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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. 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.

  3. 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

  4. 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.

  5. Changes in vegetation phenology are not reflected in atmospheric CO2 and (13) C/(12) C seasonality.

    PubMed

    Gonsamo, Alemu; D'Odorico, Petra; Chen, Jing M; Wu, Chaoyang; Buchmann, Nina

    2017-01-31

    Northern terrestrial ecosystems have shown global warming-induced advances in start, delays in end, and thus increased lengths of growing season and gross photosynthesis in recent decades. The tradeoffs between seasonal dynamics of two opposing fluxes, CO2 uptake through photosynthesis and release through respiration, determine the influence of the terrestrial ecosystem on the atmospheric CO2 and (13) C/(12) C seasonality. Here, we use four CO2 observation stations in the Northern Hemisphere, namely Alert, La Jolla, Point Barrow, and Mauna Loa Observatory, to determine how changes in vegetation productivity and phenology, respiration, and air temperature affect both the atmospheric CO2 and (13) C/(12) C seasonality. Since the 1960s, the only significant long-term trend of CO2 and (13) C/(12) C seasonality was observed at the northern most station, Alert, where the spring CO2 drawdown dates advanced by 0.65 ± 0.55 days yr(-1) , contributing to a nonsignificant increase in length of the CO2 uptake period (0.74 ± 0.67 days yr(-1) ). For Point Barrow station, vegetation phenology changes in well-watered ecosystems such as the Canadian and western Siberian wetlands contributed the most to (13) C/(12) C seasonality while the CO2 seasonality was primarily linked to nontree vegetation. Our results indicate significant increase in the Northern Hemisphere soil respiration. This means, increased respiration of (13) C depleted plant materials cancels out the (12) C gain from enhanced vegetation activities during the start and end of growing season. These findings suggest therefore that parallel warming-induced increases both in photosynthesis and respiration contribute to the long-term stability of CO2 and (13) C/(12) C seasonality under changing climate and vegetation activity. The summer photosynthesis and the soil respiration in the dormant seasons have become more vigorous which lead to increased peak-to-through CO2 amplitude. As the relative magnitude of the

  6. [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.

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. Delta13C values of grasses as a novel indicator of pollution by fossil-fuel-derived greenhouse gas CO2 in urban areas.

    PubMed

    Lichtfouse, Eric; Lichtfouse, Michel; Jaffrézic, Anne

    2003-01-01

    A novel fossil fuel pollution indicator based on the 13C/12C isotopic composition of plants has been designed. This bioindicator is a promising tool for future mapping of the sequestration of fossil fuel CO2 into urban vegetation. Theoretically, plants growing in fossil-fuel-CO2-contaminated areas, such as major cities, industrial centers, and highway borders, should assimilate a mixture of global atmospheric CO2 of delta13C value of -8.02 per thousand and of fossil fuel CO2 of average delta13C value of -27.28 per thousand. This isotopic difference should, thus, be recorded in plant carbon. Indeed, this study reveals that grasses growing near a major highway in Paris, France, have strikingly depleted delta13C values, averaging at -35.08 per thousand, versus rural grasses that show an average delta13C value of -30.59 per thousand. A simple mixing model was used to calculate the contributions of fossil-fuel-derived CO2 to the plant tissue. Calculation based on contaminated and noncontaminated isotopic end members shows that urban grasses assimilate up to 29.1% of fossil-fuel-CO2-derived carbon in their tissues. The 13C isotopic composition of grasses thus represents a promising new tool for the study of the impact of fossil fuel CO2 in major cities.

  12. Multi-day, real-time measurements of CO2 concentration, CO2/SO2 ratios, and d13C of CO2 in volcanic plume

    NASA Astrophysics Data System (ADS)

    Jost, H. J. H.; Rizzo, A. L.; Liuzzo, M.; Ancellin, M. A.

    2015-12-01

    New real-time measurements of CO2 /SO2 ratios, the CO2 concentration and δ13C of CO2 were acquired from July 16 to 20, 2014 in the active plume about 1 km away from the source at the Central Craters of Mount Etna volcano, Italy. During this innovative study we measured d13C in plume gases at a frequency of 0.1 Hz over 5 days of measurements. Assuming two member mixing processes, the extrapolated carbon-isotope composition of the volcanic CO2 ranged from -1.3‰ to +1.5‰, with uncertainties in the repeated single measurements (i.e., made over periods from 4 to 20 min) that were generally <0.7‰, and surprisingly larger variations over the 5-day study period. The range of extrapolated d13C values mostly overlaps with that obtained by discrete sampling and using isotope-ratio mass spectrometry technique (-2.5‰ < d13C < -0.5‰). However, the particular conditions of volcanic activity during the campaign lead us to propose that the carbon-isotope composition of CO2 degassed from magma can reach values (up to +1.5‰), higher than previously reported. Simultaneous measurements of the CO2 and SO2 concentrations using the MultiGAS technique were also performed. The volcanic d13C and CO2/SO2 ratios exhibited similar trends over the 5 days of measurements, with the ratios of both tracers peaking on July 16, possibly as a result of the early degassing of CO2 while an eruption was ongoing at Mount Etna. New questions about the variability of this geochemical tracer arise from the observed variations and the highest d13C values measured at Mount Etna during this campaign. The comparisons with the CO2/SO2 ratio also confirm that monitoring d13C in plume gases in real time, coupled to other geochemical tracers, is important for elucidating the magma dynamics at depth.

  13. Reconstruction of δ 13C of chemocline CO 2 (aq) in past oceans and lakes using the δ 13C of fossil isorenieratene

    NASA Astrophysics Data System (ADS)

    van Breugel, Yvonne; Schouten, Stefan; Paetzel, Matthias; Ossebaar, Jort; Sinninghe Damsté, Jaap S.

    2005-06-01

    High abundances of the diaromatic carotenoid isorenieratene derived from photosynthetic green sulfur bacteria (Chlorobiaceae) were found just below the chemocline in an anoxic fjord in Norway, throughout the annual cycle. The stable carbon isotope composition of this carotenoid co-varied with the δ 13C of CO 2 (aq) and is independent of the CO 2 and isorenieratene concentration. This constant isotopic fractionation ɛp of isorenieratene versus CO 2, 4 ± 1‰, was subsequently used in the reconstruction of δ 13C of CO 2 at the chemocline in ancient oceans and lakes. These reconstructions indicate that δ 13C of CO 2 at the chemocline is often influenced by isotopically light CO 2, formed by remineralization of organic matter. This process can, depending on the depth and stability of the chemocline, also effect the isotopic composition of the phytoplankton and, thus, isotopic records of sedimentary inorganic and organic carbon.

  14. Testing a new Method of Estimating the δ13C of Photosynthate in Trees: Stem CO2 Equilibration}

    NASA Astrophysics Data System (ADS)

    Ubierna Lopez, N.; Kavanagh, K.; Marshall, J. D.

    2006-12-01

    Modeling and prediction of forest responses to climate change often deal with the difficulty of estimating gas- exchange responses to rising CO2 concentrations and temperatures. This difficulty can be overcome with stable carbon isotopes, which provide a tool to study the coupling of the carbon and water cycles. Recently, considerable research has concentrated on trying to identify processes occurring after photosynthesis that modify the isotopic composition of a given plant tissue, which has led to questions about which plant tissue will best reflect environmental variations and photosynthetic discrimination. Here, we propose a new method that uses CO2 collected from inside the stem. A simple collection apparatus consisting of a stainless steel tube is inserted into the tree. The gas from the stem diffuses and equilibrates with the headspace. Gas samples are subsequently collected by replacing the gas inside the tubing with acidified water. This technique minimizes any change in pressure inside the system or any atmospheric contamination from outside the system. We compared the measured δ13C of stem CO2 to known leaf values in four conifer species at Mica Creek Experimental Watershed, in northern Idaho, USA. In addition, δ13C of soil respiration, δ13C leaf bulk material, δ13C phloem contents, and photosynthetic gas- exchange data were collected. We collected stem CO2 samples weekly through August 2006 during a long drought period. Mean monthly temperature was 16°C, cumulative precipitation in July and August was 33 mm, and mean maximum VPD was 4.1 kPa during this month. The most depleted species was Larix occidentalis, with δ13C = -26.97 ‰ (SE = 0.30), following by the shade-tolerant Abies grandis, with δ13C = -26.33 ‰ (SE = 0.23). In comparison, Pseudotsuga menziesii, with δ13C = -24.88 ‰ (SE =0.48) and Thuja plicata with δ13C = - 23.79 ‰ (SE = 0.30) were more enriched. These δ13C values are consistent with previous measurements of leaf bulk

  15. C4 plant isotopic composition (delta13C) evidence for urban CO2 pollution in the city of Cotonou, Benin (West Africa).

    PubMed

    Kèlomé, Nelly C; Lévêque, Jean; Andreux, Francis; Milloux, Marie-Jeanne; Oyédé, Lucien-Marc

    2006-08-01

    The carbon isotopic composition (delta13C) of plants can reveal the isotopic carbon content of the atmosphere in which they develop. The delta13C values of air and plants depend on the amount of atmospheric fossil fuel CO2, which is chiefly emitted in urban areas. A new indicator of CO2 pollution is tested using the delta13C variation in a C4 grass: Eleusine indica. A range of about 4 per thousand delta units was observed at different sites in Cotonou, the largest city in the Republic of Benin. The highest delta13C values, from -12 per thousand to -14 per thousand, were found in low traffic zones; low delta13C values, from -14 per thousand to -16 per thousand, were found in high traffic zones. The amount of fossil fuel carbon assimilated by plants represented about 20% of the total plant carbon content. An overall decrease in plant delta13C values was observed over a four-year monitoring period. This decrease was correlated with increasing vehicle traffic. The delta13C dataset and the corresponding geographical database were used to map and define zones of high and low 13C-depleted CO2 emissions in urban and sub-urban areas. The spatial distribution follows dominant wind directions, with the lowest emission zones found in the southwest of Cotonou. High CO2 emissions occurred in the north, the east and the center, providing evidence of intense anthropogenic activity related to industry and transportation.

  16. Magma-derived CO 2 emissions recorded in 14C and 13C content of plants growing in Furnas caldera, Azores

    NASA Astrophysics Data System (ADS)

    Pasquier-Cardin, Aline; Allard, Patrick; Ferreira, Teresa; Hatte, Christine; Coutinho, Rui; Fontugne, Michel; Jaudon, Michel

    1999-09-01

    The environmental impact of fumarolic and soil emanations of magma-derived carbon dioxide across Furnas caldera has been investigated by measuring the 14C and 13C content of 40 specimens of different C3 plants (leaves) growing within and outside the degassing areas. The results demonstrate a significant to large 14C depletion in many of the plants due to assimilation of 14C-free endogenous CO 2 during photosynthesis and leading to artificial radiocarbon ageing of up to 4400 years. The extent of 14C ageing broadly correlates with the intensity of gas manifestations at the sampling sites, as inferred from field observations and measurements of excess CO 2 concentrations in the volcanic ground. It also provides a time-integrated measure of the amount of volcanic CO 2 locally admixed to the ambient air; at several sites this accounts for 15 to 40% of total CO 2 (420 to 600 ppm) in enriched air. In some of the plant species ( Azalea, Camellia and fern) 14C depletion is correlated with an enrichment of 13C due to assimilation of magma-derived CO 2 with a 4‰ higher δ 13C than normal atmosphere. The rate of 13C enrichment averages ca. 0.18‰ by percent of volcanic carbon fixed in the plant and includes enhanced 13C discrimination during photosynthesis as a consequence of increased ambient pCO 2 (inferred at -0.0306‰ per added ppm of volcanic CO 2). Furnas is one of the few volcanoes where clear 13C enrichment in plants due to endogenous degassing has been evidenced. Our results can be used to estimate the local intensity of volcanic soil gas fluxes in the emanating areas of Furnas caldera. They also have implications for radiocarbon dating of past eruptive events in the caldera, since plants artificially aged by previous degassing could be trapped in volcanic deposits.

  17. 13C Tracking after 13CO2 Supply Revealed Diurnal Patterns of Wood Formation in Aspen.

    PubMed

    Mahboubi, Amir; Linden, Pernilla; Hedenström, Mattias; Moritz, Thomas; Niittylä, Totte

    2015-06-01

    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 (13)CO2 labeling system to study carbon transport and incorporation to developing wood of hybrid aspen (Populus tremula × tremuloides). Tracking of (13)C 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 (13)C incorporation to lignin and cell wall carbohydrates. No (13)C 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 (13)C labeling method for the analysis of wood formation and secondary growth in trees.

  18. 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

  19. 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

  20. Influence of 13C-enriched Foliage Respired CO2 on 13C of Ecosystem-respired CO2 Estimated From Mid-canopy CO2 Sampled During Several Hours After Sunset

    NASA Astrophysics Data System (ADS)

    Mortazavi, B.; Chanton, J.; Smith, M.

    2005-12-01

    Nighttime CO2 concentration and 13C isotopic ratio were measured in the summer and fall of 2004 by two approaches at a Biosphere Atmosphere Stable Isotope Network (BASIN) network site in Florida, USA. The site is a naturally regenerated pine ecosystem dominated by longleaf and slash pine. The first approach consisted in making measurements at multiple heights within the canopy from ground level to top of the canopy just prior to dawn. The second approach consisted in making measurements at mid- canopy at different times from 1 hour after sunset till 2 am. For each method a Keeling plot was used to estimate the isotopic composition of respired CO2 (dCr). dCr values determined with the time-series were enriched relative to those determined from multiple heights just prior to dawn. The 13C of slash pine foliage respired CO2 (dCf) was also measured at temperatures ranging from 6.6 to 30 °C. dCf was enriched initially after dark by as much as 9° and then declined, reaching constant values after a few hours. Maximum enrichment in dCf was measured at the lowest temperature and the decline in dCf towards constant values took longer at lower temperatures. The influence of 13C enriched and temporally variable nighttime foliage respired CO2 accounts for the enriched time-series dCr. A model constrained by field and experimental data was used to determine the impact of the non-constancy of dCf on the linearity and intercept of dCr Keeling plots determined from CO2 samples collected during several hours at mid-canopy height. For the months examined, results indicate that (i) Keeling plots determined from mid-canopy heights were linear despite the addition of temporally variable dCf (range: 5 °) and (ii) the enrichment in the Keeling intercepts determined from samples collected during several hours at mid-canopy compared to those determined from multiple heights were consistent with the addition of 13C enriched foliage respired CO2. A common approach that specifies the time

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

    PubMed

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

    2015-06-03

    The gastric pathogen Helicobacter pylori utilize glucose during metabolism, but the underlying mechanisms linking to oxygen-18 ((18)O) and carbon-13 ((13)C)-isotopic fractionations of breath CO2 during glucose metabolism are poorly understood. Using the excretion dynamics of (18)O/(16)O and (13)C/(12)C-isotope ratios of breath CO2, we found that individuals with Helicobacter pylori infections exhibited significantly higher isotopic enrichments of (18)O in breath CO2 during the 2h-glucose metabolism regardless of the isotopic nature of the substrate, while no significant enrichments of (18)O in breath CO2 were manifested in individuals without the infections. In contrast, the (13)C-isotopic enrichments of breath CO2 were significantly higher in individuals with Helicobacter pylori compared to individuals without infections in response to (13)C-enriched glucose uptake, whereas a distinguishable change of breath (13)C/(12)C-isotope ratios was also evident when Helicobacter pylori utilize natural glucose. Moreover, monitoring the (18)O and (13)C-isotopic exchange in breath CO2 successfully diagnosed the eradications of Helicobacter pylori infections following a standard therapy. Our findings suggest that breath (12)C(18)O(16)O and (13)C(16)O(16)O 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.

  2. Measuring the 13C content of soil-respired CO2 using a novel open chamber system.

    PubMed

    Midwood, Andrew J; Thornton, Barry; Millard, Pete

    2008-07-01

    Carbon dioxide respired by soils comes from both autotrophic and heterotrophic respiration. 13C has proved useful in differentiating between these two sources, but requires the collection and analysis of CO2 efflux from the soil. We have developed a novel, open chamber system which allows for the accurate and precise quantification of the delta13C of soil-respired CO2. The chamber was tested using online analyses, by configuring a GasBench II and continuous flow isotope ratio mass spectrometer, to measure the delta13C of the chamber air every 120 s. CO2 of known delta13C value was passed through a column of sand and, using the chamber, the CO2 concentration stabilized rapidly, but 60 min was required before the delta13C value was stable and identical to the cylinder gas (-33.3 per thousand). Changing the chamber CO2 concentration between 200 and 900 micromol.mol(-1) did not affect the measured delta13C of the efflux. Measuring the delta13C of the CO2 efflux from soil cores in the laboratory gave a spread of +/-2 per thousand, attributed to heterogeneity in the soil organic matter and roots. Lateral air movement through dry sand led to a change in the delta13C of the surface efflux of up to 8 per thousand. The chamber was used to measure small transient changes (+/-2 per thousand) in the delta13C of soil-respired CO2 from a peaty podzol after gradual heating from 12 to 35 degrees C over 12 h. Finally, soil-respired CO2 was partitioned in a labelling study and the contribution of autotrophic and heterotrophic respiration to the total efflux determined. Potential applications for the chamber in the study of soil respiration are discussed.

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. Bacteria and fungi respond differently to multifactorial climate change in a temperate heathland, traced with 13C-glycine and FACE CO2.

    PubMed

    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 (13)C-labeled glycine ((13)C2, 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 (13)C enrichment of respired CO2 and of phospholipid fatty acids (PLFAs) was determined after 24 h. (13)C-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 (13)C in all treatments, whereas fungi had minor or no glycine derived (13)C-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 (13)C-depleted (δ(13)C = 12.2‰) compared to ambient (δ(13)C = ∼-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

  8. 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

  9. A revised 1000 year atmospheric δ13C-CO2 record from Law Dome and South Pole, Antarctica

    NASA Astrophysics Data System (ADS)

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

    2013-08-01

    We present new measurements of δ13C of CO2 extracted from a high-resolution ice core from Law Dome (East Antarctica), together with firn measurements performed at Law Dome and South Pole, covering the last 150 years. Our analysis is motivated by the need to better understand the role and feedback of the carbon (C) cycle in climate change, by advances in measurement methods, and by apparent anomalies when comparing ice core and firn air δ13C records from Law Dome and South Pole. We demonstrate improved consistency between Law Dome ice, South Pole firn, and the Cape Grim (Tasmania) atmospheric δ13C data, providing evidence that our new record reliably extends direct atmospheric measurements back in time. We also show a revised version of early δ13C measurements covering the last 1000 years, with a mean preindustrial level of -6.50‰. Finally, we use a Kalman Filter Double Deconvolution to infer net natural CO2 fluxes between atmosphere, ocean, and land, which cause small δ13C deviations from the predominant anthropogenically induced δ13C decrease. The main features found from the previous δ13C record are confirmed, including the ocean as the dominant cause for the 1940 A.D. CO2 leveling. Our new record provides a solid basis for future investigation of the causes of decadal to centennial variations of the preindustrial atmospheric CO2 concentration. Those causes are of potential significance for predicting future CO2 levels and when attempting atmospheric verification of recent and future global carbon emission mitigation measures through Coupled Climate Carbon Cycle Models.

  10. 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.

  11. 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.

  12. 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

    2015-05-07

    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.

  13. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    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.

  15. Fate of xylem-transported 11C- and 13C-labeled CO2 in leaves of poplar.

    PubMed

    Bloemen, Jasper; Bauweraerts, Ingvar; De Vos, Filip; Vanhove, Christian; Vandenberghe, Stefaan; Boeckx, Pascal; Steppe, Kathy

    2015-04-01

    In recent studies, assimilation of xylem-transported CO2 has gained considerable attention as a means of recycling respired CO2 in trees. However, we still lack a clear and detailed picture on the magnitude of xylem-transported CO2 assimilation, in particular within leaf tissues. To this end, detached poplar leaves (Populus × canadensis Moench 'Robusta') were allowed to take up a dissolved (13)CO2 label serving as a proxy of xylem-transported CO2 entering the leaf from the branch. The uptake rate of the (13)C was manipulated by altering the vapor pressure deficit (VPD) (0.84, 1.29 and 1.83 kPa). Highest tissue enrichments were observed under the highest VPD. Among tissues, highest enrichment was observed in the petiole and the veins, regardless of the VPD treatment. Analysis of non-labeled leaves showed that some (13)C diffused from the labeled leaves and was fixed in the mesophyll of the non-labeled leaves. However, (13)C leaf tissue enrichment analysis with elemental analysis coupled to isotope ratio mass spectrometry was limited in spatial resolution at the leaf tissue level. Therefore, (11)C-based CO2 labeling combined with positron autoradiography was used and showed a more detailed spatial distribution within a single tissue, in particular in secondary veins. Therefore, in addition to (13)C, (11) C-based autoradiography can be used to study the fate of xylem-transported CO2 at leaf level, allowing the acquisition of data at a yet unprecedented resolution.

  16. Variation in the leaf δ(13)C is correlated with salinity tolerance under elevated CO(2) concentration.

    PubMed

    del Amor, Francisco M

    2013-02-15

    Increasing atmospheric CO(2) concentration is expected to impact agricultural systems through a direct effect on leaf gas exchange and also due to effects on the global availability of good-quality water as a result of climate warming. Thus, the planning of land use for agriculture requires new tools to identify the capability of current cultivars to adapt to growth restrictions under new ambient conditions. We hypothesized that salinity stress may produce a specific pattern of carbon isotopic composition (δ(13)C) in tomato (Solanum lycopersicum L.) at elevated CO(2) concentration ([CO(2)]) that could be used in the breeding of salinity tolerance in a near-future climate scenario. Five commercial tomato cultivars were evaluated at elevated (800 μmol mol(-1)) or standard (400 μmol mol(-1)) [CO(2)], being irrigated with a nutrient solution containing 0, 60 or 120 mM NaCl. The biomass enhanced ratio, leaf net CO(2) assimilation and stomatal conductance, leaf NO(3)(-) and Cl(-) concentrations and leaf free amino acid profile were analyzed in relation to the pattern of δ(13)C, under different saline stress conditions. The results indicate that at high [CO(2)]: (i) salinity tolerance was enhanced, but the response was strongly cultivar dependent, (ii) leaf NO(3)(-) concentration was increased whilst Cl(-) and proline concentrations decreased, and (iii) leaf δ(13)C was highly correlated with plant dry matter accumulation and with leaf proline concentration, leaf gas exchange and ion concentrations. This study shows that δ(13)C is a useful tool for the determination of the salinity tolerance of tomato at high [CO(2)], as an integrative parameter of the stress period, and was validated by traditional physiological plant stress traits.

  17. 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

  18. 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.

  19. 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

  20. Emission of highly 13C-depleted methane from an upland blanket mire

    NASA Astrophysics Data System (ADS)

    Bowes, Helen L.; Hornibrook, Edward R. C.

    2006-02-01

    Rates and δ13C values of CH4 flux are reported from an upland blanket mire (Blaen Fign) situated in Wales UK. The δ13C values of CH4 flux were similar from Sphagnum and vascular flora dominated areas despite flux rates being an order of magnitude greater from the latter. Methane flux was 13C-depleted relative to belowground CH4, indicating that transport occurred predominately via passive diffusion through vascular flora and that pore water diffusion and ebullition contributed little to CH4 flux. The strong influence of vascular flora abundance on CH4 flux strength suggests that any factors altering vegetation assemblages in blanket mires will likely impact CH4 emission rates. Methane flux from Blaen Fign was highly 13C-depleted compared to emissions from minerotrophic wetlands, suggesting that δ13C values may be useful for tracing CH4 flux from blanket mires and other types of ombrogenous peatlands to the global CH4 budget.

  1. 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

  2. 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

  3. 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

  4. 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.

  5. Mineral nutrition and elevated [CO(2)] interact to modify δ(13)C, an index of gas exchange, in Norway spruce.

    PubMed

    Marshall, John D; Linder, Sune

    2013-11-01

    The effects of the past century's increase in atmospheric CO2 concentration ([CO2]) have been recorded in the stable carbon isotope composition (δ(13)C) of the annual growth rings of trees. The isotope record frequently shows increases in photosynthetic CO2 uptake relative to stomatal conductance, which estimates the CO2 concentration gradient across the stomata (ca - ci). This variable, which is one control over the net photosynthetic rate, has been suggested as a homeostatic gas-exchange set point that is easy to estimate from δ(13)C and [CO2]. However, in high-latitude conifer forests, the literature is mixed; some studies show increases in (ca - ci) and others show homeostasis. Here we present leaf and tree-ring δ(13)C data from a controlled experiment that tested factorial combinations of elevated [CO2] (365 and 700 ∝mol mol(-1)) and fertilization on mature Norway spruce (Picea abies (L.) Karst.) trees in northern Sweden. We found first that the leaf carbon pool was contaminated by the current photosynthate in the older leaf cohorts. This is the reverse of the common observation that older photosynthate reserves can be used to produce new tissue; here the older tissue contains recent photosynthate. We found that the tree-ring data lack such contamination and in any case they better integrate over the canopy and the growing season than do leaves. In the second and third years of treatment, elevated [CO2] alone increased (ca - ci) by 38%; when combined with fertilization, it increased (ca - ci) by 60%. The results of this study support the idea that annual rings provide a clearer isotopic signal than do foliage age-classes. The tree-ring data show that inferred (ca - ci) depends not only on [CO2], but also on mineral-nutrient status. The differences in (ca - ci) are sufficiently large to account for the treatment-induced increase in wood-volume production in these stands.

  6. 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.

  7. Atmospheric CO2 concentrations and δ13C values across the Antarctic Circumpolar Current between New Zealand and Antarctica

    NASA Astrophysics Data System (ADS)

    Longinelli, Antonio; Giglio, Federico; Langone, Leonardo; Lenaz, Renzo; Ori, Carlo; Selmo, Enricomaria

    2007-02-01

    Measurements of atmospheric CO2 concentrations were repeatedly carried out on the vessel `Italica' of the Italian National Research Program in Antarctica, during cruises from Italy to Antarctica. Discrete air samples were also collected in 4-L Pyrex flasks during these cruises in order to carry out δ13C analyses on atmospheric CO2. The results acquired between New Zealand and Antarctica are reported here. The mean growth rate of the CO2 concentration from 1996 to 2003 in this area of the Southern Oceans is of about 1.8 ppmv yr-1, in good agreement with NOAA/CMDL measurements. The rates of increase from cruise to cruise are rather variable. From 1996-1997 to 1998-1999 cruise the yearly growth rate is 2.75 ppmv yr-1, close to the large growth rates measured in several areas and mainly related to the most severe El Niño event of the last years. The other yearly growth rates are of about 1.3 and 2 ppmv for the periods 1998-1999 to 2001-2002 and 2001-2002 to 2003-2004, respectively. The large difference between these two values is probably related to the uncertainty on the only two 2001-2002 discrete measurements of CO2 concentration in this area. The measured δ13C values show two completely different distributions and a large interannual variability. The 1998-1999, 2002-2003, and 2003-2004 results obtained between about 55°S and 65°S across the Antarctic Polar Front show a marked negativization of up to more than 2‰ when compared to the background values. The results are related to local source regions of CO2, as frequently found in the Southern Ocean by several authors; the negative δ13C values are tentatively related to the possible contribution of different causes. Among them, the southward negative gradient of δ13C of the dissolved inorganic carbon, the contribution from upwelling deep waters and from subsurface processes between the Northern SubAntarctic Front and the Polar Front, and, partly, the contribution of CO2 of biogenic origin, e.g. from

  8. 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 leaf

  9. Collection and storage of CO2 for 13C analysis: An application to separate soil CO2 efflux into root- and soil-derived components.

    PubMed

    Midwood, Andrew J; Gebbing, Thomas; Wendler, Renate; Sommerkorn, Martin; Hunt, John E; Millard, Peter

    2006-01-01

    Soil surface CO2 efflux is comprised of CO2 from (i) root respiration and rhizosphere microbes and (ii) heterotrophic respiration from the breakdown of soil organic matter (SOM). This efflux may be partitioned between these sources using delta13C measurements. To achieve this, continuous flow isotope ratio mass spectrometry can be used and, in conjunction with 10 mL septum-capped vials, large numbers of samples may be analysed using a Finnigan MAT Delta(plus)XP interfaced to a Gas Bench II. Here we describe a number of advances to facilitate such work, including: (i) a technique for monitoring mass spectrometer performance, (ii) improvements to sample storage, and (iii) a gas-handling system for incubating and sampling the CO2 derived from roots and soils. Mass spectrometer performance was monitored using an automated refillable vial. Compressed air analysed with this system had mean delta13C of -9.61 +/- 0.16 per thousand (+/- 1sigma, n = 28) collected over four runs. Heating the butyl rubber septa used to seal the vials at 105 degrees C for 12 h improved the sample storage. After air transportation over 12 days, the isotope composition of the CO2 at ambient concentrations was unchanged (before: -35.2 +/- 0.10 per thousand, n = 4; after: -35.3 +/- 0.10 per thousand, n = 15); without heat treatment of the septa the CO2 became slightly enriched (-35.0 +/- 0.14 per thousand, n = 15). The linearity of the Gas Bench II was found to decline above 8000 micromol CO2 mol(-1). To stay within a linear range and to allow the incubation of soil and root material we describe a gas-handling system based around a peristaltic pump. Finally, we demonstrate these methods by growing a C-4 grass (Guinea grass, Panicum maximum Jacq.) in a C-3 soil. Root respiration was found to contribute between 5 and 22% to the soil surface CO2 efflux. These methodologies will facilitate experiments aimed at measuring the isotopic composition of soil-derived CO2 across a range of ecological

  10. 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

  11. 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

  12. 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.

