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1.
Shales of very low metamorphic grade from the 2.78 to 2.45 billion-year-old (Ga) Mount Bruce Supergroup, Pilbara Craton, Western Australia, were analyzed for solvent extractable hydrocarbons. Samples were collected from ten drill cores and two mines in a sampling area centered in the Hamersley Basin near Wittenoom and ranging 200 km to the southeast, 100 km to the southwest and 70 km to the northwest. Almost all analyzed kerogenous sedimentary rocks yielded solvent extractable organic matter. Concentrations of total saturated hydrocarbons were commonly in the range of 1 to 20 ppm (μg/g rock) but reached maximum values of 1000 ppm. The abundance of aromatic hydrocarbons was ∼1 to 30 ppm. Analysis of the extracts by gas chromatography-mass spectrometry (GC-MS) and GC-MS metastable reaction monitoring (MRM) revealed the presence of n-alkanes, mid- and end-branched monomethylalkanes, ω-cyclohexylalkanes, acyclic isoprenoids, diamondoids, tri- to pentacyclic terpanes, steranes, aromatic steroids and polyaromatic hydrocarbons. Neither plant biomarkers nor hydrocarbon distributions indicative of Phanerozoic contamination were detected. The host kerogens of the hydrocarbons were depleted in 13C by 2 to 21‰ relative to n-alkanes, a pattern typical of, although more extreme than, other Precambrian samples. Acyclic isoprenoids showed carbon isotopic depletion relative to n-alkanes and concentrations of 2α-methylhopanes were relatively high, features rarely observed in the Phanerozoic but characteristic of many other Precambrian bitumens. Molecular parameters, including sterane and hopane ratios at their apparent thermal maxima, condensate-like alkane profiles, high mono- and triaromatic steroid maturity parameters, high methyladamantane and methyldiamantane indices and high methylphenanthrene maturity ratios, indicate thermal maturities in the wet-gas generation zone. Additionally, extracts from shales associated with iron ore deposits at Tom Price and Newman have unusual polyaromatic hydrocarbon patterns indicative of pyrolytic dealkylation.The saturated hydrocarbons and biomarkers in bitumens from the Fortescue and Hamersley Groups are characterized as ‘probably syngenetic with their Archean host rock’ based on their typical Precambrian molecular and isotopic composition, extreme maturities that appear consistent with the thermal history of the host sediments, the absence of biomarkers diagnostic of Phanerozoic age, the absence of younger petroleum source rocks in the basin and the wide geographic distribution of the samples. Aromatic hydrocarbons detected in shales associated with iron ore deposits at Mt Tom Price and Mt Whaleback are characterized as ‘clearly Archean’ based on their hypermature composition and covalent bonding to kerogen. 相似文献
2.
The paper presents data on the composition of biomarkers from bitumen extracts and the chemical structure of kerogen from Corg-rich sedimentary rocks before and after hydrothermal treatment in an autoclave at 300°C. Samples selected for this study are kukersite and Ordovician Dictyonema shale from the Baltics, Domanik oil shale from the Ukhta region, Upper Permian brown coal from the Pre-Ural foredeep, carbonaceous shale from the Oxfordian horizon of the Russian plate, and Upper Jurassic oil shales from the Sysola oil shale bearing region. The rocks contain type I, II, III, and II-S kerogens. The highest yield of extractable bitumen is achieved for Type II-S kerogen, whereas Type III kerogen produces the lowest amount of bitumen. The stages of organic matter thermal maturation achieved during the experiments correspond to a transition from PC2–3 to MC1–2. The 13C NMR data on kerogen indicate that the aromatic structures of geopolymers underwent significant changes. 相似文献
3.
烂泥沟金矿是以浊积岩为容矿岩石的微细浸染型金矿。有机岩石学分析表明,矿石与围岩中干酪根类型无明显差别,同属腐泥-腐植型。与围岩相比,矿石中干酪根成熟度(R0=2.74%-3.06%)和含金性(6.15-24.8μg/g)均较高;干酪根总含金量在全岩中所占的比例是围岩高于矿石。氯仿沥青“A”的检测说明,矿石样品中可溶性有机质形成于强还原和高盐度环境,沥青质和含硫有机化合物发育。研究认为,干酪根含金性与碳的活化有关;不饱和的有机基因对金的动一定转换可能具有重要意义。 相似文献
4.
