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1.
Secondary carbonate precipitates (dripstones) formed on concrete surfaces in four different environments – Mediterranean and continental open-space and indoor environments (inside a building and in a karstic cave) – were studied. The fabric of dripstones depends upon water supply, pH of mother solution and carbonate-resulting precipitation rate. Very low δ13C (average?28.2‰) and δ18O (average?18.4‰) values showed a strong positive correlation, typical for carbonate precipitated by rapid dissolution of CO2 in a highly alkaline solution and consequent disequilibrium precipitation of CaCO3. The main source of carbon is atmospheric or biogenic CO2 in the poorly ventilated karstic cave, which is reflected in even lower δ13C values. Statistical analysis of δ13C and δ18O values of the four groups of samples showed that the governing factor of isotope fractionation is not the temperature, but rather the precipitation rate.  相似文献   

2.
Abstract

Leaf carbon isotope ratios (δ13C), an indicator of long-term intercellular carbon dioxide concentration, and also stem and root carbon isotope ratios were measured on the obligate CAM species Crassula argentea cultivated in pure and mixed cultures with the succulent C3 Peperomia obtusifolia in open-air conditions under two different levels of nitrogen and water supply.

As expected, a diminished water supply and a relatively dry and hot summer climate cause a shift of δ13C values to a less strong 13C discrimination (less negative δ13C values). A diminished nitrogen supply causes a shift of the δ13C values in direction of a higher 13C discrimination (more negative δ13C values), particularly in the leaves. Competition causes also an increased 13C discrimination, especially valid for shoot axes.

The shift of 13C/12C isotope ratios in case of nitrogen deficiency is discussed to be a result of a decreased PEPCase activity in the night.  相似文献   

3.
Measurement of soil-respired CO2 at high temporal resolution and sample density is necessary to accurately identify sources and quantify effluxes of soil-respired CO2. A portable sampling device for the analysis of δ13C values in the field is described herein.

CO2 accumulated in a soil chamber was batch sampled sequentially in four gas bags and analysed by Wavelength-Scanned Cavity Ring-down Spectrometry (WS-CRDS). A Keeling plot (1/[CO2] versus δ13C) was used to derive δ13C values of soil-respired CO2. Calibration to the δ13C Vienna Peedee Belemnite scale was by analysis of cylinder CO2 and CO2 derived from dissolved carbonate standards. The performance of gas-bag analysis was compared to continuous analysis where the WS-CRDS analyser was connected directly to the soil chamber.

Although there are inherent difficulties in obtaining absolute accuracy data for δ13C values in soil-respired CO2, the similarity of δ13C values obtained for the same test soil with different analytical configurations indicated that an acceptable accuracy of the δ13C data were obtained by the WS-CRDS techniques presented here. Field testing of a variety of tropical soil/vegetation types, using the batch sampling technique yielded δ13C values for soil-respired CO2 related to the dominance of either C3 (tree, δ13C=?27.8 to?31.9 ‰) or C4 (tropical grass, δ13C=?9.8 to?13.6 ‰) photosynthetic pathways in vegetation at the sampling sites. Standard errors of the Keeling plot intercept δ13C values of soil-respired CO2 were typically<0.4 ‰ for analysis of soils with high CO2 efflux (>7–9 μmol m?2 s?1).  相似文献   

4.
Plitvice Lakes waters were collected at 14 sampling points, including springs, tributaries and lakes, for the period 2002–2007. The results of the physical and chemical conditions of calcite precipitation as well as the δ13C values of dissolved inorganic carbon (DIC) were used to study the processes influencing calcite precipitation. Significant differences between spring, lake and stream waters as well as changes in the downstream direction were observed. The correlation between δ13CDIC values and physico-chemical conditions for calcite precipitation showed that calcite precipitates in lake waters which are oversaturated with respect to CaCO3 (I sat values 4–10) and with δ13CDIC values between?11.5 and?8.5 ‰. In spring waters, the δ13CDIC values were more negative, from?14 to?12 ‰, and I sat values of 1–2 indicated that equilibrium conditions for calcite precipitation were not attained. The downstream increase in δ13CDIC correlated with the increase in the δ13C values of calcite in the lake sediments, suggesting that the freshwater calcite was mainly of autochthonous origin and precipitated within the water column in isotopic equilibrium with DIC.  相似文献   

