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Sample records for carbon isotopes support

  1. Carbon isotopic record from Upper Devonian carbonates at Dongcun in Guilin, southern China, supporting the world-wide pattern of carbon isotope excursions during Frasnian-Famennian transition

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Two positive δ13C excursions are presented in records from the Frasnian-Famennian (F-F) marine carbonate sediments in Europe, America, Africa, and Australia, having been considered as a worldwide pattern, and attributed to enhanced organic carbon burial during the F-F biological mass extinction. However, this worldwide pattern has not been revealed from the well-deposited Late Devonian sequences in southern China. In this paper, a detailed investigation has been made on the Late Devonian section at Dongcun, Guilin, southern China to constrain perturbations in δ13C of carbonates in the F-F deposited sequence. The result from this section also indicates two positive δ13C excursions during the F-F transition. The first excursion with an amplitude of 1.5‰ occurred at the bottom of linguiformis Zone, later than the early excursion existing in the Late rhenana Zone of the Late Devonian profiles in other continents, especially, in central Europe. This difference has been expected to be a result as conodont Palmatolepis linguiformis occurred earlier in southern China than other sites. The second excursion with an amplitude of 2.1‰ is located at the F-F boundary, same as the records from other continents. This result strongly supports the view that two carbon isotope positive excursions during the F-F transition are common in carbonate sediments, resulting from worldwide increases of organic carbon burial intensity.

  2. Carbon isotope geochemistry and geobiology

    Science.gov (United States)

    Desmarais, D.

    1985-01-01

    Carbon isotope fractionation values were used to understand the history of the biosphere. For example, plankton analyses confirmed that marine extinctions at the end of the Cretaceous period were indeed severe (see Hsu's article in Sundquist and Broeker, 1984). Variations in the isotopic compositions of carbonates and evaporitic sulfates during the Paleozoic reflect the relative abundances of euxinic (anoxic) marine environments and organic deposits from terrestrial flora. The carbon isotopic composition of Precambrian sediments suggest that the enzyme ribulose bisphosphate carboxylase has existed for perhaps 3.5 billion years.

  3. Isotopic niches support the resource breadth hypothesis

    Science.gov (United States)

    Rader, Jonathan A.; Newsome, Seth D.; Sabat, Pablo; Chesser, R. Terry; Dillon, Michael E.; Martinez del Rio, Carlos

    2017-01-01

    Because a broad spectrum of resource use allows species to persist in a wide range of habitat types, and thus permits them to occupy large geographical areas, and because broadly distributed species have access to more diverse resource bases, the resource breadth hypothesis posits that the diversity of resources used by organisms should be positively related with the extent of their geographic ranges.We investigated isotopic niche width in a small radiation of South American birds in the genus Cinclodes. We analysed feathers of 12 species of Cinclodes to test the isotopic version of the resource breadth hypothesis and to examine the correlation between isotopic niche breadth and morphology.We found a positive correlation between the widths of hydrogen and oxygen isotopic niches (which estimate breadth of elevational range) and widths of the carbon and nitrogen isotopic niches (which estimates the diversity of resources consumed, and hence of habitats used). We also found a positive correlation between broad isotopic niches and wing morphology.Our study not only supports the resource breadth hypothesis but it also highlights the usefulness of stable isotope analyses as tools in the exploration of ecological niches. It is an example of a macroecological application of stable isotopes. It also illustrates the importance of scientific collections in ecological studies.

  4. The separation of stable isotopes of carbon

    Science.gov (United States)

    Oziashvili, E. D.; Egiazarov, A. S.

    1989-04-01

    The present state of work on the separation of carbon isotopes by diffusion, fractional distillation, chemical isotopic exchange, and the selective excitation and dissociation of molecules in electrical discharges or in the field of laser radiation has been examined. The characteristics of new laboratory and industrial assemblies for separating carbon isotopes have been described. Promising directions of study aimed at developing effective technological processes for separating carbon isotopes have been noted. The bibliography contains 148 references.

  5. Degradation changes stable carbon isotope depth profiles in palsa peatlands

    Directory of Open Access Journals (Sweden)

    J. P. Krüger

    2014-01-01

    Full Text Available Palsa peatlands are a significant carbon pool in the global carbon cycle and are projected to change by global warming due to accelerated permafrost thaw. Our aim was to use stable carbon isotopes as indicators of palsa degradation. Depth profiles of stable carbon isotopes generally reflect organic matter dynamics in soils with an increase of δ13C values during aerobic decomposition and stable or decreasing δ13C values with depth during anaerobic decomposition. Stable carbon isotope depth profiles of undisturbed and degraded sites of hummocks as well as hollows at three palsa peatlands in northern Sweden were used to investigate the degradation processes. The depth patterns of stable isotopes clearly differ between intact and degraded hummocks at all sites. Erosion and cryoturbation at the degraded sites significantly changes the stable carbon isotope depth profiles. At the intact hummocks the uplifting of peat material by permafrost is indicated by a turning in the δ13C depth trend and this assessment is supported by a change in the C / N ratios. For hollows isotope patterns were less clear, but some hollows and degraded hollows in the palsa peatlands show differences in their stable carbon isotope depth profiles indicating enhanced degradation rates. We conclude that the degradation of palsa peatlands by accelerated permafrost thawing could be identified with stable carbon isotope depth profiles. At intact hummocks δ13C depth patterns display the uplifting of peat material by a change in peat decomposition processes.

  6. Chromium isotope uptake in carbonates

    DEFF Research Database (Denmark)

    Rodler, Alexandra

    composition of contemporaneous seawater. Marine carbonates are ubiquitous throughout Earth’s rock record rendering them a particularly interesting archive for constraining past changes in ocean chemistry. This thesis includes an investigation of the fractionation behavior of Cr isotopesduring coprecipitation......Chromium (Cr) is a redox sensitive element potentially capable of tracing fine-scale fluctuations of the oxygenation of Earth’s early surface environments and seawater. The Cr isotope composition of carbonates could perhaps be used as paleo-redox proxy to elucidate changes in the geological past...... related to the rise of oxygen and the evolution of the biosphere. However, before the Cr isotopesystem can be applied to faithfully delineate paleo-environmental changes, careful assessment of the signal robustness and a thorough understanding of the Cr cycle in Earth system processes is necessary...

  7. Chromium isotope uptake in carbonates

    DEFF Research Database (Denmark)

    Rodler, Alexandra

    composition of contemporaneous seawater. Marine carbonates are ubiquitous throughout Earth’s rock record rendering them a particularly interesting archive for constraining past changes in ocean chemistry. This thesis includes an investigation of the fractionation behavior of Cr isotopesduring coprecipitation......Chromium (Cr) is a redox sensitive element potentially capable of tracing fine-scale fluctuations of the oxygenation of Earth’s early surface environments and seawater. The Cr isotope composition of carbonates could perhaps be used as paleo-redox proxy to elucidate changes in the geological past...... related to the rise of oxygen and the evolution of the biosphere. However, before the Cr isotopesystem can be applied to faithfully delineate paleo-environmental changes, careful assessment of the signal robustness and a thorough understanding of the Cr cycle in Earth system processes is necessary...

  8. Robust optical carbon dioxide isotope analyzer Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Isotopic analysis of carbon dioxide is an important tool for characterization of the exchange and transformation of carbon between the biosphere and the atmosphere....

  9. Carbon isotopic fractionation in heterotrophic microbial metabolism

    Science.gov (United States)

    Blair, N.; Leu, A.; Munoz, E.; Olsen, J.; Kwong, E.; Des Marais, D.

    1985-01-01

    Differences in the natural-abundance carbon stable isotopic compositions between products from aerobic cultures of Escherichia coli K-12 were measured. Respired CO2 was 3.4 percent depleted in C-13 relative to the glucose used as the carbon source, whereas the acetate was 12.3 percent enriched in C-13. The acetate C-13 enrichment was solely in the carboxyl group. Even though the total cellular carbon was only 0.6 percent depleted in C-13, intracellular components exhibited a significant isotopic heterogeneity. The protein and lipid fractions were -1.1 and -2.7 percent, respectively. Aspartic and glutamic acids were -1.6 and +2.7 percent, respectively, yet citrate was isotopically identical to the glucose. Probable sites of carbon isotopic fractionation include the enzyme, phosphotransacetylase, and the Krebs cycle.

  10. Isotope engineering of carbon nanotube systems.

    Science.gov (United States)

    Simon, F; Kramberger, Ch; Pfeiffer, R; Kuzmany, H; Zólyomi, V; Kürti, J; Singer, P M; Alloul, H

    2005-07-01

    The synthesis of a unique isotope engineered system, double-wall carbon nanotubes with natural carbon outer and highly 13C enriched inner walls, is reported from isotope enriched fullerenes encapsulated in single-wall carbon nanotubes (SWCNTs). The material allows the observation of the D line of the highly defect-free inner tubes that can be related to a curvature induced enhancement of the electron-phonon coupling. Ab initio calculations explain the inhomogeneous broadening of inner tube Raman modes due to the distribution of different isotopes. Nuclear magnetic resonance shows a significant contrast of the isotope enriched inner SWCNTs compared to other carbon phases and provides a macroscopic measure of the inner tube mass content. The high curvature of the small diameter inner tubes manifests in an increased distribution of the chemical shift tensor components.

  11. Carbon isotope geochemistry in the Yalujiang estuary

    Institute of Scientific and Technical Information of China (English)

    吴莹; 张经

    2001-01-01

    The distribution of particulate organic carbon (POC) along the lower reaches is similar between the dry season and the flood season in the Yalujiang Estuary, North China. However, the values of particulate organic carbon of the upperstream in the dry season are one magnitude lower than the concentrations in the flood season. Stable carbon isotope ratios have been used to study the sources of particulate organic carbon in the Yalujiang Estuary. The isotopic composition of POC shows a range from -23.1‰ to -29.4‰ with a little seasonal variation. The isotopic evidence indicates that the POC in the Yalujiang Estuary is predominantly of terrestrial origin rather than a result of in situ plankton. The study of the ratio of POC: Chla shows that the turbidity maximum plays an important role in POC cycle in the Yalujiang Estuary. Organic detritus and soil erosion are the main contributions to POC in the turbidity maximum, especially in the flood season.

  12. Carbon isotope anomalies in carbonates of the Karelian series

    Science.gov (United States)

    Iudovich, Ia. E.; Makarikhin, V. V.; Medvedev, P. V.; Sukhanov, N. V.

    1990-07-01

    Results are presented on carbon isotope distributions in carbonates of the Karelian complex. A highly anomalous isotopic composition was found in carbonate rocks aged from 2.6 to 1.9 b.y. In the stromatolitic carbonates of the Onega water table, delta-(C-13) reaches a value of +18 percent, while the shungite layer of the Zaonega horizon is characterized by a wide dispersion (from +7.9 to -11.8 percent). These data are in good agreement with the known geochemical boundary (about 2.2 b.y. ago) in the history of the earth.

  13. Exotic Structure of Carbon Isotopes

    CERN Document Server

    Suzuki, T; Hagino, K; Suzuki, Toshio; Sagawa, Hiroyuki; Hagino, Kouichi

    2002-01-01

    We studied firstly the ground state properties of C-isotopes using a deformed Hartree-Fock (HF)+ BCS model with Skyrme interactions. Shallow deformation minima are found in several neutron$-$rich C-isotopes. It is shown also that the deformation minima appear in both the oblate and the prolate sides in $^{17}$C and $^{19}$C having almost the same binding energies. Secondly, we carried out shell model calculations to study electromagnetic moments and electric dipole transitions of the C-isotopes. We point out the clear configuration dependence of the quadrupole and magnetic moments in the odd C-isotopes, which will be useful to find out the deformations and the spin-parities of the ground states of these nuclei. We studied electric dipole states of C-isotopes focusing on the interplay between low energy Pigmy strength and giant dipole resonances. Reasonable agreement is obtained with available experimental data for the photoreaction cross sections both in the low energy region below $\\hbar \\omega $=14 MeV and ...

  14. Soil Carbon: Compositional and Isotopic Analysis

    Energy Technology Data Exchange (ETDEWEB)

    Moran, James J.; Alexander, M. L.; Laskin, Alexander

    2016-11-01

    This is a short chapter to be included in the next edition of the Encyclopedia of Soil Science. The work here describes techniques being developed at PNNL for investigating organic carbon in soils. Techniques discussed include: laser ablation isotope ratio mass spectrometry, laser ablation aerosol mass spectrometry, and nanospray desorption electrospray ionization mass spectrometry.

  15. Carbon isotopes as indicators of peatland growth?

    Science.gov (United States)

    Alewell, Christine; Krüger, Jan Paul; von Sengbusch, Pascal; Szidat, Sönke; Leifeld, Jens

    2016-04-01

    As undisturbed and/or growing peatlands store considerable amounts of carbon and are unique in their biodiversity and species assemblage, the knowledge of the current status of peatlands (growing with carbon sequestration, stagnating or degrading with carbon emissions) is crucial for landscape management and nature conservation. However, monitoring of peatland status requires long term measurements and is only feasible with expert knowledge. The latter determination is increasingly impeded in a scientific world, where taxonomic expert knowledge and funding of long term monitoring is rare. Stable carbon and nitrogen isotopes depth profiles in peatland soils have been shown to be a useful tool to monitor the degradation of peatlands due to permafrost thawing in Northern Sweden (Alewell et al., 2011; Krüger et al., 2014), drainage in Southern Finland (Krüger et al., 2016) as well as land use intensification in Northern Germany (Krüger et al., 2015). Here, we tackle the questions if we are able to differentiate between growing and degrading peats with the use of a combination of carbon stable (δ13C) and radiogenic isotope data (14C) with peat stratification information (degree of humification and macroscopic plant remains). Results indicate that isotope data are a useful tool to approximate peatland status, but that expert taxonomic knowledge will be needed for the final conclusion on peatland growth. Thus, isotope tools might be used for landscape screening to pin point sites for detailed taxonomic monitoring. As the method remains qualitative future research at these sites will need to integrate quantitative approaches to determine carbon loss or gain (soil C balances by ash content or C accumulation methods by radiocarbon data; Krüger et al., 2016). Alewell, C., R. Giesler, J. Klaminder, J. Leifeld, and M. Rollog. 2011. Stable carbon isotopes as indicators for micro-geomorphic changes in palsa peats. Biogeosciences, 8, 1769-1778. Krüger, J. P., Leifeld, J

  16. Fractionation behavior of chromium isotopes during coprecipitation with calcium carbonate

    DEFF Research Database (Denmark)

    Rodler, Alexandra; Sánchez-Pastor, Nuria; Fernández-Díaz, Lurdes;

    2015-01-01

    Interest in chromium (Cr) isotope incorporation into carbonates arises from the observation that Cr isotopic composition of carbonates could be used as a paleoclimate proxy to elucidate past fluctuations of oxygen contents in atmosphere and hydrosphere. The use of Cr isotopes to track paleoenviro......Interest in chromium (Cr) isotope incorporation into carbonates arises from the observation that Cr isotopic composition of carbonates could be used as a paleoclimate proxy to elucidate past fluctuations of oxygen contents in atmosphere and hydrosphere. The use of Cr isotopes to track...

  17. Deciphering Carbon Isotope Excursions in Separated Biogenic and Diagenetic Carbonates

    Science.gov (United States)

    Hermoso, M.; Minoletti, F.; Hesselbo, S.; Jenkyns, H.; Rickaby, R.; Diester-Haass, L.; Delsate, D.

    2008-12-01

    The long-term evolution of the carbon-isotope ratio in the sedimentary archive is classically linked with changes in primary productivity and organic matter burial. There have been sudden and pronounced shifts, so-called Carbon Isotope Excursions (CIEs) in the long-term trends as evidenced by synchronous shifts from various basins. These geochemical perturbations may have various explanations such as changes of the efficiency of the carbon sink; sudden infusion of isotopically-light carbon into the Ocean-Atmosphere system; or advection of 12C-rich source from bottom water in a stratified water column. Beside the record of primary changes in seawater chemistry, a possible diagenetic overprint may also mime such CIEs in the sedimentary record. The aim of this contribution is to illustrate through three critical intervals (the Early Toarcian, the K-P boundary and the Mid-Miocene Montery Event) how the various micron-sized sedimentary particles specifically record these CIEs, which are respectively associated with major paleoceanographical events. New techniques for getting monotaxic calcareous nannofossil assemblages from the sediment (Minoletti et al., accepted) enable the isotopic measurement at various depths within the surface water and from bottom water by analyzing early diagenetic precipitations (rhombs and micarbs). The integration of these high-resolution isotopic signals in terms of amplitudes affords to recognize diagenetic artifacts in some sections displaying coeval decrease in the carbonate content. For both Early Toarcian and K-P events, corroborative records of CIE records in both primary calcite and bottom water carbonate indicate a global C-isotope perturbation of the water column. For the Monterey event, the evolution of calcareous nannoplankton and the foraminifera isotopic records are in overall agreement, but in detail, the coccolith-discoaster and foraminifer ratio in the sediment, related to environmental changes, is likely to produce isotopic

  18. 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.

  19. Carbon isotopic composition of individual Precambrian microfossils.

    Science.gov (United States)

    House, C H; Schopf, J W; McKeegan, K D; Coath, C D; Harrison, T M; Stetter, K O

    2000-08-01

    Ion microprobe measurements of carbon isotope ratios were made in 30 specimens representing six fossil genera of microorganisms petrified in stromatolitic chert from the approximately 850 Ma Bitter Springs Formation, Australia, and the approximately 2100 Ma Gunflint Formation, Canada. The delta 13C(PDB) values from individual microfossils of the Bitter Springs Formation ranged from -21.3 +/- 1.7% to -31.9 +/- 1.2% and the delta 13C(PDB) values from microfossils of the Gunflint Formation ranged from -32.4 +/- 0.7% to -45.4 +/- 1.2%. With the exception of two highly 13C-depleted Gunflint microfossils, the results generally yield values consistent with carbon fixation via either the Calvin cycle or the acetyl-CoA pathway. However, the isotopic results are not consistent with the degree of fractionation expected from either the 3-hydroxypropionate cycle or the reductive tricarboxylic acid cycle, suggesting that the microfossils studied did not use either of these pathways for carbon fixation. The morphologies of the microfossils suggest an affinity to the cyanobacteria, and our carbon isotopic data are consistent with this assignment.

  20. Aerosol carbon isotope composition over Baltic Sea

    Science.gov (United States)

    Garbaras, Andrius; Pabedinskas, Algirdas; Masalaite, Agne; Petelski, Tomasz; Gorokhova, Elena; Sapolaite, Justina; Ezerinskis, Zilvinas; Remeikis, Vidmantas

    2017-04-01

    Particulate carbonaceous matter is significant contributor to ambient particulate matter originating from intervening sources which contribution is difficult to quantify due to source diversity, chemical complexity and processes during atmospheric transport. Carbon isotope analysis can be extremely useful in source apportionment of organic matter due to the unique isotopic signatures associated with anthropocentric (fossil fuel), continental (terrestrial plants) and marine sources, and is particularly effective when these sources are mixed (Ceburnis et al., 2011;Ceburnis et al., 2016). We will present the isotope ratio measurement results of aerosol collected during the cruise in the Baltic Sea. Sampling campaign of PM10 and size segregated aerosol particles was performed on the R/V "Oceania" in October 2015. Air mass back trajectories were prevailing both from the continental and marine areas during the sampling period. The total carbon concentration varied from 1 µg/m3 to 8 µg/m3. Two end members (δ13C = -25‰ and δ13C = -28 ‰ ) were established from the total stable carbon isotope analysis in PM10 fraction. δ13C analysis in size segregated aerosol particles revealed δ13C values being highest in the 1 - 2.5 µm range (δ13C = -24.9 ‰ ) during continental transport, while lowest TC δ13C values (δ13C ≈ -27 ‰ ) were detected in the size range D50 dual carbon pools contributing to organic matter enrichment in marine aerosol, Scientific Reports, 6, 2016. Masalaite, A., Remeikis, V., Garbaras, A., Dudoitis, V., Ulevicius, V., and Ceburnis, D.: Elucidating carbonaceous aerosol sources by the stable carbon δ13C TC ratio in size-segregated particles, Atmospheric Research, 158, 1-12, 2015.

  1. Wood anatomy and carbon-isotope discrimination support long-term hydraulic deterioration as a major cause of drought-induced dieback.

    Science.gov (United States)

    Pellizzari, Elena; Camarero, J Julio; Gazol, Antonio; Sangüesa-Barreda, Gabriel; Carrer, Marco

    2016-06-01

    Hydraulic impairment due to xylem embolism and carbon starvation are the two proposed mechanisms explaining drought-induced forest dieback and tree death. Here, we evaluate the relative role played by these two mechanisms in the long-term by quantifying wood-anatomical traits (tracheid size and area of parenchyma rays) and estimating the intrinsic water-use efficiency (iWUE) from carbon isotopic discrimination. We selected silver fir and Scots pine stands in NE Spain with ongoing dieback processes and compared trees showing contrasting vigour (declining vs nondeclining trees). In both species earlywood tracheids in declining trees showed smaller lumen area with thicker cell wall, inducing a lower theoretical hydraulic conductivity. Parenchyma ray area was similar between the two vigour classes. Wet spring and summer conditions promoted the formation of larger lumen areas, particularly in the case of nondeclining trees. Declining silver firs presented a lower iWUE than conspecific nondeclining trees, but the reverse pattern was observed in Scots pine. The described patterns in wood anatomical traits and iWUE are coherent with a long-lasting deterioration of the hydraulic system in declining trees prior to their dieback. Retrospective quantifications of lumen area permit to forecast dieback in declining trees 2-5 decades before growth decline started. Wood anatomical traits provide a robust tool to reconstruct the long-term capacity of trees to withstand drought-induced dieback.

  2. Carbon Isotope Chemistry in Molecular Clouds

    Science.gov (United States)

    Robertson, Amy N.; Willacy, Karen

    2012-01-01

    Few details of carbon isotope chemistry are known, especially the chemical processes that occur in astronomical environments like molecular clouds. Observational evidence shows that the C-12/C-13 abundance ratios vary due to the location of the C-13 atom within the molecular structure. The different abundances are a result of the diverse formation pathways that can occur. Modeling can be used to explore the production pathways of carbon molecules in an effort to understand and explain the chemical evolution of molecular clouds.

  3. Diet control on carbon isotopic composition of land snail shell carbonate

    Institute of Scientific and Technical Information of China (English)

    LIU ZongXiu; GU ZhaoYan; WU NaiQin; XU Bing

    2007-01-01

    Carbon isotope compositions for both the carbonate shells and soft bodies (organic tissue) of living land snails collected mostly from the Loess Plateau, China have been measured. The result shows that δ13C values range from -13.1‰ to -4.3‰ for the aragonite shell samples and from -26.8‰ to -18.0‰ for the soft body samples. Although the shells are enriched in 13C relative to the bodies averagely by 14.2(±0.8)‰, the shell δ13Ca values are closely correlated to the body δ13Corg values, expressed as δ13Ca = 1.021 δ13Corg + 14.38 (R = 0.965; N = 31). This relationship indicates that δ13Ca is primarily a function of the isotopic composition of the snail diets since previous studies have proved that the snail body is the same as their food in carbon isotope composition. In other words, carbon isotope compo-sition of the carbonate shell can be used as a proxy to estimate the dietary 13C abundance of the land snails. The data also support that the 13C enrichment of the carbonate shells results mainly from the equilibrium fractionations between the metabolic CO2, HCO3- in the hemolymph and shell aragonite, and partially from kinetic fractionations when snail shells form during their activity.

  4. Helium and carbon isotopes in Indian diamonds

    Science.gov (United States)

    Wiens, R.; Lal, D.; Craig, H.

    1990-09-01

    Helium and carbon isotope measurements in Indian diamonds (from Andhra Pradesh) were carried out using samples that included mined diamonds from primary kimberlite source rocks and alluvial diamonds from river gravel. The He and C isotope concentrations in diamonds from these two sources were compared, and the Indian diamonds were compared to those from other regions. Results indicate that most of the He-3 in the alluvial diamonds is of cosmogenic origin and that the alluvial diamonds may also have a significant He-4 component due to alpha particles implanted during storage in a secondary matrix. One diamond, a mined kimberlite specimen, was found to have the lowest He-4 content (0.018 microcc/g) so far recorded in diamonds.

  5. Carbon-isotopic analysis of dissolved acetate.

    Science.gov (United States)

    Gelwicks, J T; Hayes, J M

    1990-01-01

    Heating of dried, acetate-containing solids together with oxalic acid dihydrate conveniently releases acetic acid for purification by gas chromatography. For determination of the carbon-isotopic composition of total acetate, the acetate-containing zone of the chromatographic effluent can be routed directly to a combustion furnace coupled to a vacuum system allowing recovery, purification, and packaging of CO2 for mass-spectrometric analysis. For analysis of methyl carbon, acetic acid can be cryogenically trapped from the chromatographic effluent, then transferred to a tube containing excess NaOH. The tube is evacuated, sealed, and heated to 500 degrees C to produce methane by pyrolysis of sodium acetate. Subsequent combustion of the methane allows determination of the 13C content at the methyl position in the parent acetate. With typical blanks, the standard deviation of single analyses is less than 0.4% for acetate samples larger than 5 micromoles. A full treatment of uncertainties is outlined.

  6. Environmental effects on the stable carbon and oxygen isotopic ...

    African Journals Online (AJOL)

    USER

    2010-08-16

    Aug 16, 2010 ... Key words: Oxygen isotopes, carbon isotopes, Porites coral, density bands, skeletal .... isotopic ratio of CO2 gas derived from the Pee Dee Belemnite (PDB) ... water samples, a 2.0 ml of the sample was taken into a syringe and.

  7. Investigating controls on boron isotope ratios in shallow marine carbonates

    Science.gov (United States)

    Zhang, Shuang; Henehan, Michael J.; Hull, Pincelli M.; Reid, R. Pamela; Hardisty, Dalton S.; Hood, Ashleigh v. S.; Planavsky, Noah J.

    2017-01-01

    The boron isotope-pH proxy has been widely used to reconstruct past ocean pH values. In both planktic foraminifera and corals, species-specific calibrations are required in order to reconstruct absolute values of pH, due to the prevalence of so-called vital effects - physiological modification of the primary environmental signals by the calcifying organisms. Shallow marine abiotic carbonate (e.g. ooids and cements) could conceivably avoid any such calibration requirement, and therefore provide a potentially useful archive for reconstructions in deep (pre-Cenozoic) time. However, shallow marine abiotic carbonates could also be affected by local shifts in pH caused by microbial photosynthesis and respiration, something that has up to now not been fully tested. In this study, we present boron isotope measurements from shallow modern marine carbonates, from the Bahama Bank and Belize to investigate the potential of using shallow water carbonates as pH archives, and to explore the role of microbial processes in driving nominally 'abiogenic' carbonate deposition. For Bahama bank samples, our boron-based pH estimates derived from a range of carbonate types (i.e. ooids, peloids, hardground cements, carbonate mud, stromatolitic micrite and calcified filament micrite) are higher than the estimated modern mean-annual seawater pH values for this region. Furthermore, the majority (73%) of our marine carbonate-based pH estimates fall out of the range of the estimated pre-industrial seawater pH values for this region. In shallow sediment cores, we did not observe a correlation between measured pore water pH and boron-derived pH estimates, suggesting boron isotope variability is a depositional rather than early diagenetic signal. For Belize reef cements, conversely, the pH estimates are lower than likely in situ seawater pH at the time of cement formation. This study indicates the potential for complications when using shallow marine non-skeletal carbonates as marine pH archives

  8. Organic chemistry of Murchison meteorite: Carbon isotopic fractionation

    Science.gov (United States)

    Yuen, G. U.; Blair, N. E.; Desmarais, D. J.; Cronin, J. R.; Chang, S.

    1986-01-01

    The carbon isotopic composition of individual organic compounds of meteoritic origin remains unknown, as most reported carbon isotopic ratios are for bulk carbon or solvent extractable fractions. The researchers managed to determine the carbon isotopic ratios for individual hydrocarbons and monocarboxylic acids isolated from a Murchison sample by a freeze-thaw-ultrasonication technique. The abundances of monocarboxylic acids and saturated hydrocarbons decreased with increasing carbon number and the acids are more abundant than the hydrocarbon with the same carbon number. For both classes of compounds, the C-13 to C-12 ratios decreased with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic number than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with a kinetically controlled synthesis of higher homologues for lower ones.

  9. Organic chemistry of Murchison meteorite: Carbon isotopic fractionation

    Science.gov (United States)

    Yuen, G. U.; Blair, N. E.; Desmarais, D. J.; Cronin, J. R.; Chang, S.

    1986-01-01

    The carbon isotopic composition of individual organic compounds of meteoritic origin remains unknown, as most reported carbon isotopic ratios are for bulk carbon or solvent extractable fractions. The researchers managed to determine the carbon isotopic ratios for individual hydrocarbons and monocarboxylic acids isolated from a Murchison sample by a freeze-thaw-ultrasonication technique. The abundances of monocarboxylic acids and saturated hydrocarbons decreased with increasing carbon number and the acids are more abundant than the hydrocarbon with the same carbon number. For both classes of compounds, the C-13 to C-12 ratios decreased with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic number than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with a kinetically controlled synthesis of higher homologues for lower ones.

  10. The Oxidant Budget of Dissolved Organic Carbon Driven Isotope Excursions

    Science.gov (United States)

    Bristow, T. F.; Kennedy, M. J.

    2008-12-01

    Negative carbon isotope values, falling below the mantle average of about -5 per mil, in carbonate phases of Ediacaran age sedimentary rocks are widely regarded as reflecting negative excursions in the carbon isotopic composition of seawater lasting millions of years. These isotopic signals form the basis of chemostratigraphic correlations between Ediacaran aged sections in different parts of the world, and have been used to track the oxidation of the biosphere. However, these isotopic values are difficult to accommodate within limits prescribed by the current understanding of the carbon cycle, and a hypothetical Precambrian ocean dissolved organic carbon (DOC) pool 100 to 1000 times the size of the modern provides a potential source of depleted carbon not considered in Phanerozoic carbon cycle budgets. We present box model results that show the remineralization of such a DOC pool to drive an isotope excursion of the magnitude observed in the geological record exhausts global budgets of free oxygen and sulfate in 800 k.y. These results are incompatible with the estimated duration of late Ediacaran isotope excursions of more than 10 m.y., as well as geochemical and biological indicators that oceanic sulfate and oxygen levels were maintained or even increased at the same time. Therefore the carbon isotope record is probably not a useful tool for monitoring oxygen levels in the atmosphere and ocean. Covariation between the carbon and oxygen isotope records is often observed during negative excursions and is indicative of local processes or diagenetic overprinting.

  11. Carbon isotope analysis in apple nectar beverages

    Directory of Open Access Journals (Sweden)

    Ricardo Figueira

    2013-03-01

    Full Text Available The aims of this study were to use the isotope analysis method to quantify the carbon of C3 photosynthetic cycle in commercial apple nectars and to determine the legal limit to identify the beverages that do not conform to the safety standards established by the Brazilian Ministry of Agriculture, Livestock and Food Supply. These beverages (apple nectars were produced in the laboratory according to the Brazilian legislation. Adulterated nectars were also produced with an amount of pulp juice below the permitted threshold limit value. The δ13C values of the apple nectars and their fractions (pulp and purified sugar were measured to quantify the C3 source percentage. In order to demonstrate the existence of adulteration, the values found were compared to the limit values established by the Brazilian Law. All commercial apple nectars analyzed were within the legal limits, which enabled to identify the nectars that were in conformity with the Brazilian Law. The isotopic methodology developed proved efficient to quantify the carbon of C3 origin in commercial apple nectars.

  12. A Clumped Isotope Calibration for Lacustrine Carbonates

    Science.gov (United States)

    Mitsunaga, B. A.; Mering, J. A.; Petryshyn, V. A.; Dunbar, R. B.; Cohen, A. S.; Liu, X.; Kaufman, D. S.; Eagle, R.; Tripati, A.

    2014-12-01

    Our capacity to understand Earth's environmental history is highly dependent on the accuracy of past climate reconstructions. Unfortunately, many terrestrial proxies—tree rings, speleothems, leaf margin analyses, etc.—are influenced by the effects of both temperature and precipitation. Methods that can isolate the effects of temperature alone are needed, and clumped isotope thermometry has the potential to be a useful tool for determining terrestrial climates. Multiple studies have shown that the fraction of 13C—18O bonds in carbonates is inversely related to the temperature at which the rocks formed and may be a useful proxy for reconstructing temperatures on land. An in-depth survey of lacustrine carbonates, however, has not yet been published. Therefore we have been measuring the abundance of 13C18O16O in the CO2 produced by the dissolution of modern lake samples' carbonate minerals in phosphoric acid and comparing results to independently known estimates of lake water temperature and air temperature. Some of the sample types we have investigated include endogenic carbonates, freshwater gastropods, bivalves, microbialites, and ooids.

  13. Phanerozoic and Neoproterozoic Negative Carbon Isotope Excursions, Diagenesis and Terrestrialization

    Science.gov (United States)

    Paul, K.; Kennedy, M. J.

    2008-12-01

    Comprehensive data sets of Phanerozoic and late Precambrian carbon isotope data derived from carbonate rocks show a similar positive relation when cross-plotted with oxygen isotope values. The range and slope between the time periods is identical and the processes responsible for the relation have been well documented in Quaternary sediments. These processes include the stabilization of isotope values to ambient meteoric water values during shallow burial and flushing of carbonate sediments. Both data sets show strongly depleted carbon (-9 per mil PDB) and oxygen isotope values that retain seemingly systematic stratigraphic patterns with the Quaternary and Phanerozoic examples that demonstrably record meteroric water values. Similar values and patterns in the Precambrian are interpreted as primary marine in origin with significant implications for an ocean carbon mass balance not possible in the Phanerozoic carbon cycle. A similar compilation of carbonates older than one billion years do not show a relation between carbon and oxygen isotopes, lacking the negative carbon values evident in the younger record. We hypothesize that this difference records the onset of significant organic carbon on the land surface and the alteration of meteoric waters toward Phanerozoic values. We demonstrate the meteoric affinities of Neoproterozoic carbonates containing prominent negative isotope excursions recorded in the Shuram and Wonoka Formations of Oman and South Australia commonly attributed to whole ocean isotope variation. The conspicuous absence of negative carbon isotope values with normal marine oxygenisotope values in the Phanerozoic and Neoproterozic identifies a consistent relation between these time intervals and suggests that, as well accepted in the Phanerozoic, negative carbon isotope excursions less than -3 per mil are not a record of marine processes, but rather the later terrestrial biotic influence on meteoric water values.

  14. Stable carbon, nitrogen and sulfur isotopes in non-carbonate fractions of cold-seep carbonates

    Science.gov (United States)

    Feng, Dong; Peng, Yongbo; Peckmann, Jörn; Roberts, Harry; Chen, Duofu

    2017-04-01

    Sulfate-driven anaerobic oxidation of methane (AOM) supports chemosynthesis-based communities and limits the release of methane from marine sediments. This process promotes the formation of carbonates close to the seafloor along continental margins. The geochemical characteristics of the carbonate minerals of these rocks are increasingly understood, questions remain about the geochemical characteristics of the non-carbonate fractions. Here, we report stable carbon, nitrogen and sulfur isotope patterns in non-carbonate fractions of seep carbonates. The authigenic carbonates were collected from three modern seep provinces (Black Sea, Gulf of Mexico, and South China Sea) and three ancient seep deposits (Marmorito, northern Italy, Miocene; SR4 deposit of the Lincoln Creek Formation and Whiskey Creek, western Washington, USA, Eocene to Oligocene). The δ13C values of non-carbonate fractions range from ˜-25‰ to -80‰ VPDB. These values indicate that fossil methane mixed with varying amounts of pelagic organic matter is the dominant source of carbon in these fractions. The relatively small offset between the δ34S signatures of the non-carbonate fractions and the respective sulfide minerals suggests that locally produced hydrogen sulfide is the main source of sulfur in seep environments. The δ15N values of the non-carbonate fractions are generally lower than the corresponding values of deep-sea sediments, suggesting that organic nitrogen is mostly of a local origin. This study reveals the potential of using δ13C, δ15N, δ34S values to discern seep and non-seep deposits. In cases where δ13Ccarbonate values are only moderately low due to mixing processes and lipid biomarkers have been erased in the course of burial, it is difficult to trace back AOM owing to the lack of other records. This problem is even more pronounced when authigenic carbonate is not available in ancient seep environments. Acknowledgments: The authors thank BOEM and NOAA for their years' support

  15. Seagrass sediments as a global carbon sink: Isotopic constraints

    Science.gov (United States)

    Kennedy, Hilary; Beggins, Jeff; Duarte, Carlos M.; Fourqurean, James W.; Holmer, Marianne; Marbã, Núria; Middelburg, Jack J.

    2010-12-01

    Seagrass meadows are highly productive habitats found along many of the world's coastline, providing important services that support the overall functioning of the coastal zone. The organic carbon that accumulates in seagrass meadows is derived not only from seagrass production but from the trapping of other particles, as the seagrass canopies facilitate sedimentation and reduce resuspension. Here we provide a comprehensive synthesis of the available data to obtain a better understanding of the relative contribution of seagrass and other possible sources of organic matter that accumulate in the sediments of seagrass meadows. The data set includes 219 paired analyses of the carbon isotopic composition of seagrass leaves and sediments from 207 seagrass sites at 88 locations worldwide. Using a three source mixing model and literature values for putative sources, we calculate that the average proportional contribution of seagrass to the surface sediment organic carbon pool is ˜50%. When using the best available estimates of carbon burial rates in seagrass meadows, our data indicate that between 41 and 66 gC m-2 yr-1 originates from seagrass production. Using our global average for allochthonous carbon trapped in seagrass sediments together with a recent estimate of global average net community production, we estimate that carbon burial in seagrass meadows is between 48 and 112 Tg yr-1, showing that seagrass meadows are natural hot spots for carbon sequestration.

  16. Carbon isotope fractionation in protoplanetary disks

    CERN Document Server

    Woods, Paul M

    2008-01-01

    We investigate the gas-phase and grain-surface chemistry in the inner 30 AU of a typical protoplanetary disk using a new model which calculates the gas temperature by solving the gas heating and cooling balance and which has an improved treatment of the UV radiation field. We discuss inner-disk chemistry in general, obtaining excellent agreement with recent observations which have probed the material in the inner regions of protoplanetary disks. We also apply our model to study the isotopic fractionation of carbon. Results show that the fractionation ratio, 12C/13C, of the system varies with radius and height in the disk. Different behaviour is seen in the fractionation of different species. We compare our results with 12C/13C ratios in the Solar System comets, and find a stark contrast, indicative of reprocessing.

  17. Carbon isotopes of dissolved inorganic carbon reflect utilization of different carbon sources by microbial communities in two limestone aquifer assemblages

    Directory of Open Access Journals (Sweden)

    M. E. Nowak

    2017-08-01

    Full Text Available Isotopes of dissolved inorganic carbon (DIC are used to indicate both transit times and biogeochemical evolution of groundwaters. These signals can be complicated in carbonate aquifers, as both abiotic (i.e., carbonate equilibria and biotic factors influence the δ13C and 14C of DIC. We applied a novel graphical method for tracking changes in the δ13C and 14C of DIC in two distinct aquifer complexes identified in the Hainich Critical Zone Exploratory (CZE, a platform to study how water transport links surface and shallow groundwaters in limestone and marlstone rocks in central Germany. For more quantitative estimates of contributions of different biotic and abiotic carbon sources to the DIC pool, we used the NETPATH geochemical modeling program, which accounts for changes in dissolved ions in addition to C isotopes. Although water residence times in the Hainich CZE aquifers based on hydrogeology are relatively short (years or less, DIC isotopes in the shallow, mostly anoxic, aquifer assemblage (HTU were depleted in 14C compared to a deeper, oxic, aquifer complex (HTL. Carbon isotopes and chemical changes in the deeper HTL wells could be explained by interaction of recharge waters equilibrated with post-bomb 14C sources with carbonates. However, oxygen depletion and δ13C and 14C values of DIC below those expected from the processes of carbonate equilibrium alone indicate considerably different biogeochemical evolution of waters in the upper aquifer assemblage (HTU wells. Changes in 14C and 13C in the upper aquifer complexes result from a number of biotic and abiotic processes, including oxidation of 14C-depleted OM derived from recycled microbial carbon and sedimentary organic matter as well as water–rock interactions. The microbial pathways inferred from DIC isotope shifts and changes in water chemistry in the HTU wells were supported by comparison with in situ microbial community structure based on 16S rRNA analyses. Our findings

  18. Mass transfer and carbon isotope evolution in natural water systems

    Science.gov (United States)

    Wigley, T.M.L.; Plummer, L.N.; Pearson, F.J.

    1978-01-01

    This paper presents a theoretical treatment of the evolution of the carbon isotopes C13 and C14 in natural waters and in precipitates which derive from such waters. The effects of an arbitrary number of sources (such as dissolution of carbonate minerals and oxidation of organic material) and sinks (such as mineral precipitation, CO2 degassing and production of methane), and of equilibrium fractionation between solid, gas and aqueous phases are considered. The results are expressed as equations relating changes in isotopic composition to changes in conventional carbonate chemistry. One implication of the equations is that the isotopic composition of an aqueous phase may approach a limiting value whenever there are simultaneous inputs and outputs of carbonate. In order to unambiguously interpret isotopic data from carbonate precipitates and identify reactants and products in reacting natural waters, it is essential that isotopic changes are determined chiefly by reactant and product stoichiometry, independent of reaction path. We demonstrate that this is so by means of quantitative examples. The evolution equations are applied to: 1. (1) carbon-14 dating of groundwaters; 2. (2) interpretation of the isotopic composition of carbonate precipitates, carbonate cements and diagenetically altered carbonates; and 3. (3) the identification of chemical reaction stoichiometry. These applications are illustrated by examples which show the variation of ??C13 in solutions and in precipitates formed under a variety of conditions involving incongruent dissolution, CO2 degassing, methane production and mineral precipitation. ?? 1978.

  19. Dual-Carbon sources fuel the OCS deep-reef Community, a stable isotope investigation

    Science.gov (United States)

    Sulak, Kenneth J.; Berg, J.; Randall, Michael; Dennis, George D.; Brooks, R.A.

    2008-01-01

    The hypothesis that phytoplankton is the sole carbon source for the OCS deep-reef community (>60 m) was tested. Trophic structure for NE Gulf of Mexico deep reefs was analyzed via carbon and nitrogen stable isotopes. Carbon signatures for 114 entities (carbon sources, sediment, fishes, and invertebrates) supported surface phytoplankton as the primary fuel for the deep reef. However, a second carbon source, the macroalga Sargassum, with its epiphytic macroalgal associate, Cladophora liniformis, was also identified. Macroalgal carbon signatures were detected among 23 consumer entities. Most notably, macroalgae contributed 45 % of total carbon to the 13C isotopic spectrum of the particulate-feeding reef-crest gorgonian Nicella. The discontinuous spatial distribution of some sessile deep-reef invertebrates utilizing pelagic macroalgal carbon may be trophically tied to the contagious distribution of Sargassum biomass along major ocean surface features.

  20. Isotopic studies of Yucca Mountain soil fluids and carbonate pedogenesis

    Energy Technology Data Exchange (ETDEWEB)

    McConnaughey, T.A.; Whelan, J.F.; Wickland, K.P.; Moscati, R.J.

    1994-12-31

    Secondary carbonates occurring within the soils, faults, and subsurface fractures of Yucca Mountain contain some of the best available records of paleoclimate and palehydrology for the potential radioactive waste repository site. This article discusses conceptual and analytical advances being made with regard to the interpretation of stable isotope data from pedogenic carbonates, specifically related to the {sup 13}C content of soil CO{sub 2}, CaCO{sub 3}, precipitation mechanisms, and isotopic fractionations between parent fluids and precipitating carbonates. The {sup 13}C content of soil carbon dioxide from Yucca Mountain and vicinity shows most of the usual patterns expected in such contexts: Decreasing {sup 13}C content with depth decreasing {sup 13}C with altitude and reduced {sup 13}C during spring. These patterns exist within the domain of a noisy data set; soil and vegetational heterogeneities, weather, and other factors apparently contribute to isotopic variability in the system. Several soil calcification mechanisms appear to be important, involving characteristic physical and chemical environments and isotopic fractionations. When CO{sub 2} loss from thin soil solutions is an important driving factor, carbonates may contain excess heavy isotopes, compared to equilibrium precipitation with soil fluids. When root calcification serves as a proton generator for plant absorption of soil nutrients, heavy isotope deficiencies are likely. Successive cycles of dissolution and reprecipitation mix and redistribute pedogenic carbonates, and tend to isotopically homogenize and equilibrate pedogenic carbonates with soil fluids.

  1. Intramolecular carbon isotope distribution of acetic acid in vinegar.

    Science.gov (United States)

    Hattori, Ryota; Yamada, Keita; Kikuchi, Makiko; Hirano, Satoshi; Yoshida, Naohiro

    2011-09-14

    Compound-specific carbon isotope analysis of acetic acid is useful for origin discrimination and quality control of vinegar. Intramolecular carbon isotope distributions, which are each carbon isotope ratios of the methyl and carboxyl carbons in the acetic acid molecule, may be required to obtain more detailed information to discriminate such origin. In this study, improved gas chromatography-pyrolysis-gas chromatography-combustion-isotope ratio mass spectrometry (GC-Py-GC-C-IRMS) combined with headspace solid-phase microextraction (HS-SPME) was used to measure the intramolecular carbon isotope distributions of acetic acid in 14 Japanese vinegars. The results demonstrated that the methyl carbons of acetic acid molecules in vinegars produced from plants were mostly isotopically depleted in (13)C relative to the carboxyl carbon. Moreover, isotopic differences (δ(13)C(carboxyl) - δ(13)C(methyl)) had a wide range from -0.3 to 18.2‰, and these values differed among botanical origins, C3, C4, and CAM plants.

  2. Clumped-isotope thermometry of magnesium carbonates in ultramafic rocks

    Science.gov (United States)

    García del Real, Pablo; Maher, Kate; Kluge, Tobias; Bird, Dennis K.; Brown, Gordon E.; John, Cédric M.

    2016-11-01

    Magnesium carbonate minerals produced by reaction of H2O-CO2 with ultramafic rocks occur in a wide range of paragenetic and tectonic settings and can thus provide insights into a variety of geologic processes, including (1) deposition of ore-grade, massive-vein cryptocrystalline magnesite; (2) formation of hydrous magnesium carbonates in weathering environments; and (3) metamorphic carbonate alteration of ultramafic rocks. However, the application of traditional geochemical and isotopic methods to infer temperatures of mineralization, the nature of mineralizing fluids, and the mechanisms controlling the transformation of dissolved CO2 into magnesium carbonates in these settings is difficult because the fluids are usually not preserved. Clumped-isotope compositions of magnesium carbonates provide a means to determine primary mineralization or (re)equilibration temperature, which permits the reconstruction of geologic processes that govern magnesium carbonate formation. We first provide an evaluation of the acid fractionation correction for magnesium carbonates using synthetic magnesite and hydromagnesite, along with natural metamorphic magnesite and low-temperature hydromagnesite precipitated within a mine adit. We show that the acid fractionation correction for magnesium carbonates is virtually indistinguishable from other carbonate acid fractionation corrections given current mass spectrometer resolution and error. In addition, we employ carbonate clumped-isotope thermometry on natural magnesium carbonates from various geologic environments and tectonic settings. Cryptocrystalline magnesite vein deposits from California (Red Mountain magnesite mine), Austria (Kraubath locality), Turkey (Tutluca mine, Eskişehir district) and Iran (Derakht-Senjed deposit) exhibit broadly uniform Δ47 compositions that yield apparent clumped-isotope temperatures that average 23.7 ± 5.0 °C. Based on oxygen isotope thermometry, these clumped-isotope temperatures suggest

  3. Carbon isotopes of graphite: Implications on fluid history

    Directory of Open Access Journals (Sweden)

    F.J. Luque

    2012-03-01

    Full Text Available Stable carbon isotope geochemistry provides important information for the recognition of fundamental isotope exchange processes related to the movement of carbon in the lithosphere and permits the elaboration of models for the global carbon cycle. Carbon isotope ratios in fluid-deposited graphite are powerful tools for unravelling the ultimate origin of carbon (organic matter, mantle, or carbonates and help to constrain the fluid history and the mechanisms involved in graphite deposition. Graphite precipitation in fluid-deposited occurrences results from CO2- and/or CH4-bearing aqueous fluids. Fluid flow can be considered as both a closed (without replenishment of the fluid or an open system (with renewal of the fluid by successive fluid batches. In closed systems, carbon isotope systematics in graphite is mainly governed by Rayleigh precipitation and/or by changes in temperature affecting the fractionation factor between fluid and graphite. Such processes result in zoned graphite crystals or in successive graphite generations showing, in both cases, isotopic variation towards progressive 13C or 12C enrichment (depending upon the dominant carbon phase in the fluid, CO2 or CH4, respectively. In open systems, in which carbon is episodically introduced along the fracture systems, the carbon systematics is more complex and individual graphite crystals may display oscillatory zoning because of Rayleigh precipitation or heterogeneous variations of δ13C values when mixing of fluids or changes in the composition of the fluids are the mechanisms responsible for graphite precipitation.

  4. A global deglacial negative carbon isotope excursion in speleothem calcite

    Science.gov (United States)

    Breecker, D.

    2015-12-01

    δ13C values of speleothem calcite decreased globally during the last deglaciation defining a carbon isotope excursion (CIE) despite relatively constant δ13C values of carbon in the ocean-atmosphere system. The magnitude of the CIE varied with latitude, increasing poleward from ~2‰ in the tropics to as much as 7‰ at high latitudes. This recent CIE provides an interesting comparison with CIEs observed in deep time. A substantial portion of this CIE can be explained by the increase in atmospheric pCO2 that accompanied deglaciation. The dependence of C3 plant δ13C values on atmospheric pCO2 predicts a 2‰ δ13C decrease driven by the deglacial pCO2 increase. I propose that this signal was transferred to caves and thus explains nearly 100% of the CIE magnitude observed in the tropics and no less than 30% at the highest latitudes in the compilation. An atmospheric pCO2 control on speleothem δ13C values, if real, will need to be corrected for using ice core data before δ13C records can be interpreted in a paleoclimate context. The decrease in the magnitude of the equilibrium calcite-CO2 carbon isotope fractionation factor explains a maximum of 1‰ of the CIE at the highest northern latitude in the compilation, which experienced the largest deglacial warming. Much of the residual extratropical CIE was likely driven by increasing belowground respiration rates, which were presumably pronounced at high latitudes as glacial retreat exposed fresh surfaces and/or vegetation density increased. The largest increases in belowground respiration would have therefore occurred at the highest latitudes, explaining the meridional trend. This work supports the notion that increases in atmospheric pCO2 and belowground respiration rates can result in large CIEs recorded in terrestrial carbonates, which, as previously suggested, may explain the magnitude of the PETM CIE as recorded by paleosol carbonates.

  5. Late Carboniferous to Late Permian carbon isotope stratigraphy

    DEFF Research Database (Denmark)

    Buggisch, Werner; Krainer, Karl; Schaffhauser, Maria

    2015-01-01

    An integrated study of the litho-, bio-, and isotope stratigraphy of carbonates in the Southern Alps was undertaken in order to better constrain δ13C variations during the Late Carboniferous to Late Permian. The presented high resolution isotope curves are based on 1299 δ13Ccarb and 396 δ13Corg a...

  6. BIODEGRADATION OF FLUORANTHENE AS MONITORED USING STABLE CARBON ISOTOPES

    Science.gov (United States)

    The measurement of stable isotope ratios of carbon (d13C values) was investigated as a viable technique to monitor the intrinsic bioremediation of polycyclic aromatic hydrocarbons (PAHs). Biometer-flask experiments were conducted in which the bacterium, Sphingomonas paucimobilis,...

  7. Stable carbon isotope ratios from archaeological charcoal as palaeoenvironmental indicators

    CSIR Research Space (South Africa)

    Hall, G

    2008-01-01

    Full Text Available The potential to provide environmental proxies using stable carbon isotopes from modern and archaeological charcoal is explored. Experiments on modern Podocarpus (Yellowwoods) show that δ13C values of stems, branches and charcoal preserve proxy...

  8. Isotopic fractionation of alkali earth metals during carbonate precipitation

    Science.gov (United States)

    Yotsuya, T.; Ohno, T.; Muramatsu, Y.; Shimoda, G.; Goto, K. T.

    2014-12-01

    The alkaline earth metals such as magnesium, calcium and strontium play an important role in a variety of geochemical and biological processes. The element ratios (Mg/Ca and Sr/Ca) in marine carbonates have been used as proxies for reconstruction of the past environment. Recently several studies suggested that the study for the isotopic fractionation of the alkaline earth metals in marine carbonates has a potentially significant influence in geochemical research fields (e.g. Eisenhauer et al., 2009). The aim of this study is to explore the influence of carbonate polymorphs (Calcite and Aragonite) and environmental factors (e.g., temperature, precipitation rate) on the level of isotopic fractionation of the alkaline earth metals. We also examined possible correlations between the level of isotopic fractionation of Ca and that of other alkaline earth metals during carbonate precipitation. In order to determine the isotope fractionation factor of Mg, Ca and Sr during carbonate precipitation, calcite and aragonite were synthesized from calcium bicarbonate solution in which the amount of magnesium was controlled based on Kitano method. Calcium carbonates were also prepared from the mixture of calcium chlorite and sodium hydrogen carbonate solutions. The isotope fractionation factors were measured by MC-ICPMS. Results suggested that the level of isotopic fractionation of Mg during carbonate precipitation was correlated with that of Sr and that the change of the carbonate crystal structure could make differences of isotopic fractionations of Mg and Ca, however no difference was found in the case of Sr. In this presentation, the possible mechanism will be discussed.

  9. Modeling the carbon isotope composition of bivalve shells (Invited)

    Science.gov (United States)

    Romanek, C.

    2010-12-01

    The stable carbon isotope composition of bivalve shells is a valuable archive of paleobiological and paleoenvironmental information. Previous work has shown that the carbon isotope composition of the shell is related to the carbon isotope composition of dissolved inorganic carbon (DIC) in the ambient water in which a bivalve lives, as well as metabolic carbon derived from bivalve respiration. The contribution of metabolic carbon varies among organisms, but it is generally thought to be relatively low (e.g., organism and high (>90%) in the shells from terrestrial organisms. Because metabolic carbon contains significantly more C-12 than DIC, negative excursions from the expected environmental (DIC) signal are interpreted to reflect an increased contribution of metabolic carbon in the shell. This observation contrasts sharply with modeled carbon isotope compositions for shell layers deposited from the inner extrapallial fluid (EPF). Previous studies have shown that growth lines within the inner shell layer of bivalves are produced during periods of anaerobiosis when acidic metabolic byproducts (e.g., succinic acid) are neutralized (or buffered) by shell dissolution. This requires the pH of EPF to decrease below ambient levels (~7.5) until a state of undersaturation is achieved that promotes shell dissolution. This condition may occur when aquatic bivalves are subjected to external stressors originating from ecological (predation) or environmental (exposure to atm; low dissolved oxygen; contaminant release) pressures; normal physiological processes will restore the pH of EPF when the pressure is removed. As a consequence of this process, a temporal window should also exist in EPF at relatively low pH where shell carbonate is deposited at a reduced saturation state and precipitation rate. For example, EPF chemistry should remain slightly supersaturated with respect to aragonite given a drop of one pH unit (6.5), but under closed conditions, equilibrium carbon isotope

  10. Temperature and Oxygen Isotope Composition of The Ediacaran Ocean: Constraints From Clumped Isotope Carbonate Thermometry

    Science.gov (United States)

    Bonifacie, M.; Eiler, J. M.; Fike, D. A.

    2008-12-01

    The temperature and chemical variations of the early oceans on Earth are highly debated, particularly for periods associated with significant evolutionary change and/or extinction. The temperature of past oceans has been estimated based on conventional carbonate-water and/or silicate-water stable oxygen isotope thermometry. Precambrian carbonates and silicates both exhibit a long-term secular trend of increasing δ18O values with decreasing age. This trend has been used to support two opposite - though related - interpretations: the Earth's oceans gradually cooled over the course of the Proterozoic eon, from a maximum of ~ 60-90°C at ~ 2.5Ga (and were, on average, relatively warm during much of the Paleozoic era) [1]. This interpretation has been supported by Si-isotope proxies and the thermal tolerances of proteins in various classes of microbial organisms [2-3]. Alternatively, the δ18O value of the oceans has gradually increased through time [4-5], and mean Earth surface temperatures varied over a narrow range similar to modern conditions. In other terms, one either assumes an ocean of constant δ18O and infers that climate varied dramatically, or vise versa. Finally, it is possible that post- depositional processes (e.g., diagenesis, burial metamorphism, weathering) has modified the δ18O values of all or most Precambrian sedimentary carbonates and silicates, overprinting any paleoclimatic variations. Carbonate 'clumped isotope' thermometry provides a new way to independently test these hypotheses because it allows one to determine the apparent growth temperatures of carbonate minerals based on their abundances of 13C-18O bonds, as reflected by the 'Δ47' value of CO2 extracted by phosphoric acid digestion [6]. This method is thermodynamically based and independent of the δ18O of water from which the carbonate grew. We will report the initial results of measurements of 'Δ47 for a suite of carbonates from the Sultanate of Oman. This Ediacaran age (~ 635 to

  11. Isotopic studies of Yucca Mountain soil fluids and carbonate pedogenesis

    Energy Technology Data Exchange (ETDEWEB)

    McConnaughey, T.A.; Whelan, J.F.; Wickland, K.P.; Moscati, R.J. [Geological Survey, Denver, CO (United States)

    1994-12-31

    Secondary carbonates occurring within the soils, faults, and subsurface fractures of Yucca Mountain contain some of the best available records of paleoclimate and paleohydrology for the potential radioactive waste repository site. This article discusses conceptual and analytical advances being made with regard to the interpretation of stable isotope data from pedogenic carbonates, specifically related to the {sup 13}C content of soil CO{sub 2}, CaCO{sub 3} precipitation mechanisms, and isotopic fractionations between parent fluids and precipitating carbonates. The {sup 13}C content of soil carbon dioxide from Yucca Mountain and vicinity shows most of the usual patterns expected in such contexts: decreasing {sup 13}C content with depth (due mainly to increased importance of respired CO{sub 2}), decreasing {sup 13}C with altitude (partially due to relatively more C-3 vegetation), and reduced {sup 13}C during spring (due again to higher rates of respiration, and reduced gas permeability of wet soils). These patterns exist within the domain of a noisy data set; soil and vegetational heterogeneities, weather, and other factors apparently contribute to isotopic variability in the system. Several soil calcification mechanisms appear to be important, involving characteristic physical and chemical environments and isotopic fractionations. When CO{sub 2} loss from thin soil solutions is an important driving factor, carbonates may contain excess heavy isotopes, compared to equilibrium precipitation with soil fluids. When root calcification serves as a proton generator for plant absorption of soil nutrients, heavy isotope deficiencies are likely. Successive cycles of dissolution and reprecipitation mix and redistribute pedogenic carbonates, and tend to isotopically homogenize and equilibrate pedogenic carbonates with soil fluids.

  12. Relationships between tree height and carbon isotope discrimination

    Science.gov (United States)

    Nate G. McDowell; Barbara J. Bond; Lee T. Dickman; Michael G. Ryan; David Whitehead

    2011-01-01

    Understanding how tree size impacts leaf- and crown-level gas exchange is essential to predicting forest yields and carbon and water budgets. The stable carbon isotope ratio of organic matter has been used to examine the relationship of gas exchange to tree size for a host of species because it carries a temporally integrated signature of foliar photosynthesis and...

  13. Carbon isotopic study of individual alcohol compounds in modern sediments from Nansha Islands sea area, China

    Institute of Scientific and Technical Information of China (English)

    段毅; 文启彬; 郑国东; 罗斌杰

    1997-01-01

    Carbon isotopic compositions of individual n-alkanols and sterols in modern sediments from the Nan-sha Islands sea area are measured after derivatization to trimethylsilyl ethers by the new isotopic analytical technique of GC/C/IRMS. The effects of the three added silyl carbon atoms in every alcohol molecule on these compound isotopic compositions and the characteristics of their carbon isotopic compositions are studied. Then their biological sources are discussed using their carbon isotopic compositions.

  14. ANALYTICAL EMPLOYMENT OF STABLE ISOTOPES OF CARBON, NITROGEN, OXYGEN AND HYDROGEN FOR FOOD AUTHENTICATION

    Directory of Open Access Journals (Sweden)

    E. Novelli

    2011-04-01

    Full Text Available Stable isotopes of carbon, nitrogen, oxygen and hydrogen were used for analytical purposes for the discrimination of the type of production (farming vs. fishing in the case of sea bass and for geographical origin in the case of milk. These results corroborate similar experimental evidences and confirm the potential of this analytical tool to support of food traceability.

  15. Carbon isotope heterogeneities in deep Earth: Recycling of surface carbon or from core?

    Science.gov (United States)

    Satish-Kumar, Madhusoodhan

    2017-04-01

    Subduction of crustal materials, mantle melting and upwelling of deep mantle, in addition to a potential source from the core, largely controls the Earth's deep carbon cycle. Large variations in carbon isotopic composition between different reservoirs have been used widely to differentiate the source of carbon and to understand the carbon inventories and its recycling processes. However, how far high-temperature and hign-pressure conditions can affect the carbon isotope distribution, is a question still unanswered to clearly address the deep carbon cycle. I present here a review on carbon isotope fractionation processes in deep Earth and critically evaluate whether we can easily differentiate between surface carbon and deep carbon based on isotope characteristics. Recent experimental carbon isotope fractionation studies in the Fe-C system suggests that light carbon is selectively partition into metallic core during early magma ocean environment (Satish-Kumar et al., 2011). Furthermore, carbonate melts can be a medium for efficient crystallisation of diamonds in Earth's mantle (Palyanov et al., 2013). Rayleigh fractionation modelling based on fractionation suggests that core can be a reservoir of 12C enriched carbon and can itself form a reservoir which can cause heterogeneity in mantle carbon (Wood et al., 2013). In addition, high pressure experiments in the carbon-saturated model harzburgite system (Enstatite-Magnesite-Olivine-Graphite), carbonated silicate melting resulted in 13C enrichment in the carbon dissolved in the silicate melt relative to elemental graphite (Mizutani et al., 2014). 13C enrichment in carbonate melt were further confirmed in experiments where redox melting between olivine and graphite produced a carbonate melt as well as carbonate reduction experiments to form graphite. A third factor, still unconquered is the effect of pressure on isotope fractionation process. Theoretical studies as well as preliminary experimental studies have suggested

  16. Understanding the Carbon Isotopic Signature in Complex Environmental Matrices

    Directory of Open Access Journals (Sweden)

    Claudio Natali

    2014-12-01

    Full Text Available Elemental and isotopic analyses of carbon in environmental matrices usually integrate multiple sources having distinct concentration (wt% and 13C/12C isotopic ratio. Interpretation necessarily needs the characterization of the diverse end-members that usually are constituted by carbonate, organic and elemental components. In this view, we developed a routine protocol based on the analytical coupling of elementary and isotopic compositions that is able to discriminate the inorganic (TIC and organic (TOC contributions to the total carbon (TC content. The procedure is only based on thermal destabilization of the different carbon species and has been successfully applied on different environmental matrices (rocks, soils, biological samples with a mean C elemental and isotopic recovery of 99% (SD = 3% and -0.3‰ (SD = 0.3‰, respectively. The thermal speciation lead us to define precise isotopic end-members whose are unaffected by any chemical treatment of the samples. The approach allows accurate mass balance calculation that represents a powerful tool to quantify the distinct carbon species.

  17. Carbon and oxygen isotope compositions of the carbonate facies in the Vindhyan Supergroup, central India

    Indian Academy of Sciences (India)

    S Banerjee; S K Bhattacharya; S Sarkar

    2006-02-01

    The Vindhyan sedimentary succession in central India spans a wide time bracket from the Paleopro- terozoic to the Neoproterozoic period.Chronostratigraphic significance of stable carbon and oxygen isotope ratios of the carbonate phase in Vindhyan sediments has been discussed in some recent studies.However,the subtle controls of facies variation,depositional setting and post-depositional diagenesis on stable isotope compositions are not yet clearly understood.The Vindhyan Super- group hosts four carbonate units,exhibiting a wide variability in depositional processes and paleogeography.A detailed facies-specific carbon and oxygen isotope study of the carbonate units was undertaken by us to investigate the effect of these processes and to identify the least altered isotope values.It is seen that both carbon and oxygen isotope compositions have been affected by early meteoric water diagenesis.The effect of diagenetic alteration is,however,more pronounced in case of oxygen isotopes than carbon isotopes.Stable isotope compositions remained insensitive to facies only when sediments accumulated in a shallow shelf setting without being exposed.Major alteration of original isotope ratios was observed in case of shallow marine carbonates,which became exposed to meteoric fluids during early diagenetic stage.Duration of exposure possibly determined the magnitude of alteration and shift from the original values.Moreover,dolomitization is found to be accompanied by appreciable alteration of isotope compositions in some of the carbonates.The present study suggests that variations in sediment depositional settings,in particular the possibility of subaerial exposure,need to be considered while extracting chronostratigraphic signi ficance from 13C data.

  18. Carbon and Oxygen Isotope Ratios in Rona Limestone, Romania

    Directory of Open Access Journals (Sweden)

    Stela Cuna

    2001-04-01

    Full Text Available The carbon and oxygen isotopic compositions of limestones provide criteria for the evaluation of the depositional environment. For Jurassic and younger samples, the best discrimination between marine and fresh-water limestones is given by Z parameter, calculated as a linear correlation between δ13C and δ18O (‰ PDB. Rona Limestone (Upper Paleocene - Lower Eocene, outcropping on a small area in NW Transylvania (Meseş area is a local lacustrine facies. There, it divides Jibou Formation into the Lower Red Member and the Upper Variegated Member, respectively. Recently, a sequence containing a marine nannoplankton assemblage was identified in the base of Rona deposits. The main goal of our study was to characterize, based on the isotopic record, the primary environment of formation of the deposit, as well as that in which some diagenetic processes (the formation of dolomite and of green clay around the siliceous chert nodules took place. Ten samples representing limestones, dolomitic limestone, marls and the green carbonate-rich clay were studied from petrographical and mineralogical points of view, and the carbon and oxygen isotopic ratios from the carbonate (calcite component were measured. In conclusion, it was found that the procedure of extraction of CO2 we used enabled the discrimination between the isotopic prints of calcite vs. dolomite. This pleads for considering our results as a primary isotopic pattern in the bulk rock. The oxygen and carbon isotope data indicate a fresh-water depositional environment with Z<120. The δ13C mean value (-4.96 ‰ PDB is, generally, representative for fresh-water carbonates of the Tertiary period. The same environment characterized also the formation of carbonates within the green clay.

  19. Oxygen isotopic composition of carbon dioxide in the middle atmosphere

    OpenAIRE

    Liang, Mao-Chang; Blake, Geoffrey A.; Lewis, Brenton R.; Yung, Yuk L.

