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1.
The Alberta oil sands contain 1–2% organic solvent insoluble organic matter chemisorbed to the inorganic matrix. Analysis of the monocarboxylic fraction (1–14%) of the chemisorbed material has revealed the presence of C12–C32 normal, iso, anteiso alkenoic acids, mono and diunsaturated acids, cyclopropylalkanoic and cyclic terpenoid carboxylic acids. Some of the main components of the acyclic acids were similar to those which have been identified in various petroleums and Alberta oil sand bitumens (in small concentrations) by Mackenzie et al. (Advances in Organic Geochemistry 1981, pp 637–649, Wiley/Heyden, 1983), and attributed to bacterial degradation of the oils via the aerobic pathway of biosynthesis.The presence of these acids in the chemisorbed fraction and virtual absence in the bitumen lends additional support to earlier proposals that the Alberta oil sand bitumens have undergone severe microbial degradation.  相似文献   

2.
The association of oils and solid bitumens with ore deposits is widely recorded. The oils and bitumens may actually be enriched with metals. Unlike oils, metal enrichments within bitumens do not reflect the role of petroleum as a transporting agent for metals. By contrast, they may be a result of the reduction of metal ions on contact with bitumen, and may reach levels so high that ore mineral inclusions are precipitated. Metal determinations of British bitumens suggest that new metal anomalies can be detected by this approach, that some metal anomalies within bitumens may be related to ore mineralization, and that bitumens from different sources may be distinguished by their metal contents. The potential use of bitumen distribution and/or metal enrichment within bitumen for ore exploration is dependent on the metal concerned, and in particular whether the metal is transported by association with organic materials or reduced in the presence of organic materials.  相似文献   

3.
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   

4.
The Bulonggoer paleo-oil reservoir (BPR) on the northwest Junggar Basin is the first Devonian paleo-oil reservoir discovered in North Xinjiang, China. Solid bitumens occur within sandstone pores and as veins filling fractures. Samples of both types were analyzed using stable carbon isotope and reflectance measurements, as well as molecular biomarker parameters.The extremely positive δ13C values and biomarker indicators of depositional environment/lithology, such as pristane/phytane (Pr/Ph), C29/C30 hopane, diasteranes/regular steranes and dibenzothiophene/phenanthrene ratios, indicate a siliciclastic source for the BPR and their deposition in a highly reducing hypersaline environment. The presence of long chain n-alkanes and abundant tetracyclic diterpanes, C20–C21 tricyclic terpanes and perylene are indicators of higher plant organic matter input. Moreover, the bimodal distribution of C27 > C28 < C29 regular steranes and abundant methyltriaromatic steroids also support a contribution of microalgae as well as higher plants organic matter. The similar molecular composition and thermal maturity parameters indicate that the reservoir and veined solid bitumens were altered from a common paleo-petroleum, which originated from peak oil window matured source rocks.All solid bitumens from the BPR are characterized by relatively low bitumen reflectance values (Rb% < 0.7), suggesting that they were generated from low temperature processes rather than oil thermal cracking. Comparatively, the Rb% values for veined bitumens are higher than reservoir bitumens, indicating that the veined bitumens occurred earlier and experienced higher thermal conditions.  相似文献   

