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1.
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
2.
《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
3.
The stable carbon isotopic compositions of light hydrocarbon gases adsorbed in near-surface soil and sediments from the Saurashtra basin were characterized for their origin and maturity. Saurashtra is considered geologically prospective for oil and gas reserves; however, a major part of the basin is covered by the Deccan Traps, hindering the exploration of Mesozoic hydrocarbon targets. Surface geochemical prospecting, based on micro-seepage of hydrocarbons from subsurface accumulations, could be advantageous in such areas. In light of this, 150 soil samples were collected from the northwestern part of Saurashtra, around the Jamnagar area, where a thick sedimentary sequence of about 2–3 km exists under 1–1.5 km of Deccan basalt. The concentration of acid desorbed alkane gases from soil samples was found to vary (in ppb) as: methane (C1) = 3–518; ethane (C2) = 0–430; propane (C3) = 0–331; i-butane (iC4) = 0–297; n-butane (nC4) = 2–116; i-pentane (iC5) = 0–31 and n-pentane (nC5) = 0–23, respectively.Fifteen samples with high concentrations of alkane gases were measured for their δ13C1; δ13C2 and δ13C3 compositions using gas chromatography–combustion-isotope ratio mass spectrometry (GC–C-IRMS). The values for methane varied from ? 27 to ? 45.4‰, ethane from ? 20.9 to ? 27.6‰, and propane from ? 20.4 to ? 29.1‰ versus the Vienna PeeDee Belemnite (VPDB). The carbon isotope ratio distribution pattern represents isotopic characteristics pertaining to hydrocarbon gases derived from thermogenic sources. Comparisons of carbon isotopic signatures and compositional variations with the standard carbon isotopic models suggest that hydrocarbon gases found in the shallow depths of the study area are not of bacterial origin but are formed thermally from deeply buried organic matter, likely to be mainly a terrestrial source rock with a partial contribution from a marine source. These gases may have migrated to the near-surface environment, where they represent an admixture of thermally generated hydrocarbon gases from mixed sources and maturity. The maturity scale (δ13C versus Log Ro %) applied to the surface sediment samples of the Jamnagar area indicated the source material to be capable of generating oil and gas. The detection of thermogenic alkane gases in near-surface sediments offers the possibility of hydrocarbons at depth in Saurashtra. 相似文献
4.
The Mundaú–Manguaba estuarine–lagoon system (MMELS) constitutes one of the most representative ecosystems in the state of Alagoas, NE Brazil. Approximately 30% or 60,000 ha of the lower surrounding drainage basin of the MMELS are covered by sugar cane and a total of 250,000 inhabitants contribute untreated effluent to the system. Short sediment cores from MMELS were collected in 2007 at three sites: Manguaba Lagoon (C03), Mundaú Lagoon (C07) and Mundaú River (C08) in order to characterize the delivery and deposition of n-alkanes over the past 40 yr. The n-alkanes ranged from C15 to C35, with total aliphatic hydrocarbon (TAH) concentration in the range 27.8–139.5 μg g−1. An unresolved complex mixture (UCM) was observed in all sediments. The terrigenous/aquatic ratio (TAR), carbon preference index (CPI) and average chain length (ACL) showed that the terrigenous input dominated. The (δ13C) values of individual n-alkanes (C16–C33) varied between −22.6‰ and −34.2‰, suggesting a dominance of 12C-enriched n-alkanes that originated from C3 plants and lacustrine algae. The data reflect how anthropogenic input (via sewage, industrial pollution and agriculture) has influenced the organic content of the system through time. 相似文献
5.
