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1.
The Mahakam delta (Kalimantan, Indonesia) coals represent all the evolution stages between freshly-deposited plant/peat material, lignites and bituminous coals. The geochemical techniques used to study this coal series included elemental analysis, extraction of humic compounds, infrared spectroscopy and 13C nuclear magnetic resonance of the total coal.The main mechanisms of early maturation in this series are loss of oxygenated compounds, aromatisation and condensation of the organic matter. These changes, which have already been suggested for other coal series and partially reported for sedimentary organic matter, were confirmed and described in more detail for the Mahakam coal series.  相似文献   

2.
Carbon isotope compositions of both sedimentary carbonate and organic matter can be used as key proxies of the global carbon cycle and of its evolution through time,as long as they are acquired from waters where the dissolved inorganic carbon(DIC)is in isotope equilibrium with the atmospheric CO2.However,in shallow water platforms and epeiric settings,the influence of local to regional parameters on carbon cycling may lead to DIG isotope variations unrelated to the global carbon cycle.This may be especially true for the terminal Neoproterozoic,when Gondwana assembly isolated waters masses from the global ocean,and extreme positive and negative carbon isotope excursions are recorded,potentially decoupled from global signals.To improve our understanding on the type of information recorded by these excursions,we investigate the pairedδ^13Ccarb andδ^13Corg evolution for an increasingly restricted late Ediacaran-Cambrian foreland system in the West Gondwana interior:the basal Bambui Group.This succession represents a 1~(st)-order sedimentary sequence and records two majorδ^13Ccarb excursions in its two lowermost lower-rank sequences.The basal cap carbonate interval at the base of the first sequence,deposited when the basin was connected to the ocean,hosts antithetical negative and positive excursions forδ^13Ccarb andδ^13Corg,respectively,resulting inΔ^13C values lower than 25‰.From the top of the basal sequence upwards,an extremely positiveδ^13Ccarb excursion is coupled toδ^13Corg,reaching values of+14‰and-14‰,respectively.This positive excursion represents a remarkable basin-wide carbon isotope feature of the Bambui Group that occurs with only minor changes inΔ^13C values,suggesting change in the DIC isotope composition.We argue that this regional isotopic excursion is related to a disconnection between the intrabasinal and the global carbon cycles.This extreme carbon isotope excursion may have been a product of a disequilibria between the basin DIC and atmospheric CO2 induced by an active methanogenesis,favored by the basin restriction.The drawdown of sulfate reservoir by microbial sulfate reduction in a poorly ventilated and dominantly anoxic basin would have triggered methanogenesis and ultimately methane escape to the atmosphere,resulting in a^13C-enriched DIC influenced by methanogenic CO2.Isolated basins in the interior of the Gondwana supercontinent may have represented a significant source of methane inputs to the atmosphere,potentially affecting both the global carbon cycle and the climate.  相似文献   

3.
The distribution of δ13C values for organic seston and sediment was determined in three sounds in the Spartina marsh estuaries along the Georgia coast, which had high, moderate, and low inputs of freshwater. Organic matter in all three sounds had similar carbon isotope compositions, for the most part within the range of marine values (δ13C of ?18%. to ?24%.). It appears that river flow does not introduce significant quantities of particulate C3 plant material (δ13C of ?25%. to ?28%.) to Georgia estuaries. Evaluation of δ13C values of estuarine seston and three size fractions of sediment indicated that while Spartina carbon (δ13C of ?13%.) can be an important component of organic matter in intertidal sediments (mean δ13C of ?14.3%. to ?20.0%.), it is less so in subtidal sediments (mean δ13C of ?18.8%. to ?21.2%.), and it is hardly present at all in the seston (mean δ13C of ?24.5%.). δ13C values of dissolved inorganic carbon (DIC) in several water samples ranged between ?2.5%. and ?5.6%., suggesting that the isotope composition of estuarine DIC is influenced by respiratory CO2 derived from metabolism of 13C-depleted plant carbon. Phytoplankton production utilizing this comparatively light DIC could be a source of relatively negative δ13C carbon in the estuary. Additional origins of estuarine organic matter greatly depleted in 13C compared to Spartina carbon remain to be identified.  相似文献   

