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Occurrence of tetraester and mixed ether/ester-bound iso-diabolic acid membrane-spanning lipids in acidic, high-elevation mineral soils 在酸性高海拔矿质土壤中四酯和混合醚/酯结合的异双代谢酸跨膜脂质的发生
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-05-05 DOI: 10.1016/j.orggeochem.2025.105013
Francien Peterse , Klaas G.J. Nierop , Nicole J. Bale , Sarah J. Feakins , Chan-Mao Chen
Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are a suite of membrane lipids that are widely used as empirical proxies for past temperature and pH. Although the stereochemistry of their glycerol moiety suggests that they are produced by bacteria, the exact producers and the biosynthetic pathway of brGDGTs remain unclear. Here we report the occurrence of tetraester and mixed ester/ether membrane-spanning lipids with a backbone consisting of iso-diabolic acid (iso-DA) containing up to two additional methyl groups in high-elevation (>1900 masl), acidic (pH < 4.5) mineral soils from Nepal and Rwanda. These compounds are presumed intermediate products during brGDGT synthesis but had not been detected in cultures or the environment before. Interestingly, while acid hydrolysis of the GDGT fraction releases iso-DA in the soil from Nepal, monoalkyl glycerol ethers with iso-C15 and iso-C17 chains are released in the soil from Rwanda. Although speculative, these results could support both current hypotheses that brGDGT synthesis can occur via tail-to-tail condensation of two iso-C15 fatty acids to form iso-DA, as well as through the reduction of diesters to diethers and subsequent carbon–carbon linking as shown to occur during the synthesis of archaeal GDGTs.
支化甘油二烷基甘油四醚(brGDGTs)是一组膜脂,被广泛用作过去温度和ph的经验代表。尽管其甘油部分的立体化学表明它们是由细菌产生的,但brGDGTs的确切生产者和生物合成途径尚不清楚。在这里,我们报告了四酯和混合酯/醚跨膜脂类的发生,其主干由含有多达两个额外甲基的异双代谢酸(iso-DA)组成,在高海拔(>1900 masl),酸性(pH <;4.5)尼泊尔和卢旺达的矿质土壤。这些化合物被认为是brGDGT合成过程中的中间产物,但以前从未在培养物或环境中检测到。有趣的是,当GDGT部分的酸水解在尼泊尔的土壤中释放出iso-DA时,具有iso-C15和iso-C17链的单烷基甘油醚在卢旺达的土壤中释放出来。尽管是推测性的,但这些结果可以支持目前的假设,即brGDGT的合成可以通过两种isoc15脂肪酸的尾对尾缩合形成isoda,以及通过二酯还原为二醚和随后的碳-碳连接,如在古菌gdgt合成过程中所示。
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引用次数: 0
Unravelling the origin of gas in tight sandstones of the Hangjinqi gas field, Ordos Basin, China: New insights from natural gas geochemistry data 鄂尔多斯盆地杭锦旗气田致密砂岩天然气成因:来自天然气地球化学数据的新认识
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-05-03 DOI: 10.1016/j.orggeochem.2025.105012
Yang Qin , Chiyang Liu , Junfeng Zhao , Faqi He , Wei Zhang , Lihua Yang , Nan Du , Deyong Shao
The Hangjinqi gas field, a vital tight sandstone gas field on the northern Ordos Basin margin, exhibits a debatable gas origin and accumulation mechanism. Integrating geochemical analyses with gas field data for basin-wide comparisons allows us to resolve the origin of the reservoired gas. Results reveal that the Upper Paleozoic coal-measure source rocks in the Hangjinqi area share similar characteristics with those in other Upper Paleozoic gas fields, where coal seams constitute the primary effective source rocks. However, they exhibit limited hydrocarbon-generating potential coupled with low thermal maturity. Natural gas has a broad range of dryness coefficient values. The carbon-hydrogen isotopes mostly exhibit a positive carbon-hydrogen isotope series, yet 40% of the samples display ethane and propane carbon-hydrogen isotope reversals. The C5-7 and C7 light hydrocarbons are dominated by isoalkanes and methylcyclohexane, respectively. The natural gas data follow the aromatic curve in the cross-plot of the heptane and isoheptane values. The natural gas in the Hangjinqi field is typical coal-derived gas, which is derived primarily from the Carboniferous-Permian transitional facies of humic organic matter, similar to Daniudi and other gas fields. Notably, the natural gas in the Hangjinqi gas field has undergone migration and dissipation (mainly including escape and loss). The Hangjinqi gas field presents an apparent contradiction between low maturity source rocks and high maturity natural gas. Its methane carbon isotope values significantly exceed those of the Daniudi gas field but align closely with those of the Sulige and Wushenqi gas fields, which are mature-type gas fields. Natural gas migration-dissipation is not the controlling factor in regional isotopic signatures. Therefore, approximately 40–76 % of the natural gas in the Hangjinqi gas field is exogenous gas. Moreover, these exogenous gases are derived primarily from the Sulige-Wushenqi gas field to its south, indicating strong genetic affinity. Overall, most Upper Paleozoic gas fields in the Ordos Basin have short migration distances, whereas the Hangjinqi gas field represents mixtures of locally generated hydrocarbons with gases migrating longer distances.