Although oil cracking has been documented as one of the important sources of gas in many overmature marine sedimentary basins, the chemical and carbon isotopic signatures of gases of this origin are still open to question. In this study a Cambrian crude oil from the central Tarim basin, along with its main separated fractions (saturates, aromatics and asphaltenes), were pyrolyzed in sealed gold tubes to investigate how generated gases vary in chemical and carbon isotopic composition and how this variation would influence the genetic interpretation of oil cracking gas. The results indicate that the gases from cracking of aromatics and asphaltenes are much drier and more enriched in 13C than the gases from the cracking of saturates and crude oil at the same level of thermal maturity. In the experimental run of 20 °C/h, the dryness index of the gases (defined as the volume percentage of C1 in C1–5) from the cracking of saturates ranges from 26.2–90.6% with the methane carbon isotope change ranging from −54.8‰ to −35.5‰, whereas the dryness index is never lower than 60.6% for the gases from the cracking of aromatics with methane carbon isotope ranging from −39.9‰ to −32.2‰. Correspondingly, experimental data for the four samples plot in different areas in diagrams designed to distinguish oil cracking gas from kerogen cracking gas, such as ln(C2/C3) vs. δ13C2–δ13C3 and δ13C1 vs. δ13C2–δ13C3, indicating compositional variability of crude oil could assert an important influence in these diagrams. Therefore it is prudent to bring other geological constraints into consideration to avoid misinterpretation.The kinetic parameters for the bulk generation of C1–5 gas and the methane carbon isotope fractionation extrapolated to geological conditions of 2 °C/Ma and an initial temperature of 50 °C show that the temperatures of C1–5 gas generation from the aromatics and asphaltenes are lower than those from the saturates and crude oil due to their lower activation energies and frequency factors. Generation of C1–5 gases from the aromatics is modeled to be initiated about 122 °C whereas the initiation temperature for the saturates sample is 176 °C. Below 189 °C (EasyRo = 1.8%), the yields of C1–5 gases follow the order: aromatics > asphaltenes > crude oil > saturates. At similar thermal maturity levels, the methane carbon isotopic compositions are significantly different for the four samples, with an order of 13C enrichment: aromatics > asphaltenes > crude oil > saturates, however the difference in methane carbon isotopes becomes smaller with increasing temperature. This indicates that methane carbon isotopic values can be significantly different for gases cracked from oils that are compositionally diverse, especially in the early stage of methane generation. 相似文献
6.
The Qianfanling Mo deposit, located in Songxian County, western Henan province, China, is one of the newly discovered quartz-vein type Mo deposits in the East Qinling–Dabie orogenic belt. The deposit consists of molybdenite in quartz veins and disseminated molybdenite in the wall rocks. The alteration types of the wall rocks include silicification, K-feldspar alteration, pyritization, carbonatization, sericitization, epidotization and chloritization. On the basis of field evidence and petrographic analysis, three stages of hydrothermal mineralization could be distinguished: (1) pyrite–barite–quartz stage; (2) molybdenite–quartz stage; (3) quartz–calcite stage.Two types of fluid inclusions, including CO2-bearing fluid inclusions and water-rich fluid inclusions, have been recognized in quartz. Homogenization temperatures of fluid inclusions vary from 133 °C to 397 °C. Salinity ranges from 1.57 to 31.61 wt.% NaCl eq. There are a large number of daughter mineral-CO2-bearing inclusions, which is the result of fluid immiscibility. The ore-forming fluids are medium–high temperature, low to moderate salinity H2O–NaCl–CO2 system. The δ34S values of pyrite, molybdenite, and barite range from − 9.3‰ to − 7.3‰, − 9.7‰ to − 7.3‰ and 5.9‰ to 6.8‰, respectively. The δ18O values of quartz range from 9.8‰ to 11.1‰, with corresponding δ18Ofluid values of 1.3‰ to 4.3‰, and δ18D values of fluid inclusions of between − 81‰ and − 64‰. The δ13CV-PDB values of fluid inclusions in quartz and calcite have ranges of − 6.7‰ to − 2.9‰ and − 5.7‰ to − 1.8‰, respectively. Sulfur, hydrogen, oxygen and carbon isotope compositions show that the sulfur and ore-forming fluids derived from a deep-seated igneous source. During the peak collisional period between the North China Craton and the Yangtze Craton, the ore-forming fluids that derived from a deep igneous source extracted base and precious metals and flowed upwards through the channels that formed during tectonism. Fluid immiscibility and volatile exsolution led to the crystallization of molybdenite and other minerals, and the formation of economic orebodies in the Qianfanling Mo deposit. 相似文献
7.
