首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 734 毫秒
1.
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   

2.
High resolution δ13C and δ18O profiles recorded in precisely dated speleothems are widely used proxies for the climate of the past. Both δ13C and δ18O depend on several climate related effects including meteorological processes, processes occurring in the soil zone above the cave and isotope fractionation processes occurring in the solution layer on the stalagmite surface. Here we model the latter using a stalagmite isotope and growth model and determine the relationship between the stable isotope values in speleothem calcite and cave parameters, such as temperature, drip interval, water pCO2 and a mixing coefficient describing mixing processes between the solution layer and the impinging drop.The evolution of δ13C values is modelled as a Rayleigh distillation process and shows a pronounced dependence on the residence time of the solution on the stalagmite surface and the drip interval, respectively. The evolution of δ18O values, in contrast, is also influenced by buffering reactions between the bicarbonate in the solution and the drip water driving the δ18O value of the bicarbonate towards the value expected for equilibrium isotope fractionation between drip water and calcite. This attenuates the dependence of the δ18O values on drip interval. The temperature dependence of δ18O, however, is more pronounced than for δ13C and in a similar range as expected for fractionation under equilibrium conditions.We also investigate the isotopic enrichment of the δ13C and δ18O values along individual growth layers and, thus, the slopes expected for Hendy tests. The results show that a positive Hendy test is only possible if isotope fractionation occurred under disequilibrium conditions. However, a negative Hendy test does not exclude that isotope fractionation occurred under disequilibrium conditions. A more reliable indicator for disequilibrium fractionation is the enrichment of the δ13C values along an individual growth layer.  相似文献   

3.
《Applied Geochemistry》2005,20(4):713-725
Stable isotope characterization of porewater, and dissolved species, in mudrocks and argillaceous rocks is notoriously difficult. Techniques based on physical or chemical extraction of porewater can generate significant analytical artefacts. The authors report a novel, simple approach to determine the δ18O of porewater and δ13C of dissolved C in argillites. The method uses core samples placed in specifically-designed outgassing cells, sealed shortly after drilling and stored in well-controlled conditions. After 1–2 months, CO2 naturally outgassed by argillite porewater is collected, purified and analyzed for C and O isotopes. Porewater δ18O and dissolved C δ13C are calculated from CO2 isotope data using appropriate fractionation factors. This methodology was successfully applied to the Callovo-Oxfordian argillites from Bure (eastern Paris Basin, France) and the Opalinus Clay formation from Mont Terri (Switzerland). In both clay formations, results indicate that porewater is meteoric and dissolved C is of marine origin. The main advantage of the approach is that it does not induce any major physical or chemical disturbance to the clay–water system investigated. Further testing on argillaceous rocks of variable composition and organic content is needed to assess extent of applicability.  相似文献   

4.
The chemistry and isotope ratios of He, C (δ13C) and H (δD) of free gases collected in the San Vittorino plain, an intramontane depression of tectonic origin, were determined to shed light on mantle degassing in central Italy. The C isotopic composition of CO2 (δ13C–CO2 −2.0‰ to −3.8‰) and He isotope ratios (R/RA 0.12–0.27) were used to calculate the fraction of CO2 originating from mantle degassing vs. sedimentary sources. The results show that CO2 predominantly (average of 75%) derives from the thermo-metamorphic reaction of limestone. Between 6% and 22% of the CO2 in the samples derives from organic-rich sedimentary sources. The mantle source accounts for 0–6% of the total CO2; however, in two samples, located in proximity to the most important faults of the plain, the mantle accounts for 24% and 42%. The presence of faults and fractures allows upward gas migration from a deep source to the Earth’s surface, not only in the peri-Tyrrhenian sector, as generally reported by studies on natural gas emissions in central Italy, but also in the pre-Apennine and Apennine belts. Isotope ratios of CH4 (δ13C–CH4 −6.1‰ to −22.7‰; δD–CH4 −9‰ to −129‰) show that CH4 does not appear to be related to mantle or magma degassing, but it is the product of thermal degradation of organic matter (i.e. thermogenic origin) and/or the reduction of CO2 (i.e. geothermal origin). Most of the samples appear to be affected by secondary microbial oxidation processes.  相似文献   

