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.     

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.     

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.     

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.     

Geochemical characteristics and hydrocarbon generation modeling of the Jurassic source rocks in the Shoushan Basin, north Western Desert, Egypt

The Shoushan Basin is an important hydrocarbon province in the Western Desert, Egypt, but the origin of the hydrocarbons is not fully understood. In this study, organic matter content, type and maturity of the Jurassic source rocks exposed in the Shoushan Basin have been evaluated and integrated with the results of basin modeling to improve our understanding of burial history and timing of hydrocarbon generation. The Jurassic source rock succession comprises the Ras Qattara and Khatatba Formations, which are composed mainly of shales and sandstones with coal seams. The TOC contents are high and reached a maximum up to 50%. The TOC values of the Ras Qattara Formation range from 2 to 54 wt.%, while Khatatba Formation has TOC values in the range 1-47 wt.%. The Ras Qattara and Khatatba Formations have HI values ranging from 90 to 261 mgHC/gTOC, suggesting Types II-III and III kerogen. Vitrinite reflectance values range between 0.79 and 1.12 VRr %. Rock−Eval T_max values in the range 438-458 °C indicate a thermal maturity level sufficient for hydrocarbon generation. Thermal and burial history models indicate that the Jurassic source rocks entered the mature to late mature stage for hydrocarbon generation in the Late Cretaceous to Tertiary. Hydrocarbon generation began in the Late Cretaceous and maximum rates of oil with significant gas have been generated during the early Tertiary (Paleogene). The peak gas generation occurred during the late Tertiary (Neogene).     

Pore characteristic analysis of a lacustrine shale: A case study in the Ordos Basin,NW China

Organic shales deposited in a continental environment are well developed in the Ordos Basin, NW China, which is rich in hydrocarbons. However, previous research concerning shales has predominantly focused on marine shales and barely on continental shales. In this study, geochemical and mineralogical analyses, high-pressure mercury intrusion and low-pressure adsorption were performed on 18 continental shale samples obtained from a currently active shale gas play, the Chang 7 member of Yanchang Formation in the Ordos Basin. A comparison of all these techniques is provided for characterizing the complex pore structure of continental shales.Geochemical analysis reveals total organic carbon (TOC) values ranging from 0.47% to 11.44%, indicating that there is abundant organic matter (OM) in the study area. Kerogen analysis shows vitrinite reflectance (Ro) of 0.68%–1.02%, indicating that kerogen is at a mature oil generation stage. X-ray diffraction mineralogy (XRD) analysis indicates that the dominant mineral constituents of shale samples are clay minerals (which mainly consist of illite, chlorite, kaolinite, and negligible amounts of montmorillonite), quartz and feldspar, followed by low carbonate content. All-scale pore size analysis indicates that the pore size distribution (PSD) of shale pores is mainly from 0.3 to 60 nm. Note that accuracy of all-scale PSD analysis decreases for pores less than 0.3 nm and more than 10 μm. Experimental analysis indicates that mesopores (2–50 nm) are dominant in continental shales, followed by micropores (<2 nm) and macropores (50 nm–10 μm). Mesopores have the largest contribution to pore volume (PV) and specific surface area (SSA). In addition, plate- and sheet-shaped pores are dominant with poor connectivity, followed by hybrid pores. Results of research on factors controlling pore structure development show that it is principally controlled by clay mineral contents and Ro, and this is different from marine systems. This study has important significance in gaining a comprehensive understanding of continental shale pore structure and the shale gas storage–seepage mechanism.     

Assessment of the oil source-rock potential of the Pedregoso Formation (Early Miocene) in the Falcón Basin of northwestern Venezuela

The early Miocene Pedregoso Formation is one of the numerous formations rich in organic matter within the stratigraphic record of the Urumaco Trough, in the central area of the Falcón Basin. Due to its lithological characteristics and stratigraphic position, this formation is of great interest regarding the basin's petroliferous systems. The evaluation of various inorganic and organic geochemical parameters indicates that the organic matter is primarily of marine origin, deposited in a marine carbonate environment typical of reefal systems, under oxic-to-dysoxic conditions. The low variability in the TOC concentrations and in the distributions of the biomarkers extracted from the samples suggests that the paleoenvironmental conditions and the organic-matter supply remained approximately constant throughout the sedimentation of this unit. The Pedregoso type-II organic matter (marine origin) and initial organic richness value (∼1.8%) suggest that this unit has probably generated hydrocarbons within the Urumaco Trough. However, present-day thermal maturity parameters reveal that the Pedregoso organic matter is overmature (dry gas window), indicating that this unit is only capable to generate gas. In addition, the geothermal gradient, maturity parameters, and the maximum paleotemperature estimated in this study suggest that the Pedregoso Formation reached a maximum burial depth the ∼6.5 km, consistent with the value obtained from data of stratigraphic thickness in the Urumaco Trough. This implies that the thermal anomaly that affected the basin during the Late Eocene–Early Miocene did not reach the central part of the basin, and therefore, the organic matter maturation in this unit is due to the sedimentary burial.     