This study examined the distributions and stable carbon isotopic compositions of saturated fatty acids (SaFAs) in one 300 cm long sedimentary profile, which was named as Site4B in Shenhu, northern South China Sea. The concentrations of total SaFAs in sediments ranged from 1.80 to 10.16 μg/g (μg FA/g dry sediment) and showed an even-over-odd predominance in the carbon chain of C12 to C32, mostly with n-C16 and n-C18 being the two major components. The short-chain fatty acids (ScFAs; n-C12 to n-C18) mainly from marine microorganisms had average δ13C values of −26.7‰ to −28.2‰, whereas some terrigenous-sourced long-chain fatty acids (LcFAs; n-C21 to n-C32) had average δ13C values of −29.6‰ to −34.1‰. The other LcFAs (n-C24 & n-C26 ∼ n-C28; average δ13C values are −26.1‰ to −28.0‰) as well as n-C19 and n-C20 SaFAs (average δ13C values are −29.1‰ and −29.3‰, respectively) showed a mixed signal of carbon isotope compositions.The relative bioproductivity calculation (marine vs. terrigenous) demonstrated that most of organic carbon accumulation throughout the sedimentary profile was contributed by marine organism. The high marine productivity in Shenhu, South China Sea may be related to the hydrocarbon seepage which evidenced by diapiric structures. Interestingly, there is a sever fluctuation of terrigenous inputs around the depth of 97 cm below the seafloor (bsf), probably resulting from the influence of the Dansgaard–Oeschger events and the Younger Dryas event as revealed by 14C age measurements. 相似文献
8.
The Xiaguan Ag–Pb–Zn orefield (Neixiang County, Henan Province), hosting the Yindonggou, Zhouzhuang, Yinhulugou and Laozhuang fault-controlled lode deposits, is situated in the Erlangping Terrane, eastern Qinling Orogen. The quartz-sulfide vein mineralization is dominated by main alteration styles of silicic-, sericite-, carbonate-, chlorite- and sulfide alteration. Major Ag-bearing minerals are freibergite, argentite and native Ag. The deposits were formed by a CO2-rich, mesothermal (ca. 250–320 °C), low-density and low salinity (< 11 wt.% NaCl equiv.), Na+–Cl−-type fluid system. Trapping pressures of the carbonic-type fluid inclusions (FIs) decreased from ca. 280–320 MPa in the early mineralization stage to ca. 90–92 MPa in the late mineralization stage, indicating that the ore-forming depths had become progressively shallower. This further suggests that the metallogenesis may have occurred in a tectonic transition from compression to extension. Geological- and ore fluid characteristics suggest that the Xiaguan Ag–Pb–Zn orefield belongs to orogenic-type systems.The δ18OH2O values change from the Early (E)-stage (7.8–10.8 ‰), through Middle (M)-stage (6.0–9.4 ‰) to Late (L)-stage (− 1.5–3.3 ‰), with δD values changing from E-stage − 95 to − 46 ‰, through M-stage − 82 to − 70 ‰ to L-stage − 95 to − 82 ‰. δ13CCO2 values of the ore fluids in the E- and M-stage quartz vary between 0.1 ‰ and 0.9 ‰ (average: 0.3 ‰); δ13CCO2 values of L-stage FIs are − 0.2–0.1 ‰ in quartz and − 6.8 ‰ to − 3.5 ‰ in calcite. The H–O–C isotopic data indicate that the initial ore fluids were sourced from the underthrusted Qinling Group marine carbonates, and were then interacted with the ore-hosting Erlangping Group metasedimentary rocks. Inflow of circulated meteoric water may have dominated the L-stage fluid evolution.Sulfur (δ34S = 1.9–8.1 ‰) and lead isotopic compositions (206Pb/204Pb = 18.202–18.446, 207Pb/204Pb = 15.567–15.773 and 208Pb/204Pb = 38.491–39.089) of sulfides suggest that the ore-forming materials were mainly sourced from the ore-hosting metasedimentary strata. The stepped heating sericite 40Ar/39Ar detection suggests that the mineralization occurred in the Middle Jurassic to Early Cretaceous (ca. 187 − 124 Ma). Considering the regional tectonic evolution of the Erlangping Terrane, we propose that the Xiaguan Ag–Pb–Zn orefield was formed in a continent–continent collisional tectonic regime, in accordance with the tectonic model for continental collision, metallogeny and fluid flow (CMF). 相似文献
9.
