Origin of the hydrocarbon gases carbon dioxide and hydrogen sulfide in Dodan Field (SE-Turkey)

Gas occurrences consisting of carbon dioxide (CO₂), hydrogen sulfide (H₂S), and hydrocarbon (HC) gases and oil within the Dodan Field in southeastern Turkey are located in Cretaceous carbonate reservoir rocks in the Garzan and Mardin Formations. The aim of this study was to determine gas composition and to define the origin of gases in Dodan Field. For this purpose, gas samples were analyzed for their molecular and isotopic composition. The isotopic composition of CO₂, with values of −1.5‰ and −2.8‰, suggested abiogenic origin from limestone. δ³⁴S values of H₂S ranged from +11.9 to +13.4‰. H₂S is most likely formed from thermochemical sulfate reduction (TSR) and bacterial sulfate reduction (BSR) within the Bakuk Formation. The Bakuk Formation is composed of a dolomite dominated carbonate succession also containing anhydrite. TSR may occur within an evaporitic environment at temperatures of approximately 120–145 °C. Basin modeling revealed that these temperatures were reached within the Bakuk Formation at 10 Ma. Furthermore, sulfate reducing bacteria were found in oil–water phase samples from Dodan Field. As a result, the H₂S in Dodan Field can be considered to have formed by BSR and TSR.As indicated by their isotopic composition, HC gases are of thermogenic origin and were generated within the Upper Permian Kas and Gomaniibrik Formations. As indicated by the heavier isotopic composition of methane and ethane, HC gases were later altered by TSR. Based on our results, the Dodan gas field may have formed as a result of the interaction of the following processes during the last 7–8 Ma: 1) thermogenic gas generation in Permian source rocks, 2) the formation of thrust faults, 3) the lateral-up dip migration of HC-gases due to thrust faults from the Kas Formation into the Bakuk Formation, 4) the formation of H₂S and CO₂ by TSR within the Bakuk Formation, 5) the vertical migration of gases into reservoirs through the thrust fault, and 6) lateral-up dip migration within reservoir rocks toward the Dodan structure.     

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.     

Origin and distribution of hydrogen sulfide in the Yuanba gas field,Sichuan Basin,Southwest China

The Yuanba gas field in the Permian Changxing Formation (P₂c), which exhibits wide variations in its hydrogen sulfide (H₂S) concentration (1.20–12.16%), is a typical sour gas field in the northern Sichuan Basin. The sulfur-rich reservoir's solid bitumen (atomic S/C ratios are 0.032–0.142), and late calcite cement δ¹³C values, which are smaller than the δ¹³C values of the host dolostone, indicate that the H₂S originated from thermal sulfate reduction (TSR) and oil was involved in TSR. The gas souring index (GSI) of P₂c's gases is generally lower than 0.1. The ethane δ¹³C values increase as the GSI increases, although no obvious increase was observed in the methane δ¹³C values. The calcite cements' δ¹³C values (−15.36 to +4.56‰) in dolostone are heavier than the typical reported values, which implies that only limited heavy hydrocarbon gases were involved in TSR. No anhydrites developed in P₂c's reservoirs, and dissolved sulfate anions (SO₄²⁻) were mainly enriched during dolomitization. Insufficient dissolved SO₄²⁻ most likely caused the lower H₂S concentrations in the Permian to Triassic reservoirs in the northeastern Sichuan Basin compared to the Permian Khuff Formation in Saudi Arabia and the Jurassic Smackover Formation in Mississippi. Except for the SO₄²⁻ in residual water in paleo-oil zones, SO₄²⁻ from bottom water may also be involved in TSR; therefore, oil reservoirs with bottom water have more SO₄²⁻ and can produce more H₂S than pure oil reservoirs. This phenomenon may be the main cause of the great difference in the H₂S concentrations between reservoirs, while gravitational differentiation during late uplift most likely creates differences in H₂S concentrations in a single reservoir. Carbon dioxide (CO₂), which has a relatively heavy δ¹³C value (−3.9 to −0.3‰), may be the combined result of TSR, the balance between CO₂ and inorganic fluid systems, and carbonate decomposition.     

