Cavity Ring-down Spectroscopy for Carbon Isotope Analysis with 2 μm Diode Laser

International Nuclear Information System (INIS)

Hiromoto, K.; Tomita, H.; Watanabe, K.; Kawarabayashi, J.; Iguchi, T.

2009-01-01

We have made a prototype based on CRDS with 2 μm diode laser for carbon isotope analysis of CO 2 in air. The carbon isotope ratio was obtained to be (1.085±0.012)x10 -2 which shows good agreement with the isotope ratio measured by the magnetic sector-type mass spectrometer within uncertainty. Hence, we demonstrated the carbon isotope analysis based on CRDS with 2 μm tunable diode laser.

Preferential flow pathways revealed by field based stable isotope analysis of CO2 by mid-infrared laser spectroscopy

Science.gov (United States)

van Geldern, Robert; Nowak, Martin; Zimmer, Martin; Szizybalski, Alexandra; Myrttinen, Anssi; Barth, Johannes A. C.; Jost, Hj

2016-04-01

A newly developed and commercially available isotope ratio laser spectrometer for CO2 analyses has been tested during a 10-day field monitoring campaign at the Ketzin pilot site for CO2 storage in northern Germany. The laser instrument is based on tunable laser direct absorption in the mid-infrared. The instrument recorded a continuous 10-day carbon stable isotope data set with 30 minutes resolution directly on-site in a field-based laboratory container during a tracer experiment. To test the instruments performance and accuracy the monitoring campaign was accompanied by daily CO2 sampling for laboratory analyses with isotope ratio mass spectrometry (IRMS). The carbon stable isotope ratios measured by conventional IRMS technique and by the new mid-infrared laser spectrometer agree remarkably well within 2σ analytical precision (<0.3 ‰). This proves the capability of the new mid-infrared direct absorption technique to measure high precision and accurate real-time table isotope data directly in the field. The injected CO2 tracer had a distinct δ13C value that was largely different from the reservoir background value. The laser spectroscopy data revealed a prior to this study unknown, intensive dynamic with fast changing δ13C values. The arrival pattern of the tracer suggest that the observed fluctuations were probably caused by migration along separate and distinct preferential flow paths between injection well and observation well. The new technique might contribute to a better tracing of the migration of the underground CO2 plume and help to ensure the long-term integrity of the reservoir.

Stable isotope reactive transport modeling in water-rock interactions during CO2 injection

Science.gov (United States)

Hidalgo, Juan J.; Lagneau, Vincent; Agrinier, Pierre

2010-05-01

Stable isotopes can be of great usefulness in the characterization and monitoring of CO2 sequestration sites. Stable isotopes can be used to track the migration of the CO2 plume and identify leakage sources. Moreover, they provide unique information about the chemical reactions that take place on the CO2-water-rock system. However, there is a lack of appropriate tools that help modelers to incorporate stable isotope information into the flow and transport models used in CO2 sequestration problems. In this work, we present a numerical tool for modeling the transport of stable isotopes in groundwater reactive systems. The code is an extension of the groundwater single-phase flow and reactive transport code HYTEC [2]. HYTEC's transport module was modified to include element isotopes as separate species. This way, it is able to track isotope composition of the system by computing the mixing between the background water and the injected solution accounting for the dependency of diffusion on the isotope mass. The chemical module and database have been expanded to included isotopic exchange with minerals and the isotope fractionation associated with chemical reactions and mineral dissolution or precipitation. The performance of the code is illustrated through a series of column synthetic models. The code is also used to model the aqueous phase CO2 injection test carried out at the Lamont-Doherty Earth Observatory site (Palisades, New York, USA) [1]. References [1] N. Assayag, J. Matter, M. Ader, D. Goldberg, and P. Agrinier. Water-rock interactions during a CO2 injection field-test: Implications on host rock dissolution and alteration effects. Chemical Geology, 265(1-2):227-235, July 2009. [2] Jan van der Lee, Laurent De Windt, Vincent Lagneau, and Patrick Goblet. Module-oriented modeling of reactive transport with HYTEC. Computers & Geosciences, 29(3):265-275, April 2003.

On the relations between the oceanic uptake of CO2 and its carbon isotopes

International Nuclear Information System (INIS)

Heimann, M.; Maier-Reimer, E.

1994-01-01

The recent proposals to estimate the oceanic uptake of CO 2 by monitoring the oceanic change in 13 C/ 12 C isotope ratio or the air-sea 13 C/ 12 C isotopic disequilibrium is reviewed. Because the history of atmospheric CO 2 and 13 CO 2 since preindustrial times is almost the same, the oceanic penetration depth of both tracers must be the same. This dynamic constraint permits the establishment of yet a third method to estimate the global ocean uptake of CO 2 from 13 C measurements. Using available observations in conjunction with canonical values for the global carbon cycle parameters the three methods yield inconsistent oceanic CO 2 uptake rates for the time period 1970-1990, ranging from 0 to over 3 GtC year -1 . However, uncertainties in the available carbon cycle data must be taken into account. Using a non-linear estimation procedure, a consistent scenario with an oceanic CO 2 uptake rate of 2.2±0.8 GtC year -1 can be established. The method also permits an investigation of the sensitivities of the different approaches. An analysis of the results of two three-dimensional simulations with the Hamburg Model of the Oceanic Carbon Cycle shows that the 13 C isotope indeed tracks the oceanic penetration of anthropogenic CO 2 . Because of its different time history, bomb produced radiocarbon, as measured at the time of GEOSECS, correlates much less well to excess carbon. (orig.)

Long-term field performance of a tunable diode laser absorption spectrometer for analysis of carbon isotopes of CO2 in forest air

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D. R. Bowling

2008-09-01

Full Text Available Tunable diode laser absorption spectrometry (TDLAS is gaining in popularity for measuring the mole fraction [CO2] and stable isotopic composition (δ13C of carbon dioxide (CO2 in air in studies of biosphere-atmosphere gas exchange. Here we present a detailed examination of the performance of a commercially-available TDLAS located in a high-altitude subalpine coniferous forest (the Niwot Ridge AmeriFlux site, providing the first multi-year analysis of TDLAS instrument performance for measuring CO2 isotopes in the field. Air was sampled from five to nine vertical locations in and above the forest canopy every ten minutes for 2.4 years. A variety of methods were used to assess instrument performance. Measurement of two compressed air cylinders that were in place over the entire study establish the long-term field precision of 0.2 μmol mol−1 for [CO2] and 0.35‰ for δ13C, but after fixing several problems the isotope precision improved to 0.2permil (over the last several months. The TDLAS provided detail on variability of δ13C of atmospheric CO2 that was not represented in weekly flask samples, as well as information regarding the influence of large-scale (regional seasonal cycle and local forest processes on [CO2] and δ13C of CO2. There were also clear growing season and winter differences in the relative contributions of photosynthesis and respiration on the [CO2] and δ13C of forest air.

Correction of mass spectrometric isotope ratio measurements for isobaric isotopologues of O2, CO, CO2, N2O and SO2.

Science.gov (United States)

Kaiser, Jan; Röckmann, Thomas

2008-12-01

Gas isotope ratio mass spectrometers usually measure ion current ratios of molecules, not atoms. Often several isotopologues contribute to an ion current at a particular mass-to-charge ratio (m/z). Therefore, corrections have to be applied to derive the desired isotope ratios. These corrections are usually formulated in terms of isotope ratios (R), but this does not reflect the practice of measuring the ion current ratios of the sample relative to those of a reference material. Correspondingly, the relative ion current ratio differences (expressed as delta values) are first converted into isotopologue ratios, then into isotope ratios and finally back into elemental delta values. Here, we present a reformulation of this data reduction procedure entirely in terms of delta values and the 'absolute' isotope ratios of the reference material. This also shows that not the absolute isotope ratios of the reference material themselves, but only product and ratio combinations of them, are required for the data reduction. These combinations can be and, for carbon and oxygen have been, measured by conventional isotope ratio mass spectrometers. The frequently implied use of absolute isotope ratios measured by specially calibrated instruments is actually unnecessary. Following related work on CO2, we here derive data reduction equations for the species O2, CO, N2O and SO2. We also suggest experiments to measure the required absolute ratio combinations for N2O, SO2 and O2. As a prelude, we summarise historic and recent measurements of absolute isotope ratios in international isotope reference materials. Copyright 2008 John Wiley & Sons, Ltd.

High-precision dual-inlet IRMS measurements of the stable isotopes of CO2 and the N2O / CO2 ratio from polar ice core samples

Directory of Open Access Journals (Sweden)

T. K. Bauska

2014-11-01

Full Text Available An important constraint on mechanisms of past carbon cycle variability is provided by the stable isotopic composition of carbon in atmospheric carbon dioxide (δ13C-CO2 trapped in polar ice cores, but obtaining very precise measurements has proven to be a significant analytical challenge. Here we describe a new technique to determine the δ13C of CO2 at very high precision, as well as measuring the CO2 and N2O mixing ratios. In this method, ancient air is extracted from relatively large ice samples (~400 g with a dry-extraction "ice grater" device. The liberated air is cryogenically purified to a CO2 and N2O mixture and analyzed with a microvolume-equipped dual-inlet IRMS (Thermo MAT 253. The reproducibility of the method, based on replicate analysis of ice core samples, is 0.02‰ for δ13C-CO2 and 2 ppm and 4 ppb for the CO2 and N2O mixing ratios, respectively (1σ pooled standard deviation. Our experiments show that minimizing water vapor pressure in the extraction vessel by housing the grating apparatus in a ultralow-temperature freezer (−60 °C improves the precision and decreases the experimental blank of the method to −0.07 ± 0.04‰. We describe techniques for accurate calibration of small samples and the application of a mass-spectrometric method based on source fragmentation for reconstructing the N2O history of the atmosphere. The oxygen isotopic composition of CO2 is also investigated, confirming previous observations of oxygen exchange between gaseous CO2 and solid H2O within the ice archive. These data offer a possible constraint on oxygen isotopic fractionation during H2O and CO2 exchange below the H2O bulk melting temperature.

The effects of atmospheric [CO2] on carbon isotope fractionation and magnesium incorporation into biogenic marine calcite

Science.gov (United States)

Vieira, Veronica

1997-01-01

The influences of atmospheric carbon dioxide on the fractionation of carbon isotopes and the magnesium incorporation into biogenic marine calcite were investigated using samples of the calcareous alga Amphiroa and benthic foraminifer Sorites grown in the Biosphere 2 Ocean system under variable atmospheric CO2 concentrations (approximately 500 to 1200 ppm). Carbon isotope fractionation was studied in both the organic matter and the skeletal carbonate. Magnesium analysis was to be performed on the carbonate removed during decalcification. These data have not been collected due to technical problems. Carbon isotope data from Amphiroa yields a linear relation between [CO2] and Delta(sup 13)C(sub Corg)values suggesting that the fractionation of carbon isotopes during photosynthesis is positively correlated with atmospheric [CO2]. [CO2] and Delta(sup 13)C(sub Corg) values for Sorites produce a relation that is best described by a hyperbolic function where Delta(sup 13)C(sub Corg) values increase between 300 and 700 ppm and decrease from 700 to 1200 ppm. Further investigation of this relation and Sorites physiology is needed.

Oxygen isotopic signature of CO2 from combustion processes

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W. A. Brand

2011-02-01

Full Text Available For a comprehensive understanding of the global carbon cycle precise knowledge of all processes is necessary. Stable isotope (13C and 18O abundances provide information for the qualification and the quantification of the diverse source and sink processes. This study focuses on the δ18O signature of CO2 from combustion processes, which are widely present both naturally (wild fires, and human induced (fossil fuel combustion, biomass burning in the carbon cycle. All these combustion processes use atmospheric oxygen, of which the isotopic signature is assumed to be constant with time throughout the whole atmosphere. The combustion is generally presumed to take place at high temperatures, thus minimizing isotopic fractionation. Therefore it is generally supposed that the 18O signature of the produced CO2 is equal to that of the atmospheric oxygen. This study, however, reveals that the situation is much more complicated and that important fractionation effects do occur. From laboratory studies fractionation effects on the order of up to 26%permil; became obvious in the derived CO2 from combustion of different kinds of material, a clear differentiation of about 7‰ was also found in car exhausts which were sampled directly under ambient atmospheric conditions. We investigated a wide range of materials (both different raw materials and similar materials with different inherent 18O signature, sample geometries (e.g. texture and surface-volume ratios and combustion circumstances. We found that the main factor influencing the specific isotopic signatures of the combustion-derived CO2 and of the concomitantly released oxygen-containing side products, is the case-specific rate of combustion. This points firmly into the direction of (diffusive transport of oxygen to the reaction zone as the cause of the isotope fractionation. The original total 18O signature of the material appeared to have little influence, however, a contribution of specific bio

Carbon and oxygen isotope analysis of leaf biomass reveals contrasting photosynthetic responses to elevated CO2 near geologic vents in Yellowstone National Park

Directory of Open Access Journals (Sweden)

D. G. Williams

2009-01-01

Full Text Available In this study we explore the use of natural CO2 emissions in Yellowstone National Park (YNP in Wyoming, USA to study responses of natural vegetation to elevated CO2 levels. Radiocarbon (14C analysis of leaf biomass from a conifer (Pinus contortus; lodgepole pine and an invasive, non-native herb (Linaria dalmatica; Dalmation toadflax was used to trace the inputs of vent CO2 and quantify assimilation-weighted CO2 concentrations experienced by individual plants near vents and in comparable locations with no geologic CO2 exposure. The carbon and oxygen isotopic composition and nitrogen percent of leaf biomass from the same plants was used to investigate photosynthetic responses of these plants to naturally elevated atmospheric CO2 concentrations. The coupled shifts in carbon and oxygen isotope values suggest that dalmation toadflax responded to elevated CO2 exposure by increasing stomatal conductance with no change in photosynthetic capacity and lodgepole pine apparently responded by decreasing stomatal conductance and photosynthetic capacity. Lodgepole pine saplings exposed to elevated levels of CO2 likewise had reduced leaf nitrogen concentrations compared to plants with no enhanced CO2 exposure, further suggesting widespread and dominant conifer down-regulated photosynthetic capacity under elevated CO2 levels near geologic vents.

Isotope effect in the photochemical decomposition of CO{sub 2} (ice) by Lyman-{alpha} radiation

Energy Technology Data Exchange (ETDEWEB)

Yuan Chunqing; Yates, John T. Jr. [Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904 (United States)

2013-04-21

The photochemical decomposition of CO{sub 2}(ice) at 75 K by Lyman-{alpha} radiation (10.2 eV) has been studied using transmission infrared spectroscopy. An isotope effect in the decomposition of the CO{sub 2} molecule in the ice has been discovered, favoring {sup 12}CO{sub 2} photodecomposition over {sup 13}CO{sub 2} by about 10%. The effect is caused by electronic energy transfer from the excited CO{sub 2} molecule to the ice matrix, which favors quenching of the heavier electronically-excited {sup 13}CO{sub 2} molecule over {sup 12}CO{sub 2}. The effect is similar to the Menzel-Gomer-Redhead isotope effect in desorption from adsorbed molecules on surfaces when electronically excited. An enhancement of the rate of formation of lattice-trapped CO and CO{sub 3} species is observed for the photolysis of the {sup 12}CO{sub 2} molecule compared to the {sup 13}CO{sub 2} molecule in the ice. Only 0.5% of the primary photoexcitation results in O-CO bond dissociation to produce trapped-CO and trapped-CO{sub 3} product molecules and the majority of the electronically-excited CO{sub 2} molecules return to the ground state. Here either vibrational relaxation occurs (majority process) or desorption of CO{sub 2} occurs (minority process) from highly vibrationally-excited CO{sub 2} molecules in the ice. The observation of the {sup 12}C/{sup 13}C isotope effect in the Lyman-{alpha} induced photodecomposition of CO{sub 2} (ice) suggests that over astronomical time scales the isotope enrichment effect may distort historical information derived from isotope ratios in space wherever photochemistry can occur.

Multiple isotopes (O, C, Li, Sr) as tracers of CO2 and brine leakage from CO2-enhanced oil recovery activities in Permian Basin, Texas, USA

Science.gov (United States)

Phan, T. T.; Sharma, S.; Gardiner, J. B.; Thomas, R. B.; Stuckman, M.; Spaulding, R.; Lopano, C. L.; Hakala, A.

2017-12-01

Potential CO2 and brine migration or leakage into shallow groundwater is a critical issue associated with CO2 injection at both enhanced oil recovery (EOR) and carbon sequestration sites. The effectiveness of multiple isotope systems (δ18OH2O, δ13C, δ7Li, 87Sr/86Sr) in monitoring CO2 and brine leakage at a CO2-EOR site located within the Permian basin (Seminole, Texas, USA) was studied. Water samples collected from an oil producing formation (San Andres), a deep groundwater formation (Santa Rosa), and a shallow groundwater aquifer (Ogallala) over a four-year period were analyzed for elemental and isotopic compositions. The absence of any change in δ18OH2O or δ13CDIC values of water in the overlying Ogallala aquifer after CO2 injection indicates that injected CO2 did not leak into this aquifer. The range of Ogallala water δ7Li (13-17‰) overlaps the San Andres water δ7Li (13-15‰) whereas 87Sr/86Sr of Ogallala (0.70792±0.00005) significantly differs from San Andres water (0.70865±0.00003). This observation demonstrates that Sr isotopes are much more sensitive than Li isotopes in tracking brine leakage into shallow groundwater at the studied site. In contrast, deep groundwater δ7Li (21-25‰) is isotopically distinct from San Andres produced water; thus, monitoring this intermitted formation water can provide an early indication of CO2 injection-induced brine migration from the underlying oil producing formation. During water alternating with gas (WAG) operations, a significant shift towards more positive δ13CDIC values was observed in the produced water from several of the San Andres formation wells. The carbon isotope trend suggests that the 13C enriched injected CO2 and formation carbonates became the primary sources of dissolved inorganic carbon in the area surrounding the injection wells. Moreover, one-way ANOVA statistical analysis shows that the differences in δ7Li (F(1,16) = 2.09, p = 0.17) and 87Sr/86Sr (F(1,18) = 4.47, p = 0.05) values of

Defining an absolute reference frame for 'clumped' isotope studies of CO 2

Science.gov (United States)

Dennis, Kate J.; Affek, Hagit P.; Passey, Benjamin H.; Schrag, Daniel P.; Eiler, John M.

2011-11-01

We present a revised approach for standardizing and reporting analyses of multiply substituted isotopologues of CO 2 (i.e., 'clumped' isotopic species, especially the mass-47 isotopologues). Our approach standardizes such data to an absolute reference frame based on theoretical predictions of the abundances of multiply-substituted isotopologues in gaseous CO 2 at thermodynamic equilibrium. This reference frame is preferred over an inter-laboratory calibration of carbonates because it enables all laboratories measuring mass 47 CO 2 to use a common scale that is tied directly to theoretical predictions of clumping in CO 2, regardless of the laboratory's primary research field (carbonate thermometry or CO 2 biogeochemistry); it explicitly accounts for mass spectrometric artifacts rather than convolving (and potentially confusing) them with chemical fractionations associated with sample preparation; and it is based on a thermodynamic equilibrium that can be experimentally established in any suitably equipped laboratory using commonly available materials. By analyzing CO 2 gases that have been subjected to established laboratory procedures known to promote isotopic equilibrium (i.e., heated gases and water-equilibrated CO 2), and by reference to thermodynamic predictions of equilibrium isotopic distributions, it is possible to construct an empirical transfer function that is applicable to data with unknown clumped isotope signatures. This transfer function empirically accounts for the fragmentation and recombination reactions that occur in electron impact ionization sources and other mass spectrometric artifacts. We describe the protocol necessary to construct such a reference frame, the method for converting gases with unknown clumped isotope compositions to this reference frame, and suggest a protocol for ensuring that all reported isotopic compositions (e.g., Δ 47 values; Eiler and Schauble, 2004; Eiler, 2007) can be compared among different laboratories and

The isotopic composition of CO in vehicle exhaust

NARCIS (Netherlands)

Naus, S.; Röckmann, T.; Popa, M.E.

2018-01-01

We investigated the isotopic composition of CO in the exhaust of individual vehicles. Additionally, the CO 2 isotopes, and the CO:CO 2 , CH 4 :CO 2 and H 2 :CO gas ratios were measured. This was done under idling and revving conditions, and for three vehicles in a full driving cycle on a testbench.

Frequency stabilization of quantum cascade laser for spectroscopic CO2 isotope analysis

Science.gov (United States)

Han, Luo; Xia, Hua; Pang, Tao; Zhang, Zhirong; Wu, Bian; Liu, Shuo; Sun, Pengshuai; Cui, Xiaojuan; Wang, Yu; Sigrist, Markus W.; Dong, Fengzhong

2018-06-01

Using off-axis integrated cavity output spectroscopy, named OA-ICOS, the absorption spectrum of CO2 at 4.32 μm is recorded by using a quantum cascade laser (QCL). The concentration of the three isotopologues 16O12C16O, 16O13C16O and 16O12C18O is detected simultaneously. The isotope abundance ratio of 13C and 18O in CO2 gas can be obtained, which is most useful for ecological research. Since the ambient temperature has a serious influence on the output wavelength of the laser, even small temperature variations seriously affect the stability and sensitivity of the system. In this paper, a wavelength locking technique for QCL is proposed. The output of a digital potentiometer integrated in the laser current driver control is modified by software, resulting in a correction of the driving current of the laser and thus of its wavelength. This method strongly reduces the influence of external factors on the wavelength drift of lasers and thus substantially improves the stability and performance of OA-ICOS as is demonstrated with long-time measurements on CO2 in laboratory air.

Deglacial Western Equatorial Pacific pCO2 Reconstruction Using Boron Isotopes of Planktonic Foraminiferas

Science.gov (United States)

Kubota, K.; Yokoyama, Y.; Ishikawa, T.; Sagawa, T.; Ikehara, M.; Yamazaki, T.

2017-12-01

During the last deglaciation (ca. 19 - 11 ka), partial pressure of CO2 (pCO2) of the atmosphere increased by 80 μatm. Many paleoceanographers point out that the ocean had played an important role in atmospheric CO2 rise, since the ocean have 60 times larger capacity to store carbon compared to the atmosphere. However, evidence on where carbon was transferred from the ocean to the atmosphere is still lacking, hampering our understanding of global carbon cycles in glacial-interglacial timescales. Boron isotope of skeletons of marine calcifying organisms such as corals and foraminiferas can pin down where CO2 source/sink existed, because boron isotopes of marine calcium carbonates is dependent on seawater pH, from which pCO2 of the past seawater can be reconstructed. In previous studies using the boron isotope teqnique, Martinez-Boti et al. (2015, Nature) and Kubota et al. (2014, Scientific Reports) revealed that central and eastern parts of the equatorial Pacific acted as a CO2 source (i.e., CO2 emission) during the last deglaciation, suggesting the equatorial Pacific's contribution to atmospheric CO2 rise. However, some conflicting results have been confirmed in a marine sediment record from the western part of the equatorial Pacific (Palmer & Pearson, 2003, Science), making the conclusion elusive. In this presentation, we will show new results of Mg/Ca, oxygen isotope, and boron isotope measurements during the last 35 ka on two species of surface dwelling foraminiferas (Globigerinoides ruber and G. sacculifer) which was hand-picked separatedly from a well-dated marine sediment core recovered from the West Caroline Basin (KR05-15 PC01) (Yamazaki et al., 2008, GRL). From the new records, we will discuss how the equatorial Pacific behaved during the last deglaciation and how it related to the global carbon cycles.

Determining CO2 storage potential during miscible CO2 enhanced oil recovery: Noble gas and stable isotope tracers

Science.gov (United States)

Shelton, Jenna L.; McIntosh, Jennifer C.; Hunt, Andrew; Beebe, Thomas L; Parker, Andrew D; Warwick, Peter D.; 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

CO and H2 uptake and emissions by soil: variability of fluxes and their isotopic signatures

Science.gov (United States)

Popa, Maria Elena; Chen, Qianjie; Ferrero Lopez, Noelia; Röckmann, Thomas

2017-04-01

In order to study the uptake and release of H2 and CO by soil, we performed long term, high frequency measurements with an automatic soil chamber at two sites in the Netherlands (Cabauw - grassland, and Speuld - forest). The measurements were performed over different seasons and cover in total a cumulated interval of about one year. These measurements allow determining separately, for each species, the two distinct fluxes i.e. uptake and release, and investigating their temporal variability and dependencies on environmental variables. Additional experiments were performed for determining the isotopic signatures of the H2 and CO uptake and release by soil. Flask samples were filled from the soil chamber, and then analyzed in the laboratory for the stable isotopic composition of H2 (δD) and CO (δ13C and δ18O). We find that both uptake and release are present at all times, regardless of the direction of the net flux. The emissions are significant for both species and at Cabauw, there are times and places where emissions outweigh the soil uptake. For each species, the two fluxes have different behavior and dependence on external variables, which indicates that they have different origins. The isotope results also support that, for both H2 and CO, uptake and emission occur simultaneously. We were able to determine separately the isotopic effects of the two fluxes. For both H2 and CO, soil uptake is associated with a small positive fractionation (the lighter molecule is taken up faster). The soil uptake fractionation (α = kheavy/klight) was 0.945 ± 0.004 for H2; for CO, the fractionation was 0.992 for 13C and 0.985 for 18O. The isotopic composition of the H2 emitted from the grassland was -530 ± 40 ‰, less depleted that what is expected from the isotopic equilibrium of H2 with water. For CO, the isotopic composition of the soil emission is depleted in 13C compared to atmospheric CO, and lower than the average isotopic composition of plant or soil organic matter.

Climatic significance of stable isotope characteristics of air-CO2 and rainfall in Delhi area water-plant-air system

International Nuclear Information System (INIS)

Datta, P.S.; Tyagi, S.K.

2002-01-01

In recent years, there is a global concern on the role of carbon dioxide in atmosphere in affecting the climate. The present models of global atmospheric circulation suggest that oceans sequester about one-third of the CO 2 released by anthropogenic activities, and biospheric productivity is the primary cause of the interannual fluctuations in the atmospheric CO 2 . However, most of the times, the excess of CO 2 in air is associated with the presence of anthropogenic pollutants from urbanised centres. Therefore, the studies on the pattern of local variations in the isotopic composition of air CO 2 and rainfall in urban areas are expected to provide important information on the atmospheric circulation processes which affect the climate on a regional scale. Internationally, aspects of climate change have been so far demonstrated using isotopic data mainly from temperate climates, and there is limited understanding of the factors controlling stable isotopic composition of air-CO 2 and rainfall in tropical regions. In this context, to assess the magnitude of the above mentioned effects, analysis of the data on the variations in the 13 C/ 12 C and 18 O/ 16 O signatures of air-CO 2 in Delhi area water-plant-air system is presented here

Reconciling the Differences between the Measurements of CO2 Isotopes by the Phoenix and MSL Landers

Science.gov (United States)

Niles, P. B.; Mahaffy, P. R.; Atreya, S.; Pavlov, A. A.; Trainer, M.; Webster, C. R.; Wong, M.

2014-01-01

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. There have been several different measurements by landers and Earth based systems performed in recent years that have not been in agreement. In particular, measurements of the isotopic composition of martian atmospheric CO2 by the Thermal and Evolved Gas Analyzer (TEGA) instrument on the Mars Phoenix Lander and the Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory (MSL) are in stark disagreement. This work attempts to use measurements of mass 45 and mass 46 of martian atmospheric CO2 by the SAM and TEGA instruments to search for agreement as a first step towards reaching a consensus measurement that might be supported by data from both instruments.

Improved repetition rate mixed isotope CO{sub 2} TEA laser

Energy Technology Data Exchange (ETDEWEB)

Cohn, D. B., E-mail: dbctechnology@earthlink.net [DBC Technology Corp., 4221 Mesa St, Torrance, California 90505 (United States)

2014-09-15

A compact CO{sub 2} TEA laser has been developed for remote chemical detection that operates at a repetition rate of 250 Hz. It emits 700 mJ/pulse at 10.6 μm in a multimode beam with the {sup 12}C{sup 16}O{sub 2} isotope. With mixed {sup 12}C{sup 16}O{sub 2} plus {sup 13}C{sup 16}O{sub 2} isotopes it emits multiple lines in both isotope manifolds to improve detection of a broad range of chemicals. In particular, output pulse energies are 110 mJ/pulse at 9.77 μm, 250 mJ/pulse at 10 μm, and 550 mJ/pulse at 11.15 μm, useful for detection of the chemical agents Sarin, Tabun, and VX. Related work shows capability for long term sealed operation with a catalyst and an agile tuner at a wavelength shift rate of 200 Hz.

System for δ13C-CO2 and xCO2 analysis of discrete gas samples by cavity ring-down spectroscopy

Science.gov (United States)

Dickinson, Dane; Bodé, Samuel; Boeckx, Pascal

2017-11-01

A method was devised for analysing small discrete gas samples (50 mL syringe) by cavity ring-down spectroscopy (CRDS). Measurements were accomplished by inletting 50 mL syringed samples into an isotopic-CO2 CRDS analyser (Picarro G2131-i) between baseline readings of a reference air standard, which produced sharp peaks in the CRDS data feed. A custom software script was developed to manage the measurement process and aggregate sample data in real time. The method was successfully tested with CO2 mole fractions (xCO2) ranging from 20 000 ppm and δ13C-CO2 values from -100 up to +30 000 ‰ in comparison to VPDB (Vienna Pee Dee Belemnite). Throughput was typically 10 samples h-1, with 13 h-1 possible under ideal conditions. The measurement failure rate in routine use was ca. 1 %. Calibration to correct for memory effects was performed with gravimetric gas standards ranging from 0.05 to 2109 ppm xCO2 and δ13C-CO2 levels varying from -27.3 to +21 740 ‰. Repeatability tests demonstrated that method precision for 50 mL samples was ca. 0.05 % in xCO2 and 0.15 ‰ in δ13C-CO2 for CO2 compositions from 300 to 2000 ppm with natural abundance 13C. Long-term method consistency was tested over a 9-month period, with results showing no systematic measurement drift over time. Standardised analysis of discrete gas samples expands the scope of application for isotopic-CO2 CRDS and enhances its potential for replacing conventional isotope ratio measurement techniques. Our method involves minimal set-up costs and can be readily implemented in Picarro G2131-i and G2201-i analysers or tailored for use with other CRDS instruments and trace gases.

BASIN TCP Stable Isotope Composition of CO2 in Terrestrial Ecosystems

Data.gov (United States)

National Aeronautics and Space Administration — ABSTRACT: This data set reports stable isotope ratio data of CO2 (13C/12C and 18O/16O) associated with photosynthetic and respiratory exchanges across the...

BASIN TCP Stable Isotope Composition of CO2 in Terrestrial Ecosystems

Data.gov (United States)

National Aeronautics and Space Administration — This data set reports stable isotope ratio data of CO2 (13C/12C and 18O/16O) associated with photosynthetic and respiratory exchanges across the biosphere-atmosphere...

Concentration and stable carbon isotopic composition of CO2 in cave air of Postojnska jama, Slovenia

Directory of Open Access Journals (Sweden)

Magda Mandic

2013-09-01

Full Text Available Partial pressure of CO2 (pCO2 and its isotopic composition (δ13CairCO2 were measured in Postojnska jama, Slovenia, at 10 locations inside the cave and outside the cave during a one-year period. At all interior locations the pCO2 was higher and δ13CairCO2 lower than in the outside atmosphere. Strong seasonal fluctuations in both parameters were observed at locations deeper in the cave, which are isolated from the cave air circulation. By using a binary mixing model of two sources of CO2, one of them being the atmospheric CO2, we show that the excess of CO2 in the cave air has a δ13C value of -23.3 ± 0.7 ‰, in reasonable agreement with the previously measured soil-CO2 δ13C values. The stable isotope data suggest that soil CO2 is brought to the cave by drip water.

Continuous-flow IRMS technique for determining the 17O excess of CO2 using complete oxygen isotope exchange with cerium oxide

NARCIS (Netherlands)

Mrozek, D. J.; Van Der Veen, C.; Kliphuis, M.; Kaiser, J.; Wiegel, A. A.; Röckmann, T.

2015-01-01

This paper presents an analytical system for analysis of all single substituted isotopologues (12C16O17O, 12C16O18O, 13C16O16O) in nanomolar quantities of CO2 extracted from atmospheric air samples. CO2 is separated from bulk air by gas chromatography and CO2 isotope ratio measurements (ion masses

Relation between separation factor of carbon isotope and chemical reaction of CO2 with amine in nonaqueous solvent

International Nuclear Information System (INIS)

Takeshita, Kenji; Kitamoto, Asashi

1989-01-01

The separation factor for carbon isotope exchange reaction between CO 2 and amine in nonaqueous solvent was related to absorption reaction of CO 2 in a solution. The test solutions were mixtures of primary amine (such as butylamine and tert-butylamine) or secondary amine (such as diethylamine, dipropylamine and dibutylamine) diluted with nonpolar solvent (octane or triethyalmine) or polar solvent (methanol), respectively. The isotope exchange reaction consists of three steps related to chemical reaction of CO 2 in amine and nonaqueous solvent mixture, namely the reaction between CO 2 and carbamic acid, that between CO 2 and amine carbamate, and that between CO 2 and carbamic ion. Above all, the isotope separation factor between CO 2 and carbamic acid had the highest value. The overall separation factor can be higher in amine-nonaqueous solvent mixture where the concentration of carbamic acid becomes higher. (author)

13CO2/12CO2 ratio analysis in exhaled air by lead-salt tunable diode lasers for noninvasive diagnostics in gastroenterology

Science.gov (United States)

Stepanov, Eugene V.; Zyrianov, Pavel V.; Miliaev, Valerii A.; Selivanov, Yurii G.; Chizhevskii, Eugene G.; Os'kina, Svetlana; Ivashkin, Vladimir T.; Nikitina, Elena I.

1999-07-01

An analyzer of 13CO2/12CO2 ratio in exhaled air based on lead-salt tunable diode lasers is presented. High accuracy of the carbon isotope ratio detection in exhaled carbon dioxide was achieved with help of very simple optical schematics. It was based on the use of MBE laser diodes operating in pulse mode and on recording the resonance CO2 absorption at 4.2 micrometers . Special fast acquisition electronics and software were applied for spectral data collection and processing. Developed laser system was tested in a clinical train aimed to assessment eradication efficiency in therapy of gastritis associated with Helicobacter pylori infection. Data on the 13C-urea breath test used for P.pylori detection and obtained with tunable diode lasers in the course of the trail was compared with the results of Mass-Spectroscopy analysis and histology observations. The analyzer can be used also for 13CO2/12CO2 ratio detection in exhalation to perform gastroenterology breath test based on using other compounds labeled with stable isotopes.

Isotopic exchange between CO2 and H2O and labelling kinetics of photosynthetic oxygen

International Nuclear Information System (INIS)

Gerster, Richard

1971-01-01

The reaction of carbon dioxide with water has been studied by measuring the rate of oxygen exchange between C 18 O 2 and H 2 16 O. The mathematical treatment of the kinetics allows to determine with accuracy the diffusion flow between the gas and the liquid phase, in the same way as the CO 2 hydration rate. The velocity constant of this last process, whose value gives the in situ enzymatic activity of carbonic anhydrase, has been established in the case of chloroplast and Euglena suspensions and of aerial leaves. The study of the isotopic exchange between C 18 O 2 and a vegetable submitted to alternations of dark and light has allowed to calculate the isotopic abundance of the metabolized CO 2 whose value has been compared to that of the intracellular water and that of photosynthetic oxygen. In addition, a new method using 13 C 18 O 2 gives the means to measure with accuracy eventual isotopic effects. The labelling kinetics of the oxygen evolved by Euglena suspensions whose water has been enriched with 18 O have been established at different temperatures. (author) [fr

Natural high pCO2 increases autotrophy in Anemonia viridis (Anthozoa) as revealed from stable isotope (C, N) analysis

OpenAIRE

Horwitz, Rael; Borell, Esther M.; Yam, Ruth; Shemesh, Aldo; Fine, Maoz

2015-01-01

Contemporary cnidarian-algae symbioses are challenged by increasing CO2 concentrations (ocean warming and acidification) affecting organisms' biological performance. We examined the natural variability of carbon and nitrogen isotopes in the symbiotic sea anemone Anemonia viridis to investigate dietary shifts (autotrophy/heterotrophy) along a natural pCO2 gradient at the island of Vulcano, Italy. ?13C values for both algal symbionts (Symbiodinium) and host tissue of A. viridis became significa...

Oxygen isotope anomaly in tropospheric CO2 and implications for CO2 residence time in the atmosphere and gross primary productivity.

Science.gov (United States)

Liang, Mao-Chang; Mahata, Sasadhar; Laskar, Amzad H; Thiemens, Mark H; Newman, Sally

2017-10-13

The abundance variations of near surface atmospheric CO 2 isotopologues (primarily 16 O 12 C 16 O, 16 O 13 C 16 O, 17 O 12 C 16 O, and 18 O 12 C 16 O) represent an integrated signal from anthropogenic/biogeochemical processes, including fossil fuel burning, biospheric photosynthesis and respiration, hydrospheric isotope exchange with water, and stratospheric photochemistry. Oxygen isotopes, in particular, are affected by the carbon and water cycles. Being a useful tracer that directly probes governing processes in CO 2 biogeochemical cycles, Δ 17 O (=ln(1 + δ 17 O) - 0.516 × ln(1 + δ 18 O)) provides an alternative constraint on the strengths of the associated cycles involving CO 2 . Here, we analyze Δ 17 O data from four places (Taipei, Taiwan; South China Sea; La Jolla, United States; Jerusalem, Israel) in the northern hemisphere (with a total of 455 measurements) and find a rather narrow range (0.326 ± 0.005‰). A conservative estimate places a lower limit of 345 ± 70 PgC year -1 on the cycling flux between the terrestrial biosphere and atmosphere and infers a residence time of CO 2 of 1.9 ± 0.3 years (upper limit) in the atmosphere. A Monte Carlo simulation that takes various plant uptake scenarios into account yields a terrestrial gross primary productivity of 120 ± 30 PgC year -1 and soil invasion of 110 ± 30 PgC year -1 , providing a quantitative assessment utilizing the oxygen isotope anomaly for quantifying CO 2 cycling.

Deep ocean ventilation, carbon isotopes, marine sedimentation and the deglacial CO2 rise

Directory of Open Access Journals (Sweden)

C. Heinze

2011-07-01

Full Text Available The link between the atmospheric CO2 level and the ventilation state of the deep ocean is an important building block of the key hypotheses put forth to explain glacial-interglacial CO2 fluctuations. In this study, we systematically examine the sensitivity of atmospheric CO2 and its carbon isotope composition to changes in deep ocean ventilation, the ocean carbon pumps, and sediment formation in a global 3-D ocean-sediment carbon cycle model. Our results provide support for the hypothesis that a break up of Southern Ocean stratification and invigorated deep ocean ventilation were the dominant drivers for the early deglacial CO2 rise of ~35 ppm between the Last Glacial Maximum and 14.6 ka BP. Another rise of 10 ppm until the end of the Holocene is attributed to carbonate compensation responding to the early deglacial change in ocean circulation. Our reasoning is based on a multi-proxy analysis which indicates that an acceleration of deep ocean ventilation during early deglaciation is not only consistent with recorded atmospheric CO2 but also with the reconstructed opal sedimentation peak in the Southern Ocean at around 16 ka BP, the record of atmospheric δ13CCO2, and the reconstructed changes in the Pacific CaCO3 saturation horizon.

Stable isotope ratios of the atmospheric CH4, CO2 and N2O in Tokai-mura

International Nuclear Information System (INIS)

Porntepkasemsan, Boonsom; Andoh, Mariko A.; Amano, Hikaru

2000-11-01

This report presents the results and interpretation of stable isotope ratios of the atmospheric CH 4 , CO 2 and N 2 O from a variety of sources in Tokai-mura. The seasonal changes of δ 13 CH 4 , δ 13 CO 2 and δ 15 N 2 O were determined under in-situ conditions in four sampling sites and one control site. Such measurements are expected to provide a useful means of estimating the transport mechanisms of the three trace gases in the environment. These isotopic signatures were analyzed by Isotope Ratio Mass Spectrometer (IRMS, Micromass Isoprime). Our data showed the significant seasonal fluctuation in the Hosoura rice paddy during the entire growing season in 1999. Possible causes for the variation are postulated. Additional measurements on soil properties and on organic δ 13 C in rice plant are suggested. Cited outstanding original papers are summarized in the references. (author)

The isotopic composition of CO in vehicle exhaust

Science.gov (United States)

Naus, S.; Röckmann, T.; Popa, M. E.

2018-03-01

We investigated the isotopic composition of CO in the exhaust of individual vehicles. Additionally, the CO2 isotopes, and the CO:CO2, CH4:CO2 and H2:CO gas ratios were measured. This was done under idling and revving conditions, and for three vehicles in a full driving cycle on a testbench. The spread in the results, even for a single vehicle, was large: for δ13 C in CO ∼ -60 to 0‰, for δ18 O in CO ∼ +10 to +35‰, and for all gas ratios several orders of magnitude. The results show an increase in the spread of isotopic values for CO compared to previous studies, suggesting that increasing complexity of emission control in vehicles might be reflected in the isotopic composition. When including all samples, we find a weighted mean for the δ13 C and δ18 O in CO of -28.7 ± 0.5‰ and +24.8 ± 0.3‰ respectively. This result is dominated by cold petrol vehicles. Diesel vehicles behaved as a distinct group, with CO enriched in 13C and depleted in 18O, compared to petrol vehicles. For the H2:CO ratio of all vehicles, we found a value of 0.71 ± 0.31 ppb:ppb. The CO:CO2 ratio, with a mean of 19.4 ± 6.8 ppb:ppm, and the CH4:CO2 ratio, with a mean of 0.26 ± 0.05 ppb:ppm, are both higher than recent literature indicates. This is likely because our sampling distribution was biased towards cold vehicles, and therefore towards higher emission situations. The CH4:CO2 ratio was found to behave similarly to the CO:CO2 ratio, suggesting that the processes affecting CO and CH4 are similar. The δ13 C values in CO2 were close to the expected δ13 C in fuel, with no significant difference between petrol and diesel vehicles. The δ18 O values in CO2 for petrol vehicles covered a range of 20-35‰, similar to the δ18 O of CO. The δ18 O values in CO2 for diesel vehicles were close to the δ18 O in atmospheric oxygen. A set of polluted atmospheric samples, taken near a highway and inside parking garages, showed an isotopic signature of CO and a H2:CO ratio that were

Fate of injected CO2 in the Wilcox Group, Louisiana, Gulf Coast Basin: Chemical and isotopic tracers of microbial–brine–rock–CO2 interactions

Science.gov (United States)

Shelton, Jenna L.; McIntosh, Jennifer C.; Warwick, Peter D.; Lee Zhi Yi, Amelia

2014-01-01

The “2800’ sandstone” of the Olla oil field is an oil and gas-producing reservoir in a coal-bearing interval of the Paleocene–Eocene Wilcox Group in north-central Louisiana, USA. In the 1980s, this producing unit was flooded with CO2 in an enhanced oil recovery (EOR) project, leaving ∼30% of the injected CO2 in the 2800’ sandstone post-injection. This study utilizes isotopic and geochemical tracers from co-produced natural gas, oil and brine to determine the fate of the injected CO2, including the possibility of enhanced microbial conversion of CO2 to CH4 via methanogenesis. Stable carbon isotopes of CO2, CH4 and DIC, together with mol% CO2 show that 4 out of 17 wells sampled in the 2800’ sandstone are still producing injected CO2. The dominant fate of the injected CO2appears to be dissolution in formation fluids and gas-phase trapping. There is some isotopic and geochemical evidence for enhanced microbial methanogenesis in 2 samples; however, the CO2 spread unevenly throughout the reservoir, and thus cannot explain the elevated indicators for methanogenesis observed across the entire field. Vertical migration out of the target 2800’ sandstone reservoir is also apparent in 3 samples located stratigraphically above the target sand. Reservoirs comparable to the 2800’ sandstone, located along a 90-km transect, were also sampled to investigate regional trends in gas composition, brine chemistry and microbial activity. Microbial methane, likely sourced from biodegradation of organic substrates within the formation, was found in all oil fields sampled, while indicators of methanogenesis (e.g. high alkalinity, δ13C-CO2 and δ13C-DIC values) and oxidation of propane were greatest in the Olla Field, likely due to its more ideal environmental conditions (i.e. suitable range of pH, temperature, salinity, sulfate and iron concentrations).