    2007-01-01

    The isotopic composition of long-lived trace molecules provides a window into atmospheric transport and chemistry. Carbon dioxide is a particularly powerful tracer, because its abundance remains >100 parts per million by volume (ppmv) in the mesosphere. Here, we successfully reproduce the isotopic composition of CO2 in the middle atmosphere, which has not been previously reported. The mass-independent fractionation of oxygen in CO2 can be satisfactorily explained by the exchange reaction with...

  20. Chromium isotope fractionation during coprecipitation with calcium carbonate

    DEFF Research Database (Denmark)

    Rodler, Alexandra; Sánchez-Pastor, Nuria; Fernández-Díaz, Lurdes

    The chromium (Cr) isotopic composition of carbonates can potentially be used as a paleoclimate proxy to elucidate past fluctuations of oxygen contents in atmosphere and hydrosphere. The use of Cr isotopes to track paleoenvironmental changes, for example related to the rise of oxygen during the Ar...... et al., 2007, Water Air Soil Poll. 179, 381-390. [2] Sánchez-Pastor et al., 2011, Cryst. Growth Des. 11, 3081-3089....

  1. Chromium Isotopes in Marine Carbonates - an Indicator for Climatic Change?

    Science.gov (United States)

    Frei, R.; Gaucher, C.

    2010-12-01

    Chromium (Cr) stable isotopes experience an increased interest as a tracer of Cr (VI) reduction in groundwater and thus showed their potential as a monitor of remediation of anthropogenic and natural contamination in water (Berna et al., 2009; Izbicki et al., 2008). Chromium stable isotopes in Fe-rich chemical sediments (BIFs and Fe-cherts) have recently also been used as a tracer for Earth's atmospheric oxygenation through time (Frei et al., 2009). We have applied the Cr isotope system to organic-rich carbonates from a late Ediacaran succession in Uruguay (Polanco Formation), from which we have previously analyzed BIFs with extremely fractionated (δ53Cr up to 5.0 ‰) Cr isotope signatures that are part of an underlying deep water clastic sediment (shale-dominated) sequence (Yerbal Formation) deposited in a glacio-marine environment (Gaucher et al.,2004). δ53Cr values of organic rich carbonates correlate with positive and negative carbon isotope excursions (δ13C PDB between -3 and +3 ‰) and with systematic changes in strontium isotope compositions, commonly interpreted as to reflect fluctuations in organic (photosynthetic algae) production related to fluctuations in atmospheric oxygen and weathering intensities, respectively. Slightly positively fractioned δ53Cr values (up to +0.25‰), paralleling positive (δ13C PDB and 87Sr/86Sr ratio excursions would thereby trace elevated atmospheric oxygen levels/pulses possibly related to glacier retreat/melting stages that caused bioproductivity to increase. While the causal link between these multiple isotopic tracers and the mechanisms of Cr stripping into carbonates has to be further investigated in detail, the first indications from this study point to a potentially promising use of stable Cr isotopes in organic-rich carbonates to monitor fluctuations of atmospheric oxygen, particularly over the Neoproterozoic and Phanerozoic ice age periods. E.C. Berna et al. (2010) Cr stable isotopes as indicators of Cr

  2. Stable carbon isotope ratios of ambient aromatic volatile organic compounds

    Science.gov (United States)

    Kornilova, Anna; Huang, Lin; Saccon, Marina; Rudolph, Jochen

    2016-09-01

    Measurements of mixing ratios and stable carbon isotope ratios of aromatic volatile organic compounds (VOC) in the atmosphere were made in Toronto (Canada) in 2009 and 2010. Consistent with the kinetic isotope effect for reactions of aromatic VOC with the OH radical the observed stable carbon isotope ratios are on average significantly heavier than the isotope ratios of their emissions. The change of carbon isotope ratio between emission and observation is used to determine the extent of photochemical processing (photochemical age, ∫ [OH]dt) of the different VOC. It is found that ∫ [OH]dt of different VOC depends strongly on the VOC reactivity. This demonstrates that for this set of observations the assumption of a uniform ∫ [OH]dt for VOC with different reactivity is not justified and that the observed values for ∫ [OH]dt are the result of mixing of VOC from air masses with different values for ∫ [OH]dt. Based on comparison between carbon isotope ratios and VOC concentration ratios it is also found that the varying influence of sources with different VOC emission ratios has a larger impact on VOC concentration ratios than photochemical processing. It is concluded that for this data set the use of VOC concentration ratios to determine ∫ [OH]dt would result in values for ∫ [OH]dt inconsistent with carbon isotope ratios and that the concept of a uniform ∫ [OH]dt for an air mass has to be replaced by the concept of individual values of an average ∫ [OH]dt for VOC with different reactivity.

  3. Temperature dependence of carbon isotope fractionation in CAM plants

    Energy Technology Data Exchange (ETDEWEB)

    Deleens, E.; Treichel, I.; O' Leary, M.H.

    1985-09-01

    The carbon isotope fractionation associated with nocturnal malic acid synthesis in Kalanchoe daigremontiana and Bryophyllum tubiflorum was calculated from the isotopic composition of carbon-4 of malic acid, after appropriate corrections. In the lowest temperature treatment (17/sup 0/C nights, 23/sup 0/C days), the isotope fractionation for both plants is -4% per thousand (that is, malate is enriched in /sup 13/C relative to the atmosphere). For K. daigremontiana, the isotope fractionation decreases with increasing temperature, becoming approximately 0% per thousand at 27/sup 0/C/33/sup 0/C. Detailed analysis of temperature effects on the isotope fractionation indicates that stomatal aperture decreases with increasing temperature and carboxylation capacity increases. For B. tubiflorum, the temperature dependence of the isotope fractionation is smaller and is principally attributed to the normal temperature dependences of the rates of diffusion and carboxylation steps. The small change in the isotopic composition of remaining malic acid in both species which is observed during deacidification indicates that malate release, rather than decarboxylation, is rate limiting in the deacidification process. 28 references, 1 figure, 4 tables.

  4. Carbon isotope biogeochemistry of plant resins and derived hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Murray, A.P.; Edwards, D.; Hope, J.M.; Boreham, C.J. [Australian Geological Survey Organisation, Canberra (Australia)] [and others

    1998-12-31

    Hydrocarbons derived from plant resins are major components of some terrigenous oils and bitumens. These compounds are structurally distinct and this makes then useful biomarkers applicable in petroleum exploration as well as sources of biogeochemical information about palaeoenvironment and palaeobotany. Although recent studies have elucidated the molecular structure of resinites, very little information has been available for the carbon isotope composition of resinites and no studies of resin-derived compounds in oils had been performed prior to the present study. Hence, carbon stable isotope analyses were carried out on a suite of modern and fossil resins of diverse origins, including compound specific isotope analysis of individual hydrocarbons produced during resin pyrolysis. Oils derived from resinite source organic matter were also analysed. The results showed that ``Class I`` resinites derived from gymnosperms were enriched in the heavy carbon isotope compared with those from angiosperms (``Class I`` resinites). Furthermore, both fossil resinites themselves and individual hydrocarbons derived from them were isotopically heavy compared with modern plant resins. The isotopic signatures of diterpanes and triterpanes in various early Tertiary oils from Australasia and Southeast Asia reflect their origins from gymnosperms and angiosperms, respectively. (author)

  5. BOREAS TE-5 Tree Ring and Carbon Isotope Ratio Data

    Science.gov (United States)

    Hall, Forrest G. (Editor); Curd, Shelaine (Editor); Ehleriinger, Jim; Brooks, J. Renee; Flanagan, Larry

    2000-01-01

    The BOREAS TE-5 team collected several data sets to investigate the vegetation-atmosphere CO2 and H2O exchange processes. These data include tree ring widths and cellulose carbon isotope data from coniferous trees collected at the BOREAS NSA and SSA in 1993 and 1994 by the BOREAS TE-5 team. Ring width data are provided for both Picea mariana and Pinus banksiana. The carbon isotope data are provided only for Pinus banksiana. The data are provided in tabular ASCII files. The data files are available on a CD-ROM (see document number 20010000884), or from the Oak Ridge National Laboratory (ORNL) Distributed Active Archive Center (DAAC).

  6. Stable Carbon Isotope Record in a Palau Sclerosponge

    Science.gov (United States)

    Grottoli, A. G.

    2002-12-01

    The ratio of stable carbon isotopes (δ13C) deposited in the calcium carbonate skeleton of marine sclerosponges appears to record the carbon isotopic composition of seawater mixed-layer dissolved inorganic carbon (δ13CDIC). Thus the δ13C signature chronicled in sclerosponge skeletons offers a promising multi-century proxy record of seawater mixed-layer δ13CDIC throughout the tropics. Here, a high-resolution (0.1 mm) δ13C record for a 7.7 cm Acanthocheatetes wellsi sclerosponge from Palau (7N, 134W) is presented. At a published growth rate of 0.45 mm per year, this record spans ~s170 years beginning in July 2001 and going back to 1831. The δ13C values for a definitive 10-year A. wellsi record spanning 1989-1998 were similar to δ13C values here for the first 4.7 mm of the record providing supporting evidence for the growth rate. The sclerosponge δ13C shows a distinct Seuss Effect. At the time this abstract was submitted, the analysis of the first 16 mm of the sclerosponge revealed a significant decrease in δ13C with time [δ13C = 0.02 (distance) + 2.64, r2 = 0.73, p < 0.0001, where time is marked by distance in millimeters from the growing edge] corresponding to a decrease in δ13C of 0.076‰ per decade. For comparison, published low-frequency measurements in Australian, New Caledonian and Jamaican sclerosponges have yielded decreases in δ13C of ~s0.05 to 0.08 ‰ per decade over the past 40 years. Preliminary interpretation of the data indicates that the amount of atmospheric CO2 contributing to the seawater δ13CDIC at Palau is intermediate to Australia and Jamaica. In addition, visual examination of the δ13C record reveals regular fluctuation in δ13C that may correspond to annual variability in δ13CDIC. This research presents the first century or longer sclerosponge δ13C record from the northwester equatorial Pacific.

  7. Carbon Isotope Fractionation In Biotic Vs. Abiotic Anaerobic Conditions

    Science.gov (United States)

    Gebrehiwet, T. A.

    2005-12-01

    Dissimilatory metal reducing bacteria (DMRB) are thought to play an important role in the biogeochemical cycling of Fe, and nutrient elements such as C and P, in the anaerobic subsurface. The consumption of organic carbon sources (including contaminants) by these bacteria can significantly fractionate substrate C isotopes, however the effects of solution composition, electron acceptor, or electron donor on C isotopic fractionation by DMRB is at present poorly quantified. We have conducted experiments to compare the effects of bicarbonate (δ13C = -3‰) and phosphate buffers on carbon isotope fractionation by Shewanella putrefaciens strain 200R. The effects of dissolved carbonate and phosphate on δ13C values of dissolved inorganic C evolved during microbial reduction of ferric citrate (δ 13Cinitial = -25‰) were examined using sodium lactate (δ13Cinitial = -25‰) as electron donor under strict anaerobic conditions at neutral pH and 30°C, under dark and (fluorescent) light conditions. Our results suggest that bicarbonate may enhance the rate of Fe(III) reduction by S. putrefaciens, in comparison with media containing phosphate buffer but no added bicarbonate. Compared with phosphate buffered experiments, the presence of dissolved bicarbonate also resulted in a greater degree of C isotopic fractionation (ɛ=2-3‰ and ɛ=5-7‰, respectively). The effect of light on microbial Fe(III) reduction was negligible, however sterile controls showed a minor but significant quantity of carbon dioxide production in liquid media, most likely from photochemical decomposition of citrate. The abiotic experiments also showed measurable carbon isotope fractionation between the carbon dioxide produced and the organic carbon substrate which will be discussed.

  8. Experimental fractionation of stable carbon isotopes during degassing of carbon dioxide and precipitation of calcite from aqueous solutions

    Science.gov (United States)

    Müller, K.; Winde, V.; Escher, P.; von Geldern, R.; Böttcher, M. E.

    2012-04-01

    system of the solution was controlled by both, degassing and carbonate precipitation, still leading to an enrichment of the heavier carbon isotope in the residual DIC. The experimental results are evaluated for both periods, and the influence of salinity and pH is extracted. Acknowledgement: Parts of this study were supported by BMBF within the BIOACID project

  9. Stable isotope composition of atmospheric carbon monoxide. A modelling study

    Energy Technology Data Exchange (ETDEWEB)

    Gromov, Sergey S.

    2014-11-01

    This study aims at an improved understanding of the stable carbon and oxygen isotope composition of the carbon monoxide (CO) in the global atmosphere by means of numerical simulations. At first, a new kinetic chemistry tagging technique for the most complete parameterisation of isotope effects has been introduced into the Modular Earth Submodel System (MESSy) framework. Incorporated into the ECHAM/MESSy Atmospheric Chemistry (EMAC) general circulation model, an explicit treatment of the isotope effects on the global scale is now possible. The expanded model system has been applied to simulate the chemical system containing up to five isotopologues of all carbon- and oxygen-bearing species, which ultimately determine the δ{sup 13}C, δ{sup 18}O and Δ{sup 17}O isotopic signatures of atmospheric CO. As model input, a new stable isotope-inclusive emission inventory for the relevant trace gases has been compiled. The uncertainties of the emission estimates and of the resulting simulated mixing and isotope ratios have been analysed. The simulated CO mixing and stable isotope ratios have been compared to in-situ measurements from ground-based observatories and from the civil-aircraft-mounted CARIBIC-1 measurement platform. The systematically underestimated {sup 13}CO/{sup 12}CO ratios of earlier, simplified modelling studies can now be partly explained. The EMAC simulations do not support the inferences of those studies, which suggest for CO a reduced input of the highly depleted in {sup 13}C methane oxidation source. In particular, a high average yield of 0.94 CO per reacted methane (CH{sub 4}) molecule is simulated in the troposphere, to a large extent due to the competition between the deposition and convective transport processes affecting the CH{sub 4} to CO reaction chain intermediates. None of the other factors, assumed or disregarded in previous studies, however hypothesised to have the potential in enriching tropospheric CO in {sup 13}C, were found significant

  10. The clumped isotopic record of Neoproterozoic carbonates, Sultanate of Oman

    Science.gov (United States)

    Bergmann, K. D.; Eiler, J. M.; Fischer, W. W.; Osburn, M. R.; Grotzinger, J. P.

    2011-12-01

    The Huqf Supergroup of the Sultanate of Oman records several important events in latest Precambrian time, including two glaciations in the Abu Mahara Group (ca. 725 - isotope excursion in the Nafun Group (ca. isotopic excursions, hypothesized to record perturbations of the surficial Earth carbon cycle or post-depositional diagenetic processes. Rigorous interpretation of these records requires a more thorough assessment of diagenetic processes. To better understand the significance and cause of these large amplitude isotopic excursions, we employed carbonate clumped isotope thermometry. This method allows us to estimate the absolute temperature of carbonate precipitation, including recrystallization, based on the temperature dependent abundance of carbonate ions containing both 13C and 18O. These estimates are accompanied by a measurement of carbonate δ18O, which in conjunction with temperature, can be used to calculate the oxygen isotopic composition of the fluid from which the carbonate precipitated. We analyzed stratigraphically constrained samples from a range of paleoenvironments with differing burial histories (1 - >10km maximum burial depth) to constrain the temperature and fluid composition of recrystallization. Clumped isotope temperatures from Huqf Supergroup samples range from 35-175°C. The isotopic composition of the fluid these rocks equilibrated with ranges from -3.7 to 15.7% VSMOW. This large range in temperature and fluid composition separates into distinct populations that differ systematically with independent constraints on petrography, stratigraphy and burial history. The data indicate the Abu Mahara, Nafun and Ara groups have unique diagenetic histories. In central Oman, the post-glacial Abu Mahara cap dolostone shows high temperature, rock buffered diagenesis (Tavg = 176°C; δ18Ofluid = 15% VSMOW), the Nafun Group generally experienced lower temperature, fluid buffered diagenesis (Tavg = 69°C; δ18Ofluid = 1% VSMOW) and the Ara Group

  11. CO2-dependent carbon isotope fractionation in dinoflagellates relates to their inorganic carbon fluxes

    NARCIS (Netherlands)

    Hoins, M.; Eberlein, T.; Van de Waal, D.B.; Sluijs, A.|info:eu-repo/dai/nl/311474748; Reichart, G.-J.|info:eu-repo/dai/nl/165599081; Rost, B.

    2016-01-01

    Carbon isotope fractionation (εp) between the inorganic carbon source and organic matter has been proposed to be a function of pCO2. To understand the CO2-dependency of εp and species-specific differences therein, inorganic carbon fluxes in the four dinoflagellate species Alexandrium fundyense, Scri

  12. Photosynthetic carbon isotope discrimination and its relationship to the carbon isotope signals of stem, soil and ecosystem respiration.

    Science.gov (United States)

    Wingate, Lisa; Ogée, Jérôme; Burlett, Régis; Bosc, Alexandre; Devaux, Marion; Grace, John; Loustau, Denis; Gessler, Arthur

    2010-10-01

    • Photosynthetic carbon (C) isotope discrimination (Δ(Α)) labels photosynthates (δ(A) ) and atmospheric CO(2) (δ(a)) with variable C isotope compositions during fluctuating environmental conditions. In this context, the C isotope composition of respired CO(2) within ecosystems is often hypothesized to vary temporally with Δ(Α). • We investigated the relationship between Δ(Α) and the C isotope signals from stem (δ(W)), soil (δ(S)) and ecosystem (δ(E)) respired CO(2) to environmental fluctuations, using novel tuneable diode laser absorption spectrometer instrumentation in a mature maritime pine forest. • Broad seasonal changes in Δ(Α) were reflected in δ(W,) δ(S) and δ(E). However, respired CO(2) signals had smaller short-term variations than Δ(A) and were offset and delayed by 2-10 d, indicating fractionation and isotopic mixing in a large C pool. Variations in δ(S) did not follow Δ(A) at all times, especially during rainy periods and when there is a strong demand for C allocation above ground. • It is likely that future isotope-enabled vegetation models will need to develop transfer functions that can account for these phenomena in order to interpret and predict the isotopic impact of biosphere gas exchange on the C isotope composition of atmospheric CO(2).

  13. How the oxygen isotope ratio of rain water influences the isotope ratio of chicken eggshell carbonate

    Science.gov (United States)

    Price, Gregory; Grimes, Stephen

    2015-04-01

    The stable oxygen isotope ratio of chicken eggshell carbonate was analysed from chicken eggs laid under free range, and organic farming regimes from across the UK. The eggshell carbonate oxygen isotope data shows a clear depletion in delta18O distribution from the southwest to the northeast. Although consistently offset by around 1 permil, the same isotopic distribution as that seen in eggshell carbonate is observed in the delta18O ratio of rainfall and groundwater from across the UK. This distribution is related to the Rayleigh distillation of rainfall driven by westerly winds across the UK landmass. The clear relationship observed between eggshell delta18O values and that of rainwater presumably reflects the nature of free range chickens which must be drinking locally derived rainwater and supplementing their diet and water intake with locally derived food. These results suggest that the oxygen isotope value of chicken eggshells can be used as a forensic tool to identify the locality that free range and organic eggs were laid within the UK. Furthermore, if suitable material is preserved in the archaeological and geological record then such a relationship can potentially be used to establish the oxygen isotope value of rainwater from which ancient and / or ancestral birds lived.

  14. Martian carbon dioxide: Clues from isotopes in SNC meteorites

    Science.gov (United States)

    Karlsson, H. R.; Clayton, R. N.; Mayeda, T. K.; Jull, A. J. T.; Gibson, E. K., Jr.

    1993-01-01

    Attempts to unravel the origin and evolution of the atmosphere and hydrosphere on Mars from isotopic data have been hampered by the impreciseness of the measurements made by the Viking Lander and by Earth-based telescopes. The SNC meteorites which are possibly pieces of the Martian surface offer a unique opportunity to obtain more precise estimates of the planet's volatile inventory and isotopic composition. Recently, we reported results on oxygen isotopes of water extracted by pyrolysis from samples of Shergotty, Zagami, Nakhla, Chassigny, Lafayette, and EETA-79001. Now we describe complementary results on the stable isotopic composition of carbon dioxide extracted simultaneously from those same samples. We will also report on C-14 abundances obtained by accelerator mass spectrometry (AMS) for some of these CO2 samples.

  15. The origin of carbon isotope vital effects in coccolith calcite

    Science.gov (United States)

    McClelland, H. L. O.; Bruggeman, J.; Hermoso, M.; Rickaby, R. E. M.

    2017-03-01

    Calcite microfossils are widely used to study climate and oceanography in Earth's geological past. Coccoliths, readily preserved calcite plates produced by a group of single-celled surface-ocean dwelling algae called coccolithophores, have formed a significant fraction of marine sediments since the Late Triassic. However, unlike the shells of foraminifera, their zooplankton counterparts, coccoliths remain underused in palaeo-reconstructions. Precipitated in an intracellular chemical and isotopic microenvironment, coccolith calcite exhibits large and enigmatic departures from the isotopic composition of abiogenic calcite, known as vital effects. Here we show that the calcification to carbon fixation ratio determines whether coccolith calcite is isotopically heavier or lighter than abiogenic calcite, and that the size of the deviation is determined by the degree of carbon utilization. We discuss the theoretical potential for, and current limitations of, coccolith-based CO2 paleobarometry, that may eventually facilitate use of the ubiquitous and geologically extensive sedimentary archive.

  16. The origin of carbon isotope vital effects in coccolith calcite

    Science.gov (United States)

    McClelland, H. L. O.; Bruggeman, J.; Hermoso, M.; Rickaby, R. E. M.

    2017-01-01

    Calcite microfossils are widely used to study climate and oceanography in Earth's geological past. Coccoliths, readily preserved calcite plates produced by a group of single-celled surface-ocean dwelling algae called coccolithophores, have formed a significant fraction of marine sediments since the Late Triassic. However, unlike the shells of foraminifera, their zooplankton counterparts, coccoliths remain underused in palaeo-reconstructions. Precipitated in an intracellular chemical and isotopic microenvironment, coccolith calcite exhibits large and enigmatic departures from the isotopic composition of abiogenic calcite, known as vital effects. Here we show that the calcification to carbon fixation ratio determines whether coccolith calcite is isotopically heavier or lighter than abiogenic calcite, and that the size of the deviation is determined by the degree of carbon utilization. We discuss the theoretical potential for, and current limitations of, coccolith-based CO2 paleobarometry, that may eventually facilitate use of the ubiquitous and geologically extensive sedimentary archive. PMID:28262764

  17. On the isotopic composition of magmatic carbon in SNC meteorites

    Science.gov (United States)

    Wright, I. P.; Grady, M. M.; Pillinger, C. T.

    1992-01-01

    SNC meteorites are thought, from many lines of evidence, to come from Mars. A line of investigation which has been pursued in our laboratory over the years involves measurement of the stable isotopic composition of carbon, in its various forms, in SNC meteorites. In order to establish a firm basis for studying the isotopic systematics of carbon in the martian surface environment, it is first necessary to try and constrain the delta C-13 of bulk Mars. Taking all of the available information, it would seem that the delta C-13 of the Earth's mantle lies somewhere in the range of -5 to -7 percent. Preliminary assessment of magnetic carbon in SNC meteorites, would tend to suggest a delta C-13 of 20 to 30 percent, which is conspicuously different from that of the terrestrial mantle. It is not obvious why there should be such a difference between the two planets, although many explanations are possible. One of these possibilities, that previous delta C-13 measurements for magnetic carbon in SNC meteorites are in error to some degree, is being actively investigated. The most recent results seem to constrain the theta C-13 of the magnetic carbon in SNC meteorites to about -20 percent, which is not at odds with previous estimates. As such, it is considered that a detailed investigation of the carbon isotopic systematics of martian surface materials does have the necessary information with which to proceed.

  18. Compound specific isotopic fractionation patterns suggest different carbon metabolisms among Chloroflexus-like bacteria in hot spring microbial mats

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Meer, M.T.J. van der; Schouten, S.; Leeuw, J.W. de; Ward, D.M.

    2003-01-01

    Stable carbon isotope fractionations between dissolved inorganic carbon and lipid biomarkers suggest photoautotrophy by Chloroflexus-like organisms in sulfidic and nonsulfidic Yellowstone hot springs. Where co-occurring, cyanobacteria appear to cross-feed Chloroflexus-like organisms supporting photo

  19. Final Report: Fundamental Research on the Fractionation of Carbon Isotopes during Photosynthesis, New Interpretations of Terrestrial Organic Carbon within Geologic Substrates

    Energy Technology Data Exchange (ETDEWEB)

    Jahren, A. Hope [Univ. of Hawaii, Honolulu, HI (United States); Schubert, Brian A. [Univ. of Louisiana, Lafayette, LA (United States)

    2017-08-02

    The goal for the current grant period (2013 – 2016) was to quantify the effect of changing atmospheric carbon dioxide concentration (pCO2) on published terrestrial carbon isotope excursion events. This work supported four scientists across multiple career stages, and resulted in 5 published papers.

  20. Measurements and interpretation of oxygen isotopes in stratospheric carbon dioxide

    NARCIS (Netherlands)

    Mrozek, D.J.|info:eu-repo/dai/nl/325800146

    2017-01-01

    Carbon dioxide (CO2) is an important natural and anthropogenic greenhouse gas in Earth's atmosphere. Its atmospheric mole fraction has increased from about 280 ppm (parts per million) in the pre-industrial atmosphere to more than 400 ppm at present. Investigation of the stable isotopic composition

  1. Preparation of flat carbon support films

    NARCIS (Netherlands)

    Koning, RI; Oostergetel, GT; Brisson, A

    2003-01-01

    Wrinkling of carbon support films is known to limit the resolution of electron microscopy images of protein two-dimensional crystals. The origin of carbon wrinkling during preparation of the support films was investigated by reflected light microscopy. We observed that carbon films go through severa

  2. Li isotopes in foraminifera: a new proxy for past ocean dissolved inorganic carbon

    Science.gov (United States)

    Vigier, N.; Rollion-Bard, C.; Erez, J.

    2009-12-01

    Past ocean pH and pCO2 are critical parameters for establishing relationships between Earth climate and carbon cycle. For the Miocene-Pleistocene period, two main proxies have been used: carbon isotopes of di-unsaturated alkenones extracted from sea cores, and boron isotope signatures of marine carbonates [1, 2]. Both techniques lead to selfconsistent palaeooceanic pH or pCO2 estimates, but are associated with large uncertainties. Moreover, the paleovariations calculated from boron isotope measurements are a matter of debate. Additional proxies are therefore needed. Based on an in-situ analytical technique recently developed [3], we analysed a series of foraminifera - Amphistegina - cultured under various conditions (in pH, T and Dissolved Inorganic Carbon). We show that the lithium isotope signature of the foraminifera correlates with the DIC (r2 = 0.93). Conversely, there is no dependency of Li isotope signature on pH or T. A simple model of biomineralization in which growth rate is a key parameter can fit the whole dataset, including published values for other foraminifera species [4, 5]. This strongly suggests that the DIC-δ7Li correlation highlighted by the cultured Amphistegina can also be applied to other species. These results, combined with the published oceanic Li and B isotope paleovariations [2, 4, 5], allow us to estimate the ocean DIC and pCO2 evolution for the past 18Ma. The similarity with the pCO2 curve given by carbon isotopes measured in di-unsaturated alkenones is striking. This supports the use of Li isotopes as a new proxy and adds support to the existing data. It also suggests, in contrast with the common view, a less significant role of river input on the variation of the ocean Li isotope composition, at least for the period considered. [1] Pagani et al. (2005) Science 309, 600-603. [2] Pearson & Palmer (2000) Nature 406, 695-699. [3] Vigier et al. (2007) G-cubed 8, Q01003 [4] Hall et al. (2005) Mar. Geology 217, 255-265 [5] Hathorne

  3. Modeling stable isotope and organic carbon in hillslope stormflow

    Science.gov (United States)

    Dusek, Jaromir; Vogel, Tomas; Dohnal, Michal; Marx, Anne; Jankovec, Jakub; Sanda, Martin; Votrubova, Jana; Barth, Johannes A. C.; Cislerova, Milena

    2016-04-01

    Reliable prediction of water movement and fluxes of dissolved substances (such as stable isotopes and organic carbon) at both the hillslope and the catchment scales remains a challenge due to complex boundary conditions and soil spatial heterogeneity. In addition, microbially mediated transformations of dissolved organic carbon (DOC) are known to affect balance of DOC in soils, hence the transformations need to be included in a conceptual model of a DOC transport. So far, only few studies utilized stable isotope information in modeling and even fewer linked dissolved carbon fluxes to mixing and/or transport models. In this study, stormflow dynamics of oxygen-18 isotope and dissolved organic carbon was analyzed using a physically based modeling approach. One-dimensional dual-continuum vertical flow and transport model, based on Richards and advection-dispersion equations, was used to simulate the subsurface transport processes in a forest soil during several observed rainfall-runoff episodes. The transport of heat in the soil profile was described by conduction-advection equation. Water flow and transport of solutes and heat were assumed to take place in two mutually communicating porous domains, the soil matrix and the network of preferential pathways. The rate of microbial transformations of DOC was assumed to depend on soil water content and soil temperature. Oxygen-18 and dissolved organic carbon concentrations were observed in soil pore water, hillslope stormflow (collected in the experimental hillslope trench), and stream discharge (at the catchment outlet). The modeling was used to analyze the transformation of input solute signals into output hillslope signals observed in the trench stormflow. Signatures of oxygen-18 isotope in hillslope stormflow as well as isotope concentration in soil pore water were predicted reasonably well. Due to complex nature of microbial transformations, prediction of DOC rate and transport was associated with a high uncertainty.

  4. Dual Carbon and Nitrogen isotope Analysis

    African Journals Online (AJOL)

    significance of mangrove detritus as a food source for shrimps. Methods ..... although they might show preference for animal food over .... the decomposition is fast, or there is a net export of litter. ... carbon signatures of consumers. Flemming et ...

  5. Preliminary Nanosims Analysis of Carbon Isotope of Carbonates in Calcium-Aluminum-Rich Inclusions

    OpenAIRE

    Guan, Y.; Paque, J. M.; Burnett, D.S.; Eiler, J. M.

    2009-01-01

    Carbonate minerals observed in primitive meteorites are products of either terrestrial weathering or aqueous alteration in the early solar system. Most of the carbonate minerals in carbonaceous chondrites occur primarily as isolated grains in matrix, as crosscutting veins, or as replacement minerals in chondrules [e.g., 1, 2]. A few calcium-aluminum-rich inclusions (CAIs) have been reported containing carbonate minerals as well [2, 3]. The C and O isotopes of carbonates in c...

  6. Carbon isotope fluctuations in Precambrian carbonate sequences of several localities in Brazil

    Directory of Open Access Journals (Sweden)

    SIAL ALCIDES N.

    2000-01-01

    Full Text Available Carbon isotope fluctuations in Precambrian sedimentary carbonates between 2.8 Ga and 0.60 Ga in Brazil are examined in this study. The carbonate facies of the BIF of the 2.8 Ga-old Carajás Formation, state of Pará in northern Brazil, has rather homogeneous delta13C (-5 o/ooPDB, compatible with carbonatization of a silicate protolith by a CO2-rich fluid from mantle degassing. The Paleoproterozoic Gandarela Formation, state of Minas Gerais, displays a narrow delta13C variation (-1.5 to +0.5 o/oo compatible with carbon isotope signatures of carbonates deposited around 2.4 Ga worldwide. The Fecho do Funil Formation has probably recorded the Lomagundi delta13C positive anomaly (+6.4 to +7.1 o/ooPDB. The magnesite-bearing carbonates of the Orós mobile belt, state of Ceará, exhibit carbon isotope fluctuation within the range for carbonates deposited at 1.8 Ga. The C-isotope record of the Frecheirinha Formation, northwestern state of Ceará, shows negative delta13C values in its lower portion (-2 o/oo and positive values up section (+1 to +3 o/oo, which suggests this sequence is a cap carbonate deposited after a glacial event around 0.95 Ga. The Jacoca and Acauã sedimentary carbonate Formations, state of Sergipe, NE Brazil, show carbon isotope fluctuations very similar to each other (average around -5 o/oo, compatible with a deposition around 0.76 Ga. The younger Olho D'Água carbonate Formation, however, also in the state of Sergipe, displays negative delta13C values at the lower portion of the Formation, changing dramatically up section to positive values as high as +10 o/oo, a characteristic compatible with a Sturtian cap carbonate deposited around 0.69 Ga. On the light of the C isotope data discussed in this study, it seems that delta13C fluctuations in Paleoproterozoic carbonates in Brazil are within the range found globally for metasedimentary carbonates of this age. Carbon isotope data proved to be very useful in establishing relative

  7. Characteristics of carbon and hydrogen isotopic compositions of light hydrocarbons

    Institute of Scientific and Technical Information of China (English)

    沈平

    1995-01-01

    Light hydrocarbons named in the present paper refer to the natural gas-associated light oil and condensate 46 light oil and condensate samples from 11 oil-bearing basins of China were collected and their carbon and hydrogen isotopic compositions were analysed in terms of their total hydrocarbons, saturated hydrocarbons and a part of aromatic fractions, and gas-source materials and their sedimentary environments were discussed based on the above-mentioned data and the geological background of each area. From the view of carbon and hydrogen isotopic composition of total hydrocarbons and saturated hydrocarbons, it is revealed that the condensate related to coal-bearing strata is enriched in 13C and D while that related to the source material of type I-II is enriched in 12C. In general, the isotopic composition of carbon is mainly attributed to the inheriting effect of their source materials, whereas that of hydrogen principally reflects the correlationship between hydrogen isotopes and the sedimentary envi

  8. Clumped-isotope geochemistry of carbonates: A new tool for the reconstruction of temperature and oxygen isotope composition of seawater

    Energy Technology Data Exchange (ETDEWEB)

    Bernasconi, Stefano M., E-mail: Stefano.bernasconi@erdw.ethz.ch [Geological Institute, ETH Zuerich, Sonneggstrasse 5, 8092 Zuerich (Switzerland); Schmid, Thomas W.; Grauel, Anna-Lena [Geological Institute, ETH Zuerich, Sonneggstrasse 5, 8092 Zuerich (Switzerland); Mutterlose, Joerg [Institut fuer Geologie, Mineralogie und Geophysik, Ruhr Universitaet Bochum, Universitaetsstr. 150, 44801 Bochum (Germany)

    2011-06-15

    Highlights: > Clumped-isotope thermometry of carbonates is discussed. > Clumped isotopes of Belemnites show higher sea surface temperatures than commonly assumed for the lower Cretaceous. > The potential of clumped-isotope measurement on foraminifera is discussed. - Abstract: Clumped-isotope geochemistry deals with State of ordering of rare isotopes in molecules, in particular with their tendency to form bonds with other rare isotopes rather than with the most abundant ones. Among its possible applications, carbonate clumped-isotope thermometry is the one that has gained most attention because of the wide potential of applications in many disciplines of the earth sciences. In particular, it allows reconstructing the temperature of formation of carbonate minerals without knowledge of the isotopic composition of the water from which they were formed. In addition, the O isotope composition of the waters from which they were formed can be calculated using the {delta}{sup 18}O of the same carbonate sample. This feature offers new approaches in paleoclimatology for reconstructing past global geochemical cycles. In this contribution two applications of this method are presented. First the potential of a new analytical method of measurement of clumped isotopes on small samples of foraminifera, for high-resolution SST and seawater {delta}{sup 18}O reconstructions from marine sediments is shown. Furthermore the potential of clumped isotope analysis of belemnites, for reconstructing seawater {delta}{sup 18}O and temperatures in the Cretaceous is shown.

  9. Application of stable carbon isotopes in long term mesocosm studies for carbon cycle investigation

    Science.gov (United States)

    Esposito, Mario

    2016-04-01

    Carbon dioxide (CO2) is an effective greenhouse gas. The Oceans absorb ca. 30% of the anthropogenic CO2 emissions and thereby partly attenuate deleterious climate effects. A consequence of the oceanic CO2 uptake is a decreased seawater pH and planktonic community shifts. The quantification of the anthropogenic perturbation was investigated through stable carbon isotope analysis in three "long term" mesocosm experiments (Sweden 2013, Gran Canaria 2014, Norway 2015) which reproduced near natural ecosystem conditions under both controlled and modified future CO2 level (up to 2000 ppm) scenarios. Parallel measurements of the stable isotope composition of dissolved inorganic carbon (δ13CDIC) dissolved organic carbon (δ13CDOC) and particulate carbon (δ13CTPC) both from the mesocosms water column and sediment traps showed similar trends in all the three experiments. A CO2 response was noticeable in the isotopic dataset, but increased CO2 levels had only a subtle effect on the concentrations of the dissolved and particulate organic carbon pool. Distinctive δ13C signatures of the particulate carbon pool both in the water column and the sediments were detectable for the different CO2 treatments and they were strongly correlated with the δ13CDIC signatures but not with the δ13CDOC pool. The validity of the isotopic data was verified by cross-analyses of multiple substances of known isotopic signatures on a GasBench, Elemental Analyser (EA) and on an in-house TOC-IRMS setup for the analysis of δ13CDIC, δ13CTPC and δ13CDOC, respectively. Results from these mesocosm experiments proved the stable carbon isotope approach to be an effective tool for quantifying the uptake and carbon transfer among the various compartments of the marine carbon system.

  10. Carbon isotope composition of the Lower Triassic marine carbonates, Lower Yangtze Region, South China

    Institute of Scientific and Technical Information of China (English)

    ZUO; Jingxun; TONG; Jinnan; QIU; Haiou; ZHAO; Laishi

    2006-01-01

    Studies on three Lower Triassic sections located on the shallow water platform, the deep water slope and in the deep water basin in the Lower Yangtze Region, South China, show the similar trend of carbon isotope evolution. Biostratigraphic correlations among the Lower Triassic sections on the basis of standard conodont zones indicate that three negative shifts occurred in the Griesbachian, the Smithian and the late Spathian stages respectively, and one distinctly positive shift occurred in the early Spathian stage. Trend of carbon isotope evolution of the Lower Triassic reflects some significant changes in the global carbon cycle. Moreover, δ13C background values are intensively controlled by palaeogeographic environment. In general, δ13C values from deep-water slope carbonates are lighter than those from carbonate platform and heavier than those from deep-water basin carbonates. The positive carbon isotope excursion may be induced by a significant amount of organic carbon burial in marine sediments and increase in primary productivity. The large negative carbon isotope excursions during the Early Triassic in Lower Yangtze Region are interpreted to relate to volcano eruptions based on tuffaceous claystone interlayers observed near the Permian-Triassic boundary, the Induan- Olenekian boundary and the Lower Triassic-Middle Triassic boundary.

  11. Carbon isotope geochemistry of the Santa Clara River

    Science.gov (United States)

    Masiello, Caroline A.; Druffel, Ellen R. M.

    2001-06-01

    The Santa Clara River is a prototypical small mountainous river, with a headwater height greater than 1000 m and a basin area smaller than 10,000 m 2. Although individual small mountainous rivers export trivial amounts of sediment and carbon to the ocean, as a group these rivers may export a major fraction (as much as 50%) of the total global river sediment flux [Milliman and Syvitski, 1992], making their geochemistry relevant the study of the ocean's carbon cycle. In addition, many small rivers export sediment in a few high flux events, causing massive, sporadic discharge of carbon onto coastal shelves, discharge conditions very different from those of large rivers. This class of rivers is an end-member of the river-ocean carbon exchange system,. opposite the Earth's largest river, the Amazon. The carbon mass and isotopic properties of the Santa Clara River are significantly different from previously studied large rivers. During the 1997-1998 winter, all Santa Clara carbon pools were old, with flux-weighted average Δl4C values of-428±76‰ for particulate organic carbon, -73±31‰ for dissolved organic carbon, and-644±58‰ for black carbon. The age of exported carbon is primarily due to the deep erosion of old soils and not to inclusion of fossil fuel carbon. Additionally, the δ13C signatures of exported carbon pools were high relative to terrestrial carbon, bearing a signature quite similar to marine carbon (average particulate organic carbon (POC) δ13C = -22.2±0.8‰). The Santa Clara's estuary is small and drains onto the narrow eastern Pacific coastal margin, exporting this old soil organic matter directly into the ocean. If the Santa Clara export patterns are representative of this class of rivers, they may be a significant source of refractory terrestrial carbon to the ocean.

  12. A sorghum (Sorghum bicolor) mutant with altered carbon isotope ratio.

    Science.gov (United States)

    Rizal, Govinda; Karki, Shanta; Thakur, Vivek; Wanchana, Samart; Alonso-Cantabrana, Hugo; Dionora, Jacque; Sheehy, John E; Furbank, Robert; von Caemmerer, Susanne; Quick, William Paul

    2017-01-01

    Recent efforts to engineer C4 photosynthetic traits into C3 plants such as rice demand an understanding of the genetic elements that enable C4 plants to outperform C3 plants. As a part of the C4 Rice Consortium's efforts to identify genes needed to support C4 photosynthesis, EMS mutagenized sorghum populations were generated and screened to identify genes that cause a loss of C4 function. Stable carbon isotope ratio (δ13C) of leaf dry matter has been used to distinguishspecies with C3 and C4 photosynthetic pathways. Here, we report the identification of a sorghum (Sorghum bicolor) mutant with a low δ13C characteristic. A mutant (named Mut33) with a pale phenotype and stunted growth was identified from an EMS treated sorghum M2 population. The stable carbon isotope analysis of the mutants showed a decrease of 13C uptake capacity. The noise of random mutation was reduced by crossing the mutant and its wildtype (WT). The back-cross (BC1F1) progenies were like the WT parent in terms of 13C values and plant phenotypes. All the BC1F2 plants with low δ13C died before they produced their 6th leaf. Gas exchange measurements of the low δ13C sorghum mutants showed a higher CO2 compensation point (25.24 μmol CO2.mol-1air) and the maximum rate of photosynthesis was less than 5μmol.m-2.s-1. To identify the genetic determinant of this trait, four DNA pools were isolated; two each from normal and low δ13C BC1F2 mutant plants. These were sequenced using an Illumina platform. Comparison of allele frequency of the single nucleotide polymorphisms (SNPs) between the pools with contrasting phenotype showed that a locus in Chromosome 10 between 57,941,104 and 59,985,708 bps had an allele frequency of 1. There were 211 mutations and 37 genes in the locus, out of which mutations in 9 genes showed non-synonymous changes. This finding is expected to contribute to future research on the identification of the causal factor differentiating C4 from C3 species that can be used in the

  13. Impact of flood events on lacustrine carbonate isotope records

    Science.gov (United States)

    Kämpf, Lucas; Plessen, Birgit; Lauterbach, Stefan; Nantke, Carla; Meyer, Hanno; Chapligin, Bernhard; Höllerer, Hannes; Brauer, Achim

    2016-04-01

    Stable oxygen (δ 18O) and carbon (δ 13C) isotope compositions of lacustrine carbonates are among the most frequently used proxies in palaeolimnological / -environmental studies. Stable isotope analyses are often carried out on bulk carbonate samples, which are prone to contamination with detrital carbonates, transported into the lake by runoff processes and carrying the isotopic signal of catchment rocks, thus hampering the interpretation of the data in terms of past climatic and/or environmental changes. Despite the awareness of a likely detrital bias, the degree of contamination in most cases remains unknown and discrete contaminated samples undetected due to a lack of methods to disentangle endogenic and detrital carbonates in sediment records. To address this issue and provide more comprehensive insights into effects of flood-related detrital input on the bulk carbonate isotopic composition, we conducted stable isotope measurements on sediments trapped on a 3-12 day basis over a three-year period (January 2011 to November 2013) at two locations in pre-Alpine Lake Mondsee, close to the inflow of the main tributary and in the deepest part of the lake basin. Lake Mondsee was chosen for the monitoring since the pelagic sediments are annually laminated consisting of couplets of light calcite layers and dark layers made up by a mixture of detrital clastic and organic matter. Maximum calcite flux rates >1.5 g m2 d-1 were trapped between May and September, indicating the seasonal endogenic precipitation of calcite crystals. The comparison of the δ 18O composition of trapped carbonates, rain and epilimnion lake water revealed equilibrium calcite precipitation, allowing us to infer purely endogenic δ 18O (-9 to -11.3‰ VPDB) and δ 13C values (-6 to -9‰ VPDB) throughout the summer season. The endogenic calcite precipitation was interrupted by 14 peaks in carbonate flux (4 to 175 g m2 d-1) triggered by runoff events of different magnitudes (10-110 m3 s-1 peak

  14. Simultaneous tracing of carbon and nitrogen isotopes in human cells.

    Science.gov (United States)

    Nilsson, Roland; Jain, Mohit

    2016-05-24

    Stable isotope tracing is a powerful method for interrogating metabolic enzyme activities across the metabolic network of living cells. However, most studies of mammalian cells have used (13)C-labeled tracers only and focused on reactions in central carbon metabolism. Cellular metabolism, however, involves other biologically important elements, including nitrogen, hydrogen, oxygen, phosphate and sulfur. Tracing stable isotopes of such elements may help shed light on poorly understood metabolic pathways. Here, we demonstrate the use of high-resolution mass spectrometry to simultaneously trace carbon and nitrogen metabolism in human cells cultured with (13)C- and (15)N-labeled glucose and glutamine. To facilitate interpretation of the complex isotopomer data generated, we extend current methods for metabolic flux analysis to handle multivariate mass isotopomer distributions (MMIDs). We find that observed MMIDs are broadly consistent with known biochemical pathways. Whereas measured (13)C MIDs were informative for central carbon metabolism, (15)N isotopes provided evidence for nitrogen-carrying reactions in amino acid and nucleotide metabolism. This computational and experimental methodology expands the scope of metabolic flux analysis beyond carbon metabolism, and may prove important to understanding metabolic phenotypes in health and disease.

  15. Shear heating and clumped isotope reordering in carbonate faults

    Science.gov (United States)

    Siman-Tov, Shalev; Affek, Hagit P.; Matthews, Alan; Aharonov, Einat; Reches, Ze'ev

    2016-07-01

    Natural faults are expected to heat rapidly during seismic slip and to cool quite quickly after the slip event. Here we examine clumped isotope thermometry for its ability to identify such short duration elevated temperature events along frictionally heated carbonate faults. Our approach is based on measured Δ47 values that reflect the distribution of oxygen and carbon isotopes in the calcite lattice, measuring the abundance of 13Csbnd 18O bonds, which is affected by temperature. We examine three types of calcite rock samples: (1) crushed limestone grains that were rapidly heated and then cooled in static laboratory experiments, simulating the temperature cycle experienced by fault rock during an earthquake slip; (2) limestone samples that were experimentally sheared to simulate earthquake slip events; and (3) samples from Fault Mirrors (FMs) collected from principle slip surfaces of three natural carbonate faults. Extensive FM surfaces are believed to form during earthquake slip. Our experimental results show that Δ47 values decrease rapidly (in the course of seconds) with increasing temperature and shear velocity. On the other hand, carbonate shear zones from natural faults do not show such Δ47 decrease. We suggest that the Δ47 response may be controlled by nano-size grains, the high abundance of defects, and highly stressed/strained grain boundaries within the carbonate fault zone that can reduce the activation energy for diffusion, and thus lead to an increased rate of isotopic disordering during shear experiments. In our laboratory experiments the high stress and strain on grain contacts and the presence of nanograins thus allows for rapid disordering so that a change in Δ47 occurs in a very short and relatively low intensity heating events. In natural faults it may also lead to isotopic ordering after the cessation of frictional heating thus erasing the high temperature signature of Δ47.

  16. Carbon and Oxygen Isotope Stratigraphy of the Oxfordian Carbonate Rocks in Amu Darya Basin

    Institute of Scientific and Technical Information of China (English)

    Rongcai Zheng; Yanghui Pan; Can Zhao; Lei Wu; Renjin Chen; Rui Yang

    2013-01-01

    Based on the detailed research on petrologic and geochemical characteristics of deposition and diagenesis of Oxfordian carbonate rocks in Amu Darya Basin,Turkmenistan,carbon and oxygen isotopes were analyzed.The results show that the paleoenvironmental evolution reflected by the samples with well-preserved original carbon isotopes coincides with the carbon-isotope stratigraphic carve and is almost consistent with the global sea-level curve,the Mid-Oxfordian wide transgression,and the positive carbon-isotope excursion event.The Mid-Oxfordian continuing transgression not only laid the foundation for the development of the Oxfordian reef and shoal reservoirs in Amu Darya Basin but also provided an example for the Oxfordian global transgression and the resulting development of reefs and banks and high-speed organic carbon burial events.The response of oxygen isotopes in diagenetic environment showed that micrite limestones and granular limestones underwent weak diagenetic alteration,and the samples largely retained the original seawater features.Dolomitization and the precipitation of hydrothermal calcites tilling solution vugs and fractures before hydrocarbon accumulation occurred in a closed diagenetic environment where the main controlling factor is the temperature,and the diagenetic fluids were from the deep hot brine.The chalkification of the limestones after hydrocarbon accumulation occurred in the oiltield water systems.

  17. A supercritical oxidation system for the determination of carbon isotope ratios in marine dissolved organic carbon

    NARCIS (Netherlands)

    Le Clercq, Martijn; Van der Plicht, Johannes; Meijer, Harro A.J.

    1998-01-01

    An analytical oxidation system employing supercritical oxidation has been developed. It is designed to measure concentration and the natural carbon isotope ratios (C-13, C-14) Of dissolved organic carbon (DOC) and is especially suited for marine samples. The oxidation takes place in a ceramic tube a

  18. STABLE CARBON ISOTOPE ANALYSIS OF SUBFOSSIL WOOD FROM AUSTRIAN ALPS

    Science.gov (United States)

    KŁUSEK, MARZENA; PAWEŁCZYK, SŁAWOMIRA

    2015-01-01

    The presented studies were carried out in order to check the usefulness of subfossil wood for stable isotope analysis. The aim of research was also to define the optimal method of subfossil samples preparation. Subfossil samples used during the presented studies are a part of the multi-century dendrochronological scale. This chronology originates in an area situated around a small mountain lake — Schwarzersee, in Austria. The obtained results of stable carbon isotope measurements confirmed that the method of α-cellulose extraction by the application of acidic sodium chlorite and sodium hydroxide solutions removes resins and other mobile compounds from wood. Therefore, in the case of the analysed samples, the additional chemical process of extractives removing was found to be unnecessary. Studied wood samples contained an adequate proportion of α-cellulose similar to the values characteristic for the contemporary trees. This proved an adequate wood preservation which is essential for the conduction of isotopic research. PMID:26346297

  19. Boron isotope fractionation in magma via crustal carbonate dissolution.

    Science.gov (United States)

    Deegan, Frances M; Troll, Valentin R; Whitehouse, Martin J; Jolis, Ester M; Freda, Carmela

    2016-08-04

    Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ(11)B values down to -41.5‰, reflecting preferential partitioning of (10)B into the assimilating melt. Loss of (11)B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports (11)B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ(11)B melt values in arc magmas could flag shallow-level additions to the subduction cycle.

  20. Dissolved Organic Carbon Cycling in Forested Watersheds: A Carbon Isotope Approach

    Science.gov (United States)

    Schiff, S. L.; Aravena, R.; Trumbore, S. E.; Dillon, P. J.

    1990-12-01

    Dissolved organic carbon (DOC) is important in the acid-base chemistry of acid-sensitive freshwater systems; in the complexation, mobility, persistence, and toxicity of metals and other pollutants; and in lake carbon metabolism. Carbon isotopes (13C and 14C) are used to study the origin, transport, and fate of DOC in a softwater catchment in central Ontario. Precipitation, soil percolates, groundwaters, stream, beaver pond, and lake waters, and lake sediment pore water were characterized chemically and isotopically. In addition to total DOC, isotopic measurements were made on the humic and fulvic DOC fractions. The lake is a net sink for DOC. Δ14C results indicate that the turnover time of most of the DOC in streams, lakes, and wetlands is fast, less than 40 years, and on the same time scale as changes in acidic deposition. DOC in groundwaters is composed of older carbon than surface waters, indicating extensive cycling of DOC in the upper soil zone or aquifer.

  1. Patterns in Stable Isotope Values of Nitrogen and Carbon in ...

    Science.gov (United States)

    Stable isotope measurements of nitrogen and carbon (15N, 13ddC) are often used to characterize estuarine, nearshore, and open ocean ecosystems. Reliable information about the spatial distribution of base-level stable isotope values, often represented by primary producers, is critical to interpreting values in these ecosystems. While base-level isotope data are generally readily available for estuaries, nearshore coastal waters, and the open ocean, the continental shelf is less studied. To address this, and as a first step toward developing a surrogate for base-level isotopic signature in this region, we collected surface and deep water samples from the United States’ eastern continental shelf in the Western Atlantic Ocean, from the Gulf of Maine to Cape Hatteras, periodically between 2000 and 2013. During the study, particulate matter 15dN values ranged from 0.8 to 17.4‰, and 13dC values from −26.4 to −15.6‰over the region. We used spatial autocorrelation analysis and random forest modeling to examine the spatial trends and potential environmental drivers of the stable isotope values. We observed general trends toward lower values for both nitrogen and carbon isotopes at the seaward edge of the shelf. Conversely, higher 15dN and 13dC values were observed on the landward edge of the shelf, in particular in the southern portion of the sampling area. Across all sites, the magnitude of the difference between the 15dN of subsurface and surface particulate m

  2. Hydrology & isotope tools to quantify carbon sources and sinks

    Science.gov (United States)

    Barth, Johannes A. C.; Lischeid, Gunnar; Gessler, Arthur

    2010-05-01

    Vegetation is fundamental for carbon uptake and usually assumes the largest portion in the evapotranspiration term. While interception can be separated by mapping various plant types in a catchment, the water isotope method yields numbers for pure evaporation. The latter causes enrichment of the heavier isotope in the remaining water phase, while transpiration leaves the isotope signal of water unaltered over longer time periods. Evaporation can thus be quantified in an integral manner over large areas by measuring water stable isotopes at points of river discharge and by comparing them to incoming precipitation. This method has been applied on scales of several thousand square kilometres and its calibration on scales of few square kilometres will allow to better constrain uncertainties. This necessitates comparison with hydrometric methods of well-instrumented catchments in several climatic regimes. Innovative small-scale methods involve determination of effective rainfall by time series analyses of hydrological data. This in turn requires temporal resolution of daily to hourly values to apply methods such as runoff recession or principal component analyses. It is also known that continental water fluxes are related to carbon fluxes through photosynthesis that in turn recycles large amounts of water via transpiration. This is usually described by the water use efficiency (WUE) term that quantifies how many moles of water transpire to accumulate one mole of CO2. However, so far only few empirical numbers are available for the spatio-temporal variability in WUE of plants and plant communities and further field experiments combined with isoscape approaches are necessary to constrain this term on a regional scale and its dependencies on factors such as light, temperature, water availability, plant type and height. Combined data can then serve to determine catchment-wide carbon uptake via the transpiration rates. Carbon accumulation can also be determined with eddy

  3. Descriptions of carbon isotopes within the energy density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Ismail, Atef [Fundamental and Applied Sciences Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak, Malaysia and Department of Physics, Al-Azhar University, 71524 Assiut (Egypt); Cheong, Lee Yen; Yahya, Noorhana [Fundamental and Applied Sciences Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia); Tammam, M. [Department of Physics, Al-Azhar University, 71524 Assiut (Egypt)

    2014-10-24

    Within the energy density functional (EDF) theory, the structure properties of Carbon isotopes are systematically studied. The shell model calculations are done for both even-A and odd-A nuclei, to study the structure of rich-neutron Carbon isotopes. The EDF theory indicates the single-neutron halo structures in {sup 15}C, {sup 17}C and {sup 19}C, and the two-neutron halo structures in {sup 16}C and {sup 22}C nuclei. It is also found that close to the neutron drip-line, there exist amazing increase in the neutron radii and decrease on the binding energies BE, which are tightly related with the blocking effect and correspondingly the blocking effect plays a significant role in the shell model configurations.

  4. The use of carbon stable isotope ratios in drugs characterization

    Energy Technology Data Exchange (ETDEWEB)

    Magdas, D. A., E-mail: gabriela.cristea@itim-cj.ro; Cristea, G., E-mail: gabriela.cristea@itim-cj.ro; Bot, A., E-mail: gabriela.cristea@itim-cj.ro; Mirel, V., E-mail: gabriela.cristea@itim-cj.ro [National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath Str., 400293 Cluj-Napoca (Romania)

    2013-11-13

    Isotopic Ratio Mass Spectrometry (IRMS) is an effective toll to be used for drug product authentication. The isotopic composition could be used to assist in the differentiation between batches of drugs and assist in the identification of counterfeit materials on the market. Only two factors affect the isotopic ratios in pharmaceutical components: the isotopic composition of the raw materials and the synthetic processes performed upon them. Counterfeiting of pharmaceutical drugs threatens consumer confidence in drug products companies' economical well-being. In this preliminary study, the analyzed samples consist in two types of commercially available analgesics, which were purchases from Romanian pharmacies. Differences in δ{sup 13}C between batches from −29.7 to −31.6% were observed, demonstrating that this method can be used to differentiate among individual drug batches and subsequently identify counterfeits on the market. On the other hand, carbon isotopic ratios differences among producers were recorded, the variations being between −31.3 to −34.9% for the same type of analgesic, but from different manufactures.

  5. Electrical Properties of Carbon Fiber Support Systems

    CERN Document Server

    Cooper, W; Demarteau, M; Fast, J; Hanagaki, K; Johnson, M; Kuykendall, W; Lubatti, H; Matulik, M; Nomerotski, A; Quinn, B; Wang, J

    2005-01-01

    Carbon fiber support structures have become common elements of detector designs for high energy physics experiments. Carbon fiber has many mechanical advantages but it is also characterized by high conductivity, particularly at high frequency, with associated design issues. This paper discusses the elements required for sound electrical performance of silicon detectors employing carbon fiber support elements. Tests on carbon fiber structures are presented indicating that carbon fiber must be regarded as a conductor for the frequency region of 10 to 100 MHz. The general principles of grounding configurations involving carbon fiber structures will be discussed. To illustrate the design requirements, measurements performed with a silicon detector on a carbon fiber support structure at small radius are presented. A grounding scheme employing copper-kapton mesh circuits is described and shown to provide adequate and robust detector performance.

  6. Carbon isotope ratios and isotopic correlations between components in fruit juices

    Science.gov (United States)

    Wierzchnicki, Ryszard

    2013-04-01

    Nowadays food products are defined by geographical origin, method of production and by some regulations concerning terms of their authenticity. Important data for confirm the authenticity of product are providing by isotopic methods of food control. The method checks crucial criteria which characterize the authenticity of inspected product. The European Union Regulations clearly show the tendency for application of the isotopic methods for food authenticity control (wine, honey, juice). The aim of the legislation steps is the protection of European market from possibility of the commercial frauds. Method of isotope ratio mass spectrometry is very effective tool for the use distinguishably the food products of various geographical origin. The basic problem for identification of the sample origin is the lack of databases of isotopic composition of components and information about the correlations of the data. The subject of the work was study the isotopic correlations existing between components of fruits. The chemical and instrumental methods of separation: water, sugars, organic acids and pulp from fruit were implemented. IRMS technique was used to measure isotopic composition of samples. The final results for original samples of fruits (apple, strawberry etc.) will be presented and discussed. Acknowledgement: This work was supported by the Polish Ministry of Science and Higher Education under grant NR12-0043-10/2010.

  7. Environmental impact and magnitude of paleosol carbonate carbon isotope excursions marking five early Eocene hyperthermals in the Bighorn Basin, Wyoming

    NARCIS (Netherlands)

    Abels, H.A.|info:eu-repo/dai/nl/304848018; Lauretano, V.; van Yperen, Anna E.; Hopman, Tarek; Zachos, J.C.; Lourens, L.J.|info:eu-repo/dai/nl/125023103; Gingerich, P.D.; Bowen, G.J.

    2016-01-01

    Transient greenhouse warming events in the Paleocene and Eocene were associated with the addition of isotopically light carbon to the exogenic atmosphere–ocean carbon system, leading to substantial environmental and biotic change. The magnitude of an accompanying carbon isotope excursion (CIE) can b

  8. Standardization and optimization of core sampling procedure for carbon isotope analysis in eucalyptus and variation in carbon isotope ratios across species and growth conditions

    CSIR Research Space (South Africa)

    Raju, M

    2011-11-01

    Full Text Available and optimization of core sampling procedure for carbon isotope analysis in eucalyptus and variation in carbon isotope ratios across species and growth conditions Mohan Raju, B#; Nuveshen Naidoo*; Sheshshaayee, M. S; Verryn, S. D*; Kamalkannan, R^; Bindumadhava... isotope analysis in Eucalyptus. Methods Expt 1: * Cores were taken from periphery to pith in 5 year old trees of Eucalyptus * Five half sib families of Eucalyptus grandis & E. urophylla were used ? Cores were further subdivided into 5 fragments...

  9. Chromium Isotopes in Carbonate Rocks: New Insights into Proterozoic Atmospheric Oxygenation

    Science.gov (United States)

    Kah, L. C.; Gilleaudeau, G. J.; Frei, R.; Kaufman, A. J.; Azmy, K.; Bartley, J. K.; Chernyavskiy, P.; Knoll, A. H.

    2015-12-01

    There has been a long-standing debate in geobiology about the role that Earth's oxygenation played in the evolution of complex life. Temporal linkages exist between the Great Oxidation Event (GOE) and the evolution of eukaryotes, as well as Neoproterozoic rise in oxygen and the diversification of metazoans. Further advances have been hampered, however, by the lack of direct proxies that mark specific levels of atmospheric pO2 in the geologic past. Chromium (Cr) isotopes show promise in this regard because the oxidation of Cr during terrestrial weathering—which results in isotopic fractionation—is dependent on a specific threshold of atmospheric pO2 (0.1-1% of the present atmospheric level [PAL]). This threshold value broadly coincides with recent estimates of the oxygen requirements of early animals. Here we report new Cr-isotope data from four late Mesoproterozoic carbonate-dominated successions. Samples were collected from the Turukhansk Uplift (Siberia), the El Mreiti Group (Mauritania), the Vazante Group (Brazil), and the Angmaat Formation (Canada). We emphasize the application of Cr-isotopes to carbonate rocks because the broad temporal range of this lithology in the geologic record provides an opportunity to significantly expand our understanding of Proterozoic oxygenation on shorter time scales. Our data indicate that pO2 levels required to support early animals were attained long before Neoproterozoic metazoan diversification, although the large degree of isotopic heterogeneity in our dataset may indicate that pO2 > 0.1-1% PAL was only a transient phenomenon in the Mesoproterozoic. This study demonstrates the utility of Cr-isotopes as an atmospheric redox proxy in carbonate rocks and helps inform future avenues of research on Proterozoic pO2 thresholds.

  10. C isotope fractionation during heterotrophic activity driven carbonate precipitation

    Science.gov (United States)

    Balci, Nurgul; Demirel, Cansu

    2016-04-01

    Stable carbon isotopic fractionation during carbonate precipitation induced by environmentally enriched heterotrophic halophilic microorganims was experimentally investigated under various salinity (% 4.5, %8, %15) conditions at 30 °C. Halophilic heterotrophic microorganims were enriched from a hypersaline Lake Acigöl located in SW Turkey (Balci et al.,2015) and later used for the precipitation experiments (solid and liquid medium). The carbonate precipitates had relatively high δ13C values (-4.3 to -16.9 ‰) compared to the δ13C values of the organic compounds that ranged from -27.5 to -25.4 ‰. At salinity of 4.5 % δ13C values of carbonate ranged from -4.9 ‰ to -10.9 ‰ with a 13C-enrichment factor of +20 to +16 ‰ higher than the δ13C values of the associated DOC (-27.5) . At salinity 8 % δ13C values of carbonate ranged from -16.3 ‰ to -11.7 ‰ with a 13C-enrichment factor of+11.3 to+15.9 ‰ higher than the δ13C values of the associated DOC. The respected values for 15 % salinity ranged from -12.3 ‰ to -9.7 ‰ with a 13C-enrichment factor of +15.2 to+16.8 ‰ higher than the δ13C values of the associated DOC. The carbonate precipitates produced in the solid medium are more enriched in 13C relative to liquid culture experiments. These results suggest that the carbon in the solid was derived from both the bacterial oxidation of organic compounds in the medium and from the atmospheric CO2. A solid medium used in the experiments may have suppressed convective and advective mass transport favouring diffusion-controlled system. This determination suggests that the rate and equilibration of CO2 exchange with the atmosphere is the major control on C isotope composition of carbonate minerals precipitated in the experiments. Key words: Lake Acıgöl, halophilic bacteria, carbonate biomineralization, C isotopes References Nurgul Balci, Meryem Menekşe, Nevin Gül Karagüler, M. Şeref Sönmez,Patrick Meister 2015.Reproducing authigenic carbonate

  11. Carbon and nitrogen isotope systematics in diamond: Different sensitivities to isotopic fractionation or a decoupled origin?

    Science.gov (United States)

    Hogberg, K.; Stachel, T.; Stern, R. A.

    2016-11-01

    Using stable isotope data obtained on multiple aliquots of diamonds from worldwide sources, it has been argued that carbon and nitrogen in diamond are decoupled. Here we re-investigate the carbon-nitrogen relationship based on the most comprehensive microbeam data set to date of stable isotopes and nitrogen concentrations in diamonds (n = 94) from a single locality. Our diamond samples, derived from two kimberlites in the Chidliak Field (NE Canada), show large variability in δ13C (- 28.4 ‰ to - 1.1‰, mode at - 5.8‰), δ15N (- 5.8 to + 18.8‰, mode at - 3.0‰) and nitrogen contents ([N]; 3800 to less than 1 at.ppm). In combination, cathodoluminescence imaging and microbeam analyses reveal that the diamonds grew from multiple fluid pulses, with at least one major hiatus documented in some samples that was associated with a resorption event and an abrupt change from low δ13C and [N] to mantle-like δ13C and high [N]. Overall, δ13C appears to be uncorrelated to δ15N and [N] on both the inter- and intra-diamond levels. Co-variations of δ15N-log[N], however, result in at least two parallel, negatively correlated linear arrays, which are also present on the level of the individual diamonds falling on these two trends. These arrays emerge from the two principal data clusters, are characterized by slightly negative and slightly positive δ15N (about - 3 and + 2‰, respectively) and variable but overall high [N]. Using published values for the diamond-fluid nitrogen isotope fractionation factor and nitrogen partition coefficient, these trends are perfectly reproduced by a Rayleigh fractionation model. Overall, three key elements are identified in the formation of the diamond suite studied: (1.) a low δ13C and low [N] component that possibly is directly associated with an eclogitic diamond substrate or introduced during an early stage fluid event. (2.) Repeated influx of a variably nitrogen-rich mantle fluid (mildly negative δ13C and δ15N). (3.) In waning

  12. Organic carbon isotopes of the Sinian and Early Cambrian black shales on Yangtze Platform, China

    Institute of Scientific and Technical Information of China (English)

    李任伟; 卢家烂; 张淑坤; 雷加锦

    1999-01-01

    Organic matter of the Sinian and early Cambrian black shales on the Yangtze Platform belongs to the light carbon group of isotopes with the δ13C values from - 27 % to -35 % , which are lower than those of the contemporaneously deposited carbonates and phosphorites. A carbon isotope-stratified paleooceanographic model caused by upwelling is proposed, which can be used not only to interpret the characteristics of organic carbon isotopic compositions of the black shales, but also to interpret the paleogeographic difference in the organic carbon isotope compositions of various types of sedimentary rocks.

