Structures of micas synthesized at high pressures and temperatures

Thermal karst, exposed in mine shafts, has been significantly developed in the commercial stratum of oil shales. Geochemical investigations in this karst have for the first time established the secondary changes in the kerogen of the oil shales, namely, an anomalous content of bituminoid A + C, the presence of processes of aromatization, the significant amount of hydrocarbon compounds and humic acids, and changes in the elemental composition of the residual organic matter (in particular, an increase in the C/H ratio). The secondary changes suggest that a favorable geochemical and thermobaric environment existed in the thermal karst for intense bitumen formation. The results obtained are of interest in the study of the kerogen of oil shales as a possible parental source for oil and gas. —Authors.     

Anatomy and origin of a Cretaceous phosphorite-greensand giant, Egypt

Late Cretaceous epicontinental phosphorites, porcelanites/cherts, dark-coloured shales, glauconitic sandstones and bioclastic and fine-grained carbonate rocks in Egypt are examined in terms of their overall depositional and diagenetic framework and stable isotopic and organic geochemical characteristics. Two main depositional realms are interpreted and correlated through sequence stratigraphic analysis: (1) a shallow hemipelagic environment accompanying initial stages of marine transgression and conducive to the formation of organic carbon-rich shales, biosiliceous sediments and thick phosphorites, and (2) a relatively high energy depositional regime accompanying sea-level fall during which deltas advanced, glauconites were reworked seaward and prograding oyster banks became periodically exposed to episodes of fresh water diagenesis, thereby promoting solution-collapse phenomena in associated cherts. Lenticular to massive phosphorites are viewed as the result of current winnowing and concentration of authigenic grains initially precipitated in associated reducing shales and biosiliceous sediments. In eastern Egypt the phosphorites form winnowed lag layers, some of which may have been redeposited down slope in structural lows. In the west, these sands were concentrated into giant phosphorite sand waves built by reworking of penecontemporaneously deposited phosphatic muds during marine transgression. Carbon isotopic results substantiate interpretations from modern deposits for limitation of phosphate mineral precipitation with depth in sediments as a result of lattice poisoning. However, direct desorption of phosphorus to pore waters from detrital iron-oxyhydroxide phases also may have been important in the Cretaceous setting, the iron reduced in this process being available for incorporation in glauconites. The main locus for authigenic glauconite precipitation appears to be where iron fluxes from regions of lateritic weathering were highest and near the boundary between oxygenated and reduced waters. This study suggests a model for the common coexistence of glauconites and phosphorites in the geological record. Although upwelling is often advocated as the origin of nearly all giant phosphorite deposits, we suggest that some of these may have been strongly influenced by fluvially derived phosphorus borne on particulates and desorbed from these compounds upon flocculation and/or reduction in bottom waters or pore waters.     

Pyrite Formation in Organic-rich Clay, Calcitic and Coal-Forming Environments

The early diagenetic characteristics of pyrite formation processes in a Miocene freshwater sequence of mixed sediments （coal fragments in clays, sandstones or shales） alternating with continuous brown coal layers was investigated. Based on abundant minerals, the following main sedimentary environments were distinguished： the illite-montmorillonitic （I-M）, calcitic （Ct） and coal-forming environment （CL）. For these hydrogeochemically differing environments the effects of limiting factors on the pyrite formation process （availability of sulphate and Fe, amount of organic matter and participation of organic sulphur） were assessed by correlation analysis. Significant differences in the effects of these limiting factors in the particular environments were observed. These differences were explained taking in account the different oxidative activity, Fe-complex and surface complex forming properties of humic substances in dependence of pH of environment and the abundance of sorptionally active clay minerals. In environments having a relatively low pH and containing clay minerals （I-M- and CL-environments） the oxidative activity of humic substances （Hs） on pyrite precursors was greatly prevented however pyrite formation depended on reactive Fe availability as the consequence of complex formation. On the contrary, in environments with a relatively high pH, as it was the calcitic, the oxidative activity of Hs was greatly enhanced, thus oxidizing the sulfur precursors of pyrite. The oxidation degree of organic matter was probably also a consequence of the differing activity of the humic electron-acceptors.     

