 °C and a heating rate of 1.38–2.02 °C/Ma. This thermal background is consistent with the relatively high thermal regime observed in northern Chinese basins during the Late Early Cretaceous. Subsequently, the basin underwent uplift and cooling, reducing subsidence and gradually lowering formation temperatures. Full article

The present study focused on the Upper Cretaceous to Middle Miocene sequence in the Central Gulf of Suez, Egypt. The Upper Cretaceous to Middle Miocene sequence in the October field is thick and deeply buried, consisting mainly of brown limestone, chalk limestone, and reefal limestone intercalated with clastic shale. This study integrated various datasets, including total organic carbon (TOC), Rock-Eval pyrolysis, visual kerogen examination, vitrinite reflectance (%Ro), and bottom-hole temperature measurements. The main objective of this study is to delineate the source rock characteristics of these strata regarding organic richness, thermal maturity, kerogen type, timing of hydrocarbon transformation and generation. The Upper Cretaceous Brown Limestone Formation is represented by 135 samples from four wells and is considered to be a fair to excellent source rock, primarily containing type I and II kerogen. It is immature to early mature, generating oil with a low to intermediate level of hydrocarbon conversion. The Eocene Thebes Formation is represented by 105 samples from six wells and is considered to be a good to fair oil source rock with some potential for gas, primarily containing type II and II/III kerogen. Most samples are immature with a low level of hydrocarbon conversion while few are mature having an intermediate degree of hydrocarbon conversion. The Middle Miocene Lower Rudeis Formation is represented by 8 samples from two wells and considered to be a fair but immature source rock, primarily containing type III kerogen with a low level of conversion representing a potential source for gas. The Middle Miocene Belayim Formation is represented by 29 samples from three wells and is considered to be a poor to good source rock, primarily containing kerogen type II and III. Most samples are immature with a low level of hydrocarbon conversion while few are mature having an intermediate degree of hydrocarbon conversion. 1D basin model A-5 well shows that the Upper Cretaceous Brown Limestone source rock entered the early oil window at 39 Ma, progressed to the main oil window by 13 Ma, and remains in this stage today. The Eocene Thebes source rock began generating hydrocarbons at 21.3 Ma, advanced to the main oil window at 11 Ma, and has been in the late oil window since 1.6 Ma. The Middle Miocene Lower Rudeis source rock entered the early oil window at 12.6 Ma, transitioned to the main oil window at 5.7 Ma, where it remains active. In contrast, the Middle Miocene Belayim source rock has not yet reached the early oil window and remains immature, with values ranging from 0.00 to 0.55 % Ro. The transformation ratio plot shows that the Brown Limestone Formation began transforming into the Upper Cretaceous (73 Ma), reaching 29.84% by the Miocene (14.3 Ma). The Thebes Formation initiated transformation in the Late Eocene (52.3 Ma) and reached 6.42% by 16.4 Ma. The Lower Rudeis Formation began in the Middle Miocene (18.7 Ma), reaching 3.59% by 9.2 Ma. The Belayim Formation started its transformation at 11.2 Ma, reaching 0.63% by 6.8 Ma. Full article

Despite the shale revolution triggering global shale oil and gas exploration, our understanding of the sedimentary environments of deep-water organic-matter-rich shale remains unclear. The sedimentary environment and facies of some siliceous shales at the bottom of the Longmaxi Formation in the Weiyuan area of the Sichuan Basin, China, were therefore analyzed. Nano-resolution petrological characterization and genesis analysis of the siliceous shales studied were conducted using nano-resolution petrologic image datasets. We identified these siliceous shales as microbial mats formed by deep-water traction current sedimentation. The microbial mats’ formation and burial diagenesis processes were divided into seven stages. The silt-grade bioclastic carpet deposits initially, colonizing mud-grade siliceous microbes and forming the siliceous microbial mat. Subsequently, carbohydrate-rich microbes thrive in sediment voids, forming the carbohydrate-rich microbial mat. Additionally, SOM undergoes four stages of burial diagenesis process, progressing from kerogens to pre-oil bitumen generation and ultimately transforming into porous pyrobitumen and nonporous pyrobitumen. This study will improve the understanding of deep-water traction current sedimentation and has implications for guiding shale gas exploration and development. Full article

