Formation,evolution,reconstruction of black shales and their influence on shale oil and gas resource

Black shales are important products of material cycling and energy exchange among the lithosphere,atmosphere,hydrosphere,and biosphere.They are widely distributed throughout geological history and provide essential energy and mineral resources for the development of human society.They also record the evolution process of the earth and improve the understanding of the earth.This review focuses on the diagenesis and formation mechanisms of black shales sedimentation,composition,evolution,and reconstruction,which have had a significant impact on the formation and enrichment of shale oil and gas.In terms of sedimentary environment,black shales can be classified into three types:Marine,terrestrial,and marine-terrestrial transitional facies.The formation processes include mechanisms such as eolian input,hypopycnal flow,gravity-driven and offshore bottom currents.From a geological perspective,the formation of black shales is often closely related to global or regional major geological events.The enrichment of organic matter is generally the result of the interaction and coupling of several factors such as primary productivity,water redox condition,and sedimentation rate.In terms of evolution,black shales have undergone diagenetic evolution of inorganic minerals,thermal evolution of organic matter and hydrocarbon generation,interactions between organic matter and inorganic minerals,and pore evolution.In terms of reconstruction,the effects of fold deformation,uplift and erosion,and fracturing have changed the stress state of black shale reservoirs,thereby having a significant impact on the pore structure.Fluid activity promotes the formation of veins,and have changed the material composition,stress structure,and reservoir properties of black shales.Regarding resource effects,the deposition of black shales is fundamental for shale oil and gas resources,the evolution of black shales promotes the shale oil and gas formation and storage,and the reconstruction of black shales would have caused the heterogeneous distribution of oil and gas in shales.Exploring the formation mechanisms and interactions of black shales at different scales is a key to in-depth research on shale formation and evolution,as well as the key to revealing the mechanism controlling shale oil and gas accumulation.The present records can reveal how these processes worked in geological history,and improve our understanding of the coupling mechanisms among regional geological events,black shales evolution,and shale oil and gas formation and enrichment.

Geological conditions and reservoir characteristics of various shales in major shalehosted regions of China

China is home to shales of three facies:Marine shale,continental shale,and marine-continental transitional shale.Different types of shale gas are associated with significantly different formation conditions and major controlling factors.This study compared the geological characteristics of various shales and analyzed the influences of different parameters on the formation and accumulation of shale gas.In general,shales in China’s several regions exhibit high total organic carbon(TOC)contents,which lays a sound material basis for shale gas generation.Marine strata generally show high degrees of thermal evolution.In contrast,continental shales manifest low degrees of thermal evolution,necessitating focusing on areas with relatively high degrees of thermal evolution in the process of shale gas surveys for these shales.The shales of the Wufeng and Silurian formations constitute the most favorable shale gas reservoirs since they exhibit the highest porosity among the three types of shales.These shales are followed by those in the Niutitang and Longtan formations.In contrast,the shales of the Doushantuo,Yanchang,and Qingshankou formations manifest low porosities.Furthermore,the shales of the Wufeng and Longmaxi formations exhibit high brittle mineral contents.Despite a low siliceous mineral content,the shales of the Doushantuo Formation feature a high carbonate mineral content,which can increase the shales’brittleness to some extent.For marine-continental transitional shales,where thin interbeds of tight sandstone with unequal thicknesses are generally found,it is recommended that fracturing combined with drainage of multiple sets of lithologic strata should be employed to enhance their shale gas production.

