Archaean stromatolites of the Belingwe Greenstone Belt,Zimbabwe (Rhodesia)

The stromatolites of the Belingwe Greenstone Belt (approximately 2700 Ma old) are perhaps the best-developed Archaean stromatolites yet found. Exposures occur on two stratigraphic levels, both part of the “Bulawayan” in Rhodesian stratigraphic terminology (Wilson et al., 1978). The extensive outcrops show a wide variety of stromatolites, including forms similar to Baicalia, Conophyton, Irregularia and Stratifera. Many stromatolites occur in cyclic units, possibly reflecting periodic changes in lagoonal conditions. Associated sedimentary rocks were deposited in a very shallow-water environment and some display well-developed desiccation features. Currently held concepts concerning the evolution of stromatolites and their usefulness in biostratigraphy do not appear to be supported by the evidence from Belingwe.     

前寒武纪干酪根微结构的高分辨电镜研究

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。     

Pyrolysis of transvaal kerogens I. Diagenesis of kerogen in a stromatolite near Zeerust,South Africa: One possible chemical evolution process

This study represents an attempt to understand some of the many post-lithification chemical processes which affect the evolution of kerogen. Kerogens separated from four carbonate stromatolites, collected over a horizontal distance of ～ 350 km from the Malmani Dolomite of the Olifants River Group in the Transvaal Supergroup, were characterized by combined vacuum pyrolysis—gas chromatography-mass spectrometry. The relative profiles of the gas chromatographic peak distributions and intensities (·finger print patterns’) of three of the kerogen pyrolyzates were closely similar. The Zeerust stromatolite kerogen yielded a different pattern, showing a greater abundance of higher molecular weight aliphatic and alkyl aromatic hydrocarbon moieties than the other three samples. Many of the stromatolites near the Zeerust area contain epigenetic fluorite introduced by aqueous solutions. Fluid inclusion homogenization analysis showed that the emplacement temperature of fluorite in the sample studied was 100–200°C. Fluoride ion initiated base catalyzed condensations may have been a feasible cause for the production of higher molecular weight aliphatic and (indirectly) some alkyl aromatic moieties in this stromatolite, as compared to those in the other three samples. Acid-catalyzed condensations may also achieve similar results in aqueous diagenetic environments.     

Release of bound aromatic hydrocarbons from late Archean and Mesoproterozoic kerogens via hydropyrolysis

Hydrogen-lean kerogens (atomic H/C<0.4) isolated from the 2.5-billion-year-old (Ga) Mt. McRae Shale, Hamersley Group, at Tom Price, Western Australia, were studied via hydropyrolysis, a continuous-flow technique that degrades organic matter in a stream of high-pressure hydrogen assisted by a dispersed Mo catalyst. The hydropyrolysates yielded predominantly phenanthrene and pyrene, and higher polyaromatic hydrocarbons and alkylated homologues were generated in low relative concentrations. Saturated hydrocarbons were not detected. The molecular and carbon isotopic compositions of the hydropyrolysates are very similar to aromatic hydrocarbons obtained by solvent extraction of the host rocks. Because molecular structures covalently attached to kerogen are unaffected by contamination, this indicates that both the bound and extractable aromatic fractions are syngenetic with the host rocks. Therefore, the results of the hydropyrolysis experiments provide compelling evidence for preserved bitumen of Archean age. The very high proportion of nonalkylated polyaromatic hydrocarbons in the hydropyrolysates is consistent with hydrothermal dehydrogenation of the kerogen, and a marked concentration difference of pyrene in rock extracts and hydropyrolysates might be explained by hydrothermal redistribution of the bitumen. The kerogen and bitumen composition is therefore consistent with models suggesting a hydrothermal origin for the giant iron ore deposits at Mt. Tom Price. Comparison of the Archean samples with hydropyrolysates from immature Mesoproterozoic kerogens from the Roper Group, McArthur Basin, Northern Territory, and with pyrolysis experiments on Proterozoic kerogens in the literature suggests that Precambrian kerogens are frequently highly aromatic and lipid-poor regardless of their degree of thermal preservation.     