琼东南盆地深水区烃源岩生烃动力学及生气模式

In order to investigate the hydrocarbon generation process and gas potentials of source rocks in deepwater area of the Qiongdongnan Basin, kinetic parameters of gas generation(activation energy distribution and frequency factor) of the Yacheng Formation source rocks(coal and neritic mudstones) was determined by thermal simulation experiments in the closed system and the specific KINETICS Software. The results show that the activation energy(Ea) distribution of C1–C5 generation ranges from 50 to 74 kcal/mol with a frequency factor of 2.4×1015 s–1 for the neritic mudstone and the Ea distribution of C1–C5 generation ranges from 49 to 73 kcal/mol with a frequency factor of 8.92×1013 s–1 for the coal. On the basis of these kinetic parameters and combined with the data of sedimentary burial and paleothermal histories, the gas generation model of the Yacheng Formation source rocks closer to geological condition was worked out, indicating its main gas generation stage at Ro(vitrinite reflectance) of 1.25%–2.8%. Meanwhile, the gas generation process of the source rocks of different structural locations(central part, southern slope and south low uplift) in the Lingshui Sag was simulated. Among them, the gas generation of the Yacheng Formation source rocks in the central part and the southern slope of the sag entered the main gas window at 10 and 5 Ma respectively and the peak gas generation in the southern slope occurred at 3 Ma. The very late peak gas generation and the relatively large gas potential indices(GPI:20×108–60×108 m3/km2) would provide favorable conditions for the accumulation of large natural gas reserves in the deepwater area.     

琼东南盆地深水区崖城组生成天然气的化学动力学及其应用

The natural gas generation process is simulated by heating source rocks of the Yacheng Formation, including the onshore-offshore mudstone and coal with kerogens of Type II_2-III in the Qiongdongnan Basin. The aim is to quantify the natural gas generation from the Yacheng Formation and to evaluate the geological prediction and kinetic parameters using an optimization procedure based on the basin modeling of the shallow-water area. For this, the hydrocarbons produced have been grouped into four classes(C_1, C_2, C_3 and C_(4-6)). The results show that the onset temperature of methane generation is predicted to occur at 110℃ during the thermal history of sediments since 5.3 Ma by using data extrapolation. The hydrocarbon potential for ethane, propane and heavy gaseous hydrocarbons(C_(4-6)) is found to be almost exhausted at geological temperature of 200℃ when the transformation ratio(TR) is over 0.8, but for which methane is determined to be about 0.5 in the shallow-water area. In contrast, the end temperature of the methane generation in the deep-water area was over 300℃ with a TR over 0.8. It plays an important role in the natural gas exploration of the deep-water basin and other basins in the broad ocean areas of China. Therefore, the natural gas exploration for the deep-water area in the Qiongdongnan Basin shall first aim at the structural traps in the Ledong, Lingshui and Beijiao sags, and in the forward direction of the structure around the sags, and then gradually develop toward the non-structural trap in the deep-water area basin of the broad ocean areas of China.     

Mineral-forming and diagenetic processes related to Tertiary hydrocarbon seepage at the Bohemian Massif/Outer Western Carpathians interface: Evidence from the Hrabůvka quarry,Moravia, Czech Republic

Ancient hydrocarbon seepage occurred in the Hrabůvka quarry at the boundary between the basement of the Bohemian Massif (represented by folded Lower Carboniferous siliciclastics of the Culm facies) and Tertiary sedimentary cover of the Carpathian Foredeep (formed by Lower Badenian siliciclastics and calcareous clays). The unconsolidated Lower Badenian sediments contain lithified domains composed of limestone and breccias with limestone cement, whereas the basement rocks are cut by subvertical neptunic dykes filled up by limestone and calcite-marcasite-pyrite veinlets representing sealed fluid conduits. The deeply negative δ¹³C values of both vein calcite and limestone (down to −38.1‰ V-PDB) indicate that oxidation of hydrocarbons was the major source of carbon for authigenic mineralization. A fluid inclusion study suggests low fluid temperatures (<50 °C) and low and variable salinities of aqueous fluids associated with hydrocarbons (0.7–6.7 wt. % NaCl eq.). The variability of δ¹⁸O values of authigenic carbonates (−1.7 to −8.2‰ V-PDB) could reflect either slight changes in temperature of escaping fluids (mostly within 15 °C), and/or some mixing with meteoric waters. The low δ³⁴S values of vein marcasite (∼–20‰ V-CDT) are consistent with bacterial reduction of sulfate in the hydrothermal system. Low C₁/(C₂+C₃) ratios in hydrocarbon gas extracted from authigenic carbonates (9.9 and 5.8) as well as the high δ¹³C values of methane (−31.8 and −32.4‰ V-PDB) are compatible with a thermogenic source of hydrocarbons. REE data indicate sequestration of REE from finely dispersed detrital material in the apical part of the hydrothermal system. The available data are compatible with two possible scenarios of fluid origin. The hydrocarbons could have been leached from underlying Paleozoic sedimentary sequence by aqueous fluids that infiltrated into the basement after Tertiary tectonic reactivation. Alternatively, an external source of hydrocarbon-bearing fluids can be found in the adjacent Outer Western Carpathians flysch nappes containing petroleum-producing lithologies. Nevertheless, a regional flow of hydrocarbon-bearing fluids is evidenced by the occurrence of very similar hydrocarbon-bearing vein mineralizations in a wider area.     