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.     

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.     

Petroleum source rock characterisation and hydrocarbon generation modeling of the Cretaceous sediments in the Jiza sub-basin,eastern Yemen

Cretaceous sedimentary rocks of the Mukalla, Harshiyat and Qishn formations from three wells in the Jiza sub-basin were studied to describe source rock characteristics, providing information on organic matter type, paleoenvironment of deposition and hydrocarbon generation potential. This study is based on organic geochemical and petrographic analyses performed on cuttings samples. The results were then incorporated into basin models in order to understand the burial and thermal histories and timing of hydrocarbon generation and expulsion.The bulk geochemical results show that the Cretaceous rocks are highly variable with respect to their genetic petroleum generation potential. The total organic carbon (TOC) contents and petroleum potential yield (S₁ + S₂) of the Cretaceous source rocks range from 0.43 to 6.11% and 0.58–31.14 mg HC/g rock, respectively indicating non-source to very good source rock potential. Hydrogen index values for the Early to Late Cretaceous Harshiyat and Qishn formations vary between 77 and 695 mg HC/g TOC, consistent with Type I/II, II-III and III kerogens, indicating oil and gas generation potential. In contrast, the Late Cretaceous Mukalla Formation is dominated by Type III kerogen (HI < 200 mg HC/g TOC), and is thus considered to be gas-prone. The analysed Cretaceous source rock samples have vitrinite reflectance values in the range of 0.37–0.95 Ro% (immature to peak-maturity for oil generation).A variety of biomarkers including n-alkanes, regular isoprenoids, terpanes and steranes suggest that the Cretaceous source rocks were deposited in marine to deltaic environments. The biomarkers also indicate that the Cretaceous source rocks contain a mixture of aquatic organic matter (planktonic/bacterial) and terrigenous organic matter, with increasing terrigenous influence in the Late Cretaceous (Mukalla Formation).The burial and thermal history models indicate that the Mukalla and Harshiyat formations are immature to early mature. The models also indicate that the onset of oil-generation in the Qishn source rock began during the Late Cretaceous at 83 Ma and peak-oil generation was reached during the Late Cretaceous to Miocene (65–21 Ma). The modeled hydrocarbon expulsion evolution suggests that the timing of oil expulsion from the Qishn source rock began during the Miocene (>21 Ma) and persisted to present-day. Therefore, the Qishn Formation can act as an effective oil-source but only limited quantities of oil can be expected to have been generated and expelled in the Jiza sub-basin.     

The origin,type and preservation of organic matter of the Barremian–Aptian organic-rich shales in the Muglad Basin,Southern Sudan,and their relation to paleoenvironmental and paleoclimate conditions

Barremian–Aptian organic-rich shales from Abu Gabra Formation in the Muglad Basin were analysed using geochemical and petrographic analyses. These analyses were used to define the origin, type of organic matters and the influencing factors of diagenesis, including organic matter input and preservation, and their relation to paleoenvironmental and paleoclimate conditions. The bulk geochemical characteristics indicated that the organic-rich shales were deposited in a lacustrine environment with seawater influence under suboxic conditions. Their pyrolysis hydrogen index (HI) data provide evidence for a major contribution by Type I/II kerogen with HI values of >400 mg HC/g TOC and a minor Type II/III contribution with HI values <400 mg HC/g TOC. This is confirmed by kerogen microscopy, whereby the kerogen is characterized by large amounts of structured algae (Botryococcus) and structureless (amorphous) with a minor terrigenous organic matter input. An enhanced biological productivity within the photic zone of the water columns is also detected. The increased biological productivity in the organic-rich shales may be related to enhanced semi-arid/humid to humid-warm climate conditions. Therefore, a high bio-productivity in combination with good organic matter preservation favoured by enhanced algae sizes are suggested as the OM enrichment mechanisms within the studied basin.     

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.     

Pore characterization of organic-rich Lower Cambrian shales in Qiannan Depression of Guizhou Province,Southwestern China

