Isotope Composition Of CO Research Articles

Temporal analysis of d13C CO2 and CO2 efflux in soil gas emissions at Mt. Etna: a new tool for volcano monitoring

We monitored the soil gas emission of CO 2 from selected sites of Mt. Etna volcano during the period February 2009 to December 2010 by measuring periodically the soil CO 2 efflux together with the associated stable carbon isotope composition of CO 2 from February 2009 to December 2010. Correlation between the two parameters showed distinct behaviors depending on the sites as a reflection of the different interactions between crustal and sub-crustal fluids. Where deep CO 2 interacted with shallow cold ground water and/or with shallow biogenic CO 2 , a positive correlation between soil CO 2 effluxes and carbon isotopes was evident and it depended strongly on the velocity of gas through the soil. In these cases, the highest CO 2 effluxes corresponded to d 13 C CO2 values similar to those of the deep magmatic CO 2 emitted from the crater and peri-crateric gas emissions at the summit. In areas where a shallow hydrothermal system was presumed, then a similar correlation was less evident or even absent, suggesting strong control on C isotopes arising from the interactions between CO 2 gas and dissolved HCO 3 - that occur in aquifers at T>120 °C. Marked temporal variations were observed in both parameters at all sites. No significant effect of meteorological parameters was found, so the observed changes were reasonably attributed to variations in volcanic activity of Mt. Etna. In particular, the variations were attributed to increased degassing of CO 2 from incoming new magma, possibly coupled with increased hydrothermal activity in at least some of the shallow aquifers of the volcano. The largest anomalies in the monitored parameters preceded the opening of the New Southeast crater in late 2009 and therefore they could represent a key to unveiling the dynamics of the volcano.

Use of Isotope Ratio Determination (13C/12C) to Assess the Production Method of Sparkling Wine.

The production of a sparkling wine can be performed with different methods taking from a few weeks to several years, which often justifies a difference in added value for the consumer. This paper presents the use of isotope ratio δ(13)C measurements combined with physico-chemical analyses for the determination of mislabelling of sparkling wines produced by 'ancestral', 'traditional', 'closed tank' or 'gasification' methods. This work shows that the isotope composition of CO(2) compared with that of the corresponding dried residue of wine (DRW) can assess whether carbonate CO(2) in a sparkling wine originates from alcohol fermentation or from artificial gas addition. Isotopic ratios expressed as δ(13)C(CO2) and δ(13)C(DRW) measurements have been obtained for each wine by gasbench isotopic ratio mass spectroscopy and cavity ring down infrared spectroscopy, respectively. When the difference between δ(13)C(CO2) and δ(13)C(DRW) is negative, the presence of artificial CO(2) can be undoubtedly inferred, which would exclude the production methods 'ancestral' or 'traditional' for instance. Other parameters such as alcohol content, sugar and acid distributions are also important to complete the analytical panel to aid fraud tracking.

Environmental and physiological controls on the carbon isotope composition of CO2 respired by leaves and roots of a C3 woody legume (Prosopis velutina) and a C4 perennial grass (Sporobolus wrightii)

Accurate estimates of the δ(13) C value of CO(2) respired from roots (δ(13) C(R_root) ) and leaves (δ(13) C(R_leaf) ) are important for tracing and understanding changes in C fluxes at the ecosystem scale. Yet the mechanisms underlying temporal variation in these isotopic signals are not fully resolved. We measured δ(13) C(R_leaf) , δ(13) C(R_root) , and the δ(13) C values and concentrations of glucose and sucrose in leaves and roots in the C(4) grass Sporobolus wrightii and the C(3) tree Prosopis velutina in a savanna ecosystem in southeastern Arizona, USA. Night-time variation in δ(13) C(R_leaf) of up to 4.6 ± 0.6‰ in S. wrightii and 3.0 ± 0.6‰ in P. velutina were correlated with shifts in leaf sucrose concentration, but not with changes in δ(13) C values of these respiratory substrates. Strong positive correlations between δ(13) C(R_root) and root glucose δ(13) C values in P. velutina suggest large diel changes in δ(13) C(R_root) (were up to 3.9‰) influenced by short-term changes in δ(13) C of leaf-derived phloem C. No diel variation in δ(13) C(R_root) was observed in S. wrightii. Our findings show that short-term changes in δ(13) C(R_leaf) and δ(13) C(R_root) were both related to substrate isotope composition and concentration. Changes in substrate limitation or demand for biosynthesis may largely control short-term variation in the δ(13) C of respired CO(2) in these species.

