Geochemical evidence for coal-derived hydrocarbons and their charge history in the Dabei Gas Field, Kuqa Thrust Belt, Tarim Basin, NW China

Large to middle-scale thrust structures are important reservoir plays for coal-derived hydrocarbons in the foreland basins of NW China, with both gas and some accompanying oil. In the Dabei Gas Field of the Kuqa Thrust, however, the oil and gas pools are vertically distributed in a quite unique way: (1) liquid oil and some dissolved gas are present in the Dawanqi Anticline with the reservoir at 300-700 m depth, forming the only oil field in the Kuqa Thrust; (2) gas and minor accompanying oil are found in the deep reservoir of the Dabei-1 and Dabei-2 thrust traps around 5000-6000 m depth; (3) an extremely dry gas pool is found in the Dabei-3 thrust trap where the depth of the reservoir is over 7000 m. Geochemical data suggest that the hydrocarbons in the Dawanqi Anticline and the Dabei thrust traps originated from a similar source, i.e. the underlying Jurassic coal measures, with some contribution from Jurassic lacustrine shales. The Jurassic source rocks did not start to generate oil until the Miocene (around the Kangcun Stage), and extended into the Pliocene (the Kuche Stage) with the main gas generation period in the Pliocene (the Kuche Stage) and the Quaternary. Because the traps formed relatively early, the Dabei-1 and Dabei-2 thrusts could trap some of the early generated oils, but most of the early charged oil was redistributed to the shallower Dawanqi Anticline during the Kuche Stage. The Dabei-3 thrust trap formed concurrently with major gas generation and thus could not trap liquid hydrocarbons. The difference in the vertical distribution of the hydrocarbon accumulations in the Dabei Gas Field resulted from a complex interplay of source variability, structural evolution of the basin and thermal maturation.     

Alteration and multi-stage accumulation of oil and gas in the Ordovician of the Tabei Uplift,Tarim Basin,NW China: Implications for genetic origin of the diverse hydrocarbons

The Ordovician is the most important exploration target in the Tabei Uplift of the Tarim Basin, which contains a range of petroleum types including solid bitumen, heavy oil, light oil, condensate, wet gas and dry gas. The density of the black oils ranges from 0.81 g/cm³ to 1.01 g/cm³ (20 °C) and gas oil ratio (GOR) ranges from 4 m³/m³ to 9300 m³/m³. Oil-source correlations established that most of the oils were derived from the Mid-Upper Ordovician marine shale and carbonate and that the difference in oil properties is mainly attributed to hydrocarbon alteration and multi-stage accumulation. In the Tabei Uplift, there were three main periods of hydrocarbon accumulation in the late Caledonian stage (ca. 450–430 Ma), late Hercynian stage (ca. 293–255 Ma) and the late Himalayan stage (ca. 12–2 Ma). The oil charging events mainly occurred in the late Caledonian and late Hercynian stage, while gas charging occurred in the late Hercynian stage. During the late Caledonian stage, petroleum charged the reservoirs lying east of the uplift. However, due to a crustal uplifting episode in the early Hercynian (ca. 386–372 Ma), most of the hydrocarbons were transformed by processes such as biodegradation, resulting in residual solid bitumen in the fractures of the reservoirs. During the late Hercynian Stage, a major episode of oil charging into Ordovician reservoirs took place. Subsequent crustal uplift and severe alteration by biodegradation in the west-central Basin resulted in heavy oil formation. Since the late Himalayan stage when rapid subsidence of the crust occurred, the oil residing in reservoirs was exposed to high temperature cracking conditions resulting in the production of gas and charged from the southeast further altering the pre-existing oils in the eastern reservoirs. A suite of representative samples of various crude oils including condensates, lights oils and heavy oils have been collected for detailed analysis to investigate the mechanism of formation. Based on the research it was concluded that the diversity of hydrocarbon physical and chemical properties in the Tabei Uplift was mainly attributable to the processes of biodegradation and gas washing. The understanding of the processes is very helpful to predict the spatial distribution of hydrocarbon in the Tabei Uplift and provides a reference case study for other areas.     

Impact of high water pressure on oil generation and maturation in Kimmeridge Clay and Monterey source rocks: Implications for petroleum retention and gas generation in shale gas systems