Nine organic-rich shale samples of Lower Cambrian black shales were collected from a recently drilled well in the Qiannan Depression, Guizhou Province where they are widely distributed with shallower burial depth than in Sichuan Basin, and their geochemistry and pore characterization were investigated. The results show that the Lower Cambrian shales in Qiannan Depression are organic rich with TOC content ranging from 2.81% to 12.9%, thermally overmature with equivalent vitrinite reflectance values in the range of 2.92–3.25%, and clay contents are high and range from 32.4% to 53.2%. The samples have a total helium porosity ranging from 2.46% to 4.13% and total surface area in the range of 9.08–37.19 m²/g. The estimated porosity in organic matters (defined as the ratio of organic pores to the volume of total organic matters) based on the plot of TOC vs helium porosity is about 10% for the Lower Cambrian shales in Qiannan Depression and is far lower than that of the Lower Silurian shales (36%) in and around Sichan Basin. This indicates that either the organic pores in the Lower Cambrian shale samples have been more severely compacted than or they did not develop organic pores as abundantly as the Lower Silurian shales. Our studies also reveal that the micropore volumes determined by Dubinin–Radushkevich (DR) equation is usually overestimated and this overestimation is closely related to the non-micropore surface area of shales (i.e. the surface area of meso- and macro-pores). However, the modified BET equation can remove this overestimation and be conveniently used to evaluate the micropore volumes/surface area and the non-micropore surface areas of micropore-rich shales.     

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.     

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.     

The Mesozoic–Cenozoic organic facies in the Lower Tagus sub-basin (Lusitanian Basin,Portugal): Palynofacies and organic geochemistry approaches

Studies of the Mesozoic and Cenozoic sequence crossed by the Barreiro-4 borehole provide an improved understanding of the organic matter deposited in the Lower Tagus sub-basin (Lusitanian Basin, Portugal) and the implications for the potential source rock and depositional environment. This study focused on 43 samples (Middle Jurassic to Neogene) that were subjected to palynofacies and organic geochemistry analyses (Total Organic Carbon, Rock-Eval pyrolysis and molecular biomarker analysis). The palynofacies data indicate that the sequence contains mainly phytoclasts (non-opaque phytoclasts). However, the Middle Jurassic samples are dominated by Amorphous Organic Matter (AOM). Continental and/or marine palynomorphs are present in all the samples. The Cretaceous samples are characterized by small amounts of kerogen that have high contents of solid bitumen. The Total Organic Carbon (TOC) content is generally less than 1 wt.%. The Rock-Eval S1 and S2 parameters vary from 0.01 to 3.50 mgHC/g rock and 0.15 to 34.03 mgHC/g rock, respectively, with the highest values corresponding to the Cretaceous samples. The hydrogen index (HI) and oxygen index (OI) values range from 35 to 552 mgHC/g TOC and 4 to 180 mgHC/g TOC, respectively. The T_max values range from 416 to 437 °C. The biomarker analysis showed that n-alkanes with 15–30 carbon atoms are present and usually have a unimodal distribution with a predominance of low to medium molecular weight compounds. The CPI values range between 0.63 and 3.65, and the pristane/phytane ratios vary between 0.48 and 1.64, indicating alternation of oxic–anoxic conditions along the sequence. The distribution of terpanes shows small amounts of tricyclic and tetracyclic terpanes in most of the samples (except for some Cretaceous samples) and a predominance of pentacyclic terpanes. The amount of 17α (H),22,29,30-trisnorhopane (Tm) usually exceeds the amount of 18α (H),22,29,30-trinorneohopane (Ts). The 20S/(20S + 20R) and αββ/(ααα + αββ) ratios of the C29 steranes generally have values below the range of equilibrium, indicating an immature stage of the OM.     

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.     

The geochemical characteristics and factors controlling the organic matter accumulation of the Late Ordovician-Early Silurian black shale in the Upper Yangtze Basin,South China

Organic-rich black shale of the Upper Yangtze Basin from the Late Ordovician and Early Silurian is considered an excellent source rock in South China. The formation and preservation conditions of this resource are revealed by its geochemical characteristics in this study. Geochemical indices, including redox indices (V/(V + Ni), V/Cr, V/Sc, and Ni/Co) and primary productivity indices (P/Ti and Ba/Al), and paleoclimate, clastic flux and sedimentary rate analyses are presented to investigate the accumulation mechanism of organic matter. Redox indices suggest that a stagnant, anoxic environment predominated in the Upper Yangtze Basin during accumulation of Wufeng and Longmaxi formations. In contrast, ventilated and oxygenated marine conditions pervaded the Upper Yangtze Basin during deposition of Linxiang and Guanyinqiao formations. The concentrations of V and U demonstrate that accumulation of organic matter was mainly controlled by redox conditions. Besides, such factors as clastic fluxes, fresh water inflows or a mixed deposition with a rapid sedimentary rate cannot be ignored due to their influences on organic matter enrichment and preservation. However, weak co-variance relationship of TOC content and productivity proxies, including P/Ti and Ba/Al, demonstrates that the accumulation of organic matter was not controlled by primary productivity. Results of the present study suggest a depositional model that stresses the importance of tectonic movements and glacial events on the accumulation and preservation of organic matter. The model shows that the Upper Yangtze Basin was a semi-restricted basin system influenced by the isolation of Xuefeng, but also it implies that oxygen-depleted bottom water of the basin favored the accumulation and preservation of sedimentary organic matter, resulting in the formation of organic-rich black shale.     

