Pub Date : 2025-11-01Epub Date: 2025-08-27DOI: 10.1016/j.orggeochem.2025.105051
Yang Qin , Chiyang Liu , Junfeng Zhao , Faqi He , Wei Zhang , Lihua Yang , Nan Du , Deyong Shao
{"title":"Corrigendum to “Unravelling the origin of gas in tight sandstones of the Hangjinqi gas field, Ordos Basin, China: New insights from natural gas geochemistry data”. [Org. Geochem. 206 (2025) 105012]","authors":"Yang Qin , Chiyang Liu , Junfeng Zhao , Faqi He , Wei Zhang , Lihua Yang , Nan Du , Deyong Shao","doi":"10.1016/j.orggeochem.2025.105051","DOIUrl":"10.1016/j.orggeochem.2025.105051","url":null,"abstract":"","PeriodicalId":400,"journal":{"name":"Organic Geochemistry","volume":"209 ","pages":"Article 105051"},"PeriodicalIF":2.5,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145061218","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-01Epub Date: 2025-08-20DOI: 10.1016/j.orggeochem.2025.105057
Constantin Sandu , Khaled Arouri , Poorna Srinivasan , Estefania Endara Arguello , Assad H. Ghazwani , Ibrahim Atwah
Carbazoles are nitrogen-based aromatic compounds generated from kerogen alongside main oil components and were used in many studies to constrain long migration distances and filling sequences of reservoirs. These compounds have great potential to be used in constraining migration in basin models due to their tendency to selectively change their composition along the migration path. To simulate their generation, a set of kinetic parameters are desired for compound characterization within the basin simulators. This study investigates the generation of carbazoles in Type II-S source rocks through hydrous pyrolysis experiments performed between 275–360 °C, and estimates the kinetic parameters based on the measured composition of pyrolysis products in both expelled and extracted fractions. Up to 870 ppm carbazole concentration was observed in extracted fluids with an average of 27 ppm and up to 70 ppm in expelled fluids but with a much lower average of 3 ppm. Comparing the carbazole yields in the extracted and expelled fractions leads to the conclusion that the bitumen fraction likely represents a primary step in producing carbazoles within the source rock. The kinetic parameters, in the form of activation energy varied between 40 and 70 kcal/mol for the generation process and 50–300 kcal/mol for degradation. Numeric simulations, using the kinetic parameters determined and a generic thermal history for the Arabian Basin, show a differential evolution of each compound that leads to a variation of composition in generated fluids. When compared with field measurements, the modeled composition can be an invaluable tool to constrain petroleum system models.
{"title":"Generation of carbazoles in Type II-S source rocks: Experimental analysis for kinetic parameters estimation","authors":"Constantin Sandu , Khaled Arouri , Poorna Srinivasan , Estefania Endara Arguello , Assad H. Ghazwani , Ibrahim Atwah","doi":"10.1016/j.orggeochem.2025.105057","DOIUrl":"10.1016/j.orggeochem.2025.105057","url":null,"abstract":"<div><div>Carbazoles are nitrogen-based aromatic compounds generated from kerogen alongside main oil components and were used in many studies to constrain long migration distances and filling sequences of reservoirs. These compounds have great potential to be used in constraining migration in basin models due to their tendency to selectively change their composition along the migration path. To simulate their generation, a set of kinetic parameters are desired for compound characterization within the basin simulators. This study investigates the generation of carbazoles in Type II-S source rocks through hydrous pyrolysis experiments performed between 275–360 °C, and estimates the kinetic parameters based on the measured composition of pyrolysis products in both expelled and extracted fractions. Up to 870 ppm carbazole concentration was observed in extracted fluids with an average of 27 ppm and up to 70 ppm in expelled fluids but with a much lower average of 3 ppm. Comparing the carbazole yields in the extracted and expelled fractions leads to the conclusion that the bitumen fraction likely represents a primary step in producing carbazoles within the source rock. The kinetic parameters, in the form of activation energy varied between 40 and 70 kcal/mol for the generation process and 50–300 kcal/mol for degradation. Numeric simulations, using the kinetic parameters determined and a generic thermal history for the Arabian Basin, show a differential evolution of each compound that leads to a variation of composition in generated fluids. When compared with field measurements, the modeled composition can be an invaluable tool to constrain petroleum system models.</div></div>","PeriodicalId":400,"journal":{"name":"Organic Geochemistry","volume":"208 ","pages":"Article 105057"},"PeriodicalIF":2.5,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144923053","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-01Epub Date: 2025-07-30DOI: 10.1016/j.orggeochem.2025.105052
