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.     

Sedimentary and residual gas geochemical characteristics of the Lower Cambrian organic-rich shales in Southeastern Chongqing,China

To study the sedimentary environment of the Lower Cambrian organic-rich shales and isotopic geochemical characteristics of the residual shale gas, 20 black shale samples from the Niutitang Formation were collected from the Youyang section, located in southeastern Chongqing, China. A combination of geochemical, mineralogical, and trace element studies has been performed on the shale samples from the Lower Cambrian Niutitang Formation, and the results were used to determine the paleoceanic sedimentary environment of this organic-rich shale. The relationships between total organic carbon (TOC) and total sulfur (TS) content, carbon isotope value (δ¹³C_org), trace element enrichment, and mineral composition suggest that the high-TOC Niutitang shale was deposited in an anoxic environment and that the organic matter was well preserved after burial. Stable carbon isotopes and biomarkers both indicate that the organic matter in the Niutitang black shales was mainly derived from both lower aquatic organisms and algaes and belong to type I kerogen. The oil-prone Niutitang black shales have limited residual hydrocarbons, with low values of S₂, I_H, and bitumen A. The carbon isotopic distribution of the residual gas indicate that the shale gas stored in the Niutitang black shale was mostly generated from the cracking of residual bitumen and wet gas during a stage of significantly high maturity. One of the more significant observations in this work involves the carbon isotope compositions of the residual gas (C₁, C₂, and C₃) released by rock crushing. A conventional δ¹³C₁–δ¹³C₂ trend was observed, and most δ¹³C₂ values of the residual gases are heavier than those of the organic matter (OM) in the corresponding samples, indicating the splitting of ethane bonds and the release of smaller molecules, leading to ¹³C enrichment in the residual ethane.     

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.     

Stable carbon isotopic ratios of CH4-CO2-bearing fluid inclusions in fracture-fill mineralization from the Lower Saxony Basin (Germany) - A tool for tracing gas sources and maturity

The stable carbon isotopic ratios (δ¹³C) of methane (CH₄) and carbon dioxide (CO₂) of gas-rich fluid inclusions hosted in fracture-fill mineralization from the southern part of the Lower Saxony Basin, Germany have been measured online using a crushing device interfaced to an isotopic ratio mass spectrometer (IRMS). The data reveal that CH₄ trapped in inclusions seems to be derived from different source rocks with different organic matter types. The δ¹³C values of CH₄ in inclusions in quartz hosted by Carboniferous rocks range between −25 and −19‰, suggesting high-maturity coals as the source of methane. Methane in fluid inclusions in minerals hosted by Mesozoic strata has more negative carbon isotope ratios (−45 to −31‰) and appears to represent primary cracking products from type II kerogens, i.e., marine shales. There is a positive correlation between increasing homogenization temperatures of aqueous fluid inclusions and less negative δ¹³C(CH₄) values of in co-genetic gas inclusions probably indicating different mtaturity of the potential source rocks at the time the fluids were released. The CO₂ isotopic composition of CH₄-CO₂-bearing inclusions shows slight negative or even positive δ¹³C values indicating an inorganic source (e.g., water-rock interaction and dissolution of detrital, marine calcite) for CO₂ in inclusions. We conclude that the δ¹³C isotopic ratios of CH₄-CO₂-bearing fluid inclusions can be used to trace migration pathways, sources of gases, and alteration processes. Furthermore, the δ¹³C values of methane can be used to estimate the maturity of the rocks from which it was sourced. Results presented here are further supported by organic geochemical analysis of surface bitumens which coexist with the gas inclusion-rich fracture-fill mineralization and confirm the isotopic interpretations with respect to fluid source, type and maturity.     

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.     

Contrasting chemical and isotopic compositions of organic matter in Changjiang (Yangtze River) estuarine and East China Sea shelf sediments

