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1.
Abiotic methane in serpentinized peridotites (MSP) has implications for energy resource exploration, planetary geology, subsurface microbiology and astrobiology. Once considered a rare occurrence on Earth, reports of MSP are increasing for numerous localities worldwide in low temperature, land-based springs and seeps. We report the discovery of six methane-rich water springs and two ponds with active gas bubbling in the Ronda peridotite massif, in southern Spain. Water is hyperalkaline with typical hydrochemical features of active serpentinization (pH: 10.7 to 11.7, T: 17.1 to 21.5 °C, Ca–OH facies). Dissolved CH4 concentrations range from 0.1 to 3.2 mg/L. The methane stable C and H isotope ratios in the natural spring and bubbling sites (δ13CCH4: −12.3 to −37‰ VPDB; δ2HCH4: −280 to −333‰ VSMOW) indicate a predominant abiotic origin. In contrast, springs with manmade water systems, i.e., pipes or fountains, appear to have mixed biotic-abiotic origin (δ13CCH4: −44 to −69‰; δ2HCH4: −180 to −319‰). Radiocarbon (14C) analyses show that methane C in a natural spring is older than ca. 50,000 y BP, whereas dissolved inorganic carbon (DIC) analysed in all springs has an apparent 14C age ranging from modern to 2334 y BP. Therefore most, if not all, of the CH4 is allochthonous, i.e., not generated from the carbon in the hyperalkaline water. Methane is also released as bubbles in natural ponds and as diffuse seepages (∼101–102 mg CH4 m−2d−1) from the ground up to several tens of metres from the seeps and springs, albeit with no overt visual evidence. These data suggest that the gas follows independent migration pathways, potentially along faults or fracture systems, physically isolated from the hyperalkaline springs. Methane does not seem to be genetically related to the hyperalkaline water, which may only act as a carrier of the gas. Gas-bearing springs, vents and invisible microseepage in land-based peridotites are more common than previously thought. In addition to other geological sources, MSP is potentially a natural source of methane for the troposphere and requires more worldwide flux measurements.  相似文献   

2.
《Applied Geochemistry》1999,14(1):119-131
The major source of methane (CH4) in subsurface sediments on the property of a former hazardous waste treatment facility was determined using isotopic analyses measured on CH4 and associated groundwater. The site, located on an earthen pier built into a shallow wetland lake, has had a history of waste disposal practices and is surrounded by landfills and other waste management facilities. Concentrations of CH4 up to 70% were found in the headspace gases of several piezometers screened at 3 different depths (ranging from 8 to 17 m) in lacustrine and glacial till deposits. Possible sources of the CH4 included a nearby landfill, organic wastes from previous impoundments and microbial gas derived from natural organic matter in the sediments.Isotopic analyses included δ13C, δD, 14C, and 3H on select CH4 samples and δD and δ18O on groundwater samples. Methane from the deepest glacial till and intermediate lacustrine deposits had δ13C values from −79 to −82‰, typical of natural “drift gas” generated by microbial CO2-reduction. The CH4 from the shallow lacustrine deposits had δ13C values from −63 to −76‰, interpreted as a mixture between CH4 generated by microbial fermentation and the CO2-reduction processes within the subsurface sediments. The δD values of all the CH4 samples were quite negative ranging from −272 to −299‰. Groundwater sampled from the deeper zones also showed quite negative δD values that explained the light δD observed for the CH4. Radiocarbon analyses of the CH4 showed decreasing 14C activity with depth, from a high of 58 pMC in the shallow sediments to 2 pMC in the deeper glacial till. The isotopic data indicated the majority of CH4 detected in the till deposits of this site was microbial CH4 generated from naturally buried organic matter within the subsurface sediments. However, the isotopic data of CH4 from the shallow piezometers was more variable and the possibility of some mixing with oxidized landfill CH4 could not be completely ruled out.  相似文献   