Bin Cheng , Guocong Sun , An Xie , Jie Sun , Xinxin Bo , Xin Tian
The identification of secondary alteration processes in Jurassic reservoirs of the Turpan Depression and the contribution of petroleum from Permian sources remains largely unexplored. This study, based on geochemical analyses of representative oil and condensate samples, systematically integrates carbon isotope data, biomarkers, C5-C7 light hydrocarbon, and diamondoids compositions to identify secondary alterations and assess the contribution of hydrocarbons derived from Permian source rocks. The results reveal that the Jurassic oil reservoirs of wells Y7 and Qt1 have undergone extensive biodegradation, followed by subsequent oil mixing processes with slight to moderate biodegraded oils and fresh, unaltered oils, respectively. Evaporative fractionation is frequently observed in the Jurassic reservoirs, although the degree of its occurrence varies considerably. Reservoirs in the Shengbei sub-sag experienced more intense alteration compared to those in other sub-sags, with the Sb3 and Sb5 reservoirs exhibiting the highest degrees of alteration. Thermal maturity evaluations, based on saturated, aromatic, and light hydrocarbons, reveal that most samples range from peak to late oil-generation stages. Some light oils and condensates have progressed toward the condensate/wet gas stage because of higher maturity charging events. Correlation analysis indicates the coexistence of three end-member oil and condensate families within the Jurassic reservoirs, those generated from Jurassic coal-measure source rocks, those derived from Jurassic Qiketai source rocks, and those originating from Middle Permian source rocks, further suggesting that the Permian-origin hydrocarbons have made a substantial contribution to the Jurassic reservoirs in some regions, despite being generated at varying thermal maturity stages. Overall, the Jurassic oil reservoirs in the Turpan Depression have undergone multiple secondary alteration processes and experienced complex charging events from both Jurassic and Permian source rocks, resulting in a highly complicated hydrocarbon accumulation mechanisms.
{"title":"Secondary alteration and probable sources of oils and condensates in Jurassic reservoirs of the Turpan Depression, Turpan-Hami Basin, NW China","authors":"Bin Cheng , Guocong Sun , An Xie , Jie Sun , Xinxin Bo , Xin Tian","doi":"10.1016/j.orggeochem.2025.105052","DOIUrl":"10.1016/j.orggeochem.2025.105052","url":null,"abstract":"<div><div>The identification of secondary alteration processes in Jurassic reservoirs of the Turpan Depression and the contribution of petroleum from Permian sources remains largely unexplored. This study, based on geochemical analyses of representative oil and condensate samples, systematically integrates carbon isotope data, biomarkers, C<sub>5</sub>-C<sub>7</sub> light hydrocarbon, and diamondoids compositions to identify secondary alterations and assess the contribution of hydrocarbons derived from Permian source rocks. The results reveal that the Jurassic oil reservoirs of wells Y7 and Qt1 have undergone extensive biodegradation, followed by subsequent oil mixing processes with slight to moderate biodegraded oils and fresh, unaltered oils, respectively. Evaporative fractionation is frequently observed in the Jurassic reservoirs, although the degree of its occurrence varies considerably. Reservoirs in the Shengbei sub-sag experienced more intense alteration compared to those in other sub-sags, with the Sb3 and Sb5 reservoirs exhibiting the highest degrees of alteration. Thermal maturity evaluations, based on saturated, aromatic, and light hydrocarbons, reveal that most samples range from peak to late oil-generation stages. Some light oils and condensates have progressed toward the condensate/wet gas stage because of higher maturity charging events. Correlation analysis indicates the coexistence of three end-member oil and condensate families within the Jurassic reservoirs, those generated from Jurassic coal-measure source rocks, those derived from Jurassic Qiketai source rocks, and those originating from Middle Permian source rocks, further suggesting that the Permian-origin hydrocarbons have made a substantial contribution to the Jurassic reservoirs in some regions, despite being generated at varying thermal maturity stages. Overall, the Jurassic oil reservoirs in the Turpan Depression have undergone multiple secondary alteration processes and experienced complex charging events from both Jurassic and Permian source rocks, resulting in a highly complicated hydrocarbon accumulation mechanisms.