4.
Oceania supplies ∼40% of the global riverine flux of organic carbon, approximately half of which is injected onto broad continental shelves and processed in shallow deltaic systems. The Gulf of Papua, on the south coast of the large island of New Guinea, is one such deltaic clinoform complex. It receives ∼4 Mt yr−1 particulate terrestrial organic carbon with initial particle Corg loading ∼0.7 mg m−2. Corg loading is reduced to ∼0.3 mg m−2 in the topset-upper foreset zones of the delta despite additional inputs of mangrove and planktonic detritus, and high net sediment accumulation rates of 1-4 cm yr−1. Carbon isotopic analyses (δ13C, Δ14C) of ΣCO2 and Corg demonstrate rapid (<100 yr) remineralization of both terrestrial (δ13C <−28.6) and marine Corg (δ13C ∼−20.5) ranging in average age from modern (bomb) (Δ14C ∼60) to ∼1000 yr (Δ14C ∼−140). Efficient and rapid remineralization in the topset-upper foreset zone is promoted by frequent physical reworking, bioturbation, exposure, and reoxidation of deposits. The seafloor in these regions, particularly <20 m, apparently functions as a periodically mixed, suboxic batch reactor dominated by microbial biomass. Although terrestrial sources can be the primary metabolic substrates at inshore sites, relatively young marine Corg often preferentially dominates pore water ΣCO2 relative to bulk Corg in the upper foreset. Thus a small quantity of young, rapidly recycled marine organic material is often superimposed on a generally older, less reactive terrestrial background. Whereas the pore water ΣCO2 reflects both rapidly cycled marine and terrestrial sources, terrestrial material dominates the slower overall net loss of Corg from particles in the topset-upper foreset zone (i.e. recycled marine Corg leaves little residue). Preferential utilization of Corg subpools and diagenetic fractionation of C isotopes supports the reactive continuum model as a conceptual basis for net decomposition kinetics. Early diagenetic fractionation of C isotopes relative to the bulk sedimentary Corg composition can produce changes in 14C activity independent of radioactive decay. In the Gulf of Papua topset-upper foreset, Δ14C of pore water ΣCO2 averaged ∼ 300‰ greater than Corg sediment between ∼1-3 m depth in deposits. Diagenetic fractionation and decomposition aging of sedimentary Corg compromises simple application of 14C for determination of sediment accumulation rates in diagenetically reactive deposits.  相似文献   

5.
Unlike long-term heating in subsiding sedimentary basins, the near-instantaneous thermal maturation of sedimentary organic matter near magmatic intrusions is comparable to artificial thermal maturation in the laboratory in terms of short duration and limited extent. This study investigates chemical and H, C, N, O isotopic changes in high volatile bituminous coal near two Illinois dike contacts and compares observed patterns and trends with data from other published studies and from artificial maturation experiments. Our study pioneers in quantifying isotopically exchangeable hydrogen and measuring the D/H (i.e., 2H/1H) ratio of isotopically non-exchangeable organic hydrogen in kerogen near magmatic contacts. Thermal stress in coal caused a reduction of isotopically exchangeable hydrogen in kerogen from 5% to 6% in unaltered coal to 2-3% at contacts, mostly due to elimination of functional groups (e.g., OH, COOH, NH2). In contrast to all previously published data on D/H in thermally matured organic matter, the more mature kerogen near the two dike contacts is D-depleted, which is attributed to (i) thermal elimination of D-enriched functional groups, and (ii) thermal drying of hydrologically isolated coal prior to the onset of cracking reactions, thereby precluding D-transfer from relatively D-enriched water into kerogen. Maxima in organic nitrogen concentration and in the atomic N/C ratio of kerogen at a distance of ∼2.5 to ∼3.5 m from the thicker dike indicate that reactive N-compounds had been pyrolytically liberated at high temperature closer to the contact, migrated through the coal seam, and recombined with coal kerogen in a zone of lower temperature. The same principle extends to organic carbon, because a strong δ13Ckerogen vs. δ15Nkerogen correlation across 5.5 m of coal adjacent to the thicker dike indicates that coal was functioning as a flow-through reactor along a dynamic thermal gradient facilitating back-reactions between mobile pyrolysis products from the hot zone as they encounter less hot kerogen. Vein and cell filling carbonate is most abundant in highest rank coals where carbonate δ13CVPDB and δ18OVSMOW values are consistent with thermal generation of 13C-depleted and 18O-enriched CO2 from decarboxylation and pyrolysis of organic matter. Lower background concentrations of 13C-enriched carbonate in thermally unaffected coal may be linked to 13C-enrichment in residual CO2 in the process of CO2 reduction via microbial methanogenesis.Our compilation and comparison of available organic H, C, N isotopic findings on magmatic intrusions result in re-assessments of majors factors influencing isotopic shifts in kerogen during magmatic heating. (i) Thermally induced shifts in organic δD values of kerogen are primarily driven by the availability of water or steam. Hydrologic isolation (e.g., near Illinois dikes) results in organic D-depletion in kerogen, whereas more common hydrologic connectivity results in organic D-enrichment. (ii) Shifts in kerogen (or coal) δ13C and δ15N values are typically small and may follow sinusoidal patterns over short distances from magmatic contacts. Laterally limited sampling strategies may thus result in misleading and non-representative data. (iii) Fluid transport of chemically active, mobile carbon and nitrogen species and recombination reactions with kerogen result in isotopic changes in kerogen that are unrelated to the original, autochthonous part of kerogen.  相似文献   