《Applied Geochemistry》2005,20(10):1875-1889
Based on the systematic analyses of light hydrocarbon, saturate, aromatic fractions and C isotopes of over 40 oil samples along with related Tertiary source rocks collected from the western Qaidam basin, the geochemical characteristics of the Tertiary saline lacustrine oils in this region was investigated. The oils are characterized by bimodal n-alkane distributions with odd-to-even (C11–C17) and even-to-odd (C18–C28) predominance, low Pr/Ph (mostly lower than 0.6), high concentration of gammacerane, C35 hopane and methylated MTTCs, reflecting the high salinity and anoxic setting typical of a saline lacustrine depositional environment. Mango’s K1 values in the saline oils are highly variable (0.99–1.63), and could be associated with the facies-dependent parameters such as Pr/Ph and gammacerane indexes. Compared with other Tertiary oils, the studied Tertiary saline oils are marked by enhanced C28 sterane abundance (30% or more of C27–C29 homologues), possibly derived from halophilic algae. It is noted that the geochemical parameters of the oils in various oilfields exhibit regular spatial changes, which are consistent with the depositional phase variations of the source rocks. The oils have uncommon heavy C isotopic ratios (−24‰ to −26‰) and a flat shape of the individual n-alkane isotope profile, and show isotopic characteristics similar to marine organic matter. The appearance of oleanane and high 24/(24 + 27)-norcholestane ratios (0.57–0.87) in the saline oils and source rocks confirm a Tertiary organic source. 相似文献
10.
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
11.
《Chemie der Erde / Geochemistry》2015,75(1):65-72
This study was conducted on recent desert samples—including (1) soils, (2) plants, (3) the shell, and (4) organic matter from modern specimens of the land snail Eremina desertorum—which were collected at several altitudes (316–360 m above sea level) from a site in the New Cairo Petrified Forest. The soils and shellE. desertorum were analyzed for carbonate composition and isotopic composition (δ18O, δ13C). The plants and organic matterE. desertorum were analyzed for organic carbon content and δ13C. The soil carbonate, consisting of calcite plus minor dolomite, has δ18O values from −3.19 to −1.78‰ and δ13C values −1.79 to −0.27‰; covariance between the two values accords with arid climatic conditions. The local plants include C3 and C4 types, with the latter being dominant. Each type has distinctive bulk organic carbon δ13C values: −26.51 to −25.36‰ for C3-type, and −13.74 to −12.43‰ for C4-type plants.The carbonate of the shellE. desertorum is composed of aragonite plus minor calcite, with relatively homogenous isotopic compositions (δ18Omean = −0.28 ± 0.22‰; δ13Cmean = −4.46 ± 0.58‰). Most of the δ18O values (based on a model for oxygen isotope fractionation in an aragonite-water system) are consistent with evaporated water signatures. The organic matterE. desertorum varies only slightly in bulk organic carbon δ13C values (−21.78 ± 1.20‰) and these values suggest that the snail consumed more of C3-type than C4-type plants. The overall offset in δ13C values (−17.32‰) observed between shellE. desertorum carbonate and organic matterE. desertorum exceeds the value expected for vegetation input, and implies that 30% of carbon in the shellE. desertorum carbonate comes from the consumption of limestone material. 相似文献
12.
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
13.
We investigated the distribution of lipids in Lower Triassic sedimentary rocks (252–247 myr) from South China, including a shallow water microbialite in the uppermost section of the outcrop. Archaeal derived hydrocarbons were the major constituents of the microbialite from the latest Early Triassic. Among these, we detected (i) abundant C40 acyclic and monocyclic biphytanes (possibly derived from glycerol dialkyl glycerol tetraether lipids) and their degradation products, C30–39 pseudohomologues and (ii) a C25 head-to-tail linked (regular) isoprenoid hydrocarbon [possibly derived from dialkyl glycerol diether lipids (DGDs)] and its degradation products, C21–24 pseudohomologues and abundant pristane and phytane. Through combination of compound-specific stable carbon isotope analysis of isoprenoid hydrocarbons, which had average δ13C values of −35‰ to −30‰, and their molecular distribution, it was not possible to unambiguously define the archaeal source for the biphytanes in the microbialite. The δ13C values for pristane and phytane were similar to those for head-to-tail linked C21–25 isoprenoids; potential source organisms for these compounds were halophilic archaea. Except for methane seep microbialites, no other ancient or recent phototrophic microbialites have been reported to contain predominantly archaeal isoprenoid hydrocarbons. Our findings suggest the presence of a new type of microbialite. 相似文献
14.
