首页 > 最新文献

Organic Geochemistry最新文献

英文 中文
Dual-pressure pyrolysis apparatus unravelling how fluid and lithostatic pressure matter in hydrocarbon expulsion 双压力热解装置揭示了流体压力和静岩压力在排烃过程中的作用
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-02-21 DOI: 10.1016/j.orggeochem.2025.104932
Weijiao Ma, Yunpeng Wang, Jinzhong Liu, Jinbu Li
Improvement in thermal simulation technology will increases the accuracy of predictive geochemistry. A dual-pressure pyrolysis apparatus was developed, to precisely control the fluid pressure and lithostatic pressure during simulated source rock maturation. Two series of pyrolysis experiments were carried out, simulating the same generation process but different expulsion fluid pressure condition. Episodic hydrocarbon expulsion from source rocks under controlled lithostatic pressure and fluid pressure was for the first time observed through thermal simulation experiments. The results were applied to (1) hydrocarbon expulsion efficiency (HEE) analysis, and (2) compositional analysis of oil and gas expelled under different pressures. Results show that HEE is strongly influenced by both fluid and lithostatic pressures. If the oil discharged during depressurization and normal pressure is taken into account, the calculated HEE was 2–31 times the HEE that only considers the high fluid pressure expelled oil. Compared with previous experimental results, HEE under controlled dual pressure is also lower. Therefore, before applying the results of thermal simulation experiments to unconventional and deep oil/gas evaluation, sufficient attention should be paid to the pressure conditions of the experiments. Within the oil window, when the temperature and hydrostatic pressure of source rocks are dropped due to tectonic events such as uplift, they can discharge more oil and gas than before uplift, as a consequence of adjustment of over-pressured fluid to re-equilibrate to the adjacent hydrostatic conditions. In addition, during pressure and temperature reduction, the expelled fluids have a higher gas to oil ratio. This helps to indicate that sedimentary basins that experienced tectonic events still have great exploration potential. The temperature program, pressure setup, expulsion conditions in the two-series experiments is a tentative work tested on a representative source rock from the Triassic Yanchang Formation (Ordos Basin), indicating that control of fluid and lithostatic pressure are essential for improving the accuracy of thermal simulation predictions. The dual-pressure pyrolysis apparatus has high exploration relevance, particularly when quantitative results are integrated with the depositional, tectonic and thermal histories of specific source rocks.
热模拟技术的改进将提高预测地球化学的准确性。为了精确控制模拟烃源岩成熟过程中的流体压力和静岩压力,研制了双压力热解装置。进行了两个系列的热解实验,模拟了相同的生成过程,不同的排液压力条件。通过热模拟实验,首次观察到烃源岩在控制静岩压力和流体压力下的幕式排烃现象。结果应用于(1)排烃效率(HEE)分析和(2)不同压力下排烃油气成分分析。结果表明,流体压力和静岩压力对HEE的影响都很大。如果考虑减压和常压时排出的油,计算出的HEE是只考虑高压排出油的HEE的2-31倍。与以往的实验结果相比,可控双压下的HEE也更低。因此,在将热模拟实验结果应用于非常规及深部油气评价之前,应充分重视实验的压力条件。在油窗内,当烃源岩由于隆起等构造事件导致温度和静水压力下降时,由于超压流体的调整,使其重新平衡到邻近的静水条件,使其比隆起前释放更多的油气。此外,在减压和降温过程中,排出液具有更高的气油比。这有助于说明经历过构造事件的沉积盆地仍有很大的勘探潜力。两组实验的温度程序、压力设置、排烃条件是在鄂尔多斯盆地三叠系延长组典型烃源岩上进行的尝试性实验,表明流体压力和静岩压力的控制是提高热模拟预测精度的关键。双压力热解装置具有很高的勘探相关性,特别是当定量结果与特定烃源岩的沉积、构造和热史相结合时。
{"title":"Dual-pressure pyrolysis apparatus unravelling how fluid and lithostatic pressure matter in hydrocarbon expulsion","authors":"Weijiao Ma,&nbsp;Yunpeng Wang,&nbsp;Jinzhong Liu,&nbsp;Jinbu Li","doi":"10.1016/j.orggeochem.2025.104932","DOIUrl":"10.1016/j.orggeochem.2025.104932","url":null,"abstract":"<div><div>Improvement in thermal simulation technology will increases the accuracy of predictive geochemistry. A dual-pressure pyrolysis apparatus was developed, to precisely control the fluid pressure and lithostatic pressure during simulated source rock maturation. Two series of pyrolysis experiments were carried out, simulating the same generation process but different expulsion fluid pressure condition. Episodic hydrocarbon expulsion from source rocks under controlled lithostatic pressure and fluid pressure was for the first time observed through thermal simulation experiments. The results were applied to (1) hydrocarbon expulsion efficiency (HEE) analysis, and (2) compositional analysis of oil and gas expelled under different pressures. Results show that HEE is strongly influenced by both fluid and lithostatic pressures. If the oil discharged during depressurization and normal pressure is taken into account, the calculated HEE was 2–31 times the HEE that only considers the high fluid pressure expelled oil. Compared with previous experimental results, HEE under controlled dual pressure is also lower. Therefore, before applying the results of thermal simulation experiments to unconventional and deep oil/gas evaluation, sufficient attention should be paid to the pressure conditions of the experiments. Within the oil window, when the temperature and hydrostatic pressure of source rocks are dropped due to tectonic events such as uplift, they can discharge more oil and gas than before uplift, as a consequence of adjustment of over-pressured fluid to re-equilibrate to the adjacent hydrostatic conditions. In addition, during pressure and temperature reduction, the expelled fluids have a higher gas to oil ratio. This helps to indicate that sedimentary basins that experienced tectonic events still have great exploration potential. The temperature program, pressure setup, expulsion conditions in the two-series experiments is a tentative work tested on a representative source rock from the Triassic Yanchang Formation (Ordos Basin), indicating that control of fluid and lithostatic pressure are essential for improving the accuracy of thermal simulation predictions. The dual-pressure pyrolysis apparatus has high exploration relevance, particularly when quantitative results are integrated with the depositional, tectonic and thermal histories of specific source rocks.