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1.
Rice fields are an important source for the greenhouse gas methane produced by acetoclastic and hydrogenotrophic methanogenesis. Fractionation of 13C/12C can in principle be used to quantify the relative contribution of these pathways, but our knowledge of isotopic fractionation during reduction of CO2 and turnover of acetate in different methanogenic environments is still scarce. We therefore measured δ13C signatures in two types of anoxic Italian rice field soils, one with high and one with low degradable organic matter (OM) content. Both soils were incubated in the presence and absence of methyl fluoride, a specific inhibitor of acetoclastic methanogenesis. Optimization of methyl fluoride concentration resulted in complete inhibition of acetoclastic methanogenesis. CH4 was then exclusively produced by hydrogenotrophic methanogenesis, allowing determination of the isotopic signatures and fractionation factors specific for this methanogenic pathway. Acetate, which was then no longer consumed, accumulated and was used for determination of the isotopic signature of the fermentatively produced acetate (both total acetate and methyl carbon of acetate). Hence, all isotopic signatures, including fractionation factors were determined for the methanogenic soil. These data, were then used for computation of the relative contribution of the two methanogenic pathways. In the high OM soil, the contribution of acetoclastic methanogenesis to total CH4 production increased simultaneously with decreasing acetate concentration. In the low OM soil, methanogenesis from H2/CO2 was clearly greater than theoretically expected. Furthermore, isotope fractionation of hydrogenotrophic methanogenesis indicated that the in situ energy status of methanogens strongly depended on the availability of organic carbon in the rice field soil system. Collectively, our data show that the study of isotopic fractionation in methanogenic environments allows a deeper insight into the ongoing processes, which may be quite different in the same ecosystem with different content of degradable OM.  相似文献   

2.
A unique dataset from paired low- and high-temperature vents at 9°50′N East Pacific Rise provides insight into the microbiological activity in low-temperature diffuse fluids. The stable carbon isotopic composition of CH4 and CO2 in 9°50′N hydrothermal fluids indicates microbial methane production, perhaps coupled with microbial methane consumption. Diffuse fluids are depleted in 13C by ∼10‰ in values of δ13C of CH4, and by ∼0.55‰ in values of δ13C of CO2, relative to the values of the high-temperature source fluid (δ13C of CH4 =−20.1 ± 1.2‰, δ13C of CO2 =−4.08 ± 0.15‰). Mixing of seawater or thermogenic sources cannot account for the depletions in 13C of both CH4 and CO2 at diffuse vents relative to adjacent high-temperature vents. The substrate utilization and 13C fractionation associated with the microbiological processes of methanogenesis and methane oxidation can explain observed steady-state CH4 and CO2 concentrations and carbon isotopic compositions. A mass-isotope numerical box model of these paired vent systems is consistent with the hypothesis that microbial methane cycling is active at diffuse vents at 9°50′N. The detectable 13C modification of fluid geochemistry by microbial metabolisms may provide a useful tool for detecting active methanogenesis.  相似文献   