3.
The chemistry and isotope ratios of He, C (δ13C) and H (δD) of free gases collected in the San Vittorino plain, an intramontane depression of tectonic origin, were determined to shed light on mantle degassing in central Italy. The C isotopic composition of CO2 (δ13C–CO2 −2.0‰ to −3.8‰) and He isotope ratios (R/RA 0.12–0.27) were used to calculate the fraction of CO2 originating from mantle degassing vs. sedimentary sources. The results show that CO2 predominantly (average of 75%) derives from the thermo-metamorphic reaction of limestone. Between 6% and 22% of the CO2 in the samples derives from organic-rich sedimentary sources. The mantle source accounts for 0–6% of the total CO2; however, in two samples, located in proximity to the most important faults of the plain, the mantle accounts for 24% and 42%. The presence of faults and fractures allows upward gas migration from a deep source to the Earth’s surface, not only in the peri-Tyrrhenian sector, as generally reported by studies on natural gas emissions in central Italy, but also in the pre-Apennine and Apennine belts. Isotope ratios of CH4 (δ13C–CH4 −6.1‰ to −22.7‰; δD–CH4 −9‰ to −129‰) show that CH4 does not appear to be related to mantle or magma degassing, but it is the product of thermal degradation of organic matter (i.e. thermogenic origin) and/or the reduction of CO2 (i.e. geothermal origin). Most of the samples appear to be affected by secondary microbial oxidation processes.  相似文献   

4.
Molecular transport (diffusion) of methane in water-saturated sedimentary rocks results in carbon isotope fractionation. In order to quantify the diffusive isotope fractionation effect and its dependence on total organic carbon (TOC) content, experimental measurements have been performed on three natural shale samples with TOC values ranging from 0.3 to 5.74%. The experiments were conducted at 90°C and fluid pressures of 9 MPa (90 bar). Based on the instantaneous and cumulative composition of the diffused methane, effective diffusion coefficients of the 12CH4 and 13CH4 species, respectively, have been calculated.Compared with the carbon isotopic composition of the source methane (δ13C1 = −39.1‰), a significant depletion of the heavier carbon isotope (13C) in the diffused methane was observed for all three shales. The degree of depletion is highest during the initial non-steady state of the diffusion process. It then gradually decreases and reaches a constant difference (Δ δ = δ13Cdiff −δ13Csource) when approaching the steady-state. The degree of the isotopic fractionation of methane due to molecular diffusion increases with the TOC content of the shales. The carbon isotope fractionation of methane during molecular migration results practically exclusively from differences in molecular mobility (effective diffusion coefficients) of the 12CH4 and 13CH4 entities. No measurable solubility fractionation was observed.The experimental isotope-specific diffusion data were used in two hypothetical scenarios to illustrate the extent of isotopic fractionation to be expected as a result of molecular transport in geological systems with shales of different TOC contents. The first scenario considers the progression of a diffusion front from a constant source (gas reservoir) into a homogeneous “semi-infinite” shale caprock over a period of 10 Ma.In the second example, gas diffusion across a 100 m caprock sequence is analyzed in terms of absolute quantities and isotope fractionation effects. The examples demonstrate that methane losses by molecular diffusion are small in comparison with the contents of commercial size gas accumulations. The degree of isotopic fractionation is related inversely to the quantity of diffused gas so that strong fractionation effects are only observed for relatively small portions of gas.The experimental data can be readily used in numerical basin analysis to examine the effects of diffusion-related isotopic fractionation on the composition of natural gas reservoirs.  相似文献   