The occurrence characteristics of oil in shales matrix from organic geochemical screening data and pore structure properties:An experimental study Author links open overlay panel

The occurrence characteristics of shale oil are of great significance to the movability of shale oil.In this study,the occurrence characteristics of oil in the shale matrix at Funing Formation shale in Subei Basin were quantitatively evaluated by organic geochemistry and microscopic pore structure characterization experiments.The Multiple Isothermal Stages Pyrolysis(MIS)experiment results show that the content of total oil,adsorbed oil,and free oil in the shales are 3.15-11.25 mg/g,1.41-4.95 mg/g,and 1.74-6.51 mg/g,respectively.among which the silicon-rich shale has the best oil-bearing.The relative content of free oil shows an increasing trend in pores with pore diameters greater than 3 nm.When the relative content of free oil reaches 100%,the pore size of silicon-rich shale is about 200 nm,while that of calcium-rich shale,clay-rich shale,and siliceous mixed shale is about 10 nm.The occurrence law of adsorbed oil is opposite to that of free oil,which indicates that shale oil will occur in the pores and fractures in a free state in a more extensive pore size range(>200 nm).This study also enables us to further understand the occurrence characteristics of shale oil under the interaction of occurrence state and occurrence space.

Influences of different alkaline and acidic diagenetic environments on diagenetic evolution and reservoir quality of alkaline lake shales

Thin section and argon-ion polishing scanning electron microscope observations were used to analyze the sedimentary and diagenetic environments and main diagenesis of the Permian Fengcheng Formation shales in different depositional zones of Mahu Sag in the Junggar Basin,and to reconstruct their differential diagenetic evolutional processes.The diagenetic environment of shales in the lake-central zone kept alkaline,which mainly underwent the early stage(Ro<0.5%)dominated by the authigenesis of Na-carbonates and K-feldspar and the late stage(Ro>0.5%)dominated by the replacement of Na-carbonates by reedmergnerite.The shales from the marginal zone underwent a transition from weak alkaline to acidic diagenetic environments,with the early stage dominated by the authigenesis of Mg-bearing clay and silica and the late stage dominated by the dissolution of feldspar and carbonate minerals.The shales from the transitional zone also underwent a transition from an early alkaline diagenetic environment,evidenced by the formation of dolomite and zeolite,to a late acidic diagenetic environment,represented by the reedmergnerite replacement and silicification of feldspar and carbonate minerals.The differences in formation of authigenic minerals during early diagenetic stage determine the fracability of shales.The differences in dissolution of minerals during late diagenetic stage control the content of free shale oil.Dolomitic shale in the transitional zone and siltstone in the marginal zone have relatively high content of free shale oil and strong fracability,and are favorable“sweet spots”for shale oil exploitation and development.

Exploration and Mapping of Metalliferous Black Shales in the Saghro Temporary Subsidence Zones (Anti-Atlas, Morocco)

The Saghro massif constitutes a vast metallogenic province with numerous deposits and shows of base metals (lead, zinc, copper) and precious metals (gold and silver), besides various useful substances (talc, pyrophyllite, barite, fluorite). Silver/lead occurrences are concentrated along the Cryogenian Imiter series and moderately at Boumalne and Sidi Flah. Copper occupies the plutonic intrusions and intrusive rocks of the East-Central Saghro while barite deposits are widespread throughout the Cambrian cover of the East Saghro in contact with the Ediacaran basement. To justify this distribution, the new contributions of the cartography and the organic geochemistry of the black shales of Jbel Saghro have clearly shown the particularity of the Imiter black shales in terms of the richness in organic matter (TOC = 0.18%), the blackish color and the friability. The Boumalne and Sidi Flah groups present some similarities with the Imiter group, such as the sub-equatorial structuring, the friable pelites and the richness in organic matter (Boumalne TOC = 0.11% and SidiFlah TOC = 0.16%), which is a quite good show that requires to reinforce the exploration works. For Western Saghro in the Iknioun and Qalaa’t M’Gouna groups, the variations in the thickness of the volcanic cover show an irregular paleotopography with hard, greenish, organic-poor pelitic sediments (TOC = 0.01 to 0.04%). We can conclude that the formation of Imiter-type silver concentrations requires the combination of the sedimentological, the volcanic and structural factors. For Imiter-type silver these factors are: a fine pelitic and argillic casing deposited in a confined environment, a basic volcanism source of metals and other intermediate to acid generated by the hydrothermalism and heat, a convenable paleotopography and a network of fracturations to trap the mineralizations.