Archaean stromatolites from the Ngesi Group,Belingwe greenstone belt,Zimbabwe; preservation and stable isotopes — preliminary results

The petrology and stable isotope chemistry of cyanobacterial stromatolites of Archaean age (2.7 Ga) from the Cheshire and Manjeri Formations of the Belingwe greenstone belt in Zimbabwe have been examined. Palaeomagnetic data suggest that the stromatolites formed in tropical to subtropical latitudes. The Cheshire Formation shows little evidence of either anion or cation exchange during metamorphism, and the stable carbon and oxygen isotope ratios suggest a formation at temperatures perhaps considerably below 80°C. The Manjeri Formation, only slightly older, but overlain by a thick volcanic sequence, shows a low grade of metamorphism, and isotope ratios that are consistent with a metamorphic temperature of around 200°C.     

Carbon and hydrogen isotopic compositions of algae and bacteria from hydrothermal environments,Yellowstone National Park

Stromatolites forming today on a small scale in hydrothermal environments are chemical and biological analogues of much larger Precambrian formations. Carbon isotopic composition varied as a function of CO₂ concentration, pH, and species composition. Stratiform, layered stromatolites grew in silica-depositing springs at 55° to 70°C; they consisted mainly of a unicellular alga, Synechococcus, and a filamentous, photosynthetic bacterium, Chloroflexus. These thermophiles become enriched in ¹²C as the concentration of carbon dioxide in the effluent waters increases. At a concentration of 40 ppm total inorganic C, and δ¹³C of organic carbon was ～ ?12%., whereas at 900 ppm total inorganic C, the δ¹³C of similar species was ～ ?25%.. Conical stromatolites or conophytons (principally a filamentous, blue-green alga Phormidium and Chloroflexus) grew at 40°-55°C. In older, broader conophytons, Chloroflexus was the dominant organism. Their δ¹³C values were ～ ?18%. in a variety of hot springs. In carbonate-depositing springs, i.e., carbon dioxide saturated, conophytons and stromatolites consisting of a variety of blue-green algae and photosynthetic bacteria had the most negative δ¹³C values (to ?30%.). These carbon isotope ratios are directly comparable to carbon isotope ratios of kerogen from Precambrian stromatolites. The presence and activity of methanogenic bacteria or heterotrophic, aerobic and anaerobic bacteria did not alter significantly the δ¹³C of the original organic matter.The hydrogen isotopic fractionation between thermophilic organisms and water is 0 to ?74 for temperatures of 85° to 46°C, respectively. Acidophilic algae fractionated hydrogen isotopes to a lesser extent than did the photosynthetic organisms inhabiting neutral pH springs. Because organic matter retains some of its original isotopic signature, relationships of CO₂ levels, pH, temperature, and species composition between modern stromatolites and their environment and those of the Precambrian can be inferred.     

Distribution and geochemical significance of trace elements in shale rocks and their residual kerogens

There is a dearth of information about the distribution of trace elements in kerogen from shale rocks despite several reports on trace element composition in many shale samples. In this study, trace elements in shale rocks and their residual kerogens were determined by inductively coupled plasma–mass spectrometry. The results from this study show redox-sensitive elements relatively concentrated in the kerogens as compared to the shales. This may be primarily due to the adsorption and complexation ability of kerogen, which enables enrichment in Ni, Co, Cu, and Zn. For the rare earth elements (REEs), distinct distribution characteristics were observed for shales dominated by terrigenous minerals and their kerogen counterparts. However, shales with less input of terrigenous minerals showed similar REE distribution patterns to their residual kerogen. It is speculated that the distribution patterns of the REEs in shales and kerogens may be source-related.     

干酪根中类脂肪链含量的测定及石油地质意义

选取了红外光谱中2750～3000cm-1C-H振动峰面积作为反映干酪根中脂肪链含量的特征参数,并以完全饱和脂肪链的微晶石蜡为基准,建立了对干酪根中脂肪链含量进行测定的实验方法,同时讨论了实验条件、无机矿物、干酪根样品加入量等因素的影响。并通过对东营地区不同类型干酪根的低熟烃源岩样品进行的高压热模拟实验,研究了干酪根中脂肪链的百分含量与成熟度、沥青转化率及干酪根原素组成之间的关系。结果表明干酪根中脂肪链含量不仅与干酪根的类型有关,而且随成熟作用增加明显降低,其与热模拟生油量的关系和烃源岩的产烃率曲线相似,在脂肪链含量由15%降至5%时出现一个生油高峰。所以,脂肪链百分含量这一参数有可能成为烃源岩的判别及评价的一个新的重要指标。     

