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The widespread occurrence and wide structural diversity of sulfurized diterpenoids in ambers 琥珀中硫化二萜的广泛分布和结构多样性
IF 2.5 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-03-01 Epub Date: 2026-01-08 DOI: 10.1016/j.orggeochem.2026.105127
Alice Fradet , Philippe Schaeffer , Leo-Paul Magnin , Lauriane Lenen , Jan Pańczak , Bernard Gomez , Vincent Grossi , Pierre Adam
Although the presence of sulfur in amber has been previously reported, its origins and nature are not precisely known. The recent identification by NMR of sulfides related to tricyclic resin acids in a Cretaceous amber sample unambiguously showed that sulfur occurs in amber as organic sulfur compounds (OSC), at least to some extent. Molecular investigation of a large set of ambers from various botanical/geological origins and ages using GC–MS revealed that OSC are relatively widespread in ambers which was previously unknown. Their proportions relative to non-sulfurized terpenoids are variable among amber samples, and some samples proved to be devoid of OSC. In addition, it has been shown that OSC in ambers present a wide structural diversity, and comprise compounds related to tricyclic resin acids and labdanoids. Several structures could be proposed notably based on comparison with sulfurized labdanoids previously identified in sulfur-rich sediments. Laboratory sulfurization experiments involving functionalized diterpenoids from the resins of Cedrus atlantica and Araucaria columnaris and polysulfides successfully resulted in the formation of OSC identical or analogous to the natural compounds occurring in amber. This validates the predominant proposed pathways for the formation of OSC from amber. The early diagenetic sulfurization of diterpenoids in resin thus appears to be a key geochemical process influencing amber composition and contributing to the molecular diversity observed in fossil resins. The diverse OSC occurring in several amber types could potentially be used as geochemical markers of specific palaeoenvironments where sulfates are available and where the conditions of sedimentation promote, at least locally or in microenvironments, the establishment of anaerobic conditions favourable for the development of sulfate-reducing microorganisms.
虽然以前曾报道过琥珀中硫的存在,但其来源和性质尚不清楚。最近对白垩纪琥珀样品中三环树脂酸相关硫化物的核磁共振鉴定明确表明,至少在一定程度上,硫以有机硫化合物(OSC)的形式存在于琥珀中。利用GC-MS对来自不同植物/地质来源和年龄的琥珀进行了分子研究,发现琥珀中盐含量普遍存在,这是以前未知的。它们相对于未硫化萜类的比例在琥珀样品中是可变的,有些样品被证明是缺乏盐含量的。此外,琥珀中的盐碳具有广泛的结构多样性,包括与三环树脂酸和labdanoids相关的化合物。通过与先前在富硫沉积物中发现的硫化类labdanoids进行比较,可以提出几个值得注意的结构。在实验室进行的硫化实验中,用大西洋雪松和柱状杉木树脂中的功能化二萜和多硫化物成功地形成了与琥珀中天然化合物相同或类似的盐盐。这证实了琥珀形成盐盐的主要途径。因此,树脂中二萜的早期成岩硫化作用似乎是影响琥珀组成和促进化石树脂中观察到的分子多样性的关键地球化学过程。几种琥珀类型中出现的不同盐含量可能被用作特定古环境的地球化学标志,在这些古环境中,硫酸盐是可用的,而沉积条件至少在局部或微环境中促进了有利于硫酸盐还原微生物发育的厌氧条件的建立。
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引用次数: 0
Faecal n-alkanes differ significantly between two lemur species reflecting differences in consumed diet 两种狐猴的粪便正构烷烃差异显著,反映了所消耗饮食的差异
IF 2.5 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-03-01 Epub Date: 2025-12-24 DOI: 10.1016/j.orggeochem.2025.105124
Gemma Baker , James Bendle , Lydia K. Greene , Kweku Afrifa Yamoah , Matthew Allison , Sarah E. Greene
The diet of an animal reflects its species’ ecology and local food availability and is often a key metric for monitoring the health and welfare of endangered species. However, determining diets across individuals and through space and time, is an inherent challenge within ecology, being expensive and time-intensive to accomplish with observations. Faeces offer the opportunity for non-invasive sample collection and can provide a snapshot of the ingested diet of the producer. In modern ecology, faecal samples have been a prime target for genetic analyses of diet and the gut microbiome. Here, however, we explore whether high molecular weight (HMW) n-alkane biomarkers extracted from faeces can provide useful information about diet. HMW n-alkanes are commonly employed in palaeoecological reconstructions. Combining faecal HMW n-alkane analyses with gut microbiome composition and detailed foraging data applied to two species of lemur in captivity with access to naturalized forest enclosures, we show that recovered HMW n-alkanes are completely dietary in origin and not correlated to the gut microbiome. Signatures are significantly different between our two focal lemur species and seasons, reflecting differences in ingested diet. It is possible to infer changes in the relative contributions of major plant parts, particularly leaves and fruits, based on the faecal HMW n-alkane concentrations. Whereas n-alkane signatures alone are perhaps ill-suited to pinpoint plant species in animals with complex herbivorous diets, when integrated with other complementary methodologies can provide a more comprehensive dietary reconstruction. HMW n-alkanes are simple to identify and measure; only requiring commonly available and relatively affordable analytical chemistry instruments (e.g. GC-FID). Beyond discussing downstream uses of our methodology to captive and wild lemurs, other primates and herbivorous and omnivorous animals globally, our pilot study hints at the promise of the organic geochemist’s toolkit applied to dietary ecology.
