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Study on hydrocarbon retention and expulsion of kerogen based on centrifugal swelling method 基于离心膨胀法的干酪根留排烃研究
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-02-09 DOI: 10.1016/j.orggeochem.2024.104921
Tian Liang , Feng Zhu , Zhao-Wen Zhan , Xiao-Hui Lin , Yan-Rong Zou , Ping’an Peng
Centrifugal swelling experiments using n-hexadecane and 1-methylnaphthalene were carried out to explore the connection between hydrocarbon retention and expulsion in type Ⅰ kerogen. A driving force-hydrocarbon expulsion model was innovatively established through the results of differential centrifugation experiments and low field nuclear magnetic resonance. Additionally, the hydrocarbon expulsion process of kerogen was categorized into three distinct stages based on the driving force, including free, intergranular state and immovable state (adsorption and swelling) hydrocarbon expulsion. A linear correlation also was established between the T1/T2 signal and the liquid hydrocarbon content during the swelling process, revealing that low-field NMR technology could effectively detect the retention of alkane compounds in kerogen. The study revealed that when the driving force is greater than 647.4 g N, most of the shale oil retained in the kerogen is in an immobile state, which cannot be exploited. Additionally, the hydrocarbon expulsion model based on the centrifugal experiment presents several advantages, including low equipment requirements, straightforward operation, and a broad range of applications. This model can effectively support various types of laboratories conducting shale oil retention assessment work, especially those in oilfields with relatively simple experimental setups.
利用正十六烷和1-甲基萘进行离心膨胀实验,探讨了Ⅰ型干酪根中烃的留排关系。结合差速离心实验和低场核磁共振实验结果,创新性地建立了驱油驱动力-排烃模型。干酪根排烃过程可分为自由排烃阶段、粒间排烃阶段和不动(吸附和膨胀)排烃阶段。在膨胀过程中,T1/T2信号与液态烃含量之间也建立了线性相关关系,表明低场核磁共振技术可以有效检测烷烃类化合物在干酪根中的滞留。研究表明,当驱动力大于647.4 g N时,保留在干酪根中的大部分页岩油处于不动状态,无法开采。此外,基于离心实验的排烃模型具有设备要求低、操作简单、适用范围广等优点。该模型可有效支持各类实验室开展页岩油留油评价工作,特别是实验装置相对简单的油田。
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引用次数: 0
Biomarker signatures in host rocks and their co-occurring fossil plants from northern Scotland 苏格兰北部寄主岩石及其共生植物化石的生物标志物特征
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-02-09 DOI: 10.1016/j.orggeochem.2025.104948
Olumuyiwa T. Akinsanpe , Adebola O. Akinsanpe , Solomon A. Adekola , Oluwaseye P. Oyetade , Waheed G. Akande , Musa B. Usman , Abdulwahab M. Bello , Uzochukwu K. Benjamin , Adeniyi O. Olusanya , Chikezie Emele
The Devonian Period paleogeographic setting fostered the growth of diverse terrestrial and marine organisms, enhancing organic matter production and preserving terrestrial organic matter (TOM). Northern Scotland shows rock sequences with well-preserved TOM, including distinctive fossil plant fragments. The biomarker record of host rock-fossil plant system is notably fragmented. Nonetheless, the exposed outcrops of Old Red Sandstone in northern Scotland allow detailed sampling and biomarker analysis of the Devonian rocks and their co-existing fossil plants. The biomarker record of the host rocks and the co-occurring plant fossils show that the organic matter of the Rhynie Chert, Newton of Kinkell and Kerrera siltstones were derived from vascular plants. The plant biomarkers detected in the Rhynie Chert includes tetracyclic diterpenoids (kaurane and beyerane), cadalene and methylnaphthalene. These biomarkers except cadalene were also present in Den of Morphie samples, Achanarras Quarry, Kerrera plant and Newton of Kinkell siltstone-plant samples. The similarity in biomarker signatures between fossil plants and host rocks in Achanarras suggested a shared origin of organic matter. Also, the sulfur-rich euxinic conditions in the studied areas, the hydrothermal permineralization and presence of pyrite framboids in the Rhynie Chert preserved the organic matter. This was indicated by low Pr/Ph ratios and high sulfur content, enhancing preservation and reducing organic matter degradation. The study concluded that the biomarker record of the host rock-plant fossil system in northern Scotland aids the understanding of terrestrialization process and higher plant evolution in the Devonian.