Thomas Pape André Bahr Janet Rethemeyer John D. Kessler Heiko Sahling Kai-Uwe Hinrichs Stephan A. Klapp William S. Reeburgh Gerhard Bohrmann 《Chemical Geology》2010,269(3-4):350-363
Detailed knowledge of the extent of post-genetic modifications affecting shallow submarine hydrocarbons fueled from the deep subsurface is fundamental for evaluating source and reservoir properties. We investigated gases from a submarine high-flux seepage site in the anoxic Eastern Black Sea in order to elucidate molecular and isotopic alterations of low-molecular-weight hydrocarbons (LMWHC) associated with upward migration through the sediment and precipitation of shallow gas hydrates. For this, near-surface sediment pressure cores and free gas venting from the seafloor were collected using autoclave technology at the Batumi seep area at 845 m water depth within the gas hydrate stability zone.Vent gas, gas from pressure core degassing, and from hydrate dissociation were strongly dominated by methane (> 99.85 mol.% of ∑[C1–C4, CO2]). Molecular ratios of LMWHC (C1/[C2 + C3] > 1000) and stable isotopic compositions of methane (δ13C = ? 53.5‰ V-PDB; D/H around ? 175‰ SMOW) indicated predominant microbial methane formation. C1/C2+ ratios and stable isotopic compositions of LMWHC distinguished three gas types prevailing in the seepage area. Vent gas discharged into bottom waters was depleted in methane by > 0.03 mol.% (∑[C1–C4, CO2]) relative to the other gas types and the virtual lack of 14C–CH4 indicated a negligible input of methane from degradation of fresh organic matter. Of all gas types analyzed, vent gas was least affected by molecular fractionation, thus, its origin from the deep subsurface rather than from decomposing hydrates in near-surface sediments is likely.As a result of the anaerobic oxidation of methane, LMWHC in pressure cores in top sediments included smaller methane fractions [0.03 mol.% ∑(C1–C4, CO2)] than gas released from pressure cores of more deeply buried sediments, where the fraction of methane was maximal due to its preferential incorporation in hydrate lattices. No indications for stable carbon isotopic fractionations of methane during hydrate crystallization from vent gas were found. Enrichments of 14C–CH4 (1.4 pMC) in short cores relative to lower abundances (max. 0.6 pMC) in gas from long cores and gas hydrates substantiates recent methanogenesis utilizing modern organic matter deposited in top sediments of this high-flux hydrocarbon seep area. 相似文献
15.
A large number of Paleoproterozoic borate deposits are hosted by the lower units of a volcanic-sedimentary sequence in Liaoning Province, northeastern China, and are a major source of boron in China. The ore-bearing wall rocks in the deposits are serpentinized ultrabasic rocks and carbonates, with layered leptynites, leptites, amphibolites, and migmatites adjacent to the ore. Both the borate ores and country rocks contain tourmaline, although the country rocks have much lower abundances of the mineral. Based on in situ boron isotope measurements using laser ablation–multi-collector–inductively coupled plasma–mass spectrometry (LA–MC–ICP–MS), boron isotope data show that: (1) δ11B values of borate ores range from + 6.8‰ to + 13.9‰ (mean + 10.8‰); (2) tourmalines from the borate ores have δ11B values from + 9.5‰ to + 12.7‰; and (3) the wall rocks within the borate ores yield slightly lower δ11B values ranging from + 5.7‰ to + 7.6‰, and those outside the deposits from − 9.9‰ to − 5.9‰. Positive δ11B values in borates as well as in tourmalines inside the mining area indicate that boron in these Paleoproterozoic borate deposits was derived from marine evaporites. δ34SV-CDT (where V-CDT is Vienna Canyon Diablo Troilite) values of borate ores, serpentinized marbles, and anhydrites range from + 16.1‰ to + 24.7‰, whereas δ13CV-PDB (where V-PDB is Vienna Pee Dee Belemnite) values of marbles range from + 3.2‰ to + 5.9‰. These isotopic characteristics are interpreted to reflect formation in a marine evaporative environment. LA–MC–ICP–MS zircon weighted207Pb/206Pb ages of leptite and serpentinized olivine basalt from the hanging wall of the borate deposits are 2139 ± 13 Ma and 2130 ± 19 Ma, respectively. Therefore, the (~ 2.2 Ga) borate deposits may have originated from marine evaporative boron-bearing sediments, which were interbedded within bimodal volcanic rocks during the early stages of development of the Liaoji rift. 相似文献
16.