动物的饮食反映了该物种的生态和当地的食物供应,通常是监测濒危物种健康和福利的关键指标。然而,通过空间和时间来确定个体的饮食是生态学的固有挑战,通过观察来完成既昂贵又耗时。粪便为非侵入性样本收集提供了机会,并可提供生产者摄入饮食的快照。在现代生态学中,粪便样本一直是饮食和肠道微生物群遗传分析的主要目标。然而,在这里,我们探索从粪便中提取的高分子量(HMW)正构烷烃生物标志物是否可以提供有关饮食的有用信息。高分子量正构烷烃常用于古生态重建。结合粪便HMW正构烷烃分析和肠道微生物组成,以及对两种圈养狐猴的详细觅食数据,研究人员发现,恢复的HMW正构烷烃完全来自饮食,与肠道微生物组无关。我们的两个焦点狐猴物种和季节之间的特征显着不同,反映了摄入饮食的差异。根据粪便中HMW正构烷烃的浓度,可以推断出植物主要部分,特别是叶子和果实的相对贡献的变化。然而,单靠正构烷烃特征可能不适合确定具有复杂草食性饮食的动物的植物种类,当与其他互补方法相结合时,可以提供更全面的饮食重建。高分子量正构烷烃易于识别和测量;只需要常用且相对便宜的分析化学仪器(例如GC-FID)。除了讨论我们的方法在全球范围内对圈养和野生狐猴、其他灵长类动物、草食性和杂食性动物的下游应用之外,我们的试点研究还暗示了有机地球化学家工具包应用于饮食生态学的前景。
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引用次数: 0
Three genetic types of natural gas derived from the Oligocene Yacheng Formation deposited in various environments within the Qiongdongnan Basin, South China Sea 南海琼东南盆地渐新统崖城组在不同沉积环境下形成了3种成因类型的天然气
IF 2.5 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-02-01 Epub Date: 2026-01-11 DOI: 10.1016/j.orggeochem.2026.105126
Yongbin Quan , Yiming Hu , Jinhai Yang , Xi’nong Xie , Lei Tuo , Fang Hao , Heqing Feng
The Qiongdongnan Basin exhibits substantial heterogeneity in hydrocarbon composition and origin. Accurately characterizing this variation is critical for refining hydrocarbon generation models in marginal basins. The depositional facies of source rocks fundamentally control the composition and genetic types of hydrocarbons, yet this critical constraint remains poorly understood. To address this gap, biomarker profiling via GC–MS, and δ13C analysis of individual n-alkanes, benzenes, and toluene via GC-IRMS were conducted on three major thermogenic accumulations. Results identify three distinct genetic gas types tied to depositional environments: (1) Y13 is coal-type gas derived from paralic facies source rocks with dominate higher plant input, deposited under oxygenated, non-stratified conditions; (2) L17 also exhibit coal-type gas, but was derived from terrigenous-marine facies source rocks deposited in a suboxic environment with reduced higher plant input; and (3) B21 represents oil-type gas derived from shallow marine facies source rocks deposited in suboxic-dysoxic setting with further reduce terrigenous input. All hydrocarbons originate from the Oligocene Yacheng Formation, with heterogeneity arising from spatially varying depositional facies within the basin, ranging from paralic in the west to shallow marine in the east, correlating with the earlier regional subsidence and marine transgression in the east. This facies-controlled mechanism differs from traditional models that attribute gas variations to maturity, source rock intervals, or post-generation modification. This study provides a template for interpreting hydrocarbon compositions and genetic types, offering a refined framework for source rock evaluation and resource assessment in analogous marginal basins worldwide.