泥盆纪古地理环境促进了多种陆生和海洋生物的生长,促进了有机质的生产,并保存了陆源有机质。苏格兰北部的岩石序列保存完好,包括独特的化石植物碎片。寄主岩-化石植物系统生物标志物记录的碎片化程度显著。尽管如此,苏格兰北部暴露的老红砂岩的露头允许对泥盆纪岩石及其共存的化石植物进行详细的采样和生物标志物分析。寄主岩石生物标志物记录和共生植物化石表明,Rhynie Chert、Newton of Kinkell和Kerrera粉砂岩有机质来源于维管植物。在Rhynie Chert中检测到的植物生物标志物包括四环二萜(kaurane和beyerane), cadalene和methylnaphthalene。在Morphie的Den样品、Achanarras采石场、Kerrera植物和Newton of Kinkell粉砂岩植物样品中也存在除钙二烯外的其他生物标志物。阿查那拉斯地区植物化石和寄主岩石生物标志物特征的相似性表明它们具有共同的有机质来源。研究区富硫的富氧条件、热液过矿化作用和Rhynie燧石中黄铁矿的存在保存了有机质。这表明低Pr/Ph比和高硫含量,增强了保存和减少有机物降解。研究认为,苏格兰北部寄主岩-植物化石系统的生物标志物记录有助于认识泥盆纪的陆化过程和高等植物的进化。
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引用次数: 0
Protocols to assist deconvolution of co-eluting 5β– and 5α–steranes by gas chromatography–mass spectrometry 气相色谱-质谱法辅助5β -和5α -甾烷共洗脱反褶积的方案
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-02-09 DOI: 10.1016/j.orggeochem.2024.104916
Luke M. Brosnan, Paul F. Greenwood, Peter Hopper, Kliti Grice
Molecular parameters based on the relative abundance of various sterane isomers contribute valuable information about sources and thermal history of organic-matter-rich sediments. However, this application is limited for 5β– and 5α–steranes due to their co-elution on common gas chromatography (GC) columns: e.g., relative retention index of 5β20R and 5α20S cholestanes on Agilent DB1 columns = 28.081 and 28.065, respectively. Selected ion monitoring (SIM) and tandem (MS/MS) mass spectral protocols were developed to improve the analytical resolution of these compounds, exploiting slight differences in mass fragmentation patterns. Protocols were optimised on a 1:1 mixture of authentic 5α20R and 5β20R cholestane standards (5α20R in place of 5α20S). Parameters offering 5α:5β selectivity (e.g., SIM: 149/151 Da; MRM: [149 → 79]/[151 → 79]) were tested on a suite of 5α20R:5β20R standards and show an excellent correlation (R2 > 0.99) with substrate composition. The capacity to quantify the relative contribution of co-eluting 5α20S and 5β20R in more complex samples was tested by analyses of a crude oil (Blina-4, Canning Basin, Western Australia) known to have high abundances of C27-29 5α20S steranes (20S/[20S + 20R] ≈ 0.5) and spiked with 5β20R cholestane. The relative proportions of 5α20S and 5β20R were determined using 5α20R:5β20R calibration curves with good consistency and accuracy. Values deviated from the target when either analyte was particularly dominant (≥80 %), probably due to differences in ion density compared to the resolved standards. This issue may be improved with further method refinement and the true sterane deconvolution value offered by this approach will become apparent with further application to a diverse range of samples.
基于各种甾烷异构体相对丰度的分子参数为富有机质沉积物的来源和热历史提供了有价值的信息。然而,由于5β -甾烷和5α -甾烷在普通气相色谱柱上的共洗脱,这种应用受到限制:例如,5β 20r和5α20S甾烷在Agilent DB1柱上的相对保留指数分别为28.081和28.065。开发了选择性离子监测(SIM)和串联(MS/MS)质谱方案来提高这些化合物的分析分辨率,利用质量碎片模式的细微差异。以5α20R和5β20R胆甾酯标准品1:1混合(5α20R代替5α20S)为优化方案。提供5α:5β选择性的参数(例如,SIM: 149/151 Da;MRM:[149→79]/[151→79])在一套5α20R:5β20R标准上进行了测试,显示出良好的相关性(R2 >;0.99)与底物组成。通过分析含有丰富的C27-29 5α20S甾烷(20S/[20S + 20R]≈0.5)并加入5β20R甾烷的原油(西澳大利亚Canning盆地Blina-4),测试了在更复杂样品中共洗脱5α20S和5β20R的相对贡献的量化能力。采用5α20R:5β20R标定曲线测定5α20S与5β20R的相对比例,具有良好的一致性和准确性。当任何一种分析物特别占优势(≥80%)时,值偏离目标,可能是由于与分离标准物相比离子密度的差异。这个问题可以通过进一步的方法改进而得到改善,并且该方法提供的真正的甾烷反褶积值将随着进一步应用于不同范围的样品而变得明显。
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引用次数: 0
Assessing tetraether lipids as a paleotemperature proxy on western edge of the Chinese Loess Plateau: A cautionary tale 中国黄土高原西部边缘四醚脂作为古温标的评估:一个值得警惕的故事
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-02-04 DOI: 10.1016/j.orggeochem.2025.104947
Jingjing Guo , Louise Fuchs , Martin Ziegler , Youbin Sun , Francien Peterse
The 130,000-year long, high-resolution paleotemperature record obtained from branched glycerol dialkyl glycerol tetraethers (brGDGTs) stored in a loess-paleosol sequence from Yuanbao on the western Chinese Loess Plateau (CLP) does not follow global temperature variations, whereas these are recorded by traditional loess proxy records from the same section. Specifically, reconstructed temperatures are lowest during Marine Isotope Stage 5 (MIS5), even indicating colder interstadials than stadials, which contradict brGDGT-based records from other sections on the CLP. The overall low temperatures during wet periods may be explained by an increase in soil moisture availability, which dampens land surface temperatures by increasing the soil heat capacity. However, comparison of brGDGT distributions at Yuanbao with those in modern surface soils from the CLP and the global soil calibration dataset reveals a lack of modern analogues during the interval from ∼73 to 63 ka. Notably, the Isomer Ratio (IR) rapidly increases from 0.2 to 0.6 (corresponding to a pH shift of ∼2 units) during this period, indicating a drastic shift in the composition of the bacterial community that in turn may have influenced the MBT′5Me-temperature relationship. This community shift occurs after Chinese Stadial-20 around 73 ka, a weak monsoon event tentatively linked to oceanic reorganizations after the Toba eruption, suggesting that this drastic change in (hydro)climate might have impacted brGDGT producers. We thus recommend thoroughly assessing brGDGT distributions and understanding the environmental background prior to interpretating brGDGT-based temperatures in a paleoclimatic context.