Compound-specific stable carbon isotope (δ
) measurements on the aliphatic hydrocarbons released from an immature Tertiary oil shale (Göynük, Turkey) via hydropyrolysis, following solvent extraction and a milder hydrogenation treatment, have further highlighted that significant compositional differences may exist between the principal aliphatic constituents of the solvent extractable (bitumen) phase and the insoluble macromolecular network (kerogen) comprising the bulk of sedimentary organic matter. Whilst inputs from diverse sources; including algae, bacteria and terrestrial higher plants, were implied from analysis of solvent-extractable alkanes, the much larger quantities of kerogen-bound n-alkyl constituents released by hydropyrolysis had a uniform isotopic signature which could be assigned to (freshwater) algae. Remarkably, the aliphatics bound to the kerogen by relatively weak covalent bonds, liberated via catalytic hydrogenation, appeared to comprise mainly allochthonous higher plant-derived n-alkanes. These results provide further compelling evidence that the molecular constituents of bitumen and, indeed, of low-yield kerogen degradation products, are not necessarily reliable indicators of kerogen biogenicity, particularly for immature Type I source rocks. The isotopic uniformity of aliphatic n-hydrocarbons released by the high-conversion hydropyrolysis step for the ultralaminae-rich Göynük oil shale, lends further support to the theory that selective preservation of highly resistant aliphatic biomacromolecules is an important mechanism in kerogen formation, at least for alginite. 相似文献
5.
6.
High hydrogen pressure pyrolysis (hydropyrolysis) was performed on samples of solvent extracted Kimmeridge Clay Formation
source rock with a maturity equivalent to ca. 0.35% vitrinite reflectance. We describe the types and distributions of organic nitrogen compounds in the pyrolysis products
(hydropyrolysates) using GC-MS. Compounds identified included alkyl-substituted indoles, carbazoles, benzocarbazoles, quinolines
and benzoquinolines. The distributions of the isomers of methylcarbazoles, C2-alkylcarbazoles and benzocarbazoles in the hydropyrolysates were compared to a typical North Sea oil. The hydropyrolysates
compared to the North Sea oil, showed increased contributions from alkylcarbazole isomers where the nitrogen group is "exposed"
(no alkyl substituents adjacent to the nitrogen functionality) and appreciable levels of benzo[b]carbazole relative to benzo[a]- and benzo[c]carbazoles. Hydropyrolysis is found to be an ideal technique for liberating appreciable quantities of heterocyclic organic
nitrogen compounds from geomacromolecules. The products released from the immature Kimmeridge Clay are thought to represent
a potential source of nitrogen compounds in the bound phase (kerogen) able to contribute to the free bitumen phase during
catagenesis. 相似文献
7.
流体包裹体轻烃有机气体组成及对矿床成因的制约——以嵩溪大型银（锑）矿为例 总被引：1，自引：2，他引：1
嵩溪银（锑）矿是一个新发现的大型独立银矿。矿物流体包裹体超高真空四极气相质谱系统测定显 示，该矿成矿流体中存在多种轻烃有机气体，主要由Ｃ１－Ｃ４饱和烷烃组成，仅含微量Ｃ２－Ｃ４不饱和烯烃和芳烃，说明 成矿过程基本未受到高温岩浆作用的影响。化学平衡研究表明，这些轻烃气体为微生物成因和沉积岩围岩中Ⅱ类 干酪根热解成因的混合气体，其中前者占２／３以上，说明成矿中微生物活动曾起到相当大的作用；后者的平衡温度 为３００℃，远超过成矿深度所能达到的地热温度，因此这部分轻烃气体可能源于沉积盆地深处，经成矿流体长距离携 带到达较浅的矿化部位。文章从一个侧面证实嵩溪矿可能为沉积热卤水改造型矿床，而不是前人所认为的海底基 性火山喷流或中低温火山热液充填矿床。 相似文献
8.