  13. Magnitude and origin of the anthropogenic CO2 increase and 13C Suess effect in the Nordic seas since 1981

    NASA Astrophysics Data System (ADS)

    Olsen, Are; Omar, Abdirahman M.; Bellerby, Richard G. J.; Johannessen, Truls; Ninnemann, Ulysses; Brown, Kelly R.; Olsson, K. Anders; Olafsson, Jon; Nondal, Gisle; KivimäE, Caroline; Kringstad, Solveig; Neill, Craig; Olafsdottir, Solveig

    2006-09-01

    This study evaluates the anthropogenic changes of CO2 (ΔCant) and δ13C (Δδ13Cant) in the Nordic seas, the northern limb of the Atlantic Meridional Overturning Circulation, that took place between 1981 and 2002/2003. The changes have been determined by comparing data obtained during the Transient Tracers in the Ocean, North Atlantic Study (TTO-NAS) with data obtained during the Nordic seas surveys of R/V Knorr in 2002 and R/V G.O. Sars in 2003 using an extended multilinear regression approach. The estimated Δδ13Cant and ΔCant and their relationship to each other and to water mass distribution suggest that the Polar Water entering the Nordic seas from the north is undersaturated with respect to the present atmospheric anthropogenic CO2 levels and promotes a local uptake of Cant within the Nordic seas. In contrast, the Atlantic Water entering from the south appears equilibrated. It carries with it anthropogenic carbon which will be sequestered at depth as the water overturns. This preequilibration leaves no room for further uptake of Cant in the parts of the Nordic seas dominated by Atlantic Water. The upper ocean pCO2 in these regions appears to have increased at a greater rate than the atmospheric pCO2 over the last 2 decades; this is reconcilable with a large lateral advective supply of Cant.

  14. 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

  15. 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.

  16. 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-bicarbonate.

  17. (13)C and (15)N NMR characterization of amine reactivity and solvent effects in CO2 capture.

    PubMed

    Perinu, Cristina; Arstad, Bjørnar; Bouzga, Aud M; Jens, Klaus-J

    2014-08-28

    Factors influencing the reactivity of selected amine absorbents for carbon dioxide (CO2) capture, in terms of the tendency to form amine carbamate, have been studied. Four linear primary alkanolamines at varying chain lengths (MEA, 3A1P, 4A1B , and 5A1P ), two primary amines with different substituents in the β-position to the nitrogen (1A2P and ISOB), a secondary alkanolamine (DEA), and a sterically hindered primary amine (AMP) were investigated. The relationship between the (15)N NMR data of aqueous amines and their ability to form carbamate, as determined at equilibrium by quantitative (13)C NMR experiments, was analyzed, taking into account structural-chemical properties. For all the amines, the (15)N chemical shifts fairly reflected the observed reactivity for carbamate formation. In addition to being a useful tool for the investigation of amine reactivity, (15)N NMR data clearly provided evidence of the importance of solvent effects for the understanding of chemical dynamics in CO2 capture by aqueous amine absorbents.

  18. Apportioning carbon sources of authigenic carbonate of extremely 13C-depleted foraminifera from the western North Pacific sediments: Implication from the coupled 13C and 14C isotopic mass balance approach

    NASA Astrophysics Data System (ADS)

    Uchida, M.; Ohkushi, K.; Ahagon, N.; Kimoto, K.; Inagaki, F.; Shibata, Y.

    2005-12-01

    , we have quantified the relative contributions of dissolved carbon dioxide (/SigmaCO/_2) from oxidation of methane in anomaly foraminifera. At the layer of 17,840 years cal. age with planktonic foraminifera of dual isotopic data (/delta 13C: -8.1/permil and /Delta 14C: -847/permil) , relative contribution of carbon from authigenic carbonate was 17 percent of total carbonate and its /delta 13C was -48.1/permil, suggesting indirect records of enhanced incorporation of 13C-depleted CO2 formed by anaerobic methane oxidation process that use 12C-enriched methane as their main source of carbon. Moreover, biomarker and phylogenetic compositions were investigated in the light of the past activity of methanotrophic bacteria in the oxic-anoxic interface in the overlying water column and/or surface sediment. Mg/Ca ratios were also analyzed to evaluate foraminiferal 13C depleted carbonate precipitation in comparison with authigenic carbonate produced in the cold seep environment. In the conference, we discuss about what mechanism contribute to authigenic carbon precipitation in terms with carbon source with 13C-depleted foraminifera.

  19. Optimization of automated gas sample collection and isotope ratio mass spectrometric analysis of delta(13)C of CO(2) in air.

    PubMed

    Zeeman, Matthias J; Werner, Roland A; Eugster, Werner; Siegwolf, Rolf T W; Wehrle, Günther; Mohn, Joachim; Buchmann, Nina

    2008-12-01

    The application of (13)C/(12)C in ecosystem-scale tracer models for CO(2) in air requires accurate measurements of the mixing ratios and stable isotope ratios of CO(2). To increase measurement reliability and data intercomparability, as well as to shorten analysis times, we have improved an existing field sampling setup with portable air sampling units and developed a laboratory setup for the analysis of the delta(13)C of CO(2) in air by isotope ratio mass spectrometry (IRMS). The changes consist of (a) optimization of sample and standard gas flow paths, (b) additional software configuration, and (c) automation of liquid nitrogen refilling for the cryogenic trap. We achieved a precision better than 0.1 per thousand and an accuracy of 0.11 +/- 0.04 per thousand for the measurement of delta(13)C of CO(2) in air and unattended operation of measurement sequences up to 12 h.

  20. A 200 year temperature record from tree ring δ13C at the Qaidam Basin of the Tibetan Plateau after identifying the optimum method to correct for changing atmospheric CO2 and δ13C

    NASA Astrophysics Data System (ADS)

    Wang, Wenzhi; Liu, Xiaohong; Shao, Xuemei; Leavitt, Steven; Xu, Guobao; An, Wenling; Qin, Dahe

    2011-12-01

    Improved understanding of climate influences on tree ring stable carbon isotope (δ13C) ratios for Qilian juniper (Sabina przewalskii Kom.) will improve prospects for long climate reconstructions in northwestern China's Qaidam Basin, where weather stations are widely scattered with relatively short records. Here, we developed an annual-resolution δ13C series from 1800 to 2005 for trees in this extremely arid, high-elevation area. As expected, a significant decline in δ13C (of about 3.5‰) occurred from 1850 to 2005 in response to increasing atmospheric CO2 concentrations and decreasing atmospheric δ13C. High-frequency correlation analysis based on comparison of the tree ring δ13C chronology with recorded weather parameters revealed that mean temperature during the current growing season (April-August) most strongly influenced tree ring δ13C discrimination from 1956 to 2005. To clarify the climatic implications of the long-term trend, we systematically compared four previously published approaches to remove the effects of decreasing atmospheric δ13C from the climate signals. The optimal correction, which accounted for the decline in atmospheric δ13C (δ13Ccor) and for a discrimination rate of about 0.016‰ ppmv-1 for the CO2 partial pressure, captured the strongest temperature signal (r = 0.75, P < 0.001). The historical mean April-August temperatures inferred from the correlations of tree ring δ13C with climate data revealed a persistent warming trend during the past two centuries, especially since the 1980s. Our results therefore reveal a high potential for reconstruction of growing season temperatures on a millennial scale in the northeastern Tibetan Plateau.

  1. 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.

  2. [Responses of tissue carbon and delta 13C in epilithic mosses to the variations of anthropogenic CO2 and atmospheric nitrogen deposition in city area].

    PubMed

    Liu, Xue-yan; Xiao, Hua-yun; Liu, Cong-qiang; Li, You-yi; Xiao, Hong-wei

    2009-01-01

    We investigated the carbon (C) and nitrogen (N) concentrations and isotopic signatures (delta 13C and delta15 N) in epilithic mosses collected from urban sites to rural sites along four directions at Guiyang area. Mosses C (34.47%-52.76%) decreased significantly with distance from urban to rural area and strongly correlated with tissue N (0.85%-2.97%), showing atmospheric N deposition has positive effect on C assimilation of epilithic mosses, higher atmospheric N/NHx deposition at urban area has improved the photosynthesis and C fixation of mosses near urban, which also caused greater 13C discrimination for urban mosses. Mosses delta 13C signatures (-30.69% per hundred - -26.96% per hundred) got less negative with distance from urban to rural area, which was also related to the anthropogenic CO2 emissions in the city, and these 12C-enriched CO2 sources would lead to more negative mosses delta 13C through enhancing the atmospheric CO2 concentration in urban area. Moreover, according to the characteristics of mosses C and delta 13C variations with distance, it is estimated that the influences of urban anthropogenic CO2 sources on plants was mainly within 20 km from city center. This study mainly focused on the factors regulating tissue C and delta 13C of mosses in city area and the interaction between C and N in mosses, the responses of mosses C and delta 13C to urban CO2 emission and atmospheric N deposition have been revealed, which could provide new geochemical evidences for the control of city atmospheric pollution and the protection of ecosystems around city.

  3. Estimation of Insulin Resistance in Mexican Adults by the [13C]Glucose Breath Test Corrected for Endogenous Total CO2 Production

    PubMed Central

    Ibarra-Pastrana, Erika; Candia Plata, Maria del Carmen; Alvarez, Gerardo; Valencia, Mauro E.

    2012-01-01

    Objective. To evaluate the efficacy of the [13C]glucose breath test for measuring insulin resistance in Mexican adults with different glycemic states. Research Design and Methods. Fifty-eight adults underwent a [13C]glucose breath test with simultaneous measurement of total CO2 production by indirect calorimetry, at baseline and 90 minutes after the ingestion of 15 g of dextrose and 25 mg of [13C]glucose. HOMA was used as a marker of insulin resistance. Results. We found an inverse correlation between HOMA and the breath test δ13CO2 (‰), r = −0.41 (P = 0.001). After adjusting for total CO2 production, correlations between HOMA and fasting glucose were less strong but remained significant. An ROC curve was constructed using δ13CO2 (‰) and HOMA values; the cut-off point was 9.99‰ δ13CO2, corresponding to a sensitivity of 80.0 (95% CI: 51.9, 95.7) and a specificity of 67.4 (95% CI: 51.5, 80.9). Conclusions. The [13C]glucose breath test is a simple noninvasive procedure but was not sufficiently robust for an accurate diagnosis of insulin resistance. Our findings suggest that the test might be helpful in identifying individuals who are not IR, which in turn may contribute to improved diabetes prevention. PMID:22848216

  4. Estimation of Insulin Resistance in Mexican Adults by the [(13)C]Glucose Breath Test Corrected for Endogenous Total CO(2) Production.

    PubMed

    Ibarra-Pastrana, Erika; Candia Plata, Maria Del Carmen; Alvarez, Gerardo; Valencia, Mauro E

    2012-01-01

    Objective. To evaluate the efficacy of the [(13)C]glucose breath test for measuring insulin resistance in Mexican adults with different glycemic states. Research Design and Methods. Fifty-eight adults underwent a [(13)C]glucose breath test with simultaneous measurement of total CO(2) production by indirect calorimetry, at baseline and 90 minutes after the ingestion of 15 g of dextrose and 25 mg of [(13)C]glucose. HOMA was used as a marker of insulin resistance. Results. We found an inverse correlation between HOMA and the breath test δ(13)CO(2) (‰), r = -0.41 (P = 0.001). After adjusting for total CO(2) production, correlations between HOMA and fasting glucose were less strong but remained significant. An ROC curve was constructed using δ(13)CO(2) (‰) and HOMA values; the cut-off point was 9.99‰ δ(13)CO(2), corresponding to a sensitivity of 80.0 (95% CI: 51.9, 95.7) and a specificity of 67.4 (95% CI: 51.5, 80.9). Conclusions. The [(13)C]glucose breath test is a simple noninvasive procedure but was not sufficiently robust for an accurate diagnosis of insulin resistance. Our findings suggest that the test might be helpful in identifying individuals who are not IR, which in turn may contribute to improved diabetes prevention.

  5. Partitioning CO2 effluxes from an Atlantic pine forest soil between endogenous soil organic matter and recently incorporated 13C-enriched plant material.

    PubMed

    Fernandez, Irene; Cabaneiro, Ana; González-Prieto, Serafín J

    2006-04-15

    Soil CO2 effluxes from recently added 13C-labeled phytomass versus endogenous soil organic matter (SOM) were studied in an acid soil from Atlantic pine forests (NW Spain). After several cultures to incorporate fresh 13C-enriched Lolium perenne to a Humic Cambisol with predominance of humus--Al over humus--Fe complexes, potential soil C mineralization was determined by laboratory aerobic incubation (84 days). Isotopic 13C analyses of SOM fractions were assessed to know in which organic compartments the 13C was preferentially incorporated. Although in the 13C-labeled soil the C mineralization coefficient totalized less than 3% of soil C, the 13C mineralization coefficient exceeded 14%, indicating a greater lability of the newly incorporated organic matter. Organic compounds coming from added phytomass showed a higher lability and contributed considerably to the total soil CO2 effluxes (52% of total soil CO2 evolved during the first decomposition stages and 27% at the end), even though added-C comprised less than 4% of total soil C. Good determination coefficients, when values of CO2--C released were fitted to a first-order double exponential kinetic model, support the existence of two C pools of different lability. Kinetic parameters obtained with this model indicated that phytomass addition augmented the biodegradability of the labile pool (instantaneous mineralization rate k increased from 0.07 d(-1) to 0.12 d(-1)) but diminished that of the recalcitrant pool (instantaneous mineralization rate h decreased from 2.7 x 10(-4) d(-1) to 1.6 x 10(-4) d(-1)). Consequently, the differentiation between both SOM pools increased, showing the importance of SOM quality on CO2 emissions from this kind of soil to the atmosphere.

  6. 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.

    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.

  7. 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.

  8. 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

  9. 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

  10. Exploring Organic Matter Sources Through δ13C Depletion of Lipid Biomarkers at Lake El'gygytgyn, NE Siberia

    NASA Astrophysics Data System (ADS)

    Holland, A. R.; Wilkie, K. M.; Petsch, S.; Brigham-Grette, J.; Lake El'Gygytgyn Scientific Party

    2010-12-01

    Through studies of compound-specific δ13C, Lake El’gygytgyn pilot core LZ1029 has revealed unexpected information regarding organic matter source and carbon cycling in the lake throughout the past 50 kyr. Compound-specific δ13C of alkanes, fatty acids, and alcohols were analyzed to determine the changing sources of organic matter as well as the cause of a strong negative isotopic shift in the bulk sediment δ13C (-26‰ to -33‰) over the past 50 kyr. Compounds indicative of terrestrial, aquatic, bacterial, and archaeal sources were identified. An increase in lipid concentrations during the local last glacial maximum (LLGM) is interpreted to represent increased preservation due to decreasing dissolved oxygen in the water column and sediments. The majority of alkanes, fatty acids, and alcohols are long chain compounds consistent with a terrestrial plant origin, with a slight increase in aquatic (mid-chain) contribution during the LLGM. However, isotopic results indicate that long chain fatty acids (except C30) and alcohols cannot be entirely associated with terrestrial sources, as demonstrated by an average 5‰ carbon isotope excursion from interglacial to LLGM conditions. Both mid-chain (C19-C23) and short-chain (C14-C18) fatty acids display a 10‰ excursion, but mid-chain fatty acids are consistently ~7‰ depleted compared with short-chain fatty acids. Long chain n-alkanes and the C30 fatty acid demonstrate constant isotopic values throughout the LLGM, as expected from a terrestrial source. The strongest δ13C excursion from autochthonous mid- and short-chain fatty acids (average LLGM mid-chain fatty acid δ13C = -43‰) is interpreted to result from recycling of oxidized carbon within the lake with little or no exchange with atmospheric carbon. If the lake is permanently covered by ice, isotopically depleted dissolved carbon might build up in the water column from either oxidized organic matter or oxidized methane. The presence of diplopterol (LLGM δ13C

  11. A field-based method for simultaneous measurements of the δ18O and δ13C of soil CO2 efflux

    NASA Astrophysics Data System (ADS)

    Mortazavi, B.; Prater, J. L.; Chanton, J. P.

    Three approaches for determining the stable isotopic composition (δ13C and δ18O) of soil CO efflux were compared. A new technique employed mini-towers, constructed of open-topped piping, that were placed on the soil surface to collect soil-emitted CO2. Samples were collected along a vertical gradient and analyzed for CO2 concentration and isotopic composition. These data were then used to produce Keeling plots to determine the δ18O and δ13C of CO2 emitted from the soil. These results were then compared to the δ18O and δ13C of soil-respired CO2 measured with two other techniques: (1) flux chambers and (2) estimation from the application of the diffusional fractionation factor to measured values of below ground soil CO2 and to CO2 in equilibrium with soil water δ18O. Mini-tower δ18O Keeling plots were linear and highly significant (0.81< r 2 > 0.96), in contrast to chamber δ18O Keeling plots, which showed significant curvature, necessitating the use of a mass balance to calculate the δ18O of respired CO2. In the chambers, the values determined for the δ18O of soil respired CO2 approached the value of CO2 in equilibrium with surficial soil water, and the results were significantly δ18O enriched relative to the mini-tower results and the δ18O of soil CO2 efflux

  12. Simulating dynamics of δ13C of CO2 in the planetary boundary layer over a boreal forest region: covariation between surface fluxes and atmospheric mixing

    NASA Astrophysics Data System (ADS)

    Chen, Baozhang; Chen, Jing M.; Tans, Pieter P.; Huang, Lin

    2006-11-01

    Stable isotopes of CO2 contain unique information on the biological and physical processes that exchange CO2 between terrestrial ecosystems and the atmosphere. Ecosystem exchange of carbon isotopes with the atmosphere is correlated diurnally and seasonally with the planetary boundary layer (PBL) dynamics. The strength of this kind of covariation affects the vertical gradient of δ13C and thus the global δ13C distribution pattern. We need to understand the various processes involved in transport/diffusion of carbon isotope ratio in the PBL and between the PBL and the biosphere and the troposphere. In this study, we employ a one-dimensional vertical diffusion/transport atmospheric model (VDS), coupled to an ecosystem isotope model (BEPS-EASS) to simulate dynamics of 13CO2 in the PBL over a boreal forest region in the vicinity of the Fraserdale (FRD) tower (49°52'29.9''N, 81°34'12.3''W) in northern Ontario, Canada. The data from intensive campaigns during the growing season in 1999 at this site are used for model validation in the surface layer. The model performance, overall, is satisfactory in simulating the measured data over the whole course of the growing season. We examine the interaction of the biosphere and the atmosphere through the PBL with respect to δ13C on diurnal and seasonal scales. The simulated annual mean vertical gradient of δ13C in the PBL in the vicinity of the FRD tower was about 0.25‰ in 1999. The δ13C vertical gradient exhibited strong diurnal (29%) and seasonal (71%) variations that do not exactly mimic those of CO2. Most of the vertical gradient (96.5% +/-) resulted from covariation between ecosystem exchange of carbon isotopes and the PBL dynamics, while the rest (3.5%+/-) was contributed by isotopic disequilibrium between respiration and photosynthesis. This disequilibrium effect on δ13C of CO2 dynamics in PBL, moreover, was confined to the near surface layers (less than 350 m).

  13. How Closely Do the δ13C Values of Crassulacean Acid Metabolism Plants Reflect the Proportion of CO2 Fixed during Day and Night?1

    PubMed Central

    Winter, Klaus; Holtum, Joseph A.M.

    2002-01-01

    The extent to which Crassulacean acid metabolism (CAM) plant δ13C values provide an index of the proportions of CO2 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 C3 species (teak [Tectona grandis] and Clusia sp.) were grown in a cuvette, and net CO2 exchange was monitored for up to 51 d. In species exhibiting net dark CO2 fixation, between 14% and 73.3% of the carbon gain occurred in the dark. δ13C values of tissues formed inside the cuvette ranged between −28.7‰ and −11.6‰, and correlated linearly with the percentages of carbon gained in the light and in the dark. The δ13C values for new biomass obtained solely during the dark and light were estimated as −8.7‰ and −26.9‰, respectively. For each 10% contribution of dark CO2 fixation integrated over the entire experiment, the δ13C content of the tissue was, thus, approximately 1.8‰ 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 C3 plants when identified on the basis of carbon isotope content alone. PMID:12177497

  14. 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.

  15. 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

  16. 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.

  17. 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

  18. Evidence for CO2 Ice Formation and CO2 Gas Depletion in the South Polar Winter Atmosphere of Mars from Mars Climate Sounder Measurements

    NASA Astrophysics Data System (ADS)

    Kleinboehl, A.; Patel, P.; Schofield, J. T.; Kass, D. M.; Hayne, P. O.; McCleese, D. J.

    2016-09-01

    New 2D retrievals from MCS data show south polar winter atmospheric temperatures below the CO2 frost point, consistent with CO2 gas removal through condensation. Limb emission features suggest CO2 ice occurrence correlated with CO2 gas depletion.

  19. 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

  20. 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.

  1. Excretion kinetics of 13C-urea breath test: influences of endogenous CO2 production and dose recovery on the diagnostic accuracy of Helicobacter pylori infection.

    PubMed

    Som, Suman; Maity, Abhijit; Banik, Gourab Dutta; Ghosh, Chiranjit; Chaudhuri, Sujit; Daschakraborty, Sunil Baran; Ghosh, Shibendu; Pradhan, Manik

    2014-09-01

    We report for the first time the excretion kinetics of the percentage dose of (13)C recovered/h ((13)C-PDR %/h) and cumulative PDR, i.e. c-PDR (%) to accomplish the highest diagnostic accuracy of the (13)C-urea breath test ((13)C-UBT) for the detection of Helicobacter pylori infection without any risk of diagnostic errors using an optical cavity-enhanced integrated cavity output spectroscopy (ICOS) method. An optimal diagnostic cut-off point for the presence of H. pylori infection was determined to be c-PDR (%) = 1.47 % at 60 min, using the receiver operating characteristic curve (ROC) analysis to overcome the "grey zone" containing false-positive and false-negative results of the (13)C-UBT. The present (13)C-UBT exhibited 100 % diagnostic sensitivity (true-positive rate) and 100 % specificity (true-negative rate) with an accuracy of 100 % compared with invasive endoscopy and biopsy tests. Our c-PDR (%) methodology also manifested both diagnostic positive and negative predictive values of 100 %, demonstrating excellent diagnostic accuracy. We also observed that the effect of endogenous CO2 production related to basal metabolic rates in individuals was statistically insignificant (p = 0.78) on the diagnostic accuracy. However, the presence of H. pylori infection was indicated by the profound effect of urea hydrolysis rate (UHR). Our findings suggest that the current c-PDR (%) is a valid and sufficiently robust novel approach for an accurate, specific, fast and noninvasive diagnosis of H. pylori infection, which could routinely be used for large-scale screening purposes and diagnostic assessment, i.e. for early detection and follow-up of patients.

  2. CH4 and CO2 production below two contrasting peatland micro-relief forms: An inhibitor and δ(13)C study.

    PubMed

    Krohn, Johannes; Lozanovska, Ivana; Kuzyakov, Yakov; Parvin, Shahnaj; Dorodnikov, Maxim

    2017-02-03

    Two peatland micro-relief forms (microforms) - hummocks and hollows - differ by their hydrological characteristics (water table level, i.e. oxic-anoxic conditions) and vegetation communities. We studied the CH4 and CO2 production potential and the localization of methanogenic pathways in both hummocks and hollows at depths of 15, 50, 100, 150 and 200cm in a laboratory incubation experiment. For this purpose, we measured CH4 and CO2 production rates, peat elemental composition, as well as δ(13)C values of gases and solids; the specific inhibitor of methanogenesis BES (2-bromo-ethane sulfonate, 1mM) was aimed to preferentially block the acetoclastic pathway. The cumulative CH4 production of all depths was almost one fold higher in hollows than in hummocks, with no differences in CO2. With depth, CO2 and CH4 production decreased, and the relative contribution of the hydrogenotrophic pathway of methanogenesis increased. The highest methanogenic activity among all depths and both microforms was measured at 15cm of hollows (91%) at which the highest relative contribution of acetoclastic vs. hydrogenotrophic pathway (92 and 8%, respectively) was detected. For hummocks, the CH4 production was the highest at 50cm (82%), where relative contribution of acetoclastic methanogenesis comprised 89%. The addition of 1mM BES was not selective and inhibited both methanogenic pathways in the soil. Thus, BES was less efficient in partitioning the pathways compared with the δ(13)C signature. We conclude that the peat microforms - dry hummocks and wet hollows - play an important role for CH4 but not for CO2 production when the effects of living vegetation are excluded.

  3. Atmospheric CO2 concentrations and δ13C values during 2011-2012 voyage: Mediterranean, Atlantic Ocean, southern Indian Ocean and New Zealand to Antarctica

    NASA Astrophysics Data System (ADS)

    Longinelli, A.; Langone, L.; Ori, C.; Giglio, F.; Selmo, E.; Sgavetti, M.

    2013-10-01

    During the 2011-2012 hemispheric voyage of the M/V Italica from Italy to the Atlantic Ocean, southern Indian Ocean, New Zealand and Antarctica, atmospheric CO2 concentrations were continuously recorded and 52 air samples collected in 4-L Pyrex flasks for the measurement of the δ13C of atmospheric CO2. In the case of CO2 concentrations, new data include the following: 1) in the Adriatic, between Ravenna and Otranto, CO2 was never measured in order to avoid the expected heavy contribution from industrial plants; the 2011 measurements fully confirm this contribution; 2) in the Atlantic, along the Moroccan coast, high values of up to 415 ppmv were recorded, apparently due to considerable industrial development in Morocco; 3) minor CO2 concentrations were also recorded along other sections of the African coast north of the Equator, whereas relatively low constant values were recorded south of the Equator; 4) in the southern Indian Ocean, CO2 concentrations were measured almost along a parallel, yielding homogeneous values not much higher than the mean values recorded at NOAA stations in nearby areas. With only one exception, the δ13C values were systematically less negative than -9‰ (VPDB), the mean values for the three oceanic sections being the following: Atlantic Ocean -8.64 ± 0.20‰; Indian Ocean -8.54 ± 0.06‰; New Zealand to Antarctica -8.49 ± 0.02‰. A small but progressive increase in δ13C values with increasing latitude was in good agreement with the expected trend. The homogeneity of such values between New Zealand and Antarctica was remarkable, as these samples had been collected in particularly rough oceanic conditions with high winds. In spite of these particular environmental conditions these values were very close to those of samples collected in the same area in 2009 and 2010 in conditions of calm sea and low wind. This similarity contrasts sharply with the theory and models of air-sea gas exchange.

  4. 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

  5. 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.

  6. Analysis of methane production pathways in a riparian wetland of a temperate forest catchment, using δ13C of pore water CH4 and CO2

    NASA Astrophysics Data System (ADS)

    Itoh, Masayuki; Ohte, Nobuhito; Koba, Keisuke; Sugimoto, Atsuko; Tani, Makoto

    2008-09-01

    To clarify how hydrological processes affect biogenic methane (CH4) production and emission from soil surfaces, we analyzed the δ13C of CH4 and CO2 and chemical constituents dissolved in groundwater at a wetland in the headwater catchment of a temperate forest in Japan. We estimated the contribution of acetate fermentation using the δ13C isotope mass balance of dissolved CH4 and CO2. CH4 production pathways (e.g., acetate fermentation and carbonate reduction) changed temporally and spatially with hydrologically controlled redox conditions. The proportion of methanogenesis attributable to acetate fermentation usually decreased with temperature, suggesting that carbonate reduction dominated under conditions of high CO2 concentration. In particular, the groundwater table and summer temperatures were key controlling factors in the interannual and intra-annual changes in CH4 production pathways, controlling oxygen supply and consumption and, therefore, redox conditions in the soil. Under high temperature and high water table conditions during summer, the soil was strongly reduced and the proportion of carbonate reduction increased. Acetate fermentation also increased episodically, resulting in sporadic increases in δ13C-CH4. The calculated acetate contribution obviously decreased in periods of low water table and high temperature when the soil surface was relatively oxic, implying deactivation of acetoclastic methanogenesis under oxic conditions. Thus, hydrological processes control the supply of these electron donors and acceptors and therefore play an important role in determining the relative proportions of CH4-producing pathways. Our results also indicate that an increase in acetate contribution under highly reducing conditions stimulates CH4 production and emission from the soil surface.