</div></div>","PeriodicalId":400,"journal":{"name":"Organic Geochemistry","volume":"208 ","pages":"Article 105052"},"PeriodicalIF":2.5,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144724532","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-01Epub Date: 2025-04-03DOI: 10.1016/j.orggeochem.2025.104994
Ruth R. Tweedy , Caroline A.E. Strömberg , Tammo Reichgelt , Rahab N. Kinyanjui , Mbaluka Kimeu , Venanzio Munyaka , Kevin T. Uno
Reconstructing past vegetation can elucidate the timing, climate forcings, and biotic mechanisms of ecosystem change. Plant macro- and microfossils are traditionally used to study past vegetation but suffer from production and taphonomic biases, such as underrepresentation of important herbaceous vegetation components. Geochemical proxies can fill this gap, but carbon isotopes (δ13C) in isolation are unable to distinguish between structurally different C3 habitats, such as forests and grasslands. Thus, new geochemical methods to identify grassy C3 ecosystems are necessary. We present n-alkane chain length distributions of 209 plant specimens from two Kenyan C3-dominated ecosystems, representing a wide range of plant functional types (PFTs). We find that C3 PACMAD grasses produce exceptionally high abundances of long chain C33 and C35n-alkanes (ACL = 32.7, mean C33 + C35 relative abundance = 0.69), unlike other C3 PFTs which produce low abundances of C33 and C35 (ACL = 28.9–30.3, mean C33 + C35 relative abundance = 0.0–0.21). This finding highlights the importance of measuring and reporting the C35n-alkane. Our data further demonstrate that n-alkane distributions can serve as a proxy for some African C3 PACMAD grasses, offering a new paleoecological tool for distinguishing C3 vegetation types.
{"title":"African C3 grass n-alkane distributions & plant chemotaxonomy","authors":"Ruth R. Tweedy , Caroline A.E. Strömberg , Tammo Reichgelt , Rahab N. Kinyanjui , Mbaluka Kimeu , Venanzio Munyaka , Kevin T. Uno","doi":"10.1016/j.orggeochem.2025.104994","DOIUrl":"10.1016/j.orggeochem.2025.104994","url":null,"abstract":"<div><div>Reconstructing past vegetation can elucidate the timing, climate forcings, and biotic mechanisms of ecosystem change. Plant macro- and microfossils are traditionally used to study past vegetation but suffer from production and taphonomic biases, such as underrepresentation of important herbaceous vegetation components. Geochemical proxies can fill this gap, but carbon isotopes (δ<sup>13</sup>C) in isolation are unable to distinguish between structurally different C<sub>3</sub> habitats, such as forests and grasslands. Thus, new geochemical methods to identify grassy C<sub>3</sub> ecosystems are necessary. We present <em>n</em>-alkane chain length distributions of 209 plant specimens from two Kenyan C<sub>3</sub>-dominated ecosystems, representing a wide range of plant functional types (PFTs). We find that C<sub>3</sub> PACMAD grasses produce exceptionally high abundances of long chain C<sub>33</sub> and C<sub>35</sub> <em>n</em>-alkanes (ACL = 32.7, mean C<sub>33</sub> + C<sub>35</sub> relative abundance = 0.69), unlike other C<sub>3</sub> PFTs which produce low abundances of C<sub>33</sub> and C<sub>35</sub> (ACL = 28.9–30.3, mean C<sub>33</sub> + C<sub>35</sub> relative abundance = 0.0–0.21). This finding highlights the importance of measuring and reporting the C<sub>35</sub> <em>n</em>-alkane. Our data further demonstrate that <em>n</em>-alkane distributions can serve as a proxy for some African C<sub>3</sub> PACMAD grasses, offering a new paleoecological tool for distinguishing C<sub>3</sub> vegetation types.</div></div>","PeriodicalId":400,"journal":{"name":"Organic Geochemistry","volume":"208 ","pages":"Article 104994"},"PeriodicalIF":2.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144365586","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-01Epub Date: 2025-06-26DOI: 10.1016/j.orggeochem.2025.105046
