Elemental profile of black shales

A black shale sample collected from the Chimiari site(Tarbela) was analyzed for elemental contents.Inductively coupled plasma-optical emission spectrometry(ICP-OES) was employed to determine major and trace elements in the digests.Precise analysis was accomplished for the black shales,which was better than 2.0%.Result shows that the shales are very rich in Ca(25439 μg·g-1),Fe(13933 μg·g-1),Ti(6932 μg·g-1),Al(5993 μg·g-1) and K(2730 μg·g-1).     

Organic geochemistry and petrography of Lower Cretaceous Wealden black shales of the Lower Saxony Basin: The transition from lacustrine oil shales to gas shales

Ninety-seven Wealden black shale samples from three wells in the Lower Saxony Basin have been studied by organic geochemical and organic petrographical methods to determine their maturity, organic facies and depositional environment. The maturities of the three wells range from early mature (Ex-A), late to postmature (Ex-C) to overmature (Ex-B) as determined by vitrinite reflectance measurements, diamondoid ratios and other geochemical maturity parameters. Ex-C and Ex-B show distinct petrographic features related to oil generation and migration. In particular, the occurrence of dispersed solid bitumen replacing initial type I kerogen suggests a formerly active petroleum system. Structural and textural differences between early mature alginites and solid bitumen in postmature to overmature samples show an alteration of the pore system with increasing maturity. A freshwater depositional environment is indicated by widespread occurrence of botryococcus algae and other small alginite particles predominating in the immature well. These alginites are absent in the more mature gas shales of wells Ex-C and Ex-B. Geochemical evidence of algae and phytoplankton in general is provided by numerous biomarker parameters, while the occurrence of β-carotane in some samples indicates events of increased salinity, although no hypersaline conditions are inferred due to very low gammacerane indices. Increased amounts of vitrinite and inertinite in samples of Ex-B suggest locally significant terrigenous input of organic matter for some periods during Wealden Shale deposition. High sulfur/organic carbon ratios provide evidence for sulfate rich waters and (partly) anoxic bottom water conditions. While the lower mature lacustrine source rocks generate paraffinic/waxy oils, gas and condensates are produced at post-mature stages. Furthermore, maturity distribution maps from 3D numerical petroleum systems modeling reveal substantial differences in respect to petroleum generation.     

De-A-steroids in immature marine shales

Three series of de-A-diasterenes have been observed in a variety of immature marine shales. Two of them have been identified by comparison with authentic standards and the structures of the third assigned by extrapolation. The greater complexity in the number of series compared with diasterenes indicates that the ring A degradation occurred to differing extents. The rate of C-20 diagenetic isomerisation in the de-A-diasterenes proceeds at a similar rate to that in diasterenes. Two series of B-ring monoaromatic de-A-steroid hydrocarbons have also been found. Comparison with the B-ring monoaromatic anthrasteroids indicates that the de-A-compounds are 14α(H) and 14β(H) isomers. Diagenetic isomerisation of the 14α(H) isomers to the more stable 14β(H) isomers occurs at a rate similar to that in the B-ring monoaromatic anthrasteroid series.     

Low-temperature gas from marine shales

Thermal cracking of kerogens and bitumens is widely accepted as the major source of natural gas (thermal gas). Decomposition is believed to occur at high temperatures, between 100 and 200°C in the subsurface and generally above 300°C in the laboratory. Although there are examples of gas deposits possibly generated at lower temperatures, and reports of gas generation over long periods of time at 100°C, robust gas generation below 100°C under ordinary laboratory conditions is unprecedented. Here we report gas generation under anoxic helium flow at temperatures 300° below thermal cracking temperatures. Gas is generated discontinuously, in distinct aperiodic episodes of near equal intensity. In one three-hour episode at 50°C, six percent of the hydrocarbons (kerogen & bitumen) in a Mississippian marine shale decomposed to gas (C₁–C₅). The same shale generated 72% less gas with helium flow containing 10 ppm O₂ and the two gases were compositionally distinct. In sequential isothermal heating cycles (~1 hour), nearly five times more gas was generated at 50°C (57.4 μg C₁–C₅/g rock) than at 350°C by thermal cracking (12 μg C₁–C₅/g rock). The position that natural gas forms only at high temperatures over geologic time is based largely on pyrolysis experiments under oxic conditions and temperatures where low-temperature gas generation could be suppressed. Our results indicate two paths to gas, a high-temperature thermal path, and a low-temperature catalytic path proceeding 300° below the thermal path. It redefines the time-temperature dimensions of gas habitats and opens the possibility of gas generation at subsurface temperatures previously thought impossible.     

