Extended saturated and monoaromatic tricyclic terpenoid carboxylic acids found in Tasmanian tasmanite

A series of tricyclic terpenoid carboxylic acids (C₂₀–C₄₀) was found in the acidic fraction of Tasmanian tasmanite bitumen, occurring as a mixture of stereoisomers with mainly the 13β(H), 14α(H)-and 13α(H),14α(H)-configurations. These dominant acidic tricyclic constituents have the same carbon skeleton as the ubiquitous tricyclic terpane biomarkers. A novel series of ring-C monoaromatic tricyclic terpenoid carboxylic acids was also characterized. The series ranges from C₁₉ to C₃₉ and is the acidic counterpart of the recently described series of monoaromatic tricyclic terpanes.     

Diversities in biomarker compositions of Carboniferous–Permian humic coals in the Ordos Basin,China

The molecular composition of Carboniferous–Permian coals in the maturity range from 0.66 to 1.63% vitrinite reflectance has been analysed using organic geochemistry to investigate the factors influencing the biomarker compositions of humic coals. The Carboniferous–Permian coal has a variable organofacies and is mainly humic-prone. There is a significant difference in the distribution of saturated and aromatic hydrocarbons in these coals, which can be divided into three types. The Group A coals have biomarker compositions typical of humic coal, characterised by high Pr/Ph ratios, a lower abundance of tricyclic terpanes with a decreasing distribution from C₁₉ tricyclic terpane to C₂₄ tricyclic terpane and a high number of terrigenous-related biomarkers, such as C₂₄ tetracyclic terpane and C₂₉ steranes. The biomarker composition of Group B coals, which were deposited in a suboxic environment, have a higher abundance of rearranged hopanes than observed in Group A coals. In contrast, in Group C coals, the Pr/Ph ratio is less than 1.0, and the sterane and terpane distributions are very different from those in groups A and B. Group C coals generally have abnormally abundant tricyclic terpanes with a normal distribution maximising at the C₂₃ peak; C₂₇ steranes predominates in the m/z 217 mass fragmentograms. The relationships between biomarker compositions, thermal maturity, Pr/Ph ratios and depositional environments, indicate that the biomarker compositions of Carboniferous–Permian coals in Ordos Basin are mainly related to their depositional environment. This leads to the conclusion that the biomarker compositions of groups A and B coals collected from Shanxi and Taiyuan formations in the northern Ordos Basin are mainly related to their marine–terrigenous transitional environment, whereas the biomarker compositions for the Group C coals from Carboniferous strata and Shanxi Formation in the eastern Ordos Basin are associated with marine incursions.     

Geochemical characteristics and genetic types of crude oils from Qinjiatun and Qikeshu oilfields in the Lishu Fault Depression,Songliao Basin,northeastern China

The Qinjiatun and Qikeshu oilfields are new Mesozoic petroleum exploration targets in Lishu Fault Depression of Songliao Basin, northeastern China. Currently, researches on geochemistry of crude oils from Qinjiatun and Qikeshu oilfields have not been performed and the genesis of oils is still uncertain. Based on bulk analyses, the crude oils in the Qinjiatun and Qikeshu oilfields of Lishu Fault Depression from the Lower Cretaceous can be classified as three types. TypeⅠoils, from Quantou and Denglouku formations of Qikeshu oilfield, are characterized by high C24tetracyclic terpane/C26tricyclic terpanes ratios, low gammacerance/C30hopane ratios, tricyclic terpanes/hopanes ratios, C29Ts/C29norhopane ratios and 17α(H)-diahopane/17α(H)-hopane ratios, indicating a brackish lacustrine facies. TypeⅡoils, from Shahezi Formation of Qikeshu oilfield show low C24tetracyclic terpane/C26tricyclic terpanes, high gammacerance/C30hopane ratios, tricyclic terpanes/hopanes ratios, C29Ts/C29 norhopane and C30diahopane/C30hopane ratios, thus suggesting that they originated from source rocks deposited in a weak reducing brackish lacustrine environment, or clay-rich sediments. Type oilsⅢ, from some wells of Qikeshu oilfield have geochemical characteristics intermediate between those two types and may be mixture of typeⅠand Ⅱoils.     