To examine the source and preservation of organic matter in the shelf sediments of the East China Sea (ECS), we measured bulk C/N and isotopes, organic biomarkers (n-alkanes and fatty acids) and compound-specific (fatty acids) stable carbon isotope ratios in three sediment cores collected from two sites near the Changjiang Estuary and one in the ECS shelf. Contrasting chemical and isotopic compositions of organic matter were observed between the estuarine and shelf sediments. The concentrations of total n-alkanes and fatty acids in the shelf surface sediments (0–2 cm) were 5–10 times higher than those in estuarine surface sediments but they all decreased rapidly to comparable levels below the surface layer. The compositions of n-alkanes in the estuarine sediments were dominated by C₂₆-C₃₃ long-chain n-alkanes with a strong odd-to-even carbon number predominance. In contrast, the composition of n-alkanes in the shelf sediment was dominated by nC₁₅ to nC₂₂ compounds. Long-chain (>C₂₀) fatty acids (terrestrial biomarkers) accounted for a significantly higher fraction in the estuarine sediments compared to that in the shelf sediment, while short-chain (<C₂₀) saturated and unsaturated fatty acids were more abundant in the shelf surface sediments than in the estuarine sediments. Stable carbon isotopic ratios of individual fatty acids showed a general positive shift from estuarine to shelf sediments, consistent with the variations in bulk δ ¹³C_TOCTOC. These contrasts between the estuarine and shelf sediments indicate that terrestrial organic matter was mainly deposited within the Changjiang Estuary and inner shelf of ECS. Post-depositional diagenetic processes in the surface sediments rapidly altered the chemical compositions and control the preservation of organic matter in the region.     

TSR-altered oil with high-abundance thiaadamantanes of a deep-buried Cambrian gas condensate reservoir in Tarim Basin

The first exploratory well, the ZS1C well, with 158,545 m³ daily gas production was discovered in 6861–6944 m deep strata of the Cambrian gypsolyte layer of the Tarim Basin, China in 2014. The discovery opens a new target for the Cambrian-reservoired oil and gas exploration, and directly leads to large-scale oil and gas exploration of the deep-reservoired Cambrian oil and gas fields in the Basin. Comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry and a comprehensive two-dimensional gas chromatography–flame ionization detector revealed the presence of abundant adamantane compounds, 2-thiaadamantanes and 2-thiadiamantanes, and a large amount of sulfur-containing compounds in the condensate oil. The formation of organic sulfur-containing compounds, such as 2-thiaadamantanes, is an indication of sulfur incorporation from the gypsum in the stratum into oil and gas in the course of TSR. This reservoir has apparently suffered severe TSR alteration because (1) High content of H₂S, (2) H₂S sulfur isotopes, (3) CO₂ carbon isotopes, and others abundant data to support this findings. Similar sulfur isotopic composition of H₂S, oil condensate and the gypsum in the Cambrian strata indicate that the produced condensate is experienced TSR alteration. Therefore, the deep-accumulated Cambrian oil reservoir has experienced severe TSR alteration, and accumulated natural gas and condensate contains high sulfur content.     

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.     

Carbon cycling within the upper methanogenic zone of continental rise sediments; An example from the methane-rich sediments overlying the Blake Ridge gas hydrate deposits

Data from piston cores collected from Carolina Rise and Blake Ridge, and from many DSDP/ODP sites indicate that extreme ¹³C-depletion of methane and ΣCO₂ occurs within the uppermost methanogenic zone of continental rise sediments. We infer that ¹³C-depleted methane is generated near the top of the methanogenic zone when carbon of ¹³C-depleted ΣCO₂, produced by microbially-mediated anaerobic methane oxidation, is recycled back to methane through CO₂ reduction. Interstitial water and gas samples were collected in 27 piston cores, 16 of which penetrated through the sulfate reduction zone into methane-bearing sediments of the Carolina Rise and Blake Ridge. Isotopic measurements (δ¹³C_CH4, δ¹³C_CO2, δD_CH4, and δD_H2O) indicate that this methane is microbial in origin, produced by microbially-mediated CO₂ reduction. Methane samples form two distinct isotopic pools. (1) Methane from a seafloor seep site shows a mean δ¹³C_CH4 value of − 69 ± 2%., mirroring values found at ≥ 160 mbsf from a nearby DSDP site. (2) Twenty, areally-separated sites (sample depth, 10 to 25 mbsf) have δ¹³C_CH4 values ranging from −85 to −103%., and δ¹³C_CO2 as negative as −48%.. The very low δ¹³C values from the methane and CO₂ pools highlight the importance of carbon cycling within continental rise sediments at and near the sulfate-methane boundary.     