3.
Ocean drilling has revealed the existence of vast microbial populations in the deep subseafloor, but to date little is known about their metabolic activities. To better understand the biogeochemical processes in the deep biosphere, we investigate the stable carbon isotope chemistry of acetate and other carbon-bearing metabolites in sediment pore-waters. Acetate is a key metabolite in the cycling of carbon in anoxic sediments. Its stable carbon isotopic composition provides information on the metabolic processes dominating acetate turnover in situ. This study reports our findings for a methane-rich site at the northern Cascadia Margin (NE Pacific) where Expedition 311 of the Integrated Ocean Drilling Program (IODP) sampled the upper 190 m of sediment. At Site U1329, δ13C values of acetate span a wide range from −46.0‰ to −11.0‰ vs. VPDB and change systematically with sediment depth. In contrast, δ13C values of both the bulk dissolved organic carbon (DOC) (−21.6 ± 1.3‰ vs. VPDB) and the low-molecular-weight compound lactate (−20.9 ± 1.8‰ vs. VPDB) show little variability. These species are interpreted to represent the carbon isotopic composition of fermentation products. Relative to DOC, acetate is up to 23.1‰ depleted and up to 9.1‰ enriched in 13C. Broadly, 13C-depletions of acetate relative to DOC indicate flux of carbon from acetogenesis into the acetate pool while 13C-enrichments of pore-water acetate relative to DOC suggest consumption of acetate by acetoclastic methanogenesis. Isotopic relationships between acetate and lactate or DOC provide new information on the carbon flow and the presence and activity of specific functional microbial communities in distinct biogeochemical horizons of the sediment. In particular, they suggest that acetogenic CO2-reduction can coexist with methanogenic CO2-reduction, a notion contrary to the hypothesis that hydrogen levels are controlled by the thermodynamically most favorable electron-accepting process. Further, the isotopic relationship suggests a relative increase in acetate flow to acetoclastic methanogenesis with depth although its contribution to total methanogenesis is probably small. Our study demonstrates how the stable carbon isotope biogeochemistry of acetate can be used to identify pathways of microbial carbon turnover in subsurface environments. Our observations also raise new questions regarding the factors controlling acetate turnover in marine sediments.  相似文献   

4.
Production of CH4 and CO2 was quantified in anoxically incubated soil samples taken from an Italian rice field. The rates increased with temperature between 10 and 37°C. The δ13C of the accumulated CO2, CH4 and acetate changed with time in a systematic way. The data were used in mass balance equations to constrain isotopic fractionation factors and pathways of CH4 production. The calculations were further constrained by the determination of 14CH4 production from 14CO2 at steady state. At 50°C, CH4 was exclusively produced from CO2, indicating a fractionation factor of αCO2/CH4 = 1.073. Between 10 and 37°C, the results showed a temporal change in the methanogenic pathway. A relatively high (40-60%) CO2-derived fraction of CH4 production in the beginning was followed by a phase in which contribution of CO2-derived CH4 decreased to low (<15%) values, and ultimately by the steady state phase in which values increased to <40% (the theoretically expected value). The rate of change from one phase to the next increased with temperature. Incubation temperature had a strong effect on the overall fractionation of 13C during the formation and consumption of acetate, with stronger fractionation at low than at high temperature. The results further showed that, especially at low temperatures, fractionation occurred during acetate turnover and acetoclastic methanogenesis, despite the fact that steady-state conditions caused (apparent) substrate-limitation.  相似文献   

5.
Rates of anaerobic respiration are of central importance for the long-term burial of carbon (C) in peatlands, which are a relevant sink in the global C cycle. To identify constraints on anaerobic peat decomposition, we determined detailed concentration depth profiles of decomposition end-products, i.e. methane (CH4) and dissolved inorganic carbon (DIC), along with concentrations of relevant decomposition intermediates at an ombrotrophic Canadian peat bog. The magnitude of in situ net production rates of DIC and CH4 was estimated by inverse pore-water modeling. Vertical transport in the peat was slow and dominated by diffusion leading to the buildup of DIC and CH4 with depth (5500 μmol L−1 DIC, 500 μmol L−1 CH4). Highest DIC and CH4 production rates occurred close to the water table (decomposition constant kd ∼ 10−3-10−4 a−1) or in some distinct zones at depth (kd ∼ 10−4 a−1). Deeper into the peat, decomposition proceeded very slowly at about kd = 10−7 a−1. This pattern could be related to thermodynamic and transport constraints. The accumulation of metabolic end-products diminished in situ energy yields of acetoclastic methanogenesis to the threshold for microbially mediated processes (−20 to −25 kJ mol−1 CH4). The methanogenic precursor acetate also accumulated (150 μmol L−1). In line with these findings, CH4 was formed by hydrogenotrophic methanogenesis at Gibbs free energies of −35 to −40 kJ mol−1 CH4. This was indicated by an isotopic fractionation αCO2-CH4 of 1.069-1.079. Fermentative degradation of acetate, propionate and butyrate attained Gibbs free energies close to 0 kJ mol−1 substrate. Although methanogenesis was apparently limited by some other factor in some peat layers, transport and thermodynamic constraints likely impeded respiratory processes in the deeper peat. Constraints on the removal of DIC and CH4 may thus slow decomposition and contribute to the sustained burial of C in northern peatlands.  相似文献   