杭锦旗气田是鄂尔多斯盆地北缘重要的致密砂岩气田,其天然气成因和成藏机制存在争议。将地球化学分析与气田数据相结合,进行全盆地范围的比较,使我们能够确定成藏气体的来源。结果表明,杭锦旗地区上古生界煤系烃源岩与其他上古生界气田具有相似的特征,煤层是主要的有效烃源岩。然而,它们的生烃潜力有限,且热成熟度低。天然气的干燥系数值范围很广。碳-氢同位素多表现为正的碳-氢序列,但乙烷和丙烷的碳-氢同位素有40%的反转。C5-7和C7轻烃分别以异烷烃和甲基环己烷为主。天然气数据遵循正庚烷和异正庚烷值交叉图中的芳族曲线。杭锦旗气田天然气为典型的煤成气,天然气主要来自石炭—二叠系过渡相腐殖质有机质,与大牛地等气田相似。值得注意的是,杭锦旗气田的天然气经历了运移和耗散(主要包括逸出和损失)。杭锦旗气田呈现出低成熟烃源岩与高成熟天然气的明显矛盾。其甲烷碳同位素值明显超过大牛地气田,但与苏里格气田和乌胜旗气田的甲烷碳同位素值接近,均为成熟型气田。天然气的运移耗散不是区域同位素特征的控制因素。因此,杭锦旗气田约40 - 76%的天然气为外源气。此外,这些外源气体主要来自其南部的苏里格-乌胜旗气田,具有较强的成因亲和力。总体而言,鄂尔多斯盆地上古生界气田大多运移距离较短,而杭锦旗气田则是本地生烃与运移距离较远的混合气田。
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引用次数: 0
A saline lacustrine depositional environment enhances organic matter enrichment in the Permian Lucaogou shales 二叠系芦草沟页岩的咸化湖相沉积环境有利于有机质富集
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-05-01 DOI: 10.1016/j.orggeochem.2025.105009
Yin Fu , Zuodong Wang , Ting Zhang , Wenjun Wang , Yongli Wang , Wang Zhang , Xiaobin Li , Zhiyong Wang
The Permian Lucaogou Formation shales are world-class source rocks with diverse biological, environmental, and economic properties. Considerable attention has been given to depositional environmental controls on organic matter enrichment. Here, we present a systematic organic and inorganic geochemical analysis of fresh core samples taken from the Lucaogou Formation in the Malu 1 well, located in the Santanghu Basin. The organic matter source of Lucaogou shale is dominated by prokaryotic organisms. γ- and β-carotanes are present in high abundance; lower carbon number carotenoids are also detected. Based on the distribution of n-alkanes, terpanes, and steranes, it is believed that γ-carotane and β-carotane mainly originate from bacteria. Low-carbon carotenoid-derived alkanes could result from the thermal decomposition products of γ-carotane and β-carotane. The minor input of terrigenous clastic material brought elemental nutrients that likely enhanced biotic productivity. Based on organic and inorganic data, the depositional environment can be defined by two stages (I and II). The contribution of green algae increases from Stage I to Stage II. The Stage I organic matter enrichment is controlled by the state of preservation, and the Stage II organic matter is interpreted to be controlled by biotic productivity. The depositional environment and the productivity of the lake have changed synergistically, together controlling the enrichment of organic matter in the Lucaogou shales.
二叠系芦草沟组页岩是具有多种生物、环境和经济性质的世界级烃源岩。沉积环境对有机质富集的控制已引起相当大的重视。本文对三塘湖盆马鲁1井芦草沟组新岩心样品进行了系统的有机和无机地球化学分析。芦草沟页岩有机质来源以原核生物为主。γ-和β-胡萝卜素含量高;低碳数类胡萝卜素也被检测到。根据正构烷烃、萜烷和甾烷的分布,认为γ-胡萝卜烷和β-胡萝卜烷主要来源于细菌。低碳类胡萝卜素烷烃来源于γ-胡萝卜烷和β-胡萝卜烷的热分解产物。陆源碎屑物质的少量输入带来了可能提高生物生产力的元素营养。根据有机和无机资料,沉积环境可划分为ⅰ期和ⅱ期。从第一阶段到第二阶段,绿藻的贡献逐渐增加。第一阶段有机质富集受保存状态控制,第二阶段有机质被解释为受生物生产力控制。沉积环境与湖泊生产力协同变化,共同控制芦草沟页岩有机质富集。
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引用次数: 0
Microbial communities constrain the organic δ13C variations in the Lower Cambrian mudstones 微生物群落约束下寒武统泥岩有机δ13C变化
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-04-29 DOI: 10.1016/j.orggeochem.2025.104991
Biqing Zhu , Quanyou Liu , Huiyuan Xu , Dongya Zhu , Jingbin Wang , Xiaoqi Wu , Pengpeng Li , Yongqi Ruan
The Lower Cambrian organic-rich mudstones preserve extensive records of microbial life, potentially contributing to the ‘Cambrian explosion’ (∼540 to 520 Ma) and the formation of ancient petroleum resources. However, the link of organic δ13C variations to microbial communities in the Lower Cambrian Formation within the Tarim Craton, part of the Central Asian Orogenic Belt, remains incompletely understood. Here, we conducted a comprehensive biomarker and δ13C analysis of mudstone extracts. The prevalence of eukaryotic organisms relative to prokaryotes, together with increased primary productivity, results in substantial 12C enrichment in organic matter, with the converse relationship being equally valid. The Lower Cambrian mudstones formed in more reducing yet confined stratified environments. The presence of cholestane, ergostane, stigmasterane, and 4-methylsterane (e.g., dinosterane) indicates the occurrence of red algae, prasinophytes, green algae, and dinoflagellates, respectively. Notably, the predominance of ergosterane and stigmasterane over cholestane suggests a greater contribution from green algae over red algae. The even-carbon preference across the C14-C20 range is indicative of limited contributions from Gloeocapsomorpha prisca. The presence of 3β-methylhopane, 7-+8-monomethylheptadecane and 2α-methylhopane points to contributions from methanotrophs and cyanobacteria. Since methanotrophs are active in an oxygen- and sulfate-depleted environment, we speculate that 13C-rich organic matter with a high value of 3-methylhopane index (3-MHI) may be deposited in waters with expanded anoxic zones and a scarcity of photoautotrophic sulfur bacteria (e.g., Chlorobiaceae and Chromatiaceae). This study highlights the constraints of microbial communities on organic δ13C variations and enhances our understanding of the evolution of ecology and primary productivity during the Precambrian-Cambrian transition.