This study presents results for pyrolysis experiments conducted on immature Type II and IIs source rocks (Kimmeridge Clay, Dorset UK, and Monterey shale, California, USA respectively) to investigate the impact of high water pressure on source rock maturation and petroleum (oil and gas) generation. Using a 25 ml Hastalloy vessel, the source rocks were pyrolysed at low (180 and 245 bar) and high (500, 700 and 900 bar) water pressure hydrous conditions at 350 °C and 380 °C for between 6 and 24 h. For the Kimmeridge Clay (KCF) at 350 °C, Rock Eval HI of the pyrolysed rock residues were 30–44 mg/g higher between 6 h and 12 h at 900 bar than at 180 bar. Also at 350 °C for 24 h the gas, expelled oil, and vitrinite reflectance (VR) were all reduced by 46%, 61%, and 0.25% Ro respectively at 900 bar compared with 180 bar. At 380 °C the retardation effect of pressure on the KCF was less significant for gas generation. However, oil yield and VR were reduced by 47% and 0.3% Ro respectively, and Rock Eval HI was also higher by 28 mg/g at 900 bar compared with 245 bar at 12 h. The huge decrease in gas and oil yields and the VR observed with an increase in water pressure at 350 °C for 24 h and 380 °C for 12 h (maximum oil generation) were also observed for all other times and temperatures investigated for the KCF and the Monterey shale. This shows that high water pressure significantly retards petroleum generation and source rock maturation. The retardation of oil generation and expulsion resulted in significant amounts of bitumen and oil being retained in the rocks pyrolysed at high pressures, suggesting that pressure is a possible mechanism for retaining petroleum (bitumen and oil) in source rocks. This retention of petroleum within the rock provides a mechanism for oil-prone source rocks to become potential shale gas reservoirs. The implications from this study are that in geological basins, pressure, temperature and time will all exert significant control on the extent of petroleum generation and source rock maturation for Type II source rocks, and that the petroleum retained in the rocks at high pressures may explain in part why oil-prone source rocks contain the most prolific shale gas resources.     

Effects of oil cracking on fluorescence color,homogenization temperature and trapping pressure reconstruction of oil inclusions from deeply buried reservoirs in the northern Dongying Depression,Bohai Bay Basin,China

The effects of oil cracking on fluorescence color, homogenization temperature (T_ho) and trapping pressure (P_t) of oil inclusions from deeply buried reservoirs (DBRs) (3672–4359 m) in the northern Dongying Depression were determined based on fluorescence spectroscopy and homogenization temperatures of oil inclusions, kinetic modeling of crude oil cracking, and petroleum inclusion thermodynamics modeling.The modeling results demonstrate that fluorescence color, T_ho and predicted P_t have strong relationships with the transformation rate via cracking of oil to gas (T_r), and the formation temperature (T_f) that the inclusions experienced. The fluorescence color is hardly influenced at all during the initial stages of oil cracking (T_r < 13%, T_f < 160 °C), but fluorescence color begins to shift toward shorter wavelengths (blue shift) during progressive oil cracking (T_r < 24%, T_f < 190 °C). With further oil cracking, the fluorescence color may either experience no change or continue its blue shift. Eventually the fluorescence color will disappear as the aromatic compounds are completely cracked. The T_ho increases at first (T_r < 24%, T_f < 190 °C), but then decreases or even becomes negative during major oil cracking. The reconstructed P_t values show a corresponding reverse trend.Oil inclusions from DBRs and other shallow reservoirs in the Dongying Depression show an obvious blue shift in fluorescence color at a depth of approximate 4000 m (T_f = 160 °C) and generally contain solid bitumen below 4000 m, supporting the effect of oil cracking on fluorescence variation, consistent with the modeling result. The T_ho from DBRs in the Minfeng area increases with increasing burial depth (T_f < 190 °C), which is also consistent with the modeling results. However, the T_ho of oil inclusions with blue-white fluorescence from DBRs in the Shengtuo area did not show such a trend. Recent trapping, high trapping pressure and higher-maturity oil may have led to a low-degree of oil cracking, and thus less modification of T_ho in the Shengtuo area.Oil cracking results in consistent volume ratios of pyrobitumen to oil inclusions (F_vpy) in the same fluid inclusion assemblage, and the F_vpy value increases with oil cracking level, which can be used to recognize if oil cracking has occurred in oil inclusions and what level of oil cracking they have experienced.As the oil cracking model used in this study did not account for the role of pressure, it is more applicable for oil inclusions that were trapped under normally pressured conditions. Oil inclusions trapped under overpressured conditions will be less influenced by oil cracking.     

Synthetic saline-aqueous and hydrocarbon fluid inclusions trapped in calcite at temperatures and pressures relevant to hydrocarbon basins: A reconnaissance study

