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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] 《鄂尔多斯盆地杭锦旗气田致密砂岩气源解析:天然气地球化学数据的新见解》勘误。(Org。地球化学,206 (2025)105012 [j]
IF 2.5 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-11-01 Epub Date: 2025-08-27 DOI: 10.1016/j.orggeochem.2025.105051
Yang Qin , Chiyang Liu , Junfeng Zhao , Faqi He , Wei Zhang , Lihua Yang , Nan Du , Deyong Shao
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引用次数: 0
Geochemistry Articles – June 2025 地球化学文章- 2025年6月
IF 2.5 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-11-01 Epub Date: 2025-07-23 DOI: 10.1016/j.orggeochem.2025.105048
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引用次数: 0
Generation of carbazoles in Type II-S source rocks: Experimental analysis for kinetic parameters estimation II-S型烃源岩中咔唑的生成:动力学参数估计的实验分析
IF 2.5 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-10-01 Epub Date: 2025-08-20 DOI: 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.
咔唑是由干酪根与主要油组分一起生成的氮基芳香族化合物,在许多研究中用于限制油藏的长距离运移距离和充填顺序。这些化合物具有沿运移路径选择性改变其组成的趋势,因此具有很大的潜力用于限制盆地模型中的运移。为了模拟它们的生成,需要一组动力学参数来在盆地模拟器中进行复合表征。本研究通过275-360°C的加水热解实验,研究II-S型烃源岩中咔唑的生成,并根据热解产物的测定组分和萃取组分估算动力学参数。在萃取液中观察到高达870 ppm的咔唑浓度,平均为27 ppm,在排出液中高达70 ppm,但平均为3 ppm,要低得多。通过比较提取和排出馏分中咔唑的产率可以得出结论,沥青馏分可能代表了烃源岩中咔唑生成的第一步。生成过程的动力学参数为40 ~ 70 kcal/mol,降解过程的动力学参数为50 ~ 300 kcal/mol。利用确定的动力学参数和阿拉伯盆地的一般热历史进行的数值模拟显示,每种化合物的不同演化导致了生成流体成分的变化。当与现场测量相比较时,模拟的成分可以成为约束石油系统模型的宝贵工具。
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引用次数: 0
Secondary alteration and probable sources of oils and condensates in Jurassic reservoirs of the Turpan Depression, Turpan-Hami Basin, NW China 吐哈盆地吐鲁番坳陷侏罗系次生蚀变及油气可能来源
IF 2.5 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-10-01 Epub Date: 2025-07-30 DOI: 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.
吐鲁番坳陷侏罗系储层次生蚀变过程的识别以及二叠系烃源岩的贡献在很大程度上仍有待探索。本研究在对代表性油气样品进行地球化学分析的基础上,系统整合碳同位素数据、生物标志物、C5-C7轻烃和金刚石类化合物组成,识别二叠系烃源岩的次生蚀变,评估二叠系烃源岩烃源岩的贡献。结果表明,Y7井和Qt1井侏罗系油藏经历了广泛的生物降解过程,随后分别发生了轻度至中度生物降解油和新鲜未变质油的混油过程。蒸发分馏作用在侏罗系储层中是常见的,但其发生程度差异较大。生北子凹陷蚀变程度较其他子凹陷更为强烈,以Sb3和Sb5凹陷蚀变程度最高。基于饱和烃、芳烃和轻烃的热成熟度评价表明,大多数样品的产油阶段从高峰到晚期。由于较高的成熟度充注事件,一些轻质油和凝析油向凝析/湿气阶段发展。对比分析表明,侏罗系烃源岩中存在侏罗系煤系烃源岩、侏罗系七克台烃源岩和中二叠统烃源岩3个端元油、凝析油家族共存,进一步表明二叠系烃源岩对部分地区侏罗系储集层的贡献较大,尽管其生成阶段不同。总体而言,吐鲁番坳陷侏罗系油藏经历了多次次生蚀变过程,并经历了侏罗系和二叠系烃源岩复杂的充注事件,形成了高度复杂的成藏机制。
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引用次数: 0
African C3 grass n-alkane distributions & plant chemotaxonomy 非洲C3草正构烷烃分布与植物化学分类
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-10-01 Epub Date: 2025-04-03 DOI: 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 C35 n-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 C35 n-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.