琼东南盆地在油气组成和成因上具有明显的非均质性。准确表征这种变化对于完善边缘盆地生烃模式至关重要。烃源岩的沉积相从根本上控制着油气的组成和成因类型,但人们对这一关键制约因素知之甚少。为了解决这一空白,通过GC-MS进行了生物标志物分析,并通过GC-IRMS对三个主要的热成因聚集进行了单个正构烷烃、苯和甲苯的δ13C分析。结果表明:①Y13为煤型天然气,产自以高植物输入为主的近陆相烃源岩,沉积条件为含氧、非分层;(2) L17也表现为煤型气,但主要为陆相-海相烃源岩,沉积于低高植物输入的缺氧环境;(3) B21为亚氧-欠氧环境下沉积的浅海相烃源岩油型天然气,陆源输入进一步减少。所有油气均来自渐新统崖城组,其非均质性源于盆地内沉积相的空间差异,西为海陆相,东为浅海相,与早期的区域沉降和东部海侵有关。这种由相控制的机制与将天然气变化归因于成熟度、烃源岩层段或生后改造的传统模式不同。该研究为油气组成和成因类型的解释提供了模板,为全球类似边缘盆地烃源岩评价和资源评价提供了精细化的框架。
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引用次数: 0
Plant-wax n-alkanes from the central Congo Basin as palaeo-environmental and -climatic proxies 刚果盆地中部植物蜡正构烷烃作为古环境和气候的代用物
IF 2.5 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-02-01 Epub Date: 2025-11-17 DOI: 10.1016/j.orggeochem.2025.105092
Mélanie Guardiola , Gaël U.D. Bouka , Carolia Abaye , Johanna Menges , Frauke Rostek , Guillaume Leduc , Edouard Bard , Enno Schefuß , Yannick Garcin
The central Congo Basin is home to the world’s largest tropical peatland complex and is covered with swamp forest. In the face of climate change and future human activities in the region, it is important to understand the factors that determine the nature and dynamics of the peatland vegetation cover. One way to gain insight into these factors is to reconstruct the history of the central Congo Basin peatlands. Analysing lipid biomarkers extracted from peat cores such as plant wax n-alkanes enables past environmental and climatic conditions to be reconstructed. However, there is currently no information on how the production of plant waxes by different plant species influences the abundance and isotopic composition of n-alkanes in peat and other archives in the Congo Basin. In this study we analysed plant wax n-alkane abundances, δ13C and δD values according to photosynthetic pathways (C3 vs. C4), angiosperm subclasses (dicotyledons vs. monocotyledons), and source water δD values in the dominant plant types (trees, shrubs, and herbs) in the peatland area of the Cuvette Department in the Republic of the Congo. Our dataset enables the definition of a new n-alkane distribution index, named GRIND, that distinguishes between C3 (mostly dicotyledons) and C4 (monocotyledons) plants as follows: (n-C27 + n-C33 + n-C35)/(n-C25 + n-C27 + n-C29 + n-C31 + n-C33 + n-C35). This index may therefore be used to analyse Central African peat deposits and derive the relative abundance of C3 and C4 plant waxes in the past, independently of δ13C measurements. Furthermore, δ13C values from the central Congo Basin and other African sites suggest that environments with high relative humidity (> 80%) are characterised by very negative δ13C values (i.e., < –37‰) of n-C29 and n-C31 alkanes. This observation highlights the potential of n-alkane δ13C in deriving climatic information under high relative humidity conditions in Central African lowlands, and contribute to palaeo-climatic reconstructions. Finally, the δD values of n-C29 and n-C31 alkanes demonstrate that, despite contrasting apparent fractionation values associated with photosynthetic pathways and plant functional types — which can be accounted for using δ13C and pollen data in sedimentary deposits — they reliably reflect the δD of environmental water. This confirms that plant wax n-alkane δD values are effective tools for reconstructing palaeo-climatic changes in equatorial regions.
刚果盆地中部是世界上最大的热带泥炭地复合体的所在地,并覆盖着沼泽森林。面对气候变化和未来人类在该地区的活动,了解决定泥炭地植被覆盖性质和动态的因素是很重要的。了解这些因素的一种方法是重建刚果盆地中部泥炭地的历史。分析从泥炭核中提取的脂质生物标志物,如植物蜡正构烷烃,可以重建过去的环境和气候条件。然而,目前还没有关于不同植物种类生产植物蜡如何影响刚果盆地泥炭和其他档案中正构烷烃丰度和同位素组成的信息。本文根据光合途径(C3 vs. C4)、被子植物亚类(双子叶植物vs.单子叶植物)和主要植物类型(乔木、灌木和草本植物)分析了刚果共和国Cuvette省泥炭地地区植物蜡质正烷烃丰度、δ13C和δD值,以及水源水δD值。我们的数据集能够定义一个新的正构烷烃分布指数,名为GRIND,它区分C3(主要是双子叶植物)和C4(单子叶植物)植物,如下:(n-C27 + n-C33 + n-C35)/(n-C25 + n-C27 + n-C29 + n-C31 + n-C33 + n-C35)。因此,该指数可用于分析中非泥炭沉积物,并推导出过去C3和C4植物蜡的相对丰度,而不依赖于δ13C测量。此外,刚果盆地中部和非洲其他地点的δ13C值表明,在高相对湿度(> 80%)的环境中,n-C29和n-C31烷烃的δ13C值为负(< -37‰)。这一观测结果强调了正构烷烃δ13C在中非低地高相对湿度条件下获取气候信息的潜力,并有助于古气候重建。最后,n-C29和n-C31烷烃的δD值表明,尽管与光合途径和植物功能类型相关的表观分馏值存在差异(可以使用沉积沉积物中的δ13C和花粉数据来解释),但它们可靠地反映了环境水的δD。这证实了植物蜡正构烷烃δD值是重建赤道地区古气候变化的有效工具。
{"title":"Plant-wax n-alkanes from the central Congo Basin as palaeo-environmental and -climatic proxies","authors":"Mélanie Guardiola ,&nbsp;Gaël U.D. Bouka ,&nbsp;Carolia Abaye ,&nbsp;Johanna Menges ,&nbsp;Frauke Rostek ,&nbsp;Guillaume Leduc ,&nbsp;Edouard Bard ,&nbsp;Enno Schefuß ,&nbsp;Yannick Garcin","doi":"10.1016/j.orggeochem.2025.105092","DOIUrl":"10.1016/j.orggeochem.2025.105092","url":null,"abstract":"<div><div>The central Congo Basin is home to the world’s largest tropical peatland complex and is covered with swamp forest. In the face of climate change and future human activities in the region, it is important to understand the factors that determine the nature and dynamics of the peatland vegetation cover. One way to gain insight into these factors is to reconstruct the history of the central Congo Basin peatlands. Analysing lipid biomarkers extracted from