TG/plus—a pyrolysis method for following maturation of oil and gas generation zones using Tmax of methane

Thermogravimetric Fourier transform infrared spectroscopy (TG-FTIR) analyses were carried out on two sets of isolated kerogens covering a wide maturity range from low mature (0.46% R_o) through the end of oil and gas generation (maximum R_{o = 5.32%}). Data onweight percent and T_max for evolution of methane, volatile tars, ethylene, SO₂, NH₃, CO₂, and CO are reported. The T_max of methane shows the most consistent response to increasing maturation in both sets of samples. Results are comparable to those of whole rocks from an Alaskan North Slope well analyzed previously. The collective data for both whole rocks and isolated kerogens shows a generally linear correlation between %R_o and T_max of methane, with the exception of R_o of about 2.0% where a dip in the curve occurs. The slope of the correlation line was steeper for the predominantly terrigenous Wilcox kerogen than for more marine Colorado kerogen or for the Alaskan North Slope whole rock samples, probably reflecting differences in the chemical nature of various kerogen sets, which is also reflected by differences in the shapes of the pyrolysis curves of SO₂, CO₂, CO, H₂O, and ethylene. These preliminary data indicate that T_max of methane is a good maturation indicator for whole rocks and isolated kerogens up to an R_o of about 4%, which includes all of the wet gas and a considerable portion of the dry gas generation zones. This correlation was also observed for samples containing migrated bitumen, where it was not possible to obtain a reliable T_max for the volatile tar (S2) peak. The more terrigenous Wilcox kerogens also showed a good correlation of the T_max of ethylene with %R_o. T_max of ammonia evolution did not correlate with maturity and occurred 100–200°C lower than previously found for whole rocks, consistent with a whole-rock source of pyrolytic ammonia for Alaskan whole rock samples. HI and OI indices were calculated in several ways and plotted to reflect kerogen type as well as both the residual oil and gas generation potential. The ratio of pyrolyzable to combustible sulfur (evolved as SO₂) was independent of maturity and showed a clear difference between the more terrigenous Wilcox kerogens and the more marine Colorado kerogens.     

Thermogravimetry-differential thermal analysis coupled with chromatography as a thermal simulation experimental method and its application to gaseous hydrocarbons from different source rocks

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.     

Changes in the composition of bitumen extracts and chemical structure of kerogen during hydrous pyrolysis

The paper presents data on the composition of biomarkers from bitumen extracts and the chemical structure of kerogen from C_org-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 PC_2–3 to MC_1–2. The ¹³C NMR data on kerogen indicate that the aromatic structures of geopolymers underwent significant changes.     

Pyrolysis-high resolution gas chromatography and pyrolysis gas chromatography-mass spectrometry of kerogens and kerogen precursors

A series of kerogens and kerogen precursors isolated from DSDP samples, oil shales and Recent algal mats have been examined by Curie point pyrolysis-high resolution gas chromatography and gas chromatography-mass spectrometry. This study has shown that the three main types of kerogens (marine, terrestrial and mixtures of both) can be characterized using these techniques. The marine (algal) kerogens yield principally aliphatic products and the terrestrial kerogens yield more aromatic and phenolic products with some n-alkanes and n-alkenes. The yields of n-alkanes and n-alkenes increase and phenols decrease with increasing geologic age, however, pyrolysis-GC cannot be used to characterize the influence of short term diagenesis on the kerogen structure.     