Use of Laser Spectroscopy To Measure the 13C/12C and 18O/16O Compositions of Carbonate Minerals

The stable carbon and oxygen isotope compositions of carbonate minerals are utilized throughout the earth and environmental sciences for various purposes. Here, we demonstrate the first application of a prototype instrument, based on off-axis integrated cavity output laser spectroscopy, to measure the carbon and oxygen isotope composition of CO(2) gas evolved from the acidification of carbonate minerals. The carbon and oxygen isotope ratios were recorded from absorption spectra of (12)C(16)O(16)O, (13)C(16)O(16)O, and (12)C(16)O(18)O in the near-infrared wavelength region. The instrument was calibrated using CaCO(3) minerals with known δ(13)C(VPDB) and δ(18)O(VSMOW) values, which had been previously calibrated by isotope ratio mass spectrometry relative to the international isotopic standards NBS 18 and NBS 19. Individual analyses are demonstrated to have internal precision (1 SE) of better than 0.15‰ for δ(13)C and 0.6‰ for δ(18)O. Analysis of four carbonate standards of known isotopic composition over 2 months, determined using the original instrumental calibration, indicates that analyses are accurate to better than 0.5‰ for both δ(13)C and δ(18)O without application of standard-sample-standard corrections.

Short‐term dynamics of the carbon isotope composition of CO2 emitted from a wheat agroecosystem – physiological and environmental controls

Understanding environmental and physiological controls of the variations in δ(13) C of CO(2) respired (δ(13) C(R)) from different compartments of an ecosystem is important for separation of CO(2) fluxes and to assess coupling between assimilation and respiration. In a wheat field, over 3 days we characterised the temporal dynamics of δ(13) C(R) from shoots and roots, from the soil and from the whole agroecosystem. To evaluate the basis of potential variations in δ(13) C(R), we also measured δ(13) C in different organic matter pools, as well as meteorological and gas exchange parameters. We observed strong diel variations up to ca. 6% in shoot, root and soil δ(13) C(R), but not in δ(13) C of the putative organic substrates for respiration, which varied by not more than ca. 1% within 24 h. Whole ecosystem-respired CO(2) was least depleted in (13) C in the afternoon and most negative in the early morning. We assume that temporally variable respiratory carbon isotope fractionation and changes in fluxes through metabolic pathways, rather than photosynthetic carbon isotope fractionation, governs the δ(13) C of respired CO(2) at the diel scale, and thus provides insights into the metabolic processes related to respiration under field conditions.

The 13C/12C isotopic signal of day‐respired CO2 in variegated leaves of Pelargonium × hortorum

In leaves, although it is accepted that CO(2) evolved by dark respiration after illumination is naturally (13) C-enriched compared to organic matter or substrate sucrose, much uncertainty remains on whether day respiration produces (13) C-depleted or (13) C-enriched CO(2). Here, we applied equations described previously for mesocosm CO(2) exchange to investigate the carbon isotope composition of CO(2) respired by autotrophic and heterotrophic tissues of Pelargonium × hortorum leaves, taking advantage of leaf variegation. Day-respired CO(2) was slightly (13) C-depleted compared to organic matter both under 21% O(2) and 2% O(2). Furthermore, most, if not all CO(2) molecules evolved in the light came from carbon atoms that had been fixed previously before the experiments, in both variegated and green leaves. We conclude that the usual definition of day respiratory fractionation, that assumes carbon fixed by current net photosynthesis is the respiratory substrate, is not valid in Pelargonium leaves under our conditions. In variegated leaves, total organic matter was slightly (13) C-depleted in white areas and so were most primary metabolites. This small isotopic difference between white and green areas probably came from the small contribution of photosynthetic CO(2) refixation and the specific nitrogen metabolism in white leaf areas.