Factors controlling the burial of organic carbon in laminated and bioturbated sediments off NW Mexico: implications for hydrocarbon preservation

Factors controlling the burial of organic carbon (OC) in Late Quaternary sediments on the NW Mexican continental margin are assessed using a suite of box and piston cores strategically located on the shelf-slope rise with respect to the intense oxygen minimum in this region. An OC concentration maximum occurs on the mid-slope, below the core of an intense water-column O₂ minimum, due to current winnowing on the outer shelf, the preferential accumulation of organic matter in fine-grained deposits, and the offshore decrease in the settling flux of organic detritus. The organic matter at all water depths is overwhelmingly marine. Hydrogen indices (HI) are higher on the slope (>300 mg HC/g TOC) than on the shelf (<300 mg HC/g TOC), where current winnowing has promoted organic matter degradation, but there is no difference in HI in slope sediments accumulating under well oxygenated and O₂-deficient conditions. The degree of winnowing appears to be the primary factor affecting the preservational quality of organic matter deposited on this margin.Rates of accumulation of OC and opal are all higher in the interglacial intervals when compared with the glacial deposits over the last 140,000 yr. However, matrix-corrected HI values in the mid- and lower-slope cores are invariant and are similar to values in the laminated intervals from the oxygen-minimum site. Thus, cyclic changes in organic carbon accumulation on this margin have been controlled by production variations rather than differential preservation. HI values in Late Quaternary sediments from several continental margins, including NW Mexico, and euxinic basins correspond to type II kerogen, irrespective of bottom water O₂ concentrations. Therefore, the preservation of oil-prone kerogen in productive margin settings does not appear to be restricted to sediments deposited under conditions of low bottom water O₂ concentrations as envisioned in models of petroleum source-rock deposition.     

Phosphate-rich sedimentary rocks: Significance for organic facies and petroleum exploration

Phosphorus-bearing rocks and sediments can be divided into two genetically distinct classes: phosphatic shales or limestones and phosphorites. Phosphatic shales are primary sediments in which phosphate nodules or micronodules have formed diagenetically by precipitation of calcium phosphates derived mainly from organic phosphorus. The nodules form in reducing environments at shallow depths within the sediments, where loss of phosphate by diffusion to the overlying water column is minimized. Highly biogenic sediments containing large amounts of organic matter and some fine clastic debris provide ideal environments for the formation of phosphate nodules.Phosphorites, in contrast, represent concentrated accumulations of reworked phosphate nodules which originated in phosphatic shales or limestones. Currents, wave action, recrystallization, and erosion and resedimentation are important mechanisms in the concentration process.Phosphatic shales and limestones may become excellent oil source rocks if thermal maturity is achieved. They are useful facies indicators for anoxic or nearly anoxic depositional environments, and are often associated with restricted basins, or, during certain geologic periods, with broad shelves developed during transgressions. Phosphorites, in contrast, are often correlated with sea-level regressions or uplifts. They are modest source rocks because of their low organic carbon contents and the fact that they were reworked under oxidizing conditions. Nevertheless, because phosphorites are derived from, and often grade into, phosphatic shales, they also are of potential utility in the search for oil source beds.     

Paleoenvironments and origin of the sedimentary phosphorites of the Napo Formation (Late Cretaceous, Oriente Basin, Ecuador)

The Napo phosphorites were deposited at the edge of a stable marine shelf during the Upper Cretaceous (Coniacian) oceanic anoxic event (OAE 3) at the transition from bioclastic limestone to organic-rich shale facies. Phosphogenesis was triggered in the shelf margin environment by a number of factors including strong upwelling currents, high biological activity, plankton blooms, and large amounts of organic matter production and subsequent accumulation. Dissolved phosphate levels increased in the sediment from a combination of anoxic conditions and microbial activity. Once dissolved phosphate concentrations were high enough, apatite began to form around nucleic sites including mineral grains, shells, wood fragments, and foraminifera tests forming peloidal fluorine rich carbonate fluoroapatite (francolite). As the peloids formed, sedimentation continued and dissolved phosphate concentrations diminished. A period of minor winnowing ensued, and as dissolved phosphate concentrations remained low, shale layers were deposited separating the various phosphate layers.     

