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1.
The stable carbon isotopic compositions of free and sulfur (S)-bound biomarkers derived from algae, (cyano)bacteria, archaea and higher plants and total organic carbon (TOC) during the first phase of the late Cenomanian/Turonian oceanic anoxic event (OAE) were measured in black shales deposited in the southern proto-Atlantic Ocean in the Cape Verde basin (DSDP Site 367) to determine the response of these organisms to this major perturbation of the global carbon cycle resulting from widespread burial of marine organic matter. The average positive isotope excursions of TOC and biomarkers varied from 5.1‰ to 8.3‰. The δ13C values were cross correlated to infer potential common sources of biomarkers. This revealed common sources for C31 and C32 hopanes but no 1:1 relationship for pristane and phytane. The correlation of δ13CTOC with the δ13C value of sulfur (S)-bound phytane is the strongest. This is because S-bound phytane is derived from phytol that originates from all marine primary producers (algae and cyanobacteria) and thus represents a weighted average of their carbon isotopic compositions. The δ13C values of S-bound phytane and C35 hopane were also used to estimate pCO2 levels. Before the OAE burial event, pCO2 levels are estimated to be ca. 1300 ppmv using both biomarkers and the independent maximum Rubisco fractionation factors. At times of maximum organic carbon burial rates during the OAE, reconstructed pCO2 levels are estimated to be ca. 700 ppmv. However, compared to other C/T OAE sections the positive isotope excursion of S-bound phytane is also affected by an increased production during the OAE. When we compensate for this, we arrive at pCO2 levels around 1000 ppmv, a reduction of ca. 25%. This indicates that burial of organic matter can have a large effect on atmospheric CO2 levels.  相似文献   

2.
Biomarker ratios, together with stable carbon (δ13C) and hydrogen (δD) isotopic compositions of individual hydrocarbons have been determined in a suite of crude oils (n = 24) from the East Sirte Basin to delineate their sources and respective thermal maturity. The crude oil samples are divided into two main families (A and B) based on differences in source inputs and thermal maturity. Using source specific parameters including pristane/phytane (Pr/Ph), hopane/sterane, dibenzothiophene/phenanthrene (DBT/P), Pr/n-C17 and Ph/n-Cl8 ratios and the distributions of tricyclic and tetracyclic terpanes, family B oils are ascribed a marine source rock deposited under sub-oxic conditions, while family A oils have a more terrigenous source affinity. This genetic classification is supported by the stable carbon isotopic compositions (δ13C) of the n-alkanes. Using biomarker maturity parameters such as the abundance of Pr and Ph relative to n-alkanes and the distribution of sterane and hopane isomers, family A oils are shown to be more thermally mature than family B oils. The contrasting maturity of the two families is supported by differences between the stable hydrogen isotopic compositions (δD) of Pr and Ph and the n-alkanes, as well as the δ13C values of n-alkanes in their respective oils.  相似文献   

3.
Samples from two lignite seams (Lower Seam, Upper Seam) of the Lavanttal basin (Austria) and additional xylite were investigated for variations in maceral composition, petrography-based facies indicators, bulk geochemical parameters, and molecular composition of hydrocarbons. Both seams originated in a topogenous mire and evolved within a transgressive setting. The final drowning of the mire is indicated by sapropelic shales. Whereas the sapropelic shale overlying the Lower Seam was deposited in a freshwater lake, the sapropelic shale above the Upper Seam represents a brackish lake.Numerous relationships are found between petrography-based facies indicators and the geochemical composition of organic matter. The contents of macerals of the liptinite group are positively correlated with soluble organic matter (SOM) yields and hydrogen index (HI). Consistent with maceral composition and high HI values, enhanced proportions of short-chain n-alkanes, which are predominantly found in algae and microorganisms, are obtained from samples of the sapropelic shales. The final drowning of the mire is reflected by decreasing pristane/phytane ratios, due to the rise in (ground)water table and the establishment of anaerobic conditions, as well as by decreasing ratios of diasterenes/sterenes, indicating increasing pH values in the mire. The degree of gelification of plant tissue (gelification index) is governed by the microbial activity in the mire, as indicated by the hopanes concentration. The differences in floral assemblage during the formation of the Lavanttal lignite seams are reflected by major differences in tissue preservation. Preservation of plant tissue (TPI) in the Lavanttal lignite is obviously controlled by the presence/absence of decay-resistant gymnosperms in the peat-forming vegetation, and additionally influenced by the relative contribution of wood to coal formation. The results provide evidence that valuable information for coal facies characterization could be obtained by petrography-based and geochemical facies indicators. An influence of the floral assemblage (gymnosperms/angiosperms ratio) and of the contribution of algal biomass on carbon isotopic composition of the organic matter (δ13C = − 24.2 to − 28.6‰) is proposed. Carbon cycling during biogeochemical decomposition of plant tissue by bacteria is suggested to affect the δ13C values of the coal. The chemotaxonomical classification of the xylites as gymnosperm remnants, based on the molecular composition of terpenoid biomarkers, is corroborated by the carbon isotopic composition of the xylites (mean δ13C = − 24.1‰) and the extracted cellulose (mean δ13C = − 20.2‰). The higher isotopic difference of about 3.9‰ between cellulose and total organic carbon of the xylites, compared to the difference between cellulose and wood found in modern trees, is explained by the smaller effect of decomposition on δ13C of cellulose.  相似文献   

