南海北部莺歌海岭头岬近岸烃类渗漏喷口分布及气体地球化学

Natural hydrocarbon seeps in a marine environment are one of the important contributors to greenhouse gases in the atmosphere,including methane,which is significant to the global carbon cycling and climate change.Four hydrocarbon seep areas,the Lingtou Promontory,the Yinggehai Rivulet mouth,the Yazhou Bay and the Nanshan Promontory,occurring in the Yinggehai Basin delineate a near-shore gas bubble zone.The gas composition and geochemistry of venting bubbles and the spatial distribution of hydrocarbon seeps are surveyed on the near-shore Lingtou Promontory.The gas composition of the venting bubbles is mainly composed of CO_2,CH_4,N_2 and O_2,with minor amounts of non-methane hydrocarbons.The difference in the bubbles' composition is a possible consequence of gas exchange during bubble ascent.The seepage gases from the seafloor are characterized by a high CO_2 content(67.35%) and relatively positive δ~(13)C_(V_PDB) values(-0.49×10~(-3)-0.86×10~(-3)),indicating that the CO_2 is of inorganic origin.The relatively low CH_4 content(23%) and their negative δ~(13)C_(V-PDB) values(-34.43×10~(-3)--37.53×10~(-3)) and high ratios of C_1 content to C_(1-5) one(0.98-0.99)as well point to thermogenic gases.The hydrocarbon seeps on the 3.5 Hz sub-bottom profile display a linear arrangement and are sub-parallel to the No.1 fault,suggesting that the hydrocarbon seeps may be associated with fracture activity or weak zones and that the seepage gases migrate laterally from the central depression of the Yinggehai Basin.     

Geochemistry,origin and accumulation of natural gases in the deepwater area of the Qiongdongnan Basin,South China Sea

The Qiongdongnan Basin, South China Sea has received huge thickness (>12 km) of Tertiary-Quaternary sediments in the deepwater area to which great attention has been paid due to the recent discoveries of the SS22-1 and the SS17-2 commercial gas fields in the Pliocene-Upper Miocene submarine canyon system with water depth over 1300 m. In this study, the geochemistry, origin and accumulation models of these gases were investigated. The results reveal that the gases are predominated by hydrocarbon gases (98%–99% by volume), with the ratio of C₁/C_1-5 ranging from 0.92 to 0.94, and they are characterized by relatively heavy δ¹³C₁ (−36.8‰ to −39.4‰) and δD_CH4 values (−144‰ to −147‰), similar to the thermogenic gases discovered in the shallow water area of the basin. The C_5-7 light hydrocarbons associated with these gases are dominated by isoparaffins (35%–65%), implying an origin from higher plants. For the associated condensates, carbon isotopic compositions and high abundance of oleanane and presence of bicadinanes show close affinity with those from the YC13-1 gas field in the shallow water area. All these geochemical characteristics correlate well with those found in the shales of the Oligocene Yacheng Formation in the Qiongdongnan Basin. The Yacheng Formation in the deepwater area has TOC values in the range of 0.4–21% and contains type II_b–III gas-prone kerogens, indicating an excellent gas source rock. The kinetic modeling results show that the δ¹³C₁ values of the gas generated from the Yacheng source rock since 3 or 4 Ma are well matched with those of the reservoir gases, indicating that the gas pool is young and likely formed after 4 Ma. The geologic and geochemical data show that the mud diapirs and faults provide the main pathways for the upward migration of gases from the deep gas kitchen into the shallow, normally pressured reservoirs, and that the deep overpressure is the key driving force for the vertical and lateral migration of gas. This gas migration pattern implies that the South Low Uplift and the No.2 Fault zone near the deepwater area are also favorable for gas accumulation because they are located in the pathway of gas migration, and therefore more attention should be paid to them in the future.     

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.     