6.
The main purpose of this study is to model the δ13C values of methane derived from coal by combining kinetic-simulating experiment with the gas chromatography-isotope ratio mass spectrum (GC-IRMS) analysis. The stable carbon isotopic variation of methane in pyrolysates with heating temperature indicates that the assumptions for both a constant kinetic isotope effect (α) and a uniform initial isotopic composition (δ13Co) are impractical for explaining the carbon isotopic fractionation during coalification. For purposes of simplification, two approaches are used in this paper to deal with the heterogeneity of terrestrial organic matter. One is that, assuming a uniform initial isotopic composition (i.e., δ13Ci, o=δ13Co) for all methane-generating precursors in coal, the isotopic variation of methane is fitted by adjusting ΔEa, i (Ea13C, i−Ea12C, i) for each hypothetical reaction. The other is that, assuming a constant kinetic isotope effect during the whole gas formation, that is all ΔEa, i values are identical, the modeling of methane isotopic composition is achieved by changing the 13CH4 generation potential of each reaction (fi, 13C), namely, by adjusting the initial δ13C value (δ13Ci, o) for each methane-generating precursor. Results of the kinetic calculation shows that the two simulating methods can yield a similar result at a geological heating rate of 2 °C/My, which further demonstrates that those natural gases with methane δ13C value being approximately −36‰ are possibly sourced from the upper Triassic coal measure strata in the Northwestern Sichuan Basin.  相似文献   

7.
In order to investigate the migration and accumulation efficiency of hydrocarbon natural gas in the Xujiaweizi fault depression, and to provide new evidence for the classification of its genesis, a source rock pyrolysis experiment in a closed system was designed and carried out. Based on this, kinetic models for describing gas generation from organic matter and carbon isotope fractionation during this process were established, calibrated and then extrapolated to geologic conditions by combining the thermal history data of the Xushen-1 Well. The results indicate that the coal measures in the Xujiaweizi fault depression are typical ＂high-efficiency gas sources＂, the natural gas generated from them has a high migration and accumulation efficiency, and consequently a large-scale natural gas accumulation occurred in the area. The highly/over matured coal measures in the Xujiaweizi fault depression generate coaliferous gas with a high δ^13C1 value （〉 -20‰） at the late stage, making the carbon isotope composition of organic alkane gases abnormally heavy. In addition, the mixing and dissipation through the caprock of natural gas can result in the negative carbon isotope sequence （δ^13C1 〉δ^13C2 〉δ^13C3 〉δ^13C4） of organic alkane gases, and the dissipation can also lead to the abnormally heavy carbon isotope composition of organic alkane gases. As for the discovery of inorganic nonhydrocarbon gas reservoirs, it can only serve as an accessorial evidence rather than a direct evidence that the hydrocarbon gas is inorganic. As a result, it needs stronger evidence to classify the hydrocarbon natural gas in the Xujiaweizi fault depression as inorganic gas.  相似文献   

