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Sample records for 13c depleted co2

  1. The paper trail of the 13C of atmospheric CO2 since the industrial revolution period

    NASA Astrophysics Data System (ADS)

    Yakir, Dan

    2011-07-01

    The 13C concentration in atmospheric CO2 has been declining over the past 150 years as large quantities of 13C-depleted CO2 from fossil fuel burning are added to the atmosphere. Deforestation and other land use changes have also contributed to the trend. Looking at the 13C variations in the atmosphere and in annual growth rings of trees allows us to estimate CO2 uptake by land plants and the ocean, and assess the response of plants to climate. Here I show that the effects of the declining 13C trend in atmospheric CO2 are recorded in the isotopic composition of paper used in the printing industry, which provides a well-organized archive and integrated material derived from trees' cellulose. 13C analyses of paper from two European and two American publications showed, on average, a - 1.65 ± 1.00‰ trend between 1880 and 2000, compared with - 1.45 and - 1.57‰ for air and tree-ring analyses, respectively. The greater decrease in plant-derived 13C in the paper we tested than in the air is consistent with predicted global-scale increases in plant intrinsic water-use efficiency over the 20th century. Distinct deviations from the atmospheric trend were observed in both European and American publications immediately following the World War II period.

  2. Greenland CO2 and δ13C of CO2 - assigning the contamination

    NASA Astrophysics Data System (ADS)

    Jenk, T.; Rubino, M.; Etheridge, D.; Bigler, M.; Blunier, T.

    2012-04-01

    Analysis of air extracted from bubbles of Greenland ice results in considerably higher CO2 concentrations compared to records from Antarctic sites. This can not be explained by the inter-hemispheric gradient expected for past climatic conditions. Instead, it is attributed to chemical reactions between impurities in the ice, contributing excess CO2 to the atmospheric signal which was initially trapped in the bubbles. This is consistent with the fact that Greenland ice contains a significantly higher amount of impurities compared to Antarctic ice. Different candidates of CO2 producing chemical reactions were suggested by previous studies: (i) the acidification of carbonates, (ii) the oxidation of hydrocarbons and (iii) the photodecarboxilation of humic like substances. However, there is no agreement on how much each of the above reactions contributes. This study aims to identify the contribution from organic and inorganic sources to the Greenland CO2 excess. Compared to previous studies we base our analysis on an increased set of parameters and data points. We discuss data of CO2 and δ13C-CO2, both in high (2.5 cm) and low resolution (55 to 110 cm) along with parallel records of chemical impurities from three different sites in Greenland. The samples for the presented high resolution CO2 and δ13C of CO2 records were measured on a new set-up at the Centre for Ice and Climate (needle cracker, GC-IRMS).

  3. Estimation of continuous anthropogenic CO2 using CO2, CO, δ13C(CO2) and Δ14C(CO2)

    NASA Astrophysics Data System (ADS)

    Vardag, S. N.; Gerbig, C.; Janssens-Maenhout, G.; Levin, I.

    2015-07-01

    We investigate different methods for estimating anthropogenic CO2 using modelled continuous atmospheric concentrations of CO2 alone, as well as CO2 in combination with the surrogate tracers CO, δ13C(CO2) and Δ14C(CO2). These methods are applied at three hypothetical stations representing rural, urban and polluted conditions. We find that independent of the tracer used, an observation-based estimate of continuous anthropogenic CO2 is not feasible at rural measurement sites due to the low signal to noise ratio of anthropogenic CO2 estimates at such settings. At urban and polluted sites, potential future continuous Δ14C(CO2) measurements with a precision of 5 ‰ or better are most promising for anthropogenic CO2 determination (precision ca. 10-20%), but the insensitivity against CO2 contributions from biofuel emissions may reduce its accuracy in the future. Other tracers, such as δ13C(CO2) and CO could provide an accurate and already available alternative if all CO2 sources in the catchment area are well characterized with respect to their isotopic signature and CO to anthropogenic CO2 ratio. We suggest a strategy for calibrating these source characteristics on an annual basis using precise Δ14C(CO2) measurements on grab samples. The precision of anthropogenic CO2 determination using δ13C(CO2) is largely determined by the measurement precision of δ13C(CO2) and CO2. The precision when using the CO-method is mainly limited by the variation of natural CO sources and CO sinks. At present, continuous anthropogenic CO2 could be determined using the tracers δ13C(CO2) and/or CO with a precision of about 30 %, a mean bias of about 10 % and without significant diurnal discrepancies. This allows significant improvement, validation and bias reduction of highly resolved emission inventories using atmospheric observation and regional modelling.

  4. Critical evaluation of 13C natural abundance techniques to partition soil-surface CO2 efflux

    NASA Astrophysics Data System (ADS)

    Snell, H.; Midwood, A. J.; Robinson, D.

    2013-12-01

    Soil is the largest terrestrial store of carbon and the flux of CO2 from soils to the atmosphere is estimated at around 98 Pg (98 billion tonnes) of carbon per year. The CO2 efflux from the soil surface is derived from plant root and rhizosphere respiration (autotrophically fuelled) and microbial degradation of soil organic matter (heterotrophic respiration). Heterotrophic respiration is a key determinant of an ecosystem's long-term C balance, but one that is difficult to measure in the field. One approach involves partitioning the total soil-surface CO2 efflux between heterotrophic and autotrophic components; this can be done using differences in the natural abundance stable isotope ratios (δ13C) of autotrophic and heterotrophic CO2 as the end-members of a simple mixing model. In most natural, temperate ecosystems, current and historical vegetation cover (and therefore also plant-derived soil organic matter) is produced from C3 photosynthesis so the difference in δ13C between the autotrophic and heterotrophic CO2 sources is small. Successful partitioning therefore requires accurate and precise measurements of the δ13CO2 of the autotrophic and heterotrophic end-members (obtained by measuring the δ13CO2 of soil-free roots and root-free soil) and of total soil CO2 efflux. There is currently little consensus on the optimum measurement protocols. Here we systematically tested some of the most commonly used techniques to identify and minimise methodological errors. Using soil-surface chambers to sample total CO2 efflux and a cavity ring-down spectrometer to measure δ13CO2 in a partitioning study on a Scottish moorland, we found that: using soil-penetrating collars leads to a more depleted chamber measurement of total soil δ13CO2 as a result of severing roots and fungal hyphae or equilibrating with δ13CO2 at depth or both; root incubations provide an accurate estimate of in-situ root respired δ13CO2 provided they are sampled within one hour; the δ13CO2 from root

  5. Changes and their possible causes in δ13C of dark-respired CO2 and its putative bulk and soluble sources during maize ontogeny.

    PubMed

    Ghashghaie, Jaleh; Badeck, Franz W; Girardin, Cyril; Huignard, Christophe; Aydinlis, Zackarie; Fonteny, Charlotte; Priault, Pierrick; Fresneau, Chantal; Lamothe-Sibold, Marlène; Streb, Peter; Terwilliger, Valery J

    2016-04-01

    The issues of whether, where, and to what extent carbon isotopic fractionations occur during respiration affect interpretations of plant functions that are important to many disciplines across the natural sciences. Studies of carbon isotopic fractionation during dark respiration in C3 plants have repeatedly shown respired CO2 to be (13)C enriched relative to its bulk leaf sources and (13)C depleted relative to its bulk root sources. Furthermore, two studies showed respired CO2 to become progressively (13)C enriched during leaf ontogeny and (13)C depleted during root ontogeny in C3 legumes. As such data on C4 plants are scarce and contradictory, we investigated apparent respiratory fractionations of carbon and their possible causes in different organs of maize plants during early ontogeny. As in the C3 plants, leaf-respired CO2 was (13)C enriched whereas root-respired CO2 was (13)C depleted relative to their putative sources. In contrast to the findings for C3 plants, however, not only root- but also leaf-respired CO2 became more (13)C depleted during ontogeny. Leaf-respired CO2 was highly (13)C enriched just after light-dark transition but the enrichment rapidly decreased over time in darkness. We conclude that (i) although carbon isotopic fractionations in C4 maize and leguminous C3 crop roots are similar, increasing phosphoenolpyruvate-carboxylase activity during maize ontogeny could have produced the contrast between the progressive (13)C depletion of maize leaf-respired CO2 and (13)C enrichment of C3 leaf-respired CO2 over time, and (ii) in both maize and C3 leaves, highly (13)C enriched leaf-respired CO2 at light-to-dark transition and its rapid decrease during darkness, together with the observed decrease in leaf malate content, may be the result of a transient effect of light-enhanced dark respiration. PMID:26970389

  6. Soil microbial communities in a CO2-enriched and 13C-labelled treeline ecosystem with different tree species

    NASA Astrophysics Data System (ADS)

    Hiltbrunner, David; Hagedorn, Frank; Miltner, Anja; Schmidt, Michael W. I.

    2010-05-01

    The aim of this study was to estimate the responses of soil microbial communities at the alpine treeline to elevated CO2 and to gain insight into the C cycling through microbial groups under two tree species by tracking 13C signatures into phospholipid fatty acids (PLFA). In alpine treeline ecosystems, we exposed 30 year-old larch and pine trees growing on undisturbed thick mor-type organic layers to five years of elevated CO2 (+200 μmol CO2 mol-1) being depleted in 13C. Results showed that elevated CO2 increased soil respiration particularly under pine trees. However, we found negligible CO2 effects on the biomass and community structure of soil microorganisms, which might be due to small plant growth responses, and a comparatively small input of new plant-derived C into the thick organic layers with large C stocks. The tracing of 13C-depleted CO2 revealed that only a small portion of the microbial community actively metabolized new C (25%). The 13C label in individual PLFA indicated that mainly fungi were involved in the use of new substrate. Tree species affected soil microbial communities in the organic layer with a significantly higher ratio of fungal to bacterial fatty acids under pine than under larch trees. Under pine, fungal PLFA of the organic layer carried a stronger 13C label which strongly suggests a greater mycorrhizal activity that might also lead to the 60% greater input of new plant-derived C into soil organic matter under pine than under larch. In conclusion, our results show that significant responses of microbial communities in these treeline ecosystems if any would require more drastic and long lasting effects than five years of elevated CO2. Tree species have a major impact on the cycling of new plant C through soil microbial communities.

  7. The thermal desorption of CO2 from amine carbamate solutions for the 13C isotope enrichment

    NASA Astrophysics Data System (ADS)

    Dronca, S.; Varodi, C.; Gligan, M.; Stoia, V.; Baldea, A.; Hodor, I.

    2012-02-01

    The CO2 desorption from amine carbamate in non-aqueous solvents is of major importance for isotopic enrichment of 13C. A series of experiments were carried out in order to set up the conditions for the CO2 desorption. For this purpose, a laboratory- scale plant for 13C isotope separation by chemical exchange between CO2 and amine carbamate was designed and used. The decomposition of the carbamate solution was mostly produced in the desorber and completed in the boiler. Two different-length desorbers were used, at different temperatures and liquid flow rates of the amine-non-aqueous solvent solutions. The residual CO2 was determined by using volumetric and gaschromatographic methods. These results can be used for enrichment of 13C by chemical exchange between CO2 and amine carbamate in nonaqueous solvents.

  8. Continuous field measurements of delta(13)C-CO(2) and trace gases by FTIR spectroscopy.

    PubMed

    Mohn, Joachim; Zeeman, Matthias J; Werner, Roland A; Eugster, Werner; Emmenegger, Lukas

    2008-09-01

    Continuous analysis of the (13)C/(12)C ratio of atmospheric CO(2) (delta(13)C-CO(2)) is a powerful tool to quantify CO(2) flux strengths of the two major ecosystem processes assimilation and respiration. Traditional laboratory techniques such as isotope ratio mass spectrometry (IRMS) in combination with flask sampling are subject to technical limitations that do not allow to fully characterising variations of atmospheric delta(13)C-CO(2) at all relevant timescales. In our study, we demonstrate the strength of Fourier transform infrared (FTIR) spectroscopy in combination with a PLS-based calibration strategy for online analysis of delta(13)C-CO(2) in ambient air. The ability of the instrument to measure delta(13)C-CO(2) was tested on a grassland field-site and compared with standard laboratory-based IRMS measurements made on field-collected flask samples. Both methods were in excellent agreement, with an average difference of 0.4 per thousand (n=81). Simultaneously, other important trace gases such as CO, N(2)O and CH(4) were analysed by FTIR spectroscopy. PMID:18763182

  9. [Monitoring Atmospheric CO2 and delta(13)C (CO2) Background Levels at Shangdianzi Station in Beijing, China].

    PubMed

    Xia, Ling-ju; Zhou, Ling-xi; Liu, Li-xin; Zhang, Gen

    2016-04-15

    The study presented time series of atmospheric CO2 concentrations from flask sampling at SDZ regional station in Beijing during 2007 and 2013, together with delta(13)CO2) values during 2009 and 2013. The "representative data" of CO2 and delta(13)C (CO2) were selected from the complete data for further analysis. Annual CO2 concentrations increased from 385.6 x 10(-6) in 2007 to 398.1 x 10(-6) in 2013, with an average growth rate of 2.0 x 10(-6) a(-1), while the delta(13)C values decreased from -8.38% per hundred in 2009 to -8.52% per hundred in 2013, with a mean growth rate of -0.03% per hundred x a(-1). The absolute increase of CO2 from 2007 to 2008 reached the lowest level during 2007 and 2013, possibly due to relatively less carbon emissions during the 2008 Olympic Games period. The peak-to-peak amplitudes of atmospheric CO2 and delta(13)C seasonal variations were 23. 9 x 10 -6 and 1. 03%o, respectively. The isotopic signatures of CO2 sources/sinks were also discussed in this study. The delta8 value for heating season I (Jan. 01-Mar. 14) was -21.30% per hundred, while -25.39% per hundred for heating season 11 (Nov. 15-Dec.31) , and for vegetative season (Mar. 15-Nov. 14) the delta(bio) value was estimated to be -21.28% per hundred, likely suggesting the significant impact of fossil fuel and corn straw combustions during winter heating season and biological activities during vegetative season. PMID:27548943

  10. First airborne samples of a volcanic plume for δ13C of CO2 determinations

    NASA Astrophysics Data System (ADS)

    Fischer, Tobias P.; Lopez, Taryn M.

    2016-04-01

    Volcanic degassing is one of the main natural sources of CO2 to the atmosphere. Carbon isotopes of volcanic gases enable the determination of CO2 sources including mantle, organic or carbonate sediments, and atmosphere. Until recently, this work required sample collection from vents followed by laboratory analyses. Isotope ratio infrared analyzers now enable rapid analyses of plume δ13C-CO2, in situ and in real time. Here we report the first analyses of δ13C-CO2 from airborne samples. These data combined with plume samples from the vent area enable extrapolation to the volcanic source δ13C. We performed our experiment at the previously unsampled and remote Kanaga Volcano in the Western Aleutians. We find a δ13C source composition of -4.4‰, suggesting that CO2 from Kanaga is primarily sourced from the upper mantle with minimal contributions from subducted components. Our method is widely applicable to volcanoes where remote location or activity level precludes sampling using traditional methods.

  11. A method to trace root-respired CO2 using a 13C label

    NASA Astrophysics Data System (ADS)

    Cooperdock, S.; Breecker, D.; Litvak, M. E.

    2014-12-01

    In order to partition total soil respiration into root respiration and decomposition under ambient conditions in desert soils, the following method was developed using 13C-labeled CO2 in a modern juniper savannah in central New Mexico. The labeled CO2 was mixed with ambient air and pumped into a small (2.5 m diameter and 1.4 m tall) juniper tree canopy . 10 L of the 13CO2 was sufficient to generate a stream of air at 20 L/min for 1 hour with a CO2 concentration of 540 ppm and a δ13C value of approximately 35,000‰. Plastic tarpaulins were used as a wind block. The 13CO2 -labeled air was applied to the canopy during peak photosynthesis between 10 and 11 am on June 30 2014 during which canopy air CO2 was elevated by approximately 10 ppm over ambient and had δ13C values ranging from 50 to 1000 ‰. Over the next three days, gas and tissue samples were collected in order to trace the 13C label through the juniper tree. Leaf and root samples collected from the labeled tree and from several control trees were loaded into exetainer vials, flushed with CO2-free air and incubated in the dark for 5 hours in order to measure the carbon isotope composition of respired CO2. Samples of soil pore space gas were collected from wells under the labeled tree and a control tree and were transported to the laboratory in He-flushed exetainer vials. The δ13C values of CO2 in the soil gas samples and in the headspace of incubation vials were measured using an isotope ratio mass spectrometer. The δ13C values of foliar respiration were significantly higher than those of the control (by 3.6‰, p < 0.01) one and two days after labeling and δ13C values of root-respired CO2 were significantly higher (by 0.7‰, p = 0.01) than those of the control three days after labeling. In addition, δ13C values of soil respired CO2, determined from measurements of soil pore space CO2 at 50 cm three days after labeling, were significantly higher (by 0.7‰, p < 0.03)) for the labeled tree than control

  12. The Dependence of Plant δ13C on Atmospheric pCO2

    NASA Astrophysics Data System (ADS)

    Jahren, H.; Schubert, B.

    2011-12-01

    Numerous studies on multicellular plants have reported increasing carbon isotope fractionation in leaf tissue with increasing concentrations of atmospheric carbon dioxide (pCO2), but the magnitude of the effect is highly variable (i.e., 0.62 to 2.7 % per 100 ppm CO2). The majority of these experiments tested only small differences in CO2 levels (<100 ppm), with maximum concentrations of elevated pCO2 = 700 ppm. In order to quantify how carbon isotope fractionation in plant tissues is affected by the pCO2 concentration under which plants grow, we measured carbon isotope values in a total of 191 Arabidopsis thaliana and Raphanus sativus plants grown under controlled light, water, and temperature conditions, and varying the pCO2 concentrations across a trajectory of 17 different pCO2 levels ranging from 370 to 4200 ppm. From this large dataset, we show that the carbon isotope discrimination [Δδ13C = (δ13CCO2 - δ13Cplant) / (1000 + δ13Cplant)] is indeed a function of pCO2, however, the relationship is hyperbolic, rather than linear, as is typically assumed. Across the small changes in pCO2 previously studied the response appears linear, however, our expanded dataset clearly shows that increases in Δδ13C level off at high pCO2, which is consistent with the ultimate control over fractionation being the activity of Rubisco as the concentration of pCO2 inside the leaf approaches the pCO2 level outside the leaf. The hyperbolic relationship we have quantified using published and new data is extremely robust (R2 = 0.90, n = 26, P < 0.0001), and evident in n-alkanes as well as bulk tissue, suggesting the potential for application to fossil plant materials in order to reconstruct pCO2 across critical intervals.

  13. Late Ordovician land plant spore 13C fractionation records atmospheric CO2 and climate change

    NASA Astrophysics Data System (ADS)

    Beerling, D. J.; Nelson, D. M.; Pearson, A.; Wellman, C.

    2008-12-01

    Molecular systematics and spore wall ultrastructure studies indicate that late Ordovician diad and triad fossil spores were likely produced by plants most closely related to liverworts. Here, we report the first δ13C estimates of Ordovician fossil land plant spores, which were obtained using a spooling wire micro-combustion device interfaced with an isotope-ratio mass spectrometer (Sessions et al., 2005, Analytical Chemistry, 77, 6519). The spores all originate from Saudi Arabia on the west of Gondwana and date to before (Cardadoc, ca. 460 Ma), during (443Ma) and after (Llandovery, ca. 440Ma) the Hirnantian glaciation. We use these numbers along with marine carbonate δ13C records to estimate atmospheric CO2 by implementing a theoretical model that captures the strong CO2-dependency of 13C fractionation in non-vascular land plants (Fletcher et al., 2008, Nature Geoscience, 1, 43). Although provisional at this stage, reconstructed CO2 changes are consistent with the Kump et al. (2008) (Paleo. Paleo. Paleo. 152, 173) 'weathering hypothesis' whereby pre-Hirnantian cooling is caused by relatively low CO2 (ca. 700ppm) related to enhanced weathering of young basaltic rocks during the early phase of the Taconic uplift, with background values subsequently rising to around double this value by the earliest Silurian. Further analyses will better constrain atmospheric CO2 change during the late Ordovician climatic perturbation and address controversial hypotheses concerning the causes and timing of the Earth system transition into an icehouse state.

  14. Vehicle emissions of greenhouse gases and related tracers from a tunnel study: CO : CO2, N2O : CO2, CH4 : CO2, O2 : CO2 ratios, and the stable isotopes 13C and 18O in CO2 and CO

    NASA Astrophysics Data System (ADS)

    Popa, M. E.; Vollmer, M. K.; Jordan, A.; Brand, W. A.; Pathirana, S. L.; Rothe, M.; Röckmann, T.

    2014-02-01

    Measurements of CO2, CO, N2O and CH4 mole fractions, O2 / N2 ratios and the stable isotopes 13C and 18O in CO2 and CO have been performed in air samples from the Islisberg highway tunnel (Switzerland). The molar CO : CO2 ratios, with an average of (4.15 ± 0.34) ppb:ppm, are lower than reported in previous studies, pointing to a reduction in CO emissions from traffic. The 13C in CO2 reflects the isotopic composition of the fuel. 18O in CO2 is slightly depleted compared to the 18O in atmospheric O2, and shows significant variability. In contrast, the δ13C values of CO show that significant fractionation takes place during CO destruction in the catalytic converter. 13C in CO is enriched by 3‰ compared to the 13C in the fuel burnt, while the 18O content is similar to that of atmospheric O2. We compute a fractionation constant of (-2.7 ± 0.7)‰ for 13C during CO destruction. The N2O : CO2 average ratio of (1.8 ± 0.2) × 10-2 ppb:ppm is significantly lower than in past studies, showing a reduction in N2O emissions likely related to improvements in the catalytic converter technology. We also observed small CH4 emissions, with an average CH4 : CO2 ratio of (4.6 ± 0.2) × 10-2 ppb:ppm. The O2 : CO2 ratios of (-1.47 ± 0.01) ppm:ppm are very close to the expected, theoretically calculated values of O2 depletion per CO2 enhancement.

  15. Changes in δ(13)C of dark respired CO2 and organic matter of different organs during early ontogeny in peanut plants.

    PubMed

    Ghashghaie, Jaleh; Badeck, Franz W; Girardin, Cyril; Sketriené, Diana; Lamothe-Sibold, Marlène; Werner, Roland A

    2015-01-01

    Carbon isotope composition in respired CO2 and organic matter of individual organs were measured on peanut seedlings during early ontogeny in order to compare fractionation during heterotrophic growth and transition to autotrophy in a species with lipid seed reserves with earlier results obtained on beans. Despite a high lipid content in peanut seeds (48%) compared with bean seeds (1.5%), the isotope composition of leaf- and root-respired CO2 as well as its changes during ontogeny were similar to already published data on bean seedlings: leaf-respired CO2 became (13)C-enriched reaching -21.5‰, while root-respired CO2 became (13)C-depleted reaching around -31‰ at the four-leaf stage. The opposite respiratory fractionation in leaves vs. roots already reported for C3 herbs was thus confirmed for peanuts. However, contrarily to beans, the peanut cotyledon-respired CO2 was markedly (13)C-enriched, and its (13)C-depletion was noted from the two-leaf stage onwards only. Carbohydrate amounts being very low in peanut seeds, this cannot be attributed solely to their use as respiratory substrate. The potential role of isotope fractionation during glyoxylate cycle and/or gluconeogenesis on the (13)C-enriched cotyledon-respired CO2 is discussed. PMID:25704798

  16. Using Headspace Equilibration to Measure the d13C of Soil-Respired CO2

    NASA Astrophysics Data System (ADS)

    Robertson, M. A.; Powers, E.; Marshall, J.

    2007-12-01

    Soil respiration is an important component of the global carbon cycle and can account for as much as 70% of ecosystem respiration. Soil gas flux measurements have been combined with stable isotope analysis to examine ecosystem properties and processes such as water-use efficiency and the role of above ground weather in controlling soil respiration. However, current methods of measuring the δ13C of soil-respired CO2 are either inherently inaccurate or time-consuming and tedious. An alternative method of obtaining this value offers a potential solution to these problems. In this method, plastic chambers are fitted with rubber septa to allow for sample collection, then inverted and partially buried in soil. The chamber headspace is allowed to come to equilibrium with soil air. In this study we tested the viability of this method by examining whether frequent resampling of respiration chambers affected δ13C measurements, whether headspace CO2 concentration and δ13C values approached equilibrium asymptotically, and whether simulated and actual diel temperature cycles affected estimates of δ13C. All experiments were conducted on respiration chambers inverted in potting soil and placed in a Conviron growth chamber, with the exception of one field test that was conducted on respiration chambers installed in a Northern Idaho experimental forest. Samples were collected with a syringe and stored in glass vials for analysis by a ratioing mass spectrometer. We found that resampling respiration chambers as frequently as every 10 minutes had no significant effect on final δ13C values, that both chamber CO2 concentrations and δ13C values exhibited an asymptotic approach to equilibrium, and that the equilibrium value was offset from the initial flux by the amount we expected, approximately 4 ‰. However, we also found that diel temperature variation affected both headspace CO2 concentration and δ13C in the lab and in the field. We concluded that if this method is used in

  17. Depletion of 13C in Cretaceous marine organic matter: Source, diagenetic, or environmental sigal?

    USGS Publications Warehouse

    Dean, W.E.; Arthur, M.A.; Claypool, G.E.

    1986-01-01

    not produce a significant shift in ?? 13C in Miocene to Holocene sediments, and therefore probably did not produce the isotopically light Cretaceous OC. This means that Cretaceous marine plankton must have had ?? 13C values that were about 5??? lighter than modern marine plankton, and at least several per mil lighter than Cretaceous terrestrial vegetation. The reason for these lighter values, however, is not obvious. It has been proposed that concentrations of CO2 were higher during the middle Cretaceous, and this more available CO2 may be responsible for the lighter ?? 13C values of Cretaceous marine organic matter. ?? 1986.

  18. Vehicle emissions of greenhouse gases and related tracers from a tunnel study: CO : CO2, N2O : CO2, CH4 : CO2, O2 : CO2 ratios, and the stable isotopes 13C and 18O in CO2 and CO

    NASA Astrophysics Data System (ADS)

    Popa, M. E.; Vollmer, M. K.; Jordan, A.; Brand, W. A.; Pathirana, S. L.; Rothe, M.; Röckmann, T.

    2013-09-01

    Measurements of CO2, CO, N2O and CH4 mole fractions, O2/N2 ratios and the stable isotopes 13C and 18O in CO2 and CO have been performed in air samples from the highway tunnel Islisberg (Switzerland). The CO : CO2 ratios, with an average of (4.15 ± 0.34) ppb : ppm, are lower than reported by previous studies, pointing to a reduction in CO emissions from traffic. The 13C in CO2 reflects the isotopic composition of the fuel. 18O in CO2 is slightly depleted compared to the 18O in atmospheric O2, and shows significant variability. In contrast, the δ13C values of CO show that significant fractionation takes place during CO destruction in the catalytic converter. 13C in CO is enriched by 3 ‰ compared to the 13C in the fuel burnt, while the 18O content is similar to that of atmospheric O2. We compute a fractionation constant of (-2.7 ± 0.7) ‰ for 13C during CO destruction. The N2O : CO2 average ratio (1.8 ± 0.2) × 10-2 ppb : ppm is significantly lower than in past studies, showing a reduction in N2O emissions likely related to improvements in the catalytic technology. We also observed small CH4 emissions, with an average CH4 : CO2 ratio of (4.6 ± 0.2) × 10-2 ppb : ppm. The O2 : CO2 ratios of (-1.47 ± 0.01) ppm : ppm are very close to the expected, theoretically calculated values.

  19. 13C fractionation of dinoflagellates - a new proxy for past CO2 levels?

    NASA Astrophysics Data System (ADS)

    Hoins, M.; Van de Waal, D. B.; Eberlein, T.; Reichart, G.; Sluijs, A.; Rost, B.

    2012-12-01

    Reliable reconstructions of atmospheric CO2 levels prior to ~1 million years ago are required to quantify climate sensitivity as well as ocean acidification in response to past carbon cycle perturbations. Despite recent progress, however, uncertainties in reconstructed values especially from the Paleogene and older, are still very large. We aim to develop a new proxy for CO2 concentrations based on the carbon isotopic fractionation of autotrophic marine dinoflagellates. Dinoflagellates feature RubisCO (type II) with the lowest CO2 affinity of all eukaryote phytoplankton, which makes this group inherently sensitive to changes in carbonate chemistry. Along with growth and carbon production also the 13C versus 12C incorporation, i.e., the 13C fractionation (ɛp), will likely be affected. Hence, the carbon isotopic composition of dinoflagellates may ultimately reflect the prevailing atmospheric CO2 concentrations. Crucially, microfossils of dinoflagellates, i.e. organic dinoflagellate cysts, have been recovered from ocean sediments as old as the Triassic (i.e. ~215 Ma BP). We performed dilute batch experiments with four dinoflagellate species: Alexandrium tamarense, Scrippsiella trochoidea, Gonyaulax spinifera and Protoceratium reticulatum. Cells were grown at various CO2 concentrations representing the Last Glacial Maximum (180 ppm), present day (380 ppm), and future projections (and estimates for distant past levels; 950 ppm and 1400 ppm). Consistent with expectations, ɛp increased with CO2 concentration in all four species (with a slope of up to 0.19 ‰ μM-1), while growth and carbon production (μc) had little effect. ɛp in relation to CO2 varied between species and strains, but the relation of ɛp to μc/CO2 was more consistent. First results of underlying processes affecting ɛp, including carbon acquisition and leakage, will be discussed. Considering that the cysts of P. reticulatum (Operculodinium centrocarpum) and G. spinifera (Spiniferites sp.) are

  20. Estimation of continuous anthropogenic CO2: model-based evaluation of CO2, CO, δ13C(CO2) and Δ14C(CO2) tracer methods

    NASA Astrophysics Data System (ADS)

    Vardag, S. N.; Gerbig, C.; Janssens-Maenhout, G.; Levin, I.

    2015-11-01

    We investigate different methods for estimating anthropogenic CO2 using modeled continuous atmospheric concentrations of CO2 alone, as well as CO2 in combination with the surrogate tracers CO, δ13C(CO2) and Δ14C(CO2). These methods are applied at three hypothetical stations representing rural, urban and polluted conditions. We find that, independent of the tracer used, an observation-based estimate of continuous anthropogenic CO2 is not yet feasible at rural measurement sites due to the low signal-to-noise ratio of anthropogenic CO2 estimates at such settings. The tracers δ13C(CO2) and CO provide an accurate possibility to determine anthropogenic CO2 continuously, only if all CO2 sources in the catchment area are well characterized or calibrated with respect to their isotopic signature and CO to anthropogenic CO2 ratio. We test different calibration strategies for the mean isotopic signature and CO to CO2 ratio using precise Δ14C(CO2) measurements on monthly integrated as well as on grab samples. For δ13C(CO2), a calibration with annually averaged 14C(CO2) grab samples is most promising, since integrated sampling introduces large biases into anthropogenic CO2 estimates. For CO, these biases are smaller. The precision of continuous anthropogenic CO2 determination using δ13C(CO2) depends on measurement precision of δ13C(CO2) and CO2, while the CO method is mainly limited by the variation in natural CO sources and sinks. At present, continuous anthropogenic CO2 could be determined using the tracers δ13C(CO2) and/or CO with a precision of about 30 %, a mean bias of about 10 % and without significant diurnal discrepancies. Hypothetical future measurements of continuous Δ14C(CO2) with a precision of 5 ‰ are promising for anthropogenic CO2 determination (precision ca. 10-20 %) but are not yet available. The investigated tracer-based approaches open the door to improving, validating and reducing biases of highly resolved emission inventories using atmospheric

  1. Incremental vacuum dehydration-decarbonation experiments on a natural gibbsite (α-Al(OH 3)): CO 2 abundance and δ 13C values

    NASA Astrophysics Data System (ADS)

    Tabor, Neil J.; Yapp, Crayton J.

    2005-02-01

    Incremental vacuum dehydration-decarbonation experiments were performed at 190°C on chemically "cleaned" aliquots of a gibbsite-dominated, Eocene-age bauxite sample with evolution of CO 2 and H 2O. "Plateau" F (CO 2/H 2O ratios) and δ 13C values of the CO 2 derived from gibbsite were attained over the dehydration interval, X v(H 2) = 0.16 to 0.67 (i.e., 16 to 67% breakdown of gibbsite). The plateau value of F for gibbsite was 0.0043 ± 0.0003, while the corresponding δ 13C value of evolved CO 2 was -16.0‰±0.4‰. Additional experiments on chemically cleaned aliquots included (1) treatment with a solution of 0.3M Na-Citrate + 0.1M Na-Dithionite and (2) an exchange experiment with 0.1 bar of 13C-depleted CO 2 (-46‰) at 105°C for 64.5 h. Neither of these additional treatments resulted in a measurable perturbation of plateau values of F or δ 13C for CO 2 evolved from gibbsite during dehydroxylation. These results support published work on Holocene samples which suggested that CO 2 occluded in gibbsite may preserve information on δ 13C values of CO 2 in ancient terrestrial systems. The plateau values of F observed in the Eocene gibbsite indicate that it may be possible to experimentally calibrate a relationship between the concentration of CO 2 occluded in gibbsite and CO 2 in the environment at the time of crystallization. Such a calibration would significantly enhance the value of gibbsite as a source of information on ancient oxidized carbon systems.

  2. Effects of Ontogeny on δ13C of Plant- and Soil-Respired CO2 and on Respiratory Carbon Fractionation in C3 Herbaceous Species.

    PubMed

    Salmon, Yann; Buchmann, Nina; Barnard, Romain L

    2016-01-01

    Knowledge gaps regarding potential ontogeny and plant species identity effects on carbon isotope fractionation might lead to misinterpretations of carbon isotope composition (δ13C) of respired CO2, a widely-used integrator of environmental conditions. In monospecific mesocosms grown under controlled conditions, the δ13C of C pools and fluxes and leaf ecophysiological parameters of seven herbaceous species belonging to three functional groups (crops, forage grasses and legumes) were investigated at three ontogenetic stages of their vegetative cycle (young foliage, maximum growth rate, early senescence). Ontogeny-related changes in δ13C of leaf- and soil-respired CO2 and 13C/12C fractionation in respiration (ΔR) were species-dependent and up to 7‰, a magnitude similar to that commonly measured in response to environmental factors. At plant and soil levels, changes in δ13C of respired CO2 and ΔR with ontogeny were related to changes in plant physiological status, likely through ontogeny-driven changes in the C sink to source strength ratio in the aboveground plant compartment. Our data further showed that lower ΔR values (i.e. respired CO2 relatively less depleted in 13C) were observed with decreasing net assimilation. Our findings highlight the importance of accounting for ontogenetic stage and plant community composition in ecological studies using stable carbon isotopes. PMID:27010947

  3. Effects of Ontogeny on δ13C of Plant- and Soil-Respired CO2 and on Respiratory Carbon Fractionation in C3 Herbaceous Species

    PubMed Central

    Salmon, Yann; Buchmann, Nina; Barnard, Romain L.

    2016-01-01

    Knowledge gaps regarding potential ontogeny and plant species identity effects on carbon isotope fractionation might lead to misinterpretations of carbon isotope composition (δ13C) of respired CO2, a widely-used integrator of environmental conditions. In monospecific mesocosms grown under controlled conditions, the δ13C of C pools and fluxes and leaf ecophysiological parameters of seven herbaceous species belonging to three functional groups (crops, forage grasses and legumes) were investigated at three ontogenetic stages of their vegetative cycle (young foliage, maximum growth rate, early senescence). Ontogeny-related changes in δ13C of leaf- and soil-respired CO2 and 13C/12C fractionation in respiration (ΔR) were species-dependent and up to 7‰, a magnitude similar to that commonly measured in response to environmental factors. At plant and soil levels, changes in δ13C of respired CO2 and ΔR with ontogeny were related to changes in plant physiological status, likely through ontogeny-driven changes in the C sink to source strength ratio in the aboveground plant compartment. Our data further showed that lower ΔR values (i.e. respired CO2 relatively less depleted in 13C) were observed with decreasing net assimilation. Our findings highlight the importance of accounting for ontogenetic stage and plant community composition in ecological studies using stable carbon isotopes. PMID:27010947

  4. Evaluating the Influence of Solar Radiation, Coral Extension Rate and Anthropogenic CO2 on Skeletal δ13C in a Network of Fiji and Tonga Porites Corals

    NASA Astrophysics Data System (ADS)

    Dassie, E. P.; Lemley, G. M.; Linsley, B. K.; Howe, S. S.

    2011-12-01

    While stable oxygen isotope signatures in coral reefs have proven to be reliable recorders of temperature and salinity, it is difficult to interpret their skeletal 13C/12C signatures. Various studies have suggested that coral skeletal δ13C is primarily controlled by complex physiological mechanisms. However, it has also been proposed that δ13C variations in coral skeletons are related to more apparent factors such as solar radiation, skeletal extension rate, and the anthropogenic addition of 13C-depleted CO2 into the atmosphere and surface ocean ("Suess Effect"). We will present time-series variations of δ13C in six coral cores from Fiji and Tonga (South Pacific Ocean). On seasonal timescales, increases in solar radiation are correlated to increases in skeletal δ13C and visa-versa. Annually averaged data shows a correlation between increased coral δ13C and reduced coral extension rate, while a decrease in δ13C is associated with an increased extension rate. In the most recent portion of four of the coral δ13C records (from around 1900 to the core top), the value progressively decreases - a trend that is not present in either the skeletal extension rate or solar radiation data. We conclude that this decreasing δ13C trend is a consequence of the Suess Effect, as reported in other coral δ13C records. However, two of the six corals do not show this decreasing trend, which may be a result of their residence in especially shallow water (sub-tidal environments). The onset of the Suess effect in the four corals may help constrain the timing of the uptake of anthropogenic carbon by the western South Pacific Ocean. Although all factors controlling δ13C variation in corals are not completely understood, this study works towards an understanding of their relative contribution to δ13C variation.

  5. A revised atmospheric δ13C-CO2 record covering the last 1000 years from Law Dome, Antarctica

    NASA Astrophysics Data System (ADS)

    Rubino, M.; Etheridge, D. M.; Trudinger, C. M.; Allison, C.; Battle, M. O.; Bender, M. L.; Langenfelds, R.; Steele, P.; Curran, M.; Blunier, T.; Jenk, T. M.; Francey, R.

    2012-12-01

    We present a revised and expanded record of atmospheric δ13C-CO2 extracted from ice cores sampled at Law Dome (East Antarctica) and firn air sampled at Law Dome and at South Pole covering the last 1000 years. We have performed new measurements of 13C of CO2 extracted from ice, incorporated the results from new firn sampling campaigns in Antarctica and merged them with a revised version of the previous δ13C-CO2 measurements [Francey et al., 1999]. Our new measurements from Law Dome ice increase the temporal sampling density over the last 200 years and show good agreement with the results from South Pole firn, providing evidence that our new record reliably extend the Cape Grim δ13C-CO2 record back in time. We also show the preliminary measurements aimed at covering the preindustrial period with higher sample density, including the 10 ppm CO2 decrease observed in ice from Law Dome at the beginning of 1600 AD [Etheridge et al., 1996, MacFarling Meure et al., 2006]. Having higher sample density for both CO2 and δ13C-CO2 in that period allows us to infer sources and sinks of CO2 with higher confidence. Corresponding author: Mauro Rubino, mauro.rubino@csiro.au, +61(0)392394634 References Etheridge, D. et al. (1996), ISSN: 01480227. MacFarling Meure, C. et al. (2006), DOI: 10.1029/2006GL026152. Francey, R. J. et al. (1999), ISSN: 02806509.

  6. The post-Paleozoic chronology and mechanism of 13C depletion in primary marine organic matter

    NASA Technical Reports Server (NTRS)

    Popp, B. N.; Takigiku, R.; Hayes, J. M.; Louda, J. W.; Baker, E. W.

    1989-01-01

    Carbon-isotopic compositions of geoporphyrins have been measured from marine sediments of Mesozoic and Cenozoic age in order to elucidate the timing and extent of depletion of 13C in marine primary producers. These results indicate that the difference in isotopic composition of coeval marine carbonates and marine primary photosynthate was approximately 5 to 7 permil greater during the Mesozoic and early Cenozoic than at present. In contrast to the isotopic record of marine primary producers, isotopic compositions of terrestrial organic materials have remained approximately constant for this same interval of time. This difference in the isotopic records of marine and terrestrial organic matter is considered in terms of the mechanisms controlling the isotopic fractionation associated with photosynthetic fixation of carbon. We show that the decreased isotopic fractionation between marine carbonates and organic matter from the Early to mid-Cenozoic may record variations in the abundance of atmospheric CO2.

  7. Concentration And δ13C Values Of Occluded CO2 In Coexisting Gibbsite And Goethite Of A Cenomanian Paleosol

    NASA Astrophysics Data System (ADS)

    Feng, W.; Yapp, C. J.

    2009-12-01

    The concentrations and δ13C values of CO2 occluded in coexisting gibbsite and goethite from a Cenomanian paleosol in southwestern Minnesota were measured for eight samples collected from different depths in the paleosol. Each sample was split into two aliquots--one of which underwent a 5M NaOH treatment to dissolve gibbsite, while the other was treated with citrate-dithionite (CD) to selectively dissolve goethite. CO2 was extracted from the treated samples using a stepwise vacuum dehydration method. In a plot of δ13C against 1/F (where F = nCO2/nH2O), the pattern of values for increments of evolved CO2 suggests the presence of two generations of goethite. In contrast, there appears to be only one recognizable gibbsite generation, whose samples exhibit well-defined sets of plateau δ13C and F values during incremental dehydration. The gibbsite plateau δ13C values range from -12.8‰ to -9.6‰ among the samples, while the F values range from 0.0009 to 0.0046. A plot of gibbsite plateau δ13C values against 1/F suggests that for all but one sample, there is some correlation with a negative slope (δ13C = -0.023/F -5.1; r2 = 0.53). The negative slope is consistent with crystallization of the gibbsite in the presence of a mixture of three isotopic endmembers of CO2 (CO2 from oxidizing organic matter, CO2 from Earth’s atmosphere, and CO2 from dissolution of a carbonate mineral--e.g. siderite). The three-component mixing environment inferred for the gibbsite is similar to that deduced for the younger generation of goethite (generation 2). Moreover, if gibbsite and goethite formed at the same time at their various depths in this paleosol, they would be expected to show essentially the same pattern of variation of δ13C with depth. This expectation is more nearly realized in a comparison of gibbsite δ13C values with the δ13C values of generation-2 goethite than in a comparison with the robust two-component data from the older generation-1 goethite. If the

  8. 13C-DEPLETED MICROBIAL LIPIDS INDICATE SEASONAL METHANOTROPHIC ACTIVITY IN SHALLOW ESTUARINE SEDIMENTS

    EPA Science Inventory

    Compound specific isotope analysis was combined with phospholipid fatty acid (PLFA) analysis to identify methanotrophic activity in members of the sedimentary microbial community in the Altamaha and Savannah River estuaries in Georgia. 13C-depleted PLFAs indicate methane utilizat...

  9. Mechanisms linking metabolism of Helicobacter pylori to 18O and 13C-isotopes of human breath CO2

    PubMed Central

    Som, Suman; De, Anulekha; Banik, Gourab Dutta; Maity, Abhijit; Ghosh, Chiranjit; Pal, Mithun; Daschakraborty, Sunil B.; Chaudhuri, Sujit; Jana, Subhra; Pradhan, Manik

    2015-01-01

    The gastric pathogen Helicobacter pylori utilize glucose during metabolism, but the underlying mechanisms linking to oxygen-18 (18O) and carbon-13 (13C)-isotopic fractionations of breath CO2 during glucose metabolism are poorly understood. Using the excretion dynamics of 18O/16O and 13C/12C-isotope ratios of breath CO2, we found that individuals with Helicobacter pylori infections exhibited significantly higher isotopic enrichments of 18O in breath CO2 during the 2h-glucose metabolism regardless of the isotopic nature of the substrate, while no significant enrichments of 18O in breath CO2 were manifested in individuals without the infections. In contrast, the 13C-isotopic enrichments of breath CO2 were significantly higher in individuals with Helicobacter pylori compared to individuals without infections in response to 13C-enriched glucose uptake, whereas a distinguishable change of breath 13C/12C-isotope ratios was also evident when Helicobacter pylori utilize natural glucose. Moreover, monitoring the 18O and 13C-isotopic exchange in breath CO2 successfully diagnosed the eradications of Helicobacter pylori infections following a standard therapy. Our findings suggest that breath 12C18O16O and 13C16O16O can be used as potential molecular biomarkers to distinctively track the pathogenesis of Helicobacter pylori and also for eradication purposes and thus may open new perspectives into the pathogen’s physiology along with isotope-specific non-invasive diagnosis of the infection. PMID:26039789

  10. LASER BIOLOGY AND MEDICINE: Laser analysis of the 13C/12C isotope ratio in CO2 in exhaled air

    NASA Astrophysics Data System (ADS)

    Stepanov, E. V.

    2002-11-01

    Tunable diode lasers (TDLs) are applied to the diagnostics of gastroenterological diseases using respiratory tests and preparations enriched with the stable 13C isotope. This method of the analysis of the 13C/12C isotope ratio in CO2 in exhaled air is based on the selective measurement of the resonance absorption at the vibrational — rotational structure of 12CO2 and 13CO2. The CO2 transmission spectra in the region of 4.35 μm were measured with a PbEuSe double-heterostructure TDL. The accuracy of carbon isotope ratio measurements in CO2 of exhaled air performed with the TDL was ~0.5%. The data of clinical tests of the developed laser-based analyser are presented.

  11. Variations in 13C discrimination during CO2 exchange by Picea sitchensis branches in the field.

    PubMed

    Wingate, Lisa; Seibt, Ulli; Moncrieff, John B; Jarvis, Paul G; Lloyd, Jon

    2007-05-01

    We report diurnal variations in (13)C discrimination ((13)Delta) of Picea sitchensis (Bong.) Carr. branches measured in the field using a branch chamber technique. The observations were compared to predicted (13)Delta based on concurrent measurements of branch gas exchange. Observed (13)Delta values were described well by the classical model of (13)Delta including isotope effects during photorespiration, day respiration and CO(2) transfer through a series of resistances to the sites of carboxylation. A simplified linear of model (13)Delta did not capture the observed diurnal variability. At dawn and dusk, we measured very high (13)Delta values that were not predicted by either of the said models. Exploring the sensitivity of (13)Delta to possible respiratory isotope effects, we conclude that isotopic disequilibria between the gross fluxes of photosynthesis and day respiration can explain the high observed (13)Delta values during net photosynthetic gas exchange. Based on the classical model, a revised formulation incorporating an isotopically distinct substrate for day respiration was able to account well for the high observed dawn and dusk (13)Delta values. PMID:17407538

  12. Real-time measurements of CO2 and δ13C in volcanic gases emitted in atmosphere from Mt. Etna (Italy)

    NASA Astrophysics Data System (ADS)

    Jost, H. J. H.; Rizzo, A. L.; Ancellin, M. A.; Caracausi, A.; Martelli, M.; Liotta, M.

    2014-12-01

    We present new data of real-time measurements of concentration and isotope (δ13C) composition of CO2in fumarolic and plume gases emitted from Mt. Etna volcano, performed by using a Delta Ray tunable diode laser. The first two campaigns of measurements were carried out on 11 July and on 5-6 September 2013, while a third campaign was performed in mid-July 2014. Data acquired along the route Catania-Etna, while car was moving, showed an excess of 13C-depleted CO2 when passing through inhabited centers due to atmospheric pollution produced by the cars exhaust. A similar behavior was observed when accidentally measuring car exhaust of our car. Differently, volcanic gases displayed a 13C-enrichment of CO2 if compared to air. With the assumption of a two components mixing, a simple linear regression was applied to the data in order to obtain the volcanogenic δ13C of CO2. Fumaroles of Torre del Filosofo (2,900 m a.s.l.) displayed a δ13C between -3.2±0.03‰ and -3.7±0.05‰, comparable to IRMS measurements of discrete samples collected in the same date and in previous investigations. Diluted plume gases were collected at more than 1 km from the craters and showed δ13C=-2.2±0.2‰, accordingly with collected crater fumaroles. Data collected in 2014 campaign are under processing, but preliminary results confirm a less negative signature of δ13C of CO2emitted from Central Craters if compared to Torre del Filosofo fumaroles, with some interesting variations over time that need to be compared with other simultaneously acquired parameters. Considering the huge amount of data that may be acquired in a very short time by Delta Ray, we demonstrate that the addition to the atmospheric CO2 content of ~100 ppm of CO2 from an unknown source is enough to allow a mathematical calculation of the end-member with an uncertainty generally < 0.15‰. This is feasible with the assumption of a binary mixing. We thus infer that these measurements performed at Mt. Etna, if performed

  13. Correction for the 17O interference in δ(13C) measurements when analyzing CO2 with stable isotope mass spectrometry

    USGS Publications Warehouse

    Coplen, Tyler B.; Brand, Willi A.; Assonov, Sergey S.

    2010-01-01

    Measurements of δ(13C) determined on CO2 with an isotope-ratio mass spectrometer (IRMS) must be corrected for the amount of 17O in the CO2. For data consistency, this must be done using identical methods by different laboratories. This report aims at unifying data treatment for CO2 IRMS by proposing (i) a unified set of numerical values, and (ii) a unified correction algorithm, based on a simple, linear approximation formula. Because the oxygen of natural CO2 is derived mostly from the global water pool, it is recommended that a value of 0.528 be employed for the factor λ, which relates differences in 17O and 18O abundances. With the currently accepted N(13C)/N(12C) of 0.011 180(28) in VPDB (Vienna Peedee belemnite) reevaluation of data yields a value of 0.000 393(1) for the oxygen isotope ratio N(17O)/N(16O) of the evolved CO2. The ratio of these quantities, a ratio of isotope ratios, is essential for the 17O abundance correction: [N(17O)/N(16O)]/[N(13C)/N(12C)] = 0.035 16(8). The equation [δ(13C) ≈ 45δVPDB-CO2 + 2 17R/13R (45δVPDB-CO2 – λ46δVPDB-CO2)] closely approximates δ(13C) values with less than 0.010 ‰ deviation for normal oxygen-bearing materials and no more than 0.026 ‰ in extreme cases. Other materials containing oxygen of non-mass-dependent isotope composition require a more specific data treatment. A similar linear approximation is also suggested for δ(18O). The linear approximations are easy to implement in a data spreadsheet, and also help in generating a simplified uncertainty budget.

  14. 13C Suess effect in scleractinian corals mirror changes in the anthropogenic CO2 inventory of the surface oceans

    NASA Astrophysics Data System (ADS)

    Swart, P. K.; Greer, L.; Rosenheim, B. E.; Moses, C. S.; Winter, A.; Dodge, R. E.; Helmle, K. P.

    2009-12-01

    New δ13C data are presented from ten coral skeletons collected from Florida and the Caribbean. These corals range from 96 to 200 years in age and were collected between 1976 and 2002. The change in the δ13C of the skeletons (Δδ13C/Δt) of these corals has been measured between 1900 and 1990 and have been compared with 26 other published coral records from the Atlantic, Pacific, and Indian Oceans. Together these data make possible a global comparison of Δδ13C/Δt changes in coral skeletons. Of the records, 78 % show a decrease in δ13C towards the modern day, statistically significant (p<0.05) in over 64 % of these records. This decrease is attributable to the addition of anthropogenically derived CO2 to the atmosphere (13C Suess effect). Between 1900 and 1990, the average Δδ13C/Δt in coral skeletons is approximately -0.01 ‰. In the Atlantic Ocean the magnitude of the Δδ13C/Δt since 1960 (-0.019+/-0.015‰/yr) is essentially the same as the decrease observed in the atmosphere and the oceans (-0.023 to -0.029‰/yr), while in the Pacific and Indian Oceans the rate is more variable and significantly reduced (-0.007 +/-0.013 ‰ /yr). These data strongly support the notion that (i) the δ13C of the atmosphere controls ambient δ13C of the dissolved inorganic carbon which in turn is reflected in coral skeletons, (ii) the rate of decline in the coral skeletons is higher in oceans with a greater anthropogenic CO2 inventory in the surface oceans, (iii) the rate of δ13C decline is accelerating.

  15. Characterization of a Mixture of CO2 Adsorption Products in Hyperbranched Aminosilica Adsorbents by (13)C Solid-State NMR.

    PubMed

    Moore, Jeremy K; Sakwa-Novak, Miles A; Chaikittisilp, Watcharop; Mehta, Anil K; Conradi, Mark S; Jones, Christopher W; Hayes, Sophia E

    2015-11-17

    Hyperbranched amine polymers (HAS) grown from the mesoporous silica SBA-15 (hereafter "SBA-15-HAS") exhibit large capacities for CO2 adsorption. We have used static in situ and magic-angle spinning (MAS) ex situ (13)C nuclear magnetic resonance (NMR) to examine the adsorption of CO2 by SBA-15-HAS. (13)C NMR distinguishes the signal of gas-phase (13)CO2 from that of the chemisorbed species. HAS polymers possess primary, secondary, and tertiary amines, leading to multiple chemisorption reaction outcomes, including carbamate (RnNCOO(-)), carbamic acid (RnNCOOH), and bicarbonate (HCO3(-)) moieties. Carbamates and bicarbonate fall within a small (13)C chemical shift range (162-166 ppm), and a mixture was observed including carbamic acid and carbamate, the former disappearing upon evacuation of the sample. By examining the (13)C-(14)N dipolar coupling through low-field (B0 = 3 T) (13)C{(1)H} cross-polarization MAS NMR, carbamate is confirmed through splitting of the (13)C resonance. A third species that is either bicarbonate or a second carbamate is evident from bimodal T2 decay times of the ∼163 ppm peak, indicating the presence of two species comprising that single resonance. The mixture of products suggests that (1) the presence of amines and water leads to bicarbonate being present and/or (2) the multiple types of amine sites in HAS permit formation of chemically distinct carbamates. PMID:26477882

  16. Are δ13C values of n-alkanes affected by atmospheric CO2 concentrations? Results from a free-air CO2 enrichment (FACE) experiment.

    NASA Astrophysics Data System (ADS)

    Sandquist, D. R.; Williams, D. G.; Shuman, B. N.; Kim, S.; Chen, J.; Macdonald, C.

    2015-12-01

    Compound-specific carbon isotope (δ13C) analyses of leaf waxes (i.e., n-alkanes) can be linked to large-scale shifts in vegetation, such as dominant taxa, functional types, life-forms and photosynthetic pathways that are usually coupled with environmental changes in climate. However using these δ13C values to interpret finer-scale ecosystem properties, including climate attributes such as CO2 concentrations, is difficult owing to uncertainty in the magnitude of internal biosynthetic fractionations that determine the δ13C of waxes relative to that of bulk leaf material. We investigated the composition, abundance and δ13C of n-alkanes in the aboveground biomass of a C4 grass and a C3 grass exposed to experimentally controlled CO2 at ambient [490ppm] and elevated [630ppm] levels within natural grassland in Wyoming. The δ13C values of bulk tissues were predictably different based on the C3 and C4 photosynthetic pathways, but the difference between bulk tissue and n-alkanes (ɛlipid), for both C29 and C31, was consistently greater in the C4 grass. The magnitudes of these ɛlipid values were large (- 7‰ to -15‰) relative to those found in most other studies. CO2 concentration of the growing environment also had a significant effect on n-alkane δ13C values, with consistently higher values of ~ 2‰ under elevated CO2 found in both species and in both a wet and a dry year. These results underscore the importance of recognizing potential abiotic effects on leaf wax δ13C values, in addition to the biotic drivers their variation, when interpreting climate from leaf-wax biomarkers of terrestrial ecosystems.

  17. Challenges in measuring the δ13C of the soil surface CO2 efflux.

    PubMed

    Midwood, Andrew J; Millard, Peter

    2011-01-15

    The δ13C of the soil surface efflux of carbon dioxide (δ13CRS) has emerged as a powerful tool enabling investigation of a wide range of soil processes from characterising entire ecosystem respiration to detailed compound-specific isotope studies. δ13CRS can be used to trace assimilated carbon transfer below ground and to partition the overall surface efflux into heterotrophic and autotrophic components. Despite this wide range of applications no consensus currently exists on the most appropriate method of sampling this surface efflux of CO2 in order to measure δ13CRS. Here we consider and compare the methods which have been used, and examine the pitfalls. We also consider a number of analysis options, isotope ratio mass spectrometry (IRMS), tuneable diode laser spectroscopy (TDLS) and cavity ring-down laser spectroscopy (CRDS). δ13CRS is typically measured using chamber systems, which fall into three types: closed, open and dynamic. All are imperfect. Closed chambers often rely on Keeling plots to estimate δ13CRS, which may not be appropriate without free turbulent air mixing. Open chambers have the advantage of being able to maintain steady-state conditions but analytical errors may become limiting with low efflux rates. Dynamic chambers like open chambers are complex, and controlling pressure fluctuations caused by air movement is a key concern. Both open and dynamic chambers in conjunction with field portable TDLS and CRDS analysis systems have opened up the possibility of measuring δ13CRS in real time permitting new research opportunities and are on balance the most suited to this type of measurement. PMID:21181784

  18. Extreme (13)C depletion of carbonates formed during oxidation of biogenic methane in fractured granite.

    PubMed

    Drake, Henrik; Åström, Mats E; Heim, Christine; Broman, Curt; Åström, Jan; Whitehouse, Martin; Ivarsson, Magnus; Siljeström, Sandra; Sjövall, Peter

    2015-01-01

    Precipitation of exceptionally 13C-depleted authigenic carbonate is a result of, and thus a tracer for, sulphate-dependent anaerobic methane oxidation, particularly in marine sediments. Although these carbonates typically are less depleted in 13C than in the source methane, because of incorporation of C also from other sources, they are far more depleted in 13C13C as light as -69‰ V-PDB) than in carbonates formed where no methane is involved. Here we show that oxidation of biogenic methane in carbon-poor deep groundwater in fractured granitoid rocks has resulted in fracture-wall precipitation of the most extremely 13C-depleted carbonates ever reported, δ13C down to -125‰ V-PDB. A microbial consortium of sulphate reducers and methane oxidizers has been involved, as revealed by biomarker signatures in the carbonates and S-isotope compositions of co-genetic sulphide. Methane formed at shallow depths has been oxidized at several hundred metres depth at the transition to a deep-seated sulphate-rich saline water. This process is so far an unrecognized terrestrial sink of methane. PMID:25948095

  19. Extreme 13C depletion of carbonates formed during oxidation of biogenic methane in fractured granite

    PubMed Central

    Drake, Henrik; Åström, Mats E.; Heim, Christine; Broman, Curt; Åström, Jan; Whitehouse, Martin; Ivarsson, Magnus; Siljeström, Sandra; Sjövall, Peter

    2015-01-01

    Precipitation of exceptionally 13C-depleted authigenic carbonate is a result of, and thus a tracer for, sulphate-dependent anaerobic methane oxidation, particularly in marine sediments. Although these carbonates typically are less depleted in 13C than in the source methane, because of incorporation of C also from other sources, they are far more depleted in 13C13C as light as −69‰ V-PDB) than in carbonates formed where no methane is involved. Here we show that oxidation of biogenic methane in carbon-poor deep groundwater in fractured granitoid rocks has resulted in fracture-wall precipitation of the most extremely 13C-depleted carbonates ever reported, δ13C down to −125‰ V-PDB. A microbial consortium of sulphate reducers and methane oxidizers has been involved, as revealed by biomarker signatures in the carbonates and S-isotope compositions of co-genetic sulphide. Methane formed at shallow depths has been oxidized at several hundred metres depth at the transition to a deep-seated sulphate-rich saline water. This process is so far an unrecognized terrestrial sink of methane. PMID:25948095

  20. The 13C Suess effect in scleractinian corals mirror changes in the anthropogenic CO2 inventory of the surface oceans

    NASA Astrophysics Data System (ADS)

    Swart, Peter K.; Greer, Lisa; Rosenheim, Brad E.; Moses, Chris S.; Waite, Amanda J.; Winter, A.; Dodge, Richard E.; Helmle, Kevin

    2010-03-01

    New δ13C data are presented from 10 coral skeletons collected from Florida and elsewhere in the Caribbean (Dominica, Dominican Republic, Puerto Rico, and Belize). These corals range from 96 to 200 years in age and were collected between 1976 and 2002. The change in the δ13C of the skeletons from these corals between 1900 and 1990 has been compared with 27 other published coral records from the Atlantic, Pacific, and Indian Oceans. The new data presented here make possible, for the first time, a global comparison of rates of change in the δ13C value of coral skeletons. Of these records, 64% show a statistically significant (p < 0.05) decrease in δ13C towards the modern day (23 out of 37). This decrease is attributable to the addition of anthropogenically derived CO2 (13C Suess effect) to the atmosphere. Between 1900 and 1990, the average rate of change of the δ13C in all the coral skeletons living under open oceanic conditions is approximately -0.01‰ yr-1. In the Atlantic Ocean the magnitude of the decrease since 1960,-0.019 yr-1 ±0.015‰, is essentially the same as the decrease in the δ13C of atmospheric CO2 and the δ13C of the oceanic dissolved inorganic carbon (-0.023 to -0.029‰ yr-1), while in the Pacific and Indian Oceans the rate is more variable and significantly reduced (-0.007‰ yr-1 ±0.013). These data strongly support the notion that (i) the δ13C of the atmosphere controls ambient δ13C of the dissolved inorganic carbon which in turn is reflected in the coral skeletons, (ii) the rate of decline in the coral skeletons is higher in oceans with a greater anthropogenic CO2 inventory in the surface oceans, (iii) the rate of δ13C decline is accelerating. Superimposed on these secular variations are controls on the δ13C in the skeleton governed by growth rate, insolation, and local water masses.

  1. Bacteria and Fungi Respond Differently to Multifactorial Climate Change in a Temperate Heathland, Traced with 13C-Glycine and FACE CO2

    PubMed Central

    Andresen, Louise C.; Dungait, Jennifer A. J.; Bol, Roland; Selsted, Merete B.; Ambus, Per; Michelsen, Anders

    2014-01-01

    It is vital to understand responses of soil microorganisms to predicted climate changes, as these directly control soil carbon (C) dynamics. The rate of turnover of soil organic carbon is mediated by soil microorganisms whose activity may be affected by climate change. After one year of multifactorial climate change treatments, at an undisturbed temperate heathland, soil microbial community dynamics were investigated by injection of a very small concentration (5.12 µg C g−1 soil) of 13C-labeled glycine (13C2, 99 atom %) to soils in situ. Plots were treated with elevated temperature (+1°C, T), summer drought (D) and elevated atmospheric carbon dioxide (510 ppm [CO2]), as well as combined treatments (TD, TCO2, DCO2 and TDCO2). The 13C enrichment of respired CO2 and of phospholipid fatty acids (PLFAs) was determined after 24 h. 13C-glycine incorporation into the biomarker PLFAs for specific microbial groups (Gram positive bacteria, Gram negative bacteria, actinobacteria and fungi) was quantified using gas chromatography-combustion-stable isotope ratio mass spectrometry (GC-C-IRMS). Gram positive bacteria opportunistically utilized the freshly added glycine substrate, i.e. incorporated 13C in all treatments, whereas fungi had minor or no glycine derived 13C-enrichment, hence slowly reacting to a new substrate. The effects of elevated CO2 did suggest increased direct incorporation of glycine in microbial biomass, in particular in G+ bacteria, in an ecosystem subjected to elevated CO2. Warming decreased the concentration of PLFAs in general. The FACE CO2 was 13C-depleted (δ13C = 12.2‰) compared to ambient (δ13C = ∼−8‰), and this enabled observation of the integrated longer term responses of soil microorganisms to the FACE over one year. All together, the bacterial (and not fungal) utilization of glycine indicates substrate preference and resource partitioning in the microbial community, and therefore suggests a diversified response pattern to future

  2. Monitoring CO2 concentration and δ13C in an underground cavity using a commercial isotope ratio infrared spectrometer

    NASA Astrophysics Data System (ADS)

    Guillon, Sophie; Agrinier, Pierre; Pili, Éric

    2015-04-01

    CO2 stable carbon isotopes are very attractive in environmental research to investigate both natural and anthropogenic carbon sources. Laser-based isotope ratio infrared spectrometers (IRIS) allow in situ continuous monitoring of CO2 isotopes, and therefore they have a potential for unprecedented understanding of carbon sources and dynamics with a high temporal resolution. Here we present the performance assessment of a commercial IRIS analyzer, including the measurement setup and the data processing scheme that we used. Even if the analyzer performs 1-Hz measurements, an integration time of the order of 1 h is commonly needed to obtain acceptable precision for δ13C. The main sources of uncertainty on δ13C come from the concentration dependence and from the temporal instability of the analyzer. The method is applied to the in situ monitoring of the CO2 carbon isotopes in an underground cavity (Roselend Natural Laboratory, France) during several months. On a weekly timescale, the temporal variability of CO2 is dominated by transient contamination by human breath. Discarding these anthropogenic contaminations, CO2 and δ13C backgrounds do not show diurnal or seasonal fluctuations. A CO2 flux released into the tunnel by the surrounding rocks is measured. The carbon isotope composition of this CO2, identified with a Keeling plot, is consistent with a main production by microbial respiration and a minor production from weathering of carbonate minerals. The presented instrument and application study are relevant to cave monitoring, whether to understand CO2 dynamics in visited and/or painted caves for preservation purposes or to understand paleoclimate recording in speleothems.

  3. Rapid detection and characterization of surface CO2 leakage through the real-time measurement of δ13C signatures in CO2 flux from the ground

    NASA Astrophysics Data System (ADS)

    Krevor, S.; Perrin, J.; Esposito, A.; Rella, C.; Benson, S. M.

    2009-12-01

    A portable stable carbon isotope ratio analyzer for carbon dioxide, based on wavelength scanned cavity ringdown spectroscopy, has been used to detect and characterize an intentional leakage of CO2 from an underground pipeline at the ZERT experimental facility in Bozeman, Montana. Rapid (~1 hour) walking surveys of the entire 100m x 100m site were collected using this mobile, real-time instrument. The resulting concentration and 13C isotopic abundance maps were processed using simple yet powerful analysis techniques, permitting not only the identification of specific leakage locations, but providing the ability to distinguish petrogenic sources of CO2 from biogenic sources. At the site an approximately 100-meter horizontal well has been drilled below an alfalfa field at a depth between 1-3 meters below the surface. The well has perforations along the central 70 meters of the well. The overlying strata are highly permeable sand, silt, and topsoil. The flora consists generally of long grasses and was cut to a height of less than 6 inches before the start of the experiment. For 30 days starting July 15, 2009, CO2 was injected at a rate of 0.2 tonnes per day. The injection rate is designed to simulate leakage from a mature storage reservoir at an annual rate of between .001 and .01%. The isotopic composition of the gas from the tank is at δ13C signature of approximately -52‰, far more negative than either atmospheric (approx. -8‰) or CO2 from soil respiration (approx. -26‰) at the site. The CO2 isotopic and concentration measurements were taken with a Picarro WS-CRDS analyzer with 1/8” tubing connected to a sampling inlet. Simultaneous with CO2 concentrations (including 13C), position data was logged using a GPS receiver. Datapoints are taken around every second. The analyzer was powered using batteries and housed in a conventional garden cart. The surveys consisted of traverses of the site along the length of the pipeline and extending out 100 meters on either

  4. Evaluation of 4 years of continuous δ13C(CO2) data using a moving Keeling plot method

    NASA Astrophysics Data System (ADS)

    Vardag, Sanam Noreen; Hammer, Samuel; Levin, Ingeborg

    2016-07-01

    Different carbon dioxide (CO2) emitters can be distinguished by their carbon isotope ratios. Therefore measurements of atmospheric δ13C(CO2) and CO2 concentration contain information on the CO2 source mix in the catchment area of an atmospheric measurement site. This information may be illustratively presented as the mean isotopic source signature. Recently an increasing number of continuous measurements of δ13C(CO2) and CO2 have become available, opening the door to the quantification of CO2 shares from different sources at high temporal resolution. Here, we present a method to compute the CO2 source signature (δS) continuously and evaluate our result using model data from the Stochastic Time-Inverted Lagrangian Transport model. Only when we restrict the analysis to situations which fulfill the basic assumptions of the Keeling plot method does our approach provide correct results with minimal biases in δS. On average, this bias is 0.2 ‰ with an interquartile range of about 1.2 ‰ for hourly model data. As a consequence of applying the required strict filter criteria, 85 % of the data points - mainly daytime values - need to be discarded. Applying the method to a 4-year dataset of CO2 and δ13C(CO2) measured in Heidelberg, Germany, yields a distinct seasonal cycle of δS. Disentangling this seasonal source signature into shares of source components is, however, only possible if the isotopic end members of these sources - i.e., the biosphere, δbio, and the fuel mix, δF - are known. From the mean source signature record in 2012, δbio could be reliably estimated only for summer to (-25.0 ± 1.0) ‰ and δF only for winter to (-32.5 ± 2.5) ‰. As the isotopic end members δbio and δF were shown to change over the season, no year-round estimation of the fossil fuel or biosphere share is possible from the measured mean source signature record without additional information from emission inventories or other tracer measurements.

  5. Rapid detection and characterization of surface CO2 leakage through the real-time measurement of δ13C signatures in CO2 flux from the ground

    NASA Astrophysics Data System (ADS)

    Krevor, Samuel; Benson, Sally; Rella, Chris; Perrin, Jean-Christophe; Esposito, Ariel; Crosson, Eric

    2010-05-01

    The surface monitoring of CO2 over geologic sequestration sites will be an essential tool in the monitoring and verification of sequestration projects. Surface monitoring is the only tool that currently provides the opportunity to detect and quantify leakages on the order of 1000 tons/year CO2. Near-surface detection and quantification can be made complicated, however, due to large temporal and spatial variations in natural background CO2 fluxes from biological processes. In addition, current surface monitoring technologies, such as the use of IR spectroscopy in eddy covariance towers and aerial surveys, radioactive or noble gas isotopic tracers, and flux chamber gas measurements can generally accomplish one or two of the necessary tasks of leak detection, identification, and quantification, at both large spatial scales and high spatial resolution. It would be useful, however, to combine the utility of these technologies so that a much simplified surface monitoring program can be deployed. Carbon isotopes of CO2 provide an opportunity to distinguish between natural biogenic CO2 fluxes from the ground and CO2 leaking from a sequestration reservoir that has ultimate origins in a process giving it a distinct isotopic signature such as natural gas processing. Until recently, measuring isotopic compositions of gases was a time-consuming and expensive process utilizing mass-spectrometry, not practical for deployment in a high-resolution survey of a potential leakage site at the surface. Recent developments in commercially available instruments utilizing wavelength scanned cavity ringdown spectroscopy (WS-CRDS) and Fourier transform infrared spectroscopy (FT-IR) have made it possible to rapidly measure the isotopic composition of gases including the 13C and 12C isotopic composition of CO2 in a field setting. A portable stable carbon isotope ratio analyzer for carbon dioxide, based on wavelength scanned cavity ringdown spectroscopy, has been used to rapidly detect and

  6. Using regional-scale atmospheric δ13C of CO2 as an indicator of ecosystem health and function

    NASA Astrophysics Data System (ADS)

    Alden, C. B.; Miller, J. B.; White, J. W.; Yadav, V.; Michalak, A. M.

    2012-12-01

    Year to year terrestrial CO2 uptake and release is highly variable and is a result of, among other factors, weather and climate variability. One of the key ecosystem parameters that links surface-atmosphere fluxes of energy, water and carbon is stomatal conductance. By measuring and analyzing atmospheric patterns of CO2 and its 13C content over North America, we can begin to identify regional scale changes in stomatal conductance, because conductance is closely related to plant isotopic discrimination. Furthermore, 13C is a useful tracer of the differential responses of C3 and C4 plants to climate and weather anomalies, because C3 and C4 plants have very different isotopic discrimination. Both aspects of the terrestrial carbon cycle are of great interest to those seeking to understand the potential effects of global climate change on cropland and forest productivity, natural CO2 sinks, continental runoff, and continental water and energy exchange with the atmosphere. Our findings may be particularly important for parameterization of process-based models, in light of recent results suggesting that stomatal conductance models driven by vapor pressure deficit (Leuning Model) better predict atmospheric δ13C than do models driven by relative humidity (Ball-Berry Model). For the first time, spatial and temporal density of δ13C of CO2 atmospheric observations may be high enough to allow for regional inversions of δ13CO2 to optimize prior estimates of plant discrimination (and disequilibrium flux -- an isoflux resulting from the combination of a finite residence time of carbon in terrestrial biosphere pools and a changing atmospheric signature due to human burning of fossil fuels with a plant-derived δ13C signature). We perform a Bayesian synthesis inversion for 1) CO2 fluxes and 2) δ13CO2 isofluxes, over the North American region: 145-25°W longitude and 10-80°N latitude. Inversion resolution, in order to avoid aggregation errors, is 1°x1° and 3-hourly, but

  7. Using Atmospheric δ13C of CO2 observations to link the water and carbon cycles with climate

    NASA Astrophysics Data System (ADS)

    Alden, C. B.; Miller, J. B.; White, J. W.; Yadav, V.; Michalak, A. M.; Andrews, A. E.; Huang, L.