Genesis of fumarolic emissions as inferred by isotope mass balances: CO 2 and water at Vulcano Island, Italy

Science.gov (United States)

Paonita, A.; Favara, R.; Nuccio, P. M.; Sortino, F.

2002-03-01

We have developed a quantitative model of CO2 and H2O isotopic mixing between magmatic and hydrothermal gases for the fumarolic emissions of the La Fossa crater (Vulcano Island, Italy). On the basis of isotope balance equations, the model takes into account the isotope equilibrium between H2O and CO2 and extends the recent model of chemical and energy two-end-member mixing by Nuccio et al. (1999). As a result, the H2O and CO2 content and the δD, δ18O, and δ13C isotope compositions for both magmatic and hydrothermal end-members have been assessed. Low contributions of meteoric steam, added at a shallow depth, have been also recognized and quantified in the fumaroles throughout the period from 1988 to 1998. Nonequilibrium oxygen isotope exchange also seems to be occurring between ascending gases and wall rocks along some fumarolic conduits. The δ13CCO2 of the magmatic gases varies around -3 to 1‰ vs. Peedee belemnite (PDB), following a perfect synchronism with the variations of the CO2 concentration in the magmatic gases. This suggests a process of isotope fractionation because of vapor exsolution caused by magma depressurization. The hydrogen isotopes in the magmatic gases (-1 to -‰ vs. standard mean ocean water [SMOW]), as well as the above δ13CCO2 value, are coherent with a convergent tectonic setting of magma generation, where the local mantle is widely contaminated by fluids released from the subducted slab. Magma contamination in the crust probably amplifies this effect. The computed isotope composition of carbon and hydrogen in the hydrothermal vapors has been used to calculate the δD and δ13C of the entire hydrothermal system, including mixed H2O-CO2 vapor, liquid water, and dissolved carbon. We have computed values of about 10‰ vs. SMOW for water and -2 to -6.5‰ vs. PDB for CO2. On these grounds, we think that Mediterranean marine water (δDH2O ≈ 10‰) feeds the hydrothermal system. It infiltrates at depth throughout the local rocks

System for δ13C–CO2 and xCO2 analysis of discrete gas samples by cavity ring-down spectroscopy

Directory of Open Access Journals (Sweden)

D. Dickinson

2017-11-01

Full Text Available A method was devised for analysing small discrete gas samples (50 mL syringe by cavity ring-down spectroscopy (CRDS. Measurements were accomplished by inletting 50 mL syringed samples into an isotopic-CO2 CRDS analyser (Picarro G2131-i between baseline readings of a reference air standard, which produced sharp peaks in the CRDS data feed. A custom software script was developed to manage the measurement process and aggregate sample data in real time. The method was successfully tested with CO2 mole fractions (xCO2 ranging from  <  0.1 to  >  20 000 ppm and δ13C–CO2 values from −100 up to +30 000 ‰ in comparison to VPDB (Vienna Pee Dee Belemnite. Throughput was typically 10 samples h−1, with 13 h−1 possible under ideal conditions. The measurement failure rate in routine use was ca. 1 %. Calibration to correct for memory effects was performed with gravimetric gas standards ranging from 0.05 to 2109 ppm xCO2 and δ13C–CO2 levels varying from −27.3 to +21 740 ‰. Repeatability tests demonstrated that method precision for 50 mL samples was ca. 0.05 % in xCO2 and 0.15 ‰ in δ13C–CO2 for CO2 compositions from 300 to 2000 ppm with natural abundance 13C. Long-term method consistency was tested over a 9-month period, with results showing no systematic measurement drift over time. Standardised analysis of discrete gas samples expands the scope of application for isotopic-CO2 CRDS and enhances its potential for replacing conventional isotope ratio measurement techniques. Our method involves minimal set-up costs and can be readily implemented in Picarro G2131-i and G2201-i analysers or tailored for use with other CRDS instruments and trace gases.

CO2 and 12C:13C Isotopic Ratios on Phoebe and Iapetus

Science.gov (United States)

Clark, R. N.; Brown, R. H.; Cruikshank, D. P.

2016-12-01

Cassini VIMS has obtained spatially resolved 0.35 to 5.1 micron reflectance spectra of Saturn's satellites beginning with the Phoebe fly-by in 2004 and a close fly-by of Iapetus in 2007. Both surfaces contain relatively abundant CO2. The new (2016 RC19) calibration of VIMS has provided a significant increase in the data quality, such that isotopic absorption bands in CO2 are now well defined. CO2 on Saturn's icy satellites is trapped (Cruikshank et al., 2010, Icarus v206 p561; Pinilla-Alonso et al. 2011, Icarus v211, p75i), predominantly in the dark material (Clark et al. 2012, Icarus v218 p831). Clark et al. modeled the CO2 abundance as 2.8% on Iapetus and 3.7% on Phoebe. The main 12CO2 band in VIMS spectra on Iapetus occurs at 4.253 microns and Phoebe at 4.266 microns. The 13CO2 absorption is strong on Phoebe at 4.367 microns and weak on Iapetus at 4.387 microns. Converting the Phoebe, Iapetus, and a lab reflectance spectrum (of trace H2O-CO2 mixture on a diffuse substrate), we derive preliminary values for the ratio of the equivalent widths of the 12C and 13C absorptions as 19±2 on Phoebe, 82±8 on Iapetus, and 98±10 for the laboratory spectrum. These ratios are related to the 12C/13C ratio, but there may be effects due to intra-molecular and inter-molecular coupling that will contribute to systematic errors in the isotopic abundances derived using equivalent-width measurements that we've yet to quantify. We Believe the effects are small, and will be attempting to quantify them in the future. For comparison, the terrestrial value of the 12C/13C ratio is 90.17, and vibrational coupling may explain the slightly high lab mixture result. The local interstellar medium is 69±15 (Boogert et al., 2000, A&A). Because the CO2 bands on Phoebe and Iapetus dark material have different positions, and because the observed 13C absorption strengths are so different, the surface evolutions must be different. The large enrichment in 13C on Phoebe argues for significant

Groundwater data improve modelling of headwater stream CO2 outgassing with a stable DIC isotope approach

Science.gov (United States)

Marx, Anne; Conrad, Marcus; Aizinger, Vadym; Prechtel, Alexander; van Geldern, Robert; Barth, Johannes A. C.

2018-05-01

A large portion of terrestrially derived carbon outgasses as carbon dioxide (CO2) from streams and rivers to the atmosphere. Particularly, the amount of CO2 outgassing from small headwater streams is highly uncertain. Conservative estimates suggest that they contribute 36 % (i.e. 0.93 petagrams (Pg) C yr-1) of total CO2 outgassing from all fluvial ecosystems on the globe. In this study, stream pCO2, dissolved inorganic carbon (DIC), and δ13CDIC data were used to determine CO2 outgassing from an acidic headwater stream in the Uhlířská catchment (Czech Republic). This stream drains a catchment with silicate bedrock. The applied stable isotope model is based on the principle that the 13C / 12C ratio of its sources and the intensity of CO2 outgassing control the isotope ratio of DIC in stream water. It avoids the use of the gas transfer velocity parameter (k), which is highly variable and mostly difficult to constrain. Model results indicate that CO2 outgassing contributed more than 80 % to the annual stream inorganic carbon loss in the Uhlířská catchment. This translated to a CO2 outgassing rate from the stream of 34.9 kg C m-2 yr-1 when normalised to the stream surface area. Large temporal variations with maximum values shortly before spring snowmelt and in summer emphasise the need for investigations at higher temporal resolution. We improved the model uncertainty by incorporating groundwater data to better constrain the isotope compositions of initial DIC. Due to the large global abundance of acidic, humic-rich headwaters, we underline the importance of this integral approach for global applications.

Photodissociation spectroscopy of the Mg + -CO2 complex and its isotopic analogs

Science.gov (United States)

Yeh, C. S.; Willey, K. F.; Robbins, D. L.; Pilgrim, J. S.; Duncan, M. A.

1993-02-01

Mg+-CO2 ion-molecule cluster complexes are produced by laser vaporization in a pulsed nozzle cluster source. The vibronic spectroscopy in these complexes is studied with mass-selected photodissociation spectroscopy in a reflectron time-of-flight mass spectrometer. Two excited electronic states are observed (2) 2Σ+ and 2Π. The 2Π state has a vibrational progression in the metal-CO2 stretching mode (ωe'=381.8 cm-1). The complexes are linear (Mg+-OCO) and are bound by the charge-quadrupole interaction. The dissociation energy (D0`) is 14.7 kcal/mol. Corresponding spectra are measured for each of the 24, 25, and 26 isotopes of magnesium. These results are compared to theoretical predictions made by Bauschlicher and co-workers.

Oxygen isotope systematics of chondrules in the Murchison CM2 chondrite and implications for the CO-CM relationship

Science.gov (United States)

Chaumard, Noël; Defouilloy, Céline; Kita, Noriko T.

2018-05-01

High-precision oxygen three-isotope measurements of olivine and pyroxene were performed on 29 chondrules in the Murchison CM2 chondrite by secondary ion mass spectrometry (SIMS). The oxygen isotope ratios of analyzed chondrules all plot very close to the primitive chondrule minerals (PCM) line. In each of 24 chondrules, the olivine and/or pyroxene grains analyzed show indistinguishable oxygen isotope ratios. Exceptions are minor occurrences of isotopically distinguished relict olivine grains, which were found in nine chondrules. The isotope homogeneity of these phenocrysts is consistent with a co-magmatic crystallization of olivine and pyroxene from the final chondrule melts and a significant oxygen isotope exchange between the ambient gas and the melts. Homogeneous type I chondrules with Mg#'s of 98.9-99.5 have host chondrule Δ17O values ranging from -6.0‰ to -4.1‰, with one exception (Δ17O: -1.2‰; Mg#: 99.6). Homogeneous chondrules with Mg#'s poor H2O ice (∼0.3-0.4× the CI dust; Δ17O > 0‰) and at dust enrichments of ∼300-2000×. Regarding the Mg# and oxygen isotope ratios, the chondrule populations sampled by CM and CO chondrites are similar and indistinguishable. The similarity of these 16O-rich components in CO and CM chondrites is also supported by the common Fe/Mn ratio of olivine in type II chondrules. Although they accreted similar high-temperature silicates, CO chondrites are anhydrous compared to CM chondrites, suggesting they derived from different parent bodies formed inside and outside the snow line, respectively. If chondrules in CO and CM chondrites formed at the same disk locations but the CM parent body accreted later than the CO parent body, the snow line might have crossed the common chondrule-forming region towards the Sun between the time of the CO and CM parent bodies accretion.

Seasonal variability of soil CO2 flux and its carbon isotope composition in Krakow urban area, Southern Poland.

Science.gov (United States)

Jasek, Alina; Zimnoch, Miroslaw; Gorczyca, Zbigniew; Smula, Ewa; Rozanski, Kazimierz

2014-06-01

As urban atmosphere is depleted of (13)CO2, its imprint should be detectable in the local vegetation and therefore in its CO2 respiratory emissions. This work was aimed at characterising strength and isotope signature of CO2 fluxes from soil in urban areas with varying distances from anthropogenic CO2 emissions. The soil CO2 flux and its δ(13)C isotope signature were measured using a chamber method on a monthly basis from July 2009 to May 2012 within the metropolitan area of Krakow, Southern Poland, at two locations representing different levels of anthropogenic influence: a lawn adjacent to a busy street (A) and an urban meadow (B). The small-scale spatial variability of the soil CO2 flux was also investigated at site B. Site B revealed significantly higher summer CO2 fluxes (by approximately 46 %) than site A, but no significant differences were found between their δ(13)CO2 signatures.

Groundwater data improve modelling of headwater stream CO2 outgassing with a stable DIC isotope approach

Directory of Open Access Journals (Sweden)

A. Marx

2018-05-01

Full Text Available A large portion of terrestrially derived carbon outgasses as carbon dioxide (CO2 from streams and rivers to the atmosphere. Particularly, the amount of CO2 outgassing from small headwater streams is highly uncertain. Conservative estimates suggest that they contribute 36 % (i.e. 0.93 petagrams (Pg C yr−1 of total CO2 outgassing from all fluvial ecosystems on the globe. In this study, stream pCO2, dissolved inorganic carbon (DIC, and δ13CDIC data were used to determine CO2 outgassing from an acidic headwater stream in the Uhlířská catchment (Czech Republic. This stream drains a catchment with silicate bedrock. The applied stable isotope model is based on the principle that the 13C ∕ 12C ratio of its sources and the intensity of CO2 outgassing control the isotope ratio of DIC in stream water. It avoids the use of the gas transfer velocity parameter (k, which is highly variable and mostly difficult to constrain. Model results indicate that CO2 outgassing contributed more than 80 % to the annual stream inorganic carbon loss in the Uhlířská catchment. This translated to a CO2 outgassing rate from the stream of 34.9 kg C m−2 yr−1 when normalised to the stream surface area. Large temporal variations with maximum values shortly before spring snowmelt and in summer emphasise the need for investigations at higher temporal resolution. We improved the model uncertainty by incorporating groundwater data to better constrain the isotope compositions of initial DIC. Due to the large global abundance of acidic, humic-rich headwaters, we underline the importance of this integral approach for global applications.

Fingerprinting captured CO2 using natural tracers: Determining CO2 fate and proving ownership

Science.gov (United States)

Flude, Stephanie; Gilfillan, Stuart; Johnston, Gareth; Stuart, Finlay; Haszeldine, Stuart

2016-04-01

In the long term, captured CO2 will most likely be stored in large saline formations and it is highly likely that CO2 from multiple operators will be injected into a single saline formation. Understanding CO2 behavior within the reservoir is vital for making operational decisions and often uses geochemical techniques. Furthermore, in the event of a CO2 leak, being able to identify the owner of the CO2 is of vital importance in terms of liability and remediation. Addition of geochemical tracers to the CO2 stream is an effective way of tagging the CO2 from different power stations, but may become prohibitively expensive at large scale storage sites. Here we present results from a project assessing whether the natural isotopic composition (C, O and noble gas isotopes) of captured CO2 is sufficient to distinguish CO2 captured using different technologies and from different fuel sources, from likely baseline conditions. Results include analytical measurements of CO2 captured from a number of different CO2 capture plants and a comprehensive literature review of the known and hypothetical isotopic compositions of captured CO2 and baseline conditions. Key findings from the literature review suggest that the carbon isotope composition will be most strongly controlled by that of the feedstock, but significant fractionation is possible during the capture process; oxygen isotopes are likely to be controlled by the isotopic composition of any water used in either the industrial process or the capture technology; and noble gases concentrations will likely be controlled by the capture technique employed. Preliminary analytical results are in agreement with these predictions. Comparison with summaries of likely storage reservoir baseline and shallow or surface leakage reservoir baseline data suggests that C-isotopes are likely to be valuable tracers of CO2 in the storage reservoir, while noble gases may be particularly valuable as tracers of potential leakage.

13C analyses on CO2 in air using the multiflow: Application for the monitoring of atmospheric 13CO2 over hydro-electric reservoir in Quebec's Boreal region - Canada

International Nuclear Information System (INIS)

Bilodeau, G.; Hillaire-Marcel, C.; Helie, J.-F.; Fourel, F.; Varfalvy, L.

2002-01-01

The Multiflow TM preparation system is a headspace sampling device allowing extraction, purification and introduction of a gas sample into a gas-source Isotopic Ratio Mass Spectrometer for isotopic analysis. The original device was designed for 13 C measurements on CO 2 from breath tests. It has been adapted here for 13 CO 2 analysis in atmospheric low pCO 2 -samples

Compiled records of carbon isotopes in atmospheric CO2 for historical simulations in CMIP6

Directory of Open Access Journals (Sweden)

H. Graven

2017-12-01

Full Text Available The isotopic composition of carbon (Δ14C and δ13C in atmospheric CO2 and in oceanic and terrestrial carbon reservoirs is influenced by anthropogenic emissions and by natural carbon exchanges, which can respond to and drive changes in climate. Simulations of 14C and 13C in the ocean and terrestrial components of Earth system models (ESMs present opportunities for model evaluation and for investigation of carbon cycling, including anthropogenic CO2 emissions and uptake. The use of carbon isotopes in novel evaluation of the ESMs' component ocean and terrestrial biosphere models and in new analyses of historical changes may improve predictions of future changes in the carbon cycle and climate system. We compile existing data to produce records of Δ14C and δ13C in atmospheric CO2 for the historical period 1850–2015. The primary motivation for this compilation is to provide the atmospheric boundary condition for historical simulations in the Coupled Model Intercomparison Project 6 (CMIP6 for models simulating carbon isotopes in the ocean or terrestrial biosphere. The data may also be useful for other carbon cycle modelling activities.

Compiled records of carbon isotopes in atmospheric CO2 for historical simulations in CMIP6

Science.gov (United States)

Graven, Heather; Allison, Colin E.; Etheridge, David M.; Hammer, Samuel; Keeling, Ralph F.; Levin, Ingeborg; Meijer, Harro A. J.; Rubino, Mauro; Tans, Pieter P.; Trudinger, Cathy M.; Vaughn, Bruce H.; White, James W. C.

2017-12-01

The isotopic composition of carbon (Δ14C and δ13C) in atmospheric CO2 and in oceanic and terrestrial carbon reservoirs is influenced by anthropogenic emissions and by natural carbon exchanges, which can respond to and drive changes in climate. Simulations of 14C and 13C in the ocean and terrestrial components of Earth system models (ESMs) present opportunities for model evaluation and for investigation of carbon cycling, including anthropogenic CO2 emissions and uptake. The use of carbon isotopes in novel evaluation of the ESMs' component ocean and terrestrial biosphere models and in new analyses of historical changes may improve predictions of future changes in the carbon cycle and climate system. We compile existing data to produce records of Δ14C and δ13C in atmospheric CO2 for the historical period 1850-2015. The primary motivation for this compilation is to provide the atmospheric boundary condition for historical simulations in the Coupled Model Intercomparison Project 6 (CMIP6) for models simulating carbon isotopes in the ocean or terrestrial biosphere. The data may also be useful for other carbon cycle modelling activities.

Stable carbon isotope fractionation of organic cyst-forming dinoflagellates: Evaluating the potential for a CO2 proxy

Science.gov (United States)

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

2015-07-01

Over the past decades, significant progress has been made regarding the quantification and mechanistic understanding of stable carbon isotope fractionation (13C fractionation) in photosynthetic unicellular organisms in response to changes in the partial pressure of atmospheric CO2 (pCO2). However, hardly any data is available for organic cyst-forming dinoflagellates while this is an ecologically important group with a unique fossil record. We performed dilute batch experiments with four harmful dinoflagellate species known for their ability to form organic cysts: Alexandrium tamarense, Scrippsiella trochoidea, Gonyaulax spinifera and Protoceratium reticulatum. Cells were grown at a range of dissolved CO2 concentrations characterizing past, modern and projected future values (∼5-50 μmol L-1), representing atmospheric pCO2 of 180, 380, 800 and 1200 μatm. In all tested species, 13C fractionation depends on CO2 with a slope of up to 0.17‰ (μmol L)-1. Even more consistent correlations were found between 13C fractionation and the combined effects of particulate organic carbon quota (POC quota; pg C cell-1) and CO2. Carbon isotope fractionation as well as its response to CO2 is species-specific. These results may be interpreted as a first step towards a proxy for past pCO2 based on carbon isotope ratios of fossil organic dinoflagellate cysts. However, additional culture experiments focusing on environmental variables other than pCO2, physiological underpinning of the recorded response, testing for possible offsets in 13C values between cells and cysts, as well as field calibration studies are required to establish a reliable proxy.

Eddy Covariance measurements of stable CO2 and H2O isotopologues

Science.gov (United States)

Braden-Behrens, Jelka; Knohl, Alexander

2015-04-01

The analysis of the stable isotope composition of CO2 and H2O fluxes (such as 13C, 18O and 2H in H2O and CO2) has provided valuable insights into ecosystem gas exchange. The approach builds on differences in the isotope signature of different ecosystem components that are primarily caused by the preference for or the discrimination against respective isotope species by important processes within the ecosystem (e.g. photosynthesis or leaf water diffusion). With the ongoing development of laser spectrometric methods, fast and precise measurements of isotopologue mixing ratios became possible, hence also enabling Eddy Covariance (EC) based approaches to directly measure the isotopic composition of CO2 and H2Ov net fluxes on ecosystem scale. During an eight month long measurement campaign in 2015, we plan to simultaneously measure CO2 and H2Ov isotopologue fluxes using an EC approach in a managed beech forest in Thuringia, Germany. For this purpose, we will use two different laser spectrometers for high frequency measurements of isotopic compositions: For H2Ov measurements, we will use an off axis cavity output water vapour isotope analyser (WVIA, Los Gatos Research Inc.) with 5 Hz response; and for CO2 measurements, we will use a quantum cascade laser-based system (QCLAS, Aerodyne Research Inc.) with thermoelectrically cooled detectors and up to 10 Hz measurement capability. The resulting continuous isotopologue flux measurements will be accompanied by intensive sampling campaigns on the leaf scale: Water from leaf, twig, soil and precipitation samples will be analysed in the lab using isotope ratio mass spectrometry. During data analysis we will put a focus on (i) the influence of carbon and oxygen discrimination on the isotopic signature of respective net ecosystem exchange, (ii) on the relationship between evapotranspiration and leaf water enrichment, and (iii) on the 18O exchange between carbon dioxide and water. At present, we already carried out extensive

Oxygen isotope partitioning between rhyolitic glass/melt and CO2: An experimental study at 550-950 degrees C and 1 bar

International Nuclear Information System (INIS)

Palin, J.M.; Epstein, S.; Stolper, E.M.

1996-01-01

Oxygen isotope partitioning between gaseous CO 2 and a natural rhyolitic glass and melt (77.7 wt% SiO 2 , 0.16 wt% H 2 O total ) has been measured at 550-950 degrees C and approximately 1 bar. Equilibrium oxygen isotope fractionation factors (α CO2-rhyolite = ( 18 O/ 16 O) rhyolite ) determined in exchange experiments of 100-255 day duration. These values agree well with predictions based on experimentally determined oxygen isotope fractionation factors for CO 2 -silica glass and CO 2 -albitic glass/melt, if the rhyolitic glass is taken to be a simple mixture of normative silica and alkali feldspar components. The results indicate that oxygen isotope partitioning in felsic glasses and melts can be modeled by linear combinations of endmember silicate constituents. Rates of oxygen isotope exchange observed in the partitioning experiments are consistent with control by diffusion of molecular H 2 O dissolved in the glass/melt and are three orders of magnitude faster than predicted for rate control solely by diffusion of dissolved molecular CO 2 under the experimental conditions. Additional experiments using untreated and dehydrated (0.09 wt% H 2 O total ) rhyolitic glass quantatively support these interpretations. We conclude that diffusive oxygen isotope exchange in rhyolitic glass/melt, and probably other polymerized silicate materials, it controlled by the concentrations and diffusivities of dissolved oxygen-bearing volatile species rather than diffusion of network oxygen under all but the most volatile-poor conditions. 25 refs., 6 figs., 1 tab

Shell-model results in fp and fpg9/2 spaces for 61,63,65Co isotopes

International Nuclear Information System (INIS)

Srivastava, P. C.; Kota, V. K. B.

2011-01-01

Low-lying spectra and several high-spin states of odd-even 61,63,65 Co isotopes are calculated in two different shell-model spaces. First set of calculations have been carried out in fp-shell valence space (full fp space for 63,65 Co and a truncated one for 61 Co) using two recently derived fp-shell interactions, namely GXPF1A and KB3G, with 40 Ca as core. Similarly, the second set of calculations have been performed in fpg 9/2 valence space using an fpg effective interaction due to Sorlin et al., with 48 Ca as core and imposing a truncation. It is seen that the results of GXPF1A and KB3G are reasonable for 61,63 Co. For 65 Co, shell-model results show that the fpg interaction adopted in the study is inadequate and also points out that it is necessary to include orbitals higher than 1g 9/2 for neutron-rich Co isotopes.

Natural high pCO2 increases autotrophy in Anemonia viridis (Anthozoa) as revealed from stable isotope (C, N) analysis.

Science.gov (United States)

Horwitz, Rael; Borell, Esther M; Yam, Ruth; Shemesh, Aldo; Fine, Maoz

2015-03-05

Contemporary cnidarian-algae symbioses are challenged by increasing CO2 concentrations (ocean warming and acidification) affecting organisms' biological performance. We examined the natural variability of carbon and nitrogen isotopes in the symbiotic sea anemone Anemonia viridis to investigate dietary shifts (autotrophy/heterotrophy) along a natural pCO2 gradient at the island of Vulcano, Italy. δ(13)C values for both algal symbionts (Symbiodinium) and host tissue of A. viridis became significantly lighter with increasing seawater pCO2. Together with a decrease in the difference between δ(13)C values of both fractions at the higher pCO2 sites, these results indicate there is a greater net autotrophic input to the A. viridis carbon budget under high pCO2 conditions. δ(15)N values and C/N ratios did not change in Symbiodinium and host tissue along the pCO2 gradient. Additional physiological parameters revealed anemone protein and Symbiodinium chlorophyll a remained unaltered among sites. Symbiodinium density was similar among sites yet their mitotic index increased in anemones under elevated pCO2. Overall, our findings show that A. viridis is characterized by a higher autotrophic/heterotrophic ratio as pCO2 increases. The unique trophic flexibility of this species may give it a competitive advantage and enable its potential acclimation and ecological success in the future under increased ocean acidification.

Trace gases and CO sub(2) isotope records from Cabo de Rama, India

Digital Repository Service at National Institute of Oceanography (India)

Bhattacharya, S.K.; Borole, D.V.; Francey, R.J.; Allison, C.E.; Steele, L.P.; Krummel, P.; Langenfelds, R.; Masarie, K.A.; Tiwari, Y.K.; Patra, P.K.

to avoid dan- gerous climate change due to GHG forced warming. Con- centrations of CO 2 , CH 4 and N 2 O have increased at alarming rates, from preindustrial values of 280 ppm, 715 ppb and 270 ppb (circa. 1750) to 379 ppm, 1732 ppb and 319 ppb... an important effect on the con- centration and isotopic composition of atmospheric CO 2 , and the concentrations of other trace gases. Air sampling at CRI contributes to the global atmospheric composition study 10,11 . Given the potential for global impacts...

Isotope ratios of H, C, and O in CO2 and H2O of the martian atmosphere.

Science.gov (United States)

Webster, Chris R; Mahaffy, Paul R; Flesch, Gregory J; Niles, Paul B; Jones, John H; Leshin, Laurie A; Atreya, Sushil K; Stern, Jennifer C; Christensen, Lance E; Owen, Tobias; Franz, Heather; Pepin, Robert O; Steele, Andrew; Achilles, Cherie; Agard, Christophe; Alves Verdasca, José Alexandre; Anderson, Robert; Anderson, Ryan; Archer, Doug; Armiens-Aparicio, Carlos; Arvidson, Ray; Atlaskin, Evgeny; Aubrey, Andrew; Baker, Burt; Baker, Michael; Balic-Zunic, Tonci; Baratoux, David; Baroukh, Julien; Barraclough, Bruce; Bean, Keri; Beegle, Luther; Behar, Alberto; Bell, James; Bender, Steve; Benna, Mehdi; Bentz, Jennifer; Berger, Gilles; Berger, Jeff; Berman, Daniel; Bish, David; Blake, David F; Blanco Avalos, Juan J; Blaney, Diana; Blank, Jen; Blau, Hannah; Bleacher, Lora; Boehm, Eckart; Botta, Oliver; Böttcher, Stephan; Boucher, Thomas; Bower, Hannah; Boyd, Nick; Boynton, Bill; Breves, Elly; Bridges, John; Bridges, Nathan; Brinckerhoff, William; Brinza, David; Bristow, Thomas; Brunet, Claude; Brunner, Anna; Brunner, Will; Buch, Arnaud; Bullock, Mark; Burmeister, Sönke; Cabane, Michel; Calef, Fred; Cameron, James; Campbell, John; Cantor, Bruce; Caplinger, Michael; Caride Rodríguez, Javier; Carmosino, Marco; Carrasco Blázquez, Isaías; Charpentier, Antoine; Chipera, Steve; Choi, David; Clark, Benton; Clegg, Sam; Cleghorn, Timothy; Cloutis, Ed; Cody, George; Coll, Patrice; Conrad, Pamela; Coscia, David; Cousin, Agnès; Cremers, David; Crisp, Joy; Cros, Alain; Cucinotta, Frank; d'Uston, Claude; Davis, Scott; Day, Mackenzie; de la Torre Juarez, Manuel; DeFlores, Lauren; DeLapp, Dorothea; DeMarines, Julia; DesMarais, David; Dietrich, William; Dingler, Robert; Donny, Christophe; Downs, Bob; Drake, Darrell; Dromart, Gilles; Dupont, Audrey; Duston, Brian; Dworkin, Jason; Dyar, M Darby; Edgar, Lauren; Edgett, Kenneth; Edwards, Christopher; Edwards, Laurence; Ehlmann, Bethany; Ehresmann, Bent; Eigenbrode, Jen; Elliott, Beverley; Elliott, Harvey; Ewing, Ryan; Fabre, Cécile; Fairén, Alberto; Farley, Ken; Farmer, Jack; Fassett, Caleb; Favot, Laurent; Fay, Donald; Fedosov, Fedor; Feldman, Jason; Feldman, Sabrina; Fisk, Marty; Fitzgibbon, Mike; Floyd, Melissa; Flückiger, Lorenzo; Forni, Olivier; Fraeman, Abby; Francis, Raymond; François, Pascaline; Freissinet, Caroline; French, Katherine Louise; Frydenvang, Jens; Gaboriaud, Alain; Gailhanou, Marc; Garvin, James; Gasnault, Olivier; Geffroy, Claude; Gellert, Ralf; Genzer, Maria; Glavin, Daniel; Godber, Austin; Goesmann, Fred; Goetz, Walter; Golovin, Dmitry; Gómez Gómez, Felipe; Gómez-Elvira, Javier; Gondet, Brigitte; Gordon, Suzanne; Gorevan, Stephen; Grant, John; Griffes, Jennifer; Grinspoon, David; Grotzinger, John; Guillemot, Philippe; Guo, Jingnan; Gupta, Sanjeev; Guzewich, Scott; Haberle, Robert; Halleaux, Douglas; Hallet, Bernard; Hamilton, Vicky; Hardgrove, Craig; Harker, David; Harpold, Daniel; Harri, Ari-Matti; Harshman, Karl; Hassler, Donald; Haukka, Harri; Hayes, Alex; Herkenhoff, Ken; Herrera, Paul; Hettrich, Sebastian; Heydari, Ezat; Hipkin, Victoria; Hoehler, Tori; Hollingsworth, Jeff; Hudgins, Judy; Huntress, Wesley; Hurowitz, Joel; Hviid, Stubbe; Iagnemma, Karl; Indyk, Steve; Israël, Guy; Jackson, Ryan; Jacob, Samantha; Jakosky, Bruce; Jensen, Elsa; Jensen, Jaqueline Kløvgaard; Johnson, Jeffrey; Johnson, Micah; Johnstone, Steve; Jones, Andrea; Joseph, Jonathan; Jun, Insoo; Kah, Linda; Kahanpää, Henrik; Kahre, Melinda; Karpushkina, Natalya; Kasprzak, Wayne; Kauhanen, Janne; Keely, Leslie; Kemppinen, Osku; Keymeulen, Didier; Kim, Myung-Hee; Kinch, Kjartan; King, Penny; Kirkland, Laurel; Kocurek, Gary; Koefoed, Asmus; Köhler, Jan; Kortmann, Onno; Kozyrev, Alexander; Krezoski, Jill; Krysak, Daniel; Kuzmin, Ruslan; Lacour, Jean Luc; Lafaille, Vivian; Langevin, Yves; Lanza, Nina; Lasue, Jeremie; Le Mouélic, Stéphane; Lee, Ella Mae; Lee, Qiu-Mei; Lees, David; Lefavor, Matthew; Lemmon, Mark; Lepinette Malvitte, Alain; Léveillé, Richard; Lewin-Carpintier, Éric; Lewis, Kevin; Li, Shuai; Lipkaman, Leslie; Little, Cynthia; Litvak, Maxim; Lorigny, Eric; Lugmair, Guenter; Lundberg, Angela; Lyness, Eric; Madsen, Morten; Maki, Justin; Malakhov, Alexey; Malespin, Charles; Malin, Michael; Mangold, Nicolas; Manhes, Gérard; Manning, Heidi; Marchand, Geneviève; Marín Jiménez, Mercedes; Martín García, César; Martin, Dave; Martin, Mildred; Martínez-Frías, Jesús; Martín-Soler, Javier; Martín-Torres, F Javier; Mauchien, Patrick; Maurice, Sylvestre; McAdam, Amy; McCartney, Elaina; McConnochie, Timothy; McCullough, Emily; McEwan, Ian; McKay, Christopher; McLennan, Scott; McNair, Sean; Melikechi, Noureddine; Meslin, Pierre-Yves; Meyer, Michael; Mezzacappa, Alissa; Miller, Hayden; Miller, Kristen; Milliken, Ralph; Ming, Douglas; Minitti, Michelle; Mischna, Michael; Mitrofanov, Igor; Moersch, Jeff; Mokrousov, Maxim; Molina Jurado, Antonio; Moores, John; Mora-Sotomayor, Luis; Morookian, John Michael; Morris, Richard; Morrison, Shaunna; Mueller-Mellin, Reinhold; Muller, Jan-Peter; Muñoz Caro, Guillermo; Nachon, Marion; Navarro López, Sara; Navarro-González, Rafael; Nealson, Kenneth; Nefian, Ara; Nelson, Tony; Newcombe, Megan; Newman, Claire; Newsom, Horton; Nikiforov, Sergey; Nixon, Brian; Noe Dobrea, Eldar; Nolan, Thomas; Oehler, Dorothy; Ollila, Ann; Olson, Timothy; de Pablo Hernández, Miguel Ángel; Paillet, Alexis; Pallier, Etienne; Palucis, Marisa; Parker, Timothy; Parot, Yann; Patel, Kiran; Paton, Mark; Paulsen, Gale; Pavlov, Alex; Pavri, Betina; Peinado-González, Verónica; Peret, Laurent; Perez, Rene; Perrett, Glynis; Peterson, Joe; Pilorget, Cedric; Pinet, Patrick; Pla-García, Jorge; Plante, Ianik; Poitrasson, Franck; Polkko, Jouni; Popa, Radu; Posiolova, Liliya; Posner, Arik; Pradler, Irina; Prats, Benito; Prokhorov, Vasily; Purdy, Sharon Wilson; Raaen, Eric; Radziemski, Leon; Rafkin, Scot; Ramos, Miguel; Rampe, Elizabeth; Raulin, François; Ravine, Michael; Reitz, Günther; Rennó, Nilton; Rice, Melissa; Richardson, Mark; Robert, François; Robertson, Kevin; Rodriguez Manfredi, José Antonio; Romeral-Planelló, Julio J; Rowland, Scott; Rubin, David; Saccoccio, Muriel; Salamon, Andrew; Sandoval, Jennifer; Sanin, Anton; Sans Fuentes, Sara Alejandra; Saper, Lee; Sarrazin, Philippe; Sautter, Violaine; Savijärvi, Hannu; Schieber, Juergen; Schmidt, Mariek; Schmidt, Walter; Scholes, Daniel; Schoppers, Marcel; Schröder, Susanne; Schwenzer, Susanne; Sebastian Martinez, Eduardo; Sengstacken, Aaron; Shterts, Ruslan; Siebach, Kirsten; Siili, Tero; Simmonds, Jeff; Sirven, Jean-Baptiste; Slavney, Susie; Sletten, Ronald; Smith, Michael; Sobrón Sánchez, Pablo; Spanovich, Nicole; Spray, John; Squyres, Steven; Stack, Katie; Stalport, Fabien; Stein, Thomas; Stewart, Noel; Stipp, Susan Louise Svane; Stoiber, Kevin; Stolper, Ed; Sucharski, Bob; Sullivan, Rob; Summons, Roger; Sumner, Dawn; Sun, Vivian; Supulver, Kimberley; Sutter, Brad; Szopa, Cyril; Tan, Florence; Tate, Christopher; Teinturier, Samuel; ten Kate, Inge; Thomas, Peter; Thompson, Lucy; Tokar, Robert; Toplis, Mike; Torres Redondo, Josefina; Trainer, Melissa; Treiman, Allan; Tretyakov, Vladislav; Urqui-O'Callaghan, Roser; Van Beek, Jason; Van Beek, Tessa; VanBommel, Scott; Vaniman, David; Varenikov, Alexey; Vasavada, Ashwin; Vasconcelos, Paulo; Vicenzi, Edward; Vostrukhin, Andrey; Voytek, Mary; Wadhwa, Meenakshi; Ward, Jennifer; Weigle, Eddie; Wellington, Danika; Westall, Frances; Wiens, Roger Craig; Wilhelm, Mary Beth; Williams, Amy; Williams, Joshua; Williams, Rebecca; Williams, Richard B; Wilson, Mike; Wimmer-Schweingruber, Robert; Wolff, Mike; Wong, Mike; Wray, James; Wu, Megan; Yana, Charles; Yen, Albert; Yingst, Aileen; Zeitlin, Cary; Zimdar, Robert; Zorzano Mier, María-Paz

2013-07-19

Stable isotope ratios of H, C, and O are powerful indicators of a wide variety of planetary geophysical processes, and for Mars they reveal the record of loss of its atmosphere and subsequent interactions with its surface such as carbonate formation. We report in situ measurements of the isotopic ratios of D/H and (18)O/(16)O in water and (13)C/(12)C, (18)O/(16)O, (17)O/(16)O, and (13)C(18)O/(12)C(16)O in carbon dioxide, made in the martian atmosphere at Gale Crater from the Curiosity rover using the Sample Analysis at Mars (SAM)'s tunable laser spectrometer (TLS). Comparison between our measurements in the modern atmosphere and those of martian meteorites such as ALH 84001 implies that the martian reservoirs of CO2 and H2O were largely established ~4 billion years ago, but that atmospheric loss or surface interaction may be still ongoing.

Near Surface CO2 Triple Oxygen Isotope Composition

Directory of Open Access Journals (Sweden)

Sasadhar Mahata

2016-02-01

Full Text Available The isotopic composition of carbon dioxide in the atmosphere is a powerful tool for constraining its sources and sinks. In particular, the 17O oxygen anomaly [Δ17O = 1000 × ln(1 + δ17O/1000 - 0.516 × 1000 × ln(1 + δ18O/1000], with a value > 0.5‰ produced in the middle atmosphere, provides an ideal tool for probing the exchange of carbon dioxide between the biosphere/hydrosphere and atmosphere. The biosphere/hydrosphere and anthropogenic emissions give values ≤ 0.3‰. Therefore, any anomaly in near surface CO2 would reflect the balance between stratospheric input and exchange with the aforementioned surface sources. We have analyzed Δ17O values of CO2 separated from air samples collected in Taipei, Taiwan, located in the western Pacific region. The obtained mean anomaly is 0.42 ± 0.14‰ (1-σ standard deviation, in good agreement with model prediction and a published decadal record. Apart from typically used δ13C and δ18O values, the Δ17O value could provide an additional tracer for constraining the carbon cycle.

Direct gas injection method: A simple modification to an elemental analyzer/isotope ratio mass spectrometer for stable isotope analysis of N and C from N2O and CO2 gases in nanomolar concentrations

Science.gov (United States)

A simple modification to the Elemental Analyzer coupled to Isotope Ratio Mass-Spectrometer (EA-IRMS) setup is described. This modification allows the users to measure nitrous oxide (N2O) and carbon dioxide (CO2) by injecting the gases directly into an online injector placed befor...

Equilibration of metabolic CO2 with preformed CO2 and bicarbonate

International Nuclear Information System (INIS)

Hems, R.; Saez, G.T.

1983-01-01

Entry of metabolic 14 CO 2 into urea is shown to occur more readily than it equilibrates with the general pool of cellular plus extracellular bicarbonate plus CO 2 . Since the sites of CO 2 production (pyruvate dehydrogenase and oxoglutarate dehydrogenase) and of fixation (carbamoylphosphate synthetase) are intramitochondrial, it is likely that the fixation of CO 2 is also more rapid than its equilibration with the cytoplasmic pool of bicarbonate plus CO 2 . This observation may point to a more general problem concerning the interpretation of isotope data, with compartmentation or proximity of sites of production and utilisation of metabolites may result in the isotope following a preferred pathway. (Auth.)

Isotopic and Geochemical Signatures of Melgaco CO{sub 2} Rich Cold Mineralwaters, NW Portugal

Energy Technology Data Exchange (ETDEWEB)

Carreira, P. M.; Nunes, D. [Instituto Tecnologico e Nuclear, Unidade de Ciencias Quimicas e Radiofarmaceuticas, Sacavem (Portugal); Marques, J. M. [Instituto Superior Tecnico, Universidade Tecnica de Lisboa, Lisbon (Portugal); Carvalho, M. R. [Universidade de Lisboa, Faculdade de Ciencias, Departamento de Geologia, Lisbon (Portugal); Antunes da Silva, M. [UNICER Bebidas, S.A, S. Mamede de Infesta (Portugal)

2013-07-15

The isotopic and chemical compositions of CO{sub 2} rich mineral waters found in the NW of Portugal were investigated. These mineral waters are mainly related to granitic and granodioritic rocks. Based on their chemical composition, two water types are distinguished (Ca-HCO{sub 3} and Ca-Na-HCO{sub 3}), indicating different underground flow paths. Through comparison with local shallow groundwaters, water chemistry indicates that the Melgaco mineral waters evolved through water-rock interaction with the hosted rocks. Stable isotope data indicates the meteoric origin of these CO{sub 2} rich mineral waters, being recharged from about 480 up to 730 m a.s.l. Considering the {delta}{sup 18}O, {delta}{sup 2}H and the hydrochemical data, no indication of mixing seems to occur between the shallow and deep groundwater systems. The {delta}{sup 13}C determinations carried out on TDIC of the CO{sub 2} rich mineral waters point to the hypothesis of methanogenesis (upper mantle CH{sub 4} source) within the system, leading to {sup 13}C enrichment. The negligible {sup 14}C content ({approx} 2 pMC) also indicates a mantle derived carbon source for the groundwater system. (author)

Isotopic tracers of sources, wells and of CO2 reactivity in geological reservoirs

International Nuclear Information System (INIS)

Assayag, N.