6.
Methane concentration [CH4] and stable isotope ratio values (δ13C) characterize methanogenic and methanotrophic processes within two contrasting peatland ecosystems of the Fluxnet Canada Research Network: (i) a western Canada peatland fen in northern Alberta (Fen) and (ii) an eastern Canada peatland bog in southeastern Ontario (Bog). We use carbon isotope ratio discrimination of produced methane (δ13CCH4) from the precursor carbon compounds (δ13CpreC) to estimate the relative proportions of archaebacterial acetoclastic methanogenesis (AM) and hydrogenotrophic carbonate reduction methanogenesis (HM) in these terrestrial ecosystems. The [CH4] and δ13CCH4 signatures describe contrasts in the methanogenic and methanotrophic processes between the Fen and the Bog. The differences are substantiated by stable hydrogen isotope ratio (δD) separation between the dissolved δDCH4 and co-existing δDH2O. Methanogenesis at the Fen is dominated by AM, in contrast to the Bog, which is essentially HM. We suggest that this is potentially a result of differences in type/quality of organic substrates. The trajectory of 13C enrichment in δ13CCH4 values with depth at the Bog reflects a closed system, substrate depletion effect. Our Rayleigh distillation model estimates 58-76% depletion in the source dissolved inorganic carbon (DIC).  相似文献   

7.
In this study, the geochemistry and origin of natural gas and formation waters in Devonian age organic-rich shales and reservoir sandstones across the northern Appalachian Basin margin (western New York, eastern Ohio, northwestern Pennsylvania, and eastern Kentucky) were investigated. Additional samples were collected from Mississippian Berea Sandstone, Silurian Medina Sandstone and Ordovician Trenton/Black River Group oil and gas wells for comparison. Dissolved gases in shallow groundwaters in Devonian organic-rich shales along Lake Erie contain detectable CH4 (0.01–50.55 mol%) with low δ13C–CH4 values (−74.68 to −57.86‰) and no higher chain hydrocarbons, characteristics typical of microbial gas. Nevertheless, these groundwaters have only moderate alkalinity (1.14–8.72 meq/kg) and relatively low δ13C values of dissolved inorganic C (DIC) (−24.8 to −0.6‰), suggesting that microbial methanogenesis is limited. The majority of natural gases in Devonian organic-rich shales and sandstones at depth (>168 m) in the northern Appalachian Basin have a low CH4 to ethane and propane ratios (3–35 mol%; C1/C2 + C3) and high δ13C and δD values of CH4 (−53.35 to −40.24‰, and −315.0 to −174.6‰, respectively), which increase in depth, reservoir age and thermal maturity; the molecular and isotopic signature of these gases show that CH4 was generated via thermogenic processes. Despite this, the geochemistry of co-produced brines shows evidence for microbial activity. High δ13C values of DIC (>+10‰), slightly elevated alkalinity (up to 12.01 meq/kg) and low SO4 values (<1 mmole/L) in select Devonian organic-rich shale and sandstone formation water samples suggest the presence of methanogenesis, while low δ13C–DIC values (<−22‰) and relatively high SO4 concentrations (up to 12.31 mmole/L) in many brine samples point to SO4 reduction, which likely limits microbial CH4 generation in the Appalachian Basin. Together the formation water and gas results suggest that the vast majority of CH4 in the Devonian organic-rich shales and sandstones across the northern Appalachian Basin margin is thermogenic in origin. Small accumulations of microbial CH4 are present at shallow depths along Lake Erie and in western NY.  相似文献   