  13. Photosynthetic fractionation of the stable isotopes of oxygen and carbon

    Energy Technology Data Exchange (ETDEWEB)

    Guy, R.D. (Carnegie Institution of Washington, Stanford, CA (United States)); Fogel, M.L.; Berry, J.A. (Carnegie Inst. of Washington, Washington, DC (United States))

    1993-01-01

    Isotope discrimination during photosynthetic exchange of O[sub 2] and CO[sub 2] was measured using enzyme, thylakoid, and whole cell preparations. Evolved oxygen from isolated spinach thylakoids was isotopically identical (within analytical error) to its source water. Similar results were obtained with Anacystis nidulans Richter and Phaeodactylum tricornutum Bohlin cultures purged with helium. For consumptive reactions, discrimination ([triangle], where 1 + [triangle]/1000 equals the isotope effect, k[sup 16]/k[sup 18] or k[sup 12]/k[sup 13]) was determined by analysis of residual substrate (O[sub 2] or CO[sub 2]). The [triangle] for the Mehler reaction, mediated by ferredoxin or methylviologen, was 15.3[per thousand]. Oxygen isotope discrimination during oxygenation of ribulose-1,5-bisphosphate (RuBP) catalyzed by RuBP carboxylase/oxygenase (Rubisco) was 21.3[per thousand] and independent of enzyme source, unlike carbon isotope dicrimination: 30.3[per thousand] for spinach enzyme and 19.6 to 23[per thousand] for Rhodospirillum rubrum and A. nidulans enzymes, depending on reaction conditions. The [triangle] for O[sub 2] consumption catalyzed by glycolate oxidase was 22.7[per thousand]. Consistent with this, when Asparagus sprengeri Regel mesopyll cells approached the compensation point within a sealed vessel, the [delta][sup 18]O of dissolved O[sub 2] came to a steady-state value of about 21.5[per thousand] relative to the source water. The results provide improved estimates of discrimination factors in several reactions prominent in the global oxygen cycle and indicate that photorespiration plays a significant part in determining the isotopic composition of atmospheric oxygen. 47 refs., 8 figs., 2 tabs.

  14. Allochthonous carbon hypothesis for bulk OM and n-alkane PETM carbon isotope discrepancies

    Science.gov (United States)

    Baczynski, A. A.; McInerney, F. A.; Wing, S. L.; Kraus, M. J.; Fricke, H. C.

    2011-12-01

    The Paleocene-Eocene Thermal Maximum (PETM), a period of abrupt, transient, and large-scale global warming fueled by a large release of isotopically light carbon, is a relevant analogue for episodes of rapid global warming and recovery. The PETM is recorded in pedogenic carbonate, bulk organic matter, and n-alkanes as a prominent negative carbon isotope excursion (CIE) in paleosols exposed in the Bighorn Basin, WY. Here we present a composite stable carbon isotope record from n-alkanes and dispersed soil organic δ13C records from five individual sections that span the PETM in the southeastern Bighorn Basin. Four sections are from a 10km transect in the Cabin Fork area and one section was collected at Sand Creek Divide. These five new dispersed organic carbon (DOC) isotope records are compared to the previously published Polecat Bench (Magioncalda et al. 2004) and Honeycombs (Yans et al. 2006) isotope records. The high-resolution n-alkane curve shows an abrupt, negative shift in δ13C values, an extended CIE body, and a rapid recovery to more positive δ13C values. Although the five DOC records show similarly abrupt negative shifts in δ13C values, the DOC CIEs are compressed, smaller in magnitude, and return to more positive δ13C values more gradually relative to the n-alkane record. Moreover, the stratigraphic thickness of the body of the excursion and the pattern of the recovery phase are not consistent among the five DOC records. We modeled predicted DOC δ13C values from the n-alkane record by applying enrichment factors based on modern plants to the n-alkane δ13C values. The anomaly, difference between the expected and observed DOC δ13C values, was calculated for the PETM records and compared to weight percent carbon and grain size. There is no correlation between pre- and post-PETM anomaly values and grain size or weight percent carbon. PETM anomaly values, however, do trend with both grain size and weight percent carbon. The largest PETM anomaly values

  15. Control strategies for laser separation of carbon isotopes

    Indian Academy of Sciences (India)

    V Parthasarathy; A K Nayak; S K Sarkar

    2002-12-01

    Laser isotope separation (LIS) by infrared laser chemistry of polyatomic molecules has come a long way since its discovery. The last decade has seen considerable efforts in scaling up of the process for light elements like carbon, oxygen and silicon. These efforts aim at ways to improve both the enrichment factor and the throughput. The achievement is quite significant especially for carbon isotope separation wherein macroscopic operating scales have been realized. We report our studies on the IR laser chemistry of two promising systems, viz. neat CF2HCl and CF3Br/Cl2. We have investigated conditions for optimizing the dissociation yield and selectivity using natural samples containing 1.1 % C-13. We also highlight our current efforts for scaling up the process. These include the design aspects of a photochemical reactor with multipass refocusing Herriott optics for efficient photon utilization, development of a cryogenic distillation set up and a preparative gas chromatograph for large scale separation/collection of the isotopically enriched photoproduct in the post-irradiation stage.

  16. Stable carbon isotopic composition of gasolines determined by isotope ratio monitoring gas chromatography mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Smallwood, B.J.; Philp, R.P.; Allen, J.D. [University of Oklahoma, Norman, OK (United States). School of Geology and Geophysics

    2002-07-01

    A large number of underground gasoline storage facilities in the United States continuously leak gasoline into the subsurface, which makes gasoline a major groundwater contaminant. Gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) are used currently to characterize contaminated groundwater and soils. Correlations of contaminants with suspected source(s) are extremely difficult by these techniques because many gasolines have similar hydrocarbon distributions. The present study applied the technique of isotope ratio monitoring gas chromatography-mass spectrometry (irmGC-MS) to 19 gasoline samples from different areas of the USA. This allows a much better correlation of gasoline contaminants to source. Data obtained indicate a wide range of {sup {delta}}{sup 13}C values for 16 ubiquitous compounds in the gasolines. The majority of samples could be distinguished from each other on the basis of {sup {delta}}{sup 13}C hydrocarbon composition. The oxygenated additive methyl tertiary butyl ether (MTBE) was present in ten of the gasolines analyzed, and had a relatively narrow range of {sup {delta}}{sup 13}C values (-30.4 to -28.3 per mille). Preliminary investigations were also made to determine the extent of carbon isotopic fractionation after simple water washing and evaporation experiments. Results indicate that the majority of compounds did not undergo significant carbon isotopic fractionation as a result of these processes. (author)

  17. An analytical system for stable isotope analysis on carbon monoxide using continuous-flow isotope-ratio mass spectrometry

    NARCIS (Netherlands)

    Pathirana, S. L.; Van Der Veen, C.; Popa, M. E.; Röckmann, T.

    2015-01-01

    A fully automated system for the determination of δ13C and δ18O in atmospheric CO has been developed. CO is extracted from an air sample and converted into carbon dioxide (CO2) using the Schütze reagent. The isotopic composition is determined with an isotope-ratio mass spectrometer (IRMS) technique.

  18. Isotopic composition of carbon and oxygen of carbonates of oil and gas-bearing deposits of Western Siberia

    Energy Technology Data Exchange (ETDEWEB)

    Golyshev, S.I.; Cherepnin, A.V.; Rozhnev, A.N.

    1981-01-01

    There is measured the isotopic composition of carbon and oxygen in 129 samples of carbonates and carbonate cements of oil and gas-bearing Paleozoic and Mezozoic deposits of Western Siberia. The isotopic composition of samples of marine deposits varies from -1.2 to +6.1% for carbon and from 19.8 to 29.1% for oxygen and has a mean isotopic composition of 1.9 to 24.8%. Catagenetic processes lead to lightening of the isotopic composition of secondary carbonate on the average by 5% for carbon and 9% for oxygen. The most intense lightening of isotopic composition is observed in samples disposed near oil and gas deposits.

  19. About the possibility of creating a continuous range of standards with different isotopic composition of carbon

    Directory of Open Access Journals (Sweden)

    S. A. Sadykov

    2014-01-01

    Full Text Available It is established that the carbon isotopic composition in the formation of calcium carbonate is changed depending on the magnetic field strength. The formation of calcium carbonate occurred due to the interaction of calcium hydroxide with atmospheric carbon dioxide. The profile of isotopic relations13C/12C of the newly formed calcium carbonate is approximated by the equation of the parabola for certain values of tension solenoidal magnetic field. The possibility of creating standards with a continuous series of values of the content of carbon stable isotopes based on the data suggested.

  20. Isotope composition of bicarbonate carbon in bed waters of oil and gas deposits

    Energy Technology Data Exchange (ETDEWEB)

    Golyshev, S.I.; Cherepnin, A.V.; Ivanov, V.G.; Manylova, L.S.

    1981-01-01

    A study is made of the isotope composition of bicarbonate carbon in bed waters of the Jurassic water complex in southeast West Siberia. It has been established that waters of empty and transcontour structures have isotope composition of carbon 5/sup 0//oo, while in waters which contact the hydrocarbon formations, the isotope composition of carbon is lighter on the average by 5-8/sup 0//oo. The isotope composition of bicarbonate carbon in bed waters reflects both the conditions for primary sedimentation, and secondary processes associated with organic matter transformation.

  1. Dynamic and transfert of carbon in Loire catchment using carbon isotopes

    Science.gov (United States)

    Coularis, Cindy; Fontugne, Michel; Tisnérat-Laborde, Nadine; Pastor, Lucie; Siclet, Françoise

    2014-05-01

    Rivers have a major role in carbon transfer between continent and ocean. The organic matter exported from land represents a major source of DOC and POC in oceans. The composition and reactivity of this matter will influence its behavior and fate within the coastal areas and continental shelf. It is thus important to characterize the exported matter and its temporal variability. Stable carbon isotope ratios (d13C) and 14C activity can provide unique information on carbon sources, turnover and exchange processes. We present here a study of the carbon cycle in the Loire River and its major tributaries by combining carbon isotopes measurements and classical biogeochemical parameters (DOC, POC, DIC, pH, Temperature, Alkalinity, pH, chlorophyll …). Three campaigns were performed in April, July and October 2013. The changes in 14C signature due to the controlled liquid release of five nuclear power plants are used to get additional information on the carbon dynamics within the river. First results show a conservative behavior of the organic carbon concentrations contrary to the inorganic carbon all along the Loire River. However, the reactivity of the organic matter varies with rivers catchments and seasons. An inventory of the distribution of the different carbon phases within the Loire River and its tributaries is presented.

  2. Carbon isotopes in otolith amino acids identify residency of juvenile snapper (Family: Lutjanidae) in coastal nurseries

    KAUST Repository

    McMahon, Kelton

    2011-08-26

    This study explored the potential for otolith geochemistry in snapper (Family: Lutjanidae) to identify residency in juvenile nursery habitats with distinctive carbon isotope values. Conventional bulk otolith and muscle stable isotope analyses (SIA) and essential amino acid (AA) SIA were conducted on snapper collected from seagrass beds, mangroves, and coral reefs in the Red Sea, Caribbean Sea, and Pacific coast of Panama. While bulk stable isotope values in otoliths showed regional differences, they failed to distinguish nursery residence on local scales. Essential AA δ13C values in otoliths, on the other hand, varied as a function of habitat type and provided a better tracer of residence in different juvenile nursery habitats than conventional bulk otolith SIA alone. A strong linear relationship was found between paired otolith and muscle essential AA δ13C values regardless of species, geographic region, or habitat type, indicating that otolith AAs recorded the same dietary information as muscle AAs. Juvenile snapper in the Red Sea sheltered in mangroves but fed in seagrass beds, while snapper from the Caribbean Sea and Pacific coast of Panama showed greater reliance on mangrove-derived carbon. Furthermore, compound-specific SIA revealed that microbially recycled detrital carbon, not water-column-based new phytoplankton carbon, was the primary carbon source supporting snapper production on coastal reefs of the Red Sea. This study presented robust tracers of juvenile nursery residence that will be crucial for reconstructing ontogenetic migration patterns of fishes among coastal wetlands and coral reefs. This information is key to determining the importance of nursery habitats to coral reef fish populations and will provide valuable scientific support for the design of networked marine-protected areas. © 2011 Springer-Verlag.

  3. Carbon isotopes in otolith amino acids identify residency of juvenile snapper (Family: Lutjanidae) in coastal nurseries

    Science.gov (United States)

    McMahon, K. W.; Berumen, M. L.; Mateo, I.; Elsdon, T. S.; Thorrold, S. R.

    2011-12-01

    This study explored the potential for otolith geochemistry in snapper (Family: Lutjanidae) to identify residency in juvenile nursery habitats with distinctive carbon isotope values. Conventional bulk otolith and muscle stable isotope analyses (SIA) and essential amino acid (AA) SIA were conducted on snapper collected from seagrass beds, mangroves, and coral reefs in the Red Sea, Caribbean Sea, and Pacific coast of Panama. While bulk stable isotope values in otoliths showed regional differences, they failed to distinguish nursery residence on local scales. Essential AA δ13C values in otoliths, on the other hand, varied as a function of habitat type and provided a better tracer of residence in different juvenile nursery habitats than conventional bulk otolith SIA alone. A strong linear relationship was found between paired otolith and muscle essential AA δ13C values regardless of species, geographic region, or habitat type, indicating that otolith AAs recorded the same dietary information as muscle AAs. Juvenile snapper in the Red Sea sheltered in mangroves but fed in seagrass beds, while snapper from the Caribbean Sea and Pacific coast of Panama showed greater reliance on mangrove-derived carbon. Furthermore, compound-specific SIA revealed that microbially recycled detrital carbon, not water-column-based new phytoplankton carbon, was the primary carbon source supporting snapper production on coastal reefs of the Red Sea. This study presented robust tracers of juvenile nursery residence that will be crucial for reconstructing ontogenetic migration patterns of fishes among coastal wetlands and coral reefs. This information is key to determining the importance of nursery habitats to coral reef fish populations and will provide valuable scientific support for the design of networked marine-protected areas.

  4. Stable carbon isotope ratios in Astrangia danae : evidence for algal modification of carbon pools used in calcification

    Science.gov (United States)

    Cummings, C. E.; McCarty, H. B.

    1982-06-01

    Stable carbon isotope ratios have been measured in skeletons of the temperature shallow water scleractinian coral, Astrangia danae. δ13C values ranging from -5.42 to -7.30%. revealed the expected depletion of 13C in skeletal carbonate relative to sea water bicarbonate. Differences among the ratios could not be attributed to collection site and were not correlated to skeletal morphology. Values of δ13C were directly related to zooxanthellae density for all colonies, so that as zooxanthellae concentration increased, δ13C valued increased. Colonies maintained under high temperature conditions were offset from the normal, exhibiting ratios less enriched in 13C than similar colonies from natural conditions. These trends supported the models of Weber and Goreau in which the carbon pools used in calcification are modified by algal photosynthesis. Direct evidence of physiological differences between symbiotic and asymbiotic colonies of A. danae has also been provided.

  5. Carbon isotope excursions in paleosol carbonate marking five early Eocene hyperthermals in the Bighorn Basin, Wyoming

    Directory of Open Access Journals (Sweden)

    H. A. Abels

    2015-05-01

    Full Text Available Transient greenhouse warming events in the Paleocene and Eocene were associated with the addition of isotopically-light carbon to the exogenic atmosphere–ocean carbon pool, leading to substantial environmental and biotic change. The magnitude of an accompanying carbon isotope excursion (CIE can be used to constrain both the sources and amounts of carbon released during an event, as well as to correlate marine and terrestrial records with high precision. The Paleocene Eocene Thermal Maximum (PETM is well documented, but CIE records for the subsequent warming events are still rare especially from the terrestrial realm. Here, we provide new CIE records for two of the smaller hyperthermal events, I1 and I2, in paleosol carbonate, as well as two additional records of ETM2 and H2 in the Bighorn Basin. Stratigraphic comparison of this expanded, high-resolution terrestrial carbon isotope record to the deep-sea benthic foraminifera records from ODP Sites 1262 and 1263, Walvis Ridge, in the southern Atlantic Ocean corroborates that the Bighorn Basin fluvial sediments record global atmospheric change. The stratigraphic thicknesses of the eccentricity-driven hyperthermals in these archives are in line with precession-forcing of the 7 m thick fluvial overbank-avulsion sedimentary cycles. Using the CALMAG bulk oxide mean annual precipitation proxy, we reconstruct similar or slightly wetter than background soil moisture contents during the four younger hyperthermals, in contrast to drying observed during the PETM. Soil carbonate CIEs vary in magnitude proportionally with the marine CIEs for the four smaller early Eocene hyperthermals. This relationship breaks down for the PETM, with the soil carbonate CIE ~ 2–4‰ less than expected if all five linearly relate to marine CIEs. If the PETM CO2 forcing was similar but scaled to the younger hyperthermals, photosynthetic isotope fractionation or soil environmental factors are needed to explain this anomaly. We

  6. Carbon isotope excursions across the Permian-Triassic boundary in the Meishan section, Zhejiang Province, China

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Both gradual and sharp decrease in organic and carbonate carbon isotope values were detected across the Permian-Triassic boundary in the Meishan section, Changxing, Zhejiang Province, China. The gradual decrease in organic carbon isotope values started at the bottom of Bed 23, coinciding with the strong oscillations of total organic carbon (TOC) contents, indicates increasing fluxes from carbonate to organic carbon reservoir during this interval. A 2.3‰ sharp drop of inorganic carbon isotope values occurred at the uppermost part of Bed 24e. A 3.7‰ sharp drop of organic carbon isotope values occurred in Bed 26. The dramatic drop of inorganic carbon isotope value of 8‰ reported previously is not confirmed from the unweathered carbonate samples in Bed 27. The large-scale fluctuation of organic carbon isotope values in the Yinkeng Formation reflects different extent of mixing of marine and terrestrial organic matters. The gradual depletion and subsequent sharp drop of carbon isotopes near the Permian-Triassic boundary might indicate complex causes of the end-Permian mass extinction.

  7. Comparison of bulk and n-alkane PETM carbon isotope trends from the Bighorn Basin, Wyoming

    Science.gov (United States)

    Baczynski, A. A.; McInerney, F. A.; Kraus, M. J.; Wing, S.

    2010-12-01

    al. suggest a prolonged and sustained core of the CIE (113 ka) followed by a more rapid initial recovery (33 ka) to near pre-PETM δ13C values. Improving the PETM age model and refining the allocation of time within the event has important implications for understanding the carbon cycle. Carbon isotope values of individual odd-carbon-numbered, long-chain (n-C21-n-C35) n-alkanes extracted from PETM sediments tend to become more negative with increasing chain length within a particular sample. In addition, the magnitude of the negative CIE also tends to increase with increasing n-alkane chain length. Using the empirical observation that δ13C values tend to increase with increasing chain length in conifers while δ13C values decrease with increasing chain length in angiosperms, Smith et al. (2007) has suggested that plant community composition shifted from 50% conifer to an exclusively angiosperm flora at the PETM. The additional n-alkane carbon isotope data presented here is similar to previously published data and supports the plant community change hypothesis suggested by Smith et al. (2007).

  8. Diet and mobility in Early Medieval Bavaria: a study of carbon and nitrogen stable isotopes.

    Science.gov (United States)

    Hakenbeck, Susanne; McManus, Ellen; Geisler, Hans; Grupe, Gisela; O'Connell, Tamsin

    2010-10-01

    This study investigates patterns of mobility in Early Medieval Bavaria through a combined study of diet and associated burial practice. Carbon and nitrogen isotope ratios were analyzed in human bone samples from the Late Roman cemetery of Klettham and from the Early Medieval cemeteries of Altenerding and Straubing-Bajuwarenstrasse. For dietary comparison, samples of faunal bone from one Late Roman and three Early Medieval settlement sites were also analyzed. The results indicate that the average diet was in keeping with a landlocked environment and fairly limited availability of freshwater or marine resources. The diet appears not to have changed significantly from the Late Roman to the Early Medieval period. However, in the population of Altenerding, there were significant differences in the diet of men and women, supporting a hypothesis of greater mobility among women. Furthermore, the isotopic evidence from dietary outliers is supported by "foreign" grave goods and practices, such as artificial skull modification. These results reveal the potential of carbon and nitrogen isotope analysis for questions regarding migration and mobility.

  9. Mantle Degassing and Diamond Genesis:A Carbon Isotope Perspective

    Institute of Scientific and Technical Information of China (English)

    郑永飞

    1994-01-01

    The effect of Co2 and CH4 degassing from the mantle on the carbon isotopic composition of diamond has been quantitatively modeled in terms of the principles of Rayleigh distillation.Assuming the δ13 C value of -5‰ for the mantle,the outgassing of CO2 can result in the large negative δ13 C values of diamond,whereas the outgassing of CH4 can drive the δ13C values of diamond in the positive direction.The theoretical expectations can be used to explain the full range of δ13 C values from-34.4‰5 to+5‰ observed for natural diamonds.It is possible that diamond formation was triggered by the degassing of Co2 and/or CH4 from the mantle and the associated fractional crystallization of carbonate-bearing melt.

  10. Carbon isotopes and water use efficiency in C4 plants.

    Science.gov (United States)

    Ellsworth, Patrick Z; Cousins, Asaph B

    2016-06-01

    Drought is a major agricultural problem worldwide. Therefore, selection for increased water use efficiency (WUE) in food and biofuel crop species will be an important trait in plant breeding programs. The leaf carbon isotopic composition (δ(13)Cleaf) has been suggested to serve as a rapid and effective high throughput phenotyping method for WUE in both C3 and C4 species. This is because WUE, leaf carbon discrimination (Δ(13)Cleaf), and δ(13)Cleaf are correlated through their relationships with intercellular to ambient CO2 partial pressures (Ci/Ca). However, in C4 plants, changing environmental conditions may influence photosynthetic efficiency (bundle-sheath leakiness) and post-photosynthetic fractionation that will potentially alter the relationship between δ(13)Cleaf and Ci/Ca. Here we discuss how these factors influence the relationship between δ(13)Cleaf and WUE, and the potential of using δ(13)Cleaf as a meaningful proxy for WUE.

  11. The thermal history of char as disclosed by carbon isotope ratios

    DEFF Research Database (Denmark)

    Egsgaard, Helge; Ambus, Per; Ahrenfeldt, Jesper

    pyrolysis and isotope ratio mass spectrometry. The results demonstrate that the temperature history of the char is reflected in the fine variation of carbon isotopes. The compound classes responsible for the variation were identified. Key words: Isotope ratio, flash pyrolysis, hot gas cleaning...

  12. CCQM-K140: carbon stable isotope ratio delta values in honey

    Science.gov (United States)

    Dunn, P. J. H.; Goenaga-Infante, H.; Goren, A. C.; Şimşek, A.; Bilsel, M.; Ogrinc, N.; Armishaw, P.; Hai, L.

    2017-01-01

    As there can be small but measureable differences in isotope ratios between different sources of the same element/compound/material, isotope ratio measurements are applied in a number of different fields including archaeology, environmental science, geochemistry, forensic science and ecology. Isotope ratios for the light elements (H, C, N, O and S) are typically reported as δ-values which are isotope ratios expressed relative to an internationally agreed standard (this standard is the zero-point on the scale), although absolute isotope ratios which are traceable to the SI have also been reported. The IAWG has been granted a traceability exception for the use of arbitrary delta scales until SI traceability can be established at the required level of uncertainty but this goal is some years away. While the CCQM IAWG has previously organised several pilot studies on isotope ratio determination (CCQM-P75: Stable isotope delta values in methionine, 2006; CCQM-P105: Sr isotope ratios in wine, 2008; CCQM-K98: Pb isotope ratios in bronze with additional delta values in CCQM-P134, 2011), it has been a number of years since delta values of light elements have been considered and there has been no key comparison (KC). Therefore, the IAWG has included the need for a KC (CCQM-K140) based on an arbitrary delta scale in its program to support ongoing requirements to demonstrate core capabilities as well as specific claims of measurement capability (CMCs) in this area. The performance of all five of the CCQM-K140 participants was very good, illustrating their ability to obtain accurate results for carbon isotope ratios, within the calibration range afforded by internationally agreed reference materials (δ13CVPDB-LSVEC between ‑47.32 % and +535.3 %) with measurement uncertainties of between 0.08 and 0.28 %. This was despite the fact that no two participants used exactly the same approach in terms of instrumentation or data treatment. Main text To reach the main text of this

  13. Molecular carbon isotope variations in core samples taken at the Permian-Triassic boundary layers in southern China

    Science.gov (United States)

    Wang, Ruiliang; Zhang, Shuichang; Brassell, Simon; Wang, Jiaxue; Lu, Zhengyuan; Ming, Qingzhong; Wang, Xiaomei; Bian, Lizeng

    2012-07-01

    Stable carbon isotope composition (δ13C) of carbonate sediments and the molecular (biomarker) characteristics of a continuous Permian-Triassic (PT) layer in southern China were studied to obtain geochemical signals of global change at the Permian-Triassic boundary (PTB). Carbonate carbon isotope values shifted toward positive before the end of the Permian period and then shifted negative above the PTB into the Triassic period. Molecular carbon isotope values of biomarkers followed the same trend at and below the PTB and remained negative in the Triassic layer. These biomarkers were acyclic isoprenoids, ranging from C15 to C40, steranes (C27 dominates) and terpenoids that were all significantly more abundant in samples from the Permian layer than those from the Triassic layer. The Triassic layer was distinguished by the dominance of higher molecular weight (waxy) n-alkanes. Stable carbon isotope values of individual components, including n-alkanes and acyclic isoprenoids such as phytane, isop-C25, and squalane, are depleted in δ13C by up to 8-10‰ in the Triassic samples as compared to the Permian. Measured molecular and isotopic variations of organic matter in the PT layers support the generally accepted view of Permian oceanic stagnation followed by a massive upwelling of toxic deep waters at the PTB. A series of large-scale (global) outgassing events may be associated with the carbon isotope shift we measured. This is also consistent with the lithological evidence we observed of white thin-clay layers in this region. Our findings, in context with a generally accepted stagnant Permian ocean, followed by massive upwelling of toxic deep waters might be the major causes of the largest global mass extinction event that occurred at the Permian-Triassic boundary.

  14. The relationship between carbon and oxygen isotopic composition characteristics of carbonates in loess sediments and paleoclimate

    Institute of Scientific and Technical Information of China (English)

    李春园; 王先彬; 文启彬; 邵波

    1995-01-01

    Based on the carbon and oxygen isotopic compositions of carbonates in loess sediments meas-ured by the methods of stepwise heating and phosphoric acid decomposition from five pieces of samples ofpaleosol,loess and eolian sand,respectively,the distributive characteristics in different temperature steps andthe fractionation mechanisms of carbon and oxygen isotope and their relation to the paleoclirnate are discussed.The preliminary results show that,by means of stepwise heating,different carbon and oxygen isotopiccompositions are obtained in different temperature steps and carbon and oxygen isotopic compositions ofpaleosol,loess and eolian sand are in a different distributive pattern in the range of studied temperaturesteps.The results also show that the δ13C ratios in 700-800℃ are more sensitive tracers of paleoclimatethan those measured by the method of phosphoric acid decomposition.The susceptibility to climatic changesof δ18O ratios analysed by the method of phosphoric acid decomposition is higher than those analysed by themethod of stepwise heating,but the δ18O ratios measured by these two methods do not effectively reflect cli-matic changes.

  15. Abundances in red giant stars - Carbon and oxygen isotopes in carbon-rich molecular envelopes

    Science.gov (United States)

    Wannier, P. G.; Sahai, R.

    1987-01-01

    Millimeter-wave observations have been made of isotopically substituted CO toward the envelopes of 11 carbon-rich stars. In every case, C-13O was detected and model calculations were used to estimate the C-12/C-13 abundance ratio. C-17O was detected toward three, and possibly four, envelopes, with sensitive upper limits for two others. The CO-18 variant was detected in two envelopes. New results include determinations of oxygen isotopic ratios in the two carbon-rich protoplanetary nebulae CRL 26688 and CRL 618. As with other classes of red giant stars, the carbon-rich giants seem to be significantly, though variably, enriched in O-17. These results, in combination with observations in interstellar molecular clouds, indicate that current knowledge of stellar production of the CNO nuclides is far from satisfactory.

  16. Isotopic compositions of carbonates and organic carbon from upper Proterozoic successions in Namibia: stratigraphic variation and the effects of diagenesis and metamorphism.

    Science.gov (United States)

    Kaufman, A J; Hayes, J M; Knoll, A H; Germs, G J

    1991-01-01

    The carbon isotope geochemistry of carbonates and organic carbon in the late Proterozoic Damara Supergroup of Namibia, including the Nama, Witvlei, and Gariep groups on the Kalahari Craton and the Mulden and Otavi groups on the Congo Craton, has been investigated as an extension of previous studies of secular variations in the isotopic composition of late Proterozoic seawater. Subsamples of microspar and dolomicrospar were determined, through petrographic and cathodoluminescence examination, to represent the "least-altered" portions of the rock. Carbon-isotopic abundances in these phases are nearly equal to those in total carbonate, suggesting that 13C abundances of late Proterozoic fine-grained carbonates have not been significantly altered by meteoric diagenesis, although 18O abundances often differ significantly. Reduced and variable carbon-isotopic differences between carbonates and organic carbon in these sediments indicate that isotopic compositions of organic carbon have been altered significantly by thermal and deformational processes, likely associated with the Pan-African Orogeny. Distinctive stratigraphic patterns of secular variation, similar to those noted in other, widely separated late Proterozoic basins, are found in carbon-isotopic compositions of carbonates from the Nama and Otavi groups. For example, in Nama Group carbonates delta 13C values rise dramatically from -4 to +5% within a short stratigraphic interval. This excursion suggests correlation with similar excursions noted in Ediacaran-aged successions of Siberia, India, and China. Enrichment of 13C (delta 13C> +5%) in Otavi Group carbonates reflects those in Upper Riphean successions of the Akademikerbreen Group, Svalbard, its correlatives in East Greenland, and the Shaler Group, northwest Canada. The widespread distribution of successions with comparable isotopic signatures supports hypotheses that variations in delta 13C reflect global changes in the isotopic composition of late

  17. The Carbon Isotopic Content and Concentration of Ambient Formic and Acetic Acid

    Science.gov (United States)

    Johnson, Bryan Jay

    A direct method for source determination of atmospheric formic and acetic acid, through carbon isotopic analysis of the ambient acids and their potential sources, has been successfully developed and tested. These first carbon isotopic measurements of formic acid in the atmosphere were found to be fairly constant, regardless of location. This is consistent with a single dominating source of formic acid, with vegetation emissions being the most likely controlling source. Collection of relatively large quantities (0.3 -3.0 mg) of the organic acids, which was necessary for carbon isotopic measurements, was effectively accomplished by a new method using calcium hydroxide-treated filters with a high-volume sampler. Samples were collected on a regular basis at Mount Lemmon, Arizona (elevation = 9200 feet A.S.L.). Atmospheric concentrations showed a well-defined seasonal pattern, with the lowest concentrations (about 0.2 ppbv) occurring in the middle of the winter, which steadily increased to a maximum of nearly 2 ppbv in the summer. The ^{13}C content (delta ^{13}C) of HCOOH averaged -20.9 +/- 2.5 ^0/_{00 } during the growing season (April-September) and -23.2 +/- 3.5 ^0/_{00} during the non-growing season at Mount Lemmon. Isotopic measurements of formic acid from several other locations included two west coast marine sites ( delta ^{13} C range of -19.1 to -24.6 ^0/_{00} ), three Colorado Rocky Mountain samples averaging -23.2 +/- 1.0 ^0/_{00}, two from the prairie of North Dakota (-23.5 +/- 1.0 ^0/ _{00}) and three samples collected in the urban Tucson, Arizona area (- 20.8 +/- 3.4 ^0 /_{00}). Source measurements included HCOOH emissions from two species of formicine ants (-18.8 +/- 1.7 ^0/_ {00}), and HCOOH in automobile exhaust (-28 ^0/ _{00} from leaded gasoline, and -48.6 ^0/ _{00} from unleaded). Further support for a biogenic source of atmospheric HCOOH came from the carbon-14 analysis of six Mount Lemmon HCOOH samples (93-113% modern carbon), using accelerator

  18. Oxygen Isotopic Composition of Carbon Dioxide in the Middle Atmosphere

    Science.gov (United States)

    Liang, M.; Blake, G. A.; Lewis, B. R.; Yung, Y. L.

    2005-12-01

    The isotopic composition of long-lived trace gases provides a window into atmospheric transport and chemistry. Carbon dioxide is a particularly powerful tracer, because its abundance remains >100 ppmv in the mesosphere. Current models consider O3 as the main source of O(1D) in the mesosphere, but we note that the photolysis of 16O17O and 16O18O by solar Lyman-α radiation yields O(1D) 10-100 times more enriched in 17O and 18O than that from ozone photodissociation. We therefore incorporate both photochemical sources into stratospheric and mesospheric chemical transport models that quantitatively predict the unusual enhancement of 17O in CO2 from the middle atmosphere. New laboratory and atmospheric measurements are proposed to test our model and validate the use of CO2 isotopic fractionation as a tracer of atmospheric chemical and dynamical processes. Once fully understood the `anomalous' oxygen signature in CO2 can be used in turn to study biogeochemical cycles, in particular to constrain the gross carbon fluxes between the atmosphere and terrestrial biosphere.

  19. Tunable Diode Laser Measurements of Leaf-scale Carbon Isotope Discrimination and Ecosystem Respired Carbon and Oxygen Isotope Ratios in a Semi-arid Woodland

    Science.gov (United States)

    McDowell, N.; Chris, B.; Hanson, D.; Kern, S.; Meyer, C.; Pockman, W.; Powers, H.

    2005-12-01

    We present results and speculative interpretation of leaf-level carbon isotope discrimination and ecosystem respired carbon and oxygen isotope ratios from a semi-arid, C3/C4 woodland located in northern New Mexico, USA. Overstory leaf area index (LAI) is dominated by live juniper (Juniperus monosperma) trees with an LAI value of approximately 1.0 m2 per m2 ground area, and has a seasonally dynamic understory of mixed C3 forbs and C4 grasses and cacti, with a maximum LAI of 0.30 m2 per m2 ground area. Ecosystem respired carbon isotope ratios showed values characteristic of C3 dominated photosynthesis (Keeling plot intercepts of -35 to -22 per mil). Seasonal variation was typical of that found in wetter, C3 dominated forests, as was the dependence on climate (e.g. relationships with vapor pressure deficit, soil water content, and canopy conductance). Leaf-level carbon isotope discrimination of the junipers, measured by coupling a Li-Cor 6400 photosynthesis system to the TDL, provided discrimination-Ci and discrimination-vpd relationships consistent with measured ecosystem respired carbon isotope ratios. The oxygen isotope ratio of ecosystem respiration was dependent on rain water isotope composition, but was correlated with soil water content during rain-free periods. The cumulative effect of vapor pressure deficit after a rain event was tightly correlated with the oxygen isotope ratio of ecosystem respiration, suggesting the primary drivers are evaporative enrichment of soil water and perhaps nocturnal leaf enrichment. Instrument precision for carbon and oxygen isotope ratios of carbon dioxide is 0.06 to 0.18 per mil; however, overall precision is somewhat lower due to pressure and sampling effects.

  20. Carbon allocation and carbon isotope fluxes in the plant-soil-atmosphere continuum: a review

    Science.gov (United States)

    Brüggemann, N.; Gessler, A.; Kayler, Z.; Keel, S. G.; Badeck, F.; Barthel, M.; Boeckx, P.; Buchmann, N.; Brugnoli, E.; Esperschütz, J.; Gavrichkova, O.; Ghashghaie, J.; Gomez-Casanovas, N.; Keitel, C.; Knohl, A.; Kuptz, D.; Palacio, S.; Salmon, Y.; Uchida, Y.; Bahn, M.

    2011-11-01

    The terrestrial carbon (C) cycle has received increasing interest over the past few decades, however, there is still a lack of understanding of the fate of newly assimilated C allocated within plants and to the soil, stored within ecosystems and lost to the atmosphere. Stable carbon isotope studies can give novel insights into these issues. In this review we provide an overview of an emerging picture of plant-soil-atmosphere C fluxes, as based on C isotope studies, and identify processes determining related C isotope signatures. The first part of the review focuses on isotopic fractionation processes within plants during and after photosynthesis. The second major part elaborates on plant-internal and plant-rhizosphere C allocation patterns at different time scales (diel, seasonal, interannual), including the speed of C transfer and time lags in the coupling of assimilation and respiration, as well as the magnitude and controls of plant-soil C allocation and respiratory fluxes. Plant responses to changing environmental conditions, the functional relationship between the physiological and phenological status of plants and C transfer, and interactions between C, water and nutrient dynamics are discussed. The role of the C counterflow from the rhizosphere to the aboveground parts of the plants, e.g. via CO2 dissolved in the xylem water or as xylem-transported sugars, is highlighted. The third part is centered around belowground C turnover, focusing especially on above- and belowground litter inputs, soil organic matter formation and turnover, production and loss of dissolved organic C, soil respiration and CO2 fixation by soil microbes. Furthermore, plant controls on microbial communities and activity via exudates and litter production as well as microbial community effects on C mineralization are reviewed. A further part of the paper is dedicated to physical interactions between soil CO2 and the soil matrix, such as CO2 diffusion and dissolution processes within the

  1. Volcanism, mass extinction, and carbon isotope fluctuations in the Middle Permian of China.

    Science.gov (United States)

    Wignall, Paul B; Sun, Yadong; Bond, David P G; Izon, Gareth; Newton, Robert J; Védrine, Stéphanie; Widdowson, Mike; Ali, Jason R; Lai, Xulong; Jiang, Haishui; Cope, Helen; Bottrell, Simon H

    2009-05-29

    The 260-million-year-old Emeishan volcanic province of southwest China overlies and is interbedded with Middle Permian carbonates that contain a record of the Guadalupian mass extinction. Sections in the region thus provide an opportunity to directly monitor the relative timing of extinction and volcanism within the same locations. These show that the onset of volcanism was marked by both large phreatomagmatic eruptions and extinctions amongst fusulinacean foraminifers and calcareous algae. The temporal coincidence of these two phenomena supports the idea of a cause-and-effect relationship. The crisis predates the onset of a major negative carbon isotope excursion that points to subsequent severe disturbance of the ocean-atmosphere carbon cycle.

  2. Follow the Carbon: Isotopic Labeling Studies of Early Earth Aerosol.

    Science.gov (United States)

    Hicks, Raea K; Day, Douglas A; Jimenez, Jose L; Tolbert, Margaret A

    2016-11-01

    Despite the faint young Sun, early Earth might have been kept warm by an atmosphere containing the greenhouse gases CH4 and CO2 in mixing ratios higher than those found on Earth today. Laboratory and modeling studies suggest that an atmosphere containing these trace gases could lead to the formation of organic aerosol haze due to UV photochemistry. Chemical mechanisms proposed to explain haze formation rely on CH4 as the source of carbon and treat CO2 as a source of oxygen only, but this has not previously been verified experimentally. In the present work, we use isotopically labeled precursor gases and unit-mass resolution (UMR) and high-resolution (HR) aerosol mass spectrometry to examine the sources of carbon and oxygen to photochemical aerosol formed in a CH4/CO2/N2 atmosphere. UMR results suggest that CH4 contributes 70-100% of carbon in the aerosol, while HR results constrain the value from 94% to 100%. We also confirm that CO2 contributes approximately 10% of the total mass to the aerosol as oxygen. These results have implications for the geochemical interpretations of inclusions found in Archean rocks on Earth and for the astrobiological potential of other planetary atmospheres. Key Words: Atmosphere-Early Earth-Planetary atmospheres-Carbon dioxide-Methane. Astrobiology 16, 822-830.

  3. The Carnian (Late Triassic) carbon isotope excursion: new insights from the terrestrial realm

    Science.gov (United States)

    Miller, Charlotte; Kürschner, Wolfram; Peterse, Francien; Baranyi, Viktoria; Reichart, Gert-Jan

    2016-04-01

    The geological record contains evidence for numerous pronounced perturbations in the global carbon cycle, some of which are associated with eruptions from large igneous provinces (LIP), and consequently, ocean acidification and mass extinction. In the Carnian (Late Triassic), evidence from sedimentology and fossil pollen points to a significant change in climate, resulting in biotic turnover: during a period termed the 'Carnian Pluvial Event' (CPE). Additionally, during the Carnian, large volumes of flood basalts were erupted from the Wrangellia LIP (western North America). Evidence from the marine realm suggests a fundamental relationship between the CPE, a global 'wet' period, and the injection of light carbon into the atmosphere from the LIP. Here we provide the first evidence from the terrestrial realm of a significant negative δ13C excursion through the CPE recorded in the sedimentary archive of the Wiscombe Park Borehole, Devon (UK). Both total organic matter and plant leaf waxes reflect a gradual carbon isotope excursion of ~-5‰ during this time interval. Our data provides evidence for the global nature of this isotope excursion, supporting the hypothesis that the excursion was likely the result of an injection of light carbon into the atmosphere from the Wrangellia LIP.

  4. An assessment of geochemical preparation methods prior to organic carbon concentration and carbon isotope ratio analyses of fine-grained sedimentary rocks

    Science.gov (United States)

    KöNitzer, Sven F.; Leng, Melanie J.; Davies, Sarah J.; Stephenson, Michael H.

    2012-09-01

    This study summarizes organic carbon isotope (δ13C) and total organic carbon (TOC) data from a series of tests undertaken to provide an appropriate methodology for pre-analysis treatment of mudstones from an Upper Carboniferous sedimentary succession, in order to develop a consistent preparation procedure. The main treatments involved removing both inorganic carbonate and hydrocarbons (which might be extraneous) before δ13C and TOC analysis. The results show that decarbonating using hydrochloric acid causes significant reduction in δ13C and total carbon (TC) of the bulk material due to the removal of inorganic carbonate. These changes are most pronounced where soluble calcium carbonate (rather than Ca-Mg-Fe carbonate) is present. Deoiled samples show only slightly higher mean δ13C where visible bitumen was extracted from the bulk sample. Moreover, the isotopic signatures of the extracts are closely correlated to those of their respective bulk samples, suggesting that small yields of hydrocarbons were generated in situ with no isotopic fractionation. In addition, further δ13C and TC analyses were performed on samples where mixing of oil-based drilling mud with brecciated core material had been undertaken. Brecciated mudstone material did not display distinct isotopic signals compared to the surrounding fine-grained material. Overall we show that the most accurate assessment of bulk organic carbon isotopes and concentration in these samples can be achieved through decarbonating the material prior to measurement via the `rinse method'. However, our results support recent findings that pre-analysis acid treatments can cause variable and unpredictable errors in δ13C and TOC values. We believe that, despite these uncertainties, the findings presented here can be applied to paleoenvironmental studies on organic matter contained within sedimentary rocks over a range of geological ages and compositions.

  5. Long-range transport of continentally-derived particulate carbon in the marine atmosphere: evidence from stable carbon isotope studies

    OpenAIRE

    Cachier, Héléne; BUAT-MÉNARD, PATRICK; Fontugne, Michel; Chesselet, Roger

    2011-01-01

    Since 1979, we have investigated marine and non-marine sources of particulate carbon in the marine atmosphere from measurements of carbon concentration and isotopic composition 13C/12C). Aerosol samples were collected, mostly during the Sea/Air Exchange (SEAREX) Program experiments, in the northern and southern hemispheres (Sargasso Sea, Enewetak Atoll, Peru upwelling, American Samoa, New Zealand, Amsterdam Island). The concentration and the isotopic composition of particulate carbon of marin...

  6. Skeletal and isotopic composition and paleoclimatic significance of late Pleistocene carbonates, Ross Sea, Antarctica

    Energy Technology Data Exchange (ETDEWEB)

    Taviani, M. (Ist. per la Geologia Marina, Bologna (Italy)); Reid, D.E.; Anderson, J.B. (Rice Univ., Houston, TX (United States))

    1993-01-01

    Carbonates cover an extensive area of the northwestern Ross Sea continental shelf. Radiocarbon dates yield late Pleistocene (stage 3) ages for these deposits, hence the carbonates appear to be correlative with widespread tills and glacial marine deposits in the region. Four carbonate facies are recognized on the basis of skeletal composition: a barnacle/foraminifer facies, a muddy bryozoan facies, a bryozoan/barnacle/pelecypod/foraminifer facies, and a planktonic foraminiferal facies. These deposits occur on the shelf and upper slope, while carbonate turbidities derived from them occur on the adjacent continental slope and rise. Compositional analyses of Ross Sea carbonates lend support to previously recognized criteria for identifying cold water carbonates. These include: (1) the presence of an associated ice-rafted component (including dropstones); (2) a dominance of calcite relative to other carbonate minerals (the remaining fraction consists solely of aragonite); (3) allochems that are entirely skeletal; and (4) heavy oxygen isotopic compositions (in the range of +3.0 to +5.1% PDB).

  7. Carbon isotope composition of latex does not reflect temporal variations of photosynthetic carbon isotope discrimination in rubber trees (Hevea brasiliensis).

    Science.gov (United States)

    Kanpanon, Nicha; Kasemsap, Poonpipope; Thaler, Philippe; Kositsup, Boonthida; Gay, Frédéric; Lacote, Régis; Epron, Daniel

    2015-11-01

    Latex, the cytoplasm of laticiferous cells localized in the inner bark of rubber trees (Hevea brasiliensis Müll. Arg.), is collected by tapping the bark. Following tapping, latex flows out of the trunk and is regenerated, whereas in untapped trees, there is no natural exudation. It is still unknown whether the carbohydrates used for latex regeneration in tapped trees is coming from recent photosynthates or from stored carbohydrates, and in the former case, it is expected that latex carbon isotope composition of tapped trees will vary seasonally, whereas latex isotope composition of untapped trees will be more stable. Temporal variations of carbon isotope composition of trunk latex (δ(13)C-L), leaf soluble compounds (δ(13)C-S) and bulk leaf material (δ(13)C-B) collected from tapped and untapped 20-year-old trees were compared. A marked difference in δ(13)C-L was observed between tapped and untapped trees whatever the season. Trunk latex from tapped trees was more depleted (1.6‰ on average) with more variable δ(13)C values than those of untapped trees. δ(13)C-L was higher and more stable across seasons than δ(13)C-S and δ(13)C-B, with a maximum seasonal difference of 0.7‰ for tapped trees and 0.3‰ for untapped trees. δ(13)C-B was lower in tapped than in untapped trees, increasing from August (middle of the rainy season) to April (end of the dry season). Differences in δ(13)C-L and δ(13)C-B between tapped and untapped trees indicated that tapping affects the metabolism of both laticiferous cells and leaves. The lack of correlation between δ(13)C-L and δ(13)C-S suggests that recent photosynthates are mixed in the large pool of stored carbohydrates that are involved in latex regeneration after tapping.

  8. Carbon Fiber Composite Monoliths as Catalyst Supports

    Energy Technology Data Exchange (ETDEWEB)

    Contescu, Cristian I [ORNL; Gallego, Nidia C [ORNL; Pickel, Joseph M [ORNL; Blom, Douglas Allen [ORNL; Burchell, Timothy D [ORNL

    2006-01-01

    Carbon fiber composite monoliths are rigid bodies that can be activated to a large surface area, have tunable porosity, and proven performance in gas separation and storage. They are ideal as catalyst supports in applications where a rigid support, with open structure and easy fluid access is desired. We developed a procedure for depositing a dispersed nanoparticulate phase of molybdenum carbide (Mo2C) on carbon composite monoliths in the concentration range of 3 to 15 wt% Mo. The composition and morphology of this phase was characterized using X-ray diffraction and electron microscopy, and a mechanism was suggested for its formation. Molybdenum carbide is known for its catalytic properties that resemble those of platinum group metals, but at a lower cost. The materials obtained are expected to demonstrate catalytic activity in a series of hydrocarbon reactions involving hydrogen transfer. This project demonstrates the potential of carbon fiber composite monoliths as catalyst supports.

  9. Carbon Fiber Composite Monoliths for Catalyst Supports

    Energy Technology Data Exchange (ETDEWEB)

    Contescu, Cristian I [ORNL; Gallego, Nidia C [ORNL; Pickel, Joseph M [ORNL; Blom, Douglas Allen [ORNL; Burchell, Timothy D [ORNL

    2006-01-01

    Carbon fiber composite monoliths are rigid bodies that can be activated to a large surface area, have tunable porosity, and proven performance in gas separation and storage. They are ideal as catalyst supports in applications where a rigid support, with open structure and easy fluid access is desired. We developed a procedure for depositing a dispersed nanoparticulate phase of molybdenum carbide (Mo2C) on carbon composite monoliths in the concentration range of 3 to 15 wt% Mo. The composition and morphology of this phase was characterized using X-ray diffraction and electron microscopy, and a mechanism was suggested for its formation. Molybdenum carbide is known for its catalytic properties that resemble those of platinum group metals, but at a lower cost. The materials obtained are expected to demonstrate catalytic activity in a series of hydrocarbon reactions involving hydrogen transfer. This project demonstrates the potential of carbon fiber composite monoliths as catalyst supports.

  10. Using Carbon Isotopes in Cenozoic Soil Carbonates to Quantify Primary Productivity from Mid-Latitude Regions

    Science.gov (United States)

    Caves, J. K.; Kramer, S. H.; Ibarra, D. E.; Chamberlain, C. P.

    2015-12-01

    The carbon isotope composition of pedogenic carbonates (δ13Ccarb) from paleosols has been extensively used as a proxy to estimate atmospheric pCO2 over the Phanerozoic. However, a number of other factors - including the concentration of plant-respired CO2 and the isotopic composition of both atmospheric and plant-respired carbon - influence the δ13C of pedogenic carbonates. For example, δ13Ccarb records from the mid-latitudes in central Asia and western North America show increasing trends in δ13Ccarb despite decreasing pCO2 during the late Cenozoic, which suggests that other factors play an important role in determining the isotopic composition of pedogenic carbonates. Instead, we suggest that these records are primarily recording changes in primary productivity rather than changes in atmospheric pCO2 and therefore propose a novel use of paleosol carbonate records to understand paleo-ecosystem dynamics. Here, we compile existing paleosol carbonate records, and present three new records from Wyoming, to estimate soil respiration and primary productivity in western North America during the Paleogene and early Neogene. We observe both an overall increase in δ13Ccarb after the early Eocene, and spatially heterogeneous δ13Ccarb values across western US basins. We combine this δ13Ccarb data with compilations of atmospheric pCO2 to estimate soil respiration and plant productivity. The long-term increase in δ13Ccarb indicates a decrease in plant productivity as conditions became more arid across much of the western US, congruent with both records of regional uplift and of global cooling. Furthermore, significant spatial heterogeneity in δ13Ccarb indicates that regional factors, such as the presence of paleolakes and/or local paleotopography may have provided a second-order control on local and regional productivity. Thus, our results provide a first-order estimate linking changes in primary productivity with regional tectonics and global climatic change.

  11. Stable Carbon and Oxygen Isotopes of Pedogenic Carbonates in Ustic Vertisols: Implications for Paleoenvironmental Change

    Institute of Scientific and Technical Information of China (English)

    HUANG Cheng-Min; WANG Cheng-Shan; TANG Ya

    2005-01-01

    Pedogenic carbonates, found extensively in arid and semiarid regions, are important in revealing regional climatic and environmental changes as well as the carbon cycle. In addition, stable carbon and oxygen isotopic compositions of pedogenic carbonates have been used to rebuild paleoecology (biomass and vegetation) and to estimate paleotemperature and paleoprecipitation during past geological time. By utilizing the stable carbon and oxygen isotopic compositions (δ13C and δ18O) of secondary nodules in Ustic Vertisols, this study looked into the climatic and environmental changes in the dry valleys of the Yuanmou Basin, Yunnan Province, in southwestern China. The results showed that during the early Holocene, a warm-humid or hot-humid climate existed in the Yuanmou Basin, but since then fluctuations in climate have occurred, with a dry climate prevailing. A highly significant correlation (r = 0.92, n= 9) between δ13C and δ18O values of carbonates illustrated that there had been a continual shifting between cold-humid and warm-dry climates in southwestern China including the Yuanmou Basin since the early Holocene.

  12. Regional prediction of carbon isotopes in soil carbonates for Asian dust source tracer

    Science.gov (United States)

    Chen, Bing; Cui, Xinjuan; Wang, Yaqiang

    2016-10-01

    Dust particles emitted from deserts and semi-arid lands in northern China cause particulate pollution that increases the burden of disease particularly for urban population in East Asia. The stable carbon isotopes (δ13C) of carbonates in soils and dust aerosols in northern China were investigated. We found that the δ13C of carbonates in surface soils in northern China showed clearly the negative correlation (R2 = 0.73) with Normalized Difference Vegetation Index (NDVI). Using Moderate Resolution Imaging Spectroradiometer (MODIS) satellite-derived NDVI, we predicted the regional distribution of δ13C of soil carbonates in deserts, sandy lands, and steppe areas. The predictions show the mean δ13C of -0.4 ± 0.7‰ in soil carbonates in Taklimakan Desert and Gobi Deserts, and the isotope values decrease to -3.3 ± 1.1‰ in sandy lands. The increase in vegetation coverage depletes 13C in soil carbonates, thus the steppe areas are predicted by the lowest δ13C levels (-8.1 ± 1.7‰). The measurements of atmospheric dust samples at eight sites showed that the Asian dust sources were well assigned by the 13C mapping in surface soils. Predicting 13C in large geographical areas with fine resolution offers a cost-effective tracer to monitor dust emissions from sandy lands and steppe areas which show an increasing role in Asian dust loading driven by climate change and human activities.

  13. Cryogenic Calcite: A Morphologic and Isotopic Analog to the ALH84001 Carbonates

    Science.gov (United States)

    Niles, P. B.; Leshin, L. A.; Socki, R. A.; Guan, Y.; Ming, D. W.; Gibson, E. K.

    2004-01-01

    Martian meteorite ALH84001 carbonates preserve large and variable microscale isotopic compositions, which in some way reflect their formation environment. These measurements show large variations (>20%) in the carbon and oxygen isotopic compositions of the carbonates on a 10-20 micron scale that are correlated with chemical composition. However, the utilization of these data sets for interpreting the formation conditions of the carbonates is complex due to lack of suitable terrestrial analogs and the difficulty of modeling under non-equilibrium conditions. Thus, the mechanisms and processes are largely unknown that create and preserve large microscale isotopic variations in carbonate minerals. Experimental tests of the possible environments and mechanisms that lead to large microscale isotopic variations can help address these concerns. One possible mechanism for creating large carbon isotopic variations in carbonates involves the freezing of water. Carbonates precipitate during extensive CO2 degassing that occurs during the freezing process as the fluid s decreasing volume drives CO2 out. This rapid CO2 degassing results in a kinetic isotopic fractionation where the CO2 gas has a much lighter isotopic composition causing an enrichment of 13C in the remaining dissolved bicarbonate. This study seeks to determine the suitability of cryogenically formed carbonates as analogs to ALH84001 carbonates. Specifically, our objective is to determine how accurately models using equilibrium fractionation factors approximate the isotopic compositions of cryogenically precipitated carbonates. This includes determining the accuracy of applying equilibrium fractionation factors during a kinetic process, and determining how isotopic variations in the fluid are preserved in microscale variations in the precipitated carbonates.

  14. Seasonal variation in stable carbon and nitrogen isotope values of bats reflect environmental baselines.

    Directory of Open Access Journals (Sweden)

    Ana G Popa-Lisseanu

    Full Text Available The stable carbon and nitrogen isotope composition of animal tissues is commonly used to trace wildlife diets and analyze food chains. Changes in an animal's isotopic values over time are generally assumed to indicate diet shifts or, less frequently, physiological changes. Although plant isotopic values are known to correlate with climatic seasonality, only a few studies restricted to aquatic environments have investigated whether temporal isotopic variation in consumers may also reflect environmental baselines through trophic propagation. We modeled the monthly variation in carbon and nitrogen isotope values in whole blood of four insectivorous bat species occupying different foraging niches in southern Spain. We found a common pattern of isotopic variation independent of feeding habits, with an overall change as large as or larger than one trophic step. Physiological changes related to reproduction or to fat deposition prior to hibernation had no effect on isotopic variation, but juvenile bats had higher δ13C and δ15N values than adults. Aridity was the factor that best explained isotopic variation: bat blood became enriched in both 13C and 15N after hotter and/or drier periods. Our study is the first to show that consumers in terrestrial ecosystems reflect seasonal environmental dynamics in their isotope values. We highlight the danger of misinterpreting stable isotope data when not accounting for seasonal isotopic baselines in food web studies. Understanding how environmental seasonality is integrated in animals' isotope values will be crucial for developing reliable methods to use stable isotopes as dietary tracers.

  15. Carbon isotope fractionation of dissolved inorganic carbon (DIC) due to outgassing of carbon dioxide from a headwater stream

    Science.gov (United States)

    Daniel H. Doctor; Carol Kendall; Stephen D. Sebestyen; James B. Shanley; Nobuhito Ohte; Elizabeth W. Boyer

    2008-01-01

    The stable isotopic composition of dissolved inorganic carbon (δ13C-DIC) was investigated as a potential tracer of streamflow generation processes at the Sleepers River Research Watershed, Vermont, USA. Downstream sampling showed δ13C-DIC increased between 3-5% from the stream source to the outlet weir...

  16. Differential utilization of allochthonous and autochthonous carbon by aquatic insects of two shrub-steppe desert spring-streams: A stable carbon isotope analysis and critique of the method

    Energy Technology Data Exchange (ETDEWEB)

    Mize, A. L. [Old Dominion Univ., Norfolk, VA (United States)

    1993-06-01

    The purpose of this study is to assess whether the carbon supporting stream food webs comes principally from terrestrial sources or is produced within the stream. Lacking data to resolve the allochthonous/autochthonous issue with any finality, stream ecologists have alternately postulated that stream carbon was principally autochthonous or principally allochthonous. Others argued that autochthonous and allochthonous carbon resources cannot be separated and that the allochthonous/autochthonous dependence issue is unresolvable. Many investigators have seized upon stable carbon isotopes technology as the tool to resolve the controversy. Unfortunately most investigators have conceded that the results are rarely quantitative and that the qualitative relationships are ambiguous. This study points out the fallacies of trying to conjure single isotopic values for either allochthonous or autochthonous carbon. It suggests that stable carbon isotope technology is not reliable in establishing specific consumer/food source relations and that it is not suitable for assessing allochthonous/autochthonous carbon dependence in freshwater streams.

  17. Stable Isotope Studies of Crop Carbon and Water Relations: A Review

    Institute of Scientific and Technical Information of China (English)

    ZHANG Cong-zhi; ZHANG Jia-bao; ZHAO Bing-zi; ZHANG Hui; HUANG Ping

    2009-01-01

    Crop carbon and water relations research is important in the studies of water saving agriculture,breeding program,and energy and material cycles in soil plant atmosphere continuum (SPAC).The purpose of this paper is to review the current state of knowledge on stable isotopes of carbon,oxygen,and hydrogen in the research of crop carbon and water relations,such as carbon isotope discrimination (△13C) during carbon fixation process by photosynthesis,application of △13C in crop water use efficiency (WUE) and breeding programs,oxygen isotope enrichment during leaf water transpiration,CO2 fixation by photosynthesis and release by respiration,application of hydrogen isotope composition (δD) and oxygen isotope composition (δ18O) for determination of water source used by a crop,stable isotope coupling Keeling plot for investigating the carbon and water flux in ecosystem,energy and material cycle in SPAC and correlative integrative models on stable isotope.These aspects contain most of the stable isotope researches on crop carbon and water relations which have been widely explored internationally while less referred in China.Based on the reviewed literatures,some needs for future research are suggested.

  18. Bringing organic carbon isotopes and phytoliths to the table as additional constraints on paleoelevation

    Science.gov (United States)

    Sheldon, N. D.; Cotton, J. M.; Hren, M. T.; Hyland, E. G.; Smith, S. Y.; Strömberg, C. A. E.

    2015-12-01

    A commonly used tool in paleotectonic and paleoaltimetry studies is the oxygen isotopic composition of authigenic carbonates formed that formed in lakes or soils, with both spatial (e.g., shoreline to mountain top) or temporally resolved records potentially providing constraints. However, in many cases there is a substantial spread in the oxygen isotope data for a given time period, often to the point of allowing for essentially any interpretation of the data depending upon how they have been used by the investigator. One potential way of distinguishing between different potential paleotectonic or paleoaltimetric interpretations is to use carbon isotope and plant microfossil (phytolith) analyses from the same paleosols to screen the oxygen isotope data by looking for evidence of evaporative enrichment. For example, if both inorganic (carbonate) and organic carbon isotopes are measured from the same paleosol, then in it possible to determine if the two isotope record equilibrium conditions or if they record disequilibrium driven by kinetic effects. In the former case, the oxygen isotope results can be considered reliable whereas in the latter case, the oxygen isotope results can be considered unreliable and could be culled from the interpretation. Similarly, because the distribution of C4 plants varies as a function of temperature and elevation, the presence/absence or abundance of C4 plant phytoliths, or of carbon isotope compositions that require a component of C4 vegetation can also be used to constrain paleoelevation by providing a maximum elevation constraint. Worked examples will include the late Miocene-Pliocene of Catamarca, Argentina, where phytoliths and organic carbon isotopes provide a maximum elevation constraint and can be used to demonstrate that oxygen isotopes do not provide a locally useful constraint on paleoelevation, and Eocene-Miocene of southwestern Montana where organic matter and phytoliths can be used to select between different potential

  19. The Stable and Radio- Carbon Isotopic Content of Labile and Refractory Carbon in Atmospheric Particulate Matter

    Science.gov (United States)

    McNichol, A. P.; Rosenheim, B. E.; Gerlach, D. S.; Hayes, J. M.

    2006-12-01

    Studies of the isotopic content of atmospheric particulate matter are hampered by difficulties in chemically defining the pools of carbon and analytically isolating the different pools. We are conducting studies on reference materials and atmospheric aerosol samples to develop a method to measure stable and radio- carbon isotopes on the labile and refractory carbon. We are using a flow-through combustion system that allows us to combust, collect and measure the isotopic content of the gases produced at all stages of heating/oxidizing. We compare our results to those measured using a chemothermal oxidation method (CTO) (Gustafsson et al., 2001). In this method, refractory carbon is defined as the material remaining after pre- combusting a sample at 375°C in the presence of oxygen for 24 hours. The reference materials are diesel soot, apple leaves and a hybrid of the two (DiesApple), all from NIST. These provide carbon with two well-defined fractions -- the soot provides refractory carbon that is radiocarbon dead and the apple leaves provide organic carbon that is radiocarbon modern. Radiocarbon results from DiesApple indicate that the "refractory" carbon defined by the CTO method is actually a mixture of old and modern carbon that contains over 25% modern carbon. This suggests that charred material formed from the apples leaves during the pre-combustion step is contributing to the fraction we identify as refractory carbon. We are studying this by analyzing the individual materials and the mixture using our flow-through system. First results with this system indicate that the refractory fraction trapped from the DiesApple contains much less modern carbon than the CTO method, less than 7%. We will present detailed concentration and isotopic results of the generation of carbon dioxide during programmed combustion of each of the reference materials. We studied the radiocarbon content of both the total carbon (TC) and refractory carbon in the fine particulate matter (PM

  20. The magnesium isotope record of cave carbonate archives

    Directory of Open Access Journals (Sweden)

    S. Riechelmann

    2012-11-01

    Full Text Available Here we explore the potential of magnesium (δ26Mg isotope time-series data as continental climate proxies in speleothem calcite archives. For this purpose, a total of six Pleistocene and Holocene stalagmites from caves in Germany, Morocco and Peru and two flowstones from a cave in Austria were investigated. These caves represent the semi-arid to arid (Morocco, the warm-temperate (Germany, the equatorial-humid (Peru and the cold-humid (Austria climate zones. Changes in the calcite magnesium isotope signature with time are compared against carbon and oxygen isotope records from these speleothems. Similar to other proxies, the non-trivial interaction of a number of environmental, equilibrium and disequilibrium processes governs the δ26Mg fractionation in continental settings. These include the different sources of magnesium isotopes such as rainwater or snow as well as soil and host rock, soil zone biogenic activity, shifts in silicate versus carbonate weathering ratios and residence time of water in the soil and karst zone. Pleistocene stalagmites from Morocco show the lowest mean δ26Mg values (GDA: −4.26 ± 0.07‰ and HK3: −4.17 ± 0.15‰, and the data are well explained in terms of changes in aridity over time. The Pleistocene to Holocene stalagmites from Peru show the highest mean value of all stalagmites (NC-A and NC-B δ26Mg: −3.96 ± 0.04‰ but only minor variations in Mg-isotope composition, which is consistent with the rather stable equatorial climate at this site. Holocene stalagmites from Germany (AH-1 mean δ26Mg: −4.01 ± 0.07‰; BU 4 mean δ26Mg: −4.20 ± 0.10‰ suggest changes in outside air temperature was the principal driver rather than rainfall amount. The alpine Pleistocene flowstones from Austria (SPA 52: −3.00 ± 0.73‰; SPA 59: −3.70 ± 0.43‰ are affected by glacial versus interglacial climate change with outside air temperature

  1. The magnesium isotope record of cave carbonate archives

    Directory of Open Access Journals (Sweden)

    S. Riechelmann

    2012-05-01

    Full Text Available Here we explore the potential of time-series magnesium (δ26Mg isotope data as continental climate proxies in speleothem calcite archives. For this purpose, a total of six Pleistocene and Holocene stalagmites from caves in Germany, Morocco and Peru and two flowstones from a cave in Austria were investigated. These caves represent the semi-arid to arid (Morocco, the warm-temperate (Germany, the equatorial-humid (Peru and the cold-humid (Austria climate zones. Changes in the calcite magnesium isotope signature with time are placed against carbon and oxygen isotope records from these speleothems. Similar to other proxies, the non-trivial interaction of a number of environmental, equilibrium and non-equilibrium processes governs the δ26Mg fractionation in continental settings. These include the different sources of magnesium isotopes such as rain water or snow as well as soil and hostrock, soil zone biogenic activity, shifts in silicate versus carbonate weathering ratios and residence time of water in the soil and karst zone. Pleistocene stalagmites from Morocco show the lowest mean δ26Mg values (GDA: −4.26 ± 0.07 ‰ and HK3: −4.17 ± 0.15 ‰ and the data are well explained in terms of changes in aridity over time. The Pleistocene to Holocene stalagmites from Peru show the highest mean value (NC-A and NC-B δ26Mg: −3.96 ± 0.04 ‰ but only minor variations in Mg-isotope composition, which is in concert with the rather stable equatorial climate at this site. Holocene stalagmites from Germany (AH-1 mean δ26Mg: −4.01 ± 0.07 ‰; BU 4 mean δ26Mg: −4.20 ± 0.10 ‰ record changes in outside air temperature as driving factor rather than rainfall amount. The alpine Pleistocene flowstones from Austria (SPA 52: −3.00 ± 0.73 ‰; SPA 59: −3.70 ± 0.43 ‰ are affected by glacial versus interglacial climate change with outside air temperature affecting soil zone activity

  2. Clumped isotope calibration data for lacustrine carbonates: A progress report

    Science.gov (United States)

    Tripati, A.