Hydrogen isotopic composition of n-alkanes was measured in sediments from an excavated profile of the Early Cretaceous Yixian Formation in Liaoning Province, NE China, aiming to assess the significance of the δD value of n-alkanes in ancient lacustrine sediments as the indicator for determining the source inputs of organic matters and paleoclimatic conditions. The δD values of n-alkanes are in the range of − 250‰ to − 85‰ and display an obvious three-stage variation pattern through the profile, which is consistent with the distribution of the dominated n-alkanes and the profile of their δ13C values. The δD and δ13C values of n-alkanes suggest that short-chain n-alkanes are primarily derived from photosynthetic bacteria and algae; n-C29 and n-C31 are mainly originated from terrestrial higher plants; n-C28 and n-C30 may be derived from the same precursor but via the different biological mechanism of hydrogen isotopic fractionation; while the source inputs of medium-chain n-alkanes are more complicated, with n-C23 being derived from some specific algae or biosynthesized by various aquatic organisms. The paleoclimatic conditions are reconstructed via two approaches. The reconstructed hydrogen isotopic values of lake water and meteoric water (expressed as δDLW and δDMW, respectively) were at the intervals of − 51.8‰ to 17.0‰ and − 118.1‰ to − 43.5‰, respectively, indicating a general climate transition from semi-arid to arid. The calculated ΔδDLW-MW values vary from 37.0‰ to 89.1‰ and display a similar but a significant large-scale variation trend with the ΔδDC23 ‐ long (− 28.8‰ to 85.0‰; long represents long-chain n-alkanes) and ΔδDmid-long (− 15.4‰ to 43.4‰; mid represents medium-chain n-alkanes) values. The discrepancy may be attributed to the source input overlap for n-alkanes and the uncertainties of εwater/lipid values. The coupling of ΔδDC23 ‐ long, ΔδDmid-long and ΔδDLW-MW values with the paleoclimatic evidence indicates that the δD values of n-alkanes could be more sensitive to the change of paleoclimatic conditions. 相似文献
17.