    2013-12-01

    The ratio of stable carbon isotopes, 13C:12C in atmospheric CO2 (expressed as δ13C) offers unique insights into atmosphere-land CO2 fluxes and the modulating effects of stomatal conductance on this exchange. Photosynthesis discriminates against 13CO2 during uptake. The magnitude of this fractionation is strongly dependent upon ambient CO2 concentrations and water availability, as well as on the mix of C3 and C4 vegetation types. C3 and C4 plants have very different discrimination because of carboxylation pathways, and C3 stomatal conductance varies with water availability because stomata close to reduce transpiration when plants are water stressed. Further, plant stomata respond to ambient CO2 concentrations in order to optimize leaf internal [CO2] while reducing transpirative water loss. Atmospheric δ13C therefore carries information about local and upwind drought conditions and the consequent likelihood of ground-to-atmosphere water transfer via transpiration, and the balance of latent and sensible heat fluxes, as well as about local and upwind distributions of C3 and C4 vegetation and variability therein. δ13C offers a unique lens through which to identify key thresholds and relationships between climate anomalies/change and the modulating climate impacts of plant biosphere response. By unraveling this relationship at local to continental scales, we stand to gain crucial understanding of the drivers of land CO2 uptake variability as well as knowledge of how to predict future climate impacts on the carbon cycle and vice versa. We use a two-step Bayesian inversion model to optimize 1x1 degree and 3-hourly (interpreted at regional and weekly to monthly scales) fields of δ13C of assimilated biomass over North America for the year 2010, using influence functions generated with FLEXPART, driven by National Centers for Environmental Prediction Global Forecast System meteorology. Prior fluxes and fossil fuel, ocean and fire fluxes are from CarbonTracker 2011, and

  8. Atmospheric CO2 level affects plants' carbon use efficiency: insights from a 13C labeling experiment on sunflower stands

    NASA Astrophysics Data System (ADS)

    Gong, Xiaoying; Schäufele, Rudi; Schnyder, Hans

    2015-04-01

    The increase of atmospheric CO2 concentration has been shown to stimulate plant photosynthesis and (to a lesser extent) growth, thereby acting as a possible sink for the additional atmospheric CO2. However, this effect is dependent on the efficiency with which plants convert atmospheric carbon into biomass carbon, since a considerable proportion of assimilated carbon is returned to the atmosphere via plant respiration. As a core parameter for carbon cycling, carbon use efficiency of plants (CUE, the ratio of net primary production to gross primary production) quantifies the proportion of assimilated carbon that is incorporated into plant biomass. CUE has rarely been assessed based on measurements of complete carbon balance, due to methodological difficulties in measuring respiration rate of plants in light. Moreover, foliar respiration is known to be inhibited in light, thus foliar respiration rate is generally lower in light than in dark. However, this phenomenon, termed as inhibition of respiration in light (IRL), has rarely been assessed at the stand-scale and been incorporated into the calculation of CUE. Therefore, how CUE responses to atmospheric CO2 levels is still not clear. We studied CUE of sunflower stands grown at sub-ambient CO2 level (200 μmol mol-1) and elevated CO2 level (1000 μmol mol-1) using mesocosm-scale gas exchange facilities which enabled continuous measurements of 13CO2/12CO2 exchange. Appling steady-state 13C labeling, fluxes of respiration and photosynthesis in light were separated, and tracer kinetic in respiration was analyzed. This study provides the first data on CUE at a mesocosm-level including respiration in light in different CO2 environments. We found that CUE of sunflower was lower at an elevated CO2 level than at a sub-ambient CO2 level; and the ignorance of IRL lead to erroneous estimations of CUE. Variation in CUE at atmospheric CO2 levels was attributed to several mechanisms. In this study, CO2 enrichment i) affected the

  9. Divergence in delta(13)C of dark respired CO(2) and bulk organic matter occurs during the transition between heterotrophy and autotrophy in Phaseolus vulgaris plants.

    PubMed

    Bathellier, Camille; Badeck, Franz-W; Couzi, Philippe; Harscoët, Sébastien; Mauve, Caroline; Ghashghaie, Jaleh

    2008-01-01

    Substantial evidence has been published in recent years demonstrating that postphotosynthetic fractionations occur in plants, leading to (13)C-enrichment in heterotrophic (as compared with autotrophic) organs. However, less is known about the mechanism responsible for changes in these responses during plant development. The isotopic signature of both organic matter and respired CO(2) for different organs of French bean (Phaseolus vulgaris) was investigated during early ontogeny, in order to identify the developmental stage at which isotopic changes occur. Isotopic analyses of metabolites and mass balance calculations helped to constrain the metabolic processes involved. At the plant scale, apparent respiratory fractionation was constantly positive in the heterotrophic phase (c. 1 per thousand) and turned negative with autotrophy acquisition (down to -3.08 per thousand). Initially very close to that of the dry seed (-26.83 +/- 0.69 per thousand), isotopic signatures of organic matter and respired CO(2) diverged (in opposite directions) in leaves and roots after onset of photosynthesis. Respired CO(2) reached values up to -20 per thousand in leaves and became (13)C-depleted down to -29 per thousand in roots. It was concluded that isotopic differences between organs occurred subsequent to metabolic changes in the seedling during the transition from heterotrophy to autotrophy. They were especially related to respiration and respiratory fractionation. PMID:17953651

  10. REAL TIME CONTINUOUS MEASUREMENTS OF [CO2] AND δ13C AT MULTIPLE LOCATIONS USING CAVITY ENHANCED LASER ABSORPTION

    NASA Astrophysics Data System (ADS)

    McAlexander, W. I.; Rau, G. H.; Dobeck, L.; Spangler, L.

    2009-12-01

    A commercial instrument (Los Gatos Research, model 908-0003) utilizing Cavity Enhanced Laser Absorption Spectroscopy was deployed in 2009 at the ZERT carbon release site (Bozeman, MT) for real time measurement of above-ground CO2 concentration and isotope ratio (δ13C). An automated switching system sampled 13 different locations in the field, as well as two known references, over an 8 day period. Real-time Keeling plots were constructed showing distinct signatures of soil (-27.0 ‰) and fossil (-56.0 ‰) sources compared to background air (-8.2 ‰). Instrument performance gave 0.2 ‰ precision with only 100 seconds of averaging per inlet. Sequential sampling of the various inlets gave a temporal and physical mapping of the CO2 release plume that is difficult to obtain using more conventional techniques. The figures show the nature and quality of the data from one of the locations. Details concerning instrument performance, systematics, calibration, and data processing will be discussed. Fig1: Time chart of CO2 concentration and isotope ratio δ13C from one of 13 sample inlet locations at ZERT release field, July, 2009. Fig2: Keeling plot of data from Fig1 illustrating the two source mixing of soil (-27 ‰) and fossil (-56 ‰) CO2 with background air.

  11. Effect of photosynthesis on the abundance of 18O13C16O in atmospheric CO2

    NASA Astrophysics Data System (ADS)

    Hofmann, Magdalena E. G.; Pons, Thijs L.; Ziegler, Martin; Lourens, Lucas J.; Röckmann, Thomas

    2016-04-01

    The abundance of the isotopologue 18O13C16O (Δ47) in atmospheric air is a promising new tracer for the atmospheric carbon cycle (Eiler and Schauble, 2004; Affek and Eiler, 2006; Affek et al., 2007). The large gross fluxes in CO2 between the atmosphere and biosphere are supposed to play a major role in controlling its abundance. Eiler and Schauble (2004) set up a box model describing the effect of air-leaf interaction on the abundance of 18O13C16O in atmospheric air. The main assumption is that the exchange between CO2 and water within the mesophyll cells will imprint a Δ47 value on the back-diffusing CO2 that reflects the leaf temperature. Additionally, kinetic effects due to CO2 diffusion into and out of the stomata are thought to play a role. We investigated the effect of photosynthesis on the residual CO2 under controlled conditions using a leaf chamber set-up to quantitatively test the model assumptions suggested by Eiler and Schauble (2004). We studied the effect of photosynthesis on the residual CO2 using two C3 and one C4 plant species: (i) sunflower (Helianthus annuus), a C3 species with a high leaf conductance for CO2 diffusion, (ii) ivy (Hedera hibernica), a C3 species with a low conductance, and (iii), maize (Zea mays), a species with the C4 photosynthetic pathway. We also investigated the effect of different light intensities (photosynthetic photon flux density of 200, 700 and 1800 μmol m2s‑1), and thus, photosynthetic rate in sunflower and maize. A leaf was mounted in a cuvette with a transparent window and an adjustable light source. The air inside was thoroughly mixed, making the composition of the outgoing air equal to the air inside. A gas-mixing unit was attached at the entrance of the cuvette that mixed air with a high concentration of scrambled CO2 with a Δ47 value of 0 to 0.1‰ with CO2 free air to set the CO2 concentration of ingoing air at 500 ppm. The flow rate through the cuvette was adjusted to the photosynthetic activity of the

  12. Peatland CO2 emissions: Using 13C to quantify responses to land use change

    NASA Astrophysics Data System (ADS)

    Snell, Helen; Robinson, David; Midwood, Andrew J.

    2013-04-01

    Soil is the largest terrestrial carbon reservoir and annually soils emit about 98 billion tonnes of CO2which is derived from plant root and rhizosphere respiration (autotrophically fuelled by photosynthesis) and microbial degradation of soil organic carbon (heterotrophic respiration). These two processes are intrinsically linked by complex physical and biochemical interactions. In order to meet its GHG reductions targets the Scottish Government plans to increase woodland cover from 17 to 25% by the second half of this century which will inevitably lead to significant tree planting on peatland soils. Tree roots and associated mycorrhiza will alter physical and biological conditions in the soil which may affect the heterotrophic contribution to CO2 emissions and consequently the long term landscape-scale carbon balance since the difference between net primary productivity and heterotrophic respiration defines the terrestrial CO2 sink. Significant uncertainties surround the response of peatlands to tree planting and predicted climate changes. At a field site in eastern Scotland we used natural abundance stable isotopes of carbon to partition soil CO2 efflux into its heterotrophic and autotrophic components to determine whether young Scots pine plantations affect heterotrophic respiration rates in peatland soil. Rate and isotopic composition of soil CO2 efflux was measured in plantation areas and in unforested heather moorland; soil and roots were then excavated and separately incubated to establish the isotopic end members of a simple linear mixing model. Isotopic composition of soil efflux varies temporally and spatially across the site; young Scots pine trees do not increase the heterotrophic flux from soil and therefore do not lead to a net loss of soil carbon from these landscapes.

  13. 13C Tracking after 13CO2 Supply Revealed Diurnal Patterns of Wood Formation in Aspen1

    PubMed Central

    Mahboubi, Amir; Linden, Pernilla; Moritz, Thomas

    2015-01-01

    Wood of trees is formed from carbon assimilated in the photosynthetic tissues. Determining the temporal dynamics of carbon assimilation, subsequent transport into developing wood, and incorporation to cell walls would further our understanding of wood formation in particular and tree growth in general. To investigate these questions, we designed a 13CO2 labeling system to study carbon transport and incorporation to developing wood of hybrid aspen (Populus tremula × tremuloides). Tracking of 13C incorporation to wood over a time course using nuclear magnetic resonance spectroscopy revealed diurnal patterns in wood cell wall biosynthesis. The dark period had a differential effect on 13C incorporation to lignin and cell wall carbohydrates. No 13C was incorporated into aromatic amino acids of cell wall proteins in the dark, suggesting that cell wall protein biosynthesis ceased during the night. The results show previously unrecognized temporal patterns in wood cell wall biosynthesis, suggest diurnal cycle as a possible cue in the regulation of carbon incorporation to wood, and establish a unique 13C labeling method for the analysis of wood formation and secondary growth in trees. PMID:25931520

  14. Dramatic 13C-depletion in the plant methoxyl pool and its global biogeochemical implications

    NASA Astrophysics Data System (ADS)

    Keppler, F.; Kalin, R. M.; Harper, D. B.; McRoberts, C. W.; Hamilton, J. T.

    2004-12-01

    Stable isotope analysis has become a powerful tool for environmental scientists, plant biologists, ecologists and geochemists studying global elemental cycles or past climatic conditions. Thus most plant species have been photosynthetically characterised as Calvin cycle (C3), Slack-Hatch cycle (C4) and Crassulacean acid metabolism (CAM) categories using carbon isotope signatures. Moreover variations in the carbon isotope composition (d13C) of compounds, produced and destroyed in the global carbon cycle, are often used to investigate biogeochemical cycles and global source-sink relationships, as well as the underlying mechanisms. Stable isotope techniques are increasingly applied to the study of atmospheric budgets of volatile organic compounds (VOCs). We report evidence that methoxyl groups in terrestrial plants (in esters and aromatic ethers) have a unique carbon isotope signature exceptionally depleted in 13C. Plant-derived C1 volatile organic compounds (VOCs) are also highly depleted in 13C compared with Cn+1 VOCs. Our observations suggest that the plant methoxyl pool is the predominant source of C1 compounds of plant origin in the biosphere such as methanol, chloromethane, bromomethane, iodomethane, and cyanomethane. Moreover this pool, which comprises approximately 2.5% of carbon in plant biomass and represents an important substrate for methanogenesis, is likely to be a significant source of highly depleted methane entering the atmosphere. The distinct 13C depletion of methoxyl groups in plants which is reflected in isotope signatures of C1 VOCs may provide a helpful tool in constraining complex environmental processes. These isotope anomalies have a tremendous potential to improve our understanding of the global cycles of atmospheric trace gases and the biochemical pathways involved. Furthermore methoxyl groups could act as markers for biological activity in organic matter of terrestrial and extraterrestrial origin.

  15. A 13C labelling study on carbon fluxes in Arctic plankton communities under elevated CO2 levels

    NASA Astrophysics Data System (ADS)

    de Kluijver, A.; Soetaert, K.; Czerny, J.; Schulz, K. G.; Boxhammer, T.; Riebesell, U.; Middelburg, J. J.

    2012-07-01

    The effect of CO2 on carbon fluxes in Arctic plankton communities was investigated during the 2010 EPOCA mesocosm study in Ny Ålesund, Svalbard. Nine mesocosms were set up with initial pCO2 levels ranging from 185 to 1420 μatm for 5 weeks. 13C labelled bicarbonate was added at the start of the experiment to follow the transfer of carbon from dissolved inorganic carbon (DIC) into phytoplankton, bacteria, total particulate organic carbon (POC), zooplankton, and settling particles. Polar lipid derived fatty acids (PLFA) were used to trace carbon dynamics of phytoplankton and bacteria and allowed distinction of two groups of phytoplankton: phyto I (autotrophs) and phyto II (mixotrophs). Nutrients were added on day 13. A nutrient-phytoplankton-zooplankton-detritus model amended with 13C dynamics was constructed and fitted to the data to quantify uptake rates and carbon fluxes in the plankton community during the phase prior to nutrient addition (phase 1, days 0-12). During the first 12 days, a phytoplankton bloom developed that was characterized by high growth rates (0.87 days-1) for phyto I and lower growth rates (0.18 days-1) for phyto II. A large part of the carbon fixed by phytoplankton (~31%) was transferred to bacteria, while mesozooplankton grazed only ~6% of the production. After 6 days, the bloom collapsed and part of the organic matter subsequently settled into the sediment traps. The sedimentation losses of detritus in phase 1 were low (0.008 days-1) and overall export was only ~7% of production. Zooplankton grazing and detritus sinking losses prior to nutrient addition were sensitive to CO2: grazing decreased with increasing CO2, while sinking increased. Phytoplankton production increased again after nutrient addition on day 13. Although phyto II showed initially higher growth rates with increasing CO2 (days 14-22), the overall production of POC after nutrient addition (phase 2, days 14-29) decreased with increasing CO2. Significant sedimentation occurred

  16. Imprint of CO2 emission in atmosphere and biosphere on the basis of 14C and 13C measurements

    NASA Astrophysics Data System (ADS)

    Pazdur, Anna; Gabryś, Alicja; Kuc, Tadeusz; Pawełczyk, Sławomira; Piotrowska, Natalia; Rakowski, Andrzej; Różański, Kazimierz; Sensuła, Barbara

    2015-04-01

    As is shown in the IPCC (Intergovernmental Panel on Climate Change) report, the observed climate changes are caused, among others, by human activity. Mainly emission of CO2 to the atmosphere coming from the burning of fossil fuels, can have dire consequences for life on Earth and development of humankind. The report uses, among others, data obtained from isotopic measurements in the biosphere. Measurements of 14C and 13C concentration in modern atmospheric carbon dioxide and biosphere allow the determination of the decrease of the concentration of this isotope. Furthermore, the magnitude of emission to the atmosphere of carbon dioxide not containing the isotope 14C can be estimated on this basis. Such emission stems from fossil fuel combustion - petroleum, natural gas and black coal. A sensitive bioindicator of the emission are annual tree rings. The measurements of 14C concentration in tree ring material using AMS allow to see its seasonal changes. Trees, treated as an archive of changes in conjunction with information about the isotopic composition of carbon can be used for monitoring of environment as sensitive bioindicators on local, as well as on the global scale. Regular investigations of isotopic composition of carbon in trees have been carried out in the GADAM Centre for the urban areas of both Poland and worldwide. This method can be applied in the study of the emission of CO2 to the atmosphere and its spatial and temporal distribution connected with the production of energy by power plants based on fossil fuel combustion for the area of southern Poland. Modelling of CO2 emission using both 14C and 13C carbon isotopes measured in pine tree rings on the background of climatic changes will be presented. The national ecological policy in the era of global warming requires the manufacturers of energy to get involved in the development of methods suitable for monitoring the state of the environment. Hence, the interest in the area of monitoring the fossil fuel

  17. In situ measurement of magnesium carbonate formation from CO2 using static high-pressure and -temperature 13C NMR.

    PubMed

    Surface, J Andrew; Skemer, Philip; Hayes, Sophia E; Conradi, Mark S

    2013-01-01

    We explore a new in situ NMR spectroscopy method that possesses the ability to monitor the chemical evolution of supercritical CO(2) in relevant conditions for geological CO(2) sequestration. As a model, we use the fast reaction of the mineral brucite, Mg(OH)(2), with supercritical CO(2) (88 bar) in aqueous conditions at 80 °C. The in situ conversion of CO(2) into metastable and stable carbonates is observed throughout the reaction. After more than 58 h of reaction, the sample was depressurized and analyzed using in situ Raman spectroscopy, where the laser was focused on the undisturbed products through the glass reaction tube. Postreaction, ex situ analysis was performed on the extracted and dried products using Raman spectroscopy, powder X-ray diffraction, and magic-angle spinning (1)H-decoupled (13)C NMR. These separate methods of analysis confirmed a spatial dependence of products, possibly caused by a gradient of reactant availability, pH, and/or a reaction mechanism that involves first forming hydroxy-hydrated (basic, hydrated) carbonates that convert to the end-product, anhydrous magnesite. This carbonation reaction illustrates the importance of static (unmixed) reaction systems at sequestration-like conditions. PMID:22676479

  18. Extreme 13C depletion of CCl2F2 in firn air samples from NEEM, Greenland

    NASA Astrophysics Data System (ADS)

    Zuiderweg, A.; Holzinger, R.; Martinerie, P.; Schneider, R.; Kaiser, J.; Witrant, E.; Etheridge, D.; Rubino, M.; Petrenko, V.; Blunier, T.; Röckmann, T.

    2012-07-01

    A series of 12 high volume air samples collected from the S2 firn core during the North Greenland Eemian Ice Drilling (NEEM) 2009 campaign have been measured for mixing ratio and stable carbon isotope composition of the chlorofluorocarbon CFC-12 (CCl2F2). While the mixing ratio measurements compare favorably to other firn air studies, the isotope results show extreme 13C depletion at the deepest measurable depth (65 m), to values lower than δ13C = -80‰ vs. VPDB (the international stable carbon isotope scale), compared to present day surface tropospheric measurements near -40‰. Firn air modeling was used to interpret these measurements. Reconstructed atmospheric time series indicate even larger depletions (to -120‰) near 1950 AD, with subsequent rapid enrichment of the atmospheric reservoir of the compound to the present day value. Mass-balance calculations show that this change must have been caused by a large change in the isotopic composition of anthropogenic CFC-12 emissions, probably due to technological changes in the CFC production process over the last 80 yr. Propagating the mass-balance calculations into the future demonstrates that as emissions decrease to zero, isotopic fractionation by the stratospheric sinks will lead to continued 13C enrichment in atmospheric CFC-12.

  19. A new set-up for simultaneous high-precision measurements of CO2, δ13C-CO2 and δ18O-CO2 on small ice core samples

    NASA Astrophysics Data System (ADS)

    Jenk, Theo Manuel; Rubino, Mauro; Etheridge, David; Ciobanu, Viorela Gabriela; Blunier, Thomas

    2016-08-01

    Palaeoatmospheric records of carbon dioxide and its stable carbon isotope composition (δ13C) obtained from polar ice cores provide important constraints on the natural variability of the carbon cycle. However, the measurements are both analytically challenging and time-consuming; thus only data exist from a limited number of sampling sites and time periods. Additional analytical resources with high analytical precision and throughput are thus desirable to extend the existing datasets. Moreover, consistent measurements derived by independent laboratories and a variety of analytical systems help to further increase confidence in the global CO2 palaeo-reconstructions. Here, we describe our new set-up for simultaneous measurements of atmospheric CO2 mixing ratios and atmospheric δ13C and δ18O-CO2 in air extracted from ice core samples. The centrepiece of the system is a newly designed needle cracker for the mechanical release of air entrapped in ice core samples of 8-13 g operated at -45 °C. The small sample size allows for high resolution and replicate sampling schemes. In our method, CO2 is cryogenically and chromatographically separated from the bulk air and its isotopic composition subsequently determined by continuous flow isotope ratio mass spectrometry (IRMS). In combination with thermal conductivity measurement of the bulk air, the CO2 mixing ratio is calculated. The analytical precision determined from standard air sample measurements over ice is ±1.9 ppm for CO2 and ±0.09 ‰ for δ13C. In a laboratory intercomparison study with CSIRO (Aspendale, Australia), good agreement between CO2 and δ13C results is found for Law Dome ice core samples. Replicate analysis of these samples resulted in a pooled standard deviation of 2.0 ppm for CO2 and 0.11 ‰ for δ13C. These numbers are good, though they are rather conservative estimates of the overall analytical precision achieved for single ice sample measurements. Facilitated by the small sample requirement

  20. Temporal variability in (13)C of respired CO(2) in a pine and a hardwood forest subject to similar climatic conditions.

    PubMed

    Mortazavi, Behzad; Chanton, Jeffrey P; Prater, James L; Oishi, A Christopher; Oren, Ram; Katul, Gabriel

    2005-01-01

    Temporal variability in the (13)C of foliage (delta(13)C(F)), soil (delta(13)C(S)) and ecosystem (delta(13)C(R)) respired CO(2) was contrasted between a 17.2-m tall evenly aged loblolly pine forest and a 35-m tall unevenly aged mature second growth mixed broadleaf deciduous forest in North Carolina, USA, over a 2-year period. The two forests are located at the Duke Forest within a kilometer of each other and are subject to identical climate and have similar soil types. The delta(13)C(F), collected just prior to dawn, was primarily controlled by the time-lagged vapor pressure deficit (VPD) in both stands; it was used for calculating the ratio of intercellular to ambient CO(2) ( Ci/ Ca). A remarkable similarity was observed in the relationship between Ci/ Ca and time-lagged VPD in these two forests despite large differences in hydraulic characteristics. This similarity emerged as a result of physiological adjustments that compensated for differences in plant hydraulic characteristics, as predicted by a recently proposed equilibrium hypothesis, and has implications to ecophysiological models. We found that in the broadleaf forest, the delta(13)C of forest floor CO(2) efflux dominated the delta(13)C(R), while in the younger pine forest, the delta(13)C of foliage respired CO(2) dominated delta(13)C(R). This dependence resulted in a more variable delta(13)C(R) in the pine forest when compared to the broadleaf forest due to the larger photosynthetic contribution. Given the sensitivity of the atmospheric inversion models to delta(13)C(R), the results demonstrate that these models could be improved by accounting for stand characteristics, in addition to previously recognized effects of moisture availability, when estimating delta(13)C(R). PMID:15340829

  1. SOIL RESPIRED D13C SIGNATURES REFLECT ROOT EXUDATE OR ROOT TURNOVER SIGNATURES IN AN ELEVATED CO2 AND OZONE MESOCOSM EXPERIMENT

    EPA Science Inventory

    Bulk tissue and root and soil respired d13C signatures were measured throughout the soil profile in a Ponderosa Pine mesocosm experiment exposed to ambient and elevated CO2 concentrations. For the ambient treatment, root (0-1mm, 1-2mm, and >2mm) and soil d13C signatures were ?24...

  2. The effect of feeding on CO2 production and energy expenditure in ponies measured by indirect calorimetry and the 13C-bicarbonate technique.

    PubMed

    Jensen, R B; Kyrstein, T D; Junghans, P; Tauson, A H

    2015-11-01

    Energy expenditure (EE) can be estimated based on respiratory gas exchange measurements, traditionally done in respiration chambers by indirect calorimetry (IC). However, the (13)C-bicarbonate technique ((13)C-BT) might be an alternative minimal invasive method for estimation of CO(2) production and EE in the field. In this study, four Shetland ponies were used to explore the effect of feeding on CO(2) production and EE measured simultaneously by IC and (13)C-BT. The ponies were individually housed in respiration chambers and received either a single oral or intravenous (IV) bolus dose of (13)C-labelled sodium bicarbonate (NaH(13)CO(3)). The ponies were fed haylage 3 h before (T(-3)), simultaneously with (T(0)) or 3 h after (T(+3)) administration of (13)C-bicarbonate. The CO(2) produced and O(2) consumed by the ponies were measured for 6 h with both administration routes of (13)C-bicarbonate at the three different feeding times. Feeding time affected the CO(2) production (P<0.001) and O(2) consumption (P<0.001), but not the respiratory quotient (RQ) measured by IC. The recovery factor (RF) of (13)C in breath CO(2) was affected by feeding time (P<0.01) and three different RF were used in the calculation of CO(2) production measured by 13C-BT. An average RQ was used for the calculations of EE. There was no difference between IC and (13)C-BT for estimation of CO(2) production. An effect of feeding time (P<0.001) on the estimated EE was found, with higher EE when feed was offered (T(0) and T(+3)) compared with when no feed was available (T -3) during measurements. In conclusion, this study showed that feeding time affects the RF and measurements of CO(2) production and EE. This should be considered when the (13)C-BT is used in the field. IV administration of (13)C-bicarbonate is recommended in future studies with horses to avoid complex (13)C enrichment-time curves with maxima and shoulders as observed in several experiments with oral administration of (13)C

  3. Extreme 13C depletion of CCl2F2 in firn air samples from NEEM, Greenland

    NASA Astrophysics Data System (ADS)

    Zuiderweg, A.; Holzinger, R.; Martinerie, P.; Schneider, R.; Kaiser, J.; Witrant, E.; Etheridge, D.; Petrenko, V.; Blunier, T.; Röckmann, T.

    2013-01-01

    A series of 12 high volume air samples collected from the S2 firn core during the North Greenland Eemian Ice Drilling (NEEM) 2009 campaign have been measured for mixing ratio and stable carbon isotope composition of the chlorofluorocarbon CFC-12 (CCl2F2). While the mixing ratio measurements compare favorably to other firn air studies, the isotope results show extreme 13C depletion at the deepest measurable depth (65 m), to values lower than δ13C = -80‰ vs. VPDB (the international stable carbon isotope scale), compared to present day surface tropospheric measurements near -40‰. Firn air modeling was used to interpret these measurements. Reconstructed atmospheric time series indicate even larger depletions (to -120‰) near 1950 AD, with subsequent rapid enrichment of the atmospheric reservoir of the compound to the present day value. Mass-balance calculations show that this change is likely to have been caused by a large change in the isotopic composition of anthropogenic CFC-12 emissions, probably due to technological advances in the CFC production process over the last 80 yr, though direct evidence is lacking.

  4. Measurement of 13CO2 in expired air as an index of compliance to a high carbohydrate diet naturally enriched in 13C.

    PubMed

    Gay, L J; Schutz, Y; DiVetta, V; Schneiter, P; Tappy, L; Jéquier, E

    1994-09-01

    The aim of this study was to determine whether breath 13CO2 measurements could be used to assess the compliance to a diet containing carbohydrates naturally enriched in 13C. The study was divided into two periods: Period 1 (baseline of 4 days) with low 13C/12C ratio carbohydrates. Period 2 (5 days) isocaloric diet with a high 13C/12C ratio (corn, cane sugar, pineapple, millet) carbohydrates. Measurements were made of respiratory gas exchange by indirect calorimetry, urinary nitrogen excretion and breath 13CO2 every morning in post-absorptive conditions, both in resting state and during a 45-min low intensity exercise (walking on a treadmill). The subjects were 10 healthy lean women (BMI 20.4 +/- 1.7 kg/m2, % body fat 24.4 +/- 1.3%), the 13C enrichment of oxidized carbohydrate and breath 13CO2 were compared to the enrichment of exogenous dietary carbohydrates. At rest the enrichment of oxidized carbohydrate increased significantly after one day of 13C carbohydrate enriched diet and reached a steady value (103 +/- 16%) similar to the enrichment of exogenous carbohydrates. During exercise, the 13C enrichment of oxidized carbohydrate remained significantly lower (68 +/- 17%) than that of dietary carbohydrates. The compliance to a diet with a high content of carbohydrates naturally enriched in 13C may be assessed from the measurement of breath 13CO2 enrichment combined with respiratory gas exchange in resting, postabsorptive conditions. PMID:7812411

  5. Calibration of δ13C and δ18O measurements in CO2 using Off-axis Integrated Cavity Output Spectrometer (ICOS)

    NASA Astrophysics Data System (ADS)

    Joseph, Jobin; Külls, Christoph

    2014-05-01

    The δ13C and δ18O of CO2 has enormous potential as tracers to study and quantify the interaction between the water and carbon cycles. Isotope ratio mass spectrometry (IRMS) being the conventional method for stable isotopic measurements, has many limitations making it impossible for deploying them in remote areas for online or in-situ sampling. New laser based absorption spectroscopy approaches like Cavity Ring Down Spectroscopy (CRDS) and Integrated Cavity Output Spectroscopy (ICOS) have been developed for online measurements of stable isotopes at an expense of considerably less power requirement but with precision comparable to IRMS. In this research project, we introduce a new calibration system for an Off- Axis ICOS (Los Gatos Research CCIA-36d) for a wide range of varying concentrations of CO2 (800ppm - 25,000ppm), a typical CO2 flux range at the plant-soil continuum. The calibration compensates for the concentration dependency of δ13C and δ18O measurements, and was performed using various CO2 standards with known CO2 concentration and δC13 and δO18 values. A mathematical model was developed after the calibration procedure as a correction factor for the concentration dependency of δ13C and δ18O measurements. Temperature dependency of δ13C and δ18O measurements were investigated and no significant influence was found. Simultaneous calibration of δ13C and δ18O is achieved using this calibration system with an overall accuracy of (~ 0.75±0.24 ‰ for δ13C, ~ 0.81 ±0.26‰ for δ18O). This calibration procedure is found to be appropriate for making Off-Axis ICOS suitable for measuring CO2 concentration and δ13C and δ18O measurements at atmosphere-plant-soil continuum.

  6. Analysis of Changes in Biochemical Composition Under Free-Air CO2 enrichment by 13C Nuclear Magnetic Resonance: Leaf Litter, Roots, and Soils From Oak Ridge

    NASA Astrophysics Data System (ADS)

    Hockaday, W. C.; Masiello, C. A.; Baldock, J. A.; Iversen, C. M.; Norby, R. J.

    2007-12-01

    Changes in plant biochemistry as a result of increasing atmospheric carbon dioxide concentration [CO2] influence the cycling of the terrestrial carbon pool and thereby constitute a climate feedback. We have investigated molecular-level changes in the chemical composition of the organic carbon pool of a deciduous forest in Oak Ridge, Tennessee, after 9 years of free-air CO2 enrichment. We employ a novel approach based upon solid-state 13C nuclear magnetic resonance (NMR) analysis and application of a molecular mixing model. This method generates quantitative estimates of total lipids, proteins, carbohydrates, and lignin. 13C NMR spectra were acquired for acid-insoluble soil organic matter from depths of 0 - 5 cm and 5 - 15 cm in two ambient and two elevated [CO2] treatments. In the upper 5 cm, elevated [CO2] soils show a 7% increase in lignin, while lipids and proteins decrease by approximately 10%. Below 5 cm, soil lipid content decreased by 15% relative to ambient [CO2] soils. Changes in the composition of the SOM pool may be attributed to changes in plant biochemistry under elevated [CO2]. Therefore we have performed 13C NMR analysis of major aboveground and belowground biomass inputs: senesced leaves and fine roots (<1 mm diameter). Significant [CO2] effects on root chemistry are observed. Based upon these data, we are able to make a preliminary assessment of the contributions of leaf C and root C to changes in the molecular composition of the SOM pool.

  7. Concentrations and δ13C values of atmospheric CO2 in a less-urbanized environment: Are they different from large metropolitan areas?

    NASA Astrophysics Data System (ADS)

    Childree, P.; FENG, W.; Thieme, D. M.

    2012-12-01

    The carbon isotope compositions (δ13C values) and CO2 concentrations were measured for seventy-four atmospheric samples collected in the city of Valdosta to evaluate the sources of CO2 input in a less developed urban environment. The results are compared to studies conducted in larger metropolitan areas to evaluate possible difference in sources and concentrations. Sixty-one of the samples were collected at four "outdoor" sites within a ~100 km2 area around the city, while thirteen "indoor" samples were collected in classrooms on the Valdosta State University campus, located north of downtown. Four sample collection trips were made from March to April of 2012. The samples were collected from 5 AM to 6 PM to encompass possible diurnal changes in atmospheric CO2. The thirteen indoor air samples had concentrations ranging from 429 to 681 ppmV with δ13C values ranging from -14.0 to -10.3 ‰. The sixty-one outdoor samples ranged from 397 to 539 ppmV with δ13C values ranging from -13.0 to -7.0 ‰. The higher outdoor CO2 concentrations (> 450 ppmV) correspond to lower δ13C values and are for samples collected during prolonged calm periods (wind speed < 1 km/h). At higher wind speed, however, outside air masses (mostly from the Gulf of Mexico) were carried into the region, which led to decreased CO2 levels and increased δ13C values. Therefore, the elevated CO2 readings likely reflected influx of locally produced CO2. On a diagram of δ13C vs.104/CO2 (Keeling plot), the domain occupied by the Valdosta samples is mostly located within the boundaries of two endmember mixing lines: 1) mixing between global atmospheric background and petroleum burning; 2) mixing between global atmospheric background and natural gas burning. Results are compared to those from a Dallas, Texas study that showed more contribution of CO2 from soil respiration and petroleum burning. This study suggests that even in a smaller urban area, fossil fuel consumptions are still the main source of the

  8. Atmospheric CO2 and its δ13C measurements from flask sampling at Lin'an regional background station in China

    NASA Astrophysics Data System (ADS)

    Xia, Lingjun; Zhou, Lingxi; Tans, Pieter P.; Liu, Lixin; Zhang, Gen; Wang, Hongyang; Luan, Tian

    2015-09-01

    This study presents CO2 concentrations of air flask samples obtained at a regional background station Lin'an (LAN) in China from January 2009 to December 2013, as well as their stable isotope ratios (δ13C) from January 2011 to December 2013. Background data is selected to represent background characteristics of atmospheric CO2 and δ13C over Yangzte River Delta. The annual mean background CO2 concentrations vary from 395.0 ppm in 2009 to 407.6 ppm in 2013, with a growth rate of 2.8 ± 0.1 ppm yr-1 over the study period, which is higher than the global average level. The annual mean values of δ13C vary from -8.55‰ in 2011 to -8.73‰ in 2013, with a growth rate of -0.029 ± 0.010‰ yr-1. Seasonal cycles of CO2 concentrations and δ13C are observed to be obvious at LAN. The minimum and maximum values of mean seasonal CO2 cycle appear in August and January, respectively, with the peak-to-peak amplitude of 19.4 ppm. The sign of δ13C seasonal cycle is opposite to that of CO2, and the peak-to-peak amplitude is 0.85‰. The isotopic signature of CO2 sources/sinks (δs) is also discussed in this paper. The estimated δs values for heating season (December-February) is -25.4‰ and for vegetative season is -21.3‰ (March-November) suggest the significant impact of fossil fuel combustions during winter heating season and biological activities during vegetative season.

  9. Microbial 13C utilization patterns via stable isotope probing of phospholipid biomarkers in Mojave Desert soils exposed to ambient and elevated atmospheric CO2

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Changes in plant inputs under changing atmospheric CO2 can be expected to alter the size and/or composition of active soil microbial communities which determine whether soils are a C sink or source. Autotrophically-fixed 13C was traced into phospholipid fatty acid (PLFA) biomarkers in Mojave Desert...

  10. Terrestrial carbon cycle responses to drought and climate stress: New insights using atmospheric observations of CO2 and delta13C

    NASA Astrophysics Data System (ADS)

    Alden, Caroline B.

    Atmospheric concentrations of carbon dioxide (CO2) continue to rise well into the second decade of the new millennium, in spite of broad-scale human understanding of the impacts of fossil fuel emissions on the earth's climate. Natural sinks for CO2 that are relevant on human time scales---the world's oceans and land biosphere---appear to have kept pace with emissions. The continuously increasing strength of the land biosphere sink for CO2 is surpassing expectations given our understanding of the CO2 fertilization and warming effects on the balance between photosynthesis and respiration, especially in the face of ongoing forest degradation. The climate and carbon cycle links between the atmosphere and land biosphere are not well understood, especially at regional (100 km to 10,000 km) scales. The climate modulating effects of changing plant stomatal conductance in response to temperature and water availability is a key area of uncertainty. Further, the differential response to climate change of C3 and C4 plant functional types is not well known at regional scales. This work outlines the development of a novel application of atmospheric observations of delta13C of CO2 to investigate the links between climate and water and carbon cycling and the integrated responses of C3 and C4 ecosystems to climate variables. A two-step Bayesian batch inversion for 3-hourly, 1x1º CO2 fluxes (step one), and for 3-hourly 1x1º delta13C of recently assimilated carbon (step two) is created here for the first time, and is used to investigate links between regional climate indicators and changes in delta13C of the biosphere. Results show that predictable responses of regional-scale, integrated plant discrimination to temperature, precipitation and relative humidity anomalies can be recovered from atmospheric signals. Model development, synthetic data simulations to test sensitivity, and results for the year 2010 are presented here. This dissertation also includes two other applications

  11. Two episodes of 13C-depletion in organic carbon in the latest Permian: Evidence from the terrestrial sequences in northern Xinjiang, China

    NASA Astrophysics Data System (ADS)

    Cao, Changqun; Wang, Wei; Liu, Lujun; Shen, Shuzhong; Summons, Roger E.

    2008-06-01

    New analyses reveal two intervals of distinctly lower δ13C values in the terrestrial organic matter of Permian-Triassic sequences in northern Xinjiang, China. The younger negative δ13C org spike can be correlated to the conspicuous and sharp δ13C drops both in carbonate carbon and organic carbon near the Permian-Triassic event boundary (PTEB) in the marine section at Meishan. The geochemical correlation criteria are accompanied by a magnetic susceptibility pulse and higher abundances of distinctive, chain-like organic fossil remains of Reduviasporonites. The older negative δ13C org spike originates within a latest Permian regression. Significant changes in organic geochemical proxies are recorded in the equivalent interval of the marine section at Meishan. These include relatively higher concentrations of total organic carbon, isorenieratane, C 14-C 30 aryl isoprenoids and lower ratios of pristane/phytane that, together, indicate the onset of anoxic, euxinic and restricted environments within the photic zone. The massive and widespread oxidation of buried organic matter that induced these euxinic conditions in the ocean would also result in increased concentrations of 13C-depleted atmospheric CO 2. The latest Permian environmental stress marked by the older negative δ13C org episode can be correlated with the distinct changeover of ostracod assemblages and the occurrences of morphological abnormalities of pollen grains. These observations imply that biogeochemical disturbance was manifested on the land at the end of the Permian and that terrestrial organisms responded to it before the main extinction of the marine fauna.

  12. Methanogenic calcite, 13C-depleted bivalve shells, and gas hydrate from a mud volcano offshore southern California

    USGS Publications Warehouse

    Hein, J.R.; Normark, W.R.; McIntyre, B.R.; Lorenson, T.D.; Powell, C.L., II

    2006-01-01

    Methane and hydrogen sulfide vent from a cold seep above a shallowly buried methane hydrate in a mud volcano located 24 km offshore southern California in?? 800 m of water. Bivalves, authigenic calcite, and methane hydrate were recovered in a 2.1 m piston core. Aragonite shells of two bivalve species are unusually depleted in 13C (to -91??? ??13C), the most 13C-depleted shells of marine macrofauna yet discovered. Carbon isotopes for both living and dead specimens indicate that they used, in part, carbon derived from anaerobically oxidized methane to construct their shells. The ??13C values are highly variable, but most are within the range -12??? to -91???. This variability may be diagnostic for identifying cold-seep-hydrate systems in the geologic record. Authigenic calcite is abundant in the cores down to ???1.5 m subbottom, the top of the methane hydrate. The calcite is depleted in 13C (??13C = -46??? to -58???), indicating that carbon produced by anaerobically oxidized methane is the main source of the calcite. Methane sources include a geologic hydrocarbon reservoir from Miocene source rocks, and biogenic and thermogenic degradation of organic matter in basin sediments. Oxygen isotopes indicate that most calcite formed out of isotopic equilibrium with ambient bottom water, under the influence of gas hydrate dissociation and strong methane flux. High metal content in the mud volcano sediment indicates leaching of basement rocks by fluid circulating along an underlying fault, which also allows for a high flux of fossil methane. ?? 2006 Geological Society of America.

  13. Understanding 13C(CO2) and 18O(CO2 ) data obtained on CARIBIC aircraft air samples from the tropical troposphere, and the upper troposphere/ lowermost stratosphere

    NASA Astrophysics Data System (ADS)

    Assonov, Sergey S.; Brenninkmeijer, Carl A. M.; Schuck, Tanja J.; Zahn, Andreas; Taylor, Philip

    2010-05-01

    The project CARIBIC (http://caribic-atmospheric.com) aims to study atmospheric chemistry and transport by regularly measuring many compounds in the free troposphere (FT) and the upper troposphere/lowermost stratosphere (UT/LMS) by using passenger aircraft. CO2 isotope ratios were measured by CARIBIC-1 (November-1999 to April-2002, mostly d13C(CO2)) and CARIBIC-2 (June-2007 to March-2009, highest precision d13C(CO2) and d18O(CO2) data). (The latter effort has been possible due to the contribution of JRC-IRMM, Geel, Belgium.) This gives a new, unique and fairly extensive data set for the NH free troposphere and the UT/LMS region. In particular, CARIBIC-2 utilizing high-quality and high-resolution sampling gave a detailed distribution of d18O(CO2), with signals not affected by sampling and canister effects. For the first time we can demonstrate how the variability in air mass origin (recognized by using chemical tracers) is recorded by CO2 isotope signals on the inter-continental scale. There are two main mechanisms responsible: (i) UT/LMS mixing and (ii) seasonality of tropospheric CO2 as well as variable degree of mixing background air and air masses affected by CO2 sources/sinks. In the UT/LMS region both d13C(CO2), d18O(CO2) and CO2 are found to correlate well with stratospheric tracers, in particular N2O. The data for the free and upper troposphere show however little latitudinal gradient and are in good agreement with the data of selected NOAA stations in NH tropics. We discuss that CO2 distribution in the NH FT and UT (at CARIBIC flight routes) is regulated by uplift and pole-wards transport of tropical air. Next, d18O(CO2) is thought to be a new, previously not recognized tracer in the UT/LMS region as well as tracer of gross CO2 fluxes, where CO2 exchanges its oxygen with natural water pools.

  14. Variations in Magmatic He, CO2 and δ13 C during the 2005-06 Seafloor Eruption Near 9°50'N on the East Pacific Rise

    NASA Astrophysics Data System (ADS)

    Graham, D. W.; Michael, P. J.; Rubin, K. H.

    2014-12-01

    We report dissolved (glass) CO2 concentrations, plus vesicle He and C isotope compositions and He and CO2 abundances, for a suite of 23 basalt glasses from the 2005-2006 eruption on the East Pacific Rise. This sample suite provides a unique opportunity to study magma recharge along the mid-ocean ridge, to quantify degassing prior to and during eruption, and to evaluate the extent to which mantle carbon is incorporated into hydrothermal fluids and ultimately into seafloor ecosystems. Our work covers the full spatial and temporal extent of the months-long eruption (ages from 210Po-210Pb dating), and is complementary to a previous study of volatile changes with distance from the vent during part of the eruptive episode (Soule et al. 2013; EPSL). Vesicle 3He/4He is uniform at 8.56±0.04(1σ) RA. Vesicle He and CO2 abundances vary by factors of 17 and 230, respectively. The variability in CO2/He ratio is evidence for kinetic fractionation of He from CO2 during vesiculation, and reveals the potential for using vesicle CO2/He as a relative geo-speedometer for the rate of magma ascent and lava emplacement. Nearly all samples lie in a narrow range of 280-370 ppm for total CO2 (vesicles+glass) suggesting saturation at a depth of ~1.5 km in the crust, similar to the depth of the seismically imaged magma lens. Vesicle CO2/He co-varies positively with the fraction of CO2 contained in vesicles (r2=0.94) and negatively with vesicle δ13C (r2=0.83). The δ13C ranges from -2.6 to -5 per mil, and straddles the value for CO2 in EPR vent fluids (M. Lilley, pers. comm.). The C isotope results are consistent with vapor phase 13C-enrichment during CO2 exsolution from a basaltic melt, as determined experimentally (Javoy et al. 1978; Contrib Mineral Petrol). Collectively the observations are explained by quasi-closed-system degassing, where melt ascent from the magma lens was sufficiently rapid that minimal bubble loss occurred during the eruption and flow of lava onto the seafloor.

  15. In Situ 13C NMR at Elevated-Pressures and -Temperatures Investigating the Conversion of CO2 to Magnesium and Calcium Carbonate Minerals

    NASA Astrophysics Data System (ADS)

    Surface, J. A.; Conradi, M. S.; Skemer, P. A.; Hayes, S. E.

    2013-12-01

    We have constructed specialized NMR hardware to conduct in situ elevated-pressure, elevated-temperature 13C NMR studies of unmixed heterogeneous mixtures of solids, liquids, gases, and supercritical fluids. Specifically, our aim is to monitor CO2 uptake in both ultramafic rocks and in more porous geological materials to understand the mechanisms of chemisorption as a function of temperature, pressure and pH. In this in situ NMR probe, we are able to simulate processes at geologically relevant fluid pressures and temperatures, monitoring the kinetics of CO2 conversion to carbonates. The in situ NMR experiments consist of heterogeneous mixtures of rock, salty brine solution, and moderate pressure CO2 gas at elevated temperatures. The purpose of studying these reactions is to determine efficacy of carbonate formation in various geological reservoirs. Via 13C NMR, we have spectroscopically characterized and quantified the conversion of CO2 to magnesium carbonate and calcium carbonate minerals. When CO2 reacts with the calcium or magnesium in a mineral or rock sample, the 13C chemical shift, linewidth, lineshape, and relaxation times change dramatically. This change can be monitored in situ and provide instantaneous and continuous characterization that maps the chemistry that is taking place. For example, on the pathway to MgCO3 formation, there are a number of phases of Mg(OH)x(H2O)y(CO3)z that are apparent via NMR spectroscopy. We will demonstrate that NMR can be used for quantitative characterization of multiple metastable mineral phases in pure forms and in mixtures. Results are confirmed via powder XRD and Raman spectroscopy of aquo- hydro- carbonato- magnesium species and calcium carbonate species. We also have monitored the 13C spectroscopy to analyze the phase of CO2 (liquid, supercritical, or gas) and its conversion into other forms, such as bicarbonate and carbonate species, providing a "window" into the in situ pH of the reacting system. Reference: 'In Situ

  16. How well do we know VPDB? Variability of delta13C and delta18O in CO2 generated from NBS19-calcite.

    PubMed

    Brand, Willi A; Huang, Lin; Mukai, Hitoshi; Chivulescu, Alina; Richter, Jürgen M; Rothe, Michael

    2009-03-01

    In order to generate a local daughter scale from the material defining the international delta13C and delta18O stable isotope ratio scales (NBS19-calcite),1,2 the carbon and oxygen must be liberated to the gas phase, usually as CO2, using acid digestion of the calcite with H3PO4. It is during this conversion step that systematic errors can occur, giving rise to commonly observed discrepancies in isotopic measurements between different stable isotope laboratories. Scale consistency is of particular importance for air-CO2 isotope records where very small differences in isotopic composition have to be reliably compared between different laboratories and quantified over long time periods.3 The information is vital for estimating carbon budgets on regional and global scales and for understanding their variability under the conditions of climate change. Starting from this requirement a number of CO2 preparations from NBS19 were made at Environment Canada (EC) and analyzed in our laboratories together with Narcis II, a set of well-characterized CO2 samples in sealed tubes available from the National Institute for Environmental Studies (NIES).4,5 Narcis II is very homogeneous in delta13C and delta18O with the isotopic composition close to NBS19-CO2. Among our laboratories the results for delta13C agreed to within +/-0.004 per thousand. The same level of agreement in delta13C was obtained when CO2 was generated from NBS19-calcite using different experimental procedures and conditions in the other two laboratories. For delta18O, the corresponding data were +/-0.011 per thousand when using NBS19-CO2 produced at EC, but discrepancies were enhanced by almost one order of magnitude when NBS19-CO2 was prepared by the other laboratories using slightly different reaction conditions (range=0.13 per thousand).In a second series of experiments, larger amounts of CO2 prepared from NBS19 at the Max-Planck-Institut für Biogeochemie (MPI-BGC) were analyzed together with Narcis II and

  17. How closely do the delta(13)C values of Crassulacean Acid metabolism plants reflect the proportion of CO(2) fixed during day and night?

    PubMed

    Winter, Klaus; Holtum, Joseph A M

    2002-08-01

    The extent to which Crassulacean acid metabolism (CAM) plant delta(13)C values provide an index of the proportions of CO(2) fixed during daytime and nighttime was assessed. Shoots of seven CAM species (Aloe vera, Hylocereus monocanthus, Kalanchoe beharensis, Kalanchoe daigremontiana, Kalanchoe pinnata, Vanilla pauciflora, and Xerosicyos danguyi) and two C(3) species (teak [Tectona grandis] and Clusia sp.) were grown in a cuvette, and net CO(2) exchange was monitored for up to 51 d. In species exhibiting net dark CO(2) fixation, between 14% and 73.3% of the carbon gain occurred in the dark. delta(13)C values of tissues formed inside the cuvette ranged between -28.7 per thousand and -11.6 per thousand, and correlated linearly with the percentages of carbon gained in the light and in the dark. The delta(13)C values for new biomass obtained solely during the dark and light were estimated as -8.7 per thousand and -26.9 per thousand, respectively. For each 10% contribution of dark CO(2) fixation integrated over the entire experiment, the delta(13)C content of the tissue was, thus, approximately 1.8 per thousand less negative. Extrapolation of the observations to plants previously surveyed under natural conditions suggests that the most commonly expressed version of CAM in the field, "the typical CAM plant," involves plants that gain about 71% to 77% of their carbon by dark fixation, and that the isotopic signals of plants that obtain one-third or less of their carbon in the dark may be confused with C(3) plants when identified on the basis of carbon isotope content alone. PMID:12177497

  18. Photosynthetic fractionation of 13C and concentrations of dissolved CO2 in the central equatorial Pacific during the last 255,000 years

    NASA Technical Reports Server (NTRS)

    Jasper, J. P.; Hayes, J. M.; Mix, A. C.; Prahl, F. G.

    1994-01-01

    Carbon isotopically based estimates of CO2 levels have been generated from a record of the photosynthetic fractionation of 13C [is equivalent to epsilon(p)] in a central equatorial Pacific sediment core that spans the last approximately 255 ka. Contents of 13C in phytoplanktonic biomass were determined by analysis of C37 alkadienones. These compounds are exclusive products of Prymnesiophyte algae which at present grow most abundantly at depths of 70-90 m in the central equatorial Pacific. A record of the isotopic composition of dissolved CO2 was constructed from isotopic analyses of the planktonic foraminifera Neogloboquadrina dutertrei, which calcifies at 70-90 m in the same region. Values of epsilon(p), derived by comparison of the organic and inorganic delta values, were transformed to yield concentrations of dissolved CO2 [is equivalent to c(e)] based on a new, site-specific calibration of the relationship between epsilon(p) and c(e). The calibration was based on reassessment of existing epsilon(p) versus c(e) data, which support a physiologically based model in which epsilon(p) is inversely related to c(e). Values of PCO2, the partial pressure of CO2 that would be in equilibrium with the estimated concentrations of dissolved CO2, were calculated using Henry's law and the temperature determined from the alkenone-unsaturation index U(K/37). Uncertainties in these values arise mainly from uncertainties about the appropriateness (particularly over time) of the site-specific relationship between epsilon(p) and 1/c(e). These are discussed in detail and it is concluded that the observed record of epsilon(p) most probably reflects significant variations in delta pCO2, the ocean-atmosphere disequilibrium, which appears to have ranged from approximately 110 microatmospheres during glacial intervals (ocean > atmosphere) to approximately 60 microatmospheres during interglacials. Fluxes of CO2 to the atmosphere would thus have been significantly larger during glacial

  19. Real-time measurements of CH4 and CO2 flux and del13C from a proglacial wetland in southwestern Greenland.

    NASA Astrophysics Data System (ADS)

    Stern, J. C.; White, J. R.; Pratt, L. M.; Thompson, H. A.

    2015-12-01

    Arctic permafrost environments represent a large repository of stored carbon that may be mobilized as global temperatures increase, providing a substrate for microbial CH4 production. Proglacial wetlands and lakes are important targets of study to better understand how rapidly changing landscapes affected by climate warming adapt their carbon cycling. Recent advances in portable laser spectrometry have enabled rapid in situ measurements of not only greenhouse gas fluxes, but also del13C compositions of these gases. Here we use a Picarro CH4 and CO2 isotope analyzer to continuously measure CH4 and CO2 flux in situ for comparison to static closed chamber measurements where samples are collected at discrete time intervals and returned to the laboratory for analysis. Real-time, in situ analysis also allowed simple light/dark experiments to be performed on chambers containing different vegetation. In addition, this instrument can be used to measure concentration and del13C of both dissolved CH4 and CO­­2 in lake waters when appropriate gas stripped methods are used. We present data for CH4 and CO2 flux and del13C of emitted and dissolved gases from permafrost-affected wetlands and lakes associated with proglacial landscapes in southwestern Greenland near the Russell Glacier.

  20. The Werkendam natural CO2 accumulation: An analogue for CO2 storage in depleted oil reservoirs

    NASA Astrophysics Data System (ADS)

    Bertier, Pieter; Busch, Andreas; Hangx, Suzanne; Kampman, Niko; Nover, Georg; Stanjek, Helge; Weniger, Philipp

    2015-04-01

    The Werkendam natural CO2 accumulation is hosted in the Röt (Early Triassic) sandstone of the West Netherlands Basin, at a depth of 2.8 km, about 20 km south-east of Rotterdam (NL). This reservoir, in a fault-bound structure, was oil-filled prior to charging with magmatic CO2 in the early Cretaceous. It therefore offers a unique opportunity to study long-term CO2-water-rock interactions in the presence of oil. This contribution will present the results of a detailed mineralogical and geochemical characterisation of core sections from the Werkendam CO2 reservoir and an adjacent, stratigraphically equivalent aquifer. X-ray diffraction combined with X-ray fluorescence spectrometry revealed that the reservoir samples contain substantially more feldspar and more barite and siderite than those from the aquifer, while the latter have higher hematite contents. These differences are attributed to the effects hydrocarbons and related fluids on diagenesis in the closed system of the CO2 reservoir versus the open-system of the aquifer. Petrophysical analyses yielded overall higher and more anisotropic permeability for the reservoir samples, while the porosity is overall not significantly different from that of their aquifer equivalents. The differences are most pronounced in coarse-grained sandstones. These have low anhydrite contents and contain traces of calcite, while all other analyzed samples contain abundant anhydrite, dolomite/ankerite and siderite, but no calcite. Detailed petrography revealed mm-sized zones of excessive primary porosity. These are attributed to CO2-induced dissolution of precompactional, grain-replacive anhydrite cement. Diagenetic dolomite/ankerite crystals are covered by anhedral, epitaxial ankerite, separated from the crystals by bitumen coats. Since these carbonates were oil-wet before CO2-charging, the overgrowths are interpreted to have grown after CO2-charging. Their anhedral habit suggests growth in a 2-phase water-CO2 system. Isotopic

  1. Carbon transfer, partitioning and residence time in the plant-soil system: a comparison of two 13C-CO2 labelling techniques

    NASA Astrophysics Data System (ADS)

    Studer, Mirjam S.; Siegwolf, Rolf T. W.; Schmidt, Michael W. I.; Abiven, Samuel

    2014-05-01

    13C-CO2 labelling is a powerful tool to study the carbon (C) dynamics in plant-soil systems, whereby various approaches have been applied, differing in the duration of label exposure, the applied label strength and the sampling intervals. We made a direct comparison of the two main 13C-CO2 labelling techniques - pulse and continuous labelling - and evaluated if different approaches yield the same results regarding the C transfer time, C partitioning and the C residence time in different plant-soil compartments. We conducted a pulse labelling (exposure to 99 atom% 13C-CO2 for three hours, traced for eight days) and a continuous labelling (exposure to 10 atom% 13C-CO2, traced for 14 days) on identical plant-soil systems (Populus deltoides x nigra, Cambisol soil) and under controlled environmental conditions. The plant-soil systems were destructively harvested at five sampling dates, and the soil CO2 efflux was sampled throughout the experiments. The 13C distribution into leaves, petioles, stems, cuttings, roots, soil, microbial biomass and soil respiration was analysed and wee applied exponential (pulse labelling) and logistic (continuous labelling) functions to model the C dynamics. Our results confirm that pulse labelling is best suited to assess the minimum C transfer time, while continuous labelling can be applied to assess the C transfer through a compartment, including short-term storage pools. Both experiments yielded the same C partitioning patterns at the specific sampling days, however, the time of sampling was crucial. For example the results of belowground C partitioning were consistent only after eight days of labelling. The C mean residence times estimated by the rate constant of the exponential and logistic function were largely different for the two techniques, mostly due to the strong model assumptions (e.g. steady state). Pulse and continuous labelling techniques are both well suited to assess C cycling. With pulse labelling, the dynamics of fresh

  2. Metabolic Fate of the Carboxyl Groups of Malate and Pyruvate and their Influence on δ13C of Leaf-Respired CO2 during Light Enhanced Dark Respiration

    PubMed Central

    Lehmann, Marco M.; Wegener, Frederik; Barthel, Matti; Maurino, Veronica G.; Siegwolf, Rolf T. W.; Buchmann, Nina; Werner, Christiane; Werner, Roland A.

    2016-01-01

    The enhanced CO2 release of illuminated leaves transferred into darkness, termed “light enhanced dark respiration (LEDR)”, is often associated with an increase in the carbon isotope ratio of the respired CO2 (δ13CLEDR). The latter has been hypothesized to result from different respiratory substrates and decarboxylation reactions in various metabolic pathways, which are poorly understood so far. To provide a better insight into the underlying metabolic processes of δ13CLEDR, we fed position-specific 13C-labeled malate and pyruvate via the xylem stream to leaves of species with high and low δ13CLEDR values (Halimium halimifolium and Oxalis triangularis, respectively). During respective label application, we determined label-derived leaf 13CO2 respiration using laser spectroscopy and the 13C allocation to metabolic fractions during light–dark transitions. Our results clearly show that both carboxyl groups (C-1 and C-4 position) of malate similarly influence respiration and metabolic fractions in both species, indicating possible isotope randomization of the carboxyl groups of malate by the fumarase reaction. While C-2 position of pyruvate was only weakly respired, the species-specific difference in natural δ13CLEDR patterns were best reflected by the 13CO2 respiration patterns of the C-1 position of pyruvate. Furthermore, 13C label from malate and pyruvate were mainly allocated to amino and organic acid fractions in both species and only little to sugar and lipid fractions. In summary, our results suggest that respiration of both carboxyl groups of malate (via fumarase) by tricarboxylic acid cycle reactions or by NAD-malic enzyme influences δ13CLEDR. The latter supplies the pyruvate dehydrogenase reaction, which in turn determines natural δ13CLEDR pattern by releasing the C-1 position of pyruvate. PMID:27375626

  3. Metabolic Fate of the Carboxyl Groups of Malate and Pyruvate and their Influence on δ(13)C of Leaf-Respired CO2 during Light Enhanced Dark Respiration.

    PubMed

    Lehmann, Marco M; Wegener, Frederik; Barthel, Matti; Maurino, Veronica G; Siegwolf, Rolf T W; Buchmann, Nina; Werner, Christiane; Werner, Roland A

    2016-01-01

    The enhanced CO2 release of illuminated leaves transferred into darkness, termed "light enhanced dark respiration (LEDR)", is often associated with an increase in the carbon isotope ratio of the respired CO2 (δ(13)CLEDR). The latter has been hypothesized to result from different respiratory substrates and decarboxylation reactions in various metabolic pathways, which are poorly understood so far. To provide a better insight into the underlying metabolic processes of δ(13)CLEDR, we fed position-specific (13)C-labeled malate and pyruvate via the xylem stream to leaves of species with high and low δ(13)CLEDR values (Halimium halimifolium and Oxalis triangularis, respectively). During respective label application, we determined label-derived leaf (13)CO2 respiration using laser spectroscopy and the (13)C allocation to metabolic fractions during light-dark transitions. Our results clearly show that both carboxyl groups (C-1 and C-4 position) of malate similarly influence respiration and metabolic fractions in both species, indicating possible isotope randomization of the carboxyl groups of malate by the fumarase reaction. While C-2 position of pyruvate was only weakly respired, the species-specific difference in natural δ(13)CLEDR patterns were best reflected by the (13)CO2 respiration patterns of the C-1 position of pyruvate. Furthermore, (13)C label from malate and pyruvate were mainly allocated to amino and organic acid fractions in both species and only little to sugar and lipid fractions. In summary, our results suggest that respiration of both carboxyl groups of malate (via fumarase) by tricarboxylic acid cycle reactions or by NAD-malic enzyme influences δ(13)CLEDR. The latter supplies the pyruvate dehydrogenase reaction, which in turn determines natural δ(13)CLEDR pattern by releasing the C-1 position of pyruvate. PMID:27375626

  4. Concentrations and δ13C values of atmospheric CO2 from oceanic atmosphere through time: polluted and non-polluted areas

    NASA Astrophysics Data System (ADS)

    Longinelli, Antonio; Lenaz, Renzo; Ori, Carlo; Selmo, Enrico

    2005-11-01

    CO2 is one of the primary agents of global climate changes. The increase of atmospheric CO2 concentration is essentially related to human-induced emissions and, particularly, to the burning of fossil fuel whose δ13C values are quite negative. Consequently, an increase of the CO2 concentration in the atmosphere should be paralleled by a decrease of its δ13C. Continuous and/or spot measurements of CO2 concentrations were repeatedly carried out during the last decade and in the same period of the year along hemispheric courses from Italy to Antarctica on a vessel of the Italian National Research Program in Antarctica. During these expeditions, discrete air samples were also collected in 4-l Pyrex flasks in order to carry out precise carbon isotope analyses on atmospheric CO2 from different areas, including theoretically 'clean' open ocean areas, with the main purpose of comparing these open ocean results with the results obtained by the National Oceanic and Atmospheric Administration/World Meteorological Organization (NOAA/WMO) at land-based stations. According to the data obtained for these two variables, a relatively large atmospheric pollution is apparent in the Mediterranean area where the CO2 concentration has reached the value of 384 ppmv while quite negative δ13C values have been measured only occasionally. In this area, southerly winds probably help to reduce the effect of atmospheric pollution even though, despite a large variability of CO2 concentrations, these values are consistently higher than those measured in open ocean areas by a few ppmv to about 10 ppmv. A marked, though non-continuous, pollution is apparent in the area of the Bab-el-Mandeb strait where δ13C values considerably more negative than in the Central and Southern Red Sea were measured. The concentration of atmospheric CO2 over the Central Indian Ocean increased from about 361 ppmv at the end of 1996 to about 373 ppmv at the end of 2003 (mean growth rate of about 1.7 ppmv yr

  5. Biogenic Volatile Organic Compound and Respiratory CO2 Emissions after 13C-Labeling: Online Tracing of C Translocation Dynamics in Poplar Plants

    PubMed Central

    Ghirardo, Andrea; Gutknecht, Jessica; Zimmer, Ina; Brüggemann, Nicolas; Schnitzler, Jörg-Peter

    2011-01-01

    Background Globally plants are the primary sink of atmospheric CO2, but are also the major contributor of a large spectrum of atmospheric reactive hydrocarbons such as terpenes (e.g. isoprene) and other biogenic volatile organic compounds (BVOC). The prediction of plant carbon (C) uptake and atmospheric oxidation capacity are crucial to define the trajectory and consequences of global environmental changes. To achieve this, the biosynthesis of BVOC and the dynamics of C allocation and translocation in both plants and ecosystems are important. Methodology We combined tunable diode laser absorption spectrometry (TDLAS) and proton transfer reaction mass spectrometry (PTR-MS) for studying isoprene biosynthesis and following C fluxes within grey poplar (Populus x canescens) saplings. This was achieved by feeding either 13CO2 to leaves or 13C-glucose to shoots via xylem uptake. The translocation of 13CO2 from the source to other plant parts could be traced by 13C-labeled isoprene and respiratory 13CO2 emission. Principal Finding In intact plants, assimilated 13CO2 was rapidly translocated via the phloem to the roots within 1 hour, with an average phloem transport velocity of 20.3±2.5 cm h−1. 13C label was stored in the roots and partially reallocated to the plants' apical part one day after labeling, particularly in the absence of photosynthesis. The daily C loss as BVOC ranged between 1.6% in mature leaves and 7.0% in young leaves. Non-isoprene BVOC accounted under light conditions for half of the BVOC C loss in young leaves and one-third in mature leaves. The C loss as isoprene originated mainly (76–78%) from recently fixed CO2, to a minor extent from xylem-transported sugars (7–11%) and from photosynthetic intermediates with slower turnover rates (8–11%). Conclusion We quantified the plants' C loss as respiratory CO2 and BVOC emissions, allowing in tandem with metabolic analysis to deepen our understanding of ecosystem C flux. PMID:21387007

  6. Simultaneous 13C/12C and (18)O/(16)O isotope ratio measurements on CO2 based on off-axis integrated cavity output spectroscopy.

    PubMed

    Jost, Hans-Jürg; Castrillo, Antonio; Wilson, H William

    2006-03-01

    A prototype off-axis integrated cavity output spectrometer (OA-ICOS) utilizing two identical cavities together with a near-infrared (1.63 microm) external cavity tunable diode laser is described. The two-cavity design-one for a reference gas and one for a sample gas-takes advantage of classical double-beam infrared spectrometer characteristics in reducing uncertainties due to laser scan or power instabilities and major temperature variations by a factor of three or better compared with a single-cavity scheme. This is the first OA-ICOS instrument designed to determine 13C/12C and (18)O/(16)O ratios from CO2 rotation/vibration fine structure in three different combination bands. Preliminary results indicate that at 0.8 Hz a precision of 3.3 and 2.8 per thousand is obtained for delta13C and delta(18)O, respectively, over a period of 10 h and a pure CO2 gas sample at 26 hPa. By averaging 100 spectra over a subset of the data, we achieved a precision of 1.6 and 0.8 \\permil\\ for delta13C and delta(18)O, respectively. PMID:16500753

  7. 14C and 13C Constraints on CO2 Cycling in Pristine and Deforested Lowland Amazonian Rivers

    NASA Astrophysics Data System (ADS)

    Mayorga, E.; Aufdenkampe, A. K.; Krusche, A. V.; Masiello, C. A.; Quay, P. D.; Richey, J. E.

    2004-12-01

    "Lowland" rivers in the Amazon are those that, unlike the Amazon mainstem, do not drain the Andean cordillera and are not directly influenced by sediments recently eroded from the Andes. The Brazilian Amazon is predominantly drained by lowland watersheds. We examined the sources and fate of CO2 and Dissolved Inorganic Carbon (DIC) in a range of small to large lowland rivers across the region. In particular, we focused on the Ji-Parana basin, which spans the deforestation arc in the state of Rondonia. Carbonate weathering appears to be a strong source of DIC in the western lowland basins (Jurua and Purus); however, carbonate-derived DIC in these systems is completely flushed out downstream through outgassing and mixing with contemporary respiratory CO2 inputs and carbonate-free tributaries. DIC exported from carbonate-free lowland soils appers to be predominantly contemporary, but some regions in the Ji-Parana headwaters export CO2 with a mean age of several decades. In that system, replacement of C3 forests with C4 pastures appears to exert a strong influence on riverine carbon cycling from small to large rivers. Inputs from riparian grasses may play a disproportionately important role. Finally, we found tentative evidence that anoxic conditions in wetlands may result in mineralization of previously protected, aged organic matter, leading to significant aging in riverine DIC.

  8. In Situ 13C and 23Na Magic Angle Spinning NMR Investigation of Supercritical CO2 Incorporation in Smectite-Natural Organic Matter Composites

    SciTech Connect

    Bowers, Geoffrey M.; Hoyt, David W.; Burton, Sarah D.; Ferguson, Brennan O.; Varga, Tamas; Kirkpatrick, Robert J.

    2014-01-29

    This paper presents an in situ NMR study of clay-natural organic polymer systems (a hectoritehumic acid [HA] composite) under CO2 storage reservoir conditions (90 bars CO2 pressure, 50°C). The 13C and 23Na NMR data show that supercritical CO2 interacts more strongly with the composite than with the base clay and does not react to form other C-containing species over several days at elevated CO2. With and without organic matter, the data suggest that CO2 enters the interlayer space of Na-hectorite equilibrated at 43% relative humidity. The presence of supercritical CO2 also leads to increased 23Na signal intensity, reduced line width at half height, increased basal width, more rapid 23Na T1 relaxation rates, and a shift to more positive resonance frequencies. Larger changes are observed for the hectorite-HA composite than for the base clay. In light of recently reported MD simulations of other polymer-Na-smectite composites, we interpret the observed changes as an increase in the rate of Na+ site hopping in the presence of supercritical CO2, the presence of potential new Na+ sorption sites when the humic acid is present, and perhaps an accompanying increase in the number of Na+ ions actively involved in site hopping. The results suggest that the presence of organic material either in clay interlayers or on external particle surfaces can significantly affect the behavior of supercritical CO2 and the mobility of metal ions in reservoir rocks.

  9. The 'Nuts and Bolts' of 13C NMR Spectroscopy at Elevated-Pressures and -Temperatures for Monitoring In Situ CO2 Conversion to Metal Carbonates

    NASA Astrophysics Data System (ADS)

    Moore, J. K.; Surface, J. A.; Skemer, P. A.; Conradi, M. S.; Hayes, S. E.

    2013-12-01

    We will present details of newly-constructed specialized NMR designed to conduct in situ elevated-pressure, elevated-temperature 13C NMR studies on unmixed slurries of minerals in the presence of CO2 or other gases. This static probe is capable of achieving 300 bar, 300C conditions, and it is designed to spectroscopically examine 13C signals in mixtures of solids, liquids, gases, and supercritical fluids. Ultimately, our aim is to monitor CO2 uptake in both ultramafic rocks and in more porous geological materials to understand the mechanisms of chemisorption as a function of temperature, pressure and pH. We will give details of the hardware setup, and we will show a variety of static in situ NMR, as well as ex situ 'magic-angle spinning' NMR to show the analyses that are possible of minerals in pure form and in mixtures. In addition, specific NMR pulse sequences, techniques, and modeling will be described in detail. In this in situ NMR probe, we are able to simulate processes at geologically relevant fluid pressures and temperatures, monitoring the kinetics of CO2 conversion to carbonates. The in situ NMR experiments consist of heterogeneous mixtures of rock, salty brine solution, and moderate pressure CO2 gas at elevated temperatures. The purpose of studying these reactions is to determine conditions that affect the efficacy of carbonate formation in various targeted geological reservoirs (i.e., peroditite, or others). Via 13C NMR, we have spectroscopically characterized and quantified the conversion of CO2 to magnesium carbonate and calcium carbonate minerals, including metastable intermediates (such as hydromagnesite, or dypingite in the case of magnesium carbonate species, or vaterite in the case of calcium carbonate species). Such species are distinguishable from a combination of the 13C isotropic chemical shift, the static 13C lineshape, and changes in spin-lattice (T1) relaxation times. We will demonstrate that NMR can be used for quantitative

  10. Chemical structures of coal lithotypes before and after CO2 adsorption as investigated by advanced solid-state 13C nuclear magnetic resonance spectroscopy

    USGS Publications Warehouse

    Cao, X.; Mastalerz, Maria; Chappell, M.A.; Miller, L.F.; Li, Y.; Mao, J.

    2011-01-01

    Four lithotypes (vitrain, bright clarain, clarain, and fusain) of a high volatile bituminous Springfield Coal from the Illinois Basin were characterized using advanced solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. The NMR techniques included quantitative direct polarization/magic angle spinning (DP/MAS), cross polarization/total sideband suppression (CP/TOSS), dipolar dephasing, CHn selection, and recoupled C-H long-range dipolar dephasing techniques. The lithotypes that experienced high-pressure CO2 adsorption isotherm analysis were also analyzed to determine possible changes in coal structure as a result of CO2 saturation at high pressure and subsequent evacuation. The main carbon functionalities present in original vitrain, bright clarain, clarain and fusain were aromatic carbons (65.9%-86.1%), nonpolar alkyl groups (9.0%-28.9%), and aromatic C-O carbons (4.1%-9.5%). Among these lithotypes, aromaticity increased in the order of clarain, bright clarain, vitrain, and fusain, whereas the fraction of alkyl carbons decreased in the same order. Fusain was distinct from other three lithotypes in respect to its highest aromatic composition (86.1%) and remarkably small fraction of alkyl carbons (11.0%). The aromatic cluster size in fusain was larger than that in bright clarain. The lithotypes studied responded differently to high pressure CO2 saturation. After exposure to high pressure CO2, vitrain and fusain showed a decrease in aromaticity but an increase in the fraction of alkyl carbons, whereas bright clarain and clarain displayed an increase in aromaticity but a decrease in the fraction of alkyl carbons. Aromatic fused-rings were larger for bright clarain but smaller for fusain in the post-CO2 adsorption samples compared to the original lithotypes. These observations suggested chemical CO2-coal interactions at high pressure and the selectivity of lithotypes in response to CO2 adsorption. ?? 2011 Elsevier B.V.

  11. Seasonal variations in δ13C and δ18O of atmospheric CO2 measured in the urban boundary layer over Vancouver, Canada in relation to fuel emissions.

    NASA Astrophysics Data System (ADS)

    Lee, J.; Christen, A.; Ketler, R.; Nesic, Z.; Schwendenmann, L.; Semmens, C.