5.
The role of methane clathrate hydrates in the global methane budget is poorly understood because little is known about how much methane from decomposing hydrates actually reaches the atmosphere. In an attempt to quantify the role of water column methanotrophy (microbial methane oxidation) as a control on methane release, we measured water column methane profiles (concentration and δ13C) and oxidation rates at eight stations in an area of active methane venting in the Eel River Basin, off the coast of northern California. The oxidation rate measurements were made with tracer additions of 3H-CH4.Small numbers of instantaneous rate measurements are difficult to interpret in a dynamic, advecting coastal environment, but combined with the concentration and stable isotope measurements, they do offer insights into the importance of methanotrophy as a control on methane release. Fractional oxidation rates ranged from 0.2 to 0.4% of ambient methane per day in the deep water (depths >370 m), where methane concentration was high (20–300 nM), to near-undetectable rates in the upper portion of the water column (depths <370 m), where methane concentration was low (3–10 nM). Methane turnover time averaged 1.5 yr in the deep water but was on the order of decades in the upper portion of the water column. The depth-integrated water column methane oxidation rates for the deep water averaged 5.2 mmol CH4 m−2 yr−1, whereas the upper portion of the water column averaged only 0.14 mmol CH4 m−2 yr−1; the depth-integrated oxidation rate for deep water in the 25-km2 area encompassing the venting field averaged 2 × 106 g CH4 yr−1. Stable isotope values (δ13C-CH4) for individual samples ranged from −34 to −52‰ (vs. PDB, Peedee belemnite standard) in the region. These values are isotopically enriched relative to hydrates in the region (δ13C-CH4 about −57 to −69‰), further supporting our observations of extensive methane oxidation in this environment.  相似文献   

6.
Formation of iron sulfide nodules during anaerobic oxidation of methane   总被引：1，自引：0，他引：1  
The biomarker compositions of iron sulfide nodules (ISNs; upper Pliocene Valle Ricca section near Rome, Italy) that contain the ferrimagnetic mineral greigite (Fe3S4) were examined. In addition to the presence of specific terrestrial and marine biomarkers, consistent with formation in coastal marine sediments, these ISNs contain compounds thought to originate from sulfate reducing bacteria (SRB). These compounds include a variety of low-molecular-weight and branched alkanols and several non-isoprenoidal dialkyl glycerol diethers (DGDs). In addition, archaeal biomarkers, including archaeol, macrocyclic isoprenoidal DGDs and isoprenoidal glycerol dialkyl glycerol tetraethers are also present. Both SRB and archaeal lipid δ13C values are depleted in 13C (δ13C values are typically less than −50‰), which suggests that the SRB and archaea consumed 13C depleted methane. These biomarker and isotopic signatures are similar to those found in cold seeps and marine sediments where anaerobic oxidation of methane (AOM) occurs with sulfate serving as the terminal electron acceptor. Association of AOM with formation of greigite-containing ISNs could provide an explanation for documented remagnetization of the Valle Ricca sediments. Upward migration of methane, subsequent AOM and associated authigenic greigite formation are widespread processes in the geological record that have considerable potential to compromise paleomagnetic records.  相似文献   

7.
Permian Khuff reservoirs along the east coast of Saudi Arabia and in the Arabian Gulf produce dry sour gas with highly variable nitrogen concentrations. Rough correlations between N2/CH4, CO2/CH4 and H2S/CH4 suggest that non-hydrocarbon gas abundances are controlled by thermochemical sulfate reduction (TSR). In Khuff gases judged to be unaltered by TSR, methane δ13C generally falls between −40‰ and −35‰ VPDB and carbon dioxide δ13C between −3‰ and 0‰ VPDB. As H2S/CH4 increases, methane δ13C increases to as much as −3‰ and carbon dioxide δ13C decreases to as little as −28‰. These changes are interpreted to reflect the oxidation of methane to carbon dioxide.Khuff reservoir temperatures, which locally exceed 150 °C, appear high enough to drive the reduction of sulfate by methane. Anhydrite is abundant in the Khuff and fine grained nodules are commonly rimmed with secondary calcite cement. Some cores contain abundant pyrite, sphalerite and galena. Assuming that nitrogen is inert, loss of methane by TSR should increase N2/CH4 of the residual gas and leave δ15N unaltered. δ15N of Paleozoic gases in Saudi Arabia varies from −7‰ to 1‰ vs. air and supports the TSR hypothesis. N2/CH4 in gases from stacked Khuff reservoirs varies by a factor of 19 yet the variation in δ15N (0.3–0.5‰) is trivial.Because the relative abundance of hydrogen sulfide is not a fully reliable extent of reaction parameter, we have attempted to assess the extent of TSR using plots of methane δ13C versus log(N2/CH4). Observed variations in these parameters can be fitted using simple Rayleigh models with kinetic carbon isotope fractionation factors between 0.98 and 0.99. We calculate that TSR may have destroyed more than 90% of the original methane charge in the most extreme instance. The possibility that methane may be completely destroyed by TSR has important implications for deep gas exploration and the origin of gases rich in nitrogen as well as hydrogen sulfide.  相似文献   