下寒武统富含有机物的泥岩保存了大量的微生物生命记录,可能有助于“寒武纪大爆发”(~ 540 ~ 520 Ma)和古石油资源的形成。然而,塔里木克拉通(中亚造山带的一部分)下寒武统组有机δ13C变化与微生物群落的关系尚不完全清楚。在此,我们对泥岩提取物进行了全面的生物标志物和δ13C分析。真核生物相对于原核生物的普遍存在,加上初级生产力的提高,导致有机质中大量的12C富集,反之亦然。下寒武统泥岩形成于还原性较强但受限制的层状环境。胆甾烷、麦角甾烷、污名甾烷和4-甲基甾烷(如甲甾烷)的存在分别表明存在红藻、水藻、绿藻和鞭毛藻。值得注意的是,麦角甾烷和污名甾烷在胆甾烷中的优势表明,绿藻对胆甾烷的贡献大于红藻。在C14-C20范围内的均匀碳偏好表明Gloeocapsomorpha prisca的贡献有限。3β-甲基藿烷、7-+8-单甲基十七烷和2α-甲基藿烷的存在表明甲烷氧化菌和蓝藻对甲烷的贡献。由于甲烷氧化菌在缺氧和硫酸盐匮乏的环境中具有活性,我们推测在缺氧区扩大和光自养硫细菌(如Chlorobiaceae和Chromatiaceae)稀缺的水域中可能沉积了富13c且具有高3-甲基藿烷指数(3-MHI)值的有机物。该研究突出了微生物群落对有机δ13C变化的约束,增强了我们对前寒武纪-寒武纪过渡时期生态和初级生产力演化的认识。
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引用次数: 0
Introduction to Xplorer, Hybrid and Early-Career Virtual Special Issue Xplorer入门,混合和早期职业虚拟特刊
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-04-29 DOI: 10.1016/j.orggeochem.2025.105007
Huiyuan Xu , Jian Ma , Kai Mangelsdorf
The aim of this special issue is to highlight the contributions of early-career scientists in the field of organic geochemistry, showcasing their innovative ideas, state-of-the-art research methods, and novel findings. By covering a wide range of topics, from petroleum geochemistry to palaeoenvironmental reconstruction, this issue seeks to advance our understanding of the Earth system through molecular fingerprint and isotopic geochemistry. Interdisciplinary studies that bridge geological, ecological, and environmental processes are particularly encouraged, reinforcing the role of organic geochemistry as a critical tool in modern Earth sciences.
本期特刊的目的是突出早期职业科学家在有机地球化学领域的贡献,展示他们的创新思想,最先进的研究方法和新的发现。通过涵盖广泛的主题,从石油地球化学到古环境重建,本期旨在通过分子指纹和同位素地球化学促进我们对地球系统的理解。特别鼓励连接地质、生态和环境过程的跨学科研究,加强有机地球化学作为现代地球科学重要工具的作用。
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引用次数: 0
Biodegradation sequence of coal organic matter and mechanism of biomethane formation in secondary biogenic gas accumulation areas 次生生物气聚集区煤有机质生物降解序列与生物甲烷形成机制
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-04-24 DOI: 10.1016/j.orggeochem.2025.104996
Yiliang Hu , Yuan Bao , Jiahao Meng , Dan Li , Ruihui Zheng
Laboratory biodegradation experiments of organic matter (OM) in coal provide a theoretical foundation for comprehending the formation of secondary biogenic gas (SBG). However, limited research has been conducted on the microbial degradation extent and sequence of OM degradation experienced by underground coal seams throughout geological history. This study analyzes underground coal samples from the typical SBG accumulation areas in the Ordos Basin to investigate the origin and composition of OM in coal as well as their contributions to SBG formation. The findings indicate that terrigenous input is the primary source of OM in coal in these regions, which has undergone varying degrees of biodegradation. Notably, there are significant differences in the degree of biodegradation between saturated and aromatic hydrocarbons. Saturated hydrocarbons show PM grade 4–5 degradation while aromatics demonstrate PM grade 5–7 degradation. Aromatics display a higher susceptibility to biodegradation compared to saturated hydrocarbons, which differs significantly from crude oil. The degradation susceptibility sequence for saturated hydrocarbons is as follows: n-alkane > sterane > hopane. The biodegradation susceptibility of aromatic hydrocarbons depends on both the number of aromatic rings and alkyl-substituents; those with fewer rings and alkyl-substituents degrade more rapidly. Biodegradation of OM in coal plays a crucial role in SBG generation; however, a high degree of OM biodegradation does not necessarily correlate with greater accumulation of SBG due to other factors such as tectonic fractures and hydrogeological conditions that affect its preservation.