Geochemical overview and undiscovered gas resources generated from Hamitabat petroleum system in the Thrace Basin,Turkey

Since the first drill in 1957, three oil, 19 gas and condensate fields have been discovered in the Thrace Basin. However, any petroleum system with its essential elements and processes has not been assigned yet. This study consists of two parts, (1) geochemical overview of the previous work in order to get a necessary help to construct a petroleum system and (2) calculation of quantitative undiscovered hydrocarbon resources generated from this system. An extensive overview study showed that the primary reservoir and source rocks in the Thrace Basin are the Middle Eocene Hamitabat sandstones and shales, respectively, hence it appears that the most effective petroleum system of the Thrace Basin becomes the Hamitabat (!) petroleum system. Currently, 18.5 billion m³ of in-place gas, 2.0 million m³ (12.7 million bbl) in-place waxy oil as well as minor amount of associated condensate were discovered from this system. This study showed that the regional distribution of the oil and gas fields almost overlapped with the previously constructed pod of active Hamitabat shales implying that short and up-dip vertical migration pathway of hydrocarbons from the source to trapping side was available. Thermal model demonstrated that hydrocarbon generation from the Hamitabat shales commenced in the Early Miocene. The amount of quantitative gas generation based on the mean-original TOC = 0.94 wt%, mean-original HI = 217 HC/g TOC and the volume of the pod of active source rock = 49 km³ is approximately 110 billion m³ of gaseous hydrocarbons that results in a high generation–accumulation efficiency of 17% when 18.5 billion m³ of already discovered hydrocarbons are considered.     

南海北部天然气渗漏系统地球物理初探

本文主要针对南海北部大陆边缘发育的5个沉积盆地——台西南盆地、珠江口盆地、琼东南盆地、莺歌海盆地和中建南盆地,分析了近年来利用地球物理方法研究南海北部天然气渗漏系统的成果,重点包括3个方面:天然气水合物的储藏、流体运移通道以及海底表面渗漏特征。其中表征天然气水合物存在的似海底反射BSR在台西南和珠江口盆地发育明显,莺歌海盆地发现有大型气田;5个盆地流体运移活跃,其内发现了多样的运移通道:断层、底辟、气烟囱、多边形断层及水道(峡谷)等破裂结构;海底表面渗漏特征也在台西南、珠江口、莺歌海和中建南盆地均有发现。南海北部大陆边缘天然气渗漏系统广泛发育,值得进一步深入研究。     

Characteristics and petroleum origin of the Carboniferous volcanic rock reservoirs in the Shixi Bulge of Junggar Basin,western China

Shixi Bulge of the central Junggar Basin in western China is a unique region that provides insight into the geological and geochemical characteristics of large-scale petroleum reservoirs in volcanic rocks of the western Central Asian Orogenic Belt. Carboniferous volcanic rocks in the Shixi Bulge mainly consist of striped lava and agglomerate, as well as breccia lava and tight tuff. Volcanic rocks differ in porosity and permeability. Striped lava exhibits the highest porosity (average: 14.2%) but the lowest permeability (average: 0.67 × 10⁻¹⁵ m) among the rock types. Primary gas pores are widely developed and mostly filled. Secondary dissolution pores and fractures are two major reservoir storage spaces. Capillary pressure curves suggest the existence of four pore structure types of reservoir rocks. Several factors, namely, lithology, pore structure, and various diagenesis, govern the physical properties of volcanic rocks. The oil is characterized by a high concentration of tricyclic terpane, a terpane distribution of C₂₃ < C₂₁ > C₂₀, and sterane distributions of C₂₇ < C₂₈ < C₂₉ and C₂₇ > C₂₈ < C₂₉. Oil and gas geochemistry revealed that the oil is a mixture derived primarily from P₂w source rock and secondarily from P₁j source rock in the sag west of Pen-1 Well. The gases are likely gas mixtures of humic and sapropelic organic origins, with the sapropelic gas type dominant in the mixture. The gas mixture is most likely cracked from kerogen rather than oils. The Carboniferous volcanic reservoirs in Shixi Bulge share some unique characteristics that may provide useful insights into the various roles of different volcanic reservoir types in old volcanic provinces. The presence of these reservoirs will undoubtedly encourage future petroleum exploration in volcanic rocks up to the deep parts of sedimentary basins.     