5.
A number of bitumen samples have been recovered from vugs and fractures in outcropping Tertiary basalts of the Queen Charlotte Islands off the west coast of British Columbia, Canada. n-Alkanes and acyclic isoprenoids are not present and the polycyclic biomarker distribution of the four samples analyzed by GC and GC-MS has been altered. One sample contains no remaining recognizable biomarkers. Two bitumens were also obtained from Lower Jurassic potential source rocks, including one from the Sandilands Formation, which was considered previously to be the most likely source of the Tertiary bitumens. Although these two bitumens were also taken from outcrops, they are considerably less biodegraded. The Sandilands Formation bitumen contains 28, 30-bisnorhopanes and since these compounds were not detected in the Tertiary bitumens, there is no evidence from the initial results for a Sandilands Formation contribution to the hydrocarbons in the Tertiary basalts. The presence of 18α(H)-oleanane in the saturate fraction of two of the Tertiary bitumens from widely separated locations indicates that they are at least partially sourced from Tertiary organic matter.Because the distribution of biomarkers in some samples has been severely affected by biodegradation, the asphaltenes of the bitumens were hydrously-pyrolysed and the saturate fractions of the resulting pyrolysates analysed for possible additional information on the origin of the bitumens. The pyrolysates from the more degraded samples contain compounds not detected in the saturate fractions of the original bitumen and show some of the expected characteristics of the original non-degraded bitumen. However, the compounds most useful for correlation are not present in the pyrolysates apparently due to their non-incorporation into the kerogen macromolecule. Our results suggest that hydrous-pyrolysis of asphaltenes is of limited use in the correlation of biodegraded samples and in determining their origins.  相似文献   

6.
Ionising radiation is an energy source capable of generating and altering complex organic matter. A full understanding of the radiolytic formation and evolution of organic matter is essential to appreciate the budget of organic chemicals that exist in cometary and interstellar ices, carbonaceous meteorites, and to understand the results of analyses of irradiated extraterrestrial organic matter, such as that in cometary nuclei. The effects of ionising radiation on a set of 10 naturally occurring, terrestrial organic assemblages have been revealed by pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS), carbon isotopic analysis, and stepped combustion-isotope ratio mass spectrometry (SC-IRMS). Progressive radiolytic alteration of biogenic complex-hydrocarbon mixtures induces a decrease in the average size and extent of alkylation of polyaromatic hydrocarbons (PAH) and an increase in the abundance of oxygen-containing compounds, as indicated by Py-GC-MS, and an enrichment in 13C. These changes are attributed to reactions with free radicals, produced by ionising radiation. In contrast, the progressive radiolytic alteration of bitumens proposed to have derived from the radiolytic polymerisation of methane into an organic solid produces, upon pyrolysis, PAH of increasing average size and degree of alkylation. This, the opposite of the trend observed in the irradiated complex-hydrocarbons mixtures, cannot be explained in terms of the radiolytic alteration of a pre-existing array of complex organic molecules. Instead, it suggests the gradual construction of PAH from smaller molecules, supporting the hypothesis of a methane origin. Radiolytic alteration is also associated with a previously unrecognised increase in the mean combustion temperature of organic matter. This leads to predictions regarding the combustion characteristics of the irradiated organic matter present on cometary nuclei. A full understanding of the relationship between the combustion characteristics of organic polymers, radiation dose and the atomic H/C ratio should lead to the better design and implementation of in situ extraterrestrial sample analysis hardware and aid the interpretation of data from such missions. This study establishes predictable organic chemical responses of organic matter, upon exposure to ionising radiation. Our results support proposals that extraterrestrial PAH may be formed by the cosmic irradiation of simple hydrocarbons in interstellar ices. Our data may also be relevant to analogous material formed in other hydrocarbon-rich environments, such as the surface and atmosphere of Titan and other icy bodies, such as comets, and to the results of in situ analyses of extraterrestrial organic matter.  相似文献   

7.
秀山上寒武统古油藏地球化学特征及油源分析   总被引:1,自引:0,他引:1  
秀山上寒武统古油藏沥青主要富集于耿家店组粗晶白云岩晶间孔、晶间溶孔及缝合线中,有机碳含量为3.43%~7.12%,显示其较高的沥青含量。受地表水淋滤氧化作用及微生物降解作用的影响,氯仿沥青“A”及热解烃含量较低,饱和烃含量较低,芳烃、非烃含量较高,轻重烃∑C21-/∑C21+比值较低。固体碳同位素值具有明显的二分特征,范围分别为-26.7‰-25.6‰和-29.1‰-28.8‰,反映古油藏油气聚集成藏至少有两期,分别来源于不同有机质类型的母岩。根据生物标志化合物、δ13Corg及单体烃同位素对比分析,认为沥青分别来源于下寒武统黑色灰岩和黑色页岩。  相似文献   