    2014-12-01

    Recent advances in techniques to measure carbon dioxide (CO2) in urban plumes show potential for validating and monitoring emission inventories at regional to urban scale. A major challenge remains the attribution of elevated CO2 in urban plumes to different fuel and biogenic sources. Stable isotopes are a promising source of additional information. Here, we report a full year of measurements of CO2 mixing ratios, δ13C and δ18O in CO2 in the urban boundary layer over Vancouver, Canada. The goal of the work is to link seasonally changing isotopic composition to dominant fuel sources and put the urban enhancement into the context of regional background concentrations. Atmospheric composition in the urban atmosphere was measured continuously using a tunable diode laser absorption system (TGA 200, Campbell Scientific, Logan, UT, USA). In addition, end member signatures were determined by means of bag samples from representative fuel emission sources (gasoline, diesel, natural gas). While δ13C depends on the fuel type and origin (for Vancouver in 2013/14: δ13C gasoline 27.2‰; diesel -28.8‰; natural gas -41.6‰), δ18O is fractionated in catalytic converters (d18O gasoline vehicles -12.5‰; diesel -18.6‰; natural gas -22.7‰) and exhibits higher variability between samples. Additional signatures were determined for human, soil and plant respiration. During the study year, monthly mean mixing ratios in the urban atmosphere ranged between 410.5 (Jul) and 425.7 ppm (Dec), which was on average 18 ppm elevated above the regional background. As expected, mean monthly δ13C was lower in winter than summer with seasonally changing intercepts between -33.6‰ (JJF) and -27.7‰ (MJJ). Making the simple assumption that natural gas and gasoline are the only major fuel sources, natural gas would contribute ~45% to emissions in winter and ~3% in early summer, which is lower than the downscaled Local Emissions Inventory (57% in winter and 20% in summer). Mean δ18O showed

  12. Identification of /sup 13/C depleted mantle carbon in diamonds from the Roberts Victor Kimberlite, South Africa

    SciTech Connect

    Deines, P.

    1985-01-01

    The Roberts Victor Kimberlite is known for the abundance of eclogite xenoliths, some of which show an unusual depletion in /sup 18/O. The question whether the observed oxygen isotope variations can be related to carbon isotopic composition variations has been investigated. Peridotite-suite diamons (X = -5.4 per thousand vs. PDB, s = +/-0.9 per thousand, n = 65) and sulfide containing diamonds (X = -4.9, s = +/-0.9, n = 20) do not differ in their /sup 13/C content. For these samples, delta/sup 13/C is not related to diamond shape, color, minerals occluded, or the inclusion chemistry. Eclogite suite diamonds (11) can be subdivided into two groups, GI and GII, based on delta/sup 13/C : GI = (X = -15.4, s = +/-0.4, n = 8); GII = (X = -5.9, s = +/-0.4, n = 3). The composition of the gt and cpx inclusions of the two groups is distinct; e.g. cpx of GI is significantly depleted in SiO/sub 2/, MgO, and CaO, and significantly enriched in Al/sub 2/O/sub 3/, FeO and MnO, compared to cpx of GII. Comparison of the chemical composition of the inclusions in E-type diamonds with those of eclogite xenoliths showing /sup 18/O depletion suggests that /sup 13/C and /sup 18/O depletion are not likely to be related. Evaluation of compositional trends of gt and cpx in eclogite xenoliths indicates that GI and GII are not related by a single fractionation event, but represent products from different reservoirs. Equilibration conditions deduced from coexisting gt and cpx demonstrate that GI diamonds come from larger depths than eclogite xenoliths and by inference GII diamonds. The high FeO and MnO content of a gt inclusion in cpx of an eclogite xenolith is used to argue for the existence of two separate events responsible for the formation of GI and GII diamonds.

  13. Improved mass analysis of oligoribonucleotides by 13C, 15N double depletion and electrospray ionization FT-ICR mass spectrometry.

    PubMed

    Xiong, Ying; Schroeder, Kersten; Greenbaum, Nancy L; Hendrickson, Christopher L; Marshall, Alan G

    2004-03-15

    13C, 15N doubly depleted 32-ribonucleotide was synthesized enzymatically by in vitro transcription from nucleoside triphosphates isolated from E. coli grown in a minimal medium containing 12C, 14N-enriched glucose and ammonium sulfate. Following purification and desalting by reversed-phase HPLC, buffer exchange with Microcon YM-3, and ethanol precipitation, electrospray ionization Fourier transform ion cyclotron resonance mass spectra revealed greatly enhanced abundance of monoisotopic ions (by a factor of approximately 100) and a narrower isotopic distribution with higher signal-to-noise ratio. The abrupt onset and high magnitude of the monoisotopic species promise to facilitate accurate mass measurement of RNA's. PMID:15018587

  14. Monitoring the bio-stimulation of hydrocarbon-contaminated soils by measurements of soil electrical properties, and CO2 content and its 13C/12C isotopic signature

    NASA Astrophysics Data System (ADS)

    Noel, C.; Gourry, J.; Ignatiadis, I.; Colombano, S.; Dictor, M.; Guimbaud, C.; Chartier, M.; Dumestre, A.; Dehez, S.; Naudet, V.

    2013-12-01

    Hydrocarbon contaminated soils represent an environmental issue as it impacts on ecosystems and aquifers. Where significant subsurface heterogeneity exists, conventional intrusive investigations and groundwater sampling can be insufficient to obtain a robust monitoring of hydrocarbon contaminants, as the information they provide is restricted to vertical profiles at discrete locations, with no information between sampling points. In order to obtain wider information in space volume on subsurface modifications, complementary methods can be used like geophysics. Among geophysical methods, geoelectrical techniques such as electrical resistivity (ER) and induced polarization (IP) seem the more promising, especially to study the effects of biodegradation processes. Laboratory and field geoelectrical experiments to characterize soils contaminated by oil products have shown that mature hydrocarbon-contaminated soils are characterized by enhanced electrical conductivity although hydrocarbons are electrically resistive. This high bulk conductivity is due to bacterial impacts on geological media, resulting in changes in the chemical and physical properties and thus, to the geophysical properties of the ground. Moreover, microbial activity induced CO2 production and isotopic deviation of carbon. Indeed, produced CO2 will reflect the pollutant isotopic signature. Thus, the ratio δ13C(CO2) will come closer to δ13C(hydrocarbon). BIOPHY, project supported by the French National Research Agency (ANR), proposes to use electrical methods and gas analyses to develop an operational and non-destructive method for monitoring in situ biodegradation of hydrocarbons in order to optimize soil treatment. Demonstration field is located in the South of Paris (France), where liquid fuels (gasoline and diesel) leaked from some tanks in 1997. In order to stimulate biodegradation, a trench has been dug to supply oxygen to the water table and thus stimulate aerobic metabolic bioprocesses. ER and

  15. Carbon flux analysis by 13C nuclear magnetic resonance to determine the effect of CO2 on anaerobic succinate production by Corynebacterium glutamicum.

    PubMed

    Radoš, Dušica; Turner, David L; Fonseca, Luís L; Carvalho, Ana Lúcia; Blombach, Bastian; Eikmanns, Bernhard J; Neves, Ana Rute; Santos, Helena

    2014-05-01

    Wild-type Corynebacterium glutamicum produces a mixture of lactic, succinic, and acetic acids from glucose under oxygen deprivation. We investigated the effect of CO2 on the production of organic acids in a two-stage process: cells were grown aerobically in glucose, and subsequently, organic acid production by nongrowing cells was studied under anaerobic conditions. The presence of CO2 caused up to a 3-fold increase in the succinate yield (1 mol per mol of glucose) and about 2-fold increase in acetate, both at the expense of l-lactate production; moreover, dihydroxyacetone formation was abolished. The redistribution of carbon fluxes in response to CO2 was estimated by using (13)C-labeled glucose and (13)C nuclear magnetic resonance (NMR) analysis of the labeling patterns in end products. The flux analysis showed that 97% of succinate was produced via the reductive part of the tricarboxylic acid cycle, with the low activity of the oxidative branch being sufficient to provide the reducing equivalents needed for the redox balance. The flux via the pentose phosphate pathway was low (~5%) regardless of the presence or absence of CO2. Moreover, there was significant channeling of carbon to storage compounds (glycogen and trehalose) and concomitant catabolism of these reserves. The intracellular and extracellular pools of lactate and succinate were measured by in vivo NMR, and the stoichiometry (H(+):organic acid) of the respective exporters was calculated. This study shows that it is feasible to take advantage of natural cellular regulation mechanisms to obtain high yields of succinate with C. glutamicum without genetic manipulation. PMID:24610842

  16. Carbon Flux Analysis by 13C Nuclear Magnetic Resonance To Determine the Effect of CO2 on Anaerobic Succinate Production by Corynebacterium glutamicum

    PubMed Central

    Radoš, Dušica; Turner, David L.; Fonseca, Luís L.; Carvalho, Ana Lúcia; Blombach, Bastian; Eikmanns, Bernhard J.; Neves, Ana Rute

    2014-01-01

    Wild-type Corynebacterium glutamicum produces a mixture of lactic, succinic, and acetic acids from glucose under oxygen deprivation. We investigated the effect of CO2 on the production of organic acids in a two-stage process: cells were grown aerobically in glucose, and subsequently, organic acid production by nongrowing cells was studied under anaerobic conditions. The presence of CO2 caused up to a 3-fold increase in the succinate yield (1 mol per mol of glucose) and about 2-fold increase in acetate, both at the expense of l-lactate production; moreover, dihydroxyacetone formation was abolished. The redistribution of carbon fluxes in response to CO2 was estimated by using 13C-labeled glucose and 13C nuclear magnetic resonance (NMR) analysis of the labeling patterns in end products. The flux analysis showed that 97% of succinate was produced via the reductive part of the tricarboxylic acid cycle, with the low activity of the oxidative branch being sufficient to provide the reducing equivalents needed for the redox balance. The flux via the pentose phosphate pathway was low (∼5%) regardless of the presence or absence of CO2. Moreover, there was significant channeling of carbon to storage compounds (glycogen and trehalose) and concomitant catabolism of these reserves. The intracellular and extracellular pools of lactate and succinate were measured by in vivo NMR, and the stoichiometry (H+:organic acid) of the respective exporters was calculated. This study shows that it is feasible to take advantage of natural cellular regulation mechanisms to obtain high yields of succinate with C. glutamicum without genetic manipulation. PMID:24610842

  17. Multi-isotope labelling of organic matter by diffusion of 2H/18O-H2O vapour and 13C-CO2 into the leaves and its distribution within the plant

    NASA Astrophysics Data System (ADS)

    Studer, M. S.; Siegwolf, R. T. W.; Leuenberger, M.; Abiven, S.

    2015-03-01

    Isotope labelling is a powerful tool to study elemental cycling within terrestrial ecosystems. Here we describe a new multi-isotope technique to label organic matter (OM). We exposed poplars (Populus deltoides × nigra) for 14 days to an atmosphere enriched in 13CO2 and depleted in 2H218O. After 1 week, the water-soluble leaf OM (δ13C = 1346 ± 162‰) and the leaf water were strongly labelled (δ18O = -63 ± 8, δ2H = -156 ± 15‰). The leaf water isotopic composition was between the atmospheric and stem water, indicating a considerable back-diffusion of vapour into the leaves (58-69%) in the opposite direction to the net transpiration flow. The atomic ratios of the labels recovered (18O/13C, 2H/13C) were 2-4 times higher in leaves than in the stems and roots. This could be an indication of the synthesis of more condensed compounds in roots and stems (e.g. lignin vs. cellulose) or might be the result of O and H exchange and fractionation processes during phloem transport and biosynthesis. We demonstrate that the three major OM elements (C, O, H) can be labelled and traced simultaneously within the plant. This approach could be of interdisciplinary interest in the fields of plant physiology, palaeoclimatic reconstruction or soil science.

  18. A kinetic model relating the leaf uptake of carbonyl sulfide (COS) to water and CO2 fluxes and 13C fractionation

    NASA Astrophysics Data System (ADS)

    Seibt, Ulrike; Berry, Joe; Sandoval-Soto, Lisseth; Kuhn, Uwe; Kesselmeier, Jürgen

    2010-05-01

    Carbonyl sulfide (COS) is an atmospheric trace gas that holds great promise for studies of terrestrial carbon and water exchange. During photosynthesis, COS and CO2 follow the same pathway and are both taken up in enzyme reactions in leaves. We have developed a simple model of leaf COS uptake, analogous to the equations for CO2 and water fluxes. Leaf COS uptake predicted from the new equation was in good agreement with data from field and laboratory chambers, although with large uncertainties. We also obtained first estimates for the ratio of conductances of COS and water vapour. Empirically derived estimates were 2.0 ± 0.3 for laboratory data on Fagus sylvatica and 2.2 ± 0.8 for field data on Quercus agrifolia, both close to the theoretical estimate of 2.0 ± 0.2. As a consequence of the close coupling of leaf COS and CO2 uptake, the normalized uptake ratio of COS and CO2 can be used to provide estimates of Ci-Ca, the ratio of intercellular to atmospheric CO2, an important plant gas exchange parameter that cannot be measured directly. Published normalized COS to CO2 uptake ratios for leaf studies on a variety of species fall in the range of 1.5 to 4, corresponding to Ci-Ca ratios of 0.5 to 0.8. In addition, we utilize the coupling of Ci-Ca and photosynthetic 13C discrimination to derive an estimate of 2.8 ± 0.3 for the global mean normalized uptake ratio. This corresponds to a global vegetation sink of COS in the order of 900 ± 100 Gg S yr-1. Similarly, COS and 13C discrimination can be combined to obtain independent estimates of photosynthesis (GPP). The new process-oriented description provides a framework for understanding COS fluxes that should improve the usefulness of atmospheric COS data to obtain estimates of gross photosynthesis and stomatal conductance at regional to global scales.

  19. Prominent bacterial heterotrophy and sources of 13C-depleted fatty acids to the interior Canada Basin

    NASA Astrophysics Data System (ADS)

    Shah, S. R.; Griffith, D. R.; Galy, V.; McNichol, A. P.; Eglinton, T. I.

    2013-11-01

    In recent decades, the Canada Basin of the Arctic Ocean has experienced rapidly decreasing summer sea ice coverage and freshening of surface waters. It is unclear how these changes translate to deeper waters, particularly as our baseline understanding of organic carbon cycling in the deep basin is quite limited. In this study, we describe full-depth profiles of the abundance, distribution and carbon isotopic composition of fatty acids from suspended particulate matter at a seasonally ice-free station and a semi-permanently ice-covered station. Fatty acids, along with suspended particulate organic carbon (POC), are more concentrated and 13C-enriched under ice cover than in ice-free waters. But this influence, apparent at 50 m depth, does not propagate downward below 150 m depth, likely due to the weak biological pump in the central Canada Basin. Branched fatty acids have δ13C values that are similar to suspended POC at all depths and are more 13C-enriched than even-numbered saturated fatty acids at depths above 3000 m. These are likely to be produced in situ by heterotrophic bacteria incorporating organic carbon that is isotopically similar to total suspended POC. Below surface waters, there is also the suggestion of a source of saturated even-numbered fatty acids which could represent contributions from laterally advected organic carbon and/or from chemoautotrophic bacteria. At 3000 m depth and below, a greater relative abundance of long-chain (C20-24), branched and unsaturated fatty acids is consistent with a stronger influence of re-suspended sedimentary organic carbon. At these deep depths, two individual fatty acids (C12 and iso-C17) are significantly depleted in 13C, allowing for the possibility that methane oxidizing bacteria contribute fatty acids, either directly to suspended particulate matter or to shallow sediments that are subsequently mobilized and incorporated into suspended particulate matter within the deep basin.

  20. Geologic Sequestration of CO2 in a Depleted Oil Reservoir: A Field Demonstration

    NASA Astrophysics Data System (ADS)

    Westrich, H. R.; Zhang, D.; Grigg, R. B.

    2002-12-01

    Carbon dioxide (CO2) sequestration in geologic formations is the most direct carbon management strategy for long-term removal of anthropogenic CO2 from the atmosphere, and is likely to be needed for continuation of the US fossil fuel-based economy and high standard of living. Subsurface injection of CO2 into depleted oil reservoirs is a carbon sequestration strategy that might prove to be both cost effective and environmentally safe. However, there are significant R&D gaps that need to be addressed prior to sequestration of CO2 in depleted oil reservoirs, including the need of coupled physicochemical processes involving CO2, water, oil and reservoir rock, better estimates of the capacity of reservoir for long-term sequestration and ultimate fate of injected CO2, and improved geophysical monitoring technologies for accurately determining the presence and location of injected CO2. Our project is part of the DOE Carbon Sequestration program and it is directed at predicting and monitoring the migration and ultimate fate of CO2 after injection in a depleted oil reservoir. We utilize computer simulations of multiphase oil-brine-CO2 flow in the reservoir, laboratory measurements of geochemical brine-rock reactions, and geophysical surveys to monitor CO2 plume migration after injection. A principal component of this project is characterization and validation of predicted CO2 migration and fate through a field demonstration experiment. The reservoir under investigation is part of the West Pearl Queen field in southeastern New Mexico. Geologic modeling and numerical flow simulations (ECLIPSE code) have been used to study the feasibility of injection, and these techniques were used to help in designing geophysical monitoring studies to track the injected plume. Long-term static brine-rock reactions and short-term brine-CO2-oil flow through tests were performed to better understand the likely geochemical reactions that might be influence CO2 sequestration or injection. Results

  1. Safe storage and effective monitoring of CO2 in depleted gas fields.

    PubMed

    Jenkins, Charles R; Cook, Peter J; Ennis-King, Jonathan; Undershultz, James; Boreham, Chris; Dance, Tess; de Caritat, Patrice; Etheridge, David M; Freifeld, Barry M; Hortle, Allison; Kirste, Dirk; Paterson, Lincoln; Pevzner, Roman; Schacht, Ulrike; Sharma, Sandeep; Stalker, Linda; Urosevic, Milovan

    2012-01-10

    Carbon capture and storage (CCS) is vital to reduce CO(2) emissions to the atmosphere, potentially providing 20% of the needed reductions in global emissions. Research and demonstration projects are important to increase scientific understanding of CCS, and making processes and results widely available helps to reduce public concerns, which may otherwise block this technology. The Otway Project has provided verification of the underlying science of CO(2) storage in a depleted gas field, and shows that the support of all stakeholders can be earned and retained. Quantitative verification of long-term storage has been demonstrated. A direct measurement of storage efficiency has been made, confirming that CO(2) storage in depleted gas fields can be safe and effective, and that these structures could store globally significant amounts of CO(2). PMID:22184225

  2. Prominent bacterial heterotrophy and sources of 13C-depleted fatty acids to the interior Canada Basin

    NASA Astrophysics Data System (ADS)

    Shah, S. R.; Griffith, D. R.; Galy, V.; McNichol, A. P.; Eglinton, T. I.

    2013-04-01

    In recent decades, the Canada Basin of the Arctic Ocean has experienced rapidly decreasing summer sea ice coverage and freshening of surface waters. It is unclear how these changes translate to depth, particularly as our baseline understanding of organic carbon cycling in the deep basin is limited. In this study, we describe full-depth profiles of the abundance, distribution and carbon isotopic composition of fatty acids from suspended particulate matter at a seasonally ice-free station and a semi-permanently ice-covered station. Fatty acids, along with suspended particulate organic carbon (POC), are more concentrated under ice cover than in ice-free waters. But this influence, apparent at 50 m depth, does not propagate downward below 150 m depth, likely due to the weak biological pump in the central Canada Basin. Branched fatty acids have δ13C values that are similar to suspended POC at all depths and are 13C-enriched compared to even-numbered saturated fatty acids at depths above 3000 m. These are likely to be produced in situ by heterotrophic bacteria incorporating organic carbon that is isotopically similar to total suspended POC. A source of saturated even-numbered fatty acids is also suggested below surface waters which could represent contributions from laterally advected organic carbon or from chemoautotrophic bacteria. At 3000 m depth and below, a greater relative abundance of long-chain (C20-24), branched and unsaturated fatty acids is consistent with a stronger influence of re-suspended sedimentary organic carbon on benthic particulate matter. At these deep depths, two individual fatty acids (C12 and iso-C17) are significantly depleted in 13C, allowing for the possibility that methane oxidizing bacteria contribute fatty acids, either directly to suspended particulate matter or to shallow sediments that are subsequently mobilized and incorporated into suspended particulate matter within the deep basin.

  3. Understanding the role of soil erosion on co2-c loss using (13)c isotopic signatures in abandoned Mediterranean agricultural land.

    PubMed

    Novara, Agata; Keesstra, Saskia; Cerdà, Artemio; Pereira, Paulo; Gristina, Luciano

    2016-04-15

    Understanding soil water erosion processes is essential to evaluate the redistribution of soil organic carbon (SOC) within a landscape and is fundamental to assess the role of soil erosion in the global carbon (C) budget. The main aim of this study was to estimate the C redistribution and losses using (13)C natural abundance. Carbon losses in soil sediment, dissolved organic carbon (DOC) and CO2 emission were determined. Four bounded parallel plots were installed on a 10% slope. In the upper part of the plots, C3soil was replaced with C4soil. The SOC and δ(13)C were measured after 145.2mm rainfall in the upper (2m far from C4strip), middle (4m far from C4strip) lower (6m far from C4strip) trams of the plot and in the sediments collected in the Gerlach collector at the lower part of the plot. A laboratory incubation experiment was performed to evaluate the CO2 emission rate of soils in each area. OC was mainly lost in the sediments as 2.08g(-)(2) of C was lost after 145.2mm rainfall. DOC losses were only 5.61% of off-site OC loss. Three months after the beginning of the experiment, 15.90% of SOC in the upper tram of the plot had a C4 origin. The C4-SOC content decreased along the 6m length of the plot, and in the sediments collected by the Gerlach collector. CO2 emission rate was high in the upper plot tram due to the high SOC content. The discrimination of CO2 in C3 and C4 portion permitted to increase our level of understanding on the stability of SOC and its resilience to decomposition. The transport of sediments along the plot increased SOC mineralization by 43%. Our study underlined the impact of rainfall in C losses in soil and water in abandoned Mediterranean agriculture fields and the consequent implications on the C balance. PMID:26820936

  4. Interpretation of speleothem calcite δ13C variations: Evidence from monitoring soil CO2, drip water, and modern speleothem calcite in central Texas

    NASA Astrophysics Data System (ADS)

    Meyer, Kyle W.; Feng, Weimin; Breecker, Daniel O.; Banner, Jay L.; Guilfoyle, Amber

    2014-10-01

    We studied the sources and transport of carbon in two active karst systems in central Texas, Inner Space Cavern (IS) and Natural Bridge North and South Caverns (NB), to provide new insights into the interpretation of speleothem (cave calcite deposit) carbon isotope compositions. We have determined the δ13C values of soil CO2 (δ13Cs) in grassland and savanna above these caves with δ13C values of cave drip water (δ13CHCO3-) and modern speleothem calcite grown on artificial substrates (δ13Ccc). We compare δ13CHCO3- values from direct drip sites, where water was sampled immediately upon discharging from the cave ceiling, to values from indirect sites, where water was sampled after flowing along a prolonged path within the cave that allowed for longer CO2 degassing and have found that direct drip sites yield consistently lower δ13CHCO3- values. The δ13CHCO3- values of direct drip water below savanna (-10.6 ± 0.5‰ and -12.6 ± 0.2‰, in NB and IS, respectively) are indistinguishable from (IS) or similar to (NB) calculated δ13CHCO3- values in equilibrium with measured soil CO2 beneath trees (-13.5‰ to -11.3‰ for juniper trees above NB, and -13.6‰ to -12.6‰ for mixed oak and elm trees above IS, respectively). At IS, the δ13CHCO3- values of direct drip water are higher below grassland (-9.7 ± 0.3‰) than below savanna (12.6 ± 0.2‰). These results suggest that the δ13CHCO3- values of drip waters that initially enter the caves are controlled by deep-rooted plants, where present, and are minimally influenced by host-rock dissolution and/or prior calcite precipitation (PCP). The δ13CHCO3- values of indirect drip water vary seasonally with relatively low values during the summer (-10.8 ± 0.8‰ and -9.2 ± 0.4‰ under juniper savanna at NB and under grassland at IS, respectively) that are similar to the direct drip δ13CHCO3- values (-10.6 ± 0.5‰ and -9.7 ± 0.3‰ under savanna at NB and under grassland at IS, respectively). The relatively high

  5. Continuous high-resolution measurements of dissolved CH4, CO2 and δ13C-CO2 in surface water during the SWERUS-C3 expedition in the East Siberian Arctic Ocean

    NASA Astrophysics Data System (ADS)

    Geibel, Marc Christoph; Magnus Mörth, Carl; Humborg, Christoph; Semiletov, Igor

    2015-04-01

    The carbon budget in the Arctic is still unknown. Especially the fate of CH4 from subsea permafrost on the East Siberian Arctic Shelf (ESAS) is unclear. In July-September 2014 the joined SWERUS-C3 expedition on board the Swedish icebreaker ODEN was undertaken. Among its goals was to get a better insight into the fate of carbon in the Arctic, to document possible CH4 release from subsea permafrost and deep sea and to understand mechanisms and magnitudes of CH4 release to the atmosphere. During the first leg of the expedition the in situ concentration of dissolved CH4, CO2 as well as the δ13C signature of CO2 were determined. Measurements were made continuously with a Water Equilibration Gas Analyzer System (WEGAS) that was specifically developed at Stockholm University for the determination of gases dissolved in water. The aim of this study was to quantify the concentration of dissolved CO2 and CH4 in the surface water of the East Siberian Arctic Ocean (ESAO) as well as the contribution of terrestrial organic matter respiration to the dissolved inorganic carbon (DIC). Combined with continuous high-precision atmospheric measurements that were performed during the SWERUS-C3 expedition, the WEGAS dataset will allow to calculate accurate high-resolution CH4 fluxes and thus give a better insight into the current outgassing of CH4 to the atmosphere. Together with measurements of δ13C of inorganic carbon that was sampled during the expedition, the isotopic composition of the dissolved organic carbon pool will allow to quantify the of terrestrial carbon contribution to total respiration in the ESAO.

  6. Role of Geomechanics in Assessing the Feasibility of CO2 Sequestration in Depleted Hydrocarbon Sandstone Reservoirs

    NASA Astrophysics Data System (ADS)

    Fang, Zhi; Khaksar, Abbas

    2013-05-01

    Carbon dioxide (CO2) sequestration in depleted sandstone hydrocarbon reservoirs could be complicated by a number of geomechanical problems associated with well drilling, completions, and CO2 injection. The initial production of hydrocarbons (gas or oil) and the resulting pressure depletion as well as associated reduction in horizontal stresses (e.g., fracture gradient) narrow the operational drilling mud weight window, which could exacerbate wellbore instabilities while infill drilling. Well completions (casing, liners, etc.) may experience solids flowback to the injector wells when injection is interrupted due to CO2 supply or during required system maintenance. CO2 injection alters the pressure and temperature in the near wellbore region, which could cause fault reactivation or thermal fracturing. In addition, the injection pressure may exceed the maximum sustainable storage pressure, and cause fracturing and fault reactivation within the reservoirs or bounding formations. A systematic approach has been developed for geomechanical assessments for CO2 storage in depleted reservoirs. The approach requires a robust field geomechanical model with its components derived from drilling and production data as well as from wireline logs of historical wells. This approach is described in detail in this paper together with a recent study on a depleted gas field in the North Sea considered for CO2 sequestration. The particular case study shows that there is a limitation on maximum allowable well inclinations, 45° if aligning with the maximum horizontal stress direction and 65° if aligning with the minimum horizontal stress direction, beyond which wellbore failure would become critical while drilling. Evaluation of sanding risks indicates no sand control installations would be needed for injector wells. Fracturing and faulting assessments confirm that the fracturing pressure of caprock is significantly higher than the planned CO2 injection and storage pressures for an ideal

  7. Synchronous negative carbon isotope shifts in marine and terrestrial biomarkers at the onset of the early Aptian oceanic anoxic event 1a: Evidence for the release of 13C-depleted carbon into the atmosphere

    NASA Astrophysics Data System (ADS)

    van Breugel, Yvonne; Schouten, Stefan; Tsikos, Harilaos; Erba, Elisabetta; Price, Gregory D.; Sinninghe Damsté, Jaap S.

    2007-03-01

    A common feature of records of the early Aptian oceanic anoxic event (OAE) 1a is the sharp negative δ13C excursion displayed in both carbonate and organic matter at the onset of this event. A synchronous negative δ13C excursion has also been noted for terrestrial organic matter. This negative excursion has been attributed to either an injection of 13C-depleted light carbon into the atmosphere or, in case of marine sediments, recycling of 13C-depleted CO2. However, most studies were done on separate cores, and no information on the relative timing of the negative spikes in terrestrial versus marine records has been obtained. Here we examine early Aptian core sections from two geographically distal sites (Italy and the mid-Pacific) to elucidate the causes and relative timing of this negative "spike." At both sites, increased organic carbon (Corg) and decreased bulk carbonate contents characterize the interval recording OAE 1a (variously referred to as the "Selli event"). The organic material within the "Selli level" is immature and of autochthonous origin. Measured δ13C values of marine and terrestrial biomarkers largely covary with those of bulk organic carbon, with lowest values recorded at the base of the organic-rich section. By contrast, sediments enveloping the "Selli level" exhibit very low Corg contents, and their extractable Corg is predominantly of allochthonous origin. Hydrous pyrolysis techniques used to obtain an autochthonous, pre-Selli δ13C value for algal-derived pristane from corresponding sample material yielded a negative δ13C shift of up to 4‰. A negative δ13C shift of similar magnitude was also measured for the terrigenous n-alkanes. The results are collectively best explained by means of a massive, syndepositional, rapid input of 13C-depleted carbon into the atmosphere and surface oceans, likely delivered either via methane produced from the dissociation of sedimentary clathrates or perhaps by widespread thermal metamorphism of Corg

  8. Metal Carbonation of Forsterite in Supercritical CO2 and H2O Using Solid State 29Si, 13C NMR Spectroscop

    SciTech Connect

    Kwak, Ja Hun; Hu, Jian Z.; Hoyt, David W.; Sears, Jesse A.; Wang, Chong M.; Rosso, Kevin M.; Felmy, Andrew R.

    2010-03-11

    Ex situ solid state NMR was used for the first time to study fundamental mineral carbonation processes and reaction extent relevant to geologic carbon sequestration (GCS) using a model silicate mineral forsterite (Mg2SiO4)+supercriticalCO2 with and without H2O. Run conditions were 80 C and 96 atm. 29Si NMR clearly shows that in the absence of CO2, the role of H2O is to hydrolyze surface Mg-O-Si bonds to produce dissolved Mg2+, and mono- and oligomeric hydroxylated silica species. Surface hydrolysis products contain only Q0 (Si(OH)4) and Q1(Si(OH)3OSi) species. An equilibrium between Q0, Q1 and Mg2+ with a saturated concentration equivalent to less than 3.2% of the Mg2SiO4 conversion is obtained at a reaction time of up to 7 days. Using scCO2 without H2O, no reaction is observed within 7 days. Using both scCO2 and H2O, the surface reaction products for silica are mainly Q3 (SiOH(OSi)3) species accompanied by a lesser amount of Q2 (Si(OH)2(OSi)2) and Q4 (Si(OSi)4). However, no Q0 and Q1 were detected, indicating the carbonic acid formation/deprotonation and magnesite (MgCO3) precipitation reactions are faster than the forsterite hydrolysis process. Thus it can be concluded that the Mg2SiO4 hydrolysis process is the rate limiting step of the overall mineral carbonation process. 29Si NMR combined with XRD, TEM, SAED and EDX further reveal that the reaction is a surface reaction with the Mg2SiO4 crystallite in the core and with condensed Q2-Q4 species forming amorphous surface layers. 13C MAS NMR identified a possible reaction intermediate as (MgCO3)4-Mg(OH)2-5H2O. However, at long reaction times only crystallite magnesite MgCO3 products are observed.

  9. Simulations of Arctic ozone depletion with current and doubled levels of CO2

    NASA Technical Reports Server (NTRS)

    Butchart, Neal; Austin, John; Shine, Keith P.

    1994-01-01

    Results from idealized 3-D simulations of a dynamical-radiative-photochemical model of the stratosphere are presented for the Northern Hemisphere winter and spring. For a simulation of a quiescent winter, it is found that with current levels of CO2 only modest polar ozone depletion occurs, consistent with observations. For a second simulation with the same planetary wave amplitudes in the upper troposphere but with doubled CO2, the model predicts a northern hemisphere ozone hole comparable to that observed in Antarctica with almost complete ozone destruction at 20 km. Reasons for the marked difference between the simulations are identified.

  10. Interdisciplinary Investigation of CO2 Sequestration in Depleted Shale Gas Formations

    SciTech Connect

    Zoback, Mark D.; Kovscek, Anthony R.; Wilcox, Jennifer

    2013-09-30

    This project investigates the feasibility of geologic sequestration of CO2 in depleted shale gas reservoirs from an interdisciplinary viewpoint. It is anticipated that over the next two decades, tens of thousands of wells will be drilled in the 23 states in which organic-rich shale gas deposits are found. This research investigates the feasibility of using these formations for sequestration. If feasible, the number of sites where CO2 can be sequestered increases dramatically. The research embraces a broad array of length scales ranging from the ~10 nanometer scale of the pores in the shale formations to reservoir scale through a series of integrated laboratory and theoretical studies.

  11. Reconstitution of Cu2+-depleted bovine serum amine oxidase with Co2+.

    PubMed Central

    Agostinelli, E; De Matteis, G; Mondovì, B; Morpurgo, L

    1998-01-01

    Two different Cu2+-depleted derivatives of bovine serum amine oxidase (BSAO) have recently been prepared, which contain about 0.5 mol/dimer of phenylhydrazine-reactive topa quinone (TPQ) cofactor and, depending on the reagents used, about 0.2 or 0.7 residual Cu2+/dimer [Agostinelli, De Matteis, Sinibaldi, Mondovi and Morpurgo (1997) Biochem. J. 324, 497-501]. The benzylamine oxidase activity of both derivatives was <5% and increased up to approximately 20% on incorporation of Co2+, irrespective of the residual Cu2+ content, which was unaffected by the treatment according to atomic absorption and ESR spectroscopy. The residual Cu2+ ions appeared to be distributed one per dimer and to be bound to inactive subunits, whereas Co2+ was bound to active subunits. The change in the active site had an appreciable influence on the kinetic behaviour. With several amines, the kinetic parameters, Km and kc, measured for Co2+-BSAO were different from those for native BSAO. This excludes the possibility that the catalytic activity was due to residual Cu2+. Furthermore, Co2+ restored to nearly native level the intensity of the TPQ 480 nm band and the reactions with phenylhydrazine or benzylhydrazine, which had been slowed down or abolished, respectively, in Cu2+-depleted samples. The CD spectrum, measured for the derivative with low Cu2+ content, was compatible with Co2+ binding to the copper site. The amine oxidase activity of the Co2+ derivative, which cannot form a semiquinone radical as an intermediate of the catalytic reaction, strongly suggests that the Cu+-semiquinone is not an obligatory intermediate of BSAO catalytic pathway. PMID:9461534

  12. CLEAN - Large-Scale CO2 Storage for Enhanced Gas Recovery in a depleted German Gasfield

    NASA Astrophysics Data System (ADS)

    Kühn, Michael; Baltrusch, Steffi; Dahmke, Andreas; Förster, Andrea; Großmann, Jochen; Meyer, Robert; Reinicke, Kurt

    2010-05-01

    The joint research project CLEAN is a German research and development (R&D) alliance of 16 partners from science and industry. The main theme of this pilot project is to enhance gas recovery (EGR) by injection of CO2 into an almost depleted natural gas field. The research focus is on the assessment of all processes associated with the injection. At the same time, the CO2 long-term storage safety of Europe's second largest onshore gas field is analysed and evaluated. The CLEAN study site is located in Saxony-Anhalt (Germany) and is part of the natural gas field Altmark owned by GDF SUEZ E&P Deutschland GmbH. Here, the test field Altensalzwedel, which covers an area of 14 km2, represents a structurally and hydraulically enclosed substructure. The structure is characterized in detail by 12 existing deep wells. Fluviatile silt- and sandstones from Upper Rotliegend built the reservoir in around 3,500 metres depth. The caprock above the reservoir consists of massive Zechstein formations with significant deposits of evaporites. These salt layers with average thickness of several hundred metres represent a natural seal of the reservoir. At present the reservoir temperature is about 125 °C and reservoir pressures decreased from initially 425 bar to pressures between 30 and 50 bar, due to the gas production. For the substructure of Altensalzwedel it is assessed that the natural gas reservoir is depleted by 90 %. In the course of the pilot project CLEAN, less than 100,000 tonnes of CO2 will be injected for the EGR measures. An enhanced R&D program is performed to control existing wells, to advance the monitoring, and to improve the process modelling as a solid basis for a decent risk assessment, which is prerequisite for a future large-scale EGR project associated with the injection and storage of CO2. Within this field, some fundamental scientific, ecological and economical questions will be addressed and answered: Which technology is the most efficient and safe one to

  13. Canopy structure and atmospheric flows in relation to the δ13C of respired CO2 in a subalpine coniferous forest

    USGS Publications Warehouse

    Schaeffer, Sean M.; Anderson, Dean E.; Burns, Sean P.; Monson, Russell K.; Sun, Jielun; Bowling, David R.

    2008-01-01

    Stable isotopes provide insight into ecosystem carbon cycling, plant physiological processes, atmospheric boundary-layer dynamics, and are useful for the integration of processes over multiple scales. Of particular interest is the carbon isotope content (δ13C) of nocturnal ecosystem-respired CO2 (δR). Recent advances in technology have made it possible to continuously examine the variation in δR within a forest canopy over relatively long time-scales (months–years). We used tunable diode laser spectroscopy to examine δR at within- and below-canopy spatial locations in a Colorado subalpine forest (the Niwot Ridge AmeriFlux site). We found a systematic pattern of increased δR within the forest canopy (δR-c) compared to that near the ground (δR-g). Values of δR-c were weakly correlated with the previous day's mean maximum daytime vapor pressure deficit (VPD). Conversely, there was a negative but still weak correlation between δR-g and time-lagged (0–5 days) daily mean soil moisture. The topography and presence of sustained nightly drainage flows at the Niwot Ridge forest site suggests that, on nights with stable atmospheric conditions, there is little mixing of air near the ground with that in the canopy. Atmospheric stability was assessed using thresholds of friction velocity, stability above the canopy, and bulk Richardson number within the canopy. When we selectively calculated δR-g and δR-c by removing time periods when ground and canopy air were well mixed, we found stronger correlations between δR-c and VPD, and δR-g and soil moisture. This suggests that there may be fundamental differences in the environmental controls on δR at sub-canopy spatial scales. These results may help explain the wide variance observed in the correlation of δR with different environmental parameters in other studies.

  14. Analysis of accurate 13C and 18O isotope measurements of CO2 in CARIBIC aircraft air samples from the tropical troposphere, and the upper troposphere/lowermost stratosphere

    NASA Astrophysics Data System (ADS)

    Assonov, S. S.; Brenninkmeijer, C. A. M.; Schuck, T. J.; Taylor, P.

    2010-03-01

    The project CARIBIC (http://caribic-atmospheric.com) aims to study atmospheric chemistry and transport by regularly measuring many compounds in the free troposphere (FT) and the upper troposphere/lowermost stratosphere (UT/LMS) by using passenger aircraft. Here CO2 concentrations and highly accurate isotope results are presented in detail together with supporting trace gas data. 509 CARIBIC-2 samples (highest precision and accuracy δ13C(CO2) and δ18O(CO2) data) from June 2007 until March 2009, together with CARIBIC-1 samples (flights between November 1999 and April 2002, 350 samples in total, 270 for NH, mostly δ13C(CO2) data) give a fairly extensive, unique data set for the NH free troposphere and the UT/LMS region. To compare data from different years a de-trending is applied. In the UT/LMS region δ13C(CO2), δ18O(CO2) and CO2 are found to correlate well with stratospheric tracers, in particular N2O. These correlations are in good agreement with current understanding of stratospheric circulation. δ18O(CO2) appears to be a useful, hitherto unused, tracer of atmospheric transport in the UT/LMS region. By filtering out the LMS data (based on N2O distribution), the isotope variations for the free and upper troposphere are obtained. These show however little latitudinal gradient, if any, and are in good agreement with the data of selected NOAA stations in NH tropics. Correlations between δ13C(CO2) and CO2 are observed both within single flight(s) covering long distances and for certain seasons. The overall variability in de-trended δ13C(CO2) and CO2 for CARIBIC-1 and CARIBIC-2 are similar and basically agree with each other, which also underscores the high quality of measurement. Based on all correlations, we discuss that CO2 distribution in the NH FT and UT (at CARIBIC flight routes) is regulated by uplift and pole-wards transport of tropical air up to approximately 50° N. The main reasons for

  15. Analysis of 13C and 18O isotope data of CO2 in CARIBIC aircraft samples as tracers of upper troposphere/lower stratosphere mixing and the global carbon cycle

    NASA Astrophysics Data System (ADS)

    Assonov, S. S.; Brenninkmeijer, C. A. M.; Schuck, T. J.; Taylor, P.

    2010-09-01

    The project CARIBIC (http://caribic-atmospheric.com) aims to study atmospheric chemistry and transport by regularly measuring many compounds in the free troposphere and the upper troposphere/lowermost stratosphere (UT/LMS) by using passenger aircraft. Here we present CO2 concentrations and isotope results, and analyze the data together with supporting trace gas data. 509 CARIBIC-2 samples (highest precision and accuracy δ13C(CO2) and δ18O(CO2) data) from June 2007 until March 2009, together with CARIBIC-1 samples (flights between November 1999 and April 2002, 350 samples in total, 270 for NH, mostly δ13C(CO2) data) give a fairly extensive, unique data set for the NH free troposphere and the UT/LMS region. Total uncertainty of the data is the same as reported for the global monitoring program by NOAA-ESRL. To compare data from different years a de-trending is applied. In the UT/LMS region δ13C(CO2), δ18O(CO2) and CO2 are found to correlate well with stratospheric tracers, in particular N2O; δ18O(CO2) appears to be a useful, hitherto unused, tracer of atmospheric transport in the UT/LMS region and also inter-hemispheric mixing. By filtering out the LMS data (based on N2O distributions), the isotope variations for the free and upper troposphere are obtained. These variations have only small latitudinal gradients, if any, and are in good agreement with the data of selected NOAA stations in NH tropics. Correlations between δ13C(CO2) and CO2 are observed both within single flight(s) covering long distances and during certain seasons. The overall variability in de-trended δ13C(CO2) and CO2 for CARIBIC-1 and CARIBIC-2 are similar and are generally in agreement, which underscores agreement between high and low resolution sampling. Based on all correlations, we infer that the CO2 distribution in the NH troposphere along CARIBIC flight routes is chiefly regulated by uplift and pole-wards transport of

  16. Combined δ11B, δ13C, and δ18O analyses of coccolithophore calcite constrains the response of coccolith vesicle carbonate chemistry to CO2-induced ocean acidification

    NASA Astrophysics Data System (ADS)

    Liu, Yi-Wei; Tripati, Robert; Aciego, Sarah; Gilmore, Rosaleen; Ries, Justin

    2016-04-01

    Coccolithophorid algae play a central role in the biological carbon pump, oceanic carbon sequestration, and in marine food webs. It is therefore important to understand the potential impacts of CO2-induced ocean acidification on these organisms. Differences in the regulation of carbonate chemistry, pH, and carbon sources of the intracellular compartments where coccolith formation occurs may underlie the diverse calcification and growth responses to acidified seawater observed in prior experiments. Here we measured stable isotopes of boron (δ11B), carbon (δ13C) and oxygen (δ18O) within coccolith calcite, and δ13C of algal tissue to constrain carbonate system parameters in two strains of Pleurochrysis carterae (P. carterae). The two strains were cultured under variable pCO2, with water temperature, salinity, dissolved inorganic carbon (DIC), and alkalinity monitored. Notably, PIC, POC, and PIC/POC ratio did not vary across treatments, indicating that P. carterae is able to calcify and photosynthesize at relatively constant rates irrespective of pCO2 treatment. The δ11B data indicate that mean pH at the site of coccolith formation did not vary significantly in response to elevated CO2. These results suggest that P. carterae regulates calcifying vesicle pH, even amidst changes in external seawater pH. Furthermore, δ13C and δ18O data suggest that P. carterae may utilize carbon from a single internal DIC pool for both calcification and photosynthesis, and that a greater proportion of dissolved CO2 relative to HCO3‑ enters the internal DIC pool under acidified conditions. These results suggest that P. carterae is able to calcifyand photosynthesize at relatively constant rates across pCO2 treatments by maintaining pH homeostasis at their site of calcification and utilizing a greater proportion of aqueous CO2.

  17. Chemical-mechanical coupling observed for depleted oil reservoirs subjected to long-term CO2-exposure - A case study of the Werkendam natural CO2 analogue field

    NASA Astrophysics Data System (ADS)

    Hangx, Suzanne; Bakker, Elisenda; Bertier, Pieter; Nover, Georg; Busch, Andreas

    2015-10-01

    Geological storage of CO2 is one of the most promising technologies to rapidly reduce anthropogenic emissions of carbon dioxide. In order to ensure storage integrity, it is important to understand the effect of long-term CO2/brine/rock interactions on the mechanical behaviour of a storage complex. As most of these reactions are too slow to reproduce on laboratory timescales, we studied a natural CO2 analogue reservoir (the Röt Fringe Sandstone, Werkendam field, the Netherlands; 125-135 Ma of CO2-exposure) and its unreacted counterpart. We focused on CO2-induced mineralogical and porosity-permeability changes, and their effect on mechanical behaviour of both intact rock and simulated fault gouge. Overall, CO2-exposure did not lead to drastic mineralogical changes. The CO2-exposed material shows a stronger dependence of permeability on porosity, which is attributed to differences in diagenesis (closed-system diagenesis and hydrocarbon emplacement) taking place before CO2 charging. The limited extent of reaction was in part the result of bitumen coatings protecting specific mineral phases from reaction. In local, mm-sized zones displaying significant anhydrite cement dissolution, enhanced porosity was observed. For most of the reservoir the long-term mechanical behaviour after CO2-exposure could be described by the behaviour of the unreacted sandstone, while these more 'porous' zones had a lower rock strength. In addition, CO2-exposure did not affect the fault friction behaviour, and slip is expected to result in stable sliding. Simple stress path calculations predict that reservoir failure due to depletion and injection is unlikely, even for the 'porous' zones, nor will fault reactivation occur for realistic injection scenarios.

  18. Measuring the 13C/12C isotope ratio in atmospheric CO2 by means of laser absorption spectrometry: a new perspective based on a 2.05-microm diode laser.

    PubMed

    Castrillo, Antonio; Casa, Giovanni; Palmieri, Antonio; Gianfrani, Livio

    2006-03-01

    The potential use of high sensitivity laser absorption spectroscopy for measuring the 13C/12C isotope ratio in atmospheric CO2 has been demonstrated, using a GaSb-based diode laser at 2.05 microm. In this spectral region, the overlapping between relatively strong 12CO2 and 13CO2 absorption features gives rise to several line pairs which are well suitable for a spectroscopic determination of the isotope ratio. Preliminary results have demonstrated that a short-term precision better than 1 per thousand can be easily obtained, for a CO2 concentration of 1000 ppm. We extensively discuss the influence of a possible non-linearity in the detectors' response on the delta-value and suggest an instrumental development that would allow to eliminate this effect. PMID:16500754

  19. A dynamic soil chamber system coupled with a tunable diode laser for online measurements of delta-13C, delta-18O, and efflux rate of soil respired CO2

    SciTech Connect

    Powers, Heath H; Mcdowell, Nate; Hanson, David; Hunt, John

    2009-01-01

    High frequency observations of the stable isotopic composition of CO(2) effluxes from soil have been sparse due in part to measurement challenges. We have developed an open-system method that utilizes a flow-through chamber coupled to a tunable diode laser (TDL) to quantify the rate of soil CO(2) efflux and its delta(13)C and delta(18)O values (delta(13)C(R) and delta(18)O(R), respectively). We tested the method first in the laboratory using an artificial soil test column and then in a semi-arid woodland. We found that the CO(2) efflux rates of 1.2 to 7.3 micromol m(-2) s(-1) measured by the chamber-TDL system were similar to measurements made using the chamber and an infrared gas analyzer (IRGA) (R(2) = 0.99) and compared well with efflux rates generated from the soil test column (R(2) = 0.94). Measured delta(13)C and delta(18)O values of CO(2) efflux using the chamber-TDL system at 2 min intervals were not significantly different from source air values across all efflux rates after accounting for diffusive enrichment. Field measurements during drought demonstrated a strong dependency of CO(2) efflux and isotopic composition on soil water content. Addition of water to the soil beneath the chamber resulted in average changes of +6.9 micromol m(-2) s(-1), -5.0 per thousand, and -55.0 per thousand for soil CO(2) efflux, delta(13)C(R) and delta(18)O(R), respectively. All three variables initiated responses within 2 min of water addition, with peak responses observed within 10 min for isotopes and 20 min for efflux. The observed delta(18)O(R) was more enriched than predicted from temperature-dependent H(2)O-CO(2) equilibration theory, similar to other recent observations of delta(18)O(R) from dry soils (Wingate L, Seibt U, Maseyk K, Ogee J, Almeida P, Yakir D, Pereira JS, Mencuccini M. Global Change Biol. 2008; 14: 2178). The soil chamber coupled with the TDL was found to be an effective method for capturing soil CO(2) efflux and its stable isotope composition at high

  20. Field measurements of del13C in ecosystem respiration

    NASA Astrophysics Data System (ADS)

    van Asperen, Hella; Sabbatini, Simone; Nicolini, Giacomo; Warneke, Thorsten; Papale, Dario; Notholt, Justus

    2014-05-01

    Stable carbon isotope del13C-measurements are extensively used to study ecological and biogeochemical processes in ecosystems. Above terrestrial ecosystems, atmospheric del13C can vary largely due to photosynthetic fractionation. Photosynthetic processes prefer the uptake of the lighter isotope 12C (in CO2), thereby enriching the atmosphere in 13C and depleting the ecosystem carbon. At night, when ecosystem respiratory fluxes are dominant, 13C-depleted CO2 is respired and thereby depletes the atmospheric del13C-content. Different ecosystems and different parts of one ecosystem (type of plant, leaves, and roots) fractionate and respire with a different del13C-ratio signature. By determining the del13C-signature of ecosystem respiration in temporal and spatial scale, an analysis can be made of the composition of respiratory sources of the ecosystem. A field study at a dry cropland after harvest (province of Viterbo, Lazio, Italy) was performed in the summer of 2013. A FTIR (Fourier Transform Infrared Spectrometer) was set up to continuously measure CO2-, CH4-, N2O-, CO- and del13C-concentrations. The FTIR was connected to 2 different flux measurements systems: a Flux Gradient system (sampling every half hour at 1.3m and 4.2m) and 2 flux chambers (measured every hour), providing a continuous data set of the biosphere-atmosphere gas fluxes and of the gas concentrations at different heights. Keeling plot intercept values of respiratory CO2, measured by the Flux Gradient system at night, were determined to be between -25‰ and -20‰. Keeling plot intercept values of respiratory CO2, measured by the flux chamber system, varied between -24‰ and -29‰, and showed a clear diurnal pattern, suggesting different (dominant) respiratory processes between day and night.

  1. An experimental evaluation of the use of C3 δ13C plant tissue as a proxy for the paleoatmospheric δ13CO2 signature of air

    NASA Astrophysics Data System (ADS)

    Lomax, B. H.; Knight, C. A.; Lake, J. A.

    2012-09-01

    Previous work suggests that the relationship between the carbon isotope composition of air (δ13Ca) and plant leaf tissue (δ13Cp) can be used to track changes in the carbon isotope composition of paleo-atmospheric CO2. Here we test this assertion in a series of experiments using the model plant Arabidopsis thaliana grown under a range of atmospheric CO2 concentrations relevant to geologic time (380, 760, 1000, 1500, 2000 and 3000 ppm). Nested within these CO2 experiments water availability was controlled (giving two sets of experimental plants; low and high water treatment at each CO2 concentration) to manipulate stomatal opening, a key process governing carbon fixation and isotope discrimination. Results show a highly significant relationship between δ13Ca and δ13Cp under both experimental water treatments. To test the utility of δ13Cp to predict δ13Ca we compare calculated δ13Ca to measured values of δ13Ca. These data show that although there is a significant relationship between calculated and measured δ13Ca, there is disparity between the two values of δ13Ca and a large difference between calculated values under different water treatments even when grown in a common CO2 concentration. These results demonstrate that environmental factors that alter stomatal opening can severely impact on the use and reliability of δ13Cp to predict δ13Ca and as such, results should be interpreted with caution.

  2. Short-term natural δ13C variations in pools and fluxes in a beech forest: the transfer of isotopic signal from recent photosynthates to soil respired CO2

    NASA Astrophysics Data System (ADS)

    Gavrichkova, O.; Proietti, S.; Moscatello, S.; Portarena, S.; Battistelli, A.; Matteucci, G.; Brugnoli, E.

    2011-03-01

    The fate of photosynthetic products within the plant-soil continuum determines how long the reduced carbon resides within the ecosystem and when it returns back to the atmosphere in the form of respiratory CO2. We have tested the possibility of measuring natural variation in δ13C to disentangle potential times needed to transfer carbohydrates produced by photosynthesis down to roots and, in general, to belowground up to its further release in the form of soil respiration into the atmosphere in a beech (Fagus sylvatica) forest. For these purposes we have measured the variation in stable carbon and oxygen isotope compositions in plant material and in soil respired CO2 every three hours for three consequent days. Possible steps and different signs of post-photosynthetic fractionation during carbon translocation were also identified. A 12 h-periodicity was observed for variation in δ13C in soluble sugars in the top crown leaves and it can be explained by starch day/night dynamics in synthesis and breakdown and by stomatal limitations under elevated vapour pressure deficits. Photosynthetic products were transported down the trunk and mixed with older carbon pools, therefore causing the dampening of the δ13C signal variation. The strongest periodicity of 24 h was found in δ13C in soil respiration indicating changes in root contribution to the total CO2 efflux. Nevertheless, it was possible to identify the speed of carbon translocation through the plant-soil continuum. A period of 24 h was needed to transfer the C assimilated by photosynthesis from the top crown leaves to the tree trunk at breast height and additional 3 h for further respiration of that C by roots and soil microorganisms and its to subsequent diffusion back to the atmosphere.

  3. Short communication: Using diurnal patterns of (13)C enrichment of CO2 to evaluate the effects of nitrate and docosahexaenoic acid on fiber degradation in the rumen of lactating dairy cows.

    PubMed

    Klop, G; Bannink, A; Dieho, K; Gerrits, W J J; Dijkstra, J

    2016-09-01

    Nitrate decreases enteric CH4 production in ruminants, but may also negatively affect fiber degradation. In this experiment, 28 lactating Holstein dairy cows were grouped into 7 blocks. Within blocks, cows were randomly assigned to 1 of 4 isonitrogenous treatments in a 2×2 factorial arrangement: control (CON); NO3 [21g of nitrate/kg of dry matter (DM)]; DHA [3g of docosahexaenoic acid (DHA)/kg of DM]; or NO3+DHA (21g of nitrate/kg of DM and 3g of DHA/kg of DM). Cows were fed a total mixed ration consisting of 21% grass silage, 49% corn silage, and 30% concentrates on a DM basis. Based on the difference in natural (13)C enrichment and neutral detergent fiber and starch content between grass silage and corn silage, we investigated whether a negative effect on rumen fiber degradation could be detected by evaluating diurnal patterns of (13)C enrichment of exhaled carbon dioxide. A significant nitrate × DHA interaction was found for neutral detergent fiber digestibility, which was reduced on the NO3 treatment to an average of 55%, as compared with 61, 64, and 65% on treatments CON, DHA, and NO3+DHA, respectively. Feeding nitrate, but not DHA, resulted in a pronounced increase in (13)C enrichment of CO2 in the first 3 to 4 h after feeding only. Results support the hypothesis that effects of a feed additive on the rate of fiber degradation in the rumen can be detected by evaluating diurnal patterns of (13)C enrichment of CO2. To be able to detect this, the main ration components have to differ considerably in fiber and nonfiber carbohydrate content as well as in natural (13)C enrichment. PMID:27344384

  4. Depleted deep South China Sea δ13C paleoceanographic events in response to tectonic evolution in Taiwan-Luzon Strait since Middle Miocene

    NASA Astrophysics Data System (ADS)

    Chen, Wen-Huang; Huang, Chi-Yue; Lin, Yen-Jun; Zhao, Quanhong; Yan, Yi; Chen, Duofu; Zhang, Xinchang; Lan, Qing; Yu, Mengming

    2015-12-01

    The most distinctive feature of the deep South China Sea (SCS) paleoceanography is the occurrence of long-term depleted deep-sea benthic foraminiferal δ13C values. They are lower than the global and the Pacific composite records in the last 16 Ma, especially at 13.2, 10.5, 6.5, 3.0 and 1.2-0.4 Ma. This distinct deep SCS paleoceanograhic history coincides with the subduction-collision history in the Taiwan region where waters of the West Pacific (WP) and the SCS exchange. The depleted deep-sea benthic foraminiferal δ13C events indicate that the SCS deep basin became progressively a stagnant environment in the last 16 Ma due to either closure of the connection with the WP bottom water or temporary reduction of the WP deep water flowing into the deep SCS. Both the Taiwan accretionary prism and the Luzon arc became the main tectono-morphological barriers for the WP bottom water flowing into the SCS deep basin when eastward subduction of the SCS oceanic lithosphere beneath the Philippine Sea Plate started from the Middle Miocene (18-16 Ma). This began a long-term trend of depleted SCS deep-sea benthic δ13C values in the last 16 Ma. The oblique arc-continent collision since ~6.5 Ma uplifted the Taiwan accretionary prism rapidly above sea level and further isolated the SCS from the open Pacific. The collision simultaneously causes backthrusting deformations in the North Luzon Trough forearc basin and sequentially closes interarc water gates between volcanic islands from north to south. The Loho and the Taitung interarc water gates in the advanced collision zone were closed at ~3.0 Ma and ~1.2 Ma, coinciding with the very low SCS deep-sea benthic δ13C events at 3.0 and 1.2-0.4 Ma, respectively. The Taitung Canyon between the Lutao and Lanyu volcanic islands in the incipient collision zone is semi-closed presently. These closure events also lead to the result that the WP deep water intrudes westward into the SCS principally through the Bashi Channel between the Lanyu

  5. Mobile, outdoor continuous-flow isotope-ratio mass spectrometer system for automated high-frequency 13C- and 18O-CO2 analysis for Keeling plot applications.

    PubMed

    Schnyder, Hans; Schäufele, Rudi; Wenzel, Richard

    2004-01-01

    A continuous-flow isotope-ratio mass spectrometer (CF-IRMS, custom-made GasBenchII and Delta(plus)Advantage, ThermoFinnigan) was installed on a grassland site and interfaced with a closed-path infrared gas analyser (IRGA). The CF-IRMS and IRGA were housed in an air-conditioned travel van. Air was sampled at 1.5 m above the 0.07-m tall grassland canopy, drawn through a 17-m long PTFE tube at a rate of 0.25 L s(-1), and fed to the IRGA and CF-IRMS in series. The IRMS was interfaced with the IRGA via a stainless steel capillary inserted 0.5 m into the sample air outlet tube of the IRGA (forming an open split), a gas-tight pump, and a sample loop attached to the eight-port Valco valve of the continuous-flow interface. Air was pumped through the 0.25-mL sample loop at 10 mL s(-1) (a flushing frequency of 40 Hz). Air samples were analysed at intervals of approx. 2.8 min. Whole system precision was tested in the field using air mixed from pure CO2 and CO2-free air by means of mass flow controllers. The standard deviation of repeated single measurements was 0.21-0.07 per thousand for delta13C and 0.34-0.14 per thousand for delta18O of CO2 in air with mixing ratios ranging between 200-800 micromol mol(-1). The CO2 peak area measured by the IRMS was proportional to the CO2 mixing ratio (r2 = 1.00), allowing estimation of sample air CO2 mixing ratio from IRMS data. A 1-day long measurement cycle of CO2, delta13C and delta18O of air sampled above the grassland canopy was used to test the system for Keeling plot applications. Delta18O exhibited a clear diurnal cycle (4 per thousand range), but short-term (1-h interval) variability was small (average SD 0.38 per thousand). Yet, the correlation between delta18O and CO2 mixing ratio was relatively weak, and this was true for both the whole data set and 1-h subsets. Conversely, the delta13C of all 541 samples measured during the 25.2-h interval fitted well the Keeling regression (r2 = 0.99), yielding an intercept of -27.40 per

  6. Depleted δ13C Values in Salt Dome Cap Rock Organic Matter and Implications for Microbial Metabolism and Fixation

    NASA Astrophysics Data System (ADS)

    Loyd, S. J.; Lu, L.; Caesar, K. H.; Kyle, R.

    2015-12-01

    Salt domes occur throughout the Gulf Coast Region USA and are often associated with trapped hydrocarbons. These salt domes can be capped by sulfate and carbonate minerals that result from complex digenetic interactions in the subsurface. The specific natures of these interactions are poorly understood, in particular the role of microbes in facilitating mineralization and element cycling. Carbon isotope compositions of cap rock calcites (δ13Ccarb) are highly variable and range from near neutral to less than -40‰ (VPDB) indicative of methane-sourced carbon. These low values and the common coexistence of elemental sulfur and metal sulfides have spurred hypotheses invoking microbial sulfate reduction as driving carbonate mineral authigenesis. Here, we present new organic carbon isotope (δ13Corg) data that, similar to δ13Ccarb, exhibit depletions below -30 to -25‰. These δ13Corg values are lower than local liquid hydrocarbons and "normal" marine organic matter reflecting either microbial fixation of methane-sourced carbon or microbial fractionation from liquid hydrocarbon sources. The combined carbon isotope data (δ13Ccarb and δ13Corg) indicate that methane likely plays an important role in microbial cycling in salt domes. The δ13Corg values are similar to those of anaerobic oxidation of methane (AOM) related communities from methane-sulfate controlled marine sediments. Ultimately, salt dome environments may share some important characteristics with AOM systems.

  7. Sulfate-driven anaerobic oxidation of methane as the origin of extremely 13C-depleted calcite in the Doushantuo cap carbonates in South China

    NASA Astrophysics Data System (ADS)

    Peng, Y.; Bao, H.; Jiang, G.; Kaufman, A. J.; Xiao, S.; Zhou, C.; Wang, J.

    2015-12-01

    The cap carbonate in Doushantuo Formation (ca. 635 Ma) has been extensively studied for Earth systems change following the Marinoan 'snowball Earth' glaciation. An important feature of this cap carbonate is the local occurrence of extremely negative δ13Ccarb values (down to -50‰) from dark-colored calcite cements. These calcites have been interpreted as carbonate cements precipitated from cold methane seeps or as hydrothermally induced diagenetic carbonates. To test these contrasting interpretations, we mechanically separated the calcite cements from host dolostones and analyzed stable isotope compositions of pyrite, carbonate-associated sulfate (CAS), and organic carbon in both components of the Doushantuo cap carbonate in the Yangtze Gorges area, South China. The data show that δ34Spyrtie of extremely 13C-depleted calcite (22.8-73.9‰) are up to 34‰ higher than those of the dolomite (14.7-39.9‰). Similarly, δ34SCAS of calcite (37.1-80.1‰) are up to 40‰ higher than those of the dolomite (24.5-41.5‰). The δ18OCAS of calcite (12.9-22.2‰; VSMOW) are also systematically higher than those of dolomite (13.3-16.8‰; VSMOW). In contrast, δ13Corg of calcite cements (-27.2 ‰ to -46.1‰) are lower than those of the dolostones (-26.5‰ to -31.7‰). In addition, there is a strong positive correlation between δ34SCAS and δ18OCAS and a negative correlation between δ13Corg and δ34Spyrtie of the calcite (Figure 1). The data demonstrated convincingly that the 13C-depleted calcites were formed in a environment facilitated by sulfate-driven anaeorobic oxidation of methane (AOM). The co-occurrence of unusually low δ13Corg and high δ34S values requires presence of active flow of both methane and sulfate, a condition not far away from conducive seawater sulfate supply. Figure 1: Cross plots of δ34SCAS vs. δ18OCAS and δ13Corg vs δ34Spyrtie in host dolomite and in the extremely 13C-depleted calcite cements.

  8. CLEAN - Large-Scale CO2 Storage for Enhanced Gas Recovery in a depleted German Gasfield

    NASA Astrophysics Data System (ADS)

    Kuehn, M.; Förster, A.; Grossmann, J.; Meyer, R.; Pilz, P.; Reinicke, K.; Schaefer, D.; Tesmer, M.; Wendel, H.

    2011-12-01

    ) baseline stress conditions, (10) monitoring set-up comprising reservoir, cap rock and shallow aquifer compartments as well as the unsaturated zone and ground surface, (11) implementation of monitoring for the purpose of determining natural variations for the parameters, and (12) assessment of various methods with regard to temporal and spatial scales for the parameters recorded. The joint research project developed technologies and methods to be used for a CO2 based EGR within the Altmark. Furthermore, this work is a major step forward understanding the behavior of CO2 injected into a depleted gas field. The findings support the definition of national and international standards, the development of best practice guidelines and built up expertise for this new technology. Acknowledgement: CLEAN is part of the geoscientific R&D program "GEOTECHNOLOGIEN" funded by the German Federal Ministry of Education and Research (BMBF) and GDF SUEZ.

  9. Late-Quaternary variation in C3 and C4 grass abundance in southeastern Australia as inferred from δ13C analysis: Assessing the roles of climate, pCO2, and fire

    NASA Astrophysics Data System (ADS)

    Nelson, David M.; Urban, Michael A.; Kershaw, A. Peter; Hu, Feng Sheng

    2016-05-01

    Climate, atmospheric pCO2, and fire all may exert major influences on the relative abundance of C3 and C4 grasses in the present-day vegetation. However, the relative role of these factors in driving variation in C3 and C4 grass abundances in the paleorecord is uncertain, and C4 abundance is often interpreted narrowly as a proxy indicator of aridity or pCO2. We measured δ13C values of individual grains of grass (Poaceae) pollen in the sediments of two sites in southeastern Australia to assess changes in the proportions of C3 and C4 grasses during the past 25,000 years. These data were compared with shifts in pCO2, temperature, moisture balance, and fire to assess how these factors were related to long-term variation of C4 grass abundance during the late Quaternary. At Caledonia Fen, a high-elevation site in the Snowy Mountains, C4 grass abundance decreased from an average of 66% during the glacial period to 11% during the Holocene, primarily in response to increased pCO2 and temperature. In contrast, this pattern did not exist in low-elevation savannah woodlands around Tower Hill Northwest Crater, where C4 grass abundance instead varied in response to shifts in regional aridity. Fire did not appear to have strongly influenced the proportions of C3 and C4 grasses on the landscape at millennial timescales at either site. These patterns are similar to those of a recent study in East Africa, suggesting that elevation-related climatic differences influence how the abundance of C3 and C4 grasses responds to shifts in climate and pCO2. These results caution against using C4 plant abundance as a proxy indicator of either climate or pCO2 without an adequate understanding of key controlling factors.

  10. Short-term natural δ13C and δ18O variations in pools and fluxes in a beech forest: the transfer of isotopic signal from recent photosynthates to soil respired CO2

    NASA Astrophysics Data System (ADS)

    Gavrichkova, O.; Proietti, S.; Moscatello, S.; Portarena, S.; Battistelli, A.; Matteucci, G.; Brugnoli, E.

    2011-10-01

    The fate of photosynthetic products within the plant-soil continuum determines how long the reduced carbon resides within the ecosystem and when it returns back to the atmosphere in the form of respiratory CO2. We have tested the possibility of measuring natural variation in δ13C and δ18O to disentangle the potential times needed to transfer carbohydrates produced by photosynthesis down to trunk, roots and, in general, to belowground up to its further release in the form of soil respiration into the atmosphere in a beech (Fagus sylvatica) forest. We have measured the variation in stable carbon and oxygen isotope compositions in plant material and in soil respired CO2 every three hours for three consecutive days. Possible steps and different signs of post-photosynthetic fractionation during carbon translocation were also identified. A 12 h-periodicity was observed for variation in δ13C in soluble sugars in the top crown leaves and it can be explained by starch day/night dynamics in synthesis and breakdown and by stomatal limitations under elevated vapour pressure deficits. Photosynthetic products were transported down the trunk and mixed with older carbon pools, therefore causing the dampening of the δ13C signal variation. The strongest periodicity of 24 h was found in δ13C in soil respiration indicating changes in root contribution to the total CO2 efflux. Other non-biological causes like diffusion fractionation and advection induced by gas withdrawn from the measurement chamber complicate data interpretation on this step of C transfer path. Nevertheless, it was possible to identify the speed of carbohydrates' translocation from the point of assimilation to the trunk breast height because leaf-imprinted enrichment of δ18O in soluble sugars was less modified along the downward transport and was well related to environmental parameters potentially linked to stomatal conductance. The speed of carbohydrates translocation from the site of assimilation to the trunk

  11. Modeling CO2 Sequestration in Saline Aquifer and Depleted Oil Reservoir To Evaluate Regional CO2 Sequestration Potential of Ozark Plateau Aquifer System, South-Central Kansas

    SciTech Connect

    Watney, W. Lynn; Rush, Jason; Raney, Jennifer

    2014-09-30

    1. Drilled, cored, and logged three wells to the basement and collecting more than 2,700 ft of conventional core; obtained 20 mi2 of multicomponent 3D seismic imaging and merged and reprocessed more than 125 mi2 of existing 3D seismic data for use in modeling CO2- EOR oil recovery and CO2 storage in five oil fields in southern Kansas. 2. Determined the technical feasibility of injecting and sequestering CO2 in a set of four depleted oil reservoirs in the Cutter, Pleasant Prairie South, Eubank, and Shuck fields in southwest Kansas; of concurrently recovering oil from those fields; and of quantifying the volumes of CO2 sequestered and oil recovered during the process. 3. Formed a consortium of six oil operating companies, five of which own and operate the four fields. The consortium became part of the Southwest Kansas CO2-EOR Initiative for the purpose of sharing data, knowledge, and interest in understanding the potential for CO2-EOR in Kansas. 4. Built a regional well database covering 30,000 mi2 and containing stratigraphic tops from ~90,000 wells; correlated 30 major stratigraphic horizons; digitized key wells, including wireline logs and sample logs; and analyzed more than 3,000 drill stem tests to establish that fluid levels in deep aquifers below the Permian evaporites are not connected to the surface and therefore pressures are not hydrostatic. Connectivity with the surface aquifers is lacking because shale aquitards and impermeable evaporite layers consist of both halite and anhydrite. 5. Developed extensive web applications and an interactive mapping system that do the following: a. Facilitate access to a wide array of data obtained in the study, including core descriptions and analyses, sample logs, digital (LAS) well logs, seismic data, gravity and magnetics maps, structural and stratigraphic maps, inferred fault traces, earthquakes, Class I and II disposal wells, and surface lineaments. b. Provide real-time analysis of the project dataset, including

  12. Implications of high-precision measurements of 13C-18O bond ordering in CO2 for thermometry in modern bivalved mollusc shells

    NASA Astrophysics Data System (ADS)

    Petrizzo, Daniel A.; Young, Edward D.; Runnegar, Bruce N.

    2014-10-01

    We report a temperature calibration for Δ47 from bivalve carbonate that lies within error of theoretical predictions (Schauble et al., 2006; Guo et al., 2009). The temperature sensitivity of this calibration is lower than several different earlier calibrations determined using either inorganic calcite, corals, foraminiferans and coccoliths, or brachiopods and bivalved molluscs, but it agrees with more recent Δ47-temperature relationships determined from measurements of clumped-isotopes in mollusc and brachiopod shells. We demonstrate that mollusc shell temperature calibrations originating from different laboratories that have not been corrected for instrument backgrounds may differ by as much as ∼0.07‰ in Δ47 over the ∼0 to 30 °C temperature range even where dΔ47/dT agree. Because recent calibrations for Δ47 vs. T from several different laboratories agree for bivalved mollusc shells, yet differ from an early calibration for bivalved molluscs, we suggest it is unlikely that temperature-Δ47 variability is attributable to phylum-specific vital effects, and instead conclude that differences in calibration slope between phyla and/or inorganic calcite are more easily explained by variability in measurements made in different laboratories. Discrepancies in both calibration slopes and/or intercepts indicate that Δ47 values measured in natural materials may be more significantly influenced by instrument-specific effects, as well as effects from sample preparation and handling and purification of CO2 than current techniques are able to correct for, and therefore, temperatures obtained by comparing measurements of Δ47 to independently determined calcite calibrations may err by a far greater amount than acknowledged in previous studies.

  13. Utilizing continuous measurements of delta^{13}C_r, delta18O_r, and net ecosystem exchange of CO_2 and H_2O to understand the effects of inter-annual variability in drought on ecosystem functioning

    NASA Astrophysics Data System (ADS)

    Osuna, J. L.; McDowell, N. G.; Shim, J. H.; Rahn, T.; Pockman, W.

    2011-12-01

    In the semi-arid Southwestern US, seasonal drought has strengthened in recent years due to both a decrease in winter precipitation and delayed onset of the summer monsoon. A process-based understanding of ecosystem response to increased drought stress is vital to predicting the long-term stability of semi-arid biomes. To understand the processes responsible for inter-annual and seasonal variability in net ecosystem carbon and water fluxes, we compared nearly continuous measurements of ecosystem scale respiration (R_e) from an eddy covariance system with the stable carbon and oxygen isotope signals in ecosystem respired CO_2 (delta^{13}C_r and delta^{18}O_r) measured continuously by a tunable diode laser spectrometer (TDL) sampling at various canopy heights at the same site. The study site, at Los Alamos National Laboratory, converted from pitilde{n}on juniper woodland to juniper woodland after over 90% of pitilde{n}ons died in 2002-2003 following multiple years of enhanced drought leaving a high necromass at the site. We analyzed the relationships between the Bowen ratio, delta^{18}O_r, daily and annual accumulated NEE, and delta^{13}C_r to understand the (de)coupling between the response of transpiration and respiration under varying degrees of drought stress. Additionally, we explored the variability in the lag and intensity of ecosystem response to precipitation pulses depending on antecedent conditions. The response of delta^{18}O_r was more consistent across years and seasons whereas variability in the contribution of autotrophic versus heterotrophic respiration appeared to cause differing responses of delta^{13}C_r to drought stress and precipitation pulses. This result was supported by the diurnal CO_2 and H_2O fluxes indicating nearly immediate transpirational water loss initiated by most precipitation pulses. Annual accumulated precipitation (versus pulse size) was a better indicator of delta^{13}C_ r response (i.e. relative contributions of autotrophic

  14. Reactive transport modeling of the long-term effects of CO2 storage in the P18 depleted gas field

    NASA Astrophysics Data System (ADS)

    Tambach, T. J.; Koenen, M.; Wasch, L. J.; Loeve, D.; Maas, J. G.