Effect of temperature on the oxygen isotope composition of carbon dioxide [formula omitted] prepared from carbonate minerals by reaction with polyphosphoric acid: An example of the rhombohedral CaCO 3–MgCO 3 group minerals

Measurement of the ratio of 18O to 16O in CO 2 ( δ CO 2 18 O ) produced from rhombohedral carbonate minerals in the compositional range CaCO 3–MgCO 3 by reaction with polyphosphoric acid (PPA), at temperatures of between 25 and 110 °C, shows that values of δ CO 2 18 O are linearly correlated ( r o > 0.99) with the reciprocal of absolute reaction temperature (K/ T). This observation is consistent with earlier studies documenting the effect of temperature on the kinetic fractionation of oxygen isotopes between parent carbonate and product CO 2 and H 2O during acid decomposition. However, analysis of the resultant data reveals: (1) a progressive increase in d δ 18 O / dT - 1 with increasing Mg content, and (2) a significant variation in d δ 18 O / dT - 1 between individual samples of carbonate of identical lattice symmetry and similar chemical composition. The overall increase in gradient with increasing Mg content is assumed to reflect cation radius dependent factors that control the bonding environment at the interface between the metal cation exposed at the surface of the reacting carbonate solid and a H 2CO 3 transitional species during disproportionation of H 2CO 3 to CO 2 and H 2O (“cluster model” of Guo et al., 2009). Phase-specific variations in d δ 18 O / dT - 1 might result from differences in lattice structure variables (e.g., degree of lattice distortion, extent of positional disorder, and non-ideal mixing of substituent cations where carbonates depart from end-member compositions). Lattice structure variables may be dependent on geochemical conditions pertaining at the time of carbonate precipitation (e.g., biosynthetic versus inorganic precipitates) and suggests that d δ 18 O / dT - 1 has the potential to vary, within limits, in response to both the chemical composition and structure of each carbonate sample. Because the oxygen isotope composition of carbonate minerals ( δ M CO 3 18 O ) measured on the VPDB scale is defined by the oxygen isotope composition of CO 2 prepared from NBS19 (calcite) by reaction with PPA at 25 °C ( Coplen et al., 1983), the variation in d δ 18 O / dT - 1 potentially introduces a non-systematic uncertainty to the calibration of the oxygen isotope composition of CO 2 produced at higher temperatures. Calibration of other carbonate phases, using a reference frame defined by δ CO 2 18 O produced from calcite at 25 °C, is subject to additional uncertainty associated with poorly defined PPA fractionation factors ( α ( T ) CO 2 , M CO 3 ) required to compute values of δ M CO 3 18 O from δ CO 2 18 O . These additional sources of uncertainty suggest that levels of analytical precision routinely reported from the measurement of δ CO 2 18 O at higher temperatures, and used as estimates of uncertainty for δ M CO 3 18 O , do not adequately reflect real uncertainties in δ M CO 3 18 O relative to VPDB.