重建过去的植被可以阐明生态系统变化的时间、气候强迫和生物机制。植物宏观和微化石传统上用于研究过去的植被,但存在生产和分类上的偏差,例如重要的草本植被成分代表性不足。地球化学指标可以填补这一空白,但单独的碳同位素(δ13C)无法区分结构不同的C3栖息地,如森林和草原。因此,需要新的地球化学方法来识别草C3生态系统。我们介绍了来自肯尼亚两个c3主导生态系统的209个植物标本的正构烷烃链长分布,代表了广泛的植物功能类型(pft)。我们发现C3 PACMAD草的长链C33和C35正构烷烃的丰度异常高(ACL = 32.7,平均C33 + C35相对丰度= 0.69),而其他C3 PFTs的C33和C35的丰度较低(ACL = 28.9-30.3,平均C33 + C35相对丰度= 0.0-0.21)。这一发现突出了测量和报告C35正构烷烃的重要性。我们的数据进一步表明,正构烷烃分布可以作为一些非洲C3 PACMAD草的代表,为区分C3植被类型提供了一种新的古生态学工具。
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引用次数: 0
Assessing the reliability of H-brGDGTs as terrestrial paleothermometers in Plio-Pleistocene fluvio-lacustrine deposits from Northern China 华北上新世—更新世河湖沉积中H-brGDGTs作为陆相古温标的可靠性评价
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-10-01 Epub Date: 2025-06-26 DOI: 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.
支链甘油单烷基甘油四醚(brGMGTs,或H-brGDGTs)是一种广泛存在于泥炭地、湖泊和海洋缺氧沉积物中的脂质,已被提出作为湖泊和泥炭地古温度重建的新工具。然而,它们的可靠性还没有得到广泛的评估,特别是在沉积物岩心中。本文报道了华北雄安(XA) 3沉积物岩心中H-brGDGT的分布,跨度为550万年(Ma),以评价其作为陆地古温标的可靠性。7种主要的h - brgdgt在整个沉积物岩心中始终丰富。它们的异构化指数(IRH)值,河流和湖泊环境的特征表明,H-brGDGTs主要是在土壤输入微不足道的情况下就地产生的。它们的丰度和分布与广泛使用的古温度计MBT ' 5ME(5-甲基化支化GDGTs的支化四醚甲基化指数)密切相关,可能表明它们的温度依赖性。基于H-brGDGT的温度代理H-MBT ',仅包括H-1020c和H-1034b异构体,可以跟踪已发表的现代泥炭/湖泊H-brGDGT数据集和XA3沉积物岩心的温度。H-MBT重建的温度趋势与brGDGT在沉积物岩心的温度记录以及全球气候信号一致,在5.5 ~ 2.6 Ma表现为稳定升温,在~ 2.6 Ma表现为与北半球冰期(NHG)开始一致的突变降温,在2.2 ~ 0 Ma表现为振荡下降。我们的结果验证了H-brGDGTs作为水生系统中潜在的古温度计,但强调需要选择适当的基于H-brGDGTs的温度代用物和特定环境的校准来提高精度。
{"title":"Assessing the reliability of H-brGDGTs as terrestrial paleothermometers in Plio-Pleistocene fluvio-lacustrine deposits from Northern China","authors":"Shi Qian ,&nbsp;Huan Yang ,&nbsp;Jie Wu ,&nbsp;Shucheng Xie ,&nbsp;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}
引用次数: 0
Multiple sources of petroleum in the Panyu lower uplift evidenced by catalytic hydropyrolysis of petroleum asphaltenes 番禺下凸起石油沥青质的催化加氢热解证明了其多源性
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-10-01 Epub Date: 2025-06-27 DOI: 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–C16 n-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.
催化加氢热解(HyPy)是一种从地球大分子(如油根或沥青质)中释放共价结合生物标志物的有效方法。对于由于广泛成熟或二次蚀变而缺乏地球化学指标的样品,它尤其有价值。本研究对南海珠江口盆地中部番禺下凸起10个不同深度储层原油中分离的沥青质组分进行了HyPy研究。释放了大量的生物标志物和多环芳烃(PAHs),并获得了它们的分子和同位素组成。结果表明,这些结合物不受次生蚀变过程的影响,如浅层储层的生物降解或深层储层的水冲刷。HyPy产物的δ13C值比原始散装油的δ13C值高1.2‰~ 2.2‰,与传统的δ13C模式不一致(沥青质馏分通常是石油馏分中δ13C值最富集的馏分)。因此,这些储层可能代表了一个复合石油系统,涉及多个烃源岩的贡献,而不是像以前解释的那样只有一个烃源岩。这一假设也得到了产物的分子和生物标志物特征的支持,它们显示C11-C16正构烷烃和C19三环萜烷的比例升高,并且24-乙基胆甾烷显著优势(占总甾烷的52%至79%),显著超过C27和C28同源物。维管植物的有机质输入量较大,远高于推测的始新统文昌组烃源岩有机质输入量。因此,番禺下隆起较早的油气充注可能与始新统—渐新统恩平组与煤源岩层序互层有关。油样maltenes富含4-甲基甾烷、恐龙甾烷、三芳类恐龙甾烷以及少量齐墩烷,与始新统文昌组湖相烃源岩的生物标志物特征非常相似。这些发现支持了番禺下隆起油气成藏的双重贡献,其中恩平组煤质烃源岩和文昌组湖相页岩烃源岩的主要油源可能是潜在的大规模油气聚集的原因。
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引用次数: 0
Sulfur ions reduce the activation energy of steranes and terpanes under hydrothermal action 硫离子降低了水热作用下甾烷和萜烷的活化能
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-10-01 Epub Date: 2025-06-23 DOI: 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.