Geochemical characteristics and isotopic reversal of natural gases in eastern Kopeh-Dagh,NE Iran

Natural gas samples from two gas fields located in Eastern Kopeh-Dagh area were analyzed for molecular and stable isotope compositions. The gaseous hydrocarbons in both Lower Cretaceous clastic reservoir and Upper Jurassic carbonate reservoir are coal-type gases mainly derived from type III kerogen, however enriched δD values of methane implies presence of type II kerogen related material in the source rock. In comparison Upper Jurassic carbonate reservoir gases show higher dryness coefficient resulted through TSR, while presence of C₁C₅ gases in Lower Cretaceous clastic reservoir exhibit no TSR phenomenon. Carbon isotopic values indicate gas to gas cracking and TSR occurrence in the Upper Jurassic carbonate reservoir, as the result of elevated temperature experienced, prior to the following uplifts in last 33–37 million years. The δ¹³C of carbon dioxide and δ³⁴S of hydrogen sulfide in Upper Jurassic carbonate reservoir do not primarily reflect TSR, as uplift related carbonate rock dissolution by acidic gases and reaction/precipitation of light H₂S have changed these values severely. Gaseous hydrocarbons in both reservoirs exhibit enrichment in C₂ gas member, with the carbonate reservoir having higher values resulted through mixing with highly-mature-completely-reversed shale gases. It is likely that the uplifts have lifted off the pressure on shale gases, therefore facilitated the migration of the gases into overlying horizons. However it appears that the released gases during the first major uplift (33–37 million years ago) have migrated to both reservoirs, while the second migrated gases have only mixed with Upper Jurassic carbonate reservoir gases. The studied data suggesting that economic accumulations of natural gas/shale gases deeper than Upper Jurassic carbonate reservoir would be unlikely.     

Isotopic composition of gas hydrates in subsurface sediments from offshore Sakhalin Island, Sea of Okhotsk

Hydrate-bearing sediment cores were retrieved from recently discovered seepage sites located offshore Sakhalin Island in the Sea of Okhotsk. We obtained samples of natural gas hydrates and dissolved gas in pore water using a headspace gas method for determining their molecular and isotopic compositions. Molecular composition ratios C₁/_C2+ from all the seepage sites were in the range of 1,500–50,000, while δ¹³C and δD values of methane ranged from ?66.0 to ?63.2‰ VPDB and ?204.6 to ?196.7‰ VSMOW, respectively. These results indicate that the methane was produced by microbial reduction of CO₂. δ¹³C values of ethane and propane (i.e., ?40.8 to ?27.4‰ VPDB and ?41.3 to ?30.6‰ VPDB, respectively) showed that small amounts of thermogenic gas were mixed with microbial methane. We also analyzed the isotopic difference between hydrate-bound and dissolved gases, and discovered that the magnitude by which the δD hydrate gas was smaller than that of dissolved gas was in the range 4.3–16.6‰, while there were no differences in δ¹³C values. Based on isotopic fractionation of guest gas during the formation of gas hydrate, we conclude that the current gas in the pore water is the source of the gas hydrate at the VNIIOkeangeologia and Giselle Flare sites, but not the source of the gas hydrate at the Hieroglyph and KOPRI sites.     