8.
In many anoxic environments propionate is, after acetate, the second most important fermentation product, being degraded further to finally result in CH4 production. In principle, isotope discrimination can be used to assess the path of organic matter degradation to acetate, CO2 and CH4. However, nothing is known about the isotope fractionation in primary and secondary fermentation steps involving propionate, although it is an important precursor of acetate. We therefore studied the degradation of propionate with a syntrophic coculture of Syntrophobacter fumaroxidans and Methanobacterium formicicum. The isotope enrichment factor for propionate degradation to acetate, CO2 and CH4 was almost negligible (εprop 0.9‰). The fermentative production of propionate was studied in cultures with Opitutus terrae growing on pectin, xylan and starch. These polysaccharides were fermented to acetate, succinate, propionate, H2 and CO2. While the δ13C value of the initially produced propionate was similar to that of the organic substrates (ca. −28 to −25‰), the δ13C value of the other fermentation products was higher. The δ13C values of all products generally decreased during the course of fermentation. Finally, a small depletion in 13C (ca. 6‰) with respect to the organic substrate was observed for propionate, while the other fermentation products where slightly enriched. Overall, stable carbon isotope discrimination was small during both fermentative production and consumption of propionate in the anaerobic microbial cultures, so that propionate turnover probably only marginally affects isotope fractionation during anaerobic degradation of organic matter.  相似文献   

9.
Vertical profiles of concentration and C-isotopic composition of dissolved methane and carbon dioxide were observed over 26 months in the catotelm of a deep (6.5 m) peat bog in Switzerland. The dissolved concentrations of these gases increase with depth while CO2 predominates over CH4 (CO2 ca. 5 times CH4). This pattern can be reproduced by a reaction-advection-ebullition model, where CO2 and CH4 are formed in a ratio of 1:1. The less soluble methane is preferentially lost via outgassing (bubbles). The isotopic fractionation between CO2 and CH4 also increases with depth, with αC values ranging from 1.045 to 1.075. The isotopic composition of the gases traces the passage of respiration-derived CO2 (from the near surface) through a shallow zone with methanogenesis of low isotopic fractionation (splitting of fermentation-derived acetate). This solution then moves through the catotelm, where methanogenesis occurs by CO2 reduction (large isotopic fractionation). In the upper part of the catotelm the C-13-depleted respiration-derived CO2 pool buffers the isotopic composition of CO2; the δ13C of CO2 increases only slowly. At the same time strongly depleted CH4 is formed as CO2 reduction consumes the depleted CO2. In the lower part of the catotelm, the respiration-derived CO2 and shallow CH4 become less important and CO2 reduction is the dominant source of CO2 and CH4. Now, the δ13C values of both gases increase until equilibrium is reached with respect to the isotopic composition of the substrate. Thus, the δ13C values of methane reach a minimum at intermediate depth, and the deep methane has δ13C values comparable to shallow methane. A simple mixing model for the isotopic evolution is suggested. Only minor changes of the observed patterns of methanogenesis (in terms of concentration and isotopic composition) occur over the seasons. The most pronounced of these is a slightly higher rate of acetate splitting in spring.  相似文献   

10.
Aqueous alteration of primitive meteorites was among the earliest geological processes during the evolution of our solar system. ‘Clumped-isotope’ thermometry of carbonates in the CM chondrites, Cold Bokkeveld, Murray, and Murchison, demonstrates that they underwent aqueous alteration at 20-71 °C from a fluid with δ18OVSMOW of 2.0‰ to 8.1‰ and δ17OVSMOW of −0.1‰ to 3.0‰. The δ13CVPDB values of these carbonates exhibit a negative correlation with the δ18OVSMOW of their formation waters, consistent with formation and escape of 13C-depleted CH4 during aqueous alteration. Methane generation under these conditions implies that the alteration fluid was characterized by an Eh ? −0.67 and pH ? 12.5 (or lower at the highest alteration temperatures). Our findings suggest that methane generation may have been a widespread consequence of planetesimal and planetary aqueous alteration, perhaps explaining the occurrence of methane on Titan, Triton, Pluto, and other Kuiper-belt objects.  相似文献   