  7. 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.

  8. 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

  9. 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

  10. 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.

  11. 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.

  12. 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.

  13. 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).

  14. 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.

  15. Growth decline and divergent tree ring isotopic composition (δ(13) C and δ(18) O) contradict predictions of CO2 stimulation in high altitudinal forests.

    PubMed

    Gómez-Guerrero, Armando; Silva, Lucas C R; Barrera-Reyes, Miguel; Kishchuk, Barbara; Velázquez-Martínez, Alejandro; Martínez-Trinidad, Tomás; Plascencia-Escalante, Francisca Ofelia; Horwath, William R

    2013-06-01

    Human-induced changes in atmospheric composition are expected to affect primary productivity across terrestrial biomes. Recent changes in productivity have been observed in many forest ecosystems, but low-latitude upper tree line forests remain to be investigated. Here, we use dendrochronological methods and isotopic analysis to examine changes in productivity, and their physiological basis, in Abies religiosa (Ar) and Pinus hartwegii (Ph) trees growing in high-elevation forests of central Mexico. Six sites were selected across a longitudinal transect (Transverse Volcanic Axis), from the Pacific Ocean toward the Gulf of Mexico, where mature dominant trees were sampled at altitudes ranging from 3200 to 4000 m asl. A total of 60 Ar and 84 Ph trees were analyzed to describe changes in growth (annual-resolution) and isotopic composition (decadal-resolution) since the early 1900s. Our results show an initial widespread increase in basal area increment (BAI) during the first half of the past century. However, BAI has decreased significantly since the 1950s with accentuated decline after the 1980s in both species and across sites. We found a consistent reduction in atmosphere to wood (13) C discrimination, resulting from increasing water use efficiency (20-60%), coinciding with rising atmospheric CO2 . Changes in (13) C discrimination were not followed, however, by shifts in tree ring δ(18) O, indicating site- and species-specific differences in water source or uptake strategy. Our results indicate that CO2 stimulation has not been enough to counteract warming-induced drought stress, but other stressors, such as progressive nutrient limitation, could also have contributed to growth decline. Future studies should explore the distinct role of resource limitation (water vs. nutrients) in modulating the response of high-elevation ecosystems to atmospheric change.

  16. Production of hyperpolarized 13CO2 from [1-13C]pyruvate in perfused liver does reflect total anaplerosis but is not a reliable biomarker of glucose production

    PubMed Central

    Moreno, Karlos X.; Moore, Christopher L.; Burgess, Shawn C.; Sherry, A. Dean; Malloy, Craig R.

    2015-01-01

    In liver, 13CO2 can be generated from [1-13C] pyruvate via pyruvate dehydrogenase or anaplerotic entry of pyruvate into the TCA cycle followed by decarboxylation at phosphoenolpyruvate carboxykinase (PEPCK), the malic enzyme, isocitrate dehydrogenase, or α-ketoglutarate dehydrogenase. The purpose of this study was to determine the relative importance of these pathways in production of hyperpolarized (HP) 13CO2 after administration of hyper-polarized pyruvate in livers supplied with a fatty acid plus substrates for gluconeogenesis. Isolated mouse livers were perfused with a mixture of thermally-polarized 13C-enriched pyruvate, lactate and octanoate in various combinations prior to exposure to HP pyruvate. Under all perfusion conditions, HP malate, aspartate and fumarate were detected within ~ 3 s showing that HP [1-13C]pyruvate is rapidly converted to [1-13C]oxaloacetate which can subsequently produce HP 13CO2 via decarboxylation at PEPCK. Measurements using HP [2-13C]pyruvate allowed the exclusion of reactions related to TCA cycle turnover as sources of HP 13CO2. Direct measures of O2 consumption, ketone production, and glucose production by the intact liver combined with 13C isotopomer analyses of tissue extracts yielded a comprehensive profile of metabolic flux in perfused liver. Together, these data show that, even though the majority of HP 13CO2 derived from HP [1-13C]pyruvate in livers exposed to fatty acids reflects decarboxylation of [4-13C]oxaloacetate (PEPCK) or [4-13C]malate (malic enzyme), the intensity of the HP 13CO2 signal is not proportional to glucose production because the amount of pyruvate returned to the TCA cycle via PEPCK and pyruvate kinase is variable, depending upon available substrates. PMID:26543443

  17. In situ assessment of the velocity of carbon transfer by tracing 13 C in trunk CO2 efflux after pulse labelling: variations among tree species and seasons.

    PubMed

    Dannoura, Masako; Maillard, Pascale; Fresneau, Chantal; Plain, Caroline; Berveiller, Daniel; Gerant, Dominique; Chipeaux, Christophe; Bosc, Alexandre; Ngao, Jérôme; Damesin, Claire; Loustau, Denis; Epron, Daniel

    2011-04-01

    Phloem is the main pathway for transferring photosynthates belowground. In situ(13) C pulse labelling of trees 8-10 m tall was conducted in the field on 10 beech (Fagus sylvatica) trees, six sessile oak (Quercus petraea) trees and 10 maritime pine (Pinus pinaster) trees throughout the growing season. Respired (13) CO2 from trunks was tracked at different heights using tunable diode laser absorption spectrometry to determine time lags and the velocity of carbon transfer (V). The isotope composition of phloem extracts was measured on several occasions after labelling and used to estimate the rate constant of phloem sap outflux (kP ). Pulse labelling together with high-frequency measurement of the isotope composition of trunk CO2 efflux is a promising tool for studying phloem transport in the field. Seasonal variability in V was predicted in pine and oak by bivariate linear regressions with air temperature and soil water content. V differed among the three species consistently with known differences in phloem anatomy between broadleaf and coniferous trees. V increased with tree diameter in oak and beech, reflecting a nonlinear increase in volumetric flow with increasing bark cross-sectional area, which suggests changes in allocation pattern with tree diameter in broadleaf species. Discrepancies between V and kP indicate vertical changes in functional phloem properties.

  18. 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.

  19. 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.

  20. 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.

  1. Partitioning of Organic Compounds into Supercritical CO2 in Depleted Oil Reservoirs - A Review

    NASA Astrophysics Data System (ADS)

    Burant, A.; Lowry, G. V.; Karamalidis, A.

    2012-12-01

    Depleted oil reservoirs, with enhanced oil recovery, will be one of the first adopters of carbon capture and storage (CCS), which is a promising mitigation strategy for global climate change. The large scale implementation of CCS mandates better understanding of the risks associated with CO2 injection, especially in regards to potential leakage of the stored CO2. Organics, in the residual oil and dissolved in the brine, can partition into supercritical CO2 (sc-CO2) and move with that phase if it leaks. This review presents an overview of the thermodynamic models and trends in experimental partitioning data needed to understand what compounds may be expected to move with the sc-CO2. There are two main types of thermodynamic models used for predicting the solubility of organic compounds in sc-CO2, equations of state and quantitative structure activity relationships. Both can predict the partitioning behavior of one compound in sc-CO2, however only equations of state can predict solubility in multicomponent systems. In addition, equations of state have been developed to determine the effect of electrolytes on the partitioning behavior of organics dissolved in brines. There are three main trends in the partitioning behavior of organics in sc-CO2: Pure phase solubility follows trends in vapor pressure; compounds with higher volatility have higher solubility in sc-CO2. Second, the partitioning from water to sc-CO2 follows trends in Henry's constants, which follow the relative solubility of a compound in both the sc-CO2 and aqueous phases. Thirdly, the solubility of a compound can be enhanced by the presence of another; highly volatile compounds enhance the solubility of compounds with lower volatility. Finally, the review presents the gaps in experimental research that can be used to improve the modeling of the partitioning behavior of organics in sc-CO2, specifically in regards to co-solvency effects and the effects of electrolytes on the partitioning of dissolved

  2. A Portable FTIR Analyser for Field Measurements of Trace Gases and their Isotopologues: CO2, CH4, N2O, CO, del13C in CO2 and delD in water vapour

    NASA Astrophysics Data System (ADS)

    Griffith, D. W.; Bryant, G. R.; Deutscher, N. M.; Wilson, S. R.; Kettlewell, G.; Riggenbach, M.

    2007-12-01

    We describe a portable Fourier Transform InfraRed (FTIR) analyser capable of simultaneous high precision analysis of CO2, CH4, N2O and CO in air, as well as δ13C in CO2 and δD in water vapour. The instrument is based on a commercial 1 cm-1 resolution FTIR spectrometer fitted with a mid-IR globar source, 26 m multipass White cell and thermoelectrically-cooled MCT detector operating between 2000 and 7500 cm-1. Air is passed through the cell and analysed in real time without any pre-treatment except for (optional) drying. An inlet selection manifold allows automated sequential analysis of samples from one or more inlet lines, with typical measurement times of 1-10 minutes per sample. The spectrometer, inlet sampling sequence, real-time quantitative spectrum analysis, data logging and display are all under the control of a single program running on a laptop PC, and can be left unattended for continuous measurements over periods of weeks to months. Selected spectral regions of typically 100-200 cm-1 width are analysed by a least squares fitting technique to retrieve concentrations of trace gases, 13CO2 and HDO. Typical precision is better than 0.1% without the need for calibration gases. Accuracy is similar if measurements are referenced to calibration standard gases. δ13C precision is typically around 0.1‰, and for δD it is 1‰. Applications of the analyser include clean and polluted air monitoring, tower-based flux measurements such as flux gradient or integrated horizontal flux measurements, automated soil chambers, and field-based measurements of isotopic fractionation in soil-plant-atmosphere systems. The simultaneous multi-component advantages can be exploited in tracer-type emission measurements, for example of CH4 from livestock using a co-released tracer gas and downwind measurement. We have also developed an open path variant especially suited to tracer release studies and measurements of NH3 emissions from agricultural sources. An illustrative

  3. 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.

  4. 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.

  5. 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.

  6. 13C-Depleted carbon microparticles in >3700-Ma sea-floor sedimentary rocks from west greenland

    PubMed

    Rosing

    1999-01-29

    Turbiditic and pelagic sedimentary rocks from the Isua supracrustal belt in west Greenland [more than 3700 million years ago (Ma)] contain reduced carbon that is likely biogenic. The carbon is present as 2- to 5-micrometer graphite globules and has an isotopic composition of delta13C that is about -19 per mil (Pee Dee belemnite standard). These data and the mode of occurrence indicate that the reduced carbon represents biogenic detritus, which was perhaps derived from planktonic organisms.

  7. A dynamic soil chamber system coupled with a tunable diode laser for online measurements of delta13C, delta18O, and efflux rate of soil-respired CO2.

    PubMed

    Powers, Heath H; Hunt, John E; Hanson, David T; McDowell, Nate G

    2010-02-01

    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

  8. 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

  9. On the suitability of partially clathrated ice for analysis of concentration and δ 13C of palaeo-atmospheric CO 2

    NASA Astrophysics Data System (ADS)

    Schaefer, Hinrich; Lourantou, Anna; Chappellaz, Jérôme; Lüthi, Dieter; Bereiter, Bernhard; Barnola, Jean-Marc

    2011-07-01

    The stable carbon isotopic signature of carbon dioxide (δ 13CO 2) measured in the air occlusions of polar ice provides important constraints on the carbon cycle in past climates. In order to exploit this information for previous glacial periods, one must use deep, clathrated ice, where the occluded air is preserved not in bubbles but in the form of air hydrates. Therefore, it must be established whether the original atmospheric δ 13CO 2 signature can be reconstructed from clathrated ice. We present a comparative study using coeval bubbly ice from Berkner Island and ice from the bubble-clathrate transformation zone (BCTZ) of EPICA Dome C (EDC). In the EDC samples the gas is partitioned into clathrates and remaining bubbles as shown by erroneously low and scattered CO 2 concentration values, presenting a worst-case test for δ 13CO 2 reconstructions. Even so, the reconstructed atmospheric δ 13CO 2 values show only slightly larger scatter. The difference to data from coeval bubbly ice is statistically significant. However, the 0.16‰ magnitude of the offset is small for practical purposes, especially in light of uncertainty from non-uniform corrections for diffusion related fractionation that could contribute to the discrepancy. Our results are promising for palaeo-atmospheric studies of δ 13CO 2 using a ball mill dry extraction technique below the BCTZ of ice cores, where gas is not subject to fractionation into microfractures and between clathrate and bubble reservoirs.

  10. Leaf functional response to increasing atmospheric CO(2) concentrations over the last century in two northern Amazonian tree species: a historical δ(13) C and δ(18) O approach using herbarium samples.

    PubMed

    Bonal, Damien; Ponton, Stéphane; Le Thiec, Didier; Richard, Béatrice; Ningre, Nathalie; Hérault, Bruno; Ogée, Jérôme; Gonzalez, Sophie; Pignal, Marc; Sabatier, Daniel; Guehl, Jean-Marc

    2011-08-01

    We assessed the extent of recent environmental changes on leaf morphological (stomatal density, stomatal surface, leaf mass per unit area) and physiological traits (carbon isotope composition, δ(13)C(leaf) , and discrimination, Δ(13)C(leaf) , oxygen isotope composition, δ(18)O(leaf) ) of two tropical rainforest species (Dicorynia guianensis; Humiria balsamifera) that are abundant in the Guiana shield (Northern Amazonia). Leaf samples were collected in different international herbariums to cover a 200 year time-period (1790-2004) and the whole Guiana shield. Using models describing carbon and oxygen isotope fractionations during photosynthesis, different scenarios of change in intercellular CO(2) concentrations inside the leaf (C(i)), stomatal conductance (g), and photosynthesis (A) were tested in order to understand leaf physiological response to increasing air CO(2) concentrations (C(a)). Our results confirmed that both species displayed physiological response to changing C(a) . For both species, we observed a decrease of about 1.7‰ in δ(13)C(leaf) since 1950, without significant change in Δ(13)C(leaf) and leaf morphological traits. Furthermore, there was no clear change in δ(18)O(leaf) for Humiria over this period. Our simulation approach revealed that an increase in A, rather than a decrease in g, explained the observed trends for these tropical rainforest species, allowing them to maintain a constant ratio of C(i)/C(a) .

  11. 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.

  12. Identification of biomass utilizing bacteria in a carbon-depleted glacier forefield soil by the use of 13C DNA stable isotope probing.

    PubMed

    Zumsteg, Anita; Schmutz, Stefan; Frey, Beat

    2013-06-01

    As Alpine glaciers are retreating rapidly, bare soils with low organic C and N contents are becoming exposed. Carbon availability is a key factor regulating microbial diversity and ecosystem functioning in these soils. The aim of this study was to investigate how bacterial activity, community structure and composition are influenced by organic carbon availability. Bare soils were supplied with (13)C-labelled fungal (Penicillium sp.) and green algal (Chlorella sp.) biomass and the CO2 evolution and its δ(13)C signature were monitored up to 60 days. These organisms have previously been isolated near the glacier terminus. DNA stable isotope probing followed by T-RFLP profiling and sequencing of 16S rRNA genes was employed to identify consumers able to assimilate carbon from these biomass amendments. Higher respiration and higher bacterial activity indicated a more efficient utilization of algal cells than fungal cells. Flavobacterium sp. predominantly incorporated fungal-derived C, whereas the algal-derived C was mainly incorporated by Acidobacteria and Proteobacteria. This study emphasizes the important role of both fungal and algal biomass in increasing the carbon pool in recently deglaciated bare soils, as only 20% of the added C was respired as CO2, and the rest, we presume, remained in the soil.

  13. 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.

  14. 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

  15. 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.

  16. 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.

  17. 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.

  18. δ 13C of ecosystem-respired CO2 along a gradient of C3 woody-plant encroachment into C4 grassland

    NASA Astrophysics Data System (ADS)

    Sun, W.; Scott, R. L.; Resco, V.; Cable, J. M.; Huxman, T. E.; Williams, D. G.

    2006-12-01

    Woody plant encroachment into grassland has the potential to affect net primary production, in part by changing the sensitivities of photosynthesis and respiration to precipitation. Encroachment of mesquite (Prosopis) into floodplain sacaton (Sporobolus) grassland along the San Pedro River in southeastern Arizona has altered the magnitude and seasonal pattern of net ecosystem carbon exchange and ecosystem respiration. We hypothesized that because mesquite accesses ground water in these floodplain environments, its advancement and dominance in former grassland reduces the sensitivities of photosynthesis and autotrophic respiration to inputs of growing season precipitation. The observed elevated rates of ecosystem respiration following rainfall inputs are likely to result from microbial decomposition of labile organic matter derived from the highly productive mesquite trees. We used the Keeling plot method to monitor carbon-13 composition of nocturnal ecosystem-respired CO2 (δ 13CR) during the growing seasons of 2005 and 2006 at three sites spanning a gradient of mesquite invasion: C4 sacaton grassland, mixed mesquite/grass shrubland and C3 mesquite woodland. δ 13CR in the C4 grassland increased from -18.8‰ during the dry premonsoon period to -16.7‰ after the onset of summer rains, whereas δ 13CR in the mixed shrub/grass and woodland ecosystems declined from -20.9‰ to - 24‰ and from -20.8‰ to -24.7‰, respectively, following the onset of summer rains. The δ 13CR of respired CO2 was collected separately from soil, roots, leaves and surface litter to evaluate the contribution of each of these components to ecosystem respiration. Partitioning of ecosystem respiration using these isotope end-members and responses to short-term (days) changes in shallow (0-5cm) soil moisture content suggest that in former grassland now occupied by mesquite woodland, rainfall inputs primarily stimulate microbial decomposition and have little effect on autotrophic respiration

  19. 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.

  20. 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.

  1. 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

  2. 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

  3. 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

  4. 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.

  5. 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

  6. 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

  7. 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

  8. 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.

  9. Isotopic ((13)C) fractionation during plant residue decomposition and its implications for soil organic matter studies.

    PubMed

    Schweizer; Fear; Cadisch

    1999-07-01

    Carbon isotopic fractionations in plant materials and those occurring during decomposition have direct implications in studies of short-and longer-term soil organic matter dynamics. Thus the products of decomposition, the evolved CO(2) and the newly formed soil organic matter, may vary in their (13)C signature from that of the original plant material. To evaluate the importance of such fractionation processes, the variations in (13)C signatures between and within plant parts of a tropical grass (Brachiaria humidicola) and tropical legume (Desmodium ovalifolium) were measured and the changes in (13)C content (signatures) during decomposition were monitored over a period of four months. As expected the grass materials were less depleted in (13)C (-11.4 to -11.9 per thousand) than those of the legume (-27.3 to -25.8 per thousand). Root materials of the legume were less (1.5 per thousand) depleted in (13)C compared with the leaves. Plant lignin-C was strongly depleted in (13)C compared with the bulk material by up to 2.5 per thousand in the legume and up to 4.7 per thousand in the grass. Plant materials were subsequently incubated in a sand/nutrient-solution/microbial inoculum mixture. The respiration product CO(2) was trapped in NaOH and precipitated as CaCO(3), suitable for analysis using an automated C/N analyser coupled to an isotope ratio mass spectrometer. Significant depletion in (13)C of the evolved CO(2) was observed during the initial stages of decomposition probably as a result of microbial fractionation as it was not associated with the (13)C signatures of the measured more decomposable fractions (non-acid detergent fibre and cellulose). While the cumulative CO(2)-(13)C signatures of legume materials became slightly enriched with ongoing decomposition, the CO(2)-C of the grass materials remained depleted in (13)C. Associated isotopic fractionation correction factors for source identification of CO(2-)C varied with time and suggested errors of 2-19% in the

  10. 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…

  11. 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.

  12. Radiocarbon-depleted CO2 evidence for fuel biodegradation at the Naval Air Station North Island (USA) fuel farm site.

    PubMed

    Boyd, Thomas J; Pound, Michael J; Lohr, Daniel; Coffin, Richard B

    2013-05-01

    Dissolved CO(2) radiocarbon and stable carbon isotope ratios were measured in groundwater from a fuel contaminated site at the North Island Naval Air Station in San Diego, CA (USA). A background groundwater sampling well and 16 wells in the underground fuel contamination zone were evaluated. For each sample, a two end-member isotopic mixing model was used to determine the fraction of CO(2) derived from fossil fuel. The CO(2) fraction from fossil sources ranged from 8 to 93% at the fuel contaminated site, while stable carbon isotope values ranged from -14 to +5‰VPDB. Wells associated with highest historical and contemporary fuel contamination showed the highest fraction of CO(2) derived from petroleum (fossil) sources. Stable carbon isotope ratios indicated sub-regions on-site with recycled CO(2) (δ(13)CO(2) as high as +5‰VPDB) - most likely resulting from methanogenesis. Ancillary measurements (pH and cations) were used to determine that no fossil CaCO(3), for instance limestone, biased the analytical conclusions. Radiocarbon analysis is verified as a viable and definitive technique for confirming fossil hydrocarbon conversion to CO(2) (complete oxidation) at hydrocarbon-contaminated groundwater sites. The technique should also be very useful for assessing the efficacy of engineered remediation efforts and by using CO(2) production rates, contaminant mass conversion over time and per unit volume.

  13. Unexpected efficiency boosting in CO2-microemulsions: a cyclohexane depletion zone near the fluorinated surfactants evidenced by a systematic SANS contrast variation study.

    PubMed

    Pütz, Y; Grassberger, L; Lindner, P; Schweins, R; Strey, R; Sottmann, T

    2015-02-28

    Microemulsions with supercritical CO2 are promising alternatives for organic solvents, especially if both polar and non-polar components need to be dissolved. However, only fluorinated surfactants, which are known to be environmentally unfriendly, are appropriate to formulate well-structured microemulsions. While most approaches to increase the environmental performance of CO2-microemulsions deal with the design of new surfactants with a reduced degree of fluorination, we discovered that the partial substitution of CO2 by cyclohexane enables a considerable reduction of fluorinated surfactants. Thereby, the most efficient solubilization of the CO2/cyclohexane mixture, which turned out to be pressure-dependent, was found at a cyclohexane-to-CO2 mass ratio between 1 : 6 and 1 : 4. In order to elucidate this unexpected effect a systematic Small Angle Neutron Scattering (SANS) contrast variation study was performed. The analysis of the recorded scattering curves by the Generalized Indirect Fourier Transformation (GIFT) clearly shows that the scattering length density profiles differ considerably from CO2-microemulsions without cyclohexane. Instead of a nearly constant scattering length density, a density profile that varies systematically over half of the droplet radius was detected. These results clearly indicate that the observed efficiency boosting is caused by the formation of a depletion zone of cyclohexane close to the fluorinated amphiphilic film.

  14. 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 second quarter falls within the demonstration project.

  15. 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.

  16. 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

  17. Age-related variations in delta(13)C of ecosystem respiration across a coniferous forest chronosequence in the Pacific Northwest.

    PubMed

    Fessenden, Julianna E; Ehleringer, James R

    2002-02-01

    We tested the hypothesis that forest age influences the carbon isotope ratio (delta13C) of carbon reservoirs and CO2 at local and regional levels. Carbon isotope ratios of ecosystem respiration (delta13C(R)), soil respiration (delta13C(R-soil)), bulk needle tissue (delta13C(P)) and soil organic carbon (delta(13)C(SOC)) were measured in > 450-, 40- and 20-year-old temperate, mixed coniferous forests in southern Washington, USA. Values of delta13C(R), delta13C(R-soil), delta13C(P) and delta13C(SOC) showed consistent enrichment with increasing stand age. Between the youngest and oldest forests there was an approximately 1 per thousand enrichment in delta13C(P) (at similar canopy levels), delta13C(SOC) (throughout the soil column), delta13C(R-soil) (during the wet season) and delta13C(R) (during the dry season). Mean values of delta13C(R) were -25.9, -26.5 and -27.0 per thousand for the 450-, 40- and 20-year-old forests, respectively. Both delta13C(R-soil) and the difference between delta13C(R) and delta13C(R-soil) were more 13C enriched in older forests than in young forest: delta13C(R) - delta13C(R-soil) = 2.3, 1.1 and 0.5 per thousand for the 450-, 40- and 20-year-old forests, respectively. Values of delta(13)C(P) were proportionally more depleted relative to delta13C(R): delta13C(R) - delta13C(P) = 0.5, 2.2 and 2.5 per thousand for the 450-, 40- and 20-year-old forests, respectively. Values of delta13C(P) were most 13C-enriched at the top of the canopy and in the oldest forest regardless of season (overall values were -26.9, -28.7 and -29.4 per thousand for the 450-, 40- and 20-year-old forests, respectively). Values of delta13C(SOC) from shallow soil depths were similar to delta13C(P) values of upper- and mid-canopy needles. All delta13C data are consistent with the hypothesis that a decrease in stomatal conductance associated with decreased hydraulic conductance leads to increased CO2 diffusional limitations in older coniferous trees. The strong associations

  18. A ubiquitous hydrothermal episode recorded in the sheet-crack cements of a Marinoan cap dolostone of South China: Implication for the origin of the extremely 13C-depleted calcite cement

    NASA Astrophysics Data System (ADS)

    Zhou, Guanghong; Luo, Taiyi; Zhou, Mingzhong; Xing, Lecai; Gan, Tian

    2017-02-01

    Sheet-crack - primarily filled with chalcedony, quartz and calcite - is a type of significant sedimentary structure in almost all documented cap carbonates in platform-to-slope settings, which sharply overlie the global Marinoan (∼635 Ma) glacial tillite. The Jiulongwan section, located in the Yangtze Gorges areas, South China, is significant for the first discovery of extremely 13C-depleted13C down to -41‰) calcite cements in sheet-crack structure (Jiang et al., 2003a), which provides direct evidence for the methane seep hypothesis (Kennedy et al., 2001). Focusing on the calcite cements in the same section, Bristow et al. (2011) proposed a hydrothermal origin based on high temperatures (378 °C) determined by carbonate clumped isotope thermometry (CCIT). In this study, we provide evidence for the hydrothermal model using fluid inclusion technology (FIT) to quartz cements in the Jiulongwan section. The widespread sheet-crack structures in South China have uniform mineral paragenetic assemblages, which apparently reflect three stages of a hydrothermal fluid activity, including dolomitization at the early stage, silicification comprising chalcedony and quartz at the middle stage, and calcitization characterized by carbonaceous calcite filling preexisting voids at the late stage. Primary aqueous fluid inclusions from quartz crystals have homogenization temperatures of approximately 160-220 °C (mean, 192 °C, n = 31), while the salinity histogram contains two peaks at low salinity (6.3-8.3 wt.% NaCl equiv.) and high salinity (18.0-20.8 wt.% NaCl equiv.), reflecting precipitation caused by mixing of high- and low-salinity fluids. A modified and detailed hydrothermal model is proposed indicating that the sheet-crack structure resulted from successive thermal fluid activity after karstic dissolution due to postglacial isostatic rebound. This model is compatible with the unified sequence of glacio-eustatic events after the termination of Marinoan glaciation (Zhou

  19. The evolution of 13C and 18O isotope composition of DIC in a calcite depositing film of water with isotope exchange between the DIC and a CO2 containing atmosphere, and simultaneous evaporation of the water. Implication to climate proxies from stalagmites: A theoretical model

    NASA Astrophysics Data System (ADS)

    Dreybrodt, Wolfgang; Romanov, Douchko

    2016-12-01

    The most widely applied climate proxies in speleothems are the isotope compositions of carbon and oxygen expressed by δ13C and δ18O values. However, mechanisms, which are not related to climate changes, overlay the climate signal. One is the temporal increase of both, δ13C and δ18O values by kinetic processes during precipitation of calcite. Isotope exchange between DIC in the water and the CO2 in the surrounding cave atmosphere can also change isotope composition. Here we present a theoretical model of the temporal isotope evolution of DIC in a thin water layer during precipitation of calcite and simultaneous isotope exchange with the cave atmosphere, and simultaneous evaporation of water. The exchange of oxygen isotopes in the DIC with those in the water is also considered. For drip times for Tdrip < 0.2τ, where τ is the precipitation time, we find for the change of the δ13C and δ18O values, respectively, after the time Tdrip ΔDIC(Tdrip) = ((λ + ɛ)Ceq/C0 - ɛ) Tdrip/τ + ((δeqatm - δ0) Tdrip/τinatm) + (δeqwater - δ0 - ɛw Tdrip/Tev) Tdrip/Twater The first term on the right hand side is the contribution from precipitation of calcite, the second stems from isotope exchange with the CO2 of the cave atmosphere, and the third results from isotope exchange between oxygen in the DIC and the oxygen in the water. λ, ε are kinetic parameters, τ is the time scale of precipitation, (δeqatm -δ0) and (δeqwater -δ0) are the differences between the corresponding initial δ-value δ0 and the value δeqatm,water if DIC were in isotope equilibrium with the atmosphere or in the case of oxygen with the water, respectively. τinatm and τwater are the time scales of approach to isotope equilibrium by the exchange reactions. Ceq is the concentration of DIC in chemical equilibrium with the CO2 in the cave atmosphere and C0 is the initial concentration, when the water drips to the stalagmite. Tev is the time needed for complete evaporation of the water layer. ε

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. 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.