8.
This study investigated the geochemical features of the lower Paleozoic strata of Yaerdang Mountain outcrop along with the core samples from well TD2∈ in the eastern Tarim Basin,NW China.The total organic carbon abundance,hydrocarbon-generating precursor biospecies,and stable isotope ratios of organics and carbonate(δ~(13)C_(ker),δ~(13)C_(carb) and δ~(18)O_(carb)) were comprehensively studied for their possible correlative constraints during sedimentary evolution.The results revealed that the δ~(13)C_(ker)(VPDB) of Cambrian kerogens along the outcrop section varied from-34.6‰ to-28.4‰,indicating an increasing tendency from the lower Cambrian to the upper Cambrian.This was on the whole accompanied by the variation in the δ~(13)C_(carb) and δ~(18)O_(carb) along the profile,which might be associated with the changes in the sea level and also in the compositional variation of benthic and planktonic biomass.The large variation in the stable carbon isotope ratios up to 6‰ along the outcrop section reflected the heterogeneity of the Cambrian source rocks from the eastern Tarim Basin.Hence,the ~(13)C-enriched crude oils from well TD2∈might have been derived from a localized stratum of Cambrian source rocks.The results from this study showed the possibility of multiple source kitchens in the Cambrian-lower Ordovician portion of Tarim Basin.  相似文献   

9.
Several arguments indicate that the mean carbon isotopic composition of the earth's crust and the upper mantle should be around-7‰. This agrees quite well with a balance calculation (Table 7) and with what we know about the carbon isotope composition of carbonatites and diamonds. Since fractionation factors decrease with increasing temperatures, the differences in isotopic compositions found in igneous rocks might be expected to be relatively slight and not to differ very much from the mean δ-value for the earth's crust. This also applies to the elements oxygen and sulfur, and to a lesser extent even for hydrogen, but not for carbon. Hoefs (1965) has shown that all igneous rocks contain carbon in at least two different forms:
  1. an oxidized form mainly as carbonate and/or as CO2 (in fluid and gaseous inclusions) in variable concentrations between <100 ppm and several thousand ppm CO2, and
  2. a reduced form with a relatively constant concentration around 200 ppm C. To 1). If the carbonate were of primary magmatic origin, we should expect, in analogy to carbonatites or to some hydrothermal carbonates, a δ 13C-value around-7 and a δ 18O-value between ?15 to ?25‰ relative to PDB, but on the contrary, the variable δ 13C- and the relatively heavy δ 18O-values make it seem probable that the carbonate is not of pirmary magmatic origin, but of secondary, maybe groundwater origin. This does not exclude the possibility that in some cases there may also be some carbonate which is of primary magmatic origin. To 2). If the reduced carbon found in igneous rocks is indigenous to these specimens, theoretically it may occur as elemental carbon (graphite), as carbides, and as organic compounds or as all three combined together.
This reduced carbon has a very light and fairly constant isotopic composition between ?24 and ?28‰ relative to PDB in all igneous rock types. There are two very different possible explanations for these values. The first and simplest one is that this carbon is also of secondary origin, or in other words of biogenic origin—some kind of assimilation of sedimentary organic material. But since this carbon is very evenly distributed, this means that all igneous rocks with a very small, but not negligible, porosity and permeability are impregnated by surface waters containing biogenic-derived organic substances in a concentration of around 200 ppm C. Since bore samples have also been analyzed, this also means that these waters penetrate into igneous rocks even at greater depths. Due to certain similarities in carbon isotopic composition found in extraterrestrial material, in meteorites and in lunar rocks (Table 9), I favor the second possibility of explaining the rather light δ 13C values: Several mechanisms have been postulated for the formation of organic matter in our solar system (Fischer-Tropsch type synthesis, Miller-Urey reactions etc.). Evidence supporting the hypothesis of inorganically formed organic matter on the earth has accumulated since Miller (1957) first demonstrated the synthesis of organic compounds from methane, ammonia and water. It is postulated that photosynthesis is not the only process leading to isotopically light carbon, but that some of these reactions (perhaps Fischer-Tropsch type synthesis) may also yield to isotopically light carbon. In addition to these data, some gaseous CO2-samples of probably volcanic origin from Germany have been analyzed. The CO2 discharged in areas of ancient volcanic activity shows δ 13C value between ?2 and ?5‰, typical for geothermal areas (e.g. Yellowstone, New Zealand). The CO2 found in inclusions in evaporites, some of them near basaltic dikes, shows a strikingly different δ 13C composition (between ?15 and ?25%.) comparable to CO2 sampled over liquid Hawaiian lavas. On the basis of the isotope-exchange reaction CH4+2H2O ? CO2+4H2, temperature seems to be the most important parameter, being responsible for the observed differences in isotopic composition.  相似文献   