8.
We present results of geochemical studies of organic matter of the Jurassic–Cretaceous deposits in the west of the Yenisei–Khatanga regional trough. The studies were carried out on a representative set of well cores by a complex of modern organic-geochemistry methods (determination of organic-carbon content in rocks, pyrolysis, estimation of the carbon isotope composition in the kerogen of rocks, extraction, liquid and gas–liquid chromatography, and chromato-mass spectrometry). Based on the distribution of biomarkers in the studied bitumens and pyrolysis of rocks, two groups of the samples were recognized: with terrigenous (type III) and marine (type II) organic matter. The terrigenous bitumens are characterized by a low hydrogen index (HI) and a predominance of hydrocarbons C29 among steranes and C19 and C20 among tricyclanes. The marine bitumens, revealed in stratigraphic analogs of the Bazhenovo Formation and in the Malyshevka, Nizhnyaya Kheta, and Shuratovka Formations, show an even distribution of sterane homologues and a predominance of medium-molecular tricyclanes. The Pr/Ph and C35/C34 ratios and the presence of diahopanes testify to the burial of organic matter in suboxidizing sea coast environments. In the Yanov Stan (J3–K1), Gol’chikha (J2–K1), and, to a lesser extent, Malyshevka (J2), Nizhnyaya Kheta, and Shuratovka (K1) Formations, we have recognized widespread stratigraphic levels with marine organic matter of rocks. Its contents and degree of maturity permit these rocks to be considered oil-generating.  相似文献   

9.
本研究系统采集了四川盆地东北部大普光、元坝地区上三叠统须家河组、下三叠统飞仙关组、上二叠统长兴组和鄂西渝东地区中石炭统黄龙组储层固体沥青样品,进行了岩石热解、有机元素、碳同位素和饱和烃、芳烃组分GC/MS的分析,以确定其成因、性质和来源。这些沥青总体上具有低溶性(多数氯仿抽提物/TOC<8%)、高反射率(换算的Ro>1.4%)、低H/C原子比(<0.6)的性质,属焦沥青类,是古油藏原油或运移烃经热裂解成气的残留物。其中,飞仙关组、长兴组碳酸岩储层沥青的S/C原子比值普遍较高(主要在0.025~0.085范围),且硫同位素δ34S值(主要在12‰~24‰)接近硬石膏,说明可能包含有部分TSR成因的沥青。这些高热演化沥青中饱和烃生物标志物的组成和分布出现了异常变化,基本失去了其常规应用意义。芳烃中2,6-/2,10-DMP(二甲基菲)、1,7-/1,9-DMP和4-/1-MDBT(甲基二苯并噻吩)比值,可用来指示沥青烃源岩的有机质生源构成和沉积环境性质。须家河组陆相沥青中这些芳烃比值较高,表征其烃源母质中陆源有机质占优势,且形成于氧化性的环境;而飞仙关组、长兴组及黄龙组海相沥青中这些参数值低得多,意味着其烃源岩有机质生源应以水生生物为主,并沉积于还原性环境。经沥青/烃源岩的碳同位素和二苯并噻吩系列组成对比,认为须家河组储层沥青来源于本层位烃源岩,飞仙关组和长兴组沥青同源于二叠系烃源层。鄂西渝东地区的黄龙组沥青碳同位素偏重(δ13C值为-23.2‰~-26.4‰),原始烃源可能主要来自中、下志留统韩家店组及小河坝组地层。  相似文献   