Source rock characteristics and hydrocarbon generation modelling of Upper Cretaceous Mukalla Formation in the Jiza-Qamar Basin,Eastern Yemen

The Upper Cretaceous Mukalla coals and other organic-rich sediments which are widely exposed in the Jiza-Qamar Basin and believed to be a major source rocks, were analysed using organic geochemistry and petrology. The total organic carbon (TOC) contents of the Mukalla source rocks range from 0.72 to 79.90% with an average TOC value of 21.50%. The coals and coaly shale sediments are relatively higher in organic richness, consistent with source rocks generative potential. The samples analysed have vitrinite reflectance in the range of 0.84–1.10 %Ro and pyrolysis T_max in the range of 432–454 °C indicate that the Mukalla source rocks contain mature to late mature organic matter. Good oil-generating potential is anticipated from the coals and coaly shale sediments with high hydrogen indices (250–449 mg HC/g TOC). This is supported by their significant amounts of oil-liptinite macerals are present in these coals and coaly shale sediments and Py-GC (S₂) pyrograms with n-alkane/alkene doublets extending beyond nC₃₀. The shales are dominated by Type III kerogen (HI < 200 mg HC/g TOC), and are thus considered to be gas-prone.One-dimensional basin modelling was performed to analysis the hydrocarbon generation and expulsion history of the Mukalla source rocks in the Jiza-Qamar Basin based on the reconstruction of the burial/thermal maturity histories in order to improve our understanding of the of hydrocarbon generation potential of the Mukalla source rocks. Calibration of the model with measured vitrinite reflectance (Ro) and borehole temperature data indicates that the present-day heat flow in the Jiza-Qamar Basin varies from 45.0 mW/m² to 70.0 mW/m² and the paleo-heat flow increased from 80 Ma to 25 Ma, reached a peak heat-flow values of approximately 70.0 mW/m² at 25 Ma and then decreased exponentially from 25 Ma to present-day. The peak paleo-heat flow is explained by the Gulf of Aden and Red Sea Tertiary rifting during Oligocene-Middle Miocene, which has a considerable influence on the thermal maturity of the Mukalla source rocks. The source rocks of the Mukalla Formation are presently in a stage of oil and condensate generation with maturity from 0.50% to 1.10% Ro. Oil generation (0.5% Ro) in the Mukalla source rocks began from about 61 Ma to 54 Ma and the peak hydrocarbon generation (1.0% Ro) occurred approximately from 25 Ma to 20 Ma. The modelled hydrocarbon expulsion evolution suggested that the timing of hydrocarbon expulsion from the Mukalla source rocks began from 15 Ma to present-day.     

Generation characteristics of Mesozoic syn- and post-rift source rocks,Bonaparte Basin,Australia: New insights from compositional kinetic modelling

Potential source rocks on the Laminaria High, a region of the northern Bonaparte Basin on the North West Shelf of Australia, occur within the Middle Jurassic to Lower Cretaceous early to post-rift sequences. Twenty-two representative immature source rock samples from the Jurassic to Lower Cretaceous (Plover, Laminaria, Frigate, Flamingo and Echuca Shoals) sequences were analysed to define the hydrocarbon products that analogous mature source rocks could have generated during thermal maturation and filled the petroleum reservoirs in the Laminaria High region. Rock-Eval pyrolysis data indicate that all the source rocks contain type II–III organic matter and vary in organic richness and quality. Open system pyrolysis-gas chromatography on extracted rock samples show a dominance of aliphatic components in the pyrolysates. The Plover source rocks are the exception which exhibit high phenolic contents due to their predominant land-plant contribution. Most of the kerogens have the potential to generate Paraffinic–Naphthenic–Aromatic oils with low wax contents. Bulk kinetic analyses reveal a relatively broad distribution of activation energies that are directly related to the heterogeneity in the kerogens. These kinetic parameters suggest different degrees of thermal stability, with the predicted commencement of petroleum generation under geological heating conditions covering a relatively broad temperature range from 95 to 135 °C for the Upper Jurassic−Lower Cretaceous source rocks. Both shales and coals of the Middle Jurassic Plover Formation have the potential to generate oil at relatively higher temperatures (140–145 °C) than those measured for crude oils in previous studies. Hence, the Frigate and the Flamingo formations are the main potential sources of oils reservoired in the Laminaria and Corallina fields. Apart from being a reservoir, the Laminaria Formation also contains organic-rich layers, with the potential to generate oil. For the majority of samples analysed, the compositional kinetic model predictions indicate that 80% of the hydrocarbons were generated as oil and 20% as gas. The exception is the Lower Cretaceous Echuca Shoals Formation which shows the potential to generate a greater proportion (40%) of gas despite its marine source affinity, due to inertinite dominating the maceral assemblage.