Evidence of subsurface anaerobic biodegradation of hydrocarbons and potential secondary methanogenesis in terrestrial mud volcanoes

The assessment of gas origin in mud volcanoes and related petroleum systems must consider post-genetic processes which may alter the original molecular and isotopic composition of reservoir gas. Beyond eventual molecular and isotopic fractionation due to gas migration and microbial oxidation, investigated in previous studies, we now demonstrate that mud volcanoes can show signals of anaerobic biodegradation of natural gas and oil in the subsurface. A large set of gas geochemical data from more than 150 terrestrial mud volcanoes worldwide has been examined. Due to the very low amount of C₂₊ in mud volcanoes, isotopic ratios of ethane, propane and butane (generally the best tracers of anaerobic biodegradation) are only available in a few cases. However, it is observed that ¹³C-enriched propane is always associated with positive δ¹³C_CO2 values, which are known indicators of secondary methanogenesis following anaerobic biodegradation of petroleum. Data from carbon isotopic ratio of CO₂ are available for 134 onshore mud volcanoes from 9 countries (Azerbaijan, Georgia, Ukraine, Russia, Turkmenistan, Trinidad, Italy, Japan and Taiwan). Exactly 50% of mud volcanoes, all releasing thermogenic or mixed methane, show at least one sample with δ¹³C_CO2 > +5‰ (PDB). Thermogenic CH₄ associated with positive carbon isotopic ratio of CO₂ generally maintains its δ¹³C-enriched signature, which is therefore not perturbed by the lighter secondary microbial gas. There is, however, high variability in the δ¹³C_CO2 values within the same mud volcanoes, so that positive δ¹³C_CO2 values can be found in some vents and not in others, or not continuously in the same vent. This can be due to high sensitivity of δ¹³C_CO2 to gas–water–rock interactions or to the presence of differently biodegraded seepage systems in the same mud volcano. However, finding a positive δ¹³C_CO2 value should be considered highly indicative of anaerobic biodegradation and further analyses should be made, especially if mud volcanoes are to be used as pathfinders of the conditions indicative of subsurface hydrocarbon accumulations in unexplored areas.     

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.     

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.     

An isotopic perspective on the correlation of surface ocean carbon dynamics and sea ice melting in Prydz Bay (Antarctica) during austral summer

The stable carbon isotope composition of particulate organic carbon (δ¹³C_POC) and naturally occurring long-lived radionuclide ²²⁶Ra (T_1/2=1600 a) were applied to study the variations of upper ocean (<100 m) carbon dynamics in response to sea ice melting in Prydz Bay, East Antarctica during austral summer 2006. Surface δ¹³C_POC values ranged from −27.4‰ to −19.0‰ and generally decreased from inner bay (south of 67°S) toward the Antarctic Divergence. Surface water ²²⁶Ra activity concentration ranged from 0.92 to 2.09 Bq/m³ (average 1.65±0.32 Bq/m³, n=20) and increased toward the Antarctic Divergence, probably reflecting the influence of ²²⁶Ra-depleted meltwater and upwelled ²²⁶Ra-replete deep water. The fraction of meltwater, f_i, was estimated from ²²⁶Ra activity concentration and salinity using a three-component (along with Antarctic Summer Surface Water, and Prydz Bay Deep Water) mixing model. Although the fraction of meltwater is relatively minor (1.6–11.9%, average 4.1±2.7%, n=20) for the surface waters (sampled at ~6 m), a positive correlation between surface δ¹³C_POC and f_i (δ¹³C_POC=0.94×f_i−28.44, n=20, r²=0.66, p<0.0001) was found, implying that sea ice melting may have contributed to elevated δ¹³C_POC values in the inner Prydz Bay compared to the open oceanic waters. This is the first time for a relationship between δ¹³C_POC and meltwater fraction to be reported in polar oceans to our knowledge. We propose that sea ice melting may have affected surface ocean δ¹³C_POC by enhancing water column stability and providing a more favorable light environment for phytoplankton photosynthesis, resulting in drawdown of seawater CO₂ availability, likely reducing the magnitude of isotope fractionation during biological carbon fixation. Our results highlight the linkage of ice melting and δ¹³C_POC, providing insights into understanding the carbon cycling in the highly productive Antarctic waters.     

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.     

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.     

Stable isotopes of carbon and nitrogen in suspended matter and sediments from the Godavari estuary