11.
Stable carbon isotopes of organic matter and fossilized plant remains can be used to effectively reconstruct local palaeoclimate changes, especially from plants using a single photosynthetic mode. The charred grains of foxtail and common millet are chemically stable in the environment and have been preserved widely and continuously throughout the Holocene in North China. The charred remains of these species are ideal materials for reconstructing the palaeoclimate based on δ13C of foxtail and common millets heated to temperatures up to around 250 °C. This study reports δ13C values of modern millets carbonized at different temperatures. The results indicate that there are no significant changes in δ13C of intact and charred samples of foxtail millet (?0.46‰) and common millet (?0.49‰) for temperatures below 300 °C. The δ13C of charred foxtail millet formed at 250 °C were 0.2‰ higher in δ13C than the source samples. In contrast, the δ13C of charred common millet formed at 250 °C were 0.2‰ lighter in δ13C than the source samples. The δ13C values of grains were determined in part by the carbon content (i.e., starches, lignins and lipids) and the variable thermal tolerances of these compounds to heating. However, the observed 13C carbonization associated with fractionation of only 0.2‰ in grains is much less than the natural variation typically found in wood. We therefore suggest that δ13C measured in carbonized grains can serve as an effective indicator for paleoenvironmental and archaeological reconstructions.  相似文献   

12.
Fossils of megaherbivores from eight late Pleistocene 14C- and OSL-dated doline infillings of Ajoie (NW Switzerland) were discovered along the Transjurane highway in the Swiss Jura. Carbon and oxygen analyses of enamel were performed on forty-six teeth of large mammals (Equus germanicus, Mammuthus primigenius, Coelodonta antiquitatis, and Bison priscus), coming from one doline in Boncourt (~ 80 ka, marine oxygen isotope stage MIS5a) and seven in Courtedoux (51–27 ka, late MIS3), in order to reconstruct the paleoclimatic and paleoenvironmental conditions of the region. Similar enamel δ13C values for both periods, ranging from − 14.5 to − 9.2‰, indicate that the megaherbivores lived in a C3 plant-dominated environment. Enamel δ18OPO4 values range from 10.9 to 16.3‰ with a mean of 13.5 ± 1.0‰ (n = 46). Mean air temperatures (MATs) were inferred using species-specific δ18OPO4–δ18OH2O-calibrations for modern mammals and a present-day precipitation δ18OH2O-MAT relation for Switzerland. Similar average MATs of 6.6 ± 3.6°C for the deposits dated to ~ 80 ka and 6.5 ± 3.3°C for those dated to the interval 51–27 ka were estimated. This suggests that these mammals in the Ajoie area lived in mild periods of the late Pleistocene with MATs only about 2.5°C lower than modern-day temperatures.  相似文献   

13.
Stable isotopes (H, O, C) were determined for ground and surface waters collected from two relatively undisturbed massive sulfide deposits (Halfmile Lake and Restigouche) in the Bathurst Mining Camp (BMC), New Brunswick, Canada. Additional waters from active and inactive mines in the BMC were also collected. Oxygen and hydrogen isotopes of surface and shallow groundwaters from both the Halfmile Lake and Restigouche deposits are remarkably uniform (− 13 to − 14‰ and − 85 to − 95‰ for δ18OVSMOW and δ2HVSMOW, respectively). These values are lighter than predicted for northern New Brunswick and, combined with elevated deuterium excess values, suggest that recharge waters are dominated by winter precipitation, recharged during spring melting. Deeper groundwaters from the Restigouche deposit, and from active and inactive mines have heavier δ18OVSMOW ratios (up to − 10.8‰) than shallow groundwaters suggesting recharge under warmer climate or mixing with Shield-type brines. Some of the co-variation in Cl concentrations and δ18OVSMOW ratios can be explained by mixing between saline and shallow recharge water end-members. Carbon isotopic compositions of dissolved inorganic carbon (DIC) are variable, ranging from − 15 to − 5‰ δ13CVPDB for most ground and surface waters. Much of the variation in the carbon isotopes is consistent with closed system groundwater evolution involving soil zone CO2 and fracture zone carbonate minerals (calcite, dolomite and siderite; average = − 6.5‰ δ13CVPDB). The DIC of saline Restigouche deposit groundwater is isotopically heavy (∼+ 12‰ δ13CVPDB), indicating carbon isotopic fractionation from methanogenesis via CO2 reduction, consistent with the lack of dissolved sulfate in these waters and the observation of CH4-degassing during sampling.  相似文献   