We conducted reconnaissance experiments to synthesize aqueous and hydrocarbon inclusions trapped in calcite at conditions relevant to petroleum basins, and characterize the microthermometric properties of such inclusions. Fluid inclusions (FIs) were synthesized in a system of saline aqueous solution (5 or 20 wt% NaCl) coexisting with either heavy crude oil or gasoline under gas-undersaturated conditions, from 90 to 210 °C and 200–550 bar. The synthetic inclusions are not representative of gas-bearing systems, and methane (CH₄) was not detected in any aqueous inclusions. The FIs are mainly distributed along planar healed cracks, indicating that the inclusions formed by fracture healing in the calcite crystal. Microthermometric measurements were conducted on coeval aqueous and hydrocarbon inclusions, and Raman spectroscopic analyses were done on aqueous inclusions, to determine the properties of FIs trapped at these conditions.Homogenization temperatures of synthetic FIs are mostly lower than the experimental trapping temperature, although the FIs show high variability in measured homogenization temperature. Results allow comparison of T_h values for each sample with the expected T_h, isochores and pressure corrections calculated for the system H₂ONaCl. The latter parameters are broadly consistent with the known PVTX properties of H₂ONaCl fluids, suggesting little effect of hydrocarbons on the homogenization behavior, although the low precision of the T_h data limits this assessment. Nevertheless, this result is not unexpected considering that light hydrocarbons (gas) is not present in the experiments (as corroborated by Raman spectroscopy), a consequence of using “dead” oil in the experiments. Simulation of gas-bearing petroleum basins will require additional protocols for producing gas, either by in-situ cracking of the starting hydrocarbon material, or by other means. The reconnaissance experiments documented here provide a basis for such future experiments.     

Petroleum accumulation in the deeply buried reservoirs in the northern Dongying Depression,Bohai Bay Basin,China: New insights from fluid inclusions,natural gas geochemistry,and 1-D basin modeling

The deeply buried reservoirs (DBRs) from the Lijin, Shengtuo and Minfeng areas in the northern Dongying Depression of the Bohai Bay Basin, China exhibit various petroleum types (black oil-gas condensates) and pressure systems (normal pressure-overpressure) with high reservoir temperatures (154–185 °C). The pressure-volume-temperature-composition (PVTX) evolution of petroleum and the processes of petroleum accumulation were reconstructed using integrated data from fluid inclusions, stable carbon isotope data of natural gas and one-dimensional basin modeling to trace the petroleum accumulation histories.The results suggest that (1) the gas condensates in the Lijin area originated from the thermal cracking of highly mature kerogen in deeper formations. Two episodes of gas condensate charging, which were evidenced by the trapping of non-fluorescent gas condensate inclusions, occurred between 29-25.5 Ma and 8.6–5.0 Ma with strong overpressure (pressure coefficient, P_c = 1.68–1.70), resulting in the greatest contribution to the present-day gas condensate accumulation; (2) the early yellow fluorescent oil charge was responsible for the present-day black oil accumulation in well T764, while the late blue-white oil charge together with the latest kerogen cracked gas injection resulted in the present-day volatile oil accumulation in well T765; and (3) the various fluorescent colors (yellow, blue-white and blue) and the degree of bubble filling (F_v) (2.3–72.5%) of the oil inclusions in the Minfeng area show a wide range of thermal maturity (API gravity ranges from 30 to 50°), representing the charging of black oil to gas condensates. The presence of abundant blue-white fluorescent oil inclusions with high Grain-obtaining Oil Inclusion (GOI) values (35.8%, usually >5% in oil reservoirs) indicate that a paleo-oil accumulation with an approximate API gravity of 39–40° could have occurred before 25 Ma, and gas from oil cracking in deeper formations was injected into the paleo-oil reservoir from 2.8 Ma to 0 Ma, resulting in the present-day gas condensate oil accumulation. This oil and gas accumulation model results in three oil and gas distribution zones: 1) normal oil reservoirs at relatively shallow depth; 2) gas condensate reservoirs that originated from the mixture of oil cracking gas with a paleo-oil reservoir at intermediate depth; and 3) oil-cracked gas reservoirs at deeper depth.The retardation of organic matter maturation and oil cracking by high overpressure could have played an important role in the distribution of different origins of gas condensate accumulations in the Lijin and Minfeng areas. The application of oil and gas accumulation models in this study is not limited to the Dongying Depression and can be applied to other overpressured rift basins.     

Evolution of porosity and pore types in organic-rich,calcareous, Lower Toarcian Posidonia Shale

