Late Neoproterozoic to early Cambrian sulphur cycle-An isotopic investigation of sedimentary rocks from the Yangtze Platform

The sulphur cycle responds to changes in seawater chemistry, biological evolution and tectonic activity. We follow an isotopic approach in order to constrain the state of the ocean/atmosphere system during late Neoproterozoic and early Cambrian. For this purpose, a sedimentary succession deposited on the Yangtze Platform, South China, was analysed for its sulphur isotopic composition in different S-bearing phases. Redox changes were defined by the degree of pyritization (DOP) values in order to show variations in the oxygenation of the depositional environment. The sulphur isotopic composition of late Neoproterozoic to early Cambrian seawater sulphate ranges from +30‰ to +35‰ as evident from trace sulphate in unaltered carbonates and phosphorites. The isotopic composition for pyrite and organic sulphur varies between -16‰ and +23‰. The apparent sulphur isotopic fractionation between seawater sulphate and pyrite as well as organically bound sulphur varies between 7‰ and 50‰. This large fractionation, as well as its variability suggests a biological origin for pyrite and organically bound sulphur. The temporal evolution of different geochemical proxy signals is comparable for different successions across the Yangtze Platform.     

Stable isotopic geochemistry of organic carbon and pyrite sulfur from the Early Cambrian black shales in Northwestern Hunan, China

The early Cambrian black shale sequence in Northwestern Hunan Province has been investigated for its stable isotopic geochemistry of organic carbon and pyrite sulfur. The relatively low δ 13C values of organic matter, -29.7‰～-34.2‰, are interpreted as caused by the high CO2 concentration in atmosphere/ocean and an anoxic depositional environment in early Cambrian. Variable, but significantly positive δ 34S values, 10.2‰～ 28.2‰, for sedimentary pyrite reveals bacterial sulfate reduction as the pyrite-forming process but under sulfate-limited conditions. A protected anoxic basin, which had very limited access to open ocean, and its sediments, where metabolizable organic matter was rich and bioturbation was absent, are supposed to be the sulfate-limited environments and might have existed in South China in the early Cambrian.     

Variations in carbon isotopic composition in the subcontinental lithospheric mantle beneath the Yangtze and North China Cratons: Evidence from in-situ analysis of diamonds using SIMS

The components and evolution of subcontinental lithospheric mantle beneath the North China Craton and the Yangtze Craton is a current topic in the geological study of China and the carbon isotopic composition of diamond is one of the most direct probes into cratonic lithospheric mantle processes.In this paper,in-situ SIMS(Secondary Ion Mass Spectrometry) techniques were used to analyze the carbon isotope compositions at different internal growth zones of diamonds from Shandong and Liaoning in the North China Craton and Hunan in the Yangtze Craton.It was found that the carbon isotopic range of diamonds from the North China Craton are rather distinct from those of the Yangtze Craton;the former has a range of 6.0‰ to 2.0‰(relative to VPDB) with an average value of 3.0‰ in their core areas,which is consistent with global peridotitic diamonds;the diamonds from the Yangtze Craton,however,have a carbon isotopic range from 8.6‰ to 3.0‰ with an average value of 7.4‰ in their core areas,being more consistent with global eclogitic diamonds.The variations of carbon isotope ratios between different internal growth zones in individual diamonds were different in the three diamond localities studied.There was a clear correlation between changes in carbon isotopic composition and phases of diamond dissolution and new growth,while no correlation was observed between δ13C and internal inclusions.The variations suggest that the carbon isotopic compositions of mantle fluids were changing during the process of diamond crystallization,and that the heterogeneity of the carbon isotopic composition in mantle carbon reservoirs was a more important factor than carbon isotope fractionation in controlling the carbon isotopic compositions and their variation in diamonds.In addition,the preliminary results of in-situ nitrogen analyses demonstrated that the variation of carbon isotopic compositions between the core and outer growth zones does not correlate with nitrogen abundances,implying either that diamonds crystallized in an open environment or that the carbon isotopic composition and nitrogen contents in mantle fluids were controlled by other,not yet understood factors.The experimental results provide hints that the isotopic composition of carbon and its original sources were different in metasomatic fluids controlling diamond formation in the mantle beneath the North China Craton and the Yangtze Craton.     