A new method to measure carbon isotope composition of CO2 respired by trees: stem CO2 equilibration

Summary 1. Applying Keeling plot techniques to derive δ13C of respiratory input in a closed non‐equilibrated chamber can lead to large errors because steady‐state diffusion rules are violated in a non‐steady‐state environment. To avoid these errors, respiratory δ13C can be derived using equilibrated closed chambers. 2. We introduce a new method to obtain stem respired CO2δ13C (δst‐r) with closed equilibrated stem chambers (E‐SC). We present a theoretical model describing the equilibration process, test the model against field data and find excellent agreement. The method is further tested by comparing it with closed non‐equilibrated stem chambers (NE‐SC); we found no difference between these methods. 3. Our theoretical model to describe CO2 diffusion from the respiratory pool into the chamber and the equation to derive the δ13C of the efflux are general. They could be applied to other ecosystem components (e.g. soils). 4. Our method is easy to implement, cost effective, minimizes sources of error and allows for rigorous leak detection. One major limitation is its inability to detect rapid change; the equilibration process requires 15 ± 2 h. A second limitation is that it cannot be used for species that produce abundant pitch at sites of stem wounding (e.g. Pseudotsuga menziesii). 5. Investigating δ13C of CO2 respired by different ecosystem components is necessary to interpret δ13C of ecosystem respiration. This parameter has major implications with respect to global carbon cycle science.

Isotope effect in Boudouard disproportionation reaction in optically pumped CO

Isotope composition of CO 2 produced in CO–Ar mixtures optically pumped by a CO laser has been analyzed by Fourier transform infrared (FTIR) absorption spectroscopy. Carbon monoxide reactant is a higher-than-natural abundance mixture of 13CO and 12CO. Carbon monoxide in the reactor is vibrationally excited by resonance absorption of the laser radiation and is vibration–vibration (V–V) pumped up to high vibrational levels. 12CO vibrational level populations and temperature in the excited region are measured by FTIR emission spectroscopy. Highly vibrationally excited CO molecules chemically react to form CO 2, which at these conditions is expected to be enriched in 13C isotope. Chemical reaction products are analyzed by FTIR absorption spectroscopy. The results show that CO 2 in the products is enriched in 13C isotope, with enrichment coefficient varying from β = 1.25 to 1.9, and CO 2 yield varying from 70 to 170 ppm. These results are in good agreement with the master equation kinetic model.

On the metabolic origin of the carbon isotope composition of CO2 evolved from darkened light‐acclimated leaves in Ricinus communis

The (13)C isotopic signature (delta(13)C) of CO(2) respired from plants is widely used to assess carbon fluxes and ecosystem functioning. There is, however, a lack of knowledge of the metabolic basis of the delta(13)C value of respired CO(2). To elucidate the physiological mechanisms driving (12)C/(13)C fractionation during respiration, the delta(13)C of respired CO(2) from dark-acclimated leaves during the night, from darkened leaves during the light period, and from stems and roots of Ricinus communis was analysed. The delta(13)C of potential respiratory substrates, the respiratory quotient and the activities of phosphoenolpyruvatecarboxylase (PEPc) and key respiratory enzymes were also measured. It is shown here that the CO(2) evolved from darkened light-acclimated leaves during the light period is (13)C-enriched, and that this correlates with malate accumulation in the light and rapid malate decarboxylation just after the onset of darkness. Whilst CO(2) evolved from leaves was generally (13)C-enriched (but to a lesser extent during the night), CO(2) evolved from stems and roots was depleted compared with the putative respiratory substrates; the difference was mainly caused by intensive PEPc-catalysed CO(2) refixation in stems and roots. These results provide a physiological explanation for short-term variations of delta(13)C in CO(2), illustrating the effects of variations of metabolic fluxes through different biochemical pathways.

