Geochemistry and organic petrology study of Kimmeridgian organic-rich shales in the Marib-Shabowah Basin,Yemen: Origin and implication for depositional environments and oil-generation potential

Kimmeridgian organic-rich shales of the Madbi Formation from the Marib-Shabowah Basin in western Yemen were analysed to evaluate the type of organic matter, origin and depositional environments as well as their oil-generation potential. Results of the current study establishes the organic geochemical characteristics of the Kimmeridgian organic-rich shales and identifies the kerogen type based on their organic petrographic characteristics as observed under reflected white light and blue light excitation. Kerogen microscopy shows that the Kimmeridgian organic-rich shales contain a large amount of organic matter, consisting predominantly of yellow fluorescing alginite and amorphous organic matter with marine-microfossils (e.g., dinoflagellate cysts and micro-foraminiferal linings). Terrigenous organic matters (e.g., vitrinite, spores and pollen) are also present in low quantities. The high contributions of marine organic matter with minor terrigenous organic matter are also confirmed by carbon isotopic values. The organic richness of the Kimmeridgian shales is mainly due to good preservation under suboxic to relatively anoxic conditions, as indicated by the percent of numerous pyritized fragments associated with the organic matter. The biomarker parameters obtained from mass spectrometer data on m/z 191 and m/z 217 also indicate that these organic-rich shales contain mixed organic matter that were deposited in a marine environment and preserved under suboxic to relatively anoxic conditions.The Kimmeridgian organic-rich shales thus have high oil and low gas-generation potential due to oil window maturities and the nature of the organic matter, with high content of hydrogen-rich Type II and mixed Type II-III kerogens with minor contributions of Type III kerogen.     

Insights into deposition of Lower Cretaceous black shales from meager accumulation of organic matter in Albian sediments from ODP site 763, Exmouth Plateau,Northwest Australia

The amount and type of organic matter present in an exceptionally complete upper Aptian to lower Cenomanian sequence of sediments from ODP site 763 on the Exmouth Plateau has been determined. Organic carbon concentrations average 0.2%. Organic matter is marine in origin, and its production and preservation was low over the ca. 20-million-year interval recorded by this sequence. Because this section was tectonically isolated from mainland Australia in the early Aptian, it better represents global oceanic conditions than the many basin-edge locations in which Albian-age black shales have been found. Formation of the basin-edge black shales evidently resulted from rapid, turbiditic burial of organic matter rather than from enhanced oceanic production or from basin-wide anoxia during the Albian.     

Organic geochemistry and petroleum potential of Early Cretaceous Garau Formation in central part of Lurestan zone,northwest of Zagros,Iran

Deposition of organic rich black shales and dark gray limestones in the Berriasian-Turonian interval has been documented in many parts of the world. The Early Cretaceous Garau Formation is well exposed in Lurestan zone in Iran and is composed of organic-rich shales and argillaceous limestones. The present study focuses on organic matter characterization and source rock potential of the Garau Formations in central part of Lurestan zone. A total of 81 core samples from 12 exploratory wells were subjected to detailed geochemical analyses. These samples have been investigated to determine the type and origin of the organic matter as well as their petroleum-generation potential by using Rock-Eval/TOC pyrolysis, GC and GCMS techniques. The results showed that TOC content ranges from 0.5 to 4.95 percent, PI and Tmax values are in the range of 0.2 and 0.6, and 437 and 502 °C. Most organic matter is marine in origin with sub ordinary amounts of terrestrial input suggesting kerogen types II-III and III. Measured vitrinite reflectance (Rrandom%) values varying between 0.78 and 1.21% indicating that the Garau sediments are thermally mature and represent peak to late stage of hydrocarbon generation window. Hydrocarbon potentiality of this formation is assessed fair to very good capable of generating chiefly gas and some oil. Biomarker characteristics are used to provide information about source and maturity of organic matter input and depositional environment. The relevant data include normal alkane and acyclic isoprenoids, distribution of the terpane and sterane aliphatic biomarkers. The Garau Formation is characterized by low Pr/Ph ratio (<1.0), high concentrations of C27 regular steranes and the presence of tricyclic terpanes. These data indicated a carbonate/shale source rock containing a mixture of aquatic (algal and bacterial) organic matter with a minor terrigenous organic matter contribution that was deposited in a marine environment under reducing conditions. The results obtained from biomarker characteristics also suggest that the Garau Formation is thermally mature which is in agreement with the results of Rock-Eval pyrolysis.     