Familiar since antiquity, and subject in contemporary times to various characterization schemes, the exact nature of solid bitumen is not yet fully known. Bitumens have ‘random polymer-like’ molecular structures, are mobile as highly viscous fluids or were once fluids but have since turned into solids. Solid bitumens consist mainly of large moieties, of polyclyclic aromatic hydrocarbons, occasionally with finely admixed, fine-grained cryptocrystalline graphite. Solid bitumens are distinguished from kerogen, which is the syngenetic and generally finely dispersed particulate organic matter in sedimentary rock that virtually does not migrate following its deposition. Occurrences of solid bitumens are relevant to petroleum exploration as well as the search for, and evaluation of, a variety of metallic mineral deposits. Genesis of bitumen is in many cases linked to the thermal and hydrothermal history of organic matter in sedimentary rock. Apparently bitumen, or more specifically organic acids generated along with bitumen during diagenesis, may alter porosity of reservoir rocks or otherwise prepare the ground for ore deposition. Bitumen is also relatively sensitive to alteration processes, some of which, such as oxidative weathering, water leaching, biodegradation (contact) metamorphism and ionizing radiation may likewise affect its nature. Elemental composition of bitumen commonly reflects the nature of mineral deposits. Is is possible that in petroleum exploration, trace metal abundances of bitumen may eventually allow prediction of crude oil types and volumes anticipated from a given source rock? Beside transition elements, notably Ni and V, highly anomalous concentrations of U, Pt and Au occur in some solid bitumens. During the generation of petroleum from kerogen, the trend in δ13C is toward lighter values. The opposite seems to occur when liquid petroleum is subjected to thermal cracking (and /or related processes) yielding solid bitumen enriched in 13C, and isotopically light methane. In fact, except for deasphalting and possibly some irradiation processes, the result of thermal cracking, oxidation, water leaching, inspissation (drying) and bacterial degradation of crude oil is that lower molecular weight hydrocarbons are removed leaving bitumen residues enriched in aromatic hydrocarbons, heteroatomic compounds (NSO) and 13C. Such phenomena are relevant to bitumen paragenesis in petroleum reservoir rocks, to certain Phanerozoic occurrences of multiple generations of bitumens, and to bitumens in mineral deposits. 相似文献
9.
A series of hydropyrolysis (HyPy) experiments have been conducted on a small suite of authentic polycyclic aromatic hydrocarbons (PAHs: coronene, pyrene and perylene) to investigate the HyPy behaviour of these PAHs. This information may help in the interpretation of the structural significance of aromatic HyPy products, often detected in high abundance, from high maturity kerogens. The PAHs were separately treated by HyPy and were all susceptible to some extent of hydrogenation. Perylene also decomposed into low molecular weight aromatics (e.g. methylbiphenyls). Structurally, perylene is much less stable than the more condensed PAHs coronene and pyrene. The total product concentrations (wt% of starting PAH) from all HyPy experiments were consistently less than 100 wt%, probably due to either the condensation of semi-volatile products on walls of the transfer line prior to reaching the HyPy trap or the inefficient cold trapping of highly volatile products. Hydrogenation of PAHs was prevalent and was found to be significantly influenced by the addition of a Mo-S based catalyst and potentially the C/Mo ratio, but largely independent of the two final temperatures used (520 °C and 550 °C). The fully aromatised and hydrogenated products for any stable ring system may provide a general indication of the size distribution of aromatic units within the kerogen structure. 相似文献
10.
D.J. Mossman W.E.L. Minter A. Dutkiewicz D.K. Hallbauer S.C. George Q. Hennigh T.O. Reimer F.D. Horscroft 《Precambrian Research》2008,164(3-4):173-186
In the Witwatersrand approximately 40% of the gold is intimately associated with so-called “carbon” in “carbon seam reefs”, which occur in over a dozen paleoplacers, many of them concentrated at two stratigraphic levels in the 7000-m-thick succession of Archean siliciclastic sedimentary rocks. This is reduced carbon, present as kerogen admixed in various proportions with derivative (now solid) bitumen(s). Oil generation and migration were active geological processes during Early Earth history. Numerous possible source rocks for oil generation, including the carbon seams themselves, occur within the Witwatersrand basin. In the Witwatersrand ore, oil-bearing fluid inclusions are also present, derived like the bitumen, by thermal maturation of the kerogen. The presence of kerogen and bitumen in the Witwatersrand sedimentary rocks, together with a wealth of observations on the spatial distribution of the carbon seams confirm that the carbon originated in situ from living organisms in microbial mat cover, as opposed to flowing in from elsewhere as liquid hydrocarbons as some researchers have suggested. Paleochannels, which truncated auriferous carbon seams early in the depositional history, are of widespread occurrence, and micro-synsedimentary faults offset carbon seams. The carbon seams are thus indigenous biogenic markers that grew contemporaneously with placer development. The various features highlighting the nature and spatial distribution of Witwatersrand carbon seams provide a classic case where field evidence trumps laboratory data in the reconstruction of geological processes. 相似文献
11.