5.
Abstract

Naturally produced methane shows different δ13C-values with respect to its origin, e.g., geological or biological. Methane-production of ruminants is considered to be the dominant source from the animal kingdom. Isotopic values of rumen methane—given in literature—range between ?80‰ and -50‰ and are related to feed composition and also sampling techniques. Keeping cows, camels and sheep under identical feed conditions and sampling rumen gases via implanted fistulae we compared δPDB 13C-values of methane and CO2 between the species. Referring to mean values obtained from 4 or 5 samples at different times of 11 animals (n = 47) we calculated δPDB 13C-medians resulting in small but not significant differences within and significant differences between the species for CO2 and methane. The δPDB 13C-differences between methane and CO2 were statistically equal within and also between the species. Therefore a linear regression of methane values on CO2 is appropriate and leads to: δPDB 13C(methane)‰ = 1,57 * δPDB 13C(CO2)‰-47‰ with a correlation coefficient of r = 0,87.  相似文献   

6.
We report on the application of a compact and field-deployable instrument, based on a continuous-wave fiber-coupled Telecom external cavity diode laser, to measure the 13C/12C isotope ratio in CO2 from a wood-based combustion. Carbon dioxide, the most important greenhouse gas, is a major product of combustion. The measurements of the 13C/12C isotopic ratio in CO2 from combustion emission permit one to identify the CO2 source and to study the temporal and spatial variations of pollution in the atmosphere. The average value of the 13CO2/12CO2 ratio is found to be (1.1011±0.0024)%. The corresponding δ-value relative to PDB standard is (−20.17±2.14)‰, which is in good agreement with the typical value of (−25±2)‰ for wood. Simultaneous monitoring of multiple species from gas emission has been performed using direct-absorption spectroscopy. The concentrations of C2H2, CO, CO2 and H2O were determined on the basis of integrated absorbance measured by least-squares fitting a Voigt lineshape to experimental absorption spectra.  相似文献   

7.
When conducting 13CO2 plant–soil pulse labelling experiments, tracer material might cause unwanted side effects which potentially affect δ13C measurements of soil respiration (δ13CSR) and the subsequent data interpretation. First, when the soil matrix is not isolated from the atmosphere, contamination of the soil matrix with tracer material occurs leading to a physical back-diffusion from soil pores. Second, when using canopy chambers continuously, 13CO2 is permanently re-introduced into the atmosphere due to leaf respiration which then aids re-assimilation of tracer material by the canopy. Accordingly, two climate chamber experiments on European beech saplings (Fagus sylvatica L.) were conducted to evaluate the influence of soil matrix 13CO2 contamination and canopy recycling on soil 13CO2 efflux during 13CO2 plant–soil pulse labelling experiments. For this purpose, a combined soil/canopy chamber system was developed which separates soil and canopy compartments in order to (a) prevent diffusion of 13C tracer into the soil chamber during a 13CO2 canopy pulse labelling and (b) study stable isotope processes in soil and canopy individually and independently. In combination with laser spectrometry measuring CO2 isotopologue mixing ratios at a rate of 1 Hz, we were able to measure δ13C in canopy and soil at very high temporal resolution. For the soil matrix contamination experiment, 13CO2 was applied to bare soil, canopy only or, simultaneously, to soil and canopy of the beech trees. The obtained δ13CSR fluxes from the different treatments were then compared with respect to label re-appearance, first peak time and magnitude. By determining the δ13CSR decay of physical 13CO2 back-diffusion from bare soils (contamination), it was possible to separate biological and physical components in δ13CSR of a combined flux of both. A second pulse labelling experiment, with chambers permanently enclosing the canopy, revealed that 13CO2 recycling at canopy level had no effect on δ13CSR dynamics.  相似文献   