Shi Qian , Huan Yang , Jie Wu , Shucheng Xie , Qinmian Xu
Branched glycerol monoalkyl glycerol tetraethers (brGMGTs, or H-brGDGTs), lipids that occur widely in anoxic sediments of peatlands, lakes, and oceans, have been proposed as new tools for paleotemperature reconstructions in lakes and peatlands. However, their reliability has not been widely assessed, particularly in sediment cores. Here, we report the H-brGDGT distributions in the Xiong'an (XA) 3 sediment core from North China, spanning 5.5 million years (Ma), to evaluate their reliability as a terrestrial paleothermometer. Seven major H-brGDGTs are consistently abundant throughout the sediment core. Their isomerization index (IRH) values, characteristic of river and lake environments, suggest H-brGDGTs were predominantly produced in situ with negligible soil input. Their abundances and distributions are strongly related to a widely used paleothermometer, MBT′5ME (methylation index of branched tetraethers for 5-methylated branched GDGTs), likely indicating their temperature dependence. An H-brGDGT-based temperature proxy, H-MBT′, which includes only the H-1020c and H-1034b isomers, was found to track temperature in both published modern peat/lake H-brGDGT data set and the XA3 sediment core. H-MBT′ reconstructed temperature trend is consistent with the brGDGT temperature record in the sediment core as well as global climate signals, revealing stable warmth during 5.5–2.6 Ma, abrupt cooling at ∼2.6 Ma coinciding with the onset of Northern Hemisphere Glaciation (NHG), and oscillating decline during 2.2–0 Ma. Our results validate H-brGDGTs as a potential paleothermometer in aquatic systems but highlight the need for the selection of proper H-brGDGT-based temperature proxies and environment-specific calibrations to refine accuracy.
{"title":"Assessing the reliability of H-brGDGTs as terrestrial paleothermometers in Plio-Pleistocene fluvio-lacustrine deposits from Northern China","authors":"Shi Qian , Huan Yang , Jie Wu , Shucheng Xie , Qinmian Xu","doi":"10.1016/j.orggeochem.2025.105046","DOIUrl":"10.1016/j.orggeochem.2025.105046","url":null,"abstract":"<div><div>Branched glycerol monoalkyl glycerol tetraethers (brGMGTs, or H-brGDGTs), lipids that occur widely in anoxic sediments of peatlands, lakes, and oceans, have been proposed as new tools for paleotemperature reconstructions in lakes and peatlands. However, their reliability has not been widely assessed, particularly in sediment cores. Here, we report the H-brGDGT distributions in the Xiong'an (XA) 3 sediment core from North China, spanning 5.5 million years (Ma), to evaluate their reliability as a terrestrial paleothermometer. Seven major H-brGDGTs are consistently abundant throughout the sediment core. Their isomerization index (IR<sub>H</sub>) values, characteristic of river and lake environments, suggest H-brGDGTs were predominantly produced <em>in situ</em> with negligible soil input. Their abundances and distributions are strongly related to a widely used paleothermometer, MBT′<sub>5ME</sub> (methylation index of branched tetraethers for 5-methylated branched GDGTs), likely indicating their temperature dependence. An H-brGDGT-based temperature proxy, H-MBT′, which includes only the H-1020c and H-1034b isomers, was found to track temperature in both published modern peat/lake H-brGDGT data set and the XA3 sediment core. H-MBT′ reconstructed temperature trend is consistent with the brGDGT temperature record in the sediment core as well as global climate signals, revealing stable warmth during 5.5–2.6 Ma, abrupt cooling at ∼2.6 Ma coinciding with the onset of Northern Hemisphere Glaciation (NHG), and oscillating decline during 2.2–0 Ma. Our results validate H-brGDGTs as a potential paleothermometer in aquatic systems but highlight the need for the selection of proper H-brGDGT-based temperature proxies and environment-specific calibrations to refine accuracy.</div></div>","PeriodicalId":400,"journal":{"name":"Organic Geochemistry","volume":"208 ","pages":"Article 105046"},"PeriodicalIF":2.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144579680","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-01Epub Date: 2025-06-27DOI: 10.1016/j.orggeochem.2025.105045
Guangli Wang , Ying Xu , Yang Yang , Zhirong Zhang , Yuhong Liao