10.
Cryoturbated facies are found at the boundary between soil horizons and Cretaceous chalk. Several types of secondary calcite appear in soil horizons: orange coloured and rounded (partially dissolved) nodules, deeply coloured angular aggregates, transparent isolated rhombs and polycrystalline nodules, needles. The carbon and oxygen isotope compositions of these calcites are correlated: δ13C = 4.9δ18OPDB + 15.9End members of this correlation are the orange rounded nodules (δ13C ? + 8%., δ18O ? ?1.5‰) and the transparent angular polycrystalline nodules (δ13C ? ?13; δ18O ? ?6).Partially dissolved nodules have formed under periglacial climatic conditions. Crystallisation would have occurred under the following (equilibrium) environmental conditions: δ18OSMOW (soil solution) ?7, δ13C (gaseousCO2) ? ?5.2, t ? ?2°C. Soil solution was enriched in 18O by evaporation and atmospheric CO2 was enriched in 13C as compared to present day. Transparent polycrystalline nodules are compatible with present day environmental conditions: δ18O (soil solution) ranging from ?9 to ?4 and δ13C (soil CO2) ranging from ?24.5 to ?23. These nodules crystallize between May and October at soil temperatures ranging from 10 to 25°C, from evaporated soil solutions. Angular coloured aggregates may form under present day winter conditions for temperatures between 0 and 10°C. However they may also result from present accretion of fragments of periglacial nodules.All recent secondary calcite results from CO2 degassing and evaporation of soil solutions. Degassing is controlled by the gradient of CO2 partial pressure within the soil profile. During winter this gradient is low and the resulting calcite precipitation is not significant. During summer a large difference in pCO2 appears between the root zone and deep soil horizons. The degassing accounts for an increase of about 2‰ in δ13C of the total dissolved inorganic carbon and of the related solid carbonate. Evaporation is the main driving force for secondary calcite precipitation.  相似文献   

11.
δ13C values of dissolved inorganic C (DIC), dissolved organic C (DOC), and particulate organic C (POC) together with δ18O and δ2H values of water, δ34S values of dissolved SO4, and major ion concentrations were measured in the Murray River and its tributaries between November 2005 and April 2007 to constrain the origins and behaviour of riverine C. δ13CDIC values in the Murray River vary between −9.5 and −4.7‰ with a range of <3‰ within any sampling round. δ13CDIC values of the tributaries are −11.0‰ to −5.1‰. DIC concentrations of the Murray River increase from ∼25 mg/L in the middle and upper reaches of the river to 45–55 mg/L in the lower reaches. However, the mass ratio of DIC as a proportion of the total dissolved solids (TDS) decreases from ∼0.6–0.7 in the headwaters to ∼0.2–0.3 in the lower reaches of the river, with similar downstream changes in DIC/Cl ratios. This precludes simple evaporative concentration of DIC and is interpreted as the river evading CO2; this interpretation is consistent with pCO2 values that are in the range 550–11,200 ppm volume (ppmv), which are far higher than those in equilibrium with the atmosphere (∼360 ppmv). The δ13CDIC values are similar to those that would be produced by the weathering of marine limestone (δ13C ∼ 0‰). However, the lack of marine limestones cropping out in the Murray–Darling Basin and the relatively uniform δ13CDIC values of the Murray River (even in upland reaches where the dominant rock types are metamorphosed silicates and granites) make this unlikely. Rather the high pCO2 values and δ13CDIC values are best explained by a combination of mineralisation of low δ13C organic C and evasion to the atmosphere. The rate of these two processes may attain near steady state and control both DIC concentrations and δ13C values.  相似文献   