煤中有机质(OM)的室内生物降解实验为理解次生生物气的形成提供了理论基础。然而,在整个地质历史中,对地下煤层有机质的微生物降解程度和降解顺序的研究却很少。本文对鄂尔多斯盆地典型SBG聚集区的地下煤样进行了分析,探讨了煤中OM的来源、组成及其对SBG形成的贡献。研究结果表明,陆源输入是这些地区煤中有机质的主要来源,煤中有机质经历了不同程度的生物降解。值得注意的是,饱和烃和芳烃的生物降解程度存在显著差异。饱和烃表现为4-5级PM降解,芳烃表现为5-7级PM降解。芳烃与原油相比,具有较高的生物降解敏感性。饱和烃的降解敏感性顺序为:正构烷烃;泼尼松龙比;藿烷。芳烃的生物降解敏感性取决于芳烃环的数量和烷基取代基的数量;环和烷基取代基较少的化合物降解更快。煤中OM的生物降解在SBG的生成中起着至关重要的作用;然而,由于构造裂缝和水文地质条件等影响其保存的其他因素,OM的高度生物降解并不一定与SBG的大量积累相关。
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引用次数: 0
Bacteriohopanepolyols and glycerol dialkyl glycerol tetraethers record Holocene redox regime shifts in a marine inlet in eastern Prydz Bay, Antarctica 细菌藿烷多元醇和甘油二烷基甘油四醚记录了南极洲Prydz湾东部海域全新世氧化还原状态的变化
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-04-19 DOI: 10.1016/j.orggeochem.2025.105011
Z.R. van Kemenade , S. Kusch , S. Berg , E.C. Hopmans , M.T.J. van der Meer , D. Rush
Prydz Bay is located at the terminus of one of the largest marine-terminating glacial systems of East Antarctica. Consequently, its sedimentary record may hold information on the response of marine biogeochemical cycling to changes in Antarctic palaeoceanography and palaeoclimate. Bacteriohopanepolyols (BHPs) and glycerol dialkyl glycerol tetraethers (GDGTs) offer great potential for tracing such changes, as these membrane lipids have been linked to distinct biogeochemical processes and environmental niches. Here, we present the BHP and GDGT inventory of a Holocene sediment record, recovered from a marine basin in eastern Prydz Bay. BHP and GDGT lipidomics were complemented with (organic) geochemical tools to reconstruct palaeoenvironmental conditions. GDGT-based indices suggest terrestrial organic matter influx was insignificant. Our results show elevated nucleoside-BHPs in early Holocene sediments from ∼9.1 to 10.7 cal ka BP. Their presence is interpreted to reflect autochthonous production under hypoxic-anoxic water column conditions, as inferred from BHT-x ratios of ≥0.2. The record is characterized by a large diversity of rare and novel unsaturated BHPs and BHP isomers. Their occurrence is potentially related to homeoviscous adaptations of the membranes of predominantly aerobic bacteria to cold conditions (i.e., reconstructed sea surface temperatures are −2.4 to −0.8 °C based on TEX86OH). Increased abundance and diversity of these BHPs between ∼5.5–7.5 and ∼8.9–9.8 cal ka BP is likely associated with an oxygenation of the basin at this time. During the late Holocene (<3.0 cal ka BP), the water column experienced photic zone euxinia, high rates of nitrogen loss and methanogenesis, as indicated by the presence of isorenieratene, enriched δ15N values and high GDGT-0/cren ratios, respectively. BHPs in these sediments likely derive from two different ecological niches: i) the uppermost oxygenated to suboxic waters where aerobic methane oxidation occurred and ii) the deeper sulfidic waters. More reducing conditions in the late Holocene coincide with increased brGDGT cyclization and methylation, and is proposed to indicate a shift in the source bacterial niche from sediments to the water column. This study shows that GDGT and BHP distributions can be linked to distinct redox regime shifts within the basin, which appear regulated by changes in sea level and sea ice in Prydz Bay. Our findings highlight the potential use of these lipids as tracers for biogeochemical cycling in marine polar regions.