4.
Equilibrium 2H/1H fractionation factors (αeq) for various H positions in alkanes, alkenes, ketones, carboxylic acids, esters, alcohols, and ethers were calculated between 0 and 100 °C using vibrational frequencies from ab initio QM calculations (B3LYP/6-311G**). Results were then corrected using a temperature-dependent linear calibration curve based on experimental data for Hα in ketones (Wang et al., 2009). The total uncertainty in reported αeq values is estimated at 10–20‰. The effects of functional groups were found to increase the value of αeq for H next to electron-donating groups, e.g. OR, OH or O(CO)R, and to decrease the value of αeq for H next to electron-withdrawing groups, e.g. (CO)R or (CO)OR. Smaller but significant functional group effects are also observed for Hβ and sometimes Hγ. By summing over individual H positions, we estimate the equilibrium fractionation relative to water to be −90‰ to −70‰ for n-alkanes and around −100‰ for pristane and phytane. The temperature dependence of these fractionations is very weak between 0 and 100 °C. Our estimates of αeq agree well with field data for thermally mature hydrocarbons (δ2H values between −80‰ and −110‰ relative to water). Therefore the observed δ2H increase of individual hydrocarbons and the disappearance of the biosynthetic δ2H offset between n-alkyl and linear isoprenoid lipids during maturation of organic matter can be confidently attributed to H exchange towards an equilibrium state. Our results also indicate that many n-alkyl lipids are biosynthesized with δ2H values that are close to equilibrium with water. In these cases, constant down-core δ2H values for n-alkyl lipids cannot be reliably used to infer a lack of isotopic exchange.  相似文献   

5.
Solid, liquid and gaseous hydrocarbons occur throughout the Dead Sea Basin (Israel and Jordan) both in surface exposures and in drillings. The unaltered asphalts and heavy oils are characterized by very high sulfur content (ca. 11%) with δ34S = +5% and δ13C = −28% to −29%, low content of n-paraffins, pristane to phytane ratio of 0.5 and by containing almost exclusively VO-porphyrins. The distribution of n-paraffins in samples from deep sources shows a smooth enveloped miximizing at C15–20. Surface and shallow samples show clear evidence of biodegradation. The ozokerite, known only from the east side of the basin, is composed primarily of long chain n-paraffins with a maximum at C39. The gases known from the southern margin of the basin are composed mostly of methane.The source for the bitumens is unknown. Two hypotheses are discussed. The first is that the asphalts and heavy oils represent an alteration products of crude oil which migrated into the basin or which might have been generated in the basin itself. The second hypothesis favors an origin from low temperature alteration of organic matter from a thermally immature source.  相似文献   