Microscopic oil occurrence in high-maturity lacustrine shales:Qingshankou Formation,Gulong Sag,Songliao Basin

Occurrence and mobility of shale oil are prerequisites for evaluating shale oil reserves and prioritizing exploration targets,particularly for heterogeneous lacustrine shales.The Qingshankou Formation in the Gulong Sag,Songliao Basin is a classic lacustrine pure shale reservoir that contains abundant shale oil resources.The predicted geological reserves of the shale are 1.268×10^(9) t.In this study,field emission scanning electron microscope(FE-SEM),the modular automated processing system(MAPS),pyrolysisgas chromatography(Py-GC),low-pressure nitrogen gas adsorption(LPNA),Soxhlet extraction,pyrolysis,and 2-D nuclear magnetic resonance(NMR)were integrated to describe the shale oil components,microscopic occurrence,mobility,and the effective pore size distribution.Meanwhile,the related controlling factors are discussed.The shale oil in the Qingshankou Fm exists dominantly in the matrix pores of the clay minerals,with small amounts distributed in the intergranular pores of terrigenous clastic grains,intercrystalline pores of pyrite,intragranular pores of ostracod shells,and micro-fractures.Shale oil is distributed in the pore spaces of variable sizes in different lithofacies.The clay mineral-laminated shales are characterized by the broadest range of pore size and largest volume of pore spaces with shale oil distribution,while the ostracod-laminated shales have limited pore spaces retaining oil.Furthermore,the proposed integrated analysis evaluates the shale oil molecules existing in two states:movable,and adsorbed oil,respectively.The result illustrates that movable oil takes up 30.6%e79.4%of the total residual oil.TOC,mineral composition,and pore structures of the shale joint together to control the states and mobility of the shale oil.TOC values are positively correlated with the quantities of shale oil regardless of the state of oil.The mineral components significantly impact the state of shale oil.Noticeable differences in the states of oil were observed following the changing types of minerals,possibly due to their difference in adsorption capacity and wettability.Clay minerals attract more adsorbed oil than movable oil.Felsic minerals generally decrease the occurrence of total and adsorbed oil.Carbonate plays a positive role in hydrocarbon retention of all the shale oil states.As for the pore structure,the average pore size exerts a critical impact on the total,movable,and adsorbed oil content.The total pore volume and specific surface area of shales play a principal role in controlling the total yields and amounts of adsorbed oil.This research improves the understanding of the occurrence characteristics and enrichment mechanisms of shale oil in terrestrial pure shales and provides a reference for locating favorable shale oil exploration areas.

Hydrocarbon generation differences of shales composed of green algal and cyanobacteria: A case study of Mesozoic and Cenozoic saline lacustrine shales in Junggar Basin, NW China

The Mesozoic and Cenozoic strata in the Junggar basin developed two sets of shallow to semi-deep lacustrine shale, namely, the Cretaceous Qingshuihe Formation (K_(1q)) and the Paleogene Anjihaihe Formation (E_(2-3a)). Through organic petrology and scanning electron microscope (SEM) observation, it is found that the primary hydrocarbon-generating organic matter (OM) in the two sets of strata is different. The biological precursor of the E_(2-3a) OM is mainly green algae (Pediastrum), while the precursor of K_(1q) kerogen is mainly cyanobacteria (Oscillatoria). Then, the E_(2-3a) green algae-rich shale and K_(1q) cyanobacteria-rich shale were subjected to hydrous pyrolysis and kinetic analysis, respectively. The results show that the evolution modes of hydrocarbon generation of the typical shales are very different. Green algae have the characteristics of a low oil generation threshold, heavy oil quality, and no prominent oil peak, while cyanobacteria have the characteristics of late oil generation, concentrated hydrocarbon generation, and relatively light oil quality. The characteristics of oil generation can also be well reflected in the composition evolution of the crude oil components. The carbon isotope of gas, kerogen, and extracts of the E_(2-3a) green algae-rich shale are significantly heavier than the K_(1q) cyanobacteria-rich shale, which may be related to the living habits of their biological precursors, carbon source usage, photosynthesis efficiency, and carbon fixation efficiency.