Prydz湾位于东南极洲最大的海洋冰川系统之一的终点。因此,其沉积记录可能包含海洋生物地球化学循环对南极古海洋和古气候变化的响应信息。细菌藿烷多元醇(BHPs)和甘油二烷基甘油四醚(GDGTs)为追踪这些变化提供了巨大的潜力,因为这些膜脂与不同的生物地球化学过程和环境生态位有关。在这里,我们介绍了从Prydz湾东部海相盆地恢复的全新世沉积物记录的BHP和GDGT清单。将BHP和GDGT脂质组学与(有机)地球化学工具相结合,重建古环境条件。基于gdgt的指标提示陆源有机质流入不显著。我们的研究结果表明,在全新世早期沉积物中,核苷- bhps在~ 9.1 ~ 10.7 cal ka BP之间升高。根据BHT-x比值≥0.2,它们的存在被解释为反映了缺氧-缺氧水柱条件下的本地生产。记录的特点是大量的多样性罕见和新颖的不饱和必和必拓和必和必拓异构体。它们的出现可能与主要好氧细菌的膜对寒冷条件的自粘适应有关(即,基于TEX86OH重建的海面温度为−2.4至−0.8°C)。这些BHPs的丰度和多样性在~ 5.5-7.5和~ 8.9-9.8 cal ka BP之间增加,可能与此时盆地的氧化作用有关。在全新世晚期(3.0 cal ka BP),水柱经历了光区缺氧、高氮损失率和甲烷生成,分别表现为异硫氰酸的存在、丰富的δ15N值和高GDGT-0/cren比值。这些沉积物中的BHPs可能来自两个不同的生态位:i)发生好氧甲烷氧化的最上层含氧到缺氧的水域和ii)较深的硫化物水域。全新世晚期更多的还原条件与brGDGT环化和甲基化的增加相吻合,表明源细菌生态位从沉积物向水柱转移。研究表明,GDGT和BHP分布可能与盆地内明显的氧化还原状态变化有关,这种变化似乎受Prydz湾海平面和海冰变化的调节。我们的发现强调了这些脂质作为海洋极地生物地球化学循环示踪剂的潜在用途。
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引用次数: 0
Impact of terrestrial organic matter input on distributions of hydroxylated isoprenoidal GDGTs in marine sediments: Implications for OH-isoGDGT-based temperature proxies 陆源有机质输入对海洋沉积物中羟基化异戊二烯类GDGTs分布的影响:基于oh - isogdgts温度代用指标的意义
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-04-19 DOI: 10.1016/j.orggeochem.2025.105010
Devika Varma , Yord W. Yedema , Francien Peterse , Gert-Jan Reichart , Jaap S. Sinninghe Damsté , Stefan Schouten
<div><div>Isoprenoidal glycerol dialkyl glycerol tetraethers (isoGDGTs) and hydroxylated isoGDGTs (OH-isoGDGTs) are widespread in marine, lacustrine, and terrestrial environments and serve as paleoenvironmental proxies. Several indices based on their distributions, such as <span><math><msub><mrow><mi>T</mi><mi>E</mi><mi>X</mi></mrow><mn>86</mn></msub></math></span> (based on isoGDGTs), <span><math><mtext>RI-OH</mtext></math></span>, <span><math><mrow><mtext>RI-OH</mtext><mo>′</mo></mrow></math></span> (both based on OH-isoGDGTs), <span><math><mrow><mo>%</mo><mi>O</mi><mi>H</mi></mrow></math></span> and <span><math><msubsup><mrow><mi>T</mi><mi>E</mi><mi>X</mi></mrow><mrow><mn>86</mn></mrow><mrow><mi>O</mi><mi>H</mi></mrow></msubsup></math></span> (both based on isoGDGTs and OH-isoGDGTs), have been utilized as sea water temperature proxies. Although terrestrial organic matter (OM) input of isoGDGTs may affect the <span><math><msub><mrow><mi>T</mi><mi>E</mi><mi>X</mi></mrow><mn>86</mn></msub></math></span> in coastal marine settings, relatively little is known on its consequences for OH-isoGDGT distributions and related proxies. Here, we studied the distributions of OH-isoGDGTs in soils, rivers, and coastal marine settings at three locations: the Kara Sea, the Iberian margin, and the northern Gulf of Mexico, receiving terrestrial OM through the Yenisei, the Tagus and the Mississippi Rivers, respectively. In general, we observe higher relative abundances of OH-isoGDGTs (<span><math><mrow><mo>%</mo><mi>O</mi><mi>H</mi></mrow></math></span>) in coastal marine environments compared to soils and rivers from the same area. Comparison of OH-isoGDGT distributions shows that, in particular, the abundance of OH-isoGDGT with one cyclopentane moiety relative to total OH-isoGDGTs was lower in terrestrial settings. In general, the <span><math><mtext>RI-OH</mtext></math></span> was higher in terrestrial settings, while such a consistent offset was not observed for <span><math><mrow><mtext>RI-OH</mtext><mo>′</mo></mrow></math></span>. The <span><math><msubsup><mrow><mi>T</mi><mi>E</mi><mi>X</mi></mrow><mrow><mn>86</mn></mrow><mrow><mi>O</mi><mi>H</mi></mrow></msubsup></math></span> index, exhibits a distinct difference between terrestrial and marine settings, similar to the pattern observed for the <span><math><msub><mrow><mi>T</mi><mi>E</mi><mi>X</mi></mrow><mn>86</mn></msub></math></span>. This similarity is primarily attributed to the relatively minor influence of terrestrial OH-isoGDGTs compared to regular isoGDGTs in the <span><math><msubsup><mrow><mi>T</mi><mi>E</mi><mi>X</mi></mrow><mrow><mn>86</mn></mrow><mrow><mi>O</mi><mi>H</mi></mrow></msubsup></math></span> index. Despite these differences, only the coastal sediments of the Kara Sea showed indications of a potential bias of OH-isoGDGTs-based proxies caused by terrestrial OM input. However, these distributional variations may also be caused by the large salinity gradient in the Kara Sea, since it has bee