14.
Goethite (Ax-2) from Axel Heiberg Island (∼80°N) on the margin of the Arctic Ocean is the dominant mineral in a sample of “petrified” Eocene wood, but U, Th, and He measurements suggest that the goethite (α-FeOOH) crystallized in the latest Miocene/Pliocene (ca. 5.5 to 2.8 Ma). Measured δD and δ18O values of Ax-2 are −221 (±6)‰ and −9.6 (±0.5)‰, respectively. The inferred δD and δ18O values of the ancient water were about −139‰ and −18.6‰, respectively, with a calculated temperature of crystallization of 3 (±5)°C, which compares with the modern summer (J-J-A) temperature of 3 °C and contrasts with a modern MAT of −19 °C. Published results from various biological proxies on nearby Ellesmere Island indicate a Pliocene (∼4 Ma) MAT of either −6 or −0.4 °C and corresponding seasonal amplitudes of about 18 or 13 °C. A conductive heat flow model suggests that a temperature of 3 °C could represent goethite crystallization at depths of ∼100-200 cm (for MAT = −6 °C) or ∼250-450 cm (for MAT = −0.4 °C) over seasonally restricted intervals of time.The δ18O value of the Ax-2 water (−18.6‰) is more positive than the modern J-J-A precipitation (−22‰). In combination, the paleotemperatures and δ18O values of ancient waters (from Ax-2 and published results from three Eocene or Pliocene proxy sites on Axel Heiberg and Ellesmere Islands) are consistent with a warm season bias in those isotopic proxies. The results are also consistent with higher proportions of J-J-A precipitation in the annual total. If so, this emphasizes the importance of seasonality at high latitudes even in times of warmer global climates, and suggests that the Arctic hydrologic cycle, as expressed in the seasonal distribution and isotopic composition of precipitation (perhaps modified by a warmer Arctic Ocean), differed from modern.The δ13C value of the Fe(CO3)OH component in the Ax-2 goethite is +6.6‰, which is much more positive than expected if crystallizing goethite incorporated CO2 derived primarily from oxidation of relict Eocene wood with δ13C values of about −24‰. This apparent paradox may be resolved if the goethite is a product of oxidation of 13C-rich siderite, which had previously replaced wood in an Eocene methanogenic burial environment. Thus, the goethite retains a carbon isotope “memory” of a diagenetic Eocene event, but a δD and δ18O record of the latest Miocene/Pliocene Arctic climate.  相似文献   

15.
The yields and stable C and H isotopic composition of gaseous products from the reactions of pure n-C24 with (1) MgSO4; and (2) elemental S in sealed Au-tubes at a series of temperatures over the range 220–600 °C were monitored to better resolve the reaction mechanisms. Hydrogen sulfide formation from thermochemical sulfate reduction (TSR) of n-C24 with MgSO4 was initiated at 431 °C, coincident with the evolution of C2–C5 hydrocarbons. Whereas the yields of H2S increased progressively with pyrolysis temperature, the hydrocarbon yields decreased sharply above 490 °C due to subsequent S consumption. Ethane and propane were initially very 13C depleted, but became progressively heavier with pyrolysis temperature and were more 13C enriched than the values of a control treatment conducted on just n-C24 above 475 °C. TSR of MgSO4 also led to progressively higher concentrations of CO2 showing relatively low δ13C values, possibly due to input of isotopically light CO2 derived from gaseous hydrocarbon oxidation (e.g., more depleted CH4).  相似文献   