peat cores such as plant wax <em>n-</em>alkanes enables past environmental and climatic conditions to be reconstructed. However, there is currently no information on how the production of plant waxes by different plant species influences the abundance and isotopic composition of <em>n-</em>alkanes in peat and other archives in the Congo Basin. In this study we analysed plant wax <em>n-</em>alkane abundances, δ<sup>13</sup>C and δD values according to photosynthetic pathways (C<sub>3</sub> vs. C<sub>4</sub>), angiosperm subclasses (dicotyledons vs. monocotyledons), and source water δD values in the dominant plant types (trees, shrubs, and herbs) in the peatland area of the Cuvette Department in the Republic of the Congo. Our dataset enables the definition of a new <em>n</em>-alkane distribution index, named GRIND, that distinguishes between C<sub>3</sub> (mostly dicotyledons) and C<sub>4</sub> (monocotyledons) plants as follows: (<em>n-</em>C<sub>27</sub> + <em>n-</em>C<sub>33</sub> + <em>n-</em>C<sub>35</sub>)/(<em>n-</em>C<sub>25</sub> + <em>n-</em>C<sub>27</sub> + <em>n-</em>C<sub>29</sub> + <em>n-</em>C<sub>31</sub> + <em>n-</em>C<sub>33</sub> + <em>n-</em>C<sub>35</sub>). This index may therefore be used to analyse Central African peat deposits and derive the relative abundance of C<sub>3</sub> and C<sub>4</sub> plant waxes in the past, independently of δ<sup>13</sup>C measurements. Furthermore, δ<sup>13</sup>C values from the central Congo Basin and other African sites suggest that environments with high relative humidity (&gt; 80%) are characterised by very negative δ<sup>13</sup>C values (i.e., &lt; –37‰) of <em>n-</em>C<sub>29</sub> and <em>n-</em>C<sub>31</sub> alkanes. This observation highlights the potential of <em>n-</em>alkane δ<sup>13</sup>C in deriving climatic information under high relative humidity conditions in Central African lowlands, and contribute to palaeo-climatic reconstructions. Finally, the δD values of <em>n</em>-C<sub>29</sub> and <em>n</em>-C<sub>31</sub> alkanes demonstrate that, despite contrasting apparent fractionation values associated with photosynthetic pathways and plant functional types — which can be accounted for using δ<sup>13</sup>C and pollen data in sedimentary deposits — they reliably reflect the δD of environmental water. This confirms that plant wax <em>n</em>-alkane δD values are effective tools for reconstructing palaeo-climatic changes in equatorial regions.</div></div>","PeriodicalId":400,"journal":{"name":"Organic Geochemistry","volume":"212 ","pages":"Article 105092"},"PeriodicalIF":2.5,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145659138","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
Plant waxes of co-dominant cushion plant species in a bofedal peatland on the Andean Altiplano 安第斯高原泥炭地共优势垫层植物种类的植物蜡
IF 2.5 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-02-01 Epub Date: 2025-12-15 DOI: 10.1016/j.orggeochem.2025.105123
C. Cerda-Peña , S.J. Feakins , M.C. Aranda , D.H. Pérez , P. Pérez-Portilla , A. Aránguiz-Acuña , S. Contreras
Plant waxes, widely used as biomarkers for paleoenvironmental reconstructions in boreal peatlands, remain relatively understudied in Andean “bofedales” peat meaning that their application in these ecosystems requires a better understanding of local vegetation. This study therefore compares four plant wax classes – n-alkanoic acids, n-alkanes, n-alkanols, and sterols – in leaves and sheaths of Distichia muscoides and Oxychloe andina, that form cushions (or mounds), in a bofedal in northern Chile. Analyses indicate that wax concentrations were higher in D. muscoides and n-alkanoic acids were dominant in both species and showed significant differences in the average chain length (ACL; O. andina = 27.3, σ = 0.78; D. muscoides = 26.8, σ = 0.18; p < 0.05), while those for the n-alkanes were similar. Mean n-alkanol abundances were significantly higher in D. muscoides (171.5; σ = 76.7 μg/g) than in O. andina (32.1; σ = 53.5 μg/g, p < 0.05) and among sterols, β-sitosterol was the most abundant in both species. Plant wax distributions were similar between organs, except for the ACL of the n-alkanoic acids in D. muscoides (leaves = 26.8, σ = 0.2; sheaths = 25.9, σ = 0.1; p < 0.001). For both species, leaf–sheath differences in plant wax abundance and size suggest that leaves contribute most to peat (∼4× n-alkanoic acids, ∼2× n-alkanes). The study reports four compound classes detected in “cushion” plants towards their application in the bofedales peat of the Andean Altiplano. In particular we find that n-alkanes show minimal differences between species, suggesting suitability for testing for compound-specific isotopic analysis-based paleoclimate proxies in bofedales. β-Sitosterol is highly abundant and may serve as a biomarker for the presence of the studied species. Overall, the bofedales have potential as archives of plant wax from these cushion plants towards paleoenvironmental reconstructions.