10.
In the Triassic siliceous formation of Sikhote Alin, carbonaceous silicites occur in the late Olenekian-middle Anisian member (4–20 m) of alternating cherts and clayey cherts (“phtanite member”) near the section base. The silicites are represented by radiolarian and spicule-radiolarian cherts alternating with clayey cherts. They contain up to 8.5% Corg. In the majority of sections, the rocks underwent structural and mineral transformation at the mesocatagenetic stage. The slightly oxidized organic (primarily, marine sapropelic) matter contains quinones, methyl, methylene, and ether groups. The content of neutral bitumens in rocks shows a wide variation range. The carbon isotopic composition in phtanites and clayey phtanites (δ13C from ?27.3 to ?30.2‰) is identical to that in many Paleozoic-Mesozoic bitumens and oils. As compared with other Mesozoic sedimentary rocks of Sikhote Alin, the carbonaceous silicites are enriched in V, B, Mo, Ni, Cu, and Ag. Anomalously high concentrations of Ba are recorded in phtanite rock sections at the Gornaya and Khor rivers and in the vicinity of Khabarovsk. Modal value of the Au content in phtanites and clayey phtanites is three or four times higher than the clarke value in carbonaceous silicites and reaches anomalous values in some sections (e.g., Ogorodnaya River section). Carbonaceous silicites of this section are also enriched in Pt. Positive Au-Corg correlation is recorded in clayey phtanites of the Ogorodnaya River section containing more than 0.5% Corg. In organic fractions, Au and Ag are concentrated in alcohol and alcohol-benzene bitumens, asphalt acids, and asphaltenes. Migration of bitumens from high-carbonaceous clayey phtanites to the pore-fissure space of cherts and phtanites also fostered the concentration of these metals in some low-carbonaceous layers of the member.  相似文献   

11.
1 Introduction As a linkage between the biosphere and the geosphere, organic geochemistry, especially molecular markers, has become a powerful tool for investigating important geological events and the evolutionary history of ancient life on Earth (Kvenvo…  相似文献   

12.
首次在南羌塘安多县鄂斯玛地区早白垩世地层中发现沥青。从沥青有机碳含量、族组分及生物标志化合物方面综合研究了其有机地球化学特征,并进行了油源对比。研究结果表明,样品的有机碳含量为3.42%~75.01%,显示其有较高的沥青含量;族组成中重烃组分(非烃+沥青质)质量分数最高,其次为芳香烃,饱和烃质量分数最低。生物标志物研究表明,沥青的成熟度较高,沥青母岩的沉积环境为还原环境,其有机母质主要为混合来源,特别是藻类做出了重要贡献。运用生物标志化合物的相对含量指标进行油源对比研究表明,沥青可能来源于索瓦组泥岩。该研究成果对南羌塘的油气勘探具有一定意义。  相似文献   

13.
Detailed geochemistry studies were conducted to investigate the origin of solid bitumens and hydrocarbon gases in the giant Puguang gas field. Two types of solid bitumens were recognized: low sulfur content, low reflectance (LSLR) solid bitumens in sandstone reservoirs in the Xujiahe Formation and high sulfur content, high reflectance (HSHR) solid bitumens in the carbonate reservoirs in the Lower Triassic Feixianguan and Upper Permian Changxing formations. Solid bitumens in the Upper Triassic Xujiahe Formation correlate well with extracts from the Upper Triassic to Jurassic nonmarine source rocks in isotopic composition of the saturated and aromatic fractions and biomarker distribution. Solid bitumens in the Feixianguan and Changxing formations are distinctly different from extracts from the Cambrian and Silurian rocks but display reasonable correlation with extracts from the Upper Permian source rocks both in isotopic composition of the saturated and aromatic fractions and in biomarker distribution, suggesting that the Permian especially the Upper Permian Longtan Formation was the main source of solid bitumens in the carbonate reservoirs in the Feixianguan and Changxing formations in the Puguang gas field. Chemical and isotopic composition of natural gases indicates that the majority of hydrocarbon gases originated from sapropelic organic matter and was the products of thermal cracking of accumulated oils. This study indicates that source rock dominated by sapropelic organic matter existed in the Upper Permian and had made major contribution to the giant Puguang gas field, which has important implication for petroleum exploration in marine sequences in South China.  相似文献   