Low and high resolution petrographic studies have been combined with mineralogical, TOC, RockEval and porosity data to investigate controls on the evolution of porosity in stratigraphically equivalent immature, oil-window and gas-window samples from the Lower Toarcian Posidonia Shale formation. A series of 26 samples from three boreholes (Wickensen, Harderode and Haddessen) in the Hils syncline was investigated. The main primary components of the shales are microfossiferous calcite (30–50%), clay minerals (20–30%) and Type II organic matter (TOC = 7–15%, HI = 630–720 mg/gC in immature samples). Characteristic sub-centimetric light and dark lamination reflects rapid changes in the relative supply of these components. Total porosities decrease from 10 to 14% at Ro = 0.5% to 3–5% at Ro = 0.9% and then increase to 9–12% at Ro = 1.45%. These maturity-related porosity changes can be explained by (a) the primary composition of the shales, (b) carbonate diagenesis, (c) compaction and (d) the maturation, micro-migration, local trapping and gasification of heterogeneous organic phases. Calcite undergoes dissolution and reprecipitation reactions throughout the maturation sequence. Pores quantifiable in SEM (>ca. 50 nm) account for 14–25% of total porosity. At Ro = 0.5%, SEM-visible macropores¹ are associated mainly with biogenic calcite. At this maturity, clays and organic matter are not visibly porous but nevertheless hold most of the shale porosity. Porosity loss into the oil window reflects (a) compaction, (b) carbonate cementation and (c) perhaps the swelling of kerogen by retained oil. In addition, porosity is occluded by a range of bituminous phases, especially in microfossil macropores and microfractures. In the gas window, mineral-hosted porosity is still the primary form of macroporosity, most commonly observed at the organic-inorganic interface. Increasing porosity into the gas window also coincides with the formation of isolated, spongy and complex meso- and macropores within organic particles, related to thermal cracking and gas generation. This intraorganic porosity is highly heterogeneous: point-counted macroporosity of individual organic particles ranges from 0 to 40%, with 65% of organic particles containing no macropores. We suggest that this reflects the physicochemical heterogeneity of the organic phases plus the variable mechanical protection afforded by the mineral matrix to allow macroporosity to be retained. The development of organic macroporosity cannot alone account for the porosity increase observed from oil to gas window; major contributions also come from the increased volume of organic micro- and meso-porosity, and perhaps by kerogen shrinkage.     

Source rocks and petroleum systems in the Hungarian part of the Pannonian Basin: The potential for shale gas and shale oil plays

The objectives of our study were to assess the thickness, lateral extent, organic richness and maturity of the potential source rocks in Hungary and to estimate the volumes of hydrocarbons generated, in order that potential shale gas and shale oil plays could be identified and characterised.The Upper Triassic Kössen Marl in south-west Hungary could represent the best potential shale gas/shale oil play, due to its high organic richness, high maturity and the presence of fracture barriers. The area of gas- and oil-generative maturity is around 720 km² with the unexpelled petroleum estimated to be up to 9 billion barrel oil-equivalent.The Lower Jurassic sediments of the Mecsek Mountains and under the Great Plain contain fair quality gas-prone source rocks, with low shale gas potential, except for a thin Toarcian shale unit which is richer in organic matter. The latter could form a potential shale gas play under the Great Hungarian Plain, if it is thicker locally.The Lower Oligocene Tard Clay in north-east Hungary could represent the second best potential shale oil play, due to its organic richness, favourable maturity and large areal extent (4500 km²) with around 7 billion barrel oil-equivalent estimated in-place volume of petroleum.Middle Miocene marine formations could represent locally-developed shale gas plays; they have fair amounts of organic matter and a mixture of type II/III kerogen, but their vertical and lateral variability is high.The Upper Miocene lacustrine Endrőd Marl contains less organic matter and the kerogen is mainly type III, which is not favourable for shale gas generation. The high carbonate and clay content, plus the lack of upper and lower fracture barriers would represent additional production challenges.     

Bitumen biomarkers in the Mid-Proterozoic Ilímaussaq intrusion, Southwest Greenland - A challenge to the mantle gas theory

GC and GC/MS/MS analysis on rock extracts has shown that the bitumen in the peralkaline Ilímaussaq intrusion, previously assumed to be abiogenic, is biotic in origin. A biotic origin is in accordance with previously published stable carbon isotopic data on bituminous matter in the rocks. The biomarker distribution in the bitumen, including the less common bicadinanes, resembles that of oil seeps on the central West Greenland coast 2200 km farther north, whose source rocks and migration history are relatively well established. We use a recent re-construction of the subsidence and later exhumation of the West Greenland coastal region during the Mesozoic-Cenozoic (Japsen et al., 2006a, b) to anticipate that hydrocarbons migrated from deeper parts of the basin offshore west of Greenland. The rocks of Ilímaussaq were probably more deeply invaded than the surrounding granites due to their higher proportion of corroded minerals, which may explain why bitumen has not been observed elsewhere in the area.Hydrocarbon gases (C1-C5) present in fluid inclusions were also analysed, after having been released by treatment with hydrochloric acid that resulted in an almost complete disintegration of the Ilímaussaq intrusion rocks. The acid extraction method proved generally more efficient than the crushing procedure applied by others, but gave similar results for the chemical composition of the gas (CH₄: 88-97%) and isotopic ratios (δ¹³C₄CH: −1.6 to −5.0‰; δ¹³CC₂H₆: −9.2 to −12.5‰), with the exception of hydrocarbons hosted in quartz, which showed significantly lower isotopic values for methane (Graser et al., 2008). Previous researchers have suggested an abiotic origin for these hydrocarbon gases, but we suggest a biotic origin for the majority of them, not just those in quartz, assuming that the isotopic ratio of the constituents have changed due to loss of gas by diffusion. The assumption of gas loss via diffusion is supported by published studies on micro-fissures in minerals typical of the Ilímaussaq and field investigations showing diffusive loss of gas from the peralkaline Khibina and Lovozero massifs on the Kola Peninsula, Russia, which are, in many respects of mineralogy and hydrocarbon content, similar to the Ilímaussaq intrusion.Both the hydrocarbon gases and bitumen in the Khibina and Lovozero massifs have been cited as prime examples of a deep mantle source, although the carbon isotopic ratio of the bitumen clearly pointed to an organic origin. The trends in carbon isotopic ratio of methane released with time from freshly exposed rocks also supports our hypothesis of ¹³C enrichment of the methane remaining within the rock. Thus, there is good evidence that the hydrocarbons in the Kola alkaline massifs are mostly biotic in origin, in which case the probability of finding economic hydrocarbon accumulations from a deep mantle source seems exceedingly small.     