Distribution and expression of gas seeps in a gas hydrate province of the northeastern Sakhalin continental slope, Sea of Okhotsk

Multidisciplinary surveys were conducted to investigate gas seepage and gas hydrate accumulation on the northeastern Sakhalin continental slope (NESS), Sea of Okhotsk, during joint Korean–Russian–Japanese expeditions conducted from 2003 to 2007 (CHAOS and SSGH projects). One hundred sixty-one gas seeps were detected in a 2000 km² area of the NESS (between 53°45′N and 54°45′N). Active gas seeps in a gas hydrate province on the NESS were evident from features in the water column, on the seafloor, and in the subsurface: well-defined hydroacoustic anomalies (gas flares), side-scan sonar structures with high backscatter intensity (seepage structures), bathymetric structures (pockmarks and mounds), gas- and gas-hydrate-related seismic features (bottom-simulating reflectors, gas chimneys, high-amplitude reflectors, and acoustic blanking), high methane concentrations in seawater, and gas hydrates in sediment near the seafloor. These expressions were generally spatially related; a gas flare would be associated with a seepage structure (mound), below which a gas chimney was present. The spatial distribution of gas seeps on the NESS is controlled by four types of geological structures: faults, the shelf break, seafloor canyons, and submarine slides. Gas chimneys that produced enhanced reflection on high-resolution seismic profiles are interpreted as active pathways for upward gas migration to the seafloor. The chimneys and gas flares are good indicators of active seepage.     

Tracing of deeply-buried source rock: A case study of the WC9-2 petroleum pool in the Pearl River Mouth Basin, South China Sea

The identification of a deeply-buried petroleum-source rock, owing to the difficulty in sample collection, has become a difficult task for establishing its relationship with discovered petroleum pools and evaluating its exploration potential in a petroleum-bearing basin. This paper proposes an approach to trace a deeply-buried source rock. The essential points include: determination of the petroleum-charging time of a reservoir, reconstruction of the petroleum generation history of its possible source rocks, establishment of the spatial connection between the source rocks and the reservoir over its geological history, identification of its effective source rock and the petroleum system from source to trap, and evaluation of petroleum potential from the deeply-buried source rock. A case study of the W9-2 petroleum pool in the Wenchang A sag of the Pearl River Mouth Basin, South China Sea was conducted using this approach. The W9-2 reservoir produces condensate oil and gas, sourced from deeply-buried source rocks. The reservoir consists of a few sets of sandstone in the Zhuhai Formation, and the possible source rocks include an early Oligocene Enping Formation mudstone and a late Eocene Wenchang Formation mudstone, with a current burial depth from 5000 to 9000 m. The fluid inclusion data from the reservoir rock indicate the oil and the gas charged the reservoir about 18–3.5 Ma and after 4.5 Ma, respectively. The kinetic modeling results show that the main stages of oil generation of the Wenchang mudstone and the Enping mudstone occurred during 28–20 Ma and 20–12 Ma, respectively, and that the δ¹³C₁ value of the gas generated from the Enping mudstone has a better match with that of the reservoir gas than the gas from the Wenchang mudstone. Results from a 2D basin modeling further indicate that the petroleum from the Enping mudstone migrated upward along the well-developed syn-sedimentary faults in the central area of the sag into the reservoir, but that the petroleum from the Wenchang mudstone migrated laterally first toward the marginal faults of the sag and then migrated upward along the faults into shallow strata. The present results suggest that the trap structure in the central area of the sag is a favorable place for the accumulation of the Enping mudstone-derived petroleum, and that the Wenchang mudstone-derived petroleum would have a contribution to the structures along the deep faults as well as in the uplifted area around the sag.     

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.     

Characteristics of two natural gas seepages in the North Sea

Two occurrences of active gas seepages are described from the North Sea. The southernmost one, situated above a salt diapir in Norwegian block , has been studied and sampled by use of a remotely operated vehicle (ROV). This seepage consists of about 120 single seeps located within a diameter of 100 m. It is estimated to produce 24 m³ of methane gas per day (at ambient pressure, 75 m water depth). Isotope values of the methane gas and higher hydrocarbon gases in the surrounding seafloor sediments, show that their origin is from a deep seated, thermogenic source. No typical gas-induced erosion features are found on the seafloor at this location, probably due to the lack of very fine grained material.The second occurrence is located in U.K. block (Geoteam, 1984), where the seepage is associated with a very large pockmark depression, measuring 17 m in depth and 700×450 m in width. This depression represents an eroded fine grained sediment volume of 7.10⁵ cubic metres. No detailed inspection or sampling of the gas has been performed here. However seismic reflection anomalies are seen on airgun seismic records at various levels down to a depth of at least 1100 m below seafloor. The seeping gas, possibly mixed with liquids, at this location is therefore also expected to be of a thermogenic origin.     