6.
Previous studies on the coal-bed methane potential of the Zonguldak basin have indicated that the gases are thermogenic and sourced by the coal-bearing Carboniferous units. In this earlier work, the origin of coal-bed gas was only defined according to the molecular composition of gases and to organic geochemical properties of the respective source rocks, since data on isotopic composition of gases were not available. Furthermore, in the western Black Sea region there also exist other source rocks, which may have contributed to the coal-bed gas accumulations. The aim of this study is to determine the origin of coal-bed gas and to try a gas-source rock correlation. For this purpose, the molecular and isotopic compositions of 13 headspace gases from coals and adjacent sediments of two wells in the Amasra region have been analyzed. Total organic carbon (TOC) measurements and Rock-Eval pyrolysis were performed in order to characterize the respective source rocks. Coals and sediments are bearing humic type organic matter, which have hydrogen indices (HI) of up to 300 mgHC/gTOC, indicating a certain content of liptinitic material. The stable carbon isotope ratios (δ13C) of the kerogen vary from −23.1 to −27.7‰. Air-free calculated gases contain hydrocarbons up to C5, carbon dioxide (<1%) and a considerable amount of nitrogen (up to 38%). The gaseous hydrocarbons are dominated by methane (>98%). The stable carbon isotope ratios of methane, ethane and propane are defined as δ13C1: −51.1 to −48.3‰, δ13C2: −37.9 to −25.3‰, δ13C3: −26.0 to −19.2 ‰, respectively. The δD1 values of methane range from −190 to −178‰. According to its isotopic composition, methane is a mixture, partly generated bacterially, partly thermogenic. Molecular and isotopic composition of the gases and organic geochemical properties of possible source rocks indicate that the thermogenic gas generation took place in coals and organic rich shales of the Westphalian-A Kozlu formation. The bacterial input can be related to a primary bacterial methane generation during Carboniferous and/or to a recent secondary bacterial methane generation. However, some peculiarities of respective isotope values of headspace gases can also be related to the desorption process, which took place by sampling.  相似文献   

7.
Coal-derived hydrocarbons from Middle–Lower Jurassic coal-bearing strata in northwestern China are distributed in the Tarim, Junggar, Qaidam, and Turpan-Harmi basins. The former three basins are dominated by coal-derived gas fields, distributed in Cretaceous and Tertiary strata. Turpan-Harmi basin is characterized by coal-derived oil fields which occur in the coal measures. Based on analysis of gas components and carbon isotopic compositions from these basins, three conclusions are drawn in this contribution: 1) Alkane gases with reservoirs of coal measures have no carbon isotopic reversal, whereas alkane gases with reservoirs not of coal measures the extent of carbon isotopic reversal increases with increasing maturity; 2) Coal-derived alkane gases with high δ13C values are found in the Tarim and Qaidam basins (δ13C1: − 19.0 to − 29.9‰; δ13C2: − 18.8 to − 27.1‰), and those with lowest δ13C values occur in the Turpan-Harmi and Junggar basins (δ13C1: − 40.1 to − 44.0‰; δ13C2: − 24.7 to − 27.9‰); and 3) Individual specific carbon isotopic compositions of light hydrocarbons (C5–8) in the coal-derived gases are lower than those in the oil-associated gases. The discovered carbon isotopic reversal of coal-derived gases is caused by isotopic fractionation during migration and secondary alteration. The high and low carbon isotopic values of coal-derived gases in China may have some significance on global natural gas research, especially the low carbon isotope value of methane may provide some information for early thermogenic gases. Coal-derived methane typically has much heavier δ13C than that of oil-associated methane, and this can be used for gas–source rock correlation. The heavy carbon isotope of coal-derived ethane is a common phenomenon in China and it shed lights on the discrimination of gas origin. Since most giant gas fields are of coal-derived origin, comparative studies on coal-derived and oil-associated gases have great significance on future natural gas exploration in the world.  相似文献   