The fissility of some Carboniferous shales

Laminations control the fissility of a sequence of shales and mudstones from the Upper Carboniferous Coal Measures in Britain. This was established by measuring the thickness of pairs of laminations in unweathered borehole material and comparing with the thickness of shale fragments at the outcrop of the same sequence. The parallel orientation of the clay minerals is not responsible for the fissility and it could be that its importance has been overestimated. The processes responsible for the formation and preservation of the laminations will also produce a well orientated clay fabric and hence fissility and clay orientation may be indirectly related.     

The provenance of low-calcic black shales

The elemental concentration of sedimentary rocks depends on the varying reactivity of each element as it goes from the source through weathering, deposition, diagenesis, lithification, and even low rank metamorphism. However, non-reactive components of detrital particles ideally are characteristic of the original igneous source and thus are useful in provenance studies. To determine the source of detrital granitic and volcanic components of low-calcic (<1% CaCO₃) marine black shales, the concentrations of apparently non-reactive (i.e. unaffected by diagenetic, redox and/or low-rank metamorphic processes) trace elements were examined using standard trace element discrimination diagrams developed for igneous rocks. The chemical data was obtained by neutron activation analyses of about 200 stratigraphically well-documented black shale samples from the Cambrian through the Jurassic. A La-Th-Sc ternary diagram distinguishes among contributions from the upper and bulk continental crust and the oceanic crust (Taylor and McLennan 1985). All the low-calcic black shales cluster within the region of the upper crust. Th-Hf-Co ternary diagrams also are commonly used to distinguish among the upper and bulk continental crust and the oceanic crust (Taylor and McLennan 1985). As Co is redox sensitive in black shale environments, it was necessary to substitute an immobile element (i.e. example Rb) in the diagram. With this substitution of black shales all cluster in the region of the upper continental crust. To determine the provenance of the granitic component (Pearce et al. 1984), plots of Ta vs Yb and Rb vs Yb + Ta shows a cluster at the junction of the boundaries separating the volcanic arc granite (VAG), syn-collision granite (syn-COLG), and within-plate granite (WPG) fields. The majority fall within the VAG field. There are no occurrences of ocean ridge granite (ORG). The minimal contribution of basalts to marine black shales is confirmed by the ternary Wood diagram Th-Hf/3-Ta (Wood et al. 1979). The black shales plot in a cluster in a high Th region outside the various basalt fields, which suggests contribution from the continental crust.     

Adsorption of xenon and krypton on shales

Parameters for the adsorption of Xe and Kr on shales and related samples have been measured by a method that uses a mass spectrometer as a manometer. The gas partial pressures used were 10^?11 atm or less; the corresponding adsorption coverages are only small fractions of a monolayer, and Henry's Law behavior is expected and observed. Heats of adsorption in the range 2–7 kcal/mol were observed. Henry constants of the order of magnitude 1 cm³ STP g^?1 atm^?1 at 0 to 25°C are obtained by extrapolation.Adsorption properties are variable by sample, but the general range suggests that shales might be sufficiently good adsorbents that equilibrium adsorption with modern air may account for a nontrivial fraction of the atmospheric inventory of Xe (perhaps even Kr). It seems doubtful, however, that this effect can account for the deficiency (approximately a factor of 25) of atmospheric Xe in comparison with the planetary gas patterns observed in meteorites. If gas is adsorbed on interior surfaces in shale clays and can communicate with sample exteriors only through very narrow (10^?7 to 10^?6 cm) channels, and thus only very slowly, equilibrium adsorption may make substantial contributions to experimentally observed ‘trapped’ gases without the need for any further trapping mechanism.     