Influence of natural fractures on gas accumulation in the Upper Triassic tight gas sandstones in the northwestern Sichuan Basin,China

The Upper Triassic Xujiahe Formation in the northwestern Sichuan Basin, China, is a typical tight gas sandstone reservoir that contains natural fractures and has an average porosity of 1.10% and air permeability less than 0.1 md because of compaction and cementation. According to outcrops, cores and image logs, three types of natural fractures, namely, tectonic, diagenetic and overpressure-related fractures, have developed in the tight gas sandstones. The tectonic fractures include small faults, intraformational shear fractures and horizontal shear fractures, whereas the diagenetic fractures mainly include bed-parallel fractures. According to thin sections, the microfractures also include tectonic, diagenetic and overpressure-related microfractures. The diagenetic microfractures consist of transgranular, intragranular and grain-boundary fractures. Among these fractures, intraformational shear fractures, horizontal shear fractures and small faults are predominant and significant for fluid movement. Based on the Monte Carlo method, these intraformational shear fractures and horizontal shear fractures improve the reservoir porosity and permeability, thus serving as an important storage space and primary fluid-flow channels in the tight sandstones. The small faults may provide seepage channels in adjacent layers by cutting through layers. In addition, these intragranular and grain-boundary fractures increase the connectivity of the tight gas sandstones by linking tiny pores. The tectonic microfractures improve the seepage capability of the tight gas sandstones to some extent. Low-dip angle fractures are more abundant in the T₃X³ member than in the T₃X² and T₃X⁴ members. The fracture intensities of the sandstones in the T₃X³ member are greater than those in the T₃X² and T₃X⁴ members. The fracture intensities do not always decrease with increasing bed thickness for the tight sandstones. When the bed thickness of the tight sandstones is less than 1.0 m, the fracture intensities increase with increasing bed thickness in the T₃X³ member. Fluid inclusion evidence and burial history analysis indicate that the tectonic fractures developed over three periods. The first period was at the end of the Triassic to the Early Jurassic. The tectonic fractures developed during oil generation but before the matrix's porosity and permeability reduced, which suggests that these tectonic fractures could provide seepage channels for oil migration and accumulation. The second period was at the end of the Cretaceous after the matrix's porosity and permeability reduced but during peak gas generation, which indicates that gas mainly migrated and accumulated in the tectonic fractures. The third period was at the end of the Eogene to the Early Neogene. The tectonic fractures could provide seepage channels for secondary gas migration and accumulation from the Upper Triassic Xujiahe Formation into the overlying Jurassic Formation.     

Stable carbon isotope ratios of CH4-rich gas inclusions in shale-hosted fracture-fill mineralization: A tool for tracing hydrocarbon generation and migration in shale plays for oil and gas

Fluid inclusion gases in minerals from shale hosted fracture-fill mineralization have been analyzed for stable carbon isotopic ratios of CH₄ using a crushing device interfaced to an isotope ratio mass spectrometer (IRMS). The samples of Paleozoic strata under study originate from outcrops and wells in the Rhenish Massif and Campine Basin, Harz Mountains, and the upper slope of the Southern Permian Basin. Fracture-fill mineralization hosted by Mesozoic strata was sampled from drill cores in the Lower Saxony Basin. Some studied sites are candidates for shale gas exploration in Germany. Samples of Mesozoic strata are characterized by abundant calcite-filled horizontal fractures which preferentially occur in TOC-rich sections of the drilled sediments. Only rarely are vertical fractures filled with carbonates and/or quartz in drill cores from Mesozoic strata but in Paleozoic shale they occur frequently. The δ¹³C(CH₄) values of fluid inclusions in calcite from horizontal fractures hosted by Mesozoic strata suggest that gaseous hydrocarbons were generated during the oil/early gas window and that the formation of horizontal fractures seems to be related to hydraulic expulsion fracturing. The calculated maturity of the source rocks at the time of gas generation lies below the maturity derived from measured vitrinite reflectance. Thus, the formation of horizontal fractures and trapping of gas that was generated in the oil and/or early gas window obviously occurred prior to maximal burial. Rapidly increasing vitrinite reflectance data seen locally can be explained by hydrothermal alteration, as indicated by increasing δ¹³C (CH₄–CO₂) values in fluid inclusions. The formation of vertical fractures in studied Mesozoic sediments is related to stages of post-burial inversion; gas-rich inclusions in fracture filling minerals recorded the migration of gas that had probably been generated instantaneously, rather than cumulatively, from high to overmature source rocks. Since no evidence is given for the presence of early generated gas in studied Paleozoic shale, it appears likely that major gas loss from shales occurred due to deformation and uplift of these sediments in response to the Variscan Orogeny.     