Adsorbed and free gas occurrence characteristics and controlling factors of deep shales in the southern Sichuan Basin,China

Deep shale gas(3500-4500 m)will be the important succeeding field for the growth of shale gas production in China.Under the condition of high temperature and high pressure in deep shale gas reservoirs,its gas occurrence characteristics are markedly different from those of medium and shallow layers.To elucidate the gas occurrence characteristics and controlling factors of deep shales in the Wufeng-Longmaxi Formation,methane adsorption,low-temperature N2,and cO2 adsorption experi-ments were conducted.The results show that in deep shales,the mesopores provide approximately 75%of the total specific surface area(SA)and 90%of the total pore volume(PV).Based on two hypotheses and comparing the theoretical and actual adsorption capacity,it is speculated that methane is adsorbed in deep shale in the form of micropore filling,and free gas is mainly stored in the mesopores.Correlation analysis demonstrated that ToC is the key material constraint for the adsorption capacity of deep shale,and micropore SSA is the key spatial constraint.Other minerals and mesopore parameters have limited effect on the amount of adsorbed gas.Moreover,the free gas content ranges from 2.72 m^(3)/t to 6.20 m^(3)/t,with an average value of 4.60 m^(3)/t,and the free gas content ratio is approximately 58%,suggesting that the deep shale gas reservoirs are dominated by free gas.This ratio may also increase to approximately 70%when considering the formation temperature effect on adsorbed gas.Gas density,porosity,and gas saturation are the main controlling factors of free gas content,resulting in significantly larger free gas content in deep shale than in shallower formations.

Influencing mechanism of saline sediments on pore system formation and evolution in terrestrial shales

The majority of oil and gas resources in the world are related to saline sediments, which mainly occur in sedimentary strata in the form of cap rocks or salt-associated shales. A large number of shale oil resources have been discovered in the saline shale sediments of the Cenozoic terrestrial lake basin in China. The hydrocarbon generation ability and the reservoir capacity of shale control the oil and gas generation. The reservoir capacity is mainly characterized by pore type, structure and porosity. Most of China’s shale oil and gas resources belong to salt-bearing formations. The role of gypsum-salt rocks in the formation and evolution of organic matter (OM) in such formations has received extensive attention. However, systematic understanding is lacking. Research on the pore formation and evolution in shale under the action of gypsum-salt rock sediments is especially weak. Taking the shales in the third member of the Shahejie Formation (Es_(3)) of the Bohai Bay Basin as an example, the influence of halite on the formation and evolution process of pores was studied in this paper. The results show that halite and gypsum minerals were associated with OM, which made them more likely to develop OM pores. The samples with a high halite mineral content (HC) are more developed regarding the pore volume and specific surface area than those with a low HC. The formation of thick salt rocks is influenced by factors of deep thermal brine upwelling, sea erosion and arid environments. The frequent alternation between humid and arid environments led to the outbreak and death of organisms and the precipitation of gypsum-salt rock, which formed the simultaneous deposition of OM and halite minerals. Finally, we have established a model of shale pore evolution under the participation of the gypsum-salt rock, and halite minerals contribute to pore development in both Stage II and Stage IV. This study provides strong microscopic evidence for the pore system formation and evolution in salt-bearing reservoirs.

Identification, evolution and geological indications of solid bitumen in shales: A case study of the first member of Cretaceous Qingshankou Formation in Songliao Basin, NE China