大洋缺氧事件的碳稳定同位素响应

从碳稳定同位素组成及其分馏机理出发 ,系统探讨了大洋缺氧事件与海相碳酸盐和有机碳稳定同位素分馏之间的关系。缺氧事件期间 ,由于生物大批死亡和快速埋藏 ,其分解消耗海水中大量的溶解氧 ,引起大洋水体缺氧 ,富含 1 2 C的有机质从而得以大量保存 ;相应地大气和海水中富 1 3 C,同期海相碳酸盐岩碳同位素 δ值 (δ1 3C)正偏。在世界各地缺氧事件层内 ,无一例外地碳酸盐岩碳稳定同位素出现了不同程度的正偏 ,Cenomanian- Turonian 界线偏幅达～2‰。海相碳酸盐与有机质碳稳定同位素变化不仅可以提供地质历史中有机碳埋藏量的记录。研究全球碳循环变化 ,还可能追溯有机碳风化和埋藏速率的变化 ,定性地恢复大气 p CO2 变化。     

重庆北碚嘉陵江组第三—第四段碳酸盐岩碳同位素组成对古海水代表性

早三叠世海水的碳同位素组成是近年来地学研究的热点之一,但全球早三叠世碳同位素组成并没有获得统一的认识。上扬子地区早三叠世晚期普遍发育蒸发岩,地表剖面则因表生成岩作用而形成一套夹盐溶角砾岩及次生灰岩的碳酸盐地层,其地球化学信息不同程度地偏离海水,因而样品成岩蚀变性对古海水碳同位素组成的代表性的评估显得十分重要。本文以中、下三叠统界线清楚的重庆北碚剖面为对象,研究了下三叠统嘉陵江组第三、第四段和中三叠统雷口坡组底部样品的元素组成,碳、氧同位素组成及彼此之间的相互关系,选择Mn含量和氧同位素作为条件评价碳酸盐岩的成岩蚀变性及其对海水碳同位素组成的代表性,在此基础上建立了早三叠世晚期海水的碳同位素演化曲线。研究表明:(1)北碚剖面嘉陵江组第三、第四段(嘉三、嘉四段)及雷口坡组底部碳酸盐岩的Mn、Fe含量与碳同位素组成之间具有良好的负相关性,氧同位素组成和碳同位素组成之间则具有良好的正相关性,大量样品具有低δ18 O值、低δ13 C值以及较高Mn、Fe含量的特征,说明其碳同位素组成偏离海水。(2)以δ18 O-7.5‰、方解石的Mn质量分数100×10-6、白云石的Mn质量分数120×10-6为评价条件,北碚剖面嘉三、嘉四段(含雷口坡组底部)的73个样品中有38个需要在建立海水碳同位素曲线时剔除,占全部样品的52%。其中嘉四段需要剔除的样品占嘉四段样品的78%,而嘉三段的该数值为11%,说明作为原始沉积的灰岩段对海水地球化学信息保存较好,而分布盐溶角砾岩及次生灰岩的层位对海水地球化学信息保存很差。(3)氧同位素作为成岩蚀变评价标准比Mn含量更为苛刻,并可基本覆盖Mn含量评价条件,说明对于嘉三—嘉四段这样的石灰岩—白云岩—蒸发岩地层的地表剖面的样品来说,选择氧同位素作为评价条件可较好地对碳同位素的原生性进行控制。(4)白云岩对海水地球化学信息总体上保存较好,与相邻石灰岩相比,白云岩具有更高的δ18 O和δ13 C值,但其原因仍然需要进一步研究,可能与同位素分馏系数的差别以及白云岩形成于盐度更高的流体有关,因而白云岩所代表的海水地球化学信息可能不完全与伴生石灰岩相同。(5)除绿豆岩附近出现了短时间的变化超过4‰的大幅度波动以外,早三叠世晚期海水的碳同位素演化相对平稳,大致在-0.3‰~-1.8‰的范围内波动,呈现一个低幅的"V"字形,显示早三叠世晚期地球生态的恢复与碳循环系统的重建。     