2006-12-01

The aim of this research works consisted in studying the behaviour of the carbonate system (dissolved inorganic carbon: DIC) following a CO 2 injection (artificial or natural), in geological reservoirs. One part of the study consisted in improving an analytical protocol for the measurement of δ 13 C DIC and DIC, using a continuous flow mass spectrometer. As a first study, we have focused our attention on the Pavin Lake (Massif Central, France). Owing to its limnologic characteristics (meromictic lake) and a deep volcanic CO 2 contribution, it can be viewed as a natural analogue of reservoir storing important quantities of CO 2 in the bottom part. Isotopic measurements (δ 18 O, δ 13 C DIC) allowed to better constrain the dynamics of the lake (stratification, seasonal variations), the magnitudes of biological activities (photosynthesis, organic matter decay, methane oxidation, methano-genesis), carbon sources (magmatic, methano-genetic), and the hydrological budgets (sub-lacustrine inputs). The second study was conducted on the Lamont-Doherty test well site (NY, USA). It includes an instrumental borehole which cuts through most of the section of the Palisades sill and into the Newark Basin sediments. Single well push-pull tests were performed: a test solution containing conservative tracers and a reactive tracer (CO 2 ) was injected at a permeable depth interval located in basaltic and meta sedimentary rocks. After an incubation period, the test solution/groundwater mixture was extracted from the hydraulically isolated zone. Isotopic measurements (δ 18 O, δ 13 C DIC) confronted to chemical data (major elements) allowed to investigate the extent of in-situ CO 2 -water-rock interactions: essentially calcite dissolution and at a lesser extend silicate dissolution...and for one of the test, CO 2 degassing. (author)

2H Stable Isotope Analysis of Tooth Enamel: A Pilot Study

Science.gov (United States)

Holobinko, Anastasia; Kemp, Helen; Meier-Augenstein, Wolfram; Prowse, Tracy; Ford, Susan

2010-05-01

Stable isotope analysis of biogenic tissues such as tooth enamel and bone mineral has become a well recognized and increasingly important method for determining provenance of human remains, and has been used successfully in bioarchaeological studies as well as forensic investigations (Lee-Thorp, 2008; Meier-Augenstein and Fraser, 2008). Particularly, 18O and 2H stable isotopes are well established proxies as environmental indicators of climate (temperature) and source water and are therefore considered as indicators of geographic life trajectories of animals and humans (Hobson et al., 2004; Schwarcz and Walker, 2006). While methodology for 2H analysis of human hair, fingernails, and bone collagen is currently used to determine geographic origin and identify possible migration patterns, studies involving the analysis of 2H in tooth enamel appear to be nonexistent in the scientific literature. The apparent lack of research in this area is believed to have two main reasons. (1) Compared to the mineral calcium hydroxylapatite Ca10(PO4)6(OH)2, in tooth enamel forming bio-apatite carbonate ions replace some of the hydroxyl ions at a rate of one CO32 replacing two OH, yet published figures for the degree of substitution vary (Wopenka and Pasteris, 2005). (2) Most probably due to the aforementioned no published protocols exist for sample preparation and analytical method to obtain δ2H-values from the hydroxyl fraction of tooth enamel. This dilemma has been addressed through a pilot study to establish feasibility of 2H stable isotope analysis of ground tooth enamel by continuous-flow isotope ratio mass spectrometry (IRMS) coupled on-line to a high-temperature conversion elemental analyzer (TC/EA). An array of archaeological and modern teeth has been analyzed under different experimental conditions, and results from this pilot study are being presented. References: Lee-Thorp, J.A. (2008) Archaeometry, 50, 925-950 Meier-Augenstein, W. and Fraser, I. (2008) Science & Justice

Hydrogen isotope storage behavior of Zr1-xTixCo alloys

International Nuclear Information System (INIS)

Jat, Ram Avtar; Pati, Subhasis; Parida, S.C.; Agarwal, Renu; Mukerjee, S.K.

2016-01-01

Tritium storage properties similar to uranium make ZrCo as a suitable candidate material for storage, supply and recovery of hydrogen isotopes in various tritium facilities. Beside non-radioactive, nonpyrophoric at room temperature and higher storage capacity (H/f.u. up to 3, f.u. = ZrCo), it has been reported that upon repeated hydriding-dehydriding cycles, ZrCo undergoes dis-proportionation as per the reaction; ZrCo + H 2 ↔ ZrH 2 + ZrCo 2 . The present study is aimed to investigate the effect of Ti content on the hydrogen storage behavior of Zr 1-x Ti x Co alloys and the hydrogen isotope effect

Interactive Effects of CO2 Concentration and Water Regime on Stable Isotope Signatures, Nitrogen Assimilation and Growth in Sweet Pepper

Directory of Open Access Journals (Sweden)

María D. Serret

2018-01-01

Full Text Available Sweet pepper is among the most widely cultivated horticultural crops in the Mediterranean basin, being frequently grown hydroponically under cover in combination with CO2 fertilization and water conditions ranging from optimal to suboptimal. The aim of this study is to develop a simple model, based on the analysis of plant stable isotopes in their natural abundance, gas exchange traits and N concentration, to assess sweet pepper growth. Plants were grown in a growth chamber for near 6 weeks. Two [CO2] (400 and 800 μmol mol−1, three water regimes (control and mild and moderate water stress and four genotypes were assayed. For each combination of genotype, [CO2] and water regime five plants were evaluated. Water stress applied caused significant decreases in water potential, net assimilation, stomatal conductance, intercellular to atmospheric [CO2], and significant increases in water use efficiency, leaf chlorophyll content and carbon isotope composition, while the relative water content, the osmotic potential and the content of anthocyanins did change not under stress compared to control conditions support this statement. Nevertheless, water regime affects plant growth via nitrogen assimilation, which is associated with the transpiration stream, particularly at high [CO2], while the lower N concentration caused by rising [CO2] is not associated with stomatal closure. The stable isotope composition of carbon, oxygen, and nitrogen (δ13C, δ18O, and δ15N in plant matter are affected not only by water regime but also by rising [CO2]. Thus, δ18O increased probably as response to decreases in transpiration, while the increase in δ15N may reflect not only a lower stomatal conductance but a higher nitrogen demand in leaves or shifts in nitrogen metabolism associated with decreases in photorespiration. The way that δ13C explains differences in plant growth across water regimes within a given [CO2], seems to be mediated through its direct

Tracing the link between plant volatile organic compound emissions and CO2 fluxes and by stable isotopes

Science.gov (United States)

Werner, Christiane; Wegener, Frederik; Jardine, Kolby

2015-04-01

The vegetation exerts a large influence on the atmosphere through the emission of volatile organic compounds (VOCs) and the emission and uptake of the greenhouse gas CO2. Despite the enormous importance, processes controlling plant carbon allocation into primary and secondary metabolism, such as photosynthetic carbon uptake, respiratory CO2 emission and VOC synthesis, remains unclear. Moreover, vegetation-atmosphere CO2 exchange is associated with a large isotopic imprint due to photosynthetic carbon isotope discrimination and 13C-fractionation during respiratory CO2 release1. The latter has been proposed to be related to carbon partitioning in the metabolic branching points of the respiratory pathways and secondary metabolism, which are linked via a number of interfaces including the central metabolite pyruvate. Notably, it is a known substrate in a large array of secondary pathways leading to the biosynthesis of many volatile organic compounds (VOCs), such as volatile isoprenoids, oxygenated VOCs, aromatics, fatty acid oxidation products, which can be emitted by plants. Here we investigate the linkage between VOC emissions, CO2 fluxes and associated isotope effects based on simultaneous real-time measurements of stable carbon isotope composition of branch respired CO2 (CRDS) and VOC fluxes (PTR-MS). We utilized positionally specific 13C-labeled pyruvate branch feeding experiments in the mediterranean shrub (Halimium halimifolium) to trace the partitioning of C1, C2, and C3 carbon atoms of pyruvate into VOCs versus CO2 emissions in the light and in the dark. In the light, we found high emission rates of a large array of VOC including volatile isoprenoids, oxygenated VOCs, green leaf volatiles, aromatics, sulfides, and nitrogen containing VOCs. These observations suggest that in the light, H. halimifolium dedicates a high carbon flux through secondary biosynthetic pathways including the pyruvate dehydrogenase bypass, mevalonic acid, MEP/DOXP, shikimic acid, and

Carbon isotope exchange between gaseous CO2 and thin solution films: Artificial cave experiments and a complete diffusion-reaction model

Science.gov (United States)

Hansen, Maximilian; Scholz, Denis; Froeschmann, Marie-Louise; Schöne, Bernd R.; Spötl, Christoph

2017-08-01

Speleothem stable carbon isotope (δ13C) records provide important paleoclimate and paleo-environmental information. However, the interpretation of these records in terms of past climate or environmental change remains challenging because of various processes affecting the δ13C signals. A process that has only been sparsely discussed so far is carbon isotope exchange between the gaseous CO2 of the cave atmosphere and the dissolved inorganic carbon (DIC) contained in the thin solution film on the speleothem, which may be particularly important for strongly ventilated caves. Here we present a novel, complete reaction diffusion model describing carbon isotope exchange between gaseous CO2 and the DIC in thin solution films. The model considers all parameters affecting carbon isotope exchange, such as diffusion into, out of and within the film, the chemical reactions occurring within the film as well as the dependence of diffusion and the reaction rates on isotopic mass and temperature. To verify the model, we conducted laboratory experiments under completely controlled, cave-analogue conditions at three different temperatures (10, 20, 30 °C). We exposed thin (≈0.1 mm) films of a NaHCO3 solution with four different concentrations (1, 2, 5 and 10 mmol/l, respectively) to a nitrogen atmosphere containing a specific amount of CO2 (1000 and 3000 ppmV). The experimentally observed temporal evolution of the pH and δ13C values of the DIC is in good agreement with the model predictions. The carbon isotope exchange times in our experiments range from ca. 200 to ca. 16,000 s and strongly depend on temperature, film thickness, atmospheric pCO2 and the concentration of DIC. For low pCO2 (between 500 and 1000 ppmV, as for strongly ventilated caves), our time constants are substantially lower than those derived in a previous study, suggesting a potentially stronger influence of carbon isotope exchange on speleothem δ13C values. However, this process should only have an

High Precision Stable Isotope Measurements of Caribic Aircraft CO{sub 2} Samples: Global Distribution and Exchange with the Biosphere

Energy Technology Data Exchange (ETDEWEB)

Assonov, S. S. [Max Planck Institute for Chemistry, Mainz (Germany); Joint Research Centre, Institute for Reference Materials and Measurements (JRC-IRMM), European Commission, Geel (Belgium); Brenninkmeijer, C. A.M.; Schuck, T. J. [Max Planck Institute for Chemistry, Mainz (Germany); Taylor, P. [Joint Research Centre, Institute for Reference Materials and Measurements (JRC-IRMM), European Commission, Geel (Belgium)

2013-07-15

In 2007-2009 JRC-IRMM, in collaboration with the project CARIBIC (Civil Aircraft for Regular Investigation of the atmosphere Based on an Instrument Container, www.caribicatmospheric. com), conducted systematic measurements aimed to study the global distribution of CO{sub 2} isotopic composition. A large data set for the upper troposphere-lowermost stratosphere and free troposphere was obtained. For the first time it is demonstrated how CO{sub 2} isotope signals reflect global scale variability in air mass origin. Tight correlations observed arise either from stratosphere/troposphere mixing or from mixing of background air and air masses affected by CO{sub 2} sources and sinks, over long distances and throughout the seasons. The high quality {delta}{sup 18}O(CO{sub 2}) data prove to be a useful tracer reflecting long range CO{sub 2} transport and also CO{sub 2} exchange with land biosphere and soils. The data provide a benchmark for future comparisons and are available for modelling studies. (author)

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

Science.gov (United States)

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.

Catalytic recombination of dissociation products with Pt/SnO2 for rare and common isotope long-life, closed-cycle CO2 lasers

Science.gov (United States)

Brown, Kenneth G.; Sidney, B. D.; Schryer, D. R.; Upchurch, B. T.; Miller, I. M.

1986-01-01

This paper reports results on recombination of pulsed CO2 laser dissociation products with Pt/SnO2 catalysts, and supporting studies in a surrogate laboratory catalyst reactor. The closed-cycle, pulsed CO2 laser has been continuously operated for one million pulses with an overall power degradation of less than 5 percent by flowing the laser gas mixture through a 2-percent Pt/SnO2 catalyst bed. In the surrogate laboratory reactor, experiments have been conducted to determine isotopic exchange with the catalyst when using rare-isotope gases. The effects of catalyst pretreatment, sample weight, composition, and temperature on catalyst efficiency have also been determined.

Estimation of the efficiency of hydrocarbon mineralization in soil by measuring CO2-emission and variations in the isotope composition of carbon dioxide

Science.gov (United States)

Dubrovskaya, Ekaterina; Turkovskaya, Olga

2010-05-01

soil microbiota. The plants and microorganisms used had the isotopic signatures similar to that of the soil, whereas the δ13C of HD was -47.9‰. The HD mineralization level was assessed by determining the difference between the isotopic compositions of soil CO2 immediately after pollution and during remediation. In the unvegetated soil, about 13% of initially added HD was mineralized, the phytoremediation increased the total decomposition of the contaminant to 19%, and an additional plant inoculation with strain SR80 raised it to 33%. The GC analysis of soil demonstrated that contaminant loss in the plant treatments and in the inoculated plant treatment was 71 and 72%, respectively, whereas in the nonvegetated treatments, it was 64 and 66%, respectively. Thus, the elimination of the contaminant resulted from its total mineralization (CO2 emission) and partial chemical transformation.

Well-based stable carbon isotope leakage monitoring of an aquifer overlying the CO2 storage reservoir at the Ketzin pilot site, Germany

Science.gov (United States)

Nowak, Martin; Myrttinen, Anssi; Zimmer, Martin; van Geldern, Robert; Barth, Johannes A. C.

2014-05-01

At the pilot site for CO2 storage in Ketzin, a new well-based leakage-monitoring concept was established, comprising geochemical and hydraulic observations of the aquifer directly above the CO2 reservoir (Wiese et al., 2013, Nowak et al. 2013). Its purpose was to allow early detection of un-trapped CO2. Within this monitoring concept, we established a stable carbon isotope monitoring of dissolved inorganic carbon (DIC). If baseline isotope values of aquifer DIC (δ13CDIC) and reservoir CO2 (δ13CCO2) are known and distinct from each other, the δ13CDIC has the potential to serve as an an early indicator for an impact of leaked CO2 on the aquifer brine. The observation well of the overlying aquifer was equipped with an U-tube sampling system that allowed sampling of unaltered brine. The high alkaline drilling mud that was used during well drilling masked δ13CDIC values at the beginning of the monitoring campaign. However, subsequent monitoring allowed observing on-going re-equilibration of the brine, indicated by changing δ13CDIC and other geochemical values, until values ranging around -23 ‰ were reached. The latter were close to baseline values before drilling. Baselineδ13CDIC and δ13CCO2 values were used to derive a geochemical and isotope model that predicts evolution of δ13CDIC, if CO2 from the reservoir would leak into the aquifer. The model shows that equilibrium isotope fractionation would have to be considered if CO2 dissolves in the brine. The model suggests that stable carbon isotope monitoring is a suitable tool to assess the impact of injected CO2 in overlying groundwater aquifers. However, more data are required to close gaps of knowledge about fractionation behaviour within the CO2(g) - DIC system under elevated pressures and temperatures. Nowak, M., Myrttinen, A., Zimmer, M., Wiese, B., van Geldern, R., Barth, J.A.C., 2013. Well-based, Geochemical Leakage Monitoring of an Aquifer Immediately Above a CO2 Storage Reservoir by Stable Carbon

Multi-isotope tracing of CO2 leakage and water-rock interaction in a natural CCS analogue.

Science.gov (United States)

Kloppmann, Wolfram; Gemeni, Vasiliki; Lions, Julie; Koukouzas, Nikolaos; Humez, Pauline; Vasilatos, Charalampos; Millot, Romain; Pauwels, Hélène

2015-04-01

Natural analogues of CO2 accumulation and, potentially, leakage, provide a highly valuable opportunity to study (1) geochemical processes within a CO2-reservoir and the overlying aquifers or aquicludes, i.e. gas-water-rock interactions, (2) geology and tightness of reservoirs over geological timescales, (3) potential or real leakage pathways, (3) impact of leakage on shallow groundwater resources quality, and (4) direct and indirect geochemical indicators of gas leakage (Lions et al., 2014, Humez et al., 2014). The Florina Basin in NW Macedonia, Greece, contains a deep CO2-rich aquifer within a graben structure. The graben filling consists of highly heterogeneous Neogene clastic sediments constituted by components from the adjacent massifs including carbonates, schists, gneiss as well as some ultramafic volcanic rocks. Clay layers are observed that isolate hydraulically the deep, partly artesian aquifer. Organic matter, in form of lignite accumulations, is abundant in the Neogene series. The underlying bedrocks are metamorphic carbonates and silicate rocks. The origin of the CO2 accumulation is controversial (deep, partially mantle-derived D'Allessandro et al., 2008 or resulting from thermal decomposition of carbonates, Hatziyannis and Arvanitis, 2011). Groundwaters have been sampled from springs and borewells over 3 years at different depths. First results on major, minor and trace elements give evidence of water-rock interaction, mainly with carbonates but also with ultramafic components but do not indicate that CO2-seepage is the principal driver of those processes (Gemeni et al., submitted). Here we present isotope data on a selection of groundwaters (δ2H , δ18O, δ13CTDIC, 87Sr/86Sr, δ11B, δ7Li). Stable isotopes of water indicate paleo-recharge for some of the groundwaters, limited exchange with gaseous CO2 and, in one case, possibly thermal exchange processes with silicates. Sr isotope ratios vary between marine ratios and radiogenic values indicating

CO2 production in animals: analysis of potential errors in the doubly labeled water method

International Nuclear Information System (INIS)

Nagy, K.A.

1979-03-01

Laboratory validation studies indicate that doubly labeled water ( 3 HH 18 O and 2 HH 18 O) measurements of CO 2 production are accurate to within +-9% in nine species of mammals and reptiles, a bird, and an insect. However, in field studies, errors can be much larger under certain circumstances. Isotopic fraction of labeled water can cause large errors in animals whose evaporative water loss comprises a major proportion of total water efflux. Input of CO 2 across lungs and skin caused errors exceeding +80% in kangaroo rats exposed to air containing 3.4% unlabeled CO 2 . Analytical errors of +-1% in isotope concentrations can cause calculated rates of CO 2 production to contain errors exceeding +-70% in some circumstances. These occur: 1) when little decline in isotope concentractions has occured during the measurement period; 2) when final isotope concentrations closely approach background levels; and 3) when the rate of water flux in an animal is high relative to its rate of CO 2 production. The following sources of error are probably negligible in most situations: 1) use of an inappropriate equation for calculating CO 2 production, 2) variations in rates of water or CO 2 flux through time, 3) use of H 2 O-18 dilution space as a measure of body water volume, 4) exchange of 0-18 between water and nonaqueous compounds in animals (including excrement), 5) incomplete mixing of isotopes in the animal, and 6) input of unlabeled water via lungs and skin. Errors in field measurements of CO 2 production can be reduced to acceptable levels (< 10%) by appropriate selection of study subjects and recapture intervals

Isotopic separation of carbon by dissociation of CF2HCl irradiated by a Q-modulated CO2 laser

International Nuclear Information System (INIS)

Ezubchenko, A.N.; Ilyukhin, A.I.; Karchevskii, A.I.; Krasnikov, N.S.; Merzylakov, A.V.; Soloukhin, A.B.

1993-01-01

Isotopic separation of carbon by selective dissociation of CF 2 HCl by radiation from a CO 2 laser with mechanical Q-modulation has been studied experimentally. The modulation frequency was 10 4 sec -1 with a 20 W output. The peak radiation intensity is increased by a factor of 20-100 when modulated, while the average power is 0.5-0.9 that of the laser when operating in continuous mode. The authors show that under these conditions, a separation coefficient on the order of 40-50 is achieved as well as a high degree of the target isotope extraction (70%)

Metrology for stable isotope reference materials: 13C/12C and 18O/16O isotope ratio value assignment of pure carbon dioxide gas samples on the Vienna PeeDee Belemnite-CO2 scale using dual-inlet mass spectrometry.

Science.gov (United States)

Srivastava, Abneesh; Michael Verkouteren, R

2018-05-25

Isotope ratio measurements have been conducted on a series of isotopically distinct pure CO 2 gas samples using the technique of dual-inlet isotope ratio mass spectrometry (DI-IRMS). The influence of instrumental parameters, data normalization schemes on the metrological traceability and uncertainty of the sample isotope composition have been characterized. Traceability to the Vienna PeeDee Belemnite(VPDB)-CO 2 scale was realized using the pure CO 2 isotope reference materials(IRMs) 8562, 8563, and 8564. The uncertainty analyses include contributions associated with the values of iRMs and the repeatability and reproducibility of our measurements. Our DI-IRMS measurement system is demonstrated to have high long-term stability, approaching a precision of 0.001 parts-per-thousand for the 45/44 and 46/44 ion signal ratios. The single- and two-point normalization bias for the iRMs were found to be within their published standard uncertainty values. The values of 13 C/ 12 C and 18 O/ 16 O isotope ratios are expressed relative to VPDB-CO 2 using the [Formula: see text] and [Formula: see text] notation, respectively, in parts-per-thousand (‰ or per mil). For the samples, value assignments between (-25 to +2) ‰ and (-33 to -1) ‰ with nominal combined standard uncertainties of (0.05, 0.3) ‰ for [Formula: see text] and [Formula: see text], respectively were obtained. These samples are used as laboratory reference to provide anchor points for value assignment of isotope ratios (with VPDB traceability) to pure CO 2 samples. Additionally, they serve as potential parent isotopic source material required for the development of gravimetric based iRMs of CO 2 in CO 2 -free dry air in high pressure gas cylinder packages at desired abundance levels and isotopic composition values. Graphical abstract CO 2 gas isotope ratio metrology.

Interannual variability in the oxygen isotopes of atmospheric CO2 driven by El Nino

NARCIS (Netherlands)

Welp, Lisa R.; Keeling, Ralph F.; Meijer, Harro A. J.; Bollenbacher, Alane F.; Piper, Stephen C.; Yoshimura, Kei; Francey, Roger J.; Allison, Colin E.; Wahlen, Martin

2011-01-01

The stable isotope ratios of atmospheric CO2 (O-18/O-16 and C-13/C-12) have been monitored since 1977 to improve our understanding of the global carbon cycle, because biosphere-atmosphere exchange fluxes affect the different atomic masses in a measurable way(1). Interpreting the O-18/O-16

Seasonal Variations of Isotope Ratios and CO2 Concentrations in Firn Air

OpenAIRE

Weiler, Karin; Schwander, Jakob; Leuenberger, Markus; Blunier, Thomas; Mulvaney, Robert; Anderson, Philip S.; Salmon, Rhian; Sturges, William T.

2009-01-01

A first year-round firn air sampling carried out at the British Antarctic station Halley in 2003 shows isotope and CO2 changes owing to diffusive mixing driven by seasonal variations of surface temperature, and gas composition of the atmosphere. Seasonal firn temperatures are well reproduced from the atmospheric temperature history. Based on these profiles thermal diffusion is forced with thermal diffusion factors αT with respect to air. Application of the available literature data for αT (15...

Strontium isotope fractionation during strontianite (SrCO3) dissolution, precipitation and at equilibrium

Science.gov (United States)

Mavromatis, Vasileios; Harrison, Anna L.; Eisenhauer, Anton; Dietzel, Martin

2017-12-01

In this study we examine the behavior of stable Sr isotopes between strontianite [SrCO3] and reactive fluid during mineral dissolution, precipitation, and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 0.01 M NaCl solutions wherein the pH was adjusted by bubbling of a water saturated gas phase of pure CO2 or atmospheric air. The equilibrium Sr isotope fractionation between strontianite and fluid after dissolution of the solid under 1 atm CO2 atmosphere was estimated as Δ88/86SrSrCO3-fluid = δ88/86Sr SrCO3 - δ88/86Srfluid = -0.05 ± 0.01‰. On the other hand, during strontianite precipitation, an enrichment of the fluid phase in 88Sr, the heavy isotopomer, was observed. The evolution of the δ88/86Srfluid during strontianite precipitation can be modeled using a Rayleigh distillation approach and the estimated, kinetically driven, fractionation factor αSrCO3-fluid between solid and fluid is calculated to be 0.99985 ± 0.00003 corresponding to Δ88/86SrSrCO3-fluid = -0.15‰. The obtained results further support that under chemical equilibrium conditions between solid and fluid a continuous exchange of isotopes occurs until the system approaches isotopic equilibrium. This isotopic exchange is not limited to the outer surface layer of the strontianite crystal, but extends to ∼7-8 unit cells below the crystal surface. The behavior of Sr isotopes in this study is in excellent agreement with the concept of dynamic equilibrium and it suggests that the time needed for achievement of chemical equilibrium is generally shorter compared to that for isotopic equilibrium. Thus it is suggested that in natural Sr-bearing carbonates an isotopic change may still occur close to thermodynamic equilibrium, despite no observable change in aqueous elemental concentrations. As such, a secondary and ongoing change of Sr isotope signals in carbonate minerals caused by isotopic re-equilibration with fluids has to be considered in order to use Sr

Declining Atmospheric pCO2 During the Late Miocene and Early Pliocene: New Insights from Paired Alkenone and Coccolith Stable Isotope Barometry

Science.gov (United States)

Phelps, S. R.; Polissar, P. J.; deMenocal, P. B.; Swann, J. P.; Guo, M. Y.; Stoll, H. M.

2015-12-01

The relationship between atmospheric CO2 concentrations and climate is broadly understood for the Cenozoic era: warmer periods are associated with higher atmospheric carbon dioxide. This understanding is supported by atmospheric samples of the past 800,000 years from ice cores, which suggest CO2 levels play a key role in regulating global climate on glacial interglacial timescales as well. In this context, the late Miocene poses a challenge: sea-surface temperatures indicate substantial global warmth, though existing data suggest atmospheric CO2 concentrations were lower than pre-industrial values. Recent work using the stable carbon and oxygen isotopic composition of coccolith calcite has demonstrated these organisms began actively diverting inorganic carbon away from calcification and to the site of photosynthesis during the late Miocene. This process occurs in culture experiments in response to low aqueous CO2 concentrations, and suggests decreasing atmospheric pCO2 values during the late Miocene. Here we present new data from ODP Site 806 in the western equatorial Pacific Ocean that supports declining atmospheric CO2 across the late Miocene. Carbon isotope values of coccolith calcite from Site 806 demonstrate carbon limitation and re-allocation of inorganic carbon to photosynthesis starting between ~8 and 6 Ma. The timing of this limitation at Site 806 precedes shifts at other ODP sites, reflecting the higher mixed layer temperature and resultant lower CO2 solubility at Site 806. New measurements of carbon isotope values from alkenones at Site 806 show an increase in photosynthetic carbon fractionation (ɛp) accompanied the carbon limitation evident from coccolith calcite stable isotope data. While higher ɛp is typically interpreted as higher CO2 concentrations, at Site 806, our data suggest it reflects enhancement of chloroplast CO2 from active carbon transport by the coccolithophore algae in response to lower CO2 concentrations. Our new data from ODP Site

The influence of CO2 proceding from plant residue decomposition in the soil on isotopic ratio 13C/12c and plant development

International Nuclear Information System (INIS)

Martins, D.

1987-01-01

To determine the effect of plant incorporated in the soil on the microclimate of plant growth, an experiment was carried out in greenhouse and then under field conditions. Plant residue of C-3 crops δ 13 C = - 27.6 0 /00, was incorporated in the soil. This altered the isotopic composition of the CO 2 in soil air and in atmospheric air of soil layers adjacent to the surface. The soil air CO 2 isotopic composition showed that approximately 79% carbon was from the incorporated organic matter and 50% to 3% in O to 30 cm layers, respectively, in the atmospheric air adjacent to the surface. The isotopic ratio 13 C/ 12 C of plants cultivated in soil with incorporated organic matter was determined and it was noted that the envolved CO 2 was photosynthetically absorved by the plants during growth. CO 2 contribution from organic matter to the isotopic composition of C-4 plants varied from 33% to 13% during growth. Plants cultivated in soil with organic matter had a better development than those cultivated in natural soil. Productivity was on average 50% greater than the control plants. (author) [pt

Barium isotope fractionation during experimental formation of the double carbonate BaMn[CO3](2) at ambient temperature.

Science.gov (United States)

Böttcher, Michael E; Geprägs, Patrizia; Neubert, Nadja; von Allmen, Katja; Pretet, Chloé; Samankassou, Elias; Nägler, Thomas F

2012-09-01

In this study, we present the first experimental results for stable barium (Ba) isotope ((137)Ba/(134)Ba) fractionation during low-temperature formation of the anhydrous double carbonate BaMn[CO(3)](2). This investigation is part of an ongoing work on Ba fractionation in the natural barium cycle. Precipitation at a temperature of 21±1°C leads to an enrichment of the lighter Ba isotope described by an enrichment factor of-0.11±0.06‰ in the double carbonate than in an aqueous barium-manganese(II) chloride/sodium bicarbonate solution, which is within the range of previous reports for synthetic pure BaCO (3) (witherite) formation.

Carbon isotope composition of CO2-rich inclusions in cumulate-forming mantle minerals from Stromboli volcano (Italy)

Science.gov (United States)

Gennaro, Mimma Emanuela; Grassa, Fausto; Martelli, Mauro; Renzulli, Alberto; Rizzo, Andrea Luca

2017-10-01

We report on measurements of concentration and carbon isotope composition (δ13CCO2) of CO2 trapped in fluid inclusions of olivine and clinopyroxene crystals separated from San Bartolo ultramafic cumulate Xenoliths (SBX) formed at mantle depth (i.e., beneath a shallow Moho supposed to be at 14.8 km). These cumulates, erupted about 2 ka ago at Stromboli volcano (Italy), have been already investigated by Martelli et al. (2014) mainly for Sr-Nd isotopes and for their noble gases geochemistry. The concentration of CO2 varies of one order of magnitude from 3.8·10- 8 mol g- 1 to 4.8·10- 7 mol g- 1, with δ13C values between - 2.8‰ and - 1.5‰ vs V-PDB. These values overlap the range of measurements performed in the crater gases emitted at Stromboli (- 2.5‰ residence within the volcano plumbing system. Such δ13C values are higher than those commonly reported for MORB-like upper mantle (- 8 ÷ - 4‰) and likely reflect the source contamination of the local mantle wedge by CO2 coming from the decarbonation of the sediments carried by the subducting Ionian slab with a contribution of organic carbon up to 7%.

Dual stable isotopes of CH 4 from Yellowstone hot-springs suggest hydrothermal processes involving magmatic CO 2

Energy Technology Data Exchange (ETDEWEB)

Moran, James J.; Whitmore, Laura M.; Jay, Zackary J.; Jennings, Ryan deM.; Beam, Jacob P.; Kreuzer, Helen W.; Inskeep, William P.

2017-07-01

Volcanism and post-magmatism contribute both significant annual CH₄ fluxes to the atmosphere (on par with other natural sources such as forest fire and wild animal emissions) and have been implicated in past climate-change events. The Yellowstone hot spot is one of the largest volcanic systems on Earth and is known to emit methane in addition to other greenhouse gases (e.g. carbon dioxide) but the ultimate source of this methane flux has not been elucidated. Here we use dual stable isotope analysis (δ²H and δ¹³C) of CH₄(g) sampled from ten high-temperature geothermal pools in Yellowstone National Park to show that the predominant flux of CH4(g) is abiotic. The average δ¹³C and δ²H values of CH₄(g) emitted from hot springs (-26.7 (±2.4) and -236.9 (±12.0) ‰, respectively) are not consistent with biotic (microbial or thermogenic) methane sources, but are within previously reported ranges for abiotic methane production. Correlation between δ¹³C_CH4 and δ¹³C-dissolved inorganic C (DIC) also suggests that CO₂ is a parent C source for the observed CH₄(g). Moreover, CH₄-CO₂ isotopic geothermometry was used to estimate CH₄(g) formation temperatures ranging from ~ 250 - 350°C, which is just below the temperature estimated for the hydrothermal reservoir and consistent with the hypothesis that subsurface, rock-water interactions are responsible for large methane fluxes from this volcanic system. An understanding of conditions leading to the abiotic production of methane and associated isotopic signatures are central to understanding the evolutionary history of deep carbon sources on Earth.

Effects of euthanasia method on stable-carbon and stable-nitrogen isotope analysis for an ectothermic vertebrate.

Science.gov (United States)

Atwood, Meredith A

2013-04-30

Stable isotope analysis is a critical tool for understanding ecological food webs; however, results can be sensitive to sample preparation methods. To limit the possibility of sample contamination, freezing is commonly used to euthanize invertebrates and preserve non-lethal samples from vertebrates. For destructive sampling of vertebrates, more humane euthanasia methods are preferred to freezing and it is essential to evaluate how these euthanasia methods affect stable isotope results. Stable isotope ratios and elemental composition of carbon and nitrogen were used to evaluate whether the euthanasia method compromised the integrity of the sample for analysis. Specifically, the stable isotope and C:N ratios were compared for larval wood frogs (Rana sylvatica  =  Lithobates sylvaticus), an ectothermic vertebrate, that had been euthanized by freezing with four different humane euthanasia methods: CO2, benzocaine, MS-222 (tricaine methanesulfonate), and 70% ethanol. The euthanasia method was not related to the δ(13)C or δ(15)N values and the comparisons revealed no differences between freezing and any of the other treatments. However, there were slight (non-significant) differences in the isotope ratios of benzocaine and CO2 when each was compared with freezing. The elemental composition was altered by the euthanasia method employed. The percentage nitrogen was higher in CO2 treatments than in freezing, and similar (non-significant) trends were seen for ethanol treatments relative to freezing. The resulting C:N ratios were higher for benzocaine treatments than for both CO2 and ethanol. Similar (non-significant) trends suggested that the C:N ratios were also higher for animals euthanized by freezing than for both CO2 and ethanol euthanasia methods. The euthanasia method had a larger effect on elemental composition than stable isotope ratios. The percentage nitrogen and the subsequent C:N ratios were most affected by the CO2 and ethanol euthanasia methods, whereas

Isotopic analysis of boron by thermal ionization mass spectrometry

International Nuclear Information System (INIS)

Kakazu, M.H.; Sarkis, J.E.S.; Souza, I.M.S.

1991-07-01

This paper presents a methodology for isotopic analysis of boron by thermal ionization mass spectrometry technique through the ion intensity measurement of Na 2 BO + 2 in H 3 BO 3 , B o and B 4 C. The samples were loaded on single tantalum filaments by different methods. In the case of H 3 BO 3 , the method of neutralization with NaOH was used. For B 4 C the alcaline fusion with Na 2 CO 3 and for B o dissolution with 1:1 nitric sulfuric acid mixture followed by neutralization with NaOH was used. The isotopic ratio measurements were obtained by the use of s Faraday cup detector with external precision of ±0,4% and accuracy of ±0,1%, relative to H 3 BO 3 isotopic standard NBS 951. The effects of isotopic fractionation was studied in function of the time during the analyses and the different chemical forms of deposition. (author)

Uranium Isotopic Analysis with the FRAM Isotopic Analysis Code

International Nuclear Information System (INIS)

Vo, D.T.; Sampson, T.E.

1999-01-01

FRAM is the acronym for Fixed-Energy Response-Function Analysis with Multiple efficiency. This software was developed at Los Alamos National Laboratory originally for plutonium isotopic analysis. Later, it was adapted for uranium isotopic analysis in addition to plutonium. It is a code based on a self-calibration using several gamma-ray peaks for determining the isotopic ratios. The versatile-parameter database structure governs all facets of the data analysis. User editing of the parameter sets allows great flexibility in handling data with different isotopic distributions, interfering isotopes, and different acquisition parameters such as energy calibration and detector type

Catalysts for long-life closed-cycle CO2 lasers

Science.gov (United States)

Schryer, David R.; Sidney, Barry D.; Miller, Irvin M.; Hess, Robert V.; Wood, George M.; Batten, Carmen E.; Burney, Lewis G.; Hoyt, Ronald F.; Paulin, Patricia A.; Brown, Kenneth G.

1987-01-01

Long-life, closed-cycle operation of pulsed CO2 lasers requires catalytic CO-O2 recombination both to remove O2, which is formed by discharge-induced CO2 decomposition, and to regenerate CO2. Platinum metal on a tin (IV) oxide substrate (Pt/SnO2) has been found to be an effective catalyst for such recombination in the desired temperature range of 25 to 100 C. This paper presents a description of ongoing research at NASA-LaRC on Pt/SnO2 catalyzed CO-O2 recombination. Included are studies with rare-isotope gases since rare-isotope CO2 is desirable as a laser gas for enhanced atmospheric transmission. Results presented include: (1) achievement of 98% to 100% conversion of a stoichiometric mixture of CO and O2 to CO2 for 318 hours (greater than 1 x 10 to the 6th power seconds), continuous, at a catalyst temperature of 60 C, and (2) development of a technique verified in a 30-hour test, to prevent isotopic scrambling when CO-18 and O-18(2) are reacted in the presence of a common-isotope Pt/Sn O-16(2) catalyst.

Hydrogeochemical and stable isotopic investigations on CO2-rich mineral waters from Harghita Mts. (Eastern Carpathians, Romania)

Science.gov (United States)

Kis, Boglárka-Mercedesz; Baciu, Călin; Kármán, Krisztina; Kékedy-Nagy, Ladislau; Francesco, Italiano

2013-04-01

There is a worldwide interest on geothermal, mineral and groundwater as a resource for energy, drinking water supply and therapeutic needs. The increasing trend in replacing tap water with commercial bottled mineral water for drinking purposes has become an economic, hydrogeologic and medical concern in the last decades. Several investigations have been carried out worldwide on different topics related to geothermal and mineral waters, dealing with mineral water quality assessment, origin of geothermal and mineral waters, geochemical processes that influence water chemistry and water-rock interaction In Romania, the Călimani-Gurghiu-Harghita Neogene to Quaternary volcanic chain (Eastern Carpathians) is one of the most important areas from the point of view of CO2-rich mineral waters. These mineral water springs occur within other post-volcanic phenomena like dry CO2 emissions, moffettes, bubbling pools, H2S gas emissions etc. Mineral waters from this area are used for bottling, local spas and drinking purposes for local people. The number of springs, around 2000 according to literature data, shows that there is still a significant unexploited potential for good quality drinking water in this area. Within the youngest segment of the volcanic chain, the Harghita Mts., its volcaniclastic aprons and its boundary with the Transylvanian Basin, we have carried out an investigation on 23 CO2-rich mineral water springs from a hydrogeochemical and stable isotopic point of view. The mineral waters are Ca-Mg-HCO3 to Na-Cl type. Sometimes mixing between the two types can be observed. We have detected a great influence of water-rock interaction on the stable isotopic composition of the mineral waters, shown by isotopic shifts to the heavier oxygen isotope, mixing processes between shallow and deeper aquifers and local thermal anomalies. Acknowledgements: The present work was financially supported by the Romanian National Research Council, Project PN-II-ID-PCE-2011-3-0537 and by

Study of the Role of Terrestrial Processes in the Carbon Cycle Based on Measurements of the Abundance and Isotopic Composition of Atmospheric CO2

Energy Technology Data Exchange (ETDEWEB)

Piper, Stephen C; Keeling, Ralph F

2012-01-03

The main objective of this project was to continue research to develop carbon cycle relationships related to the land biosphere based on remote measurements of atmospheric CO2 concentration and its isotopic ratios 13C/12C, 18O/16O, and 14C/12C. The project continued time-series observations of atmospheric carbon dioxide and isotopic composition begun by Charles D. Keeling at remote sites, including Mauna Loa, the South Pole, and eight other sites. Using models of varying complexity, the concentration and isotopic measurements were used to study long-term change in the interhemispheric gradients in CO2 and 13C/12C to assess the magnitude and evolution of the northern terrestrial carbon sink, to study the increase in amplitude of the seasonal cycle of CO2, to use isotopic data to refine constraints on large scale changes in isotopic fractionation which may be related to changes in stomatal conductance, and to motivate improvements in terrestrial carbon cycle models. The original proposal called for a continuation of the new time series of 14C measurements but subsequent descoping to meet budgetary constraints required termination of measurements in 2007.

Measurements and modeling of CO₂ concentration and isotopes to improve process-level understanding of Arctic and boreal carbon cycling. Final Report

Energy Technology Data Exchange (ETDEWEB)

Keeling, Ralph F. [Univ. of California, San Diego, CA (United States). Scripps Inst. of Oceanography

2017-09-29

The major goal of this project was to improve understanding of processes that control the exchanges of CO₂ between the atmosphere and the land biosphere on decadal and longer time scales. The approach involves measuring the changes in atmospheric CO₂ concentration and the isotopes of CO₂ (¹³C/¹²C and ¹⁸O/¹⁶O) at background stations and uses these and other datasets to challenge and improve numerical models of the earth system. The project particularly emphasized the use of these data to improve understanding of changes occurring in boreal and arctic ecosystems over the past 50 years and to seek from these data improved understanding of large-scale processes impacting carbon cycling, such as the responses to warming, CO₂ fertilization, and disturbance. The project also led to advances in the understanding of changes in water-use efficiency of land ecosystems globally based on trends in ¹³C/¹²C. The core element of this project was providing partial support for continuing measurements of CO₂ concentrations and isotopes from the Scripps CO₂ program, initiated by C. D. Keeling in the 1960s. The measurements included analysis of flasks collected at an array of ten stations distributed from the Arctic to the Antarctic. The project also supported modeling studies and interpretive work to help understand the origins of the large ~50% increase in the amplitude of the atmospheric CO₂ cycle detected at high northern latitudes between 1960 and present and to understand the long-term trend in carbon ¹³C/¹²C of CO₂. The seasonal cycle work was advanced through collaborations with colleagues at MPI Jena and Imperial College

Stable isotope signatures reflect competitiveness between trees under changed CO2/O3 regimes

International Nuclear Information System (INIS)

Grams, T.E.E.; Matyssek, R.

2010-01-01

Here we synthesize key findings from a series of experiments to gain new insight on inter-plant competition between juvenile beech (Fagus sylvatica) and spruce (Picea abies) under the influence of increased O 3 and CO 2 concentrations. Competitiveness of plants was quantified and mechanistically interpreted as space-related resource investments and gains. Stable isotopes were addressed as temporal integrators of plant performance, such as photosynthesis and its relation to water use and nitrogen uptake. In the weaker competitor, beech, efficiency in space-related aboveground resource investment was decreased in competition with spruce and positively related to Δ 13 C, as well as stomatal conductance, but negatively related to δ 18 O. Likewise, our synthesis revealed that strong belowground competition for water in spruce was paralleled in this species by high N assimilation capacity. We suggest combining the time-integrative potential of stable isotopes with space-related investigations of competitiveness to accomplish mechanistic understanding of plant competition for resources. - Combination of space-related concepts of competitiveness with stable isotopes has potential to clarify mechanisms of competition.

Results of Am isotopic ratio analysis in irradiated MOX fuels

Energy Technology Data Exchange (ETDEWEB)

Koyama, Shin-ichi; Osaka, Masahiko; Mitsugashira, Toshiaki; Konno, Koichi [Power Reactor and Nuclear Fuel Development Corp., Oarai, Ibaraki (Japan). Oarai Engineering Center; Kajitani, Mikio

1997-04-01

For analysis of a small quantity of americium, it is necessary to separate from curium which has similar chemical property. As a chemical separation method for americium and curium, the oxidation of americium with pentavalent bismuth and subsequent co-precipitation of trivalent curium with BIP O{sub 4} were applied to analyze americium in irradiated MOX fuels which contained about 30wt% plutonium and 0.9wt% {sup 241}Am before irradiation and were irradiated up to 26.2GWd/t in the experimental fast reactor Joyo. The purpose of this study is to measure isotopic ratio of americium and to evaluate the change of isotopic ratio with irradiation. Following results are obtained in this study. (1) The isotopic ratio of americium ({sup 241}Am, {sup 242m}Am and {sup 243}Am) can be analyzed in the MOX fuels by isolating americium. The isotopic ratio of {sup 242m}Am and {sup 243}Am increases up to 0.62at% and 0.82at% at maximum burnup, respectively, (2) The results of isotopic analysis indicates that the contents of {sup 241}Am decreases, whereas {sup 242m}Am, {sup 243}Am increase linearly with increasing burnup. (author)

A system for high-quality CO2 isotope analyses of air samples collected by the CARIBIC Airbus A340-600.