庙西凹陷严重生物降解原油序列中三环萜烷的异常分布成因初探

对渤海湾盆地一系列生物降解原油的色谱-质谱分析结果表明,庙西凹陷PL15-8D与PL9-4井四个严重生物降解原油三环萜烷系列分布较为异常,主要表现为以C₂₃为主峰的后峰型、C₂₀与C₂₃为主峰的微弱双峰型以及以C₂₀与C₂₄为主峰的双峰型分布模式。强烈的生物降解作用导致C₁₉~C₂₃三环萜烷优先于C₂₄₊三环萜烷被不同程度地侵蚀,是形成这一异常分布的根本原因。三环萜烷系列相对丰度与绝对浓度的变化规律表明,不同碳数三环萜烷的生物降解作用同时发生,但其降解速率有明显差别,即抗生物降解能力不同。三环萜烷系列化合物（除C₂₀三环萜烷以外）的抗生物降解能力具有随碳数增加而增强的趋势,而C₂₀三环萜烷抗降解能力似乎强于C₂₁~C₂₃三环萜烷。原油中未检测到脱甲基三环萜烷,表明三环萜烷的降解并非通过微生物的脱甲基化作用,推测其降解途径是微生物氧化三环萜烷C环支链末端的甲基,形成对应的羧酸化合物。四个原油样品甾烷、藿烷与三环萜烷被微生物严重侵蚀,不能用于油源对比研究,而三芳甾烷未受生物降解影响,可作为研究区严重生物降解原油油源对比的有效指标。     

Prediction of source rock characteristics based on terpane biomarkers in crude oils: A multivariate statistical approach

The distributions of eight tricyclic and eight pentacyclic terpanes were determined for 216 crude oils located worldwide with subsequent simultaneous RQ-mode factor analysis and stepwise discriminate analysis for the purpose of predicting source rock features or depositional environments. Five categories of source rocks are evident: nearshore marine (i.e., paralic/deltaic); deeper-water marine; lacustrine; phosphaticrich source beds; and Ordovician age source rocks. The first two factors of the RQ-mode factor analysis describe 45 percent of the variation in the data set; the tricyclic terpanes appear to be twice as significant as pentacyclic terpanes in determining the variation among samples. Lacustrine oils are characterized by greater relative abundances of C₂₁ diterpane and gammacerane; nearshore marine sources by C₁₉ and C₂₀ diterpanes and oleanane; deeper-water marine facies by C₂₄ and C₂₅ tricyclic and C₃₁ plus C₃₂ extended hopanes; and Ordovician age oils by C₂₇ and C₂₉ pentacyclic terpanes. Although thermal maturity trends can be observed in factor space, the trends do not necessarily obscure the source rock interpretations. Also, since bacterial degradation of crude oils rarely affects tricyclic terpanes, biodegraded oils can be used in predicting source rock features. The precision to which source rock depositional environments are determined might be increased with the addition of other biomarker (e.g., steranes) and stable isotope data using multivariate statistical techniques.     

Tricyclic terpane maturity parameters: response to heating by an igneous intrusion

The effects of thermal maturation upon the abundance and composition of the tricyclic terpanes have been investigated within a single sedimentary horizon within the Dun Caan Shale Member (Isle of Skye, Scotland) intruded by a 0.9 m thick Tertiary dolerite dyke. Heating by the igneous body caused the concentrations of all 13β(H),14α(H) and 13α(H),14α(H) tricyclic terpanes to increase towards or within the effective ‘oil window’, recording generation from abundant non-hydrocarbon precursors, such as kerogen- and asphaltene-bound components. Progressive changes in tricyclic terpane composition accompany these concentration changes. An increase in the C₂₃ βα/αα maturity parameter towards the dyke resulted from the relatively greater rate of generation of the βα isomer, combined with the earlier decline in concentration (by degradation or isomerisation) of the αα component. The tricyclics/(tricyclics+hopanes) parameter shows a dramatic increase within the latter part of the oil window, due to the greater relative thermal stability of the tricyclic terpanes. The quantitative data demonstrate the importance of the processes of generation (from non-hydrocarbon fractions of the sedimentary organic matter) and thermal degradation in the operation of tricyclic terpane maturity parameters.     