Catalytic hydropyrolysis (HyPy) is an effective method for the release of covalently bound biomarkers from geo-macromolecules (e.g., kerogen or asphaltenes). It is particularly valuable for samples that lack geochemical proxies resulting from extensive maturation or secondary alteration. In this study, HyPy was carried out on asphaltene fractions isolated from crude oils collected from 10 reservoirs of various depths in the Panyu lower uplift in the central Pearl River Mouth Basin, South China Sea. Significant quantities of biomarkers and polycyclic aromatic hydrocarbons (PAHs) were released, and their molecular and isotopic compositions were obtained. The results suggest that these bound compounds were not affected by secondary alteration processes, such as biodegradation in shallow reservoirs or water washing in deeper ones. The δ13C values of the HyPy products were 1.2 ‰–2.2 ‰ more enriched than those of the original bulk oils, and are inconsistent with traditional δ13C patterns (the asphaltene fraction generally has the most enriched δ13C value among petroleum fractions). These reservoirs, therefore, may represent a composite petroleum system involving contributions from multiple source rocks rather than a single source as previously interpreted. This hypothesis is also supported by the molecular and biomarker signatures of the products, which showed elevated proportions of C11–C16n-alkanes and C19 tricyclic terpanes, and a marked dominance of 24-ethylcholestanes (ranging from 52 % to 79 % of total steranes), significantly exceeding the C27 and C28 homologues. A substantial input of organic matter from vascular plants, much higher than that of the presumed source rocks of the Eocene Wenchang Formation, was found. Therefore, the earlier petroleum charges to the Panyu lower uplift may be associated with the Eocene–Oligocene Enping Formation interbedded with coaly source rock intervals. In contrast, the maltenes of the oil samples were rich in 4-methylsteranes, dinosteranes, and triaromatic dinosteroids, as well as minor oleananes, which closely resemble the biomarker signatures of lacustrine source rocks from the Eocene Wenchang Formation. These findings support a dual contribution to the petroleum reservoirs across the Panyu lower uplift, where the major oils concerned with the coaly source rocks of the Enping Formation and the lacustrine shale source rocks of the Wenchang Formation were likely responsible for potential large hydrocarbon accumulations.
{"title":"Multiple sources of petroleum in the Panyu lower uplift evidenced by catalytic hydropyrolysis of petroleum asphaltenes","authors":"Guangli Wang , Ying Xu , Yang Yang , Zhirong Zhang , Yuhong Liao","doi":"10.1016/j.orggeochem.2025.105045","DOIUrl":"10.1016/j.orggeochem.2025.105045","url":null,"abstract":"<div><div>Catalytic hydropyrolysis (HyPy) is an effective method for the release of covalently bound biomarkers from geo-macromolecules (e.g., kerogen or asphaltenes). It is particularly valuable for samples that lack geochemical proxies resulting from extensive maturation or secondary alteration. In this study, HyPy was carried out on asphaltene fractions isolated from crude oils collected from 10 reservoirs of various depths in the Panyu lower uplift in the central Pearl River Mouth Basin, South China Sea. Significant quantities of biomarkers and polycyclic aromatic hydrocarbons (PAHs) were released, and their molecular and isotopic compositions were obtained. The results suggest that these bound compounds were not affected by secondary alteration processes, such as biodegradation in shallow reservoirs or water washing in deeper ones. The δ<sup>13</sup>C values of the HyPy products were 1.2 ‰–2.2 ‰ more enriched than those of the original bulk oils, and are inconsistent with traditional δ<sup>13</sup>C patterns (the asphaltene fraction generally has the most enriched δ<sup>13</sup>C value among petroleum fractions). These reservoirs, therefore, may represent a composite petroleum system involving contributions from multiple source rocks rather than a single source as previously interpreted. This hypothesis is also supported by the molecular and biomarker signatures of the products, which showed elevated proportions of C<sub>11</sub>–C<sub>16</sub> <em>n</em>-alkanes and C<sub>19</sub> tricyclic terpanes, and a marked dominance of 24-ethylcholestanes (ranging from 52 % to 79 % of total steranes), significantly exceeding the C<sub>27</sub> and C<sub>28</sub> homologues. A substantial input of organic matter from vascular plants, much higher than that of the presumed source rocks of the Eocene Wenchang Formation, was found. Therefore, the earlier petroleum charges to the Panyu lower uplift may be associated with the Eocene–Oligocene Enping Formation interbedded with coaly source rock intervals. In contrast, the maltenes of the oil samples were rich in 4-methylsteranes, dinosteranes, and triaromatic dinosteroids, as well as minor oleananes, which closely resemble the biomarker signatures of lacustrine source rocks from the Eocene Wenchang Formation. These findings support a dual contribution to the petroleum reservoirs across the Panyu lower uplift, where the major oils concerned with the coaly source rocks of the Enping Formation and the lacustrine shale source rocks of the Wenchang Formation were likely responsible for potential large hydrocarbon accumulations.