Science.gov (United States)

Assonov, S; Taylor, P; Brenninkmeijer, C A M

2009-05-01

In 2007, JRC-IRMM began a series of atmospheric CO2 isotope measurements, with the focus on understanding instrumental effects, corrections as well as metrological aspects. The calibration approach at JRC-IRMM is based on use of a plain CO2 sample (working reference CO2) as a calibration carrier and CO2-air mixtures (in high-pressure cylinders) to determine the method-related correction under actual analytical conditions (another calibration carrier, in the same form as the samples). Although this approach differs from that in other laboratories, it does give a direct link to the primary reference NBS-19-CO2. It also helps to investigate the magnitude and nature for each of the instrumental corrections and allows for the quantification of the uncertainty introduced. Critical tests were focused on the instrumental corrections. It was confirmed that the use of non-symmetrical capillary crimping (an approach used here to deal with small samples) systematically modifies delta13C(CO2) and delta18O(CO2), with a clear dependence on the amount of extracted CO2. However, the calibration of CO2-air mixtures required the use of the symmetrical dual-inlet mode. As a proof of our approach, we found that delta13C(CO2) on extracts from mixtures agreed (within 0.010 per thousand) with values obtained from the 'mother' CO2 used for the mixtures. It was further found that very low levels of hydrocarbons in the pumping systems and the isotope ratio mass spectrometry (IRMS) instrument itself were critical. The m/z 46 values (consequently the calculated delta18O(CO2) values) are affected by several other effects with traces of air co-trapped with frozen CO2 being the most critical. A careful cryo-distillation of the extracted CO2 is recommended. After extensive testing, optimisation, and routine automated use, the system was found to give precise data on air samples that can be traced with confidence to the primary standards. The typical total combined uncertainty in delta13C(CO2) and

On-line stable isotope measurements during plant and soil gas exchange

International Nuclear Information System (INIS)

Yakir, D.

2001-01-01

Recent techniques for on-line stable isotope measurements during plant and soil exchange of CO 2 and/or water vapor are briefly reviewed. For CO 2 , these techniques provide means for on-line measurements of isotopic discrimination during CO 2 exchange by leaves in the laboratory and in the field, of isotopic discrimination during soil respiration and during soil-atmosphere CO 2 exchange, and of isotopic discrimination in O 2 during plant respiration. For water vapor, these techniques provide means to measure oxygen isotopic composition of water vapor during leaf transpiration and for the analysis of sub microliter condensed water vapor samples. Most of these techniques involve on-line sampling of CO 2 and water vapor from a dynamic, intact soil or plant system. In the laboratory, these systems also allow on-line isotopic analysis by continuous-flow isotope ratio mass spectrometry. The information obtained with these on-line techniques is becoming increasingly valuable, and often critical, for ecophysiologial research and in the study of biosphere-atmosphere interactions. (author)

In situ Determination of CO2 and N2O Emissions and Isotopic Composition in Agricultural Soils Following a Precipitation Pulse - The Use of Real-Time CO2 and N2O Isotope Analysers

International Nuclear Information System (INIS)

Chen, Janet; Resch, Christian; Mayr, Leopold; Heiling, Maria; Dercon, Gerd

2016-01-01

Agricultural soils cover 12.6% of the Earth's surface and are essential in food production. Agricultural land can either serve as a reservoir of greenhouse gases (GHGs) in the soil, or release them into the atmosphere. Accurately estimating GHG fluxes from agricultural soils is difficult, however, due to the dynamic pattern of emissions that are largely driven by environmental factors such as water availability. Farming practices, such as mulch application, also influence soil GHG emissions. We measured effects of mulch application on emissions and isotopic composition of two GHGs, CO 2 and N 2 O, in agricultural soils by using greenhouse “mesocosms” (soil sample columns 70 cm deep and 50 cm diameter that have been subjected to a soybean-maize crop rotation since 2012).

Subsurface Water as Natural CO{sub 2} Sink

Energy Technology Data Exchange (ETDEWEB)

Gillon, M. [Centre National de la Recherche Scientifique (UMR CNRS 8148-IDES), Interaction et Dynamique des Environnements de Surface, Universite Paris 11 and Centre National de la Recherche Scientifique (UMR UAPV-INRA EMMAH), Environnement Mediterraneen et Modelisation des Agro-Hydrosystemes, Universite d' Avignon et des Pays de Vaucluse, Avignon, (France); Barbecot, F.; Gibert, E.; Massault, M. [Centre National de La Recherche Scientifique (UMR CNRS 8148-IDES), Interaction et Dynamique des Environnements de Surface, Universite Paris 11 (France)

2013-07-15

In aquifer recharge areas, groundwater mineralization acts as an important sink for CO{sub 2} (assessed at 100 Mt{sub co2}/a on a European scale). An isotopic study of C fluxes in the unsaturated zone of a sand carbonate aquifer shows that the physical and geochemical processes controlling CO{sub 2} abstraction induce changes in the isotopic composition of both dissolved and matrix carbonates. An integrated record of these fluxes toward the aquifers is evidenced through isotopic investigation of the recharge areas. It is evidenced that the unsaturated zone represents an archive of pristine conditions, and would help to quantify downward C fluxes and environmental changes related to this CO{sub 2} abstraction process. (author)

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

Science.gov (United States)

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

Stable carbon isotopes to monitor the CO2 source mix in the urban environment

Science.gov (United States)

Vogel, F. R.; Wu, L.; Ramonet, M.; Broquet, G.; Worthy, D. E. J.

2014-12-01

Urban areas are said to be responsible for approximately 71% of fossil fuel CO2 emissions while comprising only two percent of the land area [IEA, 2008]. This limited spatial expansion could facility a monitoring of anthropogenic GHGs from atmospheric observations. As major sources of emissions, cities also have a huge potential to drive emissions reductions. To effectively manage emissions, cities must however, first establish techniques to validate their reported emission statistics. A pilot study which includes continues 13CO2 data from calibrated cavity ring-down spectrometers [Vogel et al. 2013] of two "sister sites" in the vicinity of Toronto, Canada is contrasted to recent observations of 13CO2 observations in Paris during significant pollution events. Using Miller-Tans plots [Miller and Tans, 2003] for our multi-season observations reveals significant changes of the source signatures of night time CO2 emissions which reflect the importance of natural gas burning in Megacities (up to 80% of fossil fuel sources) and show-case the potential of future isotope studies to determine source sectors. Especially the winter data this approach seems suitable to determine the source contribution of different fuel types (natural gas, liquid fuels and coal) which can inform the interpretation of other Greenhouse Gases and air pollution levels.

CO2 isotope analyses using large air samples collected on intercontinental flights by the CARIBIC Boeing 767

NARCIS (Netherlands)

Assonov, S.S.; Brenninkmeijer, C.A.M.; Koeppel, C.; Röckmann, T.

2009-01-01

Analytical details for 13C and 18O isotope analyses of atmospheric CO2 in large air samples are given. The large air samples of nominally 300 L were collected during the passenger aircraft-based atmospheric chemistry research project CARIBIC and analyzed for a large number of trace gases and

Autotrophic fixation of geogenic CO2 by microorganisms contributes to soil organic matter formation and alters isotope signatures in a wetland mofette

DEFF Research Database (Denmark)

Beulig, Felix

2015-01-01

of radiocarbon and enriched in 13C compared to atmospheric CO2. Together, these isotopic signals allow us to distinguish C fixed by plants from C fixed by autotrophic microorganisms using their differences in 13C discrimination. We can then estimate that up to 27 % of soil organic matter in the 0–10 cm layer...... geogenic CO2 was fixed by plants or by CO2 assimilating microorganisms, we first used the proportional differences in radiocarbon and δ13C values to indicate the magnitude of discrimination of the stable isotopes in living plants. Deviation from this relationship was taken to indicate the presence...... can recycle significant amounts of carbon in wetland soils and might contribute to observed radiocarbon reservoir effects influencing Δ14C signatures in peat deposits....

Determination of marble provenance: limits of isotopic analysis

International Nuclear Information System (INIS)

Germann, K.; Holzmann, G.; Winkler, F.J.

1980-01-01

Provenance determination of Thessalian stelae marbles using the C/O isotopic analysis proved to be misleading, as the isotopic composition even in very small quarrying areas is heterogeneous and isotopic coincidence of marbles from very distant sources occurs. Therefore additional geological features must be taken into consideration and preference should be given to combinations of both petrographical and geochemical properties. Geological field work to establish the range of possible marble sources and the variability within these sources is one of the prerequisites of provenance studies. (author)

Use of the isotope flux ratio approach to investigate the C18O16O and 13CO2 exchange near the floor of a temperate deciduous forest

Directory of Open Access Journals (Sweden)

P. Bartlett

2012-07-01

Full Text Available Stable isotopologues of CO2, such as 13CO2 and C18OO, have been used to study the CO2 exchange between land and atmosphere. The advent of new measuring techniques has allowed near-continuous measurements of stable isotopes in the air. These measurements can be used with micrometeorological techniques, providing new tools to investigate the isotope exchange in ecosystems. The objectives of this study were to evaluate the use of the isotope flux ratio method (IFR near the forest floor of a temperate deciduous forest and to study the temporal dynamics of δ18O of CO2 flux near the forest floor by comparing IFR estimates with estimates of δ18O of net soil CO2 flux provided by an analytical model. Mixing ratios of 12C16O2, 13CO2 and C16O18O were measured within and above a temperate deciduous forest, using the tunable diode laser spectroscopy technique. The half-hourly compositions of the CO2 flux near the forest floor (δ13CF and δ18OF were calculated by IFR and compared with estimates provided by a modified Keeling plot technique (mKP and by a Lagrangian dispersion analysis (WT analysis. The mKP and IFR δ18OF estimates showed good agreement (slope = 1.03 and correlation, R2 = 0.80. The δ13CF estimates from the two methods varied in a narrow range of −32.7 and −23‰; the mean (± SE mKP and IFR δ13CF values were −27.5‰ (±0.2 and −27.3‰ (±0.1, respectively, and were statistically identical (p>0.05. WT analysis and IFR δ18OF estimates showed better correlation (R2 = 0.37 when only turbulent periods (u*>0.6 m s−1 were included in the analysis. The large amount of data captured (~95 % of half-hour periods evaluated for the IFR in comparison with mKP (27 % shows that the former provides new opportunities for studying δ18OF dynamics within forest canopies. Values of δ18OF showed large temporal variation, with values ranging from −31.4‰ (DOY 208 to −11.2‰ (DOY 221. Precipitation events caused substantial variation (~8�

Land-use change effects on fluxes and isotopic composition of CO2 and CH4 in Panama, and possible insights into the atmospheric H2 cycle

Science.gov (United States)

Pendall, E.; Schwendenmann, L.; Potvin, C.

2003-12-01

Land-use changes in tropical regions are believed to release a quantity of C to the atmosphere which is similar in magnitude to the entire "missing" sink for anthropogenic CO2. Our research attempts to evaluate carbon cycling in three land-cover systems in central Panama: cow pasture, native tree plantation, and undisturbed moist forest. In this ongoing project, we are collecting samples of air from profiles in the stable, nocturnal boundary layer, which is dominated by ecosystem respiration. Samples are analyzed for CO2 and its isotopes, CH4 and its C isotopic composition, N2O, H2, CO, and SF6. We use a flux-gradient method to estimate ecosystem-scale fluxes of trace gases from soil to the atmosphere. Keeling plot intercepts reflect the respiratory contribution of C3 and C4 biomass under contrasting land cover systems, and how this varies with pronounced wet-dry seasonal cycles. C isotopes of methane and gradients of molecular hydrogen provide insight into the source of methane production from pasture and plantation soils. Rainforest soils, in contrast, are sinks for both atmospheric methane and hydrogen. The process oriented nature of this field experiment will contribute to parameterization of carbon cycle models at a variety of spatial scales.

Hydrogen and oxygen isotope exchange reactions over illuminated and nonilluminated TiO2

International Nuclear Information System (INIS)

Sato, S.

1987-01-01

Hydrogen isotope exchange between H 2 , gaseous H 2 O, and the surface hydroxyls of TiO 2 , and oxygen isotope exchange between O 2 , CO 2 , CO, H 2 O vapor, and the hydroxyls over TiO 3 were studied at room temperature in the dark and under illumination. Hydrogen isotope exchange between H 2 O and the hydroxyls occurred rapidly in the dark, but the exchange involving H 2 did not occur at all even under illumination. Oxygen isotope exchange among H 2 O vapor, CO 2 , and the hydroxyls easily took place in the dark, but the exchange involving O 2 required band-gap illumination. Dioxygen isotope equilibration was much faster than the other photoexchange reactions. Although the oxygen exchange between O 2 and illuminated TiO 2 has been considered to involve lattice-oxygen exchange, the present experiments revealed that the hydroxyls of TiO 2 mainly participate in the exchange reaction. The oxygen exchange between O 2 and H 2 O vapor was strongly inhibited by H 2 O vapor itself probably because oxygen adsorption was retarded by adsorbed water. Oxygen in CO was not exchanged with the other substrates under any conditions tested

Carbon isotopic evidence for the associations of decreasing atmospheric CO2 level with the Frasnian-Famennian mass extinction

Science.gov (United States)

Xu, Bing; Gu, Zhaoyan; Wang, Chengyuan; Hao, Qingzhen; Han, Jingtai; Liu, Qiang; Wang, Luo; Lu, Yanwu

2012-03-01

A perturbation of the global carbon cycle has often been used for interpreting the Frasnian-Famennian (F-F) mass extinction. However, the changes of atmospheric CO2 level (pCO2) during this interval are much debatable. To illustrate the carbon cycle during F-F transition, paired inorganic (δ13Ccarb) and organic (δ13Corg) carbon isotope analyses were carried out on two late Devonian carbonate sequences (Dongcun and Yangdi) from south China. The larger amplitude shift of δ13Corg compared to δ13Ccarb and its resultant Δ13C (Δ13C = δ13Ccarb - δ13Corg) decrease indicate decreased atmospheric CO2level around the F-F boundary. The onset ofpCO2 level decrease predates that of marine regressions, which coincide with the beginning of conodont extinctions, suggesting that temperature decrease induced by decreased greenhouse effect of atmospheric CO2might have contributed to the F-F mass extinction.

Existing and emerging technologies for measuring stable isotope labelled retinol in biological samples: isotope dilution analysis of body retinol stores.

Science.gov (United States)

Preston, Tom

2014-01-01

This paper discusses some of the recent improvements in instrumentation used for stable isotope tracer measurements in the context of measuring retinol stores, in vivo. Tracer costs, together with concerns that larger tracer doses may perturb the parameter under study, demand that ever more sensitive mass spectrometric techniques are developed. GCMS is the most widely used technique. It has high sensitivity in terms of sample amount and uses high resolution GC, yet its ability to detect low isotope ratios is limited by background noise. LCMSMS may become more accessible for tracer studies. Its ability to measure low level stable isotope tracers may prove superior to GCMS, but it is isotope ratio MS (IRMS) that has been designed specifically for low level stable isotope analysis through accurate analysis of tracer:tracee ratios (the tracee being the unlabelled species). Compound-specific isotope analysis, where GC is interfaced to IRMS, is gaining popularity. Here, individual 13C-labelled compounds are separated by GC, combusted to CO2 and transferred on-line for ratiometric analysis by IRMS at the ppm level. However, commercially-available 13C-labelled retinol tracers are 2 - 4 times more expensive than deuterated tracers. For 2H-labelled compounds, GC-pyrolysis-IRMS has now become more generally available as an operating mode on the same IRMS instrument. Here, individual compounds are separated by GC and pyrolysed to H2 at high temperature for analysis by IRMS. It is predicted that GC-pyrolysis-IRMS will facilitate low level tracer procedures to measure body retinol stores, as has been accomplished in the case of fatty acids and amino acids. Sample size requirements for GC-P-IRMS may exceed those of GCMS, but this paper discusses sample preparation procedures and predicts improvements, particularly in the efficiency of sample introduction.

Does Short-term Litter Input Manipulation Affect Soil Respiration and the Carbon-isotopic Signature of Soil Respired CO2

Science.gov (United States)

Cheng, X.; Wu, J.

2016-12-01

Global change greatly alters the quality and quantity of plant litter inputs to soils, and further impacts soil organic matter (SOM) dynamics and soil respiration. However, the process-based understanding of how soil respiration may change with future shift in litter input is not fully understood. The Detritus Input and Removal Treatment (DIRT) experiment was conducted in coniferous forest (Platycladus orientalis (Linn.) Franco) ecosystem of central China to investigate the impact of above- and belowground litter input on soil respiration and the carbon-isotopic signature of soil respired CO2. Short-term (1-2 years) litter input manipulation significantly affected soil respiration, based on annual flux values, soil respiration was 31.9%, 20.5% and 37.2% lower in no litter (NL), no root (NR) and no input (NRNL), respectively, compared to control (CK). Whereas double litter (DL) treatment increased soil respiration by 9.1% compared to CK. The recalcitrance index of carbon (RIC) and the relative abundance of fungi increased under litter removal or root exclusion treatment (NL, NR and NRNL) compared to CK. Basal soil respiration was positively related to liable C and microbial biomass and negatively related to RIC and fungi to bacteria (F: B) ratio. The carbon-isotopic signature of soil respired CO2 enriched under litter removal and no input treatment, and slightly depleted under litter addition treatment compared to CK. Our results suggest that short-term litter input manipulation can affect the soil respiration by altering substrate availability and microbial community structure, and also impact the carbon-isotopic signature of soil respired CO2 possibly duo to change in the component of soil respiration and soil microclimate.

Maintaining high precision of isotope ratio analysis over extended periods of time.

Science.gov (United States)

Brand, Willi A

2009-06-01

Stable isotope ratios are reliable and long lasting process tracers. In order to compare data from different locations or different sampling times at a high level of precision, a measurement strategy must include reliable traceability to an international stable isotope scale via a reference material (RM). Since these international RMs are available in low quantities only, we have developed our own analysis schemes involving laboratory working RM. In addition, quality assurance RMs are used to control the long-term performance of the delta-value assignments. The analysis schemes allow the construction of quality assurance performance charts over years of operation. In this contribution, the performance of three typical techniques established in IsoLab at the MPI-BGC in Jena is discussed. The techniques are (1) isotope ratio mass spectrometry with an elemental analyser for delta(15)N and delta(13)C analysis of bulk (organic) material, (2) high precision delta(13)C and delta(18)O analysis of CO(2) in clean-air samples, and (3) stable isotope analysis of water samples using a high-temperature reaction with carbon. In addition, reference strategies on a laser ablation system for high spatial resolution delta(13)C analysis in tree rings is exemplified briefly.

Diode laser absorption spectrometry for (CO2)-C-13/(CO2)-C-12 isotope ratio analysis : Investigation on precision and accuracy levels

NARCIS (Netherlands)

Castrillo, A; Casa, G; Kerstel, E; Gianfrani, L

2005-01-01

Near-infrared laser spectroscopy is used to measure the C-13/C-12 isotope abundance ratio in gas phase carbon dioxide. The spectrometer, developed expressly for field applications, is based on a 2 mu m distributed feedback diode laser in combination with sensitive wavelength modulation detection. It

Pulsed CO laser for isotope separation of uranium

Energy Technology Data Exchange (ETDEWEB)

Baranov, Igor Y.; Koptev, Andrey V. [Rocket-Space Technics Department, Baltic State Technical University, 1, 1st Krasnoarmeyskaya st.,St. Petersburg, 190005 (Russian Federation)

2012-07-30

This article proposes a technical solution for using a CO laser facility for the industrial separation of uranium used in the production of fuel for nuclear power plants, employing a method of laser isotope separation of uranium with condensation repression in a free jet. The laser operation with nanosecond pulse irradiation can provide an acceptable efficiency in the separating unit and a high efficiency of the laser with the wavelength of 5.3 {mu}m. In the present work we also introduce a calculation model and define the parameters of a mode-locked CO laser with a RF discharge in the supersonic stream. The average pulsed CO laser power of 3 kW is sufficient for efficient industrial isotope separation of uranium in one stage.

14CO2 analysis of soil gas: Evaluation of sample size limits and sampling devices

Science.gov (United States)

Wotte, Anja; Wischhöfer, Philipp; Wacker, Lukas; Rethemeyer, Janet

2017-12-01

Radiocarbon (14C) analysis of CO2 respired from soils or sediments is a valuable tool to identify different carbon sources. The collection and processing of the CO2, however, is challenging and prone to contamination. We thus continuously improve our handling procedures and present a refined method for the collection of even small amounts of CO2 in molecular sieve cartridges (MSCs) for accelerator mass spectrometry 14C analysis. Using a modified vacuum rig and an improved desorption procedure, we were able to increase the CO2 recovery from the MSC (95%) as well as the sample throughput compared to our previous study. By processing series of different sample size, we show that our MSCs can be used for CO2 samples of as small as 50 μg C. The contamination by exogenous carbon determined in these laboratory tests, was less than 2.0 μg C from fossil and less than 3.0 μg C from modern sources. Additionally, we tested two sampling devices for the collection of CO2 samples released from soils or sediments, including a respiration chamber and a depth sampler, which are connected to the MSC. We obtained a very promising, low process blank for the entire CO2 sampling and purification procedure of ∼0.004 F14C (equal to 44,000 yrs BP) and ∼0.003 F14C (equal to 47,000 yrs BP). In contrast to previous studies, we observed no isotopic fractionation towards lighter δ13C values during the passive sampling with the depth samplers.

Development of indirect indicators for CO2 intrusion into freshwater

International Nuclear Information System (INIS)

Humez, P.

2012-01-01

This study deals with the impact of CO 2 leakages out of geological storage into overlying freshwater aquifers. Compared to other existing studies, the major added value of this study lies, on the one hand, in the research of new monitoring tools and isotopic approach in the context of CCS aiming at early and sensitive detection of CO 2 leakage and, on the other hand, in the application of these tools at the (limited) laboratory scale as well as at field scale. In order to test these tools, solid and liquid materials were sampled out of the major strategic drinking water Albian aquifer in the Paris Basin (France). We have then precisely characterized and used them within a batch experiment. This experiment yields interesting results which help understanding and constraining precisely the water-rock-CO 2 interactions as well as the isotopic responses. A real scale application of the method was then performed in Norway. It was an opportunity to develop this isotopic program and to track the isotopic evolution composition, while differentiating the natural processes and the system response to the CO 2 injection. When applied to the detection of CO 2 leakage context, the two case studies open the way for choosing the 'best' isotopic tools as indirect indicators of CO 2 presence in these specific systems. The efficiency of these isotopic tools comes from the recording of the CO 2 footprint all along the water-rock-CO 2 interactions. Using such tools imposes a rigorous methodology, which is tackled in this manuscript. Furthermore, future application will require adapting to the specifics of a proposed site. (author)

Isotopic tracers of sources, wells and of CO{sub 2} reactivity in geological reservoirs; Tracage isotopique des sources, puits et de la reactivite du CO{sub 2} dans les reservoirs geologiques

Energy Technology Data Exchange (ETDEWEB)

Assayag, N

2006-12-15

The aim of this research works consisted in studying the behaviour of the carbonate system (dissolved inorganic carbon: DIC) following a CO{sub 2} injection (artificial or natural), in geological reservoirs. One part of the study consisted in improving an analytical protocol for the measurement of {delta} {sup 13}C DIC and DIC, using a continuous flow mass spectrometer. As a first study, we have focused our attention on the Pavin Lake (Massif Central, France). Owing to its limnologic characteristics (meromictic lake) and a deep volcanic CO{sub 2} contribution, it can be viewed as a natural analogue of reservoir storing important quantities of CO{sub 2} in the bottom part. Isotopic measurements ({delta} {sup 18}O, {delta} {sup 13}C DIC) allowed to better constrain the dynamics of the lake (stratification, seasonal variations), the magnitudes of biological activities (photosynthesis, organic matter decay, methane oxidation, methano-genesis), carbon sources (magmatic, methano-genetic), and the hydrological budgets (sub-lacustrine inputs). The second study was conducted on the Lamont-Doherty test well site (NY, USA). It includes an instrumental borehole which cuts through most of the section of the Palisades sill and into the Newark Basin sediments. Single well push-pull tests were performed: a test solution containing conservative tracers and a reactive tracer (CO{sub 2}) was injected at a permeable depth interval located in basaltic and meta sedimentary rocks. After an incubation period, the test solution/groundwater mixture was extracted from the hydraulically isolated zone. Isotopic measurements ({delta} {sup 18}O, {delta} {sup 13}C DIC) confronted to chemical data (major elements) allowed to investigate the extent of in-situ CO{sub 2}-water-rock interactions: essentially calcite dissolution and at a lesser extend silicate dissolution...and for one of the test, CO{sub 2} degassing. (author)

Stable Isotope Quantitative N-Glycan Analysis by Liquid Separation Techniques and Mass Spectrometry.

Science.gov (United States)

Mittermayr, Stefan; Albrecht, Simone; Váradi, Csaba; Millán-Martín, Silvia; Bones, Jonathan

2017-01-01

Liquid phase separation analysis and subsequent quantitation remains a challenging task for protein-derived oligosaccharides due to their inherent structural complexity and diversity. Incomplete resolution or co-detection of multiple glycan species complicates peak area-based quantitation and associated statistical analysis when optical detection methods are used. The approach outlined herein describes the utilization of stable isotope variants of commonly used fluorescent tags that allow for mass-based glycan identification and relative quantitation following separation by liquid chromatography (LC) or capillary electrophoresis (CE). Comparability assessment of glycoprotein-derived oligosaccharides is performed by derivatization with commercially available isotope variants of 2-aminobenzoic acid or aniline and analysis by LC- and CE-mass spectrometry. Quantitative information is attained from the extracted ion chromatogram/electropherogram ratios generated from the light and heavy isotope clusters.

Stable Carbon Isotope Characterization of CO2 Loss in Acid Mine Drainage Impacted Stream Water: Observations from a Laboratory Experiment

Science.gov (United States)

Ali, H. N.; Atekwana, E. A.

2007-05-01

Water from an acid mine drainage spring, ground water from a mine tailings pile, stream water and tap water were acidified to simulate acid mine drainage (AMD) contamination. The objective was to determine how acidification of stream water by AMD affected DIC loss and carbon isotope fraction. Two 20 L HDP containers (reactors) containing samples from each source were left un-acidified and allowed to evolve under ambient conditions for several weeks in the laboratory and two others were acidified. Acidification was carried out progressively with sulfuric acid to pH <3. For acidified samples, one reactor was acidified open to the atmosphere and the other closed from contact with atmosphere and CO2(g) was collected under vacuum. The un-acidified samples did not show significant alkalinity and DIC loss, and the 13C of DIC was enriched with time. The acidified samples showed decrease in alkalinity and DIC and increase in the 13C of DIC and CO2(g) with progressive acidification. The enrichment of 13C of DIC for un-acidified samples was due to exchange with atmospheric CO2. On the other hand, the 13C enrichment in the acidified samples was due to fractionation during dehydration of HCO3- and diffusive loss of CO2(g) from the aqueous phase. The actual values measured depended on the amount of CO2 lost from the aqueous phase during acidification. Samples with greater CO2 loss (closed acidification) had greater 13C enrichment. Beyond the HCO3- titration end point, the δ13C of DIC and CO2(g) was similar and nearly constant. The result of this study suggests that AMD effects on DIC can be modeled as a first order kinetic reaction and the isotope enrichment modeled using Rayleigh distillation.

Atmospheric pCO2 Reconstructed across the Early Eocene Hyperthermals

Science.gov (United States)

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.

The dynamics of CO2 fixation in the Southern Ocean as indicated by carboxylase activities and organic carbon isotopic ratios

International Nuclear Information System (INIS)

Fontugne, M.

1991-01-01

Recent studies have suggested a direct relationship between the dissolved CO 2 concentration and carbon isotopic composition of phytoplankton in surface ocean. Thus, measurement of δ 13 C of planktonic organic matter in deep-sea ocean cores can potentially yield a record of the past atmospheric CO 2 variations. However, results are presented from 3 cruises in Indian and Atlantic sectors of the Southern Ocean (between 40-66degS) in which biochemical and physiological factors associated with photosynthetic processes lead to carbon isotopic fractionation by phytoplankton which cannot be directly related to variations within the mineral carbon pool. Simultaneous measurements of the carboxylase activities in the 13 C/ 12 C ratio of particulate organic carbon show that there is a large variability in phytoplankton carbon metabolism, especially on a seasonal scale, in spite of a relative uniformity of the environmental conditions. Phytoplankton carbon metabolism is clearly a main factor governing variations in the stable isotopic composition of organic matter in the euphotic layer. Interrelationships between light, Rubiso activity and δ 13 C are clearly shown by the data. Heterotrophic processes may also influence the carbon isotope mass balance, especially during the break-up of the ice pack. In addition to the influence of photosynthetic metabolism, the effect of the meridoneal temperature gradient is also verified by the data set. (author). 24 refs.; 5 figs

Effect of isotopic substitution on the collisional quenching of vibronically excited CO+

International Nuclear Information System (INIS)

Katayama, D.H.; Welsh, J.A.

1983-01-01

Rovibronic levels of the A 2 Pi/sub i/ state for 12 C 16 O + and 13 C 16 O + have been selectively excited by a pulsed, tunable dye laser and their time resolved fluorescence obtained as a function of helium pressure. These ions are formed by reaction of neutral carbon monoxide with helium metastable atoms created in a dc discharge. Since 13 CO + has essentially the same potential energy curves as 12 CO + , but differs primarily in its vibrational energy spacings, this experiment accentuates the role, in the collisional deactivation process, of the high lying ground state vibrational levels which are adjacent to the laser populated vibronic levels of the A 2 Pi/sub i/ state. Quenching rates are determined for the v' = 0, 1, and 2 levels which have relatively insignificant isotope shifts of a few wave numbers for the two isotopes. The difference in rates for the two isotopic ions demonstrates the importance of the positions for the high lying v'' = 10 and 11 ground state levels which have large isotope shifts of hundreds of wave numbers. A discussion of the deactivation process is given in terms of perturbations, Franck--Condon factors, energy gaps, and other considerations

Ancient and modern sites of natural CO2 leakage: Geochemistry and geochronology of Quaternary and modern travertine deposits on the Colorado Plateau, USA, and implications for CO2 sequestration

Science.gov (United States)

Priewisch, A.; Crossey, L. J.; Karlstrom, K. E.; McPherson, B. J.; Mozley, P.

2013-12-01

Travertine-precipitating springs and travertine deposits of the Colorado Plateau serve as natural analogues for evaluating potential leakage associated with geologic sequestration of carbon dioxide (CO2). Extensive Quaternary and modern travertine deposits occur along the Jemez lineament and Rio Grande rift in New Mexico and Arizona, and in the Paradox Basin in Utah, along the Little Grand Wash Fault and the Salt Wash Graben. These groundwater discharge deposits are interpreted to be sites of persistent and significant CO2 degassing along faults and above magmatic systems. Analysis of the geochemical and isotopic composition of U-series dated travertine deposits and modern travertine-precipitating waters allows evaluation of the flow paths of CO2-charged waters. Initial results from New Mexico and Arizona travertine deposits show characteristic rare earth element (REE) signatures for individual travertine deposits and yet generally overlap in concentrations of other trace elements such as Al, As, B, Ba, K, and Si. We report stable oxygen and carbon isotopes of the travertines in New Mexico, Arizona, and Utah. Different travertine deposits have different carbon-oxygen isotope variation patterns suggesting that these stable isotopes are tracers that have the ability to identify distinctive groundwater sources within and between spring groups based on the travertine record. Stable isotope analyses of travertine deposits in New Mexico and Arizona overlap substantially between deposits and cluster around -10‰ to -6‰ for δ18O and around 3.5‰ to 6.5‰ for δ13C. Travertine deposits in Utah show a distinctly different range of stable isotope values: δ18O values cluster around -14‰ to -10.5‰ and δ13C around 4.5‰ to 6.5‰. U-series dating of travertine deposits shows episodic travertine formation in New Mexico and Arizona over the last 700,000 years, and travertine accumulation over the last 400,000 years in Utah. We use U-series dating and volumetric

Ruthenium and osmium carbonyl nitrosyl complexes: Matrix infrared spectra and density functional calculations for M(CO){sub 2}(NO){sub 2} and M(CO)(NO) (M = Ru, Os)

Energy Technology Data Exchange (ETDEWEB)

Song, Zhenjun [Department of Chemistry, Tongji University, Shanghai 200092 (China); Wang, Xuefeng, E-mail: xfwang@tongji.edu.cn [Department of Chemistry, Tongji University, Shanghai 200092 (China); Key Laboratory of Yangtze River Water Environment, Ministry of Education, Tongji University (China)

2012-10-15

Highlights: Black-Right-Pointing-Pointer Laser-ablated ruthenium or osmium atom reactions with CO and NO mixtures in solid argon. Black-Right-Pointing-Pointer Metal carbonyl nitrosyls including M(CO)(NO) and 18-electron configuration M(CO){sub 2}(NO){sub 2} molecules (M = Ru, Os). Black-Right-Pointing-Pointer The observed absorption bands of reaction products are identified by isotopic substitution and DFT calculations. Black-Right-Pointing-Pointer The bonding and reaction mechanism are discussed in detail. -- Abstract: Laser-ablated ruthenium or osmium atom reactions with CO and NO mixtures in solid argon produce unsaturated metal carbonyl nitrosyls including M(CO)(NO) and 18-electron configuration M(CO){sub 2}(NO){sub 2} molecules (M = Ru, Os). The observed absorption bands of reaction products are identified by isotopic substitution, isotopic ratios and isotopic distributions ({sup 13}CO, {sup 15}NO, and mixtures). DFT (B3LYP and BP86) vibrational fundamental calculations reproduce observed frequencies and isotopic shifts very well. The bonding and reaction mechanism are discussed.

Using stable isotopes in tree rings to evaluate the impact of urban pollution on CO2 uptake by forests

International Nuclear Information System (INIS)

Savard, M.M.; Begin, Ch.; Marion, J.

2004-01-01

Contributions addressing the impact of industrial activities on tree growth are scarce; likewise, only a few studies document δ 13 C values in growth rings of natural specimens subjected to potentially toxic industrial emissions. These last studies suggest that the SO 2 emissions affect the physiology of trees and induce changes in their carbon isotope ratios. It has been reported that copper-smelter emissions reduce the C uptake of exposed trees by 35 % to 6 % relatively to unexposed trees, in growth stands located between 9 and 120 km from the smelter. In the context of the globally increasing concentrations of CO 2 in the atmosphere, what is the net impact of the large-scale annual reduction of CO 2 uptake induced by phyto-toxic pollutants? What should we expect for trees growing in regions submitted to urban diffuse pollution? It has been recently suggested on the basis of plant biomass measurements in the New York region that urban pollution can relatively reduce plant growth, but the effect is apparently greater in distant rural sites than in peri-urban and urban ones. Is this representative of numerous urban settings? If the answer to this question is yes, the pollution-effect parameter should be considered in the global annual forest C budget, particularly for the highly industrialized northern hemisphere. The specific objectives of this study are to: (1) measure the tissue increments of the stems and determine the C isotopic ratios in tree-ring cellulose of selected trees undergoing pollution stress in selected peri-urban stands; (2) present a secular time series of the CO 2 uptake by forests peripheral to a large urban region; and (3) evaluate stable isotope dendro-geochemistry as a proxy for past changes of air quality in urban and peri-urban settings. (authors)

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

Science.gov (United States)

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.

Oxygen isotope analysis of plant water without extraction procedure

International Nuclear Information System (INIS)

Gan, K.S.; Wong, S.C.; Farquhar, G.D.; Yong, J.W.H.

2001-01-01

Isotopic analyses of plant water (mainly xylem, phloem and leaf water) are gaming importance as the isotopic signals reflect plant-environment interactions, affect the oxygen isotopic composition of atmospheric O 2 and CO 2 and are eventually incorporated into plant organic matter. Conventionally, such isotopic measurements require a time-consuming process of isolating the plant water by azeotropic distillation or vacuum extraction, which would not complement the speed of isotope analysis provided by continuous-flow IRMS (Isotope-Ratio Mass Spectrometry), especially when large data sets are needed for statistical calculations in biological studies. Further, a substantial amount of plant material is needed for water extraction and leaf samples would invariably include unenriched water from the fine veins. To measure sub-microlitre amount of leaf mesophyll water, a new approach is undertaken where a small disc of fresh leaf is cut using a specially designed leaf punch, and pyrolysed directly in an IRMS. By comparing with results from pyrolysis of the dry matter of the same leaf, the 18 O content of leaf water can be determined without extraction from fresh leaves. This method is validated using a range of cellulose-water mixtures to simulate the constituents of fresh leaf. Cotton leaf water δ 18 O obtained from both methods of fresh leaf pyrolysis and azeotropic distillation will be compared. The pyrolysis technique provides a robust approach to measure the isotopic content of water or any volatile present in a homogeneous solution or solid hydrous substance

Spatially resolved δ13C analysis using laser ablation isotope ratio mass spectrometry

Science.gov (United States)

Moran, J.; Riha, K. M.; Nims, M. K.; Linley, T. J.; Hess, N. J.; Nico, P. S.

2014-12-01

Inherent geochemical, organic matter, and microbial heterogeneity over small spatial scales can complicate studies of carbon dynamics through soils. Stable isotope analysis has a strong history of helping track substrate turnover, delineate rhizosphere activity zones, and identifying transitions in vegetation cover, but most traditional isotope approaches are limited in spatial resolution by a combination of physical separation techniques (manual dissection) and IRMS instrument sensitivity. We coupled laser ablation sampling with isotope measurement via IRMS to enable spatially resolved analysis over solid surfaces. Once a targeted sample region is ablated the resulting particulates are entrained in a helium carrier gas and passed through a combustion reactor where carbon is converted to CO2. Cyrotrapping of the resulting CO2 enables a reduction in carrier gas flow which improves overall measurement sensitivity versus traditional, high flow sample introduction. Currently we are performing sample analysis at 50 μm resolution, require 65 ng C per analysis, and achieve measurement precision consistent with other continuous flow techniques. We will discuss applications of the laser ablation IRMS (LA-IRMS) system to microbial communities and fish ecology studies to demonstrate the merits of this technique and how similar analytical approaches can be transitioned to soil systems. Preliminary efforts at analyzing soil samples will be used to highlight strengths and limitations of the LA-IRMS approach, paying particular attention to sample preparation requirements, spatial resolution, sample analysis time, and the types of questions most conducive to analysis via LA-IRMS.

Research on catalysts for long-life closed-cycle CO2 laser oaperation

Science.gov (United States)

Sidney, Barry D.; Schryer, David R.; Upchurch, Billy T.; Hess, Robert V.; Wood, George M.

1987-01-01

Long-life, closed-cycle operation of pulsed CO2 lasers requires catalytic CO-O2 recombination both to remove O2, which is formed by discharge-induced CO2 decomposition, and to regenerate CO2. Platinum metal on a tin-oxide substrate (Pt/SnO2) has been found to be an effective catalyst for such recombination in the desired temperature range of 25 to 100 C. This paper presents a description of ongoing research at NASA-Langley on Pt/SnO2 catalyzed CO-O2 recombination. Included are studies with rare-isotope gases since rare-isotope CO2 is desirable as a laser gas for enhanced atmospheric transmission. Results presented include: (1) the effects of various catalyst pretreatment techniques on catalyst efficiency; (2) development of a technique, verified in a 30-hour test, to prevent isotopic scrambling when C(O-18) and (O-18)2 are reacted in the presence of a common-isotope Pt/Sn(O-16)2 catalyst; and (3) development of a mathematical model of a laser discharge prior to catalyst introduction.

Assessing methane oxidation under landfill covers and its contribution to the above atmospheric CO2 levels: The added value of the isotope (δ13C and δ18O CO2; δ13C and δD CH4) approach

International Nuclear Information System (INIS)

Widory, D.; Proust, E.; Bellenfant, G.; Bour, O.

2012-01-01

Highlights: ► Comparison of the isotope and mass balance approaches to evaluate the level of methane oxidation within a landfill. ► The level of methane oxidation is not homogenous under the landfill cover and is strongly correlated to the methane flux. ► Isotope tracking of the contribution of the methane oxidation to the CO 2 concentrations in the ambient air. - Abstract: We are presenting here a multi-isotope approach (δ 13 C and δ 18 O of CO 2 ; δ 13 C and δD of CH 4 ) to assess (i) the level(s) of methane oxidation during waste biodegradation and its migration through a landfill cover in Sonzay (France), and (ii) its contribution to the atmospheric CO 2 levels above the surface. The isotope approach is compared to the more conventional mass balance approach. Results from the two techniques are comparable and show that the CH 4 oxidation under the landfill cover is heterogenous, with low oxidation percentages in samples showing high biogas fluxes, which was expected in clay covers presenting fissures, through which CH 4 is rapidly transported. At shallow depth, more immobile biogas pockets show a higher level of CH 4 oxidation by the methanotrophic bacteria. δ 13 C of CO 2 samples taken at different heights (from below the cover up to 8 m above the ground level) were also used to identify and assess the relative contributions of its main sources both under the landfill cover and in the surrounding atmosphere.

Comparison of Landfill Methane Oxidation Measured Using Stable Isotope Analysis and CO2/CH4 Fluxes Measured by the Eddy Covariance Method

Science.gov (United States)

Xu, L.; Chanton, J.; McDermitt, D. K.; Li, J.; Green, R. B.

2015-12-01

Methane plays a critical role in the radiation balance and chemistry of the atmosphere. Globally, landfill methane emission contributes about 10-19% of the anthropogenic methane burden into the atmosphere. In the United States, 18% of annual anthropogenic methane emissions come from landfills, which represent the third largest source of anthropogenic methane emissions, behind enteric fermentation and natural gas and oil production. One uncertainty in estimating landfill methane emissions is the fraction of methane oxidized when methane produced under anaerobic conditions passes through the cover soil. We developed a simple stoichiometric model to estimate methane oxidation fraction when the anaerobic CO2 / CH4 production ratio is known, or can be estimated. The model predicts a linear relationship between CO2 emission rates and CH4 emission rates, where the slope depends on anaerobic CO2 / CH4 production ratio and the fraction of methane oxidized, and the intercept depends on non-methane-dependent oxidation processes. The model was tested using carbon dioxide emission rates (fluxes) and methane emission rates (fluxes) measured using the eddy covariance method over a one year period at the Turkey Run landfill in Georgia, USA. The CO2 / CH4 production ratio was estimated by measuring CO2 and CH4 concentrations in air sampled under anaerobic conditions deep inside the landfill. We also used a mass balance approach to independently estimate fractional oxidation based on stable isotope measurements (δ13C of methane) of gas samples taken from deep inside the landfill and just above the landfill surface. Results from the two independent methods agree well. The model will be described and methane oxidation will be discussed in relation to wind direction, location at the landfill, and age of the deposited refuse.

How much CO2 is trapped in carbonate minerals of a natural CO2 occurrence?