Hydrocarbon source rock potential evaluation of the Late Paleocene Patala Formation,Salt Range,Pakistan: Organic geochemical and palynofacies approach

Organic geochemical and palynofacies analyses were carried out on shale intervals of the Late Paleocene Patala Formation at Nammal Gorge Section, western Salt Range, Pakistan. The total organic carbon content and Rock-Eval pyrolysis results indicated that the formation is dominated by type II and type III kerogens. Rock-Eval \({T}_{\mathrm{max}}\) vs. hydrogen index (HI) and thermal alteration index indicated that the analysed shale intervals present in the formation are thermally mature. \(S_{1}\) and \(S_{2}\) yields showed poor source rock potential for the formation. Three palynofacies assemblages including palynofacies-1, palynofacies-2 and palynofacies-3 were identified, which are prone to dry gas, wet gas and oil generation, respectively. The palynofacies assessment revealed the presence of oil/gas and gas prone type II and type III kerogens in the formation and their deposition on proximal shelf with suboxic to anoxic conditions. The kerogen macerals are dominated by vitrinite and amorphinite with minor inertinite and liptinite. The kerogen macerals are of both marine and terrestrial origin, deposited on a shallow shelf. Overall, the dark black carbonaceous shales present within the formation act as a source rock for hydrocarbons with poor-to-moderate source rock quality, while the grey shales act as a poor source rock for hydrocarbon generation.     

Carbon isotopes of organic matter from the upper Jurassic oil shales from the Volgian-Pechora shale province and its accumulation mechanisms

The isotopic composition of carbon from the organic matter of late Jurassic oil shales from the Volgian-Pechora shale province is studied. The existence of a dependence between C_org content in the rock and the isotopic composition of kerogen carbon is ascertained. The content of the heavy carbon isotope increases with increasing C_org. This dependence is accounted for by the progressive accumulation of isotopically heavy hydrocarbons of the initial organic matter due to sulfurization. The data on the isotopic composition of individual n-alkanes of bitumen in the rocks and the data on the absence of isotopic fractionation between thermobitumen and the residual kerogen from oil shales from the Volgian-Pechora shale province obtained by treating shale in an autoclave in the presence of water are presented first in this paper.     

Organic matter and trace elements in Precambrian rocks from South Africa

Precambrian cherts from the Fig Tree and Onverwacht groups of South Africa contain unusually high concentrations of chromium and nickel. The organic carbon content of these cherts (0.02–1.58%) shows a considerable variation with a maximum abundance in the Onverwacht group. Atomic H/C ratios (0.08–1.38) of the associated organic matter (kerogen) support the suggestion that the carbon isotopic values of kerogen have not been isotopically enriched by metamorphic processes. Chemically bound alipathic structures amount to about 10% by weight of the organic carbon content of a chert from the lowermost Theespruit succession.     

Comparative studies of organic matter petrography of the late palaeozoic black shales from Southwestern Poland