Depositional environments of Late Cretaceous Gongila and Fika formations,Chad (Bornu) Basin,Northeast Nigeria

Organic geochemical and palynofacies studies of 172 ditch cuttings samples of possible source rock shales from the Late Cretaceous Gongila and Fika formations in the Chad Basin of NE Nigeria were carried out to determine their paleoenvironments of deposition. Although dominated by amorphous organic matter, C/S ratios and molecular parameters suggest the mostly organic lean shales (TOC contents typically below 1.5%) were deposited in a normal marine environment. Levels of oxygenation influenced by water depth in the depositional environment appear to control organic richness and quality of the dark grey shales.The organic rich (TOC > 2.0%) upper part of the Fika Formation was deposited under anoxic conditions during the Late Cretaceous and could represent an Oceanic Anoxic Event. Mature intervals where such conditions prevailed would have generated liquid hydrocarbon, although none were sampled here.A trend of increasing organic richness towards the central part of the larger Chad Basin observed in this and other studies supports the development of organic rich marine shales (average TOC contents of 2–3%) of equivalent age in the Termit Basin where water depth would have been deeper and oxygen conditions at levels that permitted preservation of marine organic matter.     

Source rock characteristics and biostratigraphy of the Lower Silurian (Telychian) organic-rich shales at Akyaka, central Taurus region, Turkey

The Akyaka section in the central Taurus region in the southern part of Turkey includes the organic matter and graptolite-rich black shales which were deposited under dysoxic to anoxic marine conditions in the Early Silurian. A biostratigraphical analysis, based on graptolite assemblages, indicates that the sediments studied may well be referable to the querichi Biozone and early Telychian, Llandovery. A total of 15 samples have been subjected to Leco and Rock-Eval pyrolysis and graptolite reflectance measurements for determination of their source rock characteristics and thermal maturity. The total organic carbon content of the graptolite-bearing shales varies from 1.75 to 3.52 wt% with an average value of 2.86 wt%. The present Rock-Eval pyrolytic yields and calculated values of hydrogen and oxygen indexes imply that the recent organic matter type is inert kerogen. The measured maximum graptolite reflectance (G_Rmax %) values are between 5.04% and 6.75% corresponding to thermally over maturity. This high maturity suggests a deep burial of the Lower Silurian sediments resulting from overburden rocks of Upper Paleozoic to Mesozoic Upper Cretaceous and Middle-Upper Eocene thrusts occurred in the region.     

Geochemistry and origin of organic-rich sediment veins in fractured granitic basement,Helmsdale, Sutherlandshire,UK

Black sediment veins up to 2 cm width penetrate the Caledonian Helmsdale Granite in the vicinity of the Helmsdale Fault, onshore Moray Firth. The black colour and geochemistry of the veins reflect a high content of organic carbon. Both Devonian and Jurassic shales are conceivable available sources, but sterane compositions relate the organic matter to the Jurassic shales. A content of extractable organic matter higher than in the shales suggests that the carbon in the veins represents oil rather than mechanically mobilized shale. The oil was present during sediment vein emplacement. The veins were emplaced forcefully, which may reflect high fluid pressure associated with post-Jurassic movement on the Helmsdale Fault.     

Origin of organic matter and paleoenvironment conditions of the Late Jurassic organic-rich shales from shabwah sub-basin (western Yemen): Constraints from petrology and biological markers