Geochemical evidence for widespread euxinia in the later Cambrian ocean

Widespread anoxia in the ocean is frequently invoked as a primary driver of mass extinction as well as a long-term inhibitor of evolutionary radiation on early Earth. In recent biogeochemical studies it has been hypothesized that oxygen deficiency was widespread in subsurface water masses of later Cambrian oceans, possibly influencing evolutionary events during this time. Physical evidence of widespread anoxia in Cambrian oceans has remained elusive and thus its potential relationship to the palaeontological record remains largely unexplored. Here we present sulphur isotope records from six globally distributed stratigraphic sections of later Cambrian marine rocks (about 499 million years old). We find a positive sulphur isotope excursion in phase with the Steptoean Positive Carbon Isotope Excursion (SPICE), a large and rapid excursion in the marine carbon isotope record, which is thought to be indicative of a global carbon cycle perturbation. Numerical box modelling of the paired carbon sulphur isotope data indicates that these isotope shifts reflect transient increases in the burial of organic carbon and pyrite sulphur in sediments deposited under large-scale anoxic and sulphidic (euxinic) conditions. Independently, molybdenum abundances in a coeval black shale point convincingly to the transient spread of anoxia. These results identify the SPICE interval as the best characterized ocean anoxic event in the pre-Mesozoic ocean and an extreme example of oxygen deficiency in the later Cambrian ocean. Thus, a redox structure similar to those in Proterozoic oceans may have persisted or returned in the oceans of the early Phanerozoic eon. Indeed, the environmental challenges presented by widespread anoxia may have been a prevalent if not dominant influence on animal evolution in Cambrian oceans.     

新疆准噶尔与华南湘中法门期碳同位素特征的对比研究

针对新疆准噶尔盆地西北缘洪古勒楞组下段是否存在弗拉-法门阶界线的问题,对比研究布龙果尔剖面该段地层以及湖南中部锡矿山剖面上泥盆统法门阶中下部碳酸盐岩的碳同位素特征,并结合已有的生物地层学证据,重新讨论洪古勒楞组下段的时代。结果表明,布龙果尔剖面洪古勒楞组下段碳同位素的变化趋势与国内外诸多典型剖面弗拉-法门期之交的δ~(13)C偏移明显不同:未见到显著正偏移;布龙果尔剖面δ~(13)C在0~1‰范围内变化,小于国际上目前已知的弗拉-法门期之交δ~(13)C正偏移的幅度(2‰~3‰)。布龙果尔剖面洪古勒楞组下段可能不存在弗拉期地层,甚至可能缺失法门阶底部(牙形石Pa.triangularis带)。法门早中期,布龙果尔剖面碳同位素曲线可与湖南锡矿山剖面同时期地层进行较好的对比,分为3个阶段:2个完整的正偏—负偏旋回以及之上的小幅正偏。主量元素特征表明,布龙果尔剖面第3-1层的下半部受陆源物质影响较大,推测可能与区域构造活动变强烈有关。     

In situ stable isotopic constraints on dolomitizing fluids for the hydrothermally-originated saddle dolomites at Keping, Tarim Basin

Detailed characterization of diagenetic fluid behaviour and evolution is commonly hindered by shortage of appropriate and economic methods to carry out in situ analysis in the tiny diagenetic mineral crystals. Using micromill sampling method, this study presents in situ stable isotopic data for the growth zones of saddle dolomite crystals in the hydrothermally-altered dolostones of Upper Cambrian (Furongian) at Keping, Tarim Basin, NW China. These data show minor and large variations in δ13C ( 0.7‰ to 1.5‰ VPDB) and δ18O ( 8.3‰ to 13.8‰ VPDB), respectively, from the cores to outer rims of the dolomite crystals and suggest that saddle dolomites precipitated from dolomitizing fluids with similar carbon sources but oscillatory temperatures during different formation stages. This scenario is confirmed by microthermometry of fluid inclusions within the growth zones of dolomite crystals. This study indicates that in situ isotope analysis could provide more detailed information related to the source and pathway of dolomitizing fluids, facilitating better characterization of dolomitizing fluids and processes.     

Carbon and oxygen isotopes analyses for the Sinian carbonates in the Helan Mountain, North China