植物蜡被广泛用作北方泥炭地古环境重建的生物标志物,但在安第斯“bofedales”泥炭地的研究相对较少,这意味着它们在这些生态系统中的应用需要更好地了解当地的植被。因此,这项研究比较了在智利北部一处森林中形成垫(或土丘)的Distichia muscoides和Oxychloe andina的叶子和鞘中的四种植物蜡类——正烷酸、正烷烃、正烷醇和甾醇。分析结果表明,蜡质浓度较高,正烷酸在两种中均占优势,平均链长差异显著(ACL: O. andina = 27.3, σ = 0.78; D. muscoides = 26.8, σ = 0.18; p < 0.05),而正烷烃的链长差异无统计学意义。正烷醇的平均丰度(171.5,σ = 76.7 μg/g)显著高于白腹草(32.1,σ = 53.5 μg/g, p < 0.05),在甾醇中,β-谷甾醇在两种植物中含量最高。植物蜡质在各器官间的分布基本一致,除了正烷酸的ACL(叶片= 26.8,σ = 0.2;鞘= 25.9,σ = 0.1; p < 0.001)。对于这两个物种,叶鞘在植物蜡丰度和大小上的差异表明,叶片对泥炭的贡献最大(~ 4×正烷酸,~ 2×正烷烃)。该研究报告了在“缓冲”植物中检测到的四种化合物类,它们将在安第斯高原的泥炭中应用。特别是,我们发现正构烷烃在物种之间的差异很小,这表明适合测试基于化合物特定同位素分析的古气候代用物。β-谷甾醇含量丰富,可作为研究物种存在的生物标志物。综上所述,这些岩斑有可能作为这些垫层植物的植物蜡的档案,用于古环境重建。
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引用次数: 0
A plethora of hopanoid transformation products co-exist in a thermally immature Jurassic black shale I: hopanoid hydrocarbons 热未成熟的侏罗系黑色页岩中存在大量的类藿烷转化产物:类藿烷烃
IF 2.5 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-02-01 Epub Date: 2025-12-24 DOI: 10.1016/j.orggeochem.2025.105120
Tim Marten , Lorenz Schwark
Hopanoids are among the most abundant natural products on Earth. Despite their widespread occurrence in soils, coals, sediments, sedimentary rocks and crude oils, their diagenetic pathways have not been fully resolved. Here, we present a diverse suite of aliphatic and aromatic hopanoids from a single sample of a thermally immature Lower Jurassic black shale. All extended saturated and Δ17,21-unsaturated hopanoid species occur as 2α-methyl analogues, which exhibit a carbon number distribution matching that of the desmethyl hopanes. This suggests similar precursor organisms for 2-methyl and desmethyl hopanoids favouring the genesis of C30+ hopanoids. Potential precursor organisms are assumed to include marine diazotrophic cyanobacteria or α-proteobacteria both affiliated with the nitrogen-cycle. Polyaromatic hopanoids occur in high concentrations, especially the C24 tetraaromatic hopane, and deviate from the extended hopanoid species in terms of carbon number distribution and A-ring methylation, indicating different origins for these hopanoids. The high aromaticity of these hopanoids suggests an origin from soil bacteria, which is consistent with an accelerated hydrological cycle and evidence for enhanced soil erosion during the early Toarcian. The co-occurrence of a multitude of hopanoid species within one sample exemplifies the complexity of hopanoid transformation products during stages of very early diagenesis. Preservation of this hopanoid complexity during diagenesis in the geosphere over a period of 183 Ma is exceptional because labile hopanoids commonly are destroyed by thermal maturation. It must be assumed that other sediments contained comparably complex hopanoid distributions, which upon later diagenesis suffered reduced variability seen in most sedimentary rocks and oils.
藿类化合物是地球上最丰富的天然产物之一。尽管它们广泛存在于土壤、煤、沉积物、沉积岩和原油中,但它们的成岩路径尚未完全解决。在这里,我们从一个热未成熟的下侏罗统黑色页岩的单一样本中发现了一套多样化的脂肪族和芳香类藿烷。所有扩展的饱和和Δ17,21-不饱和藿烷都以2α-甲基类似物的形式出现,其碳数分布与去甲基藿烷相匹配。这表明2-甲基和去甲基类hopoid的前体生物相似,有利于C30+类hopoid的形成。潜在的前体生物被认为包括海洋重氮营养蓝藻或α-变形菌,两者都与氮循环有关。多芳藿烷浓度较高,尤其是C24型四芳藿烷,其碳数分布和a环甲基化程度与扩展类藿烷不同,表明其来源不同。这些藿类化合物的高芳香性表明它们起源于土壤细菌,这与托瓦良早期加速的水文循环和土壤侵蚀加剧的证据是一致的。在一个样品中同时出现多种藿类物质,说明了在非常早期的成岩作用阶段,藿类物质转化产物的复杂性。在183ma时期的地圈成岩过程中,这种藿类复杂性的保存是特殊的,因为不稳定的藿类通常被热成熟破坏。必须假定其他沉积物含有相当复杂的hopanoid分布,在后来的成岩作用中,这种分布在大多数沉积岩和油中所见的变异性减少了。
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引用次数: 0
A plethora of hopanoid transformation products co-exist in a thermally immature Jurassic black shale II: Oxo- and thiohopanoids 在热未成熟的侏罗纪黑色页岩II中,存在大量的藿烷类转化产物:氧和硫代藿烷类
IF 2.5 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-02-01 Epub Date: 2025-12-24 DOI: 10.1016/j.orggeochem.2025.105121
Tim Marten , Lorenz Schwark
Hopanoids are ubiquitous in sediments and sedimentary rocks and are commonly applied tools for paleoenvironment reconstruction. Biohopanoids during diagenesis transform to geohopanoids when they successively lose their structural diversity. Prior to elevated thermal maturity, where only hopanes and benzohopanes persist, a large variety of intermediate hopanoid transformation products can be intermittently abundant in immature sediments. We presented in a companion paper the highly diverse hopanoid hydrocarbon inventory in one immature black shale sample from the Toarcian Posidonia Shale at Hondelage, NW-Germany that was deposited under euxinic conditions. Here, the focus is on the plethora of oxo- and thiohopanoids co-existing in the same sample. The formation of hopanoic acids requires oxic conditions whereas thiohopanoid require sulfidic conditions. These contrasting requirements suggest spatial and temporal separation of hopanoic acid versus thiohopanoid formation prior to or after incorporation into the sediment. Hopanoic acids presumably form in the oxic upper water column with potential minor