Late Jurassic organic-rich shales from Shabwah sub-basin of western Yemen were analysed based on a combined investigations of organic geochemistry and petrology to define the origin, type of organic matter and the paleoenvironment conditions during deposition. The organic-rich shales have high total sulphur content values in the range of 1.49–4.92 wt. %, and excellent source rock potential is expected based on the high values of TOC (>7%), high extractable organic matter content and hydrocarbon yield exceeding 7000 ppm. The high total sulphur content and its relation with high organic carbon content indicate that the Late Jurassic organic-rich shales of the Shabwah sub-basin were deposited in a marine environment under suboxic-anoxic conditions. This has been evidenced from kerogen microscopy and their biomarker distributions. The kerogen microscopy investigation indicated that the Late Jurassic organic-rich shales contain an abundant liptinitic organic matter (i.e., alginite, structureless (amorphous organic matters)). The presence of alginite with morphology similar to the lamalginite alga and amorphous organic matter in these shale samples, further suggests a marine origin. The biomarker distributions also provide evidence for a major contribution by aquatic algae and microorganisms with a minor terrigenous organic matter input. The biomarkers are characterized by unimodal distribution of n-alkanes, low acyclic isoprenoids compared to normal alkanes, relatively high tricyclic terpanes compared to tetracyclic terpanes, and high proportion of C₂₇ and C₂₉ regular steranes compared to C₂₈ regular sterane. Moreover, the suboxic to anoxic bottom water conditions as evidenced in these Late Jurassic shales is also supported based on relatively low pristane/phytane (Pr/Ph) ratios in the range of 0.80–1.14. Therefore, it is envisaged here that the high content of organic matter (TOC > 7 wt.%) in the analysed Late Jurassic shales is attributed to good organic matter (OM) preservation under suboxic to anoxic bottom water conditions during deposition.     

Black shales in Ukraine – A review

As a result of a long-lasting and complex geological history, organic-matter-rich fine-grained rocks (black shales) with widely varying ages can be found on Ukrainian territory. Several of them are proven hydrocarbon source rocks and may hold a significant shale gas potential.Thick Silurian black shales accumulated along the western margin of the East European Craton in a foreland-type basin. By analogy with coeval organic-matter-rich rocks in Poland, high TOC contents and gas window maturity can be expected. However, to date information on organic richness is largely missing and maturity patterns remain to be refined.Visean black shales with TOC contents as high as 8% and a Type III-II kerogen accumulated along the axis of the Dniepr-Donets rift basin (DDB). They are the likely source for conventional oil and gas. Oil-prone Serpukhovian black shales accumulated in the shallow northwestern part of the DDB. Similar black shales probably may be present in the Lviv-Volyn Basin (western Ukraine).Middle Jurassic black shales up to 500 m thick occur beneath the Carpathian Foredeep. They are the likely source for some heavy oil deposits. TOC contents up to 12% (Type II) have been recorded, but additional investigations are needed to study the vertical and lateral variability of organic matter richness and maturity.Lower Cretaceous black shales with a Type III(-II) kerogen (TOC > 2%) are widespread at the base of the Carpathian flysch nappes, but Oligocene black shales (Menilite Fm.) rich in organic matter (4–8% TOC) and containing a Type II kerogen are the main source rock for oil in the Carpathians. Their thermal maturity increases from the external to the internal nappes.Oligocene black shales are also present in Crimea (Maykop Fm.). These rocks typically contain high TOC contents, but data from Ukraine are missing.     

Petrographic and geochemical characteristics of the lacustrine black shales from the Upper Triassic Yanchang Formation of the Ordos Basin,China: Implications for the organic matter accumulation

The lacustrine black shales in the Chang7 Member from the Upper Triassic Yanchang Formation of the Ordos Basin in Central China are considered one of the most important hydrocarbon source rocks. However, the mechanism of organic accumulation in the black shales remains controversial. To resolve the controversy, with the former paleontological data of Yanchang Formation and sedimentation rate data of the Chang7 black shales, we investigated the typical intervals of the Chang7 black shales (TICBS) which were obtained by drilling in Yaowan at the southern margin of the Ordos Basin and performed various sedimentary, isotopic and geochemical analysis, including the sedimentary petrography, pyrite morphology, total organic carbon (TOC) and total sulfur (TS), the ratio of pyritic Fe to total Fe (DOP_T), major and trace elements, together with pyritic sulfur isotopes (δ³⁴S_py). The high sulfur content, enrichment of redox-sensitive trace metals, and the lower sedimentation rate of the TICBS in addition to the presence of marine spined acritarchs and coelacanth fossils indicate that the TICBS were deposited in a lacustrine environment possibly influenced by seawater. The petrographic observations show a thick layer of black shale with interlayers of thin layered siltstone (silty mudstone) and laminated tuff, which were related to the turbidity currents and volcanism, respectively. The U/Th, C-S, and Mo-U covariations, pyrite morphology, DOP_T, combined with the δ³⁴S_py, suggest that the deposition occurred beneath the anoxic-sulfidic bottom waters, which was intermittently influenced by the oxygen-containing turbidity. The Ni/Al and Cu/Al possibly show extremely high to high primary productivity in the water column, which might be connected with the substantial nutrients input from seawater or frequently erupted volcanic ash entering the lake. In addition, the coincidence of an increased abundance of TOC with increased P/Al, Ni/Al, Cu/Al and U/Th, as well as relatively consistent Ti/Al suggest that the accumulation of the organic matter might be irrelevant to the clastic influx, and was mainly controlled by the high primary productivity and anoxic-sulfidic conditions. Further, the covariations of TOC vs. P/Al and TOC vs. Ba/Al indicate that the high primary productivity led to the elevated accumulation and burial of organic matter, while the anoxic to sulfidic conditions were likely resulted from an intense degradation of the organic matter during the early diagenesis. In summary, the organic matter accumulation is ultimately attributed to the high primary productivity possibly resulted from seawater or volcanic ash entering the lake.     