Fluid circulation and formation of minerals and bitumens in the sedimentary rocks of the Outer Carpathians – Based on studies on the quartz–calcite–organic matter association

Different methods have been used to examine minerals and/or solid bitumens in three adjacent Carpathian regions of Poland, Ukraine and Slovakia. The minerals fill smaller and larger veins and cavities, where they occur either together or separately. They usually co-occur with the solid bitumens. All δ¹³C_PDB values measured for calcite lie in a relatively wide interval between −6.25‰ and +1.54‰, while most values fall into the narrower interval from below 0 to about −3‰. The general range of calcite δ¹⁸O results for the whole studied region is between +17.13‰ and +25.23‰ VSMOW or from about −11 to −5‰ VPDB, while the majority of these values are between +20.0 and 23.5‰ VSMOW (−10.53 and −8.00‰ PDB, respectively). δ¹⁸O_VSMOW results for quartz vary between +23.2 and 27.6. The carbonate percentage determined in some samples falls between from <2% CaCO₃ to >90% CaCO₃, while the TOC values changes from 0.09% to over 70%.The aliphatic fraction predominates in all studied samples, mainly in bitumens and oils. The composition of the aliphatic fraction is relatively homogeneous and points to a strong aliphatic, oil-like paraffin character of the bitumens. Such a composition is characteristic of the Carpathian oils and different from the rocks studied that contain the higher percentage of a polar fraction. The content of the aliphatic fraction in bitumens is only slightly higher than that in two oils used for comparison. The distribution of n-alkanes is variable in rocks, solid bitumens as well as inclusions in quartz and calcite. Two groups of bitumens may be distinguished. Those with a predominance of long-chain n-alkanes in the C₂₅–C₂₇ interval (in some cases from C₂₃–C₂₅ and without or with a very low concentration of short-chain n-alkanes in the interval of C₁₄–C₂₁) show also a high content of isoprenoids i.e. of pristane (Pr) and phytane (Ph). In all but one bitumen samples, Pr predominates over Ph. The second group comprises oils and rock samples with a characteristic predominance of short-chain n-alkanes in the interval from C₁₃–C₁₉ and a low percentage of the long-chain n-alkanes from the n-C₂₇–n-C₃₃ interval. Pristane and phytane exhibit a concentration comparable to that of C₁₇ and C₁₈ n-alkanes with a Pr predominance over Ph. Due to high maturity, only small amounts of the most stable compounds from the hopane group have been observed in the samples, also oleanane in one case. Among the aromatic hydrocarbons, phenanthrene and its methyl- and dimethyl-derivatives are dominant in bitumens, source rocks and inclusions in calcite and quartz. Occurrence of cyclohexylbenzene and its alkyl-derivatives as well as cyclohexylfluorenes in solid bitumens suggest that they formed from oil accumulations under the influence of relatively high temperatures in oxidizing conditions.Homogenization temperatures for aqueous/brine inclusions in quartz within the Dukla and Silesian units (Polish and Ukrainian segments) are between 125 and 183.9 °C, while salinities are low in the interval of 0.2–5.5 wt% NaCl eq. The inclusions in calcite homogenize at higher temperatures of almost 200 °C and the brine displays higher salinity than the fluid in the quartz. Two quartz generations may be distinguished by inclusion and isotope characteristics and the macroscopic diversity. Oil inclusions homogenize at 95 °C. One phase inclusions in quartz contain methane, CO₂ and nitrogen in variable proportions.     

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.     

Saddle dolomite and calcite cements as records of fluid flow during basin evolution: Paleogene carbonates,United Arab Emirates

Field observations indicate that tectonic compression, anticline formation and concomitant uplift events of marine Paleogene carbonates in eastern United Arab Emirates, which are related to the Zagros Orogeny, have induced brecciation, karstification, and carbonate cementation in vugs and along faults and fractures. Structural analysis, stable isotopes and fluid inclusion microthermometry are used to constrain the origin and geochemical evolution of the fluids. Fluid flow was related to two tectonic deformation phases. Initially, the flux of moderately ⁸⁷Sr-rich basinal NaCl–MgCl₂–H₂O brines along reactivated deep-seated strike-slip faults have resulted in the precipitation of saddle dolomite in fractures and vugs and in dolomitization of host Eocene limestones (δ¹⁸O_V-PDB −15.8‰ to −6.2‰; homogenization temperatures of 80–115 °C and salinity of 18–25 wt.% eq. NaCl). Subsequently, compression and uplift of the anticline was associated with incursion of meteoric waters and mixing with the basinal brines, which resulted in the precipitation of blocky calcite cement (δ¹⁸O_V-PDB −22‰ to −12‰; homogenization temperatures of 60–90 °C and salinity of 4.5–9 wt.% eq. NaCl). Saddle dolomite and surrounding blocky calcite have precipitated along the pre- and syn-folding E–W fracture system and its conjugate fracture sets. The stable isotopes coupled with fluid-inclusion micro-thermometry (homogenization temperatures of ≤50 °C and salinity of <1.5 wt.% eq. NaCl) of later prismatic/dogtooth and fibrous calcites, which occurred primarily along the post-folding NNE–SSW fracture system and its conjugate fracture sets, suggest cementation by descending moderately ⁸⁷Sr-rich, cool meteoric waters. This carbonate cementation history explains the presence of two correlation trends between the δ¹⁸O_V-PDB and δ¹³C_V-PDB values: (i) a negative temperature-dependent oxygen isotope fractionation trend related to burial diagenesis and to the flux of basinal brines, and (ii) positive brine-meteoric mixing trend. This integrated study approach allows better understanding of changes in fluid composition and circulation pattern during evolution of foreland basins.     