12.
The Triassic–Jurassic boundary is characterized by strong perturbations of the global carbon cycle, triggered by massive volcanic eruptions related to the onset of the Central Atlantic Magmatic Province. These perturbations are recorded by negative carbon isotope excursions (CIEs) which have been reported worldwide. In this study, Triassic–Jurassic boundary sections from the southern margin of the Central European Basin (CEB) located in northern Switzerland are analyzed for organic carbon and nitrogen isotopes in combination with particulate organic matter (POM) analyses. We reconstruct the evolution of the depositional environment from Late Triassic to Early Jurassic in northern Switzerland and show that observed negative shifts in δ13C of the total organic carbon (δ13CTOC) in the sediment are only subordinately influenced by varying organic matter (OM) composition and primarily reflect global changes in the carbon cycle. Based on palynology and the stratigraphic positions of isotopic shifts, the δ13CTOC record of the studied sections is correlated with the GSSP section at Kuhjoch (Tethyan realm) in Austria and with the St. Audrie’s Bay section (CEB realm) in southwest England. We also show that in contrast to POM analyses the applicability of organic carbon/total nitrogen (OC/TN) atomic ratios and stable isotopes of total nitrogen (δ15NTN) for detecting changes in source of OM is limited in marginal depositional environments with frequent changes in lithology and OM contents.  相似文献   

13.
Hydrocarbon distributions and stable isotope ratios of carbonates (δ13Ccar, δ18Ocar), kerogen (δ13Cker), extractable organic matter (δ13CEOM) and individual hydrocarbons of Liassic black shale samples from a prograde metamorphic sequence in the Swiss Alps were used to identify the major organic reactions with increasing metamorphic grade. The studied samples range from the diagenetic zone (<100°C) to amphibolite facies (∼550°C). The samples within the diagenetic zones (<100 and 150°C) are characterized by the dominance of C<20n-alkanes, suggesting an origin related with marine and/or bacterial inputs. The metamorphic samples (200 to 550°C) have distributions significantly dominated by C12 and C13n-alkanes, C14, C16 and C18n-alkylcyclopentanes and to a lesser extend C15, C17 and C21n-alkylcyclohexanes. The progressive 13C-enrichment (up to 3.9‰) with metamorphism of the C>17n-alkanes suggests the occurrence of cracking reactions of high molecular weight compounds. The isotopically heavier (up to 5.6‰) C<17n-alkanes in metamorphic samples are likely originated by thermal degradation of long-chain homologous with preferential release of isotopically light C1 and C2 radicals. The dominance of specific even C-number n-alkylcyclopentanes suggests an origin related to direct cyclization mechanism (without decarboxylation step) of algal or bacterial fatty acids occurring in reducing aqueous metamorphic fluid conditions. The regular increase of the concentrations of n-alkylcycloalkanes vs. C>13n-alkanes with metamorphism suggests progressive thermal release of kerogen-linked fatty acid precursors and degradation of n-alkanes. Changes of the steroid and terpenoid distributions are clearly related to increasing metamorphic temperatures. The absence of 18α(H)-22,29,30-trisnorneohopane (Ts), the occurrence of 17β(H)-trisnorhopane, 17β(H), 21α(H)-hopanes in the C29 to C31 range and 5α(H),14α(H),17α(H)-20R C27, C29 steranes in the low diagenetic samples (<100°C) are characteristic of immature bitumens. The higher thermal stress within the upper diagenetic zone (150°C) is marked by the presence of Ts, the disappearance of 17β(H)-trisnorhopane and thermodynamic equilibrium of the 22S/(22S + 22R) homohopane ratios. The increase of the ααα-sterane 20S/(20S + 20R) and 20R ββ/(ββ + αα) ratios (from 0.0 to 0.55 and from 0.0 to 0.40, respectively) in the upper diagenetic zone indicates the occurrence of isomerization reactions already at <150°C. However, the isomerization at C-20 (R → S) reaches thermodynamic equilibrium values already at the upper diagenesis (∼150°C) whereas the epimerisation at C-14 and C-17 (αα → ββ) arrives to constant values in the lower anchizone (∼200°C). The ratios Ts vs. 17α(H)-22,29,30-trisnorneohopane [(Ts/(Ts + Tm)] and 18α(H)-30-norneohopane (C29Ts) vs. 17α(H),21β(H)-30-norhopane [C29Ts/(C29Ts + C29)] increase until the medium anchizone (200 to 250°C) from 0.0 to 0.96 and from 0.0 to 0.44, respectively. An opposite trend towards lower values is observed in the higher metamorphic samples.The occurrence of specific hydrocarbons (e.g., n-alkylcyclopentanes, cadalene, hydrogenated aromatic compounds) in metamorphic samples points to kerogen degradation reactions most probably occurring in the presence of water and under reducing conditions. The changes of hydrocarbon distributions and carbon isotopic compositions of n-alkanes related to metamorphism suggest that the organic geochemistry may help to evaluate the lowest grades of prograde metamorphism.  相似文献   