contributions from oxic microniches and/or seasonally induced brief suboxic events at the sediment/water interface. In contrast, thiohopanoids presumably originate within the sulfidic water column and/or the sediment. Persistent euxinic conditions during deposition of the Posidonia Shale at Hondelage favoured formation of a variety of thiohopanoids in a shallow marine setting below a salinity-stratified water column. Thiohopanoids include previously unidentified hop-17(21)-ene thiolanes and hopane thiophenes extending to C38. Since hopanoids extending past C35 are absent for other hopanoid species, extended hopane thiophenes likely result from microbially mediated early diagenetic alkylation at the C35 position. Hopanoic acids as well as thiohopanoids occur as 2-methyl analogues and exhibit elevated abundances of C33 homologues, which dominate in desmethyl hopanoids. Precursor organisms for 2-methyl hopanoids are most likely nitrogen cycle-affiliated α-proteobacteria and/or diazotrophic cyanobacteria.
hopanoid普遍存在于沉积物和沉积岩中,是古环境重建的常用工具。生物藿烷在成岩过程中逐渐失去结构多样性,转变为地藿烷。在热成熟度升高之前,只有藿烷和苯并藿烷持续存在,各种各样的中间藿烷转化产物可以在未成熟沉积物中间歇性丰富。我们在一篇论文中介绍了德国西北部Hondelage的Toarcian Posidonia页岩在缺氧条件下沉积的一个未成熟黑色页岩样品中高度多样化的藿烷类烃库存。在这里,重点是过量的氧和硫代藿素共存于同一样品。藿烷酸的形成需要氧条件,而硫代藿烷则需要硫化条件。这些对比要求表明,在进入沉积物之前或之后,藿烷酸与硫代藿烷形成的空间和时间分离。Hopanoic酸可能在含氧上层水柱中形成,潜在的少量贡献来自于含氧微孔和/或沉积物/水界面季节性诱导的短暂缺氧事件。相反,硫代藿烷可能起源于硫化物水柱和/或沉积物。在Hondelage的Posidonia页岩沉积期间,持续的缺氧条件有利于在盐度分层水柱下的浅海环境中形成多种硫代藿烷。硫代藿烷包括先前未确定的啤酒花-17(21)-烯硫烷和延伸至C38的藿烷噻吩。由于在其他种类的藿烷中不存在延伸到C35以上的藿烷,因此延伸的藿烷噻吩可能是由微生物介导的早期成岩烃化作用在C35位置产生的。Hopanoic酸和thiohopanoids以2-甲基类似物的形式出现,并表现出C33同源物的丰度升高,这在去甲基hopanoids中占主导地位。2-甲基藿烷类化合物的前体生物最有可能是氮循环相关的α-变形菌和/或重氮营养蓝藻。
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引用次数: 0
Geochemical records from loess sediments provide insights into early hominin influence on the landscape in the Khovaling region of Southern Tajikistan, Central Asia 黄土沉积物地球化学记录揭示了早期人类对中亚塔吉克斯坦南部霍瓦林地区景观的影响
IF 2.5 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-02-01 Epub Date: 2025-11-06 DOI: 10.1016/j.orggeochem.2025.105088
Aljasil Chirakkal , Ekaterina Kulakova , Calin C. Steindal , Jago J. Birk , Anton Anoikin , Redzhep Kurbanov , Petr Sosin , Peixian Shu , David K. Wright
This study presents a multi‑proxy investigation of loess–paleosol sequences from the Khovaling Loess Plateau (KLP) in Southern Tajikistan to explore long‑term human-environment interactions during the Middle Pleistocene. This region has been the focus of numerous archaeological projects since Soviet times, as it contains evidence of some of the oldest (∼0.9 Ma) hominin occupations in Central Asia and is one of the key regions connecting eastern Asia to centers of hominin evolution that lie to the west. Previous archaeological expeditions have discovered rich collections of stone tools from alternating non-pedogenically modified loess and paleosol sequences at the archaeological sites of Karatau, Lakhuti, Obi-Mazar, and Kuldura. We analyzed lipid biomarkers such as n‑alkanes, polycyclic aromatic hydrocarbons (PAHs), together with newly generated stable isotopes (δ13C, δ15N), magnetic susceptibility, and archaeological assemblages from three sites: Obi-Mazar/Lakhuti (on‑site), and non-artifact-bearing strata from Kuldara (near‑site) and Khonako‑II (off‑site), focusing on pedocomplexes (PCs) 4, 5, and 6 and their intercalated loess layers. High odd-over-even predominance (OEP) and average chain lengths (ACL) suggest that soil organic matter is predominantly derived from higher-order terrestrial plants, with better preservation in paleosols compared to loess layers. The inverse correlations of δ13C with TOC and C/N reflect organic matter degradation, while elevated δ15N in paleosols suggests enhanced nitrogen cycling under warmer and drier conditions. Magnetic susceptibility and δ13C trends reveal a progressive shift toward open grassland ecosystems since ∼0.8  Ma, with intensified pedogenesis during interglacial stages MIS 11, 13, and 15. The spatial distribution of PAH concentrations and lithic artifact densities further highlights human-environment interactions in the KLP locality. Obi-Mazar exhibits abundant lithic materials and high PAH levels, indicating repeated occupation and frequent burning in a resource‑rich riverine setting. Kuldara exhibits moderate PAHs but minimal artifacts, whereas Khonako-II records only a minimal level of signals, reflecting a decrease in human impact with distance from the water source. Together, these findings demonstrate that Early Paleolithic hominins preferentially occupied ecologically stable, pedogenically developed zones during interglacial phases, contributing to localized fire regimes and shaping their landscapes. This study provides a refined paleoenvironmental framework for understanding hominin adaptations in Central Asia during the Middle Pleistocene.