Science.gov (United States)

Király, Csilla; Szabó, Zsuzsanna; Szamosfalvi, Ágnes; Cseresznyés, Dóra; Király, Edit; Szabó, Csaba; Falus, György

2017-04-01

Carbon Capture and Storage (CCS) is a transitional technology to decrease CO2 emissions from human fossil fuel usage and, therefore, to mitigate climate change. The most important criteria of a CO2 geological storage reservoir is that it must hold the injected CO2 for geological time scales without its significant seepage. The injected CO2 undergoes physical and chemical reactions in the reservoir rocks such as structural-stratigraphic, residual, dissolution or mineral trapping mechanisms. Among these, the safest is the mineral trapping, when carbonate minerals such as calcite, ankerite, siderite, dolomite and dawsonite build the CO2 into their crystal structures. The study of natural CO2 occurrences may help to understand the processes in CO2 reservoirs on geological time scales. This is the reason why the selected, the Mihályi-Répcelak natural CO2 occurrence as our research area, which is able to provide particular and highly significant information for the future of CO2 storage. The area is one of the best known CO2 fields in Central Europe. The main aim of this study is to estimate the amount of CO2 trapped in the mineral phase at Mihályi-Répcelak CO2 reservoirs. For gaining the suitable data, we apply petrographic, major and trace element (microprobe and LA-ICP-MS) and stable isotope analysis (mass spectrometry) and thermodynamic and kinetic geochemical models coded in PHREEQC. Rock and pore water compositions of the same formation, representing the pre-CO2 flooding stages of the Mihályi-Répcelak natural CO2 reservoirs are used in the models. Kinetic rate parameters are derived from the USGS report of Palandri and Kharaka (2004). The results of petrographic analysis show that a significant amount of dawsonite (NaAlCO3(OH)2, max. 16 m/m%) precipitated in the rock due to its reactions with CO2 which flooded the reservoir. This carbonate mineral alone traps about 10-30 kg/m3 of the reservoir rock from the CO2 at Mihályi-Répcelak area, which is an

Isotope Exchange in Oxide Catalyst

Science.gov (United States)

Hess, Robert V.; Miller, Irvin M.; Schryer, David R.; Sidney, Barry D.; Wood, George M., Jr.; Hoyt, Ronald F.; Upchurch, Billy T.; Brown, Kenneth G.

1987-01-01

Replacement technique maintains level of CO2/18 in closed-cycle CO2 lasers. High-energy, pulsed CO2 lasers using rare chemical isotopes must be operated in closed cycles to conserve gas. Rare isotopes operated in closed cycles to conserve gas. Rare isotopes as CO2/18 used for improved transmission of laser beam in atmosphere. To maintain laser power, CO2 must be regenerated, and O2 concentration kept below few tenths of percent. Conditions achieved by recombining CO and O2.

Millennial-scale changes in atmospheric CO2 levels linked to the Southern Ocean carbon isotope gradient and dust flux

Science.gov (United States)

Ziegler, Martin; Diz, Paula; Hall, Ian R.; Zahn, Rainer

2013-06-01

The rise in atmospheric CO2 concentrations observed at the end of glacial periods has, at least in part, been attributed to the upwelling of carbon-rich deep water in the Southern Ocean. The magnitude of outgassing of dissolved CO2, however, is influenced by the biological fixation of upwelled inorganic carbon and its transfer back to the deep sea as organic carbon. The efficiency of this biological pump is controlled by the extent of nutrient utilization, which can be stimulated by the delivery of iron by atmospheric dust particles. Changes in nutrient utilization should be reflected in the δ13C gradient between intermediate and deep waters. Here we use the δ13C values of intermediate- and bottom-dwelling foraminifera to reconstruct the carbon isotope gradient between thermocline and abyssal water in the subantarctic zone of the South Atlantic Ocean over the past 360,000 years. We find millennial-scale oscillations of the carbon isotope gradient that correspond to changes in dust flux and atmospheric CO2 concentrations as reported from Antarctic ice cores. We interpret this correlation as a relationship between the efficiency of the biological pump and fertilization by dust-borne iron. As the correlation is exponential, we suggest that the sensitivity of the biological pump to dust-borne iron fertilization may be increased when the background dust flux is low.

CO{sub 2}-recycling by plants: how reliable is the carbon isotope estimation?

Energy Technology Data Exchange (ETDEWEB)

Siegwolf, R T.W.; Saurer, M [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Koerner, C [Basel Univ., Basel (Switzerland)

1997-06-01

In the study of plant carbon relations, the amount of the respiratory losses from the soil was estimated, determining the gradient of the stable isotope {sup 13}C with increasing plant canopy height. According to the literature 8-26% of the CO{sub 2} released in the forests by soil and plant respiratory processes are reassimilated (recycled) by photosynthesis during the day. Our own measurements however, which we conducted in grass land showed diverging results from no indicating of carbon recycling, to a considerable {delta}{sup 13}C gradient suggesting a high carbon recycling rate. The role of other factors, such as air humidity and irradiation which influence the {delta}{sup 13}C in a canopy as well, are discussed. (author) 3 figs., 4 refs.

A Multi-scale Approach for CO2 Accounting and Risk Analysis in CO2 Enhanced Oil Recovery Sites

Science.gov (United States)

Dai, Z.; Viswanathan, H. S.; Middleton, R. S.; Pan, F.; Ampomah, W.; Yang, C.; Jia, W.; Lee, S. Y.; McPherson, B. J. O. L.; Grigg, R.; White, M. D.

2015-12-01

Using carbon dioxide in enhanced oil recovery (CO2-EOR) is a promising technology for emissions management because CO2-EOR can dramatically reduce carbon sequestration costs in the absence of greenhouse gas emissions policies that include incentives for carbon capture and storage. This study develops a multi-scale approach to perform CO2 accounting and risk analysis for understanding CO2 storage potential within an EOR environment at the Farnsworth Unit of the Anadarko Basin in northern Texas. A set of geostatistical-based Monte Carlo simulations of CO2-oil-water flow and transport in the Marrow formation are conducted for global sensitivity and statistical analysis of the major risk metrics: CO2 injection rate, CO2 first breakthrough time, CO2 production rate, cumulative net CO2 storage, cumulative oil and CH4 production, and water injection and production rates. A global sensitivity analysis indicates that reservoir permeability, porosity, and thickness are the major intrinsic reservoir parameters that control net CO2 injection/storage and oil/CH4 recovery rates. The well spacing (the distance between the injection and production wells) and the sequence of alternating CO2 and water injection are the major operational parameters for designing an effective five-spot CO2-EOR pattern. The response surface analysis shows that net CO2 injection rate increases with the increasing reservoir thickness, permeability, and porosity. The oil/CH4 production rates are positively correlated to reservoir permeability, porosity and thickness, but negatively correlated to the initial water saturation. The mean and confidence intervals are estimated for quantifying the uncertainty ranges of the risk metrics. The results from this study provide useful insights for understanding the CO2 storage potential and the corresponding risks of commercial-scale CO2-EOR fields.

Analysis of transuranic isotopes in irradiated U3Si2-Al fuel by alpha spectrometry

International Nuclear Information System (INIS)

Dian Anggraini; Aslina B Ginting; Arif Nugroho

2011-01-01

Separation and analysis of transuranic isotopes (uranium and plutonium) in irradiated U 3 Si 2 -Al plate has been done. The analysis experiment includes sample preparation (i.e. cutting, dissolving, filtering, dilution), fission products separation from heavy elements, and analysis of transuranic isotopes content with alpha spectrometer. The separation of transuranic isotopes (U, Pu) was done by two methods, i.e. direct method and ion exchanger method with zeolite. Measurement of standard transuranic isotope (AMR 43) and standard U 3 O 8 was done in advance in order to determine percentage of 235 U recovery and detector efficiency. Recovery of 235 U isotope was obtained as much as 92,58%, which fulfills validation requirement, and the detector efficiency was 0.314. Based on the measured recovery and detector efficiency, the separation was done by direct electrodeposition method of 250 µL irradiated U 3 Si 2 -Al solution. The deposited sample was subsequently analyzed with alpha spectrometer. The separation with ion exchanger was done by mixing and shaking of 300 µL irradiated U 3 Si 2 -Al solution and 0.5 gram zeolite to separate the liquid phase from the solid phase. The liquid phase was electrodeposited and analyzed with alpha spectrometer. The analysis of transuranic isotopes (U, Pu) by both methods shows different results. Heavy element ( 238 U, 236 U, 234 U, 239 Pu) content obtained by direct method was 0.0525 g/g and 235 U= 0.0076 g/g, while the separation using zeolite ion exchanger resulted in Heavy element = 0.0253 g/g and 235 U = 0.0092 g/g. (author)

Exogenous CO2 in South American sparkling wine

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Leonardelli Susiane

2016-01-01

Full Text Available The sparkling wine production and consumption have increased significantly in the last years. With the increased demand appear the necessity to check the sparkling wine authenticity, because the practice of adding CO2 in sparkling wine is not allow. A way to control the carbonation process is through the determination of CO2 δ13C, because the sugar added during the second fermentation define the CO2 isotopic value, according to elaboration process. For this reason, the aim of this study was to evaluate the relationship between values of δ13C from still wines and sparkling wines, in order to set up limit values to exogenous carbonation control. Thirty-eight still wines elaborated by microvinification and 59 samples of commercial sparkling wines were analyzed, using an isotope ratio mass spectrometer (IRMS. The most negative value of natural δ13C from still wine found was − 24.7‰, it can be to estimate that lowest values are an indicative of industrial CO2 addition. Among the commercial sparkling wine from South America evaluated in this study, 10% from the samples showed signs of carbonation. Through this research was possible to establish limits of isotopic values to determine the presence of exogenous CO2.

Carbon Monoxide Stable Isotopes: Extraction Technique Development and Urban Atmospheric Analysis

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Vimont, Isaac Josef

We have developed an extraction system to analyze isotopes of carbon monoxide (CO). We then analyzed CO isotopes for two years at Indianapolis, IN, USA. These measurements were done at three towers, one of which measured incoming, background air into the city. We quantitatively removed the background signal and determined the urban CO mole fraction and isotopic enhancements. During the winter months, we constrained the isotopic signature and concluded that the majority of CO produced during the winter was produced by fossil fuel combustion. We found that the Indianapolis fossil fuel signature differed from that of studies done in Europe. Further, we performed a limited traffic study to look at CO isotopes from traffic. While this was not conclusive, it did support our hypothesis that a larger fraction of the Indianapolis vehicle fleet may have malfunctioning catalytic systems, which biases the isotopic results, particularly for delta18O. We used the wintertime fossil fuel isotopic signature to help constrain the summertime budget. It was hypothesized that a second source of CO was significant during the summer months. Oxidation of biogenically produced volatile organic compounds (BVOC's) was one possible source. Oxidized BVOC's were consistent with the changes between our winter and summer isotopic source signatures. We then used the isotopic signatures to determine that between zero and sixty percent of the summertime CO budget was produced from oxidized VOC's. This provided the first direct evidence of a larger percentage of urban CO being produced by oxidized VOC's.

Early deglacial Atlantic overturning decline and its role in atmospheric CO2 rise inferred from carbon isotopes (δ13C

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A. Schmittner

2015-02-01

Full Text Available The reason for the initial rise in atmospheric CO2 during the last deglaciation remains unknown. Most recent hypotheses invoke Southern Hemisphere processes such as shifts in midlatitude westerly winds. Coeval changes in the Atlantic meridional overturning circulation (AMOC are poorly quantified, and their relation to the CO2 increase is not understood. Here we compare simulations from a global, coupled climate–biogeochemistry model that includes a detailed representation of stable carbon isotopes (δ13C with a synthesis of high-resolution δ13C reconstructions from deep-sea sediments and ice core data. In response to a prolonged AMOC shutdown initialized from a preindustrial state, modeled δ13C of dissolved inorganic carbon (δ13CDIC decreases in most of the surface ocean and the subsurface Atlantic, with largest amplitudes (more than 1.5‰ in the intermediate-depth North Atlantic. It increases in the intermediate and abyssal South Atlantic, as well as in the subsurface Southern, Indian, and Pacific oceans. The modeled pattern is similar and highly correlated with the available foraminiferal δ13C reconstructions spanning from the late Last Glacial Maximum (LGM, ~19.5–18.5 ka BP to the late Heinrich stadial event 1 (HS1, ~16.5–15.5 ka BP, but the model overestimates δ13CDIC reductions in the North Atlantic. Possible reasons for the model–sediment-data differences are discussed. Changes in remineralized δ13CDIC dominate the total δ13CDIC variations in the model but preformed contributions are not negligible. Simulated changes in atmospheric CO2 and its isotopic composition (δ13CCO2 agree well with ice core data. Modeled effects of AMOC-induced wind changes on the carbon and isotope cycles are small, suggesting that Southern Hemisphere westerly wind effects may have been less important for the global carbon cycle response during HS1 than previously thought. Our results indicate that during the early deglaciation the AMOC decreased

Analysis of CO2, CO and HC emission reduction in automobiles

Science.gov (United States)

Balan, K. N.; Valarmathi, T. N.; Reddy, Mannem Soma Harish; Aravinda Reddy, Gireddy; Sai Srinivas, Jammalamadaka K. M. K.; Vasan

2017-05-01

In the present scenario, the emission from automobiles is becoming a serious problem to the environment. Automobiles, thermal power stations and Industries majorly constitute to the emission of CO2, CO and HC. Though the CO2 available in the atmosphere will be captured by oceans, grasslands; they are not enough to control CO2 present in the atmosphere completely. Also advances in engine and vehicle technology continuously to reduce the emission from engine exhaust are not sufficient to reduce the HC and CO emission. This work concentrates on design, fabrication and analysis to reduce CO2, CO and HC emission from exhaust of automobiles by using molecular sieve 5A of 1.5mm. In this paper, the details of the fabrication, results and discussion about the process are discussed.

Enrichment of 13C by chemical exchange between CO2 and amine carbamate in nonaqueous solvent

International Nuclear Information System (INIS)

Raica, Paula; Axente, D.

2009-01-01

Full text: Enrichment of 13 C by chemical exchange between CO 2 and amine carbamate in nonaqueous solvent has been mathematically modelled in two ways. The height equivalent to a theoretical plate and steady-state separation, based on the two models, have been obtained. If only the isotopic exchange between CO 2 gas and amine carbamate is considered, the model can estimate the process performance for pressures close to the atmospheric one and room temperature. For process analysis at pressures higher than atmospheric one and lower temperatures, a two-step model has been developed. Using the two models the effects of pressure increasing have been studied. At atmospheric pressure and 2M DNBA - methanol solution the isotope transfer rate is lower at 5 deg. C than at 25 deg. C. The isotope transfer is supported by pressure increasing according the increase of the CO 2 concentration in the amine solution. A lower temperature determines also an increase in the concentration of dissolved CO 2 and, for this reason, at 5 deg.C and higher pressures the isotope exchange reaction rate is higher than at 25 deg. C, HETP being lower with more than 100% at 5 deg. C than at 25 deg. C. (authors)

Influence of local emissions on concentration and isotopic composition of trace gases (CO2 and CH4) under strong anthropopression: A case study from Krakow, southern Poland

International Nuclear Information System (INIS)

Florkowski, T.; Korus, A.; Kuc, T.; Lasa, J.; Necki, J.M.; Zimnoch, M.

2002-01-01

Full text: Measurements of the isotopic composition of carbon dioxide and methane together with their concentrations in the atmosphere, yield useful information on the contribution of anthropogenic sources to regional budgets of these gases and their seasonal changes. Observed correlation between isotopic composition and inverse concentration of these gases is used for estimation of mean isotopic composition of the local source. Monitoring of atmospheric CO 2 has been initiated in Krakow in 1982. The sampling point is located in a polluted urban area with strong contribution of anthropogenic gases originating both from local sources (coal burning, car traffic, leakages from city gas network, landfills) and large distant emitters - industrial district located ca. 80 km to the west from Krakow (Silesia district). Quasi-continuous measurements of CO 2 , and CH 4 concentrations in the low atmosphere are performed using gas chromatographic method. For isotope measurements, the atmospheric CO 2 is continuously sampled by sorption on molecular sieve in be-weekly intervals and radiocarbon concentration is measured by liquid scintillation spectrometer, while δ 13 C is determined by isotope ratio mass spectrometer. Measurement error (1σ for single measurement) is in the order of 0.1 ppm for CO 2 concentration, ±8 per mille for δ 14 C, and ± 0.1 per mille for δ 13 C. In 1994, a new station for regular observations of greenhouse gases in lower atmosphere was set up in the High Tatra mountains, at Kasprowy Wierch (49 deg. N, 20 deg. E, 1980 m a.s.l., 300 m above the tree line). Kasprowy Wierch, with only small influences from local sources of trace gases can be considered as a reference station for this region of Poland. The record of CO 2 and CH 4 concentration and their isotope composition obtained at Kasprowy Wierch is considered as a background level for Krakow observations. The presented study was aimed at better characterisation and quantification of the local

Carbon-Isotopic Analysis of Individual Pigments by HPLC-Moving Wire-IRMS

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Sessions, A. L.; Keely, B. J.; Hayes, J. M.

2003-12-01

We have developed a method for directly analyzing the carbon isotope ratios of individual pigments, including chlorophyll (chl) and its derivatives, by coupling a high-performance liquid chromatograph (HPLC) to an isotope-ratio mass spectrometer (IRMS) via a novel `moving-wire' interface. Pigments were separated on a reversed-phase C18 column, using a binary gradient modified from Airs et al. (2001, J. Chrom. A 917, 167-177). The HPLC effluent was dried onto a continuously-spooling nickel wire, and the involatile sample residue was combusted to CO2 and transferred to the IRMS for isotopic analysis. Replicate analyses of a standard solution yield precision for delta13C of better than 0.2‰ for injections containing ~5 μ g of chl-a. A five-fold improvement in sensitivity should be attainable using capillary HPLC to further reduce solvent volumes. The biomarker potential of tetrapyrrole pigments, combined with the geochemical information recorded by isotopic compositions, makes this combination a potent tool for biogeochemical studies. As a demonstration, we analyzed chlorophyll degradation products in sediments from a lake and a salina. First, compounds derived from bacteriochlorophylls (bchl)-c and -d were extracted from sediment cores taken at Kirisjes Lake (Larsmann Hills, Antarctica). These pigments are products of green sulfur bacteria and indicate the presence of an anoxic photic zone. The δ 13C values of bchl-related compounds are near -25‰ . Using published fractionations for Chlorobium species to extrapolate, dissolved CO2 in Kirisjes Lake probably had a δ 13C value of -12 to -21‰ and was strongly influenced by the recycling of organic carbon, possibly including methane. Second, compounds derived from chl-a, bchl-c, and bchl-d were isolated from sediments taken below a living microbial mat in the hypersaline les Salines de la Trinital (South Catalonia, Spain). The sediments contain visible remnants of past microbial mats and pigment distributions

Isotopic Discrimination During Leaf Litter Decomposition

Science.gov (United States)

Ngao, J.; Rubino, M.

2006-12-01

Methods involving stable isotopes have been successfully applied since decades in various research fields. Tracing 13C natural abundance in ecosystem compartments greatly enhanced the understanding of the C fluxes in the plant-soil-atmosphere C exchanges when compartments present different C isotopic signatures (i.e. atmospheric CO2 vs photosynthetic leaves, C3 vs C4; etc.). However, the assumption that no isotopic discrimination occurs during respiration is commonly made in numbers of C isotope-based ecological studies. Furthermore, verifications of such assumption are sparse and not enough reliable. The aim of our study is to assess the potential isotopic discrimination that may occur during litter decomposition. Leaf litter from an Arbutus unedo (L.) stand (Tolfa, Italy) was incubated in 1L jars, under constant laboratory conditions (i.e. 25 ° C and 135% WC). During the entire incubation period, gravimetric mass loss, litter respiration rates and the isotopic composition of respired CO2 are monitored at regular intervals. Data from 7 months of incubation will be presented and discussed. After two months, the litter mass loss averaged 16% of initial dry mass. During the same time-period, the respiration rate decreased significantly by 58% of the initial respiration rate. Isotopic compositions of respired CO2 ranged between -27.95‰ and - 25.69‰. Mean values did not differ significantly among the sampling days, in spite of an apparent enrichment in 13C of respired CO2 with time. The significance of these isotopic enrichment will be determined at a longer time scale. They may reveal both/either a direct microbial discrimination during respiration processes and/or a use of different litter compounds as C source along time. Further chemical and compound-specific isotopic analysis of dry matter will be performed in order to clarify these hypotheses. This work is part of the "ALICE" project, funded by the European Union's Marie Curie Fellowship Actions that aims to

Silicon isotope separation utilizing infrared multiphoton dissociation of Si2F6 irradiated with two-color CO2 laser light

International Nuclear Information System (INIS)

Yokoyama, Atsushi; Ohba, Hironori; Hashimoto, Masashi; Arai, Shigeyoshi

2002-01-01

Silicon isotope separation has been done by utilizing the Infrared Multiphoton Dissociation (IRMPD) of Si 2 F 6 irradiated with two-color CO 2 laser lights. The two-color excitation method improved the separation efficiency keeping the high enrichment factors. For example, 99.74% of 28 Si was obtained at 49.63% dissociation of Si 2 F 6 after the simultaneous irradiation of 200 pulses with 966.23 cm -1 photons (0.084 J/cm 2 ) and 954.55 cm -1 photons (0.658 J/cm 2 ), while 2000 pulses were needed to obtain 99.35% of 28 Si at 35.6% dissociation in the case of only one-color irradiation at 954.55 cm -1 (0.97 J/cm 2 ). (author)

A new method for the determination of NO2 traces using isotope dilution and mass spectrometry analysis

International Nuclear Information System (INIS)

Stevens, C.; Barat, F.; Nguyen Nghi, H.

1975-01-01

A new method for the determination of NO 2 traces, in the order of 1ppb (10 -9 ), in atmosphere and stratosphere is described. The method consists in an isotope dilution technique using 15 NO 2 , followed by the reduction of NO 2 to N 2 and a mass spectrometry analysis. A known amount of 15 NO 2 is added to the air samples. Then, NO 2 is separated from H 2 O, HNO 3 , CO 2 and N 2 O and transferred to a SiO 2 reactor by trapping at -196 deg C. In the reactor NO 2 is reduced to N 2 by reaction with electrolytic Cu heated at 580 deg C. The mass 29/mass 30 ratio corresponding to 15 N 14 N and 15 N 15 N is determined by mass spectrometry. The sensitivity of the method depends on the contamination introduced during the analysis of the sample (reagents, separation and measuring devices). The contamination is reproducible and in the order of 4.5+-0.5 10 -2 mm 3 N 2 [fr

Progress in the analysis and interpretation of N2O isotopes: Potential and future challenges

Science.gov (United States)

Mohn, Joachim; Tuzson, Béla; Zellweger, Christoph; Harris, Eliza; Ibraim, Erkan; Yu, Longfei; Emmenegger, Lukas

2017-04-01

In recent years, research on nitrous oxide (N2O) stable isotopes has significantly advanced, addressing an increasing number of research questions in biogeochemical and atmospheric sciences [1]. An important milestone was the development of quantum cascade laser based spectroscopic devices [2], which are inherently specific for structural isomers (15N14N16O vs. 14N15N16O) and capable to collect real-time data with high temporal resolution, complementary to the well-established isotope-ratio mass-spectrometry (IRMS) method. In combination with automated preconcentration, optical isotope ratio spectroscopy (OIRS) has been applied to disentangle source processes in suburban, rural and pristine environments [e.g. 3, 4]. Within the European Metrology Research Programme (EMRP) ENV52 project "Metrology for high-impact greenhouse gases (HIGHGAS)", the quality of N2O stable isotope analysis by OIRS, the comparability between laboratories, and the traceability to the international isotope ratio scales have been addressed. An inter-laboratory comparison between eleven IRMS and OIRS laboratories, organised within HIGHGAS, indicated limited comparability for 15N site preference, i.e. the difference between 15N abundance in central (N*NO) and end (*NNO) position [5]. In addition, the accuracy of the NH4NO3 decomposition reaction, which provides the link between 15N site preference and the international 15N/14N scale, was found to be limited by non-quantitative NH4NO3 decomposition in combination with substantially different isotope enrichment factors for both nitrogen atoms [6]. Results of the HIGHGAS project indicate that the following research tasks have to be completed to foster research on N2O isotopes: 1) develop improved techniques to link the 15N and 18O abundance and the 15N site preference in N2O to the international stable isotope ratio scales; 2) provide N2O reference materials, pure and diluted in an air matrix, to improve inter-laboratory compatibility. These tasks

Isotopic evidence for the infiltration of mantle and metamorphic CO2-H2O fluids from below in faulted rocks from the San Andreas Fault System

Energy Technology Data Exchange (ETDEWEB)

Pili, E.; Kennedy, B.M.; Conrad, M.E.; Gratier, J.-P.

2010-12-15

To characterize the origin of the fluids involved in the San Andreas Fault (SAF) system, we carried out an isotope study of exhumed faulted rocks from deformation zones, vein fillings and their hosts and the fluid inclusions associated with these materials. Samples were collected from segments along the SAF system selected to provide a depth profile from upper to lower crust. In all, 75 samples from various structures and lithologies from 13 localities were analyzed for noble gas, carbon, and oxygen isotope compositions. Fluid inclusions exhibit helium isotope ratios ({sup 3}He/{sup 4}He) of 0.1-2.5 times the ratio in air, indicating that past fluids percolating through the SAF system contained mantle helium contributions of at least 35%, similar to what has been measured in present-day ground waters associated with the fault (Kennedy et al., 1997). Calcite is the predominant vein mineral and is a common accessory mineral in deformation zones. A systematic variation of C- and O-isotope compositions of carbonates from veins, deformation zones and their hosts suggests percolation by external fluids of similar compositions and origin with the amount of fluid infiltration increasing from host rocks to vein to deformation zones. The isotopic trend observed for carbonates in veins and deformation zones follows that shown by carbonates in host limestones, marbles, and other host rocks, increasing with increasing contribution of deep metamorphic crustal volatiles. At each crustal level, the composition of the infiltrating fluids is thus buffered by deeper metamorphic sources. A negative correlation between calcite {delta}{sup 13}C and fluid inclusion {sup 3}He/{sup 4}He is consistent with a mantle origin for a fraction of the infiltrating CO{sub 2}. Noble gas and stable isotope systematics show consistent evidence for the involvement of mantle-derived fluids combined with infiltration of deep metamorphic H{sub 2}O and CO{sub 2} in faulting, supporting the involvement of

Inter annual variability of the global carbon cycle (1992-2005) inferred by inversion of atmospheric CO2 and δ13CO2 measurements

International Nuclear Information System (INIS)

Rayner, P.J.; Pickett-Heaps, C.; Law, R.M.; Allison, C.E.; Francey, R.J.; Trudinger, C.M.

2008-01-01

We present estimates of the surface sources and sinks of CO 2 for 1992 - 2005 deduced from atmospheric inversions. We use atmospheric CO 2 records from 67 sites and 10 δ 13 CO 2 records. We use two atmospheric models to increase the robustness of the results. The results suggest that inter annual variability is dominated by the tropical land. Statistically significant variability in the tropical Pacific supports recent ocean modeling studies in that region. The northern land also shows significant variability. In particular, there is a large positive anomaly in 2003 in north Asia, which we associate with anomalous biomass burning. Results using δ 13 CO 2 and CO 2 are statistically consistent with those using only CO 2 , suggesting that it is valid to use both types of data together. An objective analysis of residuals suggests that our treatment of uncertainties in CO 2 is conservative, while those for δ 13 CO 2 are optimistic, highlighting problems in our simple isotope model. Finally, δ 13 CO 2 measurements offer a good constraint to nearby land regions, suggesting an ongoing value in these measurements for studies of inter annual variability. (authors)

Biometrics from the carbon isotope ratio analysis of amino acids in human hair.

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Jackson, Glen P; An, Yan; Konstantynova, Kateryna I; Rashaid, Ayat H B

2015-01-01

This study compares and contrasts the ability to classify individuals into different grouping factors through either bulk isotope ratio analysis or amino-acid-specific isotope ratio analysis of human hair. Using LC-IRMS, we measured the isotope ratios of 14 amino acids in hair proteins independently, and leucine/isoleucine as a co-eluting pair, to provide 15 variables for classification. Multivariate analysis confirmed that the essential amino acids and non-essential amino acids were mostly independent variables in the classification rules, thereby enabling the separation of dietary factors of isotope intake from intrinsic or phenotypic factors of isotope fractionation. Multivariate analysis revealed at least two potential sources of non-dietary factors influencing the carbon isotope ratio values of the amino acids in human hair: body mass index (BMI) and age. These results provide evidence that compound-specific isotope ratio analysis has the potential to go beyond region-of-origin or geospatial movements of individuals-obtainable through bulk isotope measurements-to the provision of physical and characteristic traits about the individuals, such as age and BMI. Further development and refinement, for example to genetic, metabolic, disease and hormonal factors could ultimately be of great assistance in forensic and clinical casework. Copyright © 2014 Forensic Science Society. Published by Elsevier Ireland Ltd. All rights reserved.

Application of stable isotope measurements and microbiological analysis for detecting methanogenic activity in a temperate forest wetland

Science.gov (United States)

Itoh, M.; Katsuyama, C.; Kondo, N.; Ohte, N.; Kato, K.

2009-12-01

Generally, forest soils act as a sink for methane (CH4). However, wetlands in riparian zones are recently reported to be “hot spots” of CH4 emissions, especially in forests under a humid climate. To understand how environmental conditions (i.e. hydrological and/or geomorphic condition) control on CH4 production, we investigated both methanogenic pathways (CO2/H2 reduction and acetate fermentation) and metahanogenic microbial communities in a wetland in a temperate forest catchment, central Japan. We used stable carbon isotopic analysis for detecting change in methanogenic pathways, and applied microbiological analysis for understanding the structure of methanogenic community. CH4 emission rates in wetland were strongly dependent on soil temperatures, and were highest in summer and lowest in winter. δ13CO2 increased with CH4 production in every summer, suggesting preferential use of 12CO2 as substrate for CO2/H2 reduction methanogenesis during high CH4 production period. δ13CH4 also increased in summer with δ13CO2. δ13CH4 changed more wildly than δ13CO2 did in summer with normal precipitation when CH4 production was strongly activated under high temperature and high groundwater table condition. This indicates increase in acetoclastic methanogenesis under hot and wet condition, considering that acetclastic methnogens produce heavier CH4 than that from CO2/H2 reducing pathway. Methanogen community composition estimated by cloning and sequence analyses implied that both acetoclastic and CO2/H2 reducing methanogens prevailed in wetland soil sampled in summer. This was consistent with the results of isotope measuremaents. Our results contribute to understand fully how the CH4 production changes with environmental conditions, with considering the activities of both main methanogenic pathway (from CO2 and acetate).

C4 plant isotopic composition ((delta)13C) evidence for urban CO2 pollution in the city of Cotonou, Benin (West Africa)

International Nuclear Information System (INIS)

Kelome, Nelly C.; Leveque, Jean; Andreux, Francis; Milloux, Marie-Jeanne; Oyede, Lucien-Marc

2006-01-01

The carbon isotopic composition ((delta) 13 C) of plants can reveal the isotopic carbon content of the atmosphere in which they develop. The (delta) 13 C values of air and plants depend on the amount of atmospheric fossil fuel CO 2 , which is chiefly emitted in urban areas. A new indicator of CO 2 pollution is tested using the (delta) 13 C variation in a C 4 grass: Eleusine indica. A range of about 4%% delta units was observed at different sites in Cotonou, the largest city in the Republic of Benin. The highest (delta) 13 C values, from -12%% to -14%%, were found in low traffic zones; low (delta) 13 C values, from -14%% to -16%%, 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 (delta) 13 C values was observed over a four-year monitoring period. This decrease was correlated with increasing vehicle traffic. The (delta) 13 C dataset and the corresponding geographical database were used to map and define zones of high and low 13 C-depleted CO 2 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 CO 2 emissions occurred in the north, the east and the center, providing evidence of intense anthropogenic activity related to industry and transportation. (author)

The Interrelationship of pCO2, Soil Moisture Content, and Biomass Fertilization Expressed in the Carbon Isotope Signature of C3 Plant Tissue

Science.gov (United States)

Schubert, B.; Jahren, A. H.

2017-12-01

Hundreds of chamber and field experiments have shown an increase in C3 plant biomass in response to elevated atmospheric carbon dioxide (pCO2); however, secondary water and nutrient deficits are thought to limit this response. Some have hypothesized that secondary limitation might be self-alleviating under elevated pCO2 as greater root biomass imparts enhanced access to water and nutrients. Here we present results of growth chamber experiments designed to test this hypothesis: we grew 206 Arabidopsis thaliana plants within 5 growth chambers, each set at a different level of pCO2: 390, 685, 1075, 1585, and 2175 ppmv. Within each growth chamber, soil moisture content (θm) was maintained across a spectrum: 1.50, 0.83, 0.44, and 0.38 g g-1. After 3 weeks of total growth, tissues were analyzed for both biomass and net carbon isotope discrimination (Δ13C) value. From these values, we calculated Δresidual, which represents the residual effect of water stress after subtraction of the effect of pCO2 due to photorespiration. Across the full range of moisture content, Δresidual displayed a significant 2.5‰ increase with increasing pCO2. This further implies a 0.1 unit increase in ci/ca, consistent with decreased water stress at elevated pCO2. The influence of CO2 fertilization on the alleviation of water stress was further evidenced in a positive correlation between percent biomass change and Δresidual, such that a doubling of plant biomass yielded a 1.85‰ increase in carbon isotope discrimination. In addition to providing new insight into water uptake in plants growing under elevated carbon dioxide, these data underscore the importance of separating the effects of increased pCO2 (via photorespiration) and altered ci/ca (via stomatal conductance) when considering changes in the Δ13C value of C3 land plants during the Anthropocene, or across any geological period that includes a marked change in global carbon cycling.

Faults as Windows to Monitor Gas Seepage: Application to CO2 Sequestration and CO2-EOR

Directory of Open Access Journals (Sweden)

Ronald W. Klusman

2018-03-01

Full Text Available Monitoring of potential gas seepage for CO2 sequestration and CO2-EOR (Enhanced Oil Recovery in geologic storage will involve geophysical and geochemical measurements of parameters at depth and at, or near the surface. The appropriate methods for MVA (Monitoring, Verification, Accounting are needed for both cost and technical effectiveness. This work provides an overview of some of the geochemical methods that have been demonstrated to be effective for an existing CO2-EOR (Rangely, CA, USA and a proposed project at Teapot Dome, WY, USA. Carbon dioxide and CH4 fluxes and shallow soil gas concentrations were measured, followed by nested completions of 10-m deep holes to obtain concentration gradients. The focus at Teapot Dome was the evaluation of faults as pathways for gas seepage in an under-pressured reservoir system. The measurements were supplemented by stable carbon and oxygen isotopic measurements, carbon-14, and limited use of inert gases. The work clearly demonstrates the superiority of CH4 over measurements of CO2 in early detection and quantification of gas seepage. Stable carbon isotopes, carbon-14, and inert gas measurements add to the verification of the deep source. A preliminary accounting at Rangely confirms the importance of CH4 measurements in the MVA application.

Paired carbon stable-isotope records for the Cenomanian Stage (100.5 -93.9 Ma): correlation tool and Late Cretaceous pCO2 record?

Science.gov (United States)

Jarvis, Ian; Gröcke, Darren; Laurin, Jiří; Selby, David; Roest-Ellis, Sascha; Miles, Andrew; Lignum, John; Gale, Andrew; Kennedy, Jim

2016-04-01

- and long-term trends. Potential causes of the similarities and differences are examined, and it is concluded that major deviations of the paired isotope trends offer insights into long-term atmospheric pCO2 variation. The osmium 187Os/188Os isotope stratigraphy of the MCEI and OAE2 intervals provides evidence of varying volcanic CO2 input, in-part driving climate change. Spectral analyses of the δ13Corg time series reveals a strong ~100 kyr short eccentricity signal throughout the Cenomanian, with well-expressed ~40 kyr obliquity and ~20 kyr precession cycles in some intervals. A 400 kyr long eccentricity cycle is recorded in sedimentation rate changes and amplitude modulation of the 100 kyr cycle. The relative spacing of events, and comparison with the latest orbital solution La2011, further suggest that MCE I and OAE2 coincided with nodes in the ~2.2-Myr eccentricity modulation.

The isotopic record of Northern Hemisphere atmospheric carbon monoxide since 1950: implications for the CO budget

Directory of Open Access Journals (Sweden)

Z. Wang

2012-05-01

Full Text Available We present a 60-year record of the stable isotopes of atmospheric carbon monoxide (CO from firn air samples collected under the framework of the North Greenland Eemian Ice Drilling (NEEM project. CO concentration, δ¹³C, and δ¹⁸O of CO were measured by gas chromatography/isotope ratio mass spectrometry (gc-IRMS from trapped gases in the firn. We applied LGGE-GIPSA firn air models (Witrant et al., 2011 to correlate gas age with firn air depth and then reconstructed the trend of atmospheric CO and its stable isotopic composition at high northern latitudes since 1950. The most probable firn air model scenarios show that δ¹³C decreased slightly from −25.8‰ in 1950 to −26.4‰ in 2000, then decreased more significantly to −27.2‰ in 2008. δ¹⁸O decreased more regularly from 9.8‰ in 1950 to 7.1‰ in 2008. Those same scenarios show CO concentration increased gradually from 1950 and peaked in the late 1970s, followed by a gradual decrease to present day values (Petrenko et al., 2012. Results from an isotope mass balance model indicate that a slight increase, followed by a large reduction, in CO derived from fossil fuel combustion has occurred since 1950. The reduction of CO emission from fossil fuel combustion after the mid-1970s is the most plausible mechanism for the drop of CO concentration during this time. Fossil fuel CO emissions decreased as a result of the implementation of catalytic converters and the relative growth of diesel engines, in spite of the global vehicle fleet size having grown several fold over the same time period.

Co-deposition of palladium with hydrogen isotopes

International Nuclear Information System (INIS)

Dash, J.; Ambadkar, A.

2006-01-01

Palladium was co-deposited with hydrogen isotopes on a Pd cathode. This resulted in enhanced production of excess thermal power. After electrolysis the Pd Lβ/ Lα ratio was found to be increased in characteristic X-ray spectra from localized, microscopic areas on the surface of the Pd cathode. This suggests the possibility that appreciable amounts of silver are present in these areas. (authors)

Isotope dilution analysis

Energy Technology Data Exchange (ETDEWEB)

Fudge, A.

1978-12-15

The following aspects of isotope dilution analysis are covered in this report: fundamental aspects of the technique; elements of interest in the nuclear field, choice and standardization of spike nuclide; pre-treatment to achieve isotopic exchange and chemical separation; sensitivity; selectivity; and accuracy.

CO self-shielding as the origin of oxygen isotope anomalies in the early solar nebula.

Science.gov (United States)

Lyons, J R; Young, E D

2005-05-19

The abundances of oxygen isotopes in the most refractory mineral phases (calcium-aluminium-rich inclusions, CAIs) in meteorites have hitherto defied explanation. Most processes fractionate isotopes by nuclear mass; that is, 18O is twice as fractionated as 17O, relative to 16O. In CAIs 17O and 18O are nearly equally fractionated, implying a fundamentally different mechanism. The CAI data were originally interpreted as evidence for supernova input of pure 16O into the solar nebula, but the lack of a similar isotope trend in other elements argues against this explanation. A symmetry-dependent fractionation mechanism may have occurred in the inner solar nebula, but experimental evidence is lacking. Isotope-selective photodissociation of CO in the innermost solar nebula might explain the CAI data, but the high temperatures in this region would have rapidly erased the signature. Here we report time-dependent calculations of CO photodissociation in the cooler surface region of a turbulent nebula. If the surface were irradiated by a far-ultraviolet flux approximately 10(3) times that of the local interstellar medium (for example, owing to an O or B star within approximately 1 pc of the protosun), then substantial fractionation of the oxygen isotopes was possible on a timescale of approximately 10(5) years. We predict that similarly irradiated protoplanetary disks will have H2O enriched in 17O and 18O by several tens of per cent relative to CO.

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

Science.gov (United States)

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.

[Differences and sources of CO2 concentration, carbon and oxygen stable isotope composition between inside and outside of a green space system and influencing factors in an urban area].

Science.gov (United States)

Sun, Shou-jia; Meng, Ping; Zhang, Jin-song; Shu, Jian-hua; Zheng, Ning

2015-10-01

The off-axis integrated cavity output spectroscopy technique was used to measure air CO2 concentration, stable carbon (δ13C) and oxygen (δ18C) isotope ratios on the Fourth Ring Road (FRR) and in the green space system of Beijing Institute of Landscape Architecture (BILA) in summer and winter seasons. The variations of CO2 concentration, δ13C value, δ18C value and the differences of them between the FRR and the BILA, which were correlated with traffic volume and meteorological factors, were analyzed at half-hour timescale. The results showed that traffic volume on the FRR was large both in summer and winter with obvious morning and evening rush hours, and more than 150 thousands vehicles were observed everyday during the observation periods. Diurnal variation of the CO2 concentration showed a two-peak curve both on the FRR and in the green space system of the BILA. In contrast, diurnal variation of δ13C value was a two-trough curve while diurnal variation of δ18O value was a single-trough curve. The differences of CO2 concentration, δ13C value and δ18O value between the FRR and the green space system of BILA in summer were greater than those in winter. The carbon isotope partitioning results showed that in summer vehicle exhaust contributed 64.9% to total atmospheric CO2 of the FRR during measurement time, while heterotrophic respiration contributed 56.3% to total atmospheric CO2 of the green space system in BILA. However, in winter atmospheric CO2 from both the FRR and green space system mostly came from vehicle exhaust. Stepwise regression analysis indicated that differences of CO2 concentration between the FRR and green space system were significantly related to vehicle volume and solar radiation at half-hour timescale, while solar radiation and relative humidity were the main meteorological factors causing δ13 and δ18O differences between the FRR and green space system. Plants in the green space system strongly assimilated CO2 from fossil fuel burning

Calcium and titanium isotopes in refractory inclusions from CM, CO, and CR chondrites

Science.gov (United States)

Kööp, Levke; Davis, Andrew M.; Krot, Alexander N.; Nagashima, Kazuhide; Simon, Steven B.

2018-05-01

Previous studies have shown that CV and CM chondrites incorporated Ca, Al-rich inclusions (CAIs) with different isotopic characteristics, which may represent different snapshots in the isotopic evolution of the early Solar System. To better understand how the isotopic characteristics of CAIs vary between different chondrite groups, we have studied calcium and titanium isotopes in CAIs from CM, CO, and CR chondrites. We show that all three chondrite groups contain CAIs with large anomalies in 48Ca and/or 50Ti (10s of ‰ or 100s of ε-units) as well as CAIs with no anomalies resolved beyond measurement uncertainties. Isotopically, the anomalous CO and CR chondrite CAIs resemble the platy hibonite crystals (PLACs) from CM chondrites, but they are more mineralogically complex. The new data are consistent with the well-established mutual exclusivity relationship between incorporation of 26Al and the presence of large anomalies in 48Ca and 50Ti. The two highly anomalous CO chondrite CAIs have correlated anomalies in 46Ti and 50Ti, while most other highly anomalous CAIs do not. This result could indicate that the reservoir with coupled 46Ti and 50Ti that was sampled by bulk meteorites and CV chondrite CAIs already existed before arrival and/or homogeneous distribution of 26Al in the protoplanetary disk. Among the studied CM chondrite CAIs are ten spinel-hibonite inclusions (SHIBs) with known oxygen isotopic compositions. Our results show that these objects sampled a reservoir that was well-mixed in oxygen, calcium, and titanium isotopes. We further show that SHIBs tend to be slightly enriched in the heavy calcium isotopes, suggesting that their formation history was different from CV chondrite CAIs.