14.
Biogeochemical processes involving acetate in sub-seafloor sediments from piston core PC23B from the Bering Sea shelf break were inferred by examining the stable carbon isotopic relationships between acetate and other relevant carbon compounds: total organic carbon (TOC) in the sediment solid phase, and dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC) in pore water. Throughout the core, the isotopic composition of acetate (δ13Cacetate), from −31‰ to −29‰, was 13C-depleted by ca. 7‰ vs. DOC (δ13CDOC) and its depth profile approximately paralleled that of δ13CDOC, suggesting that the principal process producing acetate was fermentation of dissolved organic compounds. However, the 13C depletion in δ13Cacetate indicates some contribution of acetogenesis to total acetate production, because acetogenesis results in 13C depletion of the acetate produced. The relative contribution of acetogenesis via the H2/CO2 reaction, calculated by using a two source isotope mixing model, increased with depth in the sulfate reduction zone from 10% to 15% and was constant at 19% in the methanogenic zone. The acetogenic contribution to acetate production in the methanogenic zone underlying the sulfate reduction zone is consistent with reported observations, whereas the occurrence of acetogenesis in the sulfate reduction zone may be related to the contribution of terrestrial organic matter (OM) to the sedimentary OM in that depth interval, because the terrestrial component likely includes precursors that favor organoautotrophic acetogenesis. The high acetate concentration (up to 81 μM) and TOC content (up to 1.4%) at the same depth (<200 cmbsf) suggest that some relationship exists between acetate production rate and TOC content, or that a temperature increase during core storage at room temperature might stimulate acetate-producing microbial activity in the high TOC sediment.  相似文献   

15.
The Upper Triassic Xujiahe Formation in the Sichuan Basin, SW China consists of a series of coal measures. The first, third and fifth members of this formation are dominated by gas prone dark mudstones and coals. The mudstones contain Type II and III kerogens with average organic carbon contents around 1.96%. These source rocks are mature in the central Sichuan and highly mature in the western Sichuan Basin, characterized by gas generation with subordinate amounts of light oil or condensate oils. The source rocks are intercalated with the sandstone dominated second, fourth and sixth members of the Xujiahe Formation, thus leading to three separate self contained petroleum systems in the region. The proven gas reserves in the Xujiahe Formation are only less than that of the Triassic Feixianguan Formation and the Xujiahe Formation has the second largest gas field (Guang’an gas field) in the basin. Gases derived from the Xujiahe Formation coals generally show a normal stable carbon isotopic trend for C1–C4 n-alkanes, with the highest δ13C2 values among the nine gas pay zones in the basin (?20.7‰ to ?28.3‰), and δ13C1 values as low as ?43.0‰ in the central Sichuan. Gas accumulations with an oil leg have also been found in the eastern and southern Sichuan where the thickness of the Xujiahe Formation is significantly reduced. Gases in these accumulations tend to show low δ13C2 values (?30.0‰ to ?36.3‰), characteristic of oil prone source rocks.  相似文献   

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

17.
《Organic Geochemistry》2012,42(12):1277-1284
Compound-specific isotope measurements of organic compounds are increasingly important in palaeoclimate reconstruction. Searching for more accurate peat-based palaeoenvironmental proxies, compound-specific fractionation of stable C, H and O isotopes of organic compounds synthesized by Sphagnum were determined in a greenhouse study. Three Sphagnum species were grown under controlled climate conditions. Stable isotope ratios of cellulose, bulk organic matter (OM) and C21–C25 n-alkanes were measured to explore whether fractionation in Sphagnum is species-specific, as a result of either environmental conditions or genetic variation. The oxygen isotopic composition (δ18O) of cellulose was equal for all species and all treatments. The hydrogen isotopic composition (δD) of the n-alkanes displayed an unexpected variation among the species, with values between −154‰ for Sphagnum rubellum and −184‰ for Sphagnum fallax for the C23 n-alkane, irrespective of groundwater level. The stable carbon isotopic composition (δ13C) of the latter also showed a species-specific pattern. The pattern was similar for the carbon isotope fractionation of bulk OM, although the C23 n-alkane was >10‰ more depleted than the bulk OM. The variation in H fractionation may originate in the lipid biosynthesis, whereas C fractionation is also related to humidity conditions. Our findings clearly emphasize the importance of species identification in palaeoclimate studies based on stable isotopes from peat cores.  相似文献   