</div></div>","PeriodicalId":400,"journal":{"name":"Organic Geochemistry","volume":"208 ","pages":"Article 105045"},"PeriodicalIF":2.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144489968","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-01Epub Date: 2025-06-23DOI: 10.1016/j.orggeochem.2025.105044
Rongzhen Qiao, Meijun Li, Donglin Zhang, Hong Xiao
Steranes and terpanes, as key biomarkers in oils and source rock extracts, provide valuable information about their biological origins, depositional environment, and thermal maturity. The distribution patterns of steranes and terpanes in ultra-deep oil reservoirs within the Shuntuoguole low uplift are complex. The intensity of hydrothermal activity and the influence of sulfur ions were assessed based on the conversion of “Biphenyl–Dibenzothiophene–Phenanthrene” series compounds. The results reveal that the southern sections of F5, F12, and F4 exhibit relatively strong hydrothermal activity (F number: No. number fault zone). The southern sections of F5, F1, and F4 are more significantly impacted by sulfur ion activity under the hydrothermal action. Studies indicate that sterane and terpene concentrations decrease due to sulfur ion activity under the hydrothermal action. Tricyclic terpanes, cholestanes, C31-35 homohopanes, C30 hopane, C29 diahopane, and pregnane exhibit low stability under the influence of sulfur ion activity in the hydrothermal action. Notably, although tricyclic terpanes, cholestanes, and pregnane show low stability, they are not preferentially depleted. Combined analysis of the relative Gibbs free energies of C30 diahopane and C30 hopane showed that sulfur ions do not promote pyrolysis by altering the degradation pathways of steranes and terpanes. Instead, sulfur ions likely lower the pyrolysis threshold by reducing the activation energy, preserving the relative stability of steranes and terpanes. This study advances the understanding of organic–inorganic interactions in hydrothermal systems.
{"title":"Sulfur ions reduce the activation energy of steranes and terpanes under hydrothermal action","authors":"Rongzhen Qiao, Meijun Li, Donglin Zhang, Hong Xiao","doi":"10.1016/j.orggeochem.2025.105044","DOIUrl":"10.1016/j.orggeochem.2025.105044","url":null,"abstract":"<div><div>Steranes and terpanes, as key biomarkers in oils and source rock extracts, provide valuable information about their biological origins, depositional environment, and thermal maturity. The distribution patterns of steranes and terpanes in ultra-deep oil reservoirs within the Shuntuoguole low uplift are complex. The intensity of hydrothermal activity and the influence of sulfur ions were assessed based on the conversion of “Biphenyl–Dibenzothiophene–Phenanthrene” series compounds. The results reveal that the southern sections of F5, F12, and F4 exhibit relatively strong hydrothermal activity (F number: No. number fault zone). The southern sections of F5, F1, and F4 are more significantly impacted by sulfur ion activity under the hydrothermal action. Studies indicate that sterane and terpene concentrations decrease due to sulfur ion activity under the hydrothermal action. Tricyclic terpanes, cholestanes, C<sub>31-35</sub> homohopanes, C<sub>30</sub> hopane, C<sub>29</sub> diahopane, and pregnane exhibit low stability under the influence of sulfur ion activity in the hydrothermal action. Notably, although tricyclic terpanes, cholestanes, and pregnane show low stability, they are not preferentially depleted. Combined analysis of the relative Gibbs free energies of C<sub>30</sub> diahopane and C<sub>30</sub> hopane showed that sulfur ions do not promote pyrolysis by altering the degradation pathways of steranes and terpanes. Instead, sulfur ions likely lower the pyrolysis threshold by reducing the activation energy, preserving the relative stability of steranes and terpanes. This study advances the understanding of organic–inorganic interactions in hydrothermal systems.</div></div>","PeriodicalId":400,"journal":{"name":"Organic Geochemistry","volume":"208 ","pages":"Article 105044"},"PeriodicalIF":2.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144338788","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-01Epub Date: 2025-07-23DOI: 10.1016/j.orggeochem.2025.105049