</div></div>","PeriodicalId":400,"journal":{"name":"Organic Geochemistry","volume":"203 ","pages":"Article 104932"},"PeriodicalIF":2.6,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143464517","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
Molecular and isotope characterization of hydrocarbon products from organic-sulfur-rich mudstones during closed hydrous-pyrolysis 富硫泥岩闭水热解过程中油气产物分子及同位素表征
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-02-19 DOI: 10.1016/j.orggeochem.2025.104963
Jaime Cesar , Julito Reyes , Omid H. Ardakani , Levi J. Knapp
A series of mudstones with varying organic sulfur content were subjected to hydrous pyrolysis and the produced oil and gas were analyzed. The samples come from the late Devonian Duvernay Formation (Canada), the late Miocene Onnagawa Formation (Japan), and the early Jurassic Gordondale Member of the Fernie Formation (Canada), in order of increasing organic sulfur content. Comparison of molecular parameters in the produced oils and residual extracts showed that these have almost identical values, with linear correlation near 1:1, except for polycyclic aromatics such as alkylphenanthrenes and alkyldibenzothiophenes. The excellent correlation suggests that in an ideal scenario, in the absence of long-distance migration, hydrocarbon mixing, and secondary alteration, produced oils and residual bitumen would have very similar molecular properties. In addition, for the same %VReqv, samples with higher sulfur content exhibit an apparent higher thermal maturity according to molecular ratios such as Pr/nC18 and C30Hopane/C30Moretane. Generated gases showed source effects on their molecular and carbon isotope composition for the maturity interval analyzed herein (0.57 to 1.42 % VReqv). H2S gas was generated only from the Gordondale samples and the isotope values are presented in this study.
对一系列有机硫含量不同的泥岩进行了加水热解,并对其产出的油气进行了分析。样品分别来自晚泥盆世Duvernay组(加拿大)、晚中新世Onnagawa组(日本)和早侏罗世Gordondale组Fernie组(加拿大),有机硫含量依次递增。结果表明,除烷基菲和烷基二苯并噻吩等多环芳烃外,其分子参数基本一致,线性相关系数接近1:1。良好的相关性表明,在理想的情况下,在没有长距离运移、油气混合和二次蚀变的情况下,产出的油和残余沥青将具有非常相似的分子性质。此外,在相同的VReqv下,根据Pr/nC18和C30Hopane/C30Moretane的分子比,硫含量高的样品表现出明显更高的热成熟度。在本文所分析的成熟度区间(0.57 ~ 1.42% VReqv),生成气的分子和碳同位素组成受源影响。H2S气体仅由Gordondale样品产生,本研究给出了同位素值。
{"title":"Molecular and isotope characterization of hydrocarbon products from organic-sulfur-rich mudstones during closed hydrous-pyrolysis","authors":"Jaime Cesar ,&nbsp;Julito Reyes ,&nbsp;Omid H. Ardakani ,&nbsp;Levi J. Knapp","doi":"10.1016/j.orggeochem.2025.104963","DOIUrl":"10.1016/j.orggeochem.2025.104963","url":null,"abstract":"<div><div>A series of mudstones with varying organic sulfur content were subjected to hydrous pyrolysis and the produced oil and gas were analyzed. The samples come from the late Devonian Duvernay Formation (Canada), the late Miocene Onnagawa Formation (Japan), and the early Jurassic Gordondale Member of the Fernie Formation (Canada), in order of increasing organic sulfur content. Comparison of molecular parameters in the produced oils and residual extracts showed that these have almost identical values, with linear correlation near 1:1, except for polycyclic aromatics such as alkylphenanthrenes and alkyldibenzothiophenes. The excellent correlation suggests that in an ideal scenario, in the absence of long-distance migration, hydrocarbon mixing, and secondary alteration, produced oils and residual bitumen would have very similar molecular properties. In addition, for the same %VR<sub>eqv</sub>, samples with higher sulfur content exhibit an apparent higher thermal maturity according to molecular ratios such as Pr/<em>n</em>C<sub>18</sub> and C<sub>30</sub>Hopane/C<sub>30</sub>Moretane. Generated gases showed source effects on their molecular and carbon isotope composition for the maturity interval analyzed herein (0.57 to 1.42 % VR<sub>eqv</sub>). H<sub>2</sub>S gas was generated only from the Gordondale samples and the isotope values are presented in this study.</div></div>","PeriodicalId":400,"journal":{"name":"Organic Geochemistry","volume":"202 ","pages":"Article 104963"},"PeriodicalIF":2.6,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143438187","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
Aromatic carotenoids and their aryl isoprenoid derivatives in the early Paleozoic rocks and crude oils of the Tarim Basin, China 塔里木盆地早古生代岩石和原油中芳香族类胡萝卜素及其芳基类异戊二烯衍生物
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-02-16 DOI: 10.1016/j.orggeochem.2025.104950
Huiyuan Yang , Jiaquan Zhou , Jian Ma , Xingqian Cui