中国黄土高原元宝黄土-古土壤序列中支链甘油二烷基甘油四醚(brGDGTs)的13万年高分辨率古温度记录不符合全球温度变化,而传统的黄土代用记录则反映了全球温度变化。具体而言,在海洋同位素阶段5 (MIS5)重建温度最低,甚至表明间冰期比间冰期更冷,这与CLP上其他剖面基于brdgg的记录相矛盾。湿润期的整体低温可以用土壤水分有效性的增加来解释,土壤水分有效性通过增加土壤热容来抑制地表温度。然而,将元宝的brdgt分布与CLP和全球土壤校准数据集的现代表层土壤中的brdgt分布进行比较,发现在~ 73 ~ 63 ka区间缺乏现代类似物。值得注意的是,在此期间,异构体比(IR)从0.2迅速增加到0.6(对应于pH值的变化约2个单位),表明细菌群落的组成发生了剧烈变化,这反过来可能影响了MBT ' 5me -温度关系。这种群落转变发生在73 ka左右的中国第20期之后,这是一个弱季风事件,初步与多巴火山喷发后的海洋重组有关,表明这种(水文)气候的剧烈变化可能影响了brGDGT的产生。因此,我们建议在解释古气候背景下基于brGDGT的温度之前,彻底评估brGDGT分布并了解环境背景。
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引用次数: 0
On-line hydropyrolysis gas chromatography-mass spectrometry (HyPy-GC–MS) for kerogen-bound biomarkers 在线氢热解气相色谱-质谱法(HyPy-GC-MS)用于干酪根结合生物标志物
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-02-01 DOI: 10.1016/j.orggeochem.2024.104927
Fu Wang , Yuhong Liao , Chang Samuel Hsu
Flash pyrolysis gas chromatography-mass spectrometry (Py-GC–MS) is seldom used to release bound biomarkers, because its hydrogen-poor pyrolysis conditions usually result in a low yield of bound biomarkers and high concentrations of olefins. In this study, by using a Py-GC–MS system and immature kerogen/coal samples, we investigated the effects of heating rate (flash versus 30 °C/min), carrier/reaction gas (He versus H2), hydrogen pressure, and catalyst [(NH4)2MoO2S2] on the yields and distributions of bound biomarkers. Also, the bound biomarkers obtained by different pyrolysis conditions were compared with those from catalytic offline hydropyrolysis (HyPy) and free biomarkers from extracted organic matter (EOM). We propose a new technology of hydropyrolysis-gas chromatography-mass spectrometry (HyPy-GC–MS) to be used to release bound biomarkers. HyPy-GC–MS using low-pressure H2 at slow heating rate can increase the yield of bound biomarkers by 3–9 times, minimize the cracking of the hopanes side chain, better preserve the original sterane and terpane distributions, and have characteristics of lower maturity, compared with conventional flash Py-GC–MS without H2. Additionally, the steroidal and terpenoid yields by HyPy-GC–MS using low-pressure H2 at slow heating rate from immature kerogens were 3–6 times that by HyPy. Compared with EOM, biomarker maturity parameter derived from HyPy-GC–MS may not fully represent the actual maturity of samples. Higher hydrogen pressure can significantly facilitate the hydrogenation of unsaturated hydrocarbons into saturated hydrocarbons, but it can also decrease the yields of pyrolysates with higher carbon numbers (i.e., >C25), leading to a change in the biomarker ratios related to carbon numbers (e.g., the proportion of C27-C28-C29 ααα20R steranes and TT23/H30 ratio).