Enrichment and distribution of shale oil in the Cretaceous Qingshankou Formation,Songliao Basin,Northeast China

The Songliao Basin is a large-scale petroliferous basin in China. With a gradual decline in conventional oil production, the exploration and development of replacement resources in the basin is becoming increasingly important. Previous studies have shown that the Cretaceous Qingshankou Formation (K₂qn) has favorable geological conditions for the formation of shale oil. Thus, shale oil in the Qingshankou Formation represents a promising and practical replacement resource for conventional oil. In this study, geological field surveys, core observation, sample tests, and the analysis of well logs were applied to study the geochemical and reservoir characteristics of shales, identify shale oil beds, build shale oil enrichment models, and classify favorable exploration areas of shale oil from the Cretaceous Qingshankou Formation. The organic matter content is high in shales from the first member of the Cretaceous Qingshankou Formation (K₂qn¹), with average total organic carbon (TOC) content exceeding 2%. The organic matter is mainly derived from lower aquatic organisms in a reducing brackish to fresh water environment, resulting in mostly type I kerogen. The vitrinite reflectance (Ro) and the temperature at which the maximum is release of hydrocarbons from cracking of kerogen occurred during pyrolysis (T_max) respectively range from 0.5% to 1.1% and from 430 °C to 450 °C, indicating that the K₂qn¹ shales are in the low-mature to mature stage (Ro ranges from 0.5% to 1.2%) and currently generating a large amount of oil. The favorable depth for oil generation and expulsion is 1800–2200 m and 1900–2500 m, respectively as determined by basin modeling. The reserving space of the K₂qn¹ shale oil includes micropores and mircofractures. The micropore reservoirs are developed in shales interbedded with siltstones exhibiting high gamma ray (GR), high resistivity (Rt), low density (DEN), and slightly abnormal spontaneous potential (SP) in the well-logging curves. The microfracture reservoirs are mainly thick shales with high Rt, high AC (acoustic transit time), high GR, low DEN, and abnormal SP. Based on the shale distribution, geochemical characteristics, reservoir types, fracture development, and the process of shale oil generation and enrichment, the southern Taikang and northern Da'an are classified as two favorable shale oil exploration areas in the Songliao Basin.     

Supply of terrigenous organic matter from tidal flat to the marine environment: An example of neritic source rocks in the Eocene Pinghu Formation,Xihu Depression,East China Sea Shelf Basin

The terrigenously-dominated marine shales which were deposited in the lower Eocene Pinghu Formation were thought to be a potential source rock in the Xihu Depression of the East China Sea Shelf Basin. However, the exceptionally high total organic carbon content (TOC, >6% on average) of the tidal sand ridge samples was not compatible with their sedimentary environment, indicating coal-bearing sedimentary debris may have been transferred from the coast to the ocean. In this study, new sights into the origins and supply of organic materials in the coastal environment were proposed in the neritic organic matter of the Eocene Pinghu Formation. A discriminant model was developed using plynofacies analysis data to pinpoint the source of organic materials in marine source rocks. The discrimination results suggested that marine mudstones were associated with tidal flat mudstones rather than deltaic ones. The biomarker characteristics of mudstones deposited in various environments support this assertion, indicating that the supply of plant materials in tidal flats is the primary organic matter source for the marine environment. The organic matter abundance was elevated in tidal flats due to their superior preservation conditions. Additionally, the lithological assemblage of tidal flats suggests that tidal currents can scour marshes and then transport dispersed terrigenous organic materials to neritic areas. These findings indicate that coal-bearing sedimentary debris was likely transferred from the coast to the ocean, and tidal currents are thought to be the dominant mechanism driving organic matter from the tidal to the marine environment.     