Emerging viewpoints suggest dynamic oceanic redox states and notable biotic turnovers in the early Paleozoic, but these aspects remain controversial and require further investigation. The Tarim Basin, which harbors significant marine hydrocarbon source rocks, records a typical phase of marine deposition of the early Paleozoic. In this study, we investigated biomarker compositions and patterns of selected rocks and crude oils of Early Cambrian to Late Ordovician ages from the Tarim Basin, China. Of particular importance are fossilized C40 aromatic carotenoids and their biogenic aryl isoprenoid derivatives, which originate specifically from phototrophic sulfur bacteria inhabiting the euxinic photic zone and are indicative of redox conditions of ancient oceans. The prevalence of 2,3,6-aryl isoprenoids and isorenieratane indicates a biological origin of green sulfur bacteria, implying that the Tarim Basin witnessed euxinia in the subsurface photic zone during a certain period of the early Paleozoic. Along with other biomarker-based proxies, especially steroids and hopanoids, our results from the Tarim Basin suggest the dominance of reducing oceanic water column in the early Cambrian and the late evolution of partially oxygenated water column.
新出现的观点认为,早古生代的海洋氧化还原状态和显著的生物更替,但这些方面仍然存在争议,需要进一步研究。塔里木盆地为典型的早古生代海相沉积期,具有重要的海相烃源岩。本文对塔里木盆地早寒武世至晚奥陶世的岩石和原油进行了生物标志物组成和模式研究。特别重要的是C40芳香类胡萝卜素化石及其生物源芳基类异戊二烯衍生物,它们特别起源于居住在缺氧光带的光养硫细菌,表明古代海洋的氧化还原条件。2,3,6-芳基类异戊二烯和异戊二烷的普遍存在表明了绿硫细菌的生物起源,暗示塔里木盆地早古生代的某一时期曾在地下光带出现过绿硫菌。结合其他生物标志物,特别是甾体和藿烷类,塔里木盆地早寒武世以还原性海洋水柱为主,部分氧合水柱演化较晚。
{"title":"Aromatic carotenoids and their aryl isoprenoid derivatives in the early Paleozoic rocks and crude oils of the Tarim Basin, China","authors":"Huiyuan Yang ,&nbsp;Jiaquan Zhou ,&nbsp;Jian Ma ,&nbsp;Xingqian Cui","doi":"10.1016/j.orggeochem.2025.104950","DOIUrl":"10.1016/j.orggeochem.2025.104950","url":null,"abstract":"<div><div>Emerging viewpoints suggest dynamic oceanic redox states and notable biotic turnovers in the early Paleozoic, but these aspects remain controversial and require further investigation. The Tarim Basin, which harbors significant marine hydrocarbon source rocks, records a typical phase of marine deposition of the early Paleozoic. In this study, we investigated biomarker compositions and patterns of selected rocks and crude oils of Early Cambrian to Late Ordovician ages from the Tarim Basin, China. Of particular importance are fossilized C<sub>40</sub> aromatic carotenoids and their biogenic aryl isoprenoid derivatives, which originate specifically from phototrophic sulfur bacteria inhabiting the euxinic photic zone and are indicative of redox conditions of ancient oceans. The prevalence of 2,3,6-aryl isoprenoids and isorenieratane indicates a biological origin of green sulfur bacteria, implying that the Tarim Basin witnessed euxinia in the subsurface photic zone during a certain period of the early Paleozoic. Along with other biomarker-based proxies, especially steroids and hopanoids, our results from the Tarim Basin suggest the dominance of reducing oceanic water column in the early Cambrian and the late evolution of partially oxygenated water column.</div></div>","PeriodicalId":400,"journal":{"name":"Organic Geochemistry","volume":"202 ","pages":"Article 104950"},"PeriodicalIF":2.6,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143422292","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
Geochemical constraints on the hydrocarbon generation and expulsion in source rocks with different primary organic matter compositions: A case study on the Lucaogou Formation in the Jimusaer Sag, Junggar Basin, Northwest China 不同原生有机质组成烃源岩生排烃的地球化学约束——以准噶尔盆地吉木萨尔凹陷芦草沟组为例
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-02-16 DOI: 10.1016/j.orggeochem.2025.104952
Shiju Liu , Gang Gao , Xiangyun Shi , Wenzhe Gang , Baoli Xiang , Ming Wang , Wenzhi Zhao
This study investigates the effects of different types of primary organic matters on hydrocarbon generation and expulsion of source rocks. Samples representing three typical source rocks from the Lucaogou Formation in the Jimusaer Sag were collected and analyzed by hydrous pyrolysis, total organic carbon, Rock-Eval, gas chromatography-mass spectrometry, organic petrology, and scanning electron microscopy. Distinct differences in crude oil biomarkers were observed between telalginite- and lamalginite-rich source rocks. Telalginite-rich source rocks exhibit higher abundances of pristane, phytane, β-carotane, gammacerane, and C29 regular steranes, while lamalginite-rich source rocks are characterized by enrichments of C24 tetracyclic terpane, C29 hopane, and C28 regular steranes. These biomarkers provide insights into the primary types of organic matter and their depositional environments with high water salinity of telalginite and low salinity of lamalginite. Hydrous pyrolysis results reveal that telalginite-rich source rocks demonstrate early hydrocarbon generation and a wider oil window than lamalginite-rich source rocks. Compared to lamalginite-rich source rocks, telalginite-rich source rocks produced better quality of crude oil, exhibit a smaller specific surface area of organic matter, and greater development of organic-inorganic pores, which contribute to their higher oil expulsion. These findings are helpful to the understanding of the constraints imposed by different primary organic matters on hydrocarbon generation and expulsion of the source rocks, and the insights have significant implications for exploration and development of the shale oil resources.