本研究对塔吉克斯坦南部霍瓦令黄土高原(KLP)的黄土-古土壤序列进行了多代理调查,以探索中更新世人类与环境的长期相互作用。自苏联时代以来,该地区一直是众多考古项目的重点,因为它包含了中亚最古老(~ 0.9 Ma)人类居住的证据,是连接东亚和西部人类进化中心的关键地区之一。以前的考古考察已经在卡拉托、拉库蒂、奥比-马扎尔和库尔杜拉的考古遗址发现了丰富的石器,这些石器来自交替的非成土性改变的黄土和古土壤序列。我们分析了三个地点的脂质生物标志物,如正烷烃,多环芳烃(PAHs),以及新生成的稳定同位素(δ13C, δ15N),磁化率和考古组合:Obi-Mazar/Lakhuti(现场),以及来自Kuldara(近现场)和Khonako - II(现场外)的不含人工制品地层,重点研究了土壤复合体(PCs) 4, 5和6及其间层黄土。高奇偶优势(OEP)和平均链长(ACL)表明,古土壤有机质主要来源于高阶陆生植物,与黄土层相比,古土壤有机质保存较好。δ13C与TOC和C/N的负相关反映了有机质的降解,而δ15N的升高表明在温暖和干燥的条件下,古土壤的氮循环增强。磁化率和δ13C趋势显示自~ 0.8 Ma以来逐渐向开放草地生态系统转变,在间冰期MIS 11、13和15期间,土壤作用加剧。多环芳烃浓度和岩屑密度的空间分布进一步突出了KLP地区人类与环境的相互作用。Obi-Mazar显示出丰富的岩石材料和高多环芳烃水平,表明在资源丰富的河流环境中反复被占领和频繁燃烧。Kuldara显示出适度的多环芳烃,但人工制品很少,而Khonako-II只记录到最低水平的信号,这反映出人类对水源的影响随着距离的远近而减少。总之,这些发现表明,早旧石器时代的人类在间冰期优先占据生态稳定、土壤发育的地区,有助于局部火灾制度和塑造其景观。本研究为了解中亚中更新世时期人类适应环境提供了一个精细的古环境框架。
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引用次数: 0
Effect of water pressure on bitumen and expelled oil biomarker evolution: Insights from laboratory simulation experiments 水压对沥青和排油生物标志物演化的影响:来自实验室模拟实验的见解
IF 2.5 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-02-01 Epub Date: 2025-12-17 DOI: 10.1016/j.orggeochem.2025.105098
Ahmed Khairy , Clement N. Uguna , Waleed Sh. El Diasty , Kenneth E. Peters , Christopher H. Vane , Colin E. Snape , Sherif Farouk , Will Meredith
Biomarkers are powerful tools to assess thermal maturity of oil and rock extracts and for oil-source rock correlation. While temperature effects on biomarker evolution have been widely studied, the impact of pressure remains largely underexplored. This study examines the effect of high water pressure (up to 900 bar) on biomarker maturation in expelled oil and extracted bitumen from pyrolysis experiments on a rock sample from the Campanian–Maastrichtian Duwi Formation, Red Sea Basin, Egypt. Extracted bitumens exhibited higher maturity under anhydrous conditions compared to low-pressure hydrous samples, and this was more pronounced at 350°C. The extracted bitumen displayed higher biomarker maturity ratios than the corresponding expelled oil at 350°C, likely due to prolonged interactions of the bitumen with the rock mineral matrix. In contrast, δ13C values were similar for extracted bitumen and the corresponding expelled oil. At 320°C, high pressure reduced values of biomarker maturity ratios, particularly C31–C35 homohopane isomerisation, Ts/Tm, Ts/H30, and C29Ts/H29 ratios, whereas sterane ratios remained unaffected. At 350°C, pressure effects were less significant, with some anomalous variations, suggesting a non-systematic influence on biomarker maturation at higher temperatures. These findings demonstrate the complex role of pressure in biomarker evolution, emphasising the need to consider pressure in biomarker-based maturity assessment, particularly in overpressured basins and deep petroleum systems, where high pressure may be a dominant factor. Based on 12 source-related biomarker and isotopic ratios, chemometric analysis reveals that artificially generated oils and South Malak-1 oils from southwestern onshore Gulf of Suez are quite different, and both groups differ significantly from other natural oils from the central and northern parts of the basin. This may be due to facies variations and the effects of mixing from multiple source horizons under natural subsurface conditions.