8.
δ13C values of gaseous acetaldehyde were measured by gas chromatograph–combustion–isotope ratio mass spectrometer (GC–C–IRMS) via sodium bisulfite (NaHSO3) adsorption and cysteamine derivatisation. Gaseous acetaldehyde was collected via NaHSO3-coated Sep-Pak® silica gel cartridge, then derivatised with cysteamine, and then the δ13C value of the acetaldehyde–cysteamine derivative was measured by GC–C–IRMS. Using two acetaldehydes with different δ13C values, derivatisation experiments were carried out to cover concentrations between 0.009×10?3 and 1.96×10?3 mg·l?1) of atmospheric acetaldehyde, and then δ13C fractionation was evaluated in the derivatisation of acetaldehyde based on stoichiometric mass balance after measuring the δ13C values of acetaldehyde, cysteamine and the acetaldehyde–cysteamine derivative. δ13C measurements in the derivertisation process showed good reproducibility (<0.5 ‰) for gaseous acetaldehyde. The differences between predicted and measured δ13C values were 0.04–0.31 ‰ for acetaldehyde–cysteamine derivative, indicating that the derivatisation introduces no isotope fractionation for gaseous acetaldehyde, and obtained δ13C values of acetaldehyde in ambient air at the two sites were distinct (?34.00 ‰ at an urban site versus?31.00 ‰ at a forest site), implying potential application of the method to study atmospheric acetaldehyde.  相似文献   

9.
Pulse labelling experiments provide a common tool to study short-term processes in the plant–soil system and investigate below-ground carbon allocation as well as the coupling of soil CO2 efflux to photosynthesis. During the first hours after pulse labelling, the measured isotopic signal of soil CO2 efflux is a combination of both physical tracer diffusion into and out of the soil as well as biological tracer release via root and microbial respiration. Neglecting physical back-diffusion can lead to misinterpretation regarding time lags between photosynthesis and soil CO2 efflux in grassland or any ecosystem type where the above-ground plant parts cannot be labelled in gas-tight chambers separated from the soil. We studied the effects of physical 13CO2 tracer back-diffusion in pulse labelling experiments in grassland, focusing on the isotopic signature of soil CO2 efflux. Having accounted for back-diffusion, the estimated time lag for first tracer appearance in soil CO2 efflux changed from 0 to 1.81±0.56 h (mean±SD) and the time lag for maximum tracer appearance from 2.67±0.39 to 9.63±3.32 h (mean±SD). Thus, time lags were considerably longer when physical tracer diffusion was considered. Using these time lags after accounting for physical back-diffusion, high nocturnal soil CO2 efflux rates could be related to daytime rates of gross primary productivity (R2=0.84). Moreover, pronounced diurnal patterns in the δ13C of soil CO2 efflux were found during the decline of the tracer over 3 weeks. Possible mechanisms include diurnal changes in the relative contributions of autotrophic and heterotrophic soil respiration as well as their respective δ13C values. Thus, after accounting for physical back-diffusion, we were able to quantify biological time lags in the coupling of photosynthesis and soil CO2 efflux in grassland at the diurnal time scale.  相似文献   

10.
Stable isotope analysis was applied to describe the poultry house environment. The poultry house indoor environment was selected for this study due to the relevant health problems in animals and their caretakers. Air quality parameters including temperature, relative humidity, airflow rate, NH3, CO2 and total suspended particles, as well as mean levels of total airborne bacteria and fungi count, were measured. Carbon isotope ratios (13C/12C) were obtained in size-segregated aerosol particles. The carbon (13C/12C) and nitrogen (15N/14N) isotope ratios were measured in feed, litter, scrapings from the ventilation system, feathers and eggs. Additionally, the distribution of δ13C and δ15N values in different tissues of the chicken was examined. The airborne bacteria and fungi extracted from the air filters collected from poultry farms were grown in the laboratory in media with known isotope values and measured for stable isotope ratios. Analysis of isotope fractionation between microorganisms and their media indicated the applicability of stable isotope analysis in bulk samples for the identification of source material. The analysed examples imply that stable isotope analysis can be used to examine the indoor environment along with its biology and ecology, and serve as an informative bioanalytical tool.  相似文献   