    2015-12-01

    Our capacity to understand Earth's environmental history is highly dependent on the accuracy of reconstructions of past climates. Lake sediments provide important archives of terrestrial climate change, and represent an important tool for reconstructing paleohydrology, paleoclimate, paleoenvironment, and paleoaltimetry. Unfortunately, while multiple methods for constraining marine temperature exist, quantitative terrestrial proxies are scarcer - tree rings, speleothems, and leaf margin analyses have all been used with varying degrees of accuracy. Clumped isotope thermometry has the potential to be a useful instrument for determining terrestrial climates: multiple studies have shown the fraction of 13C—18O bonds in carbonates is inversely related to the temperature at which the rocks formed. We have been measuring the abundance of 13C18O16O in the CO2 produced by the dissolution of carbonate minerals in phosphoric acid in modern lake samples and comparing results to independently known estimates of lake water temperature. Here we discuss an extensive calibration dataset comprised of 132 analyses of 97 samples from 44 localities, including microbialites, tufas, and micrites endogenic carbonates, freshwater gastropods, bivalves, microbialites, and ooids.

  3. On-site isotopic analysis of dissolved inorganic carbon using an isotope ratio infrared spectrometer

    Science.gov (United States)

    Stoltmann, Tim; Mandic, Magda; Stöbener, Nils; Wapelhorst, Eric; Aepfler, Rebecca; Hinrichs, Kai-Uwe; Taubner, Heidi; Jost, Hj; Elvert, Marcus

    2016-04-01

    An Isotope Ratio Infrared Spectrometer (IRIS) has been adapted to perform measurements of δ13C of dissolved inorganic carbon (DIC) in marine pore waters. The resulting prototype allowed highly automated analysis of δ13C isotopic ratios and CO2 concentration. We achieved a throughput of up to 70 samples per day with DIC contents as low as 1.7 μmol C. We achieved an internal precision of 0.066 ‰ and an external precision of 0.16 ‰, which is comparable to values given for Isotope Ratio Mass Spectrometers (IRMS). The prototype instrument is field deployable, suitable for shipboard analysis of deep sea core pore waters. However, the validation of the prototype was centered around a field campaign in Eckernförde Bay, NW- Baltic Sea. As a proof of concept, a shallow site within an area of submarine groundwater discharge (SGD) and a site outside this area was investigated. We present profiles of δ13C of DIC over 50 cm exhibiting well understood methane turnover processes (anaerobic oxidation of methane). At the lowest point below the seafloor, microbial reduction of CO2 to CH4 dominates. 12CO2 is reduced preferentially over 13CO2, leading to more positive δ13C values in the remaining DIC pool; in layers closer to the surface, the oxidation of CH4 to CO2 becomes more prominent. Since the CH4 pool is enriched in 12C a shift to more negative δ13C can be observed in the DIC pool. In the upper 15 cm, the pore water DIC mixes with the sea water DIC, increasing δ13C again. Finally, we will present recent developments to further improve performance and future plans for deployments on research cruises.

  4. Observation of Large Enhancement of Charge Exchange Cross Sections with Neutron-Rich Carbon Isotopes

    CERN Document Server

    Tanihata, I; Kanungo, R; Ameil, F; Atkinson, J; Ayyad, Y; Cortina-Gil, D; Dillmann, I; Estradé, A; Evdokimov, A; Farinon, F; Geissel, H; Guastalla, G; Janik, R; Knoebel, R; Kurcewicz, J; Litvinov, Yu A; Marta, M; Mostazo, M; Mukha, I; Nociforo, C; Ong, H J; Pietri, S; Prochazka, A; Scheidenberger, C; Sitar, B; Strmen, P; Takechi, M; Tanaka, J; Toki, H; Vargas, J; Winfield, J S; Weick, H

    2015-01-01

    Production cross sections of nitrogen isotopes from high-energy carbon isotopes on hydrogen and carbon targets have been measured for the first time for a wide range of isotopes. The fragment separator FRS at GSI was used to deliver C isotope beams. The cross sections of the production of N isotopes were determined by charge measurements of forward going fragments. The cross sections show a rapid increase with the number of neutrons in the projectile. Since the production of nitrogen is mostly due to charge exchange reactions below the proton separation energies, the present data suggests a concentration of Gamow-Teller and Fermi transition strength at low excitation energies for neutron-rich isotopes. It was also observed that the cross sections were enhanced much more strongly for neutron rich isotopes in the C-target data.

  5. Distribution and carbon isotope patterns of diterpenoids and triterpenoids in modern temperate C3 trees and their geochemical significance

    Science.gov (United States)

    Diefendorf, Aaron F.; Freeman, Katherine H.; Wing, Scott L.

    2012-05-01

    Tricyclic diterpenoids and pentacyclic triterpenoids are nearly exclusively produced by gymnosperms and angiosperms, respectively. Even though both classes of terpenoids have long been recognized as plant biomarkers, their potential use as phylogenetically specific δ13C proxies remains largely unexplored. Little is known of how terpenoid abundance and carbon isotope composition vary either with plant phylogenetic position, functional group, or during synthesis. Here, we report terpenoid abundances and isotopic data for 44 tree species in 21 families, representing both angiosperms and gymnosperms, and both deciduous and evergreen leaf habits. Di- and triterpenoid abundances are significantly higher in evergreens compared to deciduous species, reflecting differences in growth strategies and increased chemical investment in longer-lived leaves. Carbon isotope abundances of terpenoid lipids are similar to leaf tissues, indicating biosynthetic isotope effects are small for both the MVA (-0.4‰) and MEP (-0.6‰) pathways. Leaf and molecular isotopic patterns for modern plants are consistent with observations of amber, resins and plant biomarkers in ancient sediments. The δ13C values of ancient diterpenoids are higher than triterpenoids by 2-5‰, consistent with observed isotopic differences between gymnosperms and angiosperms leaves, and support the relatively small lipid biosynthetic effects reported here. All other factors being equal, evergreen plants will dominate the abundance of terpenoids contributed to soils, sediments and ancient archives, with similar inputs estimated for angiosperm and gymnosperm trees when scaled by litter flux.

  6. Abundance, distribution, and isotopic composition of particulate black carbon in the northern Gulf of Mexico

    Science.gov (United States)

    Yang, Weifeng; Guo, Laodong

    2014-11-01

    There exists increasing evidence supporting the important role of black carbon in global carbon cycles. Particulate black carbon (PBC) is allochthonous and has distinct reactivities compared to the bulk particulate organic carbon (tot-POC) in marine environments. However, the abundance, geochemical behavior of PBC and its importance in oceanic carbon budget remain poorly understood. Here we report the abundance, distribution, and stable isotopic signatures of BC derived from the chemo-thermal oxidation (CTO-375) method (BCCTO) in the Gulf of Mexico. Our results show that BCCTO abundance decreased from shelf to basin, and more than a half of riverine BCCTO could be removed over the shelf. Moreover, BCCTO is much more refractory compared to the tot-POC and has δ13C values lower than those of BC-excluded POC. These results highlight the significance of PBC in marine carbon cycles and potentially suggest the need for a new end-member term in quantifying POC sources in the ocean.

  7. Stable carbon isotopic signature of methane from high-emitting wetland sites in discontinuous permafrost landscape

    Science.gov (United States)

    Marushchak, Maija; Liimatainen, Maarit; Lind, Saara; Biasi, Christina; Martikainen, Pertti

    2017-04-01

    The rising methane concentration in the atmosphere during the past years has been associated with a concurrent change in the carbon isotopic signature: The atmospheric methane is getting more and more depleted in the heavy carbon isotope. The decreasing 13C/12C ratio indicates an increasing contribution of methane from biogenic sources, most importantly wetlands and inland waters, whose global emissions are still poorly constrained. From the climate change perspective, arctic and subarctic wetlands are particularly interesting due to the strong warming and permafrost thaw predicted for these regions that will cause changes in the methane dynamics. Coupling methane flux inventories with determination of the stable isotopic signature can provide useful information about the pathways of methane production, consumption and transport in these ecosystems. Here, we present data on the emissions and carbon isotopic composition of methane from subarctic tundra wetlands at the Seida study site, Northeast European Russia. In this landscape, underlain by discontinuous permafrost, waterlogged fens represent sites of high carbon turnover and high methane release. Despite they cover less than 15% of the region, their methane emissions comprise 98% of the regional mean (± SD) release of 6.7 (± 1.8) g CH4 m-2 y-1 (Marushchak et al. 2016). The methane emission from the studied fens was clearly depleted in 13C compared to the pore water methane. The bulk mean δ13CH4 (± SD) over the growing season was -68.2 (± 2.0) ‰ which is similar to the relatively few values previously reported from tundra wetlands. We explain the depleted methane emissions by the high importance of passive transport via aerenchymous plants, a process that discriminates against the heavier isotopes. This idea is supported by the strong positive correlation observed between the methane emission and the vascular leaf area index (LAI), and the inverse relationship between the δ13CH4 of emitted methane and LAI

  8. CO2-dependent carbon isotope fractionation in dinoflagellates relates to their inorganic carbon fluxes.

    Science.gov (United States)

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

    2016-08-01

    Carbon isotope fractionation (εp) between the inorganic carbon source and organic matter has been proposed to be a function of pCO2. To understand the CO2-dependency of εp and species-specific differences therein, inorganic carbon fluxes in the four dinoflagellate species Alexandrium fundyense, Scrippsiella trochoidea, Gonyaulax spinifera and Protoceratium reticulatum have been measured by means of membrane-inlet mass spectrometry. In-vivo assays were carried out at different CO2 concentrations, representing a range of pCO2 from 180 to 1200 μatm. The relative bicarbonate contribution (i.e. the ratio of bicarbonate uptake to total inorganic carbon uptake) and leakage (i.e. the ratio of CO2 efflux to total inorganic carbon uptake) varied from 0.2 to 0.5 and 0.4 to 0.7, respectively, and differed significantly between species. These ratios were fed into a single-compartment model, and εp values were calculated and compared to carbon isotope fractionation measured under the same conditions. For all investigated species, modeled and measured εp values were comparable (A. fundyense, S. trochoidea, P. reticulatum) and/or showed similar trends with pCO2 (A. fundyense, G. spinifera, P. reticulatum). Offsets are attributed to biases in inorganic flux measurements, an overestimated fractionation factor for the CO2-fixing enzyme RubisCO, or the fact that intracellular inorganic carbon fluxes were not taken into account in the model. This study demonstrates that CO2-dependency in εp can largely be explained by the inorganic carbon fluxes of the individual dinoflagellates.

  9. Organic Geochemistry of the Hamersley Province: Relationships Among Organic Carbon Isotopes, Molecular Fossils, and Lithology

    Science.gov (United States)

    Eigenbrode, Jennifer L.

    2012-01-01

    Molecular fossils are particularly valuable ancient biosignatures that can provide key insight about microbial sources and ecology in early Earth studies. In particular, hopanes carrying 2-methyl or 3-methyl substituents are proposed to be derived from cyanobacteria and oxygen-respiring methanotrophs, respectively, based on both their modem occurrences and their Proterozoic and Phanerozoic sedimentary distributions. Steranes are likely from ancestral eukaryotes. The distribution of methylhopanes, steranes, and other biomarkers in 2.72-2.56 billion-year-old rocks from the Hamersley Province, Western Australia show relationships to lithology, facies, and isotopes of macromolecular carbon, and other biomarkers. These observations support biomarker syngenicity and thermal maturity. Moreover, ecological signatures are revealed, including a surprising relationship between isotopic values for bulk macromolecular carbon and the biomarker for methanotrophs. The record suggests that cyanobacteria were likely key organisms of shallow-water microbial ecosystems providing molecular oxygen, fixed carbon, and possibly fixed nitrogen, and methanotrophs were not alone in recycling methane and other C-13-depleted substrates.

  10. Carbon isotopic studies of individual lipids in organisms from the Nansha sea area, China

    Institute of Scientific and Technical Information of China (English)

    DUAN; Yi; SONG; Jinming; ZHANG; Hui

    2004-01-01

    Carbon isotopes of individual lipids in typical organisms from the Nansha sea area were measured by the GC-IRMS analytical technique. δ13C values of saturated fatty acids in different organisms examined are from -25.6‰ to -29.7‰ with the average values ranging from -26.4‰ to -28.2‰ and the variance range of 1.8‰ between different organisms is also observed.Unsaturated fatty acids have heavy carbon isotopic compositions and the mean differences of 2.9‰-6.8‰ compared to the same carbon number saturated fatty acids. δ13C values of n-alkanes range from -27.5‰ to -29.7‰ and their mean values, ranging from -28.6‰ to -28.9‰, are very close in different organisms. The mean difference in δ13C between the saturated fatty acids and n-alkanes is only 1.5‰, indicating that they have similar biosynthetic pathways. The carbon isotopic variations between the different carbon-number lipids are mostly within ±2.0‰, reflecting that they experienced a biosynthetic process of the carbon chain elongation. At the same time, the carbon isotopic genetic relationships between the biological and sedimentary lipids are established by comparative studies of carbon isotopic compositions of individual lipids in organisms and sediments from the Nansha sea area, which provides scientific basis for carbon isotopic applied research of individual lipids.

  11. In situ carbon isotope analysis of Archean organic matter with SIMS

    Science.gov (United States)

    Williford, K. H.; Ushikubo, T.; Lepot, K.; Hallmann, C.; Spicuzza, M. J.; Eigenbrode, J. L.; Summons, R. E.; Valley, J. W.

    2011-12-01

    rates as low as 10% relative to anthracite. Samples from the ABDP-9 (n=3; Mount McRae Shale, ~2.5 Ga), RHDH2a (n=2; Carrawine Dolomite and Jeerinah Fm, ~2.6 Ga), WRL1 (n=3; Wittenoom Fm, Marra Mamba Iron Formation, and Jeerinah Fm, ~2.6 Ga), and SV1 (n=1; Tumbiana Fm, ~2.7 Ga) drill cores, each previously analyzed for bulk organic carbon isotope composition, yielded 100 new, in situ data from Neoarchean sedimentary OM. In these samples, δ13C varies between -53.1 and -28.3% and offsets between in situ and bulk compositions range from -8.3 to 18.8%. In some cases, isotopic composition and mode of occurrence (e.g. morphology and mineral associations) are statistically correlated, enabling the identification of distinct reservoirs of OM. Our results support previous evidence for aerobiosis and depth gradients of oxidation in Neoarchean environments driven by photosynthesis and methane metabolism. The relevance of these findings to questions of bio- and syngenicity as well as the alteration history of this OM and similar, previously reported Archean OM will be discussed.

  12. Molecular and carbon isotopic compositions of gas inclusions of deep carbonate rocks in the Tarim Basin

    Institute of Scientific and Technical Information of China (English)

    ZHOU Shixin; WANG Xianbin; MENG Zifang; LI Yuan; Paul Farrimond; LI Liwu; DUAN Yi

    2004-01-01

    Gaseous components of gas inclusions in deep carbonate rocks (>5700 m) from the Tacan 1 well were analyzed by online mass spectrometry by means of either the stepwise heating technique or vacuum electromagnetism crushing. The carbon isotopic compositions of gases released by vacuum electromagnetism crushing were also measured. Although the molecular compositions of gas inclusions show differences between the two methods, the overall characteristics are that gas inclusions mainly contain CO2, whilst hydrocarbon gases, such as CH4, C2H6 and C3H8, are less abundant. The content of CO is higher in the stepwise heating experiment than that in the method of vacuum electromagnetism crushing, and there are only minor amounts of N2, H2 and O2 in gas inclusions. Methane δ13C values of gas inclusions in Lower Ordovician and Upper Cambrian rocks (from 5713.7 to 6422 m; -52‰-63‰) are similar to those of bacterial methane, but their chemical compositions do not exhibit the dry character in comparison with biogenic gases. These characteristics of deep gas inclusions may be related to the migration fractionation. Some deep natural gases with light carbon isotopic characteristics in the Tazhong Uplift may have a similar origin. The δ13C1 values of gas inclusions in Lower Cambrian rocks (7117-7124 m) are heavier (-39‰), consistent with highly mature natural gases. Carbon isotopic compositions of CO2 in the gas inclusions of deep carbonate rocks are similar (from -4‰ to -13‰) to those of deep natural gases, indicating predominantly an inorganic origin.

  13. Carbon isotope discrimination as a tool to explore C4 photosynthesis.

    Science.gov (United States)

    von Caemmerer, Susanne; Ghannoum, Oula; Pengelly, Jasper J L; Cousins, Asaph B

    2014-07-01

    Photosynthetic carbon isotope discrimination is a non-destructive tool for investigating C4 metabolism. Tuneable diode laser absorption spectroscopy provides new opportunities for making rapid, concurrent measurements of carbon isotope discrimination and CO2 assimilation over a range of environmental conditions, and this has facilitated the use of carbon isotope discrimination as a probe of C4 metabolism. In spite of the significant progress made in recent years, understanding how photosynthetic carbon isotope discrimination measured concurrently with gas exchange relates to carbon isotope composition of leaf and plant dry matter remains a challenge that requires resolution if this technique is to be successfully applied as a screening tool in crop breeding and phylogenetic research. In this review, we update our understanding of the factors and assumptions that underlie variations in photosynthetic carbon isotope discrimination in C4 leaves. Closing the main gaps in our understanding of carbon isotope discrimination during C4 photosynthesis may help advance research aimed at developing higher productivity and efficiency in key C4 food, feed, and biofuel crops.

  14. Soil organic carbon assessments in cropping systems using isotopic techniques

    Science.gov (United States)

    Martín De Dios Herrero, Juan; Cruz Colazo, Juan; Guzman, María Laura; Saenz, Claudio; Sager, Ricardo; Sakadevan, Karuppan

    2016-04-01

    Introduction of improved farming practices are important to address the challenges of agricultural production, food security, climate change and resource use efficiency. The integration of livestock with crops provides many benefits including: (1) resource conservation, (2) ecosystem services, (3) soil quality improvements, and (4) risk reduction through diversification of enterprises. Integrated crop livestock systems (ICLS) with the combination of no-tillage and pastures are useful practices to enhance soil organic carbon (SOC) compared with continuous cropping systems (CCS). In this study, the SOC and its fractions in two cropping systems namely (1) ICLS, and (2) CCS were evaluated in Southern Santa Fe Province in Argentina, and the use of delta carbon-13 technique and soil physical fractionation were evaluated to identify sources of SOC in these systems. Two farms inside the same soil cartographic unit and landscape position in the region were compared. The ICLS farm produces lucerne (Medicago sativa Merrill) and oat (Avena sativa L.) grazed by cattle alternatively with grain summer crops sequence of soybean (Glicine max L.) and corn (Zea mays L.), and the farm under continuous cropping system (CCS) produces soybean and corn in a continuous sequence. The soil in the area is predominantly a Typic Hapludoll. Soil samples from 0-5 and 0-20 cm depths (n=4) after the harvest of grain crops were collected in each system and analyzed for total organic carbon (SOC, 0-2000 μm), particulate organic carbon (POC, 50-100 μm) and mineral organic carbon (MOC, <50 μm). Delta carbon-13 was determined by isotopic ratio mass spectrometry. In addition, a site with natural vegetation (reference site, REF) was also sampled for delta carbon-13 determination. ANOVA and Tukey statistical analysis were carried out for all data. The SOC was higher in ICLS than in CCS at both depths (20.8 vs 17.7 g kg-1 for 0-5 cm and 16.1 vs 12.7 g kg-1 at 0-20 cm, respectively, P<0.05). MOC was

  15. Tree ring carbon isotopes record predisposition to drought-induced mortality and survival.

    Science.gov (United States)

    McDowell, N.; Allen, C.; Levanič, T.; Marshall, L.

    2009-04-01

    Drought-induced tree mortality is predicted to increase in intensity and frequency in mid-latitude regions over the next 50 years. We report on tree ring records of growth and carbon isotope discrimination in a variety of species from N. America and Europe that demonstrate a consistent pattern of predisposition to mortality during drought. Trees that die show greater sensitivity of growth to climate as has been previously demonstrated. Trees that die; however, have consistently lower discrimination and significantly less sensitivity of discrimination to climate than trees that survive. A simple hydraulic model based on Darcy's law successfully recreated the observed patterns of discrimination, and supports the interpretation that trees that die have consistently lower leaf-level stomatal conductance than trees that survive. Furthermore, the model supports the conclusion that these trees are less responsive to inter-annual climate variation due to chronic water stress. It appears that such chronic water stress predisposes trees to mortality. Consideration of the sensitivity of these isotope records to mesophyll conductance, photosynthetic capacity, photorespiration, and carbon recyling is critical to robust conclusions. Continued intensification of drought in mid-latitude regions may force trees undergoing chronic water stress to undergo increased mortality, resulting in ecotone shifts and regional mortality events in temperate forests.

  16. Evidence from carbon isotope measurements for diverse origins of sedimentary hydrocarbons

    Science.gov (United States)

    Freeman, K. H.; Hayes, J. M.; Trendel, J. M.; Albrecht, P.

    1990-01-01

    The organic matter found in sedimentary rocks must derive from many sources; not only from ancient primary producers but also from consumers and secondary producers. In all of these organisms, isotope effects can affect the abundance and distribution of 13C in metabolites. Here, by using an improved form of a previously described technique in which the effluent of a gas chromatograph is continuously analysed isotopically, we report evidence of the diverse origins of sedimentary organic matter. The record of 13C abundances in sedimentary carbonate and total organic carbon can be interpreted in terms of variations in the global carbon cycle. Our results demonstrate, however, that isotope variations within sedimentary organic mixtures substantially exceed those observed between samples of total organic carbon. Resolution of isotope variations at the molecular level offers a new and convenient means of refining views both of localized palaeoenvironments and of control mechanisms within the global carbon cycle.

  17. Isotopic composition of Murchison organic compounds: Intramolecular carbon isotope fractionation of acetic acid. Simulation studies of cosmochemical organic syntheses

    Science.gov (United States)

    Yuen, G. U.; Cronin, J. R.; Blair, N. E.; Desmarais, D. J.; Chang, S.

    1991-01-01

    Recently, in our laboratories, samples of Murchison acetic acid were decarboxylated successfully and the carbon isotopic composition was measured for the methane released by this procedure. These analyses showed significant differences in C-13/C-12 ratios for the methyl and carboxyl carbons of the acetic acid molecule, strongly suggesting that more than one carbon source may be involved in the synthesis of the Murchison organic compounds. On the basis of this finding, laboratory model systems simulating cosmochemical synthesis are being studied, especially those processes capable of involving two or more starting carbon sources.

  18. Carbon allocation and carbon isotope fluxes in the plant-soil-atmosphere continuum: a review

    Directory of Open Access Journals (Sweden)

    N. Brüggemann

    2011-04-01

    Full Text Available The terrestrial carbon (C cycle has received increasing interest over the past few decades, however, there is still a lack of understanding of the fate of newly assimilated C allocated within plants and to the soil, stored within ecosystems and lost to the atmosphere. Stable carbon isotope studies can give novel insights into these issues. In this review we provide an overview of an emerging picture of plant-soil-atmosphere C fluxes, as based on C isotope studies, and identify processes determining related C isotope signatures. The first part of the review focuses on isotopic fractionation processes within plants during and after photosynthesis. The second major part elaborates on plant-internal and plant-rhizosphere C allocation patterns at different time scales (diel, seasonal, interannual, including the speed of C transfer and time lags in the coupling of assimilation and respiration, as well as the magnitude and controls of plant-soil C allocation and respiratory fluxes. Plant responses to changing environmental conditions, the functional relationship between the physiological and phenological status of plants and C transfer, and interactions between C, water and nutrient dynamics are discussed. The role of the C counterflow from the rhizosphere to the aboveground parts of the plants, e.g. via CO2 dissolved in the xylem water or as xylem-transported sugars, is highlighted. The third part is centered around belowground C turnover, focusing especially on above- and belowground litter inputs, soil organic matter formation and turnover, production and loss of dissolved organic C, soil respiration and CO2 fixation by soil microbes. Furthermore, plant controls on microbial communities and activity via exudates and litter production as well as microbial community effects on C mineralization are reviewed. The last part of the paper is dedicated to physical interactions between soil CO2 and the soil matrix, such as CO

  19. Distribution and fractionation mechanism of stable carbon isotope of coalbed methane

    Institute of Scientific and Technical Information of China (English)

    QIN Shengfei; TANG Xiuyi; SONG Yan; WANG Hongyan

    2006-01-01

    The stable carbon isotope values of coalbed methane range widely,and also are generally lighter than that of gases in normal coal-formed gas fields with similar coal rank.There exists strong carbon isotope fractionation in coalbed methane and it makes the carbon isotope value lighter.The correlation between the carbon isotope value and Ro in coalbed methane is less obvious.The coaly source rock maturity cannot be judged by coalbed methane carbon isotope value.The carbon isotopes of coalbed methane become lighter in much different degree due to the hydrodynamics.The stronger the hydrodynamics is,the lighter the CBM carbon isotopic value becomes.Many previous investigations indicated that the desorption-diffusion effects make the carbon isotope value of coalbed methane lighter.However,the explanation has encountered many problems.The authors of this article suggest that the flowing groundwater dissolution to free methane in coal seams and the free methane exchange with absorbed one is the carbon isotope fractionation mechanism in coalbed methane.The flowing groundwater in coal can easily take more 13CH4 away from free gas and comparatively leave more 12CH4.This will make 12CH4 density in free gas comparatively higher than that in absorbed gas.The remaining 12CH4 in free gas then exchanges with the adsorbed methane in coal matrix.Some absorbed 13CH4 can be replaced and become free gas.Some free 12CH4 can be absorbed again into coal matrix and become absorbed gas.Part of the newly replaced 13CH4 in free gas will also be taken away by water,leaving preferentially more 12CH4.The remaining 12CH4 in free gas will exchange again with adsorbed methane in the coal matrix.These processes occur all the time.Through accumulative effect,the 12CH4 will be greatly concentrated in coal.Thus,the stable carbon isotope of coalbed methane becomes dramatically lighter.Through simulation experiment on water-dissolved methane,it had been proved that the flowing water could fractionate the

  20. Equations for lipid normalization of carbon stable isotope ratios in aquatic bird eggs.

    Directory of Open Access Journals (Sweden)

    Kyle H Elliott

    Full Text Available Stable isotope ratios are biogeochemical tracers that can be used to determine the source of nutrients and contaminants in avian eggs. However, the interpretation of stable carbon ratios in lipid-rich eggs is complicated because (13C is depleted in lipids. Variation in (13C abundance can therefore be obscured by variation in percent lipids. Past attempts to establish an algebraic equation to correct carbon isotope ratios for lipid content in eggs have been unsuccessful, possibly because they relied partly on data from coastal or migratory species that may obtain egg lipids from different habitats than egg protein. We measured carbon, nitrogen and sulphur stable isotope ratios in 175 eggs from eight species of aquatic birds. Carbon, nitrogen and sulphur isotopes were enriched in lipid-extracted egg samples compared with non extracted egg samples. A logarithmic equation using the C∶N ratio and carbon isotope ratio from the non extracted egg tissue calculated 90% of the lipid-extracted carbon isotope ratios within ±0.5‰. Calculating separate equations for eggs laid by species in different habitats (pelagic, offshore and terrestrial-influenced improved the fit. A logarithmic equation, rather than a linear equation as often used for muscle, was necessary to accurately correct for lipid content because the relatively high lipid content of eggs compared with muscle meant that a linear relationship did not accurately approximate the relationship between percent lipids and the C∶N ratio. Because lipid extraction alters sulphur and nitrogen isotope ratios (and cannot be corrected algebraically, we suggest that isotopic measurement on bulk tissue followed by algebraic lipid normalization of carbon stable isotope ratio is often a good solution for homogenated eggs, at least when it is not possible to complete separate chemical analyses for each isotope.

  1. Small mammal tooth enamel carbon isotope record of C4 grasses in late Neogene China

    Science.gov (United States)

    Arppe, Laura; Kaakinen, Anu; Passey, Benjamin H.; Zhang, Zhaoqun; Fortelius, Mikael

    2015-10-01

    The spatiotemporal pattern of the late Cenozoic spread of C4 vegetation is an important indicator of environmental change that is intertwined with the uplift of the Himalaya and Tibetan Plateau, and the development of the East Asian monsoons. To explore the spread of C4 vegetation in China and shed new light on regional climatic evolution, we measured δ13C values of more than 200 small mammal teeth (primarily rodents and lagomorphs) using a laser ablation isotope ratio mass spectrometry approach. Small mammals are highly sensitive indicators of their environment because they have limited spatial ranges and because they have minimal time-averaging of carbon isotope signatures of dietary components. The specimens originate from four classic Late Miocene fossil localities, Lufeng, Yuanmou, Lingtai, and Ertemte, along a southwest-northeast transect from Yunnan Province to Inner Mongolia. In Yunnan (Lufeng, Yuanmou) and on the Loess Plateau (Lingtai), the small mammal δ13C values record nearly pure C3 ecosystems, and mixed but C3-based ecosystems, respectively, in agreement with previous studies based on carbon isotopes of large herbivores and soil carbonates. In Inner Mongolia, the micromammalian tooth enamel δ13C record picks up the presence of C4 vegetation where large mammal samples do not, indicating a mixed yet C3-dominated ecosystem at ~ 6 Ma. As a whole, the results support a scenario of northward increasing C4 grass abundance in a pattern that mirrors northward decreasing precipitation of the summer monsoon system. The results highlight differences between large and small mammals as indicators of C4 vegetation in ancient ecosystems, particularly the ability of small mammal δ13C values to detect the presence of minor components of the vegetation structure.

  2. Environmental forcing of terrestrial carbon isotope excursion amplification across five Eocene hyperthermals

    Science.gov (United States)

    Bowen, G. J.; Abels, H.

    2015-12-01

    Abrupt changes in the isotope composition of exogenic carbon pools accompany many major episodes of global change in the geologic record. The global expression of this change in substrates that reflect multiple carbon pools provides important evidence that many events reflect persistent, global redistribution of carbon between reduced and oxidized stocks. As the diversity of records documenting any event grows, however, discrepancies in the expression of carbon isotope change among substrates are almost always revealed. These differences in magnitude, pace, and pattern of change can complicate interpretations of global carbon redistribution, but under ideal circumstances can also provide additional information on changes in specific environmental and biogeochemical systems that accompanied the global events. Here we evaluate possible environmental influences on new terrestrial records of the negative carbon isotope excursions (CIEs) associated with multiple hyperthermals of the Early Eocene, which show a common pattern of amplified carbon isotope change in terrestrial paleosol carbonate records relative to that recorded in marine substrates. Scaling relationships between climate and carbon-cycle proxies suggest that that the climatic (temperature) impact of each event scaled proportionally with the magnitude of its marine CIE, likely implying that all events involved release of reduced carbon with a similar isotopic composition. Amplification of the terrestrial CIEs, however, does not scale with event magnitude, being proportionally less for the first, largest event (the PETM). We conduct a sensitivity test of a coupled plant-soil carbon isotope model to identify conditions that could account for the observed CIE scaling. At least two possibilities consistent with independent lines of evidence emerge: first, varying effects of pCO2 change on photosynthetic carbon isotope discrimination under changing background pCO2, and second, contrasting changes in regional

  3. Mesozoic black shales, source mixing and carbon isotopes

    Science.gov (United States)

    Suan, Guillaume

    2016-04-01

    Over the last decades, considerable attention has been devoted to the paleoenvironmental and biogeochemical significance of Mesozoic black shales. Black shale-bearing successions indeed often display marked changes in the organic carbon isotope composition (δ13Corg), which have been commonly interpreted as evidence for dramatic perturbations of global carbon budgets and CO2 levels. Arguably the majority of these studies have discarded some more "local" explanations when interpreting δ13Corg profiles, most often because comparable profiles occur on geographically large and distant areas. Based on newly acquired data and selected examples from the literature, I will show that the changing contribution of organic components with distinct δ13C signatures exerts a major but overlooked influence of Mesozoic δ13Corg profiles. Such a bias occurs across a wide spectrum of sedimentological settings and ages, as shown by the good correlation between δ13Corg values and proxies of kerogen proportions (such as rock-eval, biomarker, palynofacies and palynological data) recorded in Mesozoic marginal to deep marine successions of Triassic, Jurassic and Cretaceous age. In most of these successions, labile, 12C-enriched amorphous organic matter of marine origin dominates strata deposited under anoxic conditions, while oxidation-resistant, 13C-rich terrestrial particles dominate strata deposited under well-oxygenated conditions. This influence is further illustrated by weathering profiles of Toarcian (Lower Jurassic) black shales from France, where weathered areas dominated by refractory organic matter show dramatic 13C-enrichment (and decreased total organic carbon and pyrite contents) compared to non-weathered portions of the same horizon. The implications of these results for chemostratigraphic correlations and pCO2 reconstructions of Mesozoic will be discussed, as well as strategies to overcome this major bias.

  4. Carbon turnover in tissues of a passerine bird: allometry, isotopic clocks, and phenotypic flexibility in organ size.

    Science.gov (United States)

    Bauchinger, Ulf; McWilliams, Scott

    2009-01-01

    Stable isotopes are an important tool for physiological and behavioral ecologists, although their usefulness depends on a thorough understanding of the dynamics of isotope incorporation into tissue(s) over time. In contrast to hair, claws, and feathers, most animal tissues continuously incorporate carbon (and other elements), and so carbon isotope values may change over time, depending on resource use and tissue-specific metabolic rates. Here we report the carbon turnover rate for 12 tissues from a passerine bird, the zebra finch (Taeniopygia guttata). We measured average carbon retention time (tau) for 8 d for small intestine; 10-13 d for gizzard, kidney, liver, pancreas, and proventriculus; 17-21 d for heart, brain, blood, and flight muscle; and 26-28 d for leg muscle and skin. We used these data, along with the few other published estimates, to confirm that the fractional rate of isotopic turnover for red blood cells, whole blood, liver, and leg muscle scales with body mass to approximately the -1/4 power. Our data also support several key assumptions of the "isotopic-clock" model, which uses differences in isotope value between tissues, along with estimates of turnover rate of these tissues, to predict time elapsed since a diet shift. Finally, we show that between-tissues differences in turnover rate largely, but not entirely, explain the extent of phenotypic flexibility in organs of garden warblers during their long-distance flight across the Sahara Desert during spring. More studies that measure tissue-specific protein synthesis, metabolic rate, and elemental turnover in many tissues from a variety of animals are needed.

  5. Stable carbon isotopes in tree rings: the failure of uniformitarianism

    Science.gov (United States)

    McCarroll, Danny

    2010-05-01

    When tree rings are used to reconstruct past climate we rely on the uniformitarian principle that ‘the present is the key to the past'. Relationships between measured parameters and climate that can be calibrated and verified over the instrumental period are assumed to be applicable at longer timescales. In the case of δ13C, however, the uniformitarian principle fails for two reasons. (1) The instrumental calibration period is also the period of anthropogenic increase in atmospheric CO2. δ13C is a function of the ratio of internal to ambient CO2, so maintaining constant δ13C over the industrial period requires an active plastic response, either restricting stomatal conductance or increasing assimilation rate. In some areas trees may have reached the limits of their plasticity so that over the last few decades δ13C values have been declining, independent of any changes in climate. If no correction is made, the recent response to climate will be a poor indicator of behaviour in the past. (2) Tree ring δ13C is often used to reconstruct past temperatures even though temperature rarely has a strong direct control over fractionation. The link is therefore via either sunshine or humidity, which over the calibration period may be very strongly correlated with temperature. Long isotope chronologies, when compared with independent evidence of past temperatures, however, can show periods of marked divergence. The strong covariance of temperature, sunshine and humidity over the last century may not have persisted over longer timescales with larger climatic perturbations. In the case of carbon isotopes the key to the past is not statistical inference based on recent behaviour, but a clear mechanistic understanding of the influence of climate and other factors on fractionation.

  6. Carbon allocation and carbon isotope fluxes in the plant-soil-atmosphere continuum: a review

    Directory of Open Access Journals (Sweden)

    N. Brüggemann

    2011-11-01

    Full Text Available The terrestrial carbon (C cycle has received increasing interest over the past few decades, however, there is still a lack of understanding of the fate of newly assimilated C allocated within plants and to the soil, stored within ecosystems and lost to the atmosphere. Stable carbon isotope studies can give novel insights into these issues. In this review we provide an overview of an emerging picture of plant-soil-atmosphere C fluxes, as based on C isotope studies, and identify processes determining related C isotope signatures. The first part of the review focuses on isotopic fractionation processes within plants during and after photosynthesis. The second major part elaborates on plant-internal and plant-rhizosphere C allocation patterns at different time scales (diel, seasonal, interannual, including the speed of C transfer and time lags in the coupling of assimilation and respiration, as well as the magnitude and controls of plant-soil C allocation and respiratory fluxes. Plant responses to changing environmental conditions, the functional relationship between the physiological and phenological status of plants and C transfer, and interactions between C, water and nutrient dynamics are discussed. The role of the C counterflow from the rhizosphere to the aboveground parts of the plants, e.g. via CO2 dissolved in the xylem water or as xylem-transported sugars, is highlighted. The third part is centered around belowground C turnover, focusing especially on above- and belowground litter inputs, soil organic matter formation and turnover, production and loss of dissolved organic C, soil respiration and CO2 fixation by soil microbes. Furthermore, plant controls on microbial communities and activity via exudates and litter production as well as microbial community effects on C mineralization are reviewed. A further part of the paper is dedicated to physical interactions between soil CO2 and the soil matrix, such as

  7. A Test of Carbon and Oxygen Stable Isotope Ratio Process Models in Tree Rings.

    Science.gov (United States)

    Roden, J. S.; Farquhar, G. D.

    2008-12-01

    Stable isotopes ratios of carbon and oxygen in tree ring cellulose have been used to infer environmental change. Process-based models have been developed to clarify the potential of historic tree ring records for meaningful paleoclimatic reconstructions. However, isotopic variation can be influenced by multiple environmental factors making simplistic interpretations problematic. Recently, the dual isotope approach, where the variation in one stable isotope ratio (e.g. oxygen) is used to constrain the interpretation of variation in another (e.g. carbon), has been shown to have the potential to de-convolute isotopic analysis. However, this approach requires further testing to determine its applicability for paleo-reconstructions using tree-ring time series. We present a study where the information needed to parameterize mechanistic models for both carbon and oxygen stable isotope ratios were collected in controlled environment chambers for two species (Pinus radiata and Eucalyptus globulus). The seedlings were exposed to treatments designed to modify leaf temperature, transpiration rates, stomatal conductance and photosynthetic capacity. Both species were grown for over 100 days under two humidity regimes that differed by 20%. Stomatal conductance was significantly different between species and for seedlings under drought conditions but not between other treatments or humidity regimes. The treatments produced large differences in transpiration rate and photosynthesis. Treatments that effected photosynthetic rates but not stomatal conductance influenced carbon isotope discrimination more than those that influenced primarily conductance. The various treatments produced a range in oxygen isotope ratios of 7 ‰. Process models predicted greater oxygen isotope enrichment in tree ring cellulose than observed. The oxygen isotope ratios of bulk leaf water were reasonably well predicted by current steady-state models. However, the fractional difference between models that

  8. Combination of carbon isotope ratio with hydrogen isotope ratio determinations in sports drug testing.

    Science.gov (United States)

    Piper, Thomas; Emery, Caroline; Thomas, Andreas; Saugy, Martial; Thevis, Mario

    2013-06-01

    Carbon isotope ratio (CIR) analysis has been routinely and successfully applied to doping control analysis for many years to uncover the misuse of endogenous steroids such as testosterone. Over the years, several challenges and limitations of this approach became apparent, e.g., the influence of inadequate chromatographic separation on CIR values or the emergence of steroid preparations comprising identical CIRs as endogenous steroids. While the latter has been addressed recently by the implementation of hydrogen isotope ratios (HIR), an improved sample preparation for CIR avoiding co-eluting compounds is presented herein together with newly established reference values of those endogenous steroids being relevant for doping controls. From the fraction of glucuronidated steroids 5β-pregnane-3α,20α-diol, 5α-androst-16-en-3α-ol, 3α-Hydroxy-5β-androstane-11,17-dione, 3α-hydroxy-5α-androstan-17-one (ANDRO), 3α-hydroxy-5β-androstan-17-one (ETIO), 3β-hydroxy-androst-5-en-17-one (DHEA), 5α- and 5β-androstane-3α,17β-diol (5aDIOL and 5bDIOL), 17β-hydroxy-androst-4-en-3-one and 17α-hydroxy-androst-4-en-3-one were included. In addition, sulfate conjugates of ANDRO, ETIO, DHEA, 3β-hydroxy-5α-androstan-17-one plus 17α- and androst-5-ene-3β,17β-diol were considered and analyzed after acidic solvolysis. The results obtained for the reference population encompassing n = 67 males and females confirmed earlier findings regarding factors influencing endogenous CIR. Variations in sample preparation influenced CIR measurements especially for 5aDIOL and 5bDIOL, the most valuable steroidal analytes for the detection of testosterone misuse. Earlier investigations on the HIR of the same reference population enabled the evaluation of combined measurements of CIR and HIR and its usefulness regarding both steroid metabolism studies and doping control analysis. The combination of both stable isotopes would allow for lower reference limits providing the same statistical

  9. Sensitivity analysis and quantification of uncertainty for isotopic mixing relationships in carbon cycle research

    Science.gov (United States)

    Zobitz, J. M.; Keener, J. P.; Bowling, D. R.

    2004-12-01

    Quantifying and understanding the uncertainty in isotopic mixing relationships is critical to isotopic applications in carbon cycle studies at all spatial and temporal scales. Studies associated with the North American Carbon Program will depend on stable isotope approaches and quantification of isotopic uncertainty. An important application of isotopic mixing relationships is determination of the isotopic content of large-scale respiration (δ 13CR) via an inverse relationship (a Keeling plot) between atmospheric CO2 concentrations ([CO2]) and carbon isotope ratios of CO2 (δ 13C). Alternatively, a linear relationship between [CO2] and the product of [CO2] and δ 13C (a Miller/Tans plot) can also be applied. We used an extensive dataset from the Niwot Ridge Ameriflux Site of [CO2] and δ 13C in forest air to examine contrasting approaches to determine δ 13CR and its uncertainty. These included Keeling plots, Miller/Tans plots, Model I, and Model II regressions Our analysis confirms previous observations that increasing the range of measurements ([CO2] range) reduces the uncertainty associated with δ 13CR. For carbon isotope studies, uncertainty in the isotopic measurements has a greater effect on the uncertainty of δ 13CR than the uncertainty in [CO2]. Reducing the uncertainty of isotopic measurements reduces the uncertainty of δ 13CR even when the [CO2] range of samples is small (13CR. We also find for carbon isotope studies no inherent advantage to using either a Keeling or a Miller/Tans approach to determine δ 13CR.

  10. Carbon and Sulfur Isotopic Signatures of Ancient Life and Environment at the Microbial Scale: Neoarchean Shales and Carbonates

    Science.gov (United States)

    Williford, K. H.; Ushikubo, T.; Lepot, K.; Kitajima, K.; Hallmann, C.; Spicuzza, M. J.; Kozdon, R.; Eigenbrode, J. L.; Summons, R. E.; Valley, J. W.

    2015-01-01

    An approach to coordinated, spatially resolved, in situ carbon isotope analysis of organic matter and carbonate minerals, and sulfur three- and four-isotope analysis of pyrite with an unprecedented combination of spatial resolution, precision, and accuracy is described. Organic matter and pyrite from eleven rock samples of Neoarchean drill core express nearly the entire range of delta(sup 13)C, delta(sup 34)S, Delta(sup 33)S, and Delta(sup 36)S known from the geologic record, commonly in correlation with morphology, mineralogy, and elemental composition. A new analytical approach (including a set of organic calibration standards) to account for a strong correlation between H/C and instrumental bias in SIMS delta(sup 13)C measurement of organic matter is identified. Small (2-3 microns) organic domains in carbonate matrices are analyzed with sub-permil accuracy and precision. Separate 20- to 50-micron domains of kerogen in a single approx. 0.5 cu cm sample of the approx. 2.7 Ga Tumbiana Formation have delta(sup 13)C = -52.3 +/- 0.1per mille and -34.4 +/- 0.1per mille, likely preserving distinct signatures of methanotrophy and photoautotrophy. Pyrobitumen in the approx. 2.6 Ga Jeerinah Formation and the approx. 2.5 Ga Mount McRae Shale is systematically 13C-enriched relative to co-occurring kerogen, and associations with uraniferous mineral grains suggest radiolytic alteration. A large range in sulfur isotopic compositions (including higher Delta(sup 33)S and more extreme spatial gradients in Delta(sup 33)S and Delta(sup 36)S than any previously reported) are observed in correlation with morphology and associated mineralogy. Changing systematics of delta(sup 34)S, Delta(sup 33)S, and Delta(sup 36)S, previously investigated at the millimeter to centimeter scale using bulk analysis, are shown to occur at the micrometer scale of individual pyrite grains. These results support the emerging view that the dampened signature of mass-independent sulfur isotope fractionation

  11. Carbon and sulfur isotopic signatures of ancient life and environment at the microbial scale: Neoarchean shales and carbonates.

    Science.gov (United States)

    Williford, K H; Ushikubo, T; Lepot, K; Kitajima, K; Hallmann, C; Spicuzza, M J; Kozdon, R; Eigenbrode, J L; Summons, R E; Valley, J W

    2016-03-01

    An approach to coordinated, spatially resolved, in situ carbon isotope analysis of organic matter and carbonate minerals, and sulfur three- and four-isotope analysis of pyrite with an unprecedented combination of spatial resolution, precision, and accuracy is described. Organic matter and pyrite from eleven rock samples of Neoarchean drill core express nearly the entire range of δ(13) C, δ(34) S, Δ(33) S, and Δ(36) S known from the geologic record, commonly in correlation with morphology, mineralogy, and elemental composition. A new analytical approach (including a set of organic calibration standards) to account for a strong correlation between H/C and instrumental bias in SIMS δ(13) C measurement of organic matter is identified. Small (2-3 μm) organic domains in carbonate matrices are analyzed with sub-permil accuracy and precision. Separate 20- to 50-μm domains of kerogen in a single ~0.5 cm(3) sample of the ~2.7 Ga Tumbiana Formation have δ(13) C = -52.3 ± 0.1‰ and -34.4 ± 0.1‰, likely preserving distinct signatures of methanotrophy and photoautotrophy. Pyrobitumen in the ~2.6 Ga Jeerinah Formation and the ~2.5 Ga Mount McRae Shale is systematically (13) C-enriched relative to co-occurring kerogen, and associations with uraniferous mineral grains suggest radiolytic alteration. A large range in sulfur isotopic compositions (including higher Δ(33) S and more extreme spatial gradients in Δ(33) S and Δ(36) S than any previously reported) are observed in correlation with morphology and associated mineralogy. Changing systematics of δ(34) S, Δ(33) S, and Δ(36) S, previously investigated at the millimeter to centimeter scale using bulk analysis, are shown to occur at the micrometer scale of individual pyrite grains. These results support the emerging view that the dampened signature of mass-independent sulfur isotope fractionation (S-MIF) associated with the Mesoarchean continued into the early Neoarchean, and that the connections

  12. Mechanistic studies of sesquiterpene cyclases based on their carbon isotope ratios at natural abundance.

    Science.gov (United States)

    Tan, Wenhua; Bartram, Stefan; Boland, Wilhelm

    2017-01-03

    During the process of terpene biosynthesis, C-C bond breaking and forming steps are subjected to kinetic carbon isotope effects, leading to distinct carbon isotopic signatures of the products. Accordingly, carbon isotopic signatures could be used to reveal the 'biosynthetic history' of the produced terpenoids. Five known sesquiterpene cyclases, regulating three different pathways, representing simple to complex biosynthetic sequences, were heterologously expressed and used for in vitro assays with farnesyl diphosphate as substrate. Compound specific isotope ratio mass spectrometry measurements of the enzyme substrate farnesyl diphosphate (FDP) and the products of all the five cyclases were performed. The calculated δ(13) C value for FDP, based on δ(13) C values and relative amounts of the products, was identical with its measured δ(13) C value, confirming the reliability of the approach and the precision of measurements. The different carbon isotope ratios of the products reflect the complexity of their structure and are correlated with the frequency of carbon-carbon bond forming and breaking steps on their individual biosynthetic pathways. Thus, the analysis of carbon isotopic signatures of terpenes at natural abundance can be used as a powerful tool in elucidation of associated biosynthetic mechanisms of terpene synthases and in future in vivo studies even without 'touching' the plant. © 2017 John Wiley & Sons Ltd.

  13. Is my C isotope excursion global, local, or both? Insights from the Mg and Ca isotopic composition of primary, diagenetic, and authigenic carbonates

    Science.gov (United States)

    Higgins, J. A.; Blättler, C. L.; Husson, J. M.

    2014-12-01

    The C isotopic composition of ancient limestones and dolomites is a widely used proxy for the global geochemical cycles of carbon and oxygen in the ocean-atmosphere system and a critical tool for chemostratigraphy in Precambrian rocks. Although relatively robust to diagenesis, the C isotopic composition of bulk carbonates can be reset when conditions favor high water-to-rock ratios or fluids with high C concentrations and distinct isotopic compositions. Authigenic carbonates and different pools of primary carbonate (e.g. calcite vs. aragonite) may also bias the C isotopic composition of bulk carbonates if they are both abundant and isotopically distinct. New approaches to quantifying contributions from diagenesis, authigenesis, and mixing of primary carbonates to the C isotopic composition of bulk sedimentary carbonates are needed. Here we present preliminary Mg and Ca isotope data sets of primary, diagenetic, and authigenic carbonates, both modern and ancient. We show that recrystallization, dolomitization, and authigenesis produce Mg and Ca isotope fingerprints that may be used to identify and characterize these processes in ancient carbonate sediments.

  14. Carbon isotope stratigraphy of an ancient (Ordovician) Bahamian-type carbonate platform: Implications for preservation of global seawater trends

    Science.gov (United States)

    Saltzman, M.; Leslie, S. A.; Edwards, C. T.; Diamond, C. W.; Trigg, C. R.; Sedlacek, A. R.

    2013-12-01

    Carbon isotope stratigraphy has a unique role in the interpretation of Earth history as one of the few geochemical proxies that have been widely applied throughout the geologic time scale, from the Precambrian to the Recent, as both a global correlation tool and proxy for the carbon cycle. However, in addition to consideration of the role of diagenesis, numerous studies have raised awareness of the fact that C-isotope trends derived from ancient carbonate platforms may not be representative of dissolved inorganic carbon from a well-mixed global ocean reservoir. Furthermore, the larger carbon isotopic fractionation in the formation of aragonite versus calcite from seawater must be taken into account. All three of these variables (diagenesis, water mass residence time, % aragonite) may change in response to sea level, producing trends in C-isotopes on ancient carbonate platforms that are unrelated to the global carbon cycle. Global carbon cycle fluxes may also have a cause-effect relationship with sea level changes, further complicating interpretations of stratigraphic trends in carbon isotopes from ancient platform environments. Studies of C-isotopes in modern carbonate platform settings such as the Great Bahama Bank (GBB) provide important analogues in addressing whether or not ancient platforms are likely to preserve a record of carbon cycling in the global ocean. Swart et al. (2009) found that waters of the GBB had generally the same or elevated values (ranging from +0.5‰ to +2.5‰) compared to the global oceans, interpreted as reflecting differential photosynthetic fractionation and precipitation of calcium carbonate (which lowers pH and converts bicarbonate into 12-C enriched carbon dioxide, leaving residual bicarbonate heavier). Carbonate sediments of the GBB have elevated C-isotopes, not only because of the high C-isotope composition of the overlying waters, but also due to the greater fractionation associated with precipitation of aragonite versus calcite

  15. Do stable carbon isotopes of brown coal woods record changes in Lower Miocene palaeoecology?

    NARCIS (Netherlands)

    Poole, I.J.; Dolezych, M.; Kool, J.; Burgh, J. van der; Bergen, P.F. van

    2006-01-01

    Stable carbon isotope ratios of fossil wood from the Miocene brown coal deposits in former East Germany are compared with palaeobotanical and sedimentological data to test the use of stable isotopes in determining palaeoenvironment. Significant differences in the chemical composition of samples from

  16. Carbon Isotope Tracking of the Fluvial Carbon Cycles in two Southeast Asian Watersheds

    Science.gov (United States)

    Lee, K.; Ishak, M.; Veizer, J.; Clark, I. D.

    2012-12-01

    Two rivers in Peninsular Malaysia, Langat and Kelantan, were sampled for dissolved organic and inorganic carbon (DOC/DIC) concentrations and stable carbon isotope data over the course of 20 months. Water samples were taken twice a month from three points along each river and from local groundwater reservoirs from May 2011 to December 2012. These were later analyzed for DIC/DOC concentration and d13C values. The data suggests that DOC and DIC in both basins are sourced primarily from biologically-respired carbon from a C3-vegetation dominated environment, with carbonate rock providing an additional input. Riverine PCO2 in Langat River, estimated from the DIC data, revealed over-pressurization of riverine CO2 relative to atmospheric levels during most periods of sampling, in some cases approaching 30 times that of the averaged global value of ~380 ppm. The Langat River degases CO2 during much of the year, and further calculations showed that the average annual efflux in the upstream sub-catchment of this river (~20 x 10^3 t C/yr) is comparable to the fluvial export of dissolved carbon (~12 x 10^3 t C/yr) and particulate organic carbon (~7 x 10^3 t C/yr), estimated from total suspended solid (TSS) and river flow data from the literature. However, the combined gas efflux and fluvial export of dissolved carbon only amount to roughly 6 % of total ecosystem uptake of CO2 within the sub-catchment (~600-700 x 10^3 t C/yr). The remainder of this carbon is mostly respired back into the atmosphere, although a minor portion may be stored within the watershed. These findings confirm the more complex role of rivers in the global carbon cycle, beyond that of a simple link between terrestrial and oceanic reservoirs.

  17. Non-destructive measurement of carbonic anhydrase activity and the oxygen isotope composition of soil water

    Science.gov (United States)

    Jones, Sam; Sauze, Joana; Ogée, Jérôme; Wohl, Steven; Bosc, Alexandre; Wingate, Lisa

    2016-04-01

    Carbonic anhydrases are a group of metalloenzymes that catalyse the hydration of aqueous carbon dioxide (CO2). The expression of carbonic anhydrase by bacteria, archaea and eukarya has been linked to a variety of important biological processes including pH regulation, substrate supply and biomineralisation. As oxygen isotopes are exchanged between CO2 and water during hydration, the presence of carbonic anhydrase in plants and soil organisms also influences the oxygen isotope budget of atmospheric CO2. Leaf and soil water pools have distinct oxygen isotope compositions, owing to differences in pool sizes and evaporation rates, which are imparted on CO2during hydration. These differences in the isotopic signature of CO2 interacting with leaves and soil can be used to partition the contribution of photosynthesis and soil respiration to net terrestrial CO2 exchange. However, this relies on our knowledge of soil carbonic anhydrase activity and currently, the prevalence and function of these enzymes in soils is poorly understood. Isotopic approaches used to estimate soil carbonic anhydrase activity typically involve the inversion of models describing the oxygen isotope composition of CO2 fluxes to solve for the apparent, potentially catalysed, rate of oxygen exchange during hydration. This requires information about the composition of CO2 in isotopic equilibrium with soil water obtained from destructive, depth-resolved soil water sampling. This can represent a significant challenge in data collection given the considerable potential for spatial and temporal variability in the isotopic composition of soil water and limited a priori information with respect to the appropriate sampling resolution and depth. We investigated whether we could circumvent this requirement by constraining carbonic anhydrase activity and the composition of soil water in isotopic equilibrium with CO2 by solving simultaneously the mass balance for two soil CO2 steady states differing only in the

  18. Progress and challenges in using stable isotopes to trace plant carbon and water relations across scales

    Directory of Open Access Journals (Sweden)

    C. Werner

    2012-08-01

    Full Text Available Stable isotope analysis is a powerful tool for assessing plant carbon and water relations and their impact on biogeochemical processes at different scales. Our process-based understanding of stable isotope signals, as well as technological developments, has progressed significantly, opening new frontiers in ecological and interdisciplinary research. This has promoted the broad utilisation of carbon, oxygen and hydrogen isotope applications to gain insight into plant carbon and water cycling and their interaction with the atmosphere and pedosphere. Here, we highlight specific areas of recent progress and new research challenges in plant carbon and water relations, using selected examples covering scales from the leaf to the regional scale. Further, we discuss strengths and limitations of recent technological developments and approaches and highlight new opportunities arising from unprecedented temporal and spatial resolution of stable isotope measurements.

  19. The evolution of Carbon isotopes in calcite in the presence of cyanobacteria

    Science.gov (United States)

    Grimm, Christian; Mavromatis, Vasileios; Pokrovsky, Oleg S.; Oelkers, Eric H.

    2016-04-01

    Stable isotopic compositions in carbonates are widely used as indicators of environmental conditions prevailing during mineral formation. This reconstruction is substantially based on the assumption that there is no change in the mineral composition over geological time. However, recent experimental studies have shown that carbon and magnesium isotopes in hydrous Mg-carbonates undergo continuous re-equilibration with the ambient solution even after mineral precipitation stopped ([1] and [2], respectively). To verify whether this holds true for anhydrous Ca-bearing carbonates which readily form at earth's surface environments, a series of batch system calcite precipitation experiments were performed in the presence of actively growing cyanobacteria Synechococcus sp. The bacteria were grown at ambient temperature in a BG11 culture medium (SIGMA C3061) and continuous stirring, air-bubbling and illumination. Calcite precipitation was initiated by the addition of 8.5mM CaCl2 and 0-50 mM NaHCO3 or NaHCO3-Na2CO3 mixtures. The presence of cyanobacteria is on one hand promoting CaCO3 formation due to increasing pH resulting from photosynthesis. On the other hand, actively growing cyanobacteria drastically change carbon isotope signature of the aqueous fluid phase by preferably incorporating the lighter 12C isotope into biomass [1]. This study explores the effect of continuously changing carbon isotope compositions in dissolved inorganic carbon (DIC) on precipitated calcite which is in chemical equilibrium with the ambient fluid phase. [1] Mavromatis et al. (2015). The continuous re-equilibration of carbon isotope compositions of hydrous Mg-carbonates in the presence of cyanobacteria. Chem. Geol. 404, 41-51 [2] Mavromatis et al. (2012). Magnesium isotope fractionation during hydrous magnesium carbonate precipitation with and without cyanobacteria. Geochim. Cosmochim. Acta 76, 161-174

  20. Carbon stable isotope analysis of cereal remains as a way to reconstruct water availability: preliminary results

    OpenAIRE

    Flohr, Pascal; Muldner, Gundula; Jenkins, Emma

    2011-01-01

    Reconstructing past water availability, both as rainfall and irrigation, is important to answer questions about the way society reacts to climate and its changes and the role of irrigation in the development of social complexity. Carbon stable isotope analysis of archaeobotanical remains is a potentially valuable method for reconstructing water availability. To further define the relationship between water availability and plant carbon isotope composition and to set up baseline values for the...

  1. Model-based estimation of the global carbon budget and its uncertainty from carbon dioxide and carbon isotope records

    Energy Technology Data Exchange (ETDEWEB)

    Kheshgi, Haroon S. [Corporate Research Laboratories, Exxon Research and Engineering Company, Annandale, New Jersey (United States); Jain, Atul K. [Department of Atmospheric Sciences, University of Illinois, Urbana (United States); Wuebbles, Donald J. [Department of Atmospheric Sciences, University of Illinois, Urbana (United States)

    1999-12-27

    A global carbon cycle model is used to reconstruct the carbon budget, balancing emissions from fossil fuel and land use with carbon uptake by the oceans, and the terrestrial biosphere. We apply Bayesian statistics to estimate uncertainty of carbon uptake by the oceans and the terrestrial biosphere based on carbon dioxide and carbon isotope records, and prior information on model parameter probability distributions. This results in a quantitative reconstruction of past carbon budget and its uncertainty derived from an explicit choice of model, data-based constraints, and prior distribution of parameters. Our estimated ocean sink for the 1980s is 17{+-}7 Gt C (90% confidence interval) and is comparable to the estimate of 20{+-}8 Gt C given in the recent Intergovernmental Panel on Climate Change assessment [Schimel et al., 1996]. Constraint choice is tested to determine which records have the most influence over estimates of the past carbon budget; records individually (e.g., bomb-radiocarbon inventory) have little effect since there are other records which form similar constraints. (c) 1999 American Geophysical Union.

  2. Decoupling of carbon isotope records between organic matter and carbonate prior to the Toarcian Oceanic Anoxic Event (Early Jurassic)

    Science.gov (United States)

    Bodin, Stephane; Kothe, Tim; Krencker, Francois-Nicolas; Suan, Guillaume; Heimhofer, Ulrich; Immenhauser, Adrian

    2014-05-01

    Across the Pliensbachian-Toarcian boundary (P-To, Early Jurassic), ca. 1 Myr before the Toarcian Oceanic Anoxic Event (T-OAE), an initial negative carbon isotope excursion has been documented in western Tethys sedimentary rocks. In carbonate, its amplitude (2-3 permil) is similar to the subsequent excursion recorded at the onset of the T-OAE. Being also associated with a rapid warming event, the significance of this first carbon isotope shift, in terms of paleoenvironmental interpretation and triggering mechanism, remains however elusive. Taking advantage of expanded and rather continuous sections in the High Atlas of Morocco, several high-resolution, paired organic-inorganic carbon isotope records have been obtained across the Upper Pliensbachian - Lower Toarcian interval. At the onset of the T-OAE, an abrupt 1-2 permil negative shift is recorded in both organic and inorganic phases, succeeded by a relatively longer term 1-2 permil negative trend and a final slow return to pre-excursion conditions. In accordance with previous interpretations, this pattern indicates a perturbation of the entire exogenic carbon isotope reservoir at the onset of the T-OAE by the sudden release of isotopically light carbon into the atmosphere. By contrast, there is no negative shift in carbon isotopes for the P-To event recorded in bulk organic matter of Morocco. Given the strong dominance of terrestrial particles in the bulk organic matter fraction, this absence indicates that massive input of 12C-rich carbon into the atmosphere is not likely to have happened during the P-To event. A pronounced (2 permil) and abrupt negative shift in carbon isotope is however recorded in the bulk carbonate phase. We suggest that this decoupling between organic and inorganic phase is due to changes in the nature of the bulk carbonate phase. Indeed, the negative shift occurs at the lithological transition between Pliensbachian-lowermost Toarcian limestone-marl alternations and the Lower Toarcian marl

  3. Effects of carbonate leaching on foraminifer stable isotopes ratios

    Science.gov (United States)

    Obrochta, S.; Yokoyama, Y.; Sakai, S.; Ishimura, T.

    2011-12-01

    Stable carbon and oxygen isotope ratios were measured on 125 individual epifaunal and infaunal benthic foraminifers from two discrete Holocene intervals in a shallow-water sediment core (~ 450 m) from the Timor Sea. Methane seeps are common in the area, resulting in significant precipitation of secondary calcite that is confirmed by SEM photomicrographs and has likely resulted in inconsistent downcore results. To assess the degree of removal of contaminants, individual Uvigerina peregrina were subjected to varying degrees of pretreatment prior to analysis. All foraminifers received standard cleaning with ethanol and brief sonication. A subset were further cleaned and sonicated in a dilute HCl solution (~ 0.003 M). Foraminifer tests were photographed using both reflected light and scanning electron microscopes during the course of treatment to monitor the changing degree of contaminant removal as increasingly aggressive cleaning methods were employed. Visible contamination remained on individuals not subjected to HCl treatment. The leached individuals exhibit a lower overall relative standard deviation and consistent results within morphotype groups. Based on these results, a 2% value is expected to be typical of the Holocene, though further downcore analyses are pending restoration of equipment adversely effected by the Eastern Japan 3/11 earthquake.

  4. Variation in the Carbon Isotope Compositions of Phytoliths Across a Climate Gradient

    Science.gov (United States)

    Webb, E. A.; Longstaffe, F. J.

    2008-12-01

    The carbon isotope composition of plant organic matter within a single species may vary in response to changes in temperature, relative humidity, precipitation amount, altitude, nutrient availability, light levels and amount of canopy. All of these factors affect the rate of carbon assimilation during photosynthesis. Silica phytoliths, which form in the cells and intercellular spaces of terrestrial plants, occlude some of the plant's organic matrix. Carbon sequestered in phytoliths is protected from decay and may therefore be preserved in soils after most other plant material has decomposed. The carbon isotope composition of phytoliths may therefore have potential as an archive of climatic conditions during soil accumulation. In this study, the carbon isotope compositions of modern plant tissues and their phytoliths are compared for the C4 grass species Calamovilfa longifolia across the climate gradient of the North American prairies. The carbon isotope compositions of C. longifolia tissues ranged from -15 to -10 permil, with lower values being most typical of leaf tissues and with greater variability occurring in samples from lower latitudes. Carbonaceous compounds occluded in the phytoliths, by comparison, were depleted of carbon-13 by 5 to 15 permil relative to the tissues from the same plant. Understanding the causes of this offset, which is significantly larger and more variable than reported in previous studies, is necessary before the full potential of the carbon-isotope phytolith proxy can be realized.

  5. Elemental geochemistry and strontium-isotope stratigraphy of Cenomanian to Santonian neritic carbonates in the Zagros Basin, Iran

    Science.gov (United States)

    Navidtalab, Amin; Rahimpour-Bonab, Hossain; Huck, Stefan; Heimhofer, Ulrich

    2016-12-01

    A Neo-Tethyan upper Cenomanian-Santonian neritic carbonate ramp succession (Sarvak and Ilam formations), drilled in the Zagros Basin in southwest Iran, was investigated via detailed sedimentology, microfacies analysis, elemental geochemistry and Sr-isotope stratigraphy (SIS). The succession contains two exposure surfaces, which are known as the CT-ES and mT-ES (Cenomanian-Turonian and middle Turonian, respectively), and associated prominent negative carbon-isotope excursions that represent important regional stratigraphic marker horizons. Precise knowledge about the onset of platform exposure and the duration of the exposure-related hiatus, however, is currently lacking due to a rather low-resolved shallow-water biostratigraphic framework and a bulk carbonate carbon-isotope pattern that clearly differs from global Late Cretaceous reference curves. Therefore, the existing bio-chemostratigraphic framework was complemented by bulk carbonate strontium-isotope stratigraphy (SIS). As bulk carbonate material is in particular prone to diagenetic alteration, a careful selection of least altered samples has been carried out by means of elemental geochemistry and petrography. In contrast to what could be expected, the meteoric alteration of limestones beneath both exposure surfaces is not clearly expressed by increasing iron and manganese and coeval decreasing strontium contents. On the contrary, the impact of meteoric diagenesis is well illustrated via pronounced increases in Rb concentrations and concomitant prominent positive shifts to radiogenic strontium-isotope values, an observation that clearly reflects the decay of continentally derived 87Rb into 87Sr. Rubidium corrected strontium-isotope values place the CT-ES around the Cenomanian-Turonian boundary and point to an exposure duration of less than 0.4 Myr. This rather short-term CT-ES related hiatus is supported by petrographic evidence, which indicates a youth karstification stage of strata beneath the CT

  6. STABLE CARBON ISOTOPES OF HCO//3 IN THE AQUIA AQUIFER, MARYLAND: EVIDENCE FOR AN ISOTOPICALLY HEAVY SOURCE OF CO//2.

    Science.gov (United States)

    Chapelle, Francis H.; Knobel, LeRoy L.