On the basis of sorting out current understanding of solid bitumen (SB) in shales and taking organic-rich shales in the first member of the Cretaceous Qingshankou Formation in the Songliao Basin as an example, the definition, classification, occurrence and evolution path of SB are systemtically studied, and the indicative significance of SB reflectance (Rob) on maturity and its influence on the development of reservoir space are discussed and summarized. The results show that the difference of primary maceral types is primarily responsible for the different evolution paths of SB. Most of the pre-oil bitumen is in-situ SB with only a small amount being of migrated SB, while most of the post-oil bitumen and pyrobitumen are migrated SB. From the immature to early oil maturity stage, bituminite, vitrinite, and inertinite can be distinguished from SB based on their optical characteristics under reflected light, and alginite can be differentiated from SB by their fluorescence characteristics. Under scanning electron microscope, in-situ SB and migrated SB can be effectively identified. Rob increases linearly with increasing vitrinite reflectance (Ro), as a result of a decrease of aliphatic structure and the enhancement of aromatization of SB. Within the oil window three types of secondary pores may develop in SB, including modified mineral pores, devolatilization cracks and bubble holes. At a high maturity stage spongy pores may develop in pyrobitumen. Scanning electron microscopy combined with in-situ SEM-Raman spectroscopy can further reveal the structral information of different types of SB, thus providing crucial data for understanding for understanding OM migration paths, dynamics, and distances at micro-scale.

Enlightenment of calcite veins in deep Ordovician Wufeng-Silurian Longmaxi shales fractures to migration and enrichment of shale gas in southern Sichuan Basin, SW China

The relationship between fracture calcite veins and shale gas enrichment in the deep Ordovician Wufeng Formation-Silurian Longmaxi Formation (Wufeng-Longmaxi) shales in southern Sichuan Basin was investigated through core and thin section observations, cathodoluminescence analysis, isotopic geochemistry analysis, fluid inclusion testing, and basin simulation. Tectonic fracture calcite veins mainly in the undulating part of the structure and non-tectonic fracture calcite veins are mainly formed in the gentle part of the structure. The latter, mainly induced by hydrocarbon generation, occurred at the stage of peak oil and gas generation, while the former turned up with the formation of Luzhou paleouplift during the Indosinian. Under the influence of hydrocarbon generation pressurization process, fractures were opened and closed frequently, and oil and gas episodic activities are recorded by veins. The formation pressure coefficient at the maximum paleodepth exceeds 2.0. The formation uplift stage after the Late Yanshanian is the key period for shale gas migration. Shale gas migrates along the bedding to the high part of the structure. The greater the structural fluctuation is, the more intense the shale gas migration activity is, and the loss is more. The gentler the formation is, the weaker the shale gas migration activity is, and the loss is less. The shale gas enrichment in the core of gentle anticlines and gentle synclines is relatively higher.

Paleo-productivity and petroleum source evaluation of the Nkporo and Awgu shales, Lower Benue Trough, Nigeria: Insight from inorganic geochemistry

The petroleum paleo-productivity and generative potential of the Nkporo and Awgu shales in the Lower Benue Trough (LBT) were studied. Major oxides were determined using Spectro Ciros Inductively-coupled plasma optical emission spectrometer (ICP-OES) while trace and rare earth elements were determined using an ELAN 9000 Inductively-coupled plasma mass spectrometer (ICP-MS). The shales have Co/Ni ratios greater than 0.1 suggesting oil source rocks with more marine source input due to brief marine incursion in the transition zone after deposition. The very low Ni values and moderate V values, and a lack of correlation between the TOC and sulphur content, suggests that the organic matter is of terrestrial Type Ⅲ;and the very low paleo-productivity (Ba/Al and P/Ti ratios) suggests that the organic matter is of terrestrial origin. The low V/Ni values of the Nkporo and Awgu shales (Av. ≈ 4) and the high metal concentrations indicate a matured status. From the K/Rb ratios of the Nkporo (191–259) and Awgu shales (198–261), it can be deduced that the organic matter within the shales experienced a considerable loss of K and the shales are mature to generate gaseous hydrocarbons.