Organic matter–apatite–pyrite relationships in the Botneheia Formation (Middle Triassic) of eastern Svalbard: Relevance to the formation of petroleum source rocks in the NW Barents Sea shelf

The Middle Triassic Botneheia Formation of eastern Svalbard (Edgeøya and Barentsøya) comprises an organic carbon-rich, fine-grained clastic succession (∼100 m thick) that makes the best petroleum source rock horizon in the NW Barents Sea shelf. The succession records a transgressive–regressive interplay between the prodelta depositional system sourced in the southern Barents Sea shelf (black shale facies of the lower and middle parts of the Muen Member) and the open shelf phosphogenic system related to upwelling and nutrient supply from the Panthalassic Ocean (phosphogenic black shale facies of the upper part of the Muen Member and the Blanknuten Member). The relationships between organic matter, authigenic apatite, and pyrite in these facies allow to characterize the relative roles of redox conditions and oceanic productivity in the organic carbon preservation. The accumulation of terrestrial and autochthonous marine organic matter in the black shale facies occurred under dominating oxic conditions and increasing-upward productivity related to early transgressive phase and retrogradation of the prodelta system. The phosphogenic black shale facies deposited in an oxygen-minimum zone (OMZ) of the open shelf environment during the late transgressive to regressive phases under conditions of high biological productivity, suppressed sedimentation rates, and changing bottom redox. The phosphatic black shales occurring in the lower and upper parts of the phosphogenic succession reveal depositional conditions indicative of the shallower part of OMZ, including high input of autochthonous organic matter into sediment, oxic-to-dysoxic (episodically suboxic and/or anoxic) conditions, intense phosphogenesis, and recurrent reworking of the seabed. The massive phosphatic mudstone occurring in the middle of the phosphogenic succession reflects the development of euxinia in the deeper part of OMZ during high-stand of the sea. High input of autochthonous organic matter in this environment was coupled with mineral starvation and intermittent phosphogenesis. In mature sections in eastern Svalbard, the petroleum potential of the Botneheia Formation rises from moderate to good in the black shale facies, and from good to very good in the phosphogenic black shale facies, attaining maximum in the massive phosphatic mudstone.     

Origins and maturity of organic matter in mid-Cretaceous black shales from ODP Site 1138 on the Kerguelen Plateau

We have conducted elemental, isotopic, and Rock-Eval analyses of Cenomanian–Santonian sediment samples from ODP Site 1138 in the southern Indian Ocean to assess the origin and thermal maturity of organic matter in mid-Cretaceous black shales found at this high-latitude location. Total organic carbon (TOC) concentrations range between 1 and 20 wt% in black to medium-gray sediments deposited around the Cenomanian–Turonian boundary. Results of Rock-Eval pyrolysis indicate that the organic matter is algal Type II material that has experienced modest alteration. Important contributions of nitrogen-fixing bacteria to the amplified production of organic matter implied by the high TOC concentrations is recorded in δ¹⁵N values between −5 and 1‰, and the existence of a near-surface intensified oxygen minimum zone that favored organic carbon preservation is implied by TOC/TN ratios between 20 and 40. In contrast to the marine nature of the organic matter in the Cenomanian–Turonian boundary section, deeper sediments at Site 1138 contain evidence of contributions land-derived organic matter that implies the former presence of forests on the Kerguelen Plateau until the earliest Cenomanian.     