14.
Greenschist facies rocks of the Poniklá Group (Ordovician-Silurian), Czech Republic, contain several types of carbonaceous matter that differ in their morphology, texture, reflectance and Raman characteristics. The first type consists of large (up to 3 mm) irregularly bound particles of low reflectance (Romin = 0.9%; Romax = 5.6%). The area ratio of the 1585 cm-1 to 1350 cm-1 Raman peaks (1.08–1.17) indicates an intermediate degree of graphitization. The formation of this type of highly porous particle, displaying a texture reminiscent of regular or needle coke, is attributed to the thermal alteration of the amorphous (structureless) kerogen of the precursor sediments. The second type consists of lamellar particles up to 30 μm thick, which can be associated with the latter or can occur independently in white mica-rich laminae. This type is characterized by high bireflectance (Romin = 0.6%; Romax = 11.9%) and by lower ratios (0.70–0.82) of the Raman peak areas. These particles are interpreted as the product of solid-state, diffusion-controlled graphitization of a chemically homogeneous organic material, e.g. of graptolite periderms. The third type consists of isometric, up to 2 mm large, commonly fractured grains and fragments which mainly occur in quartz-rich laminae. In reflected light, the texture is either homogeneous or consists of various types of anisotropic mozaics. The Raman peak area ratios (0.75–1.14) indicate a highly variable degree of structural ordering. These particles are considered as the remains of metamorphosed bitumens, accumulated in the sandy laminae of the original sediments. The fourth type consists of small particles of carbonaceous matter (maximum length 25 μm, thickness 1-2 μm), which occur adjacent to crystal faces of white micas. This type is probably the product of epitaxial growth of graphite from the gaseous phase. The results of this work indicate that the differences in the degree of graphitization of the carbonaceous matter in low-grade metamorphosed rocks can be mainly related to the initial nature of the sedimentary organic matter and to its premetamorphic history.  相似文献   

15.
The analysis of petroleum inclusions (PI) in parallel to residual oils (=bitumens) provided specific constraints for petroleum migration processes in the Prague Basin. Whereas organic geochemical information from bitumens is limited due to alteration, additional high quality information was obtained from C1–14-range compounds inside crystals. This was obtained by the application of a closed system for the decrepitation and thermal extraction of PI with subsequent gas chromatography (GC) and gas chromatography–mass spectrometry (GC–MS). The resulting data not only show pristine live oils, gases, residual and precipitated bitumens and a broad variation of mixtures of the groups above, but also show that gas migration and fractionation processes played a major role in the Prague Basin.  相似文献   

16.
Detailed geochemistry studies were conducted to investigate the origin of solid bitumens and hydrocarbon gases in the giant Puguang gas field. Two types of solid bitumens were recognized: low sulfur content, low reflectance (LSLR) solid bitumens in sandstone reservoirs in the Xujiahe Formation and high sulfur content, high reflectance (HSHR) solid bitumens in the carbonate reservoirs in the Lower Triassic Feixianguan and Upper Permian Changxing formations. Solid bitumens in the Upper Triassic Xujiahe Formation correlate well with extracts from the Upper Triassic to Jurassic nonmarine source rocks in isotopic composition of the saturated and aromatic fractions and biomarker distribution. Solid bitumens in the Feixianguan and Changxing formations are distinctly different from extracts from the Cambrian and Silurian rocks but display reasonable correlation with extracts from the Upper Permian source rocks both in isotopic composition of the saturated and aromatic fractions and in biomarker distribution, suggesting that the Permian especially the Upper Permian Longtan Formation was the main source of solid bitumens in the carbonate reservoirs in the Feixianguan and Changxing formations in the Puguang gas field. Chemical and isotopic composition of natural gases indicates that the majority of hydrocarbon gases originated from sapropelic organic matter and was the products of thermal cracking of accumulated oils. This study indicates that source rock dominated by sapropelic organic matter existed in the Upper Permian and had made major contribution to the giant Puguang gas field, which has important implication for petroleum exploration in marine sequences in South China.  相似文献   