Types and microstructures of pores in shales of the Ordovician Wulalike Formation at the western margin of the Ordos Basin, China

Shale samples from the Ordovician Wulalike Formation at the western margin of the Ordos Basin are studied to define the types, microstructures and connectivity of pores as well as the relationships between the pore structures and gas content of the samples by using experimental techniques such as high-resolution field emission scanning electron microscopy (FESEM), mercury injection capillary pressure (MICP), low-temperature nitrogen adsorption (LTNA), CO_(2) adsorption, and focused ion beam scanning electron microscopy (FIB-SEM). The results show that the shale has 10 different lithofacies, typical mixed sedimentary characteristics, and poorly developed pores. The reservoir space mainly consists of intercrystalline pores, dissolution pores, intergranular pores, and micro-fissures, with organic pores occasionally visible. The pore size is mostly within 0.4–250 nm range but dominated by micropores and mesopores less than 20 nm, with pore numbers peaking at pore sizes of 0.5 nm, 0.6 nm, 0.82 nm, 3 nm, and 10 nm, respectively. The pores are poorly connected and macropores are rarely seen, which may explain the low porosity and low permeability of the samples. Samples with high content of organic matter and felsic minerals are potential reservoirs for oil and gas with their favorable physical properties and high connectivity. The pores less than 5 nm contribute significantly to the specific surface area and serve as important storage space for adsorbed gas.

Geochemistry and hydrocarbon source rock potential of shales from the Palaeo-Mesoproterozoic Vindhyan Supergroup, central India

With increase in shale gas exploration, inorganic and organic geochemical investigations of shale have become extremely important. Here, we explore the six argillaceous (shale) intervals (Arangi, Koldaha, Rampur, Bijaygarh, Rewa and Sirbu shale) from Son valley sector, Vindhyan Basin with an aim to understand provenance conditions, palaeoclimate, tectonic setting and hydrocarbon generation potential. Whole rock geochemistry indicates Vindhyan sediments derived from felsic source(s) except for Sirbu shale that indicates additional influx of mafic rocks with differentiated felsic source. A comparative study of Vindhyan shale rare earth elements (REEs) points to Mahakoshals and Chhotanagpur gneissic complex (CGC) as probable sediment provenance for Vindhyan sediments. CIA analysis, after necessary corrections for K-metasomatism, suggests evolution in weathering and palaeoclimate indicating a transformation from moderate weathering conditions with warm and humid climate during lower Vindhyan deposition to intense weathering conditions with hot and humid climate during upper Vindhyan deposition. Trace (La/Y vs. Sc/Cr) and REE analysis indicates passive margin setting for Vindhyan sediments whereas a wide range spanning passive to active continental margin setting is also inferred using (Th-Sc-Zr/10) and (Th–La-Sc) ternary diagrams. However, these tectonic discriminant diagrams lack in explaining rift- or sag-related origin of any intracratonic basin such as the Vindhyan Basin. The total organic carbon (TOC) content in Vindhyan shales ranges from 0.29% to 8.44%. The thermally liberated hydrocarbon (S1) values range from 0.01 to 0.18 mg HC/g rock (milligram hydrocarbon per gram of rock sample), whereas hydrocarbon from cracking of the kerogen (S2) shows values ranging from 0.04 to 0.47 mg HC/g rock. Based on modified Van Krevelen correlation (HI vs. Tmax) diagram, organic matter from Arangi and Bijaygarh shales is characterized as thermally mature, Type III kerogen of gas prone character indicating good to very good gas generation potential.

Biodegradation of occluded hydrocarbons and kerogen macromolecules of the Permian Lucaogou shales,Junggar Basin,NW China

Three kerogen samples(JJZG-1,JJZG-2 and JJZG-3)isolated from the Permian Lucaogou shales of varying biodegradation levels(BLs≈0,3 and 7,respectively)were subjected to sequential stepwise pyrolysis combined with on-line detection of gas chromatography-mass spectrometry(GC-MS).Occluded fractions(bitumenⅡ)released at low-temperature steps(≥410℃)show consistent biodegradative signatures with that reported for solvent-extracted fractions(bitumenⅠ)of the original shales,e.g.,broad range of abundant n-alkanes,isoprenoids and regular hopanes for the non-biodegraded JJZG-1;trace n-alkanes and abundant hopanes for the moderately biodegraded JJZG-2;and no n-alkanes but still prominent hopanes including the microbially produced 25-nohopanes for the severely biodegraded JJZG-3.This consistency between bitumenⅡand bitumenⅠfractions indicates the biodegradability of the kerogenoccluded bitumenⅡwith limited protection from host kerogen.A minor level of protection was suggested by the trace distribution of n-alkanes in the bitumenⅡof JJZG-2,whereas the bitumenⅠhad no nalkanes.The kerogen itself was more resistant to biodegradation as reflected by the persistence of high abundances of both n-alkanes and hopanes in the high temperature(≥460℃)products of all three kerogen samples.However,the relative abundances of these product groups did show some evidence of biodegradation alteration,e.g.,ratios of n-C_(15)alkene/C_(27)hop-17(21)-ene at 510℃pyrolysis decreased by order of magnitude from the non-biodegraded(JJZG-1=27.4)to highly biodegraded(0.3 for JJZG-3)samples.The reduced biodegradation impact on the kerogen fraction(Cf.bitumen fractions)was also evident by the absence of 25-norhopanes in the high-temperature analysis of the JJZG-3 kerogen.