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).     

Coalbed methane reservoirs’ pore-structure characterization of different macrolithotypes in the southern Junggar Basin of Northwest China

Coalbed methane (CBM) development in the southern Junggar Basin of Northwest China has aroused extensive attention owing to its significant resource potential. The accurate characterization of coal pore structure is important for CBM exploration and production. In order to explore the relationship between coal pore structure and macrolithotype, which has rarely been studied in the southern Junggar Basin, a series of laboratory experiments were performed on eight samples of different macrolithotypes. The results show that the porosity exhibits regularity with macrolithotype in the order bright < semibright < semidull < dull, and also shows an increase with the rise of the inertinite content. The pore-size distribution results show that the dominating pores of bright and semibright coals are usually greater than that of dull and semidull coals in size. The pore-type analysis indicates that the bottleneck pores (Type B) are well developed in dull and semidull coals, while bright and semibright coals mainly host two sides (Type A), namely opened pores and one-side-closed pores (Type C). The pore-type and -size distribution strongly affect pore connectivity refers to the facts that: 1) the proportion of effective porosity increases with an increasing proportion of pores greater than 100 nm in size; and 2) that the mercury withdrawal efficiency is always lower when the pores are mostly of Type B. So the pore connectivity of semibright and bright coals is higher than that of semidull and dull coals. Furthermore, pores are developed mainly in the inertinite, with pore-type being dominated by Type B and C, secondly in the vitrinite, with pore-type being dominated by Type A and C, and less developed in the liptinite with pore-type of B and C. The pore connectivity of each maceral is in the order vitrinite > inertinite > liptinite. Finally, according to the research results, the reservoir fracturing improvement should be more arranged on the dull or semi-dull coals, and the producing layers should be bright or semi-bright coals as much as possible on the premise that the gas contents of coal layers are not much different from each other.     

Hydrocarbon prospects across Narmada-Tapti rift in Deccan trap, central India: Inferences from integrated interpretation of magnetotelluric and geochemical prospecting studies

As the Mesozoic sediments contribute most of the oil and gas reserves of the world, we present an integrated interpretation approach using magnetotellurics (MT) and surface geochemical prospecting studies to demarcate hydrocarbon prospective Gondwana (Mesozoic) formations underneath the Deccan flood basalts of Late Cretaceous age across Narmada-Tapti rift (between Bhusawal and Barwah) in Central India. The MT interpretation shows deep (∼5 km) basement structure between southern and central part of the MT profile however, it gradually becomes shallower to either ends of the profile with a predominant basement depth reduction in the northern end compared to the southern end. The geophysical results suggest thick (2-3.5 km) Mesozoic sediments in the area characterized by deep basement structure. The geochemical analysis of the near surface soil samples indicate higher concentrations of light gaseous hydrocarbons constituents over the area marked with thick sub-basalt Mesozoic formations. Analyses of the geochemical data imply that these hydrocarbons are genetically related, generated from a thermogenic source and these samples fall in the oil-producing zone. The temperature-depth estimations in the region supports favorable temperature conditions (80-120 °C) for oil generation at basement depths.     

Jurassic source rocks in the Vienna Basin (Austria): Assessment of conventional and unconventional petroleum potential