8.
《Geochimica et cosmochimica acta》1999,63(23-24):3959-3966
We propose that organic compounds found in a Miocene limestone from Marmorito (Northern Italy) are source markers for organic matter present in ancient methane vent systems (cold seeps). The limestone contains high concentrations of the tail-to-tail linked, acyclic C20 isoprenoid 2,6,11,15-tetramethylhexadecane (crocetane), a C25 homolog 2,6,10,15,19-pentamethylicosane (PME), and a distinctive glycerol ether lipid containing 3,7,11,15-tetramethylhexadecyl (phytanyl-) moieties. The chemical structures of these biomarkers indicate a common origin from archaea. Their extremely 13C-depleted isotope compositions (δ13C ≈ −108 to −115.6‰ PDB) suggest that the respective archaea have directly or indirectly introduced isotopically depleted, methane-derived carbon into their biomass. We postulate that a second major cluster of biomarkers showing heavier isotope values (δ13C ≈ −88‰) is derived from sulfate-reducing bacteria (SRB). The observed biomarkers sustain the idea that methanogenic bacteria, in a syntrophic community with SRB, are responsible for the anaerobic oxidation of methane in marine sediments. Marmorito may thus represent a conceivable ancient scenario for methane consumption performed by a defined, two-membered bacterial consortium: (1) archaea that perform reversed methanogenesis by oxidizing methane and producing CO2 and H2; and (2) SRB that consume the resulting H2. Furthermore, the respective organic molecules are, unlike other compounds, tightly bound to the crystalline carbonate phase. The Marmorito carbonates can thus be regarded as “cold seep microbialites” rather than mere “authigenic” carbonates.  相似文献   

9.
Distribution and isotopic composition (δ13C) of low molecular weight hydrocarbon gases were studied in Big Soda Lake (depth = 64 m), an alkaline, meromictic lake with permanently anoxic bottom waters. Methane increased with depth in the anoxic mixolimnion (depth = 20–35 m), reached uniform concentrations (55 μM/l) in the monimolimnion (35–64 m) and again increased with depth in monimolimnion bottom sediments (>400 μM/kg below 1 m sub-bottom depth). The μ13C[CH4] values in bottom sediment below 1 m sub-bottom depth (<?70 per mil) increased with vertical distance up the core (δ13C[CH4] = ?55 per mil at sediment surface). Monimolimnion δ13C[CH4] values (?55 to ?61 per mil) were greater than most δ13C[CH4] values found in the anoxic mixolimnion (92% of samples had δ13C[CH4] values between ?20 and ?48 per mil). No significant concentrations of ethylene or propylene were found in the lake. However ethane, propane, isobutane and n-butane concentrations all increased with water column depth, with respective maximum concentrations of 260, 80, 23 and 22 nM/l encountered between 50–60 m depth. Concentrations of ethane, propane and butanes decreased with depth in the bottom sediments. Ratios of CH4[C2H6 + C3H8] were high (250–620) in the anoxic mixolimnion, decreased to ~161 in the monimolimnion and increased with depth in the sediment to values as high as 1736. We concluded that methane has a biogenic origin in both the sediments and the anoxic water column and that C2-C4 alkanes have biogenic origins in the monimolimnion water and shallow sediments. The changes observed in δ13C[CH4] and CH4(C2H6 + C3H8) with depth in the water column and sediments are probably caused by bacteria] processes. These might include anaerobic methane oxidation and different rates of methanogenesis and C2 to C4 alkane production by microorganisms.  相似文献   