异戊二烯类甘油二烷基甘油四醚(isoGDGTs)和羟基化异ogdgts (OH-isoGDGTs)广泛存在于海洋、湖泊和陆地环境中,是古环境的代用物。基于其分布的TEX86(基于isoGDGTs)、RI-OH、RI-OH '(均基于OH-isoGDGTs)、%OH和TEX86OH(均基于isoGDGTs和OH-isoGDGTs)等指标已被用来作为海水温度指标。虽然陆相有机质(OM)输入可能会影响沿海海洋环境下的TEX86,但对其对o - isogdgt分布和相关代用物的影响知之甚少。在这里,我们研究了OH-isoGDGTs在三个地点的土壤、河流和沿海海洋环境中的分布:喀拉海、伊比利亚边缘和墨西哥湾北部,分别通过叶尼塞河、塔霍河和密西西比河接收陆地OM。总的来说,与同一地区的土壤和河流相比,我们观察到沿海海洋环境中OH- isogdgts (%OH)的相对丰度更高。对OH-isoGDGT分布的比较表明,在陆地环境中,具有一个环戊烷片段的OH-isoGDGT相对于总OH-isoGDGT的丰度更低。一般来说,在陆地环境中,RI-OH更高,而在RI-OH中没有观察到这种一致的偏移。TEX86OH指数显示了陆地和海洋环境之间的明显差异,类似于TEX86观测到的模式。这种相似性主要归因于与TEX86OH指数中的常规isogdgt相比,陆地oh - isogdgt的影响相对较小。尽管存在这些差异,但只有喀拉海沿岸沉积物显示出由陆地OM输入引起的基于oh - isogdgts的代用指标的潜在偏差。然而,这些分布变化也可能是由于喀拉海的大盐度梯度造成的,因为已经确定盐度对OH-isoGDGTs的分布有影响。我们的研究结果表明,在受大型河流流出影响的海洋环境中,在解释基于OH-isoGDGT代用物的温度估计时,应谨慎行事,这些河流流出导致大量陆地OM输入和/或具有强盐度梯度。
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Several indices based on their distributions, such as &lt;span&gt;&lt;math&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;T&lt;/mi&gt;&lt;mi&gt;E&lt;/mi&gt;&lt;mi&gt;X&lt;/mi&gt;&lt;/mrow&gt;&lt;mn&gt;86&lt;/mn&gt;&lt;/msub&gt;&lt;/math&gt;&lt;/span&gt; (based on isoGDGTs), &lt;span&gt;&lt;math&gt;&lt;mtext&gt;RI-OH&lt;/mtext&gt;&lt;/math&gt;&lt;/span&gt;, &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;mtext&gt;RI-OH&lt;/mtext&gt;&lt;mo&gt;′&lt;/mo&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt; (both based on OH-isoGDGTs), &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;mo&gt;%&lt;/mo&gt;&lt;mi&gt;O&lt;/mi&gt;&lt;mi&gt;H&lt;/mi&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt; and &lt;span&gt;&lt;math&gt;&lt;msubsup&gt;&lt;mrow&gt;&lt;mi&gt;T&lt;/mi&gt;&lt;mi&gt;E&lt;/mi&gt;&lt;mi&gt;X&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mn&gt;86&lt;/mn&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mi&gt;O&lt;/mi&gt;&lt;mi&gt;H&lt;/mi&gt;&lt;/mrow&gt;&lt;/msubsup&gt;&lt;/math&gt;&lt;/span&gt; (both based on isoGDGTs and OH-isoGDGTs), have been utilized as sea water temperature proxies. Although terrestrial organic matter (OM) input of isoGDGTs may affect the &lt;span&gt;&lt;math&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;T&lt;/mi&gt;&lt;mi&gt;E&lt;/mi&gt;&lt;mi&gt;X&lt;/mi&gt;&lt;/mrow&gt;&lt;mn&gt;86&lt;/mn&gt;&lt;/msub&gt;&lt;/math&gt;&lt;/span&gt; in coastal marine settings, relatively little is known on its consequences for OH-isoGDGT distributions and related proxies. Here, we studied the distributions of OH-isoGDGTs in soils, rivers, and coastal marine settings at three locations: the Kara Sea, the Iberian margin, and the northern Gulf of Mexico, receiving terrestrial OM through the Yenisei, the Tagus and the Mississippi Rivers, respectively. In general, we observe higher relative abundances of OH-isoGDGTs (&lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;mo&gt;%&lt;/mo&gt;&lt;mi&gt;O&lt;/mi&gt;&lt;mi&gt;H&lt;/mi&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt;) in coastal marine environments compared to soils and rivers from the same area. Comparison of OH-isoGDGT distributions shows that, in particular, the abundance of OH-isoGDGT with one cyclopentane moiety relative to total OH-isoGDGTs was lower in terrestrial settings. In general, the &lt;span&gt;&lt;math&gt;&lt;mtext&gt;RI-OH&lt;/mtext&gt;&lt;/math&gt;&lt;/span&gt; was higher in terrestrial settings, while such a consistent offset was not observed for &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;mtext&gt;RI-OH&lt;/mtext&gt;&lt;mo&gt;′&lt;/mo&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt;. The &lt;span&gt;&lt;math&gt;&lt;msubsup&gt;&lt;mrow&gt;&lt;mi&gt;T&lt;/mi&gt;&lt;mi&gt;E&lt;/mi&gt;&lt;mi&gt;X&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mn&gt;86&lt;/mn&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mi&gt;O&lt;/mi&gt;&lt;mi&gt;H&lt;/mi&gt;&lt;/mrow&gt;&lt;/msubsup&gt;&lt;/math&gt;&lt;/span&gt; index, exhibits a distinct