生物标志物是评价油、岩提取物热成熟度和油源岩对比的有力工具。虽然温度对生物标志物进化的影响已被广泛研究,但压力的影响在很大程度上仍未得到充分探索。本研究对埃及红海盆地Campanian-Maastrichtian Duwi组的岩石样品进行了热解实验,研究了高压(高达900 bar)对排出油和提取沥青中生物标志物成熟度的影响。与低压含水样品相比,提取的沥青在无水条件下表现出更高的成熟度,这在350°C时更为明显。在350°C时,提取的沥青比相应的排出油显示出更高的生物标志物成熟度比率,这可能是由于沥青与岩石矿物基质长期相互作用所致。而萃取沥青和排出油的δ13C值基本一致。在320℃下,高压降低了生物标志物的成熟度比率,特别是C31-C35高藿烷异构化、Ts/Tm、Ts/H30和C29Ts/H29比率,而甾烷比率未受影响。在350°C时,压力影响不太显著,有一些异常变化,表明高温下对生物标志物成熟的非系统影响。这些发现表明了压力在生物标志物演化中的复杂作用,强调了在基于生物标志物的成熟度评估中考虑压力的必要性,特别是在超压盆地和深部含油气系统中,高压可能是一个主导因素。化学计量学分析表明,苏伊士湾西南岸人工生成的原油与南马拉克-1原油存在较大差异,且与盆地中部和北部其他天然原油存在显著差异。这可能是由于相变化和在自然地下条件下多源层混合的影响。
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引用次数: 0
Comparison of Curie-point pyrolysis with tetramethylammonium hydroxide (TMAH) and base catalyzed methanolysis in leaf and root biomarker decomposition studies 居里点热解四甲基氢氧化铵(TMAH)和碱催化甲醇分解在叶和根生物标志物分解研究中的比较
IF 2.5 3区 地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-02-01 Epub Date: 2025-12-12 DOI: 10.1016/j.orggeochem.2025.105122
J.G. Altmann , B. Jansen , M. Palviainen , K. Kalbitz
Cutin and suberin have frequently been used as plant-part specific biomarkers in sediments and soils. The two most commonly used analytical methods described in the literature to study cutin and suberin are pyrolysis with tetramethylammonium hydroxide (TMAH) and base-catalyzed methanolysis with potassium hydroxide (KOH). Both methods are usually combined with gas chromatography (GC) to analyze and identify the resulting compounds. However, until now, a critical assessment of the compatibility of the results obtained by both methods was missing.
Here, we compared the two techniques on Scots pine (Pinus sylvestris) and Norway spruce (Picea abies) roots and needles that decomposed for three years in litterbags. KOH methanolysis released a broader suite of long-chain alcohols, diols and mid-chain hydroxy-fatty acids, identifying 19 tissue-specific biomarkers, whereas pyrolysis with TMAH yielded 10 diagnostic compounds; only seven markers overlapped. The concentrations of analogous molecules decreased in different ways over time, preventing any generalizable conclusions from being drawn about the stability of the original biopolymers.Thus, the methods are complementary rather than interchangeable. Pyrolysis yields fewer, more temporally stable signals and requires substantially less sample preparation per analysis, making it well suited to quantitative source apportionment; by contrast, methanolysis involves multi-step sample preparation and provides richer structural detail that facilitates biomarker discovery across taxa and matrices.
在沉积物和土壤中,角质和木质素经常被用作植物部分特异性的生物标志物。文献中描述的研究角质和木质素最常用的两种分析方法是四甲基氢氧化铵(TMAH)热解法和碱催化氢氧化钾(KOH)甲醇解法。这两种方法通常与气相色谱(GC)相结合来分析和鉴定所得到的化合物。然而,到目前为止,还没有对两种方法获得的结果的兼容性进行批判性评估。在这里,我们对苏格兰松(Pinus sylvestris)和挪威云杉(Picea abies)的根和针进行了两种技术的比较,这些根和针在垃圾袋中分解了三年。KOH甲醇分解释放出更广泛的长链醇、二醇和中链羟基脂肪酸,鉴定出19种组织特异性生物标志物,而TMAH热解产生10种诊断化合物;只有7个标记重叠。随着时间的推移,类似分子的浓度以不同的方式下降,这就阻止了对原始生物聚合物的稳定性得出任何可推广的结论。因此,这些方法是互补的,而不是可互换的。热解产生的信号更少,时间更稳定,每次分析所需的样品制备也更少,因此非常适合定量源分配;相比之下,甲醇分解涉及多步骤的样品制备,并提供更丰富的结构细节,促进生物标志物在分类群和基质中的发现。
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Organic Geochemistry
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