闪速热解气相色谱-质谱法(Py-GC-MS)很少用于释放结合生物标志物,因为其贫氢热解条件通常导致结合生物标志物的产率低,烯烃浓度高。在这项研究中,我们使用Py-GC-MS系统和未成熟的油根/煤样品,研究了加热速率(闪蒸vs 30°C/min)、载体/反应气体(He vs H2)、氢气压力和催化剂[(NH4)2MoO2S2]对结合生物标志物的产率和分布的影响。并将不同热解条件下得到的结合生物标志物与催化脱机加氢热解(HyPy)和萃取有机质(EOM)中得到的游离生物标志物进行了比较。我们提出了一种新的氢热解-气相色谱-质谱(HyPy-GC-MS)技术,用于释放结合的生物标志物。与不加H2的传统闪蒸Py-GC-MS相比,低压H2慢速加热的hy - gc - ms结合生物标志物的产率提高了3-9倍,最大限度地减少了藿烷侧链的裂解,更好地保留了原始甾烷和萜烷分布,具有成熟度较低的特点。此外,低压H2慢速加热下,HyPy- gc - ms从未成熟干酪根中提取甾体和萜类化合物的产率是HyPy的3-6倍。与EOM相比,HyPy-GC-MS得到的生物标志物成熟度参数可能不能完全代表样品的实际成熟度。较高的氢气压力可以显著促进不饱和烃加氢成饱和烃,但也会降低高碳数(如>;C25)热解产物的产率,导致与碳数相关的生物标志物比值(如C27-C28-C29 ααα20R甾烷比例和TT23/H30比值)发生变化。
{"title":"On-line hydropyrolysis gas chromatography-mass spectrometry (HyPy-GC–MS) for kerogen-bound biomarkers","authors":"Fu Wang ,&nbsp;Yuhong Liao ,&nbsp;Chang Samuel Hsu","doi":"10.1016/j.orggeochem.2024.104927","DOIUrl":"10.1016/j.orggeochem.2024.104927","url":null,"abstract":"<div><div>Flash pyrolysis gas chromatography-mass spectrometry (Py-GC–MS) is seldom used to release bound biomarkers, because its hydrogen-poor pyrolysis conditions usually result in a low yield of bound biomarkers and high concentrations of olefins. In this study, by using a Py-GC–MS system and immature kerogen/coal samples, we investigated the effects of heating rate (flash versus 30 °C/min), carrier/reaction gas (He versus H<sub>2</sub>), hydrogen pressure, and catalyst [(NH<sub>4</sub>)<sub>2</sub>MoO<sub>2</sub>S<sub>2</sub>] on the yields and distributions of bound biomarkers. Also, the bound biomarkers obtained by different pyrolysis conditions were compared with those from catalytic offline hydropyrolysis (HyPy) and free biomarkers from extracted organic matter (EOM). We propose a new technology of hydropyrolysis-gas chromatography-mass spectrometry (HyPy-GC–MS) to be used to release bound biomarkers. HyPy-GC–MS using low-pressure H<sub>2</sub> at slow heating rate can increase the yield of bound biomarkers by 3–9 times, minimize the cracking of the hopanes side chain, better preserve the original sterane and terpane distributions, and have characteristics<!--> <!-->of lower maturity, compared with conventional flash Py-GC–MS without H<sub>2</sub>. Additionally, the steroidal and terpenoid yields by HyPy-GC–MS using low-pressure H<sub>2</sub> at slow heating rate from immature kerogens were 3–6 times that by HyPy. Compared with EOM, biomarker maturity parameter derived from HyPy-GC–MS may not fully represent the actual maturity of samples. Higher hydrogen pressure can significantly facilitate the hydrogenation of unsaturated hydrocarbons into saturated hydrocarbons, but it can also decrease the yields of pyrolysates with higher carbon numbers (i.e., &gt;C<sub>25</sub>), leading to a change in the biomarker ratios related to carbon numbers (e.g., the proportion of C<sub>27</sub>-C<sub>28</sub>-C<sub>29</sub> ααα20R steranes and TT<sub>23</sub>/H<sub>30</sub> ratio).</div></div>","PeriodicalId":400,"journal":{"name":"Organic Geochemistry","volume":"200 ","pages":"Article 104927"},"PeriodicalIF":2.6,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143176264","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
Controlling factors and geological applications of the drimane-skeleton compound content and composition of crude oils in complex petroleum systems: New insights from the Western Pearl River Mouth Basin, South China Sea 南海珠江口西部盆地复杂含油气系统中原油驱动骨架化合物含量和组成的控制因素及地质应用
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-02-01 DOI: 10.1016/j.orggeochem.2024.104925
Peng Cheng , Yuhao Ren , Haifeng Gai , Shangli Liu , Tao Cheng , Hui Tian
Crude oils generally contain drimane-skeleton compounds, but the uncertainty of the main factors controlling drimane distributions limits their effective geological applications, especially in complex petroleum systems. In this study, the drimane-skeleton compound composition and the relative content of each drimane-skeleton compound to C30 hopane (CDSC) were systematically studied for crude oils in different structural regions of the Western Pearl River Mouth (WPRM) Basin, South China Sea. The results show that the CDSC of crude oil is mainly controlled by its organic sources. Higher CDSC values in crude oil indicates a greater contribution from terrigenous organic matter to their source rocks. For crude oils from source rocks with similar biotic inputs, the CDSC values are controlled mainly by the depositional environment. Higher CDSC values in crude oil correspond to higher concentrations of clay minerals and lower salinities. In addition, the drimane-skeleton compound composition of crude oil is largely controlled by its maturity. The ratios of drimane to homodrimane (Dr/HDr), total rearranged drimane to total drimane and homodrimane (TRDr/TDr), and 8-rearranged drimane to 9-rearranged drimane (8RDr/9RDr) synchronously increase with increasing maturity. These ratios can effectively characterize the maturity of various types of crude oils. The maturity range characterized by the drimane maturity parameters is greater than that characterized by conventional maturity parameters. Correlation diagrams based on drimane parameters and other organic geochemical parameters can be used to classify crude oils and reveal their sources and origins, which has great application potential in complex petroliferous basins, especially in deep and ultra-deep petroleum systems with abundant light oil/condensate.