  8. Linking Biogeochemistry to Microbial Diversity Using New 13C Approaches

    NASA Astrophysics Data System (ADS)

    Baggs, E. M.

    2005-12-01

    The use of 13C enables us to overcome uncertainties associated with soil C processes and to assess the links between species diversity and ecosystem function. Recent advances in stable isotope techniques enable determination of process rates, for example CH4 oxidation by direct measurement of 13C-CH4 and 13C-CO2. This overcomes uncertainties associated with reliance on changes in net CH4 emission, which may have compromised some earlier studies as both methanogenesis and CH4 oxidation may occur simultaneously in soil, providing significant advances in our understanding of the process of CH4 oxidation. These stable isotope techniques can be combined with molecular techniques (analysis of gene expression, stable isotope probing (SIP)) to relate the measured process to the microbial populations responsible. Here we will give a synthesis of results from experiments in which we applied 13C-CH4 to accurately determine CH4 oxidation rates in soils, and also present results of 13C-SIP from which we can identify the key players in the microbial population that are using the applied 13C substrate. With the 13C-CH4 technique we were able to provide direct evidence of inhibition of CH4 oxidation following fertiliser application (50-300 kg N ha-1) that was less under elevated pCO2, and evidence for anaerobic CH4 oxidation occurring in soil at 75% soil water filled pore space that would not have been apparent from changes in net CH4 emissions. 13C-SIP both through plants (using 13C-CO2) and directly into soil (using 13C-methane and -organic substrates) has revealed how key players in C utilisation vary under different soil conditions, for example, under improved and unimproved grasslands.

  9. 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.

  10. Influence of form IA RubisCO and environmental dissolved inorganic carbon on the delta13C of the clam-chemoautotroph symbiosis Solemya velum.

    PubMed

    Scott, Kathleen M; Schwedock, Julie; Schrag, Daniel P; Cavanaugh, Colleen M

    2004-12-01

    Many nutritive symbioses between chemoautotrophic bacteria and invertebrates, such as Solemya velum, have delta(13)C values of approximately -30 to -35%, considerably more depleted than phytoplankton. Most of the chemoautotrophic symbionts fix carbon with a form IA ribulose 1,5-bisphosphate carboxylase (RubisCO). We hypothesized that this form of RubisCO discriminates against (13)CO(2) to a greater extent than other forms. Solemya velum symbiont RubisCO was cloned and expressed in Escherichia coli, purified and characterized. Enzyme from this recombinant system fixed carbon most rapidly at pH 7.5 and 20-25 degrees C. Surprisingly, this RubisCO had an epsilon-value (proportional to the degree to which the enzyme discriminates against (13)CO(2)) of 24.4 per thousand, similar to form IB RubisCOs, and higher than form II RubisCOs. Samples of interstitial water from S. velum's habitat were collected to determine whether the dissolved inorganic carbon (DIC) could contribute to the negative delta(13)C values. Solemya velum habitat DIC was present at high concentrations (up to approximately 5 mM) and isotopically depleted, with delta(13)C values as low as approximately -6%. Thus environmental DIC, coupled with a high degree of isotopic fractionation by symbiont RubisCO likely contribute to the isotopically depleted delta(13)C values of S. velum biomass, highlighting the necessity of considering factors at all levels (from environmental to enzymatic) in interpreting stable isotope ratios.

  11. Glacial water mass structure and rapid δ18O and δ13C changes during the last glacial termination in the Southwest Pacific

    NASA Astrophysics Data System (ADS)

    Sikes, Elisabeth L.; Elmore, Aurora C.; Allen, Katherine A.; Cook, Mea S.; Guilderson, Thomas P.

    2016-12-01

    Changes in ocean circulation are thought to have contributed to lowering glacial atmospheric CO2 levels by enhancing deep ocean sequestration of carbon that was returned to the atmosphere during glacial terminations. High-resolution benthic foraminiferal δ13C and δ18O records from a depth transect of cores in the Southwest Pacific Ocean presented here provide evidence that both wind- and thermohaline-driven circulation drove CO2 from the ocean during the last deglaciation. Shallow geochemical stratification in the glacial Southern Ocean was followed by a short pulse of rapid δ13C enrichment to intermediate water depths during Heinrich Stadial 1, indicative of better-ventilated intermediate waters co-occurring with documented wind-driven upwelling in the Southern Ocean. Intermediate depth δ13C enrichment paused at the start of the Antarctic Cold Reversal (∼14.7 ka), implying a brief shallow restratification, while deeper layers were progressively flushed of δ13C-depleted and δ18O-enriched waters, likely caused by the increasing influence of deep waters sourced from the North Atlantic. The coincidence of atmospheric CO2 increases with these geochemical shifts in both shallow and deep cores suggests that shifts in both atmospheric and oceanic circulation contributed to the deglacial rise of CO2.

  12. 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.

  13. 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

  14. 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.

  15. Effect of seasonal changes in the pathways of methanogenesis on the δ13C values of pore water methane in a Michigan peatland

    NASA Astrophysics Data System (ADS)

    Avery, G. Brooks; Shannon, Robert D.; White, Jeffrey R.; Martens, Christopher S.; Alperin, Marc J.

    1999-06-01

    The δ13C value of pore water methane produced in a Michigan peatland varied by 11‰ during the year. This isotopic shift resulted from large seasonal changes in the pathways of methane production. On the basis of mass balance calculations, the δ13C value of methane from CO2 reduction (average = -71.4 ± 1.8‰) was depleted in 13C compared to that produced from acetate (-44.4 ± 8.2‰). The dissolved methane at the site remained heavy (approximately -51‰) during most of the year. Tracer experiments using 14C-labeled CO2 indicated that during January 110 ± 25% of the methane was produced by CO2 reduction. Because of low-methane production rates during the winter, this 13C-depleted methane had only a slight effect on the isotopic composition of the methane pool. In early spring when peat temperatures and methane production rates increased, the δ13C value of the dissolved methane in shallow peat was influenced by the isotopically light methane and approached -61‰. Peat incubation experiments conducted at 15°C in May and June (when the peat reaches its maximum temperature) indicated that an average of 84 ± 9% of the methane production was from acetate and had an average δ13C value of -48.7 ± 5.6‰. Rising acetate concentrations during April-May (approaching 1 mmol L-1(mM)) followed by a rapid decrease in acetate concentrations during May-June reflected the shift toward methane production dominated by acetate fermentation. During this period, dissolved methane in shallow peat at the site returned to heavier values (approximately -51‰) similar to that produced in the incubation experiments.

  16. 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.

  17. Contribution of carbonate weathering to the CO2 efflux from temperate forest soils.

    PubMed

    Schindlbacher, Andreas; Borken, Werner; Djukic, Ika; Brandstätter, Christian; Spötl, Christoph; Wanek, Wolfgang

    Temperate forests provide favorable conditions for carbonate bedrock weathering as the soil CO2 partial pressure is high and soil water is regularly available. As a result of weathering, abiotic CO2 can be released and contribute to the soil CO2 efflux. We used the distinct isotopic signature of the abiotic CO2 to estimate its contribution to the total soil CO2 efflux. Soil cores were sampled from forests on dolomite and limestone and were incubated under the exclusion of atmospheric CO2. Efflux and isotopic signatures of CO2 were repeatedly measured of cores containing the whole mineral soil and bedrock material (heterotrophic respiration + CO2 from weathering) and of cores containing only the mineral top-soil layer (A-horizon; heterotrophic respiration). An aliquot of the cores were let dry out during incubation to assess effects of soil moisture. Although the δ(13)C values of the CO2 efflux from the dolomite soil cores were within a narrow range (A-horizon -26.2 ± 0.1 ‰; whole soil profile wet -25.8 ± 0.1 ‰; whole soil profile dry -25.5 ± 0.1 ‰) the CO2 efflux from the separated A-horizons was significantly depleted in (13)C when compared to the whole soil profiles (p = 0.015). The abiotic contribution to the total CO2 efflux from the dolomite soil cores was 2.0 ± 0.5 % under wet and 3.4 ± 0.5 % under dry conditions. No abiotic CO2 efflux was traceable from the limestone soil cores. An overall low contribution of CO2 from weathering was affirmed by the amount and (13)C signature of the leached dissolved inorganic carbon (DIC) and the radiocarbon signature of the soil CO2 efflux in the field. Together, our data point towards no more than 1-2 % contribution of abiotic CO2 to the growing season soil CO2 efflux in the field.

  18. 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.

  19. Simulation of Carbon and Oxygen Isotopic Compositions of Air CO2 in a Black Spruce Stand

    NASA Astrophysics Data System (ADS)

    Shen, S.; Chen, J. M.; Huang, L.; Chen, B.; Higuchi, K.; Chan, D.; Shashkov, A.

    2002-05-01

    For the purpose of understanding the vertical diffusion processes of CO2 and carbon isotopes and retrieving ecosystem information from isotope measurements, a scalar conservative equation was combined with a well-documented ecosystem model for C3 plants. The model is further developed into a multi-layer canopy model with sunlit and shaded leaf separation in each layer to simulate the processes of photosynthesis, autotrophic respiration, 13C and 18O isotopic fractionation, and the vertical distribution of CO2 and isotope concentrations. Measurements made by scientists at Meteorological Service of Canada in 1998 and 1999 in a forested area near Fraserdale, Ontario, Canada were used for model validation. The measurements include hourly CO2 concentration at 20 m and 40 m heights, and flask samples of d13C and d18O at 20 m height and hourly meteorological data (temperature, wind speed and vapor pressure) measured at 10 m, 20 m and 40 m heights. The model is able to simulate the mean values and temporal variation patterns of CO2 at the measurement heights. Calculated results of d13C and d18O in air CO2 seem reasonable not only with agreeable daily ranges but also with meaningful temporal characteristics. The strong vertical stratification for CO2 was accompanied by d13C and d18O which both were most depleted immediately above the forest floor and concentrated in upper-middle layers of large LAI. During the course of the day, fluctuations in d13C and d18O were most negative in the morning and most enriched during midday with small vertical gradients. The model has been used to investigate (1) the importance of both sunlit and shaded leaf stomatal conductance in simulating the ratio of Ci/Ca and isotope fractionation in different layers of the canopy, (2) the recycling of CO2 inside the canopy and its effect on carbon isotope exchange with the atmosphere, (3) the influence of soil water potential on both d13C and d18O, and (4) the possibility of inferring ecosystem

  20. 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

  1. 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

  2. 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.

  3. 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

  4. 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.

  5. 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

  6. 13C metabolic flux analysis.

    PubMed

    Wiechert, W

    2001-07-01

    Metabolic flux analysis using 13C-labeled substrates has become an important tool in metabolic engineering. It allows the detailed quantification of all intracellular fluxes in the central metabolism of a microorganism. The method has strongly evolved in recent years by the introduction of new experimental procedures, measurement techniques, and mathematical data evaluation methods. Many of these improvements require advanced skills in the application of nuclear magnetic resonance and mass spectrometry techniques on the one hand and computational and statistical experience on the other hand. This minireview summarizes these recent developments and sketches the major practical problems. An outlook to possible future developments concludes the text.

  7. In vivo investigation of cardiac metabolism in the rat using MRS of hyperpolarized [1-13C] and [2-13C]pyruvate.

    PubMed

    Josan, Sonal; Park, Jae Mo; Hurd, Ralph; Yen, Yi-Fen; Pfefferbaum, Adolf; Spielman, Daniel; Mayer, Dirk

    2013-12-01

    Hyperpolarized (13)C MRS allows the in vivo assessment of pyruvate dehydrogenase complex (PDC) flux, which converts pyruvate to acetyl-coenzyme A (acetyl-CoA). [1-(13)C]pyruvate has been used to measure changes in cardiac PDC flux, with demonstrated increase in (13)C-bicarbonate production after dichloroacetate (DCA) administration. With [1-(13)C]pyruvate, the (13)C label is released as (13 CO2 /(13)C-bicarbonate, and, hence, does not allow us to follow the fate of acetyl-CoA. Pyruvate labeled in the C2 position has been used to track the (13)C label into the TCA (tricarboxylic acid) cycle and measure [5-(13)C]glutamate as well as study changes in [1-(13)C]acetylcarnitine with DCA and dobutamine. This work investigates changes in the metabolic fate of acetyl-CoA in response to metabolic interventions of DCA-induced increased PDC flux in the fed and fasted state, and increased cardiac workload with dobutamine in vivo in rat heart at two different pyruvate doses. DCA led to a modest increase in the (13)C labeling of [5-(13)C]glutamate, and a considerable increase in [1-(13)C]acetylcarnitine and [1,3-(13)C]acetoacetate peaks. Dobutamine resulted in an increased labeling of [2-(13)C]lactate, [2-(13)C]alanine and [5-(13)C]glutamate. The change in glutamate with dobutamine was observed using a high pyruvate dose but not with a low dose. The relative changes in the different metabolic products provide information about the relationship between PDC-mediated oxidation of pyruvate and its subsequent incorporation into the TCA cycle compared with other metabolic pathways. Using a high dose of pyruvate may provide an improved ability to observe changes in glutamate.

  8. 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

  9. 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

  10. Study of the diet effect on δ 13C of shell carbonate of the land snail Helix aspersa in experimental conditions

    NASA Astrophysics Data System (ADS)

    Metref, S.; Rousseau, D.-D.; Bentaleb, I.; Labonne, M.; Vianey-Liaud, M.

    2003-06-01

    This study aims to demonstrate the influence of the metabolic CO 2 derived from the diet and of the atmospheric CO 2 on the shell carbonate δ 13C of the pulmonate snail Helix aspersa maxima raised under controlled conditions. Adult snails were analyzed and compared with three hatching and 1-day old young snails stemming from the same breeding. One day after, the 2-day old individuals were raised during 1 month. Three groups of gastropods were fed with fresh lettuce (C 3 plant, δ 13C=-27.49‰), three groups with corn (C 4 plant, δ 13C=-11.7‰), and three groups ate alternately both (C 3+C 4). The difference between the average δ 13C values of the adult snails on the one hand and the hatched and 1-day old snails on the other hand indicates a depletion of 2.47‰. Therefore, the isotopic parents-offspring signal is not preserved. The depleted ingested albumen by the snail embryo in the egg during the building of the shell could explain this depletion. The C 3 diet experiment gave the expected isotopic composition difference between the diet (lettuce) and the shells (average Δ 13C shell-lettuce=13.75‰±0.52). This result shows a clear diet effect on the isotopic composition of the snail shells. For the C 4 experiment, the difference in carbon isotope composition between the corn and the shell (Δ 13C shell-corn) yielded an average value of 4.89‰±0.87. The main result is that Δ 13C is not constant and appears to depend on the type of ingested food. Several hypotheses can arise from this study to explain the different fractionations: (a) differences in the quality of the two diets, (b) differences in turnover rate for C 3 and C 4 feeders. The groups regularly fed with mixed diet yielded δ 13C values showing a preferential use of C 3 food for most values. The C 3-C 4 mixed dietary alternation probably led snails to use mainly the lettuce instead of the corn powder.

  11. 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.

  12. Diamond growth from subducted carbon implied by correlated δ18O-δ13C variations in diamonds and garnet inclusions

    NASA Astrophysics Data System (ADS)

    Ickert, R. B.; Stachel, T.; Harris, J. W.

    2011-12-01

    Much of our knowledge of the deep-Earth carbon cycle is derived from studies of diamond. The sources of carbon in the mantle and the mechanisms of transport and precipitation as diamond, however, are not entirely understood. Due to the chemical purity of diamond, scientific effort has focussed on syngenetic mineral inclusions and their relationship to their diamond hosts. For example, it is well known that, on a worldwide scale, diamonds with eclogitic inclusions have a distinct δ13C distribution when compared to more abundant peridotitic diamonds. Eclogitic diamonds have a distribution that extends from mantle-like δ13C values (ca. -5%), to very light carbon (<-20%). Strong 13C depletion has been explained by either invoking subducted organic carbon, or through high temperature isotopic fractionation of mantle carbon. Here we report high-precision SIMS δ18O measurements (2σ±< 0.3%) of eclogitic garnet inclusions in diamonds from the Damtshaa mine (Orapa cluster, Botswana). The δ13C values of the host diamond were determined to have a wide range (-4.4% to -18%; Deines et al. 2009; Lithos v.112 p776). From 15 inclusions, the δ18O variations range from +4.8 to +8.8 %. The relative 18O abundances are negatively correlated with the δ13C of the host diamonds, suggesting a link between high δ18O host rocks and low δ13C diamonds. Although fractionation of δ13C values is possible at high temperature, δ18O values are susceptible only to very small high temperature fractionations. For example, Cartigny et al. (2001, EPSL v.185 p85) suggested that CO2 degassing from a carbonate-bearing melt prior to diamond precipitation may be responsible for a δ13C distribution of eclogitic diamonds worldwide that is skewed to 13C depleted compositions. Our data place new constraints on that model. Depending on the C/O ratio of the melt, CO2 degassing will either have a negligible effect on the δ18O of the residual melt, or (at high C/O) induce a positive correlation between

  13. Simulating Photosynthetic 13C Fractionation at a Western Subalpine Forest for Seasonal and Multi-Decadal Time Periods with the Community Land Model (CLM 4.5)

    NASA Astrophysics Data System (ADS)

    Raczka, B. M.; Duarte, H.; Koven, C. D.; Ricciuto, D. M.; Thornton, P. E.; Lin, J. C.; Bowling, D. R.

    2015-12-01

    Terrestrial biosphere models are an important tool to diagnose and predict land-atmosphere exchanges of carbon and energy. This is critical in order to quantify the land-carbon feedback into the climate system. Ecological observations are extremely important in order to quantify model skill and to improve techniques in which to simulate ecosystem behavior. Isotope observations of 13C are especially useful in diagnosing the ecosystem response to water stress, atmospheric humidity and CO2 fertilization. We test the representation of isotopes within CLM 4.5 against site level observations of biomass and carbon fluxes measured at Niwot Ridge, Colorado. First we 'spun-up' the model for 1800 years to approximate site level conditions during the 21st century. We accomplished this by imposing a site-level reconstruction of seasonally varying atmospheric δ13C and atmospheric CO2 from 1850-2013 and site level meteorological observations from 1998-2013. We also imposed an empirical-downscaling of simulated photosynthesis to reproduce the observed photosynthesis. We found that the simulated δ13C of biomass pools was more depleted than the observed by 1-2 o/oo. This finding suggests the magnitude of photosynthetic discrimination was overestimated in the model. The model reproduced observed seasonal trends in discrimination with higher values in the spring and fall but lower values in the summer. However, if nitrogen-limitation is imposed in the model the photosynthetic downscaling influences the fractionation in such a way to obscure this observed trend. This suggests an alternative approach should be taken in order to account for nitrogen limitation. During the last century the model simulated an abrupt drop in δ13C for biomass pools, primarily because of the concurrent drop in atmospheric δ13C, but also because of increasing discrimination driven by increases in the ratio of intercellular to atmospheric CO2. Finally, we identified photosynthetic rate, and vapor pressure

  14. Synthesis of exemestane labelled with (13)C.

    PubMed

    Fontana, Erminia; Pignatti, Alberto; Giribone, Danilo; Di Salle, Enrico

    2008-08-01

    The synthesis of exemestane Aromasin, an irreversible steroidal aromatase inhibitor, specifically labelled with (13)C is reported. The preparation of [(13)C(3)]exemestane was achieved according to an eight-step procedure starting from the commercially available testosterone.

  15. Imaging pH with hyperpolarized 13C.

    PubMed

    Gallagher, Ferdia A; Kettunen, Mikko I; Brindle, Kevin M

    2011-10-01

    pH is a fundamental physiological parameter that is tightly controlled by endogenous buffers. The acid-base balance is altered in many disease states, such as inflammation, ischemia and cancer. Despite the importance of pH, there are currently no routine methods for imaging the spatial distribution of pH in humans. The enormous gain in sensitivity afforded by dynamic nuclear polarization (DNP) has provided a novel way in which to image tissue pH using MR, which has the potential to be translated into the clinic. This review explores the advantages and disadvantages of current pH imaging techniques and how they compare with DNP-based approaches for the measurement and imaging of pH with hyperpolarized (13)C. Intravenous injection of hyperpolarized (13)C-labeled bicarbonate results in the rapid production of hyperpolarized (13)CO(2) in the reaction catalyzed by carbonic anhydrase. As this reaction is close to equilibrium in the body and is pH dependent, the ratio of the (13)C signal intensities from H(13)CO(3)(-) and (13)CO(2), measured using MRS, can be used to calculate pH in vivo. The application of this technique to a murine tumor model demonstrated that it measured predominantly extracellular pH and could be mapped in the animal using spectroscopic imaging techniques. A second approach has been to use the production of hyperpolarized (13)CO(2) from hyperpolarized [1-(13)C]pyruvate to measure predominantly intracellular pH. In tissues with a high aerobic capacity, such as the heart, the hyperpolarized [1-(13)C]pyruvate undergoes rapid oxidative decarboxylation, catalyzed by intramitochondrial pyruvate dehydrogenase. Provided that there is sufficient carbonic anhydrase present to catalyze the rapid equilibration of the hyperpolarized (13)C label between CO(2) and bicarbonate, the ratio of their resonance intensities may again be used to estimate pH, which, in this case, is predominantly intracellular. As both pyruvate and bicarbonate are endogenous molecules they

  16. 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.

  17. (13)C-Labeling the carbon-fixation pathway of a highly efficient artificial photosynthetic system.

    PubMed

    Liu, Chong; Nangle, Shannon N; Colón, Brendan C; Silver, Pamela A; Nocera, Daniel G

    2017-03-15

    Interfacing the CO2-fixing microorganism, Ralstonia eutropha, to the energy derived from hydrogen produced by water splitting is a viable approach to achieving renewable CO2 reduction at high efficiencies. We employ (13)C-labeling to report on the nature of CO2 reduction in the inorganic water splitting|R. eutropha hybrid system. Accumulated biomass in a reactor under a (13)C-enriched CO2 atmosphere may be sampled at different time points during CO2 reduction. Converting the sampled biomass into gaseous CO2 allows the (13)C/(12)C ratio to be determined by gas chromatography-mass spectrometry. After 2 hours of inoculation and the initiation of water splitting, the microbes adapted and began to convert CO2 into biomass. The observed time evolution of the (13)C/(12)C ratio in accumulated biomass is consistent with a Monod model for carbon fixation. Carbon dioxide produced by catabolism was found to be minimal. This rapid response of the bacteria to a hydrogen input and to subsequent CO2 reduction at high efficiency are beneficial to achieving artificial photosynthesis for the storage of renewable energy.

  18. 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.

  19. 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.

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

    PubMed

    Birgel, D; Meister, P; Lundberg, R; Horath, T D; Bontognali, T R R; Bahniuk, A M; de Rezende, C E; Vasconcelos, C; McKenzie, J A

    2015-05-01

    Holocene stromatolites characterized by unusually positive inorganic δ(13) CPDB values (i.e. up to +16‰) 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, and they suggest that methanogenesis was a dominating process during the growth of the stromatolites. Indeed, up to 5 mm methane was measured in the porewater. The archaeal membrane lipid archaeol showing δ(13) C values between -15 and 0‰ suggests that archaea are present and producing methane in the modern lagoon sediment. Moreover, (13) C-depleted hopanoids diplopterol and 3β-methylated C32 17β(H),21β(H)-hopanoic acid (both -40‰) 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 would explain the residual (13) C-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 environment. Indeed, sulphate-reduction activity is very low in the modern sediments. In absence of an efficient carbonate-inducing metabolic process, we propose that stromatolite formation in Lagoa Salgada was abiotically induced, while the (13) C-enriched organic and inorganic carbon pools are due to methanogenesis. Unusually, (13) C-enriched stromatolitic deposits also appear in the geological record of prolonged periods in the Palaeo- and Neoproterozoic. Lagoa Salgada represents a possible modern analogue to conditions that may have been widespread in the Proterozoic, at times when low sulphate concentrations in sea water allowed methanogens to prevail over sulphate

  1. 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

  2. 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

  3. 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

  4. Decoupling of coral skeletal δ13C and solar irradiance over the past millennium caused by the oceanic Suess effect

    NASA Astrophysics Data System (ADS)

    Deng, Wenfeng; Chen, Xuefei; Wei, Gangjian; Zeng, Ti; Zhao, Jian-xin

    2017-02-01

    Many factors influence the seasonal changes in δ13C levels in coral skeletons; consequently, the climatic and environmental significance of such changes is complicated and controversial. However, it is widely accepted that the secular declining trend of coral δ13C over the past 200 years reflects the changes in the additional flux of anthropogenic CO2 from the atmosphere into the surface oceans. Even so, the centennial-scale variations, and their significance, of coral δ13C before the Industrial Revolution remain unclear. Based on an annually resolved coral δ13C record from the northern South China Sea, the centennial-scale variations of coral δ13C over the past millennium were studied. The coral δ13C and total solar irradiance (TSI) have a significant positive Pearson correlation and coupled variation during the Medieval Warm Period and Little Ice Age, when natural forcing controlled the climate and environment. This covariation suggests that TSI controls coral δ13C by affecting the photosynthetic activity of the endosymbiotic zooxanthellae over centennial timescales. However, there was a decoupling of the coral skeletal δ13C and TSI during the Current Warm Period, the period in which the climate and environment became linked to anthropogenic factors. Instead, coral δ13C levels have a significant Pearson correlation with both the atmospheric CO2 concentration and δ13C levels in atmospheric CO2. The correlation between coral δ13C and atmospheric CO2 suggests that the oceanic 13C Suess effect, caused by the addition of increasing amounts of anthropogenic 12CO2 to the surface ocean, has led to the decoupling of coral δ13C and TSI at the centennial scale.

  5. (13)C NMR Metabolomics: INADEQUATE Network Analysis.

    PubMed

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

    2015-06-02

    The many advantages of (13)C NMR are often overshadowed by its intrinsically low sensitivity. Given that carbon makes up the backbone of most biologically relevant molecules, (13)C NMR offers a straightforward measurement of these compounds. Two-dimensional (13)C-(13)C 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 semiautomated approach called INETA (INADEQUATE network analysis) for the untargeted analysis of INADEQUATE data sets using an in silico INADEQUATE database. We demonstrate this approach using isotopically labeled Caenorhabditis elegans mixtures.

  6. Study of the diet effect on d13C of shell carbonate of the land snail Helix aspersa in experimental conditions

    NASA Astrophysics Data System (ADS)

    Metref, S.; Rousseau, D. D.; Bentaleb, I.; Labonne, M.; Vianey-Liaud, M.

    2003-04-01

    This study aims to demonstrate the influence of the metabolic CO2 derived from the diet and of the atmospheric CO2 on the shell carbonate d13C of the pulmonate snail Helix aspersa maxima raised under controlled conditions. Adult snails were analyzed and compared with three hatching and one-day young snails stemming from the same breeding. One day after, the two-days old individuals were raised during one month. Three groups of gastropods were fed with fresh lettuce (C3 plant, d13C = -27.49 ppt), three groups with corn (C4 plant, d13C = -11.7 ppt), and three groups ate both (C3 + C4). The difference between the mean d13C values of the adult snails on one hand and the hatched and one-day snails on the other hand indicates a depletion of 2.47 ‰. Therefore, the isotopic parents offspring signal is not preserved. The depleted ingested albumen by the snail embryo in the egg during the built of the shell could explain this depletion. The C3 diet experiment gave the expected isotopic composition difference between the diet (lettuce) and the shells (mean D13Cshell-Lettuce = 13.75 ppt +- 0.52). This result shows a clear diet effect on the isotopic composition of the snail shells. For the C4 experiment, the difference in carbon isotope composition between the corn and the shell (D13Cshell-corn) yielded a mean value of 4.89 ppt +- 0.87. The main result is that D13C is not constant and appears to depend on the type of ingested food. Several hypothesis can raise from this study to explain the different fractionations : a) The differences in quality of the two diets seem to have placed the animals in different growth states, b) Differences in turnover rate for C3 and C4 feeders. The groups regularly fed with mixed diet yielded d13C values, showing a preferential use of C3 food for the most values. The C3-C4 mixed dietary alternation probably led snails to use mainly the lettuce instead of the corn powder.