中国豫西寒武系馒头组叠层石的沉积特征及其古环境意义

中国豫西寒武系馒头组一、二段共出露9层叠层石,占寒武纪18层叠层石中的50%,且其特征明显、形态多样,可分为圆柱状、波状、半球状和围绕竹叶状砾屑灰岩生长的叠层石等4大类8小类。本文在逐层分析豫西寒武系馒头组一、二段叠层石相序特征的基础上,通过对不同类型叠层石的宏观、中观形态特征及伴生的其它沉积特征进行详细描述,并以巴哈马Highborne Cays现代海相叠层石的生长环境和前寒武纪叠层石的沉积环境等为佐证,建立了豫西寒武系馒头组8小类11种不同叠层石的沉积环境分布模式,其中潮上带以近水平状叠层石为主,少量为缓波状、小柱状和含水平状薄泥层的叠层石;潮间带上部以缓波状、小柱状和含水平状薄泥层的叠层石为主,少量锥柱状叠层石;潮间带中部以圆柱状叠层石为主,含扁平状核形石和竹叶状砾屑,少量为锥柱状和围绕竹叶状砾屑生长的叠层石;潮间带下部至潮下带以含圆形核形石的圆柱状和半球状叠层石为主,少量含核形石的倒锥状叠层石。海平面的变化即水动力条件是叠层石生长类型变化的决定因素。     

Primary alteration—oxidation of marine algal organic matter from oil source rocks of the North Sea and Norwegian Arctic: new findings

The presence of partially oxidized algal organic matter in oil-prone marine source rocks, is the rule rather than the exception. Partially oxidized, algal kerogen can still act as a significant source of liquid hydrocarbons. However, the corresponding peak of C₁₂ + hydrocarbon generation is shifted to a considerably lower maturity level compared with that of the classical Type II kerogen. The extent of primary alteration-oxidation of marine algal kerogen is monitored by means of solid state microfluorescence spectroscopy. A new parameter, the Primary Alteration Factor (PAF) is established, and the relationships between PAF and H/C, O/C, HI, TOC and between PAF and %₀δ¹³C are determined. The present data show large variations in the bulk chemistry of immature marine algal kerogens, and reveal evidence for gradational dehydrogenation/oxidation of the source organic matter. This contrasts with the recently proposed mechanism for kerogen formation. SEM analysis reveals a relationship between the physical breakdown of algal organic matter and the formation of liptodetrinite. FTIR analysis shows that the incorporation of primary oxygen in the kerogen macromolecules is not in the form of carbonyl or carboxyl functionalities. The presence of highly unreactive, stable oxygen, associated with aromatic structures in partially oxidized algal kerogen, is suggested by resistance of the kerogen to graphitization. The FTIR data also suggest the presence of aryl ether oxygen. The present findings raise fundamental questions regarding the mechanisms of kerogen cracking and kerogen formation, and have important implications for petroleum exploration.     

Characteristics of amorphous kerogens fractionated from terrigenous sedimentary rocks

A preliminary attempt to fractionate amorphous kerogens from terrigenous bulk kerogen by a benzene-water two phase partition method under acidic condition was made. Microscopic observation revealed that amorphous kerogens and structured kerogens were fractionated effectively by this method. Characteristics of the amorphous and structured kerogens fractionated by this method were examined by some chemical analyses and compared with those of the bulk kerogen and humic acid isolated from the same rock sample (Haizume Formation, Pleistocene, Japan). The elemental and infrared (IR) analyses showed that the amorphous kerogen fraction had the highest atomic$\text{H}\text{C}$ ratio and the lowest atomic $\text{N}\text{C}$ ratio and was the richest in aliphatic structures and carbonyl and carboxyl functional groups. Quantities of fatty acids from the saponification products of each geopolymer were in agreement with the results of elemental and IR analyses. Distribution of the fatty acids was suggestive that more animal lipids participate in the formation of amorphous kerogens because of the abundance of relatively lower molecular weight fatty acids (such as C₁₆ and C₁₈ acids) in saponification products of amorphous kerogens. On the other hand, although the amorphous kerogen fraction tends to be rich in aliphatic structures compared with bulk kerogen of the same rock samples, van Krevelen plots of elemental compositions of kerogens from the core samples (Nishiyama Oil Field, Tertiary, Japan) reveal that the amorphous kerogen fraction is not necessarily characterized by markedly high atomic $\text{H}\text{C}$ ratio. This was attributed to the oxic environment of deposition and the abundance of biodegraded terrestrial amorphous organic matter in the amorphous kerogen fraction used in this work.     