We conducted detailed studies of the Sinian carbonates from the Helan Mountain, Ningxia by both field investigation and laboratory analyses of carbon and oxygen isotopes. The carbon isotopic compositions of the Sinian Zhengmuguan Formation shows variations with regularity in the five studied sections, the δ ¹³C values all gradually decrease from bottom to top, with a total range from ?4.51‰ to 0.11‰, and the biggest negative excursion reaches up to ?6.88‰. In addition, abundant macro-body fossils were also found from the Tuerkeng Formation in this study, similar to those found from the Dengying Formation in the South China Block. This observation firmly constrained the age for the Zhengmuguan and Tuerkeng formations to the Sinian period. Here we interpreted that the Zhengmuguan Formation formed during a glacial period when the extremely cold climate substantially decreased the amount of burial of organic matter in the ocean and thus led to the general negative δ ¹³C excursion. The increasing δ ¹³C values in the Tuerkeng Formation dolomites imply the ending of the glacial period in the Zhengmuguan epoch, biological recovery and increase of organic matter burial in the ocean occurred during this period. Comparing our obtained carbon and oxygen isotopes of the Zhengmuguan and Tuerkeng formations with those of coeval carbonate successions from other places all over the world, the Zhengmuguang-aged glacial deposits might be deposited after the Gaskiers glaciation. This study provides important information for paleo-ocean, paleogeographic and biological evolution in the North China Block during the Ediacaran period and adds new carbon and oxygen isotopes data for the global Sinian carbon-oxygen isotopes dataset.     

北京大学未名湖沉积物中公元1747年以来气候变化的氧碳同位素记录

对北京大学未名湖底泥层做了²¹⁰Pb计年法和¹³⁷Cs时标法定年以及氧碳同位素分析。结果表明厚度约50cm的底泥层形成于公元1747—1997年之间,湖泥中碳酸盐的氧碳同位素组成和有机物含量记录了北京地区公元1747年以来的气候变化：1866年以前冬季风盛行,气候比较寒冷干燥;1887年以后夏季风盛行,气候比较温暖湿润,其中1907—1926年是近250年以来气候最为温暖湿润的时期;介于两者之间的1867—1886年是气候急剧转型的时期,也是自然灾害频繁出现的时期。     

Carbon and sulfur isotopic compositions of basal Datangpo Formation, northeastern Guizhou, South China: implications for depositional environment

Isotopic compositions of Mn-carbonate and organic carbon from the same individual samples and sulfur isotopic compositions of pyrites in the basal Datangpo Formation were analyzed. Highly 34S-enriched pyrites （834Spyrite =31.7-59.4‰） were precipitated in rel- atively occlusive pore water under anoxic condition in sediments, which is consistent with the observation of large and scattered pyrite framboids. The sulfidic deep ocean was not ＂oxidized＂ in the early Datangpo interglacial interval, thus the level of seawater sulfate remained low and marine δ34Ssulphate remained high. Low δ13Ccar （average -7.4‰） and abnormal relationship between δ13Ccar and fractionation （ΔCar-ors） imply that the negative δ13CCar excursion may have resulted from oxidation of part of a large organic carbon reservoir. High Δcar-org （average 25.1‰） implicates high CO2 level in the atmosphere. Small standard deviation （1.0‰） of δ13CCar values indicates the Mn-carbonate was precipitated near the water-sediment interface under dysoxic conditions rather than in occlusive pore water in sediments.     

Oxygen isotope geochemistry of phosphorite and dolomite and palaeo-ocean temperature estimation: A case study from the Neoproterozoic Doushantuo Formation, Guizhou Province,South China

The Neoproterozoic Doushantuo Formation at Weng'an in Guizhou Province of South China consists of phosphorites and dolomites.Three types of samples are recongnized for the phosphate-bearing rocks.In Type I samples, interstitial phosphates occur within the dolomite rocks, whereas in Type III samples, interstitial dolomites occur within the phosphorites; both of them may have diagenetic origin.The Type II samples are interbedded phosphorites and dolomites.Oxygen isotopic compositions of phosphate and coeval carbonate were analyzed.Phosphates of Type I and II samples show similar low δ18Ophos (SMOW) values of 10.9‰～12.1‰ and 10.7‰～12.8‰, respectively, whereas Type III phosphates show higher δ18Ophos (SMOW) values of 13.2‰～15.0‰.Dolomites from Type I and II samples have δ18Ocarb (PDB) and δ13Ccarb (PDB) values of -6.2‰～-3.4‰ and -2.2‰～-0.7‰, respectively, whereas interstitial dolomites from Type III samples show lower δ18Ocarb (PDB) and δ13Ccarb (PDB) values of -12.9‰～-8.6‰ and -4.4‰～-2.6‰.Petrology and oxygen isotope data suggest that diagenetic alteration may have partially affected the studied rocks, but the dolomites from Type I and phosphates from Type III samples represent the most pristine isotopic compositions of primary carbonates and phosphates precipitated from seawater.Calculations of palaeocean temperatures from the most 18O enriched dolomite and phosphate indicate a temperature range of 32.2 ℃ to 34.0 ℃ for the seawater of the Doushantuo Formation period.Ce anomaly also suggests more oxic conditions and possibly shallower water depth in the upper strata of the Doushantuo Formation at Weng'an, Guizhou Province.     