Geochemistry and organic petrography of Cretaceous sediments of the Calabar Flank,southeastern, Nigeria

Detailed bulk geochemistry and organo-petrography of outcrop Cretaceous sediments (with no significant effects of weathering) from the Calabar Flank, southeast Nigeria were performed to understand the organic carbon source, accumulation and degradation, and paleo-climatic, paleoceanographic and paleoenvironmental conditions in West Africa during Early Cretaceous (Aptian) to Maastrichtian times. This study was based on microscopic, elemental analyses (organic carbon, nitrogen, iron and sulphur), Rock-eval pyrolysis and carbon-isotope analyses. In general, the Calabar Flank shales are characterised by highly variable total organic carbon (TOC) contents, which range between 0.1% in Aptian–Albian Mfamosing Limestone and 9.9% in the Awi Formation sediments. The organic matter (OM) is a mixture of immature to early-mature marine and terrigenous OM of types III and IV. This is indicated by low hydrogen indices (HI value (10–190 mg HC/g TOC), T_max (417–460 °C), vitrinite reflectance %R_o (0.39–0.62 %R_o), low to high C/N ratios (3.4–1158.0) and high amounts of terrigenous macerals (vitrinite + inertinite). Based on carbon isotope, C/N ratios and sulphate reduction index (SRI), OM degradation (up to 70%, SRI > 2.5) is most pronounced for shales deposited in a marine environment. The geochemical and petrographic data indicate that local factors such as low bioproductivity, down slope transport and redeposition of sediments from a fluvial–deltaic basin to nearshore facies, shallower, oxic and mildly oxygen-deficient environments, humid–arid paleogeographic conditions, specifically controlled the amount and quality of the OM during Aptian–Mastrichtian stages where marine sediments have been assumed to be deposited during the global anoxic events. Therefore, the order of the main factors controlling OM content in sediments are: input of terrigenous material transported from the land > low OM productivity by marine photoautotrophs > low preservation.     

Multiple controls on the paleoenvironment of the Early Cambrian marine black shales in the Sichuan Basin,SW China: Geochemical and organic carbon isotopic evidence

In order to understand the paleoenvironment of the Early Cambrian black shale deposition in the western part of the Yangtze Block, geochemical and organic carbon isotopic studies have been performed on two wells that have drilled through the Qiongzhusi Formation in the central and southeastern parts of Sichuan Basin. It shows that the lowest part of the Qiongzhusi Formation has high TOC abundance, while the middle and upper parts display relative low TOC content. Redox-sensitive element (Mo) and trace elemental redox indices (e.g., Ni/Co, V/Cr, U/Th and V/(V + Ni)) suggest that the high-TOC layers were deposited under anoxic conditions, whereas the low-TOC layers under relatively dysoxic/oxic conditions. The relationship of the enrichment factors of Mo and U further shows a transition from suboxic low-TOC layers to euxinic high-TOC layers. On the basis of the Mo-TOC relationship, the Qiongzhusi Formation black shales were deposited in a basin under moderately restricted conditions. Organic carbon isotopes display temporal variations in the Qiongzhusi Formation, with a positive excursion of δ¹³C_org values in the lower part and a continuous positive shift in the middle and upper parts. All these geochemical and isotopic criteria indicate a paleoenvironmental change from bottom anoxic to middle and upper dysoxic/oxic conditions for the Qiongzhusi Formation black shales. The correlation of organic carbon isotopic data for the Lower Cambrian black shales in different regions of the Yangtze Block shows consistent positive excursion of δ¹³C_org values in the lower part for each section. This excursion can be ascribed to the widespread Early Cambrian transgression in the Yangtze Block, under which black shales were deposited.     

Geochemistry,reservoir characterization and hydrocarbon generation potential of lacustrine shales: A case of YQ-1 well in the Yuqia Coalfield,northern Qaidam Basin,NW China