Deborah S. Sklarew 《Geochimica et cosmochimica acta》1979,43(12):1949-1958
The insoluble organic matter, or kerogen, in a Recent bottom mud (<1000yr old) from Mono Lake, California, has been analyzed by vacuum pyrolysis-GC-MS and compared with the kerogen from several Precambrian rocks, including the Belingwe and Transvaal stromatolites. The Mono Lake kerogen consists mainly of cyclic and acyclic aliphatic components with lesser amounts of aromatics present. It is less aromatic and more susceptible to thermal degradation than the Precambrian kerogens, and its products show a much greater diversity especially among the unsaturated aliphatics and the heteroatomic components. The presence of these compounds, most notably 2,5-dimethylfuran, in the Mono Lake kerogen indicates a relatively rapid formation and incorporation into a young kerogen and suggests that their presence in the Precambrian kerogens, such as the Belingwe stromatolite, may be consistent with an ancient biological origin.In simulated diagenesis experiments the Recent mud was heated at 150°C for 3 months or 225°C for 8 months. The former was insufficient to affect the kerogen pyrolysis products. The latter, however, caused a large decrease in the heteroatomic components and a slight increase in the abundance of n-alkanes relative to that of the cyclic and branched alkanes. This suggests that the presence of some of these components in Precambrian rocks should be consistent with a high degree of preservation of these rocks, as appears to be the case for the Belingwe and Transvaal stromatolites. 相似文献
12.
川东北飞仙关组储层固体沥青地球化学特征及其气源指示意义 总被引：6，自引：1，他引：5
运用有机岩石学、有机地球化学、催化加氢热解、GC—IRMS等方法和技术,深入研究了川东北飞仙关组储层固体沥青及可能烃源岩的地球化学特征。研究认为,飞仙关组储层固体沥青反射率高,双反射明显,为非均质结构储层焦沥青;在碳酸盐岩储层的各种孔隙中,呈脉状、球粒状、角片状或块状等他形充填,具有中间相结构和镶嵌状结构特征,反映其高温热变质成因;元素组成有S/C高、H/C低的特点,其固体碳同位素组成与长兴组烃源岩干酪根相似。储层固体沥青的可能烃源岩发育于还原—弱氧化咸水沉积环境,有机质来源于水生藻类;氯仿沥青“A”饱和烃甾萜类生物标志物对比表明,上二叠长兴组烃源岩是主要来源,飞仙关组、下志留统烃源岩亦有贡献;催化加氢产物饱和烃及其正构烷烃单体碳同位素组成显示,坡2井飞仙关组储层固体沥青与罐5井飞仙关组烃源岩具有明显的亲缘关系,这也可作为飞仙关组海槽相烃源岩对飞仙关组气藏有贡献的佐证。 相似文献
13.
本文根据高分辨电镜观察结果,描述了若干前寒武纪干酪根的微结构,讨论了干酪根微结构与母岩变质作用的关系。发现,在变生和变质过程中,干酪根微结构的变化趋势是不同的;层间距(d_(002))不是H/C比值的线性函数;干酪根的微结构可以指示母岩的变质程度。 相似文献
14.
In this paper a thermogravimetry-differential thermal analysis method coupled with chromatography （TG-DTA-GC） has been adopted to simulate the generation of gaseous hydrocarbons from different hydrocarbon source rocks such as coals, mudstones, and carbonate rocks with different maturities. The temperature programming for thermal simulation experiment is 20℃/min from ambient temperature to 700℃. As viewed from the quantities and composition of generated gaseous hydrocarbons at different temperatures, it is shown that low-mature coal has experienced the strongest exothermic reaction and the highest loss of weight in which the first exothermic peak is relatively low. Low-mature coal samples have stronger capability of generating gaseous hydrocarbons than high-mature samples. The amounts and composition of gaseous hydrocarbons generated are closely related not only to the abundance of organic carbon in source rocks, but also to the type of kerogen in the source rocks, and their thermal maturity. In the present highly mature and over-mature rock samples organic carbon, probably, has already been exhausted, so the production of gaseous hydrocarbons in large amounts is impossible. The contents of heavy components in gaseous hydrocarbons from the source rocks containing type- Ⅰ and - Ⅱ kerogens are generally high ; those of light components such as methane and ethane in gaseous hydrocarbons from the source rocks with Ⅲ-type kerogens are high as well. In the course of thermal simulation of carbonate rock samples, large amounts of gaseous hydrocarbons were produced in a high temperature range. 相似文献
15.