研究了不同类型原生有机质对烃源岩生排烃的影响。对吉木萨尔凹陷芦草沟组3个典型烃源岩样品进行了水热解、总有机碳、岩石分析、气相色谱-质谱、有机岩石学和扫描电镜分析。富藻蓝质烃源岩与富藻蓝质烃源岩原油生物标志物存在明显差异。富板藻质烃源岩具有较高的原石烷、植烷、β-胡萝卜烷、-蜡烷和C29规则甾烷丰度,而富板藻质烃源岩具有C24四环萜烷、C29藿烷和C28规则甾烷的富集特征。这些生物标志揭示了藻藻石水体盐度高、斑藻石水体盐度低的有机质主要类型及其沉积环境。含水热解结果表明,富拉藻质烃源岩比富拉藻质烃源岩生烃更早,油窗更宽。与富板藻质烃源岩相比,富板藻质烃源岩原油质量更好,有机质比表面积更小,有机-无机孔隙发育程度更高,排油能力更强。这些发现有助于认识不同原生有机质对烃源岩生排烃的制约作用,对页岩油资源的勘探开发具有重要意义。
{"title":"Geochemical constraints on the hydrocarbon generation and expulsion in source rocks with different primary organic matter compositions: A case study on the Lucaogou Formation in the Jimusaer Sag, Junggar Basin, Northwest China","authors":"Shiju Liu ,&nbsp;Gang Gao ,&nbsp;Xiangyun Shi ,&nbsp;Wenzhe Gang ,&nbsp;Baoli Xiang ,&nbsp;Ming Wang ,&nbsp;Wenzhi Zhao","doi":"10.1016/j.orggeochem.2025.104952","DOIUrl":"10.1016/j.orggeochem.2025.104952","url":null,"abstract":"<div><div>This study investigates the effects of different types of primary organic matters on hydrocarbon generation and expulsion of source rocks. Samples representing three typical source rocks from the Lucaogou Formation in the Jimusaer Sag were collected and analyzed by hydrous pyrolysis, total organic carbon, Rock-Eval, gas chromatography-mass spectrometry, organic petrology, and scanning electron microscopy. Distinct differences in crude oil biomarkers were observed between telalginite- and lamalginite-rich source rocks. Telalginite-rich source rocks exhibit higher abundances of pristane, phytane, <em>β</em>-carotane, gammacerane, and C<sub>29</sub> regular steranes, while lamalginite-rich source rocks are characterized by enrichments of C<sub>24</sub> tetracyclic terpane, C<sub>29</sub> hopane, and C<sub>28</sub> regular steranes. These biomarkers provide insights into the primary types of organic matter and their depositional environments with high water salinity of telalginite and low salinity of lamalginite. Hydrous pyrolysis results reveal that telalginite-rich source rocks demonstrate early hydrocarbon generation and a wider oil window than lamalginite-rich source rocks. Compared to lamalginite-rich source rocks, telalginite-rich source rocks produced better quality of crude oil, exhibit a smaller specific surface area of organic matter, and greater development of organic-inorganic pores, which contribute to their higher oil expulsion. These findings are helpful to the understanding of the constraints imposed by different primary organic matters on hydrocarbon generation and expulsion of the source rocks, and the insights have significant implications for exploration and development of the shale oil resources.</div></div>","PeriodicalId":400,"journal":{"name":"Organic Geochemistry","volume":"202 ","pages":"Article 104952"},"PeriodicalIF":2.6,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143422291","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
Optimized method for sequential extraction and analysis of polycyclic aromatic hydrocarbons, anhydrosugars and lipid biomarkers in speleothem carbonate and drip waters 碳酸盐岩和滴落水中多环芳烃、无水糖和脂类生物标志物序列提取分析方法的优化
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-02-15 DOI: 10.1016/j.orggeochem.2025.104961
Zhao Wang , Jonathan D. Smolen , Michael T. Hren , Yuval Burstyn , Isabel P. Montañez , Jessica L. Oster , Aida Zyba , Erica A. Scarpitti
Organic molecules such as n-alkyl lipids, terpenoids, anhydrosugars (AHs), and polycyclic aromatic hydrocarbons (PAHs) are found in karst systems, including cave deposits and drip waters, and provide a potential record of surface climate, ecosystem, and fire. However, it is analytically challenging to separate and measure multiple classes of organic compounds in these low-abundance matrices. Here, we present a simple, solid-phase sequential extraction method for the separation and purification of organic matter in carbonates (∼0.5 g, powder) and drip waters (300 mL, freeze-dried). This method offers efficient extraction and separation of hydrocarbons (FH) (saturated and PAHs) (hexane/dichloromethane; 70/30; v/v) and polar lipid compounds (FP) (e.g., AHs, sterols, and diterpenoids) (acetone) with a high recovery of standards in FH (78 ± 7 %, on average) and FP (90 ± 6 %, on average) across multiple matrices (i.e., speleothems and waters). Acid digestion was applied to the post-initial sequential extraction speleothem samples to fully liberate any remaining molecules trapped in the calcite crystals. We found that ∼10% of n-alkanes (C20-C32) and the smallest PAHs (naphthalene, methylated naphthalene, and fluorene) of total extractable hydrocarbons were left in the acid digestion, indicating that modification of the sequential extraction could be applied based on the target of interests. In total, this sequential solid-phase extraction method provides reliable separation of geochemically significant compound classes across different matrices within karst systems.
有机分子如正烷基脂类、萜类、无水糖(AHs)和多环芳烃(PAHs)在岩溶系统中被发现,包括洞穴沉积物和滴水,并提供了地表气候、生态系统和火灾的潜在记录。然而,在这些低丰度基质中分离和测量多类有机化合物在分析上具有挑战性。在这里,我们提出了一种简单的固相顺序萃取方法,用于分离和纯化碳酸盐(~ 0.5 g,粉末)和滴水(300 mL,冷冻干燥)中的有机物。该方法提供了碳氢化合物(FH)(饱和烃和多环芳烃)(己烷/二氯甲烷;70/30;v/v)和极性脂质化合物(FP)(如AHs、甾醇和二萜)(丙酮),在多种基质(即洞穴和水)中,FH(平均78±7%)和FP(平均90±6%)的标准回收率高。对初始顺序提取后的岩石样品进行酸消解,以充分释放方解石晶体中残留的分子。研究人员发现,酸消化过程中有10%的正构烷烃(C20-C32)和最小的多环芳烃(萘、甲基化萘和芴)残留,这表明可以根据感兴趣的目标对顺序提取进行修改。总的来说,这种顺序固相萃取方法提供了可靠的分离喀斯特系统中不同基质中具有地球化学意义的化合物类别。
{"title":"Optimized method for sequential extraction and analysis of polycyclic aromatic hydrocarbons, anhydrosugars and lipid biomarkers in speleothem carbonate and drip waters","authors":"Zhao Wang ,&nbsp;Jonathan D. Smolen ,&nbsp;Michael T. Hren ,&nbsp;Yuval Burstyn ,&nbsp;Isabel P. Montañez ,&nbsp;Jessica L. Oster ,&nbsp;Aida Zyba ,&nbsp;Erica A. Scarpitti","doi":"10.1016/j.orggeochem.2025.104961","DOIUrl":"10.1016/j.orggeochem.2025.104961","url":null,"abstract":"<div><div>Organic molecules such as <em>n</em>-alkyl lipids, terpenoids, anhydrosugars (AHs), and polycyclic aromatic hydrocarbons (PAHs) are found in karst systems, including cave deposits and drip waters, and provide a potential record of surface climate, ecosystem, and fire. However, it is analytically challenging to separate and measure multiple classes of organic compounds in these low-abundance matrices. Here, we present a simple, solid-phase sequential extraction method for the separation and purification of organic matter in carbonates (∼0.5 g, powder) and drip waters (300 mL, freeze-dried). This method offers efficient extraction and separation of hydrocarbons (<em>F<sub>H</sub></em>) (saturated and PAHs) (hexane/dichloromethane; 70/30; v/v) and polar lipid compounds (<em>F<sub>P</sub></em>) (e.g., AHs, sterols, and diterpenoids) (acetone) with a high recovery of standards in <em>F<sub>H</sub></em> (78 ± 7 %, on average) and <em>F<sub>P</sub></em> (90 ± 6 %, on average) across multiple matrices (i.e., speleothems and waters). Acid digestion was applied to the post-initial sequential extraction speleothem samples to fully liberate any remaining molecules trapped in the calcite crystals. We found that ∼10% of <em>n</em>-alkanes (C<sub>20</sub>-C<sub>32</sub>) and the smallest PAHs (naphthalene, methylated naphthalene, and fluorene) of total extractable hydrocarbons were left in the acid digestion, indicating that modification of the sequential extraction could be applied based on the target of interests. In total, this sequential solid-phase extraction method provides reliable separation of geochemically significant compound classes across different matrices within karst systems.</div></div>","PeriodicalId":400,"journal":{"name":"Organic Geochemistry","volume":"203 ","pages":"Article 104961"},"PeriodicalIF":2.6,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143520529","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
Study on the main controlling factors on the differential accumulation of natural gas in multiple (ultra-)deeply-buried marine strata 海相多(超)深埋地层天然气差异成藏主控因素研究
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-02-10 DOI: 10.1016/j.orggeochem.2024.104918