原油通常含有驱动烃骨架化合物,但控制驱动烃分布的主要因素的不确定性限制了它们的有效地质应用,特别是在复杂的石油系统中。本研究系统研究了南海珠江口西部盆地不同构造区原油的驱动骨架化合物组成及其与C30藿烷(CDSC)的相对含量。结果表明,原油的CDSC主要受其有机来源控制。原油中CDSC值越高,表明陆源有机质对烃源岩的贡献越大。对于生物输入相似的烃源岩原油,CDSC值主要受沉积环境控制。原油中较高的CDSC值对应于较高的粘土矿物浓度和较低的盐度。此外,原油的驱动骨架化合物组成在很大程度上受其成熟度的控制。随着成熟度的增加,驱动烷与同驱动烷的比值(Dr/HDr)、总重排驱动烷与总驱动烷和同驱动烷的比值(TRDr/TDr)、8重排驱动烷与9重排驱动烷的比值(8RDr/9RDr)同步增加。这些比值可以有效地表征不同类型原油的成熟度。驱动型成熟度参数所表征的期限范围大于常规成熟度参数所表征的期限范围。基于动力参数和其他有机地球化学参数的对比图可以对原油进行分类,揭示其来源和成因,在复杂含油气盆地,特别是在富含轻质油/凝析油的深层和超深层含油气系统中具有很大的应用潜力。
{"title":"Controlling factors and geological applications of the drimane-skeleton compound content and composition of crude oils in complex petroleum systems: New insights from the Western Pearl River Mouth Basin, South China Sea","authors":"Peng Cheng ,&nbsp;Yuhao Ren ,&nbsp;Haifeng Gai ,&nbsp;Shangli Liu ,&nbsp;Tao Cheng ,&nbsp;Hui Tian","doi":"10.1016/j.orggeochem.2024.104925","DOIUrl":"10.1016/j.orggeochem.2024.104925","url":null,"abstract":"<div><div>Crude oils generally contain drimane-skeleton compounds, but the uncertainty of the main factors controlling drimane distributions limits their effective geological applications, especially in complex petroleum systems. In this study, the drimane-skeleton compound composition and the relative content of each drimane-skeleton compound to C<sub>30</sub> hopane (C<sub>DSC</sub>) were systematically studied for crude oils in different structural regions of the Western Pearl River Mouth (WPRM) Basin, South China Sea. The results show that the C<sub>DSC</sub> of crude oil is mainly controlled by its organic sources. Higher C<sub>DSC</sub> values in crude oil indicates a greater contribution from terrigenous organic matter to their source rocks. For crude oils from source rocks with similar biotic inputs, the C<sub>DSC</sub> values are controlled mainly by the depositional environment. Higher C<sub>DSC</sub> values in crude oil correspond to higher concentrations of clay minerals and lower salinities. In addition, the drimane-skeleton compound composition of crude oil is largely controlled by its maturity. The ratios of drimane to homodrimane (Dr/HDr), total rearranged drimane to total drimane and homodrimane (TRDr/TDr), and 8-rearranged drimane to 9-rearranged drimane (8RDr/9RDr) synchronously increase with increasing maturity. These ratios can effectively characterize the maturity of various types of crude oils. The maturity range characterized by the drimane maturity parameters is greater than that characterized by conventional maturity parameters. Correlation diagrams based on drimane parameters and other organic geochemical parameters can be used to classify crude oils and reveal their sources and origins, which has great application potential in complex petroliferous basins, especially in deep and ultra-deep petroleum systems with abundant light oil/condensate.</div></div>","PeriodicalId":400,"journal":{"name":"Organic Geochemistry","volume":"200 ","pages":"Article 104925"},"PeriodicalIF":2.6,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143175325","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
Constraining the sources of archaeal tetraether lipids in multiple cold seep provinces of the Cascadia Margin 卡斯卡迪亚边缘多个冷渗省份古细菌四醚脂质来源的限制
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-02-01 DOI: 10.1016/j.orggeochem.2024.104882
Katherine J. Keller , Mark M. Baum , Xiao-Lei Liu , Kemi Ashing-Giwa , Isabel R. Baker , Jerome Blewett , Ann Pearson