Geochemical Characteristics of Different Kinds of Crude Oils in the Tarim Basin,Northwest China

Based on the compositions and distributions of biomarkers in thirty-five representative oil samples, oils from the Tarim Basin of northwestern China are mainly divided into two oil families. One oil family contains relatively low amounts of C₁₅-C₂₀ isoprenoid hydrocarbons and shows pristane predominance with Pr/Ph ratios ranging from 1.50 to 3.00. The GC/MS analytical data of these oils show the occurrence of abundant hopanes, and low concentrations of steranes and tricyclic terpanes with hopanes/steranes ratios from 6.25 to 12.24 and tricyclic terpanes/hopanes ratios from 0.03 to 0.24. These oils contain low drimane relative to homodrimane (C₁₅/C₁₆ < 1.0) and abundant rearranged bicyclanes in bicyclic sesquiterpanes. They are dominated by low carbon number (C₁₉-C₂₁) compounds in the tricyclic terpanes, and are rich in rearranged hopanes, C₂₉Ts and an unknown C₃₀ compound in pentacyclic triterpanes. These geochemical characteristics suggest that the oils were generated mainly from terrigenous organic matter. The other oil family shows remarkably different biomarker compositions and distributions. The oils revealed Pr/Ph ratios of about 1.0, high drimane/homodrimane ratios (>1.0), low hopanes/steranes ratios (0.65–2.50), high tricyclic terpanes/hopanes ratios (0.30–2.00) and a dominant peak at C₂₃ in tricyclic tepanes, suggesting a marine organic origin. Oil-source rock correlation indicates that these two oil families seem to have been derived from Mesozoic Jurassic-Triassic terrestrial source rocks (shales and coal seams) and Lower Paleozoic Ordovician-Cambrian marine source rocks, respectively.     

Geochemical Evidence for Coal and Carbonaceous Mudstone as the Possible Major Oil Source Rock in the Jurassic Turpan Basin,Northwest China

Petroleum geologists have debated whether the hydrocarbons from Jurassic coal measures are derived from the coals, carbonaceous mudstones or coal-measure mudstones in the Turpan Basin. Based on the geochemistry analysis of the 20 crude oils and 40 source rocks from the Turpan Basin, some data have been obtained as follows: carbon preference index and methylphenanthrene index of the Jurassic oils are 1.16–1.45 and 0.28–0.80, and the ααα C29 sterane 20S/(20S+20R) and C29 sterane ββ/(ββ+αα) are 0.44–0.51 and 0.4–0.54 respectively, which show the normal maturity of oils; the vitrinite reflectance of the source rocks from the Xishanyao to Badaowan Formations range from 0.47% to 0.97%, which indicate immature to mature thermal evolutionary stage and sufficient conditions for generating mass mature oil. The effect of hydrocarbon expulsion should be considered when studying the source of coal-derived oil by using Biomarkers. Biomarkers in the Jurassic oils from the basin are similar to those in the coals and carbonaceous mudstones, with a strong predominant content of pristane, relatively high ratio of C15/C16 sesquiterpenoids (>1), a relatively high content of low carbon number tricyclic terpanes and C24 tetracyclic terpane, little gammacerane and C29 Ts detected, an absolute predominant content of C29 sterane and a relatively high content of diasterane. However, the opposite characteristics are shown in mudstones, with an approximately equal content of pristane and phytane, relatively low ratio of C15/C16 sesquiterpenoids (<1), a relatively high content of high carbon number tricyclic terpanes and a low content of C24 tetracyclic terpane, peaks of gammacerane and C29 Ts detected obviously and an increasing C27 sterane content. All of these characteristics identify the coals and carbonaceous mudstones as the possible major oil source rocks in this area, and they were formed in the stronger oxidizing environment with shallower water than mudstones.     