difference between terrestrial and marine settings, similar to the pattern observed for the &lt;span&gt;&lt;math&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;T&lt;/mi&gt;&lt;mi&gt;E&lt;/mi&gt;&lt;mi&gt;X&lt;/mi&gt;&lt;/mrow&gt;&lt;mn&gt;86&lt;/mn&gt;&lt;/msub&gt;&lt;/math&gt;&lt;/span&gt;. This similarity is primarily attributed to the relatively minor influence of terrestrial OH-isoGDGTs compared to regular isoGDGTs in the &lt;span&gt;&lt;math&gt;&lt;msubsup&gt;&lt;mrow&gt;&lt;mi&gt;T&lt;/mi&gt;&lt;mi&gt;E&lt;/mi&gt;&lt;mi&gt;X&lt;/mi&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mn&gt;86&lt;/mn&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mi&gt;O&lt;/mi&gt;&lt;mi&gt;H&lt;/mi&gt;&lt;/mrow&gt;&lt;/msubsup&gt;&lt;/math&gt;&lt;/span&gt; index. Despite these differences, only the coastal sediments of the Kara Sea showed indications of a potential bias of OH-isoGDGTs-based proxies caused by terrestrial OM input. However, these distributional variations may also be caused by the large salinity gradient in the Kara Sea, since it has bee","PeriodicalId":400,"journal":{"name":"Organic Geochemistry","volume":"206 ","pages":"Article 105010"},"PeriodicalIF":2.6,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143917858","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
Thermal stability of freshwater fern Azolla biomarkers as assessed by hydrous pyrolysis 水热解法评价淡水蕨类植物杜鹃生物标志物的热稳定性
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-04-19 DOI: 10.1016/j.orggeochem.2025.105008
Klaas G.J. Nierop , Merel Mijs , Rolande Dekker , Michael D. Lewan , Eveline N. Speelman , Jan W. de Leeuw , Gert-Jan Reichart
The freshwater fern Azolla produces a unique series of ω20-hydroxy and ω9,ω10-dihydroxy lipids. These compounds were also detected in Eocene sediments (∼48.5 Ma) characterized by the occurrence of fossil remains of Azolla and are thought to be prime markers for the past occurrence of Azolla implying that they could serve as palaeo-environmental indicators of freshwater conditions. However, the suitability of these Azolla biomarkers for application to more mature sediments is unknown. In this study, Azolla caroliniana specimens were heated using hydrous pyrolysis at temperatures ranging from 220 to 365 °C for 72 h to examine the stability and degradation of the Azolla biomarkers during simulated diagenesis. Initially all ω20-hydroxy and ω9,ω10-dihydroxy lipids are converted to their ketone analogues. At 260 °C n-alkanes are formed. ω20-Hydroxy and ω9,ω10-dihydroxy lipids are degraded between 260 and 280 °C. At 300 °C, only ω20-keto-1-ols, ω20-keto fatty acids and ω20-ketones, along with their ω9 and ω10 analogues, remain to preserve their ω20, ω9 and ω10 functionalities, while at 320 °C and higher only the ω20-, ω9, and ω10-ketones were observed. At higher temperatures the proportions of n-alkanes became dominating. The high thermal stability of the ω20, ω9/ω10 functionality shows that it has a relatively high preservation potential. Hence, it may potentially be a robust source indicator of the depositional environment of Azolla-derived organic carbon reflecting freshwater or brackish surface waters.
淡水蕨类植物杜鹃花产生一系列独特的ω20-羟基和ω9、ω10-二羟基脂质。在始新世沉积物(~ 48.5 Ma)中也发现了这些化合物,这些化合物被认为是过去发生过的Azolla化石遗迹的主要标志,这意味着它们可以作为淡水条件的古环境指标。然而,这些Azolla生物标志物是否适合应用于更成熟的沉积物尚不清楚。在本研究中,采用加水热解方法,在220 - 365°C的温度范围内加热72 h,研究模拟成岩过程中杜鹃花生物标志物的稳定性和降解情况。最初,所有ω20-羟基和ω9,ω10-二羟基脂质都转化为它们的酮类类似物。在260℃时形成正构烷烃。ω20-羟基和ω9、ω10-二羟基脂质在260 ~ 280℃之间降解。在300°C时,只有ω20-酮-1-醇、ω20-酮脂肪酸和ω20-酮及其ω9和ω10类似物保留了ω20、ω9和ω10的官能团,而在320°C及以上时,只观察到ω20、ω9和ω10酮。在较高的温度下,正构烷烃的比例占主导地位。ω20、ω9/ω10官能团的高热稳定性表明其具有较高的保存潜力。因此,它可能是反映淡水或微咸地表水的氮源有机碳沉积环境的一个强有力的来源指标。
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引用次数: 0
Three major types of trimethyl-alkylbenzenes and significance for the genesis of reservoir bitumens from the northwestern Sichuan Basin, South China 四川盆地西北部三甲基烷基苯的三种主要类型及其对储层沥青成因的意义
IF 2.6 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2025-04-14 DOI: 10.1016/j.orggeochem.2025.104997
Mingyue Tao , Susu Wang , Wanglu Jia , Yongge Sun , Lian Jiang , Jian Chen , Ping’an Peng