    2012-04-01

    Depleted gas fields are an import CO2 storage sink for The Netherlands, with a total storage capacity of more than 3 Gtonne. The CO2 sources are located at relatively short distances from potential storage reservoirs and an infrastructure for (cross-border) gas transport over large distances already exists. Several depleted gas fields in the subsurface of the Netherlands have yet been evaluated as potential locations for CO2 storage (for example the K12-B field). The P18 gas field is located in the offshore of The Netherlands and is currently evaluated as potential CO2 storage reservoir. The aim of this study is to predict the long-term effects of CO2 injection into the P18 field using reactive transport modeling (TOUGHREACT). The storage reservoir is described using the mineralogy and petrophysical characteristics of three geological layers in a radial (R,Z) reservoir model with top depth of 3456 m, a thickness of 98 m, and 3300 grid cells. The initial reservoir temperature was defined as 90 degrees C with an initial (depletion) pressure of 20.0 bars. Capillary pressure curves are based on empirical relations. The CO2 is injected uniformly distributed over the model height, at a constant rate of 35 kg/s (1.1 Mton/year), and a temperature of 40 degrees C for 30 years. The well is then shut-in with a reservoir pressure of approximately 375 bar. The simulations are continued up to 10,000 years for computing the long-term effects in the reservoir. The results show that the near-well area is dried out during injection, leading to salt precipitation and reduced permeability during injection. Condensation of the evaporated water occurs outside the near-well area. Water imbibition is modelled after shut in of the well, leading to rewetting of the near-well area and redissolution of the salt. Most geochemical reactions need water to occur, including well-cement minerals, and therefore predictions of water flow after well shut-ins are important to take into account

  15. FT-IR spectra of 18O-, and 13C-enriched CO2 in the ν3 region: High accuracy frequency calibration and spectroscopic constants for 16O12C18O, 18O12C18O, and 16O13C16O

    NASA Astrophysics Data System (ADS)

    Elliott, Ben M.; Sung, Keeyoon; Miller, Charles E.

    2015-06-01

    In this report, we extend our Fourier transform infrared (FT-IR) spectroscopy measurements of CO2 in the ν3 region (2200-2450 cm-1, 65-75 THz) to the 18O-, and 13C-substituted isotopologues, using the JPL Bruker IFS-125HR Fourier Transform Spectrometer (JPL-FTS). High quality (S/N ∼ 2000) spectra were obtained separately for each of the 18O-, and 13C-isotopically enriched samples. The absolute wavenumber accuracies were better than 3 × 10-6 cm-1 (∼100 kHz) for strong, isolated transitions, calibrated against the highest accuracy reported CO and 16O12C16O (626) frequency measurements. The JPL-FTS performance and calibration procedure is shown to be reliable and consistent, achievable through vigorous maintenance of the optical alignment and regular monitoring of its instrumental line shape function. Effective spectroscopic constant fits of the 00011 ← 00001 fundamental bands for 16O12C18O (628), 18O12C18O (828), and 16O13C16O (636) were obtained with RMS residuals of 2.9 × 10-6 cm-1, 2.8 × 10-6 cm-1, and 2.9 × 10-6 cm-1, respectively. The observed bands encompassed 79 lines over the Jmax range of P67/R67, 47 lines over P70/R62, and 60 lines over P70/R70 for 628, 828, and 636, respectively. These results complement our recent work on the 17O-enriched isotopologues (Elliott et al., 2014), providing additional high-quality frequency measurements for atmospheric remote sensing applications.

  16. The impact of pCO2 and climate on D/H and 13C/12C fractionation of higher-plant biomarkers: Implications for paleoclimate and paleoelevation reconstruction during global warm periods

    NASA Astrophysics Data System (ADS)

    Hren, M. T.; Tipple, B. J.; Pagani, M.

    2012-12-01

    Stable hydrogen isotope compositions (D/H) of plant biomarkers record the hydrogen isotopic composition of leaf water at the time of plant growth. However, the magnitude of the apparent hydrogen isotope fractionation between biomarkers and precipitation can vary due to soil- or leaf-water evaporation or differing water-use strategies. As a result, climate-induced changes in soil- or leaf-water evaporation rates and/or changes in plant assemblages during periods of global warming and high atmospheric CO2 could impact apparent carbon and hydrogen isotope fractionations. We measured hydrogen and carbon isotope ratios of long-carbon chain n-alkanes from modern and ~50 million year old fossil leaves preserved in paleo-Sierra Nevada riverine sediments to determine how climate and ecosystem differences during a period of extremely high pCO2 impact the magnitude and variability of D/H and 13C/12C ratios of leaf-waxes across a topographic gradient. δDalkanes (nC27 to nC31) of individual fossil and modern leaves decrease systematically across the topographic gradient and follow the change in the D/H of precipitation due to orographic lifting and continuous rainout. Using estimated values of Eocene δDprecip at the Pacific margin (-43 to -61‰), apparent fractionations (ɛalkane - precip) for Eocene angiosperm trees are similar to that seen for modern, humid environments (~ -106 to -124‰ ±10‰ 1σ), and more negative than observed in modern sun-exposed leaves in the Sierra Nevada (-96 to -102‰) or soils (-87 to -92‰). Single site variability in leaf-wax δD from individual fossil angiosperms can exceed 20‰, but is considerably smaller than observed for modern, mixed angiosperm/gymnosperm forests of the seasonally dry Sierra Nevada range. δ13Calkane values show little or no systematic variation across the range. However, carbon isotope discrimination in ancient and modern leaves is similar, suggesting strong climatic and weak pCO2 controls on D/H and 13C/12C

  17. Coupling aboveground and belowground activities using short term fluctuations in 13C composition of soil respiration

    NASA Astrophysics Data System (ADS)

    Epron, D.; Parent, F.; Grossiord, C.; Plain, C.; Longdoz, B.; Granier, A.

    2011-12-01

    changes in partitioning between the respiration sources. This was particularly clear for eucalypt trees planted on a C4 soil in coastal Congo where soil CO2 efflux were less 13C depleted between 11am and 3pm when the xylem sap flux was maximum. This last result outlines that not only canopy photosynthesis but also canopy transpiration may affect the isotopic composition of soil CO2 efflux and should be considered in mechanistic models that account for the dynamics of soil CO2 efflux and its partitioning.

  18. Estimating the CO2 sequestration potential of depleted and fractured shale formations using CH4 production rates

    NASA Astrophysics Data System (ADS)

    Clarens, A. F.; Tao, Z.

    2013-12-01

    Oil and gas production from hydraulically fractured shale formations is an abundant new source of domestically available energy for the United States. It will also result in significant CO2 emissions with important climate implications. Several studies have suggested that fractured shale formations could be used to permanently store CO2 once they are depleted of hydrocarbons. Many of the largest shale formations being developed in the United States have temperature and pressure profiles that are similar to those of saline aquifers being widely studied for geologic carbon sequestration. Here a modeling framework was developed that can be used to estimate the sequestration capacity for a shale formation based on historical CH4 production. The model is applied to those portions of the Marcellus formation found in Pennsylvania because reliable data on well production is readily available for this state. Production data from over 300 wells was compiled and used to estimate historical production and to extrapolate projected production. In shales, much of the CO2 would be sorbed to the pore and fracture surface and so this model considers sorption kinetics as well as total sorption capacity. The results suggest that shale formations could represent a significant repository for geologic carbon sequestration. The Marcellus shale in Pennsylvania alone could store between 10.4 and 18.4 Gigatonnes of CO2 between now and 2030. This would be over 50% of total annual US CO2 emissions from stationary sources. The mass transfer and sorption kinetics results indicate that CO2 injection proceeds several times faster than CH4 production. Model estimates were most sensitive to the permeability of the formation and assumptions about the ultimate ratio of adsorbed CH4 to CO2. CH4 production is a useful basis for calculating sequestration capacity because gas mass transfer out of the formation will be impacted by the same factors (e.g., temperature, pressure, and moisture content

  19. Modeling CO2 Sequestration in Saline Aquifer and Depleted Oil Reservoirs to Evaluate Regional CO2 Sequestration Potential of Ozark Plateau Aquifer System, South-Central Kansas

    NASA Astrophysics Data System (ADS)

    Watney, W. L.; Rush, J.

    2011-12-01

    The Paleozoic-age Ozark Plateau Aquifer System (OPAS) in southern Kansas consists of a thick (>450 m) and deeply buried (>1 km) succession of Cambro-Ordovician Arbuckle Group strata (dolomite) overlain by Lower Ordovician to Lower Carboniferous-age carbonate, chert, and shale. The Arbuckle Group is a thick widespread saline aquifer in southern Kansas. A 500 meter core of the OPAS interval and immediate overlying Pennsylvanian shale caprock were cored in early 2011 in the BEREXCO Wellington KGS #1-32 well in Wellington Field, a nearly depleted oil field in Sumner County, in south-central Kansas. An exhaustive set of modern logs were run in the KGS #1-32 well including chemical, microresistivity imaging, dipole sonic, nuclear magnetic resonance, and standard porosity and resistivity wireline logs. In addition, routine and special core analyses provide vital means to calibrate these logs. Core also provide vital chemical analyses and rock samples to run flow experiments, including in situ conditions, to establish reaction kinetics of rock and connate brines with CO2. Core and logs also provide the means to calibrate a 26 km2 multicomponent 3D seismic survey that was acquired in Wellington Field in 2010. Studies of four oil fields, also part of this project, are underway in southwestern Kansas to provide additional calibration points for the western part of the regional study that covers 65,000 km2 where CO2 sequestration capacity will be measured. Several hundred deep wells have been identified to serve as type wells in the regional study area. Well logs and sample descriptions are being digitized, correlated, and mapped to define distribution of aquifers, oil reservoirs, and caprocks. Drill stem test data have been analyzed for deep wells to establish that the Arbuckle is an open aquifer connected to surface exposures 100s of km to east in central Missouri. Over 500 km2 of 3D seismic have been donated by industrial partners to aid in understanding fault and fracture

  20. Continuous measurements for isotopic ratios of CO213C, δ18O), water vapor(δD, and δ18O-H2O) in the urban area using laser IR spectroscopic techniques and their analysis with other pollutant species(CO, NOx)

    NASA Astrophysics Data System (ADS)

    Yuba, A.; Takahashi, K.; Nakayama, T.; Matsumi, Y.

    2013-12-01

    The concentration of CO2 has been increasing from a range of 275 to 285 ppmv in the previous industrial period to about 400 ppmv in 2012. IPCC reported that CO2 has the most effects on positive radiation forcing (IPCC 2007). The accurate estimation of the CO2 emission and loss flux are necessary to improve the prediction of the radiation forcing and atmospheric environment. In the urban area, CO2 concentration varies due to the anthropogenic and biogenic emission and advection. We conducted the continuous measurement of CO2 concentration and stable isotope ratio of CO213C and δ18O) using the laser isotope spectrometer in Nagoya, Japan during two weeks of winter 2011 and summer 2012. CO2 isotope laser spectrometer can continuously measureδ13, δ18O in high time resolution (10 seconds). We also measured CO, NOx and H2O concentration, and stable isotope ratio of H2O (δD and δ18O-H2O). CO2 sources in summer and winter were identified from the Keeling plot analysis of the CO2 isotope ratio (δ13C and δ18O) and relationship between CO and CO2 concentration variation. The ratio of CO concentration to CO2 concentration shows the contribution of the fossil fuel combustion or biogenic respiration. Lower ratio of CO to CO2 concentration was due to the biogenic respiration because few CO emits from the biogenic respiration. We will discuss the seasonal variation of CO2 source from the analysis of CO2 isotope ratio and CO2 concentration comparing with CO and NOx concentration variation.

  1. Students' Understanding of the Greenhouse Effect, the Societal Consequences of Reducing CO2 Emissions and the Problem of Ozone Layer Depletion.

    ERIC Educational Resources Information Center

    Andersson, Bjorn; Wallin, Anita

    2000-01-01

    Contributes to the growing body of knowledge about students' conceptions and views of environmental and natural resource issues. Questions 9th and 12th grade Swedish students' understandings of the greenhouse effect, reduction of CO2 emissions, and the depletion of the ozone layer. Observes five models of the greenhouse effect that appear among…

  2. The use of tracers to assess leakage from the sequestration of CO2 in a depleted oil reservoir, New Mexico, USA

    SciTech Connect

    Wells, A.W.; Diehl, J.R.; Bromhal, G.S.; Strazisar, B.R.; Wilson, T.H.; White, C.M.

    2007-05-01

    Geological sequestration of CO2 in depleted oil reservoirs is a potentially useful strategy for greenhouse gas management and can be combined with enhanced oil recovery. Development of methods to estimate CO2 leakage rates is essential to assure that storage objectives are being met at sequestration facilities. Perfluorocarbon tracers (PFTs) were added as three 12 h slugs at about one week intervals during the injection of 2090 tons of CO2 into the West Pearl Queen (WPQ) depleted oil formation, sequestration pilot study site located in SE New Mexico. The CO2 was injected into the Permian Queen Formation. Leakage was monitored in soil–gas using a matrix of 40 capillary adsorbent tubes (CATs) left in the soil for periods ranging from days to months. The tracers, perfluoro-1,2-dimethylcyclohexane (PDCH), perfluorotrimethylcyclohexane (PTCH) and perfluorodimethylcyclobutane (PDCB), were analyzed using thermal desorption, and gas chromatography with electron capture detection. Monitoring was designed to look for immediate leakage, such as at the injection well bore and at nearby wells, and to develop the technology to estimate overall CO2 leak rates based on the use of PFTs. Tracers were detected in soil–gas at the monitoring sites 50 m from the injection well within days of injection. Tracers continued to escape over the following years. Leakage appears to have emanated from the vicinity of the injection well in a radial pattern to about 100 m and in directional patterns to 300 m. Leakage rates were estimated for the 3 tracers from each of the 4 sets of CATs in place following the start of CO2 injection. Leakage was fairly uniform during this period. As a first approximation, the CO2 leak rate was estimated at about 0.0085% of the total CO2 sequestered per annum.

  3. Design and Implementation of a CO2 Flood Utilizing Advanced Reservoir Characterization and Horizontal Injection Wells In a Shallow Shelf Carbonate Approaching Waterflood Depletion

    SciTech Connect

    Czirr, Kirk

    1999-10-28

    The first project objective is to utilize reservoir characterization and advanced technologies to optimize the design of a carbon dioxide (CO2) project for the South Cowden Unit (SCU) located in Ector County, Texas. The SCU is a mature, relatively small, shallow shelf carbonate unit nearing waterflood depletion. The second project objective is to demonstrate the performance and economic viability of the project in the field. All work during the fourth quarter falls within the demonstration project.

  4. CH4 production via CO2 reduction in a temperate bog - A source of (C-13)-depleted CH4

    NASA Technical Reports Server (NTRS)

    Lansdown, J. M.; Quay, P. D.; King, S. L.

    1992-01-01

    The paper reports measurements, taken over two annual cycles, of the flux and delta(C-13) of CH4 released from an acidic peat bog located in the foothills of the Cascade Range in Washington state, U.S. Measurements of the rate of aceticlastic methanogenesis and CO2 reduction in peat soil, using (C-14)-labeled acetate and sodium bicarbonate, show that acetate was not an important CH4 precursor and that CO2 reduction could account for all of the CH4 production. The in situ kinetic isotope effect for CO2 reduction, calculated using the delta-(C-13) of soil water CO2 and CH4 flux, was 0.932 +/- 0.007.

  5. Hidden shift of the ionome of plants exposed to elevated CO2 depletes minerals at the base of human nutrition

    PubMed Central

    Loladze, Irakli

    2014-01-01

    Mineral malnutrition stemming from undiversified plant-based diets is a top global challenge. In C3 plants (e.g., rice, wheat), elevated concentrations of atmospheric carbon dioxide (eCO2) reduce protein and nitrogen concentrations, and can increase the total non-structural carbohydrates (TNC; mainly starch, sugars). However, contradictory findings have obscured the effect of eCO2 on the ionome—the mineral and trace-element composition—of plants. Consequently, CO2-induced shifts in plant quality have been ignored in the estimation of the impact of global change on humans. This study shows that eCO2 reduces the overall mineral concentrations (−8%, 95% confidence interval: −9.1 to −6.9, p<0.00001) and increases TNC:minerals > carbon:minerals in C3 plants. The meta-analysis of 7761 observations, including 2264 observations at state of the art FACE centers, covers 130 species/cultivars. The attained statistical power reveals that the shift is systemic and global. Its potential to exacerbate the prevalence of ‘hidden hunger’ and obesity is discussed. DOI: http://dx.doi.org/10.7554/eLife.02245.001 PMID:24867639

  6. Exploratory Simulation Studies of Caprock Alteration Induced byStorage of CO2 in Depleted Gas Reservoirs

    SciTech Connect

    Gherardi, Fabrizio; Xu, Tianfu; Pruess, Karsten

    2005-11-23

    This report presents numerical simulations of isothermalreactive flows which might be induced in the caprock of an Italiandepleted gas reservoir by the geological sequestration of carbon dioxide.Our objective is to verify that CO2 geological disposal activitiesalready planned for the study area are safe and do not induce anyundesired environmental impact.Gas-water-rock interactions have beenmodelled under two different intial conditions, i.e., assuming that i)caprock is perfectly sealed, or ii) partially fractured. Field conditionsare better approximated in terms of the "sealed caprock model". Thefractured caprock model has been implemented because it permits toexplore the geochemical beahvior of the system under particularly severeconditions which are not currently encountered in the field, and then todelineate a sort of hypothetical maximum risk scenario.Major evidencessupporting the assumption of a sealed caprock stem from the fact that nogas leakages have been detected during the exploitation phase, subsequentreservoir repressurization due to the ingression of a lateral aquifer,and during several cycles of gas storage in the latest life of reservoirmanagement.An extensive program of multidisciplinary laboratory tests onrock properties, geochemical and microseismic monitoring, and reservoirsimulation studies is underway to better characterize the reservoir andcap-rock behavior before the performance of a planned CO2 sequestrationpilot test.In our models, fluid flow and mineral alteration are inducedin the caprock by penetration of high CO2 concentrations from theunderlying reservoir, i.e., it was assumed that large amounts of CO2 havebeen already injected at depth. The main focus is on the potential effectof these geochemical transformations on the sealing efficiency of caprockformations. Batch and multi-dimensional 1D and 2D modeling has been usedto investigate multicomponent geochemical processes. Our simulationsaccount for fracture-matrix interactions, gas

  7. Keeling plots for hummingbirds: a method to estimate carbon isotope ratios of respired CO(2) in small vertebrates.

    PubMed

    Carleton, Scott A; Wolf, Blair O; del Rio, Carlos Martinez

    2004-09-01

    The carbon isotope composition of an animal's breath reveals the composition of the nutrients that it catabolizes for energy. Here we describe the use of Keeling plots, a method widely applied in ecosystem ecology, to measure the delta(13)C of respired CO(2) of small vertebrates. We measured the delta(13)C of Rufous Hummingbirds ( Selasphorus rufus) in the laboratory and of Mourning ( Zenaida macroura) and White-winged ( Z. asiatica) Doves in the field. In the laboratory, when hummingbirds were fed a sucrose based C3 diet, the delta(13)C of respired CO(2) was not significantly different from that of their diet (delta(13)C(C3 diet)). The delta(13)C of respired CO(2) for C3 fasted birds was slightly, albeit significantly, depleted in delta(13)C relative to delta(13)C(C3 diet). Six hours after birds were shifted to a sucrose based C4 diet, the isotopic composition of their breath revealed that birds were catabolizing a mixture of nutrients derived from both the C3 and the C4 diet. In the field, the delta(13)C of respired CO(2) from Mourning and White-winged Doves reflected that of their diets: the CAM saguaro cactus ( Carnegeia gigantea) and C3 seeds, respectively. Keeling plots are an easy, effective and inexpensive method to measure delta(13)C of respired CO(2) in the lab and the field. PMID:15309607

  8. Deployment of a carbon isotope ratiometer for the monitoring of CO2 sequestration leakage.

    PubMed

    McAlexander, Ian; Rau, Greg H; Liem, Jimmy; Owano, Thomas; Fellers, Ray; Baer, Douglas; Gupta, Manish

    2011-08-15

    In an effort to monitor leakage from underground CO(2) storage, a field-deployable analyzer capable of rapidly measuring the CO(2) mixing ratio and δ(13)C values (±0.05 ppm(v) ± 0.2‰, 60 s) was deployed to distinguish between biogenic and fossil CO(2) sources. The analyzer was interfaced with a multiport inlet unit to allow autonomous sampling from multiple locations. The instrument and inlet interface were deployed at the Zero Emissions Research and Technology (ZERT) site (Bozeman, Montana, July 14-22, 2009) during a controlled, subsurface release of CO(2) depleted in (13)C. A biogenic diurnal cycle was observed far from the release, and the associated Keeling plot suggested a CO(2) source (δ(13)C = -27.0 ± 0.5‰) consistent with local C(3) vegetation. Inlets near the leak showed large CO(2) mixing ratios (388/>40 000 ppm(v)) whose predominant source was the release CO(2) (inferred δ(13)C = -58.2 ± 0.7‰). Measurements 3 m from the source showed diurnal CO(2) cycles (382-2400 ppm(v)) influenced by leaked CO(2), possibly due to diel air mixing. Finally, the data from all of the sampling inlets was combined to spatially localize the leak position. PMID:21740048

  9. Analysing Groundwater Using the 13C Isotope

    NASA Astrophysics Data System (ADS)

    Awad, Sadek

    The stable isotope of the carbon atom (13C) give information about the type of the mineralisation of the groundwater existing during the water seepage and about the recharge conditions of the groundwater. The concentration of the CO2(aq.) dissolved during the infiltration of the water through the soil's layers has an effect on the mineralisation of this water. The type of the photosynthesis's cycle (C-3 or C-4 carbon cycle) can have a very important role to determine the conditions (closed or open system) of the mineralisation of groundwater. The isotope 13C of the dissolved CO2 in water give us a certain information about the origin and the area of pollution of water. The proportion of the biogenic carbon and its percentage in the mineralisation of groundwater is determined by using the isotope 13C.

  10. The imprint of anthropogenic CO2 emissions on Atlantic bluefin tuna otoliths

    NASA Astrophysics Data System (ADS)

    Fraile, Igaratza; Arrizabalaga, Haritz; Groeneveld, Jeroen; Kölling, Martin; Santos, Miguel Neves; Macías, David; Addis, Piero; Dettman, David L.; Karakulak, Saadet; Deguara, Simeon; Rooker, Jay R.

    2016-06-01

    Otoliths of Atlantic bluefin tuna (Thunnus thynnus) collected from the Mediterranean Sea and North Atlantic Ocean were analyzed to evaluate changes in the seawater isotopic composition over time. We report an annual otolith δ13C record that documents the magnitude of the δ13C depletion in the Mediterranean Sea between 1989 and 2010. Atlantic bluefin tuna in our sample (n = 632) ranged from 1 to 22 years, and otolith material corresponding to the first year of life (back-calculated birth year) was used to reconstruct seawater isotopic composition. Otolith δ18O remained relatively stable between 1989 and 2010, whereas a statistically significant decrease in δ13C was detected across the time interval investigated, with a rate of decline of 0.05‰ yr- 1 (- 0.94‰ depletion throughout the recorded period). The depletion in otolith δ13C over time was associated with the oceanic uptake of anthropogenically derived CO2.

  11. Latitudinal variations in plankton delta C-13 - Implications for CO2 and productivity in past oceans

    NASA Technical Reports Server (NTRS)

    Rau, Greg H.; Takahashi, Taro; Des Marais, David J.

    1989-01-01

    Low C-13/C-12 in present-day Antarctic plankton has been ascribed to high CO2 availability. It is reported here, however, that this high-latitude C-13 depletion develops at CO2 partial pressures that are often below that of the present atmosphere and usually below that of equatorial upwelling systems. Nevertheless, because of much lower water temperatures and hence greater CO2 solubility at high latitude, the preceding pCO2 measurements translate into Antarctic surface-water CO2 (aq) concentrations that are as much as 2.5 times higher than in equatorial waters. It is calculated that an oceanic pCO2 level greater than 800 micro-atm is a warmer low-latitude Cretaceous ocean would have been required to produce the plankton C-13 depletion preserved in Cretaceous sediments.

  12. Mixing ratio and carbon isotopic composition investigation of atmospheric CO2 in Beijing, China.

    PubMed

    Pang, Jiaping; Wen, Xuefa; Sun, Xiaomin

    2016-01-01

    The stable isotope composition of atmospheric CO2 can be used as a tracer in the study of urban carbon cycles, which are affected by anthropogenic and biogenic CO2 components. Continuous measurements of the mixing ratio and δ(13)C of atmospheric CO2 were conducted in Beijing from Nov. 15, 2012 to Mar. 8, 2014 including two heating seasons and a vegetative season. Both δ(13)C and the isotopic composition of source CO2 (δ(13)CS) were depleted in the heating seasons and enriched in the vegetative season. The diurnal variations in the CO2 mixing ratio and δ(13)C contained two peaks in the heating season, which are due to the effects of morning rush hour traffic. Seasonal and diurnal patterns of the CO2 mixing ratio and δ(13)C were affected by anthropogenic emissions and biogenic activity. Assuming that the primary CO2 sources at night (22:00-04:00) were coal and natural gas combustion during heating seasons I and II, an isotopic mass balance analysis indicated that coal combustion had average contributions of 83.83±14.11% and 86.84±12.27% and that natural gas had average contributions of 16.17±14.11% and 13.16±12.27%, respectively. The δ(13)C of background CO2 in air was the main error source in the isotopic mass balance model. Both the mixing ratio and δ(13)C of atmospheric CO2 had significant linear relationships with the air quality index (AQI) and can be used to indicate local air pollution conditions. Energy structure optimization, for example, reducing coal consumption, will improve the local air conditions in Beijing. PMID:26363727

  13. On the use of phloem sap δ13C to estimate canopy carbon discrimination

    NASA Astrophysics Data System (ADS)

    Rascher, Katherine; Máguas, Cristina; Werner, Christiane

    2010-05-01

    Although the carbon stable isotope composition (d13C) of bulk leaf material is a good integrative parameter of photosynthetic discrimination and can be used as a reliable ecological index of plant functioning; it is not a good tracer of short-term changes in photosynthetic discrimination. In contrast, d13C of phloem sap is potentially useful as an indicator of short-term changes in canopy photosynthetic discrimination. However, recent research indicates that d13C signatures may be substantially altered by metabolic processes downstream of initial leaf-level carbon fixation (e.g. post-photosynthetic fractionation). Accordingly, before phloem sap d13C can be used as a proxy for canopy level carbon discrimination an understanding of factors influencing the degree and magnitude of post-photosynthetic fractionation and how these vary between species is of paramount importance. In this study, we measured the d13C signature along the basipetal transport pathway in two co-occurring tree species in the field - an understory invasive exotic legume, Acacia longifolia, and a native pine, Pinus pinaster. We measured d13C of bulk leaf and leaf water soluble organic matter (WSOM), phloem sap sampled at two points along the plant axis and leaf and root dark respiration. In general, species differences in photosynthetic discrimination resulted in more enriched d13C values in the water-conserving P. pinaster relative to the water-spending A. longifolia. Post-photosynthetic fractionation led to differences in d13C of carbon pools along the plant axis with progressively more depleted d13C from the canopy to the trunk (~6.5 per mil depletion in A. longifolia and ~0.8per mil depletion in P. pinaster). Leaf and root respiration, d13C, were consistently enriched relative to putative substrates. We hypothesize that the pronounced enrichment of leaf respired CO2 relative to leaf WSOM may have left behind relatively depleted carbon to be loaded into the phloem resulting in d13C depletion

  14. Carbon Isotope Composition of Caribbean Sea Surface Waters: Response to the Uptake of Anthropogenic CO2

    NASA Astrophysics Data System (ADS)

    Black, D. E.; Thunell, R.; Wejnert, K. E.; Astor, Y.

    2011-12-01

    The burning of fossil fuels and deforestation have significantly increased atmospheric CO2 levels, from ~280 ppm prior to the industrial revolution to the present value of ~390 ppm. Suess (1955) was the first to show that the carbon isotopic composition of the atmosphere is changing in response to the anthropogenic input of radiocarbon-dead, 13C depleted CO2 from fossil fuel combustion. While biological processes may be the primary mechanism controlling the δ13C of marine carbon, air-sea gas exchange should allow for the transfer of the so-called 13C Suess effect (Keeling, 1979) from the atmosphere to the surface ocean. The first measurements of the δ13C of dissolved inorganic carbon of ocean surface waters were made in 1970 (Kroopnick, 1974) and serve as a baseline for assessing how the carbon isotopic composition of the oceans have changed in response to the invasion of fossil fuel CO2 over the last 40 years. However, in order to gain a longer and more complete picture of the marine δ13C Suess effect, we must rely on indirect measures of changes in surface water δ13C, most notably those preserved in carbonate secreting marine organisms. The Cariaco Basin is one of the rare locations where one can directly compare sediment records with modern instrumental data. Here we report a high resolution planktonic foraminiferal δ13C record from the basin for the last 300 years that clearly resolves the timing and magnitude of the marine 13C Suess effect associated with the oceanic uptake of anthropogenically derived CO2. Cariaco Basin sediment trap and upper-most box core sediment δ13C match both the trend and magnitude of observed δ13C changes in atmospheric CO2 over the last 15 years. The longer sediment record suggests the marine Suess effect to be -0.75 % from pre-industrial values, with most of the change occurring since 1950, coincident with the rapid rise in atmospheric CO2 noted in ice core and instrumental data. If the current anthropogenic CO2 emission

  15. Sampling Soil CO2 for Isotopic Flux Partitioning: Non Steady State Effects and Methodological Biases

    NASA Astrophysics Data System (ADS)

    Snell, H. S. K.; Robinson, D.; Midwood, A. J.

    2014-12-01

    Measurements of δ13C of soil CO2 are used to partition the surface flux into autotrophic and heterotrophic components. Models predict that the δ13CO2 of the soil efflux is perturbed by non-steady state (NSS) diffusive conditions. These could be large enough to render δ13CO2 unsuitable for accurate flux partitioning. Field studies sometimes find correlations between efflux δ13CO2 and flux or temperature, or that efflux δ13CO2 is not correlated as expected with biological drivers. We tested whether NSS effects in semi-natural soil were comparable with those predicted. We compared chamber designs and their sensitivity to changes in efflux δ13CO2. In a natural soil mesocosm, we controlled temperature to generate NSS conditions of CO2 production. We measured the δ13C of soil CO2 using in situ probes to sample the subsurface, and dynamic and forced-diffusion chambers to sample the surface efflux. Over eight hours we raised soil temperature by 4.5 OC to increase microbial respiration. Subsurface CO2 concentration doubled, surface efflux became 13C-depleted by 1 ‰ and subsurface CO2 became 13C-enriched by around 2 ‰. Opposite changes occurred when temperature was lowered and CO2 production was decreasing. Different chamber designs had inherent biases but all detected similar changes in efflux δ13CO2, which were comparable to those predicted. Measurements using dynamic chambers were more 13C-enriched than expected, probably due to advection of CO2 into the chamber. In the mesocosm soil, δ13CO2 of both efflux and subsurface was determined by physical processes of CO2 production and diffusion. Steady state conditions are unlikely to prevail in the field, so spot measurements of δ13CO2 and assumptions based on the theoretical 4.4 ‰ diffusive fractionation will not be accurate for estimating source δ13CO2. Continuous measurements could be integrated over a period suitable to reduce the influence of transient NSS conditions. It will be difficult to disentangle

  16. CO2 Fluxes and Concentrations in a Residential Area in the Southern Hemisphere

    NASA Astrophysics Data System (ADS)

    Weissert, L. F.; Salmond, J. A.; Turnbull, J. C.; Schwendenmann, L.

    2014-12-01

    While cities are generally major sources of anthropogenic carbon dioxide (CO2) emissions, recent research has shown that parts of urban areas may also act as CO2 sinks due to CO2 uptake by vegetation. However, currently available results are related to a large degree of uncertainty due to the limitations of the applied methods and the limited number of studies available from urban areas, particularly from the southern hemisphere. In this study, we explore the potential of eddy covariance and tracer measurements (13C and 14C isotopes of CO2) to quantify and partition CO2 fluxes and concentrations in a residential urban area in Auckland, New Zealand. Based on preliminary results from autumn and winter (March to July 2014) the residential area is a small source of CO2 (0.11 mol CO2 m-2 day-1). CO2 fluxes and concentrations follow a distinct diurnal cycle with a morning peak between 7:00 and 9:00 (max: 0.25 mol CO2 m-2 day-1/412 ppm) and midday low with negative CO2 fluxes (min: -0.17 mol CO2 m-2 day-1/392 ppm) between 10:00 and 15:00 local time, likely due to photosynthetic CO2 uptake by local vegetation. Soil CO2 efflux may explain that CO2 concentrations increase and remain high (401 ppm) throughout the night. Mean diurnal winter δ13C values are in anti-phase with CO2 concentrations and vary between -9.0 - -9.7‰. The depletion of δ13C compared to clean atmospheric air (-8.2‰) is likely a result of local CO2 sources dominated by gasoline combustion (appr. 60%) during daytime. A sector analysis (based on prevailing wind) of CO2 fluxes and concentrations indicates lower CO2 fluxes and concentrations from the vegetation-dominated sector, further demonstrating the influence of vegetation on local CO2 concentrations. These results provide an insight into the temporal and spatial variability CO2 fluxes/concentrations and potential CO2 sinks and sources from a city in the southern hemisphere and add valuable information to the global database of urban CO2 fluxes.

  17. Isotopic signatures of traffic-emitted CO and CO2

    NASA Astrophysics Data System (ADS)

    Popa, Maria Elena; Pathirana, Supun; Vollmer, Martin K.; Jordan, Armin; Rothe, Michael; Brand, Willi A.; Röckmann, Thomas

    2013-04-01

    Traffic is one of the main sources of CO2 and CO in highly populated regions like Western Europe. 13C and 18O isotopic signatures of traffic-emitted CO2 and CO were determined form air samples collected in the Islisberg highway tunnel (Switzerland), during a measurement and sampling campaign in 2011. The goal of the campaign was to characterize traffic emissions of the present west European vehicle fleet, at integrated fleet level. The isotopic composition of traffic CO2 reflects on average the isotopic composition of the fuel (13C) and of atmospheric oxygen (18O), although the 18O values are quite variable. In contrast, the isotopic values of CO show that significant fractionation takes place during CO formation (18O) and during the subsequent, partial CO destruction in the catalytic converter (13C). The 13C is enriched by 3 ‰ compared to the 13C in the fuel burnt, while the 18O is depleted by 7 ‰ compared to the 18O in atmospheric oxygen. We compute a kinetic isotope effect for 13C during CO destruction of 2.5 ± 0.7 ‰. The average 18O in traffic CO is 17 ‰ (VSMOW), similar to the biomass burning signature previously determined in Switzerland and Europe (e.g. Saurer et al., 2009). Thus, in the conditions represented by our study (Swiss fleet, highway driving conditions), the traffic and biomass burning CO emissions cannot be distinguished anymore based on 18O signature alone. References Saurer, M., Prévôt, A. S. H., Dommen, J., Sandradewi, J., Baltensperger, U., and Siegwolf, R. T. W.: The influence of traffic and wood combustion on the stable isotopic composition of carbon monoxide, Atmos. Chem. Phys., 9, 3147-3161, doi:10.5194/acp-9-3147-2009, 2009.

  18. The Vendian-Cambrian δ 13C record, North Iran: evidence for overturning of the ocean before the Cambrian Explosion

    NASA Astrophysics Data System (ADS)

    Kimura, Hiroto; Matsumoto, Ryo; Kakuwa, Yoshitaka; Hamdi, Bahaeddin; Zibaseresht, Hamid

    Continuous fossilliferous successions across the Precambrian/Cambrian (PC/C) boundary in the Elburz Mountains of Northern Iran show a remarkable negative δ 13C excursion just below the PC/C boundary. High concentrations of manganese, phosphorus, barium, and high abundances of fossil phytoplankton, and black shale coincide with the excursion. Worldwide stratigraphic correlation shows that the isotopic anomaly is a global event. The initial Metazoan diversification, coupled with 13C enrichment, occurs stratigraphically just above the excursion. We propose the following scenario for oceanic environmental changes before the Cambrian Faunal Explosion based on new data from Iran: A global warm climate following the last Precambrian glaciation resulted in a generally stagnant oceanic condition, so that surface water was oxic; deep water was dysoxic, depleted in 13C, and enriched in nutrients. Massive upwelling of deep water (vertical advection of nutrients and 13C-depleted CO 2) caused enhanced phytoplankton productivity and a sharp drop in δ 13C in shallow water carbonate and organic carbon. We conclude that latest Cryptozoic overturning of ocean stratification preceded the Cambrian Explosion.

  19. Design and Implementation of a CO2 Flood Utilizing Advanced Reservoir Characterization and Horizontal Injection Wells In a Shallow Shelf Carbonate Approaching Waterflood Depletion, Class II

    SciTech Connect

    Czirr, K.L.; Gaddis, M.P.; Moshell, M.K.

    2002-02-21

    The principle objective of this project is to demonstrate the economic viability and widespread applicability of an innovative reservoir management and carbon dioxide (CO2) flood project development approach for improving CO2 flood project economics in shallow shelf carbonate (SSC) reservoirs.

  20. Long-term growth of soybean and maize at elevated [CO2] under free-air concentration enrichment (FACE) reduces soil moisture depletion

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Stomatal conductance (gs) is lower when plants are grown at elevated [CO2] compared to ambient [CO2]. This is often assumed to reduce plant water use and ameliorate water stress by conserving soil moisture. However, under field conditions canopy size, canopy structure, microclimate and fluxes of wat...

  1. Stable isotope ratios of atmospheric CO_{2} and CH_{4} over Siberia measured at ZOTTO

    NASA Astrophysics Data System (ADS)

    Timokhina, Anastasiya; Prokushkin, Anatily; Lavric, Jost; Heimann, Martin

    2016-04-01

    The boreal and arctic zones of Siberia housing the large amounts of carbon stored in the living biomass of forests and wetlands, as well as in soils and specifically permafrost, play a crucial role in earth's global carbon cycle. The long-term studies of greenhouse gases (GHG) concentrations are important instruments to analyze the response of these systems to climate warming. In parallel to GHG observations, the measurements of their stable isotopic composition can provide useful information for distinguishing contribution of individual GHG source to their atmospheric variations, since each source has its own isotopic signature. In this study we report first results of laboratory analyses of the CO2 and CH4 concentrations, the stable isotope ratio of δ13C-CO2, δ18O-CO2, δ13C-CH4, δD-CH4 measured in one-liter glass flasks which were obtained from 301 height of ZOTTO (Zotino Tall Tower Observatory, near 60° N, 90° E, about 20 km west of the Yenisei River) during 2008 - 2013 and 2010 - 2013 for stable isotope composition of CO2 and CH4. The magnitudes of δ13C-CO2 and δ18O-CO2 in a seasonal cycle are -1.4±0.1‰ (-7.6 - -9.0‰) and -2.2±0.2‰ (-0.1 - -2.3‰), respectively. The δ13C-CO2 seasonal pattern opposes the CO2 concentrations, with a gradual enrichment in heavy isotope occurring during May - July, reflecting its discrimination in photosynthesis, and further depletion in August - September as photosynthetic activity decreases comparatively to ecosystem respiration. Relationship between the CO2 concentrations and respective δ13C-CO2 (Keeling plot) reveals isotopic source signature for growing season (May - September) -27.3±1.4‰ and -30.4±2.5‰ for winter (January - March). The behavior of δ18O-CO2 associated with both high photosynthetic rate in the June (enrichment of atmospheric CO2 by 18O as consequence of CO2 equilibrium with "heavy" leaf water) and respiratory activity of forest floor in June - October (depletion of respired CO2 by 18O

  2. Optoacoustic 13C-breath test analyzer

    NASA Astrophysics Data System (ADS)

    Harde, Hermann; Helmrich, Günther; Wolff, Marcus

    2010-02-01

    The composition and concentration of exhaled volatile gases reflects the physical ability of a patient. Therefore, a breath analysis allows to recognize an infectious disease in an organ or even to identify a tumor. One of the most prominent breath tests is the 13C-urea-breath test, applied to ascertain the presence of the bacterium helicobacter pylori in the stomach wall as an indication of a gastric ulcer. In this contribution we present a new optical analyzer that employs a compact and simple set-up based on photoacoustic spectroscopy. It consists of two identical photoacoustic cells containing two breath samples, one taken before and one after capturing an isotope-marked substrate, where the most common isotope 12C is replaced to a large extent by 13C. The analyzer measures simultaneously the relative CO2 isotopologue concentrations in both samples by exciting the molecules on specially selected absorption lines with a semiconductor laser operating at a wavelength of 2.744 μm. For a reliable diagnosis changes of the 13CO2 concentration of 1% in the exhaled breath have to be detected at a concentration level of this isotope in the breath of about 500 ppm.

  3. Design and Implementation of a CO2 Flood Utilizing Advanced Reservoir Characterization and Horizontal Injection Wells In a Shallow Shelf Carbonate Approaching Waterflood Depletion, Class II

    SciTech Connect

    Wier, Don R. Chimanhusky, John S.; Czirr, Kirk L.; Hallenbeck, Larry; Gerard, Matthew G.; Dollens, Kim B.; Owen, Rex; Gaddis, Maurice; Moshell, M.K.

    2002-11-18

    The purpose of this project was to economically design an optimum carbon dioxide (CO2) flood for a mature waterflood nearing its economic abandonment. The original project utilized advanced reservoir characterization and CO2 horizontal injection wells as the primary methods to redevelop the South Cowden Unit (SCU). The development plans; project implementation and reservoir management techniques were to be transferred to the public domain to assist in preventing premature abandonment of similar fields.

  4. Influence of pCO2 on carbon allocation in nodulated Medicago sativa L.

    NASA Astrophysics Data System (ADS)

    Pereyra, Gabriela; Hartmann, Henrik; Ziegler, Waldemar; Michalzik, Beate; Gonzalez-Meler, Miquel; Trumbore, Susan

    2016-04-01

    Atmospheric CO2 concentrations (pCO_2) have been related to changes in plant carbon (C) availability and photosynthetic capacity, yet there is no clear consensus as to the effect of pCO2 on the plant C balance and on nitrogen fixation in symbiotic systems. We investigated how different pCO2 (Pleistocene: 170 ppm, ambient: 400 ppm and projected future: 700 ppm) influence C allocation in nodulated Medicago sativa L. We labeled 17 week old plants with depleted 13C (-34.7±1.2‰) and traced the label over a 9-day period, to assess the redistribution of newly assimilated C across different sinks, including nodules. We analyzed N concentrations in plant tissues and found no significant differences in leaves and roots across treatments. However, growth and C fixation rates increased with pCO_2, and differences were greatest between 170 ppm and 700 ppm. Across pCO2 treatments we observed a 13C-enrichment in roots compared to leaves. We further observed the highest 13C depletion of non-structural carbohydrates (NSCs) and respired CO2 in tissues of plants grown at 700 ppm, especially in leaves and nodules. Our preliminary results suggest that sink organs like roots and nodules are fed with newly-assimilated NSCs from leaves to support respiration, and especially in 170 ppm plants represented a major respiratory loss of newly assimilated C (≈ 35{%} of the total plant respiration). Our results suggest that although plant metabolic processes like photosynthesis and respiration are affected by changes in pCO_2, nitrogen acquisition in such a symbiotic system is not.

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

    NASA Astrophysics Data System (ADS)

    Steinmann, Philipp; Eilrich, Bernd; Leuenberger, Markus; Burns, Stephen J.

    2008-12-01

    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 αC 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.

  6. Atmospheric pCO2 Reconstructed across the Early Eocene Hyperthermals

    NASA Astrophysics Data System (ADS)

    Cui, Y.; Schubert, B.

    2015-12-01

    Negative carbon isotope excursions (CIEs) are commonly associated with extreme global warming. The Early Eocene is punctuated by five such CIEs, the Paleocene-Eocene thermal maximum (PETM, ca. 55.8 Ma), H1 (ca. 53.6 Ma), H2 (ca. 53.5 Ma), I1 (ca. 53.3 Ma), and I2 (ca. 53.2 Ma), each characterized by global warming. The negative CIEs are recognized in both marine and terrestrial substrates, but the terrestrial substrates exhibit a larger absolute magnitude CIE than the marine substrates. Here we reconcile the difference in CIE magnitude between the terrestrial and marine substrates for each of these events by accounting for the additional carbon isotope fractionation by C3 land plants in response to increased atmospheric pCO2. Our analysis yields background and peak pCO2 values for each of the events. Assuming a common mechanism for each event, we calculate that background pCO2 was not static across the Early Eocene, with the highest background pCO2 immediately prior to I2, the last of the five CIEs. Background pCO2 is dependent on the source used in our analysis with values ranging from 300 to 720 ppmv provided an injection of 13C-depleted carbon with δ13C value of -60‰ (e.g. biogenic methane). The peak pCO2 during each event scales according to the magnitude of CIE, and is therefore greatest during the PETM and smallest during H2. Both background and peak pCO2 are higher if we assume a mechanism of permafrost thawing (δ13C = -25‰). Our reconstruction of pCO2 across these events is consistent with trends in the δ18O value of deep-sea benthic foraminifera, suggesting a strong link between pCO2 and temperature during the Early Eocene.

  7. Factors Controlling Diffusive CO2 Transport and Production in the Cedarburg Bog, Saukville, Wisconsin: Field Observations

    NASA Astrophysics Data System (ADS)

    Joynt, E.; Han, W. S.; Gulbranson, E. L.; Graham, J. P.

    2015-12-01

    Wetland ecosystems are vital components of the carbon cycle containing an estimated 20-30% of the global soil carbon store. The Cedarburg Bog of southeastern Wisconsin boasts a myriad of wetland habitats including the southernmost string bog found in North America. The behavior of carbon dioxide (CO2) in these systems is the response of multiple interdependent variables that are, collectively, not well understood. Modeling this behavior in future climate scenarios requires detailed representation of such relationships within highly diverse environments. In 2014 a LI-COR 8100A automated soil gas flux system was installed in a hollow of the Cedarburg Bog string bog and collectively measured diffusive CO2 concentration and flux. Supplemental groundwater data, soil temperature, and weather data (temperature, pressure, precipitation, etc.) were also included to elucidate correlations between soil CO2 flux/CO2 concentration and external forces. In 2015 field data were complemented with soil moisture data and depth profile sampling of pore water chemistry and stable carbon isotopes from peat and gaseous media in order to discern the source and evolution of CO2 at depth. Preliminary LI-COR data analysis reveals distinct diurnal and seasonal trends; CO2 concentration builds overnight while flux increases during the day, both peaking in mid-summer. Flux events average 405 mg CO2/m2 per hour but reach over 31,800 mg CO2/m2 per hour in a single event and in several instances negative flux events are observed. Correlation significance also yields a wide array of strengths among variables. Initial δ13C data from gaseous CO2 infer, on average, a more positive δ13C signature in the atmosphere compared to the surface and shallow subsurface. Temporal trends of these parameters are similar to one another, becoming depleted in δ13C through time. Further interpretation of data trends will utilize the HYDRUS-1D model to quantify relationships under changing environmental conditions.

  8. Carbon and Oxygen Stable Isotope Measurements of Martian Atmospheric CO2 by the Phoenix Lander

    NASA Technical Reports Server (NTRS)

    Niles, Paul B.; Boynton, W. V.; Hoffman, J. H.; Ming, D. W.; Hamara, D.

    2010-01-01

    Precise stable isotope measurements of the CO2 in the martian atmosphere have the potential to provide important constraints for our understanding of the history of volatiles, the carbon cycle, current atmospheric processes, and the degree of water/rock interaction on Mars [1]. The isotopic composition of the martian atmosphere has been measured using a number of different methods (Table 1), however a precise value (<1%) has yet to be achieved. Given the elevated Delta(sup 13)C values measured in carbonates in martian meteorites [2-4] it has been proposed that the martian atmosphere was enriched in 13C [8]. This was supported by measurements of trapped CO2 gas in EETA 79001[2] which showed elevated Delta(sup 13)C values (Table 1). More recently, Earth-based spectroscopic measurements of the martian atmosphere have measured the martian CO2 to be depleted in C-13 relative to CO2 in the terrestrial atmosphere[ 7, 9-11]. The Thermal and Evolved Gas Analyzer (TEGA) instrument on the Mars Phoenix Lander [12] included a magnetic-sector mass spectrometer (EGA) [13] which had the goal of measuring the isotopic composition of martian atmospheric CO2 to within 0.5%. The mass spectrometer is a miniature instrument intended to measure both the martian atmosphere as well as gases evolved from heating martian soils.

  9. Detection of inflammatory cell function using 13C magnetic resonance spectroscopy of hyperpolarized [6-13C]-arginine

    PubMed Central

    Najac, Chloé; Chaumeil, Myriam M.; Kohanbash, Gary; Guglielmetti, Caroline; Gordon, Jeremy W.; Okada, Hideho; Ronen, Sabrina M.

    2016-01-01

    Myeloid-derived suppressor cells (MDSCs) are highly prevalent inflammatory cells that play a key role in tumor development and are considered therapeutic targets. MDSCs promote tumor growth by blocking T-cell-mediated anti-tumoral immune response through depletion of arginine that is essential for T-cell proliferation. To deplete arginine, MDSCs express high levels of arginase, which catalyzes the breakdown of arginine into urea and ornithine. Here, we developed a new hyperpolarized 13C probe, [6-13C]-arginine, to image arginase activity. We show that [6-13C]-arginine can be hyperpolarized, and hyperpolarized [13C]-urea production from [6-13C]-arginine is linearly correlated with arginase concentration in vitro. Furthermore we show that we can detect a statistically significant increase in hyperpolarized [13C]-urea production in MDSCs when compared to control bone marrow cells. This increase was associated with an increase in intracellular arginase concentration detected using a spectrophotometric assay. Hyperpolarized [6-13C]-arginine could therefore serve to image tumoral MDSC function and more broadly M2-like macrophages. PMID:27507680

  10. The impact of elevated CO2 concentrations on soil microbial community, soil organic matter storage and nutrient cycling at a natural CO2 vent in NW Bohemia

    NASA Astrophysics Data System (ADS)

    Nowak, Martin; Beulig, Felix; von Fischer, Joe; Muhr, Jan; Kuesel, Kirsten; Trumbore, Susan

    2014-05-01

    Natural CO2 vents or 'mofettes' are diffusive or advective exhalations of geogenic CO2 from soils. These structures occur at several places worldwide and in most cases they are linked to volcanic activity. Characteristic for mofette soils are high CO2 concentrations of up to more than 90% as well as a lack of oxygen, low pH values and reducing conditions. Mofette soils usually are considered to be sites of carbon accumulation, which is not only due to the absence of oxygen, but might also result from lower plant litter quality due to CO2 fertilization of CO2 influenced plants and reduced availability of N and P for the decomposer community. Furthermore, fermentation processes and the formation of reduced elements by anoxic decomposition might fuel chemo-lithoautotrophic or mixotrophic microbial CO2 uptake, a process which might have important ecological functions by closing internal element cycles, formation of trace gasses as well as by re-cycling and storing of carbon. Several studies of microbial community structure revealed a shift towards CO2 utilizing prokaryotes in moffete soils compared to a reference site. Here, we use combined stable and radiocarbon isotope data from mofette soils in NW Bohemia to quantify the contribution of geogenic CO2 to soil organic carbon formation within mofette soils, either resulting from plant litter or from microbial CO2 uptake. This is possible because the geogenic CO2 has a distinct isotopic signature (δ13C = -2 o Δ14C = -1000 ) that is very different from the isotopic signature of atmospheric CO2. First results show that mofette soils have a high Corg content (20 to 40 %) compared to a reference site (2 to 20 %) and soil organic matter is enriched in 13C as well as depleted in 14C. This indicates that geogenic CO2 is re-fixed and stored as SOM. In order to quantify microbial contribution to CO2 fixation and SOM storage, microbial CO2 uptake rates were determined by incubating mofette soils with 13CO2 labelled gas. The

  11. Anomalous 13C enrichment in modern marine organic carbon

    USGS Publications Warehouse

    Arthur, M.A.; Dean, W.E.; Claypool, G.E.

    1985-01-01

    Marine organic carbon is heavier isotopically (13C enriched) than most land-plant or terrestrial organic C1. Accordingly, ??13C values of organic C in modern marine sediments are routinely interpreted in terms of the relative proportions of marine and terrestrial sources of the preserved organic matter2,3. When independent geochemical techniques are used to evaluate the source of organic matter in Cretaceous or older rocks, those rocks containing mostly marine organic C are found typically to have lighter (more-negative) ??13C values than rocks containing mostly terrestrial organic C. Here we conclude that marine photosynthesis in mid-Cretaceous and earlier oceans generally resulted in a greater fractionation of C isotopes and produced organic C having lighter ??13C values. Modern marine photosynthesis may be occurring under unusual geological conditions (higher oceanic primary production rates, lower PCO2) that limit dissolved CO2 availability and minimize carbon isotope fractionation4. ?? 1985 Nature Publishing Group.

  12. 13C measurements on organic aerosol - a comparison of sources with ambient samples

    NASA Astrophysics Data System (ADS)

    Dusek, Ulrike; Meusinger, Carl; Oyama, Beatriz; Holzinger, Rupert; Röckmann, Thomas

    2014-05-01

    The stable carbon isotopes 12C and 13C can be used to get information about sources and processing of organic aerosol (OA). We developed and tested a method to measure δ13C values of OA collected on filter samples in different volatility classes. These filter samples are introduced into an oven, where organic compounds are thermally desorbed in He at different temperatures. The compounds released at each temperature step are oxidized to CO2 using a platinum catalyst at 550 °C. The CO2 is then passed on to an isotope ratio mass spectrometer (IRMS) to measure d13C ratios. With a similar setup the chemical composition at each temperature step can be determined using a Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-ToF-MS). System evaluation with controlled test compounds showed that organic compounds usually start evaporating from the filter when their melting point is reached. Isotopic fractionation occurs only if one temperature step is within a few degrees of the melting point of the substance, so that the substance only partially evaporates. However, this effect should be limited in an ambient sample containing thousands of individual chemical compounds. δ13C values of aerosol filter samples do not depend on the sample amount used, i.e. the system shows good linearity. The reproducibility depends somewhat on the sample amount and is usually < ± 0.3 ‰ for oven temperatures up to 200 °C and < ± 0.5 ‰ for oven temperatures greater than 200 °C. We analysed aerosol samples collected in a tunnel in Brazil (vehicular emissions), laboratory generated secondary organic aerosol (SOA) from alpha-pinene ozonolysis, and ambient filter samples from a regional site in the Netherlands, an urban site in Belgium, and Sao Paulo Brazil. First results show that δ13C ratios of SOA and vehicular emissions do not change strongly with oven temperature, i.e. the more refractory organic compounds have similar isotopic composition as the more volatile compounds

  13. H2S interference on CO2 isotopic measurements using a Picarro G1101-i cavity ring-down spectrometer

    NASA Astrophysics Data System (ADS)

    Malowany, K.; Stix, J.; Van Pelt, A.; Lucic, G.

    2015-06-01

    Cavity ring-down spectrometers (CRDS) have the capacity to make isotopic measurements of CO2 where concentrations range from atmospheric (~ 400 ppm) to 6000 ppm. Following field trials, it has come to light that the spectrographic lines used for CO2 have an interference with elevated (higher than ambient) amounts of hydrogen sulfide (H2S), which causes significant depletions in the δ13C measurement by the CRDS. In order to deploy this instrument in environments with elevated H2S concentrations (i.e., active volcanoes), we require a robust method for eliminating this interference. Controlled experiments using a Picarro G1101-i optical spectrometer were done to characterize the H2S interference at varying CO2 and H2S concentrations. The addition of H2S to a CO2 standard gas reveals an increase in the 12CO2 concentration and a more significant decrease in the 13CO2 concentration, resulting in a depleted δ13C value. Reacting gas samples containing H2S with copper prior to analysis can eliminate this effect. However, experiments also revealed that the addition of H2S to CO2 results in the formation of carbonyl sulfide (OCS) and carbon disulfide (CS2), causing a decrease in the overall CO2 concentration without affecting the δ13C value. It is important for future work with CRDS, particularly in volcanic regions where H2S is abundant, to be aware of the H2S interference on the CO2 spectroscopic lines and to remove all H2S prior to analysis. We suggest employing a scrub composed of copper to remove H2S from all gas samples that have concentrations in excess of 1 ppb.

  14. Sequestering CO2 in the Built Environment

    NASA Astrophysics Data System (ADS)

    Constantz, B. R.

    2009-12-01

    Calera’s Carbonate Mineralization by Aqueous Precipitation (CMAP) technology with beneficial reuse has been called, “game-changing” by Carl Pope, Director of the Sierra Club. Calera offers a solution to the scale of the carbon problem. By capturing carbon into the built environment through carbonate mineralization, Calera provides a sound and cost-effective alternative to Geologic Sequestration and Terrestrial Sequestration. The CMAP technology permanently converts carbon dioxide into a mineral form that can be stored above ground, or used as a building material. The process produces a suite of carbonate-containing minerals of various polymorphic forms. Calera product can be substituted into blends with ordinary Portland cements and used as aggregate to produce concrete with reduced carbon, carbon neutral, or carbon negative footprints. For each ton of product produced, approximately half a ton of carbon dioxide can be sequestered using the Calera process. Coal and natural gas are composed of predominately istopically light carbon, as the carbon in the fuel is plant-derived. Thus, power plant CO2 emissions have relatively low δ13C values.The carbon species throughout the CMAP process are identified through measuring the inorganic carbon content, δ13C values of the dissolved carbonate species, and the product carbonate minerals. Measuring δ13C allows for tracking the flue gas CO2 throughout the capture process. Initial analysis of the capture of propane flue gas (δ13C ˜ -25 ‰) with seawater (δ13C ˜ -10 ‰) and industrial brucite tailings from a retired magnesium oxide plant in Moss Landing, CA (δ13C ˜ -7 ‰ from residual calcite) produced carbonate mineral products with a δ13C value of ˜ -20 ‰. This isotopically light carbon, transformed from flue gas to stable carbonate minerals, can be transferred and tracked through the capture process, and finally to the built environment. CMAP provides an economical solution to global warming by producing

  15. Indian Monsoon controlling the effect of anthropogenic emission on the seasonal variation of air-CO2 over Bangalore, India

    NASA Astrophysics Data System (ADS)

    Guha, T.; Ghosh, P.

    2012-12-01

    this study we registered large variation in mixing ratio and δ13C of CO2 in a diurnal scale; with higher mixing ratio observed during the morning time compared to the afternoon time and corresponding signature of lower δ13C values are recorded. Using this large range of diurnal variation in Keeling's approach, the average δ13C value of the source CO2 was determined. The average δ13C value of source CO2 is found to be -24.8‰ with an observed range from -24.3‰ to -25.9‰. The average value closely matches with Permian coal δ13C value indicating fossil fuel as major source. The other possible sources are biomass burning and car exhaust having similar δ13C values as well. The proportional contribution of fossil fuel combustion and productivity is mainly affecting the seasonal variation. During the dry seasons the excess contribution of biomass burning together with contribution from fossil fuel produces excess depletion in δ13C values as observed in April-May. During SWM the increase in biosphere productivity causes preferential uptake of 12C during photosynthesis and drives enrichment of δ13C values in air CO2. The role of Indian monsoon controlling the regional atmospheric CO2 variability is presented here.

  16. Understanding of δ13C behavior and its significance in the Furong Cave system through a 10-year cave monitoring study

    NASA Astrophysics Data System (ADS)

    Li, J.; Li, H. C.; Li, T.; Li, X.; Yuan, N.; Zhang, T.

    2015-12-01

    The debate about how speleothem δ13C to reflect paleoclimate and paleovegetation changes calls for understanding of δ13C behavior in a cave system. We have conducted a monitoring study in Furong Cave, Chongqing, China since 2005 involving multiple sites in the overlying soil and inside the cave. The measured proxies include pCO2 of the atmosphere, soil and cave air; dripping rate, pH, electronic conductivity, Ca2+, HCO3-, d13CDIC of the dripwaters; and deposition rate, d13C of seasonally selected carbonate deposits. The many observations from this study are: (1) Soil pCO2 is close to the atmospheric pCO2 in winter and reaches >10000 ppm during the summer due to high productivity under warm and wet climates. (2) The pCO2 in cave air is slightly higher than Soil pCO2 and atmospheric pCO2 in winter (400~900 ppm), but elevates up to ~2000 ppm around October due to seepage of soil CO2 into the cave. The cave air pCO2 exhibits double peaks following the seasonal rainfall (1st peak in April-June controlled by Indian monsoon and 2nd peak in July-September influenced by the North Western Pacific monsoon). The cave air pCO2 has about 2-3 month lag to the soil pCO2. (3) Under the influence of soil CO2 and rainfall, the d13CDIC of drpiwaters are depleted in the summer and enriched during the winter. During 2009-2011, southwestern China experienced extremely drought due to summer monsoon failure. The d13CDIC of dripwater in Furong Cave was strongly enriched because of low soil CO2 productivity, less transportation of soil CO2 into the cave, and high CO2 ratio from bedrock input. Dripping rate does not affect the d13CDIC significantly. (4) The d13C of speleothems is controlled by the open/closed system of the seepage pathway on the first order. Monitoring site MP1 owns a relatively open system shown by fast dripping rates, low Ca and HCO3- contents, and low carbonate deposition rate. The d13C of modern deposits from this site not only shows the seasonal variation following

  17. Design and Implementation of a CO(2) Flood Utilizing Advanced Reservoir Characterization and Horizontal Injection Wells in Shallow Shelf Carbonate Approaching Waterflood Depletion

    SciTech Connect

    Harpole, K.J.; Dollens, K.B.; Durrett, E.G.; Bles, J.S

    1997-10-31

    The first objective is to utilize reservoir characterization and advanced technologies to optimize the design of a carbon dioxide (CO) project for the South Cowden Unit (SCU) located in Ector County, Texas. The SCU is a mature, relatively small, shallow shelf carbonate unit nearing waterflood depletion. The second objective is to demonstrate the performance and economic viability of the project in the field. All work this quarter falls within the demonstration project.

  18. Photosynthesis and sup 13 C/ sup 12 C ratios in Amazonian rain forests

    SciTech Connect

    Van Der Merwe, N.J. ); Medina, E. )

    1989-05-01

    Measurements are reported of {sup 13}C/{sup 12}C ratios for air CO{sub 2} at different heights in two Amazonian rain forests. CO{sub 2} emitted from the forest floor is severely depleted in {sup 13}C which produces isotopically light source air throughout the forest. Air {delta}{sup 13}C values vary very little with height above ground, but are about 5 to 6{per thousand} more negative than the open atmosphere. CO{sub 2} recycling under the canopy depletes all leaf {delta}{sup 13}C values by a like amount. Additional factors further deplete leaf {delta}{sup 13}C values by 4 to 5{per thousand} at ground level; this effect decreases with height to zero in the upper canopy, yielding a gradient in {delta}{sup 13}C values.

  19. Distinct fungal and bacterial δ13C signatures can drive the increase in soil δ13C with depth

    NASA Astrophysics Data System (ADS)

    Kohl, Lukas; Laganièrea, Jérôme; Edwards, Kate A.; Billings, Sharon A.; Morrill, Penny L.; Van Biesen, Geert; Ziegler, Susan E.

    2015-04-01

    Soil microbial biomass is a key precursor of soil organic carbon (SOC), and the enrichment in 13C during SOC diagenesis has been purported to be driven by increasing proportions of microbially derived SOC. Yet, little is known about how the δ13C of soil microbial biomass - and by extension the δ13C of microbial inputs to SOC - vary in space, time, or with the composition of the microbial community. Phospholipid fatty acids (PLFA) can be analyzed to measure the variation of the natural abundance δ13C values of both individual groups of microorganisms and the microbial community as a whole. Here, we show how variations of δ13CPLFA within the soil profile provides insight into C fluxes in undisturbed soils and demonstrate that distinct δ13C of fungal and bacterial biomass and their relative abundance can drive the increase of bulk δ13CSOC with depth. We studied the variation in natural abundance δ13C signatures of PLFA in podzolic soil profiles from mesic boreal forests in Atlantic Canada. Samples from the organic horizons (L,F,H) and the mineral (B; top 10 cm) horizons were analyzed for δ13C values of PLFA specific to fungi, G+ bacteria, or G- bacteria as proxies for the δ13C of the biomass of these groups, and for δ13C values of PLFA produced by a wide range of microorganisms (e.g. 16:0) as a proxy for the δ13C value of microbial biomass as a whole. Results were compared to fungi:bacteria ratios (F:B) and bulk δ13CSOC values. The δ13C values of group-specific PLFA were driven by differences among source organisms, with fungal PLFA consistently depleted (2.1 to 6.4‰) relative to and G+ and G- bacterial PLFA in the same sample. All group-specific PLFA, however, exhibited nearly constant δ13C values throughout the soil profile, apparently unaffected by the over 2.8‰ increase in δ13CSOC with depth from the L to B horizons. This indicates that bulk SOC poorly represents the substrates actually consumed by soil microorganisms in situ. Instead, our

  20. A redetermination of absolute values for 17RVPDB-CO2 and 17RVSMOW.

    PubMed

    Assonov, Sergey S; Brenninkmeijer, Carl A M

    2003-01-01

    In a companion paper in this issue we presented a review of the current state of (17)O-corrections for CO(2) mass spectrometry and considered an approach (including algebraic formulae) of how to determine absolute values for (17)R(VPDB-CO2) and (17)R(VSMOW). Here we present the results of experiments conducted to determine these values. Two oxygen gases (one depleted in heavy isotopes and the other isotopically normal oxygen) were analysed to obtain the relative (17)O content. Samples of both gases were converted into CO(2), and the resulting CO(2) samples were analysed as well. Possible experimental and analytical errors are carefully considered and eliminated as far as feasible. Much attention was paid to understanding and dealing with cross-contamination effects occurring in the mass spectrometer. Based on the data obtained, the absolute values are calculated to be: (17)R(VPDB-CO2) = 0.00039511 +/- 0.00000094 and (17)R(VSMOW) = 0.00038672 +/- 0.00000087 (expanded uncertainties). Both values are on the original scale of Craig (Geochim. Cosmochim. Acta 1957; 12: 133-149) with (13)R(VPDB-CO2) = 0.0112372. A (17)O-correction algorithm incorporating the newly determined value for (17)R(VPDB-CO2) and lambda = 0.528 by Meijer and Li (Isot. Environ. Health Stud. 1998; 34: 349-369) is constructed. A computational test is performed to demonstrate the degree of delta(13)C bias relative to the previously known correction algorithms. delta(13)C values produced by the constructed algorithm are in the middle of the values produced by the other algorithms. We refrain, however, from giving any recommendation concerning which (17)O-correction algorithm to use in order to obtain delta(13)C data in the most accurate way. The present work illuminates the need to reconsider recommendations concerning the correction algorithm. PMID:12720281

  1. Isotopically depleted carbon in the mid-depth South Atlantic during the last deglaciation

    NASA Astrophysics Data System (ADS)

    Lund, D. C.; Tessin, A.

    2012-12-01

    The initial 30 ppmv rise in atmospheric CO2 during Heinrich Stadial 1 (HS1; 18.0-14.5 kyr BP) coincided with a 0.3‰ decrease in the δ13C of CO2 (Schmitt et al., 2012). The synchroneity of the signals implies that release of carbon from a 13C-depleted reservoir into the atmosphere was a key initiator of the last deglaciation. Using a depth transect of 6 high resolution sediment cores from the Brazil Margin, we show that benthic foraminiferal records from 1600 m to 2100 m water depth display an abrupt decrease in δ13C similar to the atmosphere. The δ13C anomaly is larger and appears to occur earlier in the Southwest Atlantic, pointing to an oceanic source. The benthic δ13C signal also leads the deglacial decrease in benthic δ18O. Our isotopic results cannot be easily explained by conservative mixing between northern and southern component waters. Rapid input of abyssal water could account for the HS1 δ13C anomalies if δ18O was compensated by warming or the input of 18O-depleted water. Alternatively, δ13C may have behaved non-conservatively during the deglaciation and reflect the input of carbon from another source. References: J. Schmitt et al., Carbon Isotope Constraints on the Deglacial CO2 Rise from Ice Cores. Science 336, 711 (May, 2012).Figure 1. Benthic δ13C time series from the Brazil Margin (black and grey lines) compared to atmospheric δ13C (Schmitt et al., 2012). Two possible curves are shown for the Brazil Margin, including no change in the regional reservoir age correction (ΔR = 0 years; black line) and a ΔR of 400 years from 12-18 kyr BP (dark grey line). Black triangles denote calendar age control points.

  2. Carbon isotope fractionation by marine phytoplankton in culture: The effects of CO2 concentration, pH, temperature, and species

    NASA Astrophysics Data System (ADS)

    Hinga, Kenneth R.; Arthur, Michael A.; Pilson, Michael E. Q.; Whitaker, Dania

    1994-03-01

    Closed cultures of marine phytoplankton were established under variable conditions of CO2 concentration, temperature, growth rate (by light limitation), and pH (but with nearly identical [CO2aq]) in order to assess the relative influence of these variables on the extent of carbon isotope fractionation relative to dissolved inorganic carbon sources. Culture biomass was not allowed to increase beyond levels that would significantly affect the dissolved carbon system in the closed cultures. In experiments with Skeletonema costatum and Emiliania huxleyi, increasing CO2 concentrations led to increased carbon isotope discrimination (resulting in organic matter progressively depleted in δ13C, i.e., a greater, more negative ɛp). ɛp values for E. huxleyi were 8-10‰ less than for S. costatum under identical conditions. For the S. costatum cultures, there was nearly a 20 ‰ range in [CO2aq]-dependent ɛp. The effect was nonlinear with a leveling off at high [CO2aq]. Over a pH range of 7.5-8.3 but at a constant [CO2aq] there was a variation in carbon isotope fractionation by S. costatum of about 9 ‰ with a minimum at pH 7.8-7.9. There was a temperature effect of ˜8‰ on fractionation even after equilibrium temperature dependency of δ13C of CO2aq was taken into account. No growth rate effect was found for S. costatum over a modest range of growth rates. Culture experiments used to determine the carbon isotope fractionation by phytoplankton species must be conducted under well-defined conditions of temperature, pH, and CO2 concentrations. Hindcasts of ancient atmospheric pCO2 from measurements of δ13C of organic carbon in marine sediments will require careful calibration because of the variety of possible factors that influence δ13Corg.

  3. Understanding carbon isotope behaviour during combustion processes: a pre-requisite to using d13C in the field of air pollution.

    NASA Astrophysics Data System (ADS)

    Negrel, P.; Widory, D.

    2006-12-01

    Recent studies have demonstrated the effectiveness of stable isotopes in the field of air pollution research, especially their success in clearly discriminating the different sources of pollution in urban environments, and in tracing their respective impacts for a given sampling location. Among them, carbon isotopes have been used to track the origin of both gases (i.e. CO2; Widory &Javoy, 2003) and particulate matter (i.e. PM2 .5 and PM10; Widory et al., 2004). But understanding the carbon isotope behaviour that leads to this discrimination during combustion processes is a pre-requisite to using them as tracers of pollution sources in the atmosphere. d13C in fuels has been extensively used as an indicator of the processes leading to the generation of their parent crude-oil. Here, we isotopically characterise fuels and combustibles sold in Paris (France), and characterise the isotopic relations existing with their combustion by-products, i.e. gases (CO2) and particles (bulk carbon). Results show that d13C in fuels is clearly related to their physical state, with natural gas being strongly depleted in 13C while coal yields the highest d13C, and liquid fuels display intermediate values. This relation is also valid for exhaust gases, though d13C values of combustion particles form a homogeneous range within which no clear distinction is observed. Combustion processes are accompanied by carbon-isotope fractionation resulting from the combustion being incomplete. Carbon-isotope fractionation is strictly negative ( 1.3‰) during the formation of combustion gases, but generally positive in particle formation even if values close to zero are observed. This study helps understanding the processes leading to the d13C discrimination observed in pollution sources' exhausts, and definitely validates the use of carbon isotopes as tracers of atmospheric pollution.

  4. Numerical modeling of self-limiting and self-enhancing caprock alteration induced by CO2 storage in a depleted gas reservoir

    SciTech Connect

    Xu, Tianfu; Gherardi, Fabrizio; Xu, Tianfu; Pruess, Karsten

    2007-09-07

    This paper presents numerical simulations of reactive transport which may be induced in the caprock of an on-shore depleted gas reservoir by the geological sequestration of carbon dioxide. The objective is to verify that CO{sub 2} geological disposal activities currently being planned for the study area are safe and do not induce any undesired environmental impact. In our model, fluid flow and mineral alteration are induced in the caprock by penetration of high CO{sub 2} concentrations from the underlying reservoir, where it was assumed that large amounts of CO{sub 2} have already been injected at depth. The main focus is on the potential effect of precipitation and dissolution processes on the sealing efficiency of caprock formations. Concerns that some leakage may occur in the investigated system arise because the seal is made up of potentially highly-reactive rocks, consisting of carbonate-rich shales (calcite+dolomite averaging up to more than 30% of solid volume fraction). Batch simulations and multi-dimensional 1D and 2D modeling have been used to investigate multicomponent geochemical processes. Numerical simulations account for fracture-matrix interactions, gas phase participation in multiphase fluid flow and geochemical reactions, and kinetics of fluid-rock interactions. The geochemical processes and parameters to which the occurrence of high CO{sub 2} concentrations are most sensitive are investigated by conceptualizing different mass transport mechanisms (i.e. diffusion and mixed advection+diffusion). The most relevant mineralogical transformations occurring in the caprock are described, and the feedback of these geochemical processes on physical properties such as porosity is examined to evaluate how the sealing capacity of the caprock could evolve in time. The simulations demonstrate that the occurrence of some gas leakage from the reservoir may have a strong influence on the geochemical evolution of the caprock. In fact, when a free CO{sub 2

  5. 13c Measurements On Air of Small Ice Samples

    NASA Astrophysics Data System (ADS)

    Eyer, M.; Leuenberger, M.