Archaeal isoprenoid glycerol dialkyl glycerol tetraether lipid (iGDGT) abundance profiles and carbon isotopic compositions reflect the relative distributions of archaeal sources, including planktonic, benthic, and methane-cycling contributions. Here, we analyze the carbon isotope ratios of iGDGTs purified from sediments of three different cold seep sites in Cascadia Margin, off the coast of Washington, USA. Together with relative abundance and glycerol configurations, we use the carbon isotope ratios to estimate the contributions of multiple archaeal sources to the sedimentary iGDGT assemblages and their impact on values of the TEX86 and methane indices. Using a Bayesian mixing model, we robustly characterize three potential endmembers by determining their characteristic lipid distributions, inferred contributions to the total sediment inventory, and carbon isotopic signatures. Despite the geographic proximity of the sample locations, we find site-specific heterogeneity in relative iGDGT abundances and δ13C values. Planktonic and benthic methane-cycling sources predominate in all cases (contributing > 98% of iGDGTs), while benthic non-methane cycling archaea contribute minimally to the sedimentary lipid pool. Environments with higher methane influence show an increased presence of anti-parallel iGDGTs, indicating that methane-cycling archaea may dominantly or exclusively synthesize iGDGTs in this configuration. Our results quantify the relationship between the methane index (MI) and methane impact in systems dominated by planktonic and benthic methane-cycling archaea. Within the framework of the TEX86 temperature proxy, this permits a quantitative demonstration that it is overly simplistic to apply a MI cutoff threshold as a binary indicator to determine methane influence, and caution is needed when taking this approach in paleoclimate reconstructions.
古菌类异戊二烯甘油二烷基甘油四醚脂(iGDGT)丰度曲线和碳同位素组成反映了古菌来源的相对分布,包括浮游生物、底栖生物和甲烷循环贡献。在这里,我们分析了从美国华盛顿海岸卡斯卡迪亚边缘三个不同冷渗点的沉积物中纯化的iGDGTs的碳同位素比率。结合相对丰度和甘油构型,我们利用碳同位素比值估算了多种古细菌来源对沉积iGDGT组合的贡献及其对TEX86和甲烷指数的影响。使用贝叶斯混合模型,我们通过确定它们的特征脂质分布,推断对总沉积物库存的贡献以及碳同位素特征来强有力地表征三个潜在的端元。尽管样品位置的地理位置接近,但我们发现相对iGDGT丰度和δ13C值存在位点特异性异质性。浮游生物和底栖生物甲烷循环源在所有情况下占主导地位(贡献>;98%的iGDGTs),而底栖非甲烷循环古菌对沉积脂池的贡献最小。甲烷影响较大的环境显示反平行iGDGTs的存在增加,表明甲烷循环古菌可能在这种构型下主要或专门合成iGDGTs。我们的研究结果量化了浮游和底栖甲烷循环古菌主导的系统中甲烷指数(MI)与甲烷影响之间的关系。在TEX86温度代理的框架内,这允许定量证明,将MI截止阈值作为确定甲烷影响的二元指标过于简单,并且在古气候重建中采用这种方法时需要谨慎。
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引用次数: 0
Contrasting particulate organic carbon and sediment trophic status in two Antarctic fjords: Hope Bay and Collins Bay 对比南极两个峡湾:希望湾和柯林斯湾的颗粒有机碳和沉积物营养状况
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-02-01 DOI: 10.1016/j.orggeochem.2024.104926
Stefanie Martínez , Luis Cerpa , Pablo Muniz , Natalia Venturini
Fjords of the Antarctic Peninsula are sensitive to climate change and important carbon sinks, due to their high sedimentation rates. We used several biogeochemical markers to establish sediment trophic status, origin, and sources of suspended and sedimentary organic carbon (OC) in two fjords, Hope Bay (HB) and Collins Bay (CB). Water samples at different depths and bottom sediments were collected in 2019/20 on board the R/V BAP Carrasco. Distinct glacier runoff settings between the two studied fjords were reflected in different physico-chemical water column conditions. Based on its isotopic and biopolymeric composition suspended particulate organic carbon (POC) in both HB and CB, can be considered fresh with high nutritional and energetic quality. Also, POC is derived from recent phytoplankton production, subjected to little bacterial degradation and zooplankton grazing. The predominance of muddy sediments and high total proteins (PRT) concentrations (2.88–3.04 mg g−1) in CB, contrasting with sandy sediments and low PRT concentrations (1.37–1.55 mg g−1) in HB, were consistent with a higher sedimentation rate in CB than in HB. The predominance of PRT-rich and fresh marine sedimentary OC in bottom sediments of the two fjords denoted the occurrence of an important benthic-pelagic coupling. Sedimentary C/N and δ13C indicated a main autochthonous marine origin of OC in bottom sediments of the two fjords. Biopolymeric carbon (BPC) concentrations showed that HB sediments are mesotrophic, whereas CB sediments are eutrophic, with a high organic load. Our results show the relevance of getting an integrated vision of both the pelagic and the benthic systems, for a better understanding of OC pathways and fate in Antarctic fjords undergoing rapid environmental changes linked to climate change.