    1985-01-01

    Identifying sources and sinks of dissolved inorganic carbon species is an important step in understanding the geochemistry of ground-water systems. This is particularly important for Atlantic Coastal Plain aquifers because bicarbonate (HCO//3** minus ) is frequently the major dissolved anion. The purpose of this paper is to document the stable carbon isotope composition of dissolved inorganic carbon in the Aquia aquifer, Maryland, and to use this data to help identify sources and sinks of dissolved HCO//3** minus . Subjects covered include hydrogeology, ground-water chemistry, sources and sinks, and others. Refs.

  7. The effectiveness of using carbonate isotope measurements of body tissues to infer diet in human evolution: Evidence from wild western chimpanzees (Pan troglodytes verus).

    Science.gov (United States)

    Fahy, Geraldine E; Boesch, Christophe; Hublin, Jean-Jacques; Richards, Michael P

    2015-11-01

    Changes in diet throughout hominin evolution have been linked with important evolutionary changes. Stable carbon isotope analysis of inorganic apatite carbonate is the main isotopic method used to reconstruct fossil hominin diets; to test its effectiveness as a paleodietary indicator we present bone and enamel carbonate carbon isotope data from a well-studied population of modern wild western chimpanzees (Pan troglodytes verus) of known sex and age from Taï, Cote d'Ivoire. We found a significant effect of age class on bone carbonate values, with adult chimpanzees being more (13)C- and (18)O-depleted compared to juveniles. Further, to investigate habitat effects, we compared our data to existing apatite data on eastern chimpanzees (P. troglodytes schweinfurthii) and found that the Taï chimpanzees are significantly more depleted in enamel δ(13)Cap and δ(18)Oap compared to their eastern counterparts. Our data are the first to present a range of tissue-specific isotope data from the same group of wild western chimpanzees and, as such, add new data to the growing number of modern non-human primate comparative isotope datasets providing valuable information for the interpretation of diet throughout hominin evolution. By comparing our data to published isotope data on fossil hominins we found that our modern chimpanzee bone and enamel data support hypotheses that the trend towards increased consumption of C4 foods after 4 Ma (millions of years ago) is unique to hominins.

  8. Carbon xerogels as supports for catalysts and electrocatalysts

    OpenAIRE

    Job, Nathalie; Berthon-Fabry, Sandrine; Lambert, Stephanie; Chatenet, Marian; Maillard, Frédéric; Brigaudet, Mathilde; Pirard, Jean-Paul

    2009-01-01

    International audience; In order to improve mass transport in the pore texture of carbon supported catalysts, the widely used supports (activated carbons or carbon blacks) can be replaced by carbon gels, i.e. texture-tailored materials obtained by drying and pyrolysis of organic gels. Carbon xerogels issued from resorcinol-formaldehyde aqueous gels were used as metal catalyst supports both in gas phase heterogeneous catalysis and in PEM fuel cell electrodes. These materials, composed of very ...

  9. The modeling of carbon isotope kinetics and its application to the evaluation of natural gas

    Institute of Scientific and Technical Information of China (English)

    Xianqing LI; Xianming XIAO; Yongchun TANG; Hui TIAN; Qiang ZHOU; Yunfeng YANG; Peng DONG; Yan WANG; Zhihong SONG

    2008-01-01

    The modeling of carbon isotope kinetics of natural gas is an issue driving pioneering research in the oil and gas geochemistry in China and internationally.Combined with the sedimentary burial history and basin geothermal history,the modeling of carbon isotope kinetics provides a new and effective means for the determination of the origin and accumulation history of natural gas pools.In this paper,we introduce the modeling of carbon isotope kinetics of natural gas formation and its applications to the assessment of natural gas maturity,the determination of the gas source,the history of gas accumulation,and the oil-gas ratio.It is shown that this approach is of great value for these applications.The carbon isotopic characteristics of natural gas are not only affected by the gas source and maturity of the source rock,but also are related to the accumulation condition and geothermal gradient in a basin.There are obvious differences in the characteristics of carbon isotope ratios between instantaneous gas and cumulative gas.Different basins have different kinetic models of carbon isotope fractionation,which depends on the gas source condition,the accumulation history and the sedimentary-tectonic history.Since the origin of natural gas in the superimposed basin in China is very complicated,and the natural gas pool is characterized by multiphase and variable gas-sources,this paper may provide a new perspective on the study and evaluation of natural gas.

  10. Fractionation between inorganic and organic carbon during the Lomagundi (2.22 2.1 Ga) carbon isotope excursion

    Science.gov (United States)

    Bekker, A.; Holmden, C.; Beukes, N. J.; Kenig, F.; Eglinton, B.; Patterson, W. P.

    2008-07-01

    The Lomagundi (2.22-2.1 Ga) positive carbon isotope excursion in shallow-marine sedimentary carbonates has been associated with the rise in atmospheric oxygen, but subsequent studies have demonstrated that the carbon isotope excursion was preceded by the rise in atmospheric oxygen. The amount of oxygen released to the exosphere during the Lomagundi excursion is constrained by the average global fractionation between inorganic and organic carbon, which is poorly characterized. Because dissolved inorganic and organic carbon reservoirs were arguably larger in the Paleoproterozoic ocean, at a time of lower solar luminosity and lower ocean redox state, decoupling between these two variables might be expected. We determined carbon isotope values of carbonate and organic matter in carbonates and shales of the Silverton Formation, South Africa and in the correlative Sengoma Argillite Formation, near the border in Botswana. These units were deposited between 2.22 and 2.06 Ga along the margin of the Kaapvaal Craton in an open-marine deltaic setting and experienced lower greenschist facies metamorphism. The prodelta to offshore marine shales are overlain by a subtidal carbonate sequence. Carbonates exhibit elevated 13C values ranging from 8.3 to 11.2‰ vs. VPDB consistent with deposition during the Lomagundi positive excursion. The total organic carbon (TOC) contents range from 0.01 to 0.6% and δ13C values range from - 24.8 to - 13.9‰. Thus, the isotopic fractionation between organic and carbonate carbon was on average 30.3 ± 2.8‰ ( n = 32) in the shallow-marine environment. The underlying Sengoma shales have highly variable TOC contents (0.14 to 21.94%) and δ13C values (- 33.7 to - 20.8‰) with an average of - 27.0 ± 3.0‰ ( n = 50). Considering that the shales were also deposited during the Lomagundi excursion, and taking δ13C values of the overlying carbonates as representative of the δ13C value of dissolved inorganic carbon during shale deposition, a carbon

  11. Spatially Resolved, In Situ Carbon Isotope Analysis of Archean Organic Matter

    Science.gov (United States)

    Williford, Kenneth H.; Ushikubo, Takayuki; Lepot, Kevin; Hallmann, Christian; Spicuzza, Michael J.; Eigenbrode, Jennifer L.; Summons, Roger E.; Valley, John W.

    2011-01-01

    Archean OM suggest that instrumental bias is consistent for 12C count rates as low as 10% relative to anthracite. Samples from the ABDP-9 (n=3; Mount McRae Shale, approximately 2.5 Ga), RHDH2a (n=2; Carrawine Dolomite and Jeerinah Fm, approximately 2.6 Ga), WRL1 (n=3; Wittenoom Fm, Marra Mamba Iron Formation, and Jeerinah Fm, approximately 2.6 Ga), and SV1 (n=1; Tumbiana Fm, approximately 2.7 Ga) drill cores, each previously analyzed for bulk organic carbon isotope composition, yielded 100 new, in situ data from Neoarchean sedimentary OM. In these samples, delta C-13 varies between -53.1 and -28.3 % and offsets between in situ and bulk compositions range from -8.3 to 18.8%. In some cases, isotopic composition and mode of occurrence (e.g. morphology and mineral associations) are statistically correlated, enabling the identification of distinct reservoirs of OM. Our results support previous evidence for gradients of oxidation with depth in Neoarchean environments driven by photosynthesis and methane metabolism. The relevance of these findings to questions of bio- and syngenicity as well as the alteration history of previously reported Archean OM will be discussed.

  12. Catalytic removal of carbon monoxide over carbon supported palladium catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Srivastava, Avanish Kumar [Defence Research and Development Establishment, Jhansi Road, Gwalior-474002 (MP) (India); Saxena, Amit [Centre for Fire Explosive and Environmental Safety, Timarpur, Delhi-110054 (India); Shah, Dilip; Mahato, T.H. [Defence Research and Development Establishment, Jhansi Road, Gwalior-474002 (MP) (India); Singh, Beer, E-mail: beerbs5@rediffmail.com [Defence Research and Development Establishment, Jhansi Road, Gwalior-474002 (MP) (India); Shrivastava, A.R.; Gutch, P.K. [Defence Research and Development Establishment, Jhansi Road, Gwalior-474002 (MP) (India); Shinde, C.P. [School of Studies in Chemistry, Jiwaji University, Gwalior-474002 (MP) (India)

    2012-11-30

    Highlights: Black-Right-Pointing-Pointer Carbon supported palladium (Pd/C) catalyst was prepared. Black-Right-Pointing-Pointer Catalytic removal of CO over Pd/C catalyst was studied under dynamic conditions. Black-Right-Pointing-Pointer Effects of Pd %, CO conc., humidity, GHSV and reaction environment were studied. - Abstract: Carbon supported palladium (Pd/C) catalyst was prepared by impregnation of palladium chloride using incipient wetness technique, which was followed by liquid phase reduction with formaldehyde. Thereafter, Pd/C catalyst was characterized using X-ray diffractometery, scanning electron microscopy, atomic absorption spectroscopy, thermo gravimetry, differential scanning calorimetry and surface characterization techniques. Catalytic removal of carbon monoxide (CO) over Pd/C catalyst was studied under dynamic conditions. Pd/C catalyst was found to be continuously converting CO to CO{sub 2} through the catalyzed reaction, i.e., CO + 1/2O{sub 2} {yields} CO{sub 2}. Pd/C catalyst provided excellent protection against CO. Effects of palladium wt%, CO concentration, humidity, space velocity and reaction environment were also studied on the breakthrough behavior of CO.

  13. Carbon isotopic evidence for microbial control of carbon supply to Orca Basin at the brine-seawater interface

    Directory of Open Access Journals (Sweden)

    S. R. Shah

    2012-12-01

    Full Text Available Orca Basin, an intraslope basin on the Texas–Louisiana continental slope, hosts a hypersaline, anoxic brine in its lowermost 200 m. This brine contains a large reservoir of reduced and aged carbon, and appears to be stable at decadal time scales: concentrations and the isotopic composition of dissolved inorganic (DIC and organic carbon (DOC are similar to previous reports. Both DIC and DOC are more "aged" within the brine pool than in overlying water, and the isotopic contrast between brine carbon and seawater carbon is much greater for DIC than DOC. While the stable carbon isotopic composition of brine DIC points towards a combination of methane and organic carbon re-mineralization as its source, radiocarbon and box model results point to the brine interface as the major source region for DIC with oxidation of methane diffusing upwards from sediments supplying only limited DIC to the brine. This conclusion is consistent with previous studies reporting microbial activity focused at the seawater-brine interface. Isotopic similarities between DIC and DOC suggest a different relationship between these two carbon reservoirs than is typically observed in deep ocean basins. Radiocarbon values implicate the seawater-brine interface region as the likely source region for DOC as well as DIC. Further investigations of the seawater-brine interface are needed to advance our understanding of the specific microbial processes contributing to dissolved carbon storage in the Orca Basin brine.

  14. PRODUCTION AND TRANSPORT OF CARBON DIOXIDE IN A CONTAMINATED VADOSE ZONE: A STABLE AND RADIOACTIVE CARBON ISOTOPE STUDY

    Science.gov (United States)

    Analyses of soil gas compositions and stable and radioactive carbon isotopes in the vadose zone above an alluvial aquifer were conducted at an organic solvent disposal site in southeast Phoenix, AZ. The study investigated the source and movement of carbon dioxide above a plume of...

  15. USE OF STABLE CARBON ISOTOPE RATIOS OF FATTY ACIDS TO EVALUATE MICROBIAL CARBON SOURCES IN TERRESTRIAL ENVIRONMENTS

    Science.gov (United States)

    We use measurements of the concentration and stable carbon isotopic ratio (D 13C) of individual microbial phospholipid fatty acids (PLFAs) in soils as indicators of live microbial biomass levels and microbial carbon source. We found that intensive sugar cane cultivation leads to ...

  16. 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.

  17. Reactive transport modelling of biogeochemical processes and carbon isotope geochemistry inside a landfill leachate plume.

    Science.gov (United States)

    van Breukelen, Boris M; Griffioen, Jasper; Röling, Wilfred F M; van Verseveld, Henk W

    2004-06-01

    The biogeochemical processes governing leachate attenuation inside a landfill leachate plume (Banisveld, the Netherlands) were revealed and quantified using the 1D reactive transport model PHREEQC-2. Biodegradation of dissolved organic carbon (DOC) was simulated assuming first-order oxidation of two DOC fractions with different reactivity, and was coupled to reductive dissolution of iron oxide. The following secondary geochemical processes were required in the model to match observations: kinetic precipitation of calcite and siderite, cation exchange, proton buffering and degassing. Rate constants for DOC oxidation and carbonate mineral precipitation were determined, and other model parameters were optimized using the nonlinear optimization program PEST by means of matching hydrochemical observations closely (pH, DIC, DOC, Na, K, Ca, Mg, NH4, Fe(II), SO4, Cl, CH4, saturation index of calcite and siderite). The modelling demonstrated the relevance and impact of various secondary geochemical processes on leachate plume evolution. Concomitant precipitation of siderite masked the act of iron reduction. Cation exchange resulted in release of Fe(II) from the pristine anaerobic aquifer to the leachate. Degassing, triggered by elevated CO2 pressures caused by carbonate precipitation and proton buffering at the front of the plume, explained the observed downstream decrease in methane concentration. Simulation of the carbon isotope geochemistry independently supported the proposed reaction network.

  18. Carbon mass-balance modeling and carbon isotope exchange processes in the Curonian Lagoon

    Science.gov (United States)

    Barisevičiūtė, Rūta; Žilius, Mindaugas; Ertürk, Ali; Petkuvienė, Jolita

    2016-04-01

    The Curonian lagoon one of the largest coastal lagoons in Europe is located in the southeastern part of the Baltic Sea and lies along the Baltic coast of Lithuania and the Kaliningrad region of Russia. It is influenced by a discharge of the Nemunas and other smaller rivers and saline water of the Baltic Sea. The narrow (width 0.4 km, deep 8-14 m) Klaipėda Strait is the only way for fresh water run-off and brackish water intrusions. This research is focused on carbon isotope fractionations related with air - water exchange, primary production and organic carbon sedimentation, mineralization and uptake from both marine and terrestrial sources.

  19. Carbon isotopic characterization of formaldehyde emitted by vehicles in Guangzhou, China

    Science.gov (United States)

    Hu, Ping; Wen, Sheng; Liu, Yonglin; Bi, Xinhui; Chan, Lo Yin; Feng, Jialiang; Wang, Xinming; Sheng, Guoying; Fu, Jiamo

    2014-04-01

    Formaldehyde (HCHO) is the most abundant carbonyl compound in the atmosphere, and vehicle exhaust emission is one of its important anthropogenic sources. However, there is still uncertainty regarding HCHO flux from vehicle emission as well as from other sources. Herein, automobile source was characterized using HCHO carbon isotopic ratio to assess its contributions to atmospheric flux and demonstrate the complex production/consumption processes during combustion in engine cylinder and subsequent catalytic treatment of exhaust. Vehicle exhausts were sampled under different idling states and HCHO carbon isotopic ratios were measured by gas chromatograph-combustion-isotopic ratio mass spectrometry (GC-C-IRMS). The HCHO directly emitted from stand-alone engines (gasoline and diesel) running at different load was also sampled and measured. The HCHO carbon isotopic ratios were from -30.8 to -25.7‰ for gasoline engine, and from -26.2 to -20.7‰ for diesel engine, respectively. For diesel vehicle without catalytic converter, the HCHO carbon isotopic ratios were -22.1 ± 2.1‰, and for gasoline vehicle with catalytic converter, the ratios were -21.4 ± 0.7‰. Most of the HCHO carbon isotopic ratios were heavier than the fuel isotopic ratios (from -29 to -27‰). For gasoline vehicle, the isotopic fractionation (Δ13C) between HCHO and fuel isotopic ratios was 7.4 ± 0.7‰, which was higher than that of HCHO from stand-alone gasoline engine (Δ13Cmax = 2.7‰), suggesting additional consumption by the catalytic converter. For diesel vehicle without catalytic converter, Δ13C was 5.7 ± 2.0‰, similar to that of stand-alone diesel engine. In general, the carbon isotopic signatures of HCHO emitted from automobiles were not sensitive to idling states or to other vehicle parameters in our study condition. On comparing these HCHO carbon isotopic data with those of past studies, the atmospheric HCHO in a bus station in Guangzhou might mainly come from vehicle emission for

  20. Detection of oxygen isotopic anomaly in terrestrial atmospheric carbonates and its implications to Mars

    OpenAIRE

    Shaheen, R.; Abramian, A.; Horn, J.; Dominguez, G.; Sullivan, R; Thiemens, Mark H.

    2010-01-01

    The debate of life on Mars centers around the source of the globular, micrometer-sized mineral carbonates in the ALH84001 meteorite; consequently, the identification of Martian processes that form carbonates is critical. This paper reports a previously undescribed carbonate formation process that occurs on Earth and, likely, on Mars. We identified micrometer-sized carbonates in terrestrial aerosols that possess excess 17O (0.4–3.9‰). The unique O-isotopic composition mechanistically describes...

  1. Stable Isotope Measurements of Carbon Dioxide, Methane, and Hydrogen Sulfide Gas Using Frequency Modulation Spectroscopy

    Science.gov (United States)

    Nowak-Lovato, K.

    2014-12-01

    Seepage from enhanced oil recovery, carbon storage, and natural gas sites can emit trace gases such as carbon dioxide, methane, and hydrogen sulfide. Trace gas emission at these locations demonstrate unique light stable isotope signatures that provide information to enable source identification of the material. Light stable isotope detection through surface monitoring, offers the ability to distinguish between trace gases emitted from sources such as, biological (fertilizers and wastes), mineral (coal or seams), or liquid organic systems (oil and gas reservoirs). To make light stable isotope measurements, we employ the ultra-sensitive technique, frequency modulation spectroscopy (FMS). FMS is an absorption technique with sensitivity enhancements approximately 100-1000x more than standard absorption spectroscopy with the advantage of providing stable isotope signature information. We have developed an integrated in situ (point source) system that measures carbon dioxide, methane and hydrogen sulfide with isotopic resolution and enhanced sensitivity. The in situ instrument involves the continuous collection of air and records the stable isotope ratio for the gas being detected. We have included in-line flask collection points to obtain gas samples for validation of isotopic concentrations using our in-house isotope ratio mass spectroscopy (IRMS). We present calibration curves for each species addressed above to demonstrate the sensitivity and accuracy of the system. We also show field deployment data demonstrating the capabilities of the system in making live dynamic measurements from an active source.

  2. Carbon and Oxygen Isotopic Ratios for Nearby Miras

    Science.gov (United States)

    Hinkle, Kenneth H.; Lebzelter, Thomas; Straniero, Oscar

    2016-07-01

    Carbon and oxygen isotopic ratios are reported for a sample of 46 Mira and SRa-type variable asymptotic giant branch (AGB) stars. Vibration-rotation first and second-overtone CO lines in 1.5-2.5 μm spectra were measured to derive isotopic ratios for 12C/13C, 16O/17O, and 16O/18O. Comparisons with previous measurements for individual stars and with various samples of evolved stars, as available in the extant literature, are discussed. Models for solar composition AGB stars of different initial masses are used to interpret our results. We find that the majority of M-stars have main sequence masses ≤2 M ⊙ and have not experienced sizable third dredge-up (TDU) episodes. The progenitors of the four S-type stars in our sample are slightly more massive. Of the six C-stars in the sample three have clear evidence relating their origin to the occurrence of TDU. Comparisons with O-rich presolar grains from AGB stars that lived before the formation of the solar system reveal variations in the interstellar medium chemical composition. The present generation of low-mass AGB stars, as represented by our sample of long period variables (LPVs), shows a large spread of 16O/17O ratios, similar to that of group 1 presolar grains and in agreement with theoretical expectations for the composition of mass 1.2-2 M ⊙ stars after the first dredge-up. In contrast, the 16O/18O ratios of present-day LPVs are definitely smaller than those of group 1 grains. This is most probably a consequence of the the decrease with time of the 16O/18O ratio in the interstellar medium due to the chemical evolution of the Milky Way. One star in our sample has an O composition similar to that of group 2 presolar grains originating in an AGB star undergoing extra-mixing. This may indicate that the extra-mixing process is hampered at high metallicity, or, equivalently, favored at low metallicity. Similarly to O-rich grains, no star in our sample shows evidence of hot bottom burning, which is expected for

  3. Carbon-bearing iron phases and the carbon isotope composition of the deep Earth.

    Science.gov (United States)

    Horita, Juske; Polyakov, Veniamin B

    2015-01-06

    The carbon budget and dynamics of the Earth's interior, including the core, are currently very poorly understood. Diamond-bearing, mantle-derived rocks show a very well defined peak at δ(13)C ≈ -5 ± 3‰ with a very broad distribution to lower values (∼-40‰). The processes that have produced the wide δ(13)C distributions to the observed low δ(13)C values in the deep Earth have been extensively debated, but few viable models have been proposed. Here, we present a model for understanding carbon isotope distributions within the deep Earth, involving Fe-C phases (Fe carbides and C dissolved in Fe-Ni metal). Our theoretical calculations show that Fe and Si carbides can be significantly depleted in (13)C relative to other C-bearing materials even at mantle temperatures. Thus, the redox freezing and melting cycles of lithosphere via subduction upwelling in the deep Earth that involve the Fe-C phases can readily produce diamond with the observed low δ(13)C values. The sharp contrast in the δ(13)C distributions of peridotitic and eclogitic diamonds may reflect differences in their carbon cycles, controlled by the evolution of geodynamical processes around 2.5-3 Ga. Our model also predicts that the core contains C with low δ(13)C values and that an average δ(13)C value of the bulk Earth could be much lower than ∼-5‰, consistent with those of chondrites and other planetary body. The heterogeneous and depleted δ(13)C values of the deep Earth have implications, not only for its accretion-differentiation history but also for carbon isotope biosignatures for early life on the Earth.

  4. Carbon Isotopes in Ocean and Land Carbon Cycle Models: Atmospheric Forcing Data and Applications for CMIP6 and Beyond

    Science.gov (United States)

    Graven, H. D.; Allison, C. E.; Etheridge, D. M.; Hammer, S.; Keeling, R. F.; Krummel, P. B.; Langenfelds, R. L.; Levin, I.; Rubino, M.; Trudinger, C. M.; Vaughn, B. H.; White, J. W. C.

    2016-12-01

    The carbon isotopic composition of ocean and land carbon reservoirs is influenced by fossil fuel burning, carbon residence time, and fractionation associated with biological and physical processes. Additionally, 14C produced during nuclear weapons testing in the 1950s and 60s has enriched 14C/C ratios in decadally overturning reservoirs. Comparisons of simulated 14C and 13C dynamics between models and with observations can provide insights to key processes in the global carbon cycle including air-sea gas exchange, ocean mixing, terrestrial drought response, and vegetation and soil carbon turnover rates. However, the inclusion of carbon isotopes in large-scale model intercomparisons has so far been limited. One study, the Ocean Carbon Cycle Model Intercomparison Project 2 (OCMIP2), used simulations of ocean 14C to identify biases in model ocean circulation that affect simulated anthropogenic CO2 uptake and marine biogeochemistry. Within the context of CMIP6, we are working to advance the use of carbon isotopes for carbon cycle science, model evaluation and model intercomparison. The variables requested for DECK, OMIP and C4MIP simulations in CMIP6 include stocks and fluxes of 14C and 13C (for models that simulate 14C and 13C). We will present the historical and future atmospheric forcing datasets for Δ14C and δ13C in CO2 that we are making available to modeling groups as part of CMIP6. The historical data uses atmospheric measurements and ice core and tree ring records. For future atmospheric forcing, we use a simple carbon cycle model with CO2 emissions and atmospheric CO2 concentration for different scenarios from ScenarioMIP. We will also describe potential applications for carbon isotope simulations from CMIP6 or other modeling activities. In particular, we will present an evaluation of terrestrial carbon turnover with simulations of bomb-derived 14C inventories in simplified off-line models based on carbon stocks and fluxes in CMIP5 terrestrial models.

  5. Detailed Carbon Isotopic Characterization of Aerosol-Derived Organic Carbon Deposited to two Temperate Watersheds

    Science.gov (United States)

    Wozniak, A. S.; Bauer, J. E.; Keesee, E. E.; McNichol, A. P.; Xu, L.; Dickhut, R. M.

    2008-12-01

    Atmospheric deposition of carbonaceous aerosols can be a quantitatively significant flux in the carbon budgets of temperate watersheds. Characterizing the sources and fates of this material is therefore critical for assessing its role in carbon and organic matter cycling in these systems. Aerosol samples were collected in the Hudson and York River watersheds throughout 2006-2007 and analyzed for quantities and isotopic signatures (δ13C, Δ14C) of total and water-soluble organic carbon (TOC, WSOC, respectively). On average ~2.4 and 2.1 mg m-2 d-1 of aerosol TOC were deposited to the Hudson and York River watersheds, respectively, and nearly half of this material was water-soluble. δ13C analyses indicated that both the TOC and the WSOC were primarily terrestrial in nature. TOC Δ14C signatures covered a broad range for both watersheds, with calculated contributions from fossil sources (e.g., anthropogenic combustion of petroleum, coal, etc.) ranging from 0% for samples collected during the summer of 2007 to approximately 50% for samples collected in the winter of 2007. Aerosol-derived WSOC Δ14C values were less variable and were nearly always enriched in 14C with respect to the corresponding TOC, indicating that contemporary aerosol material tends to partition into the aqueous phase, while fossil-derived aerosol OC is more likely to remain insoluble. However, WSOC still often showed considerable contributions from fossil OC (up to 20%). Thus, some portion of the anthropogenic fossil-derived aerosol OC is relatively soluble and may be transported hydrologically through watersheds and aquatic systems. A subset of aerosol samples from each watershed was selected for more thorough isotopic analysis of operationally-defined components of the carbonaceous material. Isotopic signatures were obtained for TOC, WSOC, total solvent-extract, and the aliphatic, aromatic, and polar components. Isotopic information on these fractions allows us to determine which components

  6. A Novel Airborne Carbon Isotope Analyzer for Methane and Carbon Dioxide Source Fingerprinting

    Science.gov (United States)

    Berman, E. S.; Huang, Y. W.; Owano, T. G.; Leifer, I.

    2014-12-01

    Recent field studies on major sources of the important greenhouse gas methane (CH4) indicate significant underestimation of methane release from fossil fuel industrial (FFI) and animal husbandry sources, among others. In addition, uncertainties still exist with respect to carbon dioxide (CO2) measurements, especially source fingerprinting. CO2 isotopic analysis provides a valuable in situ measurement approach to fingerprint CH4 and CO2as associated with combustion sources, leakage from geologic reservoirs, or biogenic sources. As a result, these measurements can characterize strong combustion source plumes, such as power plant emissions, and discriminate these emissions from other sources. As part of the COMEX (CO2 and MEthane eXperiment) campaign, a novel CO2 isotopic analyzer was installed and collected data aboard the CIRPAS Twin Otter aircraft. Developing methods to derive CH4 and CO2 budgets from remote sensing data is the goal of the summer 2014 COMEX campaign, which combines hyperspectral imaging (HSI) and non-imaging spectroscopy (NIS) with in situ airborne and surface data. COMEX leverages the synergy between high spatial resolution HSI and moderate spatial resolution NIS. The carbon dioxide isotope analyzer developed by Los Gatos Research (LGR) uses LGR's patented Off-Axis ICOS (Integrated Cavity Output Spectroscopy) technology and incorporates proprietary internal thermal control for high sensitivity and optimal instrument stability. This analyzer measures CO2 concentration as well as δ13C, δ18O, and δ17O from CO2 at natural abundance (100-3000 ppm). The laboratory accuracy is ±1.2 ppm (1σ) in CO2 from 370-1000 ppm, with a long-term (1000 s) precision of ±0.012 ppm. The long-term precision for both δ13C and δ18O is 0.04 ‰, and for δ17O is 0.06 ‰. The analyzer was field-tested as part of the COWGAS campaign, a pre-cursor campaign to COMEX in March 2014, where it successfully discriminated plumes related to combustion processes associated with

  7. Early Triassic fluctuations of the global carbon cycle: New evidence from paired carbon isotopes in the western USA basin

    Science.gov (United States)

    Caravaca, Gwénaël; Thomazo, Christophe; Vennin, Emmanuelle; Olivier, Nicolas; Cocquerez, Théophile; Escarguel, Gilles; Fara, Emmanuel; Jenks, James F.; Bylund, Kevin G.; Stephen, Daniel A.; Brayard, Arnaud

    2017-07-01

    In the aftermath of the catastrophic end-Permian mass extinction, the Early Triassic records recurrent perturbations in the carbon isotope signal, most notably during the Smithian and through the Smithian/Spathian Boundary (SSB; 1.5 myr after the Permian/Triassic boundary), which show some of the largest excursions of the Phanerozoic. The late Smithian also corresponds to major biotic turnovers and environmental changes, such as temperature fluctuations, that deeply impacted the recovery after the end-Permian mass extinction. Here we document the paired carbon isotope signal along with an analysis of the trace and major elements at the long-known Hot Springs section (southeastern Idaho, USA). This section records Early Triassic sediments from the Griesbachian-Dienerian up to the lower Spathian. We show that the organic and carbonate δ13C variations mirror the signals identified at a global scale. Particularly, the middle Smithian-SSB event represented by a negative-positive isotopic couplet is well identified and is not of diagenetic origin. We also document a positive excursion potentially corresponding to the Dienerian/Smithian Boundary. Observed Smithian-Spathian excursions are recorded similarly in both the organic and carbonate reservoirs, but the organic matter signal systematically shows unexpectedly dampened variations compared to its carbonate counterpart. Additionally, we show that variations in the net isotopic effect (i.e., Δ13C) probably resulted from a complex set of forcing parameters including either a mixing between terrestrial and marine organic matter depending on the evolution of the depositional setting, or variations in the biological fractionation. We establish that the Δ13C signal cannot be directly related to CO2-driven temperature variations at Hot Springs. Even though the carbon isotope signal mirrors the Early Triassic variations known at the global scale, the Hot Springs signal probably also reflects local influences on the carbon

  8. The impact of recycling of organic carbon on the stable carbon isotopic composition of dissolved inorganic carbon in a stratified marine system (Kyllaren fjord, Norway)

    NARCIS (Netherlands)

    Breugel, Y. van; Schouten, S.; Paetzel, M.; Nordeide, R.; Sinninghe Damsté, J.S.

    2005-01-01

    A negative carbon isotope shift in sedimentary organic carbon deposited in stratified marine and lacustrine systems has often been inferred to be a consequence of the process of recycling of respired and, therefore, 13C-depleted, dissolved inorganic carbon (DIC) formed from mineralization of descend

  9. Growth versus metabolic tissue replacement in mouse tissues determined by stable carbon and nitrogen isotope analysis

    Science.gov (United States)

    Macavoy, S. E.; Jamil, T.; Macko, S. A.; Arneson, L. S.

    2003-12-01

    Stable isotope analysis is becoming an extensively used tool in animal ecology. The isotopes most commonly used for analysis in terrestrial systems are those of carbon and nitrogen, due to differential carbon fractionation in C3 and C4 plants, and the approximately 3‰ enrichment in 15N per trophic level. Although isotope signatures in animal tissues presumably reflect the local food web, analysis is often complicated by differential nutrient routing and fractionation by tissues, and by the possibility that large organisms are not in isotopic equilibrium with the foods available in their immediate environment. Additionally, the rate at which organisms incorporate the isotope signature of a food through both growth and metabolic tissue replacement is largely unknown. In this study we have assessed the rate of carbon and nitrogen isotopic turnover in liver, muscle and blood in mice following a diet change. By determining growth rates, we were able to determine the proportion of tissue turnover caused by growth versus that caused by metabolic tissue replacement. Growth was found to account for approximately 10% of observed tissue turnover in sexually mature mice (Mus musculus). Blood carbon was found to have the shortest half-life (16.9 days), followed by muscle (24.7 days). Liver carbon turnover was not as well described by the exponential decay equations as other tissues. However, substantial liver carbon turnover was observed by the 28th day after diet switch. Surprisingly, these tissues primarily reflect the carbon signature of the protein, rather than carbohydrate, source in their diet. The nitrogen signature in all tissues was enriched by 3 - 5‰ over their dietary protein source, depending on tissue type, and the isotopic turnover rates were comparable to those observed in carbon.

  10. Variability in carbon and nitrogen isotope fractionation associated with bacterial hydrolysis of atrazine

    Science.gov (United States)

    Meyer, A.; Penning, H.; Elsner, M.

    2009-04-01

    Even after legislative prohibition in 1991 by the European Union, the pesticide atrazine and its metabolites are still detected in surface and ground water frequently exceeding the permitted drinking water concentration limit of 0,1 g/L. Despite much recent research on atrazine, its risk assessment in the environment is still a major challenge because of the difficulty of establishing mass balances in the subsurface. To obtain a better insight into the fate of atrazine, we developed compound-specific stable isotope analysis (CSIA) for atrazine. CSIA has proven valuable for assessing organic contaminants in subsurface environments, on the one hand for source identification and on the other hand to trace (bio)chemical degradation reactions through isotope fractionation in the compounds. Such assessment is based on the Rayleigh equation and therein on the isotope enrichment factor ɛ, which must be determined experimentally beforehand. In ongoing work, we therefore measured carbon and nitrogen isotope fractionation associated with biotic hydrolsis of atrazine. C and N isotope enrichment factors were determined in resting cell experiments for Pseudomonas sp. ADP, Chelatobacter heintzii and Arthrobacter aurescens TC1, strains that hydrolyse atrazine in the initial transformation reaction. Carbon and nitrogen isotope enrichment factors were distinctly different between the bacterial strains. However, when plotting shifts in carbon isotope ratios versus shifts in nitrogen isotope ratios the slopes of the different degradation experiments coincided well. These results give evidence that all bacterial strains were carrying out the same initial biochemical degradation reaction, but that the associated isotope fractionation, as represented by the enrichment factors, was masked to a different extent owing to different rate determining steps prior to the isotopically sensitive bond cleavage (commitment to catalysis). Our study therefore illustrates the benefit of multi

  11. Carbon and hydrogen isotopic effects of stomatal density in Arabidopsis thaliana

    Science.gov (United States)

    Lee, Hyejung; Feakins, Sarah J.; Sternberg, Leonel da S. L.

    2016-04-01

    Stomata are key gateways mediating carbon uptake and water loss from plants. Varied stomatal densities in fossil leaves raise the possibility that isotope effects associated with the openness of exchange may have mediated plant wax biomarker isotopic proxies for paleovegetation and paleoclimate in the geological record. Here we use Arabidopsis thaliana, a widely used model organism, to provide the first controlled tests of stomatal density on carbon and hydrogen isotopic compositions of cuticular waxes. Laboratory grown wildtype and mutants with suppressed and overexpressed stomatal densities allow us to directly test the isotope effects of stomatal densities independent of most other environmental or biological variables. Hydrogen isotope (D/H) measurements of both plant waters and plant wax n-alkanes allow us to directly constrain the isotopic effects of leaf water isotopic enrichment via transpiration and biosynthetic fractionations, which together determine the net fractionation between irrigation water and n-alkane hydrogen isotopic composition. We also measure carbon isotopic fractionations of n-alkanes and bulk leaf tissue associated with different stomatal densities. We find offsets of +15‰ for δD and -3‰ for δ13C for the overexpressed mutant compared to the suppressed mutant. Since the range of stomatal densities expressed is comparable to that found in extant plants and the Cenozoic fossil record, the results allow us to consider the magnitude of isotope effects that may be incurred by these plant adaptive responses. This study highlights the potential of genetic mutants to isolate individual isotope effects and add to our fundamental understanding of how genetics and physiology influence plant biochemicals including plant wax biomarkers.

  12. Zinc isotope evidence for a large-scale carbonated mantle beneath eastern China

    Science.gov (United States)

    Liu, Sheng-Ao; Wang, Ze-Zhou; Li, Shu-Guang; Huang, Jian; Yang, Wei

    2016-06-01

    A large set of zinc (Zn) stable isotope data for continental basalts from eastern China were reported to investigate the application of Zn isotopes as a new tracer of deep carbonate cycling. All of the basalts with ages of 120 Ma basalts from eastern China (0.27 ± 0.06‰; 2sd). Given that Zn isotope fractionation during magmatic differentiation is limited (≤0.1‰), the elevated δ66Zn values reflect the involvement of isotopically heavy crustal materials (e.g., carbonates with an average δ66Zn of ∼0.91‰) in the mantle sources. SiO2 contents of the recycled Mg (Zn)-rich carbonates in the mantle beneath eastern China since the Late Mesozoic. Since Zn is a trace element in the mantle and Zn isotopic compositions of marine carbonates and the mantle differ markedly, we highlight Zn isotopes as a new and useful tool of tracing deep carbonate cycling in the Earth's mantle.

  13. Stable Isotopic Evidence for a Pedogenic Origin of Carbonates in Trench 14 near Yucca Mountain, Nevada.

    Science.gov (United States)

    Quade, J; Cerling, T E

    1990-12-14

    Layered carbonate and silica encrust fault fractures exposed in Trench 14 near Yucca Mountain, site of the proposed high-level nuclear waste repository in southern Nevada. Comparison of the stable carbon and oxygen isotopic compositions of the fracture carbonates with those of modern soil carbonates in the area shows that the fracture carbonates are pedogenic in origin and that they likely formed in the presence of vegetation and rainfall typical of a glacial climate. Their isotopic composition differs markedly from that of carbonate associated with nearby springs. The regional water table therefore remained below the level of Trench 14 during the time that the carbonates and silica precipitated, a period probably covering parts of at least the last 300,000 years.

  14. Carbon Stable Isotopes as Indicators of Coastal Eutrophication

    Science.gov (United States)

    Coastal ecologists and managers have frequently used nitrogen stable isotopes (δ15N) to trace and monitor anthropogenic nitrogen (N) in coastal ecosystems. However, the interpretation of δ15N data can often be challenging, if not confounding, as the isotope values fractionate su...

  15. Isotope tracer study of hydrogen spillover on carbon-based adsorbents for hydrogen storage.

    Science.gov (United States)

    Lachawiec, Anthony J; Yang, Ralph T

    2008-06-17

    A composite material comprising platinum nanoparticles supported on molecular sieve templated carbon was synthesized and found to adsorb 1.35 wt % hydrogen at 298 K and 100 atm. The isosteric heat of adsorption for the material at low coverage was approximately 14 kJ/mol, and it approached a value of 10.6 kJ/mol as coverage increased for pressures at and above 1 atm. The increase in capacity is attributed to spillover, which is observed with the use of isotopic tracer TPD. IRMOF-8 bridged to Pt/C, a material known to exhibit hydrogen spillover at room temperature, was also studied with the hydrogen-deuterium scrambling reaction for comparison. The isotherms were reversible. For desorption, sequential doses of H2 and D2 at room temperature and subsequent TPD yield product distributions that are strong indicators of the surface diffusion controlled reverse spillover process.

  16. Carbon Isotope Evidence for the Stepwise Oxidation of the Proterozoic Environment

    Science.gov (United States)

    DesMarais, David J.; Strauss, Harald; Summons, Roger E.; Hayes, J. M.

    1992-01-01

    The oxidation of the Earth's crust and the increase in atmospheric oxygen early in Earth history have been linked to the accumulation of reduced carbon in sedimentary rocks. Trends in the carbon isotope composition of sedimentary organic carbon and carbonate show that during the Proterozoic aeon (2.5-0.54 Gyr ago) the organic carbon reservoir grew in size, relative to the carbonate reservoir. This increase, and the concomitant release of oxidizing power in the environment, occurred mostly during episodes of global rifting and orogeny.

  17. Soil moisture effects on the carbon isotope composition of soil respiration

    Science.gov (United States)

    Claire L. Phillips; Nick Nickerson; David Risk; Zachary E. Kayler; Chris Andersen; Alan Mix; Barbara J. Bond

    2010-01-01

    The carbon isotopic composition (δ13C) of recently assimilated plant carbon is known to depend on water-stress, caused either by low soil moisture or by low atmospheric humidity. Air humidity has also been shown to correlate with the δ13C of soil respiration, which suggests indirectly that recently fixed photosynthates...

  18. Chlorine and carbon isotope measurements can help assessing the effectivenes of a zero valent iron barrier

    Science.gov (United States)

    Cretnik, S.; Audi, C.; Bernstein, A.; Palau, J.; Soler, A.; Elsner, M.

    2012-04-01

    Chlorinated aliphatic hydrocarbons (CAH's) such as trichloroethene (TCE), cis-dichloroethene (cis-DCE) and vinylchloride (VC) are extensively used in industrial applications. One of the most promising remediation techniques for CAH's in groundwater is their removal via abiotic reductive dechlorination using Zero Valent Iron (ZVI). This is applied for the treatment of contaminated sites by installing permeable reactive barriers (PRB). In this study, isotope fractionation of chlorinated ethylenes in transformation by cast iron has been investigated, because such types of iron are commonly used in PRBs. Batch experiments have been carried out in closed flasks, containing cast iron with aqueous solutions of TCE, cDCE and VC. These substrates and their respective products have been monitored by headspace samplings for their concentration (by GC-FID) and isotope fractionation of carbon and chlorine (by GC-IRMS). A decreasing reactivity trend was observed when compounds contain less chlorine atoms, with differences in rate constants of about one order of magnitude between each of the substances TCE > cDCE > VC. This resulted in the accumulation of products with fewer chlorine atoms. Therefore a similar observation can be expected if degradation in the field is incomplete, for example in the case of aged or improperly designed PRB. Pronounced carbon and chlorine isotope fractionation was measured for each of the compounds, and characteristic dual isotope plots (C, Cl) were obtained for TCE and cDCE. These results may serve as an important reference for the interpretation of isotope data from field sites, since stable isotope fractionation is widely recognized as robust indicator for such pollutant transformations. However, carbon isotope fractionation in a given parent compound may be caused by either abiotic or biotic degradation. In the field, it can therefore be difficult to delineate the contribution of abiotic transformation by PRB in the presence of ongoing

  19. Provenance and weathering depth of carbonaceous gotland sandstone by use of carbon and oxygen isotopes

    Science.gov (United States)

    Åberg, G.; Löfvendahl, R.; Stijfhoorn, D.; Råheim, A.

    Carbon and oxygen isotope ratios of carbonates (calcite) from different sites and stratigraphic levels of the Gotland sandstone show that it might be possible to fingerprint the different quarries. Preliminary tests of nine samples of Gotland sandstone from different buildings show that the laser microprobe is an excellent tool for estimating depth of weathering on this carbonaceous sandstone. Analyses perpendicular to the stone surface gave a similar trend for the carbon and oxygen isotope ratios, although changes go deeper with δ13C than δ18O. Depth of weathering is controlled by exposure, location, biologic overgrowth and salt efflorescence. The effect of earlier conservation treatment with linseed oil can also be traced.

  20. Seasonal variation in kangaroo tooth enamel oxygen and carbon isotopes in southern Australia

    Science.gov (United States)

    Brookman, Tom H.; Ambrose, Stanley H.

    2012-09-01

    Serial sampling of tooth enamel growth increments for carbon and oxygen isotopic analyses of Macropus (kangaroo) teeth was performed to assess the potential for reconstructing paleoseasonality. The carbon isotope composition of tooth enamel apatite carbonate reflects the proportional intake of C3 and C4 vegetation. The oxygen isotopic composition of enamel reflects that of ingested and metabolic water. Tooth enamel forms sequentially from the tip of the crown to the base, so dietary and environmental changes during the tooth's formation can be detected. δ13C and δ18O values were determined for a series of enamel samples drilled from the 3rd and 4th molars of kangaroos that were collected along a 900 km north-south transect in southern Australia. The serial sampling method did not yield pronounced seasonal isotopic variation patterns in Macropus enamel. The full extent of dietary isotopic variation may be obscured by attenuation of the isotopic signal during enamel mineralisation. Brachydont (low-crowned) Macropus teeth may be less sensitive to seasonal variation in isotopic composition due to time-averaging during mineralisation. However, geographic variations observed suggest that there may be potential for tracking latitudinal shifts in vegetation zones and seasonal environmental patterns in response to climate change.

  1. Trophic ecology of small yellow croaker (Larimichthys polyactis Bleeker): stable carbon and nitrogen isotope evidence

    Institute of Scientific and Technical Information of China (English)

    JI Weiwei; CHEN Xuezhong; JIANG Yazhou; LI Shengfa

    2011-01-01

    The trophic ecology of the small yellow croaker (Larimichthys polyactis) was studied using stable isotope analyses.Samples were collected from July to September 2009 and 34 individuals from eight sites were examined for stable carbon and nitrogen isotopes.Stable carbon isotope ratios (δ13C)ranged from -20.67 to -15.43,while stable nitrogen isotope ratios (δ15N) ranged 9.18-12.23.The relationship between δ13C and δ15N suggested high resource partitioning in the sampling area.Significant differences in stable isotope values among the eight sampling sites may be linked to environmental diversities involving various physical processes (such as ocean current,wind and tide) and different carbon sources.Furthermore,the stable isotope ratios may also explain the ontogenetic variability in diet and feeding,because δ13C and δ15N varied significantly with increasing body size.The findings are consistent with other studies on diet analyses in small yellow croaker.It was also demonstrated that stable isotope analysis could be used to estimate the trophic characters of small yellow croaker in feeding patterns and migrating habits.

  2. Carbon Isotopic Values of Individual N—Alkanes in Pyrolysates of Algae

    Institute of Scientific and Technical Information of China (English)

    周文; 吴庆余; 等

    2000-01-01

    This paper presents the carbon isotopic values of individual n-alkanes in pyrolysates of algae,which are widely spread in marine and lacustrine environments.The carbon isotopic values of n-alkanes originated from different algal precursors vary greatly,and those of n-alka nes orginated from C.protothecoides,S.sp PCC 6803 and I.Galbana are even heavier than from higher plants,n-alkanes with different carbon numers derived from the sme organism may stem from different biomacromolecules.The dominant product nC31 diene yielded at 300℃ or lower temperature also is different from n-alkanes yielded at the same thermal evolution phase with respect to their origin.The catalysis of mineral components in limestone may lead to a lighter carbon isotope composition of n-alkanes.

  3. Carbon isotope anomaly in the major plant C1 pool and its global biogeochemical implications

    Directory of Open Access Journals (Sweden)

    F. Keppler

    2004-01-01

    Full Text Available We report that the most abundant C1 units of terrestrial plants, the methoxyl groups of pectin and lignin, have a unique carbon isotope signature exceptionally depleted in 13C. Plant-derived C1 volatile organic compounds (VOCs are also anomalously depleted in 13C compared with Cn+1 VOCs. The results confirm that the plant methoxyl pool is the predominant source of biospheric C1 compounds of plant origin such as methanol, chloromethane and bromomethane. Furthermore this pool, comprising ca 2.5% of carbon in plant biomass, could be an important substrate for methanogenesis and thus be envisaged as a possible source of isotopically light methane entering the atmosphere. Our findings have significant implications for the use of carbon isotope ratios in elucidation of global carbon cycling. Moreover methoxyl groups could act as markers for biological activity in organic matter of terrestrial and extraterrestrial origin.

  4. Linking carbon and water cycles using stable isotopes across scales: progress and challenges

    Directory of Open Access Journals (Sweden)

    C. Werner

    2011-03-01

    Full Text Available Stable isotope analysis is a powerful tool for tracing biogeochemical processes in the carbon and water cycles. One particularly powerful approach is to employ multiple isotopes where the simultaneous assessment of the D/H,18O/16O and/or 13C/12C in different compounds provide a unique means to investigate the coupling of water and carbon fluxes at various temporal and spatial scales. Here, we present a research update on recent advances in our process-based understanding of the utilization of carbon, oxygen and hydrogen isotopes to lend insight into carbon and water cycling. We highlight recent technological developments and approaches, their strengths and methodological precautions with examples covering scales from minutes to centuries and from the leaf to the globe.

  5. Towards a better understanding of magnesium-isotope ratios from marine skeletal carbonates

    Science.gov (United States)

    Hippler, Dorothee; Buhl, Dieter; Witbaard, Rob; Richter, Detlev K.; Immenhauser, Adrian

    2009-10-01

    This study presents magnesium stable-isotope compositions of various biogenic carbonates of several marine calcifying organisms and an algae species, seawater samples collected from the western Dutch Wadden Sea, and reference materials. The aim of this study is to explore the influence of mineralogy, taxonomy and environmental factors (e.g., seawater isotopic composition, temperature, salinity) on magnesium-isotopic (δ 26Mg) ratios of skeletal carbonates. Using high-precision multi-collector inductively coupled plasma mass spectrometry, we observed that the magnesium-isotopic composition of seawater from the semi-enclosed Dutch Wadden Sea is identical to that of open marine seawater. We further found that a considerable component of the observed variability in δ 26Mg values of marine skeletal carbonates can be attributed to differences in mineralogy. Furthermore, magnesium-isotope fractionation is species-dependent, with all skeletal carbonates being isotopically lighter than seawater. While δ 26Mg values of skeletal aragonite and high-magnesium calcite of coralline red algae indicate the absence or negligibility of metabolic influences, the δ 26Mg values of echinoids, brachiopods and bivalves likely result from a taxon-specific level of control on Mg-isotope incorporation during biocalcification. Moreover, no resolvable salinity and temperature effect were observed for coralline red algae and echinoids. In contrast, Mg-isotope data of bivalves yield ambiguous results, which require further validation. The data presented here, point to a limited use of Mg isotopes as temperature proxy, but highlight the method's potential as tracer of seawater chemistry through Earth's history.

  6. Activated Carbon, Carbon Nanofiber and Carbon Nanotube Supported Molybdenum Carbide Catalysts for the Hydrodeoxygenation of Guaiacol

    Directory of Open Access Journals (Sweden)

    Eduardo Santillan-Jimenez

    2015-03-01

    Full Text Available Molybdenum carbide was supported on three types of carbon support—activated carbon; multi-walled carbon nanotubes; and carbon nanofibers—using ammonium molybdate and molybdic acid as Mo precursors. The use of activated carbon as support afforded an X-ray amorphous Mo phase, whereas crystalline molybdenum carbide phases were obtained on carbon nanofibers and, in some cases, on carbon nanotubes. When the resulting catalysts were tested in the hydrodeoxygenation (HDO of guaiacol in dodecane, catechol and phenol were obtained as the main products, although in some instances significant amounts of cyclohexane were produced. The observation of catechol in all reaction mixtures suggests that guaiacol was converted into phenol via sequential demethylation and HDO, although the simultaneous occurrence of a direct demethoxylation pathway cannot be discounted. Catalysts based on carbon nanofibers generally afforded the highest yields of phenol; notably, the only crystalline phase detected in these samples was Mo2C or Mo2C-ζ, suggesting that crystalline Mo2C is particularly selective to phenol. At 350 °C, carbon nanofiber supported Mo2C afforded near quantitative guaiacol conversion, the selectivity to phenol approaching 50%. When guaiacol HDO was performed in the presence of acetic acid and furfural, guaiacol conversion decreased, although the selectivity to both catechol and phenol was increased.

  7. Highly Efficient Quantum Sieving in Porous Graphene-like Carbon Nitride for Light Isotopes Separation

    Science.gov (United States)

    Qu, Yuanyuan; Li, Feng; Zhou, Hongcai; Zhao, Mingwen

    2016-01-01

    Light isotopes separation, such as 3He/4He, H2/D2, H2/T2, etc., is crucial for various advanced technologies including isotope labeling, nuclear weapons, cryogenics and power generation. However, their nearly identical chemical properties made the separation challenging. The low productivity of the present isotopes separation approaches hinders the relevant applications. An efficient membrane with high performance for isotopes separation is quite appealing. Based on first-principles calculations, we theoretically demonstrated that highly efficient light isotopes separation, such as 3He/4He, can be reached in a porous graphene-like carbon nitride material via quantum sieving effect. Under moderate tensile strain, the quantum sieving of the carbon nitride membrane can be effectively tuned in a continuous way, leading to a temperature window with high 3He/4He selectivity and permeance acceptable for efficient isotopes harvest in industrial application. This mechanism also holds for separation of other light isotopes, such as H2/D2, H2/T2. Such tunable quantum sieving opens a promising avenue for light isotopes separation for industrial application. PMID:26813491

  8. Significance of Carbon Isotopes in Carbonate Sequence Stratigraphy—As Exemplified by the Permian System in Southwest China

    Institute of Scientific and Technical Information of China (English)

    覃建雄; 杨作升; 等

    1999-01-01

    Based on the research on sequence stratigraphy of the Permian in Southwest China,in conjunction with the carbon isotope data from the typical sections at Ganluo,Sichuan and Tianlin and Masan,Guangxi,the authors suggest that the genetic framework and internal architicture of different sequences possess quite different carbon isotopic characteristics.Therefore ,the following problems can be solved in terms of carbon isotopic values,evolutionary curve patterns and structures of carbonate sequences:(1) to determe the nature of sequence boundary surface and related geological events;(2) to recognize various kinds of sedimentary system tracts;(3) to discuss the internal architicture and genetic framework of the sequences and their evolution;(4) to subdivide and correlate sedimentary sequences on a regional or global scale; and (5)to enhance the resolution of sequence stratigraphic analysis.Stable carbon isotopes have proved themselves to be valid in sequence stratigraphic studies of carbonate rocks,as demonstrated by our results presented in this paper.

  9. Stable Carbon Isotope Ratios of Phenolic Compounds in Secondary Particulate Organic Matter Formed by Photooxidation of Toluene

    CERN Document Server

    Irei, Satoshi; Huang, Lin; Auld, Janeen; Collin, Fabrice; Hastie, Donald

    2014-01-01

    Compound-specific stable carbon isotope ratios for phenolic compounds in secondary particulate organic matter (POM) formed by photooxidation of toluene were studied. Secondary POM generated by photooxidation of toluene using a continuous-flow reactor and an 8 cubic meter indoor smog chamber was collected, and then extracted with acetonitrile. Eight phenolic compounds were identified in the extracts by a gas chromatograph coupled with a mass spectrometer, and their compound-specific stable carbon isotope ratios were determined by a gas chromatograph coupled with a combustion furnace followed by an isotope ratio mass spectrometer. The majority of the products, including methylnitrophenols and methylnitrocatechols, were isotopically depleted by 5 to 6 permil compared to the initial isotope ratio for toluene, whereas the isotope ratio for 4_nitrophenol remained the same as the initial isotope ratio for toluene. Based on the reaction mechanisms postulated in literature, stable carbon isotope ratios of these produc...

  10. 3D-CSIA: carbon, chlorine, and hydrogen isotope fractionation in transformation of TCE to ethene by a Dehalococcoides culture.

    Science.gov (United States)

    Kuder, Tomasz; van Breukelen, Boris M; Vanderford, Mindy; Philp, Paul

    2013-09-03

    Carbon (C), chlorine (Cl), and hydrogen (H) isotope effects were determined during dechlorination of TCE to ethene by a mixed Dehalococcoides (Dhc) culture. The C isotope effects for the dechlorination steps were consistent with data published in the past for reductive dechlorination (RD) by Dhc. The Cl effects (combined with an inverse H effect in TCE) suggested that dechlorination proceeded through nucleophilic reactions with cobalamin rather than by an electron transfer mechanism. Depletions of (37)Cl in daughter compounds, resulting from fractionation at positions away from the dechlorination center (secondary isotope effects), further support the nucleophilic dechlorination mechanism. Determination of C and Cl isotope ratios of the reactants and products in the reductive dechlorination chain offers a potential tool for differentiation of Dhc activity from alternative transformation mechanisms (e.g., aerobic degradation and reductive dechlorination proceeding via outer sphere mechanisms), in studies of in situ attenuation of chlorinated ethenes. Hydrogenation of the reaction products (DCE, VC, and ethene) showed a major preference for the (1)H isotope. Detection of depleted dechlorination products could provide a line of evidence in discrimination between alternative sources of TCE (e.g., evolution from DNAPL sources or from conversion of PCE).

  11. An automated method for 'clumped-isotope' measurements on small carbonate samples.

    Science.gov (United States)

    Schmid, Thomas W; Bernasconi, Stefano M

    2010-07-30

    Clumped-isotope geochemistry deals with the state of ordering of rare isotopes in molecules, in particular with their tendency to form bonds with other rare isotopes rather than with the most abundant ones. Among its possible applications, carbonate clumped-isotope thermometry is the one that has gained most attention because of the wide potential of applications in many disciplines of earth sciences. Clumped-isotope thermometry allows reconstructing the temperature of formation of carbonate minerals without knowing the isotopic composition of the water from which they were formed. This feature enables new approaches in paleothermometry. The currently published method is, however, limited by sample weight requirements of 10-15 mg and because measurements are performed manually. In this paper we present a new method using an automated sample preparation device coupled to an isotope ratio mass spectrometer. The method is based on the repeated analysis (n = 6-8) of 200 microg aliquots of sample material and completely automated measurements. In addition, we propose to use precisely calibrated carbonates spanning a wide range in Delta(47) instead of heated gases to correct for isotope effects caused by the source of the mass spectrometer, following the principle of equal treatment of the samples and standards. We present data for international standards (NBS 19 and LSVEC) and different carbonates formed at temperatures exceeding 600 degrees C to show that precisions in the range of 10 to 15 ppm (1 SE) can be reached for repeated analyses of a single sample. Finally, we discuss and validate the correction procedure based on high-temperature carbonates instead of heated gases.

  12. Surface area dependence of calcium isotopic reequilibration in carbonates: Implications for isotopic signatures in the weathering zone

    Science.gov (United States)

    Fernandez, N. M.; Druhan, J. L.; Potrel, A.; Jacobson, A. D.

    2016-12-01

    The concept of dynamic equilibrium carries the implicit assumption of continued isotopic exchange between a mineral and the surrounding fluid. While this effect has received much attention in the marine paleoproxy literature, it has been relatively overlooked in application to the terrestrial environment. In weathering systems, a potential consequence is that rapid reequilibration may alter or erase isotopic signatures generated during secondary mineral formation. The extent and timescale over which isotopic signatures are reset in these hydrologic systems is unknown. Using reactive transport modeling, we show isotopic reequilibration under conditions reflecting terrestrial hydrologic settings to be significant and dependent on the reactive surface area of the solid. In particular, we suggest that the non-traditional stable isotopes commonly used in application to carbonates (e.g., Ca, Mg, Sr) are sensitive to these effects due to their rapid reaction rates. We aim to characterize the dependence of Ca isotopic reequilibration on surface area during calcite precipitation via batch experiments conducted at ambient temperature over 48-hour time periods. Calcite precipitation was performed in a closed batch reactor utilizing a controlled free-drift method. The batch reactors contained mixed supersaturated solutions of CaCl2 and NaHCO3 at an initial pH of 8.54. Precipitation was initiated by seed inoculation of calcite crystals with two distinct, pre-constrained surface areas. All experiments achieved the same final state of chemical equilibrium, but as expected, the fastest approach to equilibrium occurred for experiments employing calcite seeds with the highest surface area. This implies that differences in equilibrated Ca isotope ratios (δ44/40Ca) should reflect differences in surface area. This prediction is upheld by models of the experiments, indicating a measureable difference in δ44Ca during calcite precipitation where the higher surface area corresponds to

  13. Stable carbon isotope ratios of ambient secondary organic aerosols in Toronto

    Science.gov (United States)

    Saccon, M.; Kornilova, A.; Huang, L.; Moukhtar, S.; Rudolph, J.

    2015-09-01

    A method to quantify concentrations and stable carbon isotope ratios of secondary organic aerosols has been applied to study atmospheric nitrophenols in Toronto, Canada. The sampling of five nitrophenols, all with substantial secondary formation from the photooxidation of aromatic volatile organic compounds (VOCs), was conducted in the gas phase and particulate matter (PM) together and in PM alone. Their concentrations in the atmosphere are in the low ng m-3 range and, consequently, a large volume of air (> 1000 m3) is needed to analyze samples for stable carbon isotope ratios, resulting in sampling periods of typically 24 h. While this extended sampling period increases the representativeness of average values, it at the same time reduces possibilities to identify meteorological conditions or atmospheric pollution levels determining nitrophenol concentrations and isotope ratios. Average measured carbon isotope ratios of the different nitrophenols are between -34 and -33 ‰, which is well within the range predicted by mass balance. However, the observed carbon isotope ratios cover a range of nearly 9 ‰ and approximately 20 % of the isotope ratios of the products have isotope ratios lower than predicted from the kinetic isotope effect of the first step of the reaction mechanism and the isotope ratio of the precursor. This can be explained by isotope fractionation during reaction steps following the initial reaction of the precursor VOCs with the OH radical. Limited evidence for local production of nitrophenols is observed since sampling was done in the Toronto area, an urban center with significant anthropogenic emission sources. Strong evidence for significant local formation of nitrophenols is only found for samples collected in summer. On average, the difference in carbon isotope ratios between nitrophenols in the particle phase and in the gas phase is insignificant, but for a limited number of observations in summer, a substantial difference is observed. This

  14. The preparation of 248CmF 3 deposits on self-supported carbon foils

    Science.gov (United States)

    Aaron, W. S.; Petek, M.; Zevenbergen, L. A.

    1987-06-01

    Another target preparative technique was recently added to the Isotope Research Materials Laboratory's (IRML) capabilities for custom target fabrication. In support of super-heavy-ion physics experiments, methods and equipment were developed for the preparation of 248CmF 3 deposits on carbon foils. The starting material was obtained as either a chloride or nitrate solution, converted to the flouride, and evaporated on carbon foil substrates. Deposits ranging from 40 to 570 μg/cm 2 were prepared as a 12-mm-diam spot on 45- to 60-μg/cm 2 self-supported carbon foils. The deposits were then overcoated with approximately 10 μg/cm 2 of carbon to minimize contamination problems during target handling. The high cost of 248Cm ($100/μg) and its limited availability were the key constraints in the development of preparative technology beyond the inherent radioactivity of 248Cm.

  15. Of Island Arcs and Icebergs? Strontium and Carbon Isotope Stratigraphy of Ethiopian Snowball Earth Sequences

    Science.gov (United States)

    Miller, N. R.; Stern, R. J.; Avigad, D.; Beyth, M.; Küster, D.; Gebresilassie, S.; Mehari, K.

    2004-12-01

    Negash syncline preserves a diamictite of probable glacial origin (i.e., dropstones, faceted clasts, cobbles of diverse composition) where a pronounced negative carbon excursion from values of +7 to -2 per mil accompanies the transition from upper black carbonate to diamictite deposition. The diamictite is the youngest preserved unit within the investigated structures so it is unknown if a superjacent cap carbonate was ever deposited. Zircon evaporation dates from granites intruding the base of the sequence but post-dating early deformation of the entire sequence suggest that the Tambien Group is older than 613Ma, and therefore diamictite genesis is incompatible with younger Varanger, or `Ediacaran' glacial intervals. Ages of ~800 Ma for Tsaliet equivalents in Eritrea provide an upper age constraint. The range of measured Sr isotopic compositions best overlaps Sturtian portions of available reference curves (ca. 720-750 Ma or a little older) and strongly supports the prospect that the Negash diamictite is the product of a Sturtian glacial episode.

  16. Intracellular carbon isotope distributions of continuous-culture Allochromatium vinosum grown on acetate vs. CO2.

    Science.gov (United States)

    Tang, T.; Mohr, W.; Sattin, S.; Rogers, D.; Girguis, P. R.; Pearson, A.

    2016-02-01

    Sulfur oxidizing bacteria are commonly observed in various aquatic environments, which use reduced sulfur compounds as electron donors to complete the carbon metabolism. Their carbon isotope fractionations during biosynthesis can be preserved in the fossil records. Here we grew a model sulfur oxidizing bacterium, Allochromatium vinosum, in two mode of continuous culture. One of the A. vinosum culture was grown autotrophically with CO2 as the carbon source; while the other one was grown heterotrophically on acetate. A novel protein isotope fingerprinting analysis was applied combining proteomics and protein isotope analysis together, which indicates no isotope fractionation among individual proteins, whereas the bulk protein d13C relative to bulk biomass were substantially different between autotrophic and heterotrophic cells. The same trend was also observed in d13C values of bulk amino acids, fatty acids and nucleic acids. The observed difference in major classes of organic compounds may result from the difference in biosynthetic pathways of autotrophic and heterotrophic cells. A closer look into d13C value of individual amino acids and fatty acids provides us further evidence to identify isotopic response to key reactions of central carbon metabolism as revealed by proteomic analysis. Our work suggests that we can decipher diverse microbial carbon metabolisms by combining proteomics with compound specific analysis of major classes of organic compounds.

  17. Carbon and oxygen isotope variations of the Middle-Late Triassic Al Aziziyah Formation, northwest Libya

    Science.gov (United States)

    Moustafa, Mohamed S. H.; Pope, Michael C.; Grossman, Ethan L.; Mriheel, Ibrahim Y.

    2016-06-01

    This study presents the δ13C and δ18O records from whole rock samples of the Middle-Late Triassic (Ladinian-Carnian) Al Aziziyah Formation that were deposited on a gently sloping carbonate ramp within the Jifarah Basin of Northwest Libya. The Al Aziziyah Formation consists of gray limestone, dolomite, and dolomitic limestone interbedded with shale. The Ghryan Dome and Kaf Bates sections were sampled and analyzed for carbon and oxygen isotope chemostratigraphy to integrate high-resolution carbon isotope data with an outcrop-based stratigraphy, to provide better age control of the Al Aziziyah Formation. This study also discusses the relation between the facies architecture of the Al Aziziyah Formation and the carbon isotope values. Seven stages of relative sea level rise and fall within the Ghryan Dome were identified based on facies stacking patterns, field observations and carbon stable isotopes. The Al Aziziyah Formation δ13C chemostratigraphic curve can be partially correlated with the Triassic global δ13C curve. This correlation indicates that the Al Aziziyah Formation was deposited during the Ladinian and early Carnian. No straight-forward relationship is seen between δ13C and relative sea level probably because local influences complicated systematic environmental and diagenetic isotopic effects associated with sea level change.

  18. Nitrogen-doped carbon nanotubes as a metal catalyst support

    CSIR Research Space (South Africa)

    Mabena, LF

    2011-05-01

    Full Text Available in the catalysis industry due to cost issues and properties that are not found in their bulk state. An efficient way to produce and stabilise noble metal nanoparticles is by dispersion on a suitable support. Carbon-based supports, such as carbon nanotubes, carbon...