    We have developed a new method for 13C analysis for very small air amounts of less than 0.5 cc STP, corresponding to less than 10 gram of ice. It is based on the needle-crasher technique, which we routinely use for CO2 concentration measurements by infrared laser absorption. The extracted air is slowly expanded into a large volume through a water trap held at ­100°C. This sampled air is then carried by a high helium flux through a modified Precon system of Thermo-Finnigan to separate CO2 from the air and to inject the pure CO2 gas in a low helium stream via an open split device to a Delta Plus XL mass spectrometer. The overall precision based on replicates of standard air is significantly better than 0.1 for a single analysis and is further improved by a triplicate measurement of the same sample through a specially designed gas splitter. We have used this new method for investigations on polar ice cores. The 13C measurements are important for climate reconstructions, e.g. to reconstruct the evolution and its variability in the terrestrial and oceanic carbon sinks and to identify natural variations in the marine carbon cycle. During the industrialization atmospheric 13C decreased by about -2, mainly due to the anthropogenic release of biogenic CO2 by fossil fuel burning. Reconstructions of carbon and oxygen cycles of Joos at al. [1999] using a double deconvolution method show that between 1930 and 1950 the net terrestrial release is changing to a net terrestrial uptake of CO2. A highly resolved 13C dataset of this time window would replenish the documentation of this behaviour. Further, it would be interesting to compare such data with O2/N2 measurements, known as an other partitioning tool for carbon sources and sinks. At the EGS 2002 we will present a highly resolved 13C record from Antarctic ice covering this time period.

  6. 13C measurements on organic aerosol - ambient samples versus source studies

    NASA Astrophysics Data System (ADS)

    Dusek, Ulrike; Meusinger, Carl; Oyama, Beatriz; Ramon, Wichert; de Wilde, Peter A.; Holzinger, Rupert; Röckmann, Thomas

    2013-04-01

    The stable carbon isotopes 12C and 13C can be used to get information about sources and processing of organic aerosol (OA). We developed and tested a method to measure δ13C values of OA collected on filter samples in different volatility classes. These filter samples are introduced into an oven, where organic compounds are thermally desorbed in He at different temperatures. The compounds released at each temperature step are oxidized to CO2 using a platinum catalyst at 550 °C. The CO2 is then passed on to an isotope ratio mass spectrometer (IRMS) to measure δ13C ratios. With a similar setup the chemical composition at each temperature step can be determined using a Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-ToF-MS). System evaluation with controlled test compounds showed that organic compounds usually start evaporating from the filter when their melting point is reached. Isotopic fractionation occurs only, if one temperature step is within a few degrees of the melting point of the substance, so that the substance only partially evaporates. However, this effect should be limited in an ambient sample containing thousands of individual chemical compounds. We analysed aerosol samples collected in a tunnel in Brazil (vehicular emissions), laboratory generated secondary organic aerosol (SOA) from alpha-pinene ozonolysis, and ambient filter samples from a regional site in the Netherlands and an urban site in Belgium. First results indicate that SOA is more volatile than organic aerosol from ambient or tunnel filters. The δ13C ratios of SOA and vehicular emissions do not change strongly with oven temperature, i.e. the more refractory organic compounds have similar isotopic composition as the more volatile compounds. This is in contrast to ambient organic aerosol where the more volatile compounds evaporating below 200°C are depleted with respect to the refractory compounds. Possible reasons for this difference (mixture of sources vs the role of

  7. Diagenetic mineralization in Pennsylvanian coals from Indiana, USA: 13C/12C and 18O/16O implications for cleat origin and coalbed methane generation

    USGS Publications Warehouse

    Solano-Acosta, W.; Schimmelmann, A.; Mastalerz, Maria; Arango, I.

    2008-01-01

    Cleats and fractures in southwestern Indiana coal seams are often filled with authigenic kaolinite and/or calcite. Carbon- and oxygen-stable isotope ratios of kaolinite, calcite, and coalbed CO2 were evaluated in combination with measured values and published estimates of ??18O of coalbed paleowaters that had been present at the time of mineralization. ??18Omineral and ??18Owater values jointly constrain the paleotemperature of mineralization. The isotopic evidence and the thermal and tectonic history of this part of the Illinois Basin led to the conclusion that maximum burial and heat-sterilization of coal seams approximately 272??Ma ago was followed by advective heat redistribution and concurrent precipitation of kaolinite in cleats at a burial depth of < 1600??m at ??? 78 ?? 5????C. Post-Paleozoic uplift, the development of a second generation of cleats, and subsequent precipitation of calcite occurred at shallower burial depth between ??? 500 to ??? 1300??m at a lower temperature of 43 ?? 6????C. The available paleowater in coalbeds was likely ocean water and/or tropical meteoric water with a ??18Owater ??? - 1.25??? versus VSMOW. Inoculation of coalbeds with methanogenic CO2-reducing microbes occurred at an even later time, because modern microbially influenced 13C-enriched coalbed CO2 (i.e., the isotopically fractionated residue of microbial CO2 reduction) is out of isotopic equilibrium with 13C-depleted calcite in cleats. ?? 2007 Elsevier B.V. All rights reserved.

  8. Nitrogen control of 13C enrichment in heterotrophic organs relative to leaves in a landscape-building desert plant species

    NASA Astrophysics Data System (ADS)

    Zhang, J.; Gu, L.; Bao, F.; Cao, Y.; Hao, Y.; He, J.; Li, J.; Li, Y.; Ren, Y.; Wang, F.; Wu, R.; Yao, B.; Zhao, Y.; Lin, G.; Wu, B.; Lu, Q.; Meng, P.

    2015-01-01

    A longstanding puzzle in isotope studies of C3 plant species is that heterotrophic plant organs (e.g., stems, roots, seeds, and fruits) tend to be enriched in 13C compared to the autotrophic organ (leaves) that provides them with photosynthate. Our inability to explain this puzzle suggests key deficiencies in understanding post-photosynthetic metabolic processes. It also limits the effectiveness of applications of stable carbon isotope analyses in a variety of scientific disciplines ranging from plant physiology to global carbon cycle studies. To gain insight into this puzzle, we excavated whole plant architectures of Nitraria tangutorum Bobrov, a C3 species that has an exceptional capability of fixing sands and building sand dunes, in two deserts in northwestern China. We systematically and simultaneously measured carbon isotope ratios and nitrogen and phosphorous contents of different parts of the excavated plants. We also determined the seasonal variations in leaf carbon isotope ratios on nearby intact plants of N. tangutorum. We found, for the first time, that higher nitrogen contents in heterotrophic organs were significantly correlated with increased heterotrophic 13C enrichment compared to leaves. However, phosphorous contents had no effect on the enrichment. In addition, new leaves had carbon isotope ratios similar to roots but were progressively depleted in 13C as they matured. We concluded that a nitrogen-mediated process, hypothesized to be the refixation of respiratory CO2 by phosphoenolpyruvate (PEP) carboxylase, was responsible for the differences in 13C enrichment among different heterotrophic organs, while processes such as fractionating foliar metabolism and preferentially loading into phloem of 13C-enriched sugars may contribute to the overall autotrophic-heterotrophic difference in carbon isotope compositions.

  9. Ocean biology could control atmospheric δ13C during glacial-interglacial cycle

    NASA Astrophysics Data System (ADS)

    Brovkin, Victor; Hofmann, Matthias; Bendtsen, Jørgen; Ganopolski, Andrey

    2002-05-01

    Estimates of changes in the global carbon budget are often based on the assumption that the terrestrial biosphere controls the isotopic composition of atmospheric CO2 since terrestrial plants discriminate against the 13C isotope during photosynthesis. However, this method disregards the influence of 13C fractionation by the marine biota. Here an interpretation of the glacial-interglacial shifts in the atmospheric CO2 concentration and δ13CO2 measured in the Taylor Dome ice core [Smith et al., 1999] is given by accounting for possible changes in the ocean biology based on sensitivity simulations undertaken with the intermediate complexity model CLIMBER-2. With a combined scenario of enhanced biological and solubility pumps, the model simulates glacial atmospheric CO2 and δ13CO2 similar to those inferred from the ice core. The simulations reveal that a strengthening of the oceanic biological carbon pump considerably affects the atmospheric δ13CO2.

  10. Microbial community in a sediment-hosted CO2 lake of the southern Okinawa Trough hydrothermal system

    PubMed Central

    Inagaki, Fumio; Kuypers, Marcel M. M.; Tsunogai, Urumu; Ishibashi, Jun-ichiro; Nakamura, Ko-ichi; Treude, Tina; Ohkubo, Satoru; Nakaseama, Miwako; Gena, Kaul; Chiba, Hitoshi; Hirayama, Hisako; Nunoura, Takuro; Takai, Ken; Jørgensen, Bo B.; Horikoshi, Koki; Boetius, Antje

    2006-01-01

    Increasing levels of CO2 in the atmosphere are expected to cause climatic change with negative effects on the earth's ecosystems and human society. Consequently, a variety of CO2 disposal options are discussed, including injection into the deep ocean. Because the dissolution of CO2 in seawater will decrease ambient pH considerably, negative consequences for deep-water ecosystems have been predicted. Hence, ecosystems associated with natural CO2 reservoirs in the deep sea, and the dynamics of gaseous, liquid, and solid CO2 in such environments, are of great interest to science and society. We report here a biogeochemical and microbiological characterization of a microbial community inhabiting deep-sea sediments overlying a natural CO2 lake at the Yonaguni Knoll IV hydrothermal field, southern Okinawa Trough. We found high abundances (>109 cm−3) of microbial cells in sediment pavements above the CO2 lake, decreasing to strikingly low cell numbers (107 cm−3) at the liquid CO2/CO2-hydrate interface. The key groups in these sediments were as follows: (i) the anaerobic methanotrophic archaea ANME-2c and the Eel-2 group of Deltaproteobacteria and (ii) sulfur-metabolizing chemolithotrophs within the Gamma- and Epsilonproteobacteria. The detection of functional genes related to one-carbon assimilation and the presence of highly 13C-depleted archaeal and bacterial lipid biomarkers suggest that microorganisms assimilating CO2 and/or CH4 dominate the liquid CO2 and CO2-hydrate-bearing sediments. Clearly, the Yonaguni Knoll is an exceptional natural laboratory for the study of consequences of CO2 disposal as well as of natural CO2 reservoirs as potential microbial habitats on early Earth and other celestial bodies. PMID:16959888

  11. Linking carbon isotope signatures of nighttime leaf-respiratory and daytime assimilatory CO2 fluxes observed with laser spectrometry under field conditions

    NASA Astrophysics Data System (ADS)

    Gentsch, Lydia; Ogée, Jérôme; Wingate, Lisa; Sturm, Patrick; Siegwolf, Rolf; Werner, Roland A.; Buchmann, Nina; Knohl, Alexander

    2015-04-01

    The 13C/12C ratio (δ13C) of atmospheric CO2 is a valuable tool for constraining the impact of the terrestrial biosphere on atmospheric CO2 dynamics. Alterations of the 13C signal of terrestrial net CO2 fluxes are generally attributed to variations in photosynthetic 13C discrimination. Yet, over the past decade, evidence has emerged that plant metabolism and respiration modify the initial δ13C signature of recent photosynthetic assimilates. Such postphotosynthetic δ13C modifications were reported for all plant organs, but leaf respiratory metabolism may play a central role as it impacts carbon turnover in other plant tissues. Leaf-respired CO2 is frequently 13C enriched with respect to leaf organic matter. Mechanisms potentially explaining this enrichment include the differential use of carbon sources, metabolite fragmentation or the expression of kinetic isotope effects of respiratory enzymes. For global and ecosystem-scale applications of δ13C, it is now important to study, under field conditions, the variability of δ13C in leaf-respired CO2 (δ13CRES) and the deviation of the latter from δ13C of recent assimilates (δ13CAS). Here, we present 74 days of hourly δ13C measurements for daytime assimilatory and nighttime respiratory CO2 fluxes on leafy branches of three mature Fagus sylvatica trees in a temperate forest. Measurements were conducted with a laser spectrometer (QCLAS-ISO, Aerodyne Research Inc.) measuring CO2 isotopologue mixing ratios in ambient and sampling air from photosynthetic gas exchange chambers. We used daytime measurements of photosynthetic 13C discrimination for diurnally flux-weighted estimates of δ13CAS, and found that flux-weighted δ13CRES roughly tracked previous-day shifts in δ13CAS. Deviations between flux-weighted δ13CAS and δ13CRES were further robustly predicted by previous-day assimilation, with δ13CRES displaying 13C enrichment on low and 13C depletion on high assimilation days. On the hourly timescale, δ13CRES either

  12. H2S interference on CO2 isotopic measurements using a Picarro G1101-i cavity ring-down spectrometer

    NASA Astrophysics Data System (ADS)

    Malowany, K.; Stix, J.; Van Pelt, A.; Lucic, G.

    2015-10-01

    Cavity ring-down spectrometers (CRDSs) have the capacity to make isotopic measurements of CO2 where concentrations range from atmospheric (~ 400 ppm) to 6000 ppm. Following field trials, it has come to light that the spectrographic lines used for CO2 have an interference with elevated (higher than ambient) amounts of hydrogen sulfide (H2S), which causes significant depletions in the δ13C measurement by the CRDSs. In order to deploy this instrument in environments with elevated H2S concentrations (i.e., active volcanoes), we require a robust method for eliminating this interference. Controlled experiments using a Picarro G1101-i optical spectrometer were done to characterize the H2S interference at varying CO2 and H2S concentrations. The addition of H2S to a CO2 standard gas reveals an increase in the 12CO2 concentration and a more significant decrease in the 13CO2 concentration, resulting in a depleted δ13C value. Reacting gas samples containing H2S with copper prior to analysis can eliminate this effect. Models post-dating the G1101-i carbon isotope analyzer have maintained the same spectral lines for CO2 and are likely to have a similar H2S response at elevated H2S concentrations. It is important for future work with CRDS, particularly in volcanic regions where H2S is abundant, to be aware of the H2S interference on the CO2 spectroscopic lines and to remove all H2S prior to analysis. We suggest employing a scrub composed of copper to remove H2S from all gas samples that have concentrations in excess of 1 ppb.

  13. Quantification of CO2-FLUID-ROCK Reactions Using Reactive and Non-Reactive Tracers

    NASA Astrophysics Data System (ADS)

    Matter, J.; Stute, M.; Hall, J. L.; Mesfin, K. G.; Gislason, S. R.; Oelkers, E. H.; Sigfússon, B.; Gunnarsson, I.; Aradottir, E. S.; Alfredsson, H. A.; Gunnlaugsson, E.; Broecker, W. S.

    2013-12-01

    Carbon dioxide mineralization via fluid-rock reactions provides the most effective and long-term storage option for geologic carbon storage. Injection of CO2 in geologic formations induces CO2 -fluid-rock reactions that may enhance or decrease the storage permanence and thus the long-term safety of geologic carbon storage. Hence, quantitative characterization of critical CO2 -fluid-rock interactions is essential to assess the storage efficiency and safety of geologic carbon storage. In an attempt to quantify in-situ fluid-rock reactions and CO2 transport relevant for geologic carbon storage, we are testing reactive (14C, 13C) and non-reactive (sodium fluorescein, amidorhodamine G, SF5CF3, and SF6) tracers in an ongoing CO2 injection in a basaltic storage reservoir at the CARBFIX pilot injection site in Iceland. At the injection site, CO2 is dissolved in groundwater and injected into a permeable basalt formation located 500-800 m below the surface [1]. The injected CO2 is labeled with 14C by dynamically adding calibrated amounts of H14CO3-solution into the injection stream in addition to the non-reactive tracers. Chemical and isotopic analyses of fluid samples collected in a monitoring well, reveal fast fluid-rock reactions. Maximum SF6 concentration in the monitoring well indicates the bulk arrival of the injected CO2 solution but dissolved inorganic carbon (DIC) concentration and pH values close to background, and a potentially lower 14C to SF6 ratio than the injection ratio suggest that most of the injected CO2 has reacted with the basaltic rocks. This is supported by δ13CDIC, which shows a drop from values close to the δ 13C of the injected CO2 gas (-3‰ VPDB) during breakthrough of the CO2 plume to subsequent more depleted values (-11.25‰ VPDB), indicating precipitation of carbonate minerals. Preliminary mass balance calculations using mixing relationships between the background water in the storage formation and the injected solution, suggest that

  14. Calculation of the 13C NMR shieldings of the C0 2 complexes of aluminosilicates

    NASA Astrophysics Data System (ADS)

    Tossell, J. A.

    1995-04-01

    13C NMR shieldings have been calculated using the random-phase-approximation, localized-orbital local-origins version of ab initio coupled Hartree-Fuck perturbation theory for CO 2 and and for several complexes formed by the reaction of CO 2 with molecular models for aluminosilicate glasses, H 3TOT'H3 3-n, T,T' = Si,Al. Two isomeric forms of the CO 2-aluminosilicate complexes have been considered: (1) "CO 2-like" complexes, in which the CO 2 group is bound through carbon to a bridging oxygen and (2) "CO 3-like" complexes, in which two oxygens of a central CO 3 group form bridging bonds to the two TH 3 groups. The CO 2-like isomer of CO 2-H 3SiOSiH 3 is quite weakly bonded and its 13C isotropic NMR shielding is almost identical to that in free CO 2. As Si is progressively replaced by Al in the - H terminated aluminosilicate model, the CO 2-like isomers show increasing distortion from the free CO 2 geometry and their 13C NMR shieldings decrease uniformly. The calculated 13C shielding value for H 3AlO(CO 2)AlH 3-2 is only about 6 ppm larger than that calculated for point charge stabilized CO 3-2. However, for a geometry of H 3SiO(CO 2) AlH 3-1, in which the bridging oxygen to C bond length has been artificially increased to that found in the - OH terminated cluster (OH) 3SiO(CO 2)Al(OH) 3-1, the calculated 13C shielding is almost identical to that for free CO 2. The CO 3-like isomers of the CO 2-aluminosili-cate complexes show carbonate like geometries and 13C NMR shieldings about 4-9 ppm larger than those of carbonate for all T,T' pairs. For the Si,Si tetrahedral atom pair the CO 2-like isomer is more stable energetically, while for the Si,Al and Al,Al cases the CO 3-like isomer is more stable. Addition of Na + ions to the CO 3-2 or H 3AlO(CO 2)AlH 3-2 complexes reduces the 13C NMR shieldings by about 10 ppm. Complexation with either Na + or CO 2 also reduces the 29Si NMR shieldings of the aluminosilicate models, while the changes in 27Al shielding with Na + or CO 2

  15. A large metabolic carbon contribution to the δ 13C record in marine aragonitic bivalve shells

    NASA Astrophysics Data System (ADS)

    Gillikin, David P.; Lorrain, Anne; Meng, Li; Dehairs, Frank

    2007-06-01

    It is well known that the incorporation of isotopically light metabolic carbon (C M) significantly affects the stable carbon isotope (δ 13C) signal recorded in biogenic carbonates. This can obscure the record of δ 13C of seawater dissolved inorganic carbon (δ 13C DIC) potentially archived in the shell carbonate. To assess the C M contribution to Mercenaria mercenaria shells collected in North Carolina, USA, we sampled seawater δ 13C DIC, tissue, hemolymph and shell δ 13C. All shells showed an ontogenic decrease in shell δ 13C, with as much as a 4‰ decrease over the lifespan of the clam. There was no apparent ontogenic change in food source indicated by soft tissue δ 13C values, therefore a change in the respired δ 13C value cannot be the cause of this decrease. Hemolymph δ 13C, on the other hand, did exhibit a negative relationship with shell height indicating that respired CO 2 does influence the δ 13C value of internal fluids and that the amount of respired CO 2 is related to the size or age of the bivalve. The percent metabolic C incorporated into the shell (%C M) was significantly higher (up to 37%, with a range from 5% to 37%) than has been found in other bivalve shells, which usually contain less than 10%C M. Interestingly, the hemolymph did contain less than 10%C M, suggesting that complex fractionation might occur between hemolymph and calcifying fluids. Simple shell biometrics explained nearly 60% of the observed variability in %C M, however, this is not robust enough to predict %C M for fossil shells. Thus, the metabolic effect on shell δ 13C cannot easily be accounted for to allow reliable δ 13C DIC reconstructions. However, there does seem to be a common effect of size, as all sites had indistinguishable slopes between the %C M and shell height (+0.19% per mm of shell height).

  16. 13C NMR Metabolomics: INADEQUATE Network Analysis

    PubMed Central

    Clendinen, Chaevien S.; Pasquel, Christian; Ajredini, Ramadan; Edison, Arthur S.

    2015-01-01

    The many advantages of 13C NMR are often overshadowed by its intrinsically low sensitivity. Given that carbon makes up the backbone of most biologically relevant molecules, 13C NMR offers a straightforward measurement of these compounds. Two-dimensional 13C-13C correlation experiments like INADEQUATE (incredible natural abundance double quantum transfer experiment) are ideal for the structural elucidation of natural products and have great but untapped potential for metabolomics analysis. We demonstrate a new and semi-automated approach called INETA (INADEQUATE network analysis) for the untargeted analysis of INADEQUATE datasets using an in silico INADEQUATE database. We demonstrate this approach using isotopically labeled Caenorhabditis elegans mixtures. PMID:25932900

  17. Metabolism of parenterally administered fat emulsions in the rat: studies of fatty acid oxidation with 1-13C- and 8-13C-labelled triolein.

    PubMed

    Bäurle, W; Brösicke, H; Matthews, D E; Pogan, K; Fürst, P

    1998-04-01

    To reassess the hypothesis that fatty acid catabolism occurs to completion via beta-oxidation, male Sprague-Dawley rats receiving continuous total parenteral nutrition (TPN) including 43% energy as fat were infused with [1-(13)C]- or [8-(13)C]triolein. Expired CO2 was collected continuously for 4 h and its 13C:12C ratio determined by isotope-ratio mass spectrometry. Bicarbonate retention was also assessed over 4 h by infusion of NaH14CO3 and measurement of the expired 14CO2. A possible loss of label from [8-(13)C]oleic acid from the citric acid cycle via labelled acetyl-CoA without oxidation to CO2 was assessed by infusing further animals with acetate labelled with 14C either at C atoms 1 or 2 and determination of its conversion to expired 14CO2. At isotopic steady state, 63.2 (SE 1.6)% (n 8) of the infused [1-(14)C]acetate and 46.0 (SE 1.2)% (n 8) of [2-(14)C]acetate was recovered as expired 14CO2. After correction for bicarbonate retention and non-oxidative isotope loss, 37.3 (SE 1.2)% (n 20) of the [1-(13)C]triolein was found to have been oxidized, whereas 32.6 (SE 1.0)% (n 20) of the [8-(13)C]triolein was oxidized (P < or = 0.01). The lower oxidation of the C atom at position 8 of oleic acid than that at position 1 indicates incomplete oxidative breakdown of the fatty acid after entering beta-oxidation. PMID:9624230

  18. Real-time measurements of chemical and isotope composition of atmospheric and volcanic CO2 at Mt. Etna (Italy)

    NASA Astrophysics Data System (ADS)

    Rizzo, Andrea L.; Jost, Hans-Jürg; Caracausi, Antonio; Paonita, Antonio; Liotta, Marcello; Martelli, Mauro

    2014-05-01

    We present unprecedented data of real-time measurements of chemical and isotope (δ13C) composition of CO2 in air and in fumarolic-plume gases collected at Mt. Etna volcano. Two campaigns of measurements were performed on 11 July and on 5-6 September 2013, by using a Delta Ray tunable diode laser. With the assumption of a two components mixing, a simple linear regression was applied to the data in order to obtain the volcanogenic δ13C. Data acquired along the route Catania-Etna, while car was moving, showed an excess of 13C-depleted CO2 when passing through inhabited centers due to atmospheric pollution produced by the cars exhaust. Fumaroles of Torre del Filosofo (2,900 m a.s.l.) displayed a δ13C between -3.2±0.03o and -3.7±0.05o comparable to IRMS measurements of discrete samples collected in the same date and in previous investigations. Diluted plume gases were collected at more than 1 km from the craters and showed δ13C=-2.2±0.2o accordingly with collected crater fumaroles. Considering the huge amount of data that may be acquired in a very short time by Delta Ray, we demonstrate that the addition to the atmospheric CO2 content of ~100 ppm of CO2 from an unknown source is enough to allow a mathematical calculation of the end-member with an uncertainty generally < 0.15‰This is feasible with the assumption of a binary mixing. We thus infer that the application performed at Mt. Etna may represent an historical step forward for the scientific community in volcanic surveillance.

  19. Soil respiration under mature deciduous forest trees after 7 years of CO2 enrichment

    NASA Astrophysics Data System (ADS)

    Bader, Martin; Körner, Christian

    2010-05-01

    The anthropogenic rise in atmospheric CO2 is expected to impact carbon fluxes not only at ecosystem level but also at the global scale by altering carbon cycle processes in soils. At the Swiss Canopy Crane (SCC), we examined how 7 years of free air CO2 enrichment (FACE) affected soil CO2 dynamics in a c. 100-year-old mixed deciduous forest. The use of 13C-depleted CO2 for canopy enrichment allowed us to trace the flow of recently fixed carbon (C). In the seventh year of growth at ~550 ppm CO2, soil respiratory CO2 consisted of 39% labelled C. During the growing season, soil air CO2 concentration was significantly enhanced under CO2-exposed trees. However, elevated CO2 failed to stimulate cumulative soil respiration (Rs) over the growing season. We found periodic reductions as well as increases in instantaneous rates of Rs in response to elevated CO2, depending on soil temperature and soil volumetric water content (VWC; significant 3-way interaction). During wet periods, soil water savings under CO2-enriched trees led to excessive VWC (>45%) that suppressed Rs. Elevated CO2 stimulated Rs only when VWC was ≤40% and concurrent soil temperature was high (>15 °C). Seasonal Q10 estimates of Rs were significantly lower under elevated (Q10 = 3.30) compared to ambient CO2 (Q10 = 3.97). However, this effect disappeared when 3 consecutive sampling dates of extremely high VWC were disregarded. This suggests that elevated CO2 affected Q10 mainly indirectly through changes in VWC. Fine root respiration did not differ significantly between treatments but soil microbial biomass (Cmic) increased by 14% under elevated CO2 (marginally significant). Our findings do not indicate enhanced soil C emissions in such stands under future atmospheric CO2. It remains to be shown whether C losses via leaching of dissolved organic or inorganic C (DOC, DIC) help to balance the carbon budget in this forest.

  20. Galactose oxidation using (13)C in healthy and galactosemic children.

    PubMed

    Resende-Campanholi, D R; Porta, G; Ferrioli, E; Pfrimer, K; Ciampo, L A Del; Junior, J S Camelo

    2015-03-01

    Galactosemia is an inborn error of galactose metabolism that occurs mainly as the outcome of galactose-1-phosphate uridyltransferase (GALT) deficiency. The ability to assess galactose oxidation following administration of a galactose-labeled isotope (1-(13)C-galactose) allows the determination of galactose metabolism in a practical manner. We aimed to assess the level of galactose oxidation in both healthy and galactosemic Brazilian children. Twenty-one healthy children and seven children with galactosemia ranging from 1 to 7 years of age were studied. A breath test was used to quantitate (13)CO2 enrichment in exhaled air before and at 30, 60, and 120 min after the oral administration of 7 mg/kg of an aqueous solution of 1-(13)C-galactose to all children. The molar ratios of (13)CO2 and (12)CO2 were quantified by the mass/charge ratio (m/z) of stable isotopes in each air sample by gas-isotope-ratio mass spectrometry. In sick children, the cumulative percentage of (13)C from labeled galactose (CUMPCD) in the exhaled air ranged from 0.03% at 30 min to 1.67% at 120 min. In contrast, healthy subjects showed a much broader range in CUMPCD, with values from 0.4% at 30 min to 5.58% at 120 min. The study found a significant difference in galactose oxidation between children with and without galactosemia, demonstrating that the breath test is useful in discriminating children with GALT deficiencies. PMID:25608239

  1. A Large Metabolic Carbon Ccontribution to the δ13C Record in Marine Aragonitic Bivalve Shells

    NASA Astrophysics Data System (ADS)

    Gillikin, D. P.; Lorrain, A.; Dehairs, F.

    2006-12-01

    The stable carbon isotopic signature archived in bivalve shells was originally thought to record the δ13C of seawater dissolved inorganic carbon (δ13C-DIC). However, more recent studies have shown that the incorporation of isotopically light metabolic carbon (M) significantly affects the δ13C signal recorded in biogenic carbonates. To assess the M contribution to Mercenaria mercenaria shells collected in North Carolina, USA, we sampled seawater δ13C-DIC, tissue, hemolymph and shell δ13C. We found up to a 4‰ decrease through ontogeny in shell δ13C in a 23 year old individual. There was no correlation between shell height or age and tissue δ13C. Thus, the ontogenic decrease observed in the shell δ13C could not be attributed to changes in food sources as the animal ages leading to more negative metabolic CO2, since this would require a negative relationship between tissue δ13C and shell height. Hemolymph δ13C, on the other hand, did exhibit a negative relationship with height, but the δ13C values were more positive than expected, indicating that hemolymph may not be a good proxy of extrapallial fluid δ13C. Nevertheless, the hemolymph data indicate that respired CO2 does influence the δ13C of internal fluids and that the amount of respired CO2 is related to the age of the bivalve. The percent metabolic C incorporated into the shell (%M) was significantly higher (up to 37%) than has been found in other bivalve shells, which usually contain less than 10 %M. Attempts to use shell biometrics to predict %M could not explain more than ~60% of the observed variability. Moreover, there were large differences in the %M between different sites. Thus, the metabolic effect on shell δ13C cannot easily be accounted for to allow reliable δ13C-DIC reconstructions. However, there does seem to be a common effect of size, as all sites had indistinguishable slopes between the %M and shell height (+0.19% per mm of shell height).

  2. New guidelines for δ13C measurements

    USGS Publications Warehouse

    Coplen, Tyler B.; Brand, Willi A.; Gehre, Matthias; Groning, Manfred; Meijer, Harro A. J.; Toman, Blaza; Verkouteren, R. Michael

    2006-01-01

    Consistency of δ13C measurements can be improved 39−47% by anchoring the δ13C scale with two isotopic reference materials differing substantially in 13C/12C. It is recommended thatδ13C values of both organic and inorganic materials be measured and expressed relative to VPDB (Vienna Peedee belemnite) on a scale normalized by assigning consensus values of −46.6‰ to L-SVEC lithium carbonate and +1.95‰ to NBS 19 calcium carbonate. Uncertainties of other reference material values on this scale are improved by factors up to two or more, and the values of some have been notably shifted:  the δ13C of NBS 22 oil is −30.03%.

  3. Nitrogen control of 13C enrichment in heterotrophic organs relative to leaves in a landscape-building desert plant species

    DOE PAGESBeta

    Zhang, J.; Gu, L.; Bao, F.; Cao, Y.; Hao, Y.; He, J.; Li, J.; Li, Y.; Ren, Y.; Wang, F.; et al

    2014-09-10

    A longstanding puzzle in isotope studies of C3 plant species is that heterotrophic plant organs (e.g., stems, roots, seeds, and fruits) tend to be enriched in 13C compared to the autotrophic organ (leaves) that provides them with photosynthate. Our inability to explain this puzzle suggests key deficiencies in understanding post-photosynthetic metabolic processes. It also limits the effectiveness of applications of stable carbon isotope analyses in a variety of scientific disciplines ranging from plant physiology to global carbon cycle studies. To gain insight into this puzzle, we excavated whole plant architectures of Nitraria tangutorum Bobrov, a C3 species that has anmore » exceptional capability of fixing sands and building sand dunes, in two deserts in northwestern China. We systematically and simultaneously measured carbon isotope ratios and nitrogen and phosphorous contents of different parts of the excavated plants. We also determined the seasonal variations in leaf carbon isotope ratios on nearby intact plants of N. tangutorum. We found, for the first time, that higher nitrogen contents in heterotrophic organs were significantly correlated with increased heterotrophic 13C enrichment compared to leaves. However, phosphorous contents had no effect on the enrichment. In addition, new leaves had carbon isotope ratios similar to roots but were progressively depleted in 13C as they matured. We concluded that a nitrogen-mediated process, probably the refixation of respiratory CO2 by phosphoenolpyruvate (PEP) carboxylase, was responsible for the differences in 13C enrichment among different heterotrophic organs while processes within leaves or during phloem loading may contribute to the overall autotrophic – heterotrophic difference in carbon isotope compositions.« less

  4. Nitrogen control of 13C enrichment in heterotrophic organs relative to leaves in a landscape-building desert plant species

    NASA Astrophysics Data System (ADS)

    Zhang, J.; Gu, L.; Bao, F.; Cao, Y.; Hao, Y.; He, J.; Li, J.; Li, Y.; Ren, Y.; Wang, F.; Wu, R.; Yao, B.; Zhao, Y.; Lin, G.; Wu, B.; Lu, Q.; Meng, P.

    2014-09-01

    A longstanding puzzle in isotope studies of C3 plant species is that heterotrophic plant organs (e.g., stems, roots, seeds, and fruits) tend to be enriched in 13C compared to the autotrophic organ (leaves) that provides them with photosynthate. Our inability to explain this puzzle suggests key deficiencies in understanding post-photosynthetic metabolic processes. It also limits the effectiveness of applications of stable carbon isotope analyses in a variety of scientific disciplines ranging from plant physiology to global carbon cycle studies. To gain insight into this puzzle, we excavated whole plant architectures of Nitraria tangutorum Bobrov, a C3 species that has an exceptional capability of fixing sands and building sand dunes, in two deserts in northwestern China. We systematically and simultaneously measured carbon isotope ratios and nitrogen and phosphorous contents of different parts of the excavated plants. We also determined the seasonal variations in leaf carbon isotope ratios on nearby intact plants of N. tangutorum. We found, for the first time, that higher nitrogen contents in heterotrophic organs were significantly correlated with increased heterotrophic 13C enrichment compared to leaves. However, phosphorous contents had no effect on the enrichment. In addition, new leaves had carbon isotope ratios similar to roots but were progressively depleted in 13C as they matured. We concluded that a nitrogen-mediated process, probably the refixation of respiratory CO2 by phosphoenolpyruvate (PEP) carboxylase, was responsible for the differences in 13C enrichment among different heterotrophic organs while processes within leaves or during phloem loading may contribute to the overall autotrophic - heterotrophic difference in carbon isotope compositions.

  5. Isorenieratane record in black shales from the Paris Basin, France: Constraints on recycling of respired CO2 as a mechanism for negative carbon isotope shifts during the Toarcian oceanic anoxic event

    NASA Astrophysics Data System (ADS)

    van Breugel, Yvonne; Baas, Marianne; Schouten, Stefan; Mattioli, Emanuela; Sinninghe Damsté, Jaap S.

    2006-12-01

    The prominent negative stable carbon isotope excursion in both carbonate and organic carbon recorded in organic-rich sediments deposited during the Toarcian oceanic anoxic event (OAE) has commonly been explained by recycling of 13C-depleted CO2 (the so-called Küspert model). More recently, the massive release of 13C-depleted methane or other forms of 13C-depleted carbon was also proposed to account for the observed negative δ13C excursions in organic carbon of terrigenous as well as of marine origin. The occurrence of diagenetic products of the carotenoid isorenieratene (isorenieratane and other aryl isoprenoids) in Toarcian black shales has been regarded as supporting evidence for the Küspert hypothesis as they point to strong stratification of the epicontinental seas. A section of a drill core straddling the Toarcian of the Paris Basin (Cirfontaine-en-Ornois) contained intact isorenieratane, providing evidence that photosynthetic green sulphur bacteria were present at the time of deposition, even prior to the OAE. However, the isorenieratane abundances are very low in the section where the negative δ13C excursion in organic carbon and phytane, a chemical fossil derived from chlorophyll, occurs. The abundance of the isorenieratene derivatives increases, once the δ13C records have shifted to more positive values. The δ13C of isorenieratane (generally circa -13.1 ± 0.5 ‰) indicates that the respired CO2 contribution at the chemocline was low and is thus not likely to be the main cause of the prominent up to 7‰ negative δ13C shift recorded in Toarcian organic carbon records.

  6. Preliminary studies of a canine 13C-aminopyrine demethylation blood test.

    PubMed Central

    Moeller, E M; Steiner, J M; Williams, D A; Klein, P D

    2001-01-01

    The objectives of this study were to determine whether a 13C-aminopyrine demethylation blood test is technically feasible in clinically healthy dogs, whether oral administration of 13C-aminopyrine causes a detectable increase in percent dose/min (PCD) of 13C administered as 13C-aminopyrine and recovered in gas extracted from blood, and whether gas extraction efficiency has an impact on PCD. A dose of 2 mg/kg body weight of 13C-aminopyrine dissolved in deionized water was administered orally to 6 clinically healthy dogs. Blood samples were taken from each dog 0, 30, 60, and 120 min after administration of the 13C-aminopyrine. Carbon dioxide was extracted from blood samples by addition of acid and analyzed by fractional mass spectrometry. None of the 6 dogs showed any side effects after 13C-aminopyrine administration. All 6 dogs showed a measurable increase of the PCD in gas samples extracted from blood samples at 30 min, 60 min, and 120 min after 13C-aminopyrine administration. Coefficients of variation between the triplicate samples were statistically significantly higher for the %CO2, a measure of extraction efficiency, than for PCD values (P < 0.0001). The 13C-aminopyrine demethylation blood test described here is technically feasible. Oral administration of 13C-aminopyrine did not lead to gross side effects in the 6 dogs. Clinically healthy dogs show a measurable increase of PCD in gas extracted from blood samples after oral administration of 13C-aminopyrine. Efficiency of CO2 extraction from blood samples does not have an impact on PCD determined from these blood samples. This test may prove useful to evaluate hepatic function in dogs. PMID:11227194

  7. Mars South Pole CO2 Paleoatmosphere

    NASA Astrophysics Data System (ADS)

    Schneck, T.

    2004-03-01

    Seasonal asymmetry in the CO mixing ratio is explained by condensation of CO_2. High levels of deuteration can be obtained if the gas phase is depleted of CO. UV limbs measurements found intense Cameron band emissions of CO from 1900-2700 A produced by dissociative excitation of CO_2.

  8. Evolution of the stable carbon isotope composition of atmospheric CO2 over the last glacial cycle

    NASA Astrophysics Data System (ADS)

    Eggleston, S.; Schmitt, J.; Bereiter, B.; Schneider, R.; Fischer, H.

    2016-03-01

    We present new δ13C measurements of atmospheric CO2 covering the last glacial/interglacial cycle, complementing previous records covering Terminations I and II. Most prominent in the new record is a significant depletion in δ13C(atm) of 0.5‰ occurring during marine isotope stage (MIS) 4, followed by an enrichment of the same magnitude at the beginning of MIS 3. Such a significant excursion in the record is otherwise only observed at glacial terminations, suggesting that similar processes were at play, such as changing sea surface temperatures, changes in marine biological export in the Southern Ocean (SO) due to variations in aeolian iron fluxes, changes in the Atlantic meridional overturning circulation, upwelling of deep water in the SO, and long-term trends in terrestrial carbon storage. Based on previous modeling studies, we propose constraints on some of these processes during specific time intervals. The decrease in δ13C(atm) at the end of MIS 4 starting approximately 64 kyr B.P. was accompanied by increasing [CO2]. This period is also marked by a decrease in aeolian iron flux to the SO, followed by an increase in SO upwelling during Heinrich event 6, indicating that it is likely that a large amount of δ13C-depleted carbon was transferred to the deep oceans previously, i.e., at the onset of MIS 4. Apart from the upwelling event at the end of MIS 4 (and potentially smaller events during Heinrich events in MIS 3), upwelling of deep water in the SO remained reduced until the last glacial termination, whereupon a second pulse of isotopically light carbon was released into the atmosphere.

  9. Temporal δ13C records from bottlenose dolphins (Tursiops truncatus) reflect variation in foraging location and global carbon cycling

    NASA Astrophysics Data System (ADS)

    Rossman, S. L.; Barros, N. B.; Ostrom, P. H.; Gandhi, H.; Wells, R. S.

    2010-12-01

    first year of life. Given the age of bottlenose dolphins from SB (ca. 60 years), our isotopic data provide a record beginning in 1944. While carbon isotope values show a striking decline over time, the data must be corrected for the Suess effect. The Suess effect results from burning of 13C depleted hydrocarbons which causes a decrease in the δ13C of atmospheric CO2 that subsequent depresses isotope values in food webs. To account for the Suess effect, δ13C values are adjusted by 0.15‰ per decade. Suess corrected δ13C values do not show a temporal linear trend however the average isotope value prior to 1960 is significantly higher than that after 1960 (-10.1 vs -11.66, p=0.038). While documented declines in seagrass abundance prior to 1980 may influence our data, the decline in δ13C of atmospheric CO2 is likely an important factor that controls the isotopic composition of dolphin tissues. Our results suggest that isotope-based estimates of foraging should account for the Suess effect, and that dolphins act as environmental sentinels whose δ13C values records perturbations in global carbon cycling.

  10. /sup 13/C spin diffusion of adamantane

    SciTech Connect

    Bronniman, C.E.; Szeverenyi, N.M.; Maciel, G.E.

    1983-10-15

    Two-dimensional exchange spectroscopy of natural abundance /sup 13/C--/sup 13/C spin diffusion in solid adamantane illustrates the influence that /sup 13/C--/sup 1/H dipole--dipole coupling exerts on /sup 13/C spin diffusion by determining spectral overlap in the /sup 13/C system. 2D /sup 13/C spectra were obtained for several values of mixing time tau/sub m/ and compared with spectra calculated in the limit of nearest-neighbor coupling. Good agreement is obtained for short tau/sub m/, during which the equilibration of neighboring spins dominates. For longer tau/sub m/, slower spin diffusion that is not acounted for by the simple model is seen; after nearest-neighbor spins equilibrate, communication over larger distances produces further mixing. It is possible to modify spin diffusion rates by altering experimental conditions, e.g., magic-angle spinning, low-power /sup 1/H decoupling, or spin locking /sup 13/C in the rotating frame during tau/sub m/.

  11. Online Compound-Specific δ13C and δD Determinations Using Laser Spectroscopy

    NASA Astrophysics Data System (ADS)

    Saad, N.; Hoffnagle, J.

    2012-04-01

    A unique laser spectroscopic approach for making online high-precision compound-specific isotope analysis (CSIA) of both δ13C and δD of the CO2 and H2O organic combustion products is described. The system consists of a gas chromatograph (GC) for the separation of an organic mixture coupled to a novel micro-fabricated microreactor (MFMR) for the complete combustion of each organic compound into CO2 and H2O and the precise measurements of δ13C in the CO2 gas and δ2H in the H2O vapor from the well established infrared spectrum of both gases, using an isotopic CO2 Cavity Ring-Down Spectroscopy (CRDS) analyzer and an isotopic H2O vapor CRDS analyzer, respectively. Light hydrocarbons are used as our test compounds in this study. The analyses of CH4, C2H6 and C3H8 for δ13C and δ2H values resulted in precisions of SD(δ13C)<1‰ and SD(δ2H)<2‰, respectively. These results were further compared to the gold standard method using Dual Inlet IRMS (DI-IRMS) and showed excellent agreements in isotopic measurements. The preliminary results presented here pave the way for a single CRDS analyzer-based system that simultaneously measures δ13C and δD, is field-deployable, less costly and necessitates less operator expertise than IRMS-based systems.

  12. Paleoclimate Reconstruction From the d13C Organic and d13C Carbonate Proxies in Triassic Paleosols and Sediments, Ischigualasto Basin Argentina

    NASA Astrophysics Data System (ADS)

    Moore, K. A.; Tabor, N. J.; Montañez, I. P.; Currie, B.; Shipman, T.

    2001-12-01

    Stable carbon isotopes of organic matter and paleosol carbonate from the Triassic Ischigualasto Formation, Argentina are used as a proxy of paleoatmospheric pCO2 and d13CO2. Carbon and Oxygen isotope values were determined for over 100 Triassic pedogenic carbonate nodules and associated organic matter. The d13C of carbonate ranges from -3.29 per mil to -10.56 per mil. The d13C of organic matter ranges from -21.07 per mil to -24.24 per mil. The Hydrogen and Oxygen indices and TOC values indicate that the best preserved organic matter samples yield the most negative d13C values. Reconstructed pCO2 levels were around 1000 ppm V in the early to mid- Triassic and increased to around 2000 ppm V later in the Triassic. This maximum is followed by a fall in pCO2 in the late Triassic. This previously undocumented rapid change in paleo-CO2 levels likely accompanied the evolution of mammal-like reptiles to true dinosaurs as well as rapid climate change.

  13. Large and unexpected enrichment in stratospheric 16O13C18O and its meridional variation

    PubMed Central

    Yeung, Laurence Y.; Affek, Hagit P.; Hoag, Katherine J.; Guo, Weifu; Wiegel, Aaron A.; Atlas, Elliot L.; Schauffler, Sue M.; Okumura, Mitchio; Boering, Kristie A.; Eiler, John M.

    2009-01-01

    The stratospheric CO2 oxygen isotope budget is thought to be governed primarily by the O(1D)+CO2 isotope exchange reaction. However, there is increasing evidence that other important physical processes may be occurring that standard isotopic tools have been unable to identify. Measuring the distribution of the exceedingly rare CO2 isotopologue 16O13C18O, in concert with 18O and 17O abundances, provides sensitivities to these additional processes and, thus, is a valuable test of current models. We identify a large and unexpected meridional variation in stratospheric 16O13C18O, observed as proportions in the polar vortex that are higher than in any naturally derived CO2 sample to date. We show, through photochemical experiments, that lower 16O13C18O proportions observed in the midlatitudes are determined primarily by the O(1D)+CO2 isotope exchange reaction, which promotes a stochastic isotopologue distribution. In contrast, higher 16O13C18O proportions in the polar vortex show correlations with long-lived stratospheric tracer and bulk isotope abundances opposite to those observed at midlatitudes and, thus, opposite to those easily explained by O(1D)+CO2. We believe the most plausible explanation for this meridional variation is either an unrecognized isotopic fractionation associated with the mesospheric photochemistry of CO2 or temperature-dependent isotopic exchange on polar stratospheric clouds. Unraveling the ultimate source of stratospheric 16O13C18O enrichments may impose additional isotopic constraints on biosphere–atmosphere carbon exchange, biosphere productivity, and their respective responses to climate change. PMID:19564595

  14. In vivo13C spectroscopy in the rat brain using hyperpolarized [1- 13C]pyruvate and [2- 13C]pyruvate

    NASA Astrophysics Data System (ADS)

    Marjańska, Małgorzata; Iltis, Isabelle; Shestov, Alexander A.; Deelchand, Dinesh K.; Nelson, Christopher; Uğurbil, Kâmil; Henry, Pierre-Gilles

    2010-10-01

    The low sensitivity of 13C spectroscopy can be enhanced using dynamic nuclear polarization. Detection of hyperpolarized [1- 13C]pyruvate and its metabolic products has been reported in kidney, liver, and muscle. In this work, the feasibility of measuring 13C signals of hyperpolarized 13C metabolic products in the rat brain in vivo following the injection of hyperpolarized [1- 13C]pyruvate and [2- 13C]pyruvate is investigated. Injection of [2- 13C]pyruvate led to the detection of [2- 13C]lactate, but no other downstream metabolites such as TCA cycle intermediates were detected. Injection of [1- 13C]pyruvate enabled the detection of both [1- 13C]lactate and [ 13C]bicarbonate. A metabolic model was used to fit the hyperpolarized 13C time courses obtained during infusion of [1- 13C]pyruvate and to determine the values of VPDH and VLDH.

  15. Does the Shuram δ13C excursion record Ediacaran oxygenation?

    NASA Astrophysics Data System (ADS)

    Husson, J. M.; Maloof, A. C.; Schoene, B.; Higgins, J. A.

    2013-12-01

    The most negative carbon isotope excursion in Earth history is found in carbonate rocks of the Ediacaran Period (635-542 Ma). Known colloquially as the the 'Shuram' excursion, workers have long noted its tantalizing, broad concordance with the rise of abundant macro-scale fossils in the rock record, variously interpreted as animals, giant protists, macro-algae and lichen, and known as the 'Ediacaran Biota.' Thus, the Shuram excursion has been interpreted by many in the context of a dramatically changing redox state of the Ediacaran oceans - e.g., a result of methane cycling in a low O2 atmosphere, the final destruction of a large pool of recalcitrant dissolved organic carbon (DOC), and the step-wise oxidation of the Ediacaran oceans. More recently, diagenetic interpretations of the Shuram excursion - e.g. sedimentary in-growth of very δ13C depleted authigenic carbonates, meteoric alteration of Ediacaran carbonates, late-stage burial diagenesis - have challenged the various Ediacaran redox models. A rigorous geologic context is required to discriminate between these explanatory models, and determine whether the Shuram excursion can be used to evaluate terminal Neoproterozoic oxygenation. Here, we present chemo-stratigraphic data (δ13C, δ18O, δ44/42Ca and redox sensitive trace element abundances) from 12 measured sections of the Ediacaran-aged Wonoka Formation (Fm.) of South Australia that require a syn-depositional age for the extraordinary range of δ13C values (-12 to +4‰) observed in the formation. In some locations, the Wonoka Fm. is ~700 meters (m) of mixed shelf limestones and siliclastics that record the full 16 ‰ δ13C excursion in a remarkably consistent fashion across 100s of square kilometers of basin area. Fabric-altering diagenesis, where present, occurs at the sub-meter vertical scale, only results in sub-permil offsets in δ13C and cannot be used to explain the full δ13C excursion. In other places, the Wonoka Fm. is host to deep (1 km

  16. Is late Quaternary climate change governed by self-sustained oscillations in atmospheric CO2?

    NASA Astrophysics Data System (ADS)

    Wallmann, Klaus

    2014-05-01

    A simple earth system model is developed to simulate global carbon and phosphorus cycling over the late Quaternary. It is focused on the geological cycling of C and P via continental weathering, volcanic and metamorphic degassing, hydrothermal processes and burial at the seabed. A simple ocean model is embedded in this geological model where the global ocean is represented by surface water, thermocline and deep water boxes. Concentrations of dissolved phosphorus, dissolved inorganic carbon, and total alkalinity are calculated for each box. The partial pressure of CO2 in the atmosphere (pCO2A) is determined by exchange processes with the surface ocean and the continents. It serves as key prognostic model variable and is assumed to govern surface temperatures and global sea-level. The model is formulated as autonomous system, in which the governing equations have no explicit time-dependence. For certain parameter values, the model does not converge towards a steady-state but develops stable self-sustained oscillations. These free oscillations feature pCO2A minima and maxima consistent with the ice-core record when vertical mixing in the ocean is allowed to vary in response to pCO2A-controlled temperature change. A stable 100-kyr cycle with a rapid transition from glacial to interglacial conditions is obtained when additional non-linear equations are applied to calculate deep ocean mixing, iron fertilization and the depth of organic matter degradation as function of pCO2A-controlled surface temperature. The δ13C value of carbon in the ocean/atmosphere system calculated in these model runs is consistent with the benthic δ13C record. However, the simulated 13C depletion in the glacial ocean is not driven by the decline in terrestrial carbon stocks but by sea-level change controlling the rates of organic carbon burial and weathering at continental margins. The pCO2A- and δ13C oscillations develop without any form of external Milankovitch forcing. They are induced and

  17. CO2-Neutral Fuels

    NASA Astrophysics Data System (ADS)

    Goede, Adelbert; van de Sanden, Richard

    2016-06-01

    Mimicking the biogeochemical cycle of System Earth, synthetic hydrocarbon fuels are produced from recycled CO2 and H2O powered by renewable energy. Recapturing CO2 after use closes the carbon cycle, rendering the fuel cycle CO2 neutral. Non-equilibrium molecular CO2 vibrations are key to high energy efficiency.

  18. Carbon isotope and abundance systematics of Icelandic geothermal gases, fluids and subglacial basalts with implications for mantle plume-related CO2 fluxes

    NASA Astrophysics Data System (ADS)

    Barry, P. H.; Hilton, D. R.; Füri, E.; Halldórsson, S. A.; Grönvold, K.

    2014-06-01

    We report new carbon dioxide (CO2) abundance and isotope data for 71 geothermal gases and fluids from both high-temperature (HT > 150 °C at 1 km depth) and low-temperature (LT < 150 °C at 1 km depth) geothermal systems located within neovolcanic zones and older segments of the Icelandic crust, respectively. These data are supplemented by CO2 data obtained by stepped heating of 47 subglacial basaltic glasses collected from the neovolcanic zones. The sample suite has been characterized previously for He-Ne (geothermal) and He-Ne-Ar (basalt) systematics (Füri et al., 2010), allowing elemental ratios to be calculated for individual samples. Geothermal fluids are characterized by a wide range in carbon isotope ratios (δ13C), from -18.8‰ to +4.6‰ (vs. VPDB), and CO2/3He values that span eight orders of magnitude, from 1 × 104 to 2 × 1012. Extreme geothermal values suggest that original source compositions have been extensively modified by hydrothermal processes such as degassing and/or calcite precipitation. Basaltic glasses are also characterized by a wide range in δ13C values, from -27.2‰ to -3.6‰, whereas CO2/3He values span a narrower range, from 1 × 108 to 1 × 1012. The combination of both low δ13C values and low CO2 contents in basalts indicates that magmas are extensively and variably degassed. Using an equilibrium degassing model, we estimate that pre-eruptive basaltic melts beneath Iceland contain ∼531 ± 64 ppm CO2 with δ13C values of -2.5 ± 1.1‰, in good agreement with estimates from olivine-hosted melt inclusions (Metrich et al., 1991) and depleted MORB mantle (DMM) CO2 source estimates (Marty, 2012). In addition, pre-eruptive CO2 compositions are estimated for individual segments of the Icelandic axial rift zones, and show a marked decrease from north to south (Northern Rift Zone = 550 ± 66 ppm; Eastern Rift Zone = 371 ± 45 ppm; Western Rift Zone = 206 ± 24 ppm). Notably, these results are model dependent, and selection of a lower

  19. 13C-phenylalanine breath test detects altered phenylalanine kinetics in schizophrenia patients.

    PubMed

    Teraishi, T; Ozeki, Y; Hori, H; Sasayama, D; Chiba, S; Yamamoto, N; Tanaka, H; Iijima, Y; Matsuo, J; Kawamoto, Y; Kinoshita, Y; Hattori, K; Ota, M; Kajiwara, M; Terada, S; Higuchi, T; Kunugi, H

    2012-01-01

    Phenylalanine is an essential amino acid required for the synthesis of catecholamines including dopamine. Altered levels of phenylalanine and its metabolites in blood and cerebrospinal fluid have been reported in schizophrenia patients. This study attempted to examine for the first time whether phenylalanine kinetics is altered in schizophrenia using L-[1-(13)C]phenylalanine breath test ((13)C-PBT). The subjects were 20 chronically medicated schizophrenia patients (DSM-IV) and the same number of age- and sex-matched controls. (13)C-phenylalanine (99 atom% (13)C; 100 mg) was administered orally and the breath (13)CO(2) /(12)CO(2) ratio was monitored for 120 min. The possible effect of antipsychotic medication (risperidone (RPD) or haloperidol (HPD) treatment for 21 days) on (13)C-PBT was examined in rats. Body weight (BW), age and diagnostic status were significant predictors of the area under the curve of the time course of Δ(13)CO(2) (‰) and the cumulative recovery rate (CRR) at 120 min. A repeated measures analysis of covariance controlled for age and BW revealed that the patterns of CRR change over time differed between the patients and controls and that Δ(13)CO(2) was lower in the patients than in the controls at all sampling time points during the 120 min test, with an overall significant difference between the two groups. Chronic administration of RPD or HPD had no significant effect on (13)C-PBT indices in rats. Our results suggest that (13)C-PBT is a novel laboratory test that can detect altered phenylalanine kinetics in chronic schizophrenia patients. Animal experiments suggest that the observed changes are unlikely to be attributable to antipsychotic medication. PMID:22832963

  20. High prevalence of diffusive uptake of CO2 by macroalgae in a temperate subtidal ecosystem.

    PubMed

    Cornwall, Christopher E; Revill, Andrew T; Hurd, Catriona L

    2015-05-01

    Productivity of most macroalgae is not currently considered limited by dissolved inorganic carbon (DIC), as the majority of species have CO2-concentrating mechanisms (CCM) allowing the active uptake of DIC. The alternative, diffusive uptake of CO2 (non-CCM), is considered rare (0-9% of all macroalgal cover in a given ecosystem), and identifying species without CCMs is important in understanding factors controlling inorganic carbon use by eukaryotic algae. CCM activity has higher energetic requirements than diffusive CO2 uptake, therefore when light is low, CCM activity is reduced in favour of diffusive CO2 uptake. We hypothesized that the proportional cover of macroalgae without CCMs (red and green macroalgae) would be low (<10%) across four sites in Tasmania, southern Australia at two depths (4-5 and 12-14 m); the proportion of species lacking CCMs would increase with decreasing depth; the δ(13)C values of macroalgae with CCMs would be more depleted with depth. We found the proportion of non-CCM species ranged from 0 to 90% and included species from all three macroalgal phyla: 81% of red (59 species), 14% of brown (three species) and 29% of green macroalgae (two species). The proportion of non-CCM species increased with depth at three of four sites. 35% of species tested had significantly depleted δ(13)C values at deeper depths. Non-CCM macroalgae are more abundant in some temperate reefs than previously thought. If ocean acidification benefits non-CCM species, the ramifications for subtidal macroalgal assemblages could be larger than previously considered. PMID:25739900

  1. Leaf Wax δ13C Varies with Elevation in the Peruvian Andes and Western Amazonia

    NASA Astrophysics Data System (ADS)

    Wu, M. S.; Feakins, S. J.; Ponton, C.; Peters, T.; West, A. J.; Galy, V.; Bentley, L. P.; Salinas, N.; Shenkin, A.; Martin, R.; Asner, G. P.; Malhi, Y.

    2015-12-01

    Plant leaf wax carbon isotopic composition (δ13Cwax) reflects the net isotopic effects associated with diffusion into the leaf, fixation of carbon by Rubisco and biosynthesis of individual leaf wax biochemicals. As declining pCO2 with elevation affects the first two fractionations, we expect to find an isotopic gradient in δ13Cwax, if the fractionation of leaf wax biosynthesis is constant. To test this, we report δ13Cwax values from 500 samples of leaves collected by tree-climbers from the upper canopy from 9 forest-inventory plots spanning a 3.5km elevation transect in the Peruvian Andes and western Amazonia during the CHAMBASA field campaign. These samples provide a unique opportunity to study the relationship between δ13Cwax and pCO2 in diverse species across this remote tropical montane forest and lowland rainforest. The very wet climate throughout (2-5 m rainfall per year) minimizes fractionation effects due to stomatal restrictions (i.e. water use efficiency) that may be an important factor elsewhere. Preliminary results show δ13Cwax values on average increase with elevation by ~1.5‰/km, a trend consistent with bulk plant δ13C in previous studies. The mean epsilon between bulk and C29 n-alkane is -7.3±2.2‰. Inter-sample differences are large on the order of 10‰. Shaded leaves and understory leaves are found to be depleted relative to sunlit leaves, presumably due to a lower photosynthetic rate and use of respired CO2 in the understory. C29 n-alkanes are on average ~2.5‰ more depleted than C30 n-alkanoic acids, indicating fractionation during selective decarboxylation. We further compare results from plants with soil and river sediments to provide insights into how leaf wax signals are archived in soils and exported from the landscape. We find a ~1.4‰/km gradient in forest soils similar to plants. We observe a ~2‰ offset between C29 n-alkane in plant leaves and in soils across the elevation profile, which is likely a signal of degradation

  2. The effect of atmospheric CO2 concentration on carbon isotope fractionation in C3 land plants

    NASA Astrophysics Data System (ADS)

    Schubert, Brian A.; Jahren, A. Hope

    2012-11-01

    in C3 plants at elevated pCO2. The values for Δδ13Cp we determined in our ambient pCO2 chambers are consistent with the Δδ13Cp values measured in large modern datasets of plants growing within the Earth’s wettest environments, suggesting that it may be possible to reconstruct changes in paleo-pCO2 level from plants that grew in consistently wet environments, if δ13CCO2 value and initial pCO2 level can be independently quantified. Several implications arise for the reconstruction of water availability and water-use efficiency in both ancient and recent plant Δδ13Cp values across periods of changing pCO2 level. For example, the change in Δδ13Cp implied by our relationship for the rise in pCO2 concentration observed since 1980 is of the same magnitude (= ∼0.7‰) as the isotopic correction for changes in δ13CCO2 required by the input of 13C-depleted carbon to the atmosphere. For these reasons, only the portion of the terrestrial isotopic excursion that persists after accounting for changes in pCO2 concentration should be used for the interpretation of a change in paleo-environmental conditions.

  3. Tracing CO2 fluxes and plant volatile organic compound emissions by stable isotopes

    NASA Astrophysics Data System (ADS)

    Werner, Christiane; Wegener, Frederik; Jardine, Kolby

    2014-05-01

    CO2 in the light. Simultaneously, naturally 13C depleted C-2 and C-3 carbon atoms of the acetyl-moiety are emitted as a variety of VOCs. Moreover, during light-dark transitions leaf emission bursts of the oxygenated metabolite acetaldehyde were observed as part of the PDH bypass pathway in the cytosol2. This may be a new piece of evidence for the origin of 13C-enriched δ13CO2 which is released during Light-Enhanced Dark Respiration (LEDR). Our study provides the first evidence that the isotopic signature of respired CO2 is closely linked to carbon partitioning between anabolic and catabolic pathways and plants strategies of carbon investment into secondary compound synthesis. Werner C. & Gessler A. (2011) Diel variations in the carbon isotope composition of respired CO2 and associated carbon sources: a review of dynamics and mechanisms. Biogeosciences 8, 2437-2459 Jardine K, Wegener F, Abrell L, vonHaren J, Werner C (2014) Phytogenic biosynthesis and emission of methyl acetate. PCE 37, 414-424.

  4. Toward using delta13C of ecosystem respiration to monitor canopy physiology in complex terrain.

    PubMed

    Pypker, T G; Hauck, M; Sulzman, E W; Unsworth, M H; Mix, A C; Kayler, Z; Conklin, D; Kennedy, A M; Barnard, H R; Phillips, C; Bond, B J

    2008-12-01

    In 2005 and 2006, air samples were collected at the base of a Douglas-fir watershed to monitor seasonal changes in the delta13CO2 of ecosystem respiration (delta13C(ER)). The goals of this study were to determine whether variations in delta13C(ER) correlated with environmental variables and could be used to predict expected variations in canopy-average stomatal conductance (Gs). Changes in delta13C(ER) correlated weakly with changes in vapor pressure deficit (VPD) measured 0 and 3-7 days earlier and significantly with soil matric potential (psi(m)) (P value <0.02) measured on the same day. Midday G (s) was estimated using sapflow measurements (heat-dissipation method) at four plots located at different elevations within the watershed. Values of midday Gs from 0 and 3-7 days earlier were correlated with delta13C(ER), with the 5-day lag being significant (P value <0.05). To examine direct relationships between delta13C(ER) and recent Gs, we used models relating isotope discrimination to stomatal conductance and photosynthetic capacity at the leaf level to estimate values of stomatal conductance ("Gs-I") that would be expected if respired CO2 were derived entirely from recent photosynthate. We compared these values with estimates of Gs using direct measurement of transpiration at multiple locations in the watershed. Considering that the approach based on isotopes considers only the effect of photosynthetic discrimination on delta13C(ER), the magnitude and range in the two values were surprisingly similar. We conclude that: (1) delta13C(ER) is sensitive to variations in weather, and (2) delta13C(ER) potentially could be used to directly monitor average, basin-wide variations in Gs in complex terrain if further research improves understanding of how delta13C(ER) is influenced by post-assimilation fractionation processes. PMID:18839214

  5. Fourier Transform Microwave Spectra of CO{2}-ETHYLENE Sulfide, CO{2}-ETHYLENE Oxide and CO{2}-PROPYLENE Oxide Complexes

    NASA Astrophysics Data System (ADS)

    Orita, Yukari; Kawashima, Yoshiyuki; Hirota, Eizi

    2010-06-01

    We have previously examined the difference in roles of O and S in structure and dynamics of the CO-ethylene oxide (EO) and CO-ethylene sulfide (ES) complexes. We have extended the investigation to CO{2}-EO and CO{2}-ES for comparison. We have also observed the CO{2}-propylene oxide (PO) complex, which is an important intermediate in the reaction of PO with CO{2} leading to polycarbonate. Both a-type and b-type transitions were observed for the CO{2}-EO and CO{2}-ES, but no c-type transitions were observed at all. We also detected the {34}S and {13}C isotopic species in natural abundance and the species containing {18}OCO and C{18}O% {2}, which were synthesized by burning paper in an {18}O{2} and{% 16}O{2} mixture. By analyzing the observed spectra we concluded the CO{2} moiety of CO{2}-EO and CO{2}-ES located in a plane % prependicular to the three-membered ring and bisecting the COC or CSC angle of EO or ES, respectively, as in the case of CO-EO and CO-ES complexes. An % ab initio MO calculation at the level of MP2/6-311G(d, p) yielded an optimized structure in good agreement with the experimental result. We have derived from the observed spectra the distance, the stretching force constant, and the binding energy of the bonds between the constituents of the CO{2}-EO and CO{2}-ES complexes and have found that the distances of the two complexes were shorter by 0.2Å than those in CO-EO and CO-ES, respectively, and that the intermolecular bonds were two times stronger in the CO{2} complexes than in the corresponding CO complexes. We have concluded from the observed spectra that the CO{2} moiety in CO{2}-PO is located on the PO three-membered ring plane opposite to the methyl group. The constituents in CO{2}-PO were more weakly bound than those in CO{2}-EO and CO{2}-ES. S. Sato, Y. Kawashima, Y. Tatamitani, and E. Hirota, 63rd International Symposium on Molecular Spectroscopy, WF05 (2008).

  6. CO2 and CH4 isotope compositions and production pathways in a tropical peatland

    NASA Astrophysics Data System (ADS)

    Holmes, M. Elizabeth; Chanton, Jeffrey P.; Tfaily, Malak M.; Ogram, Andrew

    2015-01-01

    While it is widely recognized that peatlands are important in the global carbon cycle, there is limited information on belowground gas production in tropical peatlands. We measured pore water methane (CH4) and carbon dioxide (CO2) concentrations and δ13C isotopic composition and CH4 and CO2 production rates in peat incubations from the Changuinola wetland in Panama. Our most striking finding was that CH4 was depleted in 13C (-94‰ in pore water and produced at -107‰ in incubated peat) relative to CH4 found in most temperate and northern wetlands, potentially impacting the accuracy of approaches that use carbon isotopes to constrain global mass balance estimates. Fractionation factors between CH4 and CO2 showed that hydrogenotrophic methanogenesis was the dominant CH4 production pathway, with up to 100% of the CH4 produced via this route. Far more CO2 than CH4 (7 to 100X) was measured in pore water, due in part to loss of CH4 through ebullition or oxidation and to the production of CO2 from pathways other than methanogenesis. We analyzed data on 58 wetlands from the literature to determine the dominant factors influencing the relative proportions of CH4 produced by hydrogenotrophic and acetoclastic methanogenesis and found that a combination of environmental parameters including pH, vegetation type, nutrient status, and latitude are correlated to the dominant methanogenic pathway. Methane production pathways in tropical peatlands do not correlate with these variables in the same way as their more northerly counterparts and thus may be differently affected by climate change.

  7. Effect of petroleum products on the decomposition of soil organic matter as assessed by 13C natural abundance

    NASA Astrophysics Data System (ADS)

    Stelmach, Wioleta; Szarlip, Paweł; Trembaczowski, Andrzej; Bieganowski, Andrzej

    2016-04-01

    Petroleum products are common contaminants in soils due to human activities. They are toxic for microorganisms and threat their functions, including decomposition of soil organic matter (SOM). The direct estimation of altered SOM decomposition - based on the CO2 emission - is impossible after oil contamination, because oil decomposition also contributes to the CO2 release. We used the natural differences in the isotopic signature (δ13C) of SOM and of oil products to partition the total CO2 for both sources and to analyze the suppression of SOM decomposition. The dynamics of 13C fractionation during the mineralization of gasoline and diesel was measured during 42 days. The 13C fractionation varied between -8.8‰ and +3.6‰ within the first 10 days, and stabilized thereafter at about -5.3‰ for gasoline and +3.2‰ for diesel. These 13C fractionations and δ13C values of CO2 emitted from the soil were used for correct partitioning of the total CO2. Contamination with gasoline reduced the CO2 efflux from SOM decomposition by a factor of 25 (from 151 to 6 mg C-CO2 kg‑1 soil during 42 days). The negative effect of diesel was much lower: the CO2 efflux from SOM was decreased by less than a factor of 2. The strong effect of gasoline versus diesel reflects the lower absorption of gasoline to mineral particles and the development of a thin film on water surfaces, leading to toxicity for microorganisms. We conclude that the small differences of 13C of SOM and of organic pollutants can be used to partition CO2 fluxes and analyze pollutant effects on SOM decomposition.

  8. Trends in stomatal density and 13C/12C ratios of Pinus flexilis needles during last glacial-interglacial cycle

    USGS Publications Warehouse

    Van De Water, Peter K.; Leavitt, Steven W.; Betancourt, J.L.

    1994-01-01

    Measurements of stomatal density and ?? 13C of limber pine (Pinus flexilis) needles (leaves) preserved in pack rat middens from the Great Basin reveal shifts in plant physiology and leaf morphology during the last 30,000 years. Sites were selected so as to offset glacial to Holocene climatic differences and thus to isolate the effects of changing atmospheric CO2 levels. Stomatal density decreased ~17 percent and ?? 13C decreased ~1.5 per mil during deglaciation from 15,000 to 12,000 years ago, concomitant with a 30 percent increase in atmospheric CO2. Water-use efficiency increased ~15 percent during deglaciation, if temperature and humidity were held constant and the proxy values for CO2 and ?? 13C of past atmospheres are accurate. The ??13C variations may help constrain hypotheses about the redistribution of carbon between the atmosphere and biosphere during the last glacial-interglacial cycle.

  9. States of 13C with abnormal radii

    NASA Astrophysics Data System (ADS)

    Demyanova, A. S.; Ogloblin, A. A.; Danilov, A. N.; Goncharov, S. A.; Belyaeva, T. L.; Sobolev, Yu. G.; Khlebnikov, S. V.; Burtebaev, N.; Trzaska, W.; Heikkinen, P.; Tyurin, G. P.; Janseitov, D.; Gurov, Yu. B.

    2016-05-01

    Differential cross-sections of the elastic and inelastic 13C + α scattering were measured at E(α) = 90 MeV. The root mean-square radii() of 13C nucleus in the states: 8.86 (1/2-), 3.09 (1/2+) and 9.90 (3/2-) MeV were determined by the Modified diffraction model (MDM). The radii of the first two levels are enhanced compared to that of the ground state of 13C, confirming the suggestion that the 8.86 MeV state is an analogue of the Hoyle state in 12C and the 3.09 MeV state has a neutron halo. Some indications to the abnormally small size of the 9.90 MeV state were obtained.

  10. Determination of the δ13C of dissolved inorganic carbon in water; RSIL lab code 1710

    USGS Publications Warehouse

    Singleton, Glenda L.; Revesz, Kinga; Coplen, Tyler B.

    2012-01-01

    The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 1710 is to present a method to determine the δ13C of dissolved inorganic carbon (DIC) of water. The DIC of water is precipitated using ammoniacal strontium chloride (SrCl2) solution to form strontium carbonate (SrCO3). The δ13C is analyzed by reacting SrCO3 with 100-percent phosphoric acid (H3PO4) to liberate carbon quantitatively as carbon dioxide (CO2), which is collected, purified by vacuum sublimation, and analyzed by dual inlet isotope-ratio mass spectrometry (DI-IRMS). The DI-IRMS is a DuPont double-focusing mass spectrometer. One ion beam passes through a slit in a forward collector and is collected in the rear collector. The other measurable ion beams are collected in the front collector. By changing the ion-accelerating voltage under computer control, the instrument is capable of measuring mass/charge (m/z) 45 or 46 in the rear collector and m/z 44 and 46 or 44 and 45, respectively, in the front collector. The ion beams from these m/z values are as follows: m/z 44 = CO2 = 12C16O16O, m/z 45 = CO2 = 13C16O16O primarily, and m/z 46 = CO2 = 12C16O18O primarily. The data acquisition and control software calculates δ13C values.

  11. Trimethylamine and Organic Matter Additions Reverse Substrate Limitation Effects on the δ13C Values of Methane Produced in Hypersaline Microbial Mats.

    PubMed

    Kelley, Cheryl A; Nicholson, Brooke E; Beaudoin, Claire S; Detweiler, Angela M; Bebout, Brad M

    2014-12-01

    Methane production has been observed in a number of hypersaline environments, and it is generally thought that this methane is produced through the use of noncompetitive substrates, such as the methylamines, dimethylsulfide and methanol. Stable isotope measurements of the produced methane have also suggested that the methanogens are operating under conditions of substrate limitation. Here, substrate limitation in gypsum-hosted endoevaporite and soft-mat hypersaline environments was investigated by the addition of trimethylamine, a noncompetitive substrate for methanogenesis, and dried microbial mat, a source of natural organic matter. The δ(13)C values of the methane produced after amendments were compared to those in unamended control vials. At all hypersaline sites investigated, the δ(13)C values of the methane produced in the amended vials were statistically lower (by 10 to 71‰) than the unamended controls, supporting the hypothesis of substrate limitation at these sites. When substrates were added to the incubation vials, the methanogens within the vials fractionated carbon isotopes to a greater degree, resulting in the production of more (13)C-depleted methane. Trimethylamine-amended samples produced lower methane δ(13)C values than the mat-amended samples. This difference in the δ(13)C values between the two types of amendments could be due to differences in isotope fractionation associated with the dominant methane production pathway (or substrate used) within the vials, with trimethylamine being the main substrate used in the trimethylamine-amended vials. It is hypothesized that increased natural organic matter in the mat-amended vials would increase fermentation rates, leading to higher H2 concentrations and increased CO2/H2 methanogenesis. PMID:25239903

  12. Trimethylamine and Organic Matter Additions Reverse Substrate Limitation Effects on the δ13C Values of Methane Produced in Hypersaline Microbial Mats

    PubMed Central

    Nicholson, Brooke E.; Beaudoin, Claire S.; Detweiler, Angela M.; Bebout, Brad M.