南极半岛的峡湾由于其高沉积速率,对气候变化非常敏感,也是重要的碳汇。利用几种生物地球化学标记,对Hope Bay (HB)和Collins Bay (CB)两个峡湾的沉积物营养状况、悬浮有机碳和沉积有机碳(OC)的来源和来源进行了研究。2019/20年,在R/V BAP Carrasco船上收集了不同深度的水样和底部沉积物。不同的物理-化学水柱条件反映了两个研究峡湾之间不同的冰川径流设置。根据其同位素和生物聚合物组成,悬浮颗粒有机碳(POC)在HB和CB中都可以被认为是新鲜的,具有较高的营养和能量品质。此外,POC来源于最近的浮游植物生产,很少受到细菌降解和浮游动物的放牧。与砂质沉积物和低PRT浓度(1.37 ~ 1.55 mg g - 1)的HB相比,CB中泥质沉积物和高PRT浓度(2.88 ~ 3.04 mg g - 1)的优势与CB中高于HB的沉降速率一致。两峡湾底部沉积物以富prt和新鲜海相沉积OC为主,表明存在重要的底-海耦合作用。沉积C/N和δ13C表明,两峡湾底部沉积物中OC主要为海相原生来源。生物聚合碳(BPC)浓度表明HB沉积物为中营养型,而CB沉积物为富营养型,具有较高的有机负荷。我们的研究结果表明,对海洋和底栖生物系统进行综合研究,有助于更好地了解南极峡湾中与气候变化相关的快速环境变化的OC路径和命运。
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引用次数: 0
Large-scale accumulation of abiotic gases associated with subduction and volcanic activities in rift basins in eastern China 中国东部裂谷盆地俯冲和火山活动相关的大规模非生物气体聚集
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-02-01 DOI: 10.1016/j.orggeochem.2024.104900
Dongya Zhu , Quanyou Liu , Xiaowei Huang , Qingqiang Meng , Jingbin Wang , Pengpeng Li , Zhijun Jin
A series of large-scale abiotic gas reservoirs have been discovered in a few rift basins in eastern China. However, the compositions of the abiotic gases in each gas reservoir differ significantly, dominated by CO2 or CH4. This study aims to explore the factors controlling the large-scale generation and accumulation of different types of abiotic gases in the reservoirs. CO2 is the major component of the abiotic gases in the Huangqiao, Huagou, and Pingfangwang reservoirs, exceeding 60 % up to 95 % and the δ13CCO2 values are generally greater than −8‰. CH4 is the major component in the Qingshen and Songnan reservoirs with content up to 94.98 %. The δ13CCH4 values are commonly greater than −30 ‰ (up to −16.8 ‰) and the alkanes exhibit a reverse sequence (δ13CCH4 > δ13CC2H6 > δ13CC3H8 > δ13CC4H10). Most of the 3He/4He ratios of the reservoirs are commonly greater than 1 Ra. The carbon isotope values and 3He/4He ratios indicate that most of the gas components (CO2 or CH4) are abiotic. The abiotic CO2 is associated with mantle-degassing, and abiotic CH4 is mantle-derived and/or attributed to Fischer-Tropsch (FT) reactions. The ratios of Fe3+/∑Fe of the basalt near the Huangqiao reservoir are higher than those near the Qingshen and Songnan reservoirs, suggesting the relatively oxygen-fugacity controls the major component of the abiotic gases. The northwestward subduction of the western Pacific Plate, starting from the Japan Trench, triggered extensive magmatic and volcanic activities, resulting in the release and accumulation of abiotic gases in the rift basins. The variation in oxygen fugacity associated with oxidizing materials (e.g., iron and manganese oxides) and carbonate and sulfate sediments carried by the subducted plate determined the presence of abiotic CO2 or CH4. As the subduction slab continues moving forward beneath the continental plate, the influence of high-oxygen-fugacity materials gradually decreases, causing the abiotic gases to transition from CO2 to CH4. The Huangqiao, Huagou, Pingfangwang, Songnan, and Qingshen gas reservoirs are located farther away from the subducting slab, which explains the gradual shift in the abiotic component in these reservoirs. In general, the majority of the abiotic gases are released from deep faults and magmatic eruptions. Therefore, we conclude that the abiotic gas reservoirs are located near deep faults and igneous rocks.