  7. Impact of climate and CO 2 on a millennium-long tree-ring carbon isotope record

    NASA Astrophysics Data System (ADS)

    Treydte, Kerstin S.; Frank, David C.; Saurer, Matthias; Helle, Gerhard; Schleser, Gerhard H.; Esper, Jan

    2009-08-01

    We present one millennium-long (1171-year), and three 100 year long annually resolved δ 13C tree-ring chronologies from ecologically varying Juniperus stands in the Karakorum Mountains (northern Pakistan), and evaluate their response to climatic and atmospheric CO 2 changes. All δ 13C records show a gradual decrease since the beginning of the 19th century, which is commonly associated with a depletion of atmospheric δ 13C due to fossil fuel burning. Climate calibration of high-frequency δ 13C variations indicates a pronounced summer temperature signal for all sites. The low-frequency component of the same records, however, deviates from long-term temperature trends, even after correction for changes in anthropogenic CO 2. We hypothesize that these high-elevation trees show a response to both climate and elevated atmospheric CO 2 concentration and the latter might explain the offset with target temperature data. We applied several corrections to tree-ring δ 13C records, considering a range of potential CO 2 discrimination changes over the past 150 years and calculated the goodness of fit with the target via calibration/verification tests ( R2, residual trend, and Durbin-Watson statistics). These tests revealed that at our sites, carbon isotope fixation on longer timescales is affected by increasing atmospheric CO 2 concentrations at a discrimination rate of about 0.012‰/ppmv. Although this statistically derived value may be site related, our findings have implications for the interpretation of any long-term trends in climate reconstructions using tree-ring δ 13C, as we demonstrate with our millennium-long δ 13C Karakorum record. While we find indications for warmth during the Medieval Warm Period (higher than today's mean summer temperature), we also show that the low-frequency temperature pattern critically depends on the correction applied. Patterns of long-term climate variation, including the Medieval Warm Period, the Little Ice Age, and 20th century

  8. Spatial and seasonal variabilities of the stable carbon isotope composition of soil CO2 concentration and flux in complex terrain

    NASA Astrophysics Data System (ADS)

    Liang, Liyin L.; Riveros-Iregui, Diego A.; Risk, David A.

    2016-09-01

    Biogeochemical processes driving the spatial variability of soil CO2 production and flux are well studied, but little is known about the variability in the spatial distribution of the stable carbon isotopes that make up soil CO2, particularly in complex terrain. Spatial differences in stable isotopes of soil CO2 could indicate fundamental differences in isotopic fractionation at the landscape level and may be useful to inform modeling of carbon cycling over large areas. We measured the spatial and seasonal variabilities of the δ13C of soil CO2 (δS) and the δ13C of soil CO2 flux (δP) in a subalpine forest ecosystem located in the Rocky Mountains of Montana. We found consistently more isotopically depleted values of δS and δP in low and wet areas of the landscape relative to steep and dry areas. Our results suggest that the spatial patterns of δS and δP are strongly mediated by soil water and soil respiration rate. More interestingly, our analysis revealed different temporal trends in δP across the landscape; in high landscape positions δP became more positive, whereas in low landscape positions δP became more negative with time. These trends might be the result of differential dynamics in the seasonality of soil moisture and its effects on soil CO2 production and flux. Our results suggest concomitant yet independent effects of water on physical (soil gas diffusivity) and biological (photosynthetic discrimination) processes that mediate δS and δP and are important when evaluating the δ13C of CO2 exchanged between soils and the atmosphere in complex terrain.

  9. 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.

  10. 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%.

  11. 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.

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

    DOE PAGES

    Zhang, J.; Gu, L.; Bao, F.; ...

    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

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. Probing metabolic processes of intact soil microbial communities using position-specific 13C-labeled glucose

    NASA Astrophysics Data System (ADS)

    Fairbanks, D. E.; Hungate, B. A.; KOCH, G. W.; Schwartz, E.; Dijkstra, P.

    2012-12-01

    Soils represent one of the largest carbon pools in the terrestrial biosphere and fluxes into or out of this pool may feedback to current climate change. Understanding the mechanisms behind microbial processes regulating C cycling, microbial turnover, and soil organic matter stabilization is hindered by our lack of understanding of the details of microbial physiology in soils. Position-specific 13C labeled metabolic tracers are proposed as a new way to probe microbial community energy production, biosynthesis, C use efficiency (the proportion of substrate incorporated into microbial biomass), and enables the determination of C fluxes through the various C metabolic pathways. We determined the 13CO2 production from microbial communities within a one hour time frame by adding six isotopomers (1-13C, 2-13C, 3-13C, 4-13C, 5-13C, 6-13C) of glucose in parallel incubations using a young volcanic soil (Pinyon-juniper wood, near Sunset Crater, Flagstaff, Arizona). We compared the measured rates of position-specific 13CO2 production with modeled results based on glucose (1-13C and U-13C) and pyruvate (1-13C and 2,3-13C) incubations. These labeling and modeling techniques may improve our ability to analyze the biochemistry and ecophysiology of intact soil microbial communities.

  18. 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

  19. 13C NMR of tunnelling methyl groups

    NASA Astrophysics Data System (ADS)

    Detken, A.

    The dipolar interactions between the protons and the central 13C nucleus of a 13CH3 group are used to study rotational tunnelling and incoherent dynamics of such groups in molecular solids. Single-crystal 13C NMR spectra are derived for arbitrary values of the tunnel frequency upsilon t. Similarities to ESR and 2H NMR are pointed out. The method is applied to three different materials. In the hydroquinone/acetonitrile clathrate, the unique features in the 13C NMR spectra which arise from tunnelling with a tunnel frequency that is much larger than the dipolar coupling between the methyl protons and the 13C nucleus are demonstrated, and the effects of incoherent dynamics are studied. The broadening of the 13C resonances is related to the width of the quasi-elastic line in neutron scattering. Selective magnetization transfer experiments for studying slow incoherent dynamics are proposed. For the strongly hindered methyl groups of L-alanine, an upper limit for upsilon is derived from the 13C NMR spectrum. In aspirinTM (acetylsalicylic acid), incoherent reorientations dominate the spectra down to the lowest temperatures studied; their rate apparently increases with decreasing temperature below 25K.

  20. 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

  1. 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

  2. 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

  3. 13C-phenylalanine breath test detects altered phenylalanine kinetics in schizophrenia patients

    PubMed Central

    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-[1-13C]phenylalanine breath test (13C-PBT). The subjects were 20 chronically medicated schizophrenia patients (DSM-IV) and the same number of age- and sex-matched controls. 13C-phenylalanine (99 atom% 13C; 100 mg) was administered orally and the breath 13CO2 /12CO2 ratio was monitored for 120 min. The possible effect of antipsychotic medication (risperidone (RPD) or haloperidol (HPD) treatment for 21 days) on 13C-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 Δ13CO2 (‰) 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 Δ13CO2 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 13C-PBT indices in rats. Our results suggest that 13C-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

  4. Ecological processes dominate the 13C land disequilibrium in a Rocky Mountain subalpine forest

    NASA Astrophysics Data System (ADS)

    Bowling, D. R.; Ballantyne, A. P.; Miller, J. B.; Burns, S. P.; Conway, T. J.; Menzer, O.; Stephens, B. B.; Vaughn, B. H.

    2014-04-01

    Fossil fuel combustion has increased atmospheric CO2 by ≈ 115 µmol mol-1 since 1750 and decreased its carbon isotope composition (δ13C) by 1.7-2‰ (the 13C Suess effect). Because carbon is stored in the terrestrial biosphere for decades and longer, the δ13C of CO2 released by terrestrial ecosystems is expected to differ from the δ13C of CO2 assimilated by land plants during photosynthesis. This isotopic difference between land-atmosphere respiration (δR) and photosynthetic assimilation (δA) fluxes gives rise to the 13C land disequilibrium (D). Contemporary understanding suggests that over annual and longer time scales, D is determined primarily by the Suess effect, and thus, D is generally positive (δR > δA). A 7 year record of biosphere-atmosphere carbon exchange was used to evaluate the seasonality of δA and δR, and the 13C land disequilibrium, in a subalpine conifer forest. A novel isotopic mixing model was employed to determine the δ13C of net land-atmosphere exchange during day and night and combined with tower-based flux observations to assess δA and δR. The disequilibrium varied seasonally and when flux-weighted was opposite in sign than expected from the Suess effect (D = -0.75 ± 0.21‰ or -0.88 ± 0.10‰ depending on method). Seasonality in D appeared to be driven by photosynthetic discrimination (Δcanopy) responding to environmental factors. Possible explanations for negative D include (1) changes in Δcanopy over decades as CO2 and temperature have risen, and/or (2) post-photosynthetic fractionation processes leading to sequestration of isotopically enriched carbon in long-lived pools like wood and soil.

  5. 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.

  6. 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).

  7. CO2 -Responsive polymers.

    PubMed

    Lin, Shaojian; Theato, Patrick

    2013-07-25

    This Review focuses on the recent progress in the area of CO2 -responsive polymers and provides detailed descriptions of these existing examples. CO2 -responsive polymers can be categorized into three types based on their CO2 -responsive groups: amidine, amine, and carboxyl groups. Compared with traditional temperature, pH, or light stimuli-responsive polymers, CO2 -responsive polymers provide the advantage to use CO2 as a "green" trigger as well as to capture CO2 directly from air. In addition, the current challenges of CO2 -responsive polymers are discussed and the different solution methods are compared. Noteworthy, CO2 -responsive polymers are considered to have a prosperous future in various scientific areas.

  8. 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.

  9. 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.

  10. 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.

  11. Mechanisms of CO2 Capture into Monoethanolamine Solution with Different CO2 Loading during the Absorption/Desorption Processes.

    PubMed

    Lv, Bihong; Guo, Bingsong; Zhou, Zuoming; Jing, Guohua

    2015-09-01

    Though the mechanism of MEA-CO2 system has been widely studied, there is few literature on the detailed mechanism of CO2 capture into MEA solution with different CO2 loading during absorption/desorption processes. To get a clear picture of the process mechanism, (13)C nuclear magnetic resonance (NMR) was used to analyze the reaction intermediates under different CO2 loadings and detailed mechanism on CO2 absorption and desorption in MEA was evaluated in this work. The results demonstrated that the CO2 absorption in MEA started with the formation of carbamate according to the zwitterion mechanism, followed by the hydration of CO2 to form HCO3(-)/CO3(2-), and accompanied by the hydrolysis of carbamate. It is interesting to find that the existence of carbamate will be influenced by CO2 loading and that it is rather unstable at high CO2 loading. At low CO2 loading, carbamate is formed fast by the reaction between CO2 and MEA. At high CO2 loading, it is formed by the reaction of CO3(-)/CO3(2-) with MEA, and the formed carbamate can be easily hydrolyzed by H(+). Moreover, CO2 desorption from the CO2-saturated MEA solution was proved to be a reverse process of absorption. Initially, some HCO3(-) were heated to release CO2 and other HCO3(-) were reacted with carbamic acid (MEAH(+)) to form carbamate, and the carbamate was then decomposed to MEA and CO2.

  12. 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.

  13. 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.

  14. Hyperpolarized 13C allows a direct measure of flux through a single enzyme-catalyzed step by NMR

    PubMed Central

    Merritt, Matthew E.; Harrison, Crystal; Storey, Charles; Jeffrey, F. Mark; Sherry, A. Dean; Malloy, Craig R.

    2007-01-01

    13C NMR is a powerful tool for monitoring metabolic fluxes in vivo. The recent availability of automated dynamic nuclear polarization equipment for hyperpolarizing 13C nuclei now offers the potential to measure metabolic fluxes through select enzyme-catalyzed steps with substantially improved sensitivity. Here, we investigated the metabolism of hyperpolarized [1-13C1]pyruvate in a widely used model for physiology and pharmacology, the perfused rat heart. Dissolved 13CO2, the immediate product of the first step of the reaction catalyzed by pyruvate dehydrogenase, was observed with a temporal resolution of ≈1 s along with H13CO3−, the hydrated form of 13CO2 generated catalytically by carbonic anhydrase. In hearts presented with the medium-chain fatty acid octanoate in addition to hyperpolarized [1-13C1]pyruvate, production of 13CO2 and H13CO3− was suppressed by ≈90%, whereas the signal from [1-13C1]lactate was enhanced. In separate experiments, it was shown that O2 consumption and tricarboxylic acid (TCA) cycle flux were unchanged in the presence of added octanoate. Thus, the rate of appearance of 13CO2 and H13CO3− from [1-13C1]pyruvate does not reflect production of CO2 in the TCA cycle but rather reflects flux through pyruvate dehydrogenase exclusively. PMID:18056642

  15. 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.

  16. 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

  17. 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.

  18. Lasers utilizing CO2 isotopes

    NASA Astrophysics Data System (ADS)

    Pechenin, Yu V.; Domanov, M. S.

    1980-08-01

    The lasing spectra and energy characteristics were investigated for lasers operating with the isotopes 12C16O2, 13C16O2, 12C18O2, and 12C16O18O. It was found that the output power of a laser utilizing the CO2 isotopes was determined by the content of a particular isotope in the carbon dioxide gas. For equal enrichments, all the isotopes investigated, with the exception of 12C16O18O, gave comparable output powers. The unsaturated gains were identical for the most intense transitions of the symmetric molecules; the gain was a factor of two less for the asymmetric molecule. The gain rose linearly with increasing enrichment. The ultimate specific power output, given by the product of the saturation power density and the gain, was practically independent of the enrichment.

  19. Microbial Community in a Sediment-Hosted CO2 Lake of the Southern Okinawa Trough Hydrothermal Field

    NASA Astrophysics Data System (ADS)

    Inagaki, F.; Kuypers, M. M.; Tsunogai, U.; Ishibashi, J.; Nakamura, K.; Treude, T.; Ohkubo, S.; Nakaseama, M.; Gena, K.; Chiba, H.; Hirayama, H.; Nunoura, T.; Takai, K.; Jorgensen, B. B.; Horikoshi, K.; Boetius, A.

    2006-12-01

    One-carbon assimilating (micro-)organisms play an important role for global carbon cycling; however, the increasing level of anthropogenic CO2 in the atmosphere has exceeded the capacity of natural biological feedback, hence as greenhouse gasses it is expected to cause climacteric change with negative effects on the earth's ecosystems and human society. To reduce CO2 emissions into the atmosphere, a variety of options have been discussed, including a disposal of CO2 into the deep ocean. However, the impact of CO2 disposal on deep-sea ecosystems as well as of the consequent microbiological feedback remains largely unknown. At the Yonaguni Knoll IV hydrothermal field, southern Okinawa Trough, we observed a natural liquid CO2 lake in sediments overlying elemental sulfur and CO2 hydrates at a water depth of 1380m. The liquid CO2 droplets were composed of 85% CO2 and 14% methane with hydrogen below the detection limit. We found high abundances (>109 cm-3) of microbial cells in sediment pavements above the CO2 lake, decreasing to strikingly low cell numbers (10&^{7} cm-3) at the liquid CO2/CO2-hydrate interface. Molecular ecological study based on the sequences of 16S rRNA genes showed that the key groups in these sediments were: (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 (mcrA, cbbL) related to one- carbon assimilation as well as the presence of highly 13C-depleted archaeal and bacterial lipid biomarkers suggest that microorganisms assimilating CO2 and/or methane dominate the liquid CO2 and CO2-hydrate-bearing sediments. We propose that 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.

  20. Application of 13C-labeling and 13C-13C COSY NMR experiments in the structure determination of a microbial natural product.

    PubMed

    Kwon, Yun; Park, Sunghyouk; Shin, Jongheon; Oh, Dong-Chan

    2014-08-01

    The elucidation of the structures of complex natural products bearing many quaternary carbons remains challenging, even in this advanced spectroscopic era. (13)C-(13)C COSY NMR spectroscopy shows direct couplings between (13)C and (13)C, which comprise the backbone of a natural product. Thus, this type of experiment is particularly useful for natural products bearing consecutive quaternary carbons. However, the low sensitivity of (13)C-based NMR experiments, due to the low natural abundance of the (13)C nucleus, is problematic when applying these techniques. Our efforts in the (13)C labeling of a microbial natural product, cyclopiazonic acid (1), by feeding (13)C-labeled glucose to the fungal culture, enabled us to acquire (13)C-(13)C COSY NMR spectra on a milligram scale that clearly show the carbon backbone of the compound. This is the first application of (13)C-(13)C COSY NMR experiments for a natural product. The results suggest that (13)C-(13)C COSY NMR spectroscopy can be routinely used for the structure determination of microbial natural products by (13)C-enrichment of a compound with (13)C-glucose.

  1. Comparative absorption of [13C]glucose and [13C]lactose by premature infants.

    PubMed

    Murray, R D; Boutton, T W; Klein, P D; Gilbert, M; Paule, C L; MacLean, W C

    1990-01-01

    Oxidation of orally administered [13C]glucose and [13C]lactose and fecal recovery of malabsorbed substrates were determined in two groups of premature infants. Eighteen studies were performed with six infants at Johns Hopkins Hospital (JHH); 24 studies were performed with nine infants at Columbus Children's Hospital (CCH). The two groups differed in that JHH infants had shorter gestations but were older when studied. Fecal 13C loss after [13C]glucose administration did not differ between the two groups. Compared with glucose, the metabolism of lactose appeared to involve more malabsorption and colonic fermentation in JHH infants than in CCH infants and resulted in higher fecal losses of substrate carbon. Maturation appeared to involve increased proximal intestinal absorption and greater retention of absorbed carbohydrate. Simultaneous absorption of substrate from the small and large intestine may limit the usefulness of breath tests for 13C in the premature infant.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. A deconvolution of the tree ring based δ13C record

    NASA Astrophysics Data System (ADS)

    Peng, Tsung-Hung; Broecker, Wallace S.; Freyer, Hans D.; Trumbore, Susan

    1983-04-01

    We assumed that the tree-ring-based 13C/12C record constructed by Freyer and Belacy (1983) to be representative of the fossil fuel and forest-soil induced 13C/12C change for atmospheric CO2. Through the use of a modification of the Oeschger et al. ocean model, we have computed the contribution of the combustion of coal, oil, and natural gas to this observed 13C/12C change. A large residual remains when the tree-ring-based record is corrected for the contribution of fossil fuel CO2. A deconvolution was performed on this residual to determine the time history and magnitude of the forest-soil reservoir changes over the past 150 years. Several important conclusions were reached. (1) The magnitude of the integrated CO2 input from these sources was about 1.6 times that from fossil fuels. (2) The forest-soil contribution reached a broad maximum centered at about 1900. (3) Over the 2 decade period covered by the Mauna Loa atmospheric CO2 content record, the input from forests and soils was about 30% that from fossil fuels. (4) The 13C/12C trend over the last 20 years was dominated by the input of fossil fuel CO2. (5) The forest-soil release did not contribute significantly to the secular increase in atmospheric CO2 observed over the last 20 years. (6) The pre-1850 atmospheric ?values must have been in the range 245 to 270×10-6 atmospheres.

  7. Characteristics of the deep ocean carbon system during the past 150,000 years: SigmaCO2 distributions, deep water flow patterns, and abrupt climate change.

    PubMed

    Boyle, E A

    1997-08-05

    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-SigmaCO2 state for eastern Pacific deep water. Both tracers indicate that the mid-depth North and tropical Atlantic Ocean almost always has lower SigmaCO2 levels than those in the Pacific. Upper waters of the Last Glacial Maximum Atlantic are more SigmaCO2-depleted and deep waters are SigmaCO2-enriched compared with the waters of the present. In the northern Indian Ocean, delta13C and Cd data are consistent with upper water SigmaCO2 depletion relative to the present. There is no evident proximate source of this SigmaCO2-depleted water, so I suggest that SigmaCO2-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).

  8. 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

  9. 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

  10. 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

  11. Interpreting the 13C / 12C ratio of carbon dioxide in an urban airshed in the Yangtze River Delta, China

    NASA Astrophysics Data System (ADS)

    Xu, Jiaping; Lee, Xuhui; Xiao, Wei; Cao, Chang; Liu, Shoudong; Wen, Xuefa; Xu, Jingzheng; Zhang, Zhen; Zhao, Jiayu

    2017-03-01

    Observations of atmospheric CO2 mole fraction and the 13C / 12C ratio (expressed as δ13C) in urban airsheds provide constraints on the roles of anthropogenic and natural sources and sinks in local and regional carbon cycles. In this study, we report observations of these quantities in Nanjing at hourly intervals from March 2013 to August 2015, using a laser-based optical instrument. Nanjing is the second largest city located in the highly industrialized Yangtze River Delta (YRD), eastern China. The mean CO2 mole fraction and δ13C were (439.7 ± 7.5) µmol mol-1 and (-8.48 ± 0.56) ‰ over this observational period. The peak monthly mean δ13C (-7.44 ‰, July 2013) was 0.74 ‰ higher than that observed at Mount Waliguan, a WMO (World Meteorological Organization) baseline site on the Tibetan Plateau and upwind of the YRD region. The highly 13C-enriched signal was partly attributed to the influence of cement production in the region. By applying the Miller-Tans method to nighttime and daytime observations to represent signals from the city of Nanjing and the YRD, respectively, we showed that the 13C / 12C ratio of CO2 sources in the Nanjing municipality was (0.21 ± 0.53) ‰ lower than that in the YRD. Flux partitioning calculations revealed that natural ecosystems in the YRD were a negligibly small source of atmospheric CO2.

  12. 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

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

    PubMed

    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 (1)D(CC) 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 (13)C-(13)C CT-COSY method that combines a variation in the CT processed with diagonal filtering to yield (1)J(CC) and RDCs. The strategy, which relies solely on cross-peak intensity modulation, is inspired in the cross-peak nulling method used for J(HH) determinations, but adapted and extended to applications where, like in sugars, large one-bond (13)C-(13)C 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

  14. CO2 laser resurfacing.

    PubMed

    Fitzpatrick, R E

    2001-07-01

    The CO2 Laser offers a variety of unique features in resurfacing facial photodamage and acne scarring. These include hemostasis, efficient removal of the epidermis in a single pass, thermally induced tissue tightening, and safe, predictable tissue interaction. Knowledge of these mechanisms will result in the capability of using the CO2 laser effectively and safely whether the goal is superficial or deep treatment.

  15. 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 ...

  16. Halloysite nanotubes capturing isotope selective atmospheric CO2.

    PubMed

    Jana, Subhra; Das, Sankar; Ghosh, Chiranjit; Maity, Abhijit; Pradhan, Manik

    2015-03-04

    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 ((12)C(16)O2, (13)C(16)O2, and (12)C(16)O(18)O) 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.

  17. Process Model for Studying Regional 13C Stable Isotope Exchange between Vegetation and Atmosphere

    NASA Astrophysics Data System (ADS)

    Chen, J. M.; Chen, B.; Huang, L.; Tans, P.; Worthy, D.; Ishizawa, M.; Chan, D.

    2007-12-01

    The variation of the stable isotope 13CO2 in the air in exchange with land ecosystems results from fractionation processes in both plants and soil during photosynthesis and respiration. Its diurnal and seasonal variations therefore contain information on the carbon cycle. We developed a model (BEPS-iso) to simulate its exchange between vegetation and the atmosphere. To be useful for regional carbon cycle studies, the model has the following characteristics: (i) it considers the turbulent mixing in the vertical profile from the soil surface to the top of the planetary boundary layer (PBL); (ii) it scales individual leaf photosynthetic discrimination to the whole canopy through the separation of sunlit and shaded leaf groups; (iii) through simulating leaf-level photosynthetic processes, it has the capacity to mechanistically examine isotope discrimination resulting from meteorological forcings, such as radiation, precipitation and humidity; and (iv) through complete modeling of radiation, energy and water fluxes, it also simulates soil moisture and temperature needed for estimating ecosystem respiration and the 13C signal from the soil. After validation using flask data acquired at 20 m level on a tower near Fraserdale, Ontario, Canada, during intensive campaigns (1998-2000), the model has been used for several purposes: (i) to investigate the diurnal and seasonal variations in the disequilibrium in 13C fractionation between ecosystem respiration and photosynthesis, which is an important step in using 13C measurements to separate these carbon cycle components; (ii) to quantify the 13C rectification in the PBL, which differs significantly from CO2 rectification because of the diurnal and seasonal disequilibriums; and (iii) to model the 13C spatial and temporal variations over the global land surface for the purpose of CO2 inversion using 13C as an additional constraint.

  18. *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.

  19. 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

  20. 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.

  1. 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.

  2. 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.

  3. Transfer of (13) C between paired Douglas-fir seedlings reveals plant kinship effects and uptake of exudates by ectomycorrhizas.

    PubMed

    Pickles, Brian J; Wilhelm, Roland; Asay, Amanda K; Hahn, Aria S; Simard, Suzanne W; Mohn, William W

    2017-04-01

    Processes governing the fixation, partitioning, and mineralization of carbon in soils are under increasing scrutiny as we develop a more comprehensive understanding of global carbon cycling. Here we examined fixation by Douglas-fir seedlings and transfer to associated ectomycorrhizal fungi, soil microbes, and full-sibling or nonsibling neighbouring seedlings. Stable isotope probing with 99% (13) C-CO2 was applied to trace (13) C-labelled photosynthate throughout plants, fungi, and soil microbes in an experiment designed to assess the effect of relatedness on (13) C transfer between plant pairs. The fixation and transfer of the (13) C label to plant, fungal, and soil microbial tissue was examined in biomass and phospholipid fatty acids. After a 6 d chase period, c. 26.8% of the (13) C remaining in the system was translocated below ground. Enrichment was proportionally greatest in ectomycorrhizal biomass. The presence of mesh barriers (0.5 or 35 μm) between seedlings did not restrict (13) C transfer. Fungi were the primary recipients of (13) C-labelled photosynthate throughout the system, representing 60-70% of total (13) C-enriched phospholipids. Full-sibling pairs exhibited significantly greater (13) C transfer to recipient roots in two of four Douglas-fir families, representing three- and fourfold increases (+ c. 4 μg excess (13) C) compared with nonsibling pairs. The existence of a root/mycorrhizal exudation-hyphal uptake pathway was supported.

  4. 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.

  5. Method for computing the oxidation of two 13C-substrates ingested simultaneously during exercise.

    PubMed

    Péronnet, F; Adopo, E; Massicotte, D; Brisson, G R; Hillaire-Marcel, C

    1993-09-01

    This study presents a method for computing the respective amounts of two simultaneously ingested exogenous substrates (A and B) that are oxidized during a period of prolonged exercise by use of 13C labeling. This method is based on the observation that the total volume of 13CO2 produced (V13CO2tot) is the sum of 1) V13CO2 arising from the oxidation of endogenous substrates (V13CO2endo), 2) V13CO2 arising from the oxidation of substrate A (V13CO2A), and 3) V13CO2 arising from the oxidation of substrate B (V13CO2B). The equation, V13CO2tot = V13CO2endo+V13CO2A+V13CO2B, with three unknowns, can be solved from the results of three experiments conducted under the same conditions but with at least two values for the isotopic composition of A and B. This method has been used on five healthy male subjects to compute the amounts of glucose and fructose oxidized when a mixture of 15 g of glucose and 15 g of fructose is ingested (in 300 ml of water) over 60 min of cycle ergometer exercise at 65% of maximal O2 uptake. Results from three experiments indicated that 9.8 +/- 3.1 and 5.7 +/- 2.1 g of glucose and fructose, respectively, were oxidized. The total amount of exogenous carbohydrates oxidized (15.5 +/- 4.3 g) is in agreement with the oxidation rates of exogenous glucose computed in similar conditions when 30 g of glucose were ingested (13 g; Péronnet et al. Med. Sci. Sports Exercise 25: 297-302, 1993). The difference between the oxidation rates of exogenous glucose and fructose is also in line with data from the literature.

  6. Outsourcing CO2 Emissions

    NASA Astrophysics Data System (ADS)

    Davis, S. J.; Caldeira, K. G.

    2009-12-01

    CO2 emissions from the burning of fossil fuels are the primary cause of global warming. Much attention has been focused on the CO2 directly emitted by each country, but relatively little attention has been paid to the amount of emissions associated with consumption of goods and services in each country. This consumption-based emissions inventory differs from the production-based inventory because of imports and exports of goods and services that, either directly or indirectly, involved CO2 emissions. Using the latest available data and reasonable assumptions regarding trans-shipment of embodied carbon through third-party countries, we developed a global consumption-based CO2 emissions inventory and have calculated associated consumption-based energy and carbon intensities. We find that, in 2004, 24% of CO2 emissions are effectively outsourced to other countries, with much of the developed world outsourcing CO2 emissions to emerging markets, principally China. Some wealthy countries, including Switzerland and Sweden, outsource over half of their consumption-based emissions, with many northern Europeans outsourcing more than three tons of emissions per person per year. The United States is both a big importer and exporter of emissions embodied in trade, outsourcing >2.6 tons of CO2 per person and at the same time as >2.0 tons of CO2 per person are outsourced to the United States. These large flows indicate that CO2 emissions embodied in trade must be taken into consideration when considering responsibility for increasing atmospheric greenhouse gas concentrations.