Organic geochemistry of marine source rocks and pyrobitumen-containing reservoir rocks of the Sichuan Basin and neighbouring areas,SW China

Three bitumen fractions were obtained and systematically analysed for the terpane and sterane composition from 30 Paleozoic source rocks and 64 bitumen-containing reservoir rocks within the Upper Sinian, Lower Cambrian, Lower Silurian, Middle Carboniferous, Upper Permian and Lower Triassic strata in the Sichuan Basin and neighbouring areas, China. These bitumen fractions include extractable oils (bitumen I), oil-bearing fluid inclusions and/or closely associated components with the kerogen or pyrobitumen/mineral matrix, released during kerogen or pyrobitumen isolation and demineralization (bitumen II), and bound compounds within the kerogen or pyrobitumen released by confined pyrolysis (bitumen III). In addition, atomic H/C and O/C ratios and carbon isotopic compositions of kerogen and pyrobitumen from some of the samples were measured. Geochemical results and geological information suggest that: (1) in the Central Sichuan Basin, hydrocarbon gases in reservoirs within the fourth section of the Upper Sinian Dengying Formation were derived from both the Lower Cambrian and Upper Sinian source rocks; and (2) in the Eastern Sichuan Basin, hydrocarbon gases in Middle Carboniferous Huanglong Formation reservoirs were mainly derived from Lower Silurian source rocks, while those in Upper Permian and Lower Triassic reservoirs were mainly derived from both Upper Permian and Lower Silurian marine source rocks. For both the source and reservoir rocks, bitumen III fractions generally show relatively lower maturity near the peak oil generation stage, while the other two bitumen fractions show very high maturities based on terpane and sterane distributions. Tricyclic terpanes evolved from the distribution pattern C₂₀ < C₂₁ < C₂₃, through C₂₀ < C₂₁ > C₂₃, finally to C₂₀ > C₂₁ > C₂₃ during severe thermal stress. The concentration of C₃₀ diahopane in bitumen III (the bound components released from confined pyrolysis) is substantially lower than in the other two bitumen fractions for four terrigenous Upper Permian source rocks, demonstrating that this compound originated from free hopanoid precursors, rather than hopanoids bound to the kerogen.     

缅甸安达曼海域中部天然气成因与气源

位于主动大陆边缘的缅甸安达曼海域中部天然气资源丰富,成因多样。天然气成因类型直接影响勘探领域与方向的确定。通过气体组分、CH4和CO2碳同位素资料,对缅甸安达曼海域中部天然气成因类型及气源岩进行了判识。结果表明:上新统部分天然气具有较轻CH4碳同位素,为生物成因气,部分碳同位素较重的天然气属于热成因气;中新统及渐新统天然气CH4碳同位素均较重,属于热成因气;CO2碳同位素显示其存在无机、有机2种成因;此外,还存在少量生物气与热成因气或无机气的混源气。认为该区无机成因CO2与CH4共存体系通过基底断裂来源于地壳深部或上地幔;上新统生物气来自上新统未熟源岩;产于上新统、中新统热成因气,来源于上新统下部、中新统或渐新统上部等深层高-过成熟烃源岩。     

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.     

Molecular and isotopic signatures in sediments and gas hydrate of the central/southwestern Ulleung Basin: high alkalinity escape fuelled by biogenically sourced methane