8.
The CO2 gas reservoir sandstones in the Hailaer Basin contain abundant dawsonite and provide an ideal laboratory to study whether any genetic relationship exists between dawsonite and the modern gas phase of CO2. The origins of dawsonite and CO2 in these sandstones were studied by petrographic and isotopic analysis. According to the paragenetic sequence of the sandstones, dawsonite grew later than CO2 charging at 110–85 Ma. The dawsonite δ18O value is 7.4‰ (SMOW), and the calculated δ18O values of the water present during dawsonite growth are from −11.4‰ to −9.2‰ (SMOW). This, combined with the NaHCO3-dominated water linked to dawsonite growth, suggests meteoric water being responsible for dawsonite growth. The δ13C values of gas phase CO2 and the ratios of 3He/4He of the associated He suggest a mantle magmatic origin of CO2-rich natural gas in Hailaer basin. Dawsonite δ13C values are −5.3‰ to −1.5‰ (average −3.4‰), and the calculated δ13C values of CO2 gas in isotopic equilibrium with dawsonite are −11.4‰ to −7.3‰. These C isotopic values are ambiguous for the dawsonite C source. From the geological context, the timing of events, together with formation water conditions for dawsonite growth, dawsonite possibly grew in meteoric-derived water, atmospherically-derived CO2 maybe, or at least the dominant, C source for dawsonite. It seems that there are few relationships between dawsonite and the modern gas phase of CO2 in the Hailaer basin.  相似文献   

9.
Isotopic compositions of carbon-bound hydrogen in individual n-alkanes and acyclic isoprenoid alkanes, from a number of crude oil samples, were measured using gas chromatography-thermal conversion-isotope ratio mass spectrometry. The precision of this technique is better than 3‰ for most alkanes, compared to the large range of δD variation among the samples (up to 160‰). The oils were selected from major genetic oil families in the Western Canada Sedimentary Basin, with source rocks ranging in age from Ordovician (and possibly Cambrian) to Cretaceous. The hydrogen isotopic composition of alkanes in crude oils is controlled by three factors: isotopic compositions of biosynthetic precursors, source water δD values, and postdepositional processes. The inherited difference in the lipid's biosynthetic origins and/or pathways is reflected by a small hydrogen isotopic variability within n-alkanes, but much larger differences in the δD values between n-alkanes and pristane/phytane. The shift toward lighter hydrogen isotopic compositions from Paleozoic to Upper Cretaceous oils in the WCSB reflects a special depositional setting and/or a minor contribution of terrestrial organic matter. The strong influence of source water δD values is demonstrated by the distinctively lower δD values of lacustrine oils than marine oils, and also by the high values for oils with source rocks deposited in evaporative environments. Thermal maturation may alter the δD values of the alkanes in the oil to some extent, but secondary oil migration does not appear to have had any significant impact. The fact that oils derived from source rocks that could be of Cambrian age still retain a strong signature of the hydrogen isotopic compositions of source organic matter, and source water, indicates that δD values are very useful for oil-source correlation and for paleoenvironmental reconstructions.  相似文献   

10.
The Daduhe gold field comprises several shear-zone-controlled Tertiary lode gold deposits distributed at the eastern margin of the Tibetan Plateau. The deposits are hosted in a Precambrian granite–greenstone terrane within the Yangtze Craton. The gold mineralization occurs mainly as auriferous quartz veins with minor sulphide minerals. Fluid inclusions in pyrite have 3He/4He ratios of 0.16 to 0.86 Ra, whereas their 40Ar/36Ar ratios range from 298 to 3288, indicating a mixing of fluids of mantle and crust origins. The δ34S values of pyrite are of 0.7–4.2‰ (n = 12), suggesting a mantle source or leaching from the mafic country rocks. δ18O values calculated from hydrothermal quartz are between − 1.5‰ and + 6.0‰ and δD values of the fluids in the fluid inclusions in quartz are − 39‰ and − 108‰. These ranges demonstrate a mixing of magmatic/metamorphic and meteoric fluids. The noble gas isotopic data, along with the stable isotopic data suggest that the ore-forming fluids have a dominantly crustal source with a significant mantle component.  相似文献   