  7. Meteoric diagenesis below a submerged platform: implications for δ13C compositions prior to pre-vascular plant evolution, Middle Ordovician, Alabama, U.S.A.

    NASA Astrophysics Data System (ADS)

    Tobin, Kenneth J.; Walker, Kenneth R.

    1994-04-01

    The Middle Ordovician "Chickamauga" Formation at Red Mountain Expressway (RME) and Tidwell Hollow (TWH) sections in Alabama (U.S.A) has a complex early diagenetic history. Early diagenetic history of the buildup facies consisted of two phases of marine cementation separated by two generations of meteoric, equant calcite with moldic dissolution separating equant calcite generations. A third generation of meteoric, equant (drusy) calcite is present after secondary marine diagenesis. Equant (drusy) calcite is interpreted as meteoric because its stable isotopic composition ( δ 13C = -0.1 to -1.6‰ , δ 18O = -4.8 to -7.3‰ ) is too variable to be accounted for by marine or mixing zone precipitation. Equant (drusy) calcite from buildup facies is mostly non-luminescent and non-ferroan. This is unlike early, ferroan equant calcite (dull to bright luminescent) from below the unconformity that overlies the "Chickamauga" Formation at RME. Meteoric diagenesis below the unconformity is unrelated to early diagenesis in the underlying buildup facies. Equant (drusy) calcite from the buildup facies at RME has a covariation of δ13C and δ18O values that forms a truncated inverted "J" and has elevated Mg values. These geochemical signatures indicate precipitation at a site that was distal from the recharge zone. Meteoric diagenesis at RME occurred during rising relative sea level and flow of meteoric fluids under a submerged platform is the only mechanism able to reconcile available stratigraphic, petrologic, and geochemical data. Ordovician meteoric δ13C values (from TWH and other formations) are slightly depleted (2-4‰) relative to coeval marine carbonate, especially when compared with post-Silurian meteoric carbonate. Minor depletion of Ordovician carbonate is the result of limited generation of light soil-gas CO 2 before the development of vascular plants.

  8. 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).

  9. Evaluation of CO2 Sorption Capacity of Granite for CO2 Geological Sequestration

    NASA Astrophysics Data System (ADS)

    Fujii, T.; Sato, Y.; Lin, H.; Sasaki, K.; Takahashi, T.; Inomata, H.; Hashida, T.

    2007-03-01

    Anthropogenic effects on climate can be mitigated through various measures. Among them being CO2 sequestration into geological reservoirs including deep saline aquifers, depleted oil/gas reservoirs and coal seams are interested in a powerful means for drastically reducing emissions of CO2. When CO2 would be injected into geological reservoir, it should be necessary to know the potential of CO2 storing into the reservoir. In this study, amount of CO2 sorption of granite was to evaluate experimentally at temperatures 50, 70, 100 and 200°C and pressure up to 20 MPa using a magnetic suspension balance (MSB), which allows to measure under supercritical condition. As a result, we confirmed that the granite have the potential of CO2 sorption. Sorption isotherms obtained from the MSB experiment showed that amount of CO2 sorption increased with the increasing pressure and decreased with the increasing temperature for all experimental conditions. Especially, amount of CO2 sorption at 50°C compared with that at other temperatures (70, 100 and 200°C) increased rapidly in the vicinity of the critical state. In addition, the granite showed a maximum of CO2 sorption into granite could reach up to about 1.0% by weight at 50°C and 14.4MPa. The present results may provide a fundamental knowledge for the development of CO2 geological sequestration technology.

  10. Isotopomer studies of gluconeogenesis and the Krebs cycle with 13C-labeled lactate.

    PubMed

    Katz, J; Wals, P; Lee, W N

    1993-12-05

    Fasted rats were intragastrically infused with either [2,3-13C]lactate or [1,2,3-13C]lactate. The infusate also contained 14C-labeled lactate and [3-3H]glucose. Glucose, alanine, glutamate, and glutamine were isolated from liver and blood. There was near complete equilibration of lactate and alanine, and the relative specific activities and relative enrichments were the same in blood and liver. Glucose was cleaved enzymatically to lactate. The compounds were examined by gas chromatography-mass spectroscopy. From the mass isotopomer spectra of the lactate, glutamate, and glutamine and their cleavage fragments the positional isotopomer composition of these compounds was obtained. The enrichment and isotopomer pattern in the lactate from cleaved glucose represents that in phosphoenolpyruvate (PEP). When [1,2,3-13C]lactate was infused the mass isotopomer spectrum of glutamates consisted only of compounds containing either one, two, or three 13C carbons per molecule (m1, m2, and m3). There was little 13C in C-4 and C-5 of glutamate. The rate of pyruvate decarboxylation is low, and 3-4% of the acetyl-CoA flux in the Krebs cycle is contributed by lactate carbon. The major isotopomers in lactate, alanine, and PEP were m3 and m2 with 13C in C-2 and C-3. The predominant isotopomer in PEP from [2,3-13C]lactate was m2 with 13C in C-2 and C-3. There was much more of m1 isotopomer with 13C in C-3 and C-2 than the m1 isotopomer with 13C in C-1. There was very little m3, the isotopomer with 13C in all three carbons. Most of the 13C in C-3 and C-4 of glucose and C-1 of glutamate was introduced via 13CO2 fixation. From the isotopomer distribution and the rate of glucose turnover we deduced, applying the analysis described in the "Appendix," the absolute rates of gluconeogenic pathways, recycling of PEP and the Cori cycle, and flux in the Krebs cycle. The flux from oxaloacetate (OAA)-->PEP was seven times that of OAA-->citrate, and about half of PEP was recycled to pyruvate via

  11. 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

  12. Soil CO2 dynamics, acidification, and chemical weathering in a temperate forest with experimental CO2 enrichment

    NASA Astrophysics Data System (ADS)

    Andrews, Jeffrey A.; Schlesinger, William H.

    2001-03-01

    Soils constitute a major component of the global carbon cycle that will be affected by anthropogenic additions of CO2 to the atmosphere. As part of the Duke Forest Free-Air CO2 Enrichment (FACE) experiment, we examined how forest growth at elevated (+200 ppmv) atmospheric CO2 concentration affects CO2 dynamics in the soil. Soil respiration and the concentration of CO2 in the soil pore space to a depth of 200 cm were measured over a 3-year period. Soil CO2 production was linked to soil acidification and mineral weathering by measuring changes in the composition of the soil solution, including alkalinity, Si, and major cations. The total flux of dissolved inorganic carbon to groundwater was then calculated from field measurements. The FACE fumigation gas contained a unique 13C signature that labeled newly fixed carbon, which was monitored in the soil system. As a result of CO2 enrichment, annual soil respiration increased by 27% and was accompanied by higher CO2 concentrations in the soil pore space. These changes to soil CO2 dynamics were most likely the result of increased root and rhizosphere respiration, as suggested by the changes to the δ13C of soil CO2. Increased soil CO2 under FACE accelerated the rates of soil acidification and mineral weathering. Thus an increase of 55% in atmospheric CO2 concentration over 2 years resulted in a 271% increase in soil solution cation concentration, a 162% increase in alkalinity, and a 25% increase in Si concentration at 200-cm depth. The flux of dissolved inorganic carbon to groundwater increased by 33%, indicating a negative feedback to changes in atmospheric CO2 that could regulate the global carbon cycle over geological time.

  13. 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.

  14. 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

  15. 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.

  16. Tracing solid waste leachate in groundwater using δ13 C from dissolved inorganic carbon.

    PubMed

    Haarstad, Ketil; Mæhlum, Trond

    2013-01-01

    Tracers can be used to monitor emissions of leachate from landfills in order to detect hydrological pathways and to evaluate environmental pollution. We investigated the stable carbon isotope ratio (δ(13)CCO (2)) in dissolved inorganic carbon and tritium ((3)H) in water, in addition to the tracers of pollution commonly found in relatively high concentrations in leachate, such as chloride (Cl), organic matter (COD), nitrogen (total and NH(4)-N), iron (Fe), electrical conductivity (EC) and pH. The sampling was performed at seven landfills in the south-eastern part of Norway during a period of 5 years. The objective was to evaluate the potential for tracing leachate in the environment with emphasis on groundwater pollution. By measuring the δ(13)CCO (2) in leachates, groundwaters and surface waters, the influence of leachate can be identified. The value of δ(13)CCO (2) varied from-5.5 to 25.9 ‰ in leachate, from-25.4 to 14.7 ‰ in groundwater and from-19.7 to-13.1 ‰ in creeks. A comparison of the carbon isotope ratio with COD, EC and the concentrations of total and NH (4)-N, Cl and Fe showed that δ(13)CCO (2) is a good tracer for leachate due to higher sensitivity compared to other parameters. The mean concentrations of all the studied parameters were higher in the leachate samples; however, only the carbon isotope ratio showed significant differences between all the groups with strong and middle pollution and samples with low pollution, showing that it can be used as a convenient tracer for leachate in groundwater and surface water. The carbon isotope ratio showed strong correlation between nitrogen, EC and bicarbonate, but not with pH. Tritium was only sporadically found in measureable concentrations and is not considered as a suitable tracer at the sampled locations.

  17. 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.

  18. 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...

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. 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

  4. Photolytic production of CO2 on Iapetus

    NASA Astrophysics Data System (ADS)

    Palmer, Eric; Brown, R. H.

    2008-09-01

    Carbon Dioxide has been detected on the surface of Iapetus by Cassini's VIMS instrument at the 4.26 micron band. This CO2 is concentrated on the equatorial leading side, where we also see an abundance of dark material. The residence time of free CO2 on the surface of Iapetus is very short, thus the CO2 is unlikely to be in the form of frost; it is more likely that the CO2 is tightly bound in the form of complexed molecules. We explore the possibility of photolytically generating CO2 from a mixture of the carbon rich material and water ice that matches the expected composition of the dark material on Iapetus' surface. An ice regolith was created with flash frozen water that was crushed into sub-millimeter shards and mixed with amorphous 13C. The regolith was placed in a vacuum chamber with a surface area of 10 cm2 and a thickness of 2 cm and exposed to UV light from a deuterium lamp with peaks of flux centered around 121 and 160 nm. Temperatures were varied between 60 and 130K at a pressure of 10-8 torr. Both CO and CO2 were produced by photolytic reactions and detected by a mass spectrometer. Applying these results to Iapetus, Jeans escape calculations show that CO2 generated by photolysis will remain gravitationally bound to Iapetus for between 100 and 200 years, ballistically scattering across the surface until it is sequestered in a polar cold trap or escapes to space. The average particle will interact with the surface more than 1000 times before escaping unless interactions with surface grains causes it to become complexed, such as adsorption. We are continuing to evaluate the photochemistry for this simulated Iapetus surface using a Nicolet IR spectrometer to identify all the products generated and estimate the associated production rate.

  5. Acetate and bicarbonate assimilation and metabolite formation in Chlamydomonas reinhardtii: a 13C-NMR study.

    PubMed

    Singh, Himanshu; Shukla, Manish R; Chary, Kandala V R; Rao, Basuthkar J

    2014-01-01

    Cellular metabolite analyses by (13)C-NMR showed that C. reinhardtii cells assimilate acetate at a faster rate in heterotrophy than in mixotrophy. While heterotrophic cells produced bicarbonate and CO2aq, mixotrophy cells produced bicarbonate alone as predominant metabolite. Experiments with singly (13)C-labelled acetate ((13)CH(3)-COOH or CH(3)-(13)COOH) supported that both the (13)C nuclei give rise to bicarbonate and CO2(aq). The observed metabolite(s) upon further incubation led to the production of starch and triacylglycerol (TAG) in mixotrophy, whereas in heterotrophy the TAG production was minimal with substantial accumulation of glycerol and starch. Prolonged incubation up to eight days, without the addition of fresh acetate, led to an increased TAG production at the expense of bicarbonate, akin to that of nitrogen-starvation. However, such TAG production was substantially high in mixotrophy as compared to that in heterotrophy. Addition of mitochondrial un-coupler blocked the formation of bicarbonate and CO2(aq) in heterotrophic cells, even though acetate uptake ensued. Addition of PSII-inhibitor to mixotrophic cells resulted in partial conversion of bicarbonate into CO2(aq), which were found to be in equilibrium. In an independent experiment, we have monitored assimilation of bicarbonate via photoautotrophy and found that the cells indeed produce starch and TAG at a much faster rate as compared to that in mixotrophy and heterotrophy. Further, we noticed that the accumulation of starch is relatively more as compared to TAG. Based on these observations, we suggest that acetate assimilation in C. reinhardtii does not directly lead to TAG formation but via bicarbonate/CO2(aq) pathways. Photoautotrophic mode is found to be the best growth condition for the production of starch and TAG and starch in C. reinhardtii.

  6. 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.

  7. Accurate measurements of 13C-13C distances in uniformly 13C-labeled proteins using multi-dimensional four-oscillating field solid-state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Straasø, Lasse Arnt; Nielsen, Jakob Toudahl; Bjerring, Morten; Khaneja, Navin; Nielsen, Niels Chr.

    2014-09-01

    Application of sets of 13C-13C internuclear distance restraints constitutes a typical key element in determining the structure of peptides and proteins by magic-angle-spinning solid-state NMR spectroscopy. Accurate measurements of the structurally highly important 13C-13C distances in uniformly 13C-labeled peptides and proteins, however, pose a big challenge due to the problem of dipolar truncation. Here, we present novel two-dimensional (2D) solid-state NMR experiments capable of extracting distances between carbonyl (13C') and aliphatic (13Caliphatic) spins with high accuracy. The method is based on an improved version of the four-oscillating field (FOLD) technique [L. A. Straasø, M. Bjerring, N. Khaneja, and N. C. Nielsen, J. Chem. Phys. 130, 225103 (2009)] which circumvents the problem of dipolar truncation, thereby offering a base for accurate extraction of internuclear distances in many-spin systems. The ability to extract reliable accurate distances is demonstrated using one- and two-dimensional variants of the FOLD experiment on uniformly 13C,15N-labeled-L-isoleucine. In a more challenging biological application, FOLD 2D experiments are used to determine a large number of 13C'-13Caliphatic distances in amyloid fibrils formed by the SNNFGAILSS fibrillating core of the human islet amyloid polypeptide with uniform 13C,15N-labeling on the FGAIL fragment.

  8. 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.

  9. Atmospheric pCO2 control on speleothem stable carbon isotope compositions

    NASA Astrophysics Data System (ADS)

    Breecker, Daniel O.

    2017-01-01

    The stable carbon isotope compositions of C3 plants are controlled by the carbon isotope composition of atmospheric CO2 (δ13Ca) and by the stomatal response to water stress. These relationships permit the reconstruction of ancient environments and assessment of the water use efficiency of forests. It is currently debated whether the δ13C values of C3 plants are also controlled by atmospheric pCO2. Here I show that globally-averaged speleothem δ13C values closely track atmospheric pCO2 over the past 90 kyr. After accounting for other possible effects, this coupling is best explained by a C3 plant δ13C sensitivity of - 1.6 ± 0.3 ‰ / 100 ppmV CO2 during the Quaternary. This is consistent with 20th century European forest tree ring δ13C records, providing confidence in the result and suggesting that the modest pCO2-driven increase in water use efficiency determined for those ecosystems and simulated by land surface models accurately approximates the global average response. The δ13C signal from C3 plants is transferred to speleothems relatively rapidly. Thus, the effect of atmospheric pCO2 should be subtracted from new and existing speleothem δ13C records so that residual δ13C shifts can be interpreted in light of the other factors known to control spleleothem δ13C values. Furthermore, global average speleothem δ13C shifts may be used to develop a continuous radiometric chronology for Pleistocene atmospheric pCO2 fluctuations and, by correlation, ice core climate records.

  10. 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

  11. 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.

  12. 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

  13. 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).

  14. High-Resolution Isotopic Monitoring of Cave Air CO2

    NASA Astrophysics Data System (ADS)

    Töchterle, Paul; Dublyansky, Yuri; Mandic, Magda; Stöbener, Nils; Jost, Hj; Spötl, Christoph

    2016-04-01

    This study aims at characterising the ventilation patterns in Spannagel Cave, a high-alpine cave system in the Zillertal Alps, Austria. A Thermo Scientific Delta Ray Isotope Ratio Infrared Spectrometer was installed in a chamber ca. 100 m behind the cave entrance to monitor pCO2 and δ13C and δ18O of CO2 at high temporal resolution (up to 1 s). The air temperature was independently monitored inside and outside the cave. This study aims at characterising the ventilation patterns in Spannagel Cave, a high-alpine cave system in the Zillertal Alps, Austria. A Thermo Scientific Delta Ray Isotope Ratio Infrared Spectrometer was installed in a chamber ca. 100 m behind the cave entrance to monitor pCO2 and δ13C and δ18O of CO2 at high temporal resolution (up to 1s). The air temperature was independently monitored inside and outside the cave. The data show two distinct patterns in terms of CO2 concentration and its isotopic composition, which are closely coupled with the temperature difference between the cave interior and the outside atmosphere. This gradient controls the direction of air flow in the cave on a seasonal to synoptic timescale (chimney-type ventilation). The summer circulation is characterised by CO2 closely resembling atmospheric values (pCO2 = 399 ± 12 ppm, δ13C = -8.5 ± 0.7 permil, δ18O = 8.1 ± 2.5 permil). The winter circulation mode features generally higher CO2 concentrations and lower isotopic compositions (pCO2 = 409 ± 14 ppm, δ13C = -10.1 ± 0.7 permil, δ18O = 2.3 ± 1.5 permil). The high temporal resolution of stable isotope data allows tracking cave air ventilation changes, including transient and short-lived ones. Moreover, the data make it possible to address concomitant geochemical processes, such as the input of atmospheric CO2 and the degassing of CO2 from seepage water. These processes would not be possible to quantify without the new generation of laser-based isotope ratio instruments represented by the Delta Ray.

  15. 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

  16. 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.

  17. 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.

  18. Environmental controls on δ13C variations of Sphagnum derived n-alkanes in the Dajiuhu peatland, central China

    NASA Astrophysics Data System (ADS)

    Huang, X.; Xue, J.; Wang, X.; WANG, H.; Meyers, P. A.; Qin, Y.; Gong, L.; Ding, W.

    2012-12-01

    Northern peatlands are one of the very important atmospheric carbon sinks and represent about 30% of the global soil organic carbon (Gorham, 1991). In peatland conditions, high water levels and consequent anoxia make them an important source of methane. A recent study revealed that methanotrophic bacteria growing on stems or in hyaline cells of Sphagnum can provide methane derived carbon for photosynthesis (Raghoebarsing et al., 2005). This interaction has been found to be globally prevalent in peat-moss ecosystems and can contribute up to 30% of carbon for Sphagnum photosynthesis (Kip et al., 2010). Due to the uptake of 13C-depleted methane-derived CO2 and the sensitivity of methane oxidizing bacteria to the surface wetness, the carbon isotopic signatures of Sphagnum derived lipids have the potential to be used as a proxy for the surface wetness in peatlands and hence as paleoclimate archives (Nichols et al., 2009). In this study, we report the δ13C variations of the Sphagnum derived n-C23 alkane in both fresh Sphagnum and surface peat samples in the Dajiuhu peatland, a small fen located in the Shennongjia forestry region, Hubei province, central China. The δ13C23 values of Sphagnum show a negative correlation with the water level, supporting the idea that that the carbon isotope fractionation of Sphagnum is mainly manifested by the diffusion resistance of CO2 in hyaline cells of Sphagnum. However, δ13C23 values of surface peats collected in Sphagnum dominated ecosystems display a positive relation with the water level when the water level is less than 30 cm. Such an inconsistency probably results from the higher potential for methane-oxidizing activity in the lower parts of Sphagnum in fen meadows. When the water level is higher than 30 cm, the influence of symbiotic methanotrophic bacteria on Sphagnum derived n-C23 alkane is weak or nearly absent. These findings provide direct evidence to support the hypothesis that the carbon isotopic signatures of Sphagnum

  19. 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

  20. 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...

  1. δ13C Degassing Dynamics of a Young Volcanic Center, Cerro Negro, Nicaragua

    NASA Astrophysics Data System (ADS)

    Lucic, G.; Stix, J.; Wing, B. A.; Muñoz, A.; Ibarra, M.; Sherwood Lollar, B.; Lacrampe-Couloume, G.

    2011-12-01

    Measurement of gas-phase δ13C values above active volcanic centers has the potential for monitoring magma dynamics associated with degassing and recharge events above subduction zones. The strong isotopic partitioning between C in the gas and melt, and C isotopic differences among magmas enables degassed CO2 to give insight into processes happening deep underground. Cerro Negro volcano in Nicaragua is an ideal center for detecting such magma interactions due to its rich history of volcanic activity and unusual eruption style. It is a subduction-driven, basaltic cinder cone that erupts on average once every 20 years with light to moderate intensity explosive eruptions (Volcanic Explosivity Index: 1-3) commonly accompanied by lava flows. Amid these eruptions are periods of extreme quiescence with very little seismic activity and gas emissions, suggesting rapid magmatic changes beneath the volcano. The brief lag time (on average 30 min). separating precursors and eruption supports this interpretation. In this study, we compare the isotopic composition of gas samples collected from fumaroles, fractures and other thermal areas on the volcano over a period of nearly 2 decades (1992-2011) in order to constrain the magmatic evolution beneath Cerro Negro. While the general systematics of the entire dataset are broadly consistent with degassing models for the natural evolution of CO2 and δ13C values, recent sampling campaigns suggest that new magma may be entering the system. Gases collected in January 2011 after 12 years of quiescence reveal CO2 concentrations ranging from 1-100%, with δ13C values varying from -1.5% to -10.4% with a mean of -3.3±0.28 % for 32 samples. Only limited spatial variability is present in this dataset: inner crater mean δ13C = -4.0±0.12 %, outer crater (-2.4±0.46 %), flanks (-4.4±0.26 %), and thermal areas to the N (-3.5±0.24 %) and SE (-2.5±0.25 %). Based on previous work, a lack of substantial spatial variation in δ values is

  2. High-resolution δ13C measurements on ancient air extracted from less than 10 cm3 of ice

    NASA Astrophysics Data System (ADS)

    Leuenberger, M. C.; Eyer, M.; Nyfeler, P.; Stauffer, B.; Stocker, T. F.

    2003-04-01

    A new method for δ13C analysis of very small air amounts of less than 0.5 cm3 STP was developed. This corresponds to less than 10 g of ice. It is based on the needle-crasher technique, which is routinely used for CO2 concentration measurements by infrared laser absorption. The extracted air is slowly expanded into a large volume through a water trap held at -70 °C where the pressure is measured. This sampled air is then carried by a high helium flux through a preconcentration system to separate CO2 cryogenically from the air. The small CO2 amount is then released into a low helium stream which forces the CO2 via an open split device to a mass spectrometer. The overall precision, based on replicates of standard air without crushing, 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. Performing δ13C measurements on ice air through the whole system, we reach a reproducibility of 0.12‰. Additional information is obtained through amplitude vs. pressure ratio determination, which results in a good control of the CO2 concentration (1 ppm precision for 1σ). The new method allows us to produce highly resolved records of atmospheric δ13C from air enclosed in ice, which is required to better understand the evolution and the temporal variability of the global carbon cycle.

  3. 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.

  4. Hyperpolarized 13C Metabolic MRI of the Human Heart

    PubMed Central

    Lau, Justin Y.C.; Chen, Albert P.; Geraghty, Benjamin J.; Perks, William J.; Roifman, Idan; Wright, Graham A.; Connelly, Kim A.

    2016-01-01

    Rationale: Altered cardiac energetics is known to play an important role in the progression toward heart failure. A noninvasive method for imaging metabolic markers that could be used in longitudinal studies would be useful for understanding therapeutic approaches that target metabolism. Objective: To demonstrate the first hyperpolarized 13C metabolic magnetic resonance imaging of the human heart. Methods and Results: Four healthy subjects underwent conventional proton cardiac magnetic resonance imaging followed by 13C imaging and spectroscopic acquisition immediately after intravenous administration of a 0.1 mmol/kg dose of hyperpolarized [1-13C]pyruvate. All subjects tolerated the procedure well with no adverse effects reported ≤1 month post procedure. The [1-13C]pyruvate signal appeared within the chambers but not within the muscle. Imaging of the downstream metabolites showed 13C-bicarbonate signal mainly confined to the left ventricular myocardium, whereas the [1-13C]lactate signal appeared both within the chambers and in the myocardium. The mean 13C image signal:noise ratio was 115 for [1-13C]pyruvate, 56 for 13C-bicarbonate, and 53 for [1-13C]lactate. Conclusions: These results represent the first 13C images of the human heart. The appearance of 13C-bicarbonate signal after administration of hyperpolarized [1-13C]pyruvate was readily detected in this healthy cohort (n=4). This shows that assessment of pyruvate metabolism in vivo in humans is feasible using current technology. Clinical Trial Registration: URL: https://www.clinicaltrials.gov. Unique identifier: NCT02648009. PMID:27635086

  5. 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.

  6. Assessing Oxidative Stress in Tumors by Measuring the Rate of Hyperpolarized [1-13C]Dehydroascorbic Acid Reduction Using 13C Magnetic Resonance Spectroscopy*

    PubMed Central

    Timm, Kerstin N.; Hu, De-En; Williams, Michael; Wright, Alan J.; Kettunen, Mikko I.; Kennedy, Brett W. C.; Larkin, Timothy J.; Dzien, Piotr; Marco-Rius, Irene; Bohndiek, Sarah E.; Brindle, Kevin M.

    2017-01-01

    Rapid cancer cell proliferation promotes the production of reducing equivalents, which counteract the effects of relatively high levels of reactive oxygen species. Reactive oxygen species levels increase in response to chemotherapy and cell death, whereas an increase in antioxidant capacity can confer resistance to chemotherapy and is associated with an aggressive tumor phenotype. The pentose phosphate pathway is a major site of NADPH production in the cell, which is used to maintain the main intracellular antioxidant, glutathione, in its reduced state. Previous studies have shown that the rate of hyperpolarized [1-13C]dehydroascorbic acid (DHA) reduction, which can be measured in vivo using non-invasive 13C magnetic resonance spectroscopic imaging, is increased in tumors and that this is correlated with the levels of reduced glutathione. We show here that the rate of hyperpolarized [1-13C]DHA reduction is increased in tumors that have been oxidatively prestressed by depleting the glutathione pool by buthionine sulfoximine treatment. This increase was associated with a corresponding increase in pentose phosphate pathway flux, assessed using 13C-labeled glucose, and an increase in glutaredoxin activity, which catalyzes the glutathione-dependent reduction of DHA. These results show that the rate of DHA reduction depends not only on the level of reduced glutathione, but also on the rate of NADPH production, contradicting the conclusions of some previous studies. Hyperpolarized [1-13C]DHA can be used, therefore, to assess the capacity of tumor cells to resist oxidative stress in vivo. However, DHA administration resulted in transient respiratory arrest and cardiac depression, which may prevent translation to the clinic. PMID:27994059

  7. 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.

  8. [Contribution of wheat rhizosphere respiration to soil respiration under elevated atmospheric CO2 and nitrogen application].

    PubMed

    Kou, Tai-ji; Xu, Xiao-feng; Zhu, Jian-guo; Xie, Zu-bin; Guo, Da-yong; Miao, Yan-fang

    2011-10-01

    With the support of free-air carbon dioxide enrichment (FACE) system and by using isotope 13C technique, and through planting wheat (Triticum aestivum L., C3 crop) on a soil having been planted with maize (Zea mays L., C4 crop) for many years, this paper studied the effects of elevated atmospheric CO2 and nitrogen application on the delta 13C value of soil emitted CO2 and the wheat rhizosphere respiration. With the growth of wheat, the delta 13C value of soil emitted CO2 had a gradual decrease. Elevated atmospheric CO2 concentration (200 micromol mol(-1)) decreased the delta 13C value of emitted CO2 at booting and heading stages significantly when the nitrogen application rate was 250 kg hm(-2) (HN), and at jointing and booting stages significantly when the nitrogen application rate was 150 kg hm(-2) (LN). Nevertheless, the elevated atmospheric CO2 promoted the proportions of wheat rhizosphere respiration to soil respiration at booting and heading stages significantly. From jointing stage to maturing stage, the proportions of wheat rhizosphere respiration to soil respiration were 24%-48% (HN) and 21%-48% (LN) under elevated atmospheric CO2, and 20%-36% (HN) and 19%-32% (LN) under ambient atmospheric CO2. Under both elevated and ambient atmospheric CO2 concentrations, the delta 13C value of emitted CO2 and the rhizosphere respiration had different responses to the increased nitrogen application rate, and there was a significant interactive effect of atmospheric CO2 concentration and nitrogen application rate on the wheat rhizosphere respiration at jointing stage.