Porphyrin geochemistry of Atlantic Jurassic-Cretaceous black shales

Late Jurassic-early Cretaceous black shales and an overlying sequence of Albian-Campanian zeolitic claystones from the Falkland Plateau (DSDP/IPOD Leg 71, Site 511) were analyzed for tetrapyrrole pigment type and abundance. The “black shale” sequence was found to be rich in DPEP-series dominated free-base, nickel (Ni) and, to a lesser extent, vanadyl (V = 0) porphyrins. A low level of organic maturity (i.e. precatagenesis) is indicated for these strata as nickel chelation by free-base porphyrins is only 50–75% complete, proceeding down-hole to 627 meters sub-bottom. Electronic and mass spectral data reveal that the proposed benzo-DPEP (BD) and tetrahydrobenzo-DPEP (THBD) series are present in the free-base and Ni species, as well as the more usual occurrence in V = 0 porphyrin arrays. Highly reducing conditions are suggested by an abundance of the PAH perylene, substantial amounts of the THBD/BD series and a redox equilibrium between free-base DPEP and 7,8-dihydro-DPEP series, which exist in a 7:1 molar ratio. The Albian-Campanian claystone strata were found to be tetrapyrrolepoor, and those pigments present were typed as Cu/Ni highly dealkylated (C₂₆ max.) etioporphyrins, thought to be derived via redeposition and oxidation of terrestrial organic matter (OM). Results from the present study are correlated to our past analyses of Jurassic-Cretaceous sediments from Atlantic margins in an effort to relate tetrapyrrole quality and quantity to basin evolution and OM sources in the proto-Atlantic.     

Important geological properties of unconventional resource shales

The revelation of vast global quantities of potentially productive gas and oil-prone shales has led to advancements in understanding important geological properties which impact reservoir performance. Based upon research on a variety of shales, several geological properties have been recognized as being common and important to hydrocarbon production. (1) transport/depositional processes include hemipelagic ‘rain’, hyperpycnal flows, turbidity current flows, tempestites, wave-reworking, and contour currents in both shallow and deep water settings. (2) Common shale minerals include clays, quartz, calcite, dolomite, apatite, and pyrite; organic constituents include spores (Tasmanites), plant remains, biogenic quartz and calcite, and arenaceous foraminifera. (3) Porosity and permeability are characteristically low with pore sizes ranging down to the nanoscale. Main pore types include intergranular (including pores within clay floccules), porous organic matter, porous fecal pellets, and microfractures. (4) Important geochemical characteristics include organic richness (>3%), maturity (>1.1%Ro for shale gas and 0.6–0.9% for shale oil) and type (I–IV), in addition to certain biomarkers which are indicators of bottom water oxicity during deposition. Remaining hydrocarbon potential [RHP = (S1 + S2)/TOC] also reflects temporal environmental changes. ‘Isotopic reversals’ can be used to detect best producing areas in shale-gas plays. (5) Lithofacies stacking patterns and sequence stratigraphy are the result of eustatic depositional history. A general sequence stratigraphic model is presented here that highlights this commonality. (6) Geomechanical properties are key to drilling, fracturing and production of hydrocarbons. Brittle-ductile couplets at several scales occur in shale sequences. (7) Geophysical properties, when calibrated to rock properties, provide a means of regionally to locally mapping the aforementioned properties. (8) Economic and societal considerations in the exploration and development of resource shales are garnering attention. Many potentially economic shale-gas and shale-oil plays are being identified globally. Risks and uncertainties associated with gas- and oil-rich shales include the lack of long-term production histories, environmental concerns related to hydraulic fracturing, uncertainty in calculating hydrocarbons-in-place, and fluctuations in supply, demand, and price.     