11.
Tree rings can be used as archives of climatic and environmental data with annual resolution. Tree rings widths, maximum late wood density and other parameters as stable composition in tree rings can be used for the reconstruction of past climatic and environmental changes. Stable carbon isotope ratios in tree rings may provide valuable information on past climatic conditions. 13C/12C ratios of plant organic matter can reflect corresponding 13C/12C ratio of atmospheric CO2 during formation of the rings. Investigations of isotopic carbon composition in tree rings from in the ecologically clean the Augustów Wilderness region in the north-eastern part of Poland (22°58′E, 53°51′N) (nowadays a sanctuary) were undertaken. Series of δ13C in α-cellulose and in wholewood were acquired. Those measurements constituted a part of more complex investigations of carbon isotope composition in tree rings including the measurements of radiocarbon concentration and tree ring widths. This article presents preliminary results. It is argued that contrary to the tree ring widths and δ13C in wholewood that do not reveal significant correlation with temperature, the variation of δ13C in the latewood α-cellulose is correlated with combined July and August temperatures.  相似文献   

12.
Abstract

Apple snails Pomacea lineata (SPIX 1827) are widespread in the tropical regions of Brazil as well as in the Pantanal wetland of Mato Grosso in the western part of the country. They have a key position in the Pantanal food web and serve as food for many animals e.g. fishes, birds, and caimans. However, little is known about their feeding preferences and growth rates. Stable isotopes have been used successfully on numerous studies as food source indicator. Therefore, the δ15N and δ13C values of snails from 0.45 to 3.03cm in length, which were collected in the rainy season from March through May, were analyzed. Snails signatures revealed ambiguous evidence for food preferences. δ15N and δ13C values ranged between ?2.8 and 12.4‰ and between ?24.2 and ?16.4‰, respectively. This range of values mirrors the highly variable isotope values of possible food sources comprising C3 and C4 macrophytes. To test whether all common food sources were similarly assimilated, feeding experiments with different diets were conducted. Snail eggs were reared in tanks and offered different but single plants. Snails fed different diets and δ13C values of the food were reflected in the animal tissue. Growth varied considerably in experiments with different diets indicating the preference for certain food sources. Also, the fractionation of nitrogen isotopes between food and animal varied from 0.1 to 17.0‰. The results are explained by different feeding habits, and it is supposed that animals fed either on the plant itself or on bacteria mats growing in the tanks. In an additional experiment juvenile snails were offered one single food with a distinctive C4 grass signature. These snails did not grow detectably, but nevertheless isotope signatures approached to values of the diet.  相似文献   

13.
We present a comparative study of two offline methods, a newly developed method and an existing one, for the measurement of the stable carbon isotopic composition (δ13C) of dissolved inorganic carbon (DIC; δ13CDIC) in natural waters. The measured δ13CDIC values of different water samples, prepared from laboratory Na2CO3, ground and oceanic waters, and a laboratory carbonate isotope standard, are found to be accurate and reproducible to within 0.5 ‰\ (1σ). The extraction of CO2 from water samples by these methods does not require pre-treatment or sample poisoning and can be applied to a variety of natural waters to address carbon cycling in the hydrosphere. In addition, we present a simple method (based on a two-end-member mixing model) to estimate the silicate-weathering contribution to DIC in a river system by using the concentration of DIC and its δ13C. This approach is tested with data from the Krishna River system as a case study, thereby quantifying the contribution of silicate and carbonate weathering to DIC, particularly during peak discharge.  相似文献   

14.
Abstract

Evaluation by empirically derived equations for the Substituent effect (α, β, γ, δ) on the 13C NMR chemical shifts for C-2, C-3, C-4, C-5, C-6, the halomethyl-substituted carbon (C-7) and the cyano or oxymic carbon (C-8) in 2-halomethyl-2-hydroxy-tetrahydrofurans 1a-c, 2, 3a, b, 4a and -5,6-tetrahydro-4H-pyrans 5a-c, 6a [with C-2-substituents (R2): CF3, CCl3 or CHCl2, C-3-substituents (R3): CN, C(Me)=NOH, CH=NOMe, C(Me)=NOMe or CH=NOH], taking as reference the 2-trifluoromethyl-2-hydroxy-tetrahydrofuran (la), is reported. From the additivity properties of the α-, β-, γ-, δ-and ?-effects for each Substituent it is possible to predict the chemical shift of each carbon of the compounds 1–6.