An evaluation of the potential of using Raman spectroscopy to determine the carbon isotope composition of CO 2 inclusions

An evaluation of the potential of using Raman spectroscopy to determine the carbon isotope composition of CO 2 inclusions

Stable carbon isotope composition and concentrations of CO 2 and CH 4 in the deep catotelm of a peat bog

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 CO 2 predominates over CH 4 (CO 2 ca. 5 times CH 4). This pattern can be reproduced by a reaction–advection–ebullition model, where CO 2 and CH 4 are formed in a ratio of 1:1. The less soluble methane is preferentially lost via outgassing (bubbles). The isotopic fractionation between CO 2 and CH 4 also increases with depth, with α C values ranging from 1.045 to 1.075. The isotopic composition of the gases traces the passage of respiration-derived CO 2 (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 CO 2 reduction (large isotopic fractionation). In the upper part of the catotelm the C-13-depleted respiration-derived CO 2 pool buffers the isotopic composition of CO 2; the δ 13C of CO 2 increases only slowly. At the same time strongly depleted CH 4 is formed as CO 2 reduction consumes the depleted CO 2. In the lower part of the catotelm, the respiration-derived CO 2 and shallow CH 4 become less important and CO 2 reduction is the dominant source of CO 2 and CH 4. Now, the δ 13C values of both gases increase until equilibrium is reached with respect to the isotopic composition of the substrate. Thus, the δ 13C values of methane reach a minimum at intermediate depth, and the deep methane has δ 13C 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.

Inferring biogenic and anthropogenic carbon dioxide sources across an urban to rural gradient

We continuously monitored CO(2) concentrations at three locations along an urban-to-rural gradient in the Salt Lake Valley, Utah from 2004 to 2006. The results showed a range of CO(2) concentrations from daily averages exceeding 500 p.p.m. at the city center to much lower concentrations in a non-urbanized, rural region of the valley. The highest values were measured in the wintertime and under stable atmospheric conditions. At all three sites, we utilized weekly measurements of the C and O isotope composition of CO(2) for a 1-year period to evaluate the CO(2) sources underlying spatial and temporal variability in CO(2) concentrations. The results of an inverse analysis of CO(2) sources and the O isotope composition of ecosystem respiration (delta(18) O (R)) showed large contributions (>50%) of natural gas combustion to atmospheric CO(2) in the wintertime, particularly at the city center, and large contributions (>60%) of biogenic respiration to atmospheric CO(2) during the growing season, particularly at the rural site. delta(18) O (R) was most enriched at the rural site and more isotopically depleted at the urban sites due to the effects of irrigation on ecosystem water pools at the urban sites. The results also suggested differences in the role of leaf versus soil respiration between the two urban sites, with seasonal variation in the contribution of leaf respiration at a residential site and relatively constant contributions of leaf respiration at the city center. These results illustrate that spatial and temporal patterns of urban CO(2) concentrations and isotopic composition can be used to infer patterns of energy use by urban residents as well as plant and soil processes in urban areas.

A new measurement technique reveals temporal variation in δ18O of leaf‐respired CO2

The oxygen isotope composition of CO(2) respired by Ricinus communis leaves (delta(18)O(R)) was measured under non-steady-state conditions with a temporal resolution of 3 min using a tunable diode laser (TDL) absorption spectrometer coupled to a portable gas exchange system. The SD of delta(18)O measurement by the TDL was +/- 0.2 per thousand and close to that of traditional mass spectrometers. Further, delta(18)O(R) values at isotopic steady state were comparable to those obtained using traditional flask sampling and mass spectrometric techniques for R. communis grown and measured in similar environmental conditions. As well as higher temporal resolution, the online TDL method described here has a number of advantages over mass spectrometric techniques. At isotopic steady state among plants grown at high light, the "one-way flux" model was required to accurately predict delta(18)O(R). A comparison of measurements and the model suggests that plants grown under low-light conditions have either a lower proportion of chloroplast CO(2) that isotopically equilibrates with chloroplast water, or more enriched delta(18)O of CO(2) in the chloroplast that has not equilibrated with local water. The high temporal resolution of isotopic measurements allowed the first measurements of delta(18)O(R) when stomatal conductance was rapidly changing. Under non-steady-state conditions, delta(18)O(R) varied between 50 and 220 per thousand for leaves of plants grown under different light and water environments, and varied by as much as 100 per thousand within 10 min for a single leaf. Stomatal conductance ranged from 0.001 to 1.586 mol m(-2) s(-1), and had an important influence on delta(18)O(R) under non-steady-state conditions not only via effects on leaf water H(2) (18)O enrichment, but also via effects on the rate of the one-way fluxes of CO(2) into and out of the leaf.