页岩孔隙结构研究进展及下扬子古生界页岩孔隙特征

天然气可以吸附或以游离态赋存在富有机质泥页岩及其夹层中,使页岩成为一种重要的非常规储集体。页岩的微米—纳米级孔隙是页岩气富集的重要场所,常规孔隙研究手段难以适用,目前,国际上尚没有关于页岩孔隙类型的统一分类方案。因此,页岩的孔隙结构特征成为页岩气勘探开发中的关键问题。总结近年来页岩孔隙结构的主要研究手段和分类,并初步分析了浙西—皖南下扬子地区古生界页岩的孔隙特征。     

An NMR survey of United States oil shales

Solid state nuclear magnetic resonance techniques were used to measure the fraction of aliphatic carbon in oil shales from United States deposits, ranging in age from Ordovician to Tertiary. The aliphatic carbon fraction was shown to correlate with the fraction of organic matter converted to oil during Fischer assay. The fraction of organic matter convertible to oil is a primary factor in evaluating the oil potential of an oil shale resource. Nuclear magnetic resonance determines this in a nondestructive, easily interpreted bulk analysis of the whole rock.     

中国潜质页岩形成和分布

我国页岩盆地发育的大地构造背景复杂,板块规模偏小且地质活动性较强,彼此之间相互影响且在中、新生代以来受外缘板块环境影响较大,表现为南海北陆、南早北晚、南升北降等重大差异,在东西方向上,也由于塔里木与华北板块之间的演变差异而出现较大区别。中国页岩的分布主要受控于板块特点及构造、沉积之间的相互匹配,板块及其相互之间的相对运动造成了不同时代沉降沉积中心的迁移变化。塔里木、华北、华南三个板块均发生了四次沉降沉积中心的转移,但总体上表现为早古生代海相时期的由东向西转移、晚古生代海陆交互相时期的背离板块汇聚中心式转移、中生代陆相和海陆交互相时期的由东向西转移、新生代陆相时期的由西向东转移。潜质页岩及页岩气主要发育在中部地区,具有时代交替、南海北陆、东西分异、时空变迁等特点。南方下古生界海相页岩气原始地质条件优越,但有机质热演化程度高且后期改造强,页岩气的有利区分布既受控于构造与沉积条件,也更决定于构造与沉积两者的相互匹配;晚古生代为主的海陆交互相页岩分布范围广、累积厚度大,常与砂岩、煤系及灰岩频繁互层,有机质热演化程度较为适中,是我国页岩气进一步勘探开发的重要目标层系。北方以中新生代陆相为代表的页岩分布受控于盆地结构,是我国页岩油发育的主体区域。针对各套潜质页岩特点,页岩气勘探宜分别考虑。     

A numerical compaction model of overpressuring in shales

A one-dimensional model of sediment compaction is presented to relate pressure, porosity, permeability, and fluid and solid-particle velocities in an evolving sedimentary basin. The burial history of a sedimentary package is followed and incorporated into rate models for diagenetic reactions to predict clay compositions with depth. The governing set of nonlinear, partial differential equations constitutes a moving boundary problem and is solved by a finite difference scheme. Sedimentation rates and a permeability-porosity function for shales are required to implement the model. Additional factors are incorporated to mimic the effect of increased fluid volume generated by dehydration from clay mineral transformations and by thermal expansion. We demonstrate that the major cause of overpressuring in sediments accumulating along passive margins is nonequilibrium compaction. Sedimentation rates and strata permeability are the most important geologic factors in the formation of overpressured zones. Smectite dehydration and aquathermal pressuring play secondary roles in the development and sustenance of overpressures.     