Ziao Geng , Meijun Li , Shuichang Zhang , Shengbao Shi , Wenqiang Wang , Lei Zhu , Tiantian Li , Jianfeng Zhang
This study analyzes the δ13C values of various polycyclic aromatic compounds (PACs), including dibenzofuran, and methyldibenzofurans in two sets of coals from the Junggar and Ordos basins in NW China. The results reveal that the δ13C values of individual PACs are primarily influenced by the source of degraded organic matter rather than thermal maturity. The significant differences in δ13C values (−11.7 ‰) between dibenzofuran (DBF) and its methylated homologues (MDBFs) imply different sources. DBF is primarily derived from higher plants, while MDBFs have multiple sources from both lichens and higher plants. However, the δ13C values of DBF and MDBF in predominantly pyrogenic samples are relatively similar. This is due to two factors: (1) The kinetic isotope effect leads to preferential demethylation of 12C-enriched MDBF isomers, and the residual MDBFs are consequently enriched in 13C isotopes. The DBF produced by this process is enriched in 12C isotope, leading to depletion of δ13C for DBF in the combustion products. (2) Greater higher plant than lichen inputs result in higher δ13C values of MDBFs also potentially causes lower δ13C values in DBF. These two factors combine to produce similar δ13C values for DBF and MDBFs in samples heavily affected by wildfires.
{"title":"Geochemical implications of the carbon isotope compositions of individual polycyclic aromatic compounds in coals from the Junggar and Ordos basins, NW China","authors":"Ziao Geng , Meijun Li , Shuichang Zhang , Shengbao Shi , Wenqiang Wang , Lei Zhu , Tiantian Li , Jianfeng Zhang","doi":"10.1016/j.orggeochem.2025.105049","DOIUrl":"10.1016/j.orggeochem.2025.105049","url":null,"abstract":"<div><div>This study analyzes the δ<sup>13</sup>C values of various polycyclic aromatic compounds (PACs), including dibenzofuran, and methyldibenzofurans in two sets of coals from the Junggar and Ordos basins in NW China. The results reveal that the δ<sup>13</sup>C values of individual PACs are primarily influenced by the source of degraded organic matter rather than thermal maturity. The significant differences in δ<sup>13</sup>C values (−11.7 ‰) between dibenzofuran (DBF) and its methylated homologues (MDBFs) imply different sources. DBF is primarily derived from higher plants, while MDBFs have multiple sources from both lichens and higher plants. However, the δ<sup>13</sup>C values of DBF and MDBF in predominantly pyrogenic samples are relatively similar. This is due to two factors: (1) The kinetic isotope effect leads to preferential demethylation of <sup>12</sup>C-enriched MDBF isomers, and the residual MDBFs are consequently enriched in <sup>13</sup>C isotopes. The DBF produced by this process is enriched in <sup>12</sup>C isotope, leading to depletion of δ<sup>13</sup>C for DBF in the combustion products. (2) Greater higher plant than lichen inputs result in higher δ<sup>13</sup>C values of MDBFs also potentially causes lower δ<sup>13</sup>C values in DBF. These two factors combine to produce similar δ<sup>13</sup>C values for DBF and MDBFs in samples heavily affected by wildfires.</div></div>","PeriodicalId":400,"journal":{"name":"Organic Geochemistry","volume":"208 ","pages":"Article 105049"},"PeriodicalIF":2.6,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144687102","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-01Epub Date: 2025-08-20DOI: 10.1016/j.orggeochem.2025.105053
Shangli Liu , Haifeng Gai , Xinyue Shi , Peng Cheng , Tengfei Li , Qin Zhou , Sui Ji , Hui Tian