  19. Late Paleocene–early Eocene carbon isotope stratigraphy from a near-terrestrial tropical section and antiquity of Indian mammals

    Indian Academy of Sciences (India)

    A Samanta; A Sarkar; M K Bera; Jyotsana Rai; S S Rathore

    2013-02-01

    Late Paleocene to early Eocene (∼56 to 51 Ma) interval is characterized by five distinct transient warming (hyperthermal) events (Paleocene–Eocene thermal maximum (PETM), H1/ETM2/ELMO, H2, I1 and I2) in a super greenhouse globe associated with negative carbon isotope excursions (CIEs). Although well-documented marine records exist at different latitudes, terrestrial PETM sections are rare. In particular, almost no terrestrial records of either the PETM or early Eocene hyperthermals (EEHs) are yet available from the tropics. Further, evolution of modern order of mammals near the PETM has been recorded in many northern continents; however, the response of mammals in the tropics to these warming events is unknown. A tropical terrestrial record of these hyperthermal/CIE events, encompassing the earliest modern order mammal bearing horizon from India, can therefore be vital in understanding climatic and biotic evolution during the earliest Cenozoic time. Here, for the first time, we report high resolution carbon isotope (13C) stratigraphy, nannofossil, and Sr isotope ratio of marine fossil carbonate from the Cambay Shale Formation of Western India. The record shows complete preservation of all the above CIE events, including the PETM, hitherto unknown from the equatorial terrestrial records. 13C chemostratigraphy further suggests that at least the present early Eocene mammal-bearing horizon, recently discovered at Vastan, does not support the `out of India' hypothesis of earliest appearance of modern mammals and subsequent dispersal to the Holarctic continents.

  20. Late Paleocene-early Eocene carbon isotope stratigraphy from a near-terrestrial tropical section and antiquity of Indian mammals

    Science.gov (United States)

    Samanta, A.; Sarkar, A.; Bera, M. K.; Rai, Jyotsana; Rathore, S. S.

    2013-02-01

    Late Paleocene to early Eocene (~56 to 51 Ma) interval is characterized by five distinct transient warming (hyperthermal) events (Paleocene-Eocene thermal maximum (PETM), H1/ETM2/ELMO, H2, I1 and I2) in a super greenhouse globe associated with negative carbon isotope excursions (CIEs). Although well-documented marine records exist at different latitudes, terrestrial PETM sections are rare. In particular, almost no terrestrial records of either the PETM or early Eocene hyperthermals (EEHs) are yet available from the tropics. Further, evolution of modern order of mammals near the PETM has been recorded in many northern continents; however, the response of mammals in the tropics to these warming events is unknown. A tropical terrestrial record of these hyperthermal/CIE events, encompassing the earliest modern order mammal bearing horizon from India, can therefore be vital in understanding climatic and biotic evolution during the earliest Cenozoic time. Here, for the first time, we report high resolution carbon isotope ( δ 13C) stratigraphy, nannofossil, and Sr isotope ratio of marine fossil carbonate from the Cambay Shale Formation of Western India. The record shows complete preservation of all the above CIE events, including the PETM, hitherto unknown from the equatorial terrestrial records. δ 13C chemostratigraphy further suggests that at least the present early Eocene mammal-bearing horizon, recently discovered at Vastan, does not support the `out of India' hypothesis of earliest appearance of modern mammals and subsequent dispersal to the Holarctic continents.

  1. Toward estimation of origin of methane at ancient seeps — Carbon isotopes of seep carbonates, lipid biomarkers, and adsorbed gas

    Science.gov (United States)

    Miyajima, Yusuke; Watanabe, Yumiko; Ijiri, Akira; Goto, Akiko; Jenkins, Robert; Hasegawa, Takashi; Sakai, Saburo; Matsumoto, Ryo

    2017-04-01

    Methane is generated mainly by microbial or thermal degradation of organic matter, and the origin of methane can be estimated based on its stable carbon isotopic signature. Seafloor seepages of methane-charged fluids have been a major source of methane to the ocean, and knowing the origin of methane at the methane seeps can provide valuable insights into the subsurface fluid circulation and biogeochemical processes. Methane seeps in the geological past are archived as authigenic methane-derived carbonate rocks, which precipitate via an alkalinity increase facilitated by microbially mediated anaerobic oxidation of methane. Here we attempted to estimate origins of methane at ancient seeps, based on several proxies preserved within the seep carbonates. We examined methane-seep carbonate rocks in the Japan Sea region, collected from lower Miocene to middle Pleistocene sediments at 11 sites on land, and also carbonate nodules collected from the seafloor off Joetsu, where thermogenic methane is seeping. Carbon isotopic compositions of the carbonates and lipid biomarkers of methane-oxidizing archaea within them were analyzed. In order to directly know original isotopic signatures of methane, we also attempted to extract adsorbed methane through acid dissolution of the powdered carbonates. Early-diagenetic carbonate phases show various δ13C values between -64.7 and -4.7‰ vs. VPDB, suggesting either biogenic or thermogenic, or both origins of methane. A lipid biomarker pentamethylicosane (PMI) extracted from the ancient carbonates has δ13C values mostly lower than -100‰ , whereas that from the modern methane-derived carbonate nodule has a higher value (-80‰ ). The δ13C values of the seeping methane (-36‰ ) and PMI in the modern Joetsu seep carbonate shows an offset of -44‰ . If this carbon isotope offset was similar at the ancient seeps, the δ13C values of PMI indicate that methane at ancient seeps in the Japan Sea region was biogenic in origin, with δ13C

  2. Iodine-to-calcium ratios in carbonates suggest a primary origin for the Precambrian Lomagundi and Shuram carbon isotope excursions

    Science.gov (United States)

    Hardisty, D. S.; Lu, Z.; Planavsky, N. J.; Osburn, M. R.; Bekker, A.; Lyons, T. W.

    2013-12-01

    Systematic increases in iodine-to-calcium ratios (I/Ca) in carbonates from both the Precambrian Lomagundi and Shuram carbonate carbon isotope (δ13Ccarb) excursion intervals suggest primary origins for these events. Iodate (IO3-), the oxidized iodine species, is the exclusive species incorporated into carbonates. The high redox sensitivity of IO3- to deoxygenation requires highly oxidizing fluids for IO3- production, making I/Ca in platform carbonates a simple indicator of the presence of oxidizing fluids in the surface ocean. Similarly, redox sensitivity makes the proxy host susceptible to diagenetic iodine loss during carbonate recrystallization in reducing pore fluids. Recent work has shown carbonates to experience near-complete iodine loss during dolomitization in the Permian, and work from our group evaluating modern and recent carbonates demonstrate the potential for diagenetic iodine loss during carbonate recrystallization. In some cases, however, such as meteoric aragonite-to-calcite transitions, oxidizing pore fluids have the potential to buffer IO3- concentrations, causing negligible alteration to primary I/Ca despite negative shifts in δ13Ccarb. These results highlight that diagenetic alterations to I/Ca and δ13Ccarb need not always be coupled, but importantly, no observed scenario promotes post-depositional addition of iodine to carbonates. This means that, independent of δ13Ccarb, systematic, stratigraphic increases in I/Ca ratios observed in the carbonate record are most easily interpreted as resulting from depositional controls such as surface ocean redox or shifts in the total marine iodine reservoir. From this, increasing I/Ca ratios coincident with rising and falling δ13Ccarb trends for the Paleoproterozic Lomagundi and Neoproterozoic Shuram events, respectively, support suggestions of a primary origin for the δ13Ccarb excursions. Significant increase in I/Ca in dolomites deposited during the Lomagundi excursion, rising from blank values in

  3. Marine Carbon-Sulfur Biogeochemical Cycles during the Steptoean Positive Carbon Isotope Excursion (SPICE) in the Jiangnan Basin, South China

    Institute of Scientific and Technical Information of China (English)

    Yang Peng; Yongbo Peng; Xianguo Lang; Haoran Ma; Kangjun Huang; Fangbing Li; Bing Shen

    2016-01-01

    ABSTRACT:Global occurrences of Steptoean Positive Carbon Isotope Excursion (SPICE) during Late Cambrian recorded a significant perturbation in marine carbon cycle, and might have had profound impacts on the biological evolution. In previous studies, SPICE has been reported from the Jiangnan slope belt in South China. To evaluate the bathymetric extent of SPICE, we investigate the limestone samples from the upper Qingxi Formation in the Shaijiang Section in the Jiangnan Basin. Our results show the positive excursions for both carbonate carbon (δ13C) and organic carbon (δ13Corg) isotopes, as well as the concurrent positive shifts in sulfur isotopes of carbonate associated sulfate (CAS, δ34SCAS) and pyrite (δ34Spyrite), unequivocally indicating the presence of SPICE in the Jiangnan Basin. A 4‰increase inδ13Ccarb of the Qingxi limestone implies the increase of the relative flux of organic carbon burial by a factor of two. Concurrent positive excursions inδ34SCAS andδ34Spyrite have been attributed to the enhanced pyrite burial in oceans with extremely low concentration and spatially heterogeneous isotopic composition of seawater sulfate. Here, we propose that the seawater sulfur isotopic heterogeneity can be generated by volatile organic sulfur compound (VOSC, such as methanethiol and dimethyl sulfide) formation in sulfidic continental margins that were widespread during SPICE. Emission of 32S-enriched VOSC in atmosphere, followed by lateral transportation and aerobic oxidation in atmosphere, and precipitation in open oceans result in a net flux of 32S from continental margins to open oceans, elevatingδ34S of seawater sulfate in continental margins. A simple box model indicates that about 35%to 75%of seawater sulfate in continental margins needs to be transported to open oceans via VOSC formation.

  4. Carbon isotope fractionation by anoxygenic phototrophic bacteria in euxinic Lake Cadagno.

    Science.gov (United States)

    Posth, N R; Bristow, L A; Cox, R P; Habicht, K S; Danza, F; Tonolla, M; Frigaard, N-U; Canfield, D E

    2017-09-03

    Anoxygenic phototrophic bacteria utilize ancient metabolic pathways to link sulfur and iron metabolism to the reduction of CO2 . In meromictic Lake Cadagno, Switzerland, both purple sulfur (PSB) and green sulfur anoxygenic phototrophic bacteria (GSB) dominate the chemocline community and drive the sulfur cycle. PSB and GSB fix carbon utilizing different enzymatic pathways and these fractionate C-isotopes to different extents. Here, these differences in C-isotope fractionation are used to constrain the relative input of various anoxygenic phototrophs to the bulk community C-isotope signal in the chemocline. We sought to determine whether a distinct isotopic signature of GSB and PSB in the chemocline persists in the settling fraction and in the sediment. To answer these questions, we also sought investigated C-isotope fractionation in the water column, settling material, and sediment of Lake Cadagno, compared these values to C-isotope fractionation of isolated anoxygenic phototroph cultures, and took a mass balance approach to investigate relative contributions to the bulk fractionation signature. We found a large C-isotope fractionation between dissolved inorganic carbon (DIC) and particulate organic carbon (POC) in the Lake Cadagno chemocline. This large fractionation between the DIC and POC was also found in culture experiments carried out with anoxygenic phototrophic bacteria isolated from the lake. In the Lake Cadagno chemocline, anoxygenic phototrophic bacteria controlled the bulk C-isotope fractionation, but the influence of GSB and PSB differed with season. Furthermore, the contribution of PSB and GSB to bulk C-isotope fractionation in the chemocline could be traced in the settling fraction and in the sediment. Taken together with other studies, such as lipid biomarker analyzes and investigations of other stratified lakes, these results offer a firmer understanding of diagenetic influences on bacterial biomass. © 2017 John Wiley & Sons Ltd.

  5. Carbon Stable Isotope Analysis of Methylmercury Toxin in Biological Materials by Gas Chromatography Isotope Ratio Mass Spectrometry.

    Science.gov (United States)

    Masbou, Jeremy; Point, David; Guillou, Gaël; Sonke, Jeroen E; Lebreton, Benoit; Richard, Pierre

    2015-12-01

    A critical component of the biogeochemical cycle of mercury (Hg) is the transformation of inorganic Hg to neurotoxic monomethylmercury (CH3Hg). Humans are exposed to CH3Hg by consuming marine fish, yet the origin of CH3Hg in fish is a topic of debate. The carbon stable isotopic composition (δ(13)C) embedded in the methyl group of CH3Hg remains unexplored. This new isotopic information at the molecular level is thought to represent a new proxy to trace the carbon source at the origin of CH3Hg. Here, we present a compound-specific stable isotope analysis (CSIA) technique for the determination of the δ(13)C value of CH3Hg in biological samples by gas chromatography combustion isotope ratio mass spectrometry analysis (GC-C-IRMS). The method consists first of calibrating a CH3Hg standard solution for δ(13)C CSIA. This was achieved by comparing three independent approaches consisting of the derivatization and halogenation of the CH3Hg standard solution. The determination of δ(13)C(CH3Hg) values on natural biological samples was performed by combining a CH3Hg selective extraction, purification, and halogenation followed by GC-C-IRMS analysis. Reference δ(13)C values were established for a tuna fish certified material (ERM-CE464) originating from the Adriatic Sea (δ(13)C(CH3Hg) = -22.1 ± 1.5‰, ± 2 SD). This value is similar to the δ(13)C value of marine algal-derived particulate organic carbon (δ(13)CPOC = -21‰).

  6. The thermal history of char as disclosed by carbon isotope ratios

    DEFF Research Database (Denmark)

    Egsgaard, Helge; Ambus, Per; Ahrenfeldt, Jesper

    In laboratory experiments, biomass char was produced under controlled conditions using wood chips from French pinewood. Different char qualities were obtained by pyrolysing the biomass at similar heating rates with end-temperatures ranging from 250 to 1000 o C. The char was analysed by flash...... pyrolysis and isotope ratio mass spectrometry. The results demonstrate that the temperature history of the char is reflected in the fine variation of carbon isotopes. The compound classes responsible for the variation were identified. Key words: Isotope ratio, flash pyrolysis, hot gas cleaning...

  7. Carbon and hydrogen isotopic composition and generation pathway of biogenic gas in China

    Institute of Scientific and Technical Information of China (English)

    SHEN Ping; WANG Xiaofeng; XU Yin; SHI Baoguang; XU Yongchang

    2009-01-01

    The carbon and hydrogen isotopic composition of biogenic gas is of great importance for the study of its generation pathway and reservoiring characteristics. In this paper, the formation pathways and reservoiring characteristics of biogenic gas reservoirs in China are described in terms of the carbon and hydrogen isotopic compositions of 31 gas samples from 10 biogenic gas reservoirs. The study shows that the hydrogen isotopic compositions of these biogenic gas reservoirs can be divided into three intervals:δDCH4>-200‰,-250‰<δDCH4<-200‰ and δDCH4<-250‰. The forerunners believed that the main generation pathway of biogenic gas under the condition of continental fresh water is acetic fermentation. Our research results showed that the generation pathway of biogenic gas under the condition of marine facies is typical CO2- reduction, the biogenic gas has heavy hydrogen isotopic composition: its δDCH4 values are higher than -200‰; that the biogenic gas under the condition of continental facies also was generated by the same way, but its hydrogen isotopic composition is lighter than that of biogenetic gas generated under typical marine facies condition: -250‰<δDCH4<-200‰, the δDCH4 values may be related to the salinity of the water medium in ancient lakes. From the relevant data of the Qaidam Basin, it can be seen that the hydrogen isotopic composition of biogenic methane has the same variation trend with increasing salinity of water medium. There are biogenic gas reservoirs formed in transitional regions under the condition of continental facies. These gas reservoirs resulted from both CO2- reduction and acetic fermentation, the formation of which may be related to the non-variant salinity of ancient water medium and the relatively high geothermal gradient, as is the case encountered in the Baoshan Basin. The biogenic gas generating in these regions has light hydrogen isotopic composition: δDCH4<-250‰, and relatively heavy carbon isotopic

  8. Responses of carbon isotope discrimination in C4 plant to variable N and water supply

    Science.gov (United States)

    Yang, Hao; Li, Shenggong

    2016-04-01

    Understanding variations and underlying mechanisms of carbon isotope discrimination (Δ) in C4 species is critical for predicting the effects of change in C3/C4 ratio of plant community on ecosystem processes and functionning. However, little is known about the effects of soil resource gradients on Δ of C4 plants. To address Δ responses to drought and nitrogen supply, the leaf carbon isotope composition, bundle sheath leakiness (BLS), and leaf gas exchange (A, gs, Ci/Ca) were measured on Cleistogenes squarrosa, a dominant C4 species in the Inner Mongolia grassland. C. squarrosa were grown in controlled-environment pots from seed under a combination of water and N supply. High N availability and drought stimulated photosynthetic rate (A) and further decreased the ratio of internal and ambient CO2 concentrations (Ci/Ca) through increasing leaf N content. BLS was higher under high N supply and was unchanged by drought. There was significant interaction between N and water supply to affect BLS and Ci/Ca. Δ was negatively related to Ci/Ca and was positively related to BLS. Tradeoff between the responses of BLS and Ci/Ca to changing environmental conditions kept leaf Δ relatively stable, which was also supported by a field N addition experiment. Our results suggested leaf Δ of C4 plant was unchanged under variable water and N environment conditions although the operating efficiency of C4 pathway and CO2 concentration in photosynthesis were changed. Our findings have implications for predicting the change of C3/C4 ratio of plant community and understanding ecosystem processes and functionning.

  9. The specific carbon isotopic compositions of branched and cyclic hydrocarbons from Fushun oil shale

    Institute of Scientific and Technical Information of China (English)

    DUAN Yi; WU Baoxiang; ZHENG Guodong; ZHANG Hui; ZHENG Chaoyang

    2004-01-01

    Various branched and cyclic hydrocarbons are isolated from the Fushun oil shale and their carbon isotopes are determined. The analytical results show that the branched and cyclic hydrocarbons are fully separated from n-alkanes by 5 A Molecular-sieve adduction using long time and cold solvent. The branched and cyclic hydrocarbon fraction obtained by this method is able to satisfy the analytic requests of GC-IRMS. The carbon isotopic compositions of these branched and cyclic hydrocarbons obtained from the sample indicate that they are derived from photoautotrophic algae, chemoautotrophic bacteria (-3.4‰ --39.0‰) and methanotrophic bacteria (-38.4‰--46.3‰). However the long-chain 2-methyl-branched alkanes indicate that their carbon isotopic compositions reflect biological origin from higher plants. The carbon isotopic composition of C30 4-methyl sterane (-22.1‰) is the heaviest in all studied ste- ranes, showing that the carbon source or growth condition for its precursor, dinoflagellate, may be different from that of regular steranes. The variation trend of δ13C values between isomers of hopanes shows that 13C-enriched precursors take precedence in process of their epimerization. Methanotrophic hopanes presented reveal the processes of strong transformation of organic matter and cycling of organic carbon in the water column and early diagenesis of oil shale.

  10. Carbon Isotope Evolution of Early Proterozoic Dolomites of Wutai Mountain Area,North China

    Institute of Scientific and Technical Information of China (English)

    钟华; 马永生; 霍卫国; 姚御元

    1994-01-01

    Carbon isotope of the early Proterozoic carbonates from the Hutuo Group of the type sec-tion in Wutai Mountain area,Shanxi Province,North China,is reported.Isotopic analyses have been madefor 484 samples of dolomites.The carbon isotope results show:(i)δ13C values distinctly change with the ge-ological time,but are relatively stable in certain horizon;(ii)like that at the Cretaceous/Tertiary and Permi-an/Triassic boundaries,δ13C values also show abrupt variation across the boundaries between the JianancunFormation and the Daguandong Formation and between the Daguandong Formation and the Huaiyincun For-mation.

  11. Determination of organic milk authenticity using carbon and nitrogen natural isotopes.

    Science.gov (United States)

    Chung, Ill-Min; Park, Inmyoung; Yoon, Jae-Yeon; Yang, Ye-Seul; Kim, Seung-Hyun

    2014-10-01

    Natural stable isotopes of carbon and nitrogen ((12)C, (13)C, (14)N, (15)N) have abundances unique to each living creature. Therefore, measurement of the stable isotope ratio of carbon and nitrogen (δ(13)C=(13)C/(12)C, δ(15)N=(15)N/(14)N) in milk provides a reliable method to determine organic milk (OM) authenticity. In the present study, the mean δ(13)C value of OM was higher than that of conventional milk (CM), whereas the mean δ(15)N value of OM was lower than that of CM; nonetheless both δ(13)C and δ(15)N values were statistically different for the OM and CM (Pauthenticity using stable isotopes of carbon and nitrogen.

  12. Forensic utility of the carbon isotope ratio of PVC tape backings

    Science.gov (United States)

    Stern, L. A.; Thompson, A. H.; Mehltretter, A. H.; McLaskey, V.; Parish, A.; Aranda, R.

    2008-12-01

    Forensic interest in adhesive tapes with PVC-backings (polyvinyl chloride, electrical tapes) derives from their use in construction of improvised explosive devices, drug packaging and in a variety of other illicit activities. Due to the range of physical characteristics and chemical compositions of such tapes, traditional microscopic and chemical analysis of the tape backings and adhesives offer a high degree of discrimination between tapes from different manufacturers and products. To evaluate whether carbon isotope ratios may be able to increase discrimination of electrical tapes, particularly with regards to different tapes of the same product, we assessed the PVC-backings of 87 rolls of black electrical tape for their δ13C values. The adhesive on these tapes was physically removed with hexane, and plasticizers within the PVC tape backings were removed by three-20 minute extractions with chloroform. The δ13C values of the PVC tape backings ranged between -23.8 and -41.5 (‰ V-PDB). The carbon isotopic variation within a product (identical brand and product identification) is significant, based on five products with at least 3 rolls (ranges of 7.4‰ (n=3), 10.0‰ (n=6), 4.2‰ (n=16), 3.8‰ (n=6), and 11.5‰ (n=8), respectively). There was no measurable carbon isotope variation in regards to the following: a) along the length of a roll (4 samples from 1 roll); b) between the center and edge of a strip of tape (1 pair); c) between rolls assumed to be from the same lot of tape (2 pairs); d) between different rolls from the same batch of tape (same product purchased at the same time and place; 5 pairs); and e) between samples of a tape at room temperature, heated to 50° C and 80° C for 1 week. For each sample within the population of 87 tapes, carbon isotopes alone exclude 80 to 100% of the tapes as a potential match, with an average exclusion power of 92.5%, using a window of ± 0.4‰. Carbon isotope variations originate from variations in starting

  13. Carbon isotope composition of low molecular weight hydrocarbons and monocarboxylic acids from Murchison meteorite

    Science.gov (United States)

    Yuen, G.; Blair, N.; Des Marais, D. J.; Chang, S.

    1984-01-01

    Carbon isotopic compositions have been measured for individual hydrocarbons and monocarboxylic acids from the Murchison meteorite, a C2 carbonaceous chondrite which fell in Australia in 1969. With few exceptions, notably benzene, the volatile products are substantially isotopically heavier than their terrestrial counterparts, signifying their extraterrestrial origin. For both classes of compounds, the ratio of C-13 to C-12 decreases with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic ratio than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with the kinetically controlled synthesis of higher homologues from lower ones. The results suggest the possibility that the production mechanisms for hydrocarbons and carboxylic acids may be similar, and impose constraints on the identity of the reactant species.

  14. Determination of the origin of dissolved inorganic carbon in groundwater around a reclaimed landfill in Otwock using stable carbon isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Porowska, Dorota, E-mail: dorotap@uw.edu.pl

    2015-05-15

    Highlights: • Research showed the origin of DIC in the groundwater around a reclaimed landfill. • Carbon isotope was used to evaluate the contributions of carbon from different sources. • The leachate-contaminated water was isotopically distinct from the natural groundwater. • DIC in the natural groundwater comes from organic matter and dissolution of carbonates. • In the contaminated water, DIC comes from organic matter in the aquifer and landfill. - Abstract: Chemical and isotopic analyses of groundwater from piezometers located around a reclaimed landfill in Otwock (Poland) were performed in order to trace the origin of dissolved inorganic carbon (DIC) in the groundwater. Due to differences in the isotopic composition of carbon from different sources, an analysis of stable carbon isotopes in the groundwater, together with the Keeling plot approach and a two-component mixing model allow us to evaluate the relative contributions of carbon from these sources in the groundwater. In the natural (background) groundwater, DIC concentrations and the isotopic composition of DIC (δ{sup 13}C{sub DIC}) comes from two sources: decomposition of organic matter and carbonate dissolution within the aquifer sediments, whereas in the leachate-contaminated groundwater, DIC concentrations and δ{sup 13}C{sub DIC} values depend on the degradation of organic matter within the aquifer sediments and biodegradation of organic matter stored in the landfill. From the mixing model, about 4–54% of the DIC pool is derived from organic matter degradation and 96–46% from carbonate dissolution in natural conditions. In the leachate-contaminated groundwater, about 20–53% of the DIC is derived from organic matter degradation of natural origin and 80–47% from biodegradation of organic matter stored in the landfill. Partial pressure of CO{sub 2} (P CO{sub 2}) was generally above the atmospheric, hence atmospheric CO{sub 2} as a source of carbon in DIC pool was negligible in the

  15. Carbonate clumped isotope paleothermometry and stable isotope results from the Eocene Fenghuo Shan Group, Hoh Xil Basin, Central Tibet

    Science.gov (United States)

    Snell, K. E.; Lippert, P. C.; Eiler, J. M.

    2009-12-01

    We present preliminary clumped isotope temperatures, calcite δ13C and δ18O values, and reconstructed water δ18O values from paleosol carbonates and calcite cemented siltstones and mudstones of the Fenghuo Shan Group from stratigraphic sections in the TouTou He subbasin of Hoh Xil Basin on the northern Tibetan Plateau. Models of plateau growth vary in the timing of initial plateau growth, and in their description of the spatial distribution of the plateau through time. Oxygen isotope paleoaltimetry studies have been used to estimate the elevation of the plateau in the past, but this technique requires assumptions about the temperature of mineral formation. Independent estimates of the temperature of mineral formation are potentially useful for identifying samples in which carbonate has undergone post-depositional recrystallization and/or isotopic exchange, and, when plausible primary depositional temperatures are found, for making more accurate estimates of δ18O of the waters from which the calcite precipitated. The calcite δ18O and δ13C values for the cements are relatively invariant with stratigraphic level, averaging -10.1±1.2‰ and -4.5±2.5‰ (PDB), respectively. These values are similar to lacustrine carbonates of similar age from the same region. The paleosol carbonates, in contrast, are 18O- and 13C-enriched relative to the cements, with average δ18O and δ13C values of -2.4±0.8 and -2.8±0.7‰. Carbonate clumped isotope paleotemperatures for the cements and the paleosol carbonates are also markedly different. The cement samples vary from 26 to 83°C and increase consistently with increasing depth, at a steep gradient of ~100°C/km. Paleosol carbonates from depths at which cements recorded 60°C, preserve temperatures of 35°C and 41°C. A calcite spar-filled fracture in one paleosol carbonate had a temperature of 41°C. Finally the reconstructed cement water δ18O values range from 2.8 to -7.6‰(SMOW), with a trend of 0.2‰/°C. The

  16. POSSIBILITY OF USING CARBON ISOTOPES IN THE ASSESSMENT OF THE POLLUTION OF GAS PHASE IN ENVIRONMENTAL RESEARCH

    Directory of Open Access Journals (Sweden)

    Dorota Porowska

    2015-10-01

    Full Text Available Carbon isotope analyses can be used for knowledge and practical purpose. They can be used to assess the genesis of carbon in geochemical environment, and may also be used to indicate environmental contamination by carbon-containing compounds. The aim of the paper is to indicate the possibilities of using carbon isotope composition for interpretation concerning the following elements of the natural environment: atmospheric air, subsurface zone (gases in soils and aeration zone in terms of natural and anthropogenic factors influencing on their quality. This method can be applied universally, when carbon sources are different in isotopic composition.

  17. Linking mercury, carbon, and nitrogen stable isotopes in Tibetan biota: Implications for using mercury stable isotopes as source tracers.

    Science.gov (United States)

    Xu, Xiaoyu; Zhang, Qianggong; Wang, Wen-Xiong

    2016-05-06

    Tibetan Plateau is located at a mountain region isolated from direct anthropogenic sources. Mercury concentrations and stable isotopes of carbon, nitrogen, and mercury were analyzed in sediment and biota for Nam Co and Yamdrok Lake. Biotic mercury concentrations and high food web magnification factors suggested that Tibetan Plateau is no longer a pristine site. The primary source of methylmercury was microbial production in local sediment despite the lack of direct methylmercury input. Strong ultraviolet intensity led to extensive photochemical reactions and up to 65% of methylmercury in water was photo-demethylated before entering the food webs. Biota displayed very high Δ(199)Hg signatures, with some highest value (8.6%) ever in living organisms. The δ(202)Hg and Δ(199)Hg in sediment and biotic samples increased with trophic positions (δ(15)N) and %methylmercury. Fish total length closely correlated to δ(13)C and Δ(199)Hg values due to dissimilar carbon sources and methylmercury pools in different living waters. This is the first mercury isotope study on high altitude lake ecosystems that demonstrated specific isotope fractionations of mercury under extreme environmental conditions.

  18. Carbon isotope fractionation of chlorinated ethenes during oxidation by Fe{sup 2+} activated persulfate

    Energy Technology Data Exchange (ETDEWEB)

    Marchesi, Massimo, E-mail: m2marche@uwaterloo.ca [Departament de Cristallografia, Mineralogia i Diposits Minerals, Universitat de Barcelona, Barcelona, Catalunya 08028 (Spain); Earth and Environmental Department, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Aravena, Ramon [Earth and Environmental Department, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Sra, Kanwartej S. [Department of Civil and Environmental Engineering, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Golder Associates Inc, Toronto, Ontario, Canada L5N 5Z7 (Canada); Thomson, Neil R. [Department of Civil and Environmental Engineering, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Otero, Neus; Soler, Albert [Departament de Cristallografia, Mineralogia i Diposits Minerals, Universitat de Barcelona, Barcelona, Catalunya 08028 (Spain); Mancini, Silvia [Golder Associates Inc, Toronto, Ontario, Canada L5N 5Z7 (Canada)

    2012-09-01

    The increased use of persulfate (S{sub 2}O{sub 8}{sup 2-}) for in situ chemical oxidation to treat groundwater and soils contaminated by chlorinated hydrocarbon compounds (CHCs) requires unbiased methods to assess treatment performance. Stable carbon isotope analysis offers a potential tool for assessing the in situ treatment performance of persulfate at sites contaminated with CHCs. This study investigated the extent of C isotope fractionation during oxidation of tetrachloroethene (PCE), trichloroethene (TCE) and cis-dichloroethene (cis-DCE) by persulfate activated by ferrous ion (Fe{sup 2+}). An average carbon isotope enrichment factor {epsilon}{sub bulk} of - 4.9 Per-Mille-Sign for PCE, - 3.6 Per-Mille-Sign for TCE and - 7.6 Per-Mille-Sign for cis-DCE were obtained in batch experiments. Variations in the initial S{sub 2}O{sub 8}{sup 2-}/Fe{sup 2+}/CHC molar ratios did not result in any significant differences in carbon isotope fractionation. The occurrence of carbon isotope fractionation during oxidation and the lack of dependence of enrichment factors upon the S{sub 2}O{sub 8}{sup 2-}/Fe{sup 2+}/CHC molar ratio demonstrate that carbon isotope analysis can potentially be used at contaminated sites as an additional technique to estimate treatment efficacy during oxidation of CHCs by Fe{sup 2+} activated persulfate. Highlights: Black-Right-Pointing-Pointer The performance of in situ chemical oxidation (ISCO) is still difficult to assess. Black-Right-Pointing-Pointer We investigated the potential of carbon isotope analysis as a new assessing tool. Black-Right-Pointing-Pointer C isotope of PCE, TCE and DCE oxidized by persulfate activated by Fe{sup 2+} was measured. Black-Right-Pointing-Pointer Enrichment factors of - 4.9 Per-Mille-Sign for PCE, - 3.6 Per-Mille-Sign for TCE and - 7.6 Per-Mille-Sign for cisDCE were obtained. Black-Right-Pointing-Pointer Carbon isotope can potentially be used to estimate the ISCO treatment efficacy.

  19. On the interference of Kr during carbon isotope analysis of methane using continuous-flow combustion–isotope ratio mass spectrometry

    NARCIS (Netherlands)

    Schmitt, J.; Seth, B.; Bock, M; van der Veen, C.; Möller, L.; Sapart, C.J.; Prokopiou, M.; Sowers, T.; Röckmann, T.; Fischer, H

    2013-01-01

    Stable carbon isotope analysis of methane ( 13C of CH4) on atmospheric samples is one key method to constrain the current and past atmospheric CH4 budget. A frequently applied measurement technique is gas chromatography (GC) isotope ratio mass spectrometry (IRMS) coupled to a combustion-preconcentra

  20. A versatile method for stable carbon isotope analysis of carbohydrates by high-performance liquid chromatography/isotope ratio mass spectrometry

    NARCIS (Netherlands)

    Boschker, H.T.S.; Moerdijk-Poortvliet, T.C.W.; Van Breugel, P.; Houtekamer, M.J.; Middelburg, J.J.

    2008-01-01

    We have developed a method to analyze stable carbon isotope (13C/12C) ratios in a variety of carbohydrates using high-performance liquid chromatography/isotope ratio mass spectrometry (HPLC/IRMS). The chromatography is based on strong anion-exchange columns with low strength NaOH eluents. An eluent

  1. A versatile method for simultaneous stable carbon isotope analysis of DNA and RNA nucleotides by liquid chromatography/isotope ratio mass spectrometry

    NARCIS (Netherlands)

    Moerdijk-Poortvliet, T.C.W.; Brasser, J.; de Ruiter, G.; Houtekamer, M.; Bolhuis, H.; Stal, L.J.; Boschker, H.T.S.

    2014-01-01

    RATIONALE Liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) is currently the most accurate and precise technique for the measurement of compound-specific stable carbon isotope ratios (13C/12C) in biological metabolites, at their natural abundance. However, until now this technique coul

  2. A versatile method for simultaneous stable carbon isotope analysis of DNA and RNA nucleotides by liquid chromatography/isotope ratio mass spectrometry

    NARCIS (Netherlands)

    Moerdijk-Poortvliet, T.C.W.; Brasser, J.; de Ruiter, G.; Houtekamer, M.; Bolhuis, H.; Stal, L.J.; Boschker, H.T.S.

    2014-01-01

    RATIONALELiquid chromatography/isotope ratio mass spectrometry (LC/IRMS) is currently the most accurate and precise technique for the measurement of compound-specific stable carbon isotope ratios (C-13/C-12) in biological metabolites, at their natural abundance. However, until now this technique cou

  3. Uranium isotopes in carbonate aquifers of arid region setting

    DEFF Research Database (Denmark)

    Alshamsi, Dalal M.; Murad, Ahmed A.; Aldahan, Ala

    2013-01-01

    Groundwater in arid and semiarid regions is vital resource for many uses and therefore information about concentrations of uranium isotopes among other chemical parameters are necessary. In the study presented here, distribution of 238U and 235U in groundwater of four selected locations in the so......Groundwater in arid and semiarid regions is vital resource for many uses and therefore information about concentrations of uranium isotopes among other chemical parameters are necessary. In the study presented here, distribution of 238U and 235U in groundwater of four selected locations...... in the southern Arabian peninsula, namely at two locations within the United Arab Emirates (UAE) and two locations in Oman are discussed. The analyses of the uranium isotopes were performed using ICP-MS and the results indicated a range of concentrations for 235U and 238 U at 3–39 ng L-1 (average: 18 ng L-1...

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

    Science.gov (United States)

    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.

  5. Modeling the Impact of Forest and Peat Fires on Carbon-Isotopic Compositions of Cretaceous Atmosphere and Vegetation

    Science.gov (United States)

    Finkelstein, D. B.; Pratt, L. M.

    2004-12-01

    Prevalence of wildfires or peat fires associated with seasonally dry conditions in the Cretaceous is supported by recent studies documenting the widespread presence of pyrolytic polycyclic aromatic hydrocarbons and fusinite. Potential roles of CO2 emissions from fire have been overlooked in many discussions of Cretaceous carbon-isotope excursions (excluding K-P boundary discussions). Enhanced atmospheric CO2 levels could increase fire frequency through elevated lightning activity. When biomass or peat is combusted, emissions of CO2 are more negative than atmospheric CO2. Five reservoirs (atmosphere, vegetation, soil, and shallow and deep oceans), and five fluxes (productivity, respiration, litter fall, atmosphere-ocean exchange, and surface-deep ocean exchange) were modeled as a closed system. The size of the Cretaceous peat reservoir was estimated by compilation of published early Cretaceous coal resources. Initial pCO2 was assumed to be 2x pre-industrial atmospheric levels (P.A.L.). Critical variables in the model are burning efficiency and post-fire growth rates. Assuming 1% of standing terrestrial biomass is consumed by wildfires each year for ten years (without combustion of peat), an increase of atmospheric CO2 (from 2.0 to 2.2x P.A.L.) and a negative carbon isotope excursion (-1.2 ‰ ) are recorded by both atmosphere and new growth. Net primary productivity linked to the residence time of the vegetation and soil reservoirs results in a negative isotope shift followed by a broad positive isotope excursion. Decreasing the rate of re-growth dampens this trailing positive shift and increases the duration of the excursion. Post-fire pCO2 and new growth returned to initial values after 72 years. Both negative and positive isotope excursions are recorded in the model in surface ocean waters. Exchange of CO2 with the surface- and deep-ocean dampens the isotopic shift of the atmosphere. Excursions are first recorded in the atmosphere (and new growth), followed by

  6. Carbon and nitrogen isotope variations in tree-rings as records of perturbations in regional carbon and nitrogen cycles.

    Science.gov (United States)

    Bukata, Andrew R; Kyser, T Kurtis

    2007-02-15

    Increasing anthropogenic pollution from urban centers and fossil fuel combustion can impact the carbon and nitrogen cycles in forests. To assess the impact of twentieth century anthropogenic pollution on forested system carbon and nitrogen cycles, variations in the carbon and nitrogen isotopic compositions of tree-rings were measured. Individual annual growth rings in trees from six sites across Ontario and one in New Brunswick, Canada were used to develop site chronologies of tree-ring delta 15N and delta 13C values. Tree-ring 615N values were approximately 0.5% per hundred higher and correlated with contemporaneous foliar samples from the same tree, but not with delta 15N values of soil samples. Temporal trends in carbon and nitrogen isotopic compositions of these tree-rings are consistent with increasing anthropogenic influence on both the carbon and nitrogen cycles since 1945. Tree-ring delta 13C values and delta 15N values are correlated at both remote and urban-proximal sites, with delta 15N values decreasing since 1945 and converging on 1% per hundred at urban-proximal sites and decreasing but not converging on a single delta 15N value in remote sites. These results indicate that temporal trends in tree-ring nitrogen and carbon isotopic compositions record the regional extent of pollution.

  7. [The isotope effect in the glycine dehydrogenase reaction is the cause of the intramolecular isotope inhomogeneity of glucose carbon of starch synthesized during photorespiration].

    Science.gov (United States)

    Ivlev, A A

    2005-01-01

    The isotope distribution of glucose-6-phosphate in the main pathways of its biosynthesis (in the processes of CO2 assimilation and photorespiration in the Calvin cycle and during resynthesis from the degradation products of lipids and proteins) was analyzed. For reconstructing the isotope distribution of glucoso-6-phosphate synthesized in the Calvin cycle during photorespiration, the functioning of the cycle with regard to its coupling with the glycolate chain, which together constitute the photorespiration chain, was considered. In the glycine dehydrogenase reaction of the glycolate cycle, there arises an isotope effect, which determines the distribution of isotopes in the glucose-6-phosphate and other photorespiration products. The isotope effect of the glycine dehydrogenase reaction increases at the expense of the exhaustion of glucose resources feeding the photorespiration chain. As a result, atoms C-3 and C-4 of glucose become enriched with the heavy isotope, and subsequent mixing of atoms and the specificity of interactions in the photorespiration chain lead to an isotope weighting of the other atoms and an uneven distribution of carbon isotopes in glucose-6-phosphate and other photorespiration products. A comparison of the glucose-6-phosphate isotope patterns in different pathways of the synthesis with the experimental data on the distribution of carbon isotopes in starch glucose of storing plant organs led to the conclusion that the starch resources are predominantly formed at the expense of glucose-6-phosphate of photorespiration. This is consistent with the earlier observed enhancement of photorespiration at the stage of plant maturation.

  8. Evaluating reaction pathways of hydrothermal abiotic organic synthesis at elevated temperatures and pressures using carbon isotopes

    Science.gov (United States)

    Fu, Qi; Socki, Richard A.; Niles, Paul B.

    2015-04-01

    Experiments were performed to better understand the role of environmental factors on reaction pathways and corresponding carbon isotope fractionations during abiotic hydrothermal synthesis of organic compounds using piston cylinder apparatus at 750 °C and 5.5 kbars. Chemical compositions of experimental products and corresponding carbon isotopic values were obtained by a Pyrolysis-GC-MS-IRMS system. Alkanes (methane and ethane), straight-chain saturated alcohols (ethanol and n-butanol) and monocarboxylic acids (formic and acetic acids) were generated with ethanol being the only organic compound with higher δ13C than CO2. CO was not detected in experimental products owing to the favorable water-gas shift reaction under high water pressure conditions. The pattern of δ13C values of CO2, carboxylic acids and alkanes are consistent with their equilibrium isotope relationships: CO2 > carboxylic acids > alkanes, but the magnitude of the fractionation among them is higher than predicted isotope equilibrium values. In particular, the isotopic fractionation between CO2 and CH4 remained constant at ∼31‰, indicating a kinetic effect during CO2 reduction processes. No "isotope reversal" of δ13C values for alkanes or carboxylic acids was observed, which indicates a different reaction pathway than what is typically observed during Fischer-Tropsch synthesis under gas phase conditions. Under constraints imposed in experiments, the anomalous 13C isotope enrichment in ethanol suggests that hydroxymethylene is the organic intermediate, and that the generation of other organic compounds enriched in 12C were facilitated by subsequent Rayleigh fractionation of hydroxymethylene reacting with H2 and/or H2O. Carbon isotope fractionation data obtained in this study are instrumental in assessing the controlling factors on abiotic formation of organic compounds in hydrothermal systems. Knowledge on how environmental conditions affect reaction pathways of abiotic synthesis of organic

  9. New approach to global barium cycle understanding: barium isotopic composition of marine carbonates and seawater.

    Science.gov (United States)

    Pretet, Chloé; Nägler, Thomas F.; Reynaud, Stéphanie; de Lange, Gert J.; Turpin, Mélanie; Immenhauser, Adrian; Böttcher, Michael E.; Samankassou, Elias

    2013-04-01

    In this communication we present the Ba isotope fractionation (delta137/134Ba) study on marine carbonates and seawater, initiated to gain a first order view of the marine Ba isotope cycle. A special focus is the question whether the nutrient type distribution of Ba in the water column, as well as different Ba sources, are reflected in Ba isotope ratios of carbonate archives. The approach ultimately aims to provide an improved Ba based paleonutrient proxy. The data set is composed of carbonates (micrites and limestone standard), coral skeleton and seawater (IAPSO standard and Mediterranean seawater). Part of the corals were cultured in monitored environments (CSM, Monaco) others originate from natural environments (shallow and warm water corals from the Bahamas/Florida and cold water corals from the Norwegian shelf). The analytical procedure includes the application of a 130Ba/135Ba double spike, a cation exchange column followed by isotope measurements on a Nu Instruments Multicollector ICP-MS. The Ba fractionation of the samples is compared to a Ba nitrate standard solution and a standard natural limestone BSC-CRM 393 (0.05 ± 0.04 ‰, 2SEM). No isotopic fractionation has been observed in the limestone standard and micrites (N=8) (-0.01 ± 0.04 ‰, 2SEM) compared to the Ba nitrate standard. On the contrary, coral skeletons show a significant positive fractionation (mean = 0.4 ± 0.05 ‰, 2 SEM). No significant difference was found between different cultured coral species. Thus no species-specific fractionation is identified within the same environmental conditions. Diagenetic influence on Ba isotopic composition was further tested on 5 natural samples with varying calcite to aragonite ratios (0 to 0.3). No significant effect was observed. Moreover, the Ba isotope composition seems independant from the Ba concentration in the studied coral skeleton, within our measurement resolution. Seawater isotopic composition (-0.05 ± 0.07 ‰, 2SD) is lighter than coral

  10. Carbonate Mineral Formation on Mars: Clues from Stable Isotope Variation Seen in Cryogenic Laboratory Studies of Carbonate Salts

    Science.gov (United States)

    Socki, Richard; Niles, Paul B.; Sun, Tao; Fu, Qi; Romanek, Christopher S.; Gibson, Everett K.

    2013-01-01

    The geologic history of water on the planet Mars is intimately connected to the formation of carbonate minerals through atmospheric CO2 and its control of the climate history of Mars. Carbonate mineral formation under modern martian atmospheric conditions could be a critical factor in controlling the martian climate in a means similar to the rock weathering cycle on Earth. The combination of evidence for liquid water on the martian surface and cold surface conditions suggest fluid freezing could be very common on the surface of Mars. Cryogenic calcite forms readily when a rise in pH occurs as a result of carbon dioxide degassing quickly from freezing Ca-bicarbonate-rich water solutions. This is a process that has been observed in some terrestrial settings such as arctic permafrost cave deposits, lakebeds of the Dry Valleys of Antarctica, and in aufeis (river icings) from rivers of N.E. Alaska. We report here the results of a series of laboratory experiments that were conducted to simulate potential cryogenic carbonate formation on the planet Mars. These results indicate that carbonates grown under martian conditions (controlled atmospheric pressure and temperature) show enrichments from starting bicarbonate fluids in both carbon and oxygen isotopes beyond equilibrium values with average delta13C(DIC-CARB) values of 20.5%0 which exceed the expected equilibrium fractionation factor of [10(sup 3) ln alpha = 13%0] at 0 degC. Oxygen isotopes showed a smaller enrichment with delta18O(H2O-CARB) values of 35.5%0, slightly exceeding the equilibrium fractionation factor of [10(sup 3) ln alpha = 34%0 ] at 0degC. Large kinetic carbon isotope effects during carbonate precipitation could substantially affect the carbon isotope evolution of CO2 on Mars allowing for more efficient removal of 13C from the Noachian atmosphere enriched by atmospheric loss. This mechanism would be consistent with the observations of large carbon isotope variations in martian materials despite the

  11. Separation of polybrominated diphenyl ethers in fish for compound-specific stable carbon isotope analysis

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Yan-Hong [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Graduate University of Chinese Academy of Sciences, Beijing, 100049 (China); Luo, Xiao-Jun, E-mail: luoxiaoj@gig.ac.cn [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Chen, Hua-Shan; Wu, Jiang-Ping; Chen, She-Jun; Mai, Bi-Xian [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China)

    2012-05-15

    A separation and isotopic analysis method was developed to accurately measure the stable carbon isotope ratios of polybrominated diphenyl ethers (PBDEs) with three to six substituted bromine atoms in fish samples. Sample extracts were treated with concentrated sulfuric acid to remove lipids, purified using complex silica gel column chromatography, and finally processed using alumina/silica (Al/Si) gel column chromatography. The purities of extracts were verified by gas chromatography and mass spectrometry (GC-MS) in the full-scan mode. The average recoveries of all compounds across the purification method were between 60% and 110%, with the exception of BDE-154. The stable carbon isotopic compositions of PBDEs can be measured with a standard deviation of less than 0.5 Per-Mille-Sign . No significant isotopic fraction was found during the purification of the main PBDE congeners. A significant change in the stable carbon isotope ratio of BDE-47 was observed in fish carcasses compared to the original isotopic signatures, implying that PBDE stable carbon isotopic compositions can be used to trace the biotransformation of PBDEs in biota. - Highlights: Black-Right-Pointing-Pointer A method for the purification of PBDEs for CSIA was developed. Black-Right-Pointing-Pointer The {delta}{sup 13}C of PBDE congeners can be measured with a standard deviation of less than 0.5 Per-Mille-Sign . Black-Right-Pointing-Pointer Common carp were exposed to a PBDE mixture to investigate debromination. Black-Right-Pointing-Pointer Ratios of the {delta}{sup 13}C values can be used to trace the debromination of PBDE in fish.

  12. Tracing carbon flow through coral reef food webs using a compound-specific stable isotope approach.

    Science.gov (United States)

    McMahon, Kelton W; Thorrold, Simon R; Houghton, Leah A; Berumen, Michael L

    2016-03-01

    Coral reefs support spectacularly productive and diverse communities in tropical and sub-tropical waters throughout the world's oceans. Debate continues, however, on the degree to which reef biomass is supported by new water column production, benthic primary production, and recycled detrital carbon (C). We coupled compound-specific stable C isotope ratio (δ(13)C) analyses with Bayesian mixing models to quantify C flow from primary producers to coral reef fishes across multiple feeding guilds and trophic positions in the Red Sea. Analyses of reef fishes with putative diets composed primarily of zooplankton (Amblyglyphidodon indicus), benthic macroalgae (Stegastes nigricans), reef-associated detritus (Ctenochaetus striatus), and coral tissue (Chaetodon trifascialis) confirmed that δ(13)C values of essential amino acids from all baseline C sources were both isotopically diagnostic and accurately recorded in consumer tissues. While all four source end-members contributed to the production of coral reef fishes in our study, a single-source end-member often dominated dietary C assimilation of a given species, even for highly mobile, generalist top predators. Microbially reworked detritus was an important secondary C source for most species. Seascape configuration played an important role in structuring resource utilization patterns. For instance, Lutjanus ehrenbergii showed a significant shift from a benthic macroalgal food web on shelf reefs (71 ± 13 % of dietary C) to a phytoplankton-based food web (72 ± 11 %) on oceanic reefs. Our work provides insights into the roles that diverse C sources play in the structure and function of coral reef ecosystems and illustrates a powerful fingerprinting method to develop and test nutritional frameworks for understanding resource utilization.

  13. Tracing carbon flow through coral reef food webs using a compound-specific stable isotope approach

    KAUST Repository

    McMahon, Kelton

    2015-11-21

    Coral reefs support spectacularly productive and diverse communities in tropical and sub-tropical waters throughout the world’s oceans. Debate continues, however, on the degree to which reef biomass is supported by new water column production, benthic primary production, and recycled detrital carbon (C). We coupled compound-specific stable C isotope ratio (δ13C) analyses with Bayesian mixing models to quantify C flow from primary producers to coral reef fishes across multiple feeding guilds and trophic positions in the Red Sea. Analyses of reef fishes with putative diets composed primarily of zooplankton (Amblyglyphidodon indicus), benthic macroalgae (Stegastes nigricans), reef-associated detritus (Ctenochaetus striatus), and coral tissue (Chaetodon trifascialis) confirmed that δ13C values of essential amino acids from all baseline C sources were both isotopically diagnostic and accurately recorded in consumer tissues. While all four source end-members contributed to the production of coral reef fishes in our study, a single-source end-member often dominated dietary C assimilation of a given species, even for highly mobile, generalist top predators. Microbially reworked detritus was an important secondary C source for most species. Seascape configuration played an important role in structuring resource utilization patterns. For instance, Lutjanus ehrenbergii showed a significant shift from a benthic macroalgal food web on shelf reefs (71 ± 13 % of dietary C) to a phytoplankton-based food web (72 ± 11 %) on oceanic reefs. Our work provides insights into the roles that diverse C sources play in the structure and function of coral reef ecosystems and illustrates a powerful fingerprinting method to develop and test nutritional frameworks for understanding resource utilization.

  14. Stable carbon and oxygen isotope study on benthic foraminifera: Implication for microhabitat preferences and interspecies correlation

    Indian Academy of Sciences (India)

    Ajoy K Bhaumik; Shiv Kumar; Shilpi Ray; G K Vishwakarma; Anil K Gupta; Pushpendra Kumar; Kalachand Sain

    2017-07-01

    Stable isotopes of benthic foraminifera have widely been applied in micropalaeontological research to understand vital effects in foraminifera. Isotopic fractionations are mainly controlled by ontogeny, bottom/pore water chemistry, habitat preference, kinetic effect and respiration. Discontinuous abundance of a species for isotopic analysis has forced us to select multiple species from down-core samples. Thus standardisation factors are required to convert isotopic values of one species with respect to other species. The present study is pursued on isotopic values of different pairs of benthic foraminifera from the Krishna–Godavari basin and Peru offshore to understand habitat-wise isotopic variation and estimation of isotopic correction factors for the paired species (Cibicides wuellerstorfi–Bulimina marginata, Ammonia spp.–Loxostomum amygdalaeformis and Bolivina seminuda–Nonionella auris). Infaunal species (B. marginata, Ammonia spp. and N. auris) show a lighter carbon isotopic excursion with respect to the epifaunal to shallow infaunal forms (C. wuellerstorfi, L. amygdalaeformis and B. seminuda). These lighter δ13C values are related to utilisation of CO2 produced by anaerobic remineralisation of organic matter. However, enrichment of δ18O for the deeper microhabitat (bearing lower pH and decreased CO32−) is only recorded in case of B. marginata. It is reverse in case of N. auris and related to utilisation of respiratory CO2 and internal dissolve inorganic carbon pool. Estimation of interspecies isotopic correction factors for the species pairs (δ13C of C. wuellerstorfi–B. marginata, L. amygdalaeformis–Ammonia spp., N. auris–B. seminuda) and δ18O of C. wuellerstorfi–B. marginata are statistically reliable and may be used in palaeoecological studies.

  15. Inferring marine sinks and sources of monohalomethanes from their carbon stable isotope composition

    Science.gov (United States)

    Bahlmann, Enno; Weinberg, Ingo; Eckhardt, Tim; Seifert, Richard; Michaelis, Walter

    2013-04-01

    Within the last years much progress in quantifying the global emissions of various halocarbons has been made. However, the current emission estimates are still assigned with large uncertainties due to the inevitably large spatial and temporal variability in observed halocarbon mixing ratios and fluxes. An improved understanding of the biogeochemical controls of the production - destruction equilibrium may substantially reduce these uncertainties and is of vital importance to address potential future changes. The δ13C values of monohalomethanes vary sensitively towards changes of both, sources and sinks making them a valuable tool to assess concurrent production and degradation processes. Here we report carbon isotope ratios for chloromethane (CH3Cl) and bromomethane (CH3Br) in background air and coastal and open ocean surface waters. The samples were taken during five sampling campaigns between September 2010 and July 2012 with the sample locations spanning from 10°N to 60°N Our results show an enrichment by about 4‰ for chloromethane in marine air masses (-36‰) as compared to continental air masses (-40‰) corroborating earlier findings. This enrichment is supported by the observation of even more enriched chloromethane in the ocean surface waters averaging -28‰ for the subtropical North East Atlantic. For bromomethane, our data show an even more pronounced enrichment by 16‰ from -44‰ in continental air masses to -28‰ in marine air masses. These isotopic differences can be attributed to the air sea exchange of these compounds in concert with the production - decomposition dynamics in surface oceans. Hydrolysis, assigned with an ɛ of 45‰, is regarded as the most important degradation process for chloromethane in surface oceans. Bromomethane from both, intrinsic sources and from the atmosphere, is known to be rapidly degraded in marine surface waters by biotic and abiotic processes. The abiotic degradation due to hydrolysis and transhalogenation

  16. Intercontinental correlation of organic carbon and carbonate stable isotope records: evidence of climate and sea-level change during the Turonian (Cretaceous)

    NARCIS (Netherlands)

    Jarvis, I.; Trabucho-Alexandre, João; Gröcke, D.R.; Uličný, D.; Laurin, J.

    2015-01-01

    Carbon (d13Corg, d13Ccarb) and oxygen (d18Ocarb) isotope records are presented for an expanded Upper Cretaceous (Turonian–Coniacian) hemipelagic succession cored in the central Bohemian Cretaceous Basin, Czech Republic. Geophysical logs, biostratigraphy and stable carbon isotope chemostratigraphy pr

  17. Intercontinental correlation of organic carbon and carbonate stable isotope records: evidence of climate and sea-level change during the Turonian (Cretaceous)

    NARCIS (Netherlands)

    Jarvis, I.; Trabucho-Alexandre, João; Gröcke, D.R.; Uličný, D.; Laurin, J.

    2015-01-01

    Carbon (d13Corg, d13Ccarb) and oxygen (d18Ocarb) isotope records are presented for an expanded Upper Cretaceous (Turonian–Coniacian) hemipelagic succession cored in the central Bohemian Cretaceous Basin, Czech Republic. Geophysical logs, biostratigraphy and stable carbon isotope chemostratigraphy

  18. New insight into the atmospheric chloromethane budget gained using stable carbon isotope ratios

    Directory of Open Access Journals (Sweden)

    F. Keppler

    2005-01-01

    Full Text Available Atmospheric chloromethane (CH3Cl plays an important role in stratospheric ozone destruction, but many uncertainties still exist regarding strengths of both sources and sinks and the processes leading to formation of this naturally occurring gas. Recent work has identified a novel chemical origin for CH3Cl, which can explain its production in a variety of terrestrial environments: the widespread structural component of plants, pectin, reacts readily with chloride ion to form CH3Cl at both ambient and elevated temperatures (Hamilton et al., 2003. It has been proposed that this abiotic chloride methylation process in terrestrial environments could be responsible for formation of a large proportion of atmospheric CH3Cl. However, more information is required to determine the global importance of this new source and its contribution to the atmospheric CH3Cl budget. A potentially powerful tool in studying the atmospheric CH3Cl budget is the use of stable carbon isotope ratios. In an accompanying paper it is reported that the reaction of CH3Cl with OH radical, the dominant sink for atmospheric CH3Cl, is accompanied by an unexpectedly large fractionation factor (Gola et al., 2005. Another recently published study shows that CH3Cl formed by the abiotic methylation process at ambient temperatures has a unique stable carbon isotope signature, extremely depleted in 13C, unequivocally distinguishing it from all other known sources (Keppler et al., 2004. Using these findings together with data existing in the literature, we here present three scenarios for an isotopic mass balance for atmospheric CH3Cl. Our calculations provide strong support for the proposal that the largest source of atmospheric CH3Cl (1800 to 2500 Gg yr-1 is the abiotic methylation of chloride in terrestrial ecosytems, primarily located in tropical and subtropical areas where turnover of biomass is highest. Furthermore our calculations also indicate that the microbial soil sink for CH3Cl is

  19. Molecular carbon isotopic evidence for the origin of geothermal hydrocarbons

    Science.gov (United States)

    Des Marais, D. J.; Donchin, J. H.; Nehring, N. L.; Truesdell, A. H.

    1981-01-01

    Isotopic measurements of individual geothermal hydrocarbons that are, as a group, of higher molecular weight than methane are reported. It is believed in light of this data that the principal source of hydrocarbons in four geothermal areas in western North America is the thermal decomposition of sedimentary or groundwater organic matter.

  20. Transient carbon isotope changes in complex systems: Finding the global signal, embracing the local signal

    Science.gov (United States)

    Bowen, G. J.; Schneider-Mor, A.; Filley, T. R.

    2008-12-01

    Global, transient carbon isotope excursions (CIEs) in the geological record are increasingly invoked as evidence of short-lived changes in carbon fluxes to/from the ocean-atmosphere-biosphere (exogenic) system. Reconstructing the dynamics of carbon cycle perturbation and response during such events requires that the global extent, magnitude, and temporal pattern of carbon isotope change are well understood. Unfortunately, no simple, globally integrated measure of exogenic δ13C change exists in the geological record: during major global perturbations even the best-case candidates such as deep-ocean carbonate δ13C values likely respond to a complex of factors including ocean carbonate chemistry and circulation. Here we consider the utility of organic carbon isotope records from two complex depositional systems common in the geological record, fossil soils and continental margin sediments, which are of interest in terms of their relationship to organic carbon cycling and records of past ecological change. Within both systems changes in ecology, climate, carbon source, residence time, and molecular composition have clear potential to modulate the preserved record of global exogenic δ13C change, compromising 1st-order interpretations of bulk or compound-specific isotopic records. Process-explicit eco- geochemical models, ideally combined with multi-substrate data, provide one approach to the isolation of global δ13C change and identification of local or regional processes reflected in such records. Examples from both systems drawn from ongoing work on the Paleocene-Eocene thermal maximum illustrate the potential pitfalls, as well as opportunities, afforded by coupled data/model assessment of transient δ13C changes in complex systems.

  1. Calcium and calcium isotope changes during carbon cycle perturbations at the end-Permian

    Science.gov (United States)

    Komar, Nemanja; Zeebe, Richard

    2016-04-01

    Negative carbon and calcium isotope excursions, as well as climate shifts, took place during the most severe mass extinction event in Earth's history, the end-Permian (˜252 Ma). Investigating the connection between carbon and calcium cycles during transient carbon cycle perturbation events, such as the end-Permian, may help resolve the intricacies between the coupled calcium-carbon cycles, as well as provide a tool for constraining the causes of mass extinction. Here, we identify the deficiencies of a simplified calcium model employed in several previous studies and we demonstrate the importance of a fully coupled carbon-cycle model when investigating the dynamics of carbon and calcium cycling. Simulations with a modified version of the LOSCAR model, which includes a fully coupled carbon-calcium cycle, indicate that increased weathering rates and ocean acidification (potentially caused by Siberian Trap volcanism) are not capable of producing trends observed in the record, as previously claimed. Our model results suggest that combined effects of carbon input via Siberian Trap volcanism (12,000 Pg C), the cessation of biological carbon export, and variable calcium isotope fractionation (due to a change in the seawater carbonate ion concentration) represents a more plausible scenario. This scenario successfully reconciles δ13C and δ44Ca trends observed in the sediment record, as well as the proposed warming of >6oC.

  2. Equilibrium magnesium isotope fractionation between aqueous Mg2+ and carbonate minerals: Insights from path integral molecular dynamics

    Science.gov (United States)

    Pinilla, Carlos; Blanchard, Marc; Balan, Etienne; Natarajan, Suresh K.; Vuilleumier, Rodolphe; Mauri, Francesco

    2015-08-01

    The theoretical determination of the isotopic fractionation between an aqueous solution and a mineral is of utmost importance in Earth sciences. While for crystals, it is well established that equilibrium isotopic fractionation factors can be calculated using a statistical thermodynamic approach based on the vibrational properties, several theoretical methods are currently used to model ions in aqueous solution. In this work, we present a systematic study to determine the reduced partition function ratio (β-factor) of aqueous Mg2+ using several levels of theory within the simulations. In particular, using an empirical force field, we compare and discuss the performance of the exact results obtained from path integral molecular dynamics (PIMD) simulations, with respect to the more traditional methods based on vibrational properties and the cluster approximation. The results show the importance of including configurational disorder for the estimation of the equilibrium isotope fractionation factor. We also show that using the vibrational frequencies computed from snapshots taken from equilibrated classical molecular dynamics represents a good approximation for the study of aqueous ions. Based on these conclusions, the β-factor of aqueous Mg2+ have been estimated from a Car-Parrinello molecular dynamics (CPMD) simulation with an ab initio force field, and combined with the β-factors of carbonate minerals (magnesite, dolomite, calcite and aragonite). Mg β-factor of Mg-bearing aragonite, calculated here for the first time, displays a lower value than the three other carbonate minerals. This is explained by a strong distortion of the cationic site leading to a decrease of the coordination number during Ca-Mg substitution. Overall, the equilibrium magnesium isotope fractionation factors between aqueous Mg2+ and carbonate minerals that derive from this methodological study support the previous theoretical results obtained from embedded cluster models.

  3. Global Cr-isotope distributions in surface seawater and incorporation of Cr isotopes into carbonate shells

    DEFF Research Database (Denmark)

    Paulukat, Cora Stefanie; Frei, Robert; Vögelin, Andrea Regula

    In this study we present the Cr-isotope composition of surface seawater from several locations worldwide. In addition to the samples from the oceans (Atlantic Ocean, Pacific Ocean, Southern Ocean and Artic Ocean) we analysed water samples from areas with a more limited water exchange (Mediterrane...

  4. Extreme hydrogen, oxygen and carbon isotope anomalies in the pore waters and carbonates of the sediments and basalts from the Norwegian Sea: Methane and hydrogen from the mantle

    Energy Technology Data Exchange (ETDEWEB)

    Lawrence, J.R. (Univ. of Houston, University Park, TX (USA)); Taviani, M. (Instituto di Geologia Marina, del C.N.R., Bologna (Italy))

    1988-08-01

    D/H ratios in the pore waters of the sediments from the Norwegian Sea decrease as a function of depth to values as low as {minus}14{per thousand}. Oxygen isotope ratios in the pore waters and carbon and oxygen isotope ratios in carbonates both in the sediments and basalts are low. Extensive alteration of basalt has been given as the explanation for the low oxygen isotope ratios. Material balance calculations suggest that alteration of volcanic material and oxidation of organic matter cannot explain the hydrogen and carbon isotope anomalies. Arguments are presented suggesting that methane and hydrogen from the mantle are oxidized to carbon dioxide and water by sulfate and ferric iron in the basaltic crust to yield the low hydrogen and carbon isotope ratios.

  5. Combined oxygen- and carbon-isotope records through the Early Jurassic: multiple global events and two modes of carbon-cycle/temperature coupling

    DEFF Research Database (Denmark)

    Hesselbo, Stephen P.; Korte, Christoph

    2010-01-01

    -isotope signature), but also some significant contrasts (oxygen-isotope based paleotemperatures which provide no evidence for warming). Significant contrast in oxygen- and carbon-isotope co-variation also occurs on a long timescale. There appear to be two modes in the co-variation of carbon and oxygen isotopes...... environmental changes were global has been strongly debated. Nevertheless, partly as a result of the international effort to define Global Stratotype Sections and Points (GSSPs), much more is now being discovered about environmental changes taking place at and around the other Jurassic Age (Stage) boundaries...... that both long-term and short-term carbon-isotope shifts from the UK Early Jurassic represent global changes in carbon cycle balances. The Sinemurian-Pliensbachian boundary event is an event of global significance and shows several similarities to the Toarcian OAE (relative sea-level change, carbon...

  6. Triassic-Jurassic organic carbon isotope stratigraphy of key sections in the western Tethys realm (Austria)

    Science.gov (United States)

    Ruhl, Micha; Kürschner, Wolfram M.; Krystyn, Leopold

    2009-05-01

    The late Triassic period is recognized as one of the five major mass extinctions in the fossil record. All these important intervals in earth history are associated with excursions in C-isotope records thought to have been caused by perturbations in the global carbon cycle. The nature and causes of C-isotopic events across the Triassic-Jurassic (T-J) transition however, are poorly understood. We present several new high resolution organic C-isotope records from the Eiberg Basin, Austria, including the proposed Global boundary Stratotype Section and Point (GSSP) for the base of the Jurassic. The Triassic-Jurassic boundary interval in these records is characterized by the initial and main negative organic carbon isotope excursions (CIE) of up to 8‰. The initial and main CIEs are biostratigraphically constrained by first and last occurrences of boundary defining macro- and microfossils (e.g. ammonites). High resolution C-isotope records appear to be an excellent correlation proxy for this period in the Eiberg Basin. Pyrolysis analysis demonstrates increased Hydrogen Index (HI) values for organic matter coinciding with the initial CIE. Terrestrial organic matter influx and mass occurrences of green algae remains may have influenced the C-isotope composition of the sedimentary organic matter. This may have contributed to the extreme amplitude of the initial CIE in the Eiberg Basin.