高分子量烃油气化探方法的模拟实验研究——以黄海沉积物为例

传统上认为大分子烃类很难通过微渗漏方式逸散到地表,但已有研究表明高分子量烃类也可以逸散到现代沉积物中。本文基于黄海现代沉积物与典型原油地球化学特征的不同,将二者进行正交配比,系统研究不同配比产物的组成特征。结果表明:随着配比实验中原油比例的增大,正构烷烃和部分芳烃的色谱指纹呈现规律性变化,其正构烷烃奇偶优势逐渐消失,烷基芳烃丰度随之增加;三环萜烷、藿烷、规则甾烷等化合物的绝对浓度,以及二苯并噻吩/菲等的比值也呈现规律性变化,其中三环帖烷、C_(24)四环萜烷/C_(26)三环萜烷和三环萜烷/藿烷三者的变化明显且平稳,其数值范围均在0~3.0,适合用于渗逸图版。将研究区采集的未知样品与配比产物的组成特征进行对比,在排除外源污染的情况下可定性判识该研究区是否存在地下油气藏;将样品的相关参数投到图版上,有望进一步定量判识样品中渗入原油的比例。该方法可以作为常规油气化探的补充,在油气藏评价方面提供诸多信息,甚至在环境污染监控等领域有望获得推广。     

Steranes and terpanes in kerogen pyrolysis for correlation of oils and source rocks

Comparison of biological marker alkanes in the kerogen pyrolyzate and bitumen from a sediment is a useful test for the indigenous nature of sediment extracts. For the pyrolysis conditions used, the bulk of the hydrocarbons is released from the kerogen matrix between 375° and 550°C; and its steriochemistry is almost the same as that observed in the extractable bitumen in a genuine source rock. Examples are given to demonstrate that, during pyrolysis, the sterane/terpane ratio decreases and secondary terpanes are generated at the expense of primary ones.The mechanism of artificial petroleum generation by pyrolysis differs from ‘natural’ diagenesis during geological time and is reflected in the composition of certain C₂₇-C₂₉ steranes, as demonstrated by simulation experiments and C₂₉-C₃₀ moretanes and hopanes. The $\text{5α}\text{5β}$-sterane ratios, jointly with $\text{17α(H)-hopane}\text{17β(H)-moretane}$ ratios, tricyclic terpane concentrations and $\text{17α(H)}\text{17β(H)}$-trisnorhopane ratios, allow the differentiation of kerogens from adjacent stratigraphies.     

Molecular geochemical characteristics of source rock in faulted lacustrine basin: A case study of the Lishu Fault Depression in southern Songliao Basin, China

Terrestrial faulted lacustrine basin is considered as a favorable place for the development of source rocks,especially the fault basins in eastern China.Based on molecular composition study of saturated and aromatic hydrocarbons in the extracts of source rocks of the Yingcheng and Shahezi formations in the Lishu Fault Depression,it is revealed that the extracts of source rocks are provided with low ratio of Pr/Ph,low content of C24 tetracyclic terpanes,high content of tricyclic terpanes and gammacerane,relatively high content of C27 steranes in the sag belt and its periphery;relatively high ratio of Pr/Ph,relatively high content of tetracyclic terpanes and gammacerane,low content of C27 steranes and obvious advantages of C29 steranes in its gentle slope belt;with high ratio of Pr/Ph,high content of C19,C20 tricyclic and C24 tetracyclic terpanes,very low content of gammacerane and C27 steranes,and high content of C29 steranes in the edge of fault depression.According to the organic matter input and sedimentary environment,three types of source rocks have been established,which,respectively,are the mode of mixing organic matter input in deep and semi-deep lake,the advantage of terrigenous input in shallow lake and terrigenous input in shore-shallow lacustrine.The first mode is supposed to generate oil and gas,while the second one tends to generate oil.The distribution characteristics of oil and gas in the Lishu Fault Depression are very likely to be controlled by hydrocarbon generating characteristic of different source rock types.     

黔北务川-正安-道真地区铝土矿系中生物标志物及其地质意义*

黔北务川-正安-道真地区铝土矿位于石炭系黄龙组和二叠系梁山组之间,主要属于沉积型铝土矿。通过气相色谱（GC）与气相色谱-质谱（GC-MS）手段分析铝土矿系钻孔岩心中的生物标志物,发现了含量丰富的正构烷烃、类异戊二烯烷烃、萜类化合物与甾类化合物。对10个样品饱和烃组分GC分析表明,正构烷烃主要呈双峰式分布特征,碳数分布n-C₁₄～n-C₃₅,CPI值范围为0.90～3.45,表现出奇偶优势。姥鲛烷/植烷（Pr/Ph）值为0.38～077,表现出明显植烷优势。对3个样品饱和烃组分GC-MS分析表明,萜烷类化合物以C₃₀藿烷占优势,相对丰度由大到小依次为五环三萜烷、三环萜烷、四环萜烷,并检测出少量的γ-蜡烷。规则甾烷C₂₇-C₂₈-C₂₉呈近L型或V型分布,并含少量4-甲基甾烷。根据生物标志物特征参数,结合岩心样品岩相学特征,确定了铝土矿系中有机质的陆上植物与低等菌藻类双重来源,铝土质沉积时为偏酸性较还原环境,明确了铝土矿系的形成过程受到来自陆上与沉积水体内两个古生态系统的双重作用。     