18.
The distribution of aromatic hydrocarbons and stable carbon isotope ratios of organic matter in a series of nine Miocene Embalut coal samples obtained from nine coal seams of Kutai Basin, East Kalimantan, Indonesia were studied. The rank of the Embalut coals ranged from lignites to low rank sub-bituminous coals (0.36–0.50% Rr), based on measurements of huminite reflectance. The aromatic hydrocarbon fractions of all coal samples were dominated by cadalene in the lower boiling point range and picene derivatives in the higher boiling point range of the gas chromatograms. Cadalene can be attributed to the contribution of Dipterocarpaceae and various hydrated picenes to the contribution of additional angiosperms to the coal forming vegetation. The picenes originate from alpha- and beta-amyrin. However, in some coal samples minor amounts of simonellite and retene were also detected which argues for an additional contribution of gymnosperms (conifers) to coal forming vegetation preferentially in the Middle Miocene and at the beginning of the Late Miocene. The results of stable carbon isotope ratios (δ13C) in most of the coal samples are consistent with their origin from angiosperms (δ13C between ?27.0‰ and ?28.0‰). During the Miocene the climate of Mahakam Delta was not uniformly moist and cooler than the present day climate. This would have been favourable for the growth of conifers, especially in the montane forests. The contribution of conifers to the Embalut coals might be a result of the cool Middle/Late Miocene climate during peat accumulation in the Kutai Basin.  相似文献   

19.
Carbon isotopic fractionation during the air/sea exchange process is not fully understood at present. Information on the equilibrium and kinetic fractionation factors is an essential requirement, together with the value of the CO2 partial pressure, for understanding the carbon cycle in the atmosphere and marine environments. Using a specially designed countercurrent equilibrator system, the fractionation factors between gaseous CO2 and dissolved inorganic carbon in sea water were determined under both kinetic and equilibrium conditions. The following results were obtained: kinetic fractionation factor for air to sea (αas) is 0.998 at 288.2 K; kinetic fractionation factor for sea to air (αsa) is 0.990; equilibrium fractionation factor (αeq) is 0.991 at pH = 8.3 and 288.2 K. From these results, the carbon isotopic ratio of CO2 passed through the air/ sea interface is estimated to be about ?10 %. for air to sea and ?8 %. for sea to air when CO2 exchange takes place between air (δ13C = ?8 %.) and surface sea water (δ13C = 2 %.) at 288.2 K.  相似文献   

20.
《Geochimica et cosmochimica acta》1999,63(23-24):3959-3966
We propose that organic compounds found in a Miocene limestone from Marmorito (Northern Italy) are source markers for organic matter present in ancient methane vent systems (cold seeps). The limestone contains high concentrations of the tail-to-tail linked, acyclic C20 isoprenoid 2,6,11,15-tetramethylhexadecane (crocetane), a C25 homolog 2,6,10,15,19-pentamethylicosane (PME), and a distinctive glycerol ether lipid containing 3,7,11,15-tetramethylhexadecyl (phytanyl-) moieties. The chemical structures of these biomarkers indicate a common origin from archaea. Their extremely 13C-depleted isotope compositions (δ13C ≈ −108 to −115.6‰ PDB) suggest that the respective archaea have directly or indirectly introduced isotopically depleted, methane-derived carbon into their biomass. We postulate that a second major cluster of biomarkers showing heavier isotope values (δ13C ≈ −88‰) is derived from sulfate-reducing bacteria (SRB). The observed biomarkers sustain the idea that methanogenic bacteria, in a syntrophic community with SRB, are responsible for the anaerobic oxidation of methane in marine sediments. Marmorito may thus represent a conceivable ancient scenario for methane consumption performed by a defined, two-membered bacterial consortium: (1) archaea that perform reversed methanogenesis by oxidizing methane and producing CO2 and H2; and (2) SRB that consume the resulting H2. Furthermore, the respective organic molecules are, unlike other compounds, tightly bound to the crystalline carbonate phase. The Marmorito carbonates can thus be regarded as “cold seep microbialites” rather than mere “authigenic” carbonates.  相似文献   

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