Burial Records of Reactive Iron in Cretaceous Black Shales and Oceanic Red Beds from Southern Tibet

One of the new directions in the field of Cretaceous research is to elucidate the mechanism of the sedimentary transition from the Cretaceous black shales to oceanic red beds. A chemical sequential extraction method was applied to these two types of rocks from southern Tibet to investigate the burial records of reactive iron. Results indicate that carbonate-associated iron and pyrite are relatively enriched in the black shales, but depleted or absent in red beds. The main feature of the reactive iron in the red beds is relative enrichment of iron oxides （largely hematite）, which occurred during syn-depostion or early diagenesis. The ratio between iron oxides and the total iron indicates an oxygen-enriched environment for red bed deposition. A comparison between the reactive iron burial records and proxies of paleo-productivity suggests that paleo-productivity decreases when the ratio between iron oxides and the total iron increases in the red beds. This phenomenon could imply that the relationship between marine redox and productivity might be one of the reasons for the sedimentary transition from Cretaceous black shale to oceanic red bed deposition.

Chemo-and Biostratigraphy of the Jurassic Oil Shales from the Qiangtang Basin,Northern Tibet,China:A Case Study of the Toarcian Oceanic Anoxic Event

The marine oil shales of the Qiangtang Basin, northern Tibet, exposed in the Biluo Co, Tuonamu, Shenglihe and Changsheshan areas are believed to be important petroleum source rocks. This work comprehensively analyzed the carbon isotopes, trace elements, and calcareous nannofosills, ammonites and bivalves of the Biluo Co section in the Qiangtang Basin. The organic carbon isotopes show a positive excursion close to 2.17‰（relative to PDB）, which, albeit significantly smaller, may also be associated with other Early Toarcian Oceanic Anoxic Events（T-OAE） in the European epicontinental seas and the Tethyan continental margins. Coinciding with the Early Toarcian transgression, the oxygen deficiency in bottom water had led to dysoxic-anoxic conditions and deposition of black shales lacking benthic fauna. Under such condition, the redox-sensitive trace metals such as Mo, V, Ni, Cr, and U were enriched, in conjunction with high planktonic productivity of Watznaueriaceae calcareous nannofossils. Comparison of the results with the records of chemo-and biostratigraphy, as well as the palaeogeography during the Early Jurassic suggests that the anoxia linked to the Early Toarcian oceanic anoxic event was mainly caused by the high surface water temperature, sea-level rise and an increase of surface water productivity.

Paleoceanographic Indicators for Early Cambrian Black Shales from the Yangtze Platform, South China: Evidence from Biomarkers and Carbon Isotopes