Analysis of a New Liquefaction Combined with Desublimation System for CO2 Separation Based on N2/CO2 Phase Equilibrium

Directory of Open Access Journals (Sweden)

Wenchao Yang

2015-09-01

Full Text Available Cryogenic CO2 capture is considered as a promising CO2 capture method due to its energy saving and environmental friendliness. The phase equilibrium analysis of CO2-mixtures at low temperature is crucial for the design and operation of a cryogenic system because it plays an important role in analysis of recovery and purity of the captured CO2. After removal of water and toxic gas, the main components in typical boiler gases are N2/CO2. Therefore, this paper evaluates the reliabilities of different cubic equations of state (EOS and mixing rules for N2/CO2. The results show that Peng-Robinson (PR and Soave-Redlich-Kwong (SRK fit the experimental data well, PR combined with the van der Waals (vdW mixing rule is more accurate than the other models. With temperature decrease, the accuracy of the model improves and the deviation of the N2 vapor fraction is 0.43% at 220 K. Based on the selected calculation model, the thermodynamic properties of N2/CO2 at low temperature are analyzed. According to the results, a new liquefaction combined with a desublimation system is proposed. The total recovery and purity of CO2 production of the new system are satisfactory enough for engineering applications. Additionally, the total energy required by the new system to capture the CO2 is about 3.108 MJ·kg−1 CO2, which appears to be at least 9% lower than desublimation separation when the initial concentration of CO2 is 40%.

Analytical developments in the measurements of boron, nitrate, phosphate and sulphate isotopes and case examples of discrimination of nitrogen and sulphur sources in pollution studies

International Nuclear Information System (INIS)

Aggarwal, J.; Sheppard, D.S.; Robinson, B.W.

1998-01-01

Methods are documented for the analysis of B isotopes, O and N isotopes in nitrates. B isotopes can be measured by negative ion thermal ionisation mass spectrometry. Nitrate is recovered from groundwaters by ion exchange and the resulting silver nitrate combusted for stable isotope gas analysis. Oxygen isotope analysis of phosphates can be determined by generating and analysing CO 2 gas from the combustion of silver phosphate produced from aqueous samples. Sulphate in ground and surface waters can be separated and concentrated by ion exchange and precipitated as barium sulphate. This is reacted with graphite to yield CO 2 and CO, the latter being spark discharged to CO 2 and the total CO 2 measured for oxygen isotope analysis. Barium sulphide from this reaction is converted to silver sulphide which is reacted with cuprous oxide to give SO 2 gas for sulphur isotope measurements. A case study of the semi-rural Manakau area in New Zealand was conducted to see if nitrate isotopes could be used to detect the source of nitrate contamination (groundwater nitrate - 3- N). Nitrogen isotope (+4 to +12 per mille) coupled with oxygen isotope measurements (+5 to +9 per mille) demonstrated that the nitrogen is not sources from fertilisers but from some combination of septic tank and animal waste. For the case study of sulphate isotope use, sulphur and oxygen isotopic compositions of sulphate in river and lake water from seven major catchments of New Zealand were determined. The isotope analyses have allowed the distinction between natural (geological, geothermal and volcanic) and anthropogenic (fertiliser) sulphur sources. (author)

Analysis of aromatic catabolic pathways in Pseudomonas putida KT 2440 using a combined proteomic approach: 2-DE/MS and cleavable isotope-coded affinity tag analysis.

Science.gov (United States)

Kim, Young Hwan; Cho, Kun; Yun, Sung-Ho; Kim, Jin Young; Kwon, Kyung-Hoon; Yoo, Jong Shin; Kim, Seung Il

2006-02-01

Proteomic analysis of Pseudomonas putida KT2440 cultured in monocyclic aromatic compounds was performed using 2-DE/MS and cleavable isotope-coded affinity tag (ICAT) to determine whether proteins involved in aromatic compound degradation pathways were altered as predicted by genomic analysis (Jiménez et al., Environ Microbiol. 2002, 4, 824-841). Eighty unique proteins were identified by 2-DE/MS or MS/MS analysis from P. putida KT2440 cultured in the presence of six different organic compounds. Benzoate dioxygenase (BenA, BenD) and catechol 1,2-dioxygenase (CatA) were induced by benzoate. Protocatechuate 3,4-dixoygenase (PcaGH) was induced by p-hydroxybenzoate and vanilline. beta-Ketoadipyl CoA thiolase (PcaF) and 3-oxoadipate enol-lactone hydrolase (PcaD) were induced by benzoate, p-hydroxybenzoate and vanilline, suggesting that benzoate, p-hydroxybenzoate and vanilline were degraded by different dioxygenases and then converged in the same beta-ketoadipate degradation pathway. An additional 110 proteins, including 19 proteins from 2-DE analysis, were identified by cleavable ICAT analysis for benzoate-induced proteomes, which complemented the 2-DE results. Phenylethylamine exposure induced beta-ketoacyl CoA thiolase (PhaD) and ring-opening enzyme (PhaL), both enzymes of the phenylacetate (pha) biodegradation pathway. Phenylalanine induced 4-hydroxyphenyl-pyruvate dioxygenase (Hpd) and homogentisate 1,2-dioxygenase (HmgA), key enzymes in the homogentisate degradation pathway. Alkyl hydroperoxide reductase (AphC) was induced under all aromatic compounds conditions. These results suggest that proteome analysis complements and supports predictive information obtained by genomic sequence analysis.

The effect of carbonic anhydrase on the kinetics and equilibrium of the oxygen isotope exchange in the CO2-H2O system: Implications for δ18O vital effects in biogenic carbonates

Science.gov (United States)

Uchikawa, Joji; Zeebe, Richard E.

2012-10-01

Interpretations of the primary paleoceanographic information recorded in stable oxygen isotope values (δ18O) of biogenic CaCO3 can be obscured by disequilibrium effects. CaCO3 is often depleted in 18O relative to the δ18O values expected for precipitation in thermodynamic equilibrium with ambient seawater as a result of vital effects. Vital effects in δ18O have been explained in terms of the influence of fluid pH on the overall δ18O of the sum of dissolved inorganic carbon (DIC) species (often referred to as "pH model") and in terms of 18O depletion as a result of the kinetic effects associated with CO2 hydration (CO2 + H2O ↔ H2CO3 ↔ HCO3- + H+) and CO2 hydroxylation (CO2 + OH- ↔ HCO3-) in the calcification sites (so-called "kinetic model"). This study addresses the potential role of an enzyme, carbonic anhydrase (CA), that catalyzes inter-conversion of CO2 and HCO3- in relation to the underlying mechanism of vital effects. We performed quantitative inorganic carbonate precipitation experiments in order to examine the changes in 18O equilibration rate as a function of CA concentration. Experiments were performed at pH 8.3 and 8.9. These pH values are comparable to the average surface ocean pH and elevated pH levels observed in the calcification sites of some coral and foraminiferal species, respectively. The rate of uncatalyzed 18O exchange in the CO2-H2O system is governed by the pH-dependent DIC speciation and the kinetic rate constant for CO2 hydration and hydroxylation, which can be summarized by a simple mathematical expression. The results from control experiments (no CA addition) are in agreement with this expression. The results from control experiments also suggest that the most recently published kinetic rate constant for CO2 hydroxylation has been overestimated. When CA is present, the 18O equilibration process is greatly enhanced at both pH levels due to the catalysis of CO2 hydration by the enzyme. For example, the time required for 18O

Numerical Analysis of S-CO{sub 2} Test Loop Transient Conditions near the Critical Point of CO{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Bae, Seong Jun; Oh, Bongseong; Ahn, Yoonhan; Baik, Seongjoon; Lee, Jekyoung; Lee, Jeong Ik [KAIST, Daejeon (Korea, Republic of)

2016-05-15

It was identified that controlling CO{sub 2} compressor operation near the critical point is one of the most important issues to operate a S-CO{sub 2} Brayton cycle with a high efficiency. Despite the growing interest in the S-CO{sub 2} Brayton cycle, a few previous research on the transient analysis of the S-CO{sub 2} system has been conducted previously. Moreover, previous studies have some limitation in the modelled test facility, and the experiment was not performed to observe specific scenario. The KAIST research team has conducted S-CO{sub 2} system transient experiments with the CO{sub 2} compressing test facility called SCO{sub 2}PE (Supercritical CO{sub 2} Pressurizing Experiment) at KAIST In this study, authors use the transient analysis code GAMMA (Gas Multidimensional Multicomponent mixture Analysis) code for analyzing the experiment. Two transient scenarios were selected in this study; over cooling and under cooling situations. The selected transient situation is of particular interest since the compressor inlet conditions start to drift away from the critical point of CO{sub 2}. The results represent that the GAMMA code can simulate the S-CO{sub 2} test facility, SCO{sub 2}PE. However, as shown in the cooling water flow rate increasing scenario, the GAMMA code shows calculation error when the phase change occurs. Furthermore, although the results of the cooling water flow rate decrease case shows reasonable agreement with the experimental data, there are still some unexplained differences between the experimental data and the GAMMA code prediction.

In situ 13CO2 pulse‐labeling in a temperate heathland – development of a mobile multi‐plot field setup

DEFF Research Database (Denmark)

Reinsch, Sabine; Ambus, Per

2013-01-01

Pulse‐labeling with 13CO2 and the subsequent analysis of 13C‐carbon via isotope ratio mass spectrometry (IRMS) have been shown to be an excellent method to investigate the terrestrial carbon cycle. Improving 13CO2 manipulation experiments will facilitate our understanding of carbon cycling...

Co-ordinated research programme on applications of stable isotope tracers in human nutrition research

International Nuclear Information System (INIS)

1992-01-01

This document provides a very brief report on the final Research Co-ordination Meeting of this Co-ordinated Research Project (CRP): the final report on the CRP will be published by the IAEA in the IAEA-TECDOC series. The present document contains a detailed proposal for a new Co-ordinated Research Programme on ''Stable Isotope Tracer Techniques for Studies on Protein-Energy Interactions'', and a brief series of notes on stable isotopic methods for investigating protein and amino-acid metabolism in man. Refs

Isotopic fractionation of gases during its migration: experiments and 2D numerical simulation

Science.gov (United States)

Kara, S.; Prinzhofer, A.

2003-04-01

Several works have been developed in the last decade on the experimental isotope fractionation of gases during migration (Prinzhofer et al., 1997 and Zhang &Krooss, 2001 among others). We add to these results new experiments on diffusion of CO_2, which becomes currently a crucial subject for environmental purpose. Our experiments showed that transport by diffusion of CO_2 through a water saturated shale induces a significant and systematic carbon isotopic fractionation with heavier (13C enriched) CO_2 migrating first. In all experiments, significant isotope fractionation was found but still remains without quantitative interpretation. To interpret these data, we developed a 2D numerical model at the pore scale. The general principle of this model is the study of transport by water solubilization/diffusion of gas in a capillary saturated with water with two different media : a mobile zone representing free water and a immobile zone representing bounded water. The model takes also into account solubilization coefficients of gas in water, as well as the migration distance and the volume of upstream and downstream reservoirs. Using our numerical model, we could reproduce the evolution of isotopic fractionations and the velocity of CO_2 migration versus the production factor F (proportion of diffused gas). We determined some physical parameters of the porous medium (bentonite) which are not directly measurable at the present time. Furthermore, we used these parameters to reproduce the curves of isotopic fractionation obtained by Pernaton (1998) on methane migration with the same porous rock. We used also a modified version of this model with infinite reservoirs to reproduce the curves of isotopic fractionation of Zhang &Krooss (2001). Application of this model to geological scale is under progress, in order to implement it into sedimentary basins modelling. REFERENCES: Zhang T. and Krooss M. (2001). Geochim. Cosmochim. Acta, Vol. 65, No.16, pp. 2723-2742. Pernaton E

A sensitivity analysis on seismic tomography data with respect to CO2 saturation of a CO2 geological sequestration field

Science.gov (United States)

Park, Chanho; Nguyen, Phung K. T.; Nam, Myung Jin; Kim, Jongwook

2013-04-01

Monitoring CO2 migration and storage in geological formations is important not only for the stability of geological sequestration of CO2 but also for efficient management of CO2 injection. Especially, geophysical methods can make in situ observation of CO2 to assess the potential leakage of CO2 and to improve reservoir description as well to monitor development of geologic discontinuity (i.e., fault, crack, joint, etc.). Geophysical monitoring can be based on wireline logging or surface surveys for well-scale monitoring (high resolution and nallow area of investigation) or basin-scale monitoring (low resolution and wide area of investigation). In the meantime, crosswell tomography can make reservoir-scale monitoring to bridge the resolution gap between well logs and surface measurements. This study focuses on reservoir-scale monitoring based on crosswell seismic tomography aiming describe details of reservoir structure and monitoring migration of reservoir fluid (water and CO2). For the monitoring, we first make a sensitivity analysis on crosswell seismic tomography data with respect to CO2 saturation. For the sensitivity analysis, Rock Physics Models (RPMs) are constructed by calculating the values of density and P and S-wave velocities of a virtual CO2 injection reservoir. Since the seismic velocity of the reservoir accordingly changes as CO2 saturation changes when the CO2 saturation is less than about 20%, while when the CO2 saturation is larger than 20%, the seismic velocity is insensitive to the change, sensitivity analysis is mainly made when CO2 saturation is less than 20%. For precise simulation of seismic tomography responses for constructed RPMs, we developed a time-domain 2D elastic modeling based on finite difference method with a staggered grid employing a boundary condition of a convolutional perfectly matched layer. We further make comparison between sensitivities of seismic tomography and surface measurements for RPMs to analysis resolution

Atmospheric inversion of the surface CO2 flux with 13CO2 constraint

Science.gov (United States)

Chen, J. M.; Mo, G.; Deng, F.

2013-10-01

Observations of 13CO2 at 73 sites compiled in the GLOBALVIEW database are used for an additional constraint in a global atmospheric inversion of the surface CO2 flux using CO2 observations at 210 sites for the 2002-2004 period for 39 land regions and 11 ocean regions. This constraint is implemented using the 13CO2/CO2 flux ratio modeled with a terrestrial ecosystem model and an ocean model. These models simulate 13CO2 discrimination rates of terrestrial photosynthesis and respiration and ocean-atmosphere diffusion processes. In both models, the 13CO2 disequilibrium between fluxes to and from the atmosphere is considered due to the historical change in atmospheric 13CO2 concentration. For the 2002-2004 period, the 13CO2 constraint on the inversion increases the total land carbon sink from 3.40 to 3.70 Pg C yr-1 and decreases the total oceanic carbon sink from 1.48 to 1.12 Pg C yr-1. The largest changes occur in tropical areas: a considerable decrease in the carbon source in the Amazon forest, and this decrease is mostly compensated by increases in the ocean region immediately west of the Amazon and the southeast Asian land region. Our further investigation through different treatments of the 13CO2/CO2 flux ratio used in the inversion suggests that variable spatial distributions of the 13CO2 isotopic discrimination rate simulated by the models over land and ocean have considerable impacts on the spatial distribution of the inverted CO2 flux over land and the inversion results are not sensitive to errors in the estimated disequilibria over land and ocean.

A simple cleanup method for the isolation of nitrate from natural water samples for O isotopes analysis

International Nuclear Information System (INIS)

Haberhauer, G.; Blochberger, K.

1999-09-01

The analysis of O-isotopic composition of nitrate has many potential applications in studies of environmental processes. O-isotope nitrate analysis require sample free of other oxygen-containing compounds. More than 100 % of non-NO 3 - oxygen relative to NO 3 - oxygen can still be found in forest soil water samples after cleanup if improper cleanup strategies, e.g., adsorption onto activated carbon, are used. Such non-NO 3 - oxygen compounds will bias O-isotropic data. Therefore, an efficient cleanup method was developed to isolate nitrate from natural water samples. In a multistep cleanup procedure using adsorption onto water-insoluble poly(vinylpyrrolidone), removal of almost all other oxygen-containing compounds, such as fulvic acids, and isolation of nitrate was achieved. The method supplied samples free of non-NO 3 - oxygen which can be directly combusted to CO 2 for subsequent O-isotope analysis. (author)

Hydrogen/deuterium fractionation factors of the aqueous ligand of cobalt in Co(H2O)62+ and Co(II)-substituted carbonic anhydrase

International Nuclear Information System (INIS)

Kassebaum, J.W.

1988-01-01

The author has measured the hydrogen/deuterium fractionation factor for the rapidly exchanging aqueous ligands of cobalt in Co(H 2 O) 6 2+ and in three Co(II)-substituted isozymes of carbonic anhydrase. The fractionation factor was determined from NMR relaxation rates at 300 MHz of the protons of water in mixed solutions of H 2 O and D 2 O containing these complexes. In each case, the paramagnetic contribution to 1/T 2 was greater than to 1/T 1 , consistent with a chemical shift mechanism affecting 1/T 2 . The fractionation factors obtained from T 2 were 0.73 ± 0.02 for Co(H 2 O) 6 2+ , 0.72 ± 0.02 for Co(II)-substituted carbonic anhydrase I, 0.77 ± 0.01 for Co(II)-substituted carbonic anhydrase II, and 1.00 ± 0.07 for Co(Il)-substituted carbonic anhydrase III. He concluded that fractionation factors in these cases determined from T 1 and T 2 measured isotope preferences for different populations of ligand sites. Since T 2 has a large contribution from a chemical shift mechanism, the fractionation factor determined from T 2 has a large contribution of the fractionation of inner shell ligands. The fractionation factor of Co(H 2 O) 6 2+ was used to interpret the solvent hydrogen isotope effects on the formation of complexes of cobalt with the bidentate ligands glycine, N,N-dimethylglycine, and acetylacetone. The contribution of the fractionation factor of the inner water shell in Co(H 2 O) 6 2+ did not account completely for the measured isotope effect, and that the hydrogen/deuterium fractionation of outer shell water makes a large contribution to the isotope effect on the formation of these complexes

Isotopic versus micrometeorologic ocean CO2 fluxes: A serious conflict

International Nuclear Information System (INIS)

Broecker, W.S.; Ledwell, J.R.; Takahashi, T.; Weiss, R.; Merlivat, L.; Memery, L.; Tsung-Hung Peng; Jahne, B.; Otto Munnich, K.

1986-01-01

Eddy correlation measurements over the ocean give CO 2 fluxes an order of magnitude or more larger than expected from mass balance or more larger than expected from mass balance measurements using radiocarbon and radon 222. In particular, Smith and Jones (1985) reported large upward and downward fluxes in a surf zone at supersaturations of 15% and attributed them to the equilibration of bubbles at elevated pressures. They argue that even on the open ocean such bubble injection may create steady state CO 2 supersaturations and that inferences of fluxes based on air-sea pCO 2 differences and radon exchange velocities must be made with caution. We defend the global average CO 2 exchange rate determined by three independent radioisotopic means: prebomb radiocarbon inventories; global surveys of mixed layer radon deficits; and oceanic uptake of bomb-produced radiocarbon. We argue that laboratory and lake data do not lead one to expect fluxes as large as reported from the eddy correlation technique; that the radon method of determining exchange velocities is indeed useful for estimating CO 2 fluxes; that supersaturations of CO 2 due to bubble injection on the open ocean are negligible; that the hypothesis that Smith and Jones advance cannot account for the fluxes that they report; and that the pCO 2 values reported by Smith and Jones are likely to be systematically much too high. The CO 2 fluxes for the ocean measured to data by the micrometeorological method can be reconciled with neither the observed concentrations of radioisotopes of radon and carbon in the oceans nor the tracer experiments carried out in lakes and in wind/wave tunnels

Unusual isotopic composition of C-CO2 from sterilized soil microcosms: a new way to separate intracellular from extracellular respiratory metabolisms.

Science.gov (United States)

Kéraval, Benoit; Alvarez, Gaël; Lehours, Anne Catherine; Amblard, Christian; Fontaine, Sebastien

2015-04-01

intact cells were observed by microscopy. These "ghost" cells were completely destroyed by the irradiation-autoclaving combination releasing large amount of soluble C. The soil respiration (O2 consumption and CO2 production) was reduced by irradiation and autoclaving but not stopped, suggesting the presence of an EXOMET. The delta 13C of CO2 released in the irradiated-autoclaved soil was strongly depleted (-70‰) indicating that this extracellular metabolism induced a substantial isotopic fractionation. Our findings suggest that two main oxidative metabolisms co-occur in soils: cell respiration and EXOMET. The isotopic fractionation induced by the EXOMET open perspectives for its quantification in non-sterilized living soils.

Multiple Nebular Gas Reservoirs Recorded by Oxygen Isotope Variation in a Spinel-rich CAI in CO3 MIL 090019

Science.gov (United States)

Simon, J. I.; Simon, S. B.; Nguyen, A. N.; Ross, D. K.; Messenger, S.

2017-01-01

We conducted NanoSIMS O-isotopic imaging of a primitive spinel-rich CAI spherule (27-2) from the MIL 090019 CO3 chondrite. Inclusions such as 27-2 are proposed to record inner nebula processes during an epoch of rapid solar nebula evolution. Mineralogical and textural analyses suggest that this CAI formed by high temperature reactions, partial melting, and condensation. This CAI exhibits radial O-isotopic heterogeneity among multiple occurrences of the same mineral, reflecting interactions with distinct nebular O-isotopic reservoirs.

Enhanced photosynthetic efficiency in trees world-wide by rising atmospheric CO2 levels

Science.gov (United States)

Ehlers, Ina; Wieloch, Thomas; Groenendijk, Peter; Vlam, Mart; van der Sleen, Peter; Zuidema, Pieter A.; Robertson, Iain; Schleucher, Jürgen

2014-05-01

The atmospheric CO2 concentration is increasing rapidly due to anthropogenic emissions but the effect on the Earth's biosphere is poorly understood. The ability of the biosphere to fix CO2 through photosynthesis will determine future atmospheric CO2 concentrations as well as future productivity of crops and forests. Manipulative CO2 enrichment experiments (e.g. FACE) are limited to (i) short time spans, (ii) few locations and (iii) large step increases in [CO2]. Here, we apply new stable isotope methodology to tree-ring archives, to study the effect of increasing CO2 concentrations retrospectively during the past centuries. We cover the whole [CO2] increase since industrialization, and sample trees with global distribution. Instead of isotope ratios of whole molecules, we use intramolecular isotope distributions, a new tool for tree-ring analysis with decisive advantages. In experiments on annual plants, we have found that the intramolecular distribution of deuterium (equivalent to ratios of isotopomer abundances) in photosynthetic glucose depends on growth [CO2] and reflects the metabolic flux ratio of photosynthesis to photorespiration. By applying this isotopomer methodology to trees from Oak Ridge FACE experiment, we show that this CO2 response is present in trees on the leaf level. This CO2 dependence constitutes a physiological signal, which is transferred to the wood of the tree rings. In trees from 13 locations on all continents the isotopomer ratio of tree-ring cellulose is correlated to atmospheric [CO2] during the past 200 years. The shift of the isotopomer ratio is universal for all 12 species analyzed, including both broad-leafed trees and conifers. Because the trees originate from sites with widely differing D/H ratios of precipitation, the generality of the response demonstrates that the signal is independent of the source isotope ratio, because it is encoded in an isotopomer abundance ratio. This decoupling of climate signals and physiological

Analysis of ex situ processes of CO2 sequestration. Final report

International Nuclear Information System (INIS)

Touze, S.; Bourgeois, F.; Baranger, P.; Durst, P.

2004-01-01

The aim of this study is to bring quantitative elements to evaluate the validation of the CO 2 mineral sequestration to limit the greenhouse effect gases. This analysis aims to calculate the CO 2 accounting of the system (internal energy production balance the energy expend) sequestrated CO 2 and produced CO 2 . The first part detailed the possible experimental solutions. Then two carbonation processes, direct and indirect, have been chosen of the analysis. (A.L.B.)

Automatic measurement system for light element isotope analysis

International Nuclear Information System (INIS)

Satake, Hiroshi; Ikegami, Kouichi.

1990-01-01

The automatic measurement system for the light element isotope analysis was developed by installing the specially designed inlet system which was controlled by a computer. The microcomputer system contains specific interface boards for the inlet system and the mass spectrometer, Micromass 602 E. All the components of the inlet and the computer system installed are easily available in Japan. Ten samples can be automatically measured as a maximum of. About 160 minutes are required for 10 measurements of δ 18 O values of CO 2 . Thus four samples can be measured per an hour using this system, while usually three samples for an hour using the manual operation. The automatized analysis system clearly has an advantage over the conventional method. This paper describes the details of this automated system, such as apparatuses used, the control procedure and the correction for reliable measurement. (author)

Chemistry of fluids from a natural analogue for a geological CO{sub 2} storage site (Montmiral, France): Lessons for CO{sub 2}-water-rock interaction assessment and monitoring

Energy Technology Data Exchange (ETDEWEB)

Pauwels, Helene [BRGM - Water Division, 3, av Claude Guillemin, 45060 Orleans Cedex (France)], E-mail: h.pauwels@brgm.fr; Gaus, Irina; Le Nindre, Yves Michel [BRGM - Water Division, 3, av Claude Guillemin, 45060 Orleans Cedex (France); Pearce, Jonathan [British Geological Survey, Kingsley Dunham Centre, Keyworth, Nottingham NG125GG (United Kingdom); Czernichowski-Lauriol, Isabelle [BRGM - Water Division, 3, av Claude Guillemin, 45060 Orleans Cedex (France)

2007-12-15

Chemical and isotope studies of natural CO{sub 2} accumulations aid in assessing the chemical effects of CO{sub 2} on rock and thus provide a potential for understanding the long-term geochemical processes involved in CO{sub 2} geological storage. Several natural CO{sub 2} accumulations were discovered during gas and oil exploration in France's carbogaseous peri-Alpine province (south-eastern France) in the 1960s. One of these, the Montmiral accumulation at a depth of more than 2400 m, is currently being exploited. The chemical composition of the water collected at the wellhead has changed in time and the final salinity exceeds 75 g/L. These changes in time can be explained by assuming that the fraction of the reservoir brine in the recovered brine-CO{sub 2}-H{sub 2}O mixture varies, resulting in variable proportions of H{sub 2}O and brine in the sampled water. The proportions can be estimated in selected samples due to the availability of gas and water flowrate data. These data enabled the reconstruction of the chemical and isotope composition of the brine. The proportions of H{sub 2}O and brine can also be estimated from isotope ({delta}{sup 2}H, {delta}{sup 18}O) composition of collected water and {delta}{sup 18}O of the sulfates or CO{sub 2}. The reconstituted brine has a salinity of more than 85 g/L and, according to its Br{sup -} content and isotope ({delta}{sup 2}H, {delta}{sup 18}O, {delta}{sup 34}S) composition, originates from an evaporated Triassic seawater that underwent dilution by meteoric water. The reconstitution of the brine's chemical composition enabled an evaluation of the CO{sub 2}-water-rock interactions based on: (1) mineral saturation indices; and (2) comparison with initial evaporated Triassic seawater. Dissolution of K- and SO{sub 4}-containing minerals such as K-feldspar and anhydrite, and precipitation of Ca and Mg containing minerals that are able to trap CO{sub 2} (carbonates) are highlighted. The changes in concentration of

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

Science.gov (United States)

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

Partitioning CO₂ fluxes with isotopologue measurements and modeling to understand mechanisms of forest carbon sequestration

Energy Technology Data Exchange (ETDEWEB)

Davidson, Eric A. [Woods Hole Research Center, Falmouth, MA (United States); Saleska, Scott [Univ. of Arizona, Tucson, AZ (United States); Savage, Kathleen [Woods Hole Research Center, Falmouth, MA (United States); Finzi, Adrien [Boston Univ., MA (United States); Moorcroft, Paul [Harvard Univ., Cambridge, MA (United States); Wehr, Richard [Univ. of Arizona, Tucson, AZ (United States)

2016-02-18

1. Project Summary and Objectives This project combines automated in situ observations of the isotopologues of CO₂ with root observations, novel experimental manipulations of belowground processes, and isotope-enabled ecosystem modeling to investigate mechanisms of below- vs. aboveground carbon sequestration at the Harvard Forest Environmental Measurements Site (EMS). The proposed objectives, which have now been largely accomplished, include: A. Partitioning of net ecosystem CO₂ exchange (NEE) into photosynthesis and respiration using long-term continuous observations of the isotopic composition of NEE, and analysis of their dynamics ; B. Investigation of the influence of vegetation phenology on the timing and magnitude of carbon allocated belowground using measurements of root growth and indices of belowground autotrophic vs. heterotrophic respiration (via trenched plots and isotope measurements); C. Testing whether plant allocation of carbon belowground stimulates the microbial decomposition of soil organic matter, using in situ rhizosphere simulation experiments wherein realistic quantities of artificial isotopically-labeled exudates are released into the soil; and D. Synthesis and interpretation of the above data using the Ecosystem Demography Model 2 (ED2).

High-power CO laser with RF discharge for isotope separation employing condensation repression

Science.gov (United States)

Baranov, I. Ya.; Koptev, A. V.

2008-10-01

High-power CO laser can be the effective tool in such applications as isotope separation using the free-jet CRISLA method. The way of transfer from CO small-scale experimental installation to industrial high-power CO lasers is proposed through the use of a low-current radio-frequency (RF) electric discharge in a supersonic stream without an electron gun. The calculation model of scaling CO laser with RF discharge in supersonic stream was developed. The developed model allows to calculate parameters of laser installation and optimize them with the purpose of reception of high efficiency and low cost of installation as a whole. The technical decision of industrial CO laser for isotope separation employing condensation repression is considered. The estimated cost of laser is some hundred thousand dollars USA and small sizes of laser head give possibility to install it in any place.

Isotope analysis of diamond-surface passivation effect of high-temperature H2O-grown atomic layer deposition-Al2O3 films

International Nuclear Information System (INIS)

Hiraiwa, Atsushi; Saito, Tatsuya; Matsumura, Daisuke; Kawarada, Hiroshi

2015-01-01

The Al 2 O 3 film formed using an atomic layer deposition (ALD) method with trimethylaluminum as Al precursor and H 2 O as oxidant at a high temperature (450 °C) effectively passivates the p-type surface conduction (SC) layer specific to a hydrogen-terminated diamond surface, leading to a successful operation of diamond SC field-effect transistors at 400 °C. In order to investigate this excellent passivation effect, we carried out an isotope analysis using D 2 O instead of H 2 O in the ALD and found that the Al 2 O 3 film formed at a conventional temperature (100 °C) incorporates 50 times more CH 3 groups than the high-temperature film. This CH 3 is supposed to dissociate from the film when heated afterwards at a higher temperature (550 °C) and causes peeling patterns on the H-terminated surface. The high-temperature film is free from this problem and has the largest mass density and dielectric constant among those investigated in this study. The isotope analysis also unveiled a relatively active H-exchange reaction between the diamond H-termination and H 2 O oxidant during the high-temperature ALD, the SC still being kept intact. This dynamic and yet steady H termination is realized by the suppressed oxidation due to the endothermic reaction with H 2 O. Additionally, we not only observed the kinetic isotope effect in the form of reduced growth rate of D 2 O-oxidant ALD but found that the mass density and dielectric constant of D 2 O-grown Al 2 O 3 films are smaller than those of H 2 O-grown films. This is a new type of isotope effect, which is not caused by the presence of isotopes in the films unlike the traditional isotope effects that originate from the presence of isotopes itself. Hence, the high-temperature ALD is very effective in forming Al 2 O 3 films as a passivation and/or gate-insulation layer of high-temperature-operation diamond SC devices, and the knowledge of the aforementioned new isotope effect will be a basis for further enhancing ALD

Use of nitrogen stable isotope analysis to understand char nitrogen evolution during the fluidized-bed co-combustion of coal and sewage sludge

Energy Technology Data Exchange (ETDEWEB)

Ana Arenillas; Roberto Garcia; Chenggong Sun; Colin E. Snape; Angel H. Moreno; Fernando Rubiera; Jose J. Pis [University of Nottingham, Nottingham (United Kingdom). Nottingham Fuel and Energy Centre, School of Chemical, Environmental and Mining Engineering

2005-04-01

NOx emissions from sewage sludge combustion are a concern, because of the usually high nitrogen content of this fuel. The interactions during co-combustion in a fluidized-bed reactor of sewage sludge and a bituminous coal were evaluated, in relation to the nitrogen evolution during the combustion process. The nitrogen stable isotope measurements provide novel results regarding the tracing of nitrogen during combustion. Our preliminary results show that the co-combustion chars retain more nitrogen than expected, with the additional nitrogen being mainly derived from the sludge. Additional measurements are planned on the resultant co-combustion gases, to aid source apportionment of the NOx arising from coal/sewage interactions. 14 refs., 3 figs., 2 tabs.

[Analysis of hydrogen isotopes by gas chromatography using a MnCl2 coated γ-Al2O3 capillary packed column].

Science.gov (United States)

Chen, Ping; Fu, Xiaolong; Hu, Peng; Xiao, Chengjian; Ren, Xingbi; Xia, Xiulong; Wang, Heyi

2017-07-08

The conventional packed column gas chromatographic analysis of hydrogen isotopes has low column efficiency, broad peak and long retention time. In this work, a γ -Al 2 O 3 with MnCl 2 coated capillary packed column was tested at cryogenic temperature. The systematic column efficiency analysis and the hydrogen isotopes analytical technique research had been carried out. The results showed that, the γ -Al 2 O 3 with MnCl 2 coating could greatly improve the surface degree of order, pore structure and adsorption properties. Also the o -H 2 peak and p -H 2 peak were eluted in a single area. The γ -Al 2 O 3 with MnCl 2 coating was packed into a 0.53 mm inner diameter and 1.0 m long fused silica capillary column. It had a good linear relationship used this column with thermal conductivity detector (TCD) to detect the volume concentrations of hydrogen isotopes from 1 to 10 mL/L, and the relative error was less than 5% for low concentration sample testing. For H 2 , HD and D 2 , the retention times can be shortened to 39, 46 and 60 s, respectively. The limits of detection were reduced to 0.046, 0.067 and 0.072 mL/L, respectively. Compared with conventional packed column, capillary packed column had sharper peak form, higher separation degree of adjacent components, shorter retention time and lower detection limits. The above results indicate that the capillary packed column with TCD detector can be used for fast detection of low concentration of hydrogen isotopes and their online analysis.

2D magnetic texture analysis of Co-Cu films

Energy Technology Data Exchange (ETDEWEB)

Bayirli, Mehmet; Karaagac, Oznur; Kockar, Hakan [Balikesir Univ. (Turkey). Physics Dept.; Alper, Mursel [Uludag Univ., Bursa (Turkey). Physics Dept.

2017-08-01

The magnetic textures for the produced magnetic materials are important concepts in accordance with technical applications. Therefore, the aim of this article is to determine 2D magnetic textures of electrodeposited Co-Cu films by the measurement of hysteresis loops at the incremented angles. For that, Co-Cu films were deposited with different Co{sup 2+} in the electrolyte. In addition, the easy-axis orientation in the films from the squareness values of the angles, M{sub p}(β) obtained by the hysteresis loops have been numerically studied using the Fourier series analysis. The differences observed in the magnetic easy-axis distributions were attributed to changes of the incorporation of Co in the films with the change of Co{sup 2+} in the electrolyte. The coefficients of Fourier series (A{sub 0} and A{sub 2n}) were also computed for 2D films. It is seen that a systematic and small decrease in A{sub 0} and an obvious decrease in A{sub 2n} (n=1) were observed with increasing incorporated Co in the films. Results imply that interactions cause slightly demagnetization effect accordance with higher incorporation of Co in the films. Furthermore, the crystal structure of the Co-Cu films analysed by X-ray diffraction revealed that the films have dominantly face-centred cubic structure. Film contents analysed by energy-dispersive X-ray spectroscopy and film morphologies observed by scanning electron microscope also support the magnetic texture analysis results found by numerical computation.

2D magnetic texture analysis of Co-Cu films

International Nuclear Information System (INIS)

Bayirli, Mehmet; Karaagac, Oznur; Kockar, Hakan; Alper, Mursel

2017-01-01

The magnetic textures for the produced magnetic materials are important concepts in accordance with technical applications. Therefore, the aim of this article is to determine 2D magnetic textures of electrodeposited Co-Cu films by the measurement of hysteresis loops at the incremented angles. For that, Co-Cu films were deposited with different Co"2"+ in the electrolyte. In addition, the easy-axis orientation in the films from the squareness values of the angles, M_p(β) obtained by the hysteresis loops have been numerically studied using the Fourier series analysis. The differences observed in the magnetic easy-axis distributions were attributed to changes of the incorporation of Co in the films with the change of Co"2"+ in the electrolyte. The coefficients of Fourier series (A_0 and A_2_n) were also computed for 2D films. It is seen that a systematic and small decrease in A_0 and an obvious decrease in A_2_n (n=1) were observed with increasing incorporated Co in the films. Results imply that interactions cause slightly demagnetization effect accordance with higher incorporation of Co in the films. Furthermore, the crystal structure of the Co-Cu films analysed by X-ray diffraction revealed that the films have dominantly face-centred cubic structure. Film contents analysed by energy-dispersive X-ray spectroscopy and film morphologies observed by scanning electron microscope also support the magnetic texture analysis results found by numerical computation.

Use of alpha spectrometry for analysis of U-isotopes in some granite samples

International Nuclear Information System (INIS)

El-Galy, M.M.; Desouky, O.A.; Khattab, M.R.; Issa, F.A.

2011-01-01

The present study aims to use the α-spectrometry, at NMA. A radiochemical technique for analysis of U-isotopes was carried out for some granite samples from Gabal Gattar and El Missikat localities and also for some reference soil samples of IAEA. Several steps of sample preparation, radiochemical separation, and source preparation were performed before analysis. The concerned sample was leached by HNO 3 , HF and H 2 O 2 acids after ashing. The ashed sample was spiked with uranium tracer ( 232 U) for chemical yield and activity calculation. Then uranium was extracted from the matrix elements with trioctylphosphine oxide (TOPO) and stripped with 1 M NH 4 F/0.1 M HCl solution. The uranium fraction was purified by co-precipitation with LaF 3 to ensure complete removal of thorium and traces of resolution degrading elements. This was followed by a final clean-up step using an anion exchange. The pure uranium fraction was electrodeposited on a stainless steel disc from HCl/oxalate solution. The obtained results from the soil reference samples indicate general similarities between the techniques of α-spectrometers of NMA, EAEA and IAEA for analysis of U-isotopes. The U-isotopes in the granite samples of high radioactivity levels need more attempts after dilution process to be in the limit detection of α-spectrometry. (author)

A New Biomarker Proxy for Palaeo-pCO2 Reconstruction in Ancient Sediments

Science.gov (United States)

Pancost, R. D.; Magness, S.; Maxwell, J. R.

2001-12-01

The carbon isotopic composition of marine organic matter has commonly been used in chemostratigraphy or as a proxy for ancient pCO2 levels. Both of these goals require that the source of organic matter be well defined, and in the case of palaeo-pCO2 investigations, the organic matter must be derived ultimately from aquatic photoautotrophs. However, additional sources, including terrestrial biomass, heterotrophs, or bacteria, can also contribute to total organic carbon (TOC). In the past decade, numerous workers have attempted to refine organic carbon isotope records using the isotopic composition of individual compounds (biomarkers) rather than the TOC. The appeal of this approach is that by examining specific biomarkers, a signal diagnostic for photoautotrophic organisms can be obtained. For compound-specific isotope analyses to be most effective, the compounds analysed must have a relatively specific source. Among the most commonly used biomarkers in palaeo-pCO2 investigations are alkenones, long-chain ketones derived exclusively from certain species of haptophyte algae. However, alkenones are absent in rocks older than the Jurassic and either absent or present in low abundances in rocks older than the Miocene. Thus, in older rocks, other biomarkers, including steranes (derived from eukaryotic sterols), phytane (presumably derived from chlorophyll), and n-alkanes (derived from algal macromolecules), are used. Unfortunately, these compounds can have alternative sources and become less reliable as isotopic proxies for photoautotrophs with increasing thermal maturity and complexity of the hydrocarbon distribution. Here we propose the use of a maleimides (1H-pyrrole-2,5-diones) as a new biomarker class for evaluating past changes in photoautotroph carbon isotopic compositions. Maleimides have three key advantages over other biomarkers in ancient rocks. First, they are degradation products of chlorophyll and have no known alternative origins in marine sediments

Reconsideration of atmospheric CO2 lifetime: potential mechanism for explaining CO2 missing sink

Science.gov (United States)

Kikuchi, R.; Gorbacheva, T.; Gerardo, R.

2009-04-01

Carbon cycle data (Intergovernmental Panel on Climate Change 1996) indicate that fossil fuel use accounts for emissions to the atmosphere of 5.5±0.5 GtC (Gigatons of carbon) annually. Other important processes in the global CO2 budget are tropical deforestation, estimated to generate about 1.6±1.0 GtC/yr; absorption by the oceans, removing about 2.0±0.8 GtC/yr; and regrowth of northern forests, taking up about 0.5±0.5 GtC/yr. However, accurate measurements of CO2 show that the atmosphere is accumulating only about 3.3±0.2 GtC/yr. The imbalance of about 1.3±1.5 GtC/yr, termed the "missing sink", represents the difference between the estimated sources and the estimated sinks of CO2; that is, we do not know where all of the anthropogenic CO2 is going. Several potential mechanisms have been proposed to explain this missing carbon, such as CO2 fertilization, climate change, nitrogen deposition, land use change, forest regrowth et al. Considering the complexity of ecosystem, most of ecosystem model cannot handle all the potential mechanisms to reproduce the real world. It has been believed that the dominant sink mechanism is the fertilizing effects of increased CO2 concentrations in the atmosphere and the addition to soils of fixed nitrogen from fossil-fuel burning and agricultural fertilizers. However, a recent analysis of long-term observations of the change in biomass and growth rates suggests that such fertilization effects are much too small to explain more than a small fraction of the observed sink. In addition, long-term experiments in which small forest patches and other land ecosystems have been exposed to elevated CO2 levels for extended periods show a rapid decrease of the fertilization effect after an initial enhancement. We will explore this question of the missing sink in atmospheric CO2 residence time. Radioactive and stable carbon isotopes (13-C/12-C) show the real CO2 lifetime is about 5 years; i.e. CO2 is quickly taken out of the atmospheric

Isotopic mixing in carbon monoxide catalyzed by zinc oxide

International Nuclear Information System (INIS)

Carnisio, G.; Garbassi, F.; Petrini, G.; Parravano, G.