11.
A reversal of the conventional carbon isotope relationship, “terrestrial-lighter-than-marine” organic matter, has been documented for two Pennsylvanian (Desmoinesian) cyclothemic sequence cores from the Midcontinent craton of the central United States. “Deep” water organic-rich phosphatic black shales contain a significant proportion of algal-derived marine organic matter (as indicated by organic petrography, Rock-Eval hydrogen index and ratios) and display the lightest δ13C-values (max −27.80‰ for kerogen) while shallower water, more oxic facies (e.g. fossiliferous shales and limestones) contain dominantly terrestrial organic matter and have heavier δ13Ckerogen-values (to −22.87‰ for a stratigraphically adjacent coal). δ13C-values for extract fractions were relatively homogeneous for the organic-rich black shales with the lightest fraction (often the aromatics) being only 1‰, or less, more negative than the kerogen. Differences between extract fractions and kerogens were much greater for oxic facies and coals (e.g. saturates nearly 5‰ lighter than the kerogen).A proposed depositional model for the black shales calls upon a large influx of nutrients and humic detritus to the marine environment from the laterally adjacent, extremely widespread Pennsylvanian (peat) swamps which were rapidly submerged by transgression of the epicontinental seas. In this setting marine organisms drew upon a CO2-reservoir which was in a state of disequilibrium with the atmosphere, being affected by isotopically light “recycled-CO2” derived from the decomposition of peaty material in the water column and possibly from the anoxic diagenesis of organic matter in the sediments.  相似文献   

12.
Ocean Drilling Program Leg 207 recovered thick sequences of Albian to Santonian organic-carbon-rich claystones at five drill-sites on the Demerara Rise in the western equatorial Atlantic Ocean. Dark-colored, finely laminated, Cenomanian–Santonian black shale sequences contain between 2% and 15% organic carbon and encompass Oceanic Anoxic Events 2 and 3. High Rock-Eval hydrogen indices signify that the bulk of the organic matter in these sequences is marine in origin. However, δ13Corg values lie mostly between −30‰ and −27‰, and TOC/TN ratios range from 15 to 42, which both mimic the source signatures of modern C3 land plants. The contradictions in organic matter source indicators provide important implications about the depositional conditions leading to the black shale accumulations. The low δ13Corg values, which are actually common in mid-Cretaceous marine organic matter, are consequences of the greenhouse climate prevailing at that time and an associated accelerated hydrologic cycle. The elevated C/N ratios, which are also typical of black shales, indicate depressed organic matter degradation associated with low-oxygen conditions in the water column that favored preservation of carbon-rich forms of marine organic matter over nitrogen-rich components. Underlying the laminated Cenomanian–Santonian sequences are homogeneous, dark-colored, lower to middle Albian siltstones that contain between 0.2% and 9% organic carbon. The organic matter in these rocks is mostly marine in origin, but it occasionally includes large proportions of land-derived material.  相似文献   

13.
Chemical and isotopic compositions have been measured on 62 microbial gases from Tertiary hemipelagic sediments in the Middle America Trench off Guatemala and from decaying kelp and surf grass currently accumulating in Scripps Submarine Canyon off southern California. Gases from the Middle America Trench have been generated primarily by the reduction of carbon dioxide; methane δ13C varies from −84‰ to −39‰, methane δD varies from −208‰ to −145‰, and carbon dioxide δ13 C varies from −27‰ to +28‰. Gases from Scripps Submarine Canyon have been generated primarily by acetate dissimilation; methane δ13 C varies from −63‰ to −43‰, methane δD varies from −331‰ to −280‰, and carbon dioxide δ13C varies from −17‰ to +3‰.Methane δ13C values as heavy as −40‰ appear to be uncommon for gases produced by carbon dioxide reduction and, in the Middle America Trench, are associated with unusually positive carbon dioxide δ13C values. However, based on the 25‰ intramolecular fractionation between acetate car☐yl carbon and methyl carbon estimated from the Scripps Submarine Canyon data, methane produced by acetate dissimilation may commonly have heavy δ13C values. The δD of methane derived from acetate is more negative than natural methanes from other origins. Microbial methane δD values appear to be controlled primarily by interstitial water δD and by the relative proportions of methane derived from carbon dioxide and acetate.The chemical and isotopic compositions of microbial gas and thermogenic gas overlap, making it difficult to determine the origins of many commercial natural gases from methane δ13C and C2+ hydrocarbon concentrations alone. Measurements of methane δD and carbon dioxide δ13C can provide useful additional information, and together with ethane δ13C data, help identify gases with mixed microbial and thermogenic origins.  相似文献   