  相似文献   

15.
Abstract

Much uncertainty still exists regarding spatial and temporal variability of stable isotope ratios (13C/12C and D/H) in different CH4-emission sources. Such variability is especially prevalent in freshwater wetlands where a range of processes can influence stable isotope compositions, resulting in variations of up to ~50‰ for δ13C-CH4 and ~150‰ for δD-CH4 values. Within a temperate-zone bog and marsh situated in southwestern Ontario, Canada, gas bubbles in pond sediments exhibit only minor seasonal and spatial variation in δ13C-CH4, δD-CH4 and δ13C-CO2 values. In pond sediments, CO2 appears to be the main source of carbon during methanogenesis either directly via CO2 reduction or indirectly through dissimilation of autotrophic acetate. In contrast, CH4 production occurs primarily via acetate fermentation at shallow depths in peat soils adjacent to ponds at each wetland. At greater depths within soils, σCO2 and H2O increasingly exert an influence on δ13C- and δD-CH4 values. Secondary alteration processes (e.g., methanotrophy or diffusive transport) are unlikely to be responsible for depth-related changes in stable isotope values of CH4. Recent models that attempt to predict δD-CH4 values in freshwater environments from D/H ratios in local precipitation do not adequately account for such changes with depth. Subenvironments (i.e., soil-forming and open water areas) in wetlands should be considered separately with respect to stable isotope signatures in CH4 emission models.  相似文献   

16.
Using a theoretical model and mass isotopic balance, biogas (methane and CO2) released from buried products at their microbial degradation was analysed in the landfill of municipal and non-toxic industrial solid organic waste near Kaluga city, Russia. The landfill contains about 1.34×106 tons of waste buried using a ‘sandwich technique’ (successive application of sand–clay and waste layers). The δ13C values of biogenic methane with respect to CO2 were?56.8 (±2.5) ‰, whereas the δ13C of CO2 peaked at+9.12‰ (+1.4±2.3‰ on average), reflecting a virtual fractionation of carbon isotopes in the course of bacterial CO2 reduction at the landfill body. After passing through the aerated soil layers, methane was partially oxidised and characterised by δ13C in the range of?50.6 to?38.2‰, evidencing enrichment in 13C, while the released carbon dioxide had δ13C of?23.3 to?4.04‰, respectively. On the mass isotopic balance for the δ13C values, the methane production in the landfill anaerobic zone and the methane emitted through the aerated landfill surface to the atmosphere, the portion of methane oxidised by methanotrophic bacteria was calculated to be from 10 to 40% (averaged about 25%). According to the theoretical estimation and field measurements, the annual rate of methane production in the landfill reached about 2.9(±1.4)×109 g C CH4 yr?1 or 5.3(±2.6)×106 m3 CH4 yr?1. The average rates of methane production in the landfill and methane emission from landfill to the atmosphere are estimated as about 53 (±26) g C CH4 m?2 d?1 (or 4 (±2) mol CH4 m?2 d?1) and 33 (±12) g C CH4 m?2 d?1 (or 2.7 (±1) mol CH4 m?2 d?1), respectively. The calculated part of methane consumed by methanotrophic bacteria in the aerated part of the landfill was 13(±7) g C CH4 m?2 d?1 (or 1.1(±0.6) mol CH4 m?2 d?1) on average.  相似文献   

17.
We present a nondispersive infrared spectrometer (NDIRS) for the measurement of the 13CO2/12CO2-ratio in breath samples. A commercial NDIR spectrometer for CO2 concentration measurements in industrial process control was modified using two separate optical channels for the 13CO2 and 12CO2 detection. Cross interference due to overlapping absorption lines of both isotopic gases was successfully eliminated. The sensitivity of this device is ± 0.4‰ of the 13CO2/12CO2-ratio in a range of 2.5 to 5% of total CO2. This is sufficient for biomedical applications. Our spectrometer is small in size, cheap and simple to operate and thus a true alternative to isotope ratio mass spectrometers (IRMS). Several biomedical applications with breath samples were demonstrated and were compared in very good agreement with IRMS.  相似文献   