17.
Raman spectra of natural and synthetic samples of stishovite have been measured with a micro-optical spectrometer system. These spectra have a pattern that is characteristic of rutile-structured oxides. The spectrum of synthetic stishovite is characterized by well-resolved bands at 231, 589, 753, and 967 cm?1, which are assigned as theB 1g,E g,A 1g, andB 2g fundamentals, respectively, of the first-order Raman spectrum of the ideal, ordered structure. Natural stishovite obtained from Meteor Crater, Arizona has a first-order Raman spectrum that is fully consistent with that of the synthetic material. The observed spectrum of the natural sample, however, is weaker and has bands in addition to those identified as fundamentals in the spectrum of the synthetic material. A broad band at ~475 cm?1 may be indicative of glass or contaminants derived from the extraction procedure. Alternatively, this band may arise from multiphonon scattering that is enhanced by poor crystallinity or structural disorder in the natural shocked sample.  相似文献   

18.
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   

19.
We have studied for the first time the organic geochemistry of the Vendian thick section stripped by the parametric well Vostok-3 in the depth range 5002–3870 m in southeastern West Siberia. The results point to the aquagene–plankton–derived and bacterial nature of the buried organic matter (OM). At some depth levels, the deposits are enriched in OM (up to 0.7–9.6%). The study of kerogens has shown that the OM is transformed to the apocatagenesis stage. The composition of biomarker hydrocarbons in bitumens has been studied, and the geochemical criteria for the petroleum presence prediction are considered.  相似文献   

20.
Enriched concentrations of vanadium and nickel have been noted in a variety of naturally occurring organic substances including crude oils, asphalts, and organic matter in some sedimentary rocks. Vanadium and nickel concentrations in bitumens extracted from a variety of organic sedimentary rock types of different geological ages and geographical areas range from less than 0.2 to 4760 ppm and less than 7 to 1240 ppm, respectively. Vanadium concentrations showed a polymodal frequency distribution, while nickel concentrations showed a near-normal frequency distribution. The concentrations of these two metals showed no significant correlations with bitumen content, organic carbon content, or proportionality between bitumen and organic contents. Enriched vanadium and nickel concentrations greater than 100 ppm are only observed in bitumens that are associated with Type II and Type I kerogens. Conversely, bitumens associated with Type III kerogens contained vanadium and nickel concentrations less than 100 ppm.The high stability of vanadium and nickel in crude oils, asphalts, and bitumens suggest that they occur in tetrapyrrole complexes. These complexes may occur as free molecules or assimulated subunits in macromolecules because of their availability in anaerobic systems, small atomic radii, and favorable electron configurations. The potential for an organic sediment to be enriched in these two metals depends upon the amount of tetrapyrroles preserved in its organic matter. Tetrapyrrole preservation preferentially decreases in organic matter as exposure time to aerobic conditions increases. The potential for vanadium and nickel enrichment is therefore the highest in organic matter derived from algae that encountered anaerobic conditions early in their depositional history. Metallation of tetrapyrrole complexes appears to occur within sediments prior to their lithification, and interstitial waters are the most likely source for enriched concentrations of vanadium and nickel. The amount of metal enrichment in a sediment depends upon the diffusion of metal cations from its overlying water body, and this source is only effective as long as the sediment system remains open. The complete metallation of tetrapyrroles is most favorable under conditions of slow sedimentation rates, which would allow open sediment systems to be maintained for long durations.  相似文献   

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