10.
Formation of the Carbon-13 (13C) and deuterium (D) doubly-substituted methane isotopologues (13CH3D) in natural gases is studied utilizing both first-principle quantum mechanism molecular calculation and direct FTIR laboratorial measurements of specifically synthesized high isotope concentration methane gas. For 13CH3D, the symmetrically breathing mode A0 emerges as IR-detectable attributed to the molecular symmetry lowering to C3v from Td of the non-isotopic methane (CH4), along with a large vibrational frequency shift from ∼3000 to ∼2250 cm−1. Our studies also indicate that the concentration of 13CH3D is dependent on the environmental temperature through isotope exchanges among methane isotopologues; and the Gibbs’ Free Energy difference due to Quantum Mechanics Zero-Point vibrational motions has the major contribution to this temperature dependency. Potential geologic applications of the 13CH3D measurement to natural gas exploration and assessments are also discussed. In order to detect the 13CH3D concentration change of each 50 °C in the natural gas system, a 10−9 resolution is desirable. Such a measurement could provide important add-on information to distinguish natural gas origin and distribution.  相似文献   

11.
The stable isotope values of carbon (δ13Cmethane) and hydrogen (δ2Hmethane) from methane molecules trapped in gas hydrates are useful for differentiation of methane from microbial and thermal origins, providing valuable information during hydrocarbon exploration. Recent studies have reported catalysis of methane hydrates when smectite clays and biosurfactants are present in hydrate-hosting sediments, but catalytic influences on the values of δ13Cmethane and δ2Hmethane are not well documented. In this study, pressure vessel methane hydrates were formed from solutions in contact with smectite clays (montmorillonite and nontronite) and biosurfactants (rhamnolipids and surfactin). Experiments show less than 1‰ differences in values of δ13Cmethane between free and encaged molecules and up to 10‰ variations in values of δ2Hmethane between free and encaged molecules. Notably, methane consumption increased in methane hydrates formed from solutions containing biosurfactants and biosurfactant–smectite mixtures. Results presented here indicate that a hydrate formed in the presence of smectite clays and biosurfactants are characterized by small shifts in free and encaged values of δ13Cmethane and δ2Hmethane and do not complicate interpretation of gas origin. In contrast, methane consumption in hydrates formed under the catalytic effect of smectite clays and biosurfactants modifies gas wetness, obscures gas origin and complicates interpretation of thermal maturity.  相似文献   

12.
Hydraulic fracturing of shale deposits has greatly increased the productivity of the natural gas industry by allowing it to exploit previously inaccessible reservoirs. Previous research has demonstrated that this practice has the potential to contaminate shallow aquifers with methane (CH4) from deeper formations. This study compares concentrations and isotopic compositions of CH4 sampled from domestic groundwater wells in Letcher County, Eastern Kentucky in order to characterize its occurrence and origins in relation to both neighboring hydraulically fractured natural gas wells and surface coal mines. The studied groundwater showed concentrations of CH4 ranging from 0.05 mg/L to 10 mg/L, thus, no immediate remediation is required. The δ13C values of CH4 ranged from −66‰ to −16‰, and δ2H values ranged from −286‰ to −86‰, suggesting an immature thermogenic and mixed biogenic/thermogenic origin. The occurrence of CH4 was not correlated with proximity to hydraulically fractured natural gas wells. Generally, CH4 occurrence corresponded with groundwater abundant in Na+, Cl−, and HCO3−, and with low concentrations of SO42−. The CH4 and SO42−concentrations were best predicted by the oxidation/reduction potential of the studied groundwater. CH4 was abundant in more reducing waters, and SO42− was abundant in more oxidizing waters. Additionally, groundwater in greater proximity to surface mining was more likely to be oxidized. This, in turn, might have increased the likelihood of CH4 oxidation in shallow groundwater.  相似文献   