16.
Gas was sampled regionally, including by drilling into faults, in the South Kanto gas-field around Tokyo Bay, Japan. Gas samples were collected from cores in a gas sampling container immediately after drilling. A value of δ13C1 = −44.3‰ was obtained for gas in the container and δ13C1 = −36.3‰ for seeping gas in a fault zone. However, typical CH4 in this dissolved-in-water gas-field is mainly depleted in 13C, and δ13C1 values range from −66‰ to −68‰ owing to microbial degradation of organic material. 13C-rich CH4 is so far uncommon in the South Kanto gas-field. Seepages were observed from the surface along the north–south fault zone. The natural gas is stored below the sandstone layer by impermeable mudstone underlying the boundary at a depth of 30 m. Gas seepages were not observed below a depth of 40 m. Gas rises along the fault zone dissolved-in-groundwater up to the shallow region and then separates from the groundwater. 13C-rich CH4 (adsorbed CH4) was found to have desorbed from drilled mudstone core samples taken at depths of 1400–1900 m in the main gas-production strata. Similarly, 13C-rich CH4 was found in black shale overlying the oceanic crust forming part of a sedimentary accretionary prism underling the Tokyo region. It also appears in the spring-water of spa wells, originating at a depth of 1200–1500 m along a tectonic line. Methane generated by microbial degradation of organic material through CO2 reduction in the South Kanto gas-field mainly originates as biogenic gas mixed with a small amount of 13C-rich CH4, derived from thermogenic gas without oil components in strata. It is assumed that 12C-rich CH4 is easily detached from core or pore water through gas production, whereas 13C-rich CH4 is strongly adsorbed on the surfaces of particles. The 13C-rich CH4 rises along the major tectonic line or up the 50 m wide normal fault zone from relatively deep sources in the Kanto region.  相似文献   

17.
The objective of this paper is to build a general correction model that takes into account all the different radiocarbon-dilution reactions and resolving the processes that are geochemically “aging” the groundwater in the Neogene Aquifer. For this, δ13C and radiocarbon in groundwater are investigated with their relationship to other chemical components in groundwater. The δ13C values in the Neogene Aquifer are influenced by various geochemical reactions like calcite dissolution, oxidation of organic matter and methanogenesis. Calcite dissolution and CH4 production increase δ13C while the oxidation of organic matter decreases δ13C in the groundwater. The reactions that modify δ13C also influence the 14C activity. Due to the complex geochemical environment, existing correction models are not applicable to this situation. A correction model for initial 14C activity is formulated in which the different C sources that influence 14C activity are taken into account. It is observed that recent dissolved organic matter plays an important role in redox reactions. The corrected 14C ages lie between −0.792 and 6.425 ka representing the maximum age. If a part of the organic matter that oxidises is fossil, the determined age will represent an overestimated age.  相似文献   

18.
Hydrocarbon seepage is a surface expression where fluids mixed with sediments and hydrocarbons are expelled through fracture systems that potentially tap into gas–petroleum reservoirs. Hydrocarbons released from most seeps appear to be thermogenic on the basis of their relative abundance and isotopic composition. The potential for subsurface microbial processes modifying these geochemical fingerprints remains poorly constrained. In this study, microcosm incubations were conducted on mud slurries supplied with/without various methanogenic precursors at temperatures ranging from ambient conditions to 90 °C, in order to assess microbial CH4 formation in the subsurface beneath hydrocarbon seeps. The analyses indicated that CH4 production was positive at ?80 °C, regardless of whether or not or which precursors were added. However, the pattern of CH4 production rates varied with the precursor and temperature. In general, the optimum CH4 production from H2/CO2 and formate occurred over a wide range of temperatures (?40 °C), whereas that from acetate, methanol and methylamine was restricted to relatively lower temperatures (40–50 °C). The CH4 recoveries, together with the C isotopic compositions of CH4, further indicated that the quantities of CH4 produced could not completely account for the quantities of precursor consumed, suggesting that a complex metabolic network was involved in the transformation of the added precursor and organic C inherited from inoculated sediments. Microbial CH4 was estimated to constitute 7–61% of the CH4 observed using experimentally-derived apparent isotope fractionations as the end member compositions. This illustrates the possibility that microbial CH4 produced at shallower depths could quantitatively and isotopically alter deeply-sourced thermogenic CH4 in hydrocarbon seep environments.  相似文献   