Oil shales,evaporites and ore deposits

The relationships between oil shales, evaporites and sedimentary ore deposits can be classified in terms of stratigraphic and geochemical coherence. Oil shale and black shale deposition commonly follows continental red beds and is in turn followed by evaporite deposition. This transgressive-regressive sequence represents an orderly succession of depositional environments in space and time and results in stratigraphic coherence. The amount of organic carbon of a sediment depends on productivity and preservation, both of which are enhanced by saline environments. Work on Great Salt Lake. Utah, allows us to estimate that only 5% of TOC originally deposited is preserved. Inorganic carbonate production is similar to TOC production, but preservation is much higher.Oil shales and black shales commonly are enriched in heavy metals through scavenging by biogenic particles and complexation by organic matter. Ore deposits are formed from such rocks through secondary enrichment processes, establishing a geochemical coherence between oil shales and ore deposits. The Permian Kupferschiefer of N. Europe is used as an example to define a Kupferschiefer type (KST) deposit. Here oxygenated brines in contact with red beds become acidified through mineral precipitation and acquire metals by dissolving oxide coatings. Oxidation of the black shale leads to further acid production and metal acquisition and eventually to sulfide deposition along a reducing front. In order to form ore bodies, the stratigraphic coherence of the red bed-black shale-evaporite succession must be joined by the geochemical coherence of the ore body-evaporite-black shale association. The Cretaceous Cu-Zn deposits of Angola, the Zambian Copperbelt as well as the Creta, Oklahoma, deposits are other KST examples. In the Zambian Copperbelt, evaporites are indicated by the carbonate lenticles thought to be pseudomorphs after gypsum-anhydrite nodules. MVT deposits are also deposited by acid brines, but at more elevated temperatures and with carbonates as principal host rocks. The Pine Point deposits are cited for their close association with evaporites.Alkaline, metal-rich brines are postulated for the HYC deposit of McArthur River, Australia. Such brines are known from the Green River Formation and deposits formed from such brines constitute the GRT class. They can be recognized by the presence of Magadi-type cherts and zeolite-analcime-K-spar tuffs. The Cu-Co ore bodies of Outokumpu, Finland, might also belong to this type. A new classification of sedimentary ore deposits is proposed, based on their geochemical environment. KST and MVT are formed from acid ore fluids, while GRT and CT (Creede type) are derived from basic ore fluids. pH of the fluids is best evaluated not from the ores themselves, but from their effect on the host-rocks.     

Effects of weathering on organic matter in shales

The most drastic changes of the organic geochemical parameters examined (organic carbon, soluble organic matter content and composition, δC¹³ insoluble organic matter) occur over the near-surface 3 m intervals of two shallow core holes drilled into outcrops of the Upper Cretaceous Mancos Shale in Utah. This observation is believed to reflect the effects of weathering under the semi-arid climate of the study area. Therefore, organic geochemical data obtained from analysis of surface samples should be interpreted with caution.     

Sealing efficiency analysis for shallow-layer caprocks in CO<Subscript>2</Subscript> geological storage

The CO₂ migrated from deeper to shallower layers may change its phase state from supercritical state to gaseous state (called phase transition). This phase transition makes both viscosity and density of CO₂ experience a sharp variation, which may induce the CO₂ further penetration into shallow layers. This is a critical and dangerous situation for the security of CO₂ geological storage. However, the assessment of caprock sealing efficiency with a fully coupled multi-physical model is still missing on this phase transition effect. This study extends our previous fully coupled multi-physical model to include this phase transition effect. The dramatic changes of CO₂ viscosity and density are incorporated into the model. The impacts of temperature and pressure on caprock sealing efficiency (expressed by CO₂ penetration depth) are then numerically investigated for a caprock layer at the depth of 800 m. The changes of CO₂ physical properties with gas partial pressure and formation temperature in the phase transition zone are explored. It is observed that phase transition revises the linear relationship of CO₂ penetration depth and time square root as well as penetration depth. The real physical properties of CO₂ in the phase transition zone are critical to the safety of CO₂ sequestration. Pressure and temperature have different impact mechanisms on the security of CO₂ geological storage.     