There are at least two sapropelic units associated with Late Palaeozoic black shales in Central Europe. The older unit, of Late Carboniferous age, is the lower part of the Anthracosia Shales in the Intrasudetic Basin, and the younger one is the well-known Zechstein Kupferschiefer in both the Foresudetic Monocline and the Northsudetic Basin. The first unit is of lacustrine origin, while the second one represents deposition in a shallow marine depositional environment. Both units contain high amounts of organic matter, thus being typical black shales.The organic matter dispersed in these shales was studied petrographically. In general, the vitrinite reflectance of the shales studied indicates variable, but moderate organic matter maturity (0.68–1.25%), equivalent to the oil window. Detailed microscopic studies of the organic material dispersed in the lower unit of the Anthracosia Shales showed that liptinite, especially alginite is the most abundant component. Secondary altered organic matter, i.e. solid hydrocarbons, rarely occurs. Organic components together with mineral matter constitute a lacustrine sapropelic association, a humic (terrestrial) association and an intermediary association. The character and predominance of alginite and lacustrine sapropelic association are indicative of an open-lacustrine depositional environment. In general, this organic composition is typical of type I kerogen.Microscopic analysis of the Kupferschiefer revealed a mixture of liptinite, vitrinite and inertinite macerals, and other organic components such as amorphous sapropelic mass (ASM) and solid bitumens. The most common organic components are liptinite macerals. Bituminite and alginite predominate, and are diagnostic macerals of this unit. The amount of bituminite locally exceeds 85 vol.%. Other liptinite macerals such as sporinite and liptodetrinite, are present in significantly lower amounts, one exception being ASM, which may be present in higher amounts. Humic constituents (vitrinite and inertinite) are rare, present in small amounts in the Kupferschiefer beds. The organic matter composition points to type II kerogen for this unit.     

Geochemical and petrographic characterization of organic matter in the Upper Jurassic Madbi shale succession (Masila Basin,Yemen): Origin,type and preservation

The Upper Jurassic Madbi Formation, located in the Masila Basin, eastern Yemen, represents the major source rock in this basin. Organic rich shales from two oilfields (Kharir and Wadi Taribah) were analysed to evaluate the type and origin of the organic matter and to determine the factors controlling its deposition. This study is based on geochemical analyses of whole rock (total organic carbon content, Rock-Eval pyrolysis and carbon isotope data) and petrographic analyses on organic matter (kerogen maceral composition and palynofacies) by optical and scanning electron microscopy. Organic petrographic composition of kerogen shows that the Madbi shale is characterized by high amounts of organic matter, consisting predominantly of yellow fluorescing amorphous organic matter and alginite of marine origin. Terrigenous organic materials such as vitrinite, spores and pollen are present in low quantities. The predominance of marine plankton, as indicated by visual kerogen analysis, is consistent with reported carbon isotopic values. It appears that the high amounts of organic matter in the Madbi shale succession might be mainly due to good preservation under suboxic–anoxic conditions. Consequently the Madbi shales possess very good petroleum generative potential, owing to high content of hydrogen rich Type II and I oil prone kerogen.     

Algal bloom episodes and the formation of bituminite and micrinite in hydrocarbon source rocks: evidence from the Devonian and Mississippian, northern Williston Basin, Canada

Organic petrology (incident light microscopy) of Middle Devonian inter-reef laminates and Devonian-Mississippian epicontinental black shales, Williston Basin, Canada, indicates that algal bloom episodes and consequential bacterial activity played a significant role in the accumulation of amorphous, bituminite III-rich organic microfacies. Corpohuminite-like algal akinete cells produced by filamentous algae during algal bloom periods are persistent maceral inclusions within the potential hydrocarbon source rock intervals. These cells (%R_{o mean} range 0.24-0.90) are regarded as positive indicators of stressful palaeoenvironmental conditions. Unicellular Tasmanites and Leiosphaeridia marine alginite and variably degraded alginite remnants (“ghosts”) within the amorphous kerogen may be products of cell lysis, photo-oxidation and microbial alteration; these processes are characteristic of algal bloom periods. Minute (ca. 1 μm) spheroidal and coccoidal bacteria-like macerals are dispersed throughout the bituminite III network, attesting to the importance of microbial activity within the water column and sediment during and after organic matter accumulation. Dispersed granules, laminations and replacement textures of micrinite-like macerals within bituminite III are interpreted as remnants of microbial alteration rather than a residual product of thermal maturation and hydrocarbon generation.     