Solid bitumen occurs extensively in the paleo-reservoirs of marine sequences in southern China. The fluids in these paleo-reservoirs have usually experienced severe secondary alteration such as biodegradation and/or thermal maturation. The concentrations of extractable organic matter (EOM) in the resulting solid bitumens are too low to satisfy the amount required for instrumental analysis such as GC–MS and GC–IRMS. It is also difficult to get enough biomarkers and n-alkanes by dry pyrolysis or hydrous pyrolysis directly because such solid bitumens are hydrogen poor due to high maturities. Catalytic hydropyrolysis (HyPy) can release much more EOM from solid bitumen at mature to highly over-mature stages than Soxhlet extraction, dry pyrolysis and hydrous pyrolysis. However, whether the biomarkers in hydropyrolysates can be used for bitumen-source or bitumen–bitumen correlations has been questionable. In this study, a soft biodegraded solid bitumen sample of low maturity was thermally altered to various maturities in a closed system. HyPy was then employed to release bound biomarkers and n-alkanes. Our results show that the geochemical parameters for source and maturity based on biomarkers released from these thermally altered bitumen residues by HyPy are insensitive to the degree of thermal alteration. Furthermore, the maturity parameters are indicative of lower maturity than bitumen maturation products at a corresponding temperature. This suggests that biomarker source and maturity parameters, based on the products of HyPy, remain valid for bitumens which have suffered both biodegradation and severe thermal maturation. The distributions of δ13C of n-alkanes in hydropyrolysates are also insensitive to the temperature used for bitumen artificial maturation. Hence, the δ13C values of n-alkanes in hydropyrolysates may also provide useful information in bitumen–bitumen correlation for paleo-reservoir solid bitumens. 相似文献
16.
Kerogen was isolated from a marine sediment from Tanner Basin, offshore California. Samples of the kerogen were heated under an inert atmosphere at various temperatures and times. The heated and unheated kerogens were subjected to alkaline potassium permanganate oxidation followed by GC/ MS analysis of the products. The kerogens yielded primarily aliphatic C2–C14 α,ω-dicarboxylic acids and benzene mono-to-pentacarboxylic acids. Yields of aliphatic dicarboxylic acids from kerogen decreased with increasing thermal alteration. Yields of benzenecarboxylic acids increased steadily with increasing thermal alteration. The data support the concept that thermal maturation during natural burial of this type of kerogen results in the generation of aliphatic hydrocarbons from an increasingly aromatic residue. 相似文献
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18.
珠江口盆地番禺低隆起-白云凹陷北坡干酪根热演化模拟与生烃 总被引：1，自引：0，他引：1
通过密封金管-高压釜体系对珠江口盆地番禺低隆起-白云凹陷北坡恩平组炭质泥岩的干酪根(PY),在24.1 MPa压力、20℃/hr(373.5~526℃)和2℃/h(343~489.2℃)两个升温速率条件下进行热模拟生烃实验,分析气态烃(C1 5)和液态烃(C6 14和C14+)的产率,以及沥青质和残余有机质碳同位素组成。同时与Green River页岩(GR)和Woodford泥岩(WF)的干酪根,分别代表典型的I型和II型干酪根进行对比研究。结果显示PY热演化产物中总油气量明显低于GR和WF干酪根,且气态烃(C1 5)最高产率是液态烃的1.5倍,揭示恩平组炭质泥岩主要以形成气态烃为主。在热演化过程中,有机质成熟度和母质类型是控制油气比的主要因素,气态烃和轻烃的产率比值主要受热演化成熟度的影响。干酪根残余有机质碳同位素和沥青质碳同位素在热演化过程中受有机质成熟度的影响较小,δ13C残余和δ13C沥青质可以间接反映原始母质的特征,为高演化烃源岩油气生成提供依据。 相似文献
19.
SUN Xiaoming David I. NORMAN SUN Kai WANG Min CHEN Binghui CHEN Jingde YU Shoujun Department of Earth Sciences Sun Yat-sen University Guangzhou Guangdong Chin E-mail: eessxm@zsu.edu.cn State Key Laboratory for Mineral Deposits Research Nanjing University Nanjing Jiangsu Chin Department of Earth Environmental Sciences New Mexico Institute of Mining Technology 《《地质学报》英文版》2003,77(2):227-236
The Songxi deposit is a newly discovered large Ag (Sb) deposit. By using a suite of high-vacuum quadrupole gas mass spectrometer systems, the authors have recognized many kinds of light hydrocarbons in fluid inclusions of minerals. These hydrocarbons are mainly composed of C1-C4 saturated alkanes, while the contents of C2-C4 unsaturated alkenes and aromatic hydrocarbons are quite low, suggesting that the metallogenic processes have not been affected by magmatic activities. Chemical equilibrium studies show that these hydrocarbons may be a mixture of organic gases generated by microorganism activity and those by thermal cracking of type-n kerogens (kukersite) in sedimentary host rocks, and the former may constitute more than two-thirds, implying that microorganism might have played an important role in the metallogenesis. The equilibrium temperature of the latter is about 300℃, which is much higher than the geothermal temperature at the estimated depth of metallogenesis. Thus, the light hydrocarbons gen 相似文献