19.
Active and inactive carbonate chimneys from the Lost City Hydrothermal Field contain up to 0.6% organic carbon with diverse lipid assemblages. The δ13C values of total organic carbon range from −21.5‰ vs. VPDB at an extinct carbonate chimney to −2.8‰ at a 70 °C, actively venting carbonate chimney. Samples collected at locations with total organic carbon with δ13C > −15‰ also contained high abundances of isoprenoidal and nonisoprenoidal diether lipids. Samples with TOC more depleted in 13C lacked or contained lower amounts of these diethers.Isoprenoidal diethers, including sn-2 hydroxyarchaeol, sn-3 hydroxyarchaeol, and putative dihydroxyarchaeol, are likely to derive from methanogenic archaea. These compounds have δ13C values ranging from −2.9 to +6.7‰ vs. VPDB. Nonisoprenoidal diethers and monoethers are presumably derived from bacteria, and have structures similar to those produced by sulfate-reducing bacteria in culture and at cold seeps. In samples that also contained abundant hydroxyarchaeols, these diethers have δ13C values between −11.8 and +3.6‰. In samples without abundant hydroxyarchaeols, the nonisoprenoidal diethers were typically more depleted in 13C, with δ13C as low as −28.7‰ in chimneys and −45‰ in fissures.The diethers at Lost City are probably derived from hydrogen-consuming methanogens and bacteria. High hydrogen concentrations favor methanogenesis over methanotrophy and allow the concurrent growth of methanogens and sulfate-reducing bacteria. The unusual enrichment of 13C in lipids can be attributed to nearly complete consumption of bioavailable carbon in vent fluids. Under carbon-limited conditions, the isotope effects that usually lead to 13C-depletion in organic material cannot be expressed. Consequently, metabolic products such as lipids and methane have δ13C values typical of abiotic carbon.  相似文献   

20.
The abundance of the doubly substituted CO2 isotopologue, 13C18O16O, in CO2 produced by phosphoric acid digestion of synthetic, inorganic calcite and natural, biogenic aragonite is proportional to the concentration of 13C-18O bonds in reactant carbonate, and the concentration of these bonds is a function of the temperature of carbonate growth. This proportionality can be described between 1 and 50 °C by the function: Δ47 = 0.0592 · 106 · T−2 − 0.02, where Δ47 is the enrichment, in per mil, of 13C18O16O in CO2 relative to the amount expected for a stochastic (random) distribution of isotopes among all CO2 isotopologues, and T is the temperature in Kelvin. This relationship can be used for a new kind of carbonate paleothermometry, where the temperature-dependent property of interest is the state of ordering of 13C and 18O in the carbonate lattice (i.e., bound together vs. separated into different CO32− units), and not the bulk δ18O or δ13C values. Current analytical methods limit precision of this thermometer to ca. ± 2 °C, 1σ. A key feature of this thermometer is that it is thermodynamically based, like the traditional carbonate-water paleothermometer, and so is suitable for interpolation and even modest extrapolation, yet is rigorously independent of the δ18O of water and δ13C of DIC from which carbonate grew. Thus, this technique can be applied to parts of the geological record where the stable isotope compositions of waters are unknown. Moreover, simultaneous determinations of Δ47 and δ18O for carbonates will constrain the δ18O of water from which they grew.  相似文献   

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