The large (>180 Kt WO3 and at least 10–15 t Au) Vostok-2 deposit is situated in a metallogenic belt of W, Sn-W, Au, and Au-W deposits formed in late to post-collisional tectonic environment after cessation of active subduction. The deposit is related to an ilmenite-series high-K calc-alkaline plutonic suite that, by its petrologic signatures, is transitional between those at W-dominant and Au-dominant reduced intrusion-related deposits. Consistently, besides large W-Cu skarns of the reduced type, the deposit incorporates quartz stockworks with significant Au-W-Bi mineralization also formed in a reduced environment. The hydrothermal stages include prograde and retrograde, essentially pyroxene skarns, hydrosilicate (amphibole, chlorite, quartz) alteration, and phyllic (quartz, sericite, albite, apatite, and carbonate) alteration assemblages. These assemblages contain abundant scheelite associated with pyrrhotite, chalcopyrite and, at the phyllic stage, also with Bi minerals, As-Bi-Sb-Te-Pb-Zn sulfides and sulfosalts, as well as Au mineralization. The fluid evolution included hot, high-pressure (420–460 °C, 1.1–1.2 kbar), low-salinity (5.4–6.0 wt% NaCl-equiv.) aqueous fluids at the retrograde skarn stage, followed by lower temperature cyclic releases of high-carbonic, low salinity to non-carbonic moderate-salinity aqueous fluids. At the hydrosilicate stage, a high-carbonic, CH4-dominated, hot (350–380 °C) low salinity fluid was followed by cooler (300–350 °C) non-carbonic moderate-salinity (5.7–14.9 wt% NaCl-equiv.) fluid. At the phyllic stage, a high-carbonic, CO2-dominated, moderately-hot (330–355 °C, 0.9 kbar) low salinity fluid was followed by cooler (230–265 °C) non-carbonic moderate-salinity (6.6–12.0 wt% NaCl-equiv.) fluid. A homogenized magmatic source of water (δ18OH2O = +8.3 to +8.7‰), and a sedimentary source of sulfur (δ34S = −6.9 to −6.2‰) and carbon (δ13Cfluid = −20.1 to −14.9‰) at the hydrosilicate stage are suggested. A magmatic source of water (δ18O = +8.6 to +9.2‰) and a sedimentary source of sulfur (δ34S = −9.3 to −4.1‰) but a magmatic (mantle- to crustal-derived) source of carbon (δ13Cfluid = −6.9 to −5.2‰) are envisaged for fluids that formed the early mineral assemblage of the phyllic stage. Then, the role of sedimentary carbon again increased toward the intermediate (δ13Cfluid = −16.4 to −14.5‰) and late (δ13Cfluid = −16.3 to −14.7‰) phyllic mineral assemblages. The magmatic differentiation was responsible for the fluid enrichment in W, whereas Au and Bi could also have been sourced from mafic magma. The decreasing temperatures, together with elevated Ca content in non-boiling fluids, promoted scheelite deposition at the early hydrothermal stages. The most intense scheelite deposition at the phyllic stage was caused by CO2 removal due to boiling of CO2-rich fluids; further cooling of non-boiling fluids favoured joint deposition of scheelite, Bi and Au. 相似文献
18.
The Anle Zn–Pb deposit, hosted by Upper Cambrian dolostone, is located in the southern Songpan–Ganzi Block in southwest China. In this deposit, ore bodies occur as stratiform lenses and consist of galena, sphalerite and pyrite as ore minerals, and quartz, dolomite and calcite as gangue minerals. The mineralization shows mainly vein, banded and brecciated structures. Four ore bodies have been found in the Anle deposit, with a combined 2.0 million tonnes (Mt) of sulfide ores at average grades of 1.64 wt.% Pb, 6.64 wt.% Zn and 45 g/t Ag. Brown, brownish-yellow and yellow sphalerite samples have δ66Zn values ranging from + 0.08 to + 0.10‰ (average + 0.09‰, n = 3), + 0.12 to + 0.38‰ (average + 0.24‰, n = 8) and + 0.40 to + 0.50‰ (average + 0.46‰, n = 3), respectively. We interpret the progressively heavier Zn isotopes from brown to yellow sphalerite as being led by kinetic Raleigh fractional crystallization. Calcite samples have δ13CPDB and δ18OSMOW values ranging from − 4.8 to − 0.2‰ (average − 1.7‰, n = 7) and + 17.9 to + 21.4‰ (average + 19.6‰, n = 7), respectively. Whole-rock δ13CPDB and δ18OSMOW values of the Cambrian ore-hosting dolostone range from + 0.1 to + 1.1‰ (average + 0.6‰, n = 3) and + 23.2 to + 24.1‰ (average + 23.6‰, n = 3), respectively. This suggests that carbon in the ore-forming fluids was provided by the host dolostone through carbonate dissolution. δ34SCDT values of sulfide samples range between − 1.3‰ and + 17.8‰ with an average value of + 6.3‰ (n = 25), lower than evaporites (such as barite + 19.8‰) in the overlaying Lower Ordovician sedimentary strata. The data suggest that sulfur in the hydrothermal fluids were derived from evaporites by thermo-chemical sulfate reduction (TSR). 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb ratios for sulfide minerals range from 17.63 to 17.86, 15.58 to 15.69 and 37.62 to 37.95, respectively. The data are similar to those of the age-corrected Cambrian ore-hosting dolostone (206Pb/204Pb = 17.70–17.98, 207Pb/204Pb = 15.58–15.65 and 208Pb/204Pb = 37.67–38.06), but lower than those of age-corrected Ordovician sandstone and slate (206Pb/204Pb = 18.54–19.58, 207Pb/204Pb = 15.73–15.81 and 208Pb/204Pb = 38.44–39.60). This indicates that ore Pb was most likely to be derived from the Cambrian ore-hosting dolostone. Therefore, our new geological and isotopic evidence suggests that the Anle Zn–Pb deposit is best classified to be an epigenetic carbonate-hosted Mississippi Valley-type (MVT) deposit. 相似文献
19.