5.
The stable carbon isotope compositions and the stomatal parameters (stomatal density and stomatal index) of four Cheirolepidiaceae species, Brachyphyllum ningxiaensis, Brachyphyllum obtusum, Pseudofrenelopsis dalatzensis and Pseudofrenelopsis gansuensis, were analyzed to recover the late Early Cretaceous atmospheric CO2 levels. The fossil plants were collected from 5 consecutive sedimentary members of the uppermost Zhonggou Formation. Based on the stomatal data, the estimated palaeo-atmospheric CO2 concentrations in the Jiuquan Basin during the late Early Cretaceous were 1060–882 ppmv based on the carboniferous standardization and were 641–531 ppmv based on the recent standardization; the pCO2 values present at first a decreasing and then an increasing trend within the sedimentary time of the five members. The δ13Cp values based on the 21 Brachyphyllum specimens showed a large variation, which ranged from −20.98‰ to −25.69‰, with an average of −24.2‰. The values also identified a C3 photosynthetic pathway for the Brachyphyllum specimens. The predicted δ13Ca values varied from −2.1‰ to −6.38‰, with an average of −5.03‰. These two proxies were irregular within the different members; therefore, the correlation with the change in atmospheric CO2 concentrations was not significant. Moreover, a water-stressed environment was proposed based on the δ13C values of the present fossil plants, a proposal that was also supported by the previous palaeobotanical, palynological and stratigraphical evidence. In the present study, an inconsistent relationship between the stable carbon isotope and the stomata values was apparent, which most likely indicated that the stomata numbers of the plant were more sensitive to the variation in the concentration of the atmospheric CO2, whereas the δ13C values were sensitive to the moisture conditions.  相似文献   

6.
The mechanism of thermochemical sulfate reduction (TSR) was investigated by separately heating n-C24 with three different sulfates (CaSO4, Na2SO4, MgSO4) in sealed gold tubes at 420 °C and measuring the stable carbon isotope values of hydrocarbon (C1-C5) and non-hydrocarbon (CO2) products. Extensive TSR was observed with the MgSO4 reactant as reflected by increasing concentrations of H2S, 13C depleted CO2 and relatively low concentrations of H2 (compared to the control). H2S yields were already very high at the first monitoring time (12 h) when the temperature had just reached 420 °C, suggesting that TSR had commenced well prior to this temperature. Only trace amounts of n-C24 and secondary C3-C5 alkanes were detected at 12 h, reflecting the efficient TSR utilization of the reactant and lower molecular weight alkane products. Ethane levels were still relatively high at 12 h, but declined thereafter as it was subject to TSR in the absence of higher molecular weight alkanes which had already been utilized. Methane yields were consistently high throughout the 48 h MgSO4 treatment. The temporal decrease in the concentrations of alkanes available for TSR may also contribute to the sharp enhancement of CO2 after 36 h. Absence or dampening of the molecular and isotopic trends of MgSO4 TSR was observed with Na2SO4 and CaSO4 respectively, directly reflecting the levels of TSR reached using these sulfate treatments.For all treatments, the δ13C values of C1-5n-alkanes showed an increase with both molecular weight and treatment time. MgSO4 TSR led to a 5-10‰ increase in the δ13C values of the C1-C5 hydrocarbons and a 20‰ decrease in the δ13C value of CO2. The significant 13C depletion of the CO2 may be due to co-production of 13C enriched MgCO3, although this remains unproven as the δ13C of MgCO3 was not measured. The difference in the δ13C values of ethane and propane (Δδ13CEP) increased in magnitude with the degree of TSR, and this trend could be used to help evaluate the occurrence and extent of TSR in subsurface gas reservoirs.  相似文献   