Classification and thermal history of petroleum based on light hydrocarbons

Classifications of oils and kerogens are described. Two indices are employed, termed the Heptane and IsoheptaneValues, based on analyses of gasoline-range hydrocarbons. The indices assess degree of paraffinicity. and allow the definition of four types of oil: normal, mature, supermature, and biodegraded. The values of these indices measured in sediment extracts are a function of maximum attained temperature and of kerogen type. Aliphatic and aromatic kerogens are definable. Only the extracts of sediments bearing aliphatic kerogens having a specific thermal history are identical to the normal oils which form the largest group (41%) in the sample set. This group was evidently generated at subsurface temperatures of the order of 138°–149°C, (280°–300°F) defined under specific conditions of burial history. It is suggested that all other petroleums are transformation products of normal oils.     

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

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(C1 5)和液态烃(C6 14和C14+)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(C1 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,δ13C残余和δ13C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。     

Organic geochemistry in Precambrian research

Cherts, shales, and carbonates containing small amounts of organic matter occur throughout the Precambrian sedimentary record. The oldest known organic-rich sediments have been dated at > 3,000 million years. Knowledge of the composition, origin, and fate of the organic content of these rocks relates to many facets of Precambrian earth history. Apart from its primary paleobiological significance, organic geochemical research is also concerned with problems in atmospheric and hydrospheric evolution, sedimentation, diagenesis, metamorphism, and ore genesis.Precambrian organic geochemistry to date has rested on the premise that ancient life process can be profitably studied at a chemical level, as well as by examination of the morphological fossils of conventional paleontology. A decade of intensive research on selected Precambrian carbonaceous and bituminous sediments has been made possible by the refinement of analytical techniques (notably gas chromatography and mass spectrometry) which are now capable of detecting and characterizing the minute quantities of complex organic mixtures found in geological materials. It has resulted in the development of criteria which allow discrimination between indigenous and adventitious organic matter. A diverse array of stable organic compounds has been isolated from Precambrian sedimentary rocks. The compounds, termed chemical fossils, are thought to be derived from ancestral microorganisms and as such have contributed to the formulation of the biological marker concept. Despite reports of possible abiotic occurrences, a biological origin for most of the organic matter preserved in Precambrian rocks (whether sedimentary or metamorphic) now appears likely.The possibility of secondary emplacement from migrating formation fluids means that an indigenous chemical fossil need not have been syngenetic with the deposition of its host sediment. No conclusive test of Precambrian age as yet exists for these compounds. The bulk of the organic material (kerogen) in Precambrian rocks is insoluble in organic and aqueous solvents. For this reason, kerogen is almost certainly both indigenous and syngenetic, but clarification of its chemical structure must await the development of new analytical procedures. The nature and extent of the modification that the soluble and insoluble organic fractions have undergone during late diagenesis and incipient metamorphism is still virtually unknown. Correlation of chemical fossils with specific biogenic precursor compounds, or a particular type of primitive organism, therefore remains equivocal. So also comparison of the organic geochemical facies of one sediment with that of another may be complicated by differences in their thermal history and mineralogy.Recent interest in the possible involvement of living and decayed microorganisms in the genesis of certain Precambrian Fe, U, Au, Cu, Pb, and Zn metal deposits signals the beginning of an important new phase in organic geochemical studies.     

海相碳酸盐岩烃源岩热解动力学研究:全岩和干酪根的对比

我国海相碳酸盐岩地层分布广泛,厚度巨大,经历的地质历史较长,特点是有机质丰度低,多处于高过成熟阶段.碳酸盐岩烃源岩评价对我国的油气资源评价与勘探至关重要.用生烃动力学方法来研究碳酸盐岩生油气过程是一个值得探索的研究方向.本文通过生烃动力学热模拟实验,求取了碳酸盐岩全岩和其干酪根不同烃类组分(甲烷、 C2～ C5气态烃)的生成动力学参数并进行对比.结果表明,在生烃动力学热解实验中,全岩和其干酪根具有相似的动力学参数,采用烃源岩应该比干酪根更符合实际,但是干酪根样品可以测得更为详细的实验数据,因此可以根据样品的情况,选择合理且易行的实验条件.在此基础上,以本文得到的参数作为参照指标,用动力学方法外推到地质实际中,可准确地提出适合我国的碳酸盐岩生烃定量模型,能为碳酸盐岩的资源评估等方面给出定量数值,从而为有效烃源岩的定量评价提供一种新的方法和途径.