Zezhang Song , Ziyu Zhang , Bing Luo , Wenjin Zhang , Changqi Liu , Xingwang Tian , Dailin Yang , Luya Wu , Bingfei Ge , Shigui Jin , Jiutao Yuan
Ultra-deep natural gas is characterized by significant burial depth, high maturity, limited biomarkers, and complicated gas-source relationships. Ultra-deep gas accumulations generally underwent complex modifications during their long evolution, making it challenging to clarify the controlling factors of gas accumulation. This study focuses on gas accumulations in multiple (ultra-)deep marine carbonate strata, ranging from the Sinian Dengying (Z2dn) to the Permian Maokou (P2m) formations, in the Penglai gas area of the central Sichuan Basin. Using unsupervised machine learning algorithms, we conducted clustering analysis on natural gas composition and isotopes (δ13C and δ2H). Furthermore, we combined reservoir microscopic analysis, isotope data (δ13C of kerogen and solid bitumen; and δ18O, δ13C, and 87Sr/86Sr of dolomite), and fluid inclusion analysis to determine the main controlling factors that differentiate gas accumulation in multiple marine carbonate strata. The results indicate that: (1) Natural gases from Z2dn-P2m strata in the Penglai gas area are mainly dry gas (dryness > 0.996). Specifically, Z2dn natural gas exhibits high non-hydrocarbon content, low C2H6, δ13CC2H6, and δ2HCH4. Conversely, the Cambrian (Є) natural gas demonstrates the opposite characteristics. The natural gas in P2m has relatively high C2H6, greater δ13CC2H6 and δ2HCH4 values. (2) The natural gas from Z2dn-P2m in the Penglai gas area is oil-cracking gas and mainly sourced from Є1q. Due to maturity, hydrocarbon gases are dominated by CH4. He and N2 are from inorganic, deep Earth sources and show differential enrichment. Influenced by hydrothermal alteration and TSR, H2S and CO2 are enriched in Z2dn. The δ13CC2H6 in natural gas follows the order: Z2dn > P2m > Cambrian. The δ13CCH4 in natural gas follows the order: Z2dn ≥ P2m > Cambrian. (3) Overall, the Z2dn-P2m differential accumulation in the Penglai gas area is primarily influenced by various factors, including multiple source rocks, deep hydrothermal transformation, and strike-slip faults.
超深层天然气具有埋藏深度大、成熟度高、生物标志物有限、气源关系复杂等特点。超深层天然气成藏在长期演化过程中经历了复杂的改造过程,这给明确天然气成藏的控制因素带来了挑战。川中蓬莱气区震旦系灯影组(Z2dn)至二叠系茅口组(P2m)多(超)深海相碳酸盐岩成藏。利用无监督机器学习算法对天然气成分和同位素(δ13C和δ2H)进行聚类分析。结合储层微观分析、干酪根和固体沥青同位素(δ13C)数据;白云岩的δ18O、δ13C和87Sr/86Sr),以及流体包裹体分析,确定多相海相碳酸盐岩地层天然气成藏的主控因素。结果表明:(1)蓬莱气区z2dn ~ p2m地层天然气以干气为主;0.996)。其中,Z2dn天然气非烃含量高,C2H6、δ13CC2H6、δ2HCH4含量低。相反,寒武纪(Є)天然气表现出相反的特征。P2m天然气C2H6较高,δ13CC2H6和δ2HCH4值较大。(2)蓬莱气区Z2dn-P2m天然气为石油裂解气,主要来源为Є1q。由于成熟度高,烃类气体以CH4为主。He和N2均为深部无机源,富集程度不同。受热液蚀变和TSR的影响,Z2dn中H2S和CO2富集。天然气中的δ13CC2H6依次为:Z2dn >;P2m祝辞寒武纪。天然气δ13CCH4的大小顺序为:Z2dn≥P2m >;寒武纪。(3)蓬莱气区Z2dn-P2m差异成藏主要受多源岩、深部热液改造、走滑断裂等多种因素影响。
{"title":"Study on the main controlling factors on the differential accumulation of natural gas in multiple (ultra-)deeply-buried marine strata","authors":"Zezhang Song ,&nbsp;Ziyu Zhang ,&nbsp;Bing Luo ,&nbsp;Wenjin Zhang ,&nbsp;Changqi Liu ,&nbsp;Xingwang Tian ,&nbsp;Dailin Yang ,&nbsp;Luya Wu ,&nbsp;Bingfei Ge ,&nbsp;Shigui Jin ,&nbsp;Jiutao Yuan","doi":"10.1016/j.orggeochem.2024.104918","DOIUrl":"10.1016/j.orggeochem.2024.104918","url":null,"abstract":"<div><div>Ultra-deep natural gas is characterized by significant burial depth, high maturity, limited biomarkers, and complicated gas-source relationships. Ultra-deep gas accumulations generally underwent complex modifications during their long evolution, making it challenging to clarify the controlling factors of gas accumulation. This study focuses on gas accumulations in multiple (ultra-)deep marine carbonate strata, ranging from the Sinian Dengying (Z<sub>2</sub>dn) to the Permian Maokou (P<sub>2</sub>m) formations, in the Penglai gas area of the central Sichuan Basin. Using unsupervised machine learning algorithms, we conducted clustering analysis on natural gas composition and isotopes (δ<sup>13</sup>C and δ<sup>2</sup>H). Furthermore, we combined reservoir microscopic analysis, isotope data (δ<sup>13</sup>C of