柴达木盆地北缘侏罗系大煤沟组7段油页岩低放射性控制因素

以探讨柴达木盆地北缘侏罗系大煤沟组7段(J2d7)油页岩低放射性的控制因素为目的,选取鱼卡地区典型井目的层段的油页岩和暗色页岩为研究对象,结合测井资料及含油率、有机地球化学、X射线衍射、元素地球化学等岩心测试分析资料,对二者的组构、水体介质条件、放射性物质供给特征及其与岩石放射性的关系进行详细对比分析。结果表明：与暗色页岩段相比,油页岩整体具有低的自然GR值,具有高的含油率、有机质丰度及沉积期还原性较强水体介质条件,具有较低的黏土矿物含量及沉积期母岩区较弱的风化程度。初步分析得出,有机质富集及贫氧水体介质条件对于区内油页岩的低放射性无明显影响,而古气候条件由温湿到逐步干热,导致陆源黏土矿物及放射性物质输入有限是油页岩低放射性形成的关键。     

Thermal alteration experiments on organic matter from recent marine sediments in relation to petroleum genesis

Three fractions of organic matter: lipid (benzene:methanol-extractable), humic acid (alkali-extractable) and kerogen (residue) were extracted from a young marine sediment (Tanner Basin, offshore southern California) and heated for different times (5–116 hr) and temperatures (150°–410°C). The volatile (gases) and liquid products, as well as residual material, were then analyzed. On a weight basis, the lipid fraction produced 58% of the total identified n-alkanes, the kerogen fraction 41%, and the humic acid <1%. Whereas n-alkanes produced from lipid show a CPI > 1.0, those produced by thermal alteration of kerogen display a CPI < 1.0. The volatiles produced by heating the lipid and humic acid fractions were largely CO₂ and water, whereas those produced from heated kerogen also included methane, hydrogen gas and small amounts of C₂–C₄ hydrocarbons. A mechanism for hydrocarbon production due to the thermal alteration of organic constituents of marine sediment is discussed.     

A biomarker and δ15N study of thermally altered Silurian cyanobacterial mats

Early Silurian cherts from the Holy Cross and Bardzkie Mountains (Poland) contain abundant microfossils morphologically resembling contemporary cyanobacteria. Most of the organic matter preserved in the cherts is highly mature and extensively degraded because of biological decomposition and progressive thermal alteration. These processes may have changed the original morphology of the deposited microbial remains, so the microfossil origin could be easily misinterpreted. The cherts were therefore examined using organic geochemical and stable isotope techniques to provide support for the presence of cyanobacterial remains. The nitrogen isotopic composition of bulk sediments and extractable organic matter ranged from +0.1‰ to ?2.2‰ and from +1.8‰ to ?1.7‰, respectively. The δ¹⁵N values are thus in good agreement with a contribution of diazotrophic cyanobacteria for both locations. Biomarkers in the Holy Cross Mts. cherts included mid-chain branched monomethyl alkanes, indicative of a cyanobacterial contribution. However, molecular fossils of a cyanobacterial origin were not detected in the Bardzkie Mts. cherts, most likely because of the greater maturity than those from the Holy Cross Mts.     

柴东欧南凹陷石炭系烃源岩有机质富集的影响因素

柴达木盆地东部地区欧南凹陷是石炭系油气运聚成藏的有利构造单元,具有一定勘探潜力,但对有机质富集机理认识不清导致对优质烃源岩分布的预测缺乏有效指导,制约了油气勘探进程.基于地球化学分析、XRD、SEM等分析测试,对石炭系烃源岩矿物组分、 有机质丰度、 干酪根类型、 热演化程度、 形成环境、TOC与主要矿物关系等进行了综合...     

Sourcing sedimentary cherts with archaeological use through the combination of chromatographic and spectroscopic techniques

The nature and distribution of organic matter in geological cherts of archaeological use can serve to estimate the sources and origins of some remains of lithic industry. For example, organic and biomarker analysis can provide information to allow a deeper insight into source catchment areas, artefact displacement or the way in which the artefacts were employed. In this work, soluble (bitumen) and insoluble (kerogen) organic matter were isolated from several chert samples with different depositional history and analysed by means of gas chromatography–mass spectrometry (GC–MS) and spectroscopic techniques such as infrared and Raman spectroscopy. Chemometric treatment of the results allowed observation of differences between organic matter content on the basis of the depositional setting of the cherts. Samples with a continental deposition seemed to preserve more organic matter with little alteration. The hydrocarbon profiles of these samples were dominated by high molecular weight n-alkanes, alkylcyclohexanes and isoprenoid groups which allowed distinguishing them from the rest of the analysed samples.     