7.
The origin and evolution of CO2 inclusions and calcite veins in peridotite xenoliths of the Pannonian Basin, Hungary, were investigated by means of petrographic investigation and stable isotope analyses. The fluid inclusions recovered in paragenetic olivine and clinopyroxene belong to distinct populations: type A (texturally early) inclusions with regular shapes (often with negative crystal forms) forming intragranular trails; type B (texturally late) inclusions defining randomly oriented trails that reach grain boundaries. Type B inclusions are often associated with silicate melt (type C) inclusions. Stable carbon isotope compositions in inclusion-hosted CO2 were obtained by vacuum crushing followed by conventional dual inlet as well as continuous flow mass spectrometry in order to eliminate possible lab artifacts. Olivines, clino- and orthopyroxenes of the host peridotite have oxygen isotope compositions from 5.3 to 6.0‰ (relative to V-SMOW), without any relationship with xenolith texture. Some of the xenoliths contained calcite in various forms: veins and infillings in silicate globules in veins, secondary carbonate veins filling cracks and metasomatic veins with diffuse margins. The former two carbonate types have δ13C values around –13‰ (relative to V-PDB) and low Sr contents (< 0.5 wt.%), whereas the third type,veins with high-temperature metasomatic features have a δ13C value of –5.0‰ and high Sr contents up to 3.4 wt.%. In spite of the mantle-like δ13C value and the unusually high Sr content typical for mantle-derived carbonate, trace element compositions have proven a crustal origin. This observation supports the conclusions of earlier studies that the carbonate melt droplets found on peridotite xenoliths in the alkaline basalts represent mobilized sedimentary carbonate. The large δ13C range and the 12C-enrichment in the carbonates can be attributed to devolatilization of the migrating carbonate or infiltration of surficial fluids containing 12C-rich dissolved carbon.Carbon isotope compositions of inclusion-hosted CO2 range from –17.8 to –4.8‰ (relative to V-PDB) with no relation to the amount of CO2 released by vacuum crushing. Low-δ13C values measured by stepwise heating under vacuum suggest that the carbon component is pristine and not related to surficial contamination, and that primary mantle fluids with δ13C values around –5‰ were at least partly preserved in the xenoliths. Tectonic reworking and heating by the basaltic magma resulted in partial CO2 release and local 13C-depletion.  相似文献   

8.
Stable isotopes of injected CO2 act as useful tracers in carbon capture and storage (CCS) because the CO2 itself is the carrier of the tracer signal and remains unaffected by sorption or partitioning effects. At the Ketzin pilot site (Germany), carbon stable isotope composition (δ13C) of injected CO2 at the injection well was analyzed over a time period of 4 months. Occurring isotope variances resulted from the injection of CO2 from two different sources (an oil refinery and a natural gas-reservoir). The two gases differed in their carbon isotope composition by more than 27‰. In order to find identifiable patterns of these variances in the reservoir, more than 250 CO2-samples were collected and analyzed for their carbon isotope ratios at an observation well 100 m distant from the injection well. An isotope ratio mass spectrometer connected to a modified Thermo Gasbench system allowed quick and cost effective isotope analyses of a high number of CO2 gas specimens. CO2 gas from the oil refinery (δ13C = −30.9‰, source A) was most frequently injected and dominated the reservoir δ13C values at the injection site. Sporadic injection of the CO2 from the natural gas-reservoir (δ13C = −3.5‰, source B) caused isotope shifts of up to +5‰ at the injection well. These variances provided a potential ideal tracer for CO2 migration behavior. Based on these findings, tracer input signals that were injected during the last 2 years of injection could be reconstructed with the aid of an isotope mixing model and CO2 delivery schedules. However, in contrast to the injection well, δ13C values at the observation well showed no variances and a constant value of −28.5‰ was measured at 600 m depth. This is in disagreement with signals that would be expected if the input signals from the injection would arrive at the observation well. The lack of isotope signals at the observation well suggests that parts of the reservoir are filled with CO2 that is immobilized.  相似文献   

9.
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   

10.
The carbon isotopic composition of CO2 from fluid inclusions in granulite facies rocks has been determined. The “primary” carbonic fluid — most probably being of Upper Mantle origin — appears to have δ 13C-values around ?15%. or even lighter up to ?20%. During the late stages of retromorphosis an enrichment in the heavy carbon isotope seems to occur resulting in δ-values between ?5 and ?7%. which, on the basis of 13C/12C ratios of carbonatites, kimberlites and diamonds have been taken up till now as representative for juvenile carbon. The implications of these findings are discussed.  相似文献   