Typification of oils in the Timan-Pechora province according to the composition of hydrocarbon biomarkers (steranes and terpanes)

Distinctive compositional features of cyclic saturated hydrocarbon biomarkers have been established in oils from the main petroliferous lithostratigraphic complexes of various structural zones in the Timan-Pechora petroliferous province (TPPP). Four geochemical families (types) of oils in TPPP are recognized based on the variations in the geochemical parameters of steranes and terpanes including sterane ratios C₂₇/C₂₉ and C₂₈/C₂₉, K¹ mat and K² mat, diasterane/regular sterane, pregnane (C_21–22)/sterane (C_21–22 + C_27–29), as well as terpane Ts/Tm parameters, adiantane C₂₉/hopane C₃₀, neoadiantane/adiantane, tryciclic terpane/pentacyclic terpane, hopane/sum of C₂₉ steranes, etc. The distribution of various types of oil in the sedimentary sequence of TPPP makes it possible to infer source rocks for each of the four selected types.     

Molecular Records of Primary Producers and Sedimentary Environmental Conditions of Late Permian Rocks in Northeast Sichuan, China

A series of biomarkers were identified in the aliphatic and aromatic fractions of the extracts from Late Permian Dalong (大隆) and Wujiaping (吴家坪) formations in Shangsi (上寺) Section, Northeast Sichuan (四川), South China, on the basis of the analysis of gas chromatography-mass spectrometry (GC-MC). The dominance of lower-molecular-weight n-alkanes throughout the profile suggests the dominant contribution of algae and bacteria to the organics preserved in the marine section. Wujiaping Formation is characterized by the elevated contribution from algae as well as other photoantotrophs such as photosynthetic bacteria as shown by the molecular ratios of hopanes to steranes or tricyclic terpanes as well as the ratio of pristane (Pr) and phytane (Ph) to C17 and C18 n-alkanes. This is in accord with the data from the microscopic measurement on the calcareous algae. In contrast, Dalong Formation is featured by enhanced contribution from bacteria and probably terrestrial organics indicated by the enhanced C24 tetracyclic terpanes relative to tricyclic terpanes. The two formations also show a distinct discrimination in sedimentary environmental conditions including redox condition and salinity. The anoxic condition was only found in the middle of the Dalong Formation as shown by the ratios of Pr/Ph and dibenzothiophene to phenanthrene, consistent with the reported data of Mo and U. An enhancedsalinity indicated by the homohopane index is observed at the shallow Wujiaping Formation. On the basis of the composition of primary productivity and the redox condition, Dalong Formation is proposed, herein, to be potential hydrocarbon source rocks in the study site. It is notable that the topmost end-Permian is characterized by a large perturbance in both the redox condition and salinity, with oxic conditions being frequently interrupted by short-term anoxia, likely showing a causal relationship with the episodic biotic crisis across the Permian-Triassic boundary.     

Organic geochemistry of geographically unrelated tasmanites

The biomarker analysis of three tasmanite rock samples from Tasmania, Alaska and Brazil showed an unusually high tricyclic terpane concentration relative to hopanes and steranes. A possible product-precursor relationship is advanced, associating Tasmanaceae alage with these tricyclic terpanes. These results support the search of possible precursor molecules in present day organisms which may be taxonomically related to these algae.     