Paleoproterozoic glaciation: Evidence from carbon isotope record of the Hutuo Group,Wutai Mountain area of Shanxi Province,China

Palaeoproterozoic global glaciation (～2.3 Ga) may have been the first “snowball” Earth event in Earth history. North China has well-exposed sedimentary deposits of this time period with minimal postdepositional alteration. Sedimentary evidence of a glaciation event has been lacking, however. Here we analyzed carbon isotope composition of the Paleoproterozoic Hutuo Group (2.5–2.2 Ga) in the Wutai Mountain area, Shanxi Province, North China. Our data show, in an older to younger chronostratigraphic order, (1) positive δ ¹³C_carb values in the Dashiling Formation of the Doucun Subgroup (3.2‰ to 1.0‰, VPDB); (2) a decrease in δ ¹³C_carb values from the Wenshan Formation to the middle Daguandong Formation (from 2.0‰ to–1.2‰), during which time the occurrence of stromatolites declined; (3) a pronounced negative excursion in the upper Daguandong Formation, at the boundary of the Daguandong and Huaiyincun formations (from 1.4‰ to ?3.3‰), where stromatolites disappeared; and (4) a gradual increase of δ ¹³C_carb values in the Beidaxing and Tianpengnao formations (from ?1.2‰ to 1.4‰), during which time stromatolites returned. We argue that the negative carbon isotope excursion recorded from the Jian’ancun Formation to the middle Daguandong Formation of the Hutuo Group may have been North China’s response to the Palaeoproterozoic global glaciation.     

廉州湾红树林大型底栖动物食物来源研究

【目的】了解可能性食物源对红树林大型底栖动物的贡献率。【方法】利用碳氮稳定同位素技术,对广西廉州湾红树林大型底栖动物及可能性食物源的碳、氮同位素比值(δ~(13) C值、δ~(15) N值)进行分析,并通过贝叶斯稳定同位素混合模型,估算不同食物源对大型底栖动物的贡献率。【结果】大型底栖动物的δ~(13) C值为-23.37‰~-18.09‰,δ~(15) N值为6.59‰~17.00‰,δ~(13) C值、δ~(15) N值的变化范围较大,表明大型底栖动物食物来源较为复杂多样。7种可能性食物源的δ~(13) C值为-29.09‰~-21.53‰,δ~(15) N值为6.85‰~15.67‰,其中红树植物的δ~(13) C值最为贫化。大型底栖动物的营养级别均小于3,表明它们基本属于初级消费者。SIAR混合模型计算结果显示,颗粒有机物(POM)对大型底栖动物有较高的贡献率,其次为表层沉积物(SOM),大型藻类、附生植物的贡献率较低,红树植物叶片、落叶、树皮对大型底栖动物的贡献率最低。【结论】POM、SOM是广西廉州湾红树林大型底栖动物重要的食物源,红树植物不是大型底栖动物碳的主要来源。     

Mo isotopes in the Lower Cambrian formation of southern China and its implications on paleo-ocean environment

Over the past decade, as one of nontraditional stable isotopes, Mo isotope has developed rapidly and now become an important geochemical proxy to trace paleo-oceanic and atmospheric evolution through geological history. In this paper, Early Cambrian formations in southern China are investigated. The results indicate that δ 97/95Mo values of Early Cambrian seawater may have been larger than 1.4‰, values that are close to those of the modern ocean. It was also found that the variations in Mo isotope composition in samples from two sections （Huangjiawan and Gezhongwu in Guizhou） were closely related to changes in redox conditions during sedimentary processes. Combining our results with existing data, a preliminary model for the evolution of seawater Mo isotope composition through geological history was provided. It indicated that Mo isotopic variations were generally consistent with the evolution of atmospheric oxygen.     