14.
Inorganic gases are commonly seen in eastern China and occasionally in southern China from the shallow water columns above hot and cold springs. The gases contain 68% to nearly 100% CO2, with δ13CCO2 and δ13C1 values in the range of −1.18‰ to −6.00‰ and −19.48‰ to −24.94‰, respectively. All of the 34 large inorganic CO2 and one inorganic methane accumulations discovered in China are distributed in eastern parts of the country, from both onshore and continental shelf basins. No commercial inorganic gas accumulation has been found in central and western China. This is a review of the occurrence and geochemical characteristics of inorganic gas accumulations in Chinese sedimentary basins. A detailed study of gas samples collected from four representative inorganic CO2 pools and one possible inorganic methane pool indicates that inorganic alkane gases typically show δ13C1 values greater than −10‰ versus PDB (mostly −30‰), with a positive stable carbon isotope sequence of δ13C1 < δ 13C2 < δ13C3 < δ 13C4. In contrast, the δ13C1 values of biogenic alkane gases are lighter than −30‰, with a negative isotope sequence (i.e. δ13C1 > δ13C2 > δ 13C3 > δ13C4). Inorganic gases also tend to show less negative δ13CCO2 values (−10‰) than biogenic gases (<−10‰).  相似文献   

15.
The Pleistocene deposits at Zhoukoudian, often referred to as the “Peking Man” site, contain dental remains from a diverse group of herbivores, including Equus sanmeniensis, Cervus elaphus, Cervus nippon, Megaloceros pachyosteus, Sus lydekkeri, and Dicerorhinus choukoutienensis. The carbon and oxygen isotopic compositions of structural carbonate within the enamel of these teeth are used to reconstruct the paleodiet and paleoenvironment of the mammals. The δ13C values of enamel from Zhoukoudian range from −2.3‰ to −13.0‰, indicating that these mammals consumed between 25% and 100% C3 plants. The presence of significant amounts of C4 plants in the diets of some herbivore species indicates that at the onset of the Middle Pleistocene local habitats included mixed C3/C4 vegetation. By approximately 470,000 yr ago, C3 plants dominated the diets of herbivores studied, suggesting that the abundance of C4 flora had decreased in the area. For all deer analyzed in this study, the values of δ13C and δ18O decrease substantially from about 720,000 to 470,000 yr ago. This trend may be due to a strengthening of the winter monsoon during the Middle Pleistocene.  相似文献   

16.
Individual and monthly precipitation samples from the polluted atmosphere of Bologna (Emilia-Romagna province) were collected during March 1996 to May 1997 and analyzed for major ions in solution and S isotopes in dissolved SO4.Weighted mean enrichment factors relative to seawater are found to be 1.0 for Na, 15.2 for K, 105 for Ca, 3.3 for Mg, 17.3 for SO4 and 663 for HCO3. Very good positive correlations are observed for the Ca2+–Mg2+–HCO3–SO2−4–NO3 system, indicating that dissolution of Ca (±Mg)-carbonate particles by H2SO4 and HNO3 from combustion of oil and gas is a major process controlling the chemical composition of rain and snow. Na+ and Cl in monthly precipitation derive essentially from sea spray, but the contribution of Na+ from continental sources is appreciable in a number of individual rains. NH+4 appears to be on average more abundant in spring and summer precipitation, its main sources being microbial activity in soils and application of fertilizers. K+ is probably of continental origin from soil dust.The S isotopic composition of SO4 is systematically positive, with mean δ34S values of +3.2±1.6‰ (n=40) in individual precipitation and +2.8±1.4‰ (n=12) in monthly precipitation. These isotopic compositions are interpreted in terms of a dominant contribution of S from anthropogenic emissions and subordinate contributions from biogenic and marine sources. Pollutant SO4 is estimated to have a δ34S value in the range +2.5 to +4.5‰, whereas a distinctive δ34S of −4.5‰ or lower indicates SO4 from oxidation of biogenic gases.The isotopic and chemical compositions of SO4 do not depend on wind direction, thus testifying to a mostly local source for pollutant S in the Bologna atmosphere.  相似文献   