The lower and middle Carboniferous shale sequences are one of the important potential hydrocarbon source rocks in the piedmont of the southwestern Tarim Basin, China (PSTB). Rock samples were collected from the lower and middle Carboniferous formations on the Kushanhe, Altash, and Aitegou outcrops in the PSTB with the intention of mapping the hydrocarbon molecules within these shale sources and disclosing the relevant geochemical implications. The ratios of Pr/Ph < 1.0 and DBT/P < 0.4 and the enrichment of C₂₃ tricyclic terpanoid indicate that the Carboniferous shale sources were deposited in a reducing and sulfate-poor marine setting with the contribution of terrestrial freshwater. Marine aquatic algae act as the major contributor, resulting in the formation of Type II₁ kerogen. The Carboniferous shale sequences contain abundant diamondoids with 2–4 cages with the predominance of methyldiamantanes, dimethyldiamantanes, and methyltriamantanes. Quantitative extended diamondoid analysis indicates the occurrence of carbonate-rich and carbonate-poor organic facies in the PSTB. Compared to the carbonate-poor facies, the carbonate-rich facies is relatively depleted in C₂₇ diasteranes and rich in gammacerane, C₂₇ regular steranes, and alkylated triamantanes. This indicates that it was deposited in the more salty and stratified water column but with less input of land higher plants. The clay catalysis effects are assumed to be responsible for the discrepancy in steranes and diamondoids. The Carboniferous shale sequences also contain abundant polycyclic aromatic hydrocarbons with 2–5 rings with the predominance of C_0–1-phenanthrenes, chrysenes, and benzofluoranthenes. Thermal maturity parameters associated with polycyclic aromatic hydrocarbons and diamondoids suggest that the Carboniferous shale sources have arrived at the late mature to highly mature stage. This study provides the detailed molecular fingerprints of the lower and middle Carboniferous shale source sequences and explores the underlying geochemical implications. This should be helpful for oil–oil and oil–source correlations and hence petroleum exploration activity in the PSTB. Full article

Carbon isotope of the kerogen (δ¹³C_org), steranes/hopanes (S/H), and C₂₈/C₂₉ sterane ratios in the source rocks from the SARK section at the Early Cambrian Yurtus Formation in the Fortunian Stage in the Tarim Basin of Northwest China reveal a positive excursion that is associated with biological diversity. The enrichment of vanadium/(vanadium + nickel) (V/(V + Ni)) ratios (0.64~0.99, averaging 0.87) for the Yurtus Formation of the Fortunian Stage provide evidence for predominant anoxic bottom water conditions. A sharply decreased V/(V + Ni) ratio in the middle Yurtus Formation suggests enhanced oxygen content of the water column in this interval. However, the total organic carbon (TOC) values in the sedimentary rocks show a marked increase in the middle Yurtus Formation, which is due to the enhanced productivity suggested by a positive δ¹³C_org increase of ~2.0‰ and enhanced S/H and C₂₈/C₂₉ sterane ratios. We suggest that the enhanced oxygen content may have contributed to the biological diversity during the Fortunian Stage in the Tarim Basin. The δ¹³C_org excursion first reported here associated with biological diversity can be correlated with that in South China and possibly elsewhere in this interval. Full article

Concretions represent an exceptional mode of fossil preservation. This is attributed to their mineralized outer mantle, which exhibits low permeability and porosity, thereby limiting diagenetic alteration. The present research employs microscopic Raman spectroscopy to assess the thermal maturity of kerogen—a highly sensitive organic material—within concretions from northeast Taiwan. Comparative analysis of kerogen from the concretion’s core, rim, and surrounding matrix reveals differential preservation states. The organic matter in the core remains relatively unaltered, whereas the rim exhibits partial graphitization, albeit to a lesser extent than the surrounding matrix. These findings indicate a progressive diagenetic gradient, with the core influenced by the least thermal alteration, followed by the rim, and the surrounding matrix that experiences the highest degree of graphitization. Therefore, the present research underscores the role of concretionary encapsulation in mitigating diagenetic modification and enhancing organic matter preservation. Full article