Sinian-Cambrian stratigraphic framework for shallow- to deep-water environments of the Yangtze Platform: an integrated approach

The Sinian (Terminal Proterozoic) and Early Cambrian shallow- to deep-water sequences of the Yangtze Platform were investigated. Based on integrated lithostratigraphic, biostratigraphic, and other approaches, the shallow-water sequence from the base of the Sinian (base of the Doushantuo Formation) to the top of the Qiongzhusian (top of the Yu'anshan Formation) was subdivided into 12 stratigraphic intervals. These 12 intervals were applied in turn to the subdivision and correlation of the sequences present in various facies of the Yangtze Platform. The high-resolution stratigraphic framework here developed can serve as a time frame for ongoing multidisciplinary analyses of the "Cambrian explosion".     

CO2 and the end-Triassic mass extinction.

The end of the Triassic period was marked by one of the largest and most enigmatic mass-extinction events in Earth's history and, with few reliable marine geochemical records, terrestrial sediments offer an important means of deciphering environmental changes at this time. Tanner et al. describe an isotopic study of Mesozoic fossil soils which suggests that the atmospheric concentration of carbon dioxide (pCO2) across the Triassic-Jurassic boundary was relatively constant (within 250 p.p.m.v.), but this is inconsistent with high-resolution evidence from the stomatal characters of fossil leaves. Here I show that the temporal resolution of the fossil-soil samples may have been inadequate for detecting a transient rise in pCO2. I also show that the fossil-soil data are consistent with a large increase in pCO2 across the Triassic-Jurassic boundary when variations in the stable carbon isotope (denoted as delta13C) in terrestrial plant leaves are taken into account. These factors suggest that the linkage between pCO2, global warming and the end-Triassic mass extinction remains intact.     

Low marine sulphate and protracted oxygenation of the Proterozoic biosphere

Progressive oxygenation of the Earth's early biosphere is thought to have resulted in increased sulphide oxidation during continental weathering, leading to a corresponding increase in marine sulphate concentration. Accurate reconstruction of marine sulphate reservoir size is therefore important for interpreting the oxygenation history of early Earth environments. Few data, however, specifically constrain how sulphate concentrations may have changed during the Proterozoic era (2.5-0.54 Gyr ago). Prior to 2.2 Gyr ago, when oxygen began to accumulate in the Earth's atmosphere, sulphate concentrations are inferred to have been <1 mM and possibly <200 microM, on the basis of limited isotopic variability preserved in sedimentary sulphides and experimental data showing suppressed isotopic fractionation at extremely low sulphate concentrations. By 0.8 Gyr ago, oxygen and thus sulphate levels may have risen significantly. Here we report large stratigraphic variations in the sulphur isotope composition of marine carbonate-associated sulphate, and use a rate-dependent model for sulphur isotope change that allows us to track changes in marine sulphate concentrations throughout the Proterozoic. Our calculations indicate sulphate levels between 1.5 and 4.5 mM, or 5-15 per cent of modern values, for more than 1 Gyr after initial oxygenation of the Earth's biosphere. Persistence of low oceanic sulphate demonstrates the protracted nature of Earth's oxygenation. It links biospheric evolution to temporal patterns in the depositional behaviour of marine iron- and sulphur-bearing minerals, biological cycling of redox-sensitive elements and availability of trace metals essential to eukaryotic development.     

The specific carbon isotopic compositions of branched and cyclic hydrocarbons from Fushun oil shale

Various branched and cyclic hydrocarbons are isolated from the Fushun oil shale and their carbon isotopes are determined. The analytical results show that the branched and cyclic hydrocarbons are fully separated from n-alkanes by 5 A molecular-sieve adduction using long time and cold solvent. The branched and cyclic hydrocarbon fraction obtained by this method is able to satisfy the analytic requests of GC-IRMS. The carbon isotopic compositions of these branched and cyclic hydrocarbons obtained from the sample indicate that they are derived from photoautotrophic algae, chemoautotrophic bacteria (-33.4‰— -39.0‰) and methanotrophic bacteria (-38.4‰— -46.3‰). However the long-chain 2-methyl-branched alkanes indicate that their carbon isotopic compositions reflect biological origin from higher plants. The carbon isotopic composition of C30 4-methyl sterane (-22.1‰) is the heaviest in all studied steranes, showing that the carbon source or growth condition for its precursor, dinoflageilate, may be different from that of regular steranes. The variation trend of δ^13C ValUes between isomers of hopanes shows that ^13C-enriched precursors take precedence in process of their epimerization. Methanotrophic hopanes presented reveal the processes of strong transformation of organic matter and cycling of organic carbon in the water column and early diagenesis of oil shale.