  7. Identification of methanogenic pathways in anaerobic digesters using stable carbon isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Laukenmann, Stephan; Polag, Daniela; Greule, Markus; Lelieveld, Jos; Keppler, Frank [Max-Planck-Institut fuer Chemie, Mainz (Germany); Heuwinkel, Hauke; Gronauer, Andreas [Landesanstalt fuer Landwirtschaft, Freising (Germany)

    2010-12-15

    In a series of anaerobic batch experiments, the stable carbon isotopes, {delta}{sup 13}C{sub CH4} and {delta}{sup 13}C{sub CO2}, were measured in biogas produced from various sources (maize, cellulose, inoculum) to identify the degradation kinetics and specific methanogenic pathways. Isotopic analysis was performed using a new absorption laser spectrometer in addition to conventional MS. A comparison of the isotopic evolution shows large isotope dynamics for maize and cellulose, indicating a temporal change in degradation pathways and/or a change in the relative contribution from different carbon fractions within the substrate. Further batch experiments with isotopically labelled acetate (either {sup 13}CH{sub 3}CO{sub 2}Na or CH{sup 13}{sub 3}CO{sub 2}Na) were carried out to study the degradation of acetate in inoculum systematically. The results suggest that the acetate is completely oxidized into CO{sub 2} which in turn is partly reduced to CH{sub 4}. Furthermore, the distinct isotopic signature CH{sub 4} and CO{sub 2} (for acetate-methyl labelling as well as for acetate-carboxy labelling) indicate that only a minor part of the produced methane derives from acetate. A substantial fraction of methane may have been produced at an earlier stage of the reaction chain or by other potential methane precursors such as formate or methanol. (Copyright copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Beyond carbon and nitrogen: guidelines for estimating three-dimensional isotopic niche space.

    Science.gov (United States)

    Rossman, Sam; Ostrom, Peggy H; Gordon, Forrest; Zipkin, Elise F

    2016-04-01

    Isotopic niche has typically been characterized through carbon and nitrogen ratios and most modeling approaches are limited to two dimensions. Yet, other stable isotopes can provide additional power to resolve questions associated with foraging, migration, dispersal and variations in resource use. The ellipse niche model was recently generalized to n-dimensions. We present an analogous methodology which incorporates variation across three stable dimensions to estimate the significant features of a population's isotopic niche space including: 1) niche volume (referred to as standard ellipsoid volume, SEV), 2) relative centroid location (CL), 3) shape and 4) area of overlap between multiple ellipsoids and 5) distance between two CLs. We conducted a simulation study showing the accuracy and precision of three dimensional niche models across a range of values. Importantly, the model correctly identifies differences in SEV and CL among populations, even with small sample sizes and in cases where the absolute values cannot precisely be recovered. We use these results to provide guidelines for sample size in conducting multivariate isotopic niche modeling. We demonstrate the utility of our approach with a case study of three bottlenose dolphin populations which appear to possess largely overlapping niches when analyzed with only carbon and nitrogen isotopes. Upon inclusion of sulfur, we see that the three dolphin ecotypes are in fact segregated on the basis of salinity and find the stable isotope niche of inshore bottlenose dolphins significantly larger than coastal and offshore populations.

  9. Carbon and oxygen isotope geochemistry of Ediacaran outer platform carbonates, Paraguay Belt, central Brazil

    Directory of Open Access Journals (Sweden)

    Claudio Riccomini

    2007-09-01

    Full Text Available After the late Cryogenian glaciation the central region of Brazil was the site of extensive deposition of platformal carbonates of the Araras Group. This group includes a basal cap carbonate sequence succeeded by transgressive, deep platform deposits of bituminous lime mudstone and shale. Facies and stratigraphic data combined with carbon and oxygen isotopic analyses of the most complete section of the transgressive deposits, exposed in the Guia syncline, were used to evaluate the depositional paleoenvironment and to test the correlation of these deposits along the belt and with other units worldwide. The studied succession consists of 150 m thick tabular beds of black to grey lime mudstone and shale with predominantly negative delta13C PDB values around -2.5 to -1‰ . The delta13C PDB profile of Guia syncline shows a clear correlation with the upper portion of Guia Formation in the Cáceres region, about 200 km to the southwest. The delta13C PDB profile of the Araras Group is comparable with delta13C PDB profiles of Ediacaran units of the southern Paraguay Belt, western Canada, and the Congo and Kalahari cratons. Moreover, facies distribution, stratigraphy and the carbon isotopic profile of the Araras Group match the middle Tsumeb Subgroup in Namibia, which reinforces the Ediacaran age assigned to the Araras Group.Após a glaciação do final do Criogeniano, a região central do Brasil foi palco de extensa deposição de carbonatos plataformais do Grupo Araras. Este grupo inclui na sua base uma seqüência de capa carbonática sucedida por depósitos transgressivos de calcilutitos betuminosos e folhelhos de plataforma profunda. Dados de fácies e estratigráficos combinados com análises isotópicas de carbono e oxigênio da seção mais completa desses depósitos transgressivos, expostos no sinclinal da Guia, foram empregados para avaliar o paleambiente deposicional e para testar a correlação desses depósitos ao longo da faixa e tamb

  10. Carbon isotopic records inpaleosols over the Pliocene in Northern China: Implication on vegetation developmentand Tibetan uplift

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Carbon isotopic composition of pedogenic carbonate can be used to estimate the proportion of C4 and C3 plants. Here we present carbon isotopic data of carbonate in a red earth section at Xifeng, central Loess Plateau. Results show that C4 vegetation increased in ~4.4 Ma B.P., stabilized between 4.0 and 3.0 Ma B.P. The character and timing of C4 expansion on the Loess Plateau are similar, but different with other localities, e.g. Pakistan and Africa, implying that regional climate changes were main factors driving the expansion of C4 plants. This event is comparable in timing with increased aridity evidenced by Xifeng grain size and North Pacific eolian dust records. Therefore we argue that the Pliocene expansion of C4 plants in northern China might have been caused by the increased aridity, which in turn might be related to rapid uplift of the Tibetan Plateau.

  11. Glucose isotope, carbon recycling, and gluconeogenesis using [U-13C]glucose and mass isotopomer analysis.

    Science.gov (United States)

    Lee, W N; Sorou, S; Bergner, E A

    1991-06-01

    Experimental determinations of glucose carbon recycling using 14C or 13C glucose tracer often underestimate true Cori cycle activity because of dilution and exchange of isotope tracer through the tricarboxylic acid (TCA) cycle. The term glucose isotope recycling therefore is used to distinguish recycling of isotope from recycling of glucose carbon, the actual quantity of circulating glucose recycled. Recently, per-labeled glucose ([U-13C6]glucose) has been used to estimate glucose appearance rate and glucose isotope recycling. Chemical structural information determined by mass isotopomer analysis has been used to correct for dilution of isotope through the TCA cycle. In this report, we present experiments in the study of glucose turnover and recycling using [U-13C6]glucose. Methods of single injection and continuous infusion of [U-13C6]glucose are compared. A formula for the calculation of a dilution factor using TCA cycle parameters is derived. In this study of six rabbits, glucose turnover rate ranged from 3.4 to 8.8 mg/kg/min, and glucose m + 3 mass isotopomer recycling from 7 to 12%. The rate of pyruvate carboxylation (Y) was comparable to that of citrate synthetase, having an average relative flux of 0.89. Applying the correction factor for tracer dilution to the observed mass isotopomer recycling, we determined glucose carbon recycling (or Cori cycle activity) to be 22-35% of hepatic glucose output.

  12. Carbon isotope fractionation reveals distinct process of CH4 emission from different compartments of paddy ecosystem

    Science.gov (United States)

    Zhang, Guangbin; Yu, Haiyang; Fan, Xianfang; Ma, Jing; Xu, Hua

    2016-06-01

    Carbon isotopic fractionations in the processes of CH4 emission from paddy field remain poorly understood. The δ13C-values of CH4 in association with production, oxidation and transport of CH4 in different pools of a paddy field were determined, and the stable carbon isotope fractionations were calibrated to assess relative contribution of acetate to CH4 production (fac) and fraction of CH4 oxidized (fox) by different pathways. The apparent isotope fractionation for CO2 conversion to CH4 (αapp) was 1.041-1.056 in the soil and 1.046-1.080 on the roots, indicating that fac was 10-60% and 0-50%, respectively. Isotope fractionation associated with CH4 oxidation (αox) was 1.021 ± 0.007 in the soil and 1.013 ± 0.005 on the roots, and the transport fractionation (ɛtransport) by rice plants was estimated to be -16.7‰ ~ -11.1‰. Rhizospheric fox was about 30-100%, and it was more important at the beginning but decreased fast towards the end of season. Large value of fox was also observed at the soil-water interface and soil and roots surfaces, respectively. The results demonstrate that carbon isotopic fractionations which might be different in different conditions were sensitive to the estimations of fac and fox in paddy field.

  13. Metal isotopes and carbonate proxy archives: Model-based perspectives on diagenesis

    Science.gov (United States)

    Fantle, M. S.; Higgins, J. A.; Griffith, E. M.

    2014-12-01

    Metal isotopes are novel tools, and have expanded the geochemical toolbox for elucidating the functioning of the Earth over various time scales. Carbonate-based stable isotope proxies now extend well beyond the traditional major elements (C and O) to include Ca, as well as trace elements such as Sr, S, Mg, B, Li, Cd, and U. Such trace isotopic proxies may contain invaluable information about the Earth system in the past, but can be susceptible to diagenetic alteration over long time scales. It is therefore critical that diagenetic effects are understood and can be recognized in ancient rocks. The extent of alteration depends on reaction rate and advection velocity in the sedimentary section, and elemental partitioning and isotopic effects associated with diagenesis. Numerical approaches, such as reactive transport models, are extremely useful tools for constraining such variables, and for testing hypotheses related to alteration of proxy records. Reactive transport models allow for constraints on calcite recrystallization rates in natural systems; data from ODP Sites 807A, 1170A, 1171A, and 806B suggest rapid recrystallization in relatively young sediments, as well as a Ca isotopic fractionation factor (α) associated with calcite recrystallization close to 1 (Δ=0). While the former is critical for addressing the fidelity and accuracy of a variety of geochemical proxies, the latter is distinctly different from that associated with the formation of carbonates in the surface ocean (Δ~ -1.35‰), suggesting considerable isotopic leverage to alter Ca isotopes during diagenesis. While Ca isotopes are generally well buffered in carbonate-rich sediments, this leverage to alter may be expressed as a reduction in the amplitude of geochemical variability in the solid or as a result of reactions near the sediment-seawater interface (as seen at ODP Site 1221 associated with chemical burndown during the PETM). Further, the Ca and Mg isotopic compositions of shallow water

  14. Late Glacial Tropical Savannas in Sundaland Inferred From Stable Carbon Isotope Records of Cave Guano

    Science.gov (United States)

    Wurster, C. M.; Bird, M. I.; Bull, I.; Dungait, J.; Bryant, C. L.; Ertunç, T.; Hunt, C.; Lewis, H. A.; Paz, V.

    2008-12-01

    During the Last Glacial Period (LGP), reduced global sea level exposed the continental shelf south of Thailand to Sumatra, Java, and Borneo to form the contiguous continent of Sundaland. However, the type and extent of vegetation that existed on much of this exposed landmass during the LGP remains speculative. Extensive bird and bat guano deposits in caves throughout this region span beyond 40,000 yr BP, and contain a wealth of untapped stratigraphic palaeoenvironmental information. Stable carbon isotope ratios of insectivorous bird and bat guano contain a reliable record of the animal's diet and, through non-specific insect predation, reflect the relative abundance of major physiological pathways in plants. Various physiological pathways of carbon fixation in plants yield differing stable carbon isotope ratios. Stable carbon isotope values of C3 plants are lower than C4 vegetation due to different enzymatic discriminations of the heavy isotope through the carbon fixing pathways. In tropical locales, grasses nearly always follow the C4 photosynthetic pathway, whereas tropical rainforest uses C3 photosynthesis, providing a proxy for vegetation and therefore climate change in the past. Here we discuss four guano stable-isotope records, based on insect cuticle and n-alkane analysis, supplemented by pollen analysis. All sites suggest a C3 dominated ecosystem for the Holocene, consistent with the wet tropical forest vegetation present at all locations. Two sites from Palawan Island, Philippines, record stable carbon isotope values of guano that document a drastic change from C3 (forest) to C4 (savanna) dominated ecosystems during the Last Glacial Maximum (LGM). A third location, at Niah Great Cave, Malaysia, indicates C3-dominant vegetation throughout the record, but does display variation in stable carbon isotope values likely linked to humidity changes. A fourth location, Batu Caves in Peninsular Malaysia, also indicates open vegetation during the LGM. Vegetation

  15. CO2-dependent carbon isotope fractionation in the dinoflagellate Alexandrium tamarense

    Science.gov (United States)

    Wilkes, Elise B.; Carter, Susan J.; Pearson, Ann

    2017-09-01

    The carbon isotopic composition of marine sedimentary organic matter is used to resolve long-term histories of pCO2 based on studies indicating a CO2-dependence of photosynthetic carbon isotope fractionation (εP). It recently was proposed that the δ13C values of dinoflagellates, as recorded in fossil dinocysts, might be used as a proxy for pCO2. However, significant questions remain regarding carbon isotope fractionation in dinoflagellates and how such fractionation may impact sedimentary records throughout the Phanerozoic. Here we investigate εP as a function of CO2 concentration and growth rate in the dinoflagellate Alexandrium tamarense. Experiments were conducted in nitrate-limited chemostat cultures. Values of εP were measured on cells having growth rates (μ) of 0.14-0.35 d-1 and aqueous carbon dioxide concentrations of 10.2-63 μmol kg-1 and were found to correlate linearly with μ/[CO2(aq)] (r2 = 0.94) in accord with prior, analogous chemostat investigations with eukaryotic phytoplankton. A maximum fractionation (εf) value of 27‰ was characterized from the intercept of the experiments, representing the first value of εf determined for an algal species employing Form II RubisCO-a structurally and catalytically distinct form of the carbon-fixing enzyme. This value is larger than theoretical predictions for Form II RubisCO and not significantly different from the ∼25‰ εf values observed for taxa employing Form ID RubisCO. We also measured the carbon isotope contents of dinosterol, hexadecanoic acid, and phytol from each experiment, finding that each class of biomarker exhibits different isotopic behavior. The apparent CO2-dependence of εP values in our experiments strengthens the proposal to use dinocyst δ13C values as a pCO2 proxy. Moreover, the similarity between the εf value for A. tamarense and the consensus value of ∼25‰ indicates that the CO2-sensitivity of carbon isotope fractionation saturates at similar CO2 levels across all three

  16. Forensic utility of carbon isotope ratio variations in PVC tape backings.

    Science.gov (United States)

    Dietz, Marianne E; Stern, Libby A; Mehltretter, Andria Hobbs; Parish, Ashley; McLasky, Velvet; Aranda, Roman

    2012-03-01

    Forensic interest in adhesive tapes with polyvinyl chloride (PVC) backings (electrical tape) derives from their use in a variety of illicit activities. Due to the range of physical characteristics, chemical compositions, and homogeneity within a single roll of tape, traditional microscopic and chemical analyses can offer a high degree of discrimination between tapes, permitting the assessment of potential associations between evidentiary tape samples. The carbon isotope ratios of tapes could provide additional discrimination among tape samples. To evaluate whether carbon isotope ratios may be able to increase discrimination of electrical tapes, particularly with regards to different rolls of tape of the same product, we assessed the δ(13)C values of backings from 87 rolls of PVC-based black electrical tape (~20 brands, >60 products) Prior to analysis, adhesives were removed to prevent contamination by adhering debris, and plasticizers were extracted because of concern over their potential mobility. This result is consistent with each of these tapes having approximately the same plasticizer δ(13)C value and proportion of carbon in these plasticizers. The δ(13)C values of the 87 PVC tape backings ranged between -23.5 and -41.3 (‰, V-PDB), with negligible carbon isotopic variation within single rolls of tape, yet large variations among tape brands and tape products. Within this tape population, carbon isotope ratios permitted an average exclusion power of 93.7%, using a window of +/-0.3‰; the combination of carbon isotope ratio measurement with additional chemical and physical analyses raises the discrimination power to over 98.9%, with only 41 out of a possible 3741 pairs of tape samples being indistinguishable. There was a linear relationship between the δ(13)C value of tape backings and the change in δ(13)C value with the extraction of plasticizers. Analyses of pre- and post-blast tape sample pairs show that carbon isotope signatures are within 0.3‰ of

  17. Carbon-13 isotope composition of the mean CO2 source in the urban atmosphere of Krakow, southern Poland

    Science.gov (United States)

    Zimnoch, Miroslaw; Jasek, Alina; Rozanski, Kazimierz

    2014-05-01

    Quantification of carbon emissions in urbanized areas constitutes an important part of the current research on the global carbon cycle. As the carbon isotopic composition of atmospheric carbon dioxide can serve as a fingerprint of its origin, systematic observations of δ13CO2 and/or Δ14CO2, combined with atmospheric CO2mixing ratio measurements can be used to better constrain the urban sources of this gas. Nowadays, high precision optical analysers based on absorption of laser radiation in the cavity allow a real-time monitoring of atmospheric CO2 concentration and its 13CO2/12CO2 ratio, thus enabling better quantification of the contribution of different anthropogenic and natural sources of this gas to the local atmospheric CO2load. Here we present results of a 2-year study aimed at quantifying carbon isotopic signature of the mean CO2 source and its seasonal variability in the urban atmosphere of Krakow, southern Poland. The Picarro G2101-i CRDS isotopic analyser system for CO2and 13CO2/12CO2 mixing ratio measurements has been installed at the AGH University of Science and Technology campus in July 2011. Air inlet was located at the top of a 20m tower mounted on the roof of the faculty building (ca. 42m a.g.l.), close to the city centre. While temporal resolution of the analyser is equal 1s, a 2-minute moving average was used for calculations of δ13CO2 and CO2 mixing ratio to reduce measurement uncertainty. The measurements were calibrated against 2 NOAA (National Oceanic and Atmospheric Administration) primary standard tanks for CO2 mixing ratio and 1 JRAC (Jena Reference Air Cylinder) isotope primary standard for δ13C. A Keeling approach based on two-component mass and isotope balance was used to derive daily mean isotopic signatures of local CO2 from individual measurements of δ13CO2 and CO2 mixing ratios. The record covers a 2-year period, from July 2011 to July 2013. It shows a clear seasonal pattern, with less negative and less variable δ13CO2 values

  18. Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition

    Science.gov (United States)

    Tripati, Aradhna K.; Hill, Pamela S.; Eagle, Robert A.; Mosenfelder, Jed L.; Tang, Jianwu; Schauble, Edwin A.; Eiler, John M.; Zeebe, Richard E.; Uchikawa, Joji; Coplen, Tyler B.; Ries, Justin B.; Henry, Drew

    2015-01-01

    “Clumped-isotope” thermometry is an emerging tool to probe the temperature history of surface and subsurface environments based on measurements of the proportion of 13C and 18O isotopes bound to each other within carbonate minerals in 13C18O16O22- groups (heavy isotope “clumps”). Although most clumped isotope geothermometry implicitly presumes carbonate crystals have attained lattice equilibrium (i.e., thermodynamic equilibrium for a mineral, which is independent of solution chemistry), several factors other than temperature, including dissolved inorganic carbon (DIC) speciation may influence mineral isotopic signatures. Therefore we used a combination of approaches to understand the potential influence of different variables on the clumped isotope (and oxygen isotope) composition of minerals.We conducted witherite precipitation experiments at a single temperature and at varied pH to empirically determine 13C-18O bond ordering (Δ47) and δ18O of CO32- and HCO3- molecules at a 25 °C equilibrium. Ab initio cluster models based on density functional theory were used to predict equilibrium 13C-18O bond abundances and δ18O of different DIC species and minerals as a function of temperature. Experiments and theory indicate Δ47 and δ18O compositions of CO32- and HCO3- ions are significantly different from each other. Experiments constrain the Δ47-δ18O slope for a pH effect (0.011 ± 0.001; 12 ⩾ pH ⩾ 7). Rapidly-growing temperate corals exhibit disequilibrium mineral isotopic signatures with a Δ47-δ18O slope of 0.011 ± 0.003, consistent with a pH effect.Our theoretical calculations for carbonate minerals indicate equilibrium lattice calcite values for Δ47 and δ18O are intermediate between HCO3− and CO32−. We analyzed synthetic calcites grown at temperatures ranging from 0.5 to 50 °C with and without the enzyme carbonic anhydrase present. This enzyme catalyzes oxygen isotopic exchange between DIC species and is present in many

  19. Carbon and Nitrogen Isotope Systematics in a Sector-Zoned Diamond from the Mir Kimberlite, Yakutia

    Science.gov (United States)

    Hauri, E.; Bulanova, G.; Pearson, G.; Griffin, B.

    2002-05-01

    A single Yakutian octahedral diamond, displaying striking cubic and octahedral growth sectors surrounded by an octahedral rim, has been analysed for carbon and nitrogen isotopic compositions by SIMS and for nitrogen concentration (by SIMS and FTIR) and nitrogen aggregation state (FTIR). A graphite "seed" inclusion identified within the diamond, enriched in K, Ca, Ti, Rb and Sr, provides evidence that the diamond may have grown from a carbonate melt/fluid interacting with upper mantle rocks. Carbon and nitrogen isotope compositions become progressively heavier from the core region (d13C = -7 to -5 and d15N= -3) towards the inner rim zones (d13C = -3 and d15N = +8.9 to +5) of the diamond. Nitrogen concentration and aggregation measurements show corresponding decreases that generally correlate with the isotopic variations. These systematic variations within the core and intermediate regions of the diamond are consistent with their formation during diamond growth from CO2-rich fluids as a continuous event, accompanied by slight progressive isotopic fractionation of carbon and nitrogen. However, the observed isotope and nitrogen abundance trends are not those predicted from thermodynamic modelling of fluid-solid equilibria in a C-N-O-H-bearing system due to changes in parameters such as fO2 (Deines, 1980; Deines et al 1989). Within the finely-zoned octahedral rim region, non-systematic variations in nitrogen abundance, nitrogen aggregation, and nitrogen and carbon isotope ratios were observed. Several interpretations are given for this phenomenon, including kinetic effects during growth of the diamond rim under different conditions from those of the core-intermediate regions, or rapidly changing fluid sources during the growth. No fractionation of nitrogen isotopes between cubic and octahedral growth zones was identified within the studied diamond, in contrast with the fractionation phenomena found in synthetic diamonds of mixed growth. Our results illustrate the

  20. Online stable carbon isotope ratio measurement in formic acid, acetic acid, methanol and ethanol in water by high performance liquid chromatography-isotope ratio mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Tagami, Keiko [National Institute of Radiological Sciences, 4-9-1, Anagawa, Inage-ku, Chiba 263-8555 (Japan)], E-mail: k_tagami@nirs.go.jp; Uchida, Shigeo [National Institute of Radiological Sciences, 4-9-1, Anagawa, Inage-ku, Chiba 263-8555 (Japan)

    2008-05-05

    A suitable analysis condition was determined for high performance liquid chromatography-isotope ratio mass spectrometry (HPLC-IRMS) while making sequential measurements of stable carbon isotope ratios of {delta}{sup 13}C in formic acid, acetic acid, methanol and ethanol dissolved in water. For this online column separation method, organic reagents are not applicable due to carbon contamination; thus, water and KH{sub 2}PO{sub 4} at low concentrations were tested as mobile phase in combination with a HyPURITY AQUASTAR{sup TM} column. Formic acid, acetic acid, methanol and ethanol were separated when 2 mM KH{sub 2}PO{sub 4} aqueous solution was used. Under the determined analysis condition for HPLC-IRMS, carbon concentrations could be measured quantitatively as well as carbon isotope ratio when carbon concentration was higher than 0.4 mM L for each chemical.

  1. Carbon isotope fractionation by the marine ammonia-oxidizing archaeon Nitrosopumilus maritimus

    OpenAIRE

    Könneke, Martin; Lipp, Julius Sebastian; Hinrichs, Kai-Uwe

    2012-01-01

    Abstract Ammonia-oxidizing archaea (AOA) are abundant and widely distributed microorganisms in aquatic and terrestrial habitats. By catalyzing the first and rate limiting step in nitrification, these chemolithoautotrophs play a significant role in the global nitrogen cycle and contribute to primary production. Here, the carbon isotopic fractionation relative to inorganic carbon source was determined for bulk biomass, biphytanes and polar lipid bound sugars of a marine AOA pure culture. Bu...

  2. Assessing diet in savanna herbivores using stable carbon isotope ratios of faeces

    Directory of Open Access Journals (Sweden)

    D. Codron

    2005-06-01

    Full Text Available In African savannas, browse-based resources (@3 plants are isotopically distinct from grasses (@4 plants. The carbon isotopic composition of the basic plant diet is recorded in animal tissues. Mammal faeces are a readily accessible, non-invasive, sample material for temporally resolved dietary reconstructions. Faeces, however, include both undigested plant matter and waste, hence accuracy of dietary calculations could potentially be compromised by shifts in plant isotopic values related to seasonal or spatial differences, or by variability in the isotopic differences between faeces and diet. A controlled feeding study of four ungulate species showed a small, consistent difference between diet and faeces of-0.9 o, irrespective of whether the diet was @3 or C4-based. Results from faeces oftaxa known to be pure grazers, pure browsers, and mixed-feeders from the Kruger National Park were entirely consistent with their diets, but the accuracy of dietary reconstructions is enhanced with data from local plant communities.

  3. Constraints on the formation and diagenesis of phosphorites using carbonate clumped isotopes

    Science.gov (United States)

    Stolper, Daniel A.; Eiler, John M.

    2016-05-01

    The isotopic composition of apatites from sedimentary phosphorite deposits has been used previously to reconstruct ancient conditions on the surface of the Earth. However, questions remain as to whether these minerals retain their original isotopic composition or are modified during burial and lithification. To better understand how apatites in phosphorites form and are diagenetically modified, we present new isotopic measurements of δ18O values and clumped-isotope-based (Δ47) temperatures of carbonate groups in apatites from phosphorites from the past 265 million years. We compare these measurements to previously measured δ18O values of phosphate groups from the same apatites. These results indicate that the isotopic composition of many of the apatites do not record environmental conditions during formation but instead diagenetic conditions. To understand these results, we construct a model that describes the consequences of diagenetic modification of phosphorites as functions of the environmental conditions (i.e., temperature and δ18O values of the fluids) during initial precipitation and subsequent diagenesis. This model captures the basic features of the dataset and indicates that clumped-isotope-based temperatures provide additional quantitative constraints on both the formational environment of the apatites and subsequent diagenetic modification. Importantly, the combination of the model with the data indicates that the δ18O values and clumped-isotope temperatures recorded by phosphorites do not record either formation or diagenetic temperatures, but rather represent an integrated history that includes both the formation and diagenetic modification of the apatites.

  4. Stable isotope composition of bulk and secondary carbonates from the Quaternary loess-paleosol sequence in Sutto, Hungary

    DEFF Research Database (Denmark)

    Koeniger, Paul; Barta, Gabriella; Thiel, Christine

    2014-01-01

    , and microscale secondary (authigenic) carbonates (calcified root cells, carbonate coatings, hypocoatings, and earthworm biospheroids) and concretions at 10 cm resolution were analysed to interpret stable isotope variations. Isotope values of bulk samples were in the range of 2.6 parts per thousand to -13.9 parts......, secondary carbonates showed more depleted values than bulk samples. Calcified root cells have the most depleted isotope composition with mean values of -16.0 parts per thousand and -11.8 parts per thousand for delta C-13 and 8180, respectively. Results indicate that loess and paleosol secondary carbonates...

  5. Long-term Carbon and Nitrogen Dynamics at SPRUCE Revealed through Stable Isotopes in Peat Profiles

    Science.gov (United States)

    Hobbie, E. A.

    2015-12-01

    Carbon and nitrogen turnover in peatlands is of considerable interest because peat is a large reservoir of stored carbon that could emit greenhouse gases in response to climate change. Because peat cores preserve a long-term record of system carbon and nitrogen dynamics, it is possible to use stable isotopes as markers of changes in carbon (C) and nitrogen (N) dynamics over time. Here, we used δ15N and δ13C patterns throughout the depth profile of peat cores to understand controls over C-N cycling in the Marcell S1 forested bog in northern Minnesota. In multiple regression analyses, δ15N and δ13C correlated strongly with depth, plot location, %C, %N, and each other. Negative correlation of δ15N with %N presumably reflected removal of 15N-depleted N via denitrification, diffusion, or plant N transfer via mycorrhizal fungi. A step increase in the depth coefficient for δ15N of ~3‰ from -25 cm to -35 cm suggested that the N removal process primarily operates at a discrete depth corresponding to the juncture between aerobic and anaerobic layers defined by the water table. Higher δ15N and lower δ13C in plots closer to uplands may reflect distinct hydrology and accompanying shifts in C and N dynamics in the lagg area fringing the bog. The Suess effect (declining δ13CO2 since the Industrial Revoluation) and aerobic decomposition lowered δ13C in recent surficial samples. Small increases in δ13C at -112 cm (4300 calibrated years BP) and -85 cm (3800 calibrated years BP) may reflect C dynamics during a suspected transitional fen stage (based on paleoecology at a nearby bog), when reduced methanotrophy retained less 13C-depleted carbon derived from methane than in later periods. The C/N decreased until about -85 cm and thereafter remained steady, suggesting that the active zone of aerobic processing during drought may extend to this depth. The inflection point in calculated carbon accumulation rates at this depth supports this conclusion.

  6. Determination of the geographical origin of Chinese teas based on stable carbon and nitrogen isotope ratios

    Institute of Scientific and Technical Information of China (English)

    Long ZHANG; Jia-rong PAN; Cheng ZHU

    2012-01-01

    The objective of this study was to investigate the geographical origin of Chinese teas using carbon and nitrogen stable isotope ratio technology.The results showed that inter-provincial dispersion of teas in Guangdong (GD),Guangxi (GX),Hainan (HA),Fujian (F J),Shandong (SD),Sichuan (SC),Chongqing (CQ),and Henan (HN) provinces was high,while in Zhejiang (ZJ),Hubei (HB),Yunnan (YN),and Anhui (AH) provinces,it was low.Tea samples from GD,GX,HA,and FJ provinces were clustered in one group and separated from those from AH and HB provinces.Thus,carbon and nitrogen stable isotope ratio technology could discriminate teas from among some provinces of China,but not from among others.Better separation might be obtained with a combination of isotopic ratios and other indexes,such as elemental data and organic components.

  7. Carbonate clumped isotope constraints on Silurian ocean temperature and seawater δ18O

    Science.gov (United States)

    Cummins, Renata C.; Finnegan, Seth; Fike, David A.; Eiler, John M.; Fischer, Woodward W.

    2014-09-01

    Much of what we know about the history of Earth's climate derives from the chemistry of carbonate minerals in the sedimentary record. The oxygen isotopic compositions (δ18O) of calcitic marine fossils and cements have been widely used as a proxy for past seawater temperatures, but application of this proxy to deep geologic time is complicated by diagenetic alteration and uncertainties in the δ18O of seawater in the past. Carbonate clumped isotope thermometry provides an independent estimate of the temperature of the water from which a calcite phase precipitated, and allows direct calculation of the δ18O of the water. The clumped isotope composition of calcites is also highly sensitive to recrystallization and can help diagnose different modes of diagenetic alteration, enabling evaluation of preservation states and identification of the most pristine materials from within a sample set-critical information for assessing the quality of paleoproxy data generated from carbonates. We measured the clumped isotope composition of a large suite of calcitic fossils (primarily brachiopods and corals), sedimentary grains, and cements from Silurian (ca. 433 Ma) stratigraphic sections on the island of Gotland, Sweden. Substantial variability in clumped isotope temperatures suggests differential preservation with alteration largely tied to rock-buffered diagenesis, complicating the generation of a stratigraphically resolved climate history through these sections. Despite the generally high preservation quality of samples from these sections, micro-scale observations of calcite fabric and trace metal composition using electron backscatter diffraction and electron microprobe analysis suggest that only a subset of relatively pristine samples retain primary clumped isotope signatures. These samples indicate that Silurian tropical oceans were likely warm (33 ± 7 °C) and similar in oxygen isotopic composition to that estimated for a "modern" ice-free world (δ18OVSMOW of -1.1 ± 1

  8. Studies of carbon--isotope fractionation. Annual progress report, December 1, 1974--November 30, 1975

    Energy Technology Data Exchange (ETDEWEB)

    Ishida, T.

    1975-12-01

    The vapor pressure isotope effect of /sup 13/C//sup 12/C-substitution in CClF/sub 3/ was measured at temperatures between 169/sup 0/ and 206/sup 0/K by means of cryogenic distillation. The /sup 13/C//sup 12/C-vapor pressure isotope effect in CHF/sub 3/ was also studied at temperatures between 161/sup 0/ and 205/sup 0/K by a similar method. The construction of a cryostat has progressed as scheduled. The investigation of carbon isotope exchange equilibria between carbon dioxide and various carbamates dissolved in various organic solvents has continued. The five-stage system of Taylor-Ghate design was improved to shorten the transient time. A single stage apparatus was designed, built, and tested. These systems are used to measure the equilibrium constants and various phase equilibria involved in the carbon dioxide--carbamate system. The investigation of the explicit method of total isotope effect has made progress. A satisfactory approximation was found for the classical partition function of a Morse oscillator. The method gives a reasonable result at rho identical with /sup 1///sub 2/..sqrt..(u/sub e//x/sub e/) greater than 1.5. The medium cluster approach was applied to isotopic methanes to investigate the effects of intermolecular distance and mutual orientations of molecules in the liquid upon vapor pressure isotope effect. It was found that all geometrical effects studied tend to vanish as the size of clusters is increased. Isotope effect in the zero-point energy shifts on condensation was calculated on the basis of London dispersion forces in liquid and a semi-empirical molecular orbital theory, and was favorably compared with experimental results. (auth)

  9. Carbon isotope fractionation of dissolved inorganic carbon (DIC) due to outgassing of carbon dioxide from a headwater stream

    Science.gov (United States)

    Doctor, D.H.; Kendall, C.; Sebestyen, S.D.; Shanley, J.B.; Ohte, N.; Boyer, E.W.

    2008-01-01

    The stable isotopic composition of dissolved inorganic carbon (??13C-DIC) was investigated as a potential tracer of streamflow generation processes at the Sleepers River Research Watershed, Vermont, USA. Downstream sampling showed ?? 13C-DIC increased between 3-5??? from the stream source to the outlet weir approximately 0??5 km downstream, concomitant with increasing pH and decreasing PCO2. An increase in ??13C-DIC of 2.4 ?? 0??1??? per log unit decrease of excess PCO2 (stream PCO2 normalized to atmospheric PCO2) was observed from downstream transect data collected during snowmelt. Isotopic fractionation of DIC due to CO2 outgassing rather than exchange with atmospheric CO2 may be the primary cause of increased ?? 13C-DIC values downstream when PCO2 of surface freshwater exceeds twice the atmospheric CO2 concentration. Although CO2 outgassing caused a general increase in stream ??13C-DIC values, points of localized groundwater seepage into the stream were identified by decreases in ??13C-DIC and increases in DIC concentration of the stream water superimposed upon the general downstream trend. In addition, comparison between snowmelt, early spring and summer seasons showed that DIC is flushed from shallow groundwater flowpaths during snowmelt and is replaced by a greater proportion of DIC derived from soil CO2 during the early spring growing season. Thus, in spite of effects from CO2 outgassing, ??13C of DIC can be a useful indicator of groundwater additions to headwater streams and a tracer of carbon dynamics in catchments. Copyright ?? 2007 John Wiley & Sons, Ltd.

  10. Chromium isotope fractionation during coprecipitation with calcium carbonate

    DEFF Research Database (Denmark)

    Rodler, Alexandra; Sánchez-Pastor, Nuria; Fernández-Díaz, Lurdes

    the Archaean and Protoerozoic, needs careful assessment of the signal robustness and necessitates a thorough understanding of the Cr cycle in Earth system processes. We conducted experiments testing the incorporation and isotopic fractionation of chromate into the calcite lattice. Our experiments indicate...... et al., 2007, Water Air Soil Poll. 179, 381-390. [2] Sánchez-Pastor et al., 2011, Cryst. Growth Des. 11, 3081-3089....

  11. Normalization of stable isotope data for carbonate minerals: implementation of IUPAC guideline

    Science.gov (United States)

    Kim, Sang-Tae; Coplen, Tyler B.; Horita, Juske

    2015-01-01

    Carbonate minerals provide a rich source of geochemical information because their δ13C and δ18O values provide information about surface and subsurface Earth processes. However, a significant problem is that the same δ18O value is not reported for the identical carbonate sample when analyzed in different isotope laboratories in spite of the fact that the International Union of Pure and Applied Chemistry (IUPAC) has provided reporting guidelines for two decades. This issue arises because (1) the δ18O measurements are performed on CO2 evolved by reaction of carbonates with phosphoric acid, (2) the acid-liberated CO2 is isotopically fractionated (enriched in 18O) because it contains only two-thirds of the oxygen from the solid carbonate, (3) this oxygen isotopic fractionation factor is a function of mineralogy, temperature, concentration of the phosphoric acid, and δ18O value of water in the phosphoric acid, (4) researchers may use any one of an assortment of oxygen isotopic fractionation factors that have been published for various minerals at various reaction temperatures, and (5) it sometimes is not clear how one should calculate δ18OVPDB values on a scale normalized such that the δ18O value of SLAP reference water is −55.5 ‰ relative to VSMOW reference water.

  12. Combined carbon and hydrogen isotope fractionation investigations for elucidating benzene biodegradation pathways

    NARCIS (Netherlands)

    Fischer, A.; Herklotz, I.; Herrmann, S.; Thullner, M.; Weelink, S.A.B.; Stams, A.J.M.; Richnow, H.H.; Vogt, C.

    2008-01-01

    Recently, combined carbon and hydrogen isotope fractionation investigations have emerged as a powerful tool for the characterization of reaction mechanisms relevant for the removal of organic pollutants. Here, we applied this approach in order to differentiate benzene biodegradation pathways under o

  13. Latitudinal differences in the amplitude of the OAE-2 carbon isotopic excursion:

    NARCIS (Netherlands)

    van Bentum, E.C.; Reichart, G.J.; Forster, A.; Sinninghe Damsté, J.S.S.

    2012-01-01

    A complete, well-preserved record of the Cenomanian/Turonian (C/T) Oceanic Anoxic Event 2 (OAE-2) was recovered from Demerara Rise in the southern North Atlantic Ocean (ODP site 1260). Across this interval, we determined changes in the stable carbon isotopic composition of sulfur-bound phytane (delt

  14. Analytical system for stable carbon isotope measurements of low molecular weight (C2-C6) hydrocarbons

    NARCIS (Netherlands)

    Zuiderweg, A.T.; Holzinger, R.; Roeckmann, T.

    2011-01-01

    We present setup, testing and initial results from a new automated system for stable carbon isotope ratio measurements on C2 to C6 atmospheric hydrocarbons. The inlet system allows analysis of trace gases from air samples ranging from a few liters for urban samples and samples with high mixing ratio

  15. Natural carbon isotopes used to study methane consumption and production in soil

    DEFF Research Database (Denmark)

    Ambus, Per; Andersen, Bertel Lohmann; Kemner, Marianne;

    2002-01-01

    Changes in the isotopic composition of carbon can be used to reveal simultaneous occurrence of methane production and oxidation in soil. The method is conducted in laboratory jar experiments as well as in the field by using flux chambers. Simultaneous occurrence of production and oxidation...

  16. Stable carbon isotope fractionation of organic cyst-forming dinoflagellates: Evaluating the potential for a CO

    NARCIS (Netherlands)

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

    2015-01-01

    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, h

  17. The puzzle of the CNO isotope ratios in AGB carbon stars

    CERN Document Server

    Abia, Carlos; Domínguez, Inma; Straniero, Oscar

    2016-01-01

    Previous determinations of the oxygen isotopic ratios in AGB carbon stars were at odds with the existing theoretical predictions. We aim to redetermine the oxygen ratios in these stars using new spectral analysis tools and further develop discussions on the carbon and nitrogen isotopic ratios in order to elucidate this problem. Oxygen isotopic ratios were derived from spectra in the K-band in a sample of galactic AGB carbon stars of different spectral types and near solar metallicity. Synthetic spectra calculated in LTE with spherical carbon-rich atmosphere models and updated molecular line lists were used. The CNO isotope ratios derived in a homogeneous way, were compared with theoretical predictions for low-mass (1.5-3 M_o) AGB stars computed with the FUNS code assuming extra mixing both during the RGB and AGB phases. For most of the stars the 16O/17O/18O ratios derived are in good agreement with theoretical predictions confirming that, for AGB stars, are established using the values reached after the FDU a...

  18. Carbon, cesium and iodine isotopes in Japanese cedar leaves from Iwaki, Fukushima

    DEFF Research Database (Denmark)

    Xu, Sheng; Cook, Gordon T.; Cresswell, Alan J.;

    2016-01-01

    Japanese cedar leaves from Iwaki, Fukushima were analyzed for carbon, cesium and iodine isotopic compositions before and after the 2011 nuclear accident. The Δ14C values reflect ambient atmospheric 14C concentrations during the year the leaves were sampled/defoliated, and also previous year...

  19. Variations of sulfur and carbon isotopes in seawater during the Doushantuo stage in late Neoproterozoic

    Institute of Scientific and Technical Information of China (English)

    ZHANG Tonggang; CHU Xuelei; ZHANG Qirui; FENG Lianjun; HUO Weiguo

    2003-01-01

    Successive analyses of sulfur and carbon isotopic compositions of carbonates strata in the Doushantuo Formation in the Yangtze area were accomplished through a method of extracting trace sulfate from carbonates. Sulfur and carbon isotopic compositions of coeval seawater were estimated from the samples that show the least diagenetic alteration. A high-resolution age curve of sulfur isotopes in seawater sulfates was obtained in the Doushantuo stage, which reflects thetrend of variation in seawater sulfur isotopes after the Neoproterozoic snowball Earth event. Similar characteristics of variation in carbon isotopes were observed in the coeval carbonates. A large positive δ34S excursion over +20‰ occurs in ancient seawater sulfates in the early Doushantuo stage. Simultaneously, the δ13C values in ancient seawater carbonates exhibit a positive excursion up to10‰. The maximum δ34S and δ13C values are +46.4‰ and +6.9‰, respectively. In the middle Doushantuo stage, the range of variation in δ34S values of seawater is relatively narrow, but δ13C values are quite high. Then, δ34S values of seawater become oscillating, and the same occurs in δ13C values. Negative excursions in δ34S and δ13C values occur simultaneously at the end of the Doushantuo stage, and the minimum δ34S and δ13C values dropped down to -10.1‰ and -5.7‰, respectively. The characteristics of variations in the sulfur and carbon isotopes of ancient seawater imply strong changes in oceanic environment that became beneficial to inhabitation and propagation of organism. The organic productivity and burial rate of organic carbon once reached a quite high level during the Doushantuo stage. However, the state of environment became unstable after the global glaciation. The global climate and environment possibly were fluctuating and reiterating. The negative excursions in δ34S and δ13C values occurring at the end of the Doushantuo stage may represent a global event, which might be related to

  20. Carbon isotopes characterize rapid changes in atmospheric carbon dioxide during the last deglaciation

    Science.gov (United States)

    Bauska, Thomas K.; Baggenstos, Daniel; Brook, Edward J.; Mix, Alan C.; Marcott, Shaun A.; Petrenko, Vasilii V.; Schaefer, Hinrich; Lee, James E.

    2016-01-01

    An understanding of the mechanisms that control CO2 change during glacial–interglacial cycles remains elusive. Here we help to constrain changing sources with a high-precision, high-resolution deglacial record of the stable isotopic composition of carbon in CO2 (δ13C-CO2) in air extracted from ice samples from Taylor Glacier, Antarctica. During the initial rise in atmospheric CO2 from 17.6 to 15.5 ka, these data demarcate a decrease in δ13C-CO2, likely due to a weakened oceanic biological pump. From 15.5 to 11.5 ka, the continued atmospheric CO2 rise of 40 ppm is associated with small changes in δ13C-CO2, consistent with a nearly equal contribution from a further weakening of the biological pump and rising ocean temperature. These two trends, related to marine sources, are punctuated at 16.3 and 12.9 ka with abrupt, century-scale perturbations in δ13C-CO2 that suggest rapid oxidation of organic land carbon or enhanced air–sea gas exchange in the Southern Ocean. Additional century-scale increases in atmospheric CO2 coincident with increases in atmospheric CH4 and Northern Hemisphere temperature at the onset of the Bølling (14.6–14.3 ka) and Holocene (11.6–11.4 ka) intervals are associated with small changes in δ13C-CO2, suggesting a combination of sources that included rising surface ocean temperature. PMID:26976561

  1. The puzzle of the CNO isotope ratios in asymptotic giant branch carbon stars

    Science.gov (United States)

    Abia, C.; Hedrosa, R. P.; Domínguez, I.; Straniero, O.

    2017-02-01

    Context. The abundance ratios of the main isotopes of carbon, nitrogen and oxygen are modified by the CNO-cycle in the stellar interiors. When the different dredge-up events mix the burning material with the envelope, valuable information on the nucleosynthesis and mixing processes can be extracted by measuring these isotope ratios. Aims: Previous determinations of the oxygen isotopic ratios in asymptotic giant branch (AGB) carbon stars were at odds with the existing theoretical predictions. We aim to redetermine the oxygen ratios in these stars using new spectral analysis tools and further develop discussions on the carbon and nitrogen isotopic ratios in order to elucidate this problem. Methods: Oxygen isotopic ratios were derived from spectra in the K-band in a sample of galactic AGB carbon stars of different spectral types and near solar metallicity. Synthetic spectra calculated in local thermodynamic equillibrium (LTE) with spherical carbon-rich atmosphere models and updated molecular line lists were used. The CNO isotope ratios derived in a homogeneous way, were compared with theoretical predictions for low-mass (1.5-3 M⊙) AGB stars computed with the FUNS code assuming extra mixing both during the RGB and AGB phases. Results: For most of the stars the 16O/17O/18O ratios derived are in good agreement with theoretical predictions confirming that, for AGB stars, are established using the values reached after the first dredge-up (FDU) according to the initial stellar mass. This fact, as far as the oxygen isotopic ratios are concerned, leaves little space for the operation of any extra mixing mechanism during the AGB phase. Nevertheless, for a few stars with large 16O/17O/18O, the operation of such a mechanism might be required, although their observed 12C/13C and 14N/15N ratios would be difficult to reconcile within this scenario. Furthermore, J-type stars tend to have lower 16O/17O ratios than the normal carbon stars, as already indicated in previous studies

  2. Effect of boron doping in the carbon support on platinum nanoparticles and carbon corrosion

    Energy Technology Data Exchange (ETDEWEB)

    Acharya, Chethan K.; Li, Wei; Kwon, Gihan; Heath Turner, C.; Lane, Alan M.; Klein, Tonya [Department of Chemical and Biological Engineering, The University of Alabama, Tuscaloosa, AL 35487 (United States); Liu, Zhufang; Nikles, David [Department of Chemistry, The University of Alabama, Tuscaloosa, AL 35487 (United States); Weaver, Mark [Department of Metallurgical and Materials Engineering, The University of Alabama, Tuscaloosa, AL 35487 (United States)

    2009-07-15

    Carbon supported catalysts can lose their activity over a period of time due to the sintering of the nanometer-sized catalyst particles. The sintering of metal clusters on carbon supports can occur due to the weak interaction between the metal and the support and also due to the corrosion of carbon, especially in fuel cell electrocatalysts. The sintering may be reduced by increasing the interaction between the metal and the support and also by increasing the corrosion resistance of carbon supports. In an effort to mitigate the growth of the nanoparticles, carbon-substituted boron defects were introduced in the carbon lattice. The interaction between the Pt nanoparticles on the pure and boron-doped carbon supports was examined using X-ray photoelectron spectroscopy (XPS). The results indicate that the interaction between the Pt nanoparticles and the boron-doped carbon support was slightly stronger than the interaction between the Pt nanoparticles and the pure carbon support. Also, by using accelerated aging tests, the boron-doped system was found to be more resistant to carbon corrosion when compared to the pristine carbon-supported Pt catalyst. (author)

  3. Influences of β-HCG administration on carbon isotope ratios of endogenous urinary steroids.

    Science.gov (United States)

    Piper, Thomas; Baume, Norbert; Strahm, Emanuel; Emery, Caroline; Saugy, Martial

    2012-05-01

    Several factors influencing the carbon isotope ratios (CIR) of endogenous urinary steroids have been identified in recent years. One of these should be the metabolism of steroids inside the body involving numerous different enzymes. A detailed look at this metabolism taking into account differences found between steroids excreted as glucuronides or as sulphates and hydrogen isotope ratios of different steroids pointed out possibility of unequal CIR at the main production sites inside the male body - the testes and the adrenal glands. By administration of β-HCG it is possible to strongly stimulate the steroid production within the testes without influencing the production at the adrenal glands. Therefore, this treatment should result in changed CIR of urinary androgens in contrast to the undisturbed pre-treatment values. Four male volunteers received three injections of β-HCG over a time course of 5 days and collected their urine samples at defined intervals after the last administration. Those samples showing the largest response in contrast to the pre-administration urines were identified by steroid profile measurements and subsequent analysed by GC/C/IRMS. CIR of androsterone, etiocholanolone, testosterone, 5α- and 5β-androstanediol and pregnanediol were compared. While pregnanediol was not influenced, most of the investigated androgens showed depleted values after treatment. The majority of differences were found to be statistically significant and nearly all showed the expected trend towards more depleted δ(13)C-values. These results support the hypothesis of different CIR at different production sites inside the human body. The impact of these findings on doping control analysis will be discussed.

  4. Carbon isotopic composition of fossil leaves from the Early Cretaceous sediments of western India

    Indian Academy of Sciences (India)

    S Chakraborty; B N Jana; S K Bhattacharya; I Robertson

    2011-08-01

    Stable carbon isotope analysis of fossil leaves from the Bhuj Formation, western India was carried out to infer the prevailing environmental conditions. Compression fossil leaves such as Pachypteris indica, Otozamite kachchhensis, Brachyphyllum royii and Dictyozamites sp. were recovered from three sedimentary successions of the Bhuj Formation, Early Cretaceous in age. A chronology was established based on faunal assemblage and palyno-stratigraphy and further constrained by carbon isotope stratigraphy. The three sampling sites were the Karawadi river bank near Dharesi; the Chawad river bank near Mathal; and the Pur river section near Trambau village in Gujarat. The Dharesi sample was also analyzed to investigate intra-leaf 13C variability. The mean 13C of the leaf was −24.6 ± 0.4‰ which implied negligible systematic change along the leaf axis. The Mathal sample was fragmented in nature and showed considerable variation in carbon isotopic composition. The Trambau sample considered to be the oldest, dating to the middle of Aptian (ca. 116 Ma), shows the most depleted value in 13C among all of them. The overall 13C trend ranging from mid Aptian (ca. 116 Ma) to early Albian (ca. 110 Ma) shows a progressive increase in 13C from −26.8 to −20.5‰. Based on these measurements the carbon isotopic composition of atmospheric carbon dioxide of the Aptian–Albian period is estimated to be between −7.4 and −1.7‰. The ratio of the partial pressure of carbon dioxide in leaf to that of the ambient atmosphere calculated based on a model is estimated to be similar to that of the modern plants. This indicates that the Early-Cretaceous plants adapted to the prevailing high carbon dioxide regime by increasing their photosynthetic uptake.

  5. Observations and sources of carbon and nitrogen isotope ratio variation of pentaerythritol tetranitrate (PETN).

    Science.gov (United States)

    Howa, John D; Lott, Michael J; Ehleringer, James R

    2014-11-01

    Isotope ratio analysis allows forensic investigators to discriminate materials that are chemically identical but differ in their isotope ratios. Here we focused on the discrimination of pentaerythritol tetranitrate (PETN), an explosive with military and civilian applications, using carbon (δ(13)C) and nitrogen (δ(15)N) isotope ratios. Our goal was to understand some of the factors influencing the isotope ratios of commercially manufactured PETN. PETN was isolated from bulk explosives using preparative HPLC, which reduced chemical and isotopic within-sample variability. We observed isotope ratio variation in a survey of 175 PETN samples from 22 manufacturing facilities, with δ(13)C values ranging from -49.7‰ to -28.0‰ and δ(15)N values ranging from -48.6‰ to +6.2‰. Both within-sample variability and variation of PETN within an explosive block were much smaller than between-sample variations. Isotopic ratios of PETN were shown to discriminate explosive blocks from the same manufacturer, whereas explosive component composition measurements by HPLC were not able to do so. Using samples collected from three industrial PETN manufacturers, we investigated the isotopic relationship between PETN and its reactants, pentaerythritol (PE) and nitric acid. Our observations showed that δ(13)C values of PETN were indistinguishable from that of the reactant pentaerythritol. Isotopic separation between nitric acid and PETN was consistent within each sampled manufacturer but differed among manufacturers, and was likely dependent upon reaction conditions. These data indicate that δ(13)C variation in PETN is dependent on δ(13)C variation of PE supplies, while δ(15)N variation in PETN is due to both nitric acid δ(15)N and reaction conditions. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

  6. Carbonate "clumped" isotope signatures in aragonitic scleractinian and calcitic gorgonian deep-sea corals

    Directory of Open Access Journals (Sweden)

    J. Kimball

    2015-12-01

    Full Text Available Deep-sea corals are a potentially valuable archive of the temperature and ocean chemistry of intermediate and deep waters. Living in near constant temperature, salinity and pH, and having amongst the slowest calcification rates observed in carbonate-precipitating biological organisms, deep-sea corals can provide valuable constraints on processes driving mineral equilibrium and disequilibrium isotope signatures. Here we report new data to further develop "clumped" isotopes as a paleothermometer in deep-sea corals as well as to investigate mineral-specific, taxon-specific, and growth-rate related effects. Carbonate clumped isotope thermometry is based on measurements of the abundance of the doubly-substituted isotopologue 13C18O16O2 in carbonate minerals, analyzed in CO2 gas liberated on phosphoric acid digestion of carbonates and reported as Δ47 values. We analyzed Δ47 in live-collected aragonitic scleractinian (Enallopsammia sp. and calcitic gorgonian (Isididae and Coralliidae deep-sea corals, and compared results to published data for other aragonitic scleractinian taxa. Measured Δ47 values were compared to in situ temperatures and the relationship between Δ47 and temperature was determined for each group to investigate taxon-specific effects. We find that aragonitic scleractinian deep-sea corals exhibit higher values than calcitic gorgonian corals and the two groups of coral produce statistically different relationship between Δ47-temperature calibrations. These data are significant in the interpretation of all carbonate "clumped" isotope calibration data as they show that distinct Δ47-temperature calibrations can be observed in different materials recovered from the same environment and analyzed using the same instrumentation, phosphoric acid composition, digestion temperature and technique, CO2 gas purification apparatus, and data handling. There are three possible explanations for the origin of these different calibrations. The offset

  7. Carbonate "clumped" isotope signatures in aragonitic scleractinian and calcitic gorgonian deep-sea corals

    Science.gov (United States)

    Kimball, Justine; Eagle, Robert; Dunbar, Robert

    2016-12-01

    Deep-sea corals are a potentially valuable archive of the temperature and ocean chemistry of intermediate and deep waters. Living in near-constant temperature, salinity, and pH and having amongst the slowest calcification rates observed in carbonate-precipitating biological organisms, deep-sea corals can provide valuable constraints on processes driving mineral equilibrium and disequilibrium isotope signatures. Here we report new data to further develop "clumped" isotopes as a paleothermometer in deep-sea corals as well as to investigate mineral-specific, taxon-specific, and growth-rate-related effects. Carbonate clumped isotope thermometry is based on measurements of the abundance of the doubly substituted isotopologue 13C18O16O2 in carbonate minerals, analyzed in CO2 gas liberated on phosphoric acid digestion of carbonates and reported as Δ47 values. We analyzed Δ47 in live-collected aragonitic scleractinian (Enallopsammia sp.) and high-Mg calcitic gorgonian (Isididae and Coralliidae) deep-sea corals and compared results to published data for other aragonitic scleractinian taxa. Measured Δ47 values were compared to in situ temperatures, and the relationship between Δ47 and temperature was determined for each group to investigate taxon-specific effects. We find that aragonitic scleractinian deep-sea corals exhibit higher values than high-Mg calcitic gorgonian corals and the two groups of coral produce statistically different relationships between Δ47-temperature calibrations. These data are significant in the interpretation of all carbonate clumped isotope calibration data as they show that distinct Δ47-temperature calibrations can be observed in different materials recovered from the same environment and analyzed using the same instrumentation, phosphoric acid composition, digestion temperature and technique, CO2 gas purification apparatus, and data handling. There are three possible explanations for the origin of these different calibrations. The offset

  8. [Net CO2 exchange and carbon isotope flux in Acacia mangium plantation].

    Science.gov (United States)

    Zou, Lu-Liu; Sun, Gu-Chou; Zhao, Ping; Cai, Xi-An; Zeng, Xiao-Ping; Wang, Quan

    2009-11-01

    By using stable carbon isotope technique, the leaf-level 13C discrimination was integrated to canopy-scale photosynthetic discrimination (Deltacanopy) through weighted the net CO2 assimilation (Anet) of sunlit and shaded leaves and the stand leaf area index (L) in an A. mangium plantation, and the carbon isotope fluxes from photosynthesis and respiration as well as their net exchange flux were obtained. There was an obvious diurnal variation in Deltacanopy, being lower at dawn and at noon time (18.47 per thousand and 19.87 per thousand, respectively) and the highest (21.21 per thousand) at dusk. From the end of November to next May, the Deltacanopy had an increasing trend, with an annual average of (20.37 +/- 0.29) per thousand. The carbon isotope ratios of CO2 from autotrophic respiration (excluding daytime foliar respiration) and heterotrophic respiration were respectively (- 28.70 +/- 0.75) per thousand and (- 26.75 +/- 1.3) per thousand in average. The delta13 C of nighttime ecosystem-respired CO2 in May was the lowest (-30.14 per thousand), while that in November was the highest (-28.01 per thousand). The carbon isotope flux of CO2 between A. mangium forest and atmosphere showed a midday peak of 178.5 and 217 micromol x m(-2) x s(-1) x per thousand in May and July, with the daily average of 638.4 and 873.2 micromol x m(-2) x s(-1) x per thousand, respectively. The carbon isotope flux of CO2 absorbed by canopy leaves was 1.6-2.5 times higher than that of CO2 emitted from respiration, suggesting that a large sum of CO2 was absorbed by A. mangium, which decreased the atmospheric CO2 concentration and improved the environment.

  9. Flow injection analysis-isotope ratio mass spectrometry for bulk carbon stable isotope analysis of alcoholic beverages.

    Science.gov (United States)

    Jochmann, Maik A; Steinmann, Dirk; Stephan, Manuel; Schmidt, Torsten C

    2009-11-25

    A new method for bulk carbon isotope ratio determination of water-soluble samples is presented that is based on flow injection analysis-isotope ratio mass spectrometry (FIA-IRMS) using an LC IsoLink interface. Advantages of the method are that (i) only very small amounts of sample are required (2-5 microL of the sample for up to 200 possible injections), (ii) it avoids complex sample preparation procedures such as needed for EA-IRMS analysis (only sample dilution and injection,) and (iii) high throughput due to short analysis times is possible (approximately 15 min for five replicates). The method was first tested and evaluated as a fast screening method with industrially produced ethanol samples, and additionally the applicability was tested by the measurement of 81 alcoholic beverages, for example, whiskey, brandy, vodka, tequila, and others. The minimal sample concentration required for precise and reproducible measurements was around 50 microL L(-1) ethanol/water (1.71 mM carbon). The limit of repeatability was determined to be r=0.49%. FIA-IRMS represents a fast screening method for beverage authenticity control. Due to this, samples can be prescreened as a decisive criterion for more detailed investigations by HPLC-IRMS or multielement GC-IRMS measurements for a verification of adulteration.

  10. Calibration of the carbonate `clumped isotope' paleotemperature proxy using mollusc shells and benthic foraminiferal tests

    Science.gov (United States)

    Came, R. E.; Curry, W. B.; Weidman, C. R.; Eiler, J. M.

    2007-12-01

    It has recently been shown that the carbonate `clumped isotope' thermometer can provide temperature constraints that depend only on the isotopic composition of carbonate (in particular, on the proportion of 13C and 18O that form bonds with each other), and that do not require assumptions about the isotopic composition of the water in which the carbonate formed (Ghosh et al., 2006). Furthermore, this novel method permits the calculation of seawater δ18O based on the clumped isotope temperature estimates and the simultaneously obtained δ18O of carbonate, thereby enabling the extraction of global ice volume estimates for both the recent and distant geologic past. Here we present clumped isotope analyses of several naturally occurring marine carbonates that calcified at known temperatures in the modern ocean. First, we analyzed benthic foraminiferal tests from six high-quality multicore tops collected in the Florida Strait, spanning a temperature range of 9.3-20.2 degrees C. Second, we analyzed shallow-water mollusc shells from a variety of different climate regimes, spanning a temperature range of 2.5-26.0 degrees C. We find that the calcitic foraminiferal species Cibicidoides spp. agrees well with the inorganic calcite precipitation experiments of Ghosh et al. (2006), while the aragonitic species Hoeglundina elegans is significantly offset. Similarly, clumped isotope results obtained from aragonitic mollusc shells also reveal an offset from the Ghosh et al. (2006) trend, although the offset observed in mollusc aragonite is quite different in nature from that observed in foraminiferal aragonite. Assuming our estimates of the growth temperatures of these naturally occurring organisms are correct, these results suggest that there are vital effects associated with the stable isotope compositions of the aragonite-precipitating organisms examined in this study; further work will be required to determine their cause. Nevertheless, the internal coherence of trends for

  11. Carbon Isotopic Fractionation During Formation of Macromolecular Organic Grain Coatings via FTT Reactions

    Science.gov (United States)

    Nuth, J. A.; Johnson, N. M.; Elsila-Cook, J.; Kopstein, M.

    2011-01-01

    Observations of carbon isotopic fractionation of various organic compounds found in meteorites may provide useful diagnostic information concerning the environments and mechanisms that were responsible for their formation. Unfortunately, carbon has only two stable isotopes, making interpretation of such observations quite problematic. Chemical reactions can increase or decrease the C-13/C-12 ratio by various amounts, but the final ratio will depend on the total reaction pathway followed from the source carbon to the final product, a path not readily discernable after 4.5 billion years. In 1970 Libby showed that the C-13/C-12 ratios of terrestrial and meteoritic carbon were similar by comparing carbon from the Murchison meteorite to that of terrestrial sediments. More recent studies have shown that the C-13/C-12 ratio of the Earth and meteorites may be considerably enriched in C-13 compared to the ratio observed in the solar wind [2], possibly suggesting that carbon produced via ion-molecule reactions in cold dark clouds could be an important source of terrestrial and meteoritic carbon. However, meteoritic carbon has been subjected to parent body processing that could have resulted in significant changes to the C-13/C-12 ratio originally present while significant variation has been observed in the C-13/C-12 ratio of the same molecule extracted from different terrestrial sources. Again we must conclude that understanding the ratio found in meteorites may be difficult.

  12. An unusual isotopic fractionation of boron in synthetic calcium carbonate precipitated from seawater and saline water

    Institute of Scientific and Technical Information of China (English)

    XIAO Yingkai; LI Shizhen; WEI Haizhen; SUN Aide; ZHOU Weijian; LIU Weiguo

    2006-01-01

    Inorganic calcium carbonate precipitation from natural seawater and saline water at various pH values was carried out experimentally. The results show the clear positive relationships between boron concentration and δ11B of inorganic calcium carbonate with the pH of natural seawater and saline water. However, the variations of boron isotopic fractionation between inorganic calcite and seawater/saline water with pH are inconsistent with the hypothesis that B(OH)4- is the dominant species incorporated into the biogenic calcite structure. The isotopic fractionation factors α Between synthetic calcium carbonate precipitate and parent solutions increase systematically as pH increases, from 0.9884 at pH 7.60 to 1.0072 at pH 8.60 for seawater and from 0.9826 at pH 7.60 to 1.0178 at pH 8.75 for saline water. An unusual boron isotopic fractionation factor of larger than 1 in synthetic calcium carbonate precipitated from seawater/saline water at higher pH is observed, which implies that a substantial amount of the isotopically heavier B(OH)3 species must be incorporated preferentially into synthetic inorganic carbonate. The results propose that the incorporation of B(OH)3 is attributed to the formation of Mg(OH)2 at higher pH of calcifying microenvironment during the synthetic calcium carbonate precipitation. The preliminary experiment of Mg(OH)2 precipitated from artificial seawater shows that heavier 11B is enriched in Mg(OH)2 precipitation, which suggests that isotopically heavier B(OH)3 species incorporated preferentially into Mg(OH)2 precipitation.This result cannot be applied to explain the boron isotopic fractionation of marine bio-carbonate because of the possibility that the unusual environment in this study appears in formation of marine bio-carbonate is infinitesimal. We, however, must pay more attention to this phenomenon observed in this study, which accidentally appears in especially natural environment.

  13. Anomalous carbon-isotope ratios in nonvolatile organic material.

    Science.gov (United States)

    Kaplan, I R; Nissenbaum, A

    1966-08-12

    Organic mats are associated with sulfur deposits in Upper Pleistocene sand ridges of the coastal plain of southern Israel; black, brittle, and non-volatile, they show parallel layering but no other apparent cellular structure. Two independent carbon-14 determinations yielded ages of 27,750+/-500 and 31,370+/-1400 years. Four carbon-13:carbon-12 determinations fell within the range deltaC(13) =-82.5 to -89.3 per mille relative to the PDB standard; these appear to be the lowest values yet reported for naturally occurring high-molecular-weight organic material. The origin of the carbon is probably complex; it must have passed through at least one biologic cycle before final deposition.