《Organic Geochemistry》2012,42(12):1269-1276
This study sought to characterize hydrogen isotopic fractionation during biosynthesis of leaf wax n-alkanes in succulent plants capable of crassulacean acid metabolism (CAM). The metabolic and physiological features of CAM represent crucial strategies for survival in hot and dry climates and have been hypothesized to impact hydrogen isotope fractionation. We measured the stable carbon and hydrogen isotopic compositions (δ13C and δD, respectively) of individual n-alkanes in 20 species of succulent plants from a global collection of the Huntington Botanical Gardens, San Marino, California. Greenhouse conditions and irrigation with water of constant δD value enabled determination of interspecies differences in net D/H fractionation between source water and leaf wax products. Carbon isotope ratios provide constraints on the extent of CAM vs. C3 photosynthesis and indicate a wide range of CAM use, with δ13C values ranging from −33.01‰ to −18.54‰ (C27–C33 n-alkanes) and −26.66‰ to −17.64‰ (bulk tissue). Despite the controlled growth environment, we observed ca. 90‰ interspecies range in δD values from −193‰ to −107‰. A positive correlation between δ13Cbulk and δDC31 values with R2 = 0.60 (δ13CC31 and δDC31 values with R2 = 0.41) implicates a metabolic isotope effect as the dominant cause of interspecies variation in the hydrogen isotopic composition of leaf wax n-alkanes in CAM-intermediate plants. 相似文献
20.
The Tongjing Cu–Au deposit is a medium-sized deposit within the Ningwu volcanic basin, east China, and is hosted by Cretaceous volcanic rocks of the Dawangshan and Niangniangshan Formations. The veined and lenticular Cu–Au orebodies are spatially and temporally related to the volcanic and subvolcanic rocks of the Niangniangshan Formation in the ore district. The wall-rock alteration is dominated by silicification, siderite alteration, carbonation, sericitization, chloritization, and kaolinization. On the basis of field evidence and petrographic observations, two stages of mineralization are recognized: (1) a siderite–quartz–sulfide stage (Stage 1) associated with the formation of chalcopyrite and pyrite in a quartz and siderite gangue; and (2) a quartz–bornite stage (Stage 2) cutting the Stage 1 phases. Stage 1 is the main mineralization stage. Quartz that formed in Stage 1 has δ18OH2O values of − 4.3‰ to 3.5‰ with δD values of fluid inclusion waters of − 97.1‰ to − 49.9‰, indicating that the ore-forming fluids were derived from early magmatic fluids and may have experienced oxygen isotopic exchange with meteoric water during Stage 1 mineralization.LA–MC–ICP–MS zircon U–Pb dating of the mineralization-related nosean-bearing phonolite and nosean-bearing phonolitic brecciated tuff at Tongjing yields ages of 129.8 ± 0.5 Ma and 128.9 ± 1.1 Ma, respectively. These results are interpreted as the crystallization age of the volcanic rocks of the Niangniangshan Formation. A hydrothermal sericite sample associated with Cu–Au mineralization at Tongjing yields a plateau 40Ar–39Ar age of 131.3 ± 1.3 Ma. These results confirm a genetic link between the volcanism and associated Cu–Au mineralization. The Tongjing Cu–Au deposit in the Ningwu basin is genetically and possibly tectonically similar to alkaline intrusion-related gold deposits elsewhere in the world. 相似文献