11.
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   

12.
Recent studies show that oxygen three isotope measurement (16O, 17O, and 18O) of water provides additional information for investigating the hydrological cycle and paleoclimate. For determining the 18O/16O value of water, a conventional CO2-water equilibration method involves measurement of the ratios of CO2 isotopologues which were equilibrated with water. However, this long-established technique was not intended to measure the 17O/16O ratio, primarily because the historic ion correction scheme does not allow for possible deviations from a fixed (and mass-dependent) relationship between 17O/16O and 18O/16O isotope ratios. Here, we propose an improved method for obtaining the 17O/16O isotope ratio of fresh water by the equilibration method and measurement of the 45/44 CO2 ion abundance ratio. Equations which we formulated for 17O/16O measurement have two features: first, instead of absolute isotope ratio (R), all equations are formulated in δ values, measured by isotope ratio mass spectrometry. Second, we include two “assigned” δ values of water standards in the equations, because the δ18O are commonly measured against two working standards to normalize the span of the δ scale. This approach clarifies that the contribution from 17O (12C16O17O+) to the molecular ion current at mass-to-charge ratio m/z 45 signal depends not on the absolute 13C/12C ratio, but on the relative δ13C differences between the working standards and the sample. The pH value of water affects δ17O estimation because δ13C of CO2 was changed in the water-CO2 system. We reevaluated this effect using a set of equations, which explicitly includes CO2 partial pressure effect on pH value. Our new estimation of pH effect is significantly smaller than previously reported value, but it does not alter the main conclusions in the previous study. The method was verified by δ17O measurements of an international standard reference water (GISP) provided by the IAEA. We applied the method to investigate 17O-excess of the ice core drilled at the Dome Fuji station, Antarctica. A total of 1320 samples from a 130 m section around Marine Isotope Stage 9.3 (∼330,000 years before present) were measured. The error of a measurement for δ17O is 0.175‰ and that of 17O-excess is 184 per meg. Although these analytical uncertainties hampered accurate estimation of the changes in 17O-excess, the averaged data indicate that 17O-excess around MIS 9.3 was higher than during the subsequent glacial period. This approach can be applied only to fresh water samples, and additional improvements will be needed to measure samples which contains significant amount of carbonate minerals.  相似文献   

13.
Few global syntheses of oxygen and carbon isotope composition of pedogenic carbonates have been attempted,unlike marine carbonates.Pedogenic carbonates represent in-situ indicators of the climate conditions prevailing on land.The δ~(18)O and δ~(13)C values of pedogenic carbonates are controlled by local and global factors,many of them not affecting the marine carbonates largely used to probe global climate changes.We compile pedogenic oxygen and carbon isotopic data(N= 12,167) from Cretaceous to Quaternary-aged paleosols to identify potential trends through time and tie them to possible controlling factors.While discrete events such as the PaleoceneEocene Thermal Maximum are clearly evidenced,our analysis reveals an increasing complexity in the distribution of the δ~(18)O vs δ~(13)C values through the Cenozoic.As could be expected,the rise of C_4 plants induces a shift towards higher δ~(13)C values during the Neogene and Quaternary.We also show that the increase in global hypsometry during the Neogene plays a major role in controlling the δ~(18)O and δ~(13)C values of pedogenic carbonates by increasing aridity downwind of orographic barriers.Finally,during the Quaternary,an increase of 3‰ inδ~(18)O values is recorded both by the pedogenic carbonates and the marine foraminifera suggesting that both indicators may be used to track global climate signal.  相似文献   

14.
Mass-spectrometric stable isotope measurements of CO2 use molecular ion currents at mass-to-charge ratios m/z 44, 45 and 46 to derive the elemental isotope ratios n(13C)/n(12C) and n(18O)/n(16O), abbreviated 13C/12C and 18O/16O, relative to a reference. The ion currents have to be corrected for the contribution of 17O-bearing isotopologues, the so-called ‘17O correction’. The magnitude of this correction depends on the calibrated isotope ratios of the reference. Isotope ratio calibrations are difficult and are therefore a matter of debate. Here, I provide a comprehensive evaluation of the existing 13C/12C (13R), 17O/16O (17R) and 18O/16O (18R) calibrations of the reference material Vienna Standard Mean Ocean Water (VSMOW) and CO2 generated from the reference material Vienna Pee Dee Belemnite (VPDB) by reaction with 100% H3PO4 at 25 °C (VPDB-CO2). I find , 18RVSMOW/10−6 = 2005.20 ± 0.45, 13RVPDB-CO2/10-6= 11124 ± 45, and 18RVPDB-CO2/10-6=2088.37±0.90. I also rephrase the calculation scheme for the 17O correction completely in terms of relative isotope ratio differences (δ values). This reveals that only ratios of isotope ratios (namely, 17R/13R and 13R17R/18R) are required for the 17O correction. These can be, and have been, measured on conventional stable isotope mass spectrometers. I then show that the remaining error for these ratios of isotope ratios can lead to significant uncertainty in the derived relative 13C/12C difference, but not for18O/16O. Even though inter-laboratory differences can be corrected for by a common ‘ratio assumption set’ and/or normalisation, the ultimate accuracy of the 17O correction is hereby limited. Errors of similar magnitude can be introduced by the assumed mass-dependent relationship between 17O/16O and 18O/16O isotope ratios. For highest accuracy in the 13C/12C ratio, independent triple oxygen isotope measurements are required. Finally, I propose an experiment that allows direct measurement of 13R17R/18R.  相似文献   