17.
For the ammonia-oxidizing bacterium Nitrosomonas europaea, grown autotrophically using semicontinuous culturing, average biomass was depleted in 13C relative to CO2 dissolved in the medium by ca. 20‰ and the total-lipid extract was depleted in 13C relative to biomass by 3.7‰. The n-alkyl lipids (weighted average of fatty acids) and isoprenoid lipids (weighted average of hopanoids) were both depleted in 13C relative to biomass by about 9‰. The large depletion in the isoprenoid lipids seems to indicate that isotopic fractionations associated with the biosynthesis of methylerythritol phosphate (MEP) affected at least two carbon positions in each isoprene unit. Among the fatty acids, trans-9-hexadecenoic acid was most depleted (13.0‰ relative to biomass), followed by cis-9- hexadecenoic acid (9.6‰) and hexadecanoic acid (6.9‰). Isotopic relationships between the three acids suggest that significant isotope effects were associated with the desaturation and cis to trans isomerization of fatty acids. Given these observations, hopanoids produced by ammonia-oxidizing bacteria growing in natural waters are likely to be depleted in 13C by 26–30‰ relative to dissolved CO2. Since CO2 at aquatic oxyclines is often depleted in 13C, the range of δ values expected for hopanoids is ca. −34‰ to −55‰. The δ values of geohopanoids observed in numerous studies and attributed to unspecified chemoautotrophs fall within this range.  相似文献   

18.
The Maastrichtian–Danian limestones of the Yacoraite Formation (northwestern Argentina) show carbon and oxygen isotopic values consistent with shallow marine conditions. The members of the formation respond to different sedimentary environments and are characterised by distinctive stable isotopes and geochemistry. The basal Amblayo Member is composed of high-energy dolomitic limestones and limestones with positive isotopic values (+2‰ δ13C, +2‰ δ18O). The top of the member reveals an isotopic shift of δ13C (−5‰) and δ18O (−10‰), probably related to a descent in the sea level. The sandy Güemes Member has isotopically negative (−2‰ δ13C, −1‰ δ18O) limestones, principally controlled by water mixing, decreased organic productivity, and compositional changes in the carbonates. The isotopically lighter limestones are calcitic, with a greater terrigenous contribution and different geochemical composition (high Si–Mn–Fe–Na, low Ca–Mg–Sr). These isotopic and lithological changes relate to the Cretaceous–Palaeogene transition. The Alemanía Member, composed of dolomitic limestones and pelites, represents a return to marine conditions and shows a gradual increase in isotopic values, reaching values similar to those of the Amblayo Member. The Juramento Member, composed of stromatolite limestones, shows isotopic variations that can be correlated with the two well-defined, shallowing-upward sequences of the member.  相似文献   

19.
Black and white dolomite crystals (mm to cm width) of different isotopic composition are associated with Triassic diapirism in central Tunisia, as well as with evaporite minerals and clays. The white dolomites occur mostly in the Jabal Hadifa diapir near the contact with Cretaceous limestones, whereas the smaller black dolomites occur in the Jabal Hamra diapir. The former dolomite has a narrow range of δ18O and δ13C values (− 3.83‰ to − 6.60‰ VPDB for δ18O; − 2.11‰ to − 2.83‰ VPDB for δ13C), whereas the latter dolomite has a wider range and more depleted values (− 4.92‰ to − 9.97‰ for δ18O; − 0.55‰ to − 6.08‰ for δ13C). However, the 87Sr / 86Sr ratios of most of the samples are near Triassic seawater values. Dolomite formation is due to at least two different fluids. The main fluid originated from deeper hydrothermal or basinal sources related to the Triassic saliferous rocks and ascended through faults during the diapiric intrusion. The second, less important fluid source is related to meteoric water originating from Cretaceous rocks.  相似文献   

20.
Stable (δ13C and δ18O) and radiogenic 87Sr/86Sr isotopic data have been used to investigate the origin of cleat dawsonite (NaAlCO3(OH)2) in the Late Permian Wittingham Coal Measures of the Upper Hunter region in the Sydney Basin, New South Wales. The δ13CPDB values have a narrow range (− 1.7‰ to + 2.4‰), with an average of + 0.3‰, suggesting a magmatic source for the carbon. In contrast, δ18OSMOW values have a wide range (+ 13.6‰ to + 19.8‰), and decrease systematically with decreasing distance from a major intrusion. This systematic variation reflects establishment of localised hydrothermal cells. Water–rock interaction between fluids associated with these hydrothermal cells, and Rb-poor volcaniclastic detritus in the coal measures, produced mantle-like 87Sr/86Sr (0.705032 to 0.706464) in the dawsonite.  相似文献   

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