Spatial distribution and geochemistry of the nearshore gas seepages and their implications to natural gas migration in the Yinggehai Basin,offshore South China Sea

About 120 gas seepage vents were documented along the west and southwest coast of the Hainan Island, South China Sea, in water depths usually less than 50 m. The principal seepage areas include the Lingtou Promontory, the Yinggehai Rivulet Mouth, Yazhou Bay, the Nanshan Promontory and the Tianya Promontory. They occur along three major zones, reflecting the control by faults and lateral conduits within the basement. It is estimated that the total gas emission from these seepage vents is 294–956 m³/year. The seepage gases are characterized by a high CH₄ content (76%), heavy δ¹³C₁ values (−38 to −33‰) and high C₁/C_1–5 ratios (0.95–1.0), resembling the thermogenic gases from the diapiric gas fields of the Yinggehai Basin. Hydrocarbon–source correlation shows that the hydrocarbons in the sediments from seepage areas can be correlated with the deeply buried Miocene source rocks and sandstone reservoirs in the central depression. The 2D basin modeling results based on a section from the source rock center to the gas seepage sites indicate that the gas-bearing fluids migrated from the source rocks upward through faults or weak zones encompassed by shale diapirism or in up-dip direction along the sandstone-rich strata of Huangliu Formation to arrive to seabed and form the nearshore gas seepages. It is suggested that the seepage gases are sourced from the Miocene source rocks in the central depression of the Yinggehai Basin. This migration model implies that the eastern slope zone between the gas source area of the central depression and the seepage zone is also favorable place for gas accumulation.     

The use of diagenetic signatures to distinguish marine from continental deposits in Triassic-Jurassic sandstone reservoirs from the UK Central Graben

Poor biostratigraphic control for some Triassic-Jurassic successions in the North Sea Basin and sub-basins necessitates the use of alternative correlation methods. This study examines the use of diagenetic signatures to distinguish continenetal from marine sandstone successions (Triassic-Jurassic) in the UK Central Graben. The key diagenetic alterations encountered in these successions include kaolinitization of the framework grains and the development of sphaerosiderite and pyrite. The δ ¹³C_V-PDB values of siderite (−8.1 to −8.5‰) and of ankerite (−10.8 to −9.2‰), indicate a strong contribution of dissolved carbon from the decay of plant material in soil. However, marine water likely influenced diagenesis during periods of relative sea level rise by providing the dissolved sulfate (SO₄²⁻) required for the precipitation of pyrite. The presence of diagenetic alterations such as kaolinitization of framework grains and cementation by sphaerosiderite could indicate that the sediments were deposited in an overall continental setting. However, the occurrence of pyrite and scattered grains of deep-green colored glauconite suggests occasional marine influence. Such information on the changes of the diagenetic realm provides important clues for establishing a framework for stratigraphic correlations. Caution should be exercised when interpreting petrographic data as subsequent episodes of telodiagenesis can complicate petrographic interpretations.     