Ever since a breakthrough of marine shales in China, lacustrine shales have been attracting by the policy makers and scientists. Organic-rich shales of the Middle Jurassic strata are widely distributed in the Yuqia Coalfield of northern Qaidam Basin. In this paper, a total of 42 shale samples with a burial depth ranging from 475.5 m to 658.5 m were collected from the Shimengou Formation in the YQ-1 shale gas borehole of the study area, including 16 samples from the Lower Member and 26 samples from the Upper Member. Geochemistry, reservoir characteristics and hydrocarbon generation potential of the lacustrine shales in YQ-1 well were preliminarily investigated using the experiments of vitrinite reflectance measurement, maceral identification, mineralogical composition, carbon stable isotope, low-temperature nitrogen adsorption, methane isothermal adsorption and rock eval pyrolysis. The results show that the Shimengou shales have rich organic carbon (averaged 3.83%), which belong to a low thermal maturity stage with a mean vitrinite reflectance (R_o) of 0.49% and an average pyrolytic temperature of the generated maximum remaining hydrocarbon (T_max) of 432.8 °C. Relative to marine shales, the lacustrine shales show low brittleness index (averaged 34.9) but high clay contents (averaged 55.1%), high total porosities (averaged 13.71%) and great Langmuir volumes (averaged 4.73 cm⁻³ g). Unlike the marine and marine-transitional shales, the quartz contents and brittleness index (BI) values of the lacustrine shales first decrease then increase with the rising TOC contents. The kerogens from the Upper Member shales are dominant by the oil-prone types, whereas the kerogens from the Lower Member shales by the gas-prone types. The sedimentary environment of the shales influences the TOC contents, thus has a close connection with the hydrocarbon potential, mineralogical composition, kerogen types and pore structure. Additionally, in terms of the hydrocarbon generation potential, the Upper Member shales are regarded as very good and excellent rocks whereas the Lower Member shales mainly as poor and fair rocks. In overall, the shales in the top of the Upper Member can be explored for shale oil due to the higher free hydrocarbon amount (S₁), whereas the shales in the Lower Member and the Upper Member, with the depths greater than 1000 m, can be suggested to explore shale gas.     

Petroleum retention in the Mandal Formation,Central Graben,Norway

Upper Jurassic organic matter-rich, marine shales of the Mandal Formation have charged major petroleum accumulations in the North Sea Central Graben including the giant Ekofisk field which straddles the graben axis. Recent exploration of marginal basin positions such as the Mandal High area or the Søgne Basin has been less successful, raising the question as to whether charging is an issue, possibly related to high thermal stability of the source organic matter or delayed expulsion from source to carrier.The Mandal Formation is in part a very prolific source rock containing mainly Type II organic matter with <12 wt.-% TOC and HI < 645 mg HC/g TOC but Type III-influenced organofacies are also present. The formation is therefore to varying degrees heterogeneous. Here we show, using geochemical mass balance modelling, that the petroleum expulsion efficiency of the Mandal Formation is relatively low as compared to the Upper Jurassic Draupne Formation, the major source rock in the Viking Graben system. Using maturity series of different initial source quality from structurally distinct regions and encompassing depositional environments from proximal to distal facies, we have examined the relationship between free hydrocarbon retention and organic matter structure. The aromaticity of the original and matured petroleum precursors in the Mandal source rock plays a major role in its gas retention capacity as cross-linked monoaromatic rings act on the outer surface of kerogen as sorptive sites. However, oil retention is a function of both kerogen and involatile bitumen compositions. Slight variations in total petroleum retention capacities within the same kerogen yields suggest that texture of organic matter (e.g. organic porosity) could play a role as well.     

Hydrogeochemical models locating sulfate-methane transition zone in marine sediments overlying black shales: A new tool to locate biogenic methane?

Precise hydrogeochemical modeling of early diagenesis is a key in the reconstruction of sedimentary basin models. This determines the mineralogical evolution of the sediment and consequently the porosity of the rock. During early diagenesis also part of the initial organic matter is converted into biogenic gas: CH₄ CO₂, and H₂S. These processes are part of complex reaction chains during sedimentation, and biogeochemical reactions leave different signals that can be observed today. In this work, we reproduce the early diagenetic processes as integrated signals over geological times in sediments of the Demerara Rise by applying chemical thermodynamics using the PHREEQC (version 2) computer code. The investigated sediments are characterized by the presence of black shales in 410–490 mbsf and by a diagenetic barite layer above in 300–350 mbsf at depth of sulfate-methane transition (SMT). We determine the parameters that influence the location of diagenetic barite peaks in sediments overlying black shales by means of a novel modeling approach. Crucial parameters are the amount of bacterial organic matter mineralization, sedimentation rates and bottom water sulfate concentrations. All parameters are intertwining and influence the sulfate-methane cycle. They affect the location of the SMT visualized by diagenetic barite peaks. However, our model approach opens a wide field in exploring early diagenetic reactions, processes and products (such as biogenic methane) over geological times mirrored by diagenetic minerals and pore water concentration profiles that can be detected in present-day sediments.     