Applications of steranes,terpanes and monoaromatics to the maturation,migration and source of crude oils

Novel biological marker parameters are applied to problems of geochemical correlation of crude oils in the McKittrick Field, California. An attempt is described to distinguish four diagenetic parameters; namely, source input, source maturation, migration and ‘in reservoir’ maturation. The tools include the absolute concentration of steranes, terpanes and paraffins (_{n + iso}) in combination with internal ratios of individual biomarkers such as primary/secondary terpanes, 17α(H)-trisnorhopane/18α(H)-trisnorhopane II (both maturation specific), 5β/5α-steranes, 5β-steranes/17α(H)-hopanes and rearranged steranes/5α-steranes (all migration oriented), 5α/5α-steranes and a number of terpane ratios of partially unknown chemical structure (source input specific).Among other new correlation parameters are: two series of mass chromatograms (m/e 253 and 239), signaling monoaromatized steranes, a series of presumably rearranged steranes (m/e 259), and a series of methylhopanes (m/e 205).The results obtained on the molecular level exceed the degree of information obtainable from organic geochemical ‘bulk’ parameters such as yields of saturates, aromatics, sulfur compounds and C¹³/C¹² ratios by far; however, both types of parameters are mutually supporting. All conclusions are consistent with subtle stratigraphie and overall geologic prerequisites.     

四川南桐地区二叠系龙潭煤层生物标记物及其地质意义

四川南桐地区二叠系龙潭煤层具有良好的生油潜力。其生物标记物包括正构和异构烷烃,类异戊二烯烷烃,倍半萜烷,二萜烷,三环萜烷,藿烷,一种未知结构的五环三萜烷(C₃₀),甾烷,4-甲基甾烷等。煤层生物标记物特征表明在其形成过程中有藻类和细菌等微生物物质的加入。     

Biodegraded Oil and Its High Molecular Weight (C_(35+)) n-alkanes in the Qianmiqiao Region in the Bohai Bay Basin, Northern China

With a production of 208.2 m3/d, heavy oil was produced by drill stem test (DST) from three shallow reservoirs in Sand Group Nos. Ⅰ and Ⅲ of the Neogene Guantao Formation (NgⅠ and NgⅢ) and the Eogene Dongying Formation (Ed) in an exploratory well Ban-14-1 within the Qianmiqiao region, Bohai Bay Basin, northern China. Based on the GC and GC-MS data of the NgⅠ and NgⅢ heavy oil samples, all n-alkanes and most isoprenoid hydrocarbons are lost and the GC baseline appears as an evident "hump", implying a large quantity of unresolved complex mixture (UCM), which typically revealed a result of heavy biodegradation. However, there still is a complete series of C14-C73 n-alkanes in the high-temperature gas chromatograms (HTGC) of the heavy oil, among which, the abundance of C30- n-alkanes are drastically reduced. The C35-C55 high molecular weight (HMW) n-alkanes are at high abundance and show a normal distribution pattern with major peak at C43 and an obvious odd-carbon-number predominance with CPI37-55 and     

现代沼泽沉积物中三、四环萜类的分布及演化特征

对甘南和滇池现代沼泽沉积物中三、四环萜类的研究表明:在现代沼泽沉积物中,具类海松烷骨架的化合物以海松烷型化合物数量最多,而松香烷型化全物数量较少;长链三环萜烷中存在C₂₁C₂₃和C₂₄化合物以C₂₃为顶点的倒“V”字型分布,正常四环萜烷呈以高碳数为主峰的“阶梯型”分布,有意义的的是样品中均含脱-A-羽扇烷和壳松烷四环萜烷。在早期成岩过程,海松烷型二萜类主要是形成烯烃和烷烃,而松香烷型二萜类主要是芳构化作用。     

塔里木盆地一类新海相原油的地球化学特征

对塔中52等井奥陶系储层产出的原油进行的分析结果表明,它们的三环萜烷系列较为特殊,主要表现为其相对丰度呈C19>C20>C21>C23>C24>C25>C26阶梯状的模式,C24四环萜烷异常丰富,且其丰度远高于C26三环萜烷,这一分布模式一般出现在淡水沼泽相和浅湖相沉积地层与原油中。在三萜烷分布特征上,其伽马蜡烷含量很低,甾烷系列和藿烷系列的分布与组成特征与该地区来源于中上奥陶统烃源岩的海相原油十分接近,同时它们的全油均具有轻的碳同位素组成,其δ13Ｃ值都小于-30‰,具有海相成因原油的特征。而塔中12井上奥陶统良里塔格组4-5段烃源岩中生物标志物的分析结果进一步证实了该类原油与那些富含宏观藻残片,且有机质类型偏腐殖型的上奥陶统海相烃源岩关系密切,是该地区油气勘探中值得关注的对象。 