Geochemistry of basal Cambrian black shales and cherts from the Northern Tarim Basin,Northwest China: Implications for depositional setting and tectonic history

Black shales and thin-bedded cherts in the basal Cambrian are widespread worldwide and they carry important information on the formation of sedimentary basins and on the tectonic history. We studied the geochemical signatures of the early Cambrian black shales and bedded cherts from the Northern Tarim Basin, China, with the objectives of understanding the depositional setting of these rocks and inferring the tectonic history in the region. Twenty two black shales, ten cherts, and two nodular phosphorites were collected from two outcrops at Xiaoerbulake and Sugaitebulake in the Northern Tarim Basin, spanning vertical sections of 8.8 and 7.5 m, respectively. A suite of techniques, including field investigations, X-ray diffraction, electron microscopy, trace element, rare earth element (REE), and isotope geochemistry, were employed to characterize the geochemical signatures of these rocks. Field evidence indicates that the black shales and bedded cherts are over- and underlain by dolomites, suggesting a shallow marine depositional environment. Mineralogical and trace element data suggest that the Tarim black shales and cherts were deposited in a suboxic continental shelf environment, and hydrothermal activity may have extracted certain trace elements from mafic continental crust and concentrated them in the sedimentary basin. REE characteristics for the cherts are very similar to those that are known to be deposited in pelagic ocean floor settings, suggesting that the hydrothermal fluids may be derived from the infant southern Tianshan Ocean in the north of the Tarim Basin. Os isotope signatures at the time of deposition (¹⁸⁷Os/¹⁸⁸Os_i = 1.1–2.7) are typical of crustal signatures, and the radiogenic Os isotope signatures rule out the mantle as a possible source of Os and other metals. A positive correlation between ¹⁸⁷Os/¹⁸⁸Os and ε_Nd is consistent with upper crust-derived basin sediments that contain a variable contribution of hydrothermal fluids possibly derived from ancient mafic continental crust. These trace element, REE, and isotope systematics collectively suggest that incorporation of hydrothermal fluids derived from ancient, mafic continental crust combined with deposition in relatively reducing conditions may have controlled the chemical and isotopic compositions of these rocks. We infer that the hydrothermal fluid was carried to the continental shelf by upwelling during the initial stages of formation of the southern Tianshan Ocean, where the fluid interacted with thinned, mafic crustal basement lithologies and was subsequently incorporated into the black shales and bedded cherts in the Northern Tarim Basin. This study provides important geochemical evidence for the creation of the Tianshan Ocean, which is a result of break-up of the Rodinia Supercontinent during the early Cambrian.     

北部湾盆地流二段油页岩地球化学特征及成因

北部湾盆地涠西南凹陷和乌石凹陷流二段普遍发育油页岩。有机地球化学分析表明,北部湾盆地流二段油页岩具有高的有机质丰度,油页岩的有机碳含量下限为3%,含油率介于3.5%~10%,达到中等和优质油页岩矿品级,同时属于优质烃源岩。全岩有机显微组分、干酪根镜检和热解等分析表明,北部湾盆地流二段油页岩藻类含量丰富,藻类是有机质的主要来源,有机质类型主要为腐殖—腐泥型,部分为腐泥型,以湖相腐殖—腐泥型油页岩为主,部分为湖相腐泥型油页岩。流二段油页岩中镍和钼等微量元素含量普遍较高,镍和钼的含量与有机碳含量之间存在很好的正相关关系,说明流二段油页岩形成时期北部湾盆地具有富营养湖泊特征。北部湾盆地流二段油页岩中还原硫含量高,普遍大于1%,流二段油页岩形成于还原的沉积环境,具有很好的有机质保存条件。高有机质生产力及湖侵体系域顶部和高位体系域底部的中深湖还原环境共同控制了北部湾盆地流二段油页岩的发育。