1978-01-01

The rate of the isotopic mixing in CO has been studied at 300 0 C, for CO partial pressures from 6 to 100 Torr and a total pressure of 250 Torr on ZnO catalysts. Significant deviations from a first-order rate in p/sub co/ were found. The rate of oxygen exchange between ZnO and gas-phase CO was also measured and the results were employed to calculate the fraction of surface sites active for the CO isotopic mixing. Values on the order of 0.001 were found. The turnover rate and surface collision efficiency varied between 0.7 and 107 min -1 and 0.13 and 2.24 x 10 -8 , respectively. H 2 additions to CO increased the rate of isotopic mixing, whereas the rate of H 2 + D 2 was decreased by the presence of CO. The H 2 + D 2 rate was faster than that of isotopic mixing in CO, but as the ratio p/sub H 2 //p/sub co/ decreased the rates became about equal. It is argued that on ZnO samples, in which the rate of CO isotopic mixing and the rate of ZnO--CO oxygen exchange were influenced in a similar manner by the CO pressure, the isotopic mixing in CO took place via the ZnO oxygen, while oxide oxygen participation was not kinetically significant for ZnO samples in which the two reactions had different kinetics. The crucial factor controlling the path followed by the isotopic mixing in CO seems to be the surface Zn/O ratio, since a close correlation was found between the former and the reaction kinetics of the CO isotopic mixing reaction. Solid-state conditions which may vary the Zn/O surface ratio (foreign additions) are indicated. The implications of these findings to the problem of product selectivity from CO-H 2 mixtures reacting on metal oxide surfaces are discussed

Volatile, Isotope, and Organic Analysis of Martian Fines with the Mars Curiosity Rover

Science.gov (United States)

Leshin, L. A.; Mahaffy, P. R.; Webster, C. R.; Cabane, M.; Coll, P.; Conrad, P. G.; Archer, P. D.; Atreya, S. K.; Brunner, A. E.; Buch, A.; Eigenbrode, J. L.; Flesch, G. J.; Franz, H. B.; Freissinet, C.; Glavin, D. P.; McAdam, A. C.; Miller, K. E.; Ming, D. W.; Morris, R. V.; Navarro-González, R.; Niles, P. B.; Owen, T.; Pepin, R. O.; Squyres, S.; Steele, A.; Stern, J. C.; Summons, R. E.; Sumner, D. Y.; Sutter, B.; Szopa, C.; Teinturier, S.; Trainer, M. G.; Wray, J. J.; Grotzinger, J. P.; Kemppinen, Osku; Bridges, Nathan; Johnson, Jeffrey R.; Minitti, Michelle; Cremers, David; Bell, James F.; Edgar, Lauren; Farmer, Jack; Godber, Austin; Wadhwa, Meenakshi; Wellington, Danika; McEwan, Ian; Newman, Claire; Richardson, Mark; Charpentier, Antoine; Peret, Laurent; King, Penelope; Blank, Jennifer; Weigle, Gerald; Schmidt, Mariek; Li, Shuai; Milliken, Ralph; Robertson, Kevin; Sun, Vivian; Baker, Michael; Edwards, Christopher; Ehlmann, Bethany; Farley, Kenneth; Griffes, Jennifer; Miller, Hayden; Newcombe, Megan; Pilorget, Cedric; Rice, Melissa; Siebach, Kirsten; Stack, Katie; Stolper, Edward; Brunet, Claude; Hipkin, Victoria; Léveillé, Richard; Marchand, Geneviève; Sánchez, Pablo Sobrón; Favot, Laurent; Cody, George; Flückiger, Lorenzo; Lees, David; Nefian, Ara; Martin, Mildred; Gailhanou, Marc; Westall, Frances; Israël, Guy; Agard, Christophe; Baroukh, Julien; Donny, Christophe; Gaboriaud, Alain; Guillemot, Philippe; Lafaille, Vivian; Lorigny, Eric; Paillet, Alexis; Pérez, René; Saccoccio, Muriel; Yana, Charles; Armiens-Aparicio, Carlos; Rodríguez, Javier Caride; Blázquez, Isaías Carrasco; Gómez, Felipe Gómez; Gómez-Elvira, Javier; Hettrich, Sebastian; Malvitte, Alain Lepinette; Jiménez, Mercedes Marín; Martínez-Frías, Jesús; Martín-Soler, Javier; Martín-Torres, F. Javier; Jurado, Antonio Molina; Mora-Sotomayor, Luis; Caro, Guillermo Muñoz; López, Sara Navarro; Peinado-González, Verónica; Pla-García, Jorge; Manfredi, José Antonio Rodriguez; Romeral-Planelló, Julio José; Fuentes, Sara Alejandra Sans; Martinez, Eduardo Sebastian; Redondo, Josefina Torres; Urqui-O'Callaghan, Roser; Mier, María-Paz Zorzano; Chipera, Steve; Lacour, Jean-Luc; Mauchien, Patrick; Sirven, Jean-Baptiste; Manning, Heidi; Fairén, Alberto; Hayes, Alexander; Joseph, Jonathan; Sullivan, Robert; Thomas, Peter; Dupont, Audrey; Lundberg, Angela; Melikechi, Noureddine; Mezzacappa, Alissa; DeMarines, Julia; Grinspoon, David; Reitz, Günther; Prats, Benito; Atlaskin, Evgeny; Genzer, Maria; Harri, Ari-Matti; Haukka, Harri; Kahanpää, Henrik; Kauhanen, Janne; Kemppinen, Osku; Paton, Mark; Polkko, Jouni; Schmidt, Walter; Siili, Tero; Fabre, Cécile; Wilhelm, Mary Beth; Poitrasson, Franck; Patel, Kiran; Gorevan, Stephen; Indyk, Stephen; Paulsen, Gale; Gupta, Sanjeev; Bish, David; Schieber, Juergen; Gondet, Brigitte; Langevin, Yves; Geffroy, Claude; Baratoux, David; Berger, Gilles; Cros, Alain; d'Uston, Claude; Forni, Olivier; Gasnault, Olivier; Lasue, Jérémie; Lee, Qiu-Mei; Maurice, Sylvestre; Meslin, Pierre-Yves; Pallier, Etienne; Parot, Yann; Pinet, Patrick; Schröder, Susanne; Toplis, Mike; Lewin, Éric; Brunner, Will; Heydari, Ezat; Achilles, Cherie; Oehler, Dorothy; Coscia, David; Israël, Guy; Dromart, Gilles; Robert, François; Sautter, Violaine; Le Mouélic, Stéphane; Mangold, Nicolas; Nachon, Marion; Stalport, Fabien; François, Pascaline; Raulin, François; Cameron, James; Clegg, Sam; Cousin, Agnès; DeLapp, Dorothea; Dingler, Robert; Jackson, Ryan Steele; Johnstone, Stephen; Lanza, Nina; Little, Cynthia; Nelson, Tony; Wiens, Roger C.; Williams, Richard B.; Jones, Andrea; Kirkland, Laurel; Treiman, Allan; Baker, Burt; Cantor, Bruce; Caplinger, Michael; Davis, Scott; Duston, Brian; Edgett, Kenneth; Fay, Donald; Hardgrove, Craig; Harker, David; Herrera, Paul; Jensen, Elsa; Kennedy, Megan R.; Krezoski, Gillian; Krysak, Daniel; Lipkaman, Leslie; Malin, Michael; McCartney, Elaina; McNair, Sean; Nixon, Brian; Posiolova, Liliya; Ravine, Michael; Salamon, Andrew; Saper, Lee; Stoiber, Kevin; Supulver, Kimberley; Van Beek, Jason; Van Beek, Tessa; Zimdar, Robert; French, Katherine Louise; Iagnemma, Karl; Goesmann, Fred; Goetz, Walter; Hviid, Stubbe; Johnson, Micah; Lefavor, Matthew; Lyness, Eric; Breves, Elly; Dyar, M. Darby; Fassett, Caleb; Blake, David F.; Bristow, Thomas; DesMarais, David; Edwards, Laurence; Haberle, Robert; Hoehler, Tori; Hollingsworth, Jeff; Kahre, Melinda; Keely, Leslie; McKay, Christopher; Wilhelm, Mary Beth; Bleacher, Lora; Brinckerhoff, William; Choi, David; Dworkin, Jason P.; Floyd, Melissa; Garvin, James; Harpold, Daniel; Jones, Andrea; Martin, David K.; Pavlov, Alexander; Raaen, Eric; Smith, Michael D.; Tan, Florence; Meyer, Michael; Posner, Arik; Voytek, Mary; Anderson, Robert C.; Aubrey, Andrew; Beegle, Luther W.; Behar, Alberto; Blaney, Diana; Brinza, David; Calef, Fred; Christensen, Lance; Crisp, Joy A.; DeFlores, Lauren; Ehlmann, Bethany; Feldman, Jason; Feldman, Sabrina; Hurowitz, Joel; Jun, Insoo; Keymeulen, Didier; Maki, Justin; Mischna, Michael; Morookian, John Michael; Parker, Timothy; Pavri, Betina; Schoppers, Marcel; Sengstacken, Aaron; Simmonds, John J.; Spanovich, Nicole; Juarez, Manuel de la Torre; Vasavada, Ashwin R.; Yen, Albert; Cucinotta, Francis; Jones, John H.; Rampe, Elizabeth; Nolan, Thomas; Fisk, Martin; Radziemski, Leon; Barraclough, Bruce; Bender, Steve; Berman, Daniel; Dobrea, Eldar Noe; Tokar, Robert; Vaniman, David; Williams, Rebecca M. E.; Yingst, Aileen; Lewis, Kevin; Cleghorn, Timothy; Huntress, Wesley; Manhès, Gérard; Hudgins, Judy; Olson, Timothy; Stewart, Noel; Sarrazin, Philippe; Grant, John; Vicenzi, Edward; Wilson, Sharon A.; Bullock, Mark; Ehresmann, Bent; Hamilton, Victoria; Hassler, Donald; Peterson, Joseph; Rafkin, Scot; Zeitlin, Cary; Fedosov, Fedor; Golovin, Dmitry; Karpushkina, Natalya; Kozyrev, Alexander; Litvak, Maxim; Malakhov, Alexey; Mitrofanov, Igor; Mokrousov, Maxim; Nikiforov, Sergey; Prokhorov, Vasily; Sanin, Anton; Tretyakov, Vladislav; Varenikov, Alexey; Vostrukhin, Andrey; Kuzmin, Ruslan; Clark, Benton; Wolff, Michael; McLennan, Scott; Botta, Oliver; Drake, Darrell; Bean, Keri; Lemmon, Mark; Schwenzer, Susanne P.; Anderson, Ryan B.; Herkenhoff, Kenneth; Lee, Ella Mae; Sucharski, Robert; Hernández, Miguel Ángel de Pablo; Ávalos, Juan José Blanco; Ramos, Miguel; Kim, Myung-Hee; Malespin, Charles; Plante, Ianik; Muller, Jan-Peter; Ewing, Ryan; Boynton, William; Downs, Robert; Fitzgibbon, Mike; Harshman, Karl; Morrison, Shaunna; Dietrich, William; Kortmann, Onno; Palucis, Marisa; Williams, Amy; Lugmair, Günter; Wilson, Michael A.; Rubin, David; Jakosky, Bruce; Balic-Zunic, Tonci; Frydenvang, Jens; Jensen, Jaqueline Kløvgaard; Kinch, Kjartan; Koefoed, Asmus; Madsen, Morten Bo; Stipp, Susan Louise Svane; Boyd, Nick; Campbell, John L.; Gellert, Ralf; Perrett, Glynis; Pradler, Irina; VanBommel, Scott; Jacob, Samantha; Rowland, Scott; Atlaskin, Evgeny; Savijärvi, Hannu; Boehm, Eckart; Böttcher, Stephan; Burmeister, Sönke; Guo, Jingnan; Köhler, Jan; García, César Martín; Mueller-Mellin, Reinhold; Wimmer-Schweingruber, Robert; Bridges, John C.; McConnochie, Timothy; Benna, Mehdi; Bower, Hannah; Blau, Hannah; Boucher, Thomas; Carmosino, Marco; Elliott, Harvey; Halleaux, Douglas; Rennó, Nilton; Wong, Michael; Elliott, Beverley; Spray, John; Thompson, Lucy; Gordon, Suzanne; Newsom, Horton; Ollila, Ann; Williams, Joshua; Vasconcelos, Paulo; Bentz, Jennifer; Nealson, Kenneth; Popa, Radu; Kah, Linda C.; Moersch, Jeffrey; Tate, Christopher; Day, Mackenzie; Kocurek, Gary; Hallet, Bernard; Sletten, Ronald; Francis, Raymond; McCullough, Emily; Cloutis, Ed; ten Kate, Inge Loes; Kuzmin, Ruslan; Arvidson, Raymond; Fraeman, Abigail; Scholes, Daniel; Slavney, Susan; Stein, Thomas; Ward, Jennifer; Berger, Jeffrey; Moores, John E.

2013-09-01

Samples from the Rocknest aeolian deposit were heated to ~835°C under helium flow and evolved gases analyzed by Curiosity’s Sample Analysis at Mars instrument suite. H2O, SO2, CO2, and O2 were the major gases released. Water abundance (1.5 to 3 weight percent) and release temperature suggest that H2O is bound within an amorphous component of the sample. Decomposition of fine-grained Fe or Mg carbonate is the likely source of much of the evolved CO2. Evolved O2 is coincident with the release of Cl, suggesting that oxygen is produced from thermal decomposition of an oxychloride compound. Elevated δD values are consistent with recent atmospheric exchange. Carbon isotopes indicate multiple carbon sources in the fines. Several simple organic compounds were detected, but they are not definitively martian in origin.

Actinide isotopic analysis systems

International Nuclear Information System (INIS)

Koenig, Z.M.; Ruhter, W.D.; Gunnink, R.

1990-01-01

This manual provides instructions and procedures for using the Lawrence Livermore National Laboratory's two-detector actinide isotope analysis system to measure plutonium samples with other possible actinides (including uranium, americium, and neptunium) by gamma-ray spectrometry. The computer program that controls the system and analyzes the gamma-ray spectral data is driven by a menu of one-, two-, or three-letter options chosen by the operator. Provided in this manual are descriptions of these options and their functions, plus detailed instructions (operator dialog) for choosing among the options. Also provided are general instructions for calibrating the actinide isotropic analysis system and for monitoring its performance. The inventory measurement of a sample's total plutonium and other actinides content is determined by two nondestructive measurements. One is a calorimetry measurement of the sample's heat or power output, and the other is a gamma-ray spectrometry measurement of its relative isotopic abundances. The isotopic measurements needed to interpret the observed calorimetric power measurement are the relative abundances of various plutonium and uranium isotopes and americium-241. The actinide analysis system carries out these measurements. 8 figs

Environmental controls on the carbon isotope composition of ecosystem-respired CO{sub 2} in contrasting forest ecosystems in Canada and the USA

Energy Technology Data Exchange (ETDEWEB)

Alstad, K.P. [Lethbridge Univ., Lethbridge, AB (Canada). Dept. of Biological Sciences; Toledo Univ., Toledo, OH (United States). Dept. of Environmental Sciences; Flanagan, L.B. [Lethbridge Univ., Lethbridge, AB (Canada). Dept. of Biological Sciences; Lai, C.T. [Utah Univ., Salt Lake City, UT (United States); San Diego State Univ., San Diego, CA (United States); Ehleringer, J.R. [Utah Univ., Salt Lake City, UT (United States)

2007-10-15

Eleven forest ecosystems in Canada and the United States were compared in order to test for differences among forest {delta}{sup 13} carbon (C) responses to seasonal variations in environmental conditions from May to October 2004. Carbon isotope composition of ecosystem-respired carbon dioxide (CO{sub 2}) was considered as a proxy for short-term changes in photosynthetic discrimination. The study compared coniferous and deciduous forests, as well as forests in boreal and coastal environments. It was hypothesized that the carbon isotope composition of ecosystem-respired CO{sub 2} varied in a manner consistent with results obtained in leaf-level studies. Results of the study showed that higher R{sup 2} values were obtained for coastal ecosystems. The relationships between {delta}{sup 13}C{sub R} and environmental conditions were consistent with results obtained from leaf-level studies. Vapour pressure deficits and soil temperatures were significant determinants of variations in {delta}{sup 13}C{sub R} in the boreal forest ecosystem. Variations in {delta}{sup 13}C{sub R} in the coastal forest ecosystem correlated with changes in photosynthetic photon flux (PPF). It was concluded that {delta}{sup 13}C{sub R} measurements can be used to assess yearly variations in ecosystem physiological responses to changing environmental conditions. 59 refs., 7 tabs., 6 figs.

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

Science.gov (United States)

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.

Basic methods of isotope analysis

International Nuclear Information System (INIS)

Ochkin, A.V.; Rozenkevich, M.B.

2000-01-01

The bases of the most applied methods of the isotope analysis are briefly presented. The possibilities and analytical characteristics of the mass-spectrometric, spectral, radiochemical and special methods of the isotope analysis, including application of the magnetic resonance, chromatography and refractometry, are considered [ru

Evidence for H2/D2 isotope effects on Fischer-Tropsch synthesis over supported ruthenium catalysts

International Nuclear Information System (INIS)

Kellner, C.S.; Bell, A.T.

1981-01-01

The effects of using D 2 rather than H 2 during Fischer-Tropsch synthesis were investigated using alumina- and silica-supported Ru catalysts. For the alumina-supported catalysts, the rate of CD 4 formation was 1.4 to 1.6 times faster than the formation of CH 4 . A noticeable isotope effect was also observed for higher molecular weight products. The magnitude of the isotope effects observed using the silica-supported catalyst was much smaller than that found using the alumina-supported catalysts. The formation of olefins relative to paraffins was found to be higher when H 2 rather than D 2 was used, independent of the catalyst support. The observed isotope effects are explained in terms of a mechanism for CO hydrogenation and are shown to arise from a complex combination of the kinetic and equilibrium isotope effects associated with elementary processes occurring on the catalyst surface

Current Travertines Precipitation from CO2-rich Groundwaters as an alert of CO2 Leakages from a Natural CO2 Storage at Ganuelas-Mazarron Tertiary Basin (Murcia, Spain)

International Nuclear Information System (INIS)

Rodrigo-Naharro, J.; Delgado, A.; Herrero, M. J.; Granados, A.; Perez del Villar, L.

2013-01-01

Carbon capture and storage technologies represent the most suitable solutions related to the high anthropogenic CO 2 emissions to the atmosphere. As a consequence, monitoring of the possible CO 2 leakages from an artificial deep geological CO 2 storage is indispensable to guarantee its safety. Fast surficial travertine precipitation related to these CO 2 leakages can be used as an alert for these escapes. Since few studies exist focusing on the long-term behaviour of an artificial CO 2 DGS, natural CO 2 storage affected by natural or artificial escapes must be studied as natural analogues for predicting the long-term behaviour of an artificial CO 2 storage. In this context, a natural CO 2 reservoir affected by artificial CO 2 escapes has been studied in this work. This study has mainly focused on the current travertines precipitation associated with the upwelling CO 2 -rich waters from several hydrogeological wells drilled in the Ganuelas-Mazarron Tertiary basin (SE Spain), and consists of a comprehensive characterisation of parent-waters and their associated carbonates, including elemental and isotopic geochemistry, mineralogy and petrography. Geochemical characterisation of groundwaters has led to recognise 4 hydrofacies from 3 different aquifers. These groundwaters have very high salinity and electrical conductivity; are slightly acid; present high dissolved inorganic carbon (DIC) and free CO 2 ; are oversaturated in both aragonite and calcite; and dissolve, mobilize and transport low quantities of heavy and/or toxic elements. Isotopic values indicate that: i) the origin of parent-waters is related to rainfalls from clouds originated in the Mediterranean Sea or continental areas; ii) the origin of C is mainly inorganic; and iii) sulphate anions come mainly from the dissolution of the Messinian gypsum from the Tertiary Basin sediments. Current travertines precipitation seems to be controlled by a combination of several factors, such as: i) a fast decrease of the

Hanford Isotope Project strategic business analysis Cesium-137 (Cs-137)

Energy Technology Data Exchange (ETDEWEB)

NONE

1995-10-01

The purpose of this business analysis is to address the beneficial reuse of Cesium 137 (Cs-137) in order to utilize a valuable national asset and possibly save millions of tax dollars. Food irradiation is the front runner application along with other uses. This business analysis supports the objectives of the Department of Energy National Isotope Strategy distributed in August 1994 which describes the DOE plans for the production and distribution of isotope products and services. As part of the Department`s mission as stated in that document. ``The Department of Energy will also continue to produce and distribute other radioisotopes and enriched stable isotopes for medical diagnostics and therapeutics, industrial, agricultural, and other useful applications on a businesslike basis. This is consistent with the goals and objectives of the National Performance Review. The Department will endeavor to look at opportunities for private sector to co-fund or invest in new ventures. Also, the Department will seek to divest from ventures that can more profitably or reliably be operated by the private sector.``

Hanford Isotope Project strategic business analysis Cesium-137 (Cs-137)

International Nuclear Information System (INIS)

1995-10-01

The purpose of this business analysis is to address the beneficial reuse of Cesium 137 (Cs-137) in order to utilize a valuable national asset and possibly save millions of tax dollars. Food irradiation is the front runner application along with other uses. This business analysis supports the objectives of the Department of Energy National Isotope Strategy distributed in August 1994 which describes the DOE plans for the production and distribution of isotope products and services. As part of the Department's mission as stated in that document. ''The Department of Energy will also continue to produce and distribute other radioisotopes and enriched stable isotopes for medical diagnostics and therapeutics, industrial, agricultural, and other useful applications on a businesslike basis. This is consistent with the goals and objectives of the National Performance Review. The Department will endeavor to look at opportunities for private sector to co-fund or invest in new ventures. Also, the Department will seek to divest from ventures that can more profitably or reliably be operated by the private sector.''

Quantitative analysis of an engineered CO2-fixing Escherichia coli reveals great potential of heterotrophic CO2 fixation.

Science.gov (United States)

Gong, Fuyu; Liu, Guoxia; Zhai, Xiaoyun; Zhou, Jie; Cai, Zhen; Li, Yin

2015-01-01

Production of fuels from the abundant and wasteful CO2 is a promising approach to reduce carbon emission and consumption of fossil fuels. Autotrophic microbes naturally assimilate CO2 using energy from light, hydrogen, and/or sulfur. However, their slow growth rates call for investigation of the possibility of heterotrophic CO2 fixation. Although preliminary research has suggested that CO2 fixation in heterotrophic microbes is feasible after incorporation of a CO2-fixing bypass into the central carbon metabolic pathway, it remains unclear how much and how efficient that CO2 can be fixed by a heterotrophic microbe. A simple metabolic flux index was developed to indicate the relative strength of the CO2-fixation flux. When two sequential enzymes of the cyanobacterial Calvin cycle were incorporated into an E. coli strain, the flux of the CO2-fixing bypass pathway accounts for 13 % of that of the central carbon metabolic pathway. The value was increased to 17 % when the carbonic anhydrase involved in the cyanobacterial carbon concentrating mechanism was introduced, indicating that low intracellular CO2 concentration is one limiting factor for CO2 fixation in E. coli. The engineered CO2-fixing E. coli with carbonic anhydrase was able to fix CO2 at a rate of 19.6 mg CO2 L(-1) h(-1) or the specific rate of 22.5 mg CO2 g DCW(-1) h(-1). This CO2-fixation rate is comparable with the reported rates of 14 autotrophic cyanobacteria and algae (10.5-147.0 mg CO2 L(-1) h(-1) or the specific rates of 3.5-23.7 mg CO2 g DCW(-1) h(-1)). The ability of CO2 fixation was created and improved in E. coli by incorporating partial cyanobacterial Calvin cycle and carbon concentrating mechanism, respectively. Quantitative analysis revealed that the CO2-fixation rate of this strain is comparable with that of the autotrophic cyanobacteria and algae, demonstrating great potential of heterotrophic CO2 fixation.

Carbon isotopes in mollusk shell carbonates

Science.gov (United States)

McConnaughey, Ted A.; Gillikin, David Paul

2008-10-01

Mollusk shells contain many isotopic clues about calcification physiology and environmental conditions at the time of shell formation. In this review, we use both published and unpublished data to discuss carbon isotopes in both bivalve and gastropod shell carbonates. Land snails construct their shells mainly from respired CO2, and shell δ13C reflects the local mix of C3 and C4 plants consumed. Shell δ13C is typically >10‰ heavier than diet, probably because respiratory gas exchange discards CO2, and retains the isotopically heavier HCO3 -. Respired CO2 contributes less to the shells of aquatic mollusks, because CO2/O2 ratios are usually higher in water than in air, leading to more replacement of respired CO2 by environmental CO2. Fluid exchange with the environment also brings additional dissolved inorganic carbon (DIC) into the calcification site. Shell δ13C is typically a few ‰ lower than ambient DIC, and often decreases with age. Shell δ13C retains clues about processes such as ecosystem metabolism and estuarine mixing. Ca2+ ATPase-based models of calcification physiology developed for corals and algae likely apply to mollusks, too, but lower pH and carbonic anhydrase at the calcification site probably suppress kinetic isotope effects. Carbon isotopes in biogenic carbonates are clearly complex, but cautious interpretation can provide a wealth of information, especially after vital effects are better understood.

The influence of clouds and diffuse radiation on ecosystem-atmosphere CO2 and CO18O exhanges

Energy Technology Data Exchange (ETDEWEB)

Still, C.J.; Riley, W.J.; Biraud, S.C.; Noone, D.C.; Buenning, N.H.; Randerson, J.T.; Torn, M.S.; Welker, J.; White, J.W.C.; Vachon, R.; Farquhar, G.D.; Berry, J.A.

2009-05-01

This study evaluates the potential impact of clouds on ecosystem CO{sub 2} and CO{sub 2} isotope fluxes ('isofluxes') in two contrasting ecosystems (a broadleaf deciduous forest and a C{sub 4} grassland), in a region for which cloud cover, meteorological, and isotope data are available for driving the isotope-enabled land surface model, ISOLSM. Our model results indicate a large impact of clouds on ecosystem CO{sub 2} fluxes and isofluxes. Despite lower irradiance on partly cloudy and cloudy days, predicted forest canopy photosynthesis was substantially higher than on clear, sunny days, and the highest carbon uptake was achieved on the cloudiest day. This effect was driven by a large increase in light-limited shade leaf photosynthesis following an increase in the diffuse fraction of irradiance. Photosynthetic isofluxes, by contrast, were largest on partly cloudy days, as leaf water isotopic composition was only slightly depleted and photosynthesis was enhanced, as compared to adjacent clear sky days. On the cloudiest day, the forest exhibited intermediate isofluxes: although photosynthesis was highest on this day, leaf-to-atmosphere isofluxes were reduced from a feedback of transpiration on canopy relative humidity and leaf water. Photosynthesis and isofluxes were both reduced in the C{sub 4} grass canopy with increasing cloud cover and diffuse fraction as a result of near-constant light limitation of photosynthesis. These results suggest that some of the unexplained variation in global mean {delta}{sup 18}O of CO{sub 2} may be driven by large-scale changes in clouds and aerosols and their impacts on diffuse radiation, photosynthesis, and relative humidity.

Silicon isotope separation utilizing infrared multiphoton dissociation of Si{sub 2}F{sub 6} irradiated with two-color CO{sub 2} laser light

Energy Technology Data Exchange (ETDEWEB)

Yokoyama, Atsushi; Ohba, Hironori; Hashimoto, Masashi [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Ishii, Takeshi; Ohya, Akio [Nuclear Development Corp., Tokai, Ibaraki (Japan); Arai, Shigeyoshi [Hill Research Co. Ltd., Tokyo (Japan)

2002-08-01

Silicon isotope separation has been done by utilizing the Infrared Multiphoton Dissociation (IRMPD) of Si{sub 2}F{sub 6} irradiated with two-color CO{sub 2} laser lights. The two-color excitation method improved the separation efficiency keeping the high enrichment factors. For example, 99.74% of {sup 28}Si was obtained at 49.63% dissociation of Si{sub 2}F{sub 6} after the simultaneous irradiation of 200 pulses with 966.23 cm{sup -1} photons (0.084 J/cm{sup 2}) and 954.55 cm{sup -1} photons (0.658 J/cm{sup 2}), while 2000 pulses were needed to obtain 99.35% of {sup 28}Si at 35.6% dissociation in the case of only one-color irradiation at 954.55 cm{sup -1} (0.97 J/cm{sup 2}). (author)

Water Isotope framework for lake water balance monitoring and modelling in the Nam Co Basin, Tibetan Plateau

Directory of Open Access Journals (Sweden)

Shichang Kang

2017-08-01

New hydrological insights: A water isotope framework for the Nam Co basin, including the Local Meteoric Water Line, limiting isotopic composition of evaporation and two hypothetical evaporation trajectories, is established. We further applied the isotope mass balance model to estimate the overall isotopic composition of input water to the Nam Co, the evaporation over inputs ratios (E/I for three consecutive years, and the water yields (Wy, depth equivalent runoff at a basin scale. Our results clearly suggest a positive water budget (i.e., E/I < 1, providing another line of evidence that the subsurface leakage from Nam Co is likely. The discrepancy between isotope-based water yields estimations and field-based runoff observations suggest that, compared to the well-studied Nyainqentanglha Mountains and southwestern mountains, the ridge-and-valley landscape in the western highlands and northwestern hogbacks are possibly low yields area, which should draw more research attentions in future hydrological investigations.

Atmospheric pCO2 reconstructed across five early Eocene global warming events

Science.gov (United States)

Cui, Ying; Schubert, Brian A.

2017-11-01

Multiple short-lived global warming events, known as hyperthermals, occurred during the early Eocene (56-52 Ma). Five of these events - the Paleocene-Eocene Thermal Maximum (PETM or ETM1), H1 (or ETM2), H2, I1, and I2 - are marked by a carbon isotope excursion (CIE) within both marine and terrestrial sediments. The magnitude of CIE, which is a function of the amount and isotopic composition of carbon added to the ocean-atmosphere system, varies significantly between marine versus terrestrial substrates. Here we use the increase in carbon isotope fractionation by C3 land plants in response to increased pCO2 to reconcile this difference and reconstruct a range of background pCO2 and peak pCO2 for each CIE, provided two potential carbon sources: methane hydrate destabilization and permafrost-thawing/organic matter oxidation. Although the uncertainty on each pCO2 estimate using this approach is low (e.g., median uncertainty = + 23% / - 18%), this work highlights the potential for significant systematic bias in the pCO2 estimate resulting from sampling resolution, substrate type, diagenesis, and environmental change. Careful consideration of each of these factors is required especially when applying this approach to a single marine-terrestrial CIE pair. Given these limitations, we provide an upper estimate for background early Eocene pCO2 of 463 +248/-131 ppmv (methane hydrate scenario) to 806 +127/-104 ppmv (permafrost-thawing/organic matter oxidation scenario). These results, which represent the first pCO2 proxy estimates directly tied to the Eocene hyperthermals, demonstrate that early Eocene warmth was supported by background pCO2 less than ∼3.5× preindustrial levels and that pCO2 > 1000 ppmv may have occurred only briefly, during hyperthermal events.

Stable isotope and modelling evidence for CO2 as a driver of glacial–interglacial vegetation shifts in southern Africa

Directory of Open Access Journals (Sweden)

F. J. Bragg

2013-03-01

Full Text Available Atmospheric CO2 concentration is hypothesized to influence vegetation distribution via tree–grass competition, with higher CO2 concentrations favouring trees. The stable carbon isotope (δ13C signature of vegetation is influenced by the relative importance of C4 plants (including most tropical grasses and C3 plants (including nearly all trees, and the degree of stomatal closure – a response to aridity – in C3 plants. Compound-specific δ13C analyses of leaf-wax biomarkers in sediment cores of an offshore South Atlantic transect are used here as a record of vegetation changes in subequatorial Africa. These data suggest a large increase in C3 relative to C4 plant dominance after the Last Glacial Maximum. Using a process-based biogeography model that explicitly simulates 13C discrimination, it is shown that precipitation and temperature changes cannot explain the observed shift in δ13C values. The physiological effect of increasing CO2 concentration is decisive, altering the C3/C4 balance and bringing the simulated and observed δ13C values into line. It is concluded that CO2 concentration itself was a key agent of vegetation change in tropical southern Africa during the last glacial–interglacial transition. Two additional inferences follow. First, long-term variations in terrestrial δ13Cvalues are not simply a proxy for regional rainfall, as has sometimes been assumed. Although precipitation and temperature changes have had major effects on vegetation in many regions of the world during the period between the Last Glacial Maximum and recent times, CO2 effects must also be taken into account, especially when reconstructing changes in climate between glacial and interglacial states. Second, rising CO2 concentration today is likely to be influencing tree–grass competition in a similar way, and thus contributing to the "woody thickening" observed in savannas worldwide. This second inference points to the importance of experiments to

Co-ordinated research programme on applications of stable isotope tracers in human nutrition research

International Nuclear Information System (INIS)

1989-01-01

This Co-ordinated Research Programme (CRP) was formally established by the Agency in October 1988, and has since then expanded to encompass 13 participants in 13 countries. Its general objective is to help establish competence in the use of stable isotope techniques, particularly in developing countries, and particularly with reference to applications of 2 H, 13 C, 15 N, and 18 O. This report summarizes the discussions that took place during the first Research Co-ordination Meeting (RCM). Working papers (progress reports) presented by the participants are included as annexes together with a preliminary report on the results of a series of intercomparison exercises involving enriched stable isotope reference materials containing 2 H, 13 C, 15 N and 18 O. For the future it was agreed that more work needs to be done to harmonize the analytical techniques being used, and to obtain support for new CRPs relating to human energy expenditure studies in pregnancy, lactation, growth and other conditions, and to studies of nitrogen turnover in relation to malnutrition and liver function. Refs, figs and tabs

Isotope analysis of lithium by thermionic mass spectrometry

International Nuclear Information System (INIS)

Kakazu, M.H.; Sarkis, J.E.S.

1991-04-01

An analytical mass spectrometric method for the isotope analysis of lithium has been studied. The analysis were carried out by using a single focusing thermoionic mass spectrometer Varian Mat TH5 with 90 sup(0) magnetic sector field and 21.4 cm deflection radius, equipped with a dual Re-filament thermal ionization ion source. The effect of different lithium chemical forms, such as, carbonate, chloride, nitrate and sulfate upon the isotopic ratios sup(6)Li/ sup(7)Li has been studied. Isotopic fractionation of lithium was studied in terms of the time of analysis. The results obtained with lithium carbonate yielded a precision of ±0.1% and an accuracy of ± 0.6%, whereas with other chemical forms yielded precisions of ±0.5% and accuracies of ±2%. A fractionation correction factor, K=1.005, was obtained for different samples of lithium carbonate isotopic standard CBNM IRM 016, which has been considered constant. (author)

Isotope labelling study of CO oxidation-assisted epoxidation of propene. Implications for oxygen activation on Au catalysts.

Science.gov (United States)

Jiang, Jian; Oxford, Sean M; Fu, Baosong; Kung, Mayfair C; Kung, Harold H; Ma, Jiantai

2010-06-07

(18)O isotope labelling studies of the CO oxidation-assisted epoxidation of propene, catalyzed by a mixture of Au/TiO(2) and TS-1, using a methanol-H(2)O solvent showed the O in the epoxide was exclusively from O(2) and not H(2)O or methanol.

Continuous measurements of stable isotopes of carbon dioxide and water vapour in an urban atmosphere: isotopic variations associated with meteorological conditions.

Science.gov (United States)

Wada, Ryuichi; Matsumi, Yutaka; Nakayama, Tomoki; Hiyama, Tetsuya; Fujiyoshi, Yasushi; Kurita, Naoyuki; Muramoto, Kenichiro; Takanashi, Satoru; Kodama, Naomi; Takahashi, Yoshiyuki

2017-12-01

Isotope ratios of carbon dioxide and water vapour in the near-surface air were continuously measured for one month in an urban area of the city of Nagoya in central Japan in September 2010 using laser spectroscopic techniques. During the passages of a typhoon and a stationary front in the observation period, remarkable changes in the isotope ratios of CO 2 and water vapour were observed. The isotope ratios of both CO 2 and water vapour decreased during the typhoon passage. The decreases can be attributed to the air coming from an industrial area and the rainout effects of the typhoon, respectively. During the passage of the stationary front, δ 13 C-CO 2 and δ 18 O-CO 2 increased, while δ 2 H-H 2 Ov and δ 18 O-H 2 Ov decreased. These changes can be attributed to the air coming from rural areas and the air surrounding the observational site changing from a subtropical air mass to a subpolar air mass during the passage of the stationary front. A clear relationship was observed between the isotopic CO 2 and water vapour and the meteorological phenomena. Therefore, isotopic information of CO 2 and H 2 Ov could be used as a tracer of meteorological information.

C{sub 4} plant isotopic composition ({delta}{sup 13}C) evidence for urban CO{sub 2} pollution in the city of Cotonou, Benin (West Africa)

Energy Technology Data Exchange (ETDEWEB)

Kelome, Nelly C.; Leveque, Jean; Andreux, Francis; Milloux, Marie-Jeanne [UMR Microbiologie et Geochimie des Sols INRA, Universite de Bourgogne, Centre des Sciences de la Terre, 6 Bd Gabriel, 21000 Dijon (France); Oyede, Lucien-Marc [Departement des Sciences de la Terre, Universite d' Abomey-Calavi, 01 B.P. 526, Cotonou (Benin)

2006-08-01

The carbon isotopic composition ({delta}{sup 13}C) of plants can reveal the isotopic carbon content of the atmosphere in which they develop. The {delta}{sup 13}C values of air and plants depend on the amount of atmospheric fossil fuel CO{sub 2}, which is chiefly emitted in urban areas. A new indicator of CO{sub 2} pollution is tested using the {delta}{sup 13}C variation in a C{sub 4} grass: Eleusine indica. A range of about 4%% delta units was observed at different sites in Cotonou, the largest city in the Republic of Benin. The highest {delta}{sup 13}C values, from -12%% to -14%%, were found in low traffic zones; low {delta}{sup 13}C values, from -14%% to -16%%, 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 {delta}{sup 13}C values was observed over a four-year monitoring period. This decrease was correlated with increasing vehicle traffic. The {delta}{sup 13}C dataset and the corresponding geographical database were used to map and define zones of high and low {sup 13}C-depleted CO{sub 2} 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 CO{sub 2} emissions occurred in the north, the east and the center, providing evidence of intense anthropogenic activity related to industry and transportation. (author)

C{sub 4} plant isotopic composition ((delta){sup 13}C) evidence for urban CO{sub 2} pollution in the city of Cotonou, Benin (West Africa)

Energy Technology Data Exchange (ETDEWEB)

Kelome, Nelly C.; Leveque, Jean; Andreux, Francis; Milloux, Marie-Jeanne [UMR Microbiologie et Geochimie des Sols INRA, Universite de Bourgogne, Centre des Sciences de la Terre, 6 Bd Gabriel, 21000 Dijon (France); Oyede, Lucien-Marc [Departement des Sciences de la Terre, Universite d' Abomey-Calavi, 01 B.P. 526, Cotonou (Benin)

2006-08-01

The carbon isotopic composition ((delta){sup 13}C) of plants can reveal the isotopic carbon content of the atmosphere in which they develop. The (delta){sup 13}C values of air and plants depend on the amount of atmospheric fossil fuel CO{sub 2}, which is chiefly emitted in urban areas. A new indicator of CO{sub 2} pollution is tested using the (delta){sup 13}C variation in a C{sub 4} grass: Eleusine indica. A range of about 4%% delta units was observed at different sites in Cotonou, the largest city in the Republic of Benin. The highest (delta){sup 13}C values, from -12%% to -14%%, were found in low traffic zones; low (delta){sup 13}C values, from -14%% to -16%%, 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 (delta){sup 13}C values was observed over a four-year monitoring period. This decrease was correlated with increasing vehicle traffic. The (delta){sup 13}C dataset and the corresponding geographical database were used to map and define zones of high and low {sup 13}C-depleted CO{sub 2} 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 CO{sub 2} emissions occurred in the north, the east and the center, providing evidence of intense anthropogenic activity related to industry and transportation. (author)

Understanding of CO{sub 2} interaction with thermally grown SiO{sub 2} on Si using IBA depth profiling techniques

Energy Technology Data Exchange (ETDEWEB)

Deokar, Geetanjali; D’Angelo, Marie; Briand, Emrick [INSP, UPMC, CNRS UMR 7588, 4 Place Jussieu, Paris F-75005 (France); Deville Cavellin, Catherine, E-mail: deville@univ-paris12.fr [INSP, UPMC, CNRS UMR 7588, 4 Place Jussieu, Paris F-75005 (France); Faculté des Sciences et Technologie UPEC, 61 Av., De Gaulle, Créteil F-94010 (France)

2013-06-01

Interactions between CO{sub 2} and SiO{sub 2} films thermally grown on Si have been studied using {sup 18}O and {sup 13}C as isotopic tracers associated with ion beam analysis (IBA) depth profiling techniques. From secondary ion mass spectrometry (SIMS) measurements no carbon from CO{sub 2} is detected in the silica while it is found in Si. These results suggest that CO{sub 2} diffuses through the silica. Exchanges of oxygen between CO{sub 2} and silica can be observed from {sup 18}O to {sup 16}O SIMS signals variation. The oxygen concentration depth profiles were determined quantitatively using the narrow resonance near 151 keV in the {sup 18}O(p,α){sup 15}N nuclear reaction (Narrow Resonance Profiling, NRP). We demonstrate that two distinct oxygen exchanges processes co-exist and we determine the diffusion coefficient of the CO{sub 2} molecule in the silica at 1100 °C.

Analysis on the electron motion in the laser mixture CO/sub 2/-N/sub 2/-He-CO

Energy Technology Data Exchange (ETDEWEB)

Braglia, G L [Parma Univ. (Italy). Ist. di Fisica; Parma Univ. (Italy). Ist. di Matematica); Bruzzese, R [Naples Univ. (Italy). Ist. Elettrotecnico; Caraffini, G L [Parma Univ. (Italy). Ist. di Matematica

1979-06-02

An analysis of the electron motion in the laser mixture CO/sub 2/-N/sub 2/-He-CO (6:34:54:6) is presented. The transport coefficients are given as a function of E/N. Special attention is turned to the operating characteristics of the laser mixture. The results obtained from the Boltzmann equation are tested by the Monte-Carlo technique for E/N=1.5 10/sup -16/ and 5.0 10/sup -16/ (V cm/sup 2/).

Laser assisted ratio analysis - An alternative to GC/IRMS for CO2

International Nuclear Information System (INIS)

Murnick, D.E.

2001-01-01

A new technique for laser based analysis of carbon isotope ratios, with the acronym LARA, based on large isotope shifts in molecular spectra, the use of fixed frequency isotopic lasers, and sensitive detection via the laser optogalvanic effect is reviewed and compared with GC/IRMS for carbon dioxide in specific applications. The possibility for development of new classes of isotope ratio measurement systems with LARA is explored. (author)

Predictive value of 14CO2 breath tests for clinical use of 13CO2 breath tests

International Nuclear Information System (INIS)

Glaubitt, D.M.H.

1975-01-01

The knowledge of the efficiency of 14 CO 2 breath tests makes possible the comparison of the efficiency of analogous tests using the stable isotope 13 C. 14 CO 2 exhalation studies render overall information. After parenteral administration of a 14 C labeled substrate, 14 CO 2 breath tests permit insight into the metabolism of the 14 C substrate and the associated intermediary metabolism. If the 14 C substrate is given orally or by intraduodenal instillation, 14 CO 2 breath tests supply information not only about gastrointenstinal absorption and digestion but also about the intermediary metabolism yielding 14 CO 2 , after the administered substrate or its degradation products have been absorbed in the gastrointestinal tract. The fraction of 14 CO 2 arising from absorption, digestion and intermediary metabolism can be estimated only by additional methods. 14 CO 2 breath tests are unable to delineate single metabolic reactions involved in the formation of carbon dioxide. Under these considerations the clinical application of 14 CO 2 breath tests may provide diagnostically useful results, especially in internal medicine and surgery. The tests are suitable for intraindividual assessment of the course of a disease and of therapeutic effects. They may be important in the research of the metabolism of 14 C labeled substrates

Carbon isotopes in biological carbonates: Respiration and photosynthesis

Science.gov (United States)

McConnaughey, Ted A.; Burdett, Jim; Whelan, Joseph F.; Paull, Charles K.

1997-02-01

Respired carbon dioxide is an important constituent in the carbonates of most air breathing animals but is much less important in the carbonates of most aquatic animals. This difference is illustrated using carbon isotope data from freshwater and terrestrial snails, ahermatypic corals, and chemoautotrophic and methanotrophic pelecypods. Literature data from fish otoliths and bird and mammal shell and bone carbonates are also considered. Environmental CO 2/O 2 ratios appear to be the major controlling variable. Atmospheric CO 2/O 2 ratios are about thirty times lower than in most natural waters, hence air breathing animals absorb less environmental CO 2 in the course of obtaining 0 2. Tissue CO 2 therefore, does not isotopically equilibrate with environmental CO 2 as thoroughly in air breathers as in aquatic animals, and this is reflected in skeletal carbonates. Animals having efficient oxygen transport systems, such as vertebrates, also accumulate more respired CO 2 in their tissues. Photosynthetic corals calcify mainly during the daytime when photosynthetic CO 2 uptake is several times faster than respiratory CO 2 release. Photosynthesis, therefore, affects skeletal δ13C more strongly than does respiration. Corals also illustrate how "metabolic" effects on skeletal isotopic composition can be estimated, despite the presence of much larger "kinetic" isotope effects.