18.
Abstract

The incidence of Crassulacean acid metabolism (CAM) in plants collected at various habitats in Madagascar was investigated by survey of carbon and hydrogen isotope ratios ((δ13C and δD values). In about 50% of the epiphytic orchids from evergreen higher and lower montane forests the δ13C values were indicative for CAM. The remainder of the species are presumably C3 plants. In all samples of malagasy epiphytic leafless orchids comprising 9 species, the δ13C values suggest extreme CAM with CO2 uptake proceeding entirely during the night. All terrestrial orchids collected in the lower montane forests obviously acquire external carbon by C3-photosynthesis, whereas Lissochilus decaryi, a terrestrial orchid from the semi-arid south of Madagascar and various other species of this genus are CAM plants. This is the first report of CAM occurrence in sympodial terrestrial orchids.

Judged by the δ13C values, all succulents (mainly Didiereaceae, Euphorbiaceae, Crassulaceae and Asclepiadaceae) collected at the xerophytic thorn-bush of the semi-arid south perform pronounced CAM. Where it applies, our δ13C measurements in the thorn-bush succulents revealed values being practically identical with those found by K. Winter in samples of the same species collected at the same site nearly 10 years earlier. This shows extreme constancy over long duration of time in the mode of CAM performed by the succulents of the malagasy thorn-bush vegetation. Since the δ13C survey now comprises all 11 known species of the Didiereaceae, it is unequivocally clear that all members of this family are CAM plants. Most of the individuals of the species of the Didiereaceae grown in a glass-house had slightly more negative δ13C values compared with those grown at the natural stands suggesting some contribution of C3-photosynthesis to carbon acquisition under the evaporatively less demanding glass-house conditions (and perhaps higher CO2 concentrations in the gas phase).

Despite of the fact that the hydrogen isotope composition of meteoric waters depends to a large extent on the altitude and temperature-climate of the site where the concerned plants grow, it was found that in samples obtained in the cooler higher evergreen montane forest as well as in the warmer lower evergreen montane forest and the lowland thorn-bush of the hot, semiarid south of Madagascar the δ values found in the organic matter (δDorg) were in the same range (between about - 10‰ to about - 90‰). This suggests that in our case the hydrogen isotope compositions of the meteoric waters were of minor importance in bringing about the δDorg values found in the plants.  相似文献   

19.
We have applied both palynological and carbon and nitrogen isotopic analyses of PM10 (particulate matter with a diameter of 10 μm or less) to trace its origin and to assess the anthropogenic impact for the area under study. The PM10 samples were collected in Wroc?aw (SW Poland) by the Regional Inspectorate for Environment Protection during the year 2007. The usefulness of the palynological observations in the case of PM10 is much lower than that for total suspended particles due to the resolution of absorbed particles, but is still helpful for distinguishing C3/C4 plants that indicate long-distance transport of pollutants. The δ13C(PM10) values varied seasonally from?26.9 to?25.1‰. The δ15N(PM10) values showed chaotic fluctuations and varied from 5.0 to 13.7‰. Our results indicated that during the heating period, the PM10 particles in Wroc?aw are derived mainly from local home heaters, whereas in the growing period, PM10 particles are derived from local transport and are partially generated by the industrial application of coal combustion outside the city of Wroc?aw.  相似文献   

20.
Abstract

The isotopic compositions of biogenic carbon dioxide and methane from different sites were investigated. The δ13C values of methane vary mainly between ?55‰ and ?75‰ whereas δ13C values of carbon dioxide were found from about + 11‰ to ?23‰. Especially the latter ones are not so typical for microbial gases. The different sites don't vary over the whole scales but form certain groups. Secondary effects like diffusion change the δ values of both components in an even more negative direction, while oxidation processes near the surface result in more positive δ13C values for methane and very negative δ13C values for carbon dioxide.  相似文献   

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