    2014-01-01

    Methane production has been observed in a number of hypersaline environments, and it is generally thought that this methane is produced through the use of noncompetitive substrates, such as the methylamines, dimethylsulfide and methanol. Stable isotope measurements of the produced methane have also suggested that the methanogens are operating under conditions of substrate limitation. Here, substrate limitation in gypsum-hosted endoevaporite and soft-mat hypersaline environments was investigated by the addition of trimethylamine, a noncompetitive substrate for methanogenesis, and dried microbial mat, a source of natural organic matter. The δ13C values of the methane produced after amendments were compared to those in unamended control vials. At all hypersaline sites investigated, the δ13C values of the methane produced in the amended vials were statistically lower (by 10 to 71‰) than the unamended controls, supporting the hypothesis of substrate limitation at these sites. When substrates were added to the incubation vials, the methanogens within the vials fractionated carbon isotopes to a greater degree, resulting in the production of more 13C-depleted methane. Trimethylamine-amended samples produced lower methane δ13C values than the mat-amended samples. This difference in the δ13C values between the two types of amendments could be due to differences in isotope fractionation associated with the dominant methane production pathway (or substrate used) within the vials, with trimethylamine being the main substrate used in the trimethylamine-amended vials. It is hypothesized that increased natural organic matter in the mat-amended vials would increase fermentation rates, leading to higher H2 concentrations and increased CO2/H2 methanogenesis. PMID:25239903

  13. CO2 laser modeling

    NASA Technical Reports Server (NTRS)

    Johnson, Barry

    1992-01-01

    The topics covered include the following: (1) CO2 laser kinetics modeling; (2) gas lifetimes in pulsed CO2 lasers; (3) frequency chirp and laser pulse spectral analysis; (4) LAWS A' Design Study; and (5) discharge circuit components for LAWS. The appendices include LAWS Memos, computer modeling of pulsed CO2 lasers for lidar applications, discharge circuit considerations for pulsed CO2 lidars, and presentation made at the Code RC Review.

  14. Oxidation of 13C-labeled methane in surface crusts of pig- and cattle slurry.

    PubMed

    Ambus, Per; Petersen, Søren O

    2005-06-01

    Storage tanks for slurry from animal production constitute important point sources for emission of CH4 into the atmosphere. Recent investigations have demonstrated that surface crust formed on top of animal slurry provides a habitat for CH4 oxidation activity, a finding which may open for new opportunities to reduce greenhouse gas emissions during storage of animal wastes. In this work, 13C-labeled CH4 was used as a tracer to examine the absolute rates of CH4 oxidation and production in intact crust materials, collected from six different pig- and cattle slurry tanks in late autumn. Methane concentrations were generally reduced in the presence of surface crust samples, with the exception of a LECA-based (light expanded clay aggregates) crust from a pig slurry tank. In four samples, CH4 consumption was induced following a 2-4 days lag phase, whereas one cattle slurry crust consumed CH4 immediately and showed a 92% decline in CH4 concentration within the first week. Consumption of 13C-labeled CH4 was paralleled by the production of 13C-labeled CO2, thus providing direct evidence that microbial oxidation of CH4 to CO2 was taking place. Between 23% and 36% of the CH4-13C consumed in the active samples was accounted for in the gas phase CO2 indicating incomplete conversion of CH4 to CO2; however, comparable amounts of 13C was immobilized in the crust samples. Overall, the results showed that significant CH4 oxidation to CO2 in slurry crust samples occurs immediately or is inducible upon exposure to CH4. PMID:16191764

  15. Natural (13) C distribution in oil palm (Elaeis guineensis Jacq.) and consequences for allocation pattern.

    PubMed

    Lamade, Emmanuelle; Tcherkez, Guillaume; Darlan, Nuzul Hijri; Rodrigues, Rosario Lobato; Fresneau, Chantal; Mauve, Caroline; Lamothe-Sibold, Marlène; Sketriené, Diana; Ghashghaie, Jaleh

    2016-01-01

    Oil palm has now become one of the most important crops, palm oil representing nearly 25% of global plant oil consumption. Many studies have thus addressed oil palm ecophysiology and photosynthesis-based models of carbon allocation have been used. However, there is a lack of experimental data on carbon fixation and redistribution within palm trees, and important C-sinks have not been fully characterized yet. Here, we carried out extensive measurement of natural (13) C-abundance (δ(13) C) in oil palm tissues, including fruits at different maturation stages. We find a (13) C-enrichment in heterotrophic organs compared to mature leaves, with roots being the most (13) C-enriched. The δ(13) C in fruits decreased during maturation, reflecting the accumulation in (13) C-depleted lipids. We further used observed δ(13) C values to compute plausible carbon fluxes using a steady-state model of (13) C-distribution including metabolic isotope effects ((12) v/(13) v). The results suggest that fruits represent a major respiratory loss (≈39% of total tree respiration) and that sink organs such as fruits are fed by sucrose from leaves. That is, glucose appears to be a quantitatively important compound in palm tissues, but computations indicate that it is involved in dynamic starch metabolism rather that C-exchange between organs. PMID:26228944

  16. Synthesis Of [2h, 13c] And [2h3, 13c]Methyl Aryl Sulfides

    DOEpatents

    Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.

    2004-03-30

    The present invention is directed to labeled compounds, [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2, .sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfides wherein the .sup.13 C methyl group attached to the sulfur of the sulfide includes exactly one, two or three deuterium atoms and the aryl group is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 are each independently, hydrogen, a C.sub.1 -C.sub.4 lower alkyl, a halogen, an amino group from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each a C.sub.1 -C.sub.4 lower alkyl, a phenyl, or an alkoxy group. The present invention is also directed to processes of preparing [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2,.sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfides wherein the .sup.13 C methyl group attached to the sulfur of the sulfide includes exactly one, two or three deuterium atoms. The present invention is also directed to the labeled compounds of [.sup.2 H.sub.1, .sup.13 C]methyl iodide and [.sup.2 H.sub.2, .sup.13 C]methyl iodide.

  17. Glacial CO2 Cycles: A Composite Scenario

    NASA Astrophysics Data System (ADS)

    Broecker, W. S.

    2015-12-01

    There are three main contributors to the glacial drawdown of atmospheric CO2 content: starvation of the supply of carbon to the ocean-atmosphere reservoir, excess CO2 storage in the deep sea, and surface-ocean cooling. In this talk, I explore a scenario in which all three play significant roles. Key to this scenario is the assumption that deep ocean storage is related to the extent of nutrient stratification of the deep Atlantic. The stronger this stratification, the larger the storage of respiration CO2. Further, it is my contention that the link between Milankovitch insolation cycles and climate is reorganizations of the ocean's thermohaline circulation leading to changes in the deep ocean's CO2 storage. If this is the case, the deep Atlantic d13C record kept in benthic foraminifera shells tells us that deep ocean CO2 storage follows Northern Hemisphere summer insolation cycles and thus lacks the downward ramp so prominent in the records of sea level, benthic 18O and CO2. Rather, the ramp is created by the damping of planetary CO2 emissions during glacial time intervals. As it is premature to present a specific scenario, I provide an example as to how these three contributors might be combined. As their magnitudes and shapes remain largely unconstrained, the intent of this exercise is to provoke creative thinking.

  18. Anaerobic Methane Oxidation in Soils - revealed using 13C-labelled methane tracers

    NASA Astrophysics Data System (ADS)

    Riekie, G. J.; Baggs, E. M.; Killham, K. S.; Smith, J. U.

    2008-12-01

    In marine sediments, anaerobic methane oxidation is a significant biogeochemical process limiting methane flux from ocean to atmosphere. To date, evidence for anaerobic methane oxidation in terrestrial environments has proved elusive, and its significance is uncertain. In this study, an isotope dilution method specifically designed to detect the process of anaerobic methane oxidation in methanogenic wetland soils is applied. Methane emissions of soils from three contrasting permanently waterlogged sites in Scotland are investigated in strictly anoxic microcosms to which 13C- labelled methane is added, and changes in the concentration and 12C/13C isotope ratios of methane and carbon dioxide are subsequently measured and used to calculate separate the separate components of the methane flux. The method used takes into account the 13C-methane associated with methanogenesis, and the amount of methane dissolved in the soil. The calculations make no prior assumptions about the kinetics of methane production or oxidation. The results indicate that methane oxidation can take place in anoxic soil environments. The clearest evidence for anaerobic methane oxidation is provided by soils from a minerotrophic fen site (pH 6.0) in Bin Forest underlain by ultra-basic and serpentine till. In the fresh soil anoxic microcosms, net consumption methane was observed, and the amount of headspace 13C-CO2 increased at a greater rate than the 12+13C-CO2, further proof of methane oxidation. A net increase in methane was measured in microcosms of soil from Murder Moss, an alkaline site, pH 6.5, with a strong calcareous influence. However, the 13C-CH4 data provided evidence of methane oxidation, both in the disappearance of C- CH4 and appearance of smaller quantities of 13C-CO2. The least alkaline (pH 5.5) microcosms, of Gateside Farm soil - a granitic till - exhibited net methanogenesis and the changes in 13C-CH4 and 13C-CO2 here followed the pattern expected if no methane is consumed

  19. Modelling urban δ13C variations in the Greater Toronto Area

    NASA Astrophysics Data System (ADS)

    Pugliese, S.; Vogel, F. R.; Murphy, J. G.; Worthy, D. E. J.; Zhang, J.; Zheng, Q.; Moran, M. D.

    2015-12-01

    Even in urbanized regions, carbon dioxide (CO2) emissions are derived from a variety of biogenic and anthropogenic sources and are influenced by atmospheric transport across borders. As policies are introduced to reduce the emission of CO2, there is a need for independent verification of emissions reporting. In this work, we aim to use carbon isotope (13CO2 and 12CO2) simulations in combination with atmospheric measurements to distinguish between CO2 sources in the Greater Toronto Area (GTA), Canada. This is being done by developing an urban δ13C framework based on existing CO2 emission data and forward modelling using a chemistry transport model, CHIMERE. The framework is designed to use region specific δ13C signatures of the dominant CO2 sources together with a CO2 inventory at a fine spatial and temporal resolution; the product is compared against highly accurate 13CO2 and 12CO2 ambient data. The strength of this framework is its potential to estimate both locally produced and regionally transported CO­2. Locally, anthropogenic CO­2 in urban areas is often derived from natural gas combustion (for heating) and gasoline/diesel combustion (for transportation); the isotopic signatures of these processes are significantly different (approximately d13CVPDB = -40 ‰ and -26 ‰ respectively) and can be used to infer their relative contributions. Furthermore, the contribution of transported CO2 can also be estimated as nearby regions often rely on other sources of heating (e.g. coal combustion), which has a very different signature (approximately d13CVPDB = -23 ‰). We present an analysis of the GTA in contrast to Paris, France where atmospheric observations are also available and 13CO2 has been studied. Utilizing our δ13C framework and differences in sectoral isotopic signatures, we quantify the relative contribution of CO2 sources on the overall measured concentration and assess the ability of this framework as a tool for tracing the evolution of sector

  20. Characteristics of the deep ocean carbon system during the past 150,000 years: ΣCO2 distributions, deep water flow patterns, and abrupt climate change

    PubMed Central

    Boyle, Edward A.

    1997-01-01

    Studies of carbon isotopes and cadmium in bottom-dwelling foraminifera from ocean sediment cores have advanced our knowledge of ocean chemical distributions during the late Pleistocene. Last Glacial Maximum data are consistent with a persistent high-ΣCO2 state for eastern Pacific deep water. Both tracers indicate that the mid-depth North and tropical Atlantic Ocean almost always has lower ΣCO2 levels than those in the Pacific. Upper waters of the Last Glacial Maximum Atlantic are more ΣCO2-depleted and deep waters are ΣCO2-enriched compared with the waters of the present. In the northern Indian Ocean, δ13C and Cd data are consistent with upper water ΣCO2 depletion relative to the present. There is no evident proximate source of this ΣCO2-depleted water, so I suggest that ΣCO2-depleted North Atlantic intermediate/deep water turns northward around the southern tip of Africa and moves toward the equator as a western boundary current. At long periods (>15,000 years), Milankovitch cycle variability is evident in paleochemical time series. But rapid millennial-scale variability can be seen in cores from high accumulation rate series. Atlantic deep water chemical properties are seen to change in as little as a few hundred years or less. An extraordinary new 52.7-m-long core from the Bermuda Rise contains a faithful record of climate variability with century-scale resolution. Sediment composition can be linked in detail with the isotope stage 3 interstadials recorded in Greenland ice cores. This new record shows at least 12 major climate fluctuations within marine isotope stage 5 (about 70,000–130,000 years before the present). PMID:11607737

  1. CO2 Accounting and Risk Analysis for CO2 Sequestration at Enhanced Oil Recovery Sites.

    PubMed

    Dai, Zhenxue; Viswanathan, Hari; Middleton, Richard; Pan, Feng; Ampomah, William; Yang, Changbing; Jia, Wei; Xiao, Ting; Lee, Si-Yong; McPherson, Brian; Balch, Robert; Grigg, Reid; White, Mark

    2016-07-19

    Using CO2 in enhanced oil recovery (CO2-EOR) is a promising technology for emissions management because CO2-EOR can dramatically reduce sequestration costs in the absence of emissions policies that include incentives for carbon capture and storage. This study develops a multiscale statistical framework to perform CO2 accounting and risk analysis in an EOR environment at the Farnsworth Unit (FWU), Texas. A set of geostatistical-based Monte Carlo simulations of CO2-oil/gas-water flow and transport in the Morrow formation are conducted for global sensitivity and statistical analysis of the major risk metrics: CO2/water injection/production rates, cumulative net CO2 storage, cumulative oil/gas productions, and CO2 breakthrough time. The median and confidence intervals are estimated for quantifying uncertainty ranges of the risk metrics. A response-surface-based economic model has been derived to calculate the CO2-EOR profitability for the FWU site with a current oil price, which suggests that approximately 31% of the 1000 realizations can be profitable. If government carbon-tax credits are available, or the oil price goes up or CO2 capture and operating expenses reduce, more realizations would be profitable. The results from this study provide valuable insights for understanding CO2 storage potential and the corresponding environmental and economic risks of commercial-scale CO2-sequestration in depleted reservoirs. PMID:27362472

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

    PubMed

    Rossier, Joël S; Maury, Valérie; Gaillard, Laetitia; Pfammatter, Elmar

    2016-01-01

    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. PMID:27198811

  3. Assessment of liver function in dogs using the 13C-galactose breath test.

    PubMed

    Silva, S; Wyse, C A; Goodfellow, M R; Yam, P S; Preston, T; Papasouliotis, K; Hall, E J

    2010-08-01

    The aim of this study was to evaluate the application of the 13C-galactose breath test (13C-GBT) in assessing canine liver function by applying it to a group of healthy dogs, and to a group with clinicopathological evidence of liver dysfunction. Breath samples were collected 30 min before ingestion of 13C-galactose, and then at regular intervals thereafter for 6 h. The proportion of 13CO2/12CO2 in the breath samples was measured by isotope-ratio mass spectrometry. There was no significant difference in recovery of 13CO2 in the diseased group, compared to the healthy controls, but there was considerable inter-subject variation in both groups, possibly due to differences in the rate of gastric emptying, which could preclude detection of alterations in hepatic metabolism of galactose. The results of this study do not support the application of the 13C-GBT for assessment of canine liver function. PMID:19546016

  4. Methanogenesis produces strong 13C-enrichment in stromatolites of Lagoa Salgada, Brazil: A modern analogue for Palaeo-/Neoproterozoic stromatolites?

    NASA Astrophysics Data System (ADS)

    Meister, Patrick; Birgel, Daniel; Lundberg, Rebecca; Horat, Thomas; Bontognali, Tomaso; Bahniuk Rumbelsperger, Anelize; Rezende, Carlos; Vásconcelos, Crisógono; McKenzie, Judith A.

    2015-04-01

    Holocene stromatolites characterized by unusually positive inorganic carbon isotope values (δ13C up to +16 ‰ relative to the Vienna Peedee Belemnite Standard; VPDB) are present in Lagoa Salgada, a seasonally brackish to hypersaline lagoon near Rio de Janeiro (Brazil). Such positive values cannot be explained by phototrophic fixation of CO2 alone. Instead, strong carbon isotope fractionation is commonly observed during methanogenesis, where isotopically light C is preferentially incorporated into methane and the residual inorganic carbon is 13C-enriched. We suggest that methanogenesis was the dominating process of organic carbon mineralization during the growth of the stromatolites. Indeed, the presence of dissolved methane in porewater (up to 5 mM) and the archaeal membrane lipid archaeol showing relatively high δ13C values (-15 to 0 ‰ VPDB) indicates that methanogenic archaea are present and active in the modern lagoon sediment. Moreover, 13C-depleted hopanoids diplopterol and 3-methylated bishomohopanoic acid (both -40‰ VPDB) are preserved in lagoon sediments and are most likely derived from aerobic methanotrophic bacteria thriving in the methane-enriched water column. Loss of isotopically light methane through the water column to the atmosphere would explain the residual 13C-enriched pool of dissolved inorganic carbon from where the carbonate constituting the stromatolites precipitated. The predominance of methanogenic archaea in the lagoon is most likely a result of sulphate limitation suppressing the activity of sulphate-reducing bacteria under brackish conditions in a seasonally humid tropical and arid environment. Also in the modern sediments, sulphate reduction activity is very low. Under dominating methanogenic conditions and in absence of an efficient carbonate-inducing metabolic process, we propose that stromatolite formation in Lagoa Salgada was abiotically induced while the 13C-enriched organic and inorganic carbon pools are due to

  5. Positive feedback between increasing atmospheric CO2 and ecosystem productivity

    NASA Astrophysics Data System (ADS)

    Gelfand, I.; Hamilton, S. K.; Robertson, G. P.

    2009-12-01

    Increasing atmospheric CO2 will likely affect both the hydrologic cycle and ecosystem productivity. Current assumptions that increasing CO2 will lead to increased ecosystem productivity and plant water use efficiency (WUE) are driving optimistic predictions of higher crop yields as well as greater availability of freshwater resources due to a decrease in evapotranspiration. The plant physiological response that drives these effects is believed to be an increase in carbon uptake either by (a) stronger CO2 gradient between the stomata and the atmosphere, or by (b) reduced CO2 limitation of enzymatic carboxylation within the leaf. The (a) scenario will lead to increased water use efficiency (WUE) in plants. However, evidence for increased WUE is mostly based on modeling studies, and experiments producing a short duration or step-wise increase in CO2 concentration (e.g. free-air CO2 enrichment). We hypothesize that the increase in atmospheric CO2 concentration is having a positive effect on ecosystem productivity and WUE. To investigate this hypothesis, we analyzed meteorological, ANPP, and soil CO2 flux datasets together with carbon isotopic ratio (13C/12C) of archived plant samples from the long term ecological research (LTER) program at Kellogg Biological Station. The datasets were collected between 1989 and 2007 (corresponding to an increase in atmospheric CO2 concentration of ~33 ppmv at Mauna Loa). Wheat (Triticum aestivum) samples taken from 1989 and 2007 show a significant decrease in the C isotope discrimination factor (Δ) over time. Stomatal conductance is directly related to Δ, and thus Δ is inversely related to plant intrinsic WUE (iWUE). Historical changes in the 13C/12C ratio (δ13C) in samples of a perennial forb, Canada goldenrod (Solidago canadensis), taken from adjacent successional fields, indicate changes in Δ upon uptake of CO2 as well. These temporal trends in Δ suggest a positive feedback between the increasing CO2 concentration in the

  6. Accurate determinations of one-bond 13C-13C couplings in 13C-labeled carbohydrates

    NASA Astrophysics Data System (ADS)

    Azurmendi, Hugo F.; Freedberg, Darón I.

    2013-03-01

    Carbon plays a central role in the molecular architecture of carbohydrates, yet the availability of accurate methods for 1DCC determination has not been sufficiently explored, despite the importance that such data could play in structural studies of oligo- and polysaccharides. Existing methods require fitting intensity ratios of cross- to diagonal-peaks as a function of the constant-time (CT) in CT-COSY experiments, while other methods utilize measurement of peak separation. The former strategies suffer from complications due to peak overlap, primarily in regions close to the diagonal, while the latter strategies are negatively impacted by the common occurrence of strong coupling in sugars, which requires a reliable assessment of their influence in the context of RDC determination. We detail a 13C-13C CT-COSY method that combines a variation in the CT processed with diagonal filtering to yield 1JCC and RDCs. The strategy, which relies solely on cross-peak intensity modulation, is inspired in the cross-peak nulling method used for JHH determinations, but adapted and extended to applications where, like in sugars, large one-bond 13C-13C couplings coexist with relatively small long-range couplings. Because diagonal peaks are not utilized, overlap problems are greatly alleviated. Thus, one-bond couplings can be determined from different cross-peaks as either active or passive coupling. This results in increased accuracy when more than one determination is available, and in more opportunities to measure a specific coupling in the presence of severe overlap. In addition, we evaluate the influence of strong couplings on the determination of RDCs by computer simulations. We show that individual scalar couplings are notably affected by the presence of strong couplings but, at least for the simple cases studied, the obtained RDC values for use in structural calculations were not, because the errors introduced by strong couplings for the isotropic and oriented phases are very

  7. Noble gas and carbon isotopic evidence for CO2-driven silicate dissolution in a recent natural CO2 field

    NASA Astrophysics Data System (ADS)

    Dubacq, Benoît; Bickle, Mike J.; Wigley, Max; Kampman, Niko; Ballentine, Chris J.; Sherwood Lollar, Barbara

    2012-08-01

    Secure storage of anthropogenic carbon dioxide (CO2) in geological reservoirs requires predicting gas-water-rock interactions over millennial timescales. Noble gases and carbon isotope measurements can be used to shed light on the nature of competing dissolution-precipitation processes over different timescales, from the fast dissolution of gaseous CO2 in groundwater to more sluggish reactions involving dissolution and precipitation of newly formed minerals in the reservoir. Here we study a compilation of gas analyses including noble gases and δ13C of CO2 from nine different natural CO2 reservoirs. Amongst these reservoirs, the Bravo Dome CO2 field (New Mexico, USA) shows distinct geochemical trends which are explained by degassing of noble gases from groundwater altering the composition of the gas phase. This groundwater degassing is synchronous with the dissolution of CO2 in groundwater. Progressive creation of alkalinity via CO2-promoted mineral dissolution is required to explain the observed positive correlation between CO2/3He and δ13C of the gas phase, a unique feature of Bravo Dome. The differences between Bravo Dome and other natural CO2 reservoirs are likely explained by the more recent filling of Bravo Dome, reflecting CO2-water-rock interactions over thousands of years rather than over millions of years in older reservoirs.

  8. *d13C composition of primary producers and role of detritus in a freshwater coastal ecosystem

    USGS Publications Warehouse

    Keough, J.R.; Hagley, C.A.; Sierszen, M.

    1998-01-01

    Stable-isotope ratio signatures of primary producers in a coastal wetland and in adjacent offshore waters of western Lake Superior indicated that phytoplankton are the primary source of carbon for the grazing food web of this ecosystem. This study outlines the possible roles of other autotrophs in this regard. Isotopic signatures of macrophytes reflected their life-form-associated constraints on diffusion of inorganic carbon. Data indicated that differences between wetland and lake phytoplankton may be explained by the isotopic signatures of their dissolved inorganic carbon (DIC) sources. Results of an in situ experiment showed that respiration associated with macrophyte decomposition is capable of enriching surrounding water with significant amounts of *d13C-depleted DIC and lowering the net *d13C ratio of DIC in water in low-turbulence situations. The *d13C ratio for wetland phytoplankton may be depleted relative to pelagic algae because the fixed carbon is derived from decomposing detritus.

  9. Decarboxylation of [1-(13)C]leucine by hydroxyl radicals.

    PubMed

    Guitton, J; Tinardon, F; Lamrini, R; Lacan, P; Desage, M; Francina, A

    1998-08-01

    The decarboxylation of [1-13C]leucine by hydroxyl radicals was studied by using gas chromatography-isotope ratio mass spectrometry (GC-IRMS) to follow the production of 13CO2. A Fenton reaction between a (Fe2+)-porphyrin and hydrogen peroxide under aerobic conditions yielded hydroxyl radicals. The decarboxylation rates (VLeu) measured by GC-IRMS were dependent on [1-13C]leucine, porphyrin and hydrogen peroxide concentrations. The 13CO2 production was also dependent on bicarbonate or carbon dioxide added in the reaction medium. Bicarbonate facilitated 13CO2 production, whereas carbon dioxide decreased 13CO2 production. Proton effects on some decarboxylation intermediates could explain bicarbonate or carbon dioxide effects. No effect on the decarboxylation rates was observed in the presence of the classical hydroxyl radicals scavengers dimethyl sulfoxide, mannitol, and uric acid. By contrast, a competitive effect with a strong decrease of the decarboxylation rates was observed in the presence of various amino acids: unlabeled leucine, valine, phenylalanine, cysteine, lysine, and histidine. Two reaction products, methyl-4 oxo-2 pentanoate and methyl-3 butanoate were identified by gas chromatography-mass spectrometry in comparison with standards. The present results suggest that [1-13C]leucine can participate to the coordination sphere of (Fe2+)-porphyrin, with a caged process of the hydroxyl radicals which cannot get out of the coordination sphere. PMID:9680180

  10. Temperature-mediated changes in microbial carbon use efficiency and 13C discrimination

    NASA Astrophysics Data System (ADS)

    Lehmeier, C. A.; Ballantyne, F., IV; Min, K.; Billings, S. A.

    2015-10-01

    Understanding how carbon dioxide (CO2) flux from soils feeds back to climate warming depends in part on our ability to quantify the efficiency with which microorganisms convert soil organic carbon (C) into either biomass or CO2. Quantifying ecosystem-level respiratory CO2 losses often also requires assumptions about stable C isotope fractionations associated with the microbial transformation of soil organic substrates. However, the diversity of organic substrates' δ13C and the challenges of measuring microbial C use efficiency (CUE) in soils fundamentally limit our ability to project soil, and thus ecosystem, C budgets in a warming climate. Here, we quantify the effect of temperature on C fluxes during metabolic transformations of cellobiose, a common microbial substrate, by a cosmopolitan soil microorganism growing at a constant rate. Specific respiration rate increased by 250 % between 13 and 26.5 °C, decreasing CUE from 77 to 56 %. Specific respiration rate was positively correlated with an increase in respiratory 13C discrimination from 4.4 to 6.7 ‰ across the same temperature range. This first demonstration of a direct link between temperature, microbial CUE and associated isotope fluxes provides a critical step towards understanding δ13C of respired CO2 at multiple scales, and towards a framework for predicting future soil C fluxes.

  11. Temperature-mediated changes in microbial carbon use efficiency and 13C discrimination

    NASA Astrophysics Data System (ADS)

    Lehmeier, Christoph A.; Ballantyne, Ford, IV; Min, Kyungjin; Billings, Sharon A.

    2016-06-01

    Understanding how carbon dioxide (CO2) flux from ecosystems feeds back to climate warming depends in part on our ability to quantify the efficiency with which microorganisms convert organic carbon (C) into either biomass or CO2. Quantifying ecosystem-level respiratory CO2 losses often also requires assumptions about stable C isotope fractionations associated with the microbial transformation of organic substrates. However, the diversity of organic substrates' δ13C and the challenges of measuring microbial C use efficiency (CUE) in their natural environment fundamentally limit our ability to project ecosystem C budgets in a warming climate. Here, we quantify the effect of temperature on C fluxes during metabolic transformations of cellobiose, a common microbial substrate, by a cosmopolitan microorganism growing at a constant rate. Biomass C specific respiration rate increased by 250 % between 13 and 26.5 °C, decreasing CUE from 77 to 56 %. Biomass C specific respiration rate was positively correlated with an increase in respiratory 13C discrimination from 4.4 to 6.7 ‰ across the same temperature range. This first demonstration of a direct link between temperature, microbial CUE, and associated isotope fluxes provides a critical step towards understanding δ13C of respired CO2 at multiple scales, and towards a framework for predicting future ecosystem C fluxes.

  12. Soil carbon and nitrogen cycling and storage throughout the soil profile in a sweetgum plantation after 11 years of CO2-enrichment

    SciTech Connect

    Iversen, Colleen M; Keller, Dr. Jason K.; Garten Jr, Charles T; Norby, Richard J

    2012-01-01

    Increased partitioning of carbon (C) to fine roots under elevated [CO2], especially deep in the soil profile, could alter soil C and nitrogen (N) cycling in forests. After more than 11 years of free-Air CO2 enrichment in a Liquidambar styraciflua L. (sweetgum) plantation in Oak Ridge, TN, USA, greater inputs of fine roots resulted in the incorporation of new C (i.e., C with a depleted 13C) into root-derived particulate organic matter (POM) pools to 90-cm depth. Even though production in the sweetgum stand was limited by soil N availability, soil C and N content increased over time, and were greater throughout the soil profile under elevated [CO2] at the conclusion of the experiment. However, greater C inputs under elevated [CO2] did not result in increased net N immobilization or C mineralization rates in long-term laboratory incubations, and did not appear to prime the decomposition of older SOM. The 13CO2 of the C mineralized from the incubated soil closely tracked the 13C of the labile POM pool in the elevated [CO2] treatment, especially in shallower soil, and did not indicate the decomposition of older (i.e., pre-experiment) SOM. While potential C mineralization rates were positively and linearly related to total soil organic matter (SOM) C content in the top 30 cm of soil, this relationship did not hold in deeper soil. Taken together with an increased mean residence time of C in deeper soil pools, these findings indicate that C inputs from relatively deep roots under elevated [CO2] may have increased potential for long-term storage. Expanded representation of biogeochemical cycling throughout the soil profile may improve model projections of future forest responses to rising atmospheric [CO2].

  13. Variation in woody plant delta(13)C along a topoedaphic gradient in a subtropical savanna parkland.

    PubMed

    Bai, Edith; Boutton, Thomas W; Liu, Feng; Wu, X Ben; Archer, Steven R

    2008-06-01

    delta(13)C values of C(3) plants are indicators of plant carbon-water relations that integrate plant responses to environmental conditions. However, few studies have quantified spatial variation in plant delta(13)C at the landscape scale. We determined variation in leaf delta(13)C, leaf nitrogen per leaf area (N(area)), and specific leaf area (SLA) in April and August 2005 for all individuals of three common woody species within a 308 x 12-m belt transect spanning an upland-lowland topoedaphic gradient in a subtropical savanna in southern Texas. Clay content, available soil moisture, and soil total N were all negatively correlated with elevation. The delta(13)C values of Prosopis glandulosa (deciduous N(2)-fixing tree legume), Condalia hookeri (evergreen shrub), and Zanthoxylum fagara (evergreen shrub) leaves increased 1-4 per thousand with decreasing elevation, with the delta(13)C value of P. glandulosa leaves being 1-3 per thousand higher than those of the two shrub species. Contrary to theory and results from previous studies, delta(13)C values were highest where soil water was most available, suggesting that some other variable was overriding or interacting with water availability. Leaf N(area) was positively correlated with leaf delta(13)C of all species (p < 0.01) and appeared to exert the strongest control over delta(13)C along this topoedaphic gradient. Since leaf N(area) is positively related to photosynthetic capacity, plants with high leaf N(area) are likely to have low p (I)/p (a) ratios and therefore higher delta(13)C values, assuming stomatal conductance is constant. Specific leaf area was not correlated significantly with leaf delta(13)C. Following a progressive growing season drought in July/August, leaf delta(13)C decreased. The lower delta(13)C in August may reflect the accumulation of (13)C-depleted epicuticular leaf wax. We suggest control of leaf delta(13)C along this topoedaphic gradient is mediated by leaf N(area) rather than by stomatal

  14. The effect of chemical processing on the δ 13C value of plant tissue

    NASA Astrophysics Data System (ADS)

    Van de Water, Peter K.

    2002-04-01

    The effect of standard processing techniques on the δ 13C value of plant tissue was tested using species representing the three photosynthetic pathways, including angiosperms and gymnosperms within the C 3 taxonomic division. The species include Cowania mexicana (C 3 angiosperm), Juniperus osteosperma (C 3 gymnosperm), Opuntia spp. (crassulacean acid metabolism [CAM] angiosperm), and Atriplex canescens (C 4 angiosperm). Each species is represented by 5 plants collected at two different sites, for a total of 10 samples. The samples were processed to whole plant tissue, holocellulose, α-cellulose, and nitrocellulose. An additional process was added with the discovery of residual Ca-oxalate crystals in holocellulose samples. Both C 3 species show δ 13C values becoming 13C enriched with increased processing. The CAM representative shows the opposite trend, with 13C depletion during the progression of treatments. The greatest range of values and most inconsistent trends occur in the C 4 representative. Removal of the Ca-oxalate fraction resulted in different mean weight percentages and δ 13C values among the species. Calculated δ 13C values of the Ca-oxalate crystals show depletion from the tissue values in the two C 3 species and enrichment in the C 4 and CAM representatives. The C. mexicana samples show the greatest change between the tissue and Ca-oxalates (7.3‰) but the least mean weight percentage (11%), whereas A. canescens shows the greatest overall change, with a -2.8‰ isotopic shift and over 48% mean weight percentage. Variability within the samples undergoing each treatment remained relatively unchanged even with increased cellulose purity. This paper provides estimates of isotopic offsets necessary to correct from one treatment to another. Significant differences in δ 13C among different treatments confirm the need to state the tissue fraction analyzed when reporting δ 13C results.

  15. Stable Carbon Isotopes (δ 13C) in Coral Skeletons: Experimental Approach and Applications for Paleoceanography

    NASA Astrophysics Data System (ADS)

    Grottoli, A. G.

    2004-12-01

    Scleractinian corals obtain fixed carbon via photosynthesis by their endosymbiotic algae (zooxanthellae) and via hetertrophy (injestion of zooplankton, δ 13C ≈ -17 to -22‰ ). Carbon dioxide (CO2) used for photosynthesis is obtained from seawater (δ 13C ≈ 0%) or from respired CO2 within the coral host. The δ 13C of the carbon used in the formation of the underlying coral skeleton is fractionated as a result of both of these metabolic processes. Here I have pooled evidence from several field and tank experiments on the effect of photosynthesis and heterotrophy of coral skeletal δ 13C. In the experiments, decreases in light levels due to shading or depth resulted in a significant decrease in skeletal δ 13C in all species studied (Pavona gigantea, Pavona clavus, Porites compressa). Decreases in photosynthesis in bleached corals also resulted in a decrease in skeletal δ 13C compared to non-bleached corals growing under the same conditions and at the same location. Skeletal δ 13C also decreased at higher than normal light levels most likely due to photoinhibition. Thus, decreases in photosynthesis due to reduced light levels, due to bleaching-induced decreases in chlorophyll a concentrations, or due to photodamage-induced decreases in functional cholorphyll a, results in significant δ 13C decreases. Comprehensive interpretation of all of the data showed that changes in photosynthesis itself can drive the changes in δ 13C. In field experiments, the addition of natural concentrations of zooplankton to the diet resulted in decreases in skeletal δ 13C. Such a decrease was more pronounced with depth and in P. gigantea compared to P. clavus. In situ feeding experiments have since confirmed these findings. However under tank conditions with unaturally high feeding rates, enhanced nitrogen supply in the diet can disrupt the coral-algal symbiosis, stimlate zooxanthellae growth and photosynthesis, and cause an incrase in skeletal δ 13C. It is proposed that under

  16. CO2 blood test

    MedlinePlus

    Bicarbonate test; HCO3-; Carbon dioxide test; TCO2; Total CO2; CO2 test - serum ... Many medicines can interfere with blood test results. Your health care provider will tell you if you need to stop taking any medicines before you have this test. DO ...

  17. Chlorophyll a specific Δ14C, δ13C and δ15N values in stream periphyton: implications for aquatic food web studies

    NASA Astrophysics Data System (ADS)

    Ishikawa, N. F.; Yamane, M.; Suga, H.; Ogawa, N. O.; Yokoyama, Y.; Ohkouchi, N.

    2015-07-01

    We determined the isotopic composition of chlorophyll a in periphytic algae attached to a streambed substrate (periphyton). The samples were collected from a stream flowing on limestone bedrock in the Seri River, central Japan. Stable isotope ratios of carbon (δ13C) and nitrogen (δ15N) and natural radiocarbon abundances (Δ14C) were measured in chlorophyll a (δ13Cchl, δ15Nchl and Δ14Cchl) and bulk (δ13Cbulk, δ15Nbulk and Δ14Cbulk) for periphyton, pure aquatic primary producer (Cladophora sp.) and terrestrial primary producer (Quercus glauca). Periphyton δ13Cbulk and δ13Cchl values did not necessarily correspond to δ13Cbulk for an algal-grazing specialist (Mayfly larva, Epeorus latifolium), suggesting that periphyton δ13C values do not faithfully trace carbon transfer between primary producers and primary consumers. Periphyton Δ14Cchl values (-258 ‰ in April and -190 ‰ in October) were slightly lower than Δ14Cbulk values (-228 ‰ in April and -179 ‰ in October), but were close to the Δ14C value for dissolved inorganic carbon (DIC) (-217 ± 31 ‰), which is a mixture of weathered carbonates (Δ14C = -1000 ‰) and dissolved atmospheric CO2 (Δ14C approximately +30 ‰ in 2013). Δ14Cchl values were also close to Δ14Cbulk for E. latifolium (-215 ‰ in April and -199 ‰ in October) and Cladophora sp. (-210 ‰), whereas the Δ14Cbulk value for Q. glauca (+27 ‰) was closer to Δ14C for atmospheric CO2. Although the bulk isotopic composition of periphyton is recognised as a surrogate for the photosynthetic algal community, natural periphyton is a mixture of aquatic and terrestrial organic materials. Our results indicate that the bulk periphyton matrix at the study site consists of 89 to 95 % algal carbon (derived from 14C-depleted DIC) and 5 to 11 % terrestrial organic carbon (derived from 14C-enriched atmospheric CO2).

  18. Exocrine pancreatic insufficiency: accuracy and clinical value of the uniformly labelled 13C-Hiolein breath test.

    PubMed Central

    Lembcke, B; Braden, B; Caspary, W F

    1996-01-01

    BACKGROUND AND AIMS: The 13C-Hiolein breath test (98% [U-13C] labelled long chain triglyceride mixture (highly labelled triolein) was evaluated as a non-invasive, non-radioactive test for exocrine pancreatic insufficiency. Accuracy and clinical validity were examined with reference to both the secretin pancreozymin test and faecal fat analysis. METHODS: A secretin pancreozymin test and faecal fat analysis were performed in 46 patients, 30 with exocrine pancreatic insufficiency and 16 with normal pancreatic function. In all of these patients and in seven healthy volunteers (controls), a 13C-Hiolein breath test was performed using 2 mg/kg [U-13C] labelled Hiolein with a standard risk snack (1.5 g/kg; 25% fat). 13CO2/12CO2 enrichment in the exhaled breath was measured by isotope ratio mass spectrometry. RESULTS: In patients with pancreatic steatorrhoea the 13CO2 response was below the 95% confidence interval of 13CO2 exhalation in the controls. These responses were also diminished (p < 0.001) compared with patients with impaired lipase output but normal fat excretion and with disease as well as healthy controls. There was a linear correlation between stimulated lipase output and the ratio of lipase output/13CO2 response (r = 0.95). Among the 40 patients in whom direct pancreatic function testing was clinically indicated, the sensitivity of the 13C-Hiolein test for detecting steatorrhoea was 91.7%, with a specificity of 85.7%. CONCLUSIONS: In patients with pancreatic disease the 13C-Hiolein breath test reflects impaired lipase output and indicates decompensated lipolysis. The 13C-Hiolein breath test is a convenient alternative to faecal fat analysis. PMID:9026480

  19. Co2 geological sequestration

    SciTech Connect

    Xu, Tianfu

    2004-11-18

    Human activities are increasingly altering the Earth's climate. A particular concern is that atmospheric concentrations of carbon dioxide (CO{sub 2}) may be rising fast because of increased industrialization. CO{sub 2} is a so-called ''greenhouse gas'' that traps infrared radiation and may contribute to global warming. Scientists project that greenhouse gases such as CO{sub 2} will make the arctic warmer, which would melt glaciers and raise sea levels. Evidence suggests that climate change may already have begun to affect ecosystems and wildlife around the world. Some animal species are moving from one habitat to another to adapt to warmer temperatures. Future warming is likely to exceed the ability of many species to migrate or adjust. Human production of CO{sub 2} from fossil fuels (such as at coal-fired power plants) is not likely to slow down soon. It is urgent to find somewhere besides the atmosphere to put these increased levels of CO{sub 2}. Sequestration in the ocean and in soils and forests are possibilities, but another option, sequestration in geological formations, may also be an important solution. Such formations could include depleted oil and gas reservoirs, unmineable coal seams, and deep saline aquifers. In many cases, injection of CO2 into a geological formation can enhance the recovery of hydrocarbons, providing value-added byproducts that can offset the cost of CO{sub 2} capture and sequestration. Before CO{sub 2} gas can be sequestered from power plants and other point sources, it must be captured. CO{sub 2} is also routinely separated and captured as a by-product from industrial processes such as synthetic ammonia production, H{sub 2} production, and limestone calcination. Then CO{sub 2} must be compressed into liquid form and transported to the geological sequestration site. Many power plants and other large emitters of CO{sub 2} are located near geological formations that are amenable to CO{sub 2} sequestration.

  20. 13C breath tests in infections and beyond.

    PubMed

    Kurpad, Anura V; Ajami, Alfred; Young, Vernon R

    2002-09-01

    Stable isotope labeled compounds are widely used as diagnostic probes in medicine. These diagnostic stable isotope probes are now being expanded in their scope, to provide precise indications of the presence or absence of etiologically significant change in metabolism due to a specific disease. This concept exploits a labeled tracer probe that is a specifically designed substrate of a "gateway" enzyme in a discrete metabolic pathway, whose turnover can be measured by monitoring unidirectional precursor product mass flow. An example of such a probe is the 13C-urea breath test, where labeled urea is given to patients with H. pylori infection. Another example of this kind of probe is used to study the tripeptide glutathione (glu-cys-gly, GSH), which is the most abundant cellular thiol, and protects cells from the toxic effects of reactive oxygen species. Within the gamma glutamyl cycle, 5-oxoproline (L-pyroglutamic acid) is a metabolite generated during GSH catabolism, and is metabolized to glutamic acid by 5-oxoprolinase. This enzyme can also utilize the substrate L-2-oxothiazolidone-4-carboxylate (OTC), to generate intracellular cysteine, which is beneficial to the cell. Thus, labeled (13C) OTC would, under enzymatic attack yield cysteine and 13CO2, and can thus track the state and capacity of glutathione metabolism. Similarly, stable isotope labeled probes can be used to track the activity of the rate of homocysteine clearance, lymphocyte CD26, and liver CYP (cytochrome P450) enzyme activity. In the future, these applications should be able to titrate, in vivo, the characteristics of various specific enzyme systems in the body and their response to stress or infection as well as to treatment regimes. PMID:12362798

  1. Venting of a separate CO2-rich gas phase from submarine arc volcanoes: Examples from the Mariana and Tonga-Kermadec arcs

    NASA Astrophysics Data System (ADS)

    Lupton, John; Lilley, Marvin; Butterfield, David; Evans, Leigh; Embley, Robert; Massoth, Gary; Christenson, Bruce; Nakamura, Ko-Ichi; Schmidt, Mark

    2008-08-01

    Submersible dives on 22 active submarine volcanoes on the Mariana and Tonga-Kermadec arcs have discovered systems on six of these volcanoes that, in addition to discharging hot vent fluid, are also venting a separate CO2-rich phase either in the form of gas bubbles or liquid CO2 droplets. One of the most impressive is the Champagne vent site on NW Eifuku in the northern Mariana Arc, which is discharging cold droplets of liquid CO2 at an estimated rate of 23 mol CO2/s, about 0.1% of the global mid-ocean ridge (MOR) carbon flux. Three other Mariana Arc submarine volcanoes (NW Rota-1, Nikko, and Daikoku), and two volcanoes on the Tonga-Kermadec Arc (Giggenbach and Volcano-1) also have vent fields discharging CO2-rich gas bubbles. The vent fluids at these volcanoes have very high CO2 concentrations and elevated C/3He and δ13C (CO2) ratios compared to MOR systems, indicating a contribution to the carbon flux from subducted marine carbonates and organic material. Analysis of the CO2 concentrations shows that most of the fluids are undersaturated with CO2. This deviation from equilibrium would not be expected for pressure release degassing of an ascending fluid saturated with CO2. Mechanisms to produce a separate CO2-rich gas phase at the seafloor require direct injection of magmatic CO2-rich gas. The ascending CO2-rich gas could then partially dissolve into seawater circulating within the volcano edifice without reaching equilibrium. Alternatively, an ascending high-temperature, CO2-rich aqueous fluid could boil to produce a CO2-rich gas phase and a CO2-depleted liquid. These findings indicate that carbon fluxes from submarine arcs may be higher than previously estimated, and that experiments to estimate carbon fluxes at submarine arc volcanoes are merited. Hydrothermal sites such as these with a separate gas phase are valuable natural laboratories for studying the effects of high CO2 concentrations on marine ecosystems.

  2. Large 13C enrichment in primary carbonates from Andean Altiplano lakes, northwest Argentina

    NASA Astrophysics Data System (ADS)

    Valero-Garcés, Blas L.; Delgado-Huertas, Antonio; Ratto, Norma; Navas, Ana

    1999-08-01

    We report here extreme 13C enrichments up to +13‰ PDB in primary calcite and aragonite precipitates in saline, well oxygenated waters from high-altitude lakes in the southern Andean Altiplano, northwestern Argentina. Biological effects, as well as variations in carbon source inputs, and in the exchange rate with atmospheric CO 2, are commonly considered the main controls on the carbon isotope values of authigenic lacustrine carbonate. We present sedimentological and geochemical evidence that favors physical processes — evaporation effects and CO 2-degassing — as major controls on 13C enrichment. We propose that large enrichments may result from the non-equilibrium gas-transfer isotope fractionation during CO 2-degassing from thermal springs and evaporation effects in arid environments. The dilution effect by large quantities of 14C-free CO 2 hinders accurate 14C chronology of these lake records based on lacustrine organic matter and aquatic plants. Our results indicate that geothermal and volcanic CO 2 sources in lake basins located in volcanic settings, and physical fractionation may have a greater significance than commonly accepted to explain lacustrine carbon isotope records.

  3. Multi-year estimates of plant and ecosystem 13C discrimination at AmeriFlux sites

    NASA Astrophysics Data System (ADS)

    Dang, X.; Lai, C.; Hollinger, D. Y.; Bush, S.; Randerson, J. T.; Law, B. E.; Schauer, A. J.; Ehleringer, J.

    2011-12-01

    We estimated plant and ecosystem 13C discrimination continuously at 8 AmeriFlux sites (Howland Forest, Harvard Forest, Wind River Forest, Rannells Prairie, Freeman Ranch, Chestnut Ridge, Metolius, and Marys River fir) over 8 years (2002-2009). We used an observation-based approach from weekly measurements of eddy covariance CO2 fluxes and their 13C/12C ratios to estimate photosynthetic 13C discrimination (△A) and respiration (δ13CR) on seasonal and interannual time scales. The coordinated, systematic flask sampling across the AmeriFlux subnetwork were used for cross-site synthesis of monthly flux estimates [Dang et al. Combining tower mixing ratio and community model data to estimate regional-scale net ecosystem carbon exchange by boundary layer inversion over 4 flux towers in the U.S.A., Journal of Geophysical Research-Biogeosciences, in press]. Here, we evaluated environmental factors that also influenced temporal variability in △A and δ13CR from daily to interannual time scales, comparing atmospheric 13C/12C measurements, leaf and needle organic matter, and tree ring cellulose. Across these major biomes that dominate the continent, we show differential ecophysiological responses to environmental stresses, among which water availability appeared to be a dominant factor. Our decadal measurement period provided robust estimates of atmospheric 13C discrimination by terrestrial ecosystems, but also suggest regions where enhanced monitoring efforts are required (e.g., 13C/12C emission from fire and urban metabolism; increased temporal resolution of 13C measurements in stress-sensitive ecosystems) to make atmospheric 13C/12C measurements an effective constraint for continental-scale assessments of the terrestrial carbon cycle.

  4. Experimental determination of C, F, and H partitioning between mantle minerals and carbonated basalt, CO2/Ba and CO2/Nb systematics of partial melting, and the CO2 contents of basaltic source regions

    NASA Astrophysics Data System (ADS)

    Rosenthal, A.; Hauri, E. H.; Hirschmann, M. M.

    2015-02-01

    To determine partitioning of C between upper mantle silicate minerals and basaltic melts, we executed 26 experiments between 0.8 and 3 GPa and 1250-1500 °C which yielded 37 mineral/glass pairs suitable for C analysis by secondary ion mass spectrometry (SIMS). To enhance detection limits, experiments were conducted with 13C-enriched bulk compositions. Independent measurements of 13C and 12C in coexisting phases produced two C partition coefficients for each mineral pair and allowed assessment of the approach to equilibrium during each experiment. Concentrations of C in olivine (ol), orthopyroxene (opx), clinopyroxene (cpx) and garnet (gt) range from 0.2 to 3.5 ppm, and resulting C partition coefficients for ol/melt, opx/melt, cpx/melt and gt/melt are, respectively, 0.0007 ± 0.0004 (n = 2), 0.0003 ± 0.0002 (n = 45), 0.0005 ± 0.0004 (n = 17) and 0.0001 ± 0.00007 (n = 5). The effective partition coefficient of C during partial melting of peridotite is 0.00055 ± 0.00025, and therefore C is significantly more incompatible than Nb, slightly more compatible than Ba, and, among refractory trace elements, most similar in behavior to U or Th. Experiments also yielded partition coefficients for F and H between minerals and melts. Combining new and previous values of DFmineral/melt yields bulk DFperidotite/melt = 0.011 ± 0.002, which suggests that F behaves similarly to La during partial melting of peridotite. Values of DHpyx/melt correlate with tetrahedral Al along a trend consistent with previously published determinations. Small-degree partial melting of the mantle results in considerable CO2/Nb fractionation, which is likely the cause of high CO2/Nb evident in some Nb-rich oceanic basalts. CO2/Ba is much less easily fractionated, with incompatible-element-enriched partial melts having lower CO2/Ba than less enriched basalts. Comparison of calculated behavior of CO2, Nb, and Ba to systematics of oceanic basalts suggests that depleted (DMM-like) sources have 75 ± 25

  5. Effects of temperature and substrate stoichiometry on microbial specific respiration rate, carbon use efficiency, and 13C fractionation

    NASA Astrophysics Data System (ADS)

    Min, K.; Lehmeier, C.; Sellers, M.; Chen, Y.; Ballantyne, F.; Billings, S. A.

    2013-12-01

    Microbial activity contributes up to 60% of soil respiration. However, uncertainty in microbial respiration with rising temperature has previously prevented better predictions of the amount and the source of carbon (C) respired from soil. Three key variables of microbial C economies are of particular interest for estimating microbially mediated C release with temperature: (1) specific respiration rate (SRR), which is microbial CO2 release per microbial biomass-C, (2) carbon use efficiency (CUE), which determines how much organic C consumed by microbes is transformed into biomass, and (3) changes in the δ13C of respired CO2 with temperature, which suggests the form of organic C mineralized and helps to partition soil respiration in plant- and microbe-derived CO2. However, it is difficult to obtain these variables in intact soils, due to confounding factors that influence the amount and δ13C of respired CO2. Here we present an experimental approach that allows us to grow an isolated microbial population on well-characterized organic substrates and directly measure SRR, CUE and δ13C of respired CO2. We explored the effect of temperature on those variables, and how it changes with C:N of the substrate provided. This is important given various substrates available for microbial decay, and the potential for changing microbial CUE with substrate C:N. This approach thus can help constrain potential microbial C loss with warming as soil organic substrates with varying C:N are decomposed. We hypothesized that (1) increased SRR and declined CUE with warming would be more evident at higher C:N, (2) apparent 13C fractionation between biomass and respired CO2 would decrease with temperature due to C limitation, and (3) this fractionation would be higher for high C:N. Pseudomonas fluorescens (a ubiquitous Gram-negative bacterium) was grown at 0.13 h-1 in a chemostat from 13 to 26.5°C. The concentration of cellobiose, the sole C source with constant δ13C, was adjusted to have

  6. Towards hyperpolarized 13C-succinate imaging of brain cancer

    NASA Astrophysics Data System (ADS)

    Bhattacharya, Pratip; Chekmenev, Eduard Y.; Perman, William H.; Harris, Kent C.; Lin, Alexander P.; Norton, Valerie A.; Tan, Chou T.; Ross, Brian D.; Weitekamp, Daniel P.

    2007-05-01

    We describe a novel 13C enriched precursor molecule, sodium 1- 13C acetylenedicarboxylate, which after hydrogenation by PASADENA (Parahydrogen and Synthesis Allows Dramatically Enhanced Nuclear Alignment) under controlled experimental conditions, becomes hyperpolarized 13C sodium succinate. Fast in vivo 3D FIESTA MR imaging demonstrated that, following carotid arterial injection, the hyperpolarized 13C-succinate appeared in the head and cerebral circulation of normal and tumor-bearing rats. At this time, no in vivo hyperpolarized signal has been localized to normal brain or brain tumor. On the other hand, ex vivo samples of brain harvested from rats bearing a 9L brain tumor, 1 h or more following in vivo carotid injection of hyperpolarized 13C sodium succinate, contained significant concentrations of the injected substrate, 13C sodium succinate, together with 13C maleate and succinate metabolites 1- 13C-glutamate, 5- 13C-glutamate, 1- 13C-glutamine and 5- 13C-glutamine. The 13C substrates and products were below the limits of NMR detection in ex vivo samples of normal brain consistent with an intact blood-brain barrier. These ex vivo results indicate that hyperpolarized 13C sodium succinate may become a useful tool for rapid in vivo identification of brain tumors, providing novel biomarkers in 13C MR spectral-spatial images.

  7. Application of a nanoEA-IRMS system for δ13C measurement of biomineral-bound organics in samples of diatom opal with nanomolar quantities of C

    NASA Astrophysics Data System (ADS)

    Méndez-Vicente, Ana; María Mejía-Ramírez, Luz; Stoll, Heather

    2013-04-01

    We describe the isotopic measurement of δ13C in very small samples of diatom opal (nanomolar quantities of C) both from fossil sediments and cultures. We use a nano-EA system composed of a combustion elemental analyzer (EA3000 series, Eurovector), with standard 18 mm diameter quartz oxidation-reduction reactors and an ash removal device that aids in removal of uncombusted opal and ensures a long reactor lifetime. This is coupled to a custom designed trapping and cromatography system (Nano-CF, Nu Instruments Ltd.) which cryogenically removes CO2 generated by sample combustion and introduces the gas into a low-flow helium carrier stream to the mass spectrometer (Nu Perspective IRMS instrument, Nu Instruments Ltd.). This technique allows for an important reduction in the minimum sample requirements for analysis compared to a typical EA, however the need to reduce the contribution of the blank to the measured values becomes all the more critical. Blank from the capsules can be minimized through specific protocols including cleaning with solvents and reducing the size of the capsule by cutting it to a smaller size, attaining blanks as low as 13.75±2.15 nmol C. Under these conditions we can accurately measure both standards and diatom reference materials in the range of 100 to 330 nmol C, with a precision of 2σ < 1 ‰. The measured δ13C is independent of sample size in this range for standards or samples with δ13C < -11 ‰, which is the compositional range expected for natural diatom samples. Furthermore, no memory effect is observed in samples with an isotopic δ13C value differing by > 10 ‰ analysed in sequence. Applied to measure biomineral-bound organics in cleaned diatom samples from sediments, the low sample size requirements of this technique allows us to analyse multiple size fractions within one sample, and explore isotopic fractionation patterns between them. We have analysed samples from sediments of both centric and pennate diatoms typically in the

  8. sup 13 C and sup 18 O isotopic disequilibrium in biological carbonates: I. Patterns

    SciTech Connect

    McConnaughey, T. )

    1989-01-01

    Biological carbonates frequently precipitate out of {sup 18}O and {sup 13}C equilibrium with ambient waters. Two patterns of isotopic disequilibrium are particularly common. Kinetic disequilibria, so designated because they apparently result from kinetic isotope effects during CO{sub 2} hydration and hydroxylation, involve simultaneous depletions of {sup 18}O and {sup 13}C as large as 4{per thousand} and 10 to 15{per thousand}, respectively. Rapid skeletogenesis favors strong kinetic effects, and approximately linear correlations between skeletal {delta}{sup 18}O and {delta}{sup 13}C are common in carbonates showing mainly the kinetic pattern. Metabolic effects involve additional positive or negative modulation of skeletal {delta}{sup 13}C, reflecting changes in the {delta}{sup 13}C of dissolved inorganic carbon, caused mainly by photosynthesis and respiration. Kinetic isotope disequilibria tend to be fairly consistent in rapidly growing parts of photosynthetic corals, and time dependent isotopic variations therefore reflect changes in environmental conditions. {delta}{sup 18}O variations from Galapagos corals yields meaningful clues regarding seawater temperature, while {delta}{sup 13}C variations reflect changes in photosynthesis, modulated by cloudiness.

  9. How secure is subsurface CO2 storage? Controls on leakage in natural CO2 reservoirs

    NASA Astrophysics Data System (ADS)

    Miocic, Johannes; Gilfillan, Stuart; McDermott, Christopher; Haszeldine, Stuart

    2014-05-01

    Carbon Capture and Storage (CCS) is the only industrial scale technology available to directly reduce carbon dioxide (CO2) emissions from fossil fuelled power plants and large industrial point sources to the atmosphere. The technology includes the capture of CO2 at the source and transport to subsurface storage sites, such as depleted hydrocarbon reservoirs or saline aquifers, where it is injected and stored for long periods of time. To have an impact on the greenhouse gas emissions it is crucial that there is no or only a very low amount of leakage of CO2 from the storage sites to shallow aquifers or the surface. CO2 occurs naturally in reservoirs in the subsurface and has often been stored for millions of years without any leakage incidents. However, in some cases CO2 migrates from the reservoir to the surface. Both leaking and non-leaking natural CO2 reservoirs offer insights into the long-term behaviour of CO2 in the subsurface and on the mechanisms that lead to either leakage or retention of CO2. Here we present the results of a study on leakage mechanisms of natural CO2 reservoirs worldwide. We compiled a global dataset of 49 well described natural CO2 reservoirs of which six are leaking CO2 to the surface, 40 retain CO2 in the subsurface and for three reservoirs the evidence is inconclusive. Likelihood of leakage of CO2 from a reservoir to the surface is governed by the state of CO2 (supercritical vs. gaseous) and the pressure in the reservoir and the direct overburden. Reservoirs with gaseous CO2 is more prone to leak CO2 than reservoirs with dense supercritical CO2. If the reservoir pressure is close to or higher than the least principal stress leakage is likely to occur while reservoirs with pressures close to hydrostatic pressure and below 1200 m depth do not leak. Additionally, a positive pressure gradient from the reservoir into the caprock averts leakage of CO2 into the caprock. Leakage of CO2 occurs in all cases along a fault zone, indicating that

  10. Design and implementation of a CO2 flood utilizing advanced reservoirs characterization and horizontal injection wells in a shallow shelf carbonate approaching water floods depletion: Technical progress report, January 1, 1997--March 31, 1997

    SciTech Connect

    Chimahusky, J.S., Casteel, J.F.

    1997-05-01

    The first objective is to utilize reservoir characterization and advanced technologies to optimize the design of a carbon dioxide (CO{sub 2}) project for the South Cowden Unit (SCU) located in Ector County, Texas. The SCU is a mature, relatively small, shallow shelf carbonate unit nearing waterflood depletion. The second objective is to demonstrate the performance and economic viability of the project in the field. All work this quarter falls within the demonstration project.

  11. Synthesis Of 2h- And 13c-Substituted Dithanes

    DOEpatents

    Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.

    2004-05-04

    The present invention is directed to labeled compounds, [2-.sup.13 C]dithane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to processes of preparing [2-.sup.13 C]dithane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to labeled compounds, e.g., [.sup.2 H.sub.1-2, .sup.13 C]methanol (arylthio)-, acetates wherein the .sup.13 C atom is directly bonded to exactly one or two deuterium atoms.

  12. Synthesis of 2H- and 13C-substituted dithanes

    DOEpatents

    Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.

    2003-01-01

    The present invention is directed to labeled compounds, [2-.sup.13 C]dithiane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to processes of preparing [2-.sup.13 C]dithiane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to labeled compounds, e.g., [.sup.2 H.sub.1-2, .sup.13 C]methanol (arylthio)-, acetates wherein the .sup.13 C atom is directly bonded to exactly one or two deuterium atoms.

  13. Increased nitrate availability in the soil of a mixed mature temperate forest subjected to elevated CO2 concentration (canopy FACE)

    NASA Astrophysics Data System (ADS)

    Schleppi, Patrick; Inga, Bucher-Wallin; Frank, Hagedorn; Christian, Körner

    2013-04-01

    In a mature temperate forest in Hofstetten, Switzerland, deciduous tree canopies were subjected to a free-air CO2 enrichment (FACE) for a period of eight years. The effect of this treatment on the availability of nitrogen (N) in the soil was assessed along three transects across the experimental area, one under Fagus sylvatica, one under Quercus robur and Q. petraea and one under Carpinus betulus. Nitrate, ammonium and dissolved organic N (DON) were analysed in soil solution obtained with suction cups. Nitrate and ammonium were also captured in buried ion-exchange resin bags. These parameters were related to the local intensity of the FACE treatment as measured from the 13C depletion of dissolved inorganic carbon in the soil solution, because the CO2 used for the treatment was depleted in 13C (Schleppi et al., 2012). Over the eight years of the experiment, the CO2 enrichment reduced DON concentrations, did not affect ammonium, but induced higher nitrate concentrations, both in soil solution and in resin bags. In the nitrate captured in the resin bags, the natural abundance of the isotope 15N strongly increased. This indicates that the CO2 enrichment accelerated net nitrification, probably as an effect of the higher soil moisture resulting from the reduced transpiration of the CO2-enriched trees. It is also possible that N mineralisation was enhanced by root exudates (priming effect) or that the uptake of inorganic N by these trees decreased slightly as the result of a reduced N demand for fine root growth. In this mature deciduous forest we did not observe any progressive N limitation due to elevated atmospheric CO2 concentrations; on the contrary, we observed an enhanced N availability over the eight years of our measurements. This may, together with the global warming projected, exacerbate problems related to N saturation and nitrate leaching, although it is uncertain how long the observed trends will last in the future. Following the experiment with deciduous

  14. Dipolar-coupling-mediated total correlation spectroscopy in solid-state 13C NMR: Selection of individual 13C- 13C dipolar interactions

    NASA Astrophysics Data System (ADS)

    Spano, Justin; Wi, Sungsool

    2010-06-01

    Herein is described a useful approach in solid-state NMR, for selecting homonuclear 13C- 13C spin pairs in a multiple- 13C homonuclear dipolar coupled spin system. This method builds upon the zero-quantum (ZQ) dipolar recoupling method introduced by Levitt and coworkers (Marin-Montesinos et al., 2006 [30]) by extending the originally introduced one-dimensional (1D) experiment into a two-dimensional (2D) method with selective irradiation scheme, while moving the 13C- 13C mixing scheme from the transverse to the longitudinal mode, together with a dramatic improvement in the proton decoupling efficiency. Selective spin-pair recoupling experiments incorporating Gaussian and cosine-modulated Gaussian pulses for inverting specific spins were performed, demonstrating the ability to detect informative, simplified/individualized, long-range 13C- 13C homonuclear dipolar coupling interactions more accurately by removing less informative, stronger, short-range 13C- 13C interactions from 2D correlation spectra. The capability of this new approach was demonstrated experimentally on uniformly 13C-labeled Glutamine and a tripeptide sample, GAL.

  15. In vivo dynamic turnover of cerebral 13C isotopomers from [U- 13C]glucose

    NASA Astrophysics Data System (ADS)

    Xu, Su; Shen, Jun

    2006-10-01

    An INEPT-based 13C MRS method and a cost-effective and widely available 11.7 Tesla 89-mm bore vertical magnet were used to detect dynamic 13C isotopomer turnover from intravenously infused [U- 13C]glucose in a 211 μL voxel located in the adult rat brain. The INEPT-based 1H → 13C polarization transfer method is mostly adiabatic and therefore minimizes signal loss due to B 1 inhomogeneity of the surface coils used. High quality and reproducible data were acquired as a result of combined use of outer volume suppression, ISIS, and the single-shot three-dimensional localization scheme built in the INEPT pulse sequence. Isotopomer patterns of both glutamate C4 at 34.00 ppm and glutamine C4 at 31.38 ppm are dominated first by a doublet originated from labeling at C4 and C5 but not at C3 (with 1JC4C5 = 51 Hz) and then by a quartet originated from labeling at C3, C4, and C5 (with 1JC3C4 = 35 Hz). A lag in the transition of glutamine C4 pattern from doublet-dominance to quartet dominance as compared to glutamate C4 was observed, which provides an independent verification of the precursor-product relationship between neuronal glutamate and glial glutamine and a significant intercompartmental cerebral glutamate-glutamine cycle between neurons and glial cells.

  16. Calculation of total meal d13C from individual food d13C.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Variations in the isotopic signature of carbon in biological samples can be used to distinguish dietary patterns and monitor shifts in metabolism. But for these variations to have meaning, the isotopic signature of the diet must be known. We sought to determine if knowledge of the 13C isotopic abund...

  17. Testing the root-priming of soil organic matter decomposition using the isotopic signature of fossil fuel CO2

    NASA Astrophysics Data System (ADS)

    Bradley, Robert; Paterson, Eric; Chapman, Steve; Thornton, Barry; Sim, Allan

    2013-04-01

    Plant roots provide various forms of soil labile carbon (i.e., rhizodeposition), which stimulate the growth of heterotrophic bacteria in the rhizosphere. This, in turn, provides a food source for phagotrophic protozoa and other bacterivores, whose carbon:nutrient ratios are generally higher than those of their food source. In order to maintain their stoichiometric composition, bacterivores release their extra nutrients into the rhizosphere, where they may be absorbed by plant roots. Thus, rhizodeposition should reduce carbon limitation, but increase nutrient demand, of the soil microbial biomass. We hypothesized that this shift towards nutrient deficiency would stimulate the production of microbial enzymes that depolymerise soil organic matter into microbial available forms. In other words, roots should stimulate the decomposition of soil organic matter. We report on experiment where we tested such a "root-priming" effect using 3 contrasting plant species (Achillea millefolium, Lolium perenne, Trifolium repens). An agricultural soil, with a delta-13C value of approximately -14 ‰ , was transferred into 30 pots and planted with seeds of each species. A ring was inserted in the middle of each pot, and no seeds were planted within the ring. Plants were grown in a growth chamber designed to deliver 13C-depleted air. The resulting plant biomass had a delta-13C value of approximately -52 ‰ . On 7 occasions during the growth trial, pots were sampled for the flux and delta-13C value of soil CO2. Using similar data from control pots without plants, we compared the expected vs. observed contributions of CO2 from roots and soil organic matter. Results from this study revealed a negative root-priming effect for all three species. We discuss the experimental conditions that could have led to this observation, as well as the novelty and potential of our experimental protocol.

  18. Use of the Biphasic (13)C-Sucrose/Glucose Breath Test to Assess Sucrose Maldigestion in Adults with Functional Bowel Disorders.

    PubMed

    Opekun, Antone R; Balesh, Albert M; Shelby, Harold T

    2016-01-01

    Sucrase insufficiency has been observed in children with of functional bowel disorders (FBD) and symptoms of dietary carbohydrate intolerance may be indistinguishable from those of FBD. A two-phase (13)C-sucrose/(13)C-glucose breath test ((13)C-S/GBT) was used to assess sucrase activity because disaccharidase assays are seldom performed in adults. When (13)C-sucrose is hydrolyzed to liberate monosaccharides, oxidation to (13)CO2 is a proportional indicator of sucrase activity. Subsequently, (13)C-glucose oxidation rate was determined after a secondary substrate ingestion (superdose) to adjust for individual habitus effects (Phase II). (13)CO2 enrichment recovery ratio from (13)C-sucrose and secondary (13)C-glucose loads reflect the individualized sucrase activity [Coefficient of Glucose Oxidation for Sucrose (CGO-S)]. To determine if sucrase insufficiency could be a factor in FBD, (13)C-S/GBT was validated using subjects with known sucrase gene mutation status by comparing (13)CO2-breath enrichment with plasma (13)C-glucose enrichment. (13)C-S/GBT was used to assess sucrose digestion in FBD patients and asymptomatic controls. (13)CO2-breath enrichment correlated with the appearance of (13)C-sucrose-derived glucose in plasma (r (2) = 0.80). Mean, control group CGO-S-enrichment outcomes were 1.01 at 60', 0.92 at 75', and 0.96 at mean 60'-75' with normal CGO-S defined as >0.85 (95% C.I.). In contrast, FBD patients demonstrated lower CGO-S values of 0.77 at 60', 0.77 at 75', and 0.76 at mean 60'-75' (Chi Square: 6.55; p < 0.01), which points to sucrose maldigestion as a cause of FBD. PMID:27579322

  19. Use of the Biphasic 13C-Sucrose/Glucose Breath Test to Assess Sucrose Maldigestion in Adults with Functional Bowel Disorders

    PubMed Central

    Balesh, Albert M.; Shelby, Harold T.

    2016-01-01

    Sucrase insufficiency has been observed in children with of functional bowel disorders (FBD) and symptoms of dietary carbohydrate intolerance may be indistinguishable from those of FBD. A two-phase 13C-sucrose/13C-glucose breath test (13C-S/GBT) was used to assess sucrase activity because disaccharidase assays are seldom performed in adults. When 13C-sucrose is hydrolyzed to liberate monosaccharides, oxidation to 13CO2 is a proportional indicator of sucrase activity. Subsequently, 13C-glucose oxidation rate was determined after a secondary substrate ingestion (superdose) to adjust for individual habitus effects (Phase II). 13CO2 enrichment recovery ratio from 13C-sucrose and secondary 13C-glucose loads reflect the individualized sucrase activity [Coefficient of Glucose Oxidation for Sucrose (CGO-S)]. To determine if sucrase insufficiency could be a factor in FBD, 13C-S/GBT was validated using subjects with known sucrase gene mutation status by comparing 13CO2-breath enrichment with plasma 13C-glucose enrichment. 13C-S/GBT was used to assess sucrose digestion in FBD patients and asymptomatic controls. 13CO2-breath enrichment correlated with the appearance of 13C-sucrose-derived glucose in plasma (r2 = 0.80). Mean, control group CGO-S-enrichment outcomes were 1.01 at 60′, 0.92 at 75′, and 0.96 at mean 60′–75′ with normal CGO-S defined as >0.85 (95% C.I.). In contrast, FBD patients demonstrated lower CGO-S values of 0.77 at 60′, 0.77 at 75′, and 0.76 at mean 60′–75′ (Chi Square: 6.55; p < 0.01), which points to sucrose maldigestion as a cause of FBD. PMID:27579322

  20. Evaluation of a [13C]-Dextromethorphan Breath Test to Assess CYP2D6 Phenotype

    PubMed Central

    Leeder, J. Steven; Pearce, Robin E.; Gaedigk, Andrea; Modak, Anil; Rosen, David I.

    2016-01-01

    A [13C]-dextromethorphan ([13C]-DM) breath test was evaluated to assess its feasibility as a rapid, phenotyping assay for CYP2D6 activity. [13C]-DM (0.5 mg/kg) was administered orally with water or potassium bicarbonate-sodium bicarbonate to 30 adult Caucasian volunteers (n = 1 each): CYP2D6 poor metabolizers (2 null alleles; PM-0) and extensive metabolizers with 1 (EM-1) or 2 functional alleles (EM-2). CYP2D6 phenotype was determined by 13CO2 enrichment measured by infrared spectrometry (delta-over-baseline [DOB] value) in expired breath samples collected before and up to 240 minutes after [13C]-DM ingestion and by 4-hour urinary metabolite ratio. The PM-0 group was readily distinguishable from either EM group by both the breath test and urinary metabolite ratio. Using a single point determination of phenotype at 40 minutes and defining PMs as subjects with a DOB ≤ 0.5, the sensitivity of the method was 100%; specificity was 95% with 95% accuracy and resulted in the misclassification of 1 EM-1 individual as a PM. Modification of the initial protocol (timing of potassium bicarbonate-sodium bicarbonate administration relative to dose) yielded comparable results, but there was a tendency toward increased DOB values. Although further development is required, these studies suggest that the [13C]-DM breath test offers promise as a rapid, minimally invasive phenotyping assay for CYP2D6 activity. PMID:18728242

  1. In vivo 31P and multilabel 13C NMR measurements for evaluation of plant metabolic pathways.

    PubMed

    Rijhwani, S K; Ho, C H; Shanks, J V

    1999-01-01

    Reliable measurements of intracellular metabolites are useful for effective plant metabolic engineering. This study explored the application of in situ 31P and 13C NMR spectroscopy for long-term measurements of intracellular pH and concentrations of several metabolites in glycolysis, glucan synthesis, and central carbon metabolic pathways in plant tissues. An NMR perfusion reactor system was designed to allow Catharanthus roseus hairy root cultures to grow for 3-6 weeks, during which time NMR spectroscopy was performed. Constant cytoplasmic pH (7.40+/-0.06), observed during the entire experiment, indicated adequate oxygenation. 13C NMR spectroscopy was performed on hairy root cultures grown in solutions containing 1-13C-, 2-13C-, and 3-13C-labeled glucose in separate experiments and the flow of label was monitored. Activities of pentose phosphate pathways, nonphotosynthetic CO2 fixation, and glucan synthesis pathways were evident from the experimental results. Scrambling of label in glucans also indicated recycling of triose phosphate and their subsequent conversion to hexose phosphates. PMID:10935751

  2. Fossil bryophytes as recorders of ancient CO2 levels: Experimental evidence and a Cretaceous case study

    NASA Astrophysics Data System (ADS)

    Fletcher, Benjamin J.; Beerling, David J.; Brentnall, Stuart J.; Royer, Dana L.

    2005-09-01

    Biological and geochemical CO2 proxies provide critical constraints on understanding the role of atmospheric CO2 in driving climate change during Earth history. As no single existing CO2 proxy is without its limitations, there is a clear need for new approaches to reconstructing past CO2 concentrations. Here we develop a new pre-Quaternary CO2 proxy based on the stable carbon isotope composition (δ13C) of astomatous land plants. In a series of CO2-controlled laboratory experiments, we show that the carbon isotope discrimination (Δ13C) of a range of bryophyte (liverwort and moss) species increases with atmospheric CO2 across the range 375 to 6000 ppm. Separate experiments establish that variations in growth temperature, water content and substrate type have minor impacts on the Δ13C of liverworts but not mosses, indicating the greater potential of liverworts to faithfully record past variations in CO2. A mechanistic model for calculating past CO2 concentrations from bryophyte Δ13C (White et al., 1994) is extended and calibrated using our experimental results. The potential for fossil liverworts to record past CO2 changes is investigated by analyzing the δ13C of specimens collected from Alexander Island, Antarctica dating to the "greenhouse" world of the mid-Cretaceous. Our analysis and isotopic model yield mid-Cretaceous CO2 concentrations of 1000-1400 ppm, in general agreement with independent proxy data and long-term carbon cycle models. The exceptionally long evolutionary history of bryophytes offers the possibility of reconstructing CO2 concentrations back to the mid-Ordovician, pre-dating all currently used quantitative CO2 proxies.