在中国东部的几个裂谷盆地中发现了一系列大型的非生物气藏。但各气藏非生物气体组成差异较大,以CO2或CH4为主。本研究旨在探讨储层中不同类型非生物气体大规模生成和聚集的控制因素。黄桥、花沟、平房旺等储层非生物气主要组分为CO2, δ13CCO2值普遍大于- 8‰,大于60% ~ 95%。CH4是青深、松南储层的主要成分,含量高达94.98%。δ13CCH4值一般大于- 30‰(最高可达- 16.8‰),烷烃呈相反顺序(δ13CCH4 >;δ13 cc2h6祝辞δ13 cc3h8祝辞δ13 cc4h10)。储层的3He/4He比值一般大于1ra。碳同位素值和3He/4He比值表明,大部分气体组分(CO2或CH4)是非生物的。非生物CO2与地幔脱气有关,非生物CH4是地幔衍生的和/或归因于费托反应(FT)。黄桥储层附近玄武岩的Fe3+/∑Fe比值高于庆深和松南储层附近,表明相对氧逸度控制了非生物气体的主要成分。西太平洋板块从日本海沟开始向西北俯冲,引发了广泛的岩浆和火山活动,导致裂谷盆地内非生物气体的释放和聚集。氧逸度的变化与氧化物质(如铁和锰氧化物)以及俯冲板块携带的碳酸盐和硫酸盐沉积物有关,确定了非生物CO2或CH4的存在。随着俯冲板块在大陆板块下继续向前移动,高氧逸度物质的影响逐渐减弱,导致非生物气体由CO2向CH4过渡。黄桥、花沟、平房王、松南、青深气藏的位置离俯冲板块较远,这说明了这些气藏非生物成分的逐渐转移。一般来说,大部分的非生物气体是从深断层和岩浆喷发中释放出来的。因此,我们认为非生物气藏位于深断裂和火成岩附近。
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引用次数: 0
Dissolved organic matter molecular composition controls potential biodegradability 溶解有机物的分子组成控制着潜在的生物降解性
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-02-01 DOI: 10.1016/j.orggeochem.2024.104924
Meiling Man, Myrna J. Simpson
Dissolved organic matter (DOM) is a heterogenous mixture of plant- and microbial-derived compounds at various stages of decomposition. However, there is a lack of detailed information about the biodegradability of DOM from different terrestrial sources that have varying molecular compositions. To circumvent this, incubation experiments were conducted for two months using DOM isolated from three different terrestrial sources: forest soil, peat and leonardite, all with distinct extents of diagenesis. The dissolved organic carbon (DOC), total dissolved nitrogen (TDN) contents, pH, and headspace CO2 production were measured. DOM composition was monitored using solution-state 1H nuclear magnetic resonance (NMR) and ultraviolet–visible (UV–VIS) analyses. To further understand microbial responses, microbial biomass and community composition was analyzed with phospholipid fatty acid (PLFA). DOM isolated from forest soil and peat demonstrated high biodegradability and decreased DOC concentrations, higher CO2 production rates and higher microbial biomass over the course of incubation. Forest soil-derived DOM composition had decreased aliphatic, and carbohydrate and peptide components in the early and late stages, respectively. Peat-derived DOM exhibited lower carbohydrate and peptide concentrations and higher carboxyl-rich alicyclic molecules (CRAM). In contrast, CRAM and aromatic enriched leonardite-derived DOM had low CO2 production and microbial biomass, and no major changes in DOM chemical composition, suggesting limited biodegradability. Further, CO2 production, microbial biomass, and DOM molecular weight and degradation indices were positively correlated with carbohydrates and peptides, and inversely related to CRAM and aromatic components. Overall, these results corroborated distinct biogeochemical dynamics with varied DOM molecular composition, and highlight that DOM enriched in bio-recalcitrant components limited microbial processing, and exhibited high geochemical stability.
溶解有机物(DOM)是植物和微生物衍生化合物在不同分解阶段的异质混合物。然而,缺乏关于不同陆地来源的DOM的生物降解性的详细信息,这些来源具有不同的分子组成。为了避免这种情况,利用从三种不同陆地来源分离的DOM进行了为期两个月的孵化实验:森林土壤、泥炭和褐铁矿,它们都具有不同程度的成岩作用。测定了溶解有机碳(DOC)、总溶解氮(TDN)含量、pH和顶空CO2产量。采用溶液态1H核磁共振(NMR)和紫外-可见(UV-VIS)分析监测DOM的组成。为了进一步了解微生物的反应,用磷脂脂肪酸(PLFA)分析了微生物生物量和群落组成。在培养过程中,从森林土壤和泥炭中分离出的DOM具有较高的生物可降解性,DOC浓度降低,二氧化碳产量增加,微生物生物量增加。森林土壤DOM组成在早期和后期分别减少脂肪、碳水化合物和多肽成分。泥炭衍生的DOM碳水化合物和多肽浓度较低,富含羧基脂环分子(CRAM)较高。相比之下,CRAM和芳香族富龙纳迪石衍生的DOM的CO2产量和微生物量都很低,DOM的化学成分没有发生大的变化,表明其生物降解性有限。CO2产量、微生物生物量、DOM分子量和降解指标与碳水化合物和多肽呈正相关,与CRAM和芳香成分呈负相关。总体而言,这些结果证实了不同DOM分子组成的不同生物地球化学动力学,并强调了富含生物顽固性成分的DOM限制了微生物的处理,并表现出较高的地球化学稳定性。
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引用次数: 0
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Organic Geochemistry
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