The Upper Jurassic marlstones (Mikulov Fm.) and marly limestones (Falkenstein Fm.) are the main source rocks for conventional hydrocarbons in the Vienna Basin in Austria. In addition, the Mikulov Formation has been considered a potential shale gas play. In this paper, organic geochemical, petrographical and mineralogical data from both formations in borehole Staatz 1 are used to determine the source potential and its vertical variability. Additional samples from other boreholes are used to evaluate lateral trends. Deltaic sediments (Lower Quarzarenite Member) and prodelta shales (Lower Shale Member) of the Middle Jurassic Gresten Formation have been discussed as secondary sources for hydrocarbons in the Vienna Basin area and are therefore included in the present study.The Falkenstein and Mikulov formations in Staatz 1 contain up to 2.5 wt%TOC. The organic matter is dominated by algal material. Nevertheless, HI values are relative low (<400 mgHC/gTOC), a result of organic matter degradation in a dysoxic environment. Both formations hold a fair to good petroleum potential. Because of its great thickness (∼1500 m), the source potential index of the Upper Jurrasic interval is high (7.5 tHC/m²). Within the oil window, the Falkenstein and Mikulov formations will produce paraffinic-naphtenic-aromatic low wax oil with low sulfur content. Whereas vertical variations are minor, limited data from the deep overmature samples suggest that original TOC contents may have increased basinwards. Based on TOC contents (typically <2.0 wt%) and the very deep position of the maturity cut-off values for shale oil/gas production (∼4000 and 5000 m, respectively), the potential for economic recovery of unconventional petroleum is limited. The Lower Quarzarenite Member of the Middle Jurassic Gresten Formation hosts a moderate oil potential, while the Lower Shale Member is are poor source rock.     

Khasib and Tannuma oil sources, East Baghdad oil field, Iraq

This work presents new insights of the generation, quality and migration pathways of the hydrocarbons in the East Baghdad Oil Field.The Khasib and Tannuma formations in East Baghdad are considered as oil reservoirs according to their high porosity (15-23%) and permeability (20-45 mD) in carbonate rocks. The hydrocarbons are trapped by structural anticline closure trending NW-SE. Gas chromatography analysis on these oil reservoirshave shown biomarkers of abundant ranges of n-alkanes of less than C22 (C17-C21) with C19 and C18 peaks. This suggests mainly liquid oil constituents of paraffinic hydrocarbons from marine algal source of restricted palaeoenvironments in the reservoir. The low non aromatic C15 + peaks are indicative for slight degradation and water washing. Oil biomarkers of Pr./Ph. = 0.85, C31/C30 < 1.0, location in triangle of C27-C29 sterane, C28/C29 of 0.6 sterane, Oleanane of 0.01 and CPI = 1.0, indicate an anoxic marine environment with carbonate deposits of Upper Jurassic to Early Cretaceous age. Four Miospores, seven Dinoflagellates and one Tasmanite species confirm affinity to the upper most Jurassic to Lower Cretaceous Chia Gara and Ratawi Formations.The recorded palynomorphs from the Khasib and Tannuma Formations are of light brown color of TAI = 2.8-3.0 and comparable to the mature palynomorphs that belong to the Chia Gara and the Lower part of Ratawi Formations.The Chia Gara Formation generated oil during Upper Cretaceous to Early Palaeogene and accumulated in structural traps of Cretaceous age, such as the Khasib and Tannuma reservoirs. The Chia Gara Formation generated and expelled high quantities of oil hydrocarbons according to their TOC wt% of 0.5-8.5 with S2 = 2.5-18.5 mg Hc/g Rock, high hydrogen index of the range 150-450 mg Hc/g Rock, good petroleum potential of 4.5-23.5 mg Hc/g Rock, mature (TAI = 2.8-3.0 and T_max = 428-443C), kerogen type II and palynofacies parameters of up to 100% AOM (Amorphous Organic Matters). This includes algae deposits in a dysoxic-anoxic to suboxic-anoxic environment.Alternative plays are discussed according to the migration pathways.     

Hydrocarbon charging and accumulation history in the Niudong Buried Hill Field in the Baxian Depression,eastern China

The Niudong Buried Hill Field, which lies in the Baxian Depression of the Bohai Bay Basin, is the deepest oil/gas accumulation in eastern China. Its Precambrian dolomite reservoir occurs at burial depths of 5860 m–6027 m. This paper attempts to document the hydrocarbon charging and accumulation history in this field, which could greatly enhance the understanding of the mechanisms for the formation of deep hydrocarbon accumulations. Our previous study of oil trapped in fluid inclusions has demonstrated that the ratio parameters of the fluorescence spectral intensities at 425 nm and 433 nm (Q_425/433 ratio), and at 419 nm and 429 nm (Q_419/429 ratio) can be more effective for revealing hydrocarbon charging history than the previously-used fluorescence parameters such as Lambda max and red/green quotient as well as fluorescence colors. The hydrocarbon charging and accumulation history in the Niudong Buried Hill Field was studied with an integrated approach involving the application of these two spectral parameters of petroleum inclusion fluorescence as well as utilization of other data including homogenization temperatures of aqueous inclusions coeval with petroleum inclusions, and cross-cutting relationships of cements and “oil veins” in pores and fractures. The results indicate that the dolomite reservoir in the Niudong Buried Hill Field experienced three episodes of hydrocarbon charging. In the first two episodes (between 38.5Ma and 25Ma), the low mature and mature oils, which were derived from source rocks in the Sha-4 Member of the Eocene Shahejie Formation, migrated into the reservoir, but part of them leaked out due to normal faulting at the updip margin of the buried hill. These early-charged oils were preserved mainly in small pores in micritic dolomites by oil-wettability and capillary pressure. In the Neogene, the basin subsided as a whole and local faults at the updip margin became inactive and played a sealing role. By approximately 13Ma, the source rocks became highly mature and the generated hydrocarbons then migrated into the reservoir and accumulated. Therefore, the last charging is the most important for hydrocarbon accumulation in the Niudong Buried Hill Field.     