13.
The main purpose of this study is to model the δ13C values of methane derived from coal by combining kinetic-simulating experiment with the gas chromatography-isotope ratio mass spectrum (GC-IRMS) analysis. The stable carbon isotopic variation of methane in pyrolysates with heating temperature indicates that the assumptions for both a constant kinetic isotope effect (α) and a uniform initial isotopic composition (δ13Co) are impractical for explaining the carbon isotopic fractionation during coalification. For purposes of simplification, two approaches are used in this paper to deal with the heterogeneity of terrestrial organic matter. One is that, assuming a uniform initial isotopic composition (i.e., δ13Ci, o=δ13Co) for all methane-generating precursors in coal, the isotopic variation of methane is fitted by adjusting ΔEa, i (Ea13C, i−Ea12C, i) for each hypothetical reaction. The other is that, assuming a constant kinetic isotope effect during the whole gas formation, that is all ΔEa, i values are identical, the modeling of methane isotopic composition is achieved by changing the 13CH4 generation potential of each reaction (fi, 13C), namely, by adjusting the initial δ13C value (δ13Ci, o) for each methane-generating precursor. Results of the kinetic calculation shows that the two simulating methods can yield a similar result at a geological heating rate of 2 °C/My, which further demonstrates that those natural gases with methane δ13C value being approximately −36‰ are possibly sourced from the upper Triassic coal measure strata in the Northwestern Sichuan Basin.  相似文献   

14.
This study presents isotope geochemical analyses conducted on water column samples and core sediments collected from the Swan Lake Basin. Water analyses include the dissolved methane (CH4) content and the ratio of carbon-13 to carbon-12 (δ13C) in dissolved inorganic carbon (DIC). The core sediments – sandy muds containing inorganic calcite, organic matter, and opal phases ± ostracods – were examined by X-ray diffraction, dated by radiocarbon (14C), analyzed for wt% organic carbon, wt% organic nitrogen, wt% organic matter, wt% calcite, δ13C of bulk-sediment insoluble organic matter (kerogen), 18O:16O ratio (δ18O) and δ13C of bulk and ostracod calcite. Of particular significance is the large enrichment in carbon-13 (δ13C = +4.5 to +20.4‰ V-PDB) in the calcite of these sediments. The 13C-enriched calcite is primarily formed from DIC in the water column of the lake as a result of the following combined processes: (i) the incorporation of 13C enriched residual carbon dioxide (CO2) after partial reduction to CH4 in the sediments and its migration into the water column-DIC pool; (ii) the preferential assimilation of 12C by phytoplankton during photosynthesis; (iii) the removal of 13C-depleted CH4 by ebullition and of organic matter by sedimentation and burial. The 13C enrichment was low between 3624 and 2470 yr BP; high between 2470 and 1299 yr BP; and moderate since 1299 yr BP. Low 13C enrichment was formed under low water-column carbon levels while higher ones were formed under elevated rates of biomass and calcite deposition. These associations seem to imply that biological productivity is the main reason for carbon-13 enrichments.  相似文献   

15.
The origin of the combustible gases in groundwater from glacial-outwash and fractured-bedrock aquifers was investigated in northern Tioga County, Pennsylvania. Thermogenic methane (CH4) and ethane (C2H6) and microbial CH4 were found. Microbial CH4 is from natural in situ processes in the shale bedrock and occurs chiefly in the bedrock aquifer. The δ13C values of CH4 and C2H6 for the majority of thermogenic gases from water wells either matched or were between values for the samples of non-native storage-field gas from injection wells and the samples of gas from storage-field observation wells. Traces of C2H6 with microbial CH4 and a range of C and H isotopic compositions of CH4 indicate gases of different origins are mixing in sub-surface pathways; gas mixtures are present in groundwater. Pathways for gas migration and a specific source of the gases were not identified. Processes responsible for the presence of microbial gases in groundwater could be elucidated with further geochemical study.  相似文献   

16.
The origin of the combustible gases in groundwater from glacial-outwash and fractured-bedrock aquifers was investigated in northern Tioga County, Pennsylvania. Thermogenic methane (CH4) and ethane (C2H6) and microbial CH4 were found. Microbial CH4 is from natural in situ processes in the shale bedrock and occurs chiefly in the bedrock aquifer. The δ13C values of CH4 and C2H6 for the majority of thermogenic gases from water wells either matched or were between values for the samples of non-native storage-field gas from injection wells and the samples of gas from storage-field observation wells. Traces of C2H6 with microbial CH4 and a range of C and H isotopic compositions of CH4 indicate gases of different origins are mixing in sub-surface pathways; gas mixtures are present in groundwater. Pathways for gas migration and a specific source of the gases were not identified. Processes responsible for the presence of microbial gases in groundwater could be elucidated with further geochemical study.  相似文献   