Total organic carbon (TOC) content is a crucial indicator in shale oil exploration due to its close correlation with shale oil content. However, the proportion of movable oil significantly decreases in high-TOC shales. Herein, eight marine shale samples from the same well, with TOC contents ranging from 1.86 % to 13.78 % and vitrinite reflectance values of 0.8–0.9 %, were analyzed to investigate the effect of TOC content on the occurrence and distribution of retained oils. Sequential extraction with various solvent mixtures revealed that extractable organic matter (EOM), as extracted by n-hexane/toluene (9:1v/v), primarily comprises saturated and aromatic hydrocarbons, which are chemically similar to the oils released by Rock-Eval pyrolysis before 300 °C (S1 peak). Therefore, the EOM is an effective way to evaluate the free oil content in shales. By contrast, the EOMs extracted by dichloromethane/methanol (93:7 v/v) and tetrahydrofuran/acetone/methanol (50:25:25 v/v/v) are mainly composed of resins and asphaltenes that correspond to the oils released during Rock-Eval pyrolysis above 300 °C, indicating their predominant occurrence as adsorbed oil. After sequential extraction, the specific surface area and pore volume of shale samples increase by an average 369 % and 254 %, respectively. Pore structure analysis reveals that organic matter (OM) content significantly affects the occurrence space of retained oil. In the case of early oil window maturity, excessive OM can lead to a low free oil ratio, low storage space, high adsorption capacity, and high threshold pore diameter of movable oil, indicating that excessive OM is unfavorable for the enrichment of movable oil. Therefore, there may be an upper TOC limit for shale oil sweet spots. For our samples, the free oil content significantly decreases when TOC exceeds 10 wt%. This threshold may vary for different shales depending on thermal maturity, kerogen type, and pore structure. Shale dominated by Type I/II kerogen typically exhibit a lower optimal TOC threshold at the main oil generation stage (Cf. Type III kerogen), further emphasizing the importance of identifying these thresholds during exploration.
{"title":"Controls of organic matter content on shale oil occurrence and distribution: Insights from retained oil composition and pore structure in marine shales","authors":"Shangli Liu , Haifeng Gai , Xinyue Shi , Peng Cheng , Tengfei Li , Qin Zhou , Sui Ji , Hui Tian","doi":"10.1016/j.orggeochem.2025.105053","DOIUrl":"10.1016/j.orggeochem.2025.105053","url":null,"abstract":"<div><div>Total organic carbon (TOC) content is a crucial indicator in shale oil exploration due to its close correlation with shale oil content. However, the proportion of movable oil significantly decreases in high-TOC shales. Herein, eight marine shale samples from the same well, with TOC contents ranging from 1.86 % to 13.78 % and vitrinite reflectance values of 0.8–0.9 %, were analyzed to investigate the effect of TOC content on the occurrence and distribution of retained oils. Sequential extraction with various solvent mixtures revealed that extractable organic matter (EOM), as extracted by <em>n</em>-hexane/toluene (9:1v/v), primarily comprises saturated and aromatic hydrocarbons, which are chemically similar to the oils released by Rock-Eval pyrolysis before 300 °C (S<sub>1</sub> peak). Therefore, the EOM is an effective way to evaluate the free oil content in shales. By contrast, the EOMs extracted by dichloromethane/methanol (93:7 v/v) and tetrahydrofuran/acetone/methanol (50:25:25 v/v/v) are mainly composed of resins and asphaltenes that correspond to the oils released during Rock-Eval pyrolysis above 300 °C, indicating their predominant occurrence as adsorbed oil. After sequential extraction, the specific surface area and pore volume of shale samples increase by an average 369 % and 254 %, respectively. Pore structure analysis reveals that organic matter (OM) content significantly affects the occurrence space of retained oil. In the case of early oil window maturity, excessive OM can lead to a low free oil ratio, low storage space, high adsorption capacity, and high threshold pore diameter of movable oil, indicating that excessive OM is unfavorable for the enrichment of movable oil. Therefore, there may be an upper TOC limit for shale oil sweet spots. For our samples, the free oil content significantly decreases when TOC exceeds 10 wt%. This threshold may vary for different shales depending on thermal maturity, kerogen type, and pore structure. Shale dominated by Type I/II kerogen typically exhibit a lower optimal TOC threshold at the main oil generation stage (Cf. Type III kerogen), further emphasizing the importance of identifying these thresholds during exploration.</div></div>","PeriodicalId":400,"journal":{"name":"Organic Geochemistry","volume":"208 ","pages":"Article 105053"},"PeriodicalIF":2.5,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144880327","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}