中国南海北部珠江口-琼东南盆地钻井岩屑地球化学特征及深水区天然气聚集特征

The Qiongdongnan Basin and Zhujiang River(Pearl River) Mouth Basin, important petroliferous basins in the northern South China Sea, contain abundant oil and gas resource. In this study, on basis of discussing impact of oil-base mud on TOC content and Rock-Eval parameters of cutting shale samples, the authors did comprehensive analysis of source rock quality, thermal evolution and control effect of source rock in gas accumulation of the Qiongdongnan and the Zhujiang River Mouth Basins. The contrast analysis of TOC contents and Rock-Eval parameters before and after extraction for cutting shale samples indicates that except for a weaker impact on Rock-Eval parameter S_2, oil-base mud has certain impact on Rock-Eval S_1, Tmax and TOC contents. When concerning oil-base mud influence on source rock geochemistry parameters, the shales in the Yacheng/Enping,Lingshui/Zhuhai and Sanya/Zhuhai Formations have mainly Type Ⅱ and Ⅲ organic matter with better gas potential and oil potential. The thermal evolution analysis suggests that the depth interval of the oil window is between 3 000 m and 5 000 m. Source rocks in the deepwater area have generated abundant gas mainly due to the late stage of the oil window and the high-supper mature stage. Gas reservoir formation condition analysis made clear that the source rock is the primary factor and fault is a necessary condition for gas accumulation. Spatial coupling of source, fault and reservoir is essential for gas accumulation and the inside of hydrocarbon-generating sag is future potential gas exploration area.     

Carbon isotopic fractionation by desorption of shale gases

Geochemical studies of shale gas and conventional reservoirs within the Triassic Yanchang Formation of Xiasiwan and Yongning Field, Ordos Basin show that methane is isotopically depleted in ¹³C as compared to δ¹³C₁ calculated by the Ro based on the relationship between δ¹³C₁ and Ro. Geochemical fractionation during the adsorption/desorption process of shale system may play a significant part in influencing δ¹³C₁ values of shale gas. Two shale core samples from confined coring of the Yanchang Formation were adopted segmented desorption experiments to examine this phenomenon. The results show that the δ¹³C₁ of desorbed gas changes little in the first few phases of the experiments at low desorption levels, but become less negative rapidly when the fraction of desorbed methane exceeds 85%. The desorption process for the last 15% fraction of the methane from the shale samples shows a wide variation in δ¹³C₁ from −49‰ to −33.9‰. Moreover, δ¹³C₁ of all desorbed methane from the shale samples is substantially depleted in ¹³C than that calculated by Ro, according to Stahl and Carey's δ¹³C₁–Ro equation for natural gas generated from sapropelic organic matter. This shows some gases with isotopically enriched in ¹³C cannot be desorbed under the temperature and pressure conditions of the desorption experiments. This observation may be the real reason for the δ¹³C₁ of shale gases and conventional reservoirs becomes more negative in Xiasiwan and Yongning Fields, Ordos Basin. The magnitude of the deviation between the δ¹³C₁ of shale gas and that calculated by Ro may be related to the adsorption capacity of shale or the proportion of absorbed gases. In this way, we may be able to evaluate the relative adsorption capacity of shale in geological conditions by δ¹³C₁ of the shale gas, or by δ¹³C₁ of conventional gas which generated by the shale with certainty. The δ¹³C₁ of conventional gas in Dingbian and Yingwang Fields have no deviation because the TOC value of the hydrocarbon source rock is relatively low.     

Hydrocarbon gases in the crystalline rocks of the Gravberg-1 well,Swedish deep gas project

Desorbed gas analyses of cuttings from the Gravberg—1 well, the culmination of the Swedish deep gas project, were undertaken every 100 m from 219 to 5907 m. A sample at 6517 m, from sidetrack 2, was also included. The desorbed gas method performed by hot acid treatment in an evacuated system was superior to both ball mill crushing and thermodesorption methods. Two types of hydrocarbon gases were found in trace quantities. One type associated with the dolerite sills was an isotopically heavy, δ¹³C₁: −11 to −15‰, dry gas, with a methane content up to 98%. The other type, occurring throughout the granitic rocks, was an isotopically lighter gas, δ¹³C₁: −21 to −39 ‰, containing 30–45% of C₂C₄ olefins and paraffins were present in almost equal amounts in the second type of gas. The dry gas observed in the dolerites is assumed to be abiogenic gas existing in inclusions of basic minerals which react with acid during the analytical procedure. The other type of hydrocarbon gas is thought to be formed from H₂ and CO₂ by a catalytic reaction since it is mainly associated with the magnetic fraction of the rock. A Fischer-Tropsch reaction over a magnetite catalyst is the most likely reaction since it produces both paraffins and olefins. Studies on thin sections of cores and coarse cuttings suggest that the wet gas is not isolated in inclusions and the changes with time observed for a few thin sections indicate that it diffuses quite freely. The potential risks of contamination from drilling fluids and bit metamorphism were examined by comparing the hydrocarbon results with changes in the mud system, rate of penetration and bit life. Hydrocarbon analyses of a few mud additives were included as well. The result of these examinations plus the results of hydrocarbon analyses of cores from pilot core holes in the Siljan Crater suggest that the hydrocarbons observed in the cuttings are indigeneous.Comparing the results of the present study with other hydrocarbon occurrences outside of the Siljan Crater indicates that the hydrocarbons found in the Gravberg—1 well occur widespread in crustal rocks.     