  9. 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.

  10. 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

  11. Carbon isotopic composition of assimilated and respired CO2 in Southeastern US pine forests

    NASA Astrophysics Data System (ADS)

    Mortazavi, B.; Conte, M. H.; Chanton, J.; Martin, T.; Teklemerian, T.; Cropper, W.; Weber, J.

    2010-12-01

    We measured the 13C of assimilated carbon [foliage organic matter (δCOM), leaf soluble carbohydrates ((δCSC), and leaf waxes ((δCW)] and respiratory carbon [foliage (δCF), soil (δCS) and ecosystem respired CO2 (δCR)] over a two-year period at two sites in central Florida that are typical of Southeastern US coastal plain pine ecosystems. Our objective was to determine how climatic variables, operating by affecting plant physiology and photosynthetic discrimination (Δ), influence the isotopic composition of assimilated carbon pools and of ecosystem respired CO2. The first site was a naturally regenerated 32 m tall stand of mature longleaf pine (Pinus palustris Mill.) with mature slash pine (Pinus elliottii) subdominants, while the second was a planted, mid-rotation 13 m tall stand of slash pine (Pinus elliottii var. elliottii Engelm.). δCOM, δCSC, δCW, and δCF of P. palustris were 13C enriched by about 2‰ relative to that of P. elliottii in the mid-rotation plantation. Despite this enrichment, mean δCR of the P. palustris stand was similar to that at the P. elliottii plantation, reflecting additional respiratory inputs from the more isotopically depleted P. elliottii subdominant and understory. In both P. palustris and P. elliottii, a small decrease was observed in δCOM over the two year study, but not in δCSC, δCF, δCS or δCR. Intriguingly, a significant 2‰ decrease was also observed in the very long chain needlewaxes (C32-36 n-alkanoic acids), but not the more abundant C24-28 waxes. As the carbon in waxes is supplied by internal storage reserves, our data suggest there may be distinct carbon source pathways for waxes of differing chain lengths. The long-term decrease in the 13C of foliar carbon and waxes also suggests recovery from severe drought conditions prior to our study. δCF and δCR were consistently 13C enriched relative to assimilated C and were insensitive to variations in vapor pressure deficit (D). The small variability in δCA and

  12. An attempt to extract climatic factors from δ13C record of sphagnum peat cores in both the hemispheres

    NASA Astrophysics Data System (ADS)

    Akagi, T.; Ooki, S.; Franzen, L.; McCulloch, R.

    2009-12-01

    The reconstruction of the atmospheric CO2 concentration of the near past less than 10,000 years ago is still poorly established, mainly because of the low time-resolution of the analysis of the air trapped in ice cores. To discuss the recent rapid change of the global climate, the CO2 record with time resolution as high as several tens years is needed. Carbon isotope ratio of sphagnum tissues may change depending on many factors. White et al. (1994) reconstructed the atmospheric CO2 concentration from δ13C data of sphagnum after the correction for a moisture condition using δ13C of carex. The work evoked the skepticism on the method from some scientists: for instance Price et al. (1997) reported that δ13C of sphagnum responded to a moisture condition parabolically, which cast a doubt on the correction method for moistness of White et al. (1994). However, our preliminary study of δ13C record of a mid-latitudal peat core from Japan presented an interesting δ13C profile resembling a high resolution record of sea level (Akagi et al., 2004), implying that the above-mentioned effects may not impose a serious constant influence over several tens of years on peat cores. To reevaluate the effectiveness of peat cores as a proxy of the atmospheric CO2, we have approached the problem from an opposite direction. Our hypothesis is that similar isotopic signals must be observed in any peat cores from the world, if the δ13C of sphagnum reflects the CO2 concentration in the atmosphere. In this paper the δ13C signals of the sphagnum collected from two high-latitudal peat cores (Farahogy, Northern Island, and Herberton, Argentine) from both the hemispheres are compared. The similarity and differences are discussed separately. The difference may be attributable to the temperature difference in both the hemispheres, and the similarity possibly to the atmospheric CO2 concentration, as the similarity again shows the fluctuation resembling the sea level fluctuation.

  13. 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

  14. Characterization of Acetate and Pyruvate Metabolism in Suspension Cultures of Zea mays by 13C NMR Spectroscopy

    PubMed Central

    Ashworth, Dennis J.; Lee, Rino Y.; Adams, Douglas O.

    1987-01-01

    Carbon-13 nuclear magnetic resonance (NMR) spectroscopy has been applied to the direct observation of acetate and pyruvate metabolism in suspension cultures of Zea mays (var Black Mexican Sweet). Growth of the corn cells in the presence of 2 millimolar [2-13C]acetate resulted in a rapid uptake of the substrate from the medium and initial labeling (0-4 hours) of primarily the intracellular glutamate and malate pools. Further metabolism of these intermediates resulted in labeling of glutamine, aspartate, and alanine. With [1-13C]acetate as the substrate very little incorporation into intermediary metabolites was observed in the 13C NMR spectra due to loss of the label as 13CO2. Uptake of [3-13C]pyruvate by the cells was considerably slower than with [2-13C]acetate; however, the labelling patterns were similar with the exception of increased [3-13C] alanine generation with pyruvate as the substrate. Growth of the cells for up to 96 hours with 2 millimolar [3-13C]pyruvate ultimately resulted in labeling of valine, leucine, isoleucine, threonine, and the polyamine putrescine. PMID:16665721

  15. /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.

  16. 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.

  17. 13C NMR Metabolomics: Applications at Natural Abundance

    PubMed Central

    2015-01-01

    13C NMR has many advantages for a metabolomics study, including a large spectral dispersion, narrow singlets at natural abundance, and a direct measure of the backbone structures of metabolites. However, it has not had widespread use because of its relatively low sensitivity compounded by low natural abundance. Here we demonstrate the utility of high-quality 13C NMR spectra obtained using a custom 13C-optimized probe on metabolomic mixtures. A workflow was developed to use statistical correlations between replicate 1D 13C and 1H spectra, leading to composite spin systems that can be used to search publicly available databases for compound identification. This was developed using synthetic mixtures and then applied to two biological samples, Drosophila melanogaster extracts and mouse serum. Using the synthetic mixtures we were able to obtain useful 13C–13C statistical correlations from metabolites with as little as 60 nmol of material. The lower limit of 13C NMR detection under our experimental conditions is approximately 40 nmol, slightly lower than the requirement for statistical analysis. The 13C and 1H data together led to 15 matches in the database compared to just 7 using 1H alone, and the 13C correlated peak lists had far fewer false positives than the 1H generated lists. In addition, the 13C 1D data provided improved metabolite identification and separation of biologically distinct groups using multivariate statistical analysis in the D. melanogaster extracts and mouse serum. PMID:25140385

  18. Interaction between rhizosphere microorganisms and plant roots: 13C fluxes in the rhizosphere after pulse labeling

    NASA Astrophysics Data System (ADS)

    Yevdokimov, I. V.; Ruser, R.; Buegger, F.; Marx, M.; Munch, J. C.

    2007-07-01

    The input dynamics of labeled C into pools of soil organic matter and CO2 fluxes from soil were studied in a pot experiment with the pulse labeling of oats and corn under a 13CO2 atmosphere, and the contribution of the root and microbial respiration to the emission of CO2 from the soil was determined from the fluxes of labeled C in the microbial biomass and the evolved carbon dioxide. A considerable amount of 13C (up to 96% of the total amount of the label found in the rhizosphere soil) was incorporated into the biomass of the rhizosphere microorganisms. The diurnal fluctuations of the labeled C pools in the microbial biomass, dissolved organic carbon, and CO2 released in the rhizosphere of oats and corn were related to the day/night changes, i.e., to the on and off periods of the photosynthetic activity of the plants. The average contribution of the corn root respiration (70% of the total CO2 emission from the soil surface) was higher than that of the oats roots (44%), which was related to the lower incorporation of rhizodeposit carbon into the microbial biomass in the soil under the corn plants than in the soil under the oats plants.

  19. 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.

  20. Malate as a key carbon source of leaf dark-respired CO2 across different environmental conditions in potato plants.

    PubMed

    Lehmann, Marco M; Rinne, Katja T; Blessing, Carola; Siegwolf, Rolf T W; Buchmann, Nina; Werner, Roland A

    2015-09-01

    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 (13)C enrichment in leaf dark-respired CO2 are not fully understood, since daily changes in δ(13)C 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 (r(2)=0.69, P≤0.001) and nighttime (r(2)=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 (13)C enriched dark-respired CO2 in potato plants, probably driven by an anapleurotic flux replenishing intermediates of the Krebs cycle.

  1. 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

  2. Non-CO2 greenhouse gases and climate change.

    PubMed

    Montzka, S A; Dlugokencky, E J; Butler, J H

    2011-08-03

    Earth's climate is warming as a result of anthropogenic emissions of greenhouse gases, particularly carbon dioxide (CO(2)) from fossil fuel combustion. Anthropogenic emissions of non-CO(2) greenhouse gases, such as methane, nitrous oxide and ozone-depleting substances (largely from sources other than fossil fuels), also contribute significantly to warming. Some non-CO(2) greenhouse gases have much shorter lifetimes than CO(2), so reducing their emissions offers an additional opportunity to lessen future climate change. Although it is clear that sustainably reducing the warming influence of greenhouse gases will be possible only with substantial cuts in emissions of CO(2), reducing non-CO(2) greenhouse gas emissions would be a relatively quick way of contributing to this goal.

  3. 15N and 13C NMR Determination of Allantoin Metabolism in Developing Soybean Cotyledons 1

    PubMed Central

    Coker, George T.; Schaefer, Jacob

    1985-01-01

    The metabolism of allantoin by immature cotyledons of soybean (Glycine max L. cv Elf) grown in culture was investigated using solid state 13C and 15N nuclear magnetic resonance. All of the nitrogens of allantoin were incorporated into protein in a manner similar to that of each other and to the amide nitrogen of glutamine. The C-2 of allantoin was not incorporated into cellular material; presumably it was lost as CO2. About 50% of the C-5 of allantoin was incorporated into cellular material as a methylene carbon; the other 50% was presumably also lost as CO2. The 13C-15N bonds of [5-13C;1-15N] and [2-13C;1,3-15N]allantoin were broken prior to the incorporation of the nitrogens into protein. These data are consistent with allantoin's degradation to two molecules of urea and one two-carbon fragment. Cotyledons grown on allantoin as a source of nitrogen accumulated 21% of the nitrogen of cotyledons grown on glutamine. Only 50% of the nitrogen of the degraded allantoin was incorporated into the cotyledon as organic nitrogen; the other 50% was recovered as NH4+ in the media in which the cotyledons had been grown. The latter results suggests that the lower accumulation of nitrogen by cotyledons grown on allantoin was in part due to failure to assimilate NH4+ produced from allantoin. The seed coats had a higher activity of glutamine synthetase and a higher rate of allantoin degradation than cotyledons indicating that seed coats play an important role in the assimilation and degradation of allantoin. PMID:16663995

  4. 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.

  5. 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; McCray, John E.

    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 CO2flooding 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 CO2retention. 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 CO2produced 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 CO2dissolution 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

  6. 13C-methionine breath tests for mitochondrial liver function assessment.

    PubMed

    Candelli, M; Miele, L; Armuzzi, A; Nista, E C; Pignataro, G; Fini, L; Cazzato, I A; Zocco, M A; Bartolozzi, F; Gasbarrini, G; Grieco, A; Gasbarrini, A

    2008-01-01

    13C-methionine breath test has been proposed as a non-invasive tool for the assessment of human hepatic mithocondrial function. Two methionine breath labeled with 13C in differents point of his molecular structure have been used for breath test analisys. Aim of this study was to compare two differently 13C-labeled methionines in the evaluation of mitochondrial oxidation in basal conditions and after an acute oxidative stress. 15 healthy male subjects (mean age 30.5 +/- 3.1) received [methyl-13C]-methionine dissolved in water. Breath samples were taken at baseline and and 10, 20, 30, 45, 60, 75, 90, 105 and 120 minutes after the ingestion of the labeled substrate. Forthy-eight hours later, subjects underwent the same test 30 minutes after ethanol ingestion (0,3 g/kg of body weight). Seven-day later, subjects underwent breath test using (L-methionine-1-13COOH) as substrate, in basal condition and after ethanol ingestion. At basal condition, the cumulative percentage of 13CO2 recovered in breath during the test period (%cum-dose) was higher using L-methionine-1-13COOH than [methyl-13C]-methionine (10.25 +/- 1.0 vs 4.07 +/- 0.8; p < 0.01). After ethanol ingestion, % cum dose was significantly decreased at 60 and 120 minutes with both methionines (120 min: 10.25 +/- 1.0 vs 5.03% +/- 1.8; < 0.01 and 4.07 +/- 0.8 vs 2.16% +/- 0.9; p < 0.01, respectively). However, %cum-dose during L-methionine-1-13C-breath test was significantly lower than that observed during methyl-13C-methionine breath test (120 minutes: 5.03% +/- 1.8 vs 2.16% +/- 0.9; p < 0.01). In conclusion, breath test based on L-methionine-1-13COOH seems to show a greater reliability when compared to [methyl-13C]-methionine to assess mitochondrial function because a larger amount of labeled carbon that reaches the Krebs' cicle.

  7. 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

  8. Hyperpolarized 13C MR Markers of Renal Tumor Aggressiveness

    DTIC Science & Technology

    2013-10-01

    reliably distinguish renal cancer aggressiveness for optimal triage of therapies . Hyperpolarized (HP) 13C magnetic resonance spectroscopic imaging (MRSI...reliably distinguish renal cancer aggressiveness for optimal triage of therapies . Hyperpolarized (HP) 13C magnetic resonance spectroscopic imaging (MRSI) is... cancer and normal tissues were obtained from nephrectomy specimens and sliced using Krumdieck slicer. With a precision gauge micrometer, the slice

  9. 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...

  10. 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.

  11. 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.

  12. Emerging Patterns In The Isotopic Composition Of Soil CO2 Concentrations, Soil CO2 Production, And Soil-Atmosphere CO2 Exchange At The Watershed Scale: On The Intersection Between Hydrology And Biology In The Critical Zone

    NASA Astrophysics Data System (ADS)

    Riveros-Iregui, D. A.; Liang, L.; Lorenzo, T. M.

    2014-12-01

    Stable isotopes are commonly used to understand how physical and biological processes mediate the exchange of carbon between terrestrial ecosystems and the atmosphere. Numerous studies have described fundamental relationships between environmental variables, the carbon isotopic composition (δ13C) of recently assimilated sugars in plants, litter, soil carbon, or recently respired CO2. However, studies that examine the spatial variability of the 13C content of forest soils at the landscape scale are lacking. We report on measurements of the carbon isotopic composition of soil CO2 concentrations (δ13CC), soil CO2 production (δ13CP), and soil-atmosphere CO2 exchange (δ13CD) across a subalpine forest of the northern Rocky Mountains of Montana over two growing seasons. We evaluate the variability of these measurements across different landscape positions. Our analysis demonstrates that soil moisture and the lateral redistribution of soil water are strong predictors of the spatial variability of δ13CC, δ13CP, and δ13CD at the watershed scale. We suggest that there are concomitant yet independent effects of soil water on physical (i.e., soil gas diffusivity) and biological (i.e., photosynthetic activity) processes that mediate the 13C composition of forest soils. We show systematic spatial variability in the δ13C of forest soils at the landscape scale that can be useful to accurately predict and model land-atmosphere CO2 exchange over complex terrain.

  13. NMR structure analysis of uniformly 13C-labeled carbohydrates.

    PubMed

    Fontana, Carolina; Kovacs, Helena; Widmalm, Göran

    2014-06-01

    In this study, a set of nuclear magnetic resonance experiments, some of them commonly used in the study of (13)C-labeled proteins and/or nucleic acids, is applied for the structure determination of uniformly (13)C-enriched carbohydrates. Two model substances were employed: one compound of low molecular weight [(UL-(13)C)-sucrose, 342 Da] and one compound of medium molecular weight ((13)C-enriched O-antigenic polysaccharide isolated from Escherichia coli O142, ~10 kDa). The first step in this approach involves the assignment of the carbon resonances in each monosaccharide spin system using the anomeric carbon signal as the starting point. The (13)C resonances are traced using (13)C-(13)C correlations from homonuclear experiments, such as (H)CC-CT-COSY, (H)CC-NOESY, CC-CT-TOCSY and/or virtually decoupled (H)CC-TOCSY. Based on the assignment of the (13)C resonances, the (1)H chemical shifts are derived in a straightforward manner using one-bond (1)H-(13)C correlations from heteronuclear experiments (HC-CT-HSQC). In order to avoid the (1) J CC splitting of the (13)C resonances and to improve the resolution, either constant-time (CT) in the indirect dimension or virtual decoupling in the direct dimension were used. The monosaccharide sequence and linkage positions in oligosaccharides were determined using either (13)C or (1)H detected experiments, namely CC-CT-COSY, band-selective (H)CC-TOCSY, HC-CT-HSQC-NOESY or long-range HC-CT-HSQC. However, due to the short T2 relaxation time associated with larger polysaccharides, the sequential information in the O-antigen polysaccharide from E. coli O142 could only be elucidated using the (1)H-detected experiments. Exchanging protons of hydroxyl groups and N-acetyl amides in the (13)C-enriched polysaccharide were assigned by using HC-H2BC spectra. The assignment of the N-acetyl groups with (15)N at natural abundance was completed by using HN-SOFAST-HMQC, HNCA, HNCO and (13)C-detected (H)CACO spectra.

  14. 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.

  15. Nature and Dynamics of Carbon Accrued in a Forest Soil During Five Years of Atmospheric CO2 Enrichment

    NASA Astrophysics Data System (ADS)

    Jastrow, J. D.; O'Brien, S. L.; Dria, K. J.; Moran, K. K.; Filley, T. R.; Boutton, T. W.

    2004-12-01

    The potential for enhanced soil C storage to partially offset rising atmospheric CO2 concentrations is being evaluated by long-term field CO2 enrichment experiments. Although plant productivity is often stimulated in such experiments, the fate of increased detrital inputs to soil has yet to be definitively resolved, in part because detecting changes in soil C against the relatively large, spatially heterogeneous pool of existing soil organic matter has proven difficult. Even when significant changes in whole soil C are evident, predictions of the potential for long-term sequestration will require detailed studies of C dynamics and stability in functionally meaningful soil organic matter pools. In our studies at the free-air CO2 enrichment (FACE) experiment on a sweetgum (Liquidambar styraciflua L.) forest plantation in Oak Ridge, Tennessee, we are using (1) repeated sampling over time, (2) the isotopic tracer provided by the highly depleted 13C signature of the CO2 source used for fumigation, and (3) physical and chemical fractionation procedures to determine the fate and dynamics of FACE-derived C inputs to soil organic matter. After five years of CO2 enrichment, soil C accumulated at a linear rate in both unprotected and aggregate-protected pools, suggesting that additional C inputs were being processed and cycled in much the same manner as under ambient conditions. However, selective analysis of the biopolymer composition (lignin, suberin, and cutin) and oxidation state of the organic matter in physically and chemically isolated soil fractions will be used to assess the source, nature and potential stability of the C accrued in protected and unprotected pools.

  16. Forecasting global atmospheric CO2

    NASA Astrophysics Data System (ADS)

    Agustí-Panareda, A.; Massart, S.; Chevallier, F.; Boussetta, S.; Balsamo, G.; Beljaars, A.; Ciais, P.; Deutscher, N. M.; Engelen, R.; Jones, L.; Kivi, R.; Paris, J.-D.; Peuch, V.-H.; Sherlock, V.; Vermeulen, A. T.; Wennberg, P. O.; Wunch, D.

    2014-11-01

    A new global atmospheric carbon dioxide (CO2) real-time forecast is now available as part of the pre-operational Monitoring of Atmospheric Composition and Climate - Interim Implementation (MACC-II) service using the infrastructure of the European Centre for Medium-Range Weather Forecasts (ECMWF) Integrated Forecasting System (IFS). One of the strengths of the CO2 forecasting system is that the land surface, including vegetation CO2 fluxes, is modelled online within the IFS. Other CO2 fluxes are prescribed from inventories and from off-line statistical and physical models. The CO2 forecast also benefits from the transport modelling from a state-of-the-art numerical weather prediction (NWP) system initialized daily with a wealth of meteorological observations. This paper describes the capability of the forecast in modelling the variability of CO2 on different temporal and spatial scales compared to observations. The modulation of the amplitude of the CO2 diurnal cycle by near-surface winds and boundary layer height is generally well represented in the forecast. The CO2 forecast also has high skill in simulating day-to-day synoptic variability. In the atmospheric boundary layer, this skill is significantly enhanced by modelling the day-to-day variability of the CO2 fluxes from vegetation compared to using equivalent monthly mean fluxes with a diurnal cycle. However, biases in the modelled CO2 fluxes also lead to accumulating errors in the CO2 forecast. These biases vary with season with an underestimation of the amplitude of the seasonal cycle both for the CO2 fluxes compared to total optimized fluxes and the atmospheric CO2 compared to observations. The largest biases in the atmospheric CO2 forecast are found in spring, corresponding to the onset of the growing season in the Northern Hemisphere. In the future, the forecast will be re-initialized regularly with atmospheric CO2 analyses based on the assimilation of CO2 products retrieved from satellite measurements and

  17. 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

  18. 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.

  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.

  20. 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.

  1. Intercomparison of two cavity ring-down spectroscopy analyzers for atmospheric 13CO2 / 12CO2 measurement

    NASA Astrophysics Data System (ADS)

    Pang, Jiaping; Wen, Xuefa; Sun, Xiaomin; Huang, Kuan

    2016-08-01

    Isotope ratio infrared spectroscopy (IRIS) permits continuous in situ measurement of CO2 isotopic composition under ambient conditions. Previous studies have mainly focused on single IRIS instrument performance; few studies have considered the comparability among different IRIS instruments. In this study, we carried out laboratory and ambient measurements using two Picarro CO2δ13C analyzers (G1101-i and G2201-i (newer version)) and evaluated their performance and comparability. The best precision was 0.08-0.15 ‰ for G1101-i and 0.01-0.04 ‰ for G2201-i. The dependence of δ13C on CO2 concentration was 0.46 ‰ per 100 ppm and 0.09 ‰ per 100 ppm, the instrument drift ranged from 0.92-1.09 ‰ and 0.19-0.37 ‰, and the sensitivity of δ13C to the water vapor mixing ratio was 1.01 ‰ / % H2O and 0.09 ‰ / % H2O for G1101-i and G2201-i, respectively. The accuracy after correction by the two-point mixing ratio gain and offset calibration method ranged from -0.04-0.09 ‰ for G1101-i and -0.13-0.03 ‰ for G2201-i. The sensitivity of δ13C to the water vapor mixing ratio improved from 1.01 ‰ / % H2O before the upgrade of G1101-i (G1101-i-original) to 0.15 ‰ / % H2O after the upgrade of G1101-i (G1101-i-upgraded). Atmospheric δ13C measured by G1101-i and G2201-i captured the rapid changes in atmospheric δ13C signals on hourly to diurnal cycle scales, with a difference of 0.07 ± 0.24 ‰ between G1101-i-original and G2201-i and 0.05 ± 0.30 ‰ between G1101-i-upgraded and G2201-i. A significant linear correlation was observed between the δ13C difference of G1101-i-original and G2201-i and the water vapor concentration, but there was no significant correlation between the δ13C difference of G1101-i-upgraded and G2201-i and the water vapor concentration. The difference in the Keeling intercept values decreased from 1.24 ‰ between G1101-i-original and G2201-i to 0.36 ‰ between G1101-i-upgraded and G2201-i, which indicates the importance of consistency

  2. 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

  3. 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.

  4. 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).

  5. Forecasting global atmospheric CO2

    NASA Astrophysics Data System (ADS)

    Agustí-Panareda, A.; Massart, S.; Chevallier, F.; Boussetta, S.; Balsamo, G.; Beljaars, A.; Ciais, P.; Deutscher, N. M.; Engelen, R.; Jones, L.; Kivi, R.; Paris, J.-D.; Peuch, V.-H.; Sherlock, V.; Vermeulen, A. T.; Wennberg, P. O.; Wunch, D.

    2014-05-01

    A new global atmospheric carbon dioxide (CO2) real-time forecast is now available as part of the pre-operational Monitoring of Atmospheric Composition and Climate - Interim Implementation (MACC-II) service using the infrastructure of the European Centre for Medium-Range Weather Forecasts (ECMWF) Integrated Forecasting System (IFS). One of the strengths of the CO2 forecasting system is that the land surface, including vegetation CO2 fluxes, is modelled online within the IFS. Other CO2 fluxes are prescribed from inventories and from off-line statistical and physical models. The CO2 forecast also benefits from the transport modelling from a state-of-the-art numerical weather prediction (NWP) system initialized daily with a wealth of meteorological observations. This paper describes the capability of the forecast in modelling the variability of CO2 on different temporal and spatial scales compared to observations. The modulation of the amplitude of the CO2 diurnal cycle by near-surface winds and boundary layer height is generally well represented in the forecast. The CO2 forecast also has high skill in simulating day-to-day synoptic variability. In the atmospheric boundary layer, this skill is significantly enhanced by modelling the day-to-day variability of the CO2 fluxes from vegetation compared to using equivalent monthly mean fluxes with a diurnal cycle. However, biases in the modelled CO2 fluxes also lead to accumulating errors in the CO2 forecast. These biases vary with season with an underestimation of the amplitude of the seasonal cycle both for the CO2 fluxes compared to total optimized fluxes and the atmospheric CO2 compared to observations. The largest biases in the atmospheric CO2 forecast are found in spring, corresponding to the onset of the growing season in the Northern Hemisphere. In the future, the forecast will be re-initialized regularly with atmospheric CO2 analyses based on the assimilation of CO2 satellite retrievals, as they become available in

  6. 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.

  7. 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

  8. Seasonal variations in bulk tissue, fatty acid and monosaccharide delta(13)C values of leaves from mesotrophic grassland plant communities under different grazing managements.

    PubMed

    Dungait, Jennifer A J; Docherty, Gordon; Straker, Vanessa; Evershed, Richard P

    2010-03-01

    Leaves of 26 grass, herb, shrub and tree species were collected from mesotrophic grasslands to assess natural variability in bulk, fatty acid and monosaccharide delta(13)C values under different grazing management (cattle- or deer-grazed) on three sample dates (May, July and October) such that interspecific and spatiotemporal variations in whole leaf tissues and compound-specific delta(13)C values could be determined. The total mean leaf bulk delta(13)C value for plants was -28.9 per thousand with a range of values spanning 7.5 per thousand. Significant interspecific variation between bulk leaf delta(13)C values was only determined in October (P=<0.001) when delta(13)C values of the leaf tissues from both sites was on average 1.5 per thousand depleted compared to during July and May. Samples from May were significantly different between fields (P=0.03) indicating an effect from deer- or cattle-grazing in young leaves. The average individual monosaccharide delta(13)C value was 0.8 per thousand higher compared with whole leaf tissues. Monosaccharides were the most abundant components of leaf biomass, i.e. arabinose, xylose, mannose, galactose and glucose, and therefore, fluctuations in their individual delta(13)C values had a major influence on bulk delta(13)C values. An average depletion of ca. 1 per thousand in the bulk delta(13)C values of leaves from the deer-grazed field compared to the cattle-grazed field could be explained by a general depletion of 1.1 per thousand in glucose delta(13)C values, as glucose constituted >50% total leaf monosaccharides. In October, delta(13)C values of all monosaccharides varied between species, with significant variation in delta(13)C values of mannose and glucose in July, and mannose in May. This provided an explanation for the noted variability in the tissue bulk delta(13)C values observed in October 1999. The fatty acids C(16:0), C(18:2) and C(18:3) were highly abundant in all plant species. Fatty acid delta(13)C values were

  9. 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

  10. Enrichment of 13C in diacids and related compounds during photochemical processing of aqueous aerosols: New proxy for organic aerosols aging

    NASA Astrophysics Data System (ADS)

    Pavuluri, Chandra Mouli; Kawamura, Kimitaka

    2016-11-01

    To investigate the applicability of compound specific stable carbon isotope ratios (δ13C) of organics in assessment of their photochemical aging in the atmosphere, batch UV irradiation experiments were conducted on two ambient (anthropogenic and biogenic) aerosol samples in aqueous phase for 0.5–120 h. The irradiated samples were analyzed for δ13C of diacids, glyoxylic acid (ωC2) and glyoxal. δ13C of diacids and related compounds became larger with irradiation time (i.e., aging), except for few cases. In general, δ13C of C2-C4 diacids showed an increasing trend with decreasing chain length. Based on δ13C of diacids and related compounds and their relations to their concentrations, we found that C2 and C3 are enriched with 13C during the photochemical decomposition and production from their higher homologues and oxoacids. Photochemical breakdown of higher (≥C3) to lower diacids is also important in the enrichment of 13C in C3-C9 diacids whereas their production from primary precursors causes depletion of 13C. In case of ωC2 and glyoxal, their photochemical production and further oxidation to highly oxygenated compounds both cause the enrichment of 13C. This study reveals that δ13C of diacids and related compounds can be used as a proxy to trace the aging of organic aerosols during long-range atmospheric transport.

  11. Enrichment of 13C in diacids and related compounds during photochemical processing of aqueous aerosols: New proxy for organic aerosols aging

    PubMed Central

    Pavuluri, Chandra Mouli; Kawamura, Kimitaka

    2016-01-01

    To investigate the applicability of compound specific stable carbon isotope ratios (δ13C) of organics in assessment of their photochemical aging in the atmosphere, batch UV irradiation experiments were conducted on two ambient (anthropogenic and biogenic) aerosol samples in aqueous phase for 0.5–120 h. The irradiated samples were analyzed for δ13C of diacids, glyoxylic acid (ωC2) and glyoxal. δ13C of diacids and related compounds became larger with irradiation time (i.e., aging), except for few cases. In general, δ13C of C2-C4 diacids showed an increasing trend with decreasing chain length. Based on δ13C of diacids and related compounds and their relations to their concentrations, we found that C2 and C3 are enriched with 13C during the photochemical decomposition and production from their higher homologues and oxoacids. Photochemical breakdown of higher (≥C3) to lower diacids is also important in the enrichment of 13C in C3-C9 diacids whereas their production from primary precursors causes depletion of 13C. In case of ωC2 and glyoxal, their photochemical production and further oxidation to highly oxygenated compounds both cause the enrichment of 13C. This study reveals that δ13C of diacids and related compounds can be used as a proxy to trace the aging of organic aerosols during long-range atmospheric transport. PMID:27811980

  12. 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

  13. Constraining 3-PG with a new δ13C submodel: a test using the δ13C of tree rings.

    PubMed

    Wei, Liang; Marshall, John D; Link, Timothy E; Kavanagh, Kathleen L; DU, Enhao; Pangle, Robert E; Gag, Peter J; Ubierna, Nerea

    2014-01-01

    A semi-mechanistic forest growth model, 3-PG (Physiological Principles Predicting Growth), was extended to calculate δ(13)C in tree rings. The δ(13)C estimates were based on the model's existing description of carbon assimilation and canopy conductance. The model was tested in two ~80-year-old natural stands of Abies grandis (grand fir) in northern Idaho. We used as many independent measurements as possible to parameterize the model. Measured parameters included quantum yield, specific leaf area, soil water content and litterfall rate. Predictions were compared with measurements of transpiration by sap flux, stem biomass, tree diameter growth, leaf area index and δ(13)C. Sensitivity analysis showed that the model's predictions of δ(13)C were sensitive to key parameters controlling carbon assimilation and canopy conductance, which would have allowed it to fail had the model been parameterized or programmed incorrectly. Instead, the simulated δ(13)C of tree rings was no different from measurements (P > 0.05). The δ(13)C submodel provides a convenient means of constraining parameter space and avoiding model artefacts. This δ(13)C test may be applied to any forest growth model that includes realistic simulations of carbon assimilation and transpiration.

  14. Single shot three‐dimensional pulse sequence for hyperpolarized 13C MRI

    PubMed Central

    Wang, Jiazheng; Wright, Alan J.; Hu, De‐en; Hesketh, Richard

    2016-01-01

    Purpose Metabolic imaging with hyperpolarized 13C‐labeled cell substrates is a promising technique for imaging tissue metabolism in vivo. However, the transient nature of the hyperpolarization, and its depletion following excitation, limits the imaging time and the number of excitation pulses that can be used. We describe here a single‐shot three‐dimensional (3D) imaging sequence and demonstrate its capability to generate 13C MR images in tumor‐bearing mice injected with hyperpolarized [1‐13C]pyruvate. Methods The pulse sequence acquires a stack‐of‐spirals at two spin echoes after a single excitation pulse and encodes the kz‐dimension in an interleaved manner to enhance robustness to B0 inhomogeneity. Spectral‐spatial pulses are used to acquire dynamic 3D images from selected hyperpolarized 13C‐labeled metabolites. Results A nominal spatial/temporal resolution of 1.25 × 1.25 × 2.5 mm3 × 2 s was achieved in tumor images of hyperpolarized [1‐13C]pyruvate and [1‐13C]lactate acquired in vivo. Higher resolution in the z‐direction, with a different k‐space trajectory, was demonstrated in measurements on a thermally polarized [1‐13C]lactate phantom. Conclusion The pulse sequence is capable of imaging hyperpolarized 13C‐labeled substrates at relatively high spatial and temporal resolutions and is robust to moderate system imperfections. Magn Reson Med 77:740–752, 2017. © 2016 The Authors Magnetic Resonance in Medicine published by Wiley Periodicals, Inc. on behalf of International Society for Magnetic Resonance in Medicine. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. PMID:26916384

  15. 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

  16. (13)C metabolic flux analysis of recombinant expression hosts.

    PubMed

    Young, Jamey D

    2014-12-01

    Identifying host cell metabolic phenotypes that promote high recombinant protein titer is a major goal of the biotech industry. (13)C metabolic flux analysis (MFA) provides a rigorous approach to quantify these metabolic phenotypes by applying isotope tracers to map the flow of carbon through intracellular metabolic pathways. Recent advances in tracer theory and measurements are enabling more information to be extracted from (13)C labeling experiments. Sustained development of publicly available software tools and standardization of experimental workflows is simultaneously encouraging increased adoption of (13)C MFA within the biotech research community. A number of recent (13)C MFA studies have identified increased citric acid cycle and pentose phosphate pathway fluxes as consistent markers of high recombinant protein expression, both in mammalian and microbial hosts. Further work is needed to determine whether redirecting flux into these pathways can effectively enhance protein titers while maintaining acceptable glycan profiles.

  17. Synthesis of Site-Specifically (13)C Labeled Linoleic Acids.

    PubMed

    Offenbacher, Adam R; Zhu, Hui; Klinman, Judith P

    2016-10-12

    Soybean lipoxygenase-1 (SLO-1) catalyzes the C-H abstraction from the reactive carbon (C-11) in linoleic acid as the first and rate-determining step in the formation of alkylhydroperoxides. While previous labeling strategies have focused on deuterium labeling to ascertain the primary and secondary kinetic isotope effects for this reaction, there is an emerging interest and need for selectively enriched (13)C isotopologues. In this report, we present synthetic strategies for site-specific (13)C labeled linoleic acid substrates. We take advantage of a Corey-Fuchs formyl to terminal (13)C-labeled alkyne conversion, using (13)CBr4 as the labeling source, to reduce the number of steps from a previous fatty acid (13)C synthetic labeling approach. The labeled linoleic acid substrates are useful as nuclear tunneling markers and for extracting active site geometries of the enzyme-substrate complex in lipoxygenase.

  18. Methanogenic capabilities of ANME-archaea deduced from (13) C-labelling approaches.

    PubMed

    Bertram, Sebastian; Blumenberg, Martin; Michaelis, Walter; Siegert, Michael; Krüger, Martin; Seifert, Richard

    2013-08-01

    Anaerobic methanotrophic archaea (ANME) are ubiquitous in marine sediments where sulfate dependent anaerobic oxidation of methane (AOM) occurs. Despite considerable progress in the understanding of AOM, physiological details are still widely unresolved. We investigated two distinct microbial mat samples from the Black Sea that were dominated by either ANME-1 or ANME-2. The (13) C lipid stable isotope probing (SIP) method using labelled substances, namely methane, bicarbonate, acetate, and methanol, was applied, and the substrate-dependent methanogenic capabilities were tested. Our data provide strong evidence for a versatile physiology of both, ANME-1 and ANME-2. Considerable methane production rates (MPRs) from CO2 -reduction were observed, particularly from ANME-2 dominated samples and in the presence of methane, which supports the hypothesis of a co-occurrence of methanotrophy and methanogenesis in the AOM systems (AOM/MPR up to 2:1). The experiments also revealed strong methylotrophic capabilities through (13) C-assimilation from labelled methanol, which was independent of the presence of methane. Additionally, high MPRs from methanol were detected in both of the mat samples. As demonstrated by the (13) C-uptake into lipids, ANME-1 was found to thrive also under methane free conditions. Finally, C35 -isoprenoid hydrocarbons were identified as new lipid biomarkers for ANME-1, most likely functioning as a hydrogen sink during methanogenesis.

  19. Is CO2 ice permanent?

    NASA Technical Reports Server (NTRS)

    Lindner, Bernhard Lee

    1992-01-01

    Carbon dioxide ice has been inferred to exist at the south pole in summertime, but Earth based measurements in 1969 of water vapor in the Martian atmosphere suggest that all CO2 ice sublined from the southern polar cap and exposed underlying water ice. This implies that the observed summertime CO2 ice is of recent origin. It appears possible to construct an energy balance model that maintains seasonal CO2 ice at the south pole year round and still reasonably simulates the polar cap regression and atmospheric pressure data. This implies that the CO2 ice observed in the summertime south polar cap could be seasonal in origin, and that minor changes in climate could cause CO2 ice to completely vanish, as would appear to have happened in 1969. However, further research remains before it is certain whether the CO2 ice observed in the summertime south polar cap is seasonal or is part of a permanent reservoir.

  20. Effects of Ergot Alkaloids on Liver Function of Piglets as Evaluated by the 13C-Methacetin and 13C-α-Ketoisocaproic Acid Breath Test

    PubMed Central

    Dänicke, Sven; Diers, Sonja

    2013-01-01

    Ergot alkaloids (the sum of individual ergot alkaloids are termed as total alkaloids, TA) are produced by the fungus Claviceps purpurea, which infests cereal grains commonly used as feedstuffs. Ergot alkaloids potentially modulate microsomal and mitochondrial hepatic enzymes. Thus, the aim of the present experiment was to assess their effects on microsomal and mitochondrial liver function using the 13C-Methacetin (MC) and 13C-α-ketoisocaproic acid (KICA) breath test, respectively. Two ergot batches were mixed into piglet diets, resulting in 11 and 22 mg (Ergot 5-low and Ergot 5-high), 9 and 14 mg TA/kg (Ergot 15-low and Ergot 15-high) and compared to an ergot-free control group. Feed intake and live weight gain decreased significantly with the TA content (p < 0.001). Feeding the Ergot 5-high diet tended to decrease the 60-min-cumulative 13CO2 percentage of the dose recovery (cPDR60) by 26% and 28% in the MC and KICA breath test, respectively, compared to the control group (p = 0.065). Therefore, both microsomal and mitochondrial liver function was slightly affected by ergot alkaloids. PMID:23322130

  1. Measurements and interpretation of δ13C of methane from termites, rice paddies, and wetlands in Kenya

    NASA Astrophysics Data System (ADS)

    Tyler, Stanley C.; Zimmerman, Patrick R.; Cumberbatch, Colin; Greenberg, James P.; Westberg, Curtis; Darlington, Johanna P. E. C.

    1988-12-01

    Ratios of 13C/12C have been measured in methane from a variety of sources in tropical Kenya. Ranges of δ13C in CH4 for termites (most values range from -56 to -64‰, one is at -44‰ one is at ˜-73‰), rice paddies (range -57 to -63‰), and wetlands (range -45 to - 50‰ for Lake Baringo, ˜-55‰ in the Moloi River, ˜-62‰ and ˜-31‰ in two swamp areas) are presented. The data are interpreted with the help of additional measurements of δ13C of CO2 gas, and organic carbon in plant material, termite bodies, and termite fungus combs. The implications of these findings are related to the problem of studying the atmospheric methane budget.

  2. An in Vivo 13C NMR Analysis of the Anaerobic Yeast Metabolism of 1-13C-Glucose

    NASA Astrophysics Data System (ADS)

    Giles, Brent J.; Matsche, Zenziwe; Egeland, Ryan D.; Reed, Ryan A.; Morioka, Scott S.; Taber, Richard L.

    1999-11-01

    A biochemistry laboratory experiment that studies the dynamics of the anaerobic yeast metabolism of 1-13C-D-glucose via NMR is described. Fleischmann's Active Dry yeast, under anaerobic conditions, produces primarily 2-13C-ethanol and some 1-13C-glycerol as end products. An experiment is described in which the yeast is subjected to osmotic shock from an increasing sodium chloride concentration. Under these conditions, the yeast increases the ratio of glycerol to ethanol. The experiment can be accomplished in a single laboratory period.

  3. Tracing carbon uptake from a natural CO2 spring into tree rings: an isotope approach.

    PubMed

    Saurer, Matthias; Cherubini, Paolo; Bonani, Georges; Siegwolf, Rolf

    2003-10-01

    We analyzed 14C, 13C and 18O isotope variations over a 50-year period in tree rings of Quercus ilex L. trees growing at a natural CO2 spring in a Mediterranean ecosystem. We compared trees from two sites, one with high and one with low exposure to CO2 from the spring. The spring CO2 is free of 14C. Thus, this carbon can be traced in the wood, and the amount originating from the spring calculated. The amount decreased over time, from about 40% in 1950 to 15% at present for the site near the spring, indicating a potential difficulty in the use of natural CO2 springs for elevated CO2 research. The reason for the decrease may be decreasing emission from the spring or changes in stand structure, e.g., growth of the canopy into regions with lower concentrations. We used the 14C-calculated CO2 concentration in the canopy to determine the 13C discrimination of the plants growing under elevated CO2 by calculating the effective canopy air 13C/12C isotopic composition. The trees near the spring showed a 2.5 per thousand larger 13C discrimination than the more distant trees at the beginning of the investigated period, i.e., for the young trees, but this difference gradually disappeared. Higher discrimination under elevated CO2 indicated reduced photosynthetic capacity or increased stomatal conductance. The latter assumption is unlikely as inferred from the 18O data, which were insensitive to CO2 concentration. In conclusion, we found evidence for a downward adjustment of photosynthesis under elevated CO2 in Q. ilex in this dry, nutrient-poor environment.

  4. 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.

  5. 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.

  6. 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

  7. 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

  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. Impact of oceanic circulation changes on atmospheric δ13CO2

    NASA Astrophysics Data System (ADS)

    Menviel, L.; Mouchet, A.; Meissner, K. J.; Joos, F.; England, M. H.

    2015-12-01

    δ13CO2 measured in Antarctic ice cores provides constraints on oceanic and terrestrial carbon cycle processes linked with millennial-scale and glacial/interglacial changes in atmospheric CO2. However, the interpretation of δ13CO2 is not straightforward. Using two Earth system models of intermediate complexity we perform a set of sensitivity experiments in which the formation rates of North Atlantic Deep Water (NADW), North Pacific Deep Water (NPDW), Antarctic Bottom Water (AABW) and Antarctic Intermediate Water (AAIW) are varied. We study the impact of these circulation changes on atmospheric δ13CO2 as well as on the oceanic δ13C distribution. In general, we find that the formation rates of AABW, NADW, NPDW and AAIW are negatively correlated with changes in δ13CO2: namely strong oceanic ventilation decreases atmospheric δ13CO2. However, since large scale ocean circulation reorganizations also impact nutrient utilization and the Earth's climate the relationship between atmospheric δ13CO2 levels and ocean ventilation rate is not unequivocal. In both models atmospheric δ13CO2 is very sensitive to changes in AABW formation rates: increased AABW formation enhances the upwelling of low δ13C waters to the surface and decreases atmospheric δ13CO2. By contrast, the impact of NADW changes on atmospheric δ13CO2 is less robust and might be model dependent.

  10. Partitioning CO2 production with stable carbon isotopes in a peatland ecosystem

    NASA Astrophysics Data System (ADS)

    Corbett, J.; Chanton, J.; tfaily, M. M.; Cooper, W. T.; Burdige, D. J.; Glaser, P. H.

    2011-12-01

    We developed an isotope mass-balance model to predict the percent of CO2 formed from either organic-matter fermentation or methanogenesis using pore water δ13C-CO2 and δ13C-CH4 in a peatland ecosystem. Our second objective was to determine percent CH4 loss using CO2 and CH4 concentrations and the predicted percent of CO2 from methanogenesis. The assumption that methanogenesis produces equimolar amounts of CH4 and CO2 and multiple field and incubation measurements that show higher concentrations of CO2 indicate that organic-matter fermentation is an important respiration pathway in these systems. Lower concentrations of CH4 could be accounted for by ebullition and vascular-plant transport. A closed system incubation study was done to determine if predicted CO2 and CH4 concentrations calculated using isotopes compared to measured concentration values. The average difference between the two approaches was 3.5%. Using the model to analyze field measurements, we found that a higher percent of CO2 was produced from methanogenesis than organic matter fermentation in both bog and fen environments. At depths, bogs had a slightly higher percent of CO2 from methanogenesis (100%) than did fens (90%). Surface depths shallower than 50cm produced a significantly larger (20%) amount of CO2 from organic-matter fermentation than deeper depths. Bogs and fens showed a similar amount of methane loss between 85-100% depending on depth.

  11. 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.

  12. Variability and directionality of temporal changes in δ(13)C and δ (15)N of aquatic invertebrate primary consumers.

    PubMed

    Woodland, Ryan J; Magnan, Pierre; Glémet, Hélène; Rodríguez, Marco A; Cabana, Gilbert

    2012-05-01

    Seasonal oscillations in the carbon (δ(13)C) and nitrogen (δ(15)N) isotope signatures of aquatic algae can cause seasonal enrichment-depletion cycles in the isotopic composition of planktonic invertebrates (e.g., copepods). Yet, there is growing evidence that seasonal enrichment-depletion cycles also occur in the isotope signatures of larger invertebrate consumers, taxa used to define reference points in isotope-based trophic models (e.g., trophic baselines). To evaluate the general assumption of temporal stability in non-zooplankton aquatic invertebrates, δ(13)C and δ(15)N time series data from the literature were analyzed for seasonality and the influence of biotic (feeding group) and abiotic (trophic state, climate regime) factors on isotope temporal patterns. The amplitude of δ(13)C and δ(15)N enrichment-depletion cycles was negatively related to body size, although all size-classes of invertebrates displayed a winter-to-summer enrichment in δ(13)C and depletion in δ(15)N. Among feeding groups, periphytic grazers were more variable and displayed larger temporal changes in δ(13)C than detritivores. For nitrogen, temporal variability and magnitude of directional change of δ(15)N was most strongly related to ecosystem trophic state (eutrophic > mesotrophic, oligotrophic). This study provides evidence of seasonality in the isotopic composition of aquatic invertebrates across very broad geographical and ecological gradients as well as identifying factors that are likely to modulate the strength and variability of seasonality. These results emphasize the need for researchers to recognize the likelihood of temporal changes in non-zooplankton aquatic invertebrate consumers at time scales relevant to seasonal studies and, if present, to account for temporal dynamics in isotope trophic models.

  13. CO2 interaction with geomaterials.

    SciTech Connect

    Guthrie, George D.; Al-Saidi, Wissam A.; Jordan, Kenneth D.; Voora, Vamsee, K.; Romanov, Vyacheslav N.; Lopano, Christina L; Myshakin, Eugene M.; Hur, Tae Bong; Warzinski, Robert P.; Lynn, Ronald J.; Howard, Bret H.; Cygan, Randall Timothy

    2010-09-01

    This work compares the sorption and swelling processes associated with CO2-coal and CO2-clay interactions. We investigated the mechanisms of interaction related to CO2 adsortion in micropores, intercalation into sub-micropores, dissolution in solid matrix, the role of water, and the associated changes in reservoir permeability, for applications in CO2 sequestration and enhanced coal bed methane recovery. The structural changes caused by CO2 have been investigated. A high-pressure micro-dilatometer was equipped to investigate the effect of CO2 pressure on the thermoplastic properties of coal. Using an identical dilatometer, Rashid Khan (1985) performed experiments with CO2 that revealed a dramatic reduction in the softening temperature of coal when exposed to high-pressure CO2. A set of experiments was designed for -20+45-mesh samples of Argonne Premium Pocahontas No.3 coal, which is similar in proximate and ultimate analysis to the Lower Kittanning seam coal that Khan used in his experiments. No dramatic decrease in coal softening temperature has been observed in high-pressure CO2 that would corroborate the prior work of Khan. Thus, conventional polymer (or 'geopolymer') theories may not be directly applicable to CO2 interaction with coals. Clays are similar to coals in that they represent abundant geomaterials with well-developed microporous structure. We evaluated the CO2 sequestration potential of clays relative to coals and investigated the factors that affect the sorption capacity, rates, and permanence of CO2 trapping. For the geomaterials comparison studies, we used source clay samples from The Clay Minerals Society. Preliminary results showed that expandable clays have CO2 sorption capacities comparable to those of coal. We analyzed sorption isotherms, XRD, DRIFTS (infrared reflectance spectra at non-ambient conditions), and TGA-MS (thermal gravimetric analysis) data to compare the effects of various factors on CO2 trapping. In montmorillonite, CO2

  14. 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.

  15. 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.

  16. Gradients in the carbon isotopic composition of Ordovician shallow water carbonates: A potential pitfall in estimates of ancient CO2 and O2

    NASA Astrophysics Data System (ADS)

    Saltzman, Matthew R.; Edwards, Cole T.

    2017-04-01

    The carbon isotopic composition of the global dissolved inorganic carbon (DIC) reservoir is best estimated from open ocean pelagic carbonate sediments (δ13Ccarb). However, this is not practical for most of geologic time because seafloor subduction has removed the pre-Jurassic record and these time periods may have lacked planktonic calcifying organisms, and therefore shallow water carbonate platform or periplatform sediments are utilized. Shallow water deposits are susceptible to a wide range of post-depositional alteration processes and syn-depositional controls on δ13Ccarb that include carbonate mineralogy, water mass restriction, and a host of related variables (e.g., pH, temperature, organic decomposition, evaporation and CO2 solubility) that can produce local gradients in DIC. The degree to which shallow water δ13C curves diverge from open marine deposits may be critical to understanding how well global carbon cycle isotope mass balance models can predict organic carbon burial rates, but documentation of such divergence is often hindered by factors that limit chronostratigraphic correlation in restricted water masses (e.g., endemic faunas). Here we integrate strontium isotope (87Sr/86Sr) stratigraphy and biostratigraphy to compare δ13C curves in a case study along a depth transect in Middle-Late Ordovician carbonate platform settings. The restricted tidal flat and more open marine deposits are offset by a maximum of ∼2‰ during sea level drop and ∼0‰ during highstand flooding of the platform. Global carbon cycle models such as GEOCARBSULF use published δ13Ccarb curves to drive organic carbon burial rates under the assumption that δ13Ccarb reflects a global seawater signal. We show here the potential pitfalls of using a published δ13Ccarb curve that violates this global assumption. For the 460 million year Middle-Late Ordovician time bin in GEOCARBSULF, improper usage of our locally depleted δ13C curve to drive global organic carbon burial would

  17. Leaves: Elevated CO2 levels

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Burning fossil fuels and land use changes such as deforestation and urbanization have led to a dramatic rise in the concentration of carbon dioxide (CO2) in the atmosphere since the onset of the Industrial Revolution. The highly dilute CO2 from the atmosphere enters plant leaves where it is concentr...

  18. Time lag between photosynthesis and CO2 efflux from soil

    NASA Astrophysics Data System (ADS)

    Kuzyakov, Y.; Gavrichkova, O.

    2009-04-01

    Important part of CO2 efflux from planted soils is root-derived CO2, meaning that it originates directly and indirectly from roots: directly from root respiration, and indirectly from respiration of rhizosphere microorganisms decomposing organic substances released by roots into the soil (rhizodeposits). Recent studies have shown that apart of well studied effect of soil temperature and soil water content, the C supply of assimilates from photosynthetically active plant organs have a significant effect on the root-derived CO2. In fact, the effect of photosynthesis on root-derived CO2 is often masked by temperature because root biomass typically peaks in summer. However, roots can only respire the C that was allocated belowground, and so the effect of temperature on root respiration is likely to be constrained by photosynthesis. If models of soil respiration are to incorporate photosynthetic C inputs it is necessary to understand how these two fluxes are coupled and what are the factors affecting the time lag between C uptake and its following respiration by roots and associated microorganisms. We reviewed literature and own studies relevant for estimation of the delay of C assimilation by photosynthesis and CO2 efflux from soil. The most of the studies were based on pulse labeling of annual plants in the atmosphere with 14CO2 or 13CO2 and subsequent chase of 14C or 13C in the CO2 efflux from soil. We analyzed the dynamics of the CO2 efflux curves and evaluated 3 parameters: 1) the first appearance of labeled CO2 from soil, 2) maximum of labeled CO2, and 3) disappearance of the labeled CO2 from the total CO2 efflux from soil. Numerous studies showed that newly assimilated C cycles quickly within the ecosystem, being found in root respiration already some minutes after its assimilation. Reported time lags in situ and laboratory experiments varied from minutes to days. For annual and perennial grasses the first appearance of labeled CO2 from soil was measured within

  19. 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.

  20. CO2 Sequestration short course

    SciTech Connect

    DePaolo, Donald J.; Cole, David R; Navrotsky, Alexandra; Bourg, Ian C

    2014-12-08

    Given the public’s interest and concern over the impact of atmospheric greenhouse gases (GHGs) on global warming and related climate change patterns, the course is a timely discussion of the underlying geochemical and mineralogical processes associated with gas-water-mineral-interactions encountered during geological sequestration of CO2. The geochemical and mineralogical processes encountered in the subsurface during storage of CO2 will play an important role in facilitating the isolation of anthropogenic CO2 in the subsurface for thousands of years, thus moderating rapid increases in concentrations of atmospheric CO2 and mitigating global warming. Successful implementation of a variety of geological sequestration scenarios will be dependent on our ability to accurately predict, monitor and verify the behavior of CO2 in the subsurface. The course was proposed to and accepted by the Mineralogical Society of America (MSA) and The Geochemical Society (GS).

  1. 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.

  2. 13C-based metabolic flux analysis: fundamentals and practice.

    PubMed

    Yang, Tae Hoon

    2013-01-01

    Isotope-based metabolic flux analysis is one of the emerging technologies applied to system level metabolic phenotype characterization in metabolic engineering. Among the developed approaches, (13)C-based metabolic flux analysis has been established as a standard tool and has been widely applied to quantitative pathway characterization of diverse biological systems. To implement (13)C-based metabolic flux analysis in practice, comprehending the underlying mathematical and computational modeling fundamentals is of importance along with carefully conducted experiments and analytical measurements. Such knowledge is also crucial when designing (13)C-labeling experiments and properly acquiring key data sets essential for in vivo flux analysis implementation. In this regard, the modeling fundamentals of (13)C-labeling systems and analytical data processing are the main topics we will deal with in this chapter. Along with this, the relevant numerical optimization techniques are addressed to help implementation of the entire computational procedures aiming at (13)C-based metabolic flux analysis in vivo.

  3. A scientific workflow framework for (13)C metabolic flux analysis.

    PubMed

    Dalman, Tolga; Wiechert, Wolfgang; Nöh, Katharina

    2016-08-20

    Metabolic flux analysis (MFA) with (13)C labeling data is a high-precision technique to quantify intracellular reaction rates (fluxes). One of the major challenges of (13)C MFA is the interactivity of the computational workflow according to which the fluxes are determined from the input data (metabolic network model, labeling data, and physiological rates). Here, the workflow assembly is inevitably determined by the scientist who has to consider interacting biological, experimental, and computational aspects. Decision-making is context dependent and requires expertise, rendering an automated evaluation process hardly possible. Here, we present a scientific workflow framework (SWF) for creating, executing, and controlling on demand (13)C MFA workflows. (13)C MFA-specific tools and libraries, such as the high-performance simulation toolbox 13CFLUX2, are wrapped as web services and thereby integrated into a service-oriented architecture. Besides workflow steering, the SWF features transparent provenance collection and enables full flexibility for ad hoc scripting solutions. To handle compute-intensive tasks, cloud computing is supported. We demonstrate how the challenges posed by (13)C MFA workflows can be solved with our approach on the basis of two proof-of-concept use cases.

  4. Synthesis and applications of {sup 13}C glycerol

    SciTech Connect

    Stocking, E.; Khalsa, O.; Martinez, R.A.; Silks, L.A. III

    1994-12-01

    Due in part to the use of labeled glycerol for the {sup 13}C enrichment of biomolecules, we are currently developing new synthetic routes to various isotopomers of glycerol. Judging from our experience, traditional methods of glycerol synthesis are not easily adapted for isotopic enrichment and/or have poor overall yields (12 to 15%). Furthermore, the use of glycerol for enrichment can be prohibitively expensive and its availability is limited by the le