Stable isotope composition of CO 2 outgassed from cores of argillites: a simple method to constrain δ18O of porewater and δ13C of dissolved carbon in mudrocks

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 δ 18O of porewater and δ 13C 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, CO 2 naturally outgassed by argillite porewater is collected, purified and analyzed for C and O isotopes. Porewater δ 18O and dissolved C δ 13C are calculated from CO 2 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.

The carbon isotope composition of CO2 respired by trunks: comparison of four sampling methods

The (13)C natural abundance of CO(2) respired by plants has been used in the laboratory to examine the discrimination processes that occur during respiration. Currently, field measurements are being expanded to interpret the respiration delta(13)C signature measured at ecosystem and global levels. In this context, forests are particularly important to consider as they represent 80% of the continental biomass. The objective of this investigation was to compare four methods of sampling the CO(2) respired by trunks for the determination of its carbon isotope composition: three in situ methods using chambers placed on the trunk, and one destructive method using cores of woody tissues. The in situ methods were based either on a Keeling plot approach applied at the tissue level or on an initial flush of the chamber with nitrogen or with CO(2)-free air. In parallel, we investigated the possibility of an apparent discrimination during tissue respiration by comparing the delta(13)C signature of the respired CO(2) and that of the organic matter. The study was performed on six tree species widely distributed in temperate and mediterranean areas. The four methods were not significantly different when overall means were considered. However, considering the individual data, the Keeling plot approach and the nitrogen flush methods gave fairly homogeneous results, whereas the CO(2)-free air method produced more variable results. The core method was not correlated with any of the chamber methods. Regardless of the methodology, the respired CO(2) generally was enriched in (13)C relative to the total organic matter. This apparent enrichment during respiration was variable, reaching as much as 3-5 per thousand. This study showed that, on the whole, the different sampling techniques gave similar results, but one should be aware of the variability associated with each method.

The carbon isotope composition of ancient CO2 based on higher-plant organic matter.

Carbon isotope ratios in higher-plant organic matter (delta(13)C(plant)) have been shown in several studies to be closely related to the carbon isotope composition of the ocean-atmosphere carbon reservoir, and, in particular, the isotopic composition of CO(2). These studies have primarily been focused on geological intervals in which major perturbations occur in the oceanic carbon reservoir, as documented in organic carbon and carbonates phases (e.g. Permian-Triassic and Triassic-Jurassic boundary, Early Toarcian, Early Aptian, Cenomanian-Turonian boundary, Palaeocene-Eocene Thermal Maximum (PETM)). All of these events, excluding the Cenomanian-Turonian boundary, record negative carbon isotope excursions, and many authors have postulated that the cause of such excursions is the massive release of continental-margin marine gas-hydrate reservoirs (clathrates). Methane has a very negative carbon isotope composition (delta(13)C, ca. 60 per thousand ) in comparison with higher-plant and marine organic matter, and carbonate. The residence time of methane in the ocean-atmosphere reservoir is short (ca. 10 yr) and is rapidly oxidized to CO(2), causing the isotopic composition of CO(2) to become more negative from its assumed background value (delta(13)C, ca. -7 per thousand ). However, to date, only the Early Toarcian, Early Aptian and PETM are well-constrained chronometric sequences that could attribute clathrate release as a viable cause to create such rapid negative delta(13)C excursions. Notwithstanding this, the isotopic analysis of higher-plant organic matter (e.g. charcoal, wood, leaves, pollen) has the ability to (i) record the isotopic composition of palaeoatmospheric CO(2) in the geological record, (ii) correlate marine and non-marine stratigraphic successions, and (iii) confirm that oceanic carbon perturbations are not purely oceanographic in their extent and affect the entire ocean-atmosphere system. A case study from the Isle of Wight, UK, indicates that the carbon isotope composition of palaeoatmospheric CO(2) during the Mid-Cretaceous had a background value of 3 per thousand, but fluctuated rapidly to more positive (ca. +0.5 per thousand ) and negative values (ca. 10 per thousand ) during carbon cycle perturbations (e.g. carbon burial events, carbonate platform drowning, large igneous province formation). Hence, fluctuations in the carbon isotope composition of palaeoatmospheric CO(2) would compromise our use of palaeo-CO(2) proxies that are dependent on constant carbon isotope ratios of CO(2).