Geochemical characteristics of tight gas and gas-source correlation in the Daniudi gas field,the Ordos Basin,China

The molecular composition, stable carbon and hydrogen isotopes and light hydrocarbons of the Upper Paleozoic tight gas in the Daniudi gas field in the Ordos Basin were investigated to study the geochemical characteristics. Tight gas in the Daniudi gas field displays a dryness coefficient (C₁/C_1–5) of 0.845–0.977 with generally positive carbon and hydrogen isotopic series, and the C₇ and C_5–7 light hydrocarbons of tight gas are dominated by methylcyclohexane and iso-alkanes, respectively. The identification of gas origin and gas-source correlation indicate that tight gas is coal-type gas, and the gases reservoired in the Lower Permian Shanxi Fm. (P₁s) and Lower Shihezi Fm. (P₁x) had a good affinity and were derived from the P₁s coal-measure source rocks, whereas the gas reservoired in the Upper Carboniferous Taiyuan Fm. (C₃t) was derived from the C₃t coal-measure source rocks. The molecular and methane carbon isotopic fractionations of natural gas support that the P₁x gas was derived from the P₁s source rocks. The differences of geochemical characteristics of the C₃t gas from different areas in the field suggest the effect of maturity difference of the source rocks rather than the diffusive migration, and the large-scale lateral migration of the C₃t gas seems unlikely. Comparative study indicates that the differences of the geochemical characteristics of the P₁s gases from the Yulin and Daniudi gas fields originated likely from the maturity difference of the in-situ source rocks, rather than the effect of large-scale lateral migration of the P₁s gases.     

琼东南深水区海陆过渡相富生烃凹陷评价及优选

琼东南盆地古近系崖城组被证实为海陆过渡相烃源岩,但是深水盆地内6个凹陷的特征及演化存在显著差异,如何确定最富生烃的凹陷直接关系到深水钻探的成效。本文在深水凹陷区域构造形成机制、沉积环境演变特征以及海陆过渡相烃源岩有机质特征分析的基础上,充分利用现有钻井和地震资料,首先依据地震相模式分析方法预测了烃源岩层段沉积相分布,并根据沉积相与有机相的对应关系,预测了有机相分布;同时采用地震速度岩性定量分析技术确定出各凹陷烃源岩厚度分布,并利用地震反演速度及区域内泥岩孔隙度和烃源岩Ro的关系,定量预测了源岩热成熟度分布;然后依据烃源岩有机相、厚度和热成熟度等参数计算了崖城组各层段生气量和生气强度;最后以这两个参数为主,结合资源量和油气发现概况,建立了深水区富生烃凹陷评价标准,以此对6个凹陷进行综合评价优选。研究认为陵水、乐东、宝岛和长昌四个凹陷是Ⅰ类(最富生烃)凹陷,而松南和北礁凹陷为Ⅱ类(较富生烃)凹陷。该评价结果对南海北部深水区下一步勘探部署和目标钻探有重要的指导意义。     

Molecular and isotopic characteristics of gas hydrate-bound hydrocarbons in southern and central Lake Baikal

We investigated the molecular composition (methane, ethane, and propane) and stable isotope composition (methane and ethane) of hydrate-bound gas in sediments of Lake Baikal. Hydrate-bearing sediment cores were retrieved from eight gas seep sites, located in the southern and central Baikal basins. Empirical classification of the methane stable isotopes (δ¹³C and δD) for all the seep sites indicated the dominant microbial origin of methane via methyl-type fermentation; however, a mixture of thermogenic and microbial gases resulted in relatively high methane δ¹³C signatures at two sites where ethane δ¹³C indicated a typical thermogenic origin. At one of the sites in the southern Baikal basin, we found gas hydrates of enclathrated microbial ethane in which ¹³C and deuterium were both highly depleted (mean δ¹³C and δD of –61.6‰ V-PDB and –285.4‰ V-SMOW, respectively). To the best of our knowledge, this is the first report of C₂ δ¹³C–δD classification for hydrate-bound gas in either freshwater or marine environments.     

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.