17.
Natural gas in the Xujiahe Formation of the Sichuan Basin is dominated by hydrocarbon (HC) gas, with 78–79% methane and 2–19% C2+ HC. Its dryness coefficient (C1/C1–5) is mostly < 0.95. The gas in fluid inclusions, which has low contents of CH4 and heavy hydrocarbons (C2+) and higher contents of non-hydrocarbons (e.g. CO2), is a typical wet gas produced by thermal degradation of kerogen. Gas produced from the Upper Triassic Xujiahe Formation (here denoted field gas) has light carbon isotope values for methane (δ13C1: −45‰ to −36‰) and heavier values for ethane (δ13C2: −30‰ to −25‰). The case is similar for gas in fluid inclusions, but δ13C1 = −36‰ to −45‰ and δ13C2 = −24.8‰ to −28.1‰, suggesting that the gas experienced weak isotopic fractionation due to migration and water washing. The field gas has δ13CCO2 values of −15.6‰ to −5.6‰, while the gas in fluid inclusions has δ13CCO2 values of −16.6‰ to −9‰, indicating its organic origin. Geochemical comparison shows that CO2 captured in fluid inclusions mainly originated from source rock organic matter, with little contribution from abiogenic CO2. Fluid inclusions originate in a relatively closed system without fluid exchange with the outside following the gas capture process, so that there is no isotopic fractionation. They thus present the original state of gas generated from the source rocks. These research results can provide a theoretical basis for gas generation, evolution, migration and accumulation in the basin.  相似文献   

18.
《Applied Geochemistry》2005,20(11):2017-2037
The Tertiary Thrace Basin located in NW Turkey comprises 9 km of clastic-sedimentary column ranging in age from Early Eocene to Recent in age. Fifteen natural gas and 10 associated condensate samples collected from the 11 different gas fields along the NW–SE extending zone of the northern portion of the basin were evaluated on the basis of their chemical and individual C isotopic compositions. For the purpose of the study, the genesis of CH4, thermogenic C2+ gases, and associated condensates were evaluated separately.Methane appears to have 3 origins: Group-1 CH4 is bacteriogenic (Calculated δ13CC1–C = −61.48‰; Silivri Field) and found in Oligocene reservoirs and mixed with the thermogenic Group-2 CH4. They probably formed in the Upper Oligocene coal and shales deposited in a marshy-swamp environment of fluvio-deltaic settings. Group-2 (δ13CC1–C = −35.80‰; Hamitabat Field) and Group-3 (δ13C1–C = −49.10‰; Değirmenköy Field) methanes are thermogenic and share the same origin with the Group-2 and Group-3 C2+ gases. The Group-2 C2+ gases include 63% of the gas fields. They are produced from both Eocene (overwhelmingly) and Oligocene reservoirs. These gases were almost certainly generated from isotopically heavy terrestrial kerogen (δ13C = −21‰) present in the Eocene deltaic Hamitabat shales. The Group-3 C2+ gases, produced from one field, were generated from isotopically light marine kerogen (δ13C = −29‰). Lower Oligoce ne Mezardere shales deposited in pro-deltaic settings are believed to be the source of these gases.The bulk and individual n-alkane isotopic relationships between the rock extracts, gases, condensates and oils from the basin differentiated two Groups of condensates, which can be genetically linked to the Group-2 and -3 thermogenic C2+ gases. However, it is crucial to note that condensates do not necessarily correlate to their associated gases.Maturity assessments on the Group-1 and -2 thermogenic gases based on their estimated initial kerogen isotope values (δ13C = −21‰; −29‰) and on the biomarkers present in the associated condensates reveal that all the hydrocarbons including gases, condensates and oils are the products of primary cracking at the early mature st age (Req = 0.55–0.81%). It is demonstrated that the open-system source conditions required for such an early-mature hydrocarbon expulsion exist and are supported by fault systems of the basin.  相似文献   