15.
Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on δ13C values of CO2 to trace the migration of injected CO2 in the subsurface. More recently the use of δ18O values of both CO2 and reservoir fluids has been proposed as a method for quantifying in situ CO2 reservoir saturations due to O isotope exchange between CO2 and H2O and subsequent changes in δ18OH2O values in the presence of high concentrations of CO2. To verify that O isotope exchange between CO2 and H2O reaches equilibrium within days, and that δ18OH2O values indeed change predictably due to the presence of CO2, a laboratory study was conducted during which the isotope composition of H2O, CO2, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50 °C and up to 19 MPa) and varying CO2 pressures. Conditions typical for the Pembina Cardium CO2 Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that δ18O values of CO2 were on average 36.4 ± 2.2‰ (1σ, n = 15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5‰ for the experimental temperatures of 50 °C. By using 18O enriched water for the experiments it was demonstrated that changes in the δ18O values of water were predictably related to the fraction of O in the system sourced from CO2 in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO2 is related to the total volumetric saturation of CO2 and water as a fraction of the total volume of the system, it is concluded that changes in δ18O values of reservoir fluids can be used to calculate reservoir saturations of CO2 in CCS settings given that the δ18O values of CO2 and water are sufficiently distinct.  相似文献   

16.
The 13C/12C ratio of carbon compounds is used to identify sources and sinks in the global carbon cycle. However, the relatively enriched 13C content observed for marine organic carbon remains enigmatic. The majority of oceanic carbon is fixed by algae and cyanobacteria via the Calvin-Benson-Bassham cycle, yet isotopic discrimination by the CO2 fixation enzyme, RubisCO (ribulose 1,5-bisphosphate carboxylase/oxygenase), has only been measured for a single marine cyanobacterium. Different forms of RubisCO occur in different phytoplankton species (overall amino acid identity varying by as much as ∼75%) and thus may vary in the degree to which they fractionate carbon. Here we measured isotope discrimination by RubisCO from the coccolithophore Emiliania huxleyi, a cosmopolitan species used as a marine algal model.E. huxleyi RubisCO discriminated substantially less (ε = 11.1‰) against 13CO2 than other RubisCO enzymes (18-29‰), despite having Michaelis-Menten kinetic parameters (KCO2 = 72 μM; Vmax = 0.66 μmol min−1 mg−1 protein) similar to those measured for RubisCO enzymes from different organisms. If widespread, decreased isotope discrimination of 13C by phytoplankton RubisCO may be a major factor influencing the enriched 13C content of marine organic carbon. This finding emphasizes the necessity of (a) determining ε values for RubisCOs of other marine phytoplankton and (b) re-evaluation of δ13C values from physiological, environmental, and geological studies.  相似文献   

17.
We present here, an experimental set-up developed for the first time in India for the determination of mixing ratio and carbon isotopic ratio of air-CO2. The set-up includes traps for collection and extraction of CO2 from air samples using cryogenic procedures, followed by the measurement of CO2 mixing ratio using an MKS Baratron gauge and analysis of isotopic ratios using the dual inlet peripheral of a high sensitivity isotope ratio mass spectrometer (IRMS) MAT 253. The internal reproducibility (precision) for the δ 13C measurement is established based on repeat analyses of CO2±0.03‰. The set-up is calibrated with international carbonate and air-CO2 standards. An in-house air-CO2 mixture, ‘OASIS AIRMIX’ is prepared mixing CO2 from a high purity cylinder with O2 and N2 and an aliquot of this mixture is routinely analyzed together with the air samples. The external reproducibility for the measurement of the CO2 mixing ratio and carbon isotopic ratios are ±7 (n?=?169) $\upmu $ mol·mol???1 and ±0.05 (n?=?169) ‰ based on the mean of the difference between two aliquots of reference air mixture analyzed during daily operation carried out during November 2009–December 2011. The correction due to the isobaric interference of N2O on air-CO2 samples is determined separately by analyzing mixture of CO2 (of known isotopic composition) and N2O in varying proportions. A +0.2‰ correction in the δ 13C value for a N2O concentration of 329 ppb is determined. As an application, we present results from an experiment conducted during solar eclipse of 2010. The isotopic ratio in CO2 and the carbon dioxide mixing ratio in the air samples collected during the event are different from neighbouring samples, suggesting the role of atmospheric inversion in trapping the emitted CO2 from the urban atmosphere during the eclipse.  相似文献   