Natural marine gas hydrate was discovered in Korean territorial waters during a 2007 KIGAM cruise to the central/southwestern Ulleung Basin, East Sea. The first data on the geochemical characterization of hydrate-bound water and gas are presented here for cold seep site 07GHP-10 in the central basin sector, together with analogous data for four sites (07GHP-01, 07GHP-02, 07GHP-03, and 07GHP-14) where no hydrates were detected in other cores from the central/southwestern sectors. Hydrate-bound water displayed very low concentrations of major ions (Cl⁻, SO₄²⁻, Na⁺, Mg²⁺, K⁺, and Ca²⁺), and more positive δD (15.5‰) and δ¹⁸O (2.3‰) signatures compared to seawater. Cl^– freshening and more positive isotopic values were also observed in the pore water at gas hydrate site 07GHP-10. The inferred sulfate–methane interface (SMI) was very shallow (<5 mbsf) at least at four sites, suggesting the widespread occurrence of anaerobic oxidation of methane (AOM) at shallow sediment depths, and possibly high methane flux. Around the SMI, pore water alkalinity was very high (>40 mM), but the carbon isotopic ratios of dissolved inorganic carbon (δ¹³C_DIC) did not show minimum values typical of AOM. Moreover, macroscopic authigenic carbonates were not observed at any of the core sites. This can plausibly be explained by carbon with high δ¹³C values diffusing upward from below the SMI, increasing alkalinity via deep methanogenesis and eventually escaping as alkalinity into the water column, with minor precipitation as solid phase. This contrasts, but is not inconsistent with recent reports of methane-fuelled carbonate formation at other sites in the southwestern basin sector. Methane was the main hydrocarbon component (>99.85%) of headspace, void, and hydrate-bound gases, C₁/C₂₊ ratios were at least 1,000, and δ¹³C_CH4 and δD_CH4 values were in the typical range of methane generated by microbial reduction of CO₂. This is supported by the δ¹³C_C2H6 signatures of void and hydrate-bound gases, and helps clarify some contradictory interpretations existing for the Ulleung Basin as a whole. In combination, these findings suggest that deep biogenic gas and pore waters migrate upward through pathways such as hydrofractures, and measurably influence the shallow carbon cycle. As a result, cation-adjusted alkalinity/removed sulfate diagrams cannot always serve to estimate the degree of alkalinity produced by sulfate reduction and AOM in high methane flux areas.     

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.     

Petroleum composition in the Cuu Long Basin (Mekong Basin) offshore southern Vietnam

The Cuu Long Basin (Mekong Basin) is a rift basin off southern Vietnam, and the most important petroleum producing basin in the country. However, information on petroleum type and characteristics has hitherto been largely unavailable to the public. This paper presents petroleum geochemical data on nine oil samples from four different producing fields in the Cuu Long Basin: the Dragon (Rong), Black Lion (Sutu-Den), Sunrise (Rang ?ong) and White Tiger (Bach Ho) Fields. The oils are highly paraffinic with bimodal normal alkane distributions and show moderate pristane to phytane ratios and a conspicuous hyperbolic decrease in abundance with increasing carbon number of hopane homologues from C₃₀ to C₃₅. The TPP-index of Holba et al. (Holba, A.G., Dzou, L.I., Wood, G.D., Ellis, L., Adam, P., Schaeffer, P., Albrecht, P., Greene, T., Hughes, W.B., 2003. Application of tetracyclic polyprenoids as indicators of input from fresh–brackish water environments. Organic Geochemistry 34, 441–469) is equal to 1 in all samples which in combination with tricyclic triperpane T26/T25 ratios >1 and the n-alkane and hopane distributions mentioned above provide a strong indication of an origin from lacustrine source rocks. This is supported by the absence of marine C₃₀ desmethyl steranes (i.e. 24-n-propylcholestanes) and marine diatom-derived norcholestanes. Based on the overall biological marker distributions, the lakes probably belonged to the overfilled or balanced-fill types defined by Bohacs et al. (Bohacs, K.M., Carroll, A.R., Neal, J.E., Mankiewicz, P.J., 2000. Lake-basin type, source potential, and hydrocarbon character. An integrated sequence-stratigraphic–geochemical framework. AAPG Studies in Geology 46, 3–34). The oils were generated from source rocks at early- to mid-oil-window maturity, presumably Oligocene lacustrine shales that are present in the syn-rift succession. Oils from individual fields may, however, be distinguished by a combination of biological marker parameters, such as the oleanane index, the gammacerane index, the relative abundance of tricyclic terpanes, the proportions of diasteranes and 28-norspergulane, complemented by other parameters. The oils of the Cuu Long Basin show an overall similarity to the B-10 oil from the Song Hong Basin off northern Vietnam, but are markedly different from the seepage oils known from Dam Thi Nai on the coast of central Vietnam.     

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.