kerogen and solid bitumen; and δ<sup>18</sup>O, δ<sup>13</sup>C, and <sup>87</sup>Sr/<sup>86</sup>Sr of dolomite), and fluid inclusion analysis to determine the main controlling factors that differentiate gas accumulation in multiple marine carbonate strata. The results indicate that: (1) Natural gases from Z<sub>2</sub>dn-P<sub>2</sub>m strata in the Penglai gas area are mainly dry gas (dryness &gt; 0.996). Specifically, Z<sub>2</sub>dn natural gas exhibits high non-hydrocarbon content, low C<sub>2</sub>H<sub>6</sub>, δ<sup>13</sup>C<sub>C<sub>2</sub>H<sub>6</sub></sub>, and δ<sup>2</sup>H<sub>CH<sub>4</sub></sub>. Conversely, the Cambrian (Є) natural gas demonstrates the opposite characteristics. The natural gas in P<sub>2</sub>m has relatively high C<sub>2</sub>H<sub>6</sub>, greater δ<sup>13</sup>C<sub>C<sub>2</sub>H<sub>6</sub></sub> and δ<sup>2</sup>H<sub>CH<sub>4</sub></sub> values. (2) The natural gas from Z<sub>2</sub>dn-P<sub>2</sub>m in the Penglai gas area is oil-cracking gas and mainly sourced from Є<sub>1</sub>q. Due to maturity, hydrocarbon gases are dominated by CH<sub>4</sub>. He and N<sub>2</sub> are from inorganic, deep Earth sources and show differential enrichment. Influenced by hydrothermal alteration and TSR, H<sub>2</sub>S and CO<sub>2</sub> are enriched in Z<sub>2</sub>dn. The δ<sup>13</sup>C<sub>C<sub>2</sub></sub><sub>H<sub>6</sub></sub> in natural gas follows the order: Z<sub>2</sub>dn &gt; P<sub>2</sub>m &gt; Cambrian. The δ<sup>13</sup>C<sub>CH<sub>4</sub></sub> in natural gas follows the order: Z<sub>2</sub>dn ≥ P<sub>2</sub>m &gt; Cambrian. (3) Overall, the Z<sub>2</sub>dn-P<sub>2</sub>m differential accumulation in the Penglai gas area is primarily influenced by various factors, including multiple source rocks, deep hydrothermal transformation, and strike-slip faults.</div></div>","PeriodicalId":400,"journal":{"name":"Organic Geochemistry","volume":"201 ","pages":"Article 104918"},"PeriodicalIF":2.6,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143378489","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
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。
{"title":"Study on hydrocarbon retention and expulsion of kerogen based on centrifugal swelling method","authors":"Tian Liang ,&nbsp;Feng Zhu ,&nbsp;Zhao-Wen Zhan ,&nbsp;Xiao-Hui Lin ,&nbsp;Yan-Rong Zou ,&nbsp;Ping’an Peng","doi":"10.1016/j.orggeochem.2024.104921","DOIUrl":"10.1016/j.orggeochem.2024.104921","url":null,"abstract":"<div><div>Centrifugal swelling experiments using <em>n</em>-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 T<sub>1</sub>/T<sub>2</sub> 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.</div></div>","PeriodicalId":400,"journal":{"name":"Organic Geochemistry","volume":"201 ","pages":"Article 104921"},"PeriodicalIF":2.6,"publicationDate":"2025-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143373026","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
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。
{"title":"Biomarker signatures in host rocks and their co-occurring fossil plants from northern Scotland","authors":"Olumuyiwa T. Akinsanpe ,&nbsp;Adebola O. Akinsanpe ,&nbsp;Solomon A. Adekola ,&nbsp;Oluwaseye P. Oyetade ,&nbsp;Waheed G. Akande ,&nbsp;Musa B. Usman ,&nbsp;Abdulwahab M. Bello ,&nbsp;Uzochukwu K. Benjamin ,&nbsp;Adeniyi O. Olusanya ,&nbsp;Chikezie Emele","doi":"10.1016/j.orggeochem.2025.104948","DOIUrl":"10.1016/j.orggeochem.2025.104948","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":400,"journal":{"name":"Organic Geochemistry","volume":"201 ","pages":"Article 104948"},"PeriodicalIF":2.6,"publicationDate":"2025-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143373025","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
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。