黑色页岩的资源功能和环境效应

利用ICP—MS等分析技术对典型黑色页岩的微量元素及P、S等组分进行了分析,探讨了黑色页岩的化学特征、风化机制和微量元素富集特征,阐明了黑色页岩的资源功能和环境效应。结果表明,黑色页岩不但富含多种矿产资源,产有大型、超大型多金属矿床,而且可用作复合化肥以改良土壤。同时,黑色页岩因风化分解释放CO2、产生酸性矿排水、释出重金属元素等而可能对环境产生严重影响,引起环境问题。开发利用黑色页岩不但要充分认识其资源功能特征,拓宽其应用途径,而且要特别注意其可能引发的环境问题。     

Rate-independent fracture toughness of gray and black kerogen-rich shales

The objective of this investigation is to characterize the influence of the loading rate, scratch speed, mineralogy, morphology, anisotropy, and total organic content on the scratch toughness of organic-rich shale. We focus our study on a gray shale, Toarcian shale (Paris basin, France) and a black shale, Niobrara shale (northeastern Colorado, USA). Microscopic scratch tests are performed for varying scratch speeds and loading rates. We consider several orientations for scratch testing. For all gas shale specimens, the scratch toughness is found to increase with increasing scratch speed. In the asymptotic regime of high speeds, there is a convergence toward a single constant value irrespective of the loading rate. To understand this evolution of the scratch toughness, a nonlinear fracture mechanics model is built that integrates fracture dissipation with the various forms of viscous processes. In particular, a coupling is shown between the fracture energy and the viscoelastic characteristics. An inverse approach which combines scratch and indentation testing makes it possible to represent all tests in a single curve and retrieve the rate-independent fracture toughness of kerogen-rich shale materials. The presence of organic matter drastically alters the creep and fracture properties at the microscopic length-scale. The fracture behavior is anisotropic with the divider orientation yielding the highest fracture toughness value and the short transverse orientation yielding the lowest fracture toughness. Elucidating the fracture-composition-morphology relationships in organic-rich shale will promote advances in science and engineering for energy-related applications such as hydraulic fracturing in unconventional reservoirs or \(\hbox {CO}_2\) sequestration in depleted reservoirs.     

Geology of the Devonian black shales of the Appalachian Basin

Black shales of Devonian age in the Appalachian Basin are a unique rock sequence. The high content of organic matter, which imparts the characteristic lithology, has for years attracted considerable interest in the shales as a possible source of energy. The recent energy shortage prompted the U.S. Department of Energy through the Eastern Gas Shales Project of the Morgantown Energy Technology Center to underwrite a research program to determine the geologic, geochemical, and structural characteristics of the Devonian black shales in order to enhance the recovery of gas from the shales. Geologic studies by Federal and State agencies and academic institutions produced a regional stratigraphic network that correlates the 15 ft black shale sequence in Tennessee with 3000 ft of interbedded black and gray shales in central New York. These studies correlate the classic Devonian black shale sequence in New York with the Ohio Shale of Ohio and Kentucky and the Chattanooga Shale of Tennessee and southwestern Virginia. Biostratigraphic and lithostratigraphic markers in conjunction with gamma-ray logs facilitated long-range correlations within the Appalachian Basin. Basinwide correlations, including the subsurface rocks, provided a basis for determining the areal distribution and thickness of the important black shale units. The organic carbon content of the dark shales generally increases from east to west across the basin and is sufficient to qualify as a hydrocarbon source rock. Significant structural features that involve the black shale and their hydrocarbon potential are the Rome trough, Kentucky River and Irvine-Paint Creek fault zone, and regional decollements and ramp zones.     

Main features of mudslides in tectonised highly fissured clay shales

AbstractMudslides are widespread in the world, especially in areas occupied by highly-fissured plastic stiff clays. Despite their strong impact on structures, infrastructures and, in general, human activity, the knowledge concerning the causes and mechanisms of mudslides is still rather limited. The paper reports some results of long-term research on mudslides in tectonised highly-fissured plastic clay shales carried out through laboratory and in situ tests, monitoring and numerical analyses.