Spatial distribution of the carbon and nitrogen content and their isotopic enrichment in suspended matter and sediments were measured in the Godavari estuary to identify the sources and transformation mechanism of organic matter. Significant variability in isotopic distribution was found over the entire length of the Godavari estuary, suggesting multiple sources of organic matter. The mean isotopic ratios (δ¹³C_sed −25.1 ± 0.9, δ¹³C_sus −24.9 ± 1, δ¹⁵N_sed 8.0 ± 2 and δ¹⁵N_sus 6.5 ± 0.9‰) and elemental concentrations (C_sed 0.45 ± 0.2%, C_sus 0.9 ± 0.7%, N_sed 0.07 ± 0.05% and N_sus 0.16 ± 0.1%) support a predominantly terrigenous source. Significant enrichment in the isotopic ratios of δ¹³C from the upper to lower estuary in both suspended (−27.5 and −24.3‰, respectively) and sedimentary (−26.2 and −24.9‰, respectively) phases indicates a decrease in the influence of terrigeneous material toward the mouth of the estuary. A significant positive relationship exists between the δ¹³C of suspended and sediment, which indicates that these two organic carbon pools are likely coupled in the form of a significant exchange between the two phases. A positive relationship exists between chlorophyll a and suspended organic matter, which may mean that a significant source of organic carbon is the in situ produced phytoplankton. But, applying a simple mixing model to our isotopes, data yielded about 46% as the contribution of the terrestrial source to suspended matter, which may support the excessive heterotrophic activity in the Godavari estuary reported earlier.     

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.     

Paragenesis of fluids under evaporates in the Volga-Ural Basin

To unravel the mystery of the relationship between evaporates, Ca–Cl brines and accumulations of oil and N₂ in the basins of ancient cratons, their N₂, CH₄ and He concentration ratios, as well as the isotopic composition (δ¹⁵N, δ¹³C and ³He/⁴He) were compared within the Volga-Ural basin. The study allowed subsalt fluids from Volga-Ural Basin to divide into two genetic groups. The first one is found within the basin's platform area. It includes Ca–Cl brines, high-viscosity heavy oil, bitumen and N₂, which has concentrations higher than that of CH₄ and positive values of δ¹⁵N. The second one is tied to the edge of the platform, the Ural Foredeep and Peri-Caspian Depression. In this group, only the oil and gas reservoirs, which have more CH₄ than N₂, and possibly negative values of δ¹⁵N, were discovered. Interaction of gas components in compared fluids indicates great role of degassing in the formation of their composition. It is suggested that the fluids of the first group (N₂ > CH₄) is what remains, and the second group (N₂ < CH₄) is what is disappears from the rocks during their metamorphism and degassing.     

Fluid flow reconstruction in karstified Panormide platform limestones (north-central Sicily): Implications for hydrocarbon prospectivity in the Sicilian fold and thrust belt

Diagenetic analysis based on field and petrographic observations, isotope and microthermometric data was used to reconstruct the fluid flow history of the Cretaceous shallow water limestones from the Panormide platform exposed in north-central Sicily. Analysis focused on diagenetic products in cavities and dissolution enlarged fractures of the karstified limestones that occur just below a regional unconformity. The fluid flow history could be broken down into five stages that were linked to the kinematic and burial history of the region. (1) Petrography (zoned cathodoluminescence and speleothem textures) and stable isotopes (6.5 < δ¹⁸O_V-PDB < ?3.5‰ and 0 < δ¹³C_V-PDB < ?14‰) indicate that the earliest calcite phase was associated with karstification during emergence of the platform. Limestone dissolution at this stage is important with regard to possible reservoir creation in the Panormide palaeogeographic domain. (2) Fine-grained micrite sedimentation, dated as latest Cretaceous by nannopalaeontology and its ⁸⁷Sr/⁸⁶Sr isotope ratio (0.7078), marks replacement by marine fluids during subsequent submergence of the karstified platform. (3) The following calcite cement was still precipitated by marine-derived fluids (?7.0 < δ¹⁸O_V-PDB < ?5.0‰ and ?3.0 < δ¹³C_V-PDB < 0.5‰/T_m = ?2 to ?5 °C), but at increasingly higher temperatures (T_h = 60–120 °C). This has been interpreted as precipitation during Oligocene foredeep burial. (4) Hot (T_h = 130–180 °C), low saline (T_m < ?2.5 °C) fluids with increasingly higher calculated δ¹⁸O_SMOW signatures (+6 to +14‰) subsequently invaded the karst system. These fluids most likely migrated during fold and thrust belt development. The low salinity and relatively high δ¹⁸O_SMOW signatures of the fluids are interpreted to be the result of clay dewatering reactions. The presence of bitumen and associated fluorite with hydrocarbon inclusions at this stage in the paragenesis constrains the timing of oil migration in the region. (5) Finally, high saline fluids with elevated ⁸⁷Sr/⁸⁶Sr (0.7095–0.7105) signatures invaded the karst system. This last fluid flow event was possibly coeval with localized dolomitization and calcite cementation along high-angle faults of Pliocene age, as suggested by identical radiogenic signatures of these diagenetic products.     

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

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