Trimethyl-alkylbenzenes in oil are an important class of molecular marker for determining biological sources, source rock depositional environment and maturity. They can be classified into three major types based on the type of side chain, including trimethyl-isoprenoid-, trimethyl-isohexyl-, and trimethyl-n-alkyl-benzenes. Although they have been studied separately for many years, recent studies have elucidated complicated co-elution of trimethyl-isoprenoid-benzenes and trimethyl-n-alkyl-benzenes on commonly used chromatographic columns. Moreover, simultaneous detections of these three types of trimethyl-alkylbenzenes were rarely reported. Reservoir bitumens, widely distributed along the northwestern margin of the Sichuan Basin, exhibit maturity characteristics that provide crucial insights for regional petroleum exploration in this ancient, giant petroliferous basin. So far, there has been no report on detection of these compounds from these reservoir bitumens, which may have suffered from severe biodegradation resulting in challenges to the understanding of genesis of these bitumens. In this study, asphaltenes, which are resistant to biodegradation, were carefully examined and asphaltene-bound hydrocarbons were compared to free hydrocarbons for the distribution of trimethyl-alkylbenzenes. Three main conclusions were drawn. Firstly, three major types of trimethyl-alkylbenzenes were detected through comparisons with available standards and well-characterized oils. These are 2,3,6-trimethyl-aryl isoprenoids (2,3,6-TMIPBs), 2,3,6-trimethyl-isohexylbenzene (2,3,6-TMiHB, C15), and trimethyl-n-alkylbenzenes (TMnABs, mainly 2,4,5-/2,3,5-, 2,3,6-, 2,3,4-trimethyl series), which show significant differences in concentrations for both free and asphaltene-bound hydrocarbons. Secondly, four groups of reservoir bitumens having distinct isotopic compositions also show large differences in the distributions of 2,3,6-TMIPBs and 2,3,6-TMiHB, providing further constraints on both biological sources and depositional environments for their source rocks. For the major group mainly sourced from the upper Ediacaran to lower Cambrian source rocks, abundant 2,3,6-TMIPBs and isorenieratane were detected. This finding, combined with global distributions of multiple kinds of C40 aromatic carotenoids (isorenieratane, chlorobactane, okenane) in the upper Ediacaran to lower Cambrian source rocks and their generated oils, indicates that photic zone euxinia was prevalent in ancient oceans, which may be of great significance for biological evolution in this key geological period. Thirdly, the ratios of 2,3,6-TMIPBs and 2,3,6-TMiHB to TMnABs have suggested subtle differences in the maturity of free hydrocarbons and asphaltenes, which can be used to reveal complex genetic processes for these bitumens, including at least two oil charging phases, different degrees of secondary cracking of asphaltenes mainly from early charg
石油中的三甲基烷基苯是判断生物烃源岩、烃源岩沉积环境和成熟度的重要分子标志。根据侧链的类型,它们可以分为三种主要类型,包括三甲基-类异戊二烯-、三甲基-异己基-和三甲基-正烷基苯。虽然它们已经分别研究了多年,但最近的研究已经阐明了三甲基-异戊二烯类苯和三甲基-正烷基苯在常用色谱柱上的复杂共洗脱。此外,同时检测这三种类型的三甲基烷基苯的报道很少。储层沥青广泛分布于四川盆地西北缘,其成熟度特征为该古巨型含油气盆地的区域油气勘探提供了重要的参考。到目前为止,还没有从这些储层沥青中检测到这些化合物的报道,这些沥青可能遭受了严重的生物降解,这给了解这些沥青的成因带来了挑战。在这项研究中,沥青质是一种抗生物降解的物质,研究人员仔细检查了沥青质结合的碳氢化合物与游离碳氢化合物的分布,并将其与三甲基烷基苯进行了比较。得出了三个主要结论。首先,通过与现有标准和表征良好的油品进行比较,检测出三种主要类型的三甲基烷基苯。它们是2,3,6-三甲基芳基异戊二烯类(2,3,6- tmipbs), 2,3,6-三甲基异己基苯(2,3,6- tmihb, C15)和三甲基-n-烷基苯(tmnab,主要是2,4,5-/2,3,5-,2,3,6-,2,3,4-三甲基系列),它们在游离和沥青质结合的碳氢化合物浓度上都有显著差异。②4组不同同位素组成的储层沥青在2,3,6- tmipb和2,3,6- tmihb的分布上也存在较大差异,为其烃源岩的生物源和沉积环境提供了进一步的约束。主要来源于上埃迪卡拉统至下寒武统烃源岩的主要组中,含有丰富的2、3、6- tmipb和异氰戊烷。结合上埃迪卡拉统至下寒武统烃源岩及其生油中多种C40芳香类胡萝卜素(异戊二烷、氯苯烷、克烯烷)的全球分布,表明古海洋中普遍存在光带含氧藻,这对这一关键地质时期的生物演化可能具有重要意义。②2、3、6- tmipb和2、3、6-TMiHB与tmnab的比值表明,游离烃和沥青质的成熟度存在细微差异,揭示了这些沥青的复杂成因过程,包括至少两个原油充注阶段,沥青质的不同程度次生裂解主要来自早期充注油,次生裂解产物与高成熟烃源岩晚期充注油混合。一个新的三元图,显示了C15 2,3,6- tmipb, 2,3,6- tmihb和tmnab的相对浓度,更清楚地阐明了这些差异。总的来说,这项研究显示了多种类型的三甲基烷基苯在理解复杂的石油充电历史方面的巨大潜力。
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Organic Geochemistry
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