18.
Organic carbon isotope composition was studied in the sedimentary cover of the southern Siberian Platform and its surrounding fold systems. The rocks experienced catagenesis, metamorphism, and metasomatism. The chloroform bitumoid (CB) has a stable carbon isotope composition within a wide range of postsedimentation transformations. The average values of δ13C in CB of the sedimentary cover are ?29.5‰. Metamorphism and, especially, ore metasomatism, at the Sukhoi Log deposit caused a 2‰ increase in the heavy carbon isotope concentration of CB as compared to that of the platform deposits. The narrow variations in carbon isotope composition of the bitumoid are defined by their derivation from lipids, whose components are almost insusceptible to changes in the PT conditions. Kerogen from platform deposits is more strongly depleted than CB in the heavy carbon isotope (δ13Cav ? 32.2‰). The insoluble carbonaceous matter (ICM) of the metamorphic shales is significantly enriched in the heavy carbon isotope (δ13Cav ? 21.9‰). The highest changes in carbon isotope composition were found in concentrates of ICM from metasomatically altered rocks of the Sukhoi Log deposit (δ13Cav ? 17.5‰). The heavier carbon isotope composition caused by metamorphism and metasomatism is evidently defined by isotopic exchange between the carbonate carbon and CO2 of metasomatic solutions, on one hand, and ICM of shales, on the other.  相似文献   

19.
Evidence from laboratory experiments indicates that fractionation against the heavy stable isotope of carbon (Δ13C) by bryophytes (liverworts and mosses) is strongly dependent on atmospheric CO2. This physiological response may therefore provide the basis for developing a new terrestrial CO2 proxy [Fletcher, B.J., Beerling, D.J., Brentnall, S.J., Royer, D.L., 2005. Fossil bryophytes as recorders of ancient CO2 levels: experimental evidence and a Cretaceous case study. Global Biogeochem. Cycles19, GB3012]. Here, we establish a theoretical basis for the proxy by developing an extended model of bryophyte carbon isotope fractionation (BRYOCARB) that integrates the biochemical theory of photosynthetic CO2 assimilation with controls on CO2 supply by diffusion from the atmosphere. The BRYOCARB model is evaluated against measurements of the response of liverwort photosynthesis and Δ13C to variations in atmospheric O2, temperature and irradiance at different CO2 concentrations. We show that the bryophyte proxy is at least as sensitive to variations in atmosphere CO2 as the two other leading carbon isotope-based approaches to estimating palaeo-CO2 levels (δ13C of phytoplankton and of paleosols). Mathematical inversion of BRYOCARB provides a mechanistic means of estimating atmospheric CO2 levels from fossil bryophyte carbon that can explicitly account for the effects of past differences in O2 and climate.  相似文献   

20.
The early Aptian abrupt carbon isotope excursion in marine carbonate and sedimentary organic matter reflects a major perturbation in the global carbon cycle. However, until now almost all the evidences of this event came from marine deposits. Here we present organic-carbon isotope (δ13Corg) data from the non-marine Jehol Group in western Liaoning, China. The lacustrine δ13Corg curve is marked by a relative long-lasting δ13Corg minimum followed by two stages of positive δ13Corg excursions that are well correlated with contemporaneous marine records. The carbon isotope correlation shows that the lacustrine strata of the Jehol Group were deposited at the same time of the early Aptian Oceanic Anoxic Event (OAE1a). The relative long-lasting δ13Corg minimum supports the hypothesis that volcanic CO2 emission may have played the main role in triggering the negative δ13C excursion and global warming at the onset of this event. In addition, the onset of δ13Corg minimum is concomitant with the radiation of the Jehol Biota, implying that the evolutionary radiation of the Jehol Biota may have been closely related with the increase in atmospheric CO2 and temperature.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号