The lower Cambrian Niutitang Formation, a widespread black shale deposition, is of geological interest because of its polymetallic beds, Cambrian explosion, depositional ages, dramatic environmental changes and so on. Previous study focused mainly on inorganic geochemistry and few studies have investigated the organic fractions of upper Neoproterozoic-lower Cambrian strata in South China. Here we report a study of biomarkers plus organic carbon isotopes for black shales from Ganziping, Hunan Province （China）. All the saturated hydrocarbon fractions have a unimodal distribution of n-alkanes, a high content of short-chain alkanes and maximize at C 19 or C 20 （C 23 for sample Gzh00-1）. The C 27 /C 29 sterane ratio ranges from 0.77 to 1.20 and 4-methylsteranes are in low abundance. These parameters indicate that algae and bacteria are the important primary producers. Furthermore, biomarker maturity proxies show the samples to be higher maturity. The low Pr/Ph values （0.7） suggest that the samples were deposited under anoxic conditions and, likely, under stratified water columns. In addition, 25-norhopanes and gammacerane are present as diagnostic indicators of normal marine salinity and dysoxic to anoxic conditions. During the Early Tommotian, known to coincide with a transgression event, small shelly fossils increased in abundance and diversity. Moreover, positive δ 13 C org excursions close to 1.4‰ occur at the base of the Tommotian stage. In summary, the Early Cambrian black shales were deposited under dramatic paleoenvironmental changes, including oceanic anoxia, higher primary productivity and sea-level rise.

Pore Characteristics and Factors Controlling Lacustrine Shales from the Upper Cretaceous Qingshankou Formation of the Songliao Basin,Northeast China:A Study Combining SEM,Low-temperature Gas Adsorption and MICP Experiments

To investigate pore characteristics and the factors controlling lacustrine shales,geochemical,mineralogical and petrophysical experiments were performed on 23 shale samples from the Qingshankou Formation of the Songliao Basin,China.A comparison of mercury injection capillary pressure(MICP)and low-temperature N2 adsorption pore-size distribution showed that MICP has a higher pore-size distribution(PSD)line in its overlapping pore diameter range,which may be elevated by the higher pressure of MICP.Therefore,in the overlapping range,low-temperature N2 adsorption data were preferred in pore characterization.Negative correlations were observed between pore volumes and TOC content,indicating organic matter pores are not well-developed in the studied samples.This may be related to their low grade of maturity and type I kerogens.There existed negative relationships between pore volumes and S1,which illustrated that liquid hydrocarbons occupied some pore space.Micropore volume had a better correlation with S1 than mesopore and macropore volumes,which suggests that liquid hydrocarbons preferentially occur in micropores.No obvious relationships between pore volumes and quartz or feldspar were observed,while pore volumes increased with the increasing clay mineral content.These relationships indicate that intraparticle pores in clay minerals represent the principal pore type.

Factors Controlling Low Uranium and Thorium Concentrations in the Cayirhan Bituminous Shales(CBS)in the Beypazari(Ankara)Area,Turkey

In this study uranium and thorium contents and depositional characteristics of ay rhan bituminous shales（ BS）, west of Ankara（central Anatolia）, are investigated. Samples used were collected from boreholes opened by Park Holding Ltd. A total of 25 samples were taken from bituminous shale levels in boreholes drilled at 6 different locations in the study area. The H rka formation which hosts bituminous shale deposits is a volcanosedimentary sequence and all lithofacies indicate that a lacustrine environment where the water level was continuously changed. In addition to hydrocarbon generation potential, bituminous shales also accumulate significant amount of radioactive elements such as uranium and thorium. The average uranium and thorium concentrations of BS（1.83/2.62 ppm） are much lower than averages of UC, NASK and PAAS（uranium： 2.70/2.66/3.10 ppm; thorium： 8.50/12.30/14.60 ppm）. Low uranium contents in comparison to those of similar lacustrine environments might be attributed to that waters of depositional environment of BS contain low concentration of dissolved uranium and redox conditions were of oxic and dioxic character. Correlation data indicate that U and Th have a similar source and are associated predominantly with clays and phosphates and dominantly with organic material. Radioactive elements in the basin might be derived from Paleozoic granites and metamorphites（e.g. gneiss, schist） which comprise the basement and volcanism which was active in the region throughout the Miocene period. These elements are probably associated with uraniferous phosphate minerals（e.g. autunite, torbernite） which occur in granite, gneiss and schist. BS with average TOC content of 10.96 % shows very good/perfect source rock potential. Positive correlations between Gamma-Ray values and U, Th and K concentrations imply that radioactivity might be originated from these three elements.