  14. Stable carbon isotope ratios of intact GDGTs indicate heterogeneous sources to marine sediments

    Science.gov (United States)

    Pearson, Ann; Hurley, Sarah J.; Walter, Sunita R. Shah; Kusch, Stephanie; Lichtin, Samantha; Zhang, Yi Ge

    2016-05-01

    Thaumarchaeota, the major sources of marine glycerol dibiphytanyl glycerol tetraether lipids (GDGTs), are believed to fix the majority of their carbon directly from dissolved inorganic carbon (DIC). The δ13C values of GDGTs (δ13CGDGT) may be powerful tools for reconstructing variations in the ocean carbon cycle, including paleoproductivity and water mass circulation, if they can be related to values of δ13CDIC. To date, isotope measurements primarily are made on the C40 biphytane skeletons of GDGTs, rather than on complete tetraether structures. This approach erases information revealed by the isotopic heterogeneity of GDGTs within a sample and may impart an isotopic fractionation associated with the ether cleavage. To circumvent these issues, we present δ13C values for GDGTs from twelve recent sediments representing ten continental margin locations. Samples are purified by orthogonal dimensions of HPLC, followed by measurement of δ13C values by Spooling Wire Microcombustion (SWiM)-isotope ratio mass spectrometry (IRMS) with 1σ precision and accuracy of ±0.25‰. Using this approach, we confirm that GDGTs, generally around -19‰, are isotopically "heavy" compared to other marine lipids. However, measured δ13CGDGT values are inconsistent with predicted values based on the 13C content of DIC in the overlying water column and the previously-published biosynthetic isotope fractionation for a pure culture of an autotrophic marine thaumarchaeon. In some sediments, the isotopic composition of individual GDGTs differs, indicating multiple source inputs. The data appear to confirm that crenarchaeol primarily is a biomarker for Thaumarchaeota, but its δ13C values still cannot be explained solely by autotrophic carbon fixation. Overall the complexity of the results suggests that both organic carbon assimilation (ca. 25% of total carbon) and multiple source(s) of exogenous GDGTs (contributing generally <30% of input to sediments) are necessary to explain the observed

  15. Organic Carbon Isotopic Evolution during the Ediacaran-Cambrian Transition Interval in Eastern Guizhou, South China: Paleoenvironmental and Stratigraphic Implications

    Institute of Scientific and Technical Information of China (English)

    YANG Xinglian; ZHU Maoyan; GUO Qingjun; ZHAO Yuanlong

    2007-01-01

    Secular variations of carbon isotopic composition of organic carbon can be used in the study of global environmental variation, the carbon cycle, stratigraphic delimitation, and biological evolution, etc. Organic carbon isotopic analysis of the Nangao and Zhalagou sections in eastern Guizhou reveals a negative excursion near the Precambrian-Cambrian boundary that correlates with a distinct carbonate carbon isotopic negative excursion at this boundary globally. Our results also demonstrate that several alternating positive and negative shifts occur in the Meishucunian, and an obvious negative anomaly appears at the boundary between the Meishucunian and Qiongzhusian. The isotope values are stable in the middle and lower parts but became more positive in the upper part of the Qiongzhusian. Evolution of organic carbon isotopes from the two sections in the deepwater facies can be well correlated with that of the carbonate carbon isotopes from the section in the shallow water facies. Integrated with other stratigraphic tools, we can precisely establish a lower Cambrian stratigraphic framework from shallow shelf to deep basin of the Yangtze Platform.

  16. Mixing of water in a carbonate aquifer, southern Italy, analysed through stable isotope investigations

    Directory of Open Access Journals (Sweden)

    Petrella Emma

    2013-01-01

    Full Text Available Mixing of water was analysed in a carbonate aquifer, southern Italy, through stable isotope investigations (18O,δ2H. The input signal (rainwater was compared with the isotopic content of a 35-meter groundwater vertical prof ile, over a 1-year period. Within the studied aquifer, recharge and f low are diffuse in a well-connected f issure network.At the test site, the comparison between input and groundwater isotopic signals illustrates that no eff icient mixing takes place in the whole unsaturated zone, between the fresh inf iltration water and the stored water.When analysing the stable isotope composition of groundwater, signif icant variations were observed above the threshold elevation of 1062 m asl, while a nearly constant composition was observed below the same threshold. Thus, temporal variations in stable isotope composition of rainwater are completely attenuated just in the deeper phreatic zone.On the whole, taking into consideration also the results of previous studies in the same area, the investigations showed that physical characteristics of the carbonate bedrock, as well as aquifer heterogeneity, are factors of utmost importance in inf luencing the complete mixing of water. These f indings suggest a more complex scenario at catchment scale.

  17. Organic carbon isotope ratios of recent sediments from coastal lagoons of the Gulf of Mexico, Mexico

    Science.gov (United States)

    Botello, Alfonso V.; Mandelli, Enrique F.; Macko, Steve; Parker, Patrick L.

    1980-03-01

    The stable carbon isotope composition sedimentary organic carbon was determined in the sediments of seven coastal lagoons of the Gulf of Mexico, Mexico. For most of the lagoons the δ13C values for sediments ranged from -20.1 to -23.9%. Anomalously low values, -26.8 to 29.3%. were determined in sediments of two of the studied lagoons, probably due to the presence of organic carbon from anthropogenic sources, naturally absent in these environments. The δ13C values determined in the tissues of oysters collected at the same time in the different lagoons were very similar to those recorded in the sediments.

  18. Methane carbon supports aquatic food webs to the fish level.

    Directory of Open Access Journals (Sweden)

    Angela M Sanseverino

    Full Text Available Large amounts of the greenhouse gas methane (CH(4 are produced by anaerobic mineralization of organic matter in lakes. In spite of extensive freshwater CH(4 emissions, most of the CH(4 is typically oxidized by methane oxidizing bacteria (MOB before it can reach the lake surface and be emitted to the atmosphere. In turn, it has been shown that the CH(4-derived biomass of MOB can provide the energy and carbon for zooplankton and macroinvertebrates. In this study, we demonstrate the presence of specific fatty acids synthesized by MOB in fish tissues having low carbon stable isotope ratios. Fish species, zooplankton, macroinvertebrates and the water hyacinth Eichhornia crassipes were collected from a shallow lake in Brazil and analyzed for fatty acids (FA and carbon stable isotope ratios (δ(13C. The fatty acids 16:1ω8c, 16:1ω8t, 16:1ω6c, 16:1ω5t, 18:1ω8c and 18:1ω8t were used as signature for MOB. The δ(13C ratios varied from -27.7‰ to -42.0‰ and the contribution of MOB FA ranged from 0.05% to 0.84% of total FA. Organisms with higher total content of MOB FAs presented lower δ(13C values (i.e. they were more depleted in (13C, while organisms with lower content of MOB signature FAs showed higher δ(13C values. An UPGMA cluster analysis was carried out to distinguish grouping of organisms in relation to their MOB FA contents. This combination of stable isotope and fatty acid tracers provides new evidence that assimilation of methane-derived carbon can be an important carbon source for the whole aquatic food web, up to the fish level.

  19. Use of stable carbon and nitrogen isotope ratios in size segregated aerosol particles for the O/I penetration evaluation

    Science.gov (United States)

    Garbaras, Andrius; Garbariene, Inga; Masalaite, Agne; Ceburnis, Darius; Krugly, Edvinas; Kvietkus, Kestutis; Remeikis, Vidmantas; Martuzevicius, Dainius

    2015-04-01

    particles penetrates from outside to inside. Observed isotope ratio depletion indicates that information about aerosol sources can be lost if measurements are performed only inside house. Using carbon and nitrogen isotope ratios data set, we were able to identify and distinguish main aerosol sources (traffic, heating activities) and penetration of aerosol particles from outdoor to indoor. Acknowledgment This work was supported by Research Council of Lithuania under grant "Pollution Control in Biomass Combustion: from Pollutant Formation to Human Exposure" (BioMassPoll), Project no. ATE05/2012. EPA Ireland is acknowledged for the fellowship grant of D. Ceburnis 1. Garbaras, A. Masalaite, I. Garbariene, D. Ceburnis, E. Krugly V. Remeikis, E. Puida K. Kvietkus, D. Martuzevicius, Stable carbon fractionation in size-segregated aerosol particles produced by controlled biomass burning, Journal of Aerosol Science, Vol. 79, p. 86-96 (2015); 2. D. Ceburnis, A. Garbaras, S. Szidat, M. Rinaldi, S. Fahrni, N. Perron, L. Wacker, S. Leinert, V. Remeikis, M. C. Facchini, A. S. H. Prevot, S. G. Jennings, and C. D. O'Dowd, Quantification of the carbonaceous matter origin in submicron marine aerosol particles by dual carbon isotope analysis, Atmospheric Chemistry and Physics, Vol 11, pp. 8593-8606 (2011); 3. V. Ulevicius, S. Bycenkiene, V. Remeikis, A. Garbaras, S. Kecorius, J. Andriejauskiene, D. Jasineviciene, G. Mocnik, Characterization of pollution events in the East Baltic region affected by regional biomass fire emissions, Atmospheric Research, Vol. 98 (2-4), pp. 190-200 (2010).

  20. The carbon isotope composition of atmospheric CO 2 in Paris

    Science.gov (United States)

    Widory, David; Javoy, Marc

    2003-10-01

    One characteristic of air pollution in the urban environment is high CO 2 concentrations resulting from human activities. Determining the relative contributions of the different CO 2 sources can be addressed simply and elegantly by combining isotope and concentration measurements. Using this approach on atmospheric CO 2 samples collected in Paris, its suburbs and the open country provides fairly accurate conclusions. Our results show that air pollution within the first few metres above ground results basically from binary mixtures among which road traffic is the main contributor and, in particular, vehicles using unleaded gasoline (˜90% of the total). Heating sources, which account for 50% of the CO 2 input below the atmospheric inversion level, and vehicles using diesel contribute very little. Human respiration has a recognisable signature at street level under certain circumstances. The combined isotope and concentration analysis provides a sensitive tracer of local variations, even detecting the occasional prevalence of human respiration and the onset of actions in which natural gas is burnt. It also detects surprising inlets of 'clean air' (CO 2-wise) in the very centre of the city.

  1. Carbon and oxygen isotopic ratios for nearby miras

    CERN Document Server

    Hinkle, K H; Straniero, O

    2016-01-01

    C and O isotopic ratios are reported for a sample of 46 Mira and SRa-type variable AGB stars. Vibration-rotation 1st and 2nd overtone CO lines in 1.5 to 2.5 $\\mu$m spectra were measured to derive isotopic ratios for 12C/13C, 16O/17O, and 16O/18O. Comparisons with previous measurements for individual stars and with various samples of evolved stars are discussed. Models for solar composition AGB stars of different initial masses are used to interpret our results. We find that the majority of the M stars had main sequence masses < 2 Msun and have not experienced sizable third dredge-up episodes. The progenitors of the four S-type stars in our sample are slightly more massive. Of the 6 C stars in the sample three have clear evidence relating their origin to the occurrence of the third dredge-up. Comparisons with O-rich presolar grains from AGB stars that lived before the formation of the solar system reveal variations in the interstellar medium chemical composition. The present generation of low-mass AGB stars...

  2. Assessing the duration and possible causes of the earliest Toarcian carbon isotopic excursion

    Science.gov (United States)

    Krencker, Francois-Nicolas; Bodin, Stéphane; Suan, Guillaume; Kabiri, Lahcen; Immenhauser, Adrian

    2013-04-01

    The early Toarcian stage (Early Jurassic) records two short-lived events of major faunal turnover and environmental perturbation. The first event (eT-E) occurs during the earliest Toarcian (early Polymorphum chronozone) and has been documented only in a few sites worldwide. The second event, better known as the Toarcian Oceanic Anoxic Event (T-OAE) has been documented in numerous sites from Northern Siberia to Argentina. Both events are marked by negative carbon isotope excursions (CIE) recorded in carbonate and organic substrate. Therefore they are thought to be associated with major changes in carbon cycling. Similarities between the eT-E and the T-OAE thus lead to the conclusion that these events might have been triggered by similar mechanisms. If this is the case, the CIEs associated with both events should have a comparable duration. In order to valid or falsify this hypothesis, it is therefore crucial to constrain the duration of both events. The duration of the T-OAE CIE was assessed in several papers by cyclostratigraphic analyses thanks to favourable outcropping condition. It is however not the case for the eT-E CIE, this latter being often associated with sedimentary condensation or hiatal surfaces. We make use of the high palaeo-subsidence rates of the Lower Toarcian Moroccan shelf leading to extended sections in the High Atlas Basin. The Foum Tillicht section was sampled in increments of 20 cm across a stratigraphic interval of 50 m, covering the Polymorphum chronozone. Carbon and oxygen isotopes analyses were performed on micritic and organic matter. Ammonites and nannofossils biostratigraphy aided in calibrating geochemical analyses. Carbon isotopes data display a rhythmic pattern. Preliminary results indicate that the eT-E negative carbon isotope excursion lasted around 400 kyr.

  3. Simulating stable carbon and chlorine isotope ratios in dissolved chlorinated groundwater pollutants with BIOCHLOR-ISO

    Science.gov (United States)

    Höhener, Patrick

    2016-12-01

    BIOCHLOR is a well-known simple tool for evaluating the transport of dissolved chlorinated solvents in groundwater, ideal for rapid screening and teaching. This work extends the BIOCHLOR model for the calculation of stable isotope ratios of carbon and chlorine isotopes in chloroethenes. An exact solution for the three-dimensional reactive transport of a chain of degrading compounds including sorption is provided in a spreadsheet and applied for modeling the transport of individual isotopes 12C, 13C, 35Cl, 37Cl from a constant source. The model can consider secondary isotope effects that can occur in the breaking of Csbnd Cl bonds. The model is correctly reproducing results for δ13C and δ37Cl modeled by a previously published 1-D numerical model without secondary isotope effects, and is also reproducing results from a microcosm experiment with secondary chlorine isotope effects. Two applications of the model using field data from literature are further given and discussed. The new BIOCHLOR-ISO model is distributed as a spreadsheet (MS EXCEL) along with this publication.

  4. Oxygen isotope fractionation in the vacuum ultraviolet photodissociation of carbon monoxide: Wavelength, pressure and temperature dependency.

    Energy Technology Data Exchange (ETDEWEB)

    Chakraborty, Subrata; Davis, Ryan; Ahmed, Musahid; Jackson, Teresa L.; Thiemens, Mark H.

    2012-01-03

    Several absorption bands exist in the VUV region of Carbon monoxide (CO). Emission spectra indicate that these bands are all predissociative. An experimental investigation of CO photodissociation by vacuum ultraviolet photons (90 to 108 nm; ~13 to 11 eV) from the Advanced Light Source Synchrotron and direct measurement of the associated oxygen isotopic composition of the products are presented here. A wavelength dependency of the oxygen isotopic composition in the photodissociation product was observed. Slope values (δ'{sup 18}O/ δ'{sup 17}O) ranging from 0.76 to 1.32 were observed in oxygen three-isotope space (δ'{sup 18}O vs. δ'{sup 17}O) which correlated with increasing synchrotron photon energy, and indicate a dependency of the upper electronic state specific dissociation dynamics (e.g., perturbation and coupling associated with a particular state). An unprecedented magnitude in isotope separation was observed for photodissociation at the 105 and 107 nm synchrotron bands and are found to be associated with accidental predissociation of the vibrational states ({nu} = 0 and 1) of the upper electronic state E{sup 1}Π. For each synchrotron band, a large (few hundred per mil) extent of isotopic fractionation was observed and the range of fractionation is a combination of column density and exposure time. A significant temperature dependency in oxygen isotopic fractionation was observed, indicating a rotational level dependency in the predissociation process.

  5. FAR-DEEP: organic carbon isotope chemostratigraphy of early Paleoproterozoic sediments from Fennoscandia

    Science.gov (United States)

    Illing, C. J.; Strauss, H.; Summons, R. E.; Kump, L.; Fallick, A. E.; Melezhik, V.; Far-Deep Scientists

    2010-12-01

    One major objective of the Fennoscandian Arctic Russia - Drilling Early Earth Project (FAR-DEEP) is to reconstruct ancient microbial ecosystems and the evolution of key metabolic pathways during the Archean-Proterozoic Transition (APT). Fifteen drill cores with a total length of 3650m were retrieved in three areas (Imandra/Varzuga and Pechenga Greenstone belts and Onega Basin) in northern Russia. Cores cover a time interval of some 700 my and have archived several important changes in Earth’s environment. Among them, the Great Oxygenation Event (GOE) at ca. 2350 million years ago resulted in large-scale environmental changes (e.g. Melezhik et al., 2005). Of similar importance, but specifically for global carbon cycling, are the Lomagundi-Jatuli Event (LJE; e.g. Melezhik et al., 2007) and the Shunga Event (SE; e.g. Melezhik et al., 2009). This work presents preliminary carbon isotope results for sedimentary organic matter (δ13Corg) contained in the major sedimentary formations cored by FAR-DEEP. The samples were processed via sealed tube combustion. The total variation in δ13Corg between -40 and -17 ‰ agrees well with previously published data (e.g. Eigenbrode and Freeman, 2006). But more informative than the organic carbon isotopic composition alone is the isotopic difference (Δ13C) between the organic (δ13Corg) and carbonate carbon (δ13Ccarb) isotopic composition: Δ13C = δ13Ccarb - δ13Corg This parameter provides information about the isotopic fractionation associated with biosynthesis and carbon cycling (e.g., Des Marais, 2001). Sediments from the lower Kuetsjärvi Formation (core 5A) and the upper part of the Tulomozero Formation (cores 10A, 10B, 11A), covering the LJE, display Δ13C values between 30 and 37‰. This isotopic difference continuous through the SE (cores 12A/B and 13). The broad parallel evolution of δ13Corg and δ13Ccarb indicates that respective perturbations affected the global carbon cycle. However, further refinement will be

  6. Universality and diversity in a phonon-transmission histogram of isotope-disordered carbon nanotubes.

    Science.gov (United States)

    Yamamoto, Takahiro; Sasaoka, Kenji; Watanabe, Satoshi

    2011-05-27

    Universal fluctuations in phonon transmission and other features of phonon-transmission histograms are investigated by performing numerical simulations of coherent-phonon transport in isotope-disordered carbon nanotubes. Interestingly, the phonon-transmission fluctuation in the diffusive regime is universal, irrespective of the average phonon transmission, the tube chirality, and the concentrations, and masses of isotopes. We also find that the histogram, which has a Gaussian distribution in the diffusive regime, has a log-normal distribution in the localization regime. © 2011 American Physical Society

  7. Effect of Different Carbon Substrates on Nitrate Stable Isotope Fractionation During Microbial Denitrification

    DEFF Research Database (Denmark)

    Wunderlich, Anja; Meckenstock, Rainer; Einsiedl, Florian

    2012-01-01

    .1 ± 0.8‰; ε18O, −23.7 ± 1.8‰ to −19.9 ± 0.8‰). The observed isotope effects did not depend on the growth kinetics which were similar for the three types of electron donors. We suggest that different carbon sources change the observed isotope enrichment factors by changing the relative kinetics...... of nitrate transport across the cell wall compared to the kinetics of the intracellular nitrate reduction step of microbial denitrification....

  8. Reconstruction of limnology and microbialite formation conditions from carbonate clumped isotope thermometry.

    Science.gov (United States)

    Petryshyn, V A; Lim, D; Laval, B L; Brady, A; Slater, G; Tripati, A K

    2015-01-01

    Quantitative tools for deciphering the environment of microbialite formation are relatively limited. For example, the oxygen isotope carbonate-water geothermometer requires assumptions about the isotopic composition of the water of formation. We explored the utility of using 'clumped' isotope thermometry as a tool to study the temperatures of microbialite formation. We studied microbialites recovered from water depths of 10-55 m in Pavilion Lake, and 10-25 m in Kelly Lake, spanning the thermocline in both lakes. We determined the temperature of carbonate growth and the (18)O/(16)O ratio of the waters that microbialites grew in. Results were then compared to current limnological data from the lakes to reconstruct the history of microbialite formation. Modern microbialites collected at shallow depths (11.7 m) in both lakes yield clumped isotope-based temperatures of formation that are within error of summer water temperatures, suggesting that clumped isotope analyses may be used to reconstruct past climates and to probe the environments in which microbialites formed. The deepest microbialites (21.7-55 m) were recovered from below the present-day thermoclines in both lakes and yield radioisotope ages indicating they primarily formed earlier in the Holocene. During this time, pollen data and our reconstructed water (18)O/(16)O ratios indicate a period of aridity, with lower lake levels. At present, there is a close association between both photosynthetic and heterotrophic communities, and carbonate precipitation/microbialite formation, with biosignatures of photosynthetic influences on carbonate detected in microbialites from the photic zone and above the thermocline (i.e., depths of generally <20 m). Given the deeper microbialites are receiving <1% of photosynthetically active radiation (PAR), it is likely these microbialites primarily formed when lower lake levels resulted in microbialites being located higher in the photic zone, in warm surface waters. © 2014 John

  9. Stable carbon isotope fractionation during the biodegradation of lambda-cyhalothrin

    Energy Technology Data Exchange (ETDEWEB)

    Shen, Xiaoli [MOE Key Laboratory of Environmental Remediation and Ecosystem Health, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Department of Environmental Engineering, Quzhou University, Quzhou 324000 (China); Xu, Zemin [MOE Key Laboratory of Environmental Remediation and Ecosystem Health, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Zhang, Xichang [Laboratory for Teaching in Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Yang, Fangxing, E-mail: fxyang@zju.edu.cn [MOE Key Laboratory of Environmental Remediation and Ecosystem Health, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Department of Effect-Directed Analysis, Helmholtz Centre for Environmental Research — UFZ, Leipzig 04318 (Germany)

    2015-11-01

    In this study, the microbial degradation of lambda-cyhalothrin in soil was investigated using compound-specific stable isotope analysis. The results revealed that lambda-cyhalothrin was biodegraded in soil under laboratory conditions. The half-lives of lambda-cyhalothrin were determined to be 49 and 161 days in non-sterile and sterile soils spiked with 2 mg/kg lambda-cyhalothrin and 84 and 154 days in non-sterile and sterile soils spiked with 10 mg/kg lambda-cyhalothrin, respectively. The biodegradation of lambda-cyhalothrin resulted in carbon isotope fractionation, which shifted from − 29.0‰ to − 26.5‰ in soil spiked with 2 mg/kg lambda-cyhalothrin, and to − 27.5‰ with 10 mg/kg lambda-cyhalothrin. A relationship was established between the stable carbon isotope fraction and the residual concentrations of lambda-cyhalothrin by the Rayleigh equation in which the carbon isotope enrichment factor ε of the microbial degradation of lambda-cyhalothrin in the soil was calculated as − 2.53‰. This study provides an approach to quantitatively evaluate the biodegradation of lambda-cyhalothrin in soil in field studies. - Highlights: • Abiotic and biotic degradation of lambda-cyhalothrin were observed in soil. • Biodegradation of lambda-cyhalothrin was evaluated by CSIA. • Biodegradation of lambda-cyhalothrin leads to carbon isotope fractionation. • An enrichment factor ε of lambda-cyhalothrin was determined as − 2.53‰.

  10. The influence of traffic and wood combustion on the stable isotopic composition of carbon monoxide

    Directory of Open Access Journals (Sweden)

    M. Saurer

    2009-05-01

    Full Text Available Carbon monoxide in the atmosphere is originating from various combustion and oxidation processes. Recently, the proportion of CO resulting from the combustion of wood for domestic heating may have increased due to political measures promoting this renewable energy source. Here, we used the stable isotope composition of CO (δ13C and δ18O for the characterization of different CO sources in Switzerland, along with other indicators for traffic and wood combustion (NOx-concentration, aerosol light absorption at different wavelengths. We assessed diurnal variations of the isotopic composition of CO at 3 sites during winter: a village site dominated by domestic heating, a site close to a motorway and a rural site. The isotope ratios of wood combustion emissions were studied at a test facility, indicating significantly lower δ18O of CO from wood combustion compared to traffic emissions. At the village and the motorway site, we observed very pronounced diurnal δ18O-variations of CO with an amplitude of up to 8‰. Solving the isotope mass balance equation for three distinct sources (wood combustion, traffic, clean background air resulted in diurnal patterns consistent with other indicators for wood burning and traffic. The average night-time contribution of wood-burning to total CO was 70% at the village site, 49% at the motorway site and 29% at the rural site based on the isotope mass balance. The results, however, depend strongly on the pure source isotope values, which are not very well known. We therefore additionally applied a combined CO/NOx-isotope model for verification. Here, we separated the CO emissions into different sources based on distinct CO/NOx emissions ratios for wood combustion and traffic, and inserted this information in the isotope mass balance equation. Accordingly, a highly significant agreement between measured and calculated δ18

  11. Carbon isotope geochemistry of the Santa Clara River

    OpenAIRE

    2001-01-01

    The Santa Clara River is a prototypical small mountainous river, with a headwater height greater than 1000 m and a basin area smaller than 10,000 m 2. Although individual small mountainous rivers export trivial amounts of sediment and carbon to the ocean, as a group these rivers may export a major fraction (as much as 50%) of the total global river sediment flux [Milliman and Syvitski, 1992], making their geochemistry relevant the study of the ocean's carbon cycle. In addition, many small riv...

  12. A universal carbonate ion effect on stable oxygen isotope ratios in unicellular planktonic calcifying organisms

    Directory of Open Access Journals (Sweden)

    P. Ziveri

    2012-03-01

    Full Text Available The oxygen isotopic composition (δ18O of calcium carbonate of planktonic calcifying organisms is a key tool for reconstructing both past seawater temperature and salinity. The calibration of paloeceanographic proxies relies in general on empirical relationships derived from field experiments on extant species. Laboratory experiments have more often than not revealed that variables other than the target parameter influence the proxy signal, which makes proxy calibration a challenging task. Understanding these secondary or "vital" effects is crucial for increasing proxy accuracy. We present data from laboratory experiments showing that oxygen isotope fractionation during calcification in the coccolithophore Calcidiscus leptoporus and the calcareous dinoflagellate Thoracosphaera heimii is dependent on carbonate chemistry of seawater in addition to its dependence on temperature. A similar result has previously been reported for planktonic foraminifera, supporting the idea that the [CO32−] effect on δ18O is universal for unicellular calcifying planktonic organisms. The slopes of the δ18O/[CO32−] relationships range between –0.0243‰ (μmol kg−1−1 (calcareous dinoflagellate T. heimii and the previously published –0.0022‰ (μmol kg−1−1 (non-symbiotic planktonic foramifera Orbulina universa, while C. leptoporus has a slope of –0.0048 ‰ (μmol kg−1−1. We present a simple conceptual model, based on the contribution of δ18O-enriched HCO3 to the CO32− pool in the calcifying vesicle, which can explain the [CO32−] effect on δ18O for the different unicellular calcifiers. This approach provides a new insight into biological fractionation in calcifying organisms

  13. Late Permian-earliest Triassic high-resolution organic carbon isotope and palynofacies records from Kap Stosch (East Greenland)

    Science.gov (United States)

    Sanson-Barrera, Anna; Hochuli, Peter A.; Bucher, Hugo; Schneebeli-Hermann, Elke; Weissert, Helmut; Adatte, Thierry; Bernasconi, Stefano M.

    2015-10-01

    During and after the end Permian mass extinction terrestrial and marine biota underwent major changes and reorganizations. The latest Permian and earliest Triassic is also characterized by major negative carbon isotope shifts reflecting fundamental changes in the carbon cycle. The present study documents a high-resolution bulk organic carbon isotope record and palynofacies analysis spanning the latest Permian-earliest Triassic of East Greenland. An almost 700 meter thick composite section from Kap Stosch allowed discriminating 6 chemostratigraphic intervals that provide the basis for the correlation with other coeval records across the world, and for the recognition of basin wide transgressive-regressive events documenting tectonic activity during the opening of the Greenland-Norway Basin. The identification of the main factors that influenced the organic carbon isotope signal during the earliest Triassic (Griesbachian to Dienerian) was possible due to the combination of bulk organic carbon isotope, palynofacies and Rock-Eval data. Two negative carbon isotopic shifts in the Kap Stosch record can be correlated with negative shifts recorded in coeval sections across the globe. A first negative shift precedes the base of the Triassic as defined by the first occurrence of the conodont Hindeodus parvus in the Meishan reference section, and the second one coincides with the suggested Griesbachian-Dienerian boundary. This new organic carbon isotope record from the extended Kap Stosch section from the Boreal Realm documents regional and global carbon cycle signals of the interval between the latest Palaeozoic and the onset of the Mesozoic.

  14. Variations in expression of carbon isotope fractionation of chlorinated ethenes during biologically enhanced PCE dissolution close to a source zone.

    Science.gov (United States)

    Morrill, P L; Sleep, B E; Seepersad, D J; McMaster, M L; Hood, E D; LeBron, C; Major, D W; Edwards, E A; Lollar, B Sherwood

    2009-11-03

    The stable carbon isotope values of tetrachloroethene (PCE) and its degradation products were monitored during studies of biologically enhanced dissolution of PCE dense nonaqueous phase liquid (DNAPL) to determine the effect of PCE dissolution on observed isotope values. The degradation of PCE was monitored in a 2-dimensional model aquifer and in a pilot test cell (PTC) at Dover Air Force Base, both with emplaced PCE DNAPL sources. Within the plume down gradient from the source, the isotopic fractionation of dissolved PCE and its degradation products were consistent with those observed in biodegradation laboratory studies. However, close to the source zone significant shifts in the isotope values of dissolved PCE were not observed in either the model aquifer or PTC due to the constant input of newly dissolved, non fractionated PCE, and the small isotopic fractionation associated with PCE reductive dechlorination by the mixed microbial culture used. Therefore the identification of reductive dechlorination in the presence of PCE DNAPL was based upon the appearance of daughter products and the isotope values of those daughter products. An isotope model was developed to simulate isotope values of PCE during the dissolution and degradation of PCE adjacent to a DNAPL source zone. With the exception of very high degradation rate constants (>1/day) stable carbon isotope values of PCE estimated by the model remained within error of the isotope value of the PCE DNAPL, consistent with measured isotope values in the model aquifer and in the PTC.

  15. Predicting 13C-18O clumped isotope fractionation in dissolved inorganic carbon and rapidly precipitated carbonate minerals

    Science.gov (United States)

    Hill, P. S.; Tripati, A. K.; Schauble, E. A.

    2012-12-01

    The occurrence of multiply substituted isotopologues in carbonates forms the basis for clumped isotope thermometry. It is important to understand how clumping may be affected by environmental factors under both equilibrium and disequilbrium conditions. "Clumping" of heavy isotopes into bonds with each other in dissolved inorganic carbon (DIC) species is of particular interest because natural carbonates that precipitate too rapidly to reach internal isotopic exchange equilibrium may instead inherit the clumping signature of DIC in the parent solution. DIC speciation is dependent on pH, suggesting that clumping signatures inherited by rapidly precipitated carbonate minerals could also be affected by pH. To better understand these disequilibrium clumped isotope signatures (and their effects on inferred temperatures of formation), we have developed theoretical models of the individual DIC species, composite DIC solutions, and bulk carbonate minerals. We used 4 different techniques for modelling the hydration of DIC: gas phase, implicit solvation, explicit solvation (ion with 3 water molecules) and supermolecular clusters (ion plus 21 to 32 water molecules with geometries generated by molecular dynamics). For each solvation technique, we performed sensitivity testing by combining different levels of theory (7 ab initio/hybrid methods, each with 5 different sizes of basis sets) to understand the limits of each technique. We looked at the degree of convergence with the most complex (and accurate) models in order to select the most reliable and efficient modelling methods. Overall, our models predict a difference between Δ47 ( HCO3-) and Δ47 (CO32-) > .025‰, enough to potentially perturb inferred formation temperatures by ≥ 5°C. This difference is fairly consistent at most levels of theory we tested. The models also predict that a carbonate mineral precipitating very rapidly (i.e., forming under isotopic disequilibrium conditions) in a DIC solution of low to

  16. Clumped isotope thermometry of modern and early Cretaceous molluscan carbonate from high-latitude seas (Invited)

    Science.gov (United States)

    Henkes, G. A.; Price, G. D.; Ambrose, W. G.; Carroll, M. L.; Passey, B. H.

    2010-12-01

    The carbonate clumped isotope thermometer is based on the temperature sensitivity of the relative abundance of carbonate ion groups containing 13C-18O bonds. One application of clumped isotope thermometry is to determine the temperature of ancient seawater from the skeletal material of calcium carbonate-secreting marine organisms. The relationship between Δ47, a parameter describing isotopic clumping, and the temperature of carbonate biomineralization has been well-defined for fish otoliths, corals, foraminifera, and coccolithophore tests, but few data have been published for brachiopods and bivalve mollusks. A comprehensive evaluation of the Δ47-temperature relationship for mollusks is required for paleotemperature interpretations from the marine fossil record. Here we present a more comprehensive calibration for modern mollusks, including bivalves, cephalopods, and gastropods. Further, we focus on a subset of cold water, high-latitude species collected in the northern Barents Sea. The observed Δ47-temperature relationship is similar to the theoretical relationship presented by Guo et al. (2009) but deviates at low temperatures from the original Ghosh et al. (2007) calibration curve. This divergence could be related to methodological differences or unaccounted differences in the biomineralization of mollusks versus that of other carbonate-secreting organisms at low temperature. One advantage of clumped isotope thermometry over traditional oxygen isotope thermometry is that it does not require assumptions about the isotopic composition of the water in which the carbonate formed. This may be particularly useful in Mesozoic paleoceanography where the oxygen isotope value of seawater is uncertain. Using clumped isotope thermometry applied to early Cretaceous (Valangian) belemnite carbonate from the Yatria River, sub-polar Urals, Siberia, we find shell growth temperatures of 20-26°C at a paleolatitude of ~60-65°N. Our data imply average seawater δ18O values of 0

  17. Carbon-Supported Iron Oxide Particles

    DEFF Research Database (Denmark)

    Meaz, T.; Mørup, Steen; Koch, C. Bender

    1996-01-01

    A carbon black ws impregnated with 6 wt% iron using an aqueous solution of iron nitrate. The impregnated carbon was initially dried at 125 C. The effect of heating of the iron oxide phase was investigated at temperatures between 200 and 600 C using Mossbauer spectroscopy. All heat treatments were...... done in an oxygen-containing atmosphere. Ferrihydrite is formed and is stable at and below a temperature of 300 C. At 600 C small particles of maghemite is the dominant iron oxide. A transformation reaction is suggested....

  18. Carbon-Supported Iron Oxide Particles

    DEFF Research Database (Denmark)

    Meaz, T.; Mørup, Steen; Koch, C. Bender

    1996-01-01

    A carbon black ws impregnated with 6 wt% iron using an aqueous solution of iron nitrate. The impregnated carbon was initially dried at 125 C. The effect of heating of the iron oxide phase was investigated at temperatures between 200 and 600 C using Mossbauer spectroscopy. All heat treatments were...... done in an oxygen-containing atmosphere. Ferrihydrite is formed and is stable at and below a temperature of 300 C. At 600 C small particles of maghemite is the dominant iron oxide. A transformation reaction is suggested....

  19. Dual carbon isotope characterization of total organic carbon in wintertime carbonaceous aerosols from northern India

    Science.gov (United States)

    Bikkina, Srinivas; Andersson, August; Sarin, M. M.; Sheesley, R. J.; Kirillova, E.; Rengarajan, R.; Sudheer, A. K.; Ram, K.; Gustafsson, Örjan

    2016-05-01

    Large-scale emissions of carbonaceous aerosols (CA) from South Asia impact both regional climate and air quality, yet their sources are not well constrained. Here we use source-diagnostic stable and radiocarbon isotopes (δ13C and Δ14C) to characterize CA sources at a semiurban site (Hisar: 29.2°N, 75.2°E) in the NW Indo-Gangetic Plain (IGP) and a remote high-altitude location in the Himalayan foothills (Manora Peak: 29.4°N, 79.5°E, 1950 m above sea level) in northern India during winter. The Δ14C of total aerosol organic carbon (TOC) varied from -178‰ to -63‰ at Hisar and from -198‰ to -1‰ at Manora Peak. The absence of significant differences in the 14C-based fraction biomass of TOC between Hisar (0.81 ± 0.03) and Manora Peak (0.82 ± 0.07) reveals that biomass burning/biogenic emissions (BBEs) are the dominant sources of CA at both sites. Combining this information with δ13C, other chemical tracers (K+/OC and SO42-/EC) and air mass back trajectory analyses indicate similar source regions in the IGP (e.g., Punjab and Haryana). These results highlight that CA from BBEs in the IGP are not only confined to the atmospheric boundary layer but also extend to higher elevations of the troposphere, where the synoptic-scale circulations could substantially influence their abundances both to the Himalayas and over the downwind oceanic regions such as the Indian Ocean. Given the vast emissions of CA from postharvest crop residue combustion practices in the IGP during early Northeast Monsoon, this information is important for both improved process and model understanding of climate and health effects, as well as in guiding policy decision aiming at reducing emissions.

  20. Temporal Variability in Carbon Isotope Composition of Leaf-Respired Carbon Dioxide

    Science.gov (United States)

    Barbour, M. M.; Hanson, D. T.; Bickford, C. P.; McDowell, N. G.

    2005-12-01

    The stable carbon isotope composition of leaf-respired CO2 (δ13CRl) has enormous potential to allow partitioning of ecosystem respiration into various components, to provide information on key physiological processes, and to trace carbon fluxes through plants and ecosystems. However, difficulties in measuring and understanding variation in δ13CRl have limited its application. We coupled an open gas exchange system (LI-6400, LiCor) to a tunable diode laser (TGA100A, Campbell Scientific) enabling measurement of leaf respiratory CO2 fluxes and δ13CRl every three minutes, with a precision of at least ±0.3 per mil. We also measured oxygen consumption rates, allowing calculation of the respiratory quotient ( RQ) and indicating likely respiratory substrates. Castor bean ( Ricinus communis) plants grown at high and low light were placed in the dark after different lengths of time exposed to sunlight and variation in δ13CRl measured to test the patterns in variation in δ13CRl predicted by existing biochemical models. CO2 respired by leaves previously exposed to high cumulative incident irradiance was up to 11 per mil more enriched than phloem sap sugars for the first 10 to 15 minutes after plants had been moved into the dark . This enrichment rapidly decreased, so that by 30 minutes in the dark δ13CRl was 5 per mil more enriched than phloem sap sugars. CO2 production rates were also initially very high and rapidly decreased. RQ for plants grown in high light varied between 0.8 and 1.2, indicating that carbohydrates and/or organic acids were the respiratory substrates. δ13CRl measured 30 to 80 minutes after plants had been moved into the dark increased with increasing δ13C of phloem sap sugars. The RQ values of plants grown at low light suggested that the respiratory substrates were fatty acids or amino acids ( RQ of around 0.6), or lipids ( RQ less than 0.4). δ13CRl values were enriched by either 4 per mil ( RQ = 0.3) or 12 per mil ( RQ = 0.5) compared to phloem

  1. Carbon isotope constraints on the deglacial CO₂ rise from ice cores.

    Science.gov (United States)

    Schmitt, Jochen; Schneider, Robert; Elsig, Joachim; Leuenberger, Daiana; Lourantou, Anna; Chappellaz, Jérôme; Köhler, Peter; Joos, Fortunat; Stocker, Thomas F; Leuenberger, Markus; Fischer, Hubertus

    2012-05-11

    The stable carbon isotope ratio of atmospheric CO(2) (δ(13)C(atm)) is a key parameter in deciphering past carbon cycle changes. Here we present δ(13)C(atm) data for the past 24,000 years derived from three independent records from two Antarctic ice cores. We conclude that a pronounced 0.3 per mil decrease in δ(13)C(atm) during the early deglaciation can be best explained by upwelling of old, carbon-enriched waters in the Southern Ocean. Later in the deglaciation, regrowth of the terrestrial biosphere, changes in sea surface temperature, and ocean circulation governed the δ(13)C(atm) evolution. During the Last Glacial Maximum, δ(13)C(atm) and atmospheric CO(2) concentration were essentially constant, which suggests that the carbon cycle was in dynamic equilibrium and that the net transfer of carbon to the deep ocean had occurred before then.

  2. Stable isotope probing and Raman spectroscopy for monitoring carbon flow in a food chain and revealing metabolic pathway.

    Science.gov (United States)

    Li, Mengqiu; Huang, Wei E; Gibson, Christopher M; Fowler, Patrick W; Jousset, Alexandre

    2013-02-05

    Accurately measuring carbon flows is a challenge for understanding processes such as diverse intracellular metabolic pathways and predator-prey interactions. Combined with stable isotope probing (SIP), single-cell Raman spectroscopy was demonstrated for the first time to link the food chain from carbon substrate to bacterial prey up to predators at the single-cell level in a quantitative and nondestructive manner. Escherichia coli OP50 with different (13)C content, which were grown in a mixture of (12)C- and fully carbon-labeled (13)C-glucose (99%) as a sole carbon source, were fed to the nematode. The (13)C signal in Caenorhabditis elegans was proportional to the (13)C content in E. coli. Two Raman spectral biomarkers (Raman bands for phenylalanine at 1001 cm(-1) and thymine at 747 cm(-1) Raman bands), were used to quantify the (13)C content in E. coli and C. elegans over a range of 1.1-99%. The phenylalanine Raman band was a suitable biomarker for prokaryotic cells and thymine Raman band for eukaryotic cells. A biochemical mechanism accounting for the Raman red shifts of phenylalanine and thymine in response to (13)C-labeling is proposed in this study and is supported by quantum chemical calculation. This study offers new insights of carbon flow via the food chain and provides a research tool for microbial ecology and investigation of biochemical pathways.

  3. Can amino acid carbon isotope ratios distinguish primary producers in a mangrove ecosystem?

    Science.gov (United States)

    Larsen, Thomas; Wooller, Matthew J; Fogel, Marilyn L; O'Brien, Diane M

    2012-07-15

    The relative contribution of carbon from terrestrial vs. marine primary producers to mangrove-based food webs can be challenging to resolve with bulk carbon isotope ratios (δ(13)C). In this study we explore whether patterns of δ(13)C values among amino acids (AAs) can provide an additional tool for resolving terrestrial and marine origins of carbon. Amino acid carbon isotope ratios (δ(13)C(AA)) were measured for several terrestrial and marine primary producers in a mangrove ecosystem at Spanish Lookout Caye (SLC), Belize, using gas chromatography-combustion-isotope ratio mass spectrometry. The δ(13)C values of essential amino acids (δ(13)C(EAA)) were measured to determine whether they could be used to differentiate terrestrial and marine producers using linear discriminant analysis. Marine and terrestrial producers had distinct patterns of δ(13)C(EAA) values in addition to their differences in bulk δ(13)C values. Microbial mat samples and consumers (Crassostrea rhizophorae, Aratus pisonii, Littoraria sp., Lutjanus griseus) were most similar to marine producers. Patterns of δ(13)C(EAA) values for terrestrial producers were very similar to those described for other terrestrial plants. The findings suggest that δ(13)C(EAA) values may provide another tool for estimating the contribution of terrestrial and marine sources to detrital foodwebs. Preliminary analyses of consumers indicate significant use of aquatic resources, consistent with other studies of mangrove foodwebs. Copyright © 2012 John Wiley & Sons, Ltd.

  4. Late Ordovician (Turinian-Chatfieldian) carbon isotope excursions and their stratigraphic and paleoceanographic significance

    Science.gov (United States)

    Ludvigson, Greg A.; Witzke, B.J.; Gonzalez, Luis A.; Carpenter, S.J.; Schneider, C.L.; Hasiuk, F.

    2004-01-01

    Five positive carbon isotope excursions are reported from Platteville-Decorah strata in the Upper Mississippi Valley. All occur in subtidal carbonate strata, and are recognized in the Mifflin, Grand Detour, Quimbys Mill, Spechts Ferry, and Guttenberg intervals. The positive carbon isotope excursions are developed in a Platteville-Decorah succession in which background ??13C values increase upward from about -2??? at the base to about 0??? Vienna Pee Dee belemnite (VPDB) at the top. A regional north-south ??13C gradient, with lighter values to the north and heavier values to the south is also noted. Peak excursion ??13C values of up to +2.75 are reported from the Quimbys Mill excursion, and up to +2.6 from the Guttenberg excursion, although there are considerable local changes in the magnitudes of these events. The Quimbys Mill, Spechts Ferry, and Guttenberg carbon isotope excursions occur in units that are bounded by submarine disconformities, and completely starve out in deeper, more offshore areas. Closely spaced chemostratigraphic profiles of these sculpted, pyrite-impregnated hardground surfaces show that they are associated with very abrupt centimeter-scale negative ??13C shifts of up to several per mil, possibly resulting from the local diagenetic effects of incursions of euxinic bottom waters during marine flooding events. ?? 2004 Elsevier B.V. All rights reserved.

  5. Can Mg isotopes be used to trace cyanobacteria-mediated magnesium carbonate precipitation in alkaline lakes?

    Science.gov (United States)

    Shirokova, L. S.; Mavromatis, V.; Bundeleva, I.; Pokrovsky, O. S.; Bénézeth, P.; Pearce, C.; Gérard, E.; Balor, S.; Oelkers, E. H.

    2011-07-01

    The fractionation of Mg isotopes was determined during the cyanobacterial mediated precipitation of hydrous magnesium carbonate precipitation in both natural environments and in the laboratory. Natural samples were obtained from Lake Salda (SE Turkey), one of the few modern environments on the Earth's surface where hydrous Mg-carbonates are the dominant precipitating minerals. This precipitation was associated with cyanobacterial stromatolites which were abundant in this aquatic ecosystem. Mg isotope analyses were performed on samples of incoming streams, groundwaters, lake waters, stromatolites, and hydromagnesite-rich sediments. Laboratory Mg carbonate precipitation experiments were conducted in the presence of purified Synechococcus sp cyanobacteria that were isolated from the lake water and stromatolites. The hydrous magnesium carbonates nesquehonite (MgCO3·3H2O) and dypingite (Mg5(CO3)4(OH)25(H2O)) were precipitated in these batch reactor experiments from aqueous solutions containing either synthetic NaHCO3/MgCl2 mixtures or natural Lake Salda water, in the presence and absence of live photosynthesizing Synechococcus sp. Bulk precipitation rates were not to affected by the presence of bacteria when air was bubbled through the system. In the stirred non-bubbled reactors, conditions similar to natural settings, bacterial photosynthesis provoked nesquehonite precipitation, whilst no precipitation occurred in bacteria-free systems in the absence of air bubbling, despite the fluids achieving a similar or higher degree of supersaturation. The extent of Mg isotope fractionation (Δ26Mgsolid-solution) between the mineral and solution in the abiotic experiments was found to be identical, within uncertainty, to that measured in cyanobacteria-bearing experiments, and ranges from -1.4 to -0.7 ‰. This similarity refutes the use of Mg isotopes to validate microbial mediated precipitation of hydrous Mg carbonates.

  6. Climate warming, euxinia and carbon isotope perturbations during the Carnian (Triassic) Crisis in South China

    Science.gov (United States)

    Sun, Y. D.; Wignall, P. B.; Joachimski, M. M.; Bond, D. P. G.; Grasby, S. E.; Lai, X. L.; Wang, L. N.; Zhang, Z. T.; Sun, S.

    2016-06-01

    The Carnian Humid Episode (CHE), also known as the Carnian Pluvial Event, and associated biotic changes are major enigmas of the Mesozoic record in western Tethys. We show that the CHE also occurred in eastern Tethys (South China), suggestive of a much more widespread and probably global climate perturbation. Oxygen isotope records from conodont apatite indicate a double-pulse warming event. The CHE coincided with an initial warming of 4 °C. This was followed by a transient cooling period and then a prolonged ∼7 °C warming in the later Carnian (Tuvalian 2). Carbon isotope perturbations associated with the CHE of western Tethys occurred contemporaneously in South China, and mark the start of a prolonged period of carbon cycle instability that persisted until the late Carnian. The dry-wet transition during the CHE coincides with the negative carbon isotope excursion and the temperature rise, pointing to an intensification of hydrologic cycle activities due to climatic warming. While carbonate platform shutdown in western Tethys is associated with an influx of siliciclastic sediment, the eastern Tethyan carbonate platforms are overlain by deep-water anoxic facies. The transition from oxygenated to euxinic facies was via a condensed, manganiferous carbonate (MnO content up to 15.1 wt%), that records an intense Mn shuttle operating in the basin. Significant siliciclastic influx in South China only occurred after the CHE climatic changes and was probably due to foreland basin development at the onset of the Indosinian Orogeny. The mid-Carnian biotic crisis thus coincided with several phenomena associated with major extinction events: a carbonate production crisis, climate warming, δ13 C oscillations, marine anoxia, biotic turnover and flood basalt eruptions (of the Wrangellia Large Igneous Province).

  7. What Carbon Sources Support Groundwater Microbial Activity in Riparian Forests?

    Science.gov (United States)

    Gurwick, N. P.; Groffman, P. M.; McCorkle, D. C.; Stolt, M. H.; Kellogg, D. Q.; Gold, A. J.

    2004-05-01

    A major question in riparian research is the source of energy to support subsurface microbial denitrification activity. The supply of microbially-available carbon frequently limits microbial activity in the subsurface. Therefore, identifying the relative importance of carbon sources in the riparian subsurface helps explain the sustainability and spatial heterogeneity of denitrification rates. We have investigated the importance of buried, carbon-rich soil horizons, deep roots and dissolved organic carbon as potential carbon sources to support groundwater denitrification in riparian forests in Rhode Island. We used field observations, laboratory incubations and in-situ experiments to evaluate these sources at four sites in different geomorphic settings. In particular, we measured the 14C-DIC signature and DIC concentration of ambient groundwater and groundwater that had been degassed, re-introduced into the well, and incubated in-situ. Buried horizons appear to be an important source of carbon in the subsurface, as shown by active respiration in laboratory incubations; greater microbial biomass in buried carbon-rich soils compared to surrounding carbon-poor soils; and the presence of very old carbon (>1,000 ybp) in DIC 225 cm beneath the surface. DIC collected from shallower wells showed no clear evidence of ancient carbon. Roots also appear to be important, creating hotspots of carbon availability and denitrification in the generally carbon poor subsurface matrix. Dissolved organic carbon did not stimulate denitrification in aquifer microcosms in the laboratory, suggesting that this was not an important carbon source for denitrification in our sites. Determining which carbon source is fueling denitrification has practical implications. Where buried horizons are the key source, surface management of the riparian zone will likely have little direct influence on groundwater denitrification. Where roots are the key source, changes in the plant community are likely to

  8. Utility of 5A molecular sieves to measure carbon isotope ratios in lipid biomarkers.

    Science.gov (United States)

    Tolosa, Imma; Ogrinc, Nives

    2007-09-21

    A procedure using 5A zeolite sorption to separate cyclic/branched organic compounds from the linear ones was developed and carbon isotopic fractionation effects were investigated in different families of compounds, e.g. within the hydrocarbon and alcohol compounds. The 5A sieve has a pore size such that only linear components can be incorporated into the pores whereas the cyclic/branched compounds are remaining free in the organic solution. The sorbed compounds were released from the molecular sieve with HF and solvent extracted with hexane. The method enables the isolation of linear saturated classes, such as n-alkanes and n-fatty alcohols from branched/cyclic compounds without isotopic fractionation for compound-specific isotope analysis (CSIA) of delta(13)C. However, alkene hydrocarbons, sterols and some aromatics were completely or partly degraded with the molecular sieve.

  9. Martian Cryogenic Carbonate Formation: Stable Isotope Variations Observed in Laboratory Studies

    Science.gov (United States)

    Socki, Richard A.; Niles, Paul B.; Sun, Tao; Fu, Qi; Romanek, Christopher S.; Gibson, Everett K. Jr.

    2014-01-01

    The history of water on Mars is tied to the formation of carbonates through atmospheric CO2 and its control of the climate history of the planet. Carbonate mineral formation under modern martian atmospheric conditions could be a critical factor in controlling the martian climate in a means similar to the rock weathering cycle on Earth. The combination of evidence for liquid water on the martian surface and cold surface conditions suggest fluid freezing could be very common on the surface of Mars. Cryogenic calcite forms easily from freezing solutions when carbon dioxide degasses quickly from Ca-bicarbonate-rich water, a process that has been observed in some terrestrial settings such as arctic permafrost cave deposits, lake beds of the Dry Valleys of Antarctica, and in aufeis (river icings) from rivers of N.E. Alaska. A series of laboratory experiments were conducted that simulated cryogenic carbonate formation on Mars in order to understand their isotopic systematics. The results indicate that carbonates grown under martian conditions show variable enrichments from starting bicarbonate fluids in both carbon and oxygen isotopes beyond equilibrium values.

  10. A STUDY ON CARBON ISOTOPE OF CO2 AND CH4 IN WESTERN DIENG PLATEU BY GAS CHROMATOGRAPHY- ISOTOPE RATIO MASS SPECTROMETER (GC-IRMS

    Directory of Open Access Journals (Sweden)

    Hanik Humaida

    2010-06-01

    Full Text Available The carbon isotope can be used to evaluate volcanism phenomenon of volcano. The study of carbon isotope of CO2 and CH4 was carried out in western Dieng Plateau by mass-spectrometer. Before analysis, sampel was separated by gas chromatography using a Porapak-Q column and a FID (Flame Ionization Detector detector. The gas was oxidized by copper oxide at 850oC before being ionized in mass-spectrometer for isotope analysis. The CO2 content in Candradimuka crater (-4.10 O/OO, indicated that the gas may be as volcanic gas. The other CO2 from Sumber and western Gua Jimat, had isotope value  of -10.05 and -12.07 O/OO, respectively, indicating contamination from crustal and subduction material. The carbon isotope of CH4 gas from Pancasan village was -63.42 O/OO, that may be categorized as biogenic gas.   Keywords: isotope, CO2, CH4, Dieng.

  11. Palaeo-equatorial temperatures and carbon-cycle evolution at the Triassic- Jurassic boundary: A stable isotope perspective from shallow-water carbonates from the UAE

    Science.gov (United States)

    Honig, M. R.; John, C. M.

    2013-12-01

    The Triassic-Jurassic boundary was marked by global changes including carbon-cycle perturbations and the opening of the Atlantic Ocean. These changes were accompanied by one of the major extinction events of the Phanerozoic. The carbon-cycle perturbations have been recorded in carbon isotope curves from bulk carbonates, organic carbon and fossil wood in several Tethyan locations and have been used for chemostratigraphic purposes. Here we present data from shallow-marine carbonates deposited on a homoclinal Middle Eastern carbonate ramp (United Arab Emirates). Our site was located at the equator throughout the Late Triassic and the Early Jurassic, and this study provides the first constraints of environmental changes at the low-latitudes for the Triassic-Jurassic boundary. Shallow-marine carbonate depositional systems are extremely sensitive to palaeoenvironmental changes and their usefulness for chemostratigraphy is being debated. However, the palaeogeographic location of the studied carbonate ramp gives us a unique insight into a tropical carbonate factory at a time of severe global change. Stable isotope measurements (carbon and oxygen) are being carried out on micrite, ooids and shell material along the Triassic-Jurassic boundary. The stable isotope results on micrite show a prominent negative shift in carbon isotope values of approximately 2 ‰ just below the inferred position of the Triassic-Jurassic boundary. A similar isotopic trend is also observed across the Tethys but with a range of amplitudes (from ~2 ‰ to ~4 ‰). These results seem to indicate that the neritic carbonates from our studied section can be used for chemostratigraphic purposes, and the amplitudes of the carbon isotope shifts provide critical constraints on the magnitude of carbon-cycle perturbations at low latitudes across the Triassic-Jurassic boundary. Seawater temperatures across the Triassic-Jurassic boundary will be constrained using the clumped isotope palaeo-thermometer applied

  12. Carbon isotopic characteristics and their genetic relationships for individual lipids in plants and sediments from a marsh sedimentary environment

    Institute of Scientific and Technical Information of China (English)

    DUAN Yi; ZHANG Hui; ZHENG Chaoyang; WU Baoxiang; ZHENG Guodong

    2005-01-01

    The carbon isotopes of individual lipids in herbaceous plants and tree leaves in Ruoergai marsh were measured by the GC-IRMS analytical technique in order to understand the inherent relationships of carbon isotopes between sedimentary and plant lipids from typical marsh environment. The analytical results show that the carbon isotopic compositions of n-alkanes in different kinds of plants differ significantly. Mean δ13C values of n-alkanes in herbaceous plants (-32.2‰―-36.9‰) are 3.3‰ lower than those in woody plant (-27.2‰― -35.0‰). The carbon isotopic compositions of fatty acids in organisms (-30.3‰― -36.2‰) are very similar to those of n-alkanes and the δ13C values for unsaturated fatty acids are within the range of those for saturated fatty acids. The differences in δ13C values between plant lipids are obvious and range from 2.4‰ to 7.8‰. It is observed that the carbon isotopic compositions of sedimentary lipids are closely related to those of plant lipids. The carbon isotopic compositions (-27.0‰―-36.9‰) of n-alkanes, ≥C16 fatty acids, n-alkanols, sterols and n-alkanones in the sediments are similar to those of plant lipids and the carbon isotopic compositions of short-chain sedimentary lipids are similar to those of long-chain sedimentary homologues. These indicate that the sedimentary lipids are derived from high plants. However, the δ13C values of C14:0 and C15:0 fatty acids in the sediments are lighter than those of the same carbon number saturated homologues in plants, reflecting the genetic features partially derived from bacteria. These data provide scientific evidence for carbon isotope-applied research of individual lipids.

  13. Sulfur, carbon, hydrogen, and oxygen isotope geochemistry of the Idaho cobalt belt

    Science.gov (United States)

    Johnson, Craig A.; Bookstrom, Arthur A.; Slack, John F.

    2012-01-01

    Cobalt-copper ± gold deposits of the Idaho cobalt belt, including the deposits of the Blackbird district, have been analyzed for their sulfur, carbon, hydrogen, and oxygen isotope compositions to improve the understanding of ore formation. Previous genetic hypotheses have ranged widely, linking the ores to the sedimentary or diagenetic history of the host Mesoproterozoic sedimentary rocks, to Mesoproterozoic or Cretaceous magmatism, or to metamorphic shearing. The δ34S values are nearly uniform throughout the Blackbird dis- trict, with a mean value for cobaltite (CoAsS, the main cobalt mineral) of 8.0 ± 0.4‰ (n = 19). The data suggest that (1) sulfur was derived at least partly from sedimentary sources, (2) redox reactions involving sulfur were probably unimportant for ore deposition, and (3) the sulfur was probably transported to sites of ore for- mation as H2S. Hydrogen and oxygen isotope compositions of the ore-forming fluid, which are calculated from analyses of biotite-rich wall rocks and tourmaline, do not uniquely identify the source of the fluid; plausible sources include formation waters, metamorphic waters, and mixtures of magmatic and isotopically heavy meteoric waters. The calculated compositions are a poor match for the modified seawaters that form vol- canogenic massive sulfide (VMS) deposits. Carbon and oxygen isotope compositions of siderite, a mineral that is widespread, although sparse, at Blackbird, suggest formation from mixtures of sedimentary organic carbon and magmatic-metamorphic carbon. The isotopic compositions of calcite in alkaline dike rocks of uncertain age are consistent with a magmatic origin. Several lines of evidence suggest that siderite postdated the emplacement of cobalt and copper, so its significance for the ore-forming event is uncertain. From the stable isotope perspective, the mineral deposits of the Idaho cobalt belt contrast with typical VMS and sedimentary exhalative deposits. They show characteristics of deposit

  14. Method for determination of stable carbon isotope ratio of methylnitrophenols in atmospheric PM

    Directory of Open Access Journals (Sweden)

    S. Moukhtar

    2011-05-01

    Full Text Available A technique for the measurement of the stable isotope ratio of methylnitrophenols in atmospheric particulate matter (PM is presented. It has been found in numerous laboratory studies that these compounds are photooxidation products of toluene in PM. Atmospheric samples from rural and suburban areas were collected for evaluation of the procedure. PM was collected on quartz fibre filters using dichotomous high volume air samplers for PM 2.5. Methylnitrophenols were extracted from the filters using acetonitrile. The sample was then purified using a combination of high-performance liquid chromatography (HPLC and solid phase extraction (SPE. The final solution was then divided into two aliquots. To one aliquot, a derivatising agent, Bis(trimethylsilyltrifluoroacetamide (BSTFA, was added to the solution for Gas Chromatography/Mass Spectroscopy (GC/MS analysis. The second half of the sample was stored at low temperature. When GC/MS analysis showed high enough concentrations the remaining sample was derivatized with BSTFA and analysed for stable isotope ratio using a Gas Chromatography/Isotope Ratio Mass Spectrometry (GC-IRMS.

    In all atmospheric PM samples analysed, 2-methyl-4-nitrophenol was found to be the most abundant methylnitrophenol. Nevertheless, due to low pollution levels occurring in the rural area, no samples had concentrations high enough to perform stable carbon isotope composition measurements of the methylnitrophenols. Samples collected in the suburban area could be analysed for carbon stable isotope ratio using GC-IRMS.

    The procedure described in this paper provides a very sensitive and selective method for the analysis of methylnitrophenols in atmospheric PM at concentrations as low as 1 pg m−3. For accurate (within ±0.5‰ stable isotope ratio analysis significantly higher concentrations in the range of 100 pg m−3 or more are required.

  15. The extinction of Equidae and Proboscidea in South America. A test using Carbon isotope data

    Directory of Open Access Journals (Sweden)

    Prado, J. L.

    2011-12-01

    Full Text Available Carbon isotopes, preserved in 166 samples of fossil teeth and bone, provide key data for understanding the ecology of extinct horses and gomphotheres during the Plio-Pleistocene in South America. To analyze the patterns of dietary partitioning throughout this time we divided the samples into 19 groups, taking into account the genus and the age of the corresponding localities. In this study, the diets of both groups are assessed to test extinction hypotheses. The strong resource partitioning among herbivores assumed under Co-evolutionary disequilibrium hypothesis is supported by isotopic data of horses from latest Pleistocene. Hippidon and Equus had very different diets. In contrast, species of gomphotheres from late Pleistocene in South America seem to have had less specialized diets containing a broad mix of both C3 and C4 plants, which is in line with the dietary assumptions of the mosaic-nutrient hypothesis, but does not support the assumptions of Co-evolutionary disequilibrium hypothesis.

    Los isótopos del carbono preservados en 166 muestras de dientes y huesos fósiles son un dato clave para entender la ecología de los de caballos y gonfoterios durante el Plio-Pleistoceno en América del Sur. Para analizar los cambios en las reconstrucciones de la dieta durante este lapso temporal hemos dividido las muestras en 19 grupos, teniendo en cuenta la sistemática y la cronología de cada localidad. En este estudio, las dietas de ambos grupos son evaluadas para probar las hipótesis sobre su extinción. El alto fraccionamiento en el uso de los recursos entre los herbívoros que asume la hipótesis del desequilibrio co-evolutivo es sustentada por los datos isotópicos de los caballos del Pleistoceno tardío. Hippidion y Equus tenían una dieta muy diferente. En contraste, las especies de gonfoterios de finales del Pleistoceno parecen tener una dieta menos especializada con una combinación de

  16. The significance of an Early Jurassic (Toarcian) carbon-isotope excursion in Haida Gwaii (Queen Charlotte Islands), British Columbia, Canada

    Science.gov (United States)

    Caruthers, Andrew H.; Gröcke, Darren R.; Smith, Paul L.

    2011-07-01

    During the Early Toarcian there was a significant disruption in the short-term active carbon reservoir as revealed by carbon-isotope records, which show a broad positive shift that is interrupted by a large 5-7‰ negative excursion (δ 13C org). Carbon-isotope excursion co-occurs with the deposition of organic-rich shales in many areas. This perturbation in carbon isotopes is thought to be indicative of severe climate change and marine anoxia. The two leading hypotheses as to the cause of this event invoke either global or regional controls. Here we present carbon-isotope data from Haida Gwaii, British Columbia, Canada showing a significant perturbation within a temporally constrained Early Toarcian succession that was deposited in the northeastern paleo-Pacific Ocean. These data reinforce the concept that the short-term active carbon reservoir was affected globally, and assist with the correlation of ammonite zonal schemes between western North America and Europe. The δ 13C org data show a broad positive shift that is interrupted by a sharp and pronounced negative excursion of 7‰ (8.5‰ in δ 13C wood) in the Early Toarcian Kanense Zone. This negative excursion also coincides with increasing total organic carbon (TOC) from ~ 0.4% to ~ 1.2%. These data suggest that the Early Toarcian carbon-isotope perturbation was indeed global and imprinted itself on all active global reservoirs of the exchangeable carbon cycle (deep marine, shallow marine, atmospheric).

  17. Carbon Isotopic Studies of Assimilated and Ecosystem Respired CO2 in a Southeastern Pine Forest. Final Report and Conference Proceedings

    Energy Technology Data Exchange (ETDEWEB)

    Conte, Maureen H

    2008-04-10

    Carbon dioxide is the major “greenhouse” gas responsible for global warming. Southeastern pine forests appear to be among the largest terrestrial sinks of carbon dioxide in the US. This collaborative study specifically addressed the isotopic signatures of the large fluxes of carbon taken up by photosynthesis and given off by respiration in this ecosystem. By measuring these isotopic signatures at the ecosystem level, we have provided data that will help to more accurately quantify the magnitude of carbon fluxes on the regional scale and how these fluxes vary in response to climatic parameters such as rainfall and air temperature. The focus of the MBL subcontract was to evaluate how processes operating at the physiological and ecosystem scales affects the resultant isotopic signature of plant waxes that are emitted as aerosols into the convective boundary layer. These wax aerosols provide a large-spatial scale integrative signal of isotopic discrimination of atmospheric carbon dioxide by terrestrial photosynthesis (Conte and Weber 2002). The ecosystem studies have greatly expanded of knowledge of wax biosynthetic controls on their isootpic signature The wax aerosol data products produced under this grant are directly applicable as input for global carbon modeling studies that use variations in the concentration and carbon isotopic composition of atmospheric carbon dioxide to quantify the magnitude and spatial and temporal patterns of carbon uptake on the global scale.

  18. [Carbon isotope (13C/12C) effect of photorespiration in photosynthetic organisms. Evidence for existence, probable mechanism].

    Science.gov (United States)

    Ivlev, A A

    2002-01-01

    Experimental evidence in favor of the new phenomenon predicted for photosynthesizing organisms, the fractionation of carbon isotopes in photorespiration is presented. A possible mechanism of this process is discussed. The fractionation of carbon in isotopes photorespiration occurs in the oxygenase phase of the functioning of ribulosebisphosphate carboxylase/oxygenase (rubisco), the key enzyme of photosynthesis, which is capable to act as carboxylase and oxygenase. Which function of the enzyme is active depends on CO2/O2 concentration ratio, which periodically changes in a cell. The key reaction in the mechanism of carbon isotope fractionation in photorespiration is glycine decarboxylation, which results in the splitting and removal from the cell of CO2 enriched with 12C and the accumulation of 13C photorespiratory carbon flow. The coupling of photorespiration and CO2 photoassimilation gives rise to two isotopically different carbon flows, which fill up separate carbohydrate pools, which are the sources of carbon in the following syntheses in the dark phase of photosynthesis. This enables one to identify, from the carbon isotope ratio of metabolites, their involvement in the photorespiratory and assimilatory carbon flows, to investigate the pathways of carbon metabolism, and to estimate more thoroughly the biosynthetic role of photorespiration.

  19. Using a laser-based CO2 carbon isotope analyser to investigate gas transfer in geological media

    Science.gov (United States)

    Guillon, S.; Pili, E.; Agrinier, P.

    2012-05-01

    CO2 stable carbon isotopes are very attractive in environmental research to investigate both natural and anthropogenic carbon sources. Laser-based CO2 carbon isotope analysis provides continuous measurement at high temporal resolution and is a promising alternative to isotope ratio mass spectrometry (IRMS). We performed a thorough assessment of a commercially available CO2 Carbon Isotope Analyser (CCIA DLT-100, Los Gatos Research) that allows in situ measurