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1.
《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
2.
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
3.
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
4.
《International Geology Review》2012,54(10):938-947
Carbon stable-isotope compositions of coexisting carbon dioxide and methane from geothermal springs across the Central Andes of northern Chile and Bolivia are reported. A total of 60 samples were analyzed for δ13CCO2 and, of these, 10 were selected for δ13CCH4 analyses. The Central Andes are characterized by an active volcanic arc and an unusually thick (up to 75 km) continental crust behind the arc, beneath the high plateau region of the Altiplano. Furthermore, helium-isotope evidence suggests active mantle degassing in a 350-km-wide zone beneath the thick continental crust in the Central Andes (Hoke et al., 1994). The present results show a wide range of δ13CCO2 (-14.9 to -0.6‰) and a surprisingly heavy δ13CCH4 (?20.9 to ?12.3‰). The difference between δ13CCO2 and δ13CCH4 (δ13CCO2-CH4 ) for individual samples varies between 1.5‰ and 13.5‰. The δ13CCO2 results show wide and overlapping ranges in the samples collected from the Precordillera, the Volcanic Arc (or Western Cordillera), the Altiplano, and the Eastern Cordillera. The widest ranges occur in the Eastern Cordillera (?15.0 to ?4.8‰) and the Altiplano (?20 to ?6‰). The δ13CCO2 results for geothermal samples from the Volcanic Arc range between ?8.0‰ (Surire) and ?0.6‰ (Abra de Nappa), whereas δ13CCO2 measured in gases collected from geothermal springs in the Precordillera range from ?10 to ?5‰. The relationships between 3He/4He, δ13CCO2 , and δ13CCH4 are used to distinguish between crustal and mantle origins. The wide (21‰) range in the is interpreted to reflect contributions from different CO2 sources that include organic and inorganic crustal and mantle carbon. Assuming isotopic equilibrium between coexisting methane and carbon dioxide, Δ13CCO2-CH4 suggests very high equilibrium temperatures, in excess of 530°C, for some geothermal systems that also are characterized by a high (up to 63%) mantle-derived helium component. δ13CCH4 results suggest that methane has not formed by bacteriogenic processes or by thermal decomposition of organic matter, but rather abiogenically through the high-temperature reaction between H2 and CO2. The δ13CCH4 results for the samples from the Volcanic Arc and from two CO2-rich geothermal springs in the Altiplano (Coipasa-2 and Belen de Andamarca) are similar to those reported from hydrothermal fluids emitted from the East Pacific Rise (Welhan, 1988) and White Island, New Zealand (Hulston and McCabe, 1962), suggesting a mantle-derived carbon component in the methane. 相似文献
5.
The barium deposits in Ankang and Xunyang counties,Shaanxi Province,China,occur in the northernmost part of the world-class barium metallogenic belt in south Qinling.The deposits are hosted by the Lower Silurian carbonaceous siliceous rocks,with a unique combination of barite and witherite.The homogenization temperatures of fluid inclusions in the barite are mainly concentrated between 135 and 155 ℃,whereas those from the witherite have two peaks of 165-175 ℃,and 215-225℃,respectively.Laser Raman analysis of fluid inclusions indicates that the vapor phase of fluid inclusions in barite is dominated by H_2O,although some contains N_2,H_2S,and CH_4.The compositions of the vapor and liquid phases of fluid inclusions in witherite can be divided into two end-members,one dominated by H_2O without other volatiles,and the other containing CH_4,C_2H_6,C_3H_8,C_2H_4,and C_6H_6 in addition to H_2O.CO_2,H_2S,and some CH_4 are interpreted as products of chemical reactions during mineralization.Organic gases(CH_4,C_2H_6,C_3H_8,C_2H_4,and C_6H_6) in the fluids were critical in the formation of barium sulfate versus carbonate.The δ~(34)S values of barite range from 38.26‰ to54.23‰(CDT),the δ~(34)S values of sulfides coexisting with barium minerals vary from 22.44‰ to25.11‰(CDT),and those in the wall rock from 11.60‰ to 19.06‰(CDT).We propose that the SO_4~(2-)generally experienced bacterial sulfate reduction in seawater before mineralization,and some SO_4~(2-)also experienced thermochemical sulfate reduction in hydrothermal system during mineralization.The δ~(13)C values of witherite range from-27.30‰ to-11.80‰(PDB),suggesting that carbon was sourced from organic substances(like CH_4,C_2H_4,and C_2H_6).The formation of witherite was possibly associated with thermochemical sulfate reduction,which caused the consumption of the organic gases and SO_4~(2-) in the hydrothermal solutions,consequently inhibiting barite formation.The important conditions for forming witherite include high fluid temperatures,high Ba~(2+) concentrations,CO_2 in the fluids,low HS~- concentrations,and the subsequent rapid diffusion of H_2S during thermochemical sulfate reduction of the fluids. 相似文献
6.
《Applied Geochemistry》2001,16(4):419-436
The chemical and isotopic compositions of gases from hydrocarbon systems of the Taranaki Basin of New Zealand (both offshore and onshore) show wide variation. The most striking difference between the western and south-eastern groups of gases is the helium content and its isotopic ratio. In the west, the Maui gas is over an order of magnitude higher in helium concentration (up to 190 μmol mol−1) and its 3He/4He ratio of 3.8 RA (where RA=the air 3He/4He ratio of 1.4×10−6) is approximately half that of upper mantle helium issuing from volcanic vents of the Taupo Volcanic Zone. In the SE, the Kupe South and most Kapuni natural gases have only a minor mantle helium input of 0.03–0.32 RA and low total helium concentrations of 10–19 μmol mol−1. The 3He/C ratio (where C represents the total carbon in the gas phase) of the samples measured including those from a recent study of on-shore Taranaki natural gases are generally high at locations where the surface heat flow is high. The 3He/CO2 ratio of the Maui gases of 5 to 18×10−9 is higher than the MORB value of 0.2 to 0.5×10−9, a feature found in other continental basins such as the Pannonian and Vienna basins and in many high helium wells in the USA. Extrapolation to zero CO2/3He and CO2/C indicates δ13C(CO2) values between −7 and −5‰ close to that of MORB CO2. The remaining CO2 would appear to be mostly organically-influenced with δ13C(CO2) c.−15‰. There is some evidence of marine carbonate CO2 in the gases from the New Plymouth field. The radiogenic 4He content (Herad) varies across the Taranaki Basin with the highest Herad/C ratios occurring in the Maui field. δ13C(CH4) becomes more enriched in 13C with increasing Herad and hydrocarbon maturity. Because 3He/4He is related to the ratio of mantle to radiogenic crustal helium and 3He/C is virtually constant in the Maui field, there is a correlation between RC/RA (where RC=air-corrected 3He/4He) and δ13C(CH4) in the Maui and New Plymouth fields, with the more negative δ13C(CH4) values corresponding to high 3He/4He ratios. A correlation between 3He/4He and δ13C(CO2) was also observed in the Maui field. In the fields adjacent to Mt Taranaki (2518 m andesitic volcano), correlations of some parameters, particularly CO2/CH4, C2H6/CH4 and δ13C(CH4), are present with increasing depth of the gas reservoir and with distance from the volcanic cone. 相似文献
7.
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
8.
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
9.
《Applied Geochemistry》1993,8(1):1-8
Six gas samples were collected from five thermal springs in the Semail Nappe ophiolite and the calcareous (calcite and dolomite) Hajar Formation, northern Oman. The3He/4He,4He/20Ne,40Ar/36Ar and38Ar/36Ar ratios, chemical compositions (H2, N2, CO2, CH4, O2, Ar and He), and stable isotope compositions (δDH2, δDH2O, δ13CCO2, δ13CCH4, and δ15NN2) are reported. Samples from the ophiolite region are significantly anoxic with major constituents of H2, CH4 and N2, while those from calcite and dolomite regions are ordinary gas seeps, consisting of N2, CO2 and/or O2. The former H2-rich gas is characterized by relatively high3He/4He ratio (0.4–0.8 Ratm) with low He content (<5 ppm), atmospheric40Ar/36Ar ratio, low N2/Ar ratio (<55) and high δ15NN2 value (∼1 ‰). On the other hand, the latter N2-rich gas shows relatively low3He/4He ratio (0.1–0.4 Ratm) with high He concentration (>300 ppm), slight radiogenic40Ar/36Ar ratio, high N2/Ar ratio (77–97) and low δ15NN2 value (<0‰). Observed δDH2 value of −536‰ in H2-rich gas is distinguished from the literature value of −699‰ in the ophiolite region, giving discrepant isotope formation temperatures. 相似文献
10.
O. E. Kikvadze V. Yu. Lavrushin B. G. Pokrovskii B. G. Polyak 《Lithology and Mineral Resources》2014,49(6):491-504
Variations in the carbon isotope composition in gases and waters of mud volcanoes in the Taman Peninsula are studied. The δ13C values in CH4 and CO2 vary from ?59.5 to ?44.0‰ (δ13Cav = ?52.4 ± 5.4‰) and from ?17.8 to +22.8‰ (δ13Cav = +6.9 ± 9.3‰), respectively. In waters from most mud volcanoes of the peninsula, this parameter ranges from +3.3 to +33.1‰, although locally lower values are also recorded (up to ?12‰. Fractionation of carbon isotopes in the CO2-HCO3 system corresponds to the isotope equilibrium under Earth’s surface temperatures. The growth of carbon dioxide concentration in the gaseous phase and increase in the HCO3 ion concentration in their water phase is accompanied by the enrichment of the latter with the heavy 13C isotope. The δ13CTDIC value in the water-soluble carbon depends on the occurrence time of water on the Earth’s surface (exchange with atmospheric CO2, methane oxidation, precipitation of carbonates, and other processes), in addition to its primary composition. In this connection, fluctuations in δ13CTDIC values in mud volcanoes with stagnant waters may amount to 10–20‰. In the clayey pulp, concentrations of carbonate matter recalculated to CaCO3 varies from 1–4 to 36–50 wt %. The δ13C value in the latter ranges from ?3.6 to +8.4‰. Carbonate matter of the clayey pulp represents a mixture of sedimentogenic and authigenic carbonates. Therefore, it is usually unbalanced in terms of the carbon isotope composition with the water-soluble CO2 forms. 相似文献
11.
《Applied Geochemistry》2001,16(3):323-338
Chemical and isotopic compositions are reported for water, and CO2 and noble gases in groundwater and soda springs from Bioko, Principé, São Tomé and Annobon, all islands located in the off-shore part of the Cameroon Volcanic Line in West Africa. The soda spring waters are of Ca–Mg–HCO3 type, with δD and δ18O values that range from −20 to −8‰ and −5.4 to −2.7‰ respectively, indicative of a meteoric origin. CO2 is the main gas species in the springs. δ13C–CO2 values vary from −2.8 to −5.0‰, overlapping the observed mantle C range (−3 to −8‰). CO2/3He ratios (3–9×109) suggest that most C (∼90%) in the samples is derived from the mantle. Neon has atmospheric isotopic compositions, while Ar is slightly enriched in radiogenic 40Ar. 3He/4He ratios (3.0 to 10.1×10−6 or 2.1 to 7.2Ra, where Ra is the atmospheric ratio of 1.4×10−6) are much higher than those for typical crustal fluids (∼10−8) but lower than those expected for fluids derived from ‘high-3He/4He’ hotspots like Loihi and Iceland. This precludes significant contributions of such fluids in the source regions of the gases, and by inference, in the magmatism of these oceanic islands. Alternatively, approximately 90% of the He in São Tomé gases is inferred to be derived from a source similar to the MORB source. The 3He/4He ratio for the Bioko gas (6.6×10−6) may be derived from a source with a higher time integrated (U+Th)/3He ratio than the MORB source. 相似文献
12.
A suite of natural gases from the northern Songliao Basin in NE China were characterized for their molecular and carbon isotopic composition. Gases from shallow reservoirs display clear geochemical evidence of alteration by biodegradation, with very high dryness (C1/C2+ > 100), high C2/C3 and i-C4/n-C4 ratios, high nitrogen content and variable carbon dioxide content. Isotopic values show wide range variations (δ13CCH4 from −79.5‰ to −45.0‰, δ13CC2H6 from −53.7‰ to −32.2‰, δ13CC3H8 from −36.5‰ to −20.1‰, δ13CnC4H10 from −32.7‰ to −24.5‰, and δ13CCO2 from −21.6‰ to +10.5‰). A variety of genetic types can be recognized on the basis of chemical and isotopic composition together with their geological occurrence. Secondary microbial gas generation was masked by primary microbial gas and the mixing of newly generated methane with thermogenic methane already in place in the reservoir can cause very complicated isotopic signatures. System openness also was considered for shallow biodegraded gas accumulations. Gases from the Daqing Anticline are relatively wet with 13C enriched methane and 13C depleted CO2, representing typically thermogenic origin. Gases within the Longhupao-Da’an Terrace have variable dryness, 13C enriched methane and variable δ13C of CO2, suggesting dominant thermogenic origin and minor secondary microbial methane augment. The Puqian-Ao’nan Uplift contains relatively dry gas with 13C depleted methane and 13C enriched CO2, typical for secondary microbial gas with a minor part of thermogenic methane. Gas accumulations in the Western Slope are very dry with low carbon dioxide concentrations. Some gases contain 13C depleted methane, ethane and propane, indicating low maturity/primary microbial origin. Recognition of varying genetic gas types in the Songliao Basin helps explain the observed dominance of gas in the shallow reservoir and could serve as an analogue for other similar shallow gas systems. 相似文献
13.
《Applied Geochemistry》1999,14(5):607-620
Molecular and isotopic analyses of core gas samples from 3 permafrost research core holes (92GSCTAGLU, 92GSCKUMAK, 92GSCUNIPKAT; sample core depths ranging from 0.36 to 413.82 m) in the Mackenzie Delta of the Northwest Territories of Canada reveal the presence of hydrocarbon gases from both microbial and thermogenic sources. Analyses of most headspace and blended gas samples from the ice-bonded permafrost portion of the core holes yielded C1/(C2+C3) hydrocarbon gas ratios and CH4–C isotopic compositions (δ13C CH4) indicative of microbially sourced CH4 gas. However, near the base of ice-bonded permafrost and into the underlying non-frozen stratigraphic section, an increase in ethane (C2) concentrations, decreases in C1/(C2+C3) hydrocarbon gas ratios, and CH4–C isotopic (δ13C CH4) data indicate the presence of hydrocarbon gases derived from a thermogenic source. The thermogenic gas below permafrost in the Mackenzie Delta likely migrated from deeper hydrocarbon accumulations and/or directly from thermally mature hydrocarbon source rocks. 相似文献
14.
LIU Quanyou ZHANG Tongwei JIN Zhijun QIN Shengfei TANG Yongchun LIU Wenhui 《《地质学报》英文版》2011,85(4):911-922
Based on the pyrolysis products for the Jurassic low-mature coal under programmed temperature,and chemical and carbon isotopic compositions of natural gas from the Kuqa Depression, the genetic origin of natural gas was determined,and then a gas filling model was established,in combination with the geological background of the Kuqa Depression.The active energy of CH_4,C_2H_6 and C_3H_8 was gotten after the data of pyrolysis gas products under different heating rates(2℃/h and 20℃/h)were fitted by the Gas O... 相似文献
15.
Purification protocols to extract pollen from lake sediments contain chemicals that alter the carbon and oxygen pollen-isotope values according to pollen characteristics and family affiliation. Modern (raw) pollen of broad-leaved (Alnus glutinosa, Betula pendula, Carpinus betulus, Corylus avellana, Fagus sylvatica and Quercus robur) and coniferous tree species (Picea abies and Pinus sylvestris) were treated with potassium hydroxide (KOH), hydrofluoric acid (HF), sodium hypochlorite (NaClO) and sulphuric acid (H2SO4) to test the impact on δ13Cpollen and δ18Opollen and assess the applicability in purification protocols. Pollen of broad-leaved and coniferous trees reacted differently to chemical exposure, but response patterns are generally alike. Alterations of δ13Cpollen values vary between + 1.0‰ (B. pendula, NaClO-treatment) and −5.0‰ (P. sylvestris, H2SO4-treatment). The δ13Cpollen values of raw and chemically treated samples seem to be related after treatments with KOH, NaClO and HF, whereas the application of H2SO4 led to inconsistent changes among species. The impact of chemicals on δ18Opollen are more diverse and offsets range between +1.1‰ (C. avellana, NaClO-treatment) and −17.9‰ (P. sylvestris, H2SO4-treatment). In general, the use of isotope-altering chemicals in purification protocols should be brought to a minimum, but the application of KOH and NaClO seems mostly unproblematic before δ13Cpollen and δ18Opollen analysis. 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.
Kinga M. Rvsz Kevin J. Breen Alfred J. Baldassare Robert C. Burruss 《Applied Geochemistry》2010,25(12):1845-1859
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
18.
The petroliferous central Junggar Basin in northwest China is predominantly an oil exploration region. However, its gas exploration also might have good prospects. Thus to assist in gas exploration, the geochemistry and origins of gases are discussed in this paper based on relatively comprehensive analyses of compositions, carbon isotopes and light hydrocarbons of gases. Based on the results, the gas genetic types are grouped into families and combined with the geological setting (e.g., biomarkers of retrograde condensates and source rock characteristics). We show that there are four representative genetic types of gases. The first consists of gases derived from Permian lacustrine mudstones with type I–II kerogen and type III kerogen sources in the Penyijingxi sag. Their representative geochemical feature is δ13C2 ranging from −31.4‰ to −24.7‰. The second is gas sourced from Carboniferous tufaceous mudstones of type III kerogen in the Dishuiquan sag, whose representative geochemical feature is the heaviest values of δ13C1 in the studied samples, ranging from −32.0‰ to −30.4‰. The third consists of gases sourced from Jurassic coals and mudstones in the Shawan–Fukang sag. The light hydrocarbon fingerprints of these gases are similar to those of gases and oils typically derived from Jurassic source rocks in the southern Junggar Basin. The fourth is gas most likely generated from the degradation of crude oil. It is mainly found in the Luliang area and has dryness values as much as 0.999 and δ13C1 ranging from −54.8‰ to −43.2‰. Among these four types of gases, the first (mainly sourced from the Permian lacustrine mudstones in the Penyijingxi sag) is the predominant type. 相似文献
19.
《Resource Geology》2018,68(1):37-50
The large, newly discovered Lijiagou pegmatite spodumene deposit, is located southeast of the Ke'eryin pegmatite ore field, in the central Songpan–Garze Fold Belt (SGFB), Eastern Tibet. The Lijiagou albite spodumene pegmatites are unzoned, granite‐pegmatites of the subtype LCT (Lithium, Cesium, and Tantalum) and consist of medium‐ to coarse‐grained spodumene, lepidolite, microcline, albite, quartz, muscovite, and accessory amounts of beryl, cassiterite, columbite–tantalite and zircon. Secondary fluid inclusions in quartz and spodumene include two‐phase aqueous inclusions (V + L), mono‐phase vapor inclusions (V); three‐phase CO2‐rich CO2–H2O inclusions (CO2 + V + L) and less abundant liquid inclusions (L). The homogenization temperature of the fluid inclusions are low (257.3 to 204.3°C in early stage, 250.3 to 199.6°C in middle stage, 218.7 to 200.6°C in late stage). Fluid inclusions were formed during the long cooling period from the temperature of the pegmatite emplacement. Liquid–vapor–gas boiling was extensive during the middle and late stages. The salinity of the corresponding stages are 15.4 to 13.0 wt.% NaCl equiv., 12.5 to 9.1 wt.% NaCl equiv. and 9.8 to 7.8 wt.% NaCl equiv., respectively. δ18O values of fluid are 7.2 to 5.2‰, 5.6 to 3.9‰ and 2.7 to −0.2‰ from early to late stages; and δD range from −75.1 to −76.8‰, −59.0 to −73.5‰ and −61.6 to −85.5‰ respectively. The δ13C of CO2 values are −5.6 to −6.6‰, −8.5 to −19.9‰, −11.8 to −18.7‰ from early to late stages, suggesting that CO2 in the fluids were probably sourced from a magmatic system, possibly with some mixing of CO2 dissolved in groundwater. δD and δ18O values of fluid indicate that the fluids were originally magmatic water and mixed with some meteoric water in late stage. The magma evolution sequence in the Ke'eryin orefield, from the central two‐mica granite through the Lijiagou deposit out to the distal pegmatites, with the ages gradually decreasing, indicates that the Ke'eryin complex rocks are the product of multistage magmatic activity. The large Lijiagou spodumene deposit is a typical magmatic, fractional crystallization related pegmatite deposit. 相似文献
20.
The Huijiabao gold district is one of the major producers for Carlin-type gold deposits in southwestern Guizhou Province, China, including Taipingdong, Zimudang, Shuiyindong, Bojitian and other gold deposits/occurrences. Petrographic observation, microthermometric study and Laser Raman spectroscopy were carried out on the fluid inclusions within representative minerals in various mineralization stages from these four gold deposits. Five types of fluid inclusions have been recognized in hydrothermal minerals of different ore-forming stages: aqueous inclusions, CO2 inclusions, CO2–H2O inclusions, hydrocarbon inclusions, and hydrocarbon–H2O inclusions. The ore-forming fluids are characterized by a H2O + CO2 + CH4 ± N2 system with medium to low temperature and low salinity. From early mineralization stage to later ones, the compositions of the ore-forming fluids experienced an evolution of H2O + NaCl → H2O + NaCl + CO2 + CH4 ± N2 → H2O + NaCl ± CH4 ± CO2 with a slight decrease in homogenization temperature and salinity. The δ18O values of the main-stage quartz vary from 15.2‰ to 24.1‰, while the δDH2O and calculated δ18OH2O values of the ore-forming fluids range from −56.9 to −116.3‰ and from 2.12‰ to 12.7‰, respectively. The δ13CPDB and δ18OSMOW values of hydrothermal calcite change in the range of −9.1‰ to −0.5‰ and 11.1–23.2‰, respectively. Stable isotopic characteristics indicate that the ore-forming fluid was mainly composed of ore- and hydrocarbon-bearing basinal fluid. The dynamic fractionation of the sulfur in the diagenetic pyrite is controlled by bacterial reduction of marine sulfates. The hydrothermal sulfides and the diagenetic pyrite from the host rocks are very similar in their sulfur isotopic composition, suggesting that the sulfur in the ore-forming fluids was mainly derived from dissolution of diagenetic pyrite. The study of fluid inclusions indicates that immiscibility of H2O–NaCl–CO2 fluids took place during the main mineralization stage and caused the precipitation and enrichment of gold. 相似文献