{"title":"Protocols to assist deconvolution of co-eluting 5β– and 5α–steranes by gas chromatography–mass spectrometry","authors":"Luke M. Brosnan,&nbsp;Paul F. Greenwood,&nbsp;Peter Hopper,&nbsp;Kliti Grice","doi":"10.1016/j.orggeochem.2024.104916","DOIUrl":"10.1016/j.orggeochem.2024.104916","url":null,"abstract":"<div><div>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 5β20<em>R</em> and 5α20<em>S</em> 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 5α20<em>R</em> and 5β20<em>R</em> cholestane standards (5α20<em>R</em> in place of 5α20<em>S</em>). Parameters offering 5α:5β selectivity (e.g., SIM: 149/151 Da; MRM: [149 → 79]/[151 → 79]) were tested on a suite of 5α20<em>R</em>:5β20<em>R</em> standards and show an excellent correlation (<em>R</em><sup>2</sup> &gt; 0.99) with substrate composition. The capacity to quantify the relative contribution of co-eluting 5α20<em>S</em> and 5β20<em>R</em> in more complex samples was tested by analyses of a crude oil (Blina-4, Canning Basin, Western Australia) known to have high abundances of C<sub>27-29</sub> 5α20<em>S</em> steranes (20<em>S</em>/[20<em>S</em> + 20<em>R</em>] ≈ 0.5) and spiked with 5β20<em>R</em> cholestane. The relative proportions of 5α20<em>S</em> and 5β20<em>R</em> were determined using 5α20<em>R</em>:5β20<em>R</em> 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.</div></div>","PeriodicalId":400,"journal":{"name":"Organic Geochemistry","volume":"201 ","pages":"Article 104916"},"PeriodicalIF":2.6,"publicationDate":"2025-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143373039","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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。
{"title":"Assessing tetraether lipids as a paleotemperature proxy on western edge of the Chinese Loess Plateau: A cautionary tale","authors":"Jingjing Guo ,&nbsp;Louise Fuchs ,&nbsp;Martin Ziegler ,&nbsp;Youbin Sun ,&nbsp;Francien Peterse","doi":"10.1016/j.orggeochem.2025.104947","DOIUrl":"10.1016/j.orggeochem.2025.104947","url":null,"abstract":"<div><div>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′<sub>5Me</sub>-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.</div></div>","PeriodicalId":400,"journal":{"name":"Organic Geochemistry","volume":"201 ","pages":"Article 104947"},"PeriodicalIF":2.6,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143145071","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
期刊
Organic Geochemistry
全部 Acc. Chem. Res. ACS Applied Bio Materials ACS Appl. Electron. Mater. ACS Appl. Energy Mater. ACS Appl. Mater. Interfaces ACS Appl. Nano Mater. ACS Appl. Polym. Mater. ACS BIOMATER-SCI ENG ACS Catal. ACS Cent. Sci. ACS Chem. Biol. ACS Chemical Health & Safety ACS Chem. Neurosci. ACS Comb. Sci. ACS Earth Space Chem. ACS Energy Lett. ACS Infect. Dis. ACS Macro Lett. ACS Mater. Lett. ACS Med. Chem. Lett. ACS Nano ACS Omega ACS Photonics ACS Sens. ACS Sustainable Chem. Eng. ACS Synth. Biol. Anal. Chem. BIOCHEMISTRY-US Bioconjugate Chem. BIOMACROMOLECULES Chem. Res. Toxicol. Chem. Rev. Chem. Mater. CRYST GROWTH DES ENERG FUEL Environ. Sci. Technol. Environ. Sci. Technol. Lett. Eur. J. Inorg. Chem. IND ENG CHEM RES Inorg. Chem. J. Agric. Food. Chem. J. Chem. Eng. Data J. Chem. Educ. J. Chem. Inf. Model. J. Chem. Theory Comput. J. Med. Chem. J. Nat. Prod. J PROTEOME RES J. Am. Chem. Soc. LANGMUIR MACROMOLECULES Mol. Pharmaceutics Nano Lett. Org. Lett. ORG PROCESS RES DEV ORGANOMETALLICS J. Org. Chem. J. Phys. Chem. J. Phys. Chem. A J. Phys. Chem. B J. Phys. Chem. C J. Phys. Chem. Lett. Analyst Anal. Methods Biomater. Sci. Catal. Sci. Technol. Chem. Commun. Chem. Soc. Rev. CHEM EDUC RES PRACT CRYSTENGCOMM Dalton Trans. Energy Environ. Sci. ENVIRON SCI-NANO ENVIRON SCI-PROC IMP ENVIRON SCI-WAT RES Faraday Discuss. Food Funct. Green Chem. Inorg. Chem. Front. Integr. Biol. J. Anal. At. Spectrom. J. Mater. Chem. A J. Mater. Chem. B J. Mater. Chem. C Lab Chip Mater. Chem. Front. Mater. Horiz. MEDCHEMCOMM Metallomics Mol. Biosyst. Mol. Syst. Des. Eng. Nanoscale Nanoscale Horiz. Nat. Prod. Rep. New J. Chem. Org. Biomol. Chem. Org. Chem. Front. PHOTOCH PHOTOBIO SCI PCCP Polym. Chem.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
×
提示
确定
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1