19.
Although the sediments of coastal marine mangrove forests have been considered a minor source of atmospheric methane, these estimates have been based on sparse data from similar areas. We have gathered evidence that shows that external nutrient and freshwater loading in mangrove sediments may have a significant effect on methane flux. Experiments were performed to examine methane fluxes from anaerobic sediments in a mangrove forest subjected to secondary sewage effluents on the southwestern coast of Puerto Rico. Emission rates were measured in situ using a static chamber technique, and subsequent laboratory analysis of samples was by gas chromatography using a flame ionization detector. Results indicate that methane flux rates were lowest at the landward fringe nearest to the effluent discharge, higher in the seaward fringe occupied by red mangroves, and highest in the transition zone between black and red mangrove communities, with average values of 4 mg CH4 m?2 d?1, 42 mg CH4 m?2 d?1, and 82 mg CH4 m?2 d?1, respectively. Overall mean values show these sediments may emit as much as 40 times more methane than unimpacted pristine areas. Pneumatophores ofAviciennia germinans have been found to serve as conduits to the atmosphere for this gas. Fluctuating water level overlying the mangrove sediment is an important environmental factor controlling seasonal and interannual CH4 flux variations. Environmental controls such as freshwater inputs and increased nutrient loading influence in situ methane emissions from these environments.  相似文献   

20.
Natural gas reservoirs in organic-rich shales in the Appalachian and Michigan basins in the United States are currently being produced via hydraulic fracturing. Stratigraphically-equivalent shales occur in the Canadian portion of the basins in southwestern Ontario with anecdotal evidence of gas shows, yet there has been no commercial shale gas production to date. To provide baseline data in the case of future environmental issues related to hydraulic fracturing and shale gas production, such as leakage of natural gas, saline water, and/or hydraulic fracturing fluids, and to evaluate hydrogeochemical controls on natural gas accumulations in shallow groundwater in general, this study investigates the origin and distribution of natural gas and brine in shallow aquifers across southwestern Ontario. An extensive geochemical database of major ion and trace metal chemistry and methane concentrations of 1010 groundwater samples from shallow, domestic wells in bedrock and overburden aquifers throughout southwestern Ontario was utilized. In addition, select wells (n = 36) were resampled for detailed dissolved gas composition, δ13C of CH4, C2, C3, and CO2, and δD of CH4. Dissolved gases in groundwater from bedrock and overburden wells were composed primarily of CH4 (29.7–98.6 mol% of total gas volume), N2 (0.8–66.2 mol%), Ar + O2 (0.2–3.4 mol%), and CO2 (0–1.2 mol%). Ethane was detected, but only in low concentrations (<0.041 mol%), and no other higher chain hydrocarbons were present, except for one well in overburden overlying the Dundee Formation, which contained 0.81 mol% ethane and 0.21 mol% propane. The highest methane concentrations (30 to >100 in situ % saturation) were found in bedrock wells completed in the Upper Devonian Kettle Point Formation, Middle Devonian Hamilton Group and Dundee Formation, and in surficial aquifers overlying these organic-rich shale-bearing formations, indicating that bedrock geology is the primary control on methane occurrences. A few (n = 40) samples showed Na–Cl–Br evidence of brine mixing with dilute groundwater, however only one of these samples contained high (>60 in situ % saturation) CH4. The relatively low δ13C values of CH4 (−89.9‰ to −57.3‰), covariance of δD values of CH4 and H2O, positive correlation between δ13C values of CH4 and CO2, and lack of higher chain hydrocarbons (C3+) in all but one dissolved gas sample indicates that the methane in groundwater throughout the study area is primarily microbial in origin. The presence or absence of alternative electron acceptors (e.g. dissolved oxygen, Fe, NO3, SO4), in addition to organic substrates, controls the occurrence of microbial CH4 in shallow aquifers. Microbial methane has likely been accumulating in the study area, since at least the Late Pleistocene to the present, as indicated by the co-variance and range of δD values of CH4 (−314‰ to −263‰) and associated groundwater (−19‰ to −6‰ δD-H2O).  相似文献   

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