  3. Capnography: monitoring CO2.

    PubMed

    Casey, Georgina

    2015-10-01

    MONITORING RESPIRATORY and metabolic function by using capnography to measure end tidal carbon dioxide is standard practice in anaesthesia. It is also becoming more common in intensive care units and during procedural sedation. End tidal carbon dioxide (EtCO2) monitoring may also be used to assess effectiveness of cardiopulmonary resuscitation. Capnography is now emerging in general medical and surgical wards to monitor respiratory depression in patients using opioid analgesics. Using EtCO2 to monitor respiratory function offers many benefits over pulse oximetry. It is important to understand the differences between these two monitoring methods, and why capnography is increasingly favoured in many situations. An understanding of the physiological processes involved in CO2 excretion allows nurses to use capnography in a safe and meaningful way, while monitoring at-risk patients in acute care. PMID:26638570

  4. Assessing the use of delta(13)C natural abundance in separation of root and microbial respiration in a Danish beech (Fagus sylvatica L.) forest.

    PubMed

    Formánek, Pavel; Ambus, Per

    2004-01-01

    Our understanding of forest biosphere-atmosphere interactions is fundamental for predicting forest ecosystem responses to climatic changes. Currently, however, our knowledge is incomplete partly due to inability to separate the major components of soil CO(2) effluxes, viz. root respiration, microbial decomposition of soil organic matter and microbial decomposition of litter material. In this study we examined whether the delta(13)C characteristics of solid organic matter and respired CO(2) from different soil-C components and root respiration in a Danish beech forest were useful to provide information on the root respiration contribution to total CO(2) effluxes. The delta(13)C isotopic analyses of CO(2) were performed using a FinniganMAT Delta(PLUS) isotope-ratio mass spectrometer coupled in continuous flow mode to a trace gas preparation-concentration unit (PreCon). Gas samples in 2-mL crimp seal vials were analysed in a fully automatic mode with an experimental standard error +/-0.11 per thousand. We observed that the CO(2) derived from root-free mineral soil horizons (A, B(W)) was more enriched in (13)C (delta(13)C range -21.6 to -21.2 per thousand ) compared with CO(2) derived from root-free humus layers (delta(13)C range -23.6 to -23.4 per thousand ). The CO(2) evolved from root respiration in isolated young beech plants revealed a value intermediate between those for the soil humus and mineral horizons, delta(13)C(root) = -22.2 per thousand, but was associated with great variability (SE +/- 1.0 per thousand ) due to plant-specific differences. delta(13)C of CO(2) from in situ below-ground respiration averaged -22.8 per thousand, intermediate between the values for the humus layer and root respiration, but variability was great (SE +/- 0.4 per thousand ) due to pronounced spatial patterns. Overall, we were unable to statistically separate the CO(2) of root respiration vs. soil organic matter decomposition based solely on delta(13)C signatures, yet the trend in

  5. Chlorophyll a-specific Δ14C, δ13C and δ15N values in stream periphyton: implications for aquatic food web studies

    NASA Astrophysics Data System (ADS)

    Ishikawa, N. F.; Yamane, M.; Suga, H.; Ogawa, N. O.; Yokoyama, Y.; Ohkouchi, N.

    2015-11-01

    Periphytic algae attached to a streambed substrate (periphyton) are an important primary producer in stream ecosystems. We determined the isotopic composition of chlorophyll a in periphyton collected from a stream flowing on limestone bedrock in the Seri River, central Japan. Stable isotope ratios of carbon (δ13C) and nitrogen (δ15N) and natural radiocarbon abundances (Δ14C) were measured in chlorophyll a (δ13Cchl, δ15Nchl and Δ14Cchl) and bulk (δ13Cbulk, δ15Nbulk and Δ14Cbulk) for periphyton, a pure aquatic primary producer (Cladophora sp.) and a terrestrial primary producer (Quercus glauca). Periphyton δ13Cbulk and δ13Cchl values did not necessarily correspond to δ13Cbulk for an algal-grazing specialist (Epeorus latifolium). Periphyton Δ14Cchl values (-258 ‰ in April and -190 ‰ in October) were slightly lower than Δ14Cbulk values (-228 ‰ in April and -179 ‰ in October) but were close to the Δ14C value for dissolved inorganic carbon (DIC; -217 ± 31 ‰), which is a mixture of weathered carbonates (Δ14C = -1000 ‰), CO2 derived from aquatic and terrestrial organic matters (variable Δ14C) and dissolved atmospheric CO2 (Δ14C approximately +30 ‰ in 2013). Δ14Cchl values were also close to Δ14Cbulk for E. latifolium (-215 ‰ in April and -199 ‰ in October) and Cladophora sp. (-210 ‰), whereas the Δ14Cbulk value for Q. glauca (+27 ‰) was closer to Δ14C for atmospheric CO2. Although the bulk isotopic composition of periphyton is recognised as a surrogate for the photosynthetic algal community, natural periphyton is a mixture of aquatic and terrestrial organic materials. Our results indicate that the bulk periphyton matrix at the study site consists of 89 to 95 % algal carbon (derived from 14C-depleted DIC) and 5 to 11 % terrestrial organic carbon (derived from 14C-enriched atmospheric CO2).

  6. The cluster and single-particle states in 13C (α,α)13C reactions

    NASA Astrophysics Data System (ADS)

    Mynbayev, N. A.; Nurmukhanbetova, A. K.; Goldberg, V. Z.; Rogachev, G. V.; Golovkov, M. S.; Koloberdin, M.; Ivanov, I.; Nauruzbayev, D. K.; Berdibek, Sh S.; Rakhymzhanov, A. M.; Tribble, R. E.

    2016-06-01

    The excitation functions of elastic scattering of 13C on alpha particle have been measured using the thick-target inverse kinematic method at the heavy ion DC-60 cyclotron. The helium gas was used as a target and also as a degrader to stop the beam. New data (including 180°degree) of the resonances close to the threshold in 17O have been obtained.

  7. Microbial metabolism in soil at low temperatures: Mechanisms unraveled by position-specific 13C labeling

    NASA Astrophysics Data System (ADS)

    Bore, Ezekiel

    2016-04-01

    Microbial transformation of organic substances in soil is the most important process of the C cycle. Most of the current studies base their information about transformation of organic substances on incubation studies under laboratory conditions and thus, we have a profound knowledge on SOM transformations at ambient temperatures. However, metabolic pathway activities at low temperature are not well understood, despite the fact that the processes are relevant for many soils globally and seasonally. To analyze microbial metabolism at low soil temperatures, isotopomeres of position-specifically 13C labeled glucose were incubated at three temperature; 5, -5 -20 oC. Soils were sampled after 1, 3 and 10 days and additionally after 30 days for samples at -20 °C. The 13C from individual molecule position was quantifed in respired CO2, bulk soil, extractable organic C and extractable microbial biomass by chloroform fumigation extraction (CFE) and cell membranes of microbial communities classified by 13C phospholipid fatty acid (PLFA) analysis. 13CO2 released showed a dominance of the flux from C-1 position at 5 °C. Consequently, at 5 °C, pentose phosphate pathway activity is a dominant metabolic pathway of glucose metabolization. In contrast to -5 °C and -20 oC, metabolic behaviors completely switched towards a preferential respiration of the glucose C-4 position. With decreasing temperature, microorganism strongly shifted towards metabolization of glucose via glycolysis which indicates a switch to cellular maintenance. High recoveries of 13C in extractable microbial biomass at -5 °C indicates optimal growth condition for the microorganisms. PLFA analysis showed high incorporation of 13C into Gram negative bacteria at 5 °C but decreased with temperature. Gram positive bacteria out-competed Gram negatives with decreasing temperature. This study revealed a remarkable microbial activity at temperatures below 0 °C, differing significantly from that at ambient

  8. CARBON-13 NUCLEAR MAGNETIC RESONANCE. 13C CHEMICAL SHIFTS AND 13C-199HG COUPLING CONSTANTS FOR SOME ORGANOMERCURY COMPOUNDS

    EPA Science Inventory

    The (13)C shieldings and (13)C-(199)Hg coupling constants of fourteen phenyl- and seven alkyl- and alkenyl-mercury compounds have been obtained. Substituent effects on the (13)C shieldings are similar to those in nonmercurated phenyl compounds, with a similar relationship between...

  9. CO2-neutral fuels

    NASA Astrophysics Data System (ADS)

    Goede, A. P. H.

    2015-08-01

    The need for storage of renewable energy (RE) generated by photovoltaic, concentrated solar and wind arises from the fact that supply and demand are ill-matched both geographically and temporarily. This already causes problems of overcapacity and grid congestion in countries where the fraction of RE exceeds the 20% level. A system approach is needed, which focusses not only on the energy source, but includes conversion, storage, transport, distribution, use and, last but not least, the recycling of waste. Furthermore, there is a need for more flexibility in the energy system, rather than relying on electrification, integration with other energy systems, for example the gas network, would yield a system less vulnerable to failure and better adapted to requirements. For example, long-term large-scale storage of electrical energy is limited by capacity, yet needed to cover weekly to seasonal demand. This limitation can be overcome by coupling the electricity net to the gas system, considering the fact that the Dutch gas network alone has a storage capacity of 552 TWh, sufficient to cover the entire EU energy demand for over a month. This lecture explores energy storage in chemicals bonds. The focus is on chemicals other than hydrogen, taking advantage of the higher volumetric energy density of hydrocarbons, in this case methane, which has an approximate 3.5 times higher volumetric energy density. More importantly, it allows the ready use of existing gas infrastructure for energy storage, transport and distribution. Intermittent wind electricity generated is converted into synthetic methane, the Power to Gas (P2G) scheme, by splitting feedstock CO2 and H2O into synthesis gas, a mixture of CO and H2. Syngas plays a central role in the synthesis of a range of hydrocarbon products, including methane, diesel and dimethyl ether. The splitting is accomplished by innovative means; plasmolysis and high-temperature solid oxygen electrolysis. A CO2-neutral fuel cycle is

  10. Assessing in situ mineralization of recalcitrant organic compounds in vadose zone sediments using delta13C and 14C measurements.

    PubMed

    Kirtland, Brian C; Aelion, C Marjorie; Stone, Peter A

    2005-01-01

    Few techniques exist to measure the biodegradation of recalcitrant organic compounds such as chlorinated hydrocarbons (CHC) in situ, yet predictions of biodegradation rates are needed for assessing monitored natural attenuation. Traditional techniques measuring O2, CO2, or chemical concentrations (in situ respiration, metabolite and soil air monitoring) may not be sufficiently sensitive to estimate biodegradation rates for these compounds. This study combined isotopic measurements (14C and delta13C of CO2 and delta13C of CHCs) in conjunction with traditional methods to assess in situ biodegradation of perchloroethylene (PCE) and its metabolites in PCE-contaminated vadose zone sediments. CHC, ethene, ethane, methane, O2, and CO2 concentrations were measured over 56 days using gas chromatography (GC). delta13C of PCE, trichloroethylene (TCE) and cis-1,2-dichloroethylene (DCE), delta13C and 14C of vadose zone CO2 and sediment organic matter, and delta13C, 14C, and deltaD of methane were measured using a GC-isotope ratio mass spectrometer or accelerator mass spectrometer. PCE metabolites accounted for 0.2% to 18% of CHC concentration suggesting limited reductive dechlorination. Metabolites TCE and DCE were significantly enriched in (13)C with respect to PCE indicating metabolite biodegradation. Average delta13C-CO2 in source area wells (-23.5 per thousand) was significantly lower compared to background wells (-18.4 per thousand) indicating CHC mineralization. Calculated CHC mineralization rates were 0.003 to 0.01 mg DCE/kg soil/day based on lower 14C values of CO2 in the contaminated wells (63% to 107% modern carbon (pMC)) relative to the control well (117 pMC). Approximately 74% of the methane was calculated to be derived from in situ CHC biodegradation based on the 14C measurement of methane (29 pMC). 14C-CO2 analyses was a sensitive measurement for quantifying in situ recalcitrant organic compound mineralization in vadose zone sediments for which limited

  11. Investigating the Multiple Food Sources and N Chemistry of Invasive Earthworms at the Rhinelander, WI, Free Air CO2 Enrichment (FACE) Experiment

    NASA Astrophysics Data System (ADS)

    Top, S. M.; Filley, T. R.

    2013-12-01

    Rising levels of atmospheric CO2 can directly and indirectly alter biogeochemical cycling in forest ecosystems through changes to plant productivity, tissue chemistry, and associated feedbacks to microbial and faunal communities. At the Rhinelander free air CO2 enrichment site (FACE), Rhinelander WI, we examined the consumption and movement of plant tissue and soil by invasive earthworm species using a multi-proxy stable isotope and amino acid chemistry analysis of plant and soil, as well as fecal matter extracted from invasive earthworms present at the site. Using an isotopic mixing model that exploits the 13C-depleted CO2 source and a previous 15N labeling in the FACE experiment, we determined potential sources to the earthworm fecal matter and the movement of amino compounds. For epigeic, surface dwelling earthworms, the stable isotope modeling showed the largest contribution to the C and N in fecal matter was from leaf litter (up to 80%) which was depleted in amino acid C under elevated CO2 conditions. Fecal matter from the endogeic, mineral soil dwelling earthworms was primarily derived from 0-5 cm soil (up to 56%) and fine root tissue (up to 70%). Additionally, amino acid C in this group of earthworms had a proportionately greater relative concentration compared to the epigeic species and the 0-5cm soil. Here we demonstrate that earthworms are incorporating multiple sources (leaf litter, root, and soil) into their fecal matter, which then get deposited throughout the soil profile, where nutrients could become available for plant use.

  12. Fish tissue lipid-C:N relationships for correcting ä13C values and estimating lipid content in aquatic food web studies

    EPA Science Inventory

    Normalizing 13C values of animal tissue for lipid content is necessary to accurately interpret food web relationships from stable isotope analysis. This is because lipids are 13C-depleted relative to proteins and carbohydrates, and because lipid content varies among speci...

  13. Combined Effects of Ocean Acidification and Light or Nitrogen Availabilities on 13C Fractionation in Marine Dinoflagellates.

    PubMed

    Hoins, Mirja; Eberlein, Tim; Groβmann, Christian H; Brandenburg, Karen; Reichart, Gert-Jan; Rost, Björn; Sluijs, Appy; Van de Waal, Dedmer B

    2016-01-01

    Along with increasing oceanic CO2 concentrations, enhanced stratification constrains phytoplankton to shallower upper mixed layers with altered light regimes and nutrient concentrations. Here, we investigate the effects of elevated pCO2 in combination with light or nitrogen-limitation on 13C fractionation (εp) in four dinoflagellate species. We cultured Gonyaulax spinifera and Protoceratium reticulatum in dilute batches under low-light ('LL') and high-light ('HL') conditions, and grew Alexandrium fundyense and Scrippsiella trochoidea in nitrogen-limited continuous cultures ('LN') and nitrogen-replete batches ('HN'). The observed CO2-dependency of εp remained unaffected by the availability of light for both G. spinifera and P. reticulatum, though at HL εp was consistently lower by about 2.7‰ over the tested CO2 range for P. reticulatum. This may reflect increased uptake of (13C-enriched) bicarbonate fueled by increased ATP production under HL conditions. The observed CO2-dependency of εp disappeared under LN conditions in both A. fundyense and S. trochoidea. The generally higher εp under LN may be associated with lower organic carbon production rates and/or higher ATP:NADPH ratios. CO2-dependent εp under non-limiting conditions has been observed in several dinoflagellate species, showing potential for a new CO2-proxy. Our results however demonstrate that light- and nitrogen-limitation also affect εp, thereby illustrating the need to carefully consider prevailing environmental conditions. PMID:27153107

  14. Combined Effects of Ocean Acidification and Light or Nitrogen Availabilities on 13C Fractionation in Marine Dinoflagellates

    PubMed Central

    Hoins, Mirja; Eberlein, Tim; Groβmann, Christian H.; Brandenburg, Karen; Reichart, Gert-Jan; Rost, Björn; Sluijs, Appy; Van de Waal, Dedmer B.

    2016-01-01

    Along with increasing oceanic CO2 concentrations, enhanced stratification constrains phytoplankton to shallower upper mixed layers with altered light regimes and nutrient concentrations. Here, we investigate the effects of elevated pCO2 in combination with light or nitrogen-limitation on 13C fractionation (εp) in four dinoflagellate species. We cultured Gonyaulax spinifera and Protoceratium reticulatum in dilute batches under low-light (‘LL’) and high-light (‘HL’) conditions, and grew Alexandrium fundyense and Scrippsiella trochoidea in nitrogen-limited continuous cultures (‘LN’) and nitrogen-replete batches (‘HN’). The observed CO2-dependency of εp remained unaffected by the availability of light for both G. spinifera and P. reticulatum, though at HL εp was consistently lower by about 2.7‰ over the tested CO2 range for P. reticulatum. This may reflect increased uptake of (13C-enriched) bicarbonate fueled by increased ATP production under HL conditions. The observed CO2-dependency of εp disappeared under LN conditions in both A. fundyense and S. trochoidea. The generally higher εp under LN may be associated with lower organic carbon production rates and/or higher ATP:NADPH ratios. CO2-dependent εp under non-limiting conditions has been observed in several dinoflagellate species, showing potential for a new CO2-proxy. Our results however demonstrate that light- and nitrogen-limitation also affect εp, thereby illustrating the need to carefully consider prevailing environmental conditions. PMID:27153107

  15. A capillary absorption spectrometer for stable carbon isotope ratio (13C/12C) analysis in very small samples

    NASA Astrophysics Data System (ADS)

    Kelly, J. F.; Sams, R. L.; Blake, T. A.; Newburn, M.; Moran, J.; Alexander, M. L.; Kreuzer, H.

    2012-02-01

    A capillary absorption spectrometer (CAS) suitable for IR laser isotope analysis of small CO2 samples is presented. The system employs a continuous-wave (cw) quantum cascade laser to study nearly adjacent rovibrational transitions of different isotopologues of CO2 near 2307 cm-1 (4.34 μm). This initial CAS system can achieve relative isotopic precision of about 10 ppm 13C, or ˜1‰ (per mil in delta notation relative to Vienna Pee Dee Belemnite) with 20-100 picomoles of entrained sample within the hollow waveguide for CO2 concentrations ˜400-750 ppm. Isotopic analyses of such gas fills in a 1-mm ID hollow waveguide of 0.8 m overall physical path length can be carried out down to ˜2 Torr. Overall 13C/12C ratios can be calibrated to ˜2‰ accuracy with diluted CO2 standards. A novel, low-cost method to reduce cw-fringing noise resulting from multipath distortions in the hollow waveguide is presented, which allows weak absorbance features to be studied at the few ppm level (peak-to-rms) after 1000 scans are co-added in ˜10 s. The CAS is meant to work directly with converted CO2 samples from a laser ablation-catalytic combustion micro-sampler to provide 13C/12C ratios of small biological isolates currently operating with spatial resolutions ˜50 μm.

  16. The diel imprint of leaf metabolism on the δ13 C signal of soil respiration under control and drought conditions.

    PubMed

    Barthel, Matthias; Hammerle, Albin; Sturm, Patrick; Baur, Thomas; Gentsch, Lydia; Knohl, Alexander

    2011-12-01

    Recent (13) CO(2) canopy pulse chase labeling studies revealed that photosynthesis influences the carbon isotopic composition of soil respired CO(2) (δ(13) C(SR)) even on a diel timescale. However, the driving mechanisms underlying these short-term responses remain unclear, in particular under drought conditions. The gas exchange of CO(2) isotopes of canopy and soil was monitored in drought/nondrought-stressed beech (Fagus sylvatica) saplings after (13) CO(2) canopy pulse labeling. A combined canopy/soil chamber system with gas-tight separated soil and canopy compartments was coupled to a laser spectrometer measuring mixing ratios and isotopic composition of CO(2) in air at high temporal resolution. The measured δ(13) C(SR) signal was then explained and substantiated by a mechanistic carbon allocation model. Leaf metabolism had a strong imprint on diel cycles in control plants, as a result of an alternating substrate supply switching between sugar and transient starch. By contrast, diel cycles in drought-stressed plants were determined by the relative contributions of autotrophic and heterotrophic respiration throughout the day. Drought reduced the speed of the link between photosynthesis and soil respiration by a factor of c. 2.5, depending on the photosynthetic rate. Drought slows the coupling between photosynthesis and soil respiration and alters the underlying mechanism causing diel variations of δ(13) C(SR). PMID:21851360

  17. Study on CO2 global recycling system.

    PubMed

    Takeuchi, M; Sakamoto, Y; Niwa, S

    2001-09-28

    In order to assist in finding ways to mitigate CO2 emission and to slow the depletion of fossil fuels we have established and evaluated a representative system, which consists of three technologies developed in our laboratory. These technologies were in CO2 recovery, hydrogen production and methanol synthesis and in addition we established the necessary supporting systems. Analysis of outline designs of the large scale renewable energy power generation system and this system and energy input for building plant, energy input for running plant has been conducted based on a case using this system for a 1000-MW coal fired power plant, followed by an evaluation of the material balance and energy balance. The results are as follows. Energy efficiency is 34%, the CO2 reduction rate is 41%, the balance ratio of the energy and CO2 of the system is 2.2 and 1.8, respectively, on the assumption that the primary renewable energy is solar thermal power generation, the stationary CO2 emission source is a coal-fired power plant and the generation efficiency of the methanol power plant is 60%. By adopting the system, 3.7 million tons of CO2 can be recovered, approximately 2.7 million tons of methanol can be produced, and 15.4 billion kWh of electricity can be generated per year. Compared to generating all electrical power using only coal, approximately 2.6 million tons of coal per year can be saved and approximately 2.15 million tons of CO2 emission can be reduced. Therefore, it is clearly revealed that this system would be effective to reduce CO2 emissions and to utilize renewable energy. PMID:11589395

  18. What is the main driver of atmospheric CO2 dynamic: ocean or permafrost?

    NASA Astrophysics Data System (ADS)

    Zimov, S. A.; Zimov, N.

    2010-12-01

    Majority have assumed that during the Last Deglaciation (LD) ocean was a strong source of carbon (C) transporting hundreds of gigatons of C into the terrestrial and atmospheric storages. Increase in the δ13C of foraminifera shells during the LD by 0.3-0.4 per mil considered as an evidence of such a source. However terrestrial and oceanic branches of the biological carbon cycle have very similar carbon isotopic signatures and carbon storage capacities. So the same δ13C increase could be caused by an oceanic bio-productivity increase and the increase of C in bottom sediments (Brovkin et al. 2002). Additionally it has been shown experimentally that at 90 ppmv increase in atmospheric CO2, due to changes in the concentration of carbonate ions in sea water, would cause the δ13C of foraminifera shells to increase by at least 0.25-0.5 per mil (Spero et al. 1997). At all stable parameters to equilibrate for 90 ppm CO2 increase in the atmosphere ocean inorganic C reservoir should have increased by 1800 Gt C (Sigman et al. 2000). Therefore it is very hard to find a mechanism which would allow ocean in LD to release carbon instead of absorbing it, and such a mechanism haven’t been found so far. Methane (CH4) produced by steppe-tundra biome (ST) soil thawing has a unique isotopic signal depleted in all isotopes. Inclusion of this source into a model of the atmospheric methane isotope budget allowed us to reconstruct the dynamics of methane’s main sources. Results indicated that thawing of ST soils during the deglaciation, were the largest methane source and resulted in 255 Gt C emitted in the form of CH4 to the atmosphere (Zimov, see AGU 2010). When soil turns anaerobic only minor portion of soil C converts into CH4. Bigger portion of ST didn’t turn anaerobic at all and all decomposing C was turned into CO2. Besides that part of the soil CH4 flux was consumed by methanotrophs. Therefore C storage in ST soils were many times higher then CH4 emission into the atmosphere

  19. The 13C/2H-glucose test for determination of small intestinal lactase activity.

    PubMed

    Vonk, R J; Stellaard, F; Priebe, M G; Koetse, H A; Hagedoorn, R E; De Bruijn, S; Elzinga, H; Lenoir-Wijnkoop, I; Antoine, J M

    2001-03-01

    To diagnose hypolactasia, determination of lactase enzyme activity in small intestinal biopsy material is considered to be the golden standard. Because of its strongly invasive character and the sampling problems, alternative methods have been looked for. We analysed the 13C-glucose response in serum after consumption of 25 g of naturally enriched 13C-lactose. As an internal standard, 0.5 g of 2H-glucose was added and the 2H-glucose response in serum was measured simultaneously. The studies were performed in healthy volunteers with a background of genetically determined lactase nonpersistence (n = 12; low lactase activity) and lactase persistence (n = 27; high lactase activity). The results were compared with those of the lactose hydrogen breath test, the lactose 13CO2 breath test and the previously described 13C-lactose digestion test. After consumption of 13C-lactose and 2H-glucose, the mean ratio 13C-glucose/2H-glucose concentration in serum at 45-75 min was 0.26 +/- 0.09 in the low lactase activity group and 0.93 +/- 0.17 in the high lactase activity group (P < 0.01). Threshold of the ratio between digesters and maldigesters was calculated as 0.46. Accuracy of the new test was superior to all other tests. We conclude that the 13C/2H-glucose test has the potential of determining the small intestinal lactase activity in vivo and of estimating the amount of lactose which is digested in the small intestine. PMID:11264650

  20. Synthesis Of [2h, 13c]M [2h2m 13c], And [2h3,, 13c] Methyl Aryl Sulfones And Sulfoxides

    DOEpatents

    Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.; Schmidt, Jurgen G.

    2004-07-20

    The present invention is directed to labeled compounds, [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2, .sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfones and [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2, .sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfoxides, wherein the .sup.13 C methyl group attached to the sulfur of the sulfone or sulfoxide includes exactly one, two or three deuterium atoms and the aryl group is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure: ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently, hydrogen, a C.sub.1 -C.sub.4 lower alkyl, a halogen, an amino group from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each a C.sub.1 -C.sub.4 lower alkyl, a phenyl, or an alkoxy group. The present invention is also directed to processes of preparing methyl aryl sulfones and methyl aryl sulfoxides.

  1. 13C labelled cholesteryl octanoate breath test for assessing pancreatic exocrine insufficiency

    PubMed Central

    Ventrucci, M; Cipolla, A; Ubalducci, G; Roda, A; Roda, E

    1998-01-01

    Background—A non-invasive test for assessment of fat digestion has been developed based on the intraluminal hydrolysis of cholesteryl-[1-13C]octanoate by pancreatic esterase. 
Aims—To determine the diagnostic performance of this breath test in the assessment of exocrine pancreatic function. 
Methods—The test was performed in 20 healthy controls, 22 patients with chronic pancreatic disease (CPD), four with biliopancreatic diversion (BPD), and 32 with non-pancreatic digestive diseases (NPD); results were compared with those of other tubeless tests (faecal chymotrypsin and fluorescein dilaurate test). 
Results—Hourly recoveries of 13CO2 were significantly lower in CPD when compared with healthy controls or NPD. In patients with CPD with mild to moderate insufficiency, the curve of 13CO2 recovery was similar to that of healthy controls, while in those with severe insufficiency it was flat. In three patients with CPD with severe steatorrhoea, a repeat test after pancreatic enzyme supplementation showed a significant rise in 13CO2 recovery. The four BPD patients had low and delayed 13CO2 recovery. Only eight of the 32 patients with NPD had abnormal breath test results. There was a significant correlation between the results of the breath test and those of faecal chymotrypsin, the fluorescein dilaurate test, and faecal fat measurements. For the diagnosis of pancreatic disease using the three hour cumulative 13CO2 recovery test, the sensitivity was 68.2% and specificity 75.0%; values were similar to those of the other two tubeless pancreatic function tests. In seven healthy controls, nine patients with CPD, and nine with NPD a second breath test was performed using Na-[1-13C]octanoate and a pancreatic function index was calculated as the ratio of 13C recovery obtained in the two tests: at three hours this index was abnormal in eight patients with CPD and in three with NPD. 
Conclusion—The cholesteryl-[1-13C]octanoate breath test can be useful for the

  2. A Proof of Concept Study to Detect Urease Producing Bacteria in Lungs Using Aerosolized 13C-Urea

    PubMed Central

    Timmins, Graham; Davies, Lea; Heynekamp, Theresa; Harkins, Michelle; Sharp, Zachary D.; Kelly, H. William

    2016-01-01

    This is a “proof of concept” study to determine whether inhalation of 13C-urea can be safely used to detect the presence of urease producing bacteria in the airways of patients with cystic fibrosis (CF) by detecting 13CO2 in breath. This was a prospective, 2-part, open label, single-center, single-arm, single-administration, dose-escalation investigational device exemption trial. First, the safety of 20 and 50 mg inhaled 13C-urea was evaluated in 6 healthy adult participants. Then, 3 adult CF participants colonized with Pseudomonas aeruginosa were enrolled for each dose of inhaled 13C-urea. The safety of inhaled 13C-urea was assessed by spirometry and physical examination. 13C-urea was administered using a jet nebulizer, followed by serial spirometry (10 min and 30 min post inhalation) and collection of exhaled breath at 5, 10, and 15 min post inhalation. There was no clinical significant change in any of the spirometry values compared to baseline in healthy participants and CF patients. Mean of 13CO2/12CO2 delta over baseline (DOB) values in CF participants at 5, 10, and 15 min post inhalation was as follows: 20 mg dose 4‰ (2.2‰–4.9‰), 1‰ (1.0‰–1.4‰), and 1‰ (0.4‰–1.5‰); 50 mg dose: 10‰ (6.2‰–14.5‰), 3‰ (2.1‰–4.3‰), and 1.5‰ (0.6‰–2.3‰). Inhaled 13C-urea for detection of urease producing bacteria was safe, and preliminary data suggest that 13CO2/12CO2 DOB values may be higher in CF patients with P. aeruginosa at 5–10 min after inhalation of 13C-urea. A future direction is to investigate use of inhaled 13C-urea in young children who have difficulty producing sputum for culturing. PMID:27458537

  3. Exploring variations in microbial carbon sources and cycling in the deep terrestrial subsurface using PLFA and δ13C analysis

    NASA Astrophysics Data System (ADS)

    Simkus, D.; Slater, G. F.; Wilkie, K. M.; Li, L.; Sherwood Lollar, B.; Onstott, T. C.; Wommack, E.; Sakowski, E.

    2012-12-01

    In deep crystalline rock of the terrestrial subsurface, water-filled fracture networks represent potential microbial habitats. The geochemical environments within such fraction systems, and concurrently potential microbial carbon sources and metabolic activities, can vary widely. In systems where organic carbon is limited or highly recalcitrant, microbial ecosystems must rely on autotrophy of dissolved inorganic carbon (DIC) or metabolism of organic compounds produced abiotically via water-rock interaction. In either case, CH4 is a key potential species as it is produced autotrophically by CO2-reducing organisms, as well as abiotically by reactions analogous to the Fischer-Tropsch synthesis. Utilization of this methane by microbial communities requires the ability to oxidize it, either aerobically or anaerobically. In this study, the concentrations, distribution and δ13C compositions of phospholipid fatty acids (PLFA), as well as DIC and CH4 pools, were characterized in boreholes in mines in the Johannesburg area of South Africa. Water flow rates from these boreholes were in the liters per minute range and concurrent gas flow rates ranged from 3 to 800 mL/min. Water temperature, pH, Eh and salinity ranged from 27 to 55 °C, from 7.3 to 8.9, from -130 to 375 mV and from 0.2 to 110 ppt, respectively. CH4 concentrations ranged from 2 to 70 % of gas by volume and δ13C of methane ranged from -55 to -36 ‰. δ18O and δ2H analysis indicated that waters in the majority of boreholes were paleometeoric. One borehole was indicated to be off the global meteoric water line, consistent with large extents of water-rock interaction. PLFA concentrations and distributions varied between boreholes, indicating variations in the microbial communities, concurrent with variations in the environments being sampled. δ13C of PLFA also varied between boreholes; for instance, δ13C values of PLFA in the Beatrix mine 326 Bh2 ranged from -55 to -65 ‰ , whereas in Bh1, located circa 100 m

  4. Stable carbon isotope analysis in a South Texas cave: Investigating sources of CO2 production

    NASA Astrophysics Data System (ADS)

    Thompson, Reece

    Studies of interactions between modern local climate, cave atmosphere, and ?13C ratios are needed to determine sources of CO2 in caves, and the cycles of seasonal variations that alter karst geochemistry. A seasonal study, focusing on the analysis of stable isotopes collected from a modern cave system, was conducted in Robber Baron Cave (RBC) in order to identify sources of CO2 in its atmosphere. Determining what conditions affect cave morphology and the transfer path of carbon through a cave system is necessary in order to assess the role of caves in the carbon cycle and correctly interpret past ecological changes. This study investigates the extent that stable isotopic values of carbon in CO2 are affected by CO2 sourced from soils, bedrock, atmospheric air, and vegetation, and how ?13C signals are transmitted in a modern cave system. This study also measures how ventilation affects CO2 concentration and ?13C on seasonal scales. In-cave air grab samples were collected monthly at various transects located in RBC in order to measure CO2 composition in addition to factors such as temperature, and barometric pressure. Soil gas and limestone bedrock were also collected and tested for ?13C composition. Air samples were analyzed using an Ambient Air-Model G2101-I Picarro Cavity Ring-Down Spectroscopy Analyzer for both the concentration and ?13C isotopic value of CO2. These values were then compared to isotopic values of known sources of CO2 in order to determine possible sources of CO2 that result in high CO2 concentrations found in RBC. The background stable isotopic value of carbon from CO2 measured in RBC is -19.1‰ VPDB.

  5. A bicyclic autotrophic CO2 fixation pathway in Chloroflexus aurantiacus.

    PubMed

    Herter, Sylvia; Fuchs, Georg; Bacher, Adelbert; Eisenreich, Wolfgang

    2002-06-01

    Phototrophic CO(2) assimilation by the primitive, green eubacterium Chloroflexus aurantiacus has been shown earlier to proceed in a cyclic mode via 3-hydroxypropionate, propionyl-CoA, succinyl-CoA, and malyl-CoA. The metabolic cycle could be closed by cleavage of malyl-CoA affording glyoxylate (the primary CO(2) fixation product) with regeneration of acetyl-CoA serving as the starter unit of the cycle. The pathway of glyoxylate assimilation to form gluconeogenic precursors has not been elucidated to date. We could now show that the incubation of cell extract with a mixture of glyoxylate and [1,2,3-(13)C(3)]propionyl-CoA afforded erythro-beta-[1,2,2'-(13)C(3)]methylmalate and [1,2,2'-(13)C(3)]citramalate. Similar experiments using a partially purified protein fraction afforded erythro-beta-[1,2,2'-(13)C(3)]methylmalyl-CoA and [1,2,2'-(13)C(3)]mesaconyl-CoA. Cell extracts of C. aurantiacus were also shown to catalyze the conversion of citramalate into pyruvate and acetyl-CoA in a succinyl-CoA-dependent reaction. The data suggest that glyoxylate obtained by the cleavage of malyl-CoA can be utilized by condensation with propionyl-CoA affording erythro-beta-methylmalyl-CoA, which is converted to acetyl-CoA and pyruvate. This reaction sequence regenerates acetyl-CoA, which serves as the precursor of propionyl-CoA in the 3-hydroxypropionate cycle. Autotrophic CO(2) fixation proceeds by combination of the 3-hydroxypropionate cycle with the methylmalyl-CoA cycle. The net product of that bicyclic autotrophic CO(2) fixation pathway is pyruvate serving as an universal building block for anabolic reactions. PMID:11929869

  6. Effects of eustatic sea-level change, ocean dynamics, and iron fertilization on atmospheric pCO2 and seawater composition over the last 130 000 years

    NASA Astrophysics Data System (ADS)

    Wallmann, K.; Schneider, B.; Sarnthein, M.

    2015-06-01

    We developed and employed an earth system model to explore the forcings of atmospheric pCO2 change and the chemical and isotopic evolution of seawater over the last glacial cycle. Concentrations of dissolved phosphorus, reactive nitrogen, molecular oxygen, dissolved inorganic carbon (DIC), total alkalinity (TA), 13C-DIC and 14C-DIC were calculated for 24 ocean boxes. The bi-directional water fluxes between these model boxes were derived from a 3-D circulation field of the modern ocean (Opa 8.2, NEMO) and tuned such that tracer distributions calculated by the box model were consistent with observational data from the modern ocean. To model the last 130 kyr, we employed records of past changes in sea-level, ocean circulation, and dust deposition. According to the model, about half of the glacial pCO2 drawdown may be attributed to marine regressions. The glacial sea-level low-stands implied steepened ocean margins, a reduced burial of particulate organic carbon, phosphorus, and neritic carbonate at the margin seafloor, a decline in benthic denitrification, and enhanced weathering of emerged shelf sediments. In turn, they led to a distinct rise in the standing stocks of DIC, TA, and nutrients in the global ocean, promoted the glacial sequestration of atmospheric CO2 in the ocean, and added 13C- and 14C-depleted DIC to the ocean as recorded in benthic foraminifera signals. The other half of the glacial drop in pCO2 was linked to reduced deep ocean dynamics, a shoaling of Atlantic meridional overturning circulation, and a rise in iron fertilization. The increased transit time of deep waters in the glacial ocean led to significant 14C depletions with respect to the atmosphere. The deglacial rapid and stepwise rise in atmospheric pCO2 was induced by upwelling both in the Southern Ocean and subarctic North Pacific and promoted by a drop in dust-borne iron discharge to the Southern Ocean. The deglacial sea-level rise led to a gradual decline in nutrient, DIC, and TA stocks

  7. Unraveling carbohydrate transport mechanisms in young beech trees (Fagus sylvatica f. purpurea) by 13CO2 efflux measurements from stem and soil

    NASA Astrophysics Data System (ADS)

    Thoms, Ronny; Muhr, Jan; Keitel, Claudia; Kayler, Zachary; Gavrichkova, Olga; Köhler, Michael; Gessler, Arthur; Gleixner, Gerd

    2016-04-01

    Transport mechanisms of soluble carbohydrates and diurnal CO2 efflux from tree stems and surrounding soil are well studied. However, the effect of transport carbohydrates on respiration and their interaction with storage processes is largely unknown. Therefore, we performed a set of 13CO2 pulse labeling experiments on young trees of European beech (Fagus sylvatica f. purpurea). We labeled the whole tree crowns in a closed transparent plastic chamber with 99% 13CO2 for 30 min. In one experiment, only a single branch was labeled and removed 36 hours after labeling. In all experiments, we continuously measured the 13CO2 efflux from stem, branch and soil and sampled leaf and stem material every 3 h for 2 days, followed by a daily sampling of leaves in the successive 5 days. The compound specific δ 13C value of extracted soluble carbohydrates from leaf and stem material was measured by high-performance liquid chromatography linked with an isotope ratio mass spectrometer (HPLC-IRMS). The 13CO2 signal from soil respiration occurred only few hours after labeling indicating a very high transport rate of carbohydrates from leaf to roots and to the rhizosphere. The label was continuously depleted within the next 5 days. In contrast, we observed a remarkable oscillating pattern of 13CO2 efflux from the stem with maximum 13CO2 enrichment at noon and minima at night time. This oscillation suggests that enriched carbohydrates are respired during the day, whereas in the night the enriched sugars are not respired. The observed oscillation in stem 13CO2 enrichment remained unchanged even when only single branches were labelled and cut right afterwards. Thus, storage and conversion of carbohydrates only occurred within the stem. The δ13C patterns of extracted soluble carbohydrates showed, that a transformation of transitory starch to carbohydrates and vice versa was no driver of the oscillating 13CO2 efflux from the stem. Carbohydrates might have been transported in the phloem to

  8. Recent advances in mapping environmental microbial metabolisms through 13C isotopic fingerprints.

    PubMed

    Tang, Joseph Kuo-Hsiang; You, Le; Blankenship, Robert E; Tang, Yinjie J

    2012-11-01

    After feeding microbes with a defined (13)C substrate, unique isotopic patterns (isotopic fingerprints) can be formed in their metabolic products. Such labelling information not only can provide novel insights into functional pathways but also can determine absolute carbon fluxes through the metabolic network via metabolic modelling approaches. This technique has been used for finding pathways that may have been mis-annotated in the past, elucidating new enzyme functions, and investigating cell metabolisms in microbial communities. In this review paper, we summarize the applications of (13)C approaches to analyse novel cell metabolisms for the past 3 years. The isotopic fingerprints (defined as unique isotopomers useful for pathway identifications) have revealed the operations of the Entner-Doudoroff pathway, the reverse tricarboxylic acid cycle, new enzymes for biosynthesis of central metabolites, diverse respiration routes in phototrophic metabolism, co-metabolism of carbon nutrients and novel CO(2) fixation pathways. This review also discusses new isotopic methods to map carbon fluxes in global metabolisms, as well as potential factors influencing the metabolic flux quantification (e.g. metabolite channelling, the isotopic purity of (13)C substrates and the isotopic effect). Although (13)C labelling is not applicable to all biological systems (e.g. microbial communities), recent studies have shown that this method has a significant value in functional characterization of poorly understood micro-organisms, including species relevant for biotechnology and human health. PMID:22896564

  9. Recent advances in mapping environmental microbial metabolisms through 13C isotopic fingerprints

    PubMed Central

    Tang, Joseph Kuo-Hsiang; You, Le; Blankenship, Robert E.; Tang, Yinjie J.

    2012-01-01

    After feeding microbes with a defined 13C substrate, unique isotopic patterns (isotopic fingerprints) can be formed in their metabolic products. Such labelling information not only can provide novel insights into functional pathways but also can determine absolute carbon fluxes through the metabolic network via metabolic modelling approaches. This technique has been used for finding pathways that may have been mis-annotated in the past, elucidating new enzyme functions, and investigating cell metabolisms in microbial communities. In this review paper, we summarize the applications of 13C approaches to analyse novel cell metabolisms for the past 3 years. The isotopic fingerprints (defined as unique isotopomers useful for pathway identifications) have revealed the operations of the Entner–Doudoroff pathway, the reverse tricarboxylic acid cycle, new enzymes for biosynthesis of central metabolites, diverse respiration routes in phototrophic metabolism, co-metabolism of carbon nutrients and novel CO2 fixation pathways. This review also discusses new isotopic methods to map carbon fluxes in global metabolisms, as well as potential factors influencing the metabolic flux quantification (e.g. metabolite channelling, the isotopic purity of 13C substrates and the isotopic effect). Although 13C labelling is not applicable to all biological systems (e.g. microbial communities), recent studies have shown that this method has a significant value in functional characterization of poorly understood micro-organisms, including species relevant for biotechnology and human health. PMID:22896564

  10. Diatom Frustule-Bound δ13c Measurements and Reconstruction of Εp

    NASA Astrophysics Data System (ADS)

    Stoll, H. M.; Mejia Ramirez, L. M.; Mendez-Vicente, A.; Abrevaya, L.; Bolton, C. T.; Anderson, R. F.

    2014-12-01

    Diatom frustules contain embedded organic matter such as amino acids, which may offer a potential phase for measuring the carbon isotopic fractionation during marine photosynthesis (ɛp). We describe optimal sample preparation methods for cleaning external organic matter and separating frustules into various size classes while reducing significance of opal from radiolaria and silicoflagellates. Analysis of discrete separated fractions of diatom opal from each sediment sample is facilitated by our new method for analysis of very small sample sizes using NanoEA with cryotrapping of evolved CO2. We evaluate the fidelity with which frustule-bound organic matter captures the variation in ɛp by comparing δ13C of frustule-bound organic matter with that of total cellular carbon in diatoms grown in culture, and by comparing the δ13C of frustule-bound organic matter in core tops with that of δ13C of diatom-produced biomarkers in the overlying water column. In core-top transects, frustule-bound δ13C is consistent with strong growth rate control over fractionation during photosynthesis (ɛp). Finally, we evaluate the temporal trends in carbon isotopic fractionation during photosynthesis since the Late Miocene in samples from the Eastern Equatorial Pacific.

  11. Strength and limits using 13C phospholipid fatty acid analysis in soil ecology

    NASA Astrophysics Data System (ADS)

    Watzinger, Andrea

    2016-04-01

    This presentation on microbial phospholipid biomarkers, their isotope analysis and their ability to reveal soil functions summarizes experiences gained by the author for more than 10 years. The amount and composition of phospholipid fatty acids (PLFAs) measured in environmental samples strongly depend on the methodology. To achieve comparable results the extraction, separation and methylation method must be kept constant. PLFAs patterns are sensitive to microbial community shifts even though the taxonomic resolution of PLFAs is low. The possibility to easily link lipid biomarkers with stable isotope techniques is identified as a major advantage when addressing soil functions. Measurement of PLFA isotopic ratios is sensitive and enables detecting isotopic fractionation. The difference between the carbon isotopic ratio of single PLFAs and their substrate (δ13C) can vary between -6 and +11‰. This difference derives from the fractionation during biosynthesis and from substrate inhomogeneity. Consequently, natural abundance studies are restricted to quantifying substrate uptake of the total microbial biomass. In contrast, artificial labelling enables quantifying carbon uptake into single PLFAs, but labelling success depends on homogeneous and undisturbed label application. Current developments in microbial ecology (e.g. 13C and 15N proteomics) and isotope techniques (online monitoring of CO2 isotope ratios) will likely improve soil functional interpretations in the future. 13C PLFA analysis will continue to contribute because it is affordable, sensitive and allows frequent sampling combined with the use of small amounts of 13C label.

  12. Malate as a key carbon source of leaf dark-respired CO2 across different environmental conditions in potato plants

    PubMed Central

    Lehmann, Marco M.; Rinne, Katja T.; Blessing, Carola; Siegwolf, Rolf T. W.; Buchmann, Nina; Werner, Roland A.

    2015-01-01

    Dissimilation of carbon sources during plant respiration in support of metabolic processes results in the continuous release of CO2. The carbon isotopic composition of leaf dark-respired CO2 (i.e. δ 13 C R) shows daily enrichments up to 14.8‰ under different environmental conditions. However, the reasons for this 13C enrichment in leaf dark-respired CO2 are not fully understood, since daily changes in δ13C of putative leaf respiratory carbon sources (δ 13 C RS) are not yet clear. Thus, we exposed potato plants (Solanum tuberosum) to different temperature and soil moisture treatments. We determined δ 13 C R with an in-tube incubation technique and δ 13 C RS with compound-specific isotope analysis during a daily cycle. The highest δ 13 C RS values were found in the organic acid malate under different environmental conditions, showing less negative values compared to δ 13 C R (up to 5.2‰) and compared to δ 13 C RS of soluble carbohydrates, citrate and starch (up to 8.8‰). Moreover, linear relationships between δ 13 C R and δ 13 C RS among different putative carbon sources were strongest for malate during daytime (r2=0.69, P≤0.001) and nighttime (r2=0.36, P≤0.001) under all environmental conditions. A multiple linear regression analysis revealed δ 13 C RS of malate as the most important carbon source influencing δ 13 C R. Thus, our results strongly indicate malate as a key carbon source of 13C enriched dark-respired CO2 in potato plants, probably driven by an anapleurotic flux replenishing intermediates of the Krebs cycle. PMID:26139821

  13. /sup 13/C nuclear magnetic resonance studies of cardiac metabolism

    SciTech Connect

    Seeholzer, S.H.

    1985-01-01

    The last decade has witnessed the increasing use of Nuclear Magnetic Resonance (NMR) techniques for following the metabolic fate of compounds specifically labeled with /sup 13/C. The goals of the present study are: (1) to develop reliable quantitative procedures for measuring the /sup 13/C enrichment of specific carbon sites in compounds enriched by the metabolism of /sup 13/C-labeled substrates in rat heart, and (2) to use these quantitative measurements of fractional /sup 13/C enrichment within the context of a mathematical flux model describing the carbon flow through the TCA cycle and ancillary pathways, as a means for obtaining unknown flux parameters. Rat hearts have been perfused in vitro with various combinations of glucose, acetate, pyruvate, and propionate to achieve steady state flux conditions, followed by perfusion with the same substrates labeled with /sup 13/C in specific carbon sites. The hearts were frozen at different times after addition of /sup 13/C-labeled substrates and neutralized perchloric acid extracts were used to obtain high resolution proton-decoupled /sup 13/C NMR spectra at 90.55 MHz. The fractional /sup 13/C enrichment (F.E.) of individual carbon sites in different metabolites was calculated from the area of the resolved resonances after correction for saturation and nuclear Overhauser effects. These F.E. measurements by /sup 13/C NMR were validated by the analysis of /sup 13/C-/sup 1/H scalar coupling patterns observed in /sup 1/H NMR spectra of the extracted metabolites. The results obtained from perfusion of hearts glucose plus either (2-/sup 13/C) acetate or (3-/sup 13/C) pyruvate are similar to those obtained by previous investigators using /sup 14/C-labeled substrates.

  14. CO2 Exsolution from CO2 Saturated Water: Core-Scale Experiments and Focus on Impacts of Pressure Variations.

    PubMed

    Xu, Ruina; Li, Rong; Ma, Jin; Jiang, Peixue

    2015-12-15

    For CO2 sequestration and utilization in the shallow reservoirs, reservoir pressure changes are due to the injection rate changing, a leakage event, and brine withdrawal for reservoir pressure balance. The amounts of exsolved CO2 which are influenced by the pressure reduction and the subsequent secondary imbibition process have a significant effect on the stability and capacity of CO2 sequestration and utilization. In this study, exsolution behavior of the CO2 has been studied experimentally using a core flooding system in combination with NMR/MRI equipment. Three series of pressure variation profiles, including depletion followed by imbibitions without or with repressurization and repetitive depletion and repressurization/imbibition cycles, were designed to investigate the exsolution responses for these complex pressure variation profiles. We found that the exsolved CO2 phase preferentially occupies the larger pores and exhibits a uniform spatial distribution. The mobility of CO2 is low during the imbibition process, and the residual trapping ratio is extraordinarily high. During the cyclic pressure variation process, the first cycle has the largest contribution to the amount of exsolved CO2. The low CO2 mobility implies a certain degree of self-sealing during a possible reservoir depletion. PMID:26509211

  15. Global carbon sinks and their variability inferred from atmospheric O2 and delta13C.

    PubMed

    Battle, M; Bender, M L; Tans, P P; White, J W; Ellis, J T; Conway, T; Francey, R J

    2000-03-31

    Recent time-series measurements of atmospheric O2 show that the land biosphere and world oceans annually sequestered 1.4 +/- 0.8 and 2.0 +/- 0.6 gigatons of carbon, respectively, between mid-1991 and mid-1997. The rapid storage of carbon by the land biosphere from 1991 to 1997 contrasts with the 1980s, when the land biosphere was approximately neutral. Comparison with measurements of delta13CO2 implies an isotopic flux of 89 +/- 21 gigatons of carbon per mil per year, in agreement with model- and inventory-based estimates of this flux. Both the delta13C and the O2 data show significant interannual variability in carbon storage over the period of record. The general agreement of the independent estimates from O2 and delta13C is a robust signal of variable carbon uptake by both the land biosphere and the oceans. PMID:10741962

  16. Determination of 15N/14N and 13C/12C in Solid and Aqueous Cyanides

    USGS Publications Warehouse

    Johnson, C.A.

    1996-01-01

    The stable isotopic compositions of nitrogen and carbon in cyanide compounds can be determined by combusting aliquots in sealed tubes to form N2 gas and CO2 gas and analyzing the gases by mass spectrometry. Free cyanide (CN-aq + HCNaq) in simple solutions can also be analyzed by first precipitating the cyanide as copper(II) ferrocyanide and then combusting the precipitate. Reproducibility is ??0.5??? or better for both ??15N and ??13C. If empirical corrections are made on the basis of carbon yields, the reproducibility of ??13C can be improved to ??0.2???. The analytical methods described herein are sufficiently accurate and precise to apply stable isotope techniques to problems of cyanide degradation in natural waters and industrial process solutions.

  17. Short-term effects of CO(2) and O(2) on citrate metabolism in illuminated leaves.

    PubMed

    Tcherkez, Guillaume; Mahé, Aline; Guérard, Florence; Boex-Fontvieille, Edouard R A; Gout, Elisabeth; Lamothe, Marlène; Barbour, Margaret M; Bligny, Richard

    2012-12-01

    Although there is now a considerable literature on the inhibition of leaf respiration (CO(2) evolution) by light, little is known about the effect of other environmental conditions on day respiratory metabolism. In particular, CO(2) and O(2) mole fractions are assumed to cause changes in the tricarboxylic acid pathway (TCAP) but the amplitude and even the direction of such changes are still a matter of debate. Here, we took advantage of isotopic techniques, new simple equations and instant freeze sampling to follow respiratory metabolism in illuminated cocklebur leaves (Xanthium strumarium L.) under different CO(2) /O(2) conditions. Gas exchange coupled to online isotopic analysis showed that CO(2) evolved by leaves in the light came from 'old' carbon skeletons and there was a slight decrease in (13) C natural abundance when [CO(2) ] increased. This suggested the involvement of enzymatic steps fractionating more strongly against (13) C and thus increasingly limiting for the metabolic respiratory flux as [CO(2) ] increased. Isotopic labelling with (13) C(2) -2,4-citrate lead to (13) C-enriched Glu and 2-oxoglutarate (2OG), clearly demonstrating poor metabolism of citrate by the TCAP. There was a clear relationship between the ribulose-1,5-bisphosphate oxygenation-to-carboxylation ratio (v(o) /v(c) ) and the (13) C commitment to 2OG, demonstrating that 2OG and Glu synthesis via the TCAP is positively influenced by photorespiration. PMID:22646810

  18. Climate reconstruction from pollen and δ13C using inverse vegetation modeling. Implication for past and future climates

    NASA Astrophysics Data System (ADS)

    Hatté, C.; Rousseau, D.-D.; Guiot, J.

    2009-01-01

    An improved inverse vegetation model has been designed to better specify both temperature and precipitation estimates from vegetation descriptions. It is based on the BIOME4 vegetation model and uses both vegetation δ13C and biome as constraints. Previous inverse models based on only one of the two proxies were already improvements over standard reconstruction methods such as the modern analog since these did not take into account some external forcings, for example CO2 concentration. This new approach makes it possible to describe a potential "isotopic niche" defined by analogy with the "climatic niche" theory. Boreal and temperate biomes simulated by BIOME4 are considered in this study. We demonstrate the impact of CO2 concentration on biome existence domains by replacing a "most likely biome" with another with increased CO2 concentration. Additionally, the climate imprint on δ13C between and within biomes is shown: the colder the biome, the lighter its potential isotopic niche; and the higher the precipitation, the lighter the δ13C. For paleoclimate purposes, previous inverse models based on either biome or δ13C did not allow informative paleoclimatic reconstructions of both precipitation and temperature. Application of the new approach to the Eemian of La Grande Pile palynological and geochemical records reduces the range in precipitation values by more than 50% reduces the range in temperatures by about 15% compared to previous inverse modeling approaches. This shows evidence of climate instabilities during Eemian period that can be correlated with independent continental and marine records.

  19. Climate reconstruction from pollen and δ13C records using inverse vegetation modeling - Implication for past and future climates

    NASA Astrophysics Data System (ADS)

    Hatté, C.; Rousseau, D.-D.; Guiot, J.

    2009-04-01

    An improved inverse vegetation model has been designed to better specify both temperature and precipitation estimates from vegetation descriptions. It is based on the BIOME4 vegetation model and uses both vegetation δ13C and biome as constraints. Previous inverse models based on only one of the two proxies were already improvements over standard reconstruction methods such as the modern analog since these did not take into account some external forcings, for example CO2 concentration. This new approach makes it possible to describe a potential "isotopic niche" defined by analogy with the "climatic niche" theory. Boreal and temperate biomes simulated by BIOME4 are considered in this study. We demonstrate the impact of CO2 concentration on biome existence domains by replacing a "most likely biome" with another with increased CO2 concentration. Additionally, the climate imprint on δ13C between and within biomes is shown: the colder the biome, the lighter its potential isotopic niche; and the higher the precipitation, the lighter the δ13C. For paleoclimate purposes, previous inverse models based on either biome or δ13C did not allow informative paleoclimatic reconstructions of both precipitation and temperature. Application of the new approach to the Eemian of La Grande Pile palynological and geochemical records reduces the range in precipitation values by more than 50% reduces the range in temperatures by about 15% compared to previous inverse modeling approaches. This shows evidence of climate instabilities during Eemian period that can be correlated with independent continental and marine records.

  20. 13C-egg white breath test: a non-invasive test of pancreatic trypsin activity in the small intestine

    PubMed Central

    Evenepoel, P; Hiele, M; Geypens, B; Geboes, K; Rutgeerts, P; Ghoos, Y

    2000-01-01

    BACKGROUND—The recent availability of egg white protein highly enriched with 13C has allowed breath test technology to be adapted for the study of protein digestion and absorption. Pancreatic trypsin is considered to be the key enzyme in the proteolytic cascade.
AIM—To evaluate trypsin activity in the small intestine of healthy volunteers and patients with pancreatic disease by a recently developed 13C-egg white breath test.
METHODS—A total of 48 healthy volunteers and 30 patients with pancreatic disease were studied after ingestion of a test meal consisting of 22 g 13C-labelled egg protein. Breath samples were taken before and after ingestion of the meal and analysed for 13CO2 concentration. Moreover, pancreatic trypsin output after maximal stimulation was measured in 13 patients and nine healthy volunteers.
RESULTS—The six hour cumulative 13CO2 excretion in breath was significantly lower in patients than controls (mean (SEM): 6.23 (0.82)% v 19.16 (0.58)%, p<0.0001). An excellent correlation was found between the six hour cumulative 13CO2 excretion and trypsin activity after maximal pancreatic stimulation.
CONCLUSION—The non-invasive 13C-egg white breath test is promising as an indirect pancreatic proteolytic function test.


Keywords: breath test; pancreatic disease; trypsin; protein; assimilation PMID:10601055

  1. Changes in biomass and δ 13C of POC during mesoscale iron fertilization in the Southern Ocean

    NASA Astrophysics Data System (ADS)

    Altabet, M. A.; Timothy, D. A.; McIlvin, M.; Feng, P.

    2002-12-01

    Although δ 13C of marine sediments has been used to infer past changes in [CO2] aq, the roles of physiological state (manifested through growth rate), cell size and species assemblage also have strong influences on δ 13C of phytoplankton and sinking particulates. As part of the Southern Ocean Fe Experiment (SOFeX), we tracked δ 13C of particulate matter during Fe-induced blooms in high-nitrate, low-silicate and low-chlorophyll waters north of the polar front (52 oS, 167 oW) and in high-nitrate, high-silicate and low-chlorophyll waters south of the polar front (66 oS, 172 oW). Interpretation of results from the north patch is confounded, not only by our limited sample set, but also because our sampling did not catch the full extent of the bloom that occurred there. At the southerly patch, there was a significant accumulation of POC (~10 μM C over an 18 day period), while control stations showed little or no biomass accumulation. The biomass accumulation in the southern patch was accompanied by a drop in pCO2, but we did not detect a significant change in δ 13C of the particulates, although changes in size fractionated samples have yet to be determined. Our results will be interpreted in light of changes in species composition, growth rate and [CO2] aq.

  2. Diurnal and Seasonal Variation in the Carbon Isotope Composition of Leaf- and Root- respired CO2 in C3 and C4 Species

    NASA Astrophysics Data System (ADS)

    Sun, W.; Resco, V.; Chen, S.; Williams, D. G.

    2008-12-01

    The carbon isotope signature of leaf (δ13Cl) and root (δ13Cr) dark- respired CO2 records and integrates short-term metabolic changes. Plants with C3 and C4 photosynthetic metabolism are expected to differ in diurnal and seasonal patterns in δ13Cl and δ13Cr because of differences in photorespiration, isotopic fractionation at metabolic branch points and allocation patterns. A thorough understanding of the environmental and metabolic controls on δ13Cl and δ13Cr is necessary to interpret the δ13C of ecosystem respired CO2 and partition the CO2 efflux into autotrophic and heterotrophic respiration sources. We measured δ13Cl in two C3 tree species (Prosopis velutina and Celtis reticulata), a C3 herb (Viguiera dentata) and a C4 grass (Sporobolus wrightii), and δ13Cr in P. velutina and S. wrightii in a semiarid savanna in southeastern Arizona, USA. δ13Cl during the dry pre-monsoon period was relatively enriched in 13C during daytime periods and became depleted in 13C at night relative to daytime values for all species with the exception of S. wrightii, the C4 grass. δ13Cl in S. wrightii was strongly influenced by seasonal differences in water availability with a larger diurnal amplitude in δ13Cl (8.2 +/- 0.6‰) during the wet monsoon period compared to that in the dry pre-monsoon period (4.4 +/- 0.4‰). The δ13C values of starch and lipid fractions remained constant over diurnal periods within the pre-monsoon and monsoon seasons. For C3 species, δ13Cl and δ13C of the cumulative, flux-weighted photosynthate pool estimated from gas exchange were strongly positively correlated, suggesting that progressive 13C-enrichment of leaf-respired CO2 during the daytime period resulted from changes in the δ13C signature of respiratory substrates associated with short-term changes in photosynthetic 13C discrimination. Rapid decreases in δ13Cl following the daytime period was likely caused by decreases in the ratio of PDH:acetyl-CoA oxidation rather than by a shift in

  3. CO2 laser radar

    NASA Astrophysics Data System (ADS)

    Brown, D.; Callan, R.; Constant, G.; Davies, P. H.; Foord, R.

    CO2 laser-based radars operating at 10 microns are both highly energy-efficient and eye-safe, as well as compact and rugged; they also furnish covertness-enhancing fine pointing accuracy, and are difficult to jam or otherwise confuse. Two modes of operation are generally employed: incoherent, in which the laser is simply used as a high power illumination source, and in the presently elaborated coherent or heterodyne mode. Applications encompass terrain-following and obstacle avoidance, Doppler discrimination of missile and aircraft targets, pollutant gas detection, wind measurement for weapons-aiming, and global wind field monitoring.

  4. Simple 13C-urea breath test with infra-red spectrophotometer.

    PubMed

    Taniguchi, Y; Kimura, K; Sohara, H; Shirasaki, A; Kawada, H; Satoh, K; Kihira, K; Wang, X M; Takimoto, T; Goto, Y; Takatori, K; Iida, K; Kajiwara, M

    1996-11-01

    When mass spectrophotometric analysis is used for the 13C-urea breath test to assess H. pylori infection, it is costly, complicated, and time-consuming. To overcome these disadvantages, we utilized an infra-red spectrophotometer as a substitute for the mass spectrophotometer. A total of 153 patients (181 tests) analyzed with peptic ulcers or non-ulcer dyspepsia were investigated. Breath samples were collected 15 min after ingestion of 13C-urea (100 mg in 30 ml water). An infra-red spectrophotometer was used to determine the concentration of 13CO2 in the expirate. The 13CO2/12CO2 ratio was also measured by mass spectrophotometry to compare results with those of infra-red spectrophotometric analysis. Direct detection of H. pylori was qualified in biopsy specimens. Of the 181 biopsies, 138 were positive for H. pylori infection and 43 were negative. With the urea breath test, the mean value in the positive group was significantly higher than that in the negative group (0.062 +/- 0.044 vs 0.011 +/- 0.014, respectively). The cut-off level, 0.01, was determined as delta 13C atom %. The sensitivity of infra-red spectrophotometry was 97.8% (135/138) and specificity was 74.4% (32/43). There was an extremely high coefficient of correlation (r = 0.996) between mass and infra-red photometric analysis. Infra-red spectrometry appears to have great potential not only for diagnosing H. pylori infection but also for assessing treatment results. Its advantages include technical simplicity, cost-effectiveness, and high accuracy. PMID:8959516

  5. Non-stationary (13)C-metabolic flux ratio analysis.

    PubMed

    Hörl, Manuel; Schnidder, Julian; Sauer, Uwe; Zamboni, Nicola

    2013-12-01

    (13)C-metabolic flux analysis ((13)C-MFA) has become a key method for metabolic engineering and systems biology. In the most common methodology, fluxes are calculated by global isotopomer balancing and iterative fitting to stationary (13)C-labeling data. This approach requires a closed carbon balance, long-lasting metabolic steady state, and the detection of (13)C-patterns in a large number of metabolites. These restrictions mostly reduced the application of (13)C-MFA to the central carbon metabolism of well-studied model organisms grown in minimal media with a single carbon source. Here we introduce non-stationary (13)C-metabolic flux ratio analysis as a novel method for (13)C-MFA to allow estimating local, relative fluxes from ultra-short (13)C-labeling experiments and without the need for global isotopomer balancing. The approach relies on the acquisition of non-stationary (13)C-labeling data exclusively for metabolites in the proximity of a node of converging fluxes and a local parameter estimation with a system of ordinary differential equations. We developed a generalized workflow that takes into account reaction types and the availability of mass spectrometric data on molecular ions or fragments for data processing, modeling, parameter and error estimation. We demonstrated the approach by analyzing three key nodes of converging fluxes in central metabolism of Bacillus subtilis. We obtained flux estimates that are in agreement with published results obtained from steady state experiments, but reduced the duration of the necessary (13)C-labeling experiment to less than a minute. These results show that our strategy enables to formally estimate relative pathway fluxes on extremely short time scale, neglecting cellular carbon balancing. Hence this approach paves the road to targeted (13)C-MFA in dynamic systems with multiple carbon sources and towards rich media. PMID:23860906

  6. Molecular Behavior CO2 and CO2-H2O Mixtures at Interfaces

    NASA Astrophysics Data System (ADS)

    Cole, D. R.; Chialvo, A.; Rother, G.; Vlcek, L.

    2010-12-01

    Injection of CO2 into subsurface geologic formations has been identified as a key strategy for mitigating the impact of anthropogenic emissions of CO2. Regardless of the formation type, the CO2 will encounter a complex heterogeneous porous matrix with widely varying pore size and pore distribution, interconnectivity, and surface composition. A small but non-trivial percentage of the pore space is comprised of voids that range from 100 nm down to a few nm in size. These nanoporous environments are more dominant in the cap or seal rocks, such as shale or clay-rich mudstones that act as confining barriers to leakage of CO2 out of the storage reservoir. A concern is the prevention of leakage from the host formation by an effective cap or seal rock which has low porosity and permeability characteristics. Shales comprise the majority of cap rocks encountered in subsurface injection sites with pore sizes typically less than 100 nm and whose surface chemistries are dominated by quartz (SiO2) and clays. We investigated the behavior of pure CO2 and CO2-H2O mixtures interacting with simple substrates, e.g. SiO2 and muscovite, that act as proxies for more complex mineralogical systems. SANS results were described for sorption properties of supercritical CO2 inside mesoporous silica aerogel (95% porosity; 5-40 nm pores), a proxy for the quartz sub-system. The Adsorbed Phase Model (APM) allows, for the first time, a means to quantify the physical properties (e.g. excess, absolute and total adsorption) of the adsorbed phase formed by fluids inside porous media in terms of the mean density and volume of the sorption phase. The results show clear evidence for fluid depletion for conditions above the critical density. Classical molecular dynamics (CMD) modeling of CO2-silica aerogel interactions also indicates the presence of fluid depletion for conditions above the critical density consistent with SANS results. CMD was also used to assess the microscopic behavior of CO2-H2O mixture

  7. CO2 laser preionisation

    NASA Technical Reports Server (NTRS)

    Spiers, Gary D.

    1991-01-01

    The final report for work done during the reporting period of January 25, 1990 to January 24, 1991 is presented. A literature survey was conducted to identify the required parameters for effective preionization in TEA CO2 lasers and the methods and techniques for characterizing preionizers are reviewed. A numerical model of the LP-140 cavity was used to determine the cause of the transverse mode stability improvement obtained when the cavity was lengthened. The measurement of the voltage and current discharge pulses on the LP-140 were obtained and their subsequent analysis resulted in an explanation for the low efficiency of the laser. An assortment of items relating to the development of high-voltage power supplies is also provided. A program for analyzing the frequency chirp data files obtained with the HP time and frequency analyzer is included. A program to calculate the theoretical LIMP chirp is also included and a comparison between experiment and theory is made. A program for calculating the CO2 linewidth and its dependence on gas composition and pressure is presented. The program also calculates the number of axial modes under the FWHM of the line for a given resonator length. A graphical plot of the results is plotted.

  8. CO2 storage capacity estimation: Methodology and gaps

    USGS Publications Warehouse

    Bachu, S.; Bonijoly, D.; Bradshaw, J.; Burruss, R.; Holloway, S.; Christensen, N.P.; Mathiassen, O.M.

    2007-01-01

    Implementation of CO2 capture and geological storage (CCGS) technology at the scale needed to achieve a significant and meaningful reduction in CO2 emissions requires knowledge of the available CO2 storage capacity. CO2 storage capacity assessments may be conducted at various scales-in decreasing order of size and increasing order of resolution: country, basin, regional, local and site-specific. Estimation of the CO2 storage capacity in depleted oil and gas reservoirs is straightforward and is based on recoverable reserves, reservoir properties and in situ CO2 characteristics. In the case of CO2-EOR, the CO2 storage capacity can be roughly evaluated on the basis of worldwide field experience or more accurately through numerical simulations. Determination of the theoretical CO2 storage capacity in coal beds is based on coal thickness and CO2 adsorption isotherms, and recovery and completion factors. Evaluation of the CO2 storage capacity in deep saline aquifers is very complex because four trapping mechanisms that act at different rates are involved and, at times, all mechanisms may be operating simultaneously. The level of detail and resolution required in the data make reliable and accurate estimation of CO2 storage capacity in deep saline aquifers practical only at the local and site-specific scales. This paper follows a previous one on issues and development of standards for CO2 storage capacity estimation, and provides a clear set of definitions and methodologies for the assessment of CO2 storage capacity in geological media. Notwithstanding the defined methodologies suggested for estimating CO2 storage capacity, major challenges lie ahead because of lack of data, particularly for coal beds and deep saline aquifers, lack of knowledge about the coefficients that reduce storage capacity from theoretical to effective and to practical, and lack of knowledge about the interplay between various trapping mechanisms at work in deep saline aquifers. ?? 2007 Elsevier Ltd

  9. Revised estimates of atmospheric CO/sub 2/ variations based on the tree ring /sup 13/C record

    SciTech Connect

    Peng, T.H.; Freyer, H.D.

    1983-01-01

    The composite mean /sup 13/C record for the Northern Hemisphere was revised. The overall decrease of delta /sup 13/C from 1800 to 1980 was estimated to be about -1.5/sup 0///sub 00/, which is 0.5/sup 0///sub 00/ less than the previous estimate. Therefore, the contribution of /sup 13/C-depleted CO/sub 2/ to the atmosphere from the forest and soil source was reevaluated, using the modified box-diffusion ocean model and Freyer's revised /sup 13/C record. On the basis of the assumption that this revised tree ring /sup 13/C record represents changes in the /sup 13/C//sup 12/C ratio induced in atmospheric CO/sub 2/ due to deforestation and soil manipulation and combustion of fossil fuels, the following results are obtained: (1) the magnitude of the integrated CO/sub 2/ release from the terrestrial biosphere since 1800 is about 90% of that from fossil fuel; (2) over the two-decade period covered by the Mauna Loa atmospheric CO/sub 2/ record, the input from the forest plus soil source is about 15% of that from fossil fuels; (3) the /sup 13/C//sup 12/C trend over the last two decades has been dominated by the input of fossil fuel CO/sub 2/; and (4) the pre-1850 atmospheric CO/sub 2/ content is estimated to be about 266 x 10/sup -6/ atm. 15 references, 5 figures, 1 table.

  10. Taphonomy of deciduous leaves and changes in the d13C signal after deposition in fresh water settings

    NASA Astrophysics Data System (ADS)

    Reimann, Simon; Roth-Nebelsick, Anita; Nebelsick, James; Grein, Michaela

    2016-04-01

    Carbon isotopic signals from fossil plant material are an important source of information for palaeoecology and palaeoclimatology. Usually, the 13C isotope is depleted in plant material, compared to the atmospheric 13C content, because 13C is discriminated against 12C during the process of photosynthesis. The degree of 13C discrimination depends on the photosynthetic pathway (C3, C4 and CAM) and is substantially affected by environmental factors (for example, water stress). Various plant material components, however, differ also with respect to their 13C content. It is generally assumed that the d13C signal found in fossil plants reflects that of the living plant to a sufficient degree. Obtaining information on possible alterations during the taphonomic process is, however, desirable. In this study, changes in d13C of deciduous leaves are monitored, from the living leaf still attached to the tree to leaves deposited in fresh water setting for one or more years, thus focusing on early stages of taphonomy. The considered taxa are species from Quercus (oak) and Fagus (beech). Deposited leaves from three fresh water environments in Southwestern Germany were studied: active stream in a forest, still water pond in a forest, and a waterlogged moor environment. Additionally to the isotope measurements, the degree of leaf tissue degradation and colonization with degrading organisms were observed with Scanning Electron Microscopy.

  11. Diethers enriched in 13C suggest carbon-limitation at the Lost City Hydrothermal Field

    NASA Astrophysics Data System (ADS)

    Bradley, A. S.; Hayes, J. M.; Summons, R. E.