Oil-oil and oil-source rock correlations in the Alpine Foreland Basin of Austria: Insights from biomarker and stable carbon isotope studies

The Alpine Foreland Basin is a minor oil and moderate gas province in central Europe. In the Austrian part of the Alpine Foreland Basin, oil and minor thermal gas are thought to be predominantly sourced from Lower Oligocene horizons (Schöneck and Eggerding formations). The source rocks are immature where the oil fields are located and enter the oil window at ca. 4 km depth beneath the Alpine nappes indicating long-distance lateral migration. Most important reservoirs are Upper Cretaceous and Eocene basal sandstones.Stable carbon isotope and biomarker ratios of oils from different reservoirs indicate compositional trends in W-E direction which reflect differences in source, depositional environment (facies), and maturity of potential source rocks. Thermal maturity parameters from oils of different fields are only in the western part consistent with northward displacement of immature oils by subsequently generated oils. In the eastern part of the basin different migration pathways must be assumed. The trend in S/(S + R) isomerisation of ααα-C₂₉ steranes versus the αββ (20R)/ααα (20R) C₂₉ steranes ratio from oil samples can be explained by differences in thermal maturation without involving long-distance migration. The results argue for hydrocarbon migration through highly permeable carrier beds or open faults rather than relatively short migration distances from the source. The lateral distance of oil fields to the position of mature source rocks beneath the Alpine nappes in the south suggests minimum migration distances between less than 20 km and more than 50 km.Biomarker compositions of the oils suggest Oligocene shaly to marly successions (i.e. Schoeneck, Dynow, and Eggerding formations) as potential source rocks, taking into account their immature character. Best matches are obtained between the oils and units a/b (marly shale) and c (black shale) of the “normal” Schöneck Formation, as well as with the so-called “Oberhofen Facies”. Results from open system pyrolysis-gas chromatography of potential source rocks indicate slightly higher sulphur content of the resulting pyrolysate from unit b. The enhanced dibenzothiophene/phenanthrene ratios of oils from the western part of the basin would be consistent with a higher contribution of unit b to hydrocarbon expulsion in this area. Differences in the relative contribution of sedimentary units to oil generation are inherited from thickness variations of respective units in the overthrusted sediments. The observed trend towards lighter δ¹³C values of hydrocarbon fractions from oil fields in a W-E direction are consistent with lower δ¹³C values of organic matter in unit c.     

Thermal maturity,source rock potential and kinetics of hydrocarbon generation in Permian shales from the Damodar Valley basin,Eastern India

This study investigates the source rock characteristics of Permian shales from the Jharia sub-basin of Damodar Valley in Eastern India. Borehole shales from the Raniganj, Barren Measure and Barakar Formations were subjected to bulk and quantitative pyrolysis, carbon isotope measurements, mineral identification and organic petrography. The results obtained were used to predict the abundance, source and maturity of kerogen, along with kinetic parameters for its thermal breakdown into simpler hydrocarbons.The shales are characterized by a high TOC (>3.4%), mature to post-mature, heterogeneous Type II–III kerogen. Raniganj and Barren Measure shales are in mature, late oil generation stage (Rr%_Raniganj = 0.99–1.22; Rr%_{Barren Measure} = 1.1–1.41). Vitrinite is the dominant maceral in these shales. Barakar shows a post-mature kerogen in gas generation stage (Rr%_Barakar = 1.11–2.0) and consist mainly of inertinite and vitrinite. The δ¹³C_org value of kerogen concentrate from Barren Measure shale indicates a lacustrine/marine origin (−24.6–−30.84‰ vs. VPDB) and that of Raniganj and Barakar (−22.72–−25.03‰ vs. VPDB) show the organic provenance to be continental. The δ¹³C ratio of thermo-labile hydrocarbons (C₁–C₃) in Barren Measure suggests a thermogenic source.Discrete bulk kinetic parameters indicate that Raniganj has lower activation energies (ΔE = 42–62 kcal/mol) compared to Barren Measure and Barakar (ΔE = 44–68 kcal/mol). Temperature for onset (10%), middle (50%) and end (90%) of kerogen transformation is least for Raniganj, followed by Barren Measure and Barakar. Mineral content is dominated by quartz (42–63%), siderite (9–15%) and clay (14–29%). Permian shales, in particular the Barren Measure, as inferred from the results of our study, demonstrate excellent properties of a potential shale gas system.     