Metagenetic methane generation in gas shales I. Screening protocols using immature samples

The gas generative potential of organic matter is one key parameter for the calculation of total gas in place (GIP) when evaluating thermogenic shale gas plays. Having first demonstrated that late gas-forming structures are present in coals of anthracite rank (>2% R₀) we go on to examine other rocks at the immature stage of maturity and report on how to recognise which might generate significant amounts of late dry gas at geologic temperatures well in excess of 200 °C in the zone of metagenesis (R₀ > 2.0%), i.e. subsequent to primary and secondary gas generation by thermal cracking of kerogen or retained oil. Such a distinction could clearly be of major value when assessing risks and pinning down “sweet spots”. A large selection (51 samples) of source rocks, i.e. shales and coals, stemming from different depositional environments and containing various types of organic matter which contribute to the formation of petroleum in putative gas shales were investigated using open- and closed-system pyrolysis methods for the characterisation of kerogen type, molecular structure, and late gas generative behaviour. A novel, rapid closed-system pyrolysis method, which consists of heating crushed whole rock samples in MSSV-tubes from 200 °C to 2 different end temperatures (560 °C; 700 °C) at 2 °C/min, provides the basis for a newly proposed approach to discriminate between source rocks with low, high, or intermediate late gas potential. It is noteworthy that late gas potential goes largely unnoticed when only open-system pyrolysis screening-methods are used. High late gas potentials seem to be mainly associated with heterogeneous admixtures or structures in terrestrially influenced, in some cases marine, Type III and Type II/III coals and shales. Aromatic and/or phenolic signatures are therefore indicative of the possible presence of elevated late gas potential at high maturities. High temperature methane was calculated to potentially contribute an additional 10–40 mg/g TOC, which would equal up to 30% of the total initial primary petroleum potential in many cases. Low late gas potentials are associated with homogeneous, paraffinic organic matter of aquatic lacustrine and marine origin. Source rocks exhibiting intermediate late gas potentials might generate up to 20 mg/g TOC late dry gas and seem to be associated with heterogeneous marine source rocks containing algal or bacterial derived precursor structures of high aromaticity, or with aquatic organic matter containing only minor amounts of aromatic/phenolic higher land plant material.     

Lacustrine massive mudrock in the Eocene Jiyang Depression,Bohai Bay Basin,China: Nature,origin and significance

Massive mudrock refers to mudrock with internally homogeneous characteristics and an absence of laminae. Previous studies were primarily conducted in the marine environment, while notably few studies have investigated lacustrine massive mudrock. Based on core observation in the lacustrine environment of the Jiyang Depression, Bohai Bay Basin, China, massive mudrock is a common deep water fine-grained sedimentary rock. There are two types of massive mudrock. Both types are sharply delineated at the bottom and top contacts, abundant in angular terrigenous debris, and associated with oxygen-rich (higher than 2 ml O₂/L H₂O) but lower water salinities in comparison to adjacent black shales. In addition, type 1 is laterally isolated and contains abundant sand injections and contorted layers formed in the depositional process, but type 2 exactly distributes in the distal part of deep water gravity-driven sandstone units, and shows scoured bases, high-angle mineral crytsals, and fining-upward trend. It is suggested that type 1 is a muddy mass transport deposit (MMTD) formed by slide, slump, and/or debris flow, and type 2 is a turbiditic mudrock deposited by settling from dilute turbidity currents. A warm and humid climate and high subsidence rate are two main triggering events. Because of its mass movement nature, MMTD preserves the mineralogic composition and organic matter characteristics of the source sediment. By contrast, dilute turbidity currents are able to greatly entrain biochemically-formed micrite and planktonic organisms from the water column, and deposit them in the turbiditic mudrock. Because of their different ability to deposit organic matter, MMTD have poor or fair source rock potential, but the turbiditic mudrock is able to be a potentially effective source rock. The minerals in the massive mudrock are disorganized and chaotic, which cause fractures to develop in various directions, thereby, enhancing the vertical migration of oil and gas molecules to horizontal wellbore in shale reservoir exploitation.