    2004-12-01

    Active and inactive carbonate vent structures from the Lost City Hydrothermal Field (LCHF) contain up to 0.6% organic carbon including diverse lipids. Values of δ 13C for total organic carbon (TOC) range from -18.7‰ vs. VPDB at the active, high-temperature vent known as "The Beehive" (90° C), to -3.1‰ at Marker 7 (active, 70° C). Samples with relatively high levels of 13C also contained high amounts of isoprenoidal and nonisoprenoidal diethers. Samples more depleted in 13C lacked or contained low amounts of these diethers. The correlation between high 13C and abundant diethers is supported by compound-specific isotopic analyses. Archaeal and bacterial diethers are enriched in 13C relative to photosynthetically derived marine carbon. The biomarkers sn-2 hydroxyarchaeol, sn-3 hydroxyarchaeol, and dihydroxyarchaeol - considered diagnostic for methane-cycling archaea - had δ values ranging from -8.5 to +4.8‰ . Phylogenetic data confirms the presence at these vents of a single group of methanogens, related to the Methanosarcinales (Schrenk et al., 2004). Diethers with non-isoprenoidal alkyl chains are also present, are of presumed bacterial origin, and may indicated the presence of sulfate-reducing bacteria. Values of δ for these compounds range from -7.3 to +1.0‰ . At the Beehive vent, diether lipids are absent and the TOC is depleted in 13C. Coexistence of isotopically similar hydroxyarchaeols and nonisoprenoidal glycerol diethers is typical of marine, cold-seep environments at which concentrations of H2 are low and methane is oxidized anaerobically. At the LCHF, however, concentrations of H2 in pore waters reach 15 mM (Proskurowski et al., 2003). This H2, produced by serpentinization reactions, drives production (rather than oxidation) of methane. Simultaneously, sulfate-reducing bacteria can flourish as carbon-fixing autotrophs. Under such conditions, carbon may be the limiting substrate, its nearly complete consumption accounting for the enrichment of

  12. Functional groups identified by solid state 13C NMR spectroscopy

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Animal manure is generally high in organic matter intensity so it is well suitable for 13C nuclear magnetic resonance (NMR) analysis. Solid-state 13C NMR techniques used in characterizing organic matter and its components include, but are not limited to, cross-polarization /magic angle spinning (CP...

  13. Determining CO2 storage potential during miscible CO2 enhanced oil recovery: noble gas and stable isotope tracers

    USGS Publications Warehouse

    Shelton, Jenna L.; McIntosh, Jennifer C.; Hunt, Andrew; Beebe, Thomas L; Parker, Andrew D; Warwick, Peter; Drake, Ronald; John E. McCray

    2016-01-01

    Rising atmospheric carbon dioxide (CO2) concentrations are fueling anthropogenic climate change. Geologic sequestration of anthropogenic CO2 in depleted oil reservoirs is one option for reducing CO2 emissions to the atmosphere while enhancing oil recovery. In order to evaluate the feasibility of using enhanced oil recovery (EOR) sites in the United States for permanent CO2 storage, an active multi-stage miscible CO2 flooding project in the Permian Basin (North Ward Estes Field, near Wickett, Texas) was investigated. In addition, two major natural CO2 reservoirs in the southeastern Paradox Basin (McElmo Dome and Doe Canyon) were also investigated as they provide CO2 for EOR operations in the Permian Basin. Produced gas and water were collected from three different CO2 flooding phases (with different start dates) within the North Ward Estes Field to evaluate possible CO2 storage mechanisms and amounts of total CO2 retention. McElmo Dome and Doe Canyon were sampled for produced gas to determine the noble gas and stable isotope signature of the original injected EOR gas and to confirm the source of this naturally-occurring CO2. As expected, the natural CO2 produced from McElmo Dome and Doe Canyon is a mix of mantle and crustal sources. When comparing CO2 injection and production rates for the CO2 floods in the North Ward Estes Field, it appears that CO2 retention in the reservoir decreased over the course of the three injections, retaining 39%, 49% and 61% of the injected CO2 for the 2008, 2010, and 2013 projects, respectively, characteristic of maturing CO2 miscible flood projects. Noble gas isotopic composition of the injected and produced gas for the flood projects suggest no active fractionation, while δ13CCO2 values suggest no active CO2 dissolution into formation water, or mineralization. CO2 volumes capable of dissolving in residual formation fluids were also estimated along with the potential to store pure-phase supercritical CO2. Using a combination of

  14. Canopy CO2 enrichment permits tracing the fate of recently assimilated carbon in a mature deciduous forest.

    PubMed

    Keel, Sonja G; Siegwolf, Rolf T W; Körner, Christian

    2006-01-01

    How rapidly newly assimilated carbon (C) is invested into recalcitrant structures of forests, and how closely C pools and fluxes are tied to photosynthesis, is largely unknown. A crane and a purpose-built free-air CO2 enrichment (FACE) system permitted us to label the canopy of a mature deciduous forest with 13C-depleted CO2 for 4 yr and continuously trace the flow of recent C through the forest without disturbance. Potted C4 grasses in the canopy ('isometers') served as a reference for the C-isotope input signal. After four growing seasons, leaves were completely labelled, while newly formed wood (tree rings) still contained 9% old C. Distinct labels were found in fine roots (38%) and sporocarps of mycorrhizal fungi (62%). Soil particles attached to fine roots contained 9% new C, whereas no measurable signal was detected in bulk soil. Soil-air CO2 consisted of 35% new C, indicating that considerable amounts of assimilates were rapidly returned back to the atmosphere. These data illustrate a relatively slow dilution of old mobile C pools in trees, but a pronounced allocation of very recent assimilates to C pools of short residence times. PMID:16995919

  15. CO2 Laser Market

    NASA Astrophysics Data System (ADS)

    Simonsson, Samuel

    1989-03-01

    It gives me a great deal of pleasure to introduce our final speaker of this morning's session for two reasons: First of all, his company has been very much in the news not only in our own community but in the pages of Wall Street Journal and in the world economic press. And, secondly, we would like to welcome him to our shores. He is a temporary resident of the United States, for a few months, forsaking his home in Germany to come here and help with the start up of a new company which we believe, probably, ranks #1 as the world supplier of CO2 lasers now, through the combination of former Spectra Physics Industrial Laser Division and Rofin-Sinar GMBH. Samuel Simonsson is the Chairman of the Board of Rofin-Sinar, Inc., here in the U.S. and managing director of Rofin-Sinar GMBH. It is a pleasure to welcome him.

  16. Whole-core analysis by sup 13 C NMR

    SciTech Connect

    Vinegar, H.J.; Tutunjian, P.N. ); Edelstein, W.A.; Roemer, P.B. )

    1991-06-01

    This paper reports on a whole-core nuclear magnetic resonance (NMR) system that was used to obtain natural abundance {sup 13}C spectra. The system enables rapid, nondestructive measurements of bulk volume of movable oil, aliphatic/aromatic ratio, oil viscosity, and organic vs. carbonate carbon. {sup 13}C NMR can be used in cores where the {sup 1}H NMR spectrum is too broad to resolve oil and water resonances separately. A 5 1/4-in. {sup 13}C/{sup 1}H NMR coil was installed on a General Electric (GE) CSI-2T NMR imager/spectrometer. With a 4-in.-OD whole core, good {sup 13}C signal/noise ratio (SNR) is obtained within minutes, while {sup 1}H spectra are obtained in seconds. NMR measurements have been made of the {sup 13}C and {sup 1}H density of crude oils with a wide range of API gravities. For light- and medium-gravity oils, the {sup 13}C and {sup 1}H signal per unit volume is constant within about 3.5%. For heavy crudes, the {sup 13}C and {sup 1}H density measured by NMR is reduced by the shortening of spin-spin relaxation time. {sup 13}C and {sup 1}H NMR spin-lattice relaxation times were measured on a suite of Cannon viscosity standards, crude oils (4 to 60{degrees} API), and alkanes (C{sub 5} through C{sub 16}) with viscosities at 77{degrees}F ranging from 0.5 cp to 2.5 {times} 10{sup 7} cp. The {sup 13}C and {sup 1}H relaxation times show a similar correlation with viscosity from which oil viscosity can be estimated accurately for viscosities up to 100 cp. The {sup 13}C surface relaxation rate for oils on water-wet rocks is very low. Nonproton decoupled {sup 13}C NMR is shown to be insensitive to kerogen; thus, {sup 13}C NMR measures only the movable hydrocarbon content of the cores. In carbonates, the {sup 13}C spectrum also contains a carbonate powder pattern useful in quantifying inorganic carbon and distinguishing organic from carbonate carbon.

  17. Accurate quantitative 13C NMR spectroscopy: repeatability over time of site-specific 13C isotope ratio determination.

    PubMed

    Caytan, Elsa; Botosoa, Eliot P; Silvestre, Virginie; Robins, Richard J; Akoka, Serge; Remaud, Gérald S

    2007-11-01

    The stability over time (repeatability) for the determination of site-specific 13C/12C ratios at natural abundance by quantitative 13C NMR spectroscopy has been tested on three probes: enriched bilabeled [1,2-13C2]ethanol; ethanol at natural abundance; and vanillin at natural abundance. It is shown in all three cases that the standard deviation for a series of measurements taken every 2-3 months over periods between 9 and 13 months is equal to or smaller than the standard deviation calculated from 5-10 replicate measurements made on a single sample. The precision which can be achieved using the present analytical 13C NMR protocol is higher than the prerequisite value of 1-2 per thousand for the determination of site-specific 13C/12C ratios at natural abundance (13C-SNIF-NMR). Hence, this technique permits the discrimination of very small variations in 13C/12C ratios between carbon positions, as found in biogenic natural products. This observed stability over time in 13C NMR spectroscopy indicates that further improvements in precision will depend primarily on improved signal-to-noise ratio. PMID:17900175

  18. State-of-the-Art Direct 13C and Indirect 1H-[13C] NMR Spectroscopy In Vivo

    PubMed Central

    de Graaf, Robin A.; Rothman, Douglas L.; Behar, Kevin L.

    2013-01-01

    Carbon-13 NMR spectroscopy in combination with 13C-labeled substrate infusion is a powerful technique to measure a large number of metabolic fluxes non-invasively in vivo. It has been used to quantify glycogen synthesis rates, establish quantitative relationships between energy metabolism and neurotransmission and evaluate the importance of different substrates. All measurements can, in principle, be performed through direct 13C NMR detection or via indirect 1H-[13C] NMR detection of the protons attached to 13C nuclei. The choice for detection scheme and pulse sequence depends on the magnetic field strength, whereas substrate selection depends on the metabolic pathways that are studied. 13C NMR spectroscopy remains a challenging technique that requires several non-standard hardware modifications, infusion of 13C-labeled substrates and sophisticated processing and metabolic modeling. Here the various aspects of direct 13C and indirect 1H-[13C] NMR are reviewed with the aim of providing a practical guide. PMID:21919099

  19. A field and laboratory method for monitoring the concentration and isotopic composition of soil CO2.

    PubMed

    Breecker, Dan; Sharp, Zachary D

    2008-01-01

    The stable isotope composition of nmol size gas samples can be determined accurately and precisely using continuous flow isotope ratio mass spectrometry (IRMS). We have developed a technique that exploits this capability in order to measure delta13C and delta18O values and, simultaneously, the concentration of CO2 in sub-mL volume soil air samples. A sampling strategy designed for monitoring CO2 profiles at particular locations of interest is also described. This combined field and laboratory technique provides several advantages over those previously reported: (1) the small sample size required allows soil air to be sampled at a high spatial resolution, (2) the field setup minimizes sampling times and does not require powered equipment, (3) the analytical method avoids the introduction of air (including O2) into the mass spectrometer thereby extending filament life, and (4) pCO2, delta13C and delta18O are determined simultaneously. The reproducibility of measurements of CO2 in synthetic tank air using this technique is: +/-0.08 per thousand (delta13C), +/-0.10 per thousand (delta18O), and +/-0.7% (pCO2) at 5550 ppm. The reproducibility for CO2 in soil air is estimated as: +/-0.06 per thousand (delta13C), +/-0.06 per thousand (delta18O), and +/-1.6% (pCO2). Monitoring soil CO2 using this technique is applicable to studies concerning soil respiration and ecosystem gas exchange, the effect of elevated atmospheric CO2 (e.g. free air carbon dioxide enrichment) on soil processes, soil water budgets including partitioning evaporation from transpiration, pedogenesis and weathering, diffuse solid-earth degassing, and the calibration of speleothem and pedogenic carbonate delta13C values as paleoenvironmental proxies. PMID:18186546

  20. delta13C and water-use efficiency in Australian grasstrees and South African conifers over the last century.

    PubMed

    Swanborough, Perry W; Lamont, Byron B; February, Edmund C

    2003-07-01

    Annual or biannual time courses of plant delta13C (delta13C(p)) over the last century (70-100 years) were recorded for leafbases of four grasstrees (Xanthorrhoea preissii) at four sites in mediterranean Australia and wood of four conifers (Widdringtonia cedarbergensis) at two sites in mediterranean South Africa. There was a strong downward trend of 2-5.5(per thousand ) from 1935 to 1940 to the present in the eight plants. Trends were more variable from 1900 to 1940 with plants at two sites of each species showing an upward trend of 1-2.5 per thousand. Accepting that delta13C of the air (delta13C(a)) fell by almost 2 per thousand over the last century, the ratio of leaf intercellular CO2 to atmospheric CO2 (c(i)/c(a)) rose in five plants and remained unchanged in three over that period. Changes in c(i)/c(a) rather than delta13C(a) were more closely correlated with changes in delta13C(p) and accounted for 6.7-71.8% (22.6 c(i)/c(a)) and 28.2-93.3% (delta13C(a)) of the variation in delta13C(p). We doubt that possible changing patterns of rainfall, water availability, temperature, shade, air pollution or clearing for agriculture have contributed to the overall trend for c(i)/c(a) to rise over time. Instead, we provide evidence (concentrations of Fe and Mn in the grasstree leafbases) that decreasing photosynthetic capacity associated with falling nutrient availability due to the reduced occurrence of fire may have contributed to rising c(i)/c(a). Intrinsic water-use efficiency (W(i)) as a function of (c(a)-c(i)) usually increased linearly over the period, with the two exceptions explained by their marked increase in c(i)/c(a). We conclude that grasstrees may provide equivalent delta13C(p )and W(i) data to long-lived conifers and that their interpretation requires a consideration of the causes of variation in both c(i)/c(a )and delta13C(a). PMID:12728309

  1. Long-term trends in cellulose delta13 C and water-use efficiency of tropical Cedrela and Swietenia from Brazil.

    PubMed

    Hietz, Peter; Wanek, Wolfgang; Dünisch, Oliver

    2005-06-01

    Elevated CO(2) concentrations ([CO(2)]) affect plant water relations and photosynthesis, and the increase in atmospheric [CO(2)] over the past 100-200 years has been related to changes in stomatal density and the carbon isotope ratio (delta(13)C) in tree rings and leaves from herbarium specimens. Because many tropical trees do not produce annual growth rings and their wood is therefore difficult to date, no trends in delta(13)C of tropical trees have been reported. Wood from Cedrela odorata L. (tropical cedar) and Swietenia macrophylla King (bigleaf mahogany), which do produce annual rings, was collected from a primary rain forest in Aripuanã, Brazil (10 degrees 09' S, 59 degrees 26' W). We measured wood cellulose delta(13)C in 10-year growth increments from 37 Cedrela trees (between 11 and 151 years old in 2001) and 16 Swietenia trees (48-126 years old). A comparison of delta(13)C in cellulose of trees from different decades and of trees of different cambial ages showed that the amount of delta(13)C was largely related to the decade the wood was produced in, and not, or only to a minor extent, to tree age. Cellulose delta(13)C decreased from -26.0 to -27.3 per thousand in Cedrela and from -25.7 to -27.1 per thousand in Swietenia, with the largest changes occurring during the past 50 years. Based on these data and the trends in atmospheric [CO(2)] and delta(13)CO(2), we calculated that the internal [CO(2)] increased from about 220 to 260 ppm and that intrinsic water-use efficiency increased by 34% in Cedrela and by 52% in Swietenia. This may have implications for the water cycle and may explain the trend toward increased tree growth and turnover observed in some tropical forests. PMID:15805094

  2. C-13/C-12 ratio in methane from the flooded Amazon forest

    NASA Technical Reports Server (NTRS)

    Tyler, Stanley C.; Blake, Donald R.; Rowland, F. Sherwood

    1987-01-01

    The C1-C4 hydrocarbon concentrations and the C-13/C-12 ratio in CH4 detected in air samples collected in the Amazon region (3.5 deg S latitude and 5.9 deg W longitude) are analyzed. It is observed that the CH4 concentrations of each sample are enhanced over the background concentration for remote locations, and the C-13/C-12 ratio in this biogenic methane is depleted in C-13 relative to atmospheric CH4. It is concluded, from the C2-C4 hydrocarbon data, that minor yields of C2-C4 hyrocarbons are released coincident with CH4; however, the minor yields do not contribute to the regionally enhanced concentrations of hydrocarbons found in Amazonia and the global atmosphere release of C2-C4 compounds.

  3. Sensitivity-enhanced IPAP experiments for measuring one-bond 13C '- 13C α and 13C α- 1H α residual dipolar couplings in proteins

    NASA Astrophysics Data System (ADS)

    Ding, Keyang; Gronenborn, Angela M.

    2004-04-01

    Sensitivity-enhanced 2D IPAP experiments using the accordion principle for measuring one-bond 13C '- 13C α and 1H α- 13C α dipolar couplings in proteins are presented. The resolution of the resulting spectra is identical to that of the decoupled HSQC spectra and the sensitivity of the corresponding 1D acquisitions are only slightly lower than those obtained with 3D HNCO and 3D HN(COCA)HA pulse sequences due to an additional delay 2 Δ. For cases of limited resolution in the 2D 15N- 1H N HSQC spectrum the current pulse sequences can easily be modified into 3D versions by introducing a poorly digitized third dimension, if so desired. The experiments described here are a valuable addition to the suites available for determination of residual dipolar couplings in biological systems.

  4. Seasonal and interannual variability in 13C composition of ecosystem carbon fluxes in the U.S. Southern Great Plains

    NASA Astrophysics Data System (ADS)

    Torn, Margaret S.; Biraud, Sebastien C.; Still, Christopher J.; Riley, William J.; Berry, Joe A.

    2011-04-01

    The δ13C value of terrestrial CO2 fluxes (δbio) provides important information for inverse models of CO2 sources and sinks as well as for studies of vegetation physiology, C3 and C4 vegetation fluxes, and ecosystem carbon residence times. From 2002-2009, we measured atmospheric CO2 concentration and δ13C-CO2 at four heights (2 to 60 m) in the U.S. Southern Great Plains (SGP) and computed δbio weekly. This region has a fine-scale mix of crops (primarily C3 winter wheat) and C4 pasture grasses. δbio had a large and consistent seasonal cycle of 6-8‰. Ensemble monthly mean δbio ranged from -25.8 ± 0.4‰ (±SE) in March to -20.1 ± 0.4‰ in July. Thus, C3 vegetation contributed about 80% of ecosystem fluxes in winter-spring and 50% in summer-fall. In contrast, prairie-soil δ13C values were about -15‰, indicating that historically the region was dominated by C4 vegetation and had more positive δbio values. Based on a land-surface model, isofluxes (δbio× NEE) in this region have large seasonal amplitude because δbio and net ecosystem exchange (NEE) covary. Interannual variability in isoflux was driven by variability in NEE. The large seasonal amplitude in δbio and isoflux imply that carbon inverse analyses require accurate estimates of land cover and temporally resolved 13CO2 and CO2 fluxes.

  5. Quality assurance of PASADENA hyperpolarization for 13C biomolecules

    PubMed Central

    Hövener, Jan-Bernd; Chekmenev, Eduard Y.; Harris, Kent C.; Perman, William H.; Tran, Thao T.; Bhattacharya, Pratip

    2009-01-01

    Object Define MR quality assurance procedures for maximal PASADENA hyperpolarization of a biological 13C molecular imaging reagent. Materials and methods An automated PASADENA polarizer and a parahydrogen generator were installed. 13C enriched hydroxyethyl acrylate, 1-13C, 2,3,3-d3 (HEA), was converted to hyperpolarized hydroxyethyl propionate, 1-13C, 2,3,3-d3 (HEP) and fumaric acid, 1-13C, 2,3-d2 (FUM) to hyperpolarized succinic acid, 1-13C, 2,3-d2 (SUC), by reaction with parahydrogen and norbornadiene rhodium catalyst. Incremental optimization of successive steps in PASADENA was implemented. MR spectra and in vivo images of hyperpolarized 13C imaging agents were acquired at 1.5 and 4.7 T. Results Application of quality assurance (QA) criteria resulted in incremental optimization of the individual steps in PASADENA implementation. Optimal hyperpolarization of HEP of P = 20% was achieved by calibration of the NMR unit of the polarizer (B0 field strength ± 0.002 mT). Mean hyperpolarization of SUC, P = [15.3 ± 1.9]% (N = 16) in D2O, and P = [12.8 ± 3.1]% (N = 12) in H2O, was achieved every 5–8 min (range 13–20%). An in vivo 13C succinate image of a rat was produced. Conclusion PASADENA spin hyperpolarization of SUC to 15.3% in average was demonstrated (37,400 fold signal enhancement at 4.7 T). The biological fate of 13C succinate, a normally occurring cellular intermediate, might be monitored with enhanced sensitivity. PMID:19067009

  6. Study of Urban environmental quality through Isotopes δ13C

    NASA Astrophysics Data System (ADS)

    González-Sosa, E.; Mastachi-Loza, C.; Becerril-Piña, R.; Ramos-Salinas, N. M.

    2012-04-01

    Usually, trees with similar pH values on their bark develop epiphytes of similar species, the acidity to be a factor for growth. The aim of the study was evaluate the air quality through isotope δ13C in order to define the levels of environmental quality in the city of Queretaro, Mexico. In this work were collected at least 4 epiphytes positioned in trees of the species Prosopis Laevigata at 25 sites of Queretaro City. The samples were analyzed for trace elements with an inductively coupled plasma atomic emission spectroscopy (ICP). The collecting took place during dry period, in May and early rain June 2011 period, and on four sectors to identify the spatial distribution of pollution, using isotopic analysis of concentration of δ 13C. According with the results there are significant differences among the species in each of the sampled areas. The 5 February Avenue presented greater diversity and richness of δ13C, followed by those who were surveyed in the proximity of the UAQ and finally in the middle-east area. An average value of δ13C-17.92%, followed by those surveyed in the vicinity of the UAQ that correspond to sector I and II with an concentration of δ13C-17.55% and δ13C-17.22%, and finally the samples collected in trees scattered in the East-Sector II and IV with a value of δ13C-17.02% and δ13C-15.62%, respectively. Also were observed differences between the dry and wet period. It is likely that these results of δ 13C in moist period reflect the drag of the isotopes due to rain events that could mark a trend in the dilution of this element, however there is a trend in terms of abundance and composition of finding more impact in those species sampled in dry period, in May and early June 2011.

  7. Ar + CO2 and He + CO2 Plasmas in ASTRAL

    NASA Astrophysics Data System (ADS)

    Boivin, R. F.; Gardner, A.; Munoz, J.; Kamar, O.; Loch, S.

    2007-11-01

    Spectroscopy study of the ASTRAL helicon plasma source running Ar + CO2 and He + CO2 gas mixes is presented. ASTRAL produces plasmas with the following parameters: ne = 10^10 - 10^13 cm-3, Te = 2 - 10 eV and Ti = 0.03 - 0.5 eV, B-field <= 1.3 kGauss, rf power <= 2 kWatt. A 0.33 m scanning monochromator is used for this study. Using Ar + CO2 gas mixes, very different plasmas are observed as the concentration of CO2 is changed. At low CO2 concentration, the bluish plasma is essentially atomic and argon transitions dominate the spectra. Weak C I and O I lines are present in the 750 - 1000 nm range. At higher CO2 concentration, the plasma becomes essentially molecular and is characterized by intense, white plasma columns. Here, spectra are filled with molecular bands (CO2, CO2^+, CO and CO^+). Limited molecular dissociative excitation processes associated with the production of C I and O I emission are also observed. On the other hand, He + CO2 plasmas are different. Here, rf matches are only possible at low CO2 concentration. Under these conditions, the spectra are characterized by strong C I and O I transitions with little or no molecular bands. Strong dissociative processes observed in these plasmas can be link to the high Te associated with He plasmas. An analysis of the spectra with possible scientific and industrial applications will be presented.

  8. Halloysite Nanotubes Capturing Isotope Selective Atmospheric CO2

    PubMed Central

    Jana, Subhra; Das, Sankar; Ghosh, Chiranjit; Maity, Abhijit; Pradhan, Manik

    2015-01-01

    With the aim to capture and subsequent selective trapping of CO2, a nanocomposite has been developed through selective modification of the outer surface of the halloysite nanotubes (HNTs) with an organosilane to make the nanocomposite a novel solid-phase adsorbent to adsorb CO2 from the atmosphere at standard ambient temperature and pressure. The preferential adsorption of three major abundant isotopes of CO2 (12C16O2, 13C16O2, and 12C16O18O) from the ambient air by amine functionalized HNTs has been explored using an optical cavity-enhanced integrated cavity output spectroscopy. CO2 adsorption/desorption cycling measurements demonstrate that the adsorbent can be regenerated at relatively low temperature and thus, recycled repeatedly to capture atmospheric CO2. The amine grafted halloysite shows excellent stability even in oxidative environments and has high efficacy of CO2 capture, introducing a new route to the adsorption of isotope selective atmospheric CO2. PMID:25736700

  9. Using Position-Specific 13C and 14C Labeling and 13C-PLFA Analysis to Assess Microbial Transformations of Free Versus Sorbed Alanine

    NASA Astrophysics Data System (ADS)

    Apostel, C.; Herschbach, J.; Bore, E. K.; Kuzyakov, Y.; Dippold, M. A.

    2015-12-01

    Sorption of charged or partially charged low molecular weight organic substances (LMWOS) to soil mineral surfaces delays microbial uptake and therefore mineralization of LMWOS to CO2, as well as all other biochemical transformations. We used position-specific labeling, a tool of isotope applications novel to soil sciences, to compare the transformation mechanisms of sorbed and non-sorbed alanine in soil. Alanine as an amino acid links C- and N-cycles in soil and therefore is a model substance for the pool of LMWOS. To assess transformations of sorbed alanine, we added position-specific and uniformly 13C and 14C labeled alanine tracer to soil that had previously been sterilized by γ-radiation. The labeled soil was added to non-sterilized soil from the same site and incubated. Soil labeled with the same tracers without previous sorption was prepared and incubated as well. We captured the respired CO2 and determined its 14C-activity at increasing time intervals. The incorporation of 14C into microbial biomass was determined by chloroform fumigation extraction (CFE), and utilization of individual C positions by distinct microbial groups was evaluated by 13C-phospholipid fatty acid analysis (PLFA). A dual peak in the respired CO2 revealed two sorption mechanisms. To compare the fate of individual C atoms independent of their concentration and pool size in soil, we applied the divergence index (DI). The DI reveals the convergent or divergent behavior of C from individual molecule positions during microbial utilization. Alanine C-1 position was mainly oxidized to CO2, while its C-2 and C-3 were preferentially incorporated in microbial biomass and PLFA. This indicates that sorption by the COOH group does not protect this group from preferential oxidation. Microbial metabolism was determinative for the preferential oxidation of individual molecule positions. The use of position-specific labeling revealed mechanisms and kinetics of microbial utilization of sorbed and non

  10. Monitoring of near surface CO2

    NASA Astrophysics Data System (ADS)

    Faber, E.; Möller, I.; Teschner, M.; Poggenburg, J.; Spickenbom, K.; Schulz, H. J.

    2009-04-01

    Monitoring of near surface CO2 ECKHARD FABER1, INGO MÖLLER1, MANFRED TESCHNER1, JÜRGEN POGGENBURG1, KAI SPICKENBOM1, HANS-MARTIN SCHULZ1,2 1Bundesanstalt für Geowissenschaften und Rohstoffe (BGR), Stilleweg 2, D-30655 Hannover, e.faber@bgr.de 2present adress: GeoForschungsZentrum Potsdam (GFZ), Telegrafenberg, D-14473 Potsdam Underground gas storage and sequestration of carbon dioxide is one of the methods to reduce the input of antropogenic CO2 into the atmosphere and its greenhouse effect. Storage of CO2 is planned in depleted reservoirs, in aquifers and in salt caverns. Storage sites must have very small leakage rates to safely store the CO2 for centuries. Thus, a careful investigation and site selection is crucial. However, any leakage of CO2 to the surface is potentially dangerous for humans and environment. Therefore, instruments and systems for the detection of any CO2 escaping the storage sites and reaching the atmosphere have to be developed. Systems to monitor gases in deep wells, groundwater and surface sediments for leaking CO2 are developed, tested and are contnuously improved. Our group is mainly analysing CO2 in shallow (down to 3 m) soil samples using automatically operating monitoring systems. The systems are equipped with sensors to measure CO2 (and other gases) concentrations and other environmental parameters (atmospheric pressure, ambient and soil temperatures, etc.). Data are measured in short intervals (minute to subminute), are stored locally and are transferred by telemetrical systems into the BGR laboratory (Weinlich et al., 2006). In addition to soil gases monitoring systems technical equipment is available for continuous underwater gas flow measurements. Several of those monitoring systems are installed in different areas like Czech Republic, Austria, Italy and Germany. To detect any leaking gas from a sequestration site after CO2 injection, the naturally existing CO2 concentration (before injection) must be known. Thus, the natural

  11. Diploptene δ13C values from contemporary thermokarst lake sediments show complex spatial variation

    NASA Astrophysics Data System (ADS)

    Davies, Kimberley L.; Pancost, Richard D.; Edwards, Mary E.; Anthony, Katey M. Walter; Langdon, Peter G.; Chaves Torres, Lidia

    2016-05-01

    Cryospheric changes in northern high latitudes are linked to significant greenhouse gas flux to the atmosphere, for example, methane that originates from organic matter decomposition in thermokarst lakes. The set of pathways that link methane production in sediments, via oxidation in the lake system, to the flux of residual methane to the atmosphere is complex and exhibits temporal and spatial variation. The isotopic signal of bacterial biomarkers (hopanoids, e.g. diploptene) in sediments has been used to identify contemporary ocean-floor methane seeps and, in the geological record, periods of enhanced methane production (e.g. the PETM). The biomarker approach could potentially be used to assess temporal changes in lake emissions through the Holocene via the sedimentary biomarker record. However, there are no data on the consistency of the signal of isotopic depletion in relation to source or on the amount of noise (unexplained variation) in biomarker values from modern lake sediments. We assessed methane oxidation as represented by the isotopic signal of biomarkers from methane oxidising bacteria (MOB) in multiple surface sediment samples in three distinct areas known to emit varying levels of methane in two shallow Alaskan thermokarst lakes. Diploptene was present and had δ13C values lower than -38 ‰ in all sediments analysed, suggesting methane oxidation was widespread. However, there was considerable variation in δ13C values within each area. The most 13C-depleted diploptene was found in an area of high methane ebullition in Ace Lake (diploptene δ13C values between -68.2 and -50.1 ‰). In contrast, significantly higher diploptene δ13C values (between -42.9 and -38.8 ‰) were found in an area of methane ebullition in Smith Lake. δ13C values of diploptene between -56.8 and -46.9 ‰ were found in the centre of Smith Lake, where ebullition rates are low but diffusive methane efflux occurs. The small-scale heterogeneity of the samples may reflect patchy

  12. Method for tracing simulated CO2 leak in terrestrial environment with a 13CO2 tracer

    NASA Astrophysics Data System (ADS)

    Moni, Christophe; Rasse, Daniel

    2013-04-01

    Facilities for the geological storage of carbon dioxide (CO2) as part of carbon capture and storage (CCS) schemes will be designed to prevent any leakage from the defined 'storage complex'. However, developing regulations and guidance throughout the world (e.g. the EC Directive and the USEPA Vulnerability Evaluation Framework) recognize the importance of assessing the potential for environmental impacts from CO2 storage. RISCS, a European (FP7) project, aims to improve understanding of those impacts that could plausibly occur in the hypothetical case that unexpected leakage occurs. As part of the RISCS project the potential impacts that an unexpected CO2 leaks might have on a cropland ecosystems was investigated. A CO2 exposure field experiment based on CO2 injection at 85 cm depth under an oats culture was designed. To facilitate the characterization of the simulated leaking zone the gas used for injection was produced from natural gas and had a δ13C of -46‰. The aim of the present communication is to depict how the injected gas was traced within the soil-vegetation-atmosphere continuum using 13CO2 continuous cavity ring-down spectrometry (CRDS). Four subsurface experimental injection plots (6m x 3m) were set up. In order to test the effects of different intensity of leakage, the field experiment was designed as to create a longitudinal CO2 gradient for each plot. For this purpose gas supply pipes were inserted at one extremity of each plot at the base of a 45 cm thick layer of sand buried 40 cm below the surface under the clayey plough layer of Norwegian moraine soils. Soil CO2 concentration and isotopic signature were punctually recorded: 1) in the soil at 20 cm depth at 6 positions distributed on the central transect, 2) at the surface following a (50x50 cm) grid sampling pattern, and 3) in the canopy atmosphere at 10, 20, 30 cm along three longitudinal transects (seven sampling point per transect). Soil CO2 fluxes and isotopic signature were finally

  13. Strategy for Enhancement of (13)C-Photo-CIDNP NMR Spectra by Exploiting Fractional (13)C-Labeling of Tryptophan.

    PubMed

    Eisenreich, Wolfgang; Joshi, Monika; Illarionov, Boris; Kacprzak, Sylwia; Lukaschek, Michail; Kothe, Gerd; Budisa, Nediljko; Fischer, Markus; Bacher, Adelbert; Weber, Stefan

    2015-10-29

    The photo-CIDNP effect has proven to be useful to strongly enhance NMR signals of photochemically active proteins simply by irradiation with light. The evolving characteristic patterns of enhanced absorptive and emissive NMR lines can be exploited to elucidate the photochemistry and photophysics of light-driven protein reactions. In particular, by the assignment of (13)C NMR resonances, redox-active amino acids may be identified and thereby electron-transfer pathways unraveled, in favorable cases, even with (13)C at natural abundance. If signal enhancement is weak, uniform (13)C isotope labeling is traditionally applied to increase the signal strength of protein (13)C NMR. However, this typically leads to cross relaxation, which transfers light-induced nuclear-spin polarization to adjacent (13)C nuclei, thereby preventing an unambiguous analysis of the photo-CIDNP effect. In this contribution, two isotope labeling strategies are presented; one leads to specific but ubiquitous (13)C labeling in tryptophan, and the other is based on fractional isotope labeling affording sets of isotopologs with low probability of next-neighbor isotope accumulation within individual tryptophan molecules. Consequently, cross relaxation is largely avoided while the signal enhancement by (13)C enrichment is preserved. This results in significantly simplified polarization patterns that are easier to analyze with respect to the generation of light-generated nuclear-spin polarization. PMID:26244593

  14. IRMS detection of testosterone manipulated with 13C labeled standards in human urine by removing the labeled 13C.

    PubMed

    Wang, Jingzhu; Yang, Rui; Yang, Wenning; Liu, Xin; Xing, Yanyi; Xu, Youxuan

    2014-12-10

    Isotope ratio mass spectrometry (IRMS) is applied to confirm testosterone (T) abuse by determining the carbon isotope ratios (δ(13)C value). However, (13)C labeled standards can be used to control the δ(13)C value and produce manipulated T which cannot be detected by the current method. A method was explored to remove the (13)C labeled atom at C-3 from the molecule of androsterone (Andro), the metabolite of T in urine, to produce the resultant (A-nor-5α-androstane-2,17-dione, ANAD). The difference in δ(13)C values between Andro and ANAD (Δδ(13)CAndro-ANAD, ‰) would change significantly in case manipulated T is abused. Twenty-one volunteers administered T manipulated with different (13)C labeled standards. The collected urine samples were analyzed with the established method, and the maximum value of Δδ(13)CAndro-ANAD post ingestion ranged from 3.0‰ to 8.8‰. Based on the population reference, the cut-off value of Δδ(13)CAndro-ANAD for positive result was suggested as 1.2‰. The developed method could be used to detect T manipulated with 3-(13)C labeled standards. PMID:25441891

  15. Biosynthetic uniform 13C,15N-labelling of zervamicin IIB. Complete 13C and 15N NMR assignment.

    PubMed

    Ovchinnikova, Tatyana V; Shenkarev, Zakhar O; Yakimenko, Zoya A; Svishcheva, Natalia V; Tagaev, Andrey A; Skladnev, Dmitry A; Arseniev, Alexander S

    2003-01-01

    Zervamicin IIB is a member of the alpha-aminoisobutyric acid containing peptaibol antibiotics. A new procedure for the biosynthetic preparation of the uniformly 13C- and 15N-enriched peptaibol is described This compound was isolated from the biomass of the fungus-producer Emericellopsis salmosynnemata strain 336 IMI 58330 obtained upon cultivation in the totally 13C, 15N-labelled complete medium. To prepare such a medium the autolysed biomass and the exopolysaccharides of the obligate methylotrophic bacterium Methylobacillus flagellatus KT were used. This microorganism was grown in totally 13C, 15N-labelled minimal medium containing 13C-methanol and 15N-ammonium chloride as the only carbon and nitrogen sources. Preliminary NMR spectroscopic analysis indicated a high extent of isotope incorporation (> 90%) and led to the complete 13C- and 15N-NMR assignment including the stereospecific assignment of Aib residues methyl groups. The observed pattern of the structurally important secondary chemical shifts of 1H(alpha), 13C=O and 13C(alpha) agrees well with the previously determined structure of zervamicin IIB in methanol solution. PMID:14658801

  16. 13C-tryptophan breath test detects increased catabolic turnover of tryptophan along the kynurenine pathway in patients with major depressive disorder

    PubMed Central

    Teraishi, Toshiya; Hori, Hiroaki; Sasayama, Daimei; Matsuo, Junko; Ogawa, Shintaro; Ota, Miho; Hattori, Kotaro; Kajiwara, Masahiro; Higuchi, Teruhiko; Kunugi, Hiroshi

    2015-01-01

    Altered tryptophan–kynurenine (KYN) metabolism has been implicated in major depressive disorder (MDD). The l-[1-13C]tryptophan breath test (13C-TBT) is a noninvasive, stable-isotope tracer method in which exhaled 13CO2 is attributable to tryptophan catabolism via the KYN pathway. We included 18 patients with MDD (DSM-IV) and 24 age- and sex-matched controls. 13C-tryptophan (150 mg) was orally administered and the 13CO2/12CO2 ratio in the breath was monitored for 180 min. The cumulative recovery rate during the 180-min test (CRR0–180; %), area under the Δ13CO2-time curve (AUC; %*min), and the maximal Δ13CO2 (Cmax; %) were significantly higher in patients with MDD than in the controls (p = 0.004, p = 0.008, and p = 0.002, respectively). Plasma tryptophan concentrations correlated negatively with Cmax in both the patients and controls (p = 0.020 and p = 0.034, respectively). Our results suggest that the 13C-TBT could be a novel biomarker for detecting a subgroup of MDD with increased tryptophan–KYN metabolism. PMID:26524975

  17. Stable carbon isotope ratio in atmospheric CO2 collected by new diffusive devices.

    PubMed

    Proto, Antonio; Cucciniello, Raffaele; Rossi, Federico; Motta, Oriana

    2014-02-01

    In this paper, stable carbon isotope ratios (δ (13)C) were determined in the atmosphere by using a Ca-based sorbent, CaO/Ca12Al14O33 75:25 w/w, for passively collecting atmospheric CO2, in both field and laboratory experiments. Field measurements were conducted in three environments characterized by different carbon dioxide sources. In particular, the environments under consideration were a rather heavily trafficked road, where the source of CO2 is mostly vehicle exhaust, a rural unpolluted area, and a private kitchen where the major source of CO2 was gas combustion. Samplers were exposed to the free atmosphere for 3 days in order to allow collection of sufficient CO2 for δ(13)C analysis, then the collected CO2 was desorbed from the adsorbent with acid treatment, and directly analyzed by nondispersive infrared (NDIR) instrument. δ (13)C results confirmed that the samplers collected representative CO2 samples and no fractionation occurred during passive trapping, as also confirmed by an appositely designed experiment conducted in the laboratory. Passive sampling using CaO/Ca12Al14O33 75:25 w/w proved to be an easy and reliable method to collect atmospheric carbon dioxide for δ (13)C analysis in both indoor and outdoor places. PMID:24281683

  18. Harding Iceland spar: a new delta 18O-delta 13C carbonate standard for hydrothermal minerals.

    USGS Publications Warehouse

    Landis, G.P.

    1983-01-01

    An isotopically homogenous calcite, Iceland spar from the Iceberg claim, near the Harding pegmatite of N New Mexico, has delta 18O +11.78 + or - 0.07per mille (=+22.15per mille for CO2) and delta 13C -4.80 + or - 0.02per mille and has been prepared in quantities suitable for use as a working standard in MS.-R.A.H.

  19. Seasonal and interannual variations of atmospheric CO2 and climate

    USGS Publications Warehouse

    Dettinger, M.D.; Ghil, M.

    1998-01-01

    Interannual variations of atmospheric CO2 concentrations at Mauna Loa are almost masked by the seasonal cycle and a strong trend; at the South Pole, the seasonal cycle is small and is almost lost in the trend and interannual variations. Singular-spectrum analysis (SSA) issued here to isolate and reconstruct interannual signals at both sites and to visualize recent decadal changes in the amplitude and phase of the seasonal cycle. Analysis of the Mauna Loa CO2 series illustrates a hastening of the CO2 seasonal cycle, a close temporal relation between Northern Hemisphere (NH) mean temperature trends and the amplitude of the seasonal CO2 cycle, and tentative ties between the latter and seasonality changes in temperature over the NH continents. Variations of the seasonal CO2 cycle at the South Pole differ from those at Mauna Loa: it is phase changes of the seasonal cycle at the South Pole, rather than amplitude changes, that parallel hemispheric and global temperature trends. The seasonal CO2 cycles exhibit earlier occurrences of the seasons by 7 days at Mauna Loa and 18 days at the South Pole. Interannual CO2 variations are shared at the two locations, appear to respond to tropical processes, and can be decomposed mostly into two periodicities, around (3 years)-1 and (4 years)-1, respectively. Joint SSA analyses of CO2 concentrations and tropical climate indices isolate a shared mode with a quasi-triennial (QT) period in which the CO2 and sea-surface temperature (SST) participation are in phase opposition. The other shared mode has a quasi-quadrennial (QQ) period and CO2 variations are in phase with the corresponding tropical SST variations throughout the tropics. Together these interannual modes exhibit a mean lag between tropical SSTs and CO2 variations of about 6-8 months, with SST leading. Analysis of the QT and QQ signals in global gridded SSTs, joint SSA of CO2 and ??13C isotopic ratios, and SSA of CO2 and NH-land temperatures indicate that the QT variations in

  20. Delta Ray Road Trip: Measuring δ13C, δ18O and concentration of CO2 across Canada

    NASA Astrophysics Data System (ADS)

    Jost, Hansjurg; Stow, Peter; Mandic, Luka

    2016-04-01

    The Delta Ray Road Trip was conceived to demonstrate that there is now an instrument capable of being taken to the sample collection point and in fact taken to the samples along an 8000 km route across Canada. The concept was to drive a Thermo Scientific Delta Ray Isotope Ratio Infrared Spectrometer from coast to coast across the 2nd largest country in the world. This route took the Delta Ray from a coastal environment, through forests, arable farm land, urban and industrial centres, across prairies and over mountains. The vehicle was a standard RV with as few modifications as possible. Along the way there were stops at most of the major universities in Canada as well as the AGU-GAC-MAC conference in Montreal, where indoor measurements were performed. Date was uploaded in quasi realtime to a website. We will present data acquired during the trip and discuss the lessons learned.

  1. Mapping Mantle Mixing and the Extent of Superplume Influence Using He-Ne-Ar-CO2-N2 Isotopes: The Case of the East Africa Rift System

    NASA Astrophysics Data System (ADS)

    Hilton, D. R.; Halldorsson, S. A.; Scarsi, P.; Castillo, P.; Abebe, T.; Kulongoski, J. T.

    2014-12-01

    Earth's mantle possesses distinct and variable volatile characteristics as sampled by magmatic activity in different tectonic environments. In general, trace element depleted mid-ocean ridge basalts, with low Sr and Pb isotope values (but high ɛNd and ɛHf), release mantle-derived noble gases characterised by 3He/4He ~8 ± 1RA, (21Ne/22Ne)ex ~0.06 and 40Ar/36Ar ≥ 10,000 with CO2 and N2 having δ13C~-5‰ and δ15N ~-5‰, respectively. In contrast, enriched intraplate lavas possess higher 3He/4He (up to 50RA), lower (21Ne/22Ne)ex ~0.035 and 40Ar/36Ar ≤ 10,000 with generally higher but variable δ13C and δ15N. These isotopic attributes of mantle-derived volatiles can be exploited to map the extent, and mixing characteristics, of enriched (plume) mantle with depleted asthenospheric mantle ± the effects of over-riding lithosphere and/or crust. The East African Rift System (EARS) is superimposed upon two massive plateaux - the Ethiopia and Kenya domes - regarded as geophysical manifestations of a superplume source, a huge thermochemical anomaly originated at the core-mantle boundary and providing dynamic support for the plateaux. We present new volatile isotopic and relative abundance data (on the same samples) for geothermal fluids (He-CO2-N2), lavas (He-Ne-Ar) and xenoliths (He-Ne-Ar-CO2-N2) which provide an unprecedented overview of the distribution of mantle volatiles of the Ethiopia Dome, from the Red Sea via the Afar region and Main Ethiopian Rift (MER) to the Turkana Depression. Notably, peaks in geothermal fluid 3He/4He (16RA) and δ15N (+6.5‰) are coincident within the MER but the maximum δ13C (-0.78‰) lies ~100 km to the south. Highs in 3He/4He (14RA), δ13C (~-1‰) and δ15N (+3.4‰) for mafic crystals occur in the Afar region ~ 500km to the north. We assess the significance of the off-set in these volatile isotope signals, for sampling volatile heterogeneity in the plume source and/or the relative sensitivity of different volatiles to

  2. 13C-18O bonding (Δ47) in deep-sea corals: a calibration study

    NASA Astrophysics Data System (ADS)

    Kimball, J. B.; Tripati, A.; Dunbar, R. B.; Eagle, R.

    2013-12-01

    Deep-sea corals are a potentially valuable archive of temperature in intermediate and deep waters, regions for which a paucity of temperature data exists. These archives could give valuable insight into the natural variability of areas of the ocean that play an active role in large-scale climate dynamics. Due to significant 'vital effects' (i.e., non-equilibrium mineral compositions) in δ18O, however, deep-sea coral have been challenging to develop as a paleotemperature proxy. Clumped-isotope paleothermometry is a new method that may circumvent some of the known complications with δ18O paleotemperature analysis in deep-sea coral. This geothermometer is based on the ordering of heavy 13C-18O ';clumps' in carbonate minerals. Initial calibration studies have shown that the method is independent from the solution chemistry of the precipitating fluids as well as 'vital effects' in deep-sea corals and other types of carbonates. Some kinetic effects have been observed in tropical corals and speleothems. Here we report new data in order to further develop clumped isotopes as a paleothermometer in deep-sea corals as well as to investigate taxon-specific effects. 13C-18O bond ordering was analyzed in live-collected scleractinian (Enallopsammia sp.) and gorgonian (Isididae and Coralliidae) deep-sea corals. We determined mass 47 anomalies in samples (Δ47), which refers to the parts per thousand excess of 13C-18O-16O in CO2 produced on acid digestion of a sample, relative to the amount predicted to be present if isotopes were randomly distributed amongst all CO2 isotopologues. Measured Δ47 values were compared to in situ temperatures and the relationship between Δ47 and temperature was determined for each group to investigate taxon-specific effects.

  3. Global patterns in leaf 13C discrimination and implications for studies of past and future climate.

    PubMed

    Diefendorf, Aaron F; Mueller, Kevin E; Wing, Scott L; Koch, Paul L; Freeman, Katherine H

    2010-03-30

    Fractionation of carbon isotopes by plants during CO(2) uptake and fixation (Delta(leaf)) varies with environmental conditions, but quantitative patterns of Delta(leaf) across environmental gradients at the global scale are lacking. This impedes interpretation of variability in ancient terrestrial organic matter, which encodes climatic and ecological signals. To address this problem, we converted 3,310 published leaf delta(13)C values into mean Delta(leaf) values for 334 woody plant species at 105 locations (yielding 570 species-site combinations) representing a wide range of environmental conditions. Our analyses reveal a strong positive correlation between Delta(leaf) and mean annual precipitation (MAP; R(2) = 0.55), mirroring global trends in gross primary production and indicating stomatal constraints on leaf gas-exchange, mediated by water supply, are the dominant control of Delta(leaf) at large spatial scales. Independent of MAP, we show a lesser, negative effect of altitude on Delta(leaf) and minor effects of temperature and latitude. After accounting for these factors, mean Delta(leaf) of evergreen gymnosperms is lower (by 1-2.7 per thousand) than for other woody plant functional types (PFT), likely due to greater leaf-level water-use efficiency. Together, environmental and PFT effects contribute to differences in mean Delta(leaf) of up to 6 per thousand between biomes. Coupling geologic indicators of ancient precipitation and PFT (or biome) with modern Delta(leaf) patterns has potential to yield more robust reconstructions of atmospheric delta(13)C values, leading to better constraints on past greenhouse-gas perturbations. Accordingly, we estimate a 4.6 per thousand decline in the delta(13)C of atmospheric CO(2) at the onset of the Paleocene-Eocene Thermal Maximum, an abrupt global warming event approximately 55.8 Ma. PMID:20231481

  4. Natural abundance and 13C-enriched characterisation of atmospheric methane uptake in a forest soil

    NASA Astrophysics Data System (ADS)

    Maxfield, Peter; Hornibrook, Edward; Evershed, Richard

    2013-04-01

    Whilst much attention is focused on CH4 emission inventories, CH4 sinks are sometimes overlooked and not accurately accounted for in national budgets. Two primary reasons for this disjunction include uncertainties about the magnitude and mechanism of terrestrial CH4 oxidation, and an under-appreciation of the quantity of CH4 that is removed from the atmosphere by microorganisms. These uncertainties in part are caused by a lack of high-resolution field data that quantify microbial soil CH4 sink. To fully characterize the soil CH4 sink, isotopic fractionation of CH4during uptake and the fate of CH4 carbon following oxidation by soil microorganisms should be quantified in addition to CH4 fluxes. Here we report on field tests studying CH4 uptake in soil using a Picarro G2201-i cavity ringdown spectrometer (CRDS). Short term atmospheric CH4 uptake was continuously measured in a forest soil in Leigh Woods, UK where the soil methanotrophic community and soil CH4 uptake kinetic isotopic effect (KIE) had been previously quantified using stable isotope probing and conventional stable isotope analysis techniques (Maxfield et al., 2008). Two methodological approaches were tested: (i) direct measurement of the soil CH4 uptake KIE at subambient CH4 concentrations, and (ii) methanotrophic carbon conversion efficiency (CCE) where CCE was evaluated through monitoring the direct conversion of 13C-labelled CH4 to 13C-labelled CO2. The suitability of the G2201-i analyzer as a continuous isotopic CH4 and CO2 analyzer for use at both subambient CH4 concentrations and high 13C-enrichments will be discussed. Maxfield, P.J., Evershed, R.P. and Hornibrook, E.R.C. (2008) Physical and biological controls on the in situ kinetic isotope effect associated with oxidation of atmospheric CH4 in mineral soils. Environmental Science & Technology, 42, 7824-7830.

  5. Using a laser-based CO2 carbon isotope analyser to investigate gas transfer in geological media

    NASA Astrophysics Data System (ADS)

    Guillon, S.; Pili, E.; Agrinier, P.

    2012-05-01

    CO2 stable carbon isotopes are very attractive in environmental research to investigate both natural and anthropogenic carbon sources. Laser-based CO2 carbon isotope analysis provides continuous measurement at high temporal resolution and is a promising alternative to isotope ratio mass spectrometry (IRMS). We performed a thorough assessment of a commercially available CO2 Carbon Isotope Analyser (CCIA DLT-100, Los Gatos Research) that allows in situ measurement of δ 13C in CO2. Using a set of reference gases of known CO2 concentration and carbon isotopic composition, we evaluated the precision, long-term stability, temperature sensitivity and concentration dependence of the analyser. Despite good precision calculated from Allan variance (5.0 ppm for CO2 concentration, and 0.05 ‰ for δ 13C at 60 s averaging), real performances are altered by two main sources of error: temperature sensitivity and dependence of δ 13C on CO2 concentration. Data processing is required to correct for these errors. Following application of these corrections, we achieve an accuracy of 8.7 ppm for CO2 concentration and 1.3 ‰ for δ 13C, which is worse compared to mass spectrometry performance, but still allowing field applications. With this portable analyser we measured CO2 flux degassed from rock in an underground tunnel. The obtained carbon isotopic composition agrees with IRMS measurement, and can be used to identify the carbon source.

  6. Sources of excess CO2 in Greenland ice cores

    NASA Astrophysics Data System (ADS)

    Jenk, T. M.; Rubino, M.; Etheridge, D. M.; Bigler, M.; Blunier, T.

    2012-12-01

    Analysis of air extracted from bubbles of Greenland ice show higher CO2 concentrations compared to coeval data from Antarctica with unexpected high variations of several ppm CO2 in adjacent samples. Both offset and variations are too large to be of atmospheric origin such as the inter-hemispheric gradient and can also not be explained by analytical uncertainties. Higher ice temperatures and impurity content favour post depositional processes such as reactions between the contained chemical species; this could explain enhanced variability and higher CO2 concentrations in Greenlandic compared to Antarctic ice. Various chemical reaction mechanisms leading to such CO2 in-situ production have been proposed (i.e. acidification of carbonates, oxidation of aldehydes and photodecarboxilation of humic like substances). We tested the above hypotheses combining analysis of CO2, δ13C-CO2 and chemical impurities in samples of various age and depth resolution including three Greenlandic sites (Eurocore, GRIP, NGRIP) which allowed quantification of inorganic and organic source contribution to the observed excess CO2 by using an isotopic mass balance model. The model output was investigated by comparison to the reaction-specific tracers of chemical impurities. In agreement with previous studies, our results suggest that the amount of excess CO2 in Greenland ice increases with time. We find the isotopic signature of the excess CO2 to have a more negative δ13C compared to the coeval atmospheric value. The isotopic mass balance model attributes the excess CO2 to a combination of organic and inorganic sources. The contribution from the organic source is dominant and increases with time, pointing to ongoing production in the ice for more than 1000 years. The contribution of the carbonate source is much smaller, independent of the age of the ice and tendentially enhanced in layers associated with high peaks of dust concentrations. The mechanisms and kinetics of the involved processes

  7. Parallel δ 13C and Conifer Physiognomic Trends Across the Triassic-Jurassic Boundary

    NASA Astrophysics Data System (ADS)

    Whiteside, J. H.; Olsen, P. E.; Sambrotto, R. N.; Cornet, B.

    2003-12-01

    The Triassic-Jurassic mass extinction event ( ˜200 Ma) had a profound effect on biotic evolution, and herein we describe trends in cheirolepidaceous conifer leaf physiognomy from the Pangean tropics (present northeastern USA) that at least broadly parallel a negative δ 13C excursion recorded in the same strata. The physiognomic changes appear at an abrupt (<10 ky) negative carbon isotope excursion (1) synchronous with a previously described palynological extinction level, fern spike, and Ir anomaly (2), and continue through a prolonged negative excursion, lasting 900 ky (through all three CAMP basaltic extrusive events), encompassing most of the Hettangian age. The physiognomic changes seen in the cheirolepidaceous conifer leafy shoot forms Brachyphyllum and Pagiophyllum through the δ 13C excursions include primarily the development of microphyllous leaves with thickened cuticle and sunken papillate stomata (3). These floral modifications are consistent with intense thermal stress plausibly due to very high atmospheric CO2 concentrations and corroborate McElwain's (4) thermal damage hypothesis for the Triassic-Jurassic transition that was originally based on different plant taxa from the higher Pangean latitudes in present Greenland and Sweden. Subsequently, a 2- to 5-fold increase in the area of leafy shoots in strata of latest Hettangian age suggest a return to lower thermal stress levels perhaps due to lower CO2, despite the fact that eastern North America continued to drift into more arid latitudes. The floral physiognomic changes associated with the negative δ 13C excursion and likely very elevated CO2 levels is in many ways a microcosm of the Mesozoic in which the dominance of cheiroleps apparently overlaps with the highest CO2 levels of the Mesozoic (5). References. (1) Whiteside JH, Olsen PE, Sambrotto RN. 2003. Geol. Soc. Amer. Abst. Prog. (in press). (2) Olsen PE et al., Science 296:1305-1307 (3) Cornet B. 1989. in Olsen PE, Schlische RW, Gore PJW

  8. The sources and sinks of CO2 in caves under mixed woodland and grassland vegetation

    NASA Astrophysics Data System (ADS)

    Breecker, Daniel O.; Payne, Ashley E.; Quade, Jay; Banner, Jay L.; Ball, Carolyn E.; Meyer, Kyle W.; Cowan, Brian D.

    2012-11-01

    We measured concentrations and stable carbon isotope compositions of carbon dioxide in the atmospheres of three caves in central Texas and one cave in southern Arizona in order to identify CO2 sources and sinks. The vegetation above the caves studied is either savannah (two caves, above which vegetation has been minimally disturbed) or discrete patches of grassland and woodland (two caves, above which vegetation has been highly disturbed). We tested two hypotheses concerning CO2 in the cave atmospheres: (1) cave ventilation by tropospheric air is the primary sink for CO2 and (2) CO2 is primarily derived from the deepest rooting plants growing above the caves. Within caves, we monitored CO2 at individual locations on monthly and daily time-scales and measured CO2 along transects with increasing distance from the cave entrances. We also measured CO2 in the pore spaces of soils under grasses and trees above each of the caves. We calculated δ13C values of respired CO2 (δ13Cr) for all gas samples using measured δ13C values and CO2 concentrations. We then identified the sources of cave CO2 by comparing cave-air and soil CO2δ13Cr values. At all locations in each Texas cave, CO2 concentrations were highest (lowest) and δ13C values were lowest (highest) during the summer (winter). Cave-air CO2 concentrations consistently increased and δ13C values consistently decreased with distance from the cave entrances. Similar but smaller magnitude seasonal variations in CO2 concentrations occurred in the Arizona cave and no seasonal or spatial variation in the δ13C of cave-air CO2 was observed. The mean δ13Cr values of CO2 in soils under grass were 3.5-4.5‰ higher than the δ13Cr values of CO2 in soils under trees. In the caves under savannah, mean δ13Cr values of cave-air CO2 (-24‰ in both caves) were within 1‰ of the mean δ13Cr values of CO2 in soils under trees. In caves covered by large, contiguous areas of grassland, the δ13Cr values of cave-air CO2 were similar

  9. Abundance anomaly of the 13C species of CCH

    NASA Astrophysics Data System (ADS)

    Sakai, N.; Saruwatari, O.; Sakai, T.; Takano, S.; Yamamoto, S.

    2010-03-01

    Aims: We have observed the N = 1-0 lines of CCH and its 13C isotopic species toward a cold dark cloud, TMC-1 and a star-forming region, L1527, to investigate the 13C abundances and formation pathways of CCH. Methods: The observations have been carried out with the IRAM 30 m telescope. Results: We have successfully detected the lines of 13CCH and C13CH toward the both sources and found a significant intensity difference between the two 13C isotopic species. The [C13CH] /[13CCH] abundance ratios are 1.6 ± 0.4 (3σ) and 1.6 ± 0.1 (3σ) for TMC-1 and L1527, respectively. The abundance difference between C13CH and 13CCH means that the two carbon atoms of CCH are not equivalent in the formation pathway. On the other hand, the [CCH]/[C13CH] and [CCH]/[13CCH] ratios are evaluated to be larger than 170 and 250 toward TMC-1, and to be larger than 80 and 135 toward L1527, respectively. Therefore, both of the 13C species are significantly diluted in comparison with the interstellar 12C/13C ratio of 60. The dilution is discussed in terms of a behavior of 13C in molecular clouds.

  10. Determining Clumped Isotope (Δ47) Signatures of CO2 During Ion-Molecule Isotopic Exchange Reactions

    NASA Astrophysics Data System (ADS)

    Sarna, J.; Priyadarshi, A.; Pourmorady, P.; Tripati, A.; Estaris, J.

    2015-12-01

    The abundance of multiply-substituted isotopologues such as 13C16O18O can be used to understand fundamental mechanisms that controls isotopic fractionation in chemical reactions. Knowledge of the energy-dependent ion-molecule isotopic exchange rate for 13C16O18O may also provide important insights into the CO2 ion-molecular exchange that occurs in the source of the mass spectrometer. It may offer an explanation for the recently observed nonlinearities associated with clumped isotope measurements. We designed a controlled set of laboratory experiments to investigate variations in the abundance of 13C16O18O associated with different ion-molecular isotopic exchange reactions. In our experiments, we characterize the effects of changing ionization energy, reaction time, CO2 amount, the presence of different compounds, and reaction chamber temperature on the clumped isotopic composition of CO2.

  11. On the status of IAEA delta-13C stable isotope reference materials.

    NASA Astrophysics Data System (ADS)

    Assonov, Sergey; Groening, Manfred; Fajgelj, Ales

    2016-04-01

    For practical reasons all isotope measurements are performed on relative scales realized through the use of international, scale-defining primary standards. In fact these standards were materials (artefacts, similar to prototypes of meter and kg) selected based on their properties. The VPDB delta-13C scale is realised via two highest-level reference materials NBS19 and LSVEC, the first defining the scale and the second aimed to normalise lab-to-lab calibrations. These two reference materials (RMs) have been maintained and distributed by IAEA and NIST. The priority task is to maintain these primary RMs at the required uncertainty level, thus ensuring the long-term scale consistency. The second task is to introduce replacements when needed (currently for exhausted NBS19, work in progress). The next is to produce a family of lower level RMs (secondary, tertiary) addressing needs of various applications (with different delta values, in different physical-chemical forms) and their needs for the uncertainty; these RMs should be traceable to the highest level RMs. Presently three is a need for a range of RMs addressing existing and newly emerging analytical techniques (e.g. optical isotopic analysers) in form of calibrated CO2 gases with different delta-13C values. All that implies creating a family of delta-13C stable isotope reference materials. Presently IAEA works on replacement for NBS19 and planning new RMs. Besides, we found that LSVEC (introduced as second anchor for the VPDB scale in 2006) demonstrate a considerable scatter of its delta-13C value which implies a potential bias of the property value and increased value uncertainty which may conflict with uncertainty requirements for atmospheric monitoring. That is not compatible with the status of LSVEC, and therefore it should be replaced as soon as possible. The presentation will give an overview of the current status, the strategic plan of developments and the near future steps.

  12. Measuring DNA synthesis rates with [1-13C]glycine.

    PubMed

    Chen, P; Abramson, F P

    1998-05-01

    We have devised and evaluated a stable-isotopic method for measuring DNA synthesis rates. The probe is [1-13C]-glycine that is incorporated into purines via de novo biosynthesis. The human hepatoma cell line HEP G2 was grown in medium containing [1-13C]glycine, the cells were harvested at various times, and the DNA was extracted. Following hydrolysis to the nucleosides, a reversed-phase HPLC separation was used to provide separate peaks for deoxythymidine (dT), deoxyadenosine (dA), and deoxyguanosine (dG). The HPLC effluent was continuously fed into a chemical reaction interface and an isotope ratio mass spectrometer (HPLC/CRI/IRMS). The isotope ratio of the CO2 produced in the CRI was used to monitor for enrichment. The cells were grown continuously for 5 days in labeled medium and also in a 1-day pulse labeling experiment where the washout of label was observed for the subsequent 9 days. As predicted from the role of glycine in de novo purine biosynthesis, the isotope ratio of the pyrimidine dT did not change. However, for the two purines, dA and dG, the characteristic log growth behavior of the cells was observed in their 13C/12C ratios and good agreement in the doubling time was obtained for each type of experiment. Parallel experiments that measured the HEP G2 doubling time in culture using tritiated thymidine incorporation and direct cell counts were carried out compare to our new method with established ones. We believe that the use of [1-13C]-glycine and the HPLC/CRI/IRMS is a highly sensitive and selective approach that forms the basis of a method that can measure DNA synthesis rates using a nonradioactive, nontoxic tracer. PMID:9599574

  13. Quantifying the chemical composition of soil organic carbon with solid-state 13C NMR

    NASA Astrophysics Data System (ADS)

    Baldock, J. A.; Sanderman, J.

    2011-12-01

    The vulnerability of soil organic carbon (SOC) to biological decomposition and mineralisation to CO2 is defined at least partially by its chemical composition. Highly aromatic charcoal-like SOC components are more stable to biological decomposition than other forms of carbon including cellulose. Solid-state 13C NMR has gained wide acceptance as a method capable of defining SOC chemical composition and mathematical fitting processes have been developed to estimate biochemical composition. Obtaining accurate estimates depends on an ability to quantitatively detect all carbon present in a sample. Often little attention has been paid to defining the proportion of organic carbon present in a soil that is observable in solid-state 13C NMR analyses of soil samples. However, if such data is to be used to inform carbon cycling studies, it is critical that quantitative assessments of SOC observability be undertaken. For example, it is now well established that a significant discrimination exists against the detection of the low proton content polyaromatic structures typical of charcoal using cross polarisation 13C NMR analyses. Such discrimination does not exist where direct polarisation analyses are completed. In this study, the chemical composition of SOC as defined by cross polarisation and direct polarisation13C NMR analyses will be compared for Australian soils collected from under a diverse range of agricultural managements and climatic conditions. Results indicate that where significant charcoal C contents exist, it is highly under-represented in the acquired CP spectra. For some soils, a discrimination against alkyl carbon was also evident. The ability to derive correction factors to compensate for such discriminations will be assessed and presented.

  14. Seasonal variations of dissolved inorganic carbon and δ13C of surface waters: application of a modified gas evolution technique

    NASA Astrophysics Data System (ADS)

    Atekwana, E. A.; Krishnamurthy, R. V.

    1998-03-01

    Seasonal concentrations and δ13C of dissolved inorganic carbon (DIC) in a river-tributary system in Kalamazoo, southwest Michigan, USA, have been measured using a modified gas evolution technique. The technique makes use of evacuated glass septum tubes pre-loaded with phosphoric acid and a magnetic stir bar. Water samples are injected into these septum tubes in the field, which eliminates problems associated with CO 2 loss/gain during sample storage and transfer to the vacuum line during DIC extraction. Using this technique, a precision of 1% and 0.1‰ can be achieved for DIC concentrations and δ13C DIC measurements, respectively. As this technique provides reliable measurements of DIC concentrations and carbon isotope ratios, it was used to evaluate the processes that control DIC in the river-tributary system. Results of DIC concentration and δ13C DIC measurements of water samples from the river-tributary system show that the DIC pool is mostly dominated by groundwater. The DIC concentrations and δ13C DIC are within the ranges measured for the most isotopically evolved groundwater in this region. Seasonal variations superimposed on the baseline values are attributed to secondary processes such as CO 2 invasion from the atmosphere, enhanced recharge from lakes and biological activities of photosynthesis, respiration, and decay. With the onset of spring, there is a concurrent increase in the DIC concentration and δ13C DIC of these streams. A simultaneous increase in concentration and 13C enrichment of the riverine DIC pool is consistent with CO 2 invasion and recharge from lakes. During the summer, biological activity is the predominant control on shifts in the DIC pool. Although photosynthesis, respiration and decay occur during this time, decreases in the DIC concentration and increases in the 13C DIC indicates CO 2 removal from the pool by photosynthesis. In the late summer-early fall, photosynthesis declines and respiration and decay cause an increase in

  15. Interactive effects of elevated CO2 and nitrogen deposition on fatty acid molecular and isotope composition of above- and belowground tree biomass and forest soil fractions.

    PubMed

    Griepentrog, Marco; Eglinton, Timothy I; Hagedorn, Frank; Schmidt, Michael W I; Wiesenberg, Guido L B

    2015-01-01

    Atmospheric carbon dioxide (CO2) and reactive nitrogen (N) concentrations have been increasing due to human activities and impact the global carbon (C) cycle by affecting plant photosynthesis and decomposition processes in soil. Large amounts of C are stored in plants and soils, but the mechanisms behind the stabilization of plant- and microbial-derived organic matter (OM) in soils are still under debate and it is not clear how N deposition affects soil OM dynamics. Here, we studied the effects of 4 years of elevated (13C-depleted) CO2 and N deposition in forest ecosystems established in open-top chambers on composition and turnover of fatty acids (FAs) in plants and soils. FAs served as biomarkers for plant- and microbial-derived OM in soil density fractions. We analyzed above- and belowground plant biomass of beech and spruce trees as well as soil density fractions for the total organic C and FA molecular and isotope (δ13C) composition. FAs did not accumulate relative to total organic C in fine mineral fractions, showing that FAs are not effectively stabilized by association with soil minerals. The δ13C values of FAs in plant biomass increased under high N deposition. However, the N effect was only apparent under elevated CO2 suggesting a N limitation of the system. In soil fractions, only isotope compositions of short-chain FAs (C16+18) were affected. Fractions of 'new' (experimental-derived) FAs were calculated using isotope depletion in elevated CO2 plots and decreased from free light to fine mineral fractions. 'New' FAs were higher in short-chain compared to long-chain FAs (C20-30), indicating a faster turnover of short-chain compared to long-chain FAs. Increased N deposition did not significantly affect the quantity of 'new' FAs in soil fractions, but showed a tendency of increased amounts of 'old' (pre-experimental) C suggesting that decomposition of 'old' C is retarded by high N inputs. PMID:24953725

  16. Global and Regional Constraints on Exchanges of CO2 Between the Atmosphere and Terrestrial Biosphere

    NASA Astrophysics Data System (ADS)

    Piper, S. C.

    2001-12-01

    The vigorous atmospheric circulation rapidly mixes CO2 that is exchanged with the terrestrial biosphere and oceans. Therefore, at time scales greater than 1 year, the approximate interhemispheric exchange time of the atmosphere, an average of CO2 measurements from a network of surface stations can be used to accurately determine the global net change in atmospheric CO2. By subtracting CO2 produced by fossil fuel combustion, which is well characterized by national statistics, the global the sum of terrestrial biospheric and oceanic net fluxes, here termed the "nonfossil" CO2 flux, can also be accurately determined. The nonfossil CO2 flux averaged -2.1+/-0.3 PgC/yr and -3.2+/-0.4 PgC/yr in the 1980s and 1990s respectively (negative denotes out of the atmosphere), and varied in annual average from about 0 to -4 PgC/yr over these two decades. Two primary methods have been used to further partition the nonfossil CO2 flux between land and oceans: the O2 and 13C/12C methods, which rely, respectively, on measurements of atmospheric O2 (actually O2/N2 for technical reasons) and of the 13C/12C ratio of CO2. Burning of fossil fuel consumes atmospheric O2 and releases CO2 with a 13C/12C ratio lower than that of atmospheric CO2 whereas uptake of CO2 by terrestrial plants releases O2, and increases the atmospheric 13C/12C ratio owing to the preferential assimilation of 12CO2 relative to 13CO2. In contrast, the uptake of CO2 by the oceans has little effect on either the atmospheric O2 or 13C/12C ratio. Therefore, the net CO2 uptake or release from the terrestrial biosphere can be calculated in either method by subtracting the change owing to fossil fuel emissions from the measured change in the atmosphere, utilizing known stoichiometric ratios of O2 and CO2 in the O2 method, and isotopic fractionation factors in the 13C/12C method. Currently, the O2 method gives a net global terrestrial biospheric CO2 flux of -0.2+/-0.7 PgC/yr and -1.4+/-0.7 PgC/yr for the 1980s and the 1990s

  17. Fossil chironomid d13C as a new proxy for past methanogenic contribution to benthic food-webs in lakes?

    NASA Astrophysics Data System (ADS)

    van Hardenbroek, M.; Heiri, O. M.; Grey, J.; Bodelier, P. L. E.; Lotter, A. F.

    2009-04-01

    Lake sediments are an important source of atmospheric methane. Methanogenic archaea in lake sediments produce 13C-depleted methane that is partly released to the water column and the atmosphere. Another part is utilized by methane oxidizing bacteria (MOB) that are an important food source for deposit-feeding chironomid larvae (Diptera: Chironomidae). If methane-derived carbon is a significant component of the chironomid diet this will lead to strongly negative d13C in the tissue and exoskeleton of chironomid larvae. Chironomid cuticles, especially the strongly sclerotized head capsules, are well preserved as fossils in lake sediments. If the relationship between modern methane fluxes in lakes and chironomid d13C can be established this would therefore provide an approach for estimating past methane fluxes based on d13C of fossil chironomid remains. Using culturing experiments we show that the stable carbon isotope signature of MOB and other food sources can be traced in chironomid muscle tissue as well as in the fossilizing exoskeleton. In addition we measured d13C in chironomid larval head capsules and other invertebrate remains from a range of surface and downcore sediment samples. Small intra-specific variability (-27.1 ± 0.08 permille) was measured in replicate samples of chironomid head capsules of Corynocera ambigua (n=7). d13C of chironomid head capsules from a several different taxa ranged from -28.0 to -25.8 permille, but in some instances we observed d13C values as low as -36.9 to -31.5 permille, suggesting that carbon from MOB can be successfully traced in fossil and subfossil chironomid remains. Our results demonstrate that the stable carbon isotope signature of MOB is incorporated into chironomid head capsules. Future research will focus on quantifying the relationship between methane fluxes, MOB, and head capsule d13C in order to reconstruct past methane fluxes based on the lake sediment record.

  18. Changes in delta 13C stable isotopes in multiple tissues of insect predators fed isotopically distinct prey.

    PubMed

    Gratton, Claudio; Forbes, Andrew E

    2006-04-01

    Traditionally, researchers have used measurements of carbon stable isotopes to infer the composition of consumers' diets. However, since consumer's tissues may process carbon isotopes differently, particularly following a diet shift, it is possible to use measurements of carbon isotopes in multiple tissues to determine not only the composition of an individual's diet, but also the temporal dynamics thereof. This study examined how stable isotopes of carbon (13C/12C, expressed as delta 13C) changed in different adult tissues of two predacious beetles, Harmonia axyridis and Coccinella septempunctata (Coleoptera: Coccinellidae). In the laboratory, we switched ladybeetles from a C3-based diet (soybean aphids, Aphis glycines) to a C4-based one (corn leaf aphids, Rhopalosiphum maidis). The delta 13C of metabolically active tissues such as the body fat and reproductive organs changed rapidly (< or =5 days) following the diet shift. Tissues expected to be more metabolically inert, such as wings, changed more slowly over the same period. Although these general patterns were largely similar between males and females, females had more rapid changes in delta 13C in fat and reproductive tissues. However, females showed a significant depletion in delta 13C after 10 days, while males' delta 13C continued to increase. Given the results of this experiment, it is now possible to distinguish between ladybeetles eating a mixed diet (beetles with multiple tissues at similar, intermediate, equilibrial delta 13C signatures) from those that have shifted diets (beetles with different tissues at distinctly different delta 13C values). Thus, this approach can be used broadly to infer not only what constitutes the diet of a consumer, but also the temporal history of dietary intake. PMID:16341886