Stable isotope compositions of CO(2) in background air and at polluted sites in Hungary.

CO(2) samples were collected from air at three sites in Hungary for comparison of polluted and background areas. In order to reduce the uncertainties caused by the varying amount of N(2)O, a gas chromatography (GC)-based vacuum separation was applied. The reliability of the procedure was demonstrated by careful standardization and comparison with global network data. The stable isotope data show complex diurnal and seasonal variations that can be explained by fractionations during photosynthesis and respiration. The isotopic characteristics of pollution-derived (anthropogenic) and biogenic CO(2) appear to be indistinguishable at the study sites. However, the sites at unpolluted areas reveal a seasonal variation in the carbon isotope composition of biogenic CO(2) that may be related to changes in soil biogenic activities. The atmospheric background CO(2) shows constant delta(13)C in the region. Finally, the study demonstrates the need for careful standardization of sampling in order to make the data obtained from different sampling systems comparable.

Carbon isotope systematics and CO 2 sources in The Geysers-Clear Lake region, northern California, USA

Carbon isotope analyses of calcite veins, organic carbon, CO 2 and CH 4 from 96 rock and 46 gas samples show that metamorphic calcite veins and disseminated, organically-derived carbon from Franciscan Complex and Great Valley Sequence rocks have provided a primary carbon source for geothermal fluids during past and present hydrothermal activity across The Geysers-Clear Lake region. The stable isotope compositions of calcite veins vary widely on a regional scale, but overall they document the presence of 13C-poor fluids in early subduction-related vein-precipitating events. δ 13C values of calcite veins from the SB-15-D corehole within The Geysers steam field indicate that carbon-bearing fluids in the recent geothermal system have caused the original diverse δ 13C values of the veins to be reset. Across The Geysers-Clear Lake region the carbon isotope composition of CO 2 gas associated with individual geothermal reservoirs shows a general increasing trend in δ 13C values from west to east. In contrast, δ 13C values of CH 4 do not exhibit any spatial trends. The results from this study indicate that regional variations in δ 13C–CO 2 values result from differences in the underlying lithologies. Regional CO 2 contains significant amounts of carbon related to degradation of organic carbon and dissolution of calcite veins and is not related to equilibrium reactions involving CH 4. CO 2 from degassing of underlying magma chambers is not recognizable in this region.

Carbon isotope composition of Antarctic plants

Carbon isotope compositions of Antarctic land plants are first reported. The most interesting feature is the isotope specificity of the species. For example Usnea antarctica from different locations shows relatively narrow range of the δ 13C-values from −22.44 to −21.29‰ (7 samples), Drepanocladus sp. from −24.86 to −23.49‰ (8 samples), and Andreaea depressincrvis from −23.87 to −23.23‰ (3 samples) etc. Usually, in inhabited lands and parts of the world with rich flora and developed soil, isotopic specificity of species is masked by variations of carbon isotope composition of CO 2. In Antarctic conditions influence of local sources of CO 2 on the isotope composition of CO 2 is appeared to be minimal. Therefore the δ 13C-variations inherent to individual plant physiology and biochemistry can be distinguished on the background of the stable level of the atmospheric CO 2 δ 13C-value. The latter is best to reflect the global state of the carbon cycle.