Gas geochemistry of the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope: Implications for gas hydrate exploration in the Arctic

Gases were analyzed from well cuttings, core, gas hydrate, and formation tests at the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well, drilled within the Milne Point Unit, Alaska North Slope. The well penetrated a portion of the Eileen gas hydrate deposit, which overlies the more deeply buried Prudhoe Bay, Milne Point, West Sak, and Kuparuk River oil fields. Gas sources in the upper 200 m are predominantly from microbial sources (C₁ isotopic compositions ranging from −86.4 to −80.6‰). The C₁ isotopic composition becomes progressively enriched from 200 m to the top of the gas hydrate-bearing sands at 600 m. The tested gas hydrates occur in two primary intervals, units D and C, between 614.0 m and 664.7 m, containing a total of 29.3 m of gas hydrate-bearing sands. The hydrocarbon gases in cuttings and core samples from 604 to 914 m are composed of methane with very little ethane. The isotopic composition of the methane carbon ranges from −50.1 to −43.9‰ with several outliers, generally decreasing with depth. Gas samples collected by the Modular Formation Dynamics Testing (MDT) tool in the hydrate-bearing units were similarly composed mainly of methane, with up to 284 ppm ethane. The methane isotopic composition ranged from −48.2 to −48.0‰ in the C sand and from −48.4 to −46.6‰ in the D sand. Methane hydrogen isotopic composition ranged from −238 to −230‰, with slightly more depleted values in the deeper C sand. These results are consistent with the concept that the Eileen gas hydrates contain a mixture of deep-sourced, microbially biodegraded thermogenic gas, with lesser amounts of thermogenic oil-associated gas, and coal gas. Thermal gases are likely sourced from existing oil and gas accumulations that have migrated up-dip and/or up-fault and formed gas hydrate in response to climate cooling with permafrost formation.     

Effects of petroleum hydrocarbons on the hepatic cytochrome P450 1A1 system in rainbow trout

Effects on the hepatic cytochrome P450 1A1 system were investigated in juvenile rainbow trout i.p. injected with three different aromatic containing fractions: kerosene, light gas oil or heavy gas oil, originated from distilled North Sea crude oil. Kerosene treatment resulted in no effect on the P450 1A1 system, light gas oil injection caused a weak induction of EROD activities and heavy gas oil treatment resulted in a prominent induction of EROD activities as well as accumulation of CYP1A1 mRNA and P450 1A1 protein levels. The effects of heavy gas oil were compared with effects of β-napthoflavone (β-NF) on the P450 1A1 system. It was obvious that important discrepancies seemed to exist between EROD activities and corresponding CYP1A1 mRNA and P450 1A1 levels in rainbow trout treated with either heavy gas oil or β-NF i.e. heavy gas oil treatment resulted in higher specific EROD activities (EROD/P450 1A1) compared to β-NF. GC-MS analyses revealed that liver and bile from heavy gas oil treated rainbow trout in addition to naphthalene also contained polycyclic aromatic hydrocarbons such as phenanthrenes, anthracene, pyrenes, fluoranthene benz(a)anthracene and chrysene, while none of these compounds were detected in control trout.     

Cause of shale gas geochemical anomalies and mechanisms for gas enrichment and depletion in high-maturity shales

This article reviews the abnormal characteristics of shale gases (natural gases produced from organic-rich shales) and discusses the cause of the anomalies and mechanisms for gas enrichment and depletion in high-maturity organic-rich shales. The reported shale gas geochemical anomalies include rollover of iso-alkane/normal alkane ratios, rollover of ethane and propane isotopic compositions, abnormally light ethane and propane δ¹³C values as well as isotope reversals among methane, ethane and propane. These anomalies reflect the complex histories of gas generation and associated isotopic fractionation as well as in-situ “mixing and accumulation” of gases generated from different precursors at different thermal maturities. A model was proposed to explain the observed geochemical anomalies. Gas generation from kerogen cracking at relatively low thermal maturity accounted for the increase of iso-alkane/normal alkane ratios and ethane and propane δ¹³C values (normal trend). Simultaneous cracking of kerogen, retained oil and wet gas and associated isotopic fractionation at higher maturity caused decreasing iso-alkane/normal alkane ratios, lighter ethane and propane δ¹³C and corresponding conversion of carbon isotopic distribution patterns from normal through partial reversal to complete reversal. Relatively low oil expulsion efficiency at peak oil generation, low expulsion efficiency at peak gas generation and little gas loss during post-generation evolution are necessary for organic-rich shales to display the observed geochemical anomalies. High organic matter richness, high thermal maturity (high degrees of kerogen-gas and oil-gas conversions) and late-stage (the stage of peak gas generation and post-generation evolution) closed system accounted for gas enrichment in shales. Loss of free gases during post-generation evolution may result in gas depletion or even undersaturation (total gas content lower than the gas sorption capacity) in high-maturity organic-rich shales.