Isotopic labeling as a tool to establish intramolecular vibrational coupling: The reaction of 2-propanol on Mo(110)

International Nuclear Information System (INIS)

Uvdal, P.; Wiegand, B.C.; Serafin, J.G.; Friend, C.M.

1992-01-01

The reactions of 2-propanol on Mo(110) were investigated using temperature programmed reaction, high resolution electron energy loss, and x-ray photoelectron spectroscopies. 2-Propanol forms 2-propoxide upon adsorption at 120 K on Mo(110). The 2-propoxide intermediate deoxygenates via selective γ C--H bond scission to eliminate propene as well as C--O bond hydrogenolysis to form trace amounts of propane. The C--O bond of 2-propoxide is estimated to be nearly perpendicular to the surface. Selective isotopic labeling was used to establish the coupling between the C--O stretch and modes associated with the hydrocarbon framework. The degree of coupling was strongly affected by bonding to the surface, primarily due to weakening of the C--O bond when 2-propoxide is bound to Mo(110). Selective isotopic labeling was, therefore, essential in making vibrational assignments and in identifying key reaction steps. Only a small kinetic isotope effect was observed during reaction of (CD 3 )(CH 3 )CHOH, consistent with a substantial component of C--O bond breaking in the transition state for propene elimination. Coupling of the C--O stretch to motion of the methyl group is also suggested to be important in the transition state for propene elimination

A three-dimensional synthesis study of delta O-18 in atmospheric CO2 .1. Surface fluxes

NARCIS (Netherlands)

Ciais, P; Denning, AS; Tans, PP; Berry, JA; Randall, DA; Collatz, GJ; Sellers, PJ; White, JWC; Trolier, M; Meijer, HAJ; Francey, RJ; Monfray, P; Heimann, M

1997-01-01

The isotope O-18 in CO2 is of particular interest in studying the global carbon cycle because it is sensitive to the processes by which the global land biosphere absorbs and respires CO2. Carbon dioxide and water exchange isotopically both in leaves and in soils, and the O-18 character of

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.

Science.gov (United States)

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. © 2014 John Wiley & Sons Ltd.

Second law analysis of the transcritical CO2 refrigeration cycle

International Nuclear Information System (INIS)

Fartaj, Amir; Ting, David S.-K.; Yang, Wendy W.

2004-01-01

Because of the global warming impact of HFCs, the use of natural refrigerants has received worldwide attention. Efficient use of refrigerants is of pressing concern to the present automotive and HVAC industries. The natural refrigerant, carbon dioxide (CO 2 ), exhibits promise for use in automotive air conditioning systems, in particular the transcritical CO 2 refrigeration cycle. The objective of this work is to identify the main factors that affect CO 2 system performance. A second law of thermodynamic analysis on the entire CO 2 refrigeration cycle is conducted so that the effectiveness of the components of the system can be deduced and ranked, allowing future efforts to focus on improving the components that have the highest potential for advancement. The analysis reveals that the compressor and the gas cooler exhibit the largest non-idealities within the system, and hence, efforts should be focused on improving these components

Geochemical Study of Natural CO{sub 2} Emissions in the French Massif Central: How to Predict Origin, Processes and Evolution of CO{sub 2} Leakage; Etude geochimique des emissions naturelles de CO{sub 2} du Massif Central: origine et processus de migration du gaz

Energy Technology Data Exchange (ETDEWEB)

Battani, A.; Deville, E.; Faure, J.L.; Jeandel, E.; Noirez, S.; Tocque, E.; Benoit, Y.; Schmitz, J.; Parlouar, D. [Institut francais du petrole, IFP, 92 - Rueil-Malmaison (France); Sarda, P. [Paris-11 Univ., 91 - Orsay (France); Gal, F.; Le Pierres, K.; Brach, M.; Braibant, G.; Beny, C. [Bureau de Recherches Geologiques et Minieres (BRGM), 45 - Orleans (France); Pokryszka, Z.; Charmoille, A.; Bentivegna, G. [Institut National de l' Environnement Industriel et des Risques (INERIS), Parc Technologique ALATA, 60 - Verneuil-en-Halatte (France); Pironon, J.; De Donato, P.; Garnier, C.; Cailteau, C.; Barres, O.; Radilla, G.; Bauer, A. [Institut National Polytechnique de Lorraine (INPL), 54 - Vandoeuvre-les-Nancy (France)

2010-07-15

This study presents an overview of some results obtained within the French ANR (National Agency of Research) supported Geocarbone-Monitoring research program. The measurements were performed in Sainte-Marguerite, located in the French Massif Central. This site represents a natural laboratory for CO{sub 2}/fluid/rock interactions studies, as well as CO{sub 2} migration mechanisms towards the surface. The CO{sub 2} leaking character of the studied area also allows to test and validate measurements methods and verifications for the future CO{sub 2} geological storage sites. During these surveys, we analyzed soil CO{sub 2} fluxes and concentrations. We sampled and analyzed soil gases, and gas from carbo-gaseous bubbling springs. A one-month continuous monitoring was also tested, to record the concentration of CO{sub 2} both in atmosphere and in the soil at a single point. We also developed a new methodology to collect soil gas samples for noble gas abundances and isotopic analyses, as well as carbon isotopic ratios. Our geochemical results, combined with structural geology, show that the leaking CO{sub 2} has a very deep origin, partially mantle derived. The gas rises rapidly along normal and strike-slip active faults. CO{sub 2} soil concentrations (also showing a mantle derived component) and CO{sub 2} fluxes are spatially variable, and reach high values. The recorded atmospheric CO{sub 2} is not very high, despite the important CO{sub 2} degassing throughout the whole area. (authors)

On the isotope effects of ZrCoX3 (X = H, D and T): a first-principles study

International Nuclear Information System (INIS)

Chattaraj, D.; Parida, S.C.; Dash, Smruti; Majumder, C.

2013-01-01

In the ITER project, the ZrCo-X (X= H, D and T) systems have gained considerable attention because of its use in the hydrogen isotope storage. The isotopic effects on the ZrCoX 3 (X= H, D and T) compounds have been studied in terms of the variation of the thermodynamic parameters using the DFT and frozen phonon approach. A significant difference between the ZrCoH 3 and its isotopic analogues has been noticed in terms of zero point energy (ZPE) and phonon frequencies. The zero point energies are 65.47 kJ/mol, 48.07 kJ/mol and 39.32 kJ/mol for ZrCoH 3 , ZrCoD 3 and ZrCoT 3 , respectively. The enthalpy of formation of ZrCoX 3 compounds, including the ZPE contributions, are -124.84, -142.24 and -150.99 kJ/(mole of compound) for X = H, D and T, respectively. (author)

Autotrophic fixation of geogenic CO2 by microorganisms contributes to soil organic matter formation and alters isotope signatures in a wetland mofette

DEFF Research Database (Denmark)

Beulig, Felix

2015-01-01

To quantify the contribution of autotrophic microorganisms to organic matter (OM) formation in soils, we investigated natural CO2 vents (mofettes) situated in a wetland in northwest Bohemia (Czech Republic). Mofette soils had higher soil organic matter (SOM) concentrations than reference soils due...... of radiocarbon and enriched in 13C compared to atmospheric CO2. Together, these isotopic signals allow us to distinguish C fixed by plants from C fixed by autotrophic microorganisms using their differences in 13C discrimination. We can then estimate that up to 27 % of soil organic matter in the 0–10 cm layer...... ranged up to 1.59 ± 0.16 μg gdw−1 d−1. We inferred that the negative δ13C shift was caused by the activity of autotrophic microorganisms using the Calvin–Benson–Bassham (CBB) cycle, as indicated from quantification of cbbL/cbbM marker genes encoding for RubisCO by quantitative polymerase chain reaction...

Characterization of methane oxidation in a simulated landfill cover system by comparing molecular and stable isotope mass balances.

Science.gov (United States)

Schulte, Marcel; Jochmann, Maik A; Gehrke, Tobias; Thom, Andrea; Ricken, Tim; Denecke, Martin; Schmidt, Torsten C

2017-11-01

Biological methane oxidation may be regarded as a method of aftercare treatment for landfills to reduce climate relevant methane emissions. It is of social and economic interest to estimate the behavior of bacterial methane oxidation in aged landfill covers due to an adequate long-term treatment of the gas emissions. Different approaches assessing methane oxidation in laboratory column studies have been investigated by other authors recently. However, this work represents the first study in which three independent approaches, ((i) mass balance, (ii) stable isotope analysis, and (iii) stoichiometric balance of product (CO 2 ) and reactant (CH 4 ) by CO 2 /CH 4 -ratio) have been compared for the estimation of the biodegradation by a robust statistical validation on a rectangular, wide soil column. Additionally, an evaluation by thermal imaging as a potential technique for the localization of the active zone of bacterial methane oxidation has been addressed in connection with stable isotope analysis and CO 2 /CH 4 -ratios. Although landfills can be considered as open systems the results for stable isotope analysis based on a closed system correlated better with the mass balance than calculations based on an open system. CO 2 /CH 4 -ratios were also in good agreement with mass balance. In general, highest values for biodegradation were determined from mass balance, followed by CO 2 /CH 4 -ratio, and stable isotope analysis. The investigated topsoil proved to be very suitable as a potential cover layer by removing up to 99% of methane for CH 4 loads of 35-65gm -2 d -1 that are typical in the aftercare phase of landfills. Finally, data from stable isotope analysis and the CO 2 /CH 4 -ratios were used to trace microbial activity within the reactor system. It was shown that methane consumption and temperature increase, as a cause of high microbial activity, correlated very well. Copyright © 2017 Elsevier Ltd. All rights reserved.

Utilization of stable isotopes for characterizing an underground gas generator; Utilisation des isotopes stables pour caracteriser un gazogene souterrain

Energy Technology Data Exchange (ETDEWEB)

Pirard, J P; Antenucci, D; Renard, X [Liege Univ. (Belgium); Letolle, R [Paris-6 Univ., 75 (France)

1994-12-31

The principles of isotopic exchange and isotope ratio result interpretation are first reviewed; then, in the framework of an underground coal gasification project in Belgium, experiments and modelling of the underground gas generator have been carried out: isotopic abundances of carbon, hydrogen and oxygen have been measured in the gasifying agent (O{sub 2}, H{sub 2}O) and in the effluent (CO{sub 2}, CO, H{sub 2}, H{sub 2}O, CH{sub 4}, O{sub 2}, heavy oils and various organic and mineral substances). Gasification kinetics and temperatures have been evaluated and isotope application to thermometry is discussed. 1 fig., 9 refs.

MIR hollow waveguide (HWG) isotope ratio analyzer for environmental applications

Science.gov (United States)

Wang, Zhenyou; Zhuang, Yan; Deev, Andrei; Wu, Sheng

2017-05-01

An advanced commercial Mid-InfraRed Isotope Ratio (IR2) analyzer was developed in Arrow Grand Technologies based on hollow waveguide (HWG) as the sample tube. The stable carbon isotope ratio, i.e. δ13C, was obtained by measuring the selected CO2 absorption peaks in the MIR. Combined with a GC and a combustor, it has been successfully employed to measure compound specific δ13C isotope ratios in the field. By using both the 1- pass HWG and 5-path HWG, we are able to measure δ13C isotope ratio at a broad CO2 concentration of 300 ppm-37,500 ppm. Here, we demonstrate its applications in environmental studies. The δ13C isotope ratio and concentration of CO2 exhaled by soil samples was measured in real time with the isotope analyzer. The concentration was found to change with the time. We also convert the Dissolved Inorganic Carbon (DIC) into CO2, and then measure the δ13C isotope ratio with an accuracy of better than 0.3 ‰ (1 σ) with a 6 min test time and 1 ml sample usage. Tap water, NaHCO3 solvent, coca, and even beer were tested. Lastly, the 13C isotope ratio of CO2 exhaled by human beings was obtained <10 seconds after simply blowing the exhaled CO2 into a tube with an accuracy of 0.5‰ (1 σ) without sample preconditioning. In summary, a commercial HWG isotope analyzer was demonstrated to be able to perform environmental and health studies with a high accuracy ( 0.3 ‰/Hz1/2 1 σ), fast sampling rate (up to 10 Hz), low sample consumption ( 1 ml), and broad CO2 concentration range (300 ppm-37,500 ppm).

Abiotic and seasonal control of soil-produced CO2 efflux in karstic ecosystems located in Oceanic and Mediterranean climates

Science.gov (United States)

Garcia-Anton, Elena; Cuezva, Soledad; Fernandez-Cortes, Angel; Alvarez-Gallego, Miriam; Pla, Concepcion; Benavente, David; Cañaveras, Juan Carlos; Sanchez-Moral, Sergio

2017-09-01

This study characterizes the processes involved in seasonal CO2 exchange between soils and shallow underground systems and explores the contribution of the different biotic and abiotic sources as a function of changing weather conditions. We spatially and temporally investigated five karstic caves across the Iberian Peninsula, which presented different microclimatic, geologic and geomorphologic features. The locations present Mediterranean and Oceanic climates. Spot air sampling of CO2 (g) and δ13CO2 in the caves, soils and outside atmospheric air was periodically conducted. The isotopic ratio of the source contribution enhancing the CO2 concentration was calculated using the Keeling model. We compared the isotopic ratio of the source in the soil (δ13Cs-soil) with that in the soil-underground system (δ13Cs-system). Although the studied field sites have different features, we found common seasonal trends in their values, which suggests a climatic control over the soil air CO2 and the δ13CO2 of the sources of CO2 in the soil (δ13Cs-soil) and the system (δ13Cs-system). The roots respiration and soil organic matter degradation are the main source of CO2 in underground environments, and the inlet of the gas is mainly driven by diffusion and advection. Drier and warmer conditions enhance soil-exterior CO2 interchange, reducing the CO2 concentration and increasing the δ13CO2 of the soil air. Moreover, the isotopic ratio of the source of CO2 in both the soil and the system tends to heavier values throughout the dry and warm season. We conclude that seasonal variations of soil CO2 concentration and its 13C/12C isotopic ratio are mainly regulated by thermo-hygrometric conditions. In cold and wet seasons, the increase of soil moisture reduces soil diffusivity and allows the storage of CO2 in the subsoil. During dry and warm seasons, the evaporation of soil water favours diffusive and advective transport of soil-derived CO2 to the atmosphere. The soil CO2 diffusion is

Calculation of Site-specific Carbon-isotope Fractionation in Pedogenic Oxide Minerals

Energy Technology Data Exchange (ETDEWEB)

Rustad, James R.; Zarzycki, Piotr

2008-07-29

Ab initio molecular dynamics and quantum chemistry techniques are used to calculate the structure, vibrational frequencies, and carbon-isotope fractionation factors of the carbon dioxide component [CO2(m)] of soil (oxy)hydroxide minerals goethite, diaspore, and gibbsite. We have identified two possible pathways of incorporation of CO2(m) into (oxy)hydroxide crystal structures: one in which the C4+ substitutes for four H+ [CO2(m)A] and another in which C4+ substitutes for (Al3+,Fe3+) + H+ [CO2(m)B]. Calculations of isotope fractionation factors give large differences between the two structures, with the CO2(m)A being isotopically lighter than CO2(m)B by ≈10 per mil in the case of gibbsite and nearly 20 per mil in the case of goethite. The reduced partition function ratio of CO2(m)B structure in goethite differs from CO2(g) by <1 per mil. The predicted fractionation for gibbsite is >10 per mil higher, close to those measured for calcite and aragonite. The surprisingly large difference in the carbon-isotope fractionation factor between the CO2(m)A and CO2(m)B structures within a given mineral suggests that the isotopic signatures of soil (oxy)hydroxide could be heterogeneous.

Partitioning CO₂ fluxes with isotopologue measurements and modeling to understand mechanisms of forest carbon sequestration

Energy Technology Data Exchange (ETDEWEB)

Saleska, Scott [Univ. of Arizona, Tucson, AZ (United States). Dept. of Ecology and Evolutionary Biology; Davidson, Eric [Woods Hole Research Center, Falmouth, MA (United States); Finzi, Adrien [Boston Univ., MA (United States). Dept. of Biology; Wehr, Richard [Univ. of Arizona, Tucson, AZ (United States); Moorcroft, Paul [Harvard Univ., Cambridge, MA (United States). Dept. of Organismic and Evolutionary Biology

2016-01-28

This project combines automated in situ observations of the isotopologues of CO₂ with root observations, novel experimental manipulations of below ground processes, and isotope-enabled ecosystem modeling to investigate mechanisms of below- vs. above ground carbon sequestration at the Harvard Forest Environmental Measurements Site (EMS). The proposed objectives, which have now been largely accomplished, include: (A) Partitioning of net ecosystem CO2 exchange (NEE) into photosynthesis and respiration using long-term continuous observations of the isotopic composition of NEE, and analysis of their dynamics; (B) Investigation of the influence of vegetation phenology on the timing and magnitude of carbon allocated below ground using measurements of root growth and indices of below ground autotrophic vs. heterotrophic respiration (via trenched plots andisotope measurements); (C) Testing whether plant allocation of carbon below ground stimulates the microbial decomposition of soil organic matter, using in situ rhizosphere simulation experiments wherein realistic quantities of artificial isotopically-labeled exudates are released into the soil; and (D) Synthesis and interpretation of the above data using the Ecosystem Demography Model 2 (ED2).

A new CF-IRMS system for quantifying stable isotopes of carbon monoxide from ice cores and small air samples

Directory of Open Access Journals (Sweden)

Z. Wang

2010-10-01

Full Text Available We present a new analysis technique for stable isotope ratios (δ¹³C and δ¹⁸O of atmospheric carbon monoxide (CO from ice core samples. The technique is an online cryogenic vacuum extraction followed by continuous-flow isotope ratio mass spectrometry (CF-IRMS; it can also be used with small air samples. The CO extraction system includes two multi-loop cryogenic cleanup traps, a chemical oxidant for oxidation to CO₂, a cryogenic collection trap, a cryofocusing unit, gas chromatography purification, and subsequent injection into a Finnigan Delta Plus IRMS. Analytical precision of 0.2‰ (±1δ for δ¹³C and 0.6‰ (±1δ for δ¹⁸O can be obtained for 100 mL (STP air samples with CO mixing ratios ranging from 60 ppbv to 140 ppbv (~268–625 pmol CO. Six South Pole ice core samples from depths ranging from 133 m to 177 m were processed for CO isotope analysis after wet extraction. To our knowledge, this is the first measurement of stable isotopes of CO in ice core air.

Pressure dependent isotopic fractionation in the photolysis of formaldehyde-d2

DEFF Research Database (Denmark)

Nilsson, E.J.K.; Schmidt, Johan Albrecht; Johnson, Matthew Stanley

2014-01-01

role in the observed pressure dependent photolytic fractionation of deuterium. The model shows that part of the fractionation is a result of competition between the isotopologue dependent rates of unimolecular dissociation and collisional relaxation. We suggest that the remaining fractionation is due......The isotope effects in formaldehyde photolysis are the key link between the δD of methane emissions and the δD of atmospheric in situ hydrogen production. A few recent studies have suggested that a pressure dependence in the isotopic fractionation can partly explain enrichment of deuterium...... with altitude in the atmosphere. The mechanism and the extent of this pressure dependency is, however, not adequately described. In the present work D2CO and H2CO were photolyzed in a static reaction chamber at bath gas pressures of 50, 200, 400, 600 and 1000 mbar; these experiments compliment and extend our...

Current Travertines Precipitation from CO{sub 2}-rich Groundwaters as an alert of CO{sub 2} Leakages from a Natural CO{sub 2} Storage at Ganuelas-Mazarron Tertiary Basin (Murcia, Spain)

Energy Technology Data Exchange (ETDEWEB)

Rodrigo-Naharro, J.; Delgado, A.; Herrero, M. J.; Granados, A.; Perez del Villar, L.

2013-02-01

Carbon capture and storage technologies (CCS) represent the most suitable solutions related to the high anthropogenic CO{sub 2} emissions to the atmosphere. As a consequence, monitoring of the possible CO{sub 2} leakages from an artificial deep geological CO{sub 2} storage (DGS) is indispensable to guarantee its safety. Fast surficial travertine precipitation related to these CO{sub 2} leakages can be used as an alert for these escapes. Since few studies exist focusing on the long-term behaviour of an artificial CO{sub 2} DGS, natural CO{sub 2} storage affected by natural or artificial escapes must be studied as natural analogues for predicting the long-term behaviour of an artificial CO{sub 2} storage. In this context, a natural CO{sub 2} reservoir affected by artificial CO{sub 2} escapes has been studied in this work. This study has mainly focused on the current travertines precipitation associated with the upwelling CO{sub 2}-rich waters from several hydrogeological wells drilled in the Ganuelas-Mazarron Tertiary basin (SE Spain), and consists of a comprehensive characterisation of parent-waters and their associated carbonates, including elemental and isotopic geochemistry, mineralogy and petrography. Geochemical characterisation of groundwaters has led to recognise 4 hydrofacies from 3 different aquifers. These groundwaters have very high salinity and electrical conductivity; are slightly acid; present high dissolved inorganic carbon (DIC) and free CO{sub 2}; are oversaturated in both aragonite and calcite; and dissolve, mobilize and transport low quantities of heavy and/or toxic elements. Isotopic values indicate that: i) the origin of parent-waters is related to rainfalls from clouds originated in the Mediterranean Sea or continental areas; ii) the origin of C is mainly inorganic; and iii) sulphate anions come mainly from the dissolution of the Messinian gypsum from the Tertiary Basin sediments. Current travertines precipitation seems to be controlled by a

Deuterium isotope differences in 2-propanone (CH3)2CO/(CD3)2CO: a high-pressure sound-speed, density, and heat capacities study

International Nuclear Information System (INIS)

Szydlowski, J.; Gomes de Azevedo, R.; Rebelo, L.P.N.; Esperanca, J.M.S.S.; Guedes, H.J.R.

2005-01-01

A new high-pressure, non-intrusive ultrasonic microcell [J. Chem. Thermodyn. 36 (2004) 211-222] was used to carry out sound-speed measurements in deuteriated 2-propanone (acetone-d 6 ) in broad ranges of temperature (288 6 . (p, ρ, T) data for acetone-d 6 were also determined but in a narrower T, p range (298 to 333 K; 0.1 to 60 MPa). In this interval, several thermodynamic properties were thus determined, such as: isentropic (κ s ) and isothermal (κ T ) compressibility, isobaric thermal expansivity (α p ), isobaric (c p ) and isochoric (c v ) specific heat capacity, and the thermal pressure coefficient (γ v ). Comparisons with our data for acetone-h 6 enabled us to establish the magnitude and sign of deuterium isotope effects for identical properties. These effects are a consequence of distinct vibrational mode frequencies in an isotope-invariant force constants' field. Molar heat capacities and their isotope effects were theoretically determined by employing an Einstein-like model for the vibrational frequencies of acetone-h 6 and acetone-d 6

C{sub 4} plant isotopic composition ({delta} {sup 13}C) evidence for urban CO{sub 2} pollution in the city of Cotonou, Benin (West Africa)

Energy Technology Data Exchange (ETDEWEB)

Kelome, Nelly C. [UMR Microbiologie et Geochimie des Sols INRA, Universite de Bourgogne, Centre des Sciences de la Terre, 6 Bd Gabriel, 21000 Dijon (France); Departement des Sciences de la Terre, Universite d' Abomey-Calavi, 01 B.P. 526, Cotonou (Benin); Leveque, Jean [UMR Microbiologie et Geochimie des Sols INRA, Universite de Bourgogne, Centre des Sciences de la Terre, 6 Bd Gabriel, 21000 Dijon (France)]. E-mail: jleveque@ubourgogne.fr; Andreux, Francis [UMR Microbiologie et Geochimie des Sols INRA, Universite de Bourgogne, Centre des Sciences de la Terre, 6 Bd Gabriel, 21000 Dijon (France); Milloux, Marie-Jeanne [UMR Microbiologie et Geochimie des Sols INRA, Universite de Bourgogne, Centre des Sciences de la Terre, 6 Bd Gabriel, 21000 Dijon (France); Oyede, Lucien-Marc [Departement des Sciences de la Terre, Universite d' Abomey-Calavi, 01 B.P. 526, Cotonou (Benin)

2006-08-01

The carbon isotopic composition ({delta} {sup 13}C) of plants can reveal the isotopic carbon content of the atmosphere in which they develop. The {delta} {sup 13}C values of air and plants depend on the amount of atmospheric fossil fuel CO{sub 2}, which is chiefly emitted in urban areas. A new indicator of CO{sub 2} pollution is tested using the {delta} {sup 13}C variation in a C{sub 4} grass: Eleusine indica. A range of about 4 per mille delta units was observed at different sites in Cotonou, the largest city in the Republic of Benin. The highest {delta} {sup 13}C values, from - 12 per mille to - 14 per mille , were found in low traffic zones; low {delta} {sup 13}C values, from - 14 per mille to - 16 per mille , 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 {delta} {sup 13}C values was observed over a four-year monitoring period. This decrease was correlated with increasing vehicle traffic. The {delta} {sup 13}C dataset and the corresponding geographical database were used to map and define zones of high and low {sup 13}C-depleted CO{sub 2} 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 CO{sub 2} emissions occurred in the north, the east and the center, providing evidence of intense anthropogenic activity related to industry and transportation.

History of CO/sub 2/

Energy Technology Data Exchange (ETDEWEB)

Degens, E T

1979-01-01

Upon arrival on earth, the reduced carbon pool split into a series of compartments: core, mantle, crust, hydrosphere, atmosphere, and biosphere. This distribution pattern is caused by the ability of carbon to adjust structurally to a wide range of pressure and temperature, and to form simple and complex molecules with oxygen, hydrogen and nitrogen. Transformation also involved oxidation of carbon to CO/sub 2/ which is mediated at depth by minerals, such as magnetite, and by water vapor above critical temperature. Guided by mineral-organic interactions, simple carbon compounds evolved in near surface environments towards physiologically interesting biochemicals. Life, as an autocatalytic system, is considered an outgrowth of such a development. This article discusses environmental parameters that control the CO/sub 2/ system, past and present. Mantle and crustal evolution is the dynamo recharging the CO/sub 2/ in sea and air; the present rate of CO/sub 2/ release from the magma is 0.05 x 10/sup 15/ g C per year. Due to the enormous buffer capacity of the chemical system ocean, such rates are too small to seriously effect the level of CO/sub 2/ in our atmosphere. In the light of geological field data and stable isotope work, it is concluded that the CO/sub 2/ content in the atmosphere has remained fairly uniform since early Precambrian time; CO/sub 2/ should thus have had little impact on paleoclimate. In contrast, the massive discharge of man-made CO/sub 2/ into our atmosphere may have serious consequences for climate, environment and society in the years to come.

Fossil fuel CO2 estimation by atmospheric 14C measurement and CO2 mixing ratios in the city of Debrecen, Hungary

International Nuclear Information System (INIS)

Molnar, M.; Svingor, E.; Haszpra, L.; Ivo Svetlik; Veres, M.

2010-01-01

A field unit was installed in the city of Debrecen (East Hungary) during the summer of 2008 to monitor urban atmospheric fossil fuel CO 2 . To establish a reference level simultaneous CO 2 sampling has been carried out at a rural site (Hegyhatsal) in Western Hungary. Using the Hungarian background 14 CO 2 observations from the rural site atmospheric fossil fuel CO 2 component for the city of Debrecen was reported in a regional 'Hungarian' scale. A well visible fossil fuel CO 2 peak (10-15 ppm) with a maximum in the middle of winter 2008 (January) was observed in Debrecen air. Significant local maximum (∼20 ppm) in fossil fuel CO 2 during Octobers of 2008 and 2009 was also detected. Stable isotope results are in agreement with the 14 C based fossil fuel CO 2 observations as the winter of 2008 and 2009 was different in atmospheric δ 13 C variations too. The more negative δ 13 C of atmospheric CO 2 in the winter of 2008 means more fossil carbon in the atmosphere than during the winter of 2009. (author)

Calculation of radiation production of high specific activity isotopes 192Ir and 60Co

International Nuclear Information System (INIS)

Zhou Quan; Zhong Wenfa; Xu Xiaolin

1997-01-01

The high specific activity isotopes: 192 Ir and 60 Co in the high neutron flux reactor are calculated with the method of reactor physics. The results of calculation are analyzed in two aspects: the production of isotopes and the influence to parameters of the reactor, and hence a better case is proposed as a reference to the production

Whole-body CO2 production as an index of the metabolic response to sepsis

Science.gov (United States)

Whole-body carbon dioxide (CO2) production (RaCO2) is an index of substrate oxidation and energy expenditure; therefore, it may provide information about the metabolic response to sepsis. Using stable isotope techniques, we determined RaCO2 and its relationship to protein and glucose metabolism in m...

Electrochemical impedance spectroscopy analysis with a symmetric cell for LiCoO2 cathode degradation correlated with Co dissolution

Directory of Open Access Journals (Sweden)

Hiroki Nara

2016-04-01

Full Text Available Static degradation of LiCoO2 cathodes is a problem that hinders accurate analysis using our developed separable symmetric cell. Therefore, in this study we investigate the static degradation of LiCoO2 cathodes in separable symmetric cells by electrochemical impedance spectroscopy (EIS and inductively coupled plasma analyses. EIS measurements of LiCoO2 cathodes are conducted in various electrolytes, with different anions and with or without HF and/or H2O. This allows us to determine the static degradation of LiCoO2 cathodes relative to their increase of charge transfer resistance. The increase of the charge transfer resistance of the LiCoO2 cathodes is attributed to cobalt dissolution from the active material of LiCoO2. Cobalt dissolution from LiCoO2 is revealed to occur even at low potential in the presence of HF, which is generated from LiPF6 and H2O. The results indicate that avoidance of HF generation is important for the analysis of lithium-ion battery electrodes by using the separable cell. These findings reveal the condition to achieve accurate analysis by EIS using the separable cell.

Spectroscopic analysis of PMMA/PVC blends containing CoCl2

Directory of Open Access Journals (Sweden)

N.S. Alghunaim

2015-01-01

Full Text Available Composites of polymethyl methacrylate (PMMA and polyvinyl chloride (PVC polymer blend containing different concentrations (⩽10 wt. of cobalt chloride (CoCl2 were prepared by casting techniques. The changes of the structural, spectroscopic, optical and thermal parameters of the samples are studied using different tools. FT-IR spectroscopy confirmed the complexation between the blends and Co+2-ions. The decrease or increase of IR band intensity with some shifts of other bands suggests an interaction and compatibility between PMMA/PVC blends with CoCl2 take place. The Ultra violet and visible (UV/Vis spectra indicated that the presence of band gap energy depends on increasing of CoCl2 contents. The absorption intensity of the samples doped with CoCl2 becomes faint lower than the pure blend. The values of energy gap for direct and indirect transition decreases with the increase of CoCl2 due to the presence of charge transfer between PMMA/PVC and CoCl2. The thermogravimetric analysis (TGA curves for all the samples have the same behavior and more steps of decomposition were observed. The reduction of mass loss for samples containing CoCl2 compared to the pure blend was observed and it was attributed to crosslink formation between the blend and CoCl2.

A sublimation technique for high-precision measurements of δ13CO2 and mixing ratios of CO2 and N2O from air trapped in ice cores

Directory of Open Access Journals (Sweden)

H. Fischer

2011-07-01

Full Text Available In order to provide high precision stable carbon isotope ratios (δ13CO2 or δ13C of CO2 from small bubbly, partially and fully clathrated ice core samples we developed a new method based on sublimation coupled to gas chromatography-isotope ratio mass spectrometry (GC-IRMS. In a first step the trapped air is quantitatively released from ~30 g of ice and CO2 together with N2O are separated from the bulk air components and stored in a miniature glass tube. In an off-line step, the extracted sample is introduced into a helium carrier flow using a minimised tube cracker device. Prior to measurement, N2O and organic sample contaminants are gas chromatographically separated from CO2. Pulses of a CO2/N2O mixture are admitted to the tube cracker and follow the path of the sample through the system. This allows an identical treatment and comparison of sample and standard peaks. The ability of the method to reproduce δ13C from bubble and clathrate ice is verified on different ice cores. We achieve reproducibilities for bubble ice between 0.05 ‰ and 0.07 ‰ and for clathrate ice between 0.05 ‰ and 0.09 ‰ (dependent on the ice core used. A comparison of our data with measurements on bubble ice from the same ice core but using a mechanical extraction device shows no significant systematic offset. In addition to δ13C, the CO2 and N2O mixing ratios can be volumetrically derived with a precision of 2 ppmv and 8 ppbv, respectively.

Oxygen isotopic signature of CO2 from combustion processes

NARCIS (Netherlands)

Schumacher, M.; Werner, R. A.; Meijer, H. A. J.; Brand, W. A.; Geilmann, H.; Neubert, R. E. M.; Kaiser, J.; Jansen, Henk G.

2011-01-01

For a comprehensive understanding of the global carbon cycle precise knowledge of all processes is necessary. Stable isotope (C-13 and O-18) abundances provide information for the qualification and the quantification of the diverse source and sink processes. This study focuses on the delta O-18

Co-ordinated research programme applications of stable isotope tracers in human nutrition research

International Nuclear Information System (INIS)

1992-01-01

The objective of this Co-ordinated Research Programme is to help establish competence in the use of stable isotope techniques, particularly in developing countries. This report summarizes the discussions that took, place during the Second Research Co-ordination Meeting, held in Bangalore in November 1990. Working papers presented by the participants are included as annexes. Refs, figs and tabs

NETL CO₂ Storage prospeCtive Resource Estimation Excel aNalysis (CO₂-SCREEN) User's Manual

Energy Technology Data Exchange (ETDEWEB)

Sanguinito, Sean M. [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Goodman, Angela [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Levine, Jonathan [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)

2017-04-03

This user’s manual guides the use of the National Energy Technology Laboratory’s (NETL) CO₂ Storage prospeCtive Resource Estimation Excel aNalysis (CO₂-SCREEN) tool, which was developed to aid users screening saline formations for prospective CO₂ storage resources. CO₂- SCREEN applies U.S. Department of Energy (DOE) methods and equations for estimating prospective CO₂ storage resources for saline formations. CO2-SCREEN was developed to be substantive and user-friendly. It also provides a consistent method for calculating prospective CO₂ storage resources that allows for consistent comparison of results between different research efforts, such as the Regional Carbon Sequestration Partnerships (RCSP). CO₂-SCREEN consists of an Excel spreadsheet containing geologic inputs and outputs, linked to a GoldSim Player model that calculates prospective CO₂ storage resources via Monte Carlo simulation.

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

Science.gov (United States)

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

Redox substoichiometry in isotope dilution analysis Pt. 2

International Nuclear Information System (INIS)

Kambara, T.; Suzuki, J.; Yoshioka, H.; Nakajima, N.

1978-01-01

Isotope dilution analysis using the redox substoichiometric principle has been applied to the determination of antimony content in metallic zinc. As the substoichiometric reaction, the oxidation of trivalent to pentavalent antimony with potassium permanganate was used, followed by separation of these species by the BHPA extraction of trivalent antimony. Determination of antimony contents less than 0.5 μg was found to be possible with good accuracy, without separation of zinc ions. The antimony content in a metallic zinc sample was determined to be 19.7+-0.8 ppm, in good agreement with the results obtained by the other analytical methods. (author)

Analysis of dissolved organic carbon concentration and 13C isotopic signature by TOC-IRMS - assessment of analytical performance

Science.gov (United States)

Kirkels, Frédérique; Cerli, Chiara; Federherr, Eugen; Kalbitz, Karsten

2013-04-01

Stable carbon isotopes provide a powerful tool to assess carbon pools and their dynamics. Dissolved organic carbon (DOC) has been recognized to play an important role in ecosystem functioning and carbon cycling and has therefore gained increased research interest. However, direct measurement of 13C isotopic signature of carbon in the dissolved phase is technically challenging particularly using high temperature combustion. Until recently, mainly custom-made systems existed which were modified for coupling of TOC instruments with IRMS for simultaneous assessment of C content and isotopic signature. The variety of coupled systems showed differences in their analytical performances. For analysis of DOC high temperature combustion is recognized as best performing method, owing to its high efficiency of conversion to CO2 also for highly refractory components (e.g. humic, fulvic acids) present in DOC and soil extracts. Therefore, we tested high temperature combustion TOC coupled to IRMS (developed by Elementar Group) for bulk measurements of DOC concentration and 13C signature. The instruments are coupled via an Interface to exchange the carrier gas from O2 to He and to concentrate the derived CO2 for the isotope measurement. Analytical performance of the system was assessed for a variety of organic compounds characterized by different stability and complexity, including humic acid and DOM. We tested injection volumes between 0.2-3 ml, thereby enabling measurement of broad concentration ranges. With an injection volume of 0.5 ml (n=3, preceded by 1 discarded injection), DOC and 13C signatures for concentrations between 5-150 mg C/L were analyzed with high precision (standard deviation (SD) predominantly TOC-IRMS in comparison with other systems capable of determining C concentration and isotopic signatures. We recognize the advantages of this system providing: - High sample throughput, short measurement time (15 minutes), flexible sample volume - Easy maintenance

Macro economic analysis of CO2 emission limits for China

International Nuclear Information System (INIS)

Zhang, Z.X.; Folmer, H.; Van Beek, P.

1995-01-01

Using a newly developed time-recursive dynamic CGE model for energy and environmental policy analysis of the Chinese economy, a business-as-usual scenario is first developed assuming no specific policy intervention to limit the growth rate of CO2 emissions. Counter factual policy simulation is then carried out to compute the macroeconomic implications of a carbon tax to limit the Chinese energy-related CO2 emissions. 2 tabs., 5 refs

Isotope analysis of diamond-surface passivation effect of high-temperature H{sub 2}O-grown atomic layer deposition-Al{sub 2}O{sub 3} films

Energy Technology Data Exchange (ETDEWEB)

Hiraiwa, Atsushi, E-mail: hiraiwa@aoni.waseda.jp, E-mail: qs4a-hriw@asahi-net.or.jp [Institute for Nanoscience and Nanotechnology, Waseda University, 513 Waseda-tsurumaki, Shinjuku, Tokyo 162-0041 (Japan); Saito, Tatsuya; Matsumura, Daisuke; Kawarada, Hiroshi, E-mail: kawarada@waseda.jp [Faculty of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo 169-8555 (Japan)

2015-06-07

The Al{sub 2}O{sub 3} film formed using an atomic layer deposition (ALD) method with trimethylaluminum as Al precursor and H{sub 2}O as oxidant at a high temperature (450 °C) effectively passivates the p-type surface conduction (SC) layer specific to a hydrogen-terminated diamond surface, leading to a successful operation of diamond SC field-effect transistors at 400 °C. In order to investigate this excellent passivation effect, we carried out an isotope analysis using D{sub 2}O instead of H{sub 2}O in the ALD and found that the Al{sub 2}O{sub 3} film formed at a conventional temperature (100 °C) incorporates 50 times more CH{sub 3} groups than the high-temperature film. This CH{sub 3} is supposed to dissociate from the film when heated afterwards at a higher temperature (550 °C) and causes peeling patterns on the H-terminated surface. The high-temperature film is free from this problem and has the largest mass density and dielectric constant among those investigated in this study. The isotope analysis also unveiled a relatively active H-exchange reaction between the diamond H-termination and H{sub 2}O oxidant during the high-temperature ALD, the SC still being kept intact. This dynamic and yet steady H termination is realized by the suppressed oxidation due to the endothermic reaction with H{sub 2}O. Additionally, we not only observed the kinetic isotope effect in the form of reduced growth rate of D{sub 2}O-oxidant ALD but found that the mass density and dielectric constant of D{sub 2}O-grown Al{sub 2}O{sub 3} films are smaller than those of H{sub 2}O-grown films. This is a new type of isotope effect, which is not caused by the presence of isotopes in the films unlike the traditional isotope effects that originate from the presence of isotopes itself. Hence, the high-temperature ALD is very effective in forming Al{sub 2}O{sub 3} films as a passivation and/or gate-insulation layer of high-temperature-operation diamond SC devices, and the knowledge of

Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide

Science.gov (United States)

Wiegel, Aaron A.; Cole, Amanda S.; Hoag, Katherine J.; Atlas, Elliot L.; Schauffler, Sue M.; Boering, Kristie A.

2013-10-01

We report observations of stratospheric CO2 that reveal surprisingly large anomalous enrichments in 17O that vary systematically with latitude, altitude, and season. The triple isotope slopes reached 1.95 ± 0.05(1σ) in the middle stratosphere and 2.22 ± 0.07 in the Arctic vortex versus 1.71 ± 0.03 from previous observations and a remarkable factor of 4 larger than the mass-dependent value of 0.52. Kinetics modeling of laboratory measurements of photochemical ozone-CO2 isotope exchange demonstrates that non-mass-dependent isotope effects in ozone formation alone quantitatively account for the 17O anomaly in CO2 in the laboratory, resolving long-standing discrepancies between models and laboratory measurements. Model sensitivities to hypothetical mass-dependent isotope effects in reactions involving O3, O(1D), or CO2 and to an empirically derived temperature dependence of the anomalous kinetic isotope effects in ozone formation then provide a conceptual framework for understanding the differences in the isotopic composition and the triple isotope slopes between the laboratory and the stratosphere and between different regions of the stratosphere. This understanding in turn provides a firmer foundation for the diverse biogeochemical and paleoclimate applications of 17O anomalies in tropospheric CO2, O2, mineral sulfates, and fossil bones and teeth, which all derive from stratospheric CO2.

Use of isotope techniques in lake dynamics investigations. Proceedings of a final research co-ordination meeting

International Nuclear Information System (INIS)

2001-03-01

The Co-ordinated Research Programme (CRP) on the Use of Isotope Techniques in Lake Dynamics Investigations was launched with the aim of assessing the potential of environmental isotope techniques in studying the dynamics of surface water bodies and related problems such as: dynamics of solutes; sediment focusing; establishment of water balance components; vulnerability to pollution. The CRP enabled a number of isotope and geochemical studies to be carried out on small and large water bodies, with the general aim of understanding of the dynamics of these systems under the growing anthropogenic influence. This publication is a compilation of the papers presented at the final Research Co-ordination Meeting (RCM) held in Rehovot, Israel, from 10 to 13 March 1997. Individual contributions have been indexed separately

Metabolic flux analysis of the phenylpropanoid pathway in wound-healing potato tuber tissue using stable isotope-labeled tracer and LC-MS spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Matsuda, Fumio; Morino, Keiko; Miyashita, Masahiro; Miyagawa, Hisashi [Kyoto Univ. (Japan). Department of Agriculture

2003-05-01

The metabolic flux of two phenylpropanoid metabolites, N-p-coumaroyloctopamine (p-CO) and chlorogenic acid (CGA), in the wound-healing potato tuber tissue was quantitatively analyzed by a newly developed method based upon the tracer experiment using stable isotope-labeled compounds and LC-MS. Tuber disks were treated with aqueous solution of L-phenyl-d{sub 5}-alanine, and the change in the ratio of stable isotope-labeled compound to non-labeled (isotope abundance) was monitored for p-CO and CGA in the tissue extract by LC-MS. The time-dependent change in the isotope abundance of each metabolite was fitted to an equation that was derived from the formation and conversion kinetics of each compound. Good correlations were obtained between the observed and calculated isotope abundances for both p-CO and CGA. The rates of p-CO formation and conversion (i.e. fluxes) were 1.15 and 0.96 nmol (g FW){sup -1}h{sup -1}, respectively, and for CGA, the rates 4.63 and 0.42 nmol (g FW){sup -1}h{sup -1}, respectively. This analysis enabled a direct comparison of the biosynthetic activity between these two compounds. (author)

Comparison of gas chromatography/isotope ratio mass spectrometry and liquid chromatography/isotope ratio mass spectrometry for carbon stable-isotope analysis of carbohydrates.