甾烷和萜烷作为原油和烃源岩提取物的重要生物标志物,可为原油和烃源岩的生物来源、沉积环境和热成熟度提供有价值的信息。顺脱郭勒低凸起超深层油藏中甾烷和萜烷的分布规律复杂。基于“联苯-二苯并噻吩-菲”系列化合物的转化,评价了热液活性强度和硫离子的影响。结果表明,F5、F12、F4南段表现出较强的热液活动(F数:No。数字断层)。在热液作用下,F5、F1、F4南段受硫离子活性的影响更为显著。研究表明,在水热作用下,硫离子的活性降低了甾烷和萜烯的浓度。三环萜烷、胆甾烷、C31-35高藿烷、C30藿烷、C29二藿烷和孕烷在水热作用中受硫离子活性的影响,稳定性较低。值得注意的是,虽然三环萜烷、胆甾烷和孕烷的稳定性较低,但它们并不优先被消耗。结合C30藿烷和C30藿烷的相对吉布斯自由能分析表明,硫离子并不通过改变甾烷和萜烷的降解途径来促进热解。相反,硫离子可能通过降低活化能来降低热解阈值,从而保持甾烷和萜烷的相对稳定性。该研究促进了对热液系统中有机-无机相互作用的认识。
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引用次数: 0
Geochemical implications of the carbon isotope compositions of individual polycyclic aromatic compounds in coals from the Junggar and Ordos basins, NW China 准噶尔盆地和鄂尔多斯盆地煤中单个多环芳烃碳同位素组成的地球化学意义
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-10-01 Epub Date: 2025-07-23 DOI: 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.
本文分析了准噶尔盆地和鄂尔多斯盆地两套煤中二苯并呋喃和甲基二苯并呋喃等多环芳香族化合物的δ13C值。结果表明,各pac的δ13C值主要受降解有机质来源的影响,而不受热成熟度的影响。二苯并呋喃(DBF)及其甲基化同源物(mdbf)的δ13C值差异显著(- 11.7‰),表明其来源不同。DBF主要来源于高等植物,而mdbf有多种来源,既来自地衣,也来自高等植物。而在主要热原样品中,DBF和MDBF的δ13C值比较接近。这是由于两个因素造成的:(1)动力学同位素效应导致富12c的MDBF异构体优先去甲基化,剩余的MDBF因此富集于13C同位素。该过程生成的DBF富含12C同位素,导致燃烧产物中DBF δ13C的损耗。(2)高等植物投入比地衣投入大,会导致mdbf δ13C值升高,也可能导致DBF δ13C值降低。这两个因素结合在一起,使受野火严重影响的样品中DBF和mdbf的δ13C值相似。
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引用次数: 0
Controls of organic matter content on shale oil occurrence and distribution: Insights from retained oil composition and pore structure in marine shales 有机质含量对页岩油赋存分布的控制作用——来自海相页岩储油成分和孔隙结构的启示
IF 2.5 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-10-01 Epub Date: 2025-08-20 DOI: 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.
总有机碳(TOC)含量与页岩油含量密切相关,是页岩油勘探的重要指标。然而,在高toc页岩中,可动油的比例明显降低。以同一井的8个海相页岩样品(TOC含量为1.86% ~ 13.78%,镜质体反射率为0.8 ~ 0.9%)为研究对象,探讨TOC含量对储集油赋存分布的影响。不同溶剂混合物的连续萃取表明,正己烷/甲苯(9:1v/v)萃取的可萃取有机质(EOM)主要由饱和烃和芳烃组成,其化学性质与300°C (S1峰)前Rock-Eval热解释放的油相似。因此,EOM是评价页岩游离油含量的有效方法。相比之下,二氯甲烷/甲醇(93:7 v/v)和四氢呋喃/丙酮/甲醇(50:25:25 v/v/v)萃取的EOMs主要由树脂和沥青质组成,对应于300°C以上岩石热解过程中释放的油,表明它们主要以吸附油的形式存在。连续提取后,页岩样品的比表面积和孔隙体积分别平均增加了369%和254%。孔隙结构分析表明,有机质含量对储集油的赋存空间有显著影响。在油窗成熟较早的情况下,过量的有机质会导致可动油游离油比低、储油空间小、吸附容量大、阈值孔径高,表明过量的有机质不利于可动油富集。因此,页岩油甜点区可能存在TOC上限。对于我们的样品,当TOC超过10 wt%时,游离油含量显着降低。根据热成熟度、干酪根类型和孔隙结构的不同,这一阈值可能会有所不同。以I/II型干酪根为主的页岩在主生油阶段(参见III型干酪根)的最佳TOC阈值通常较低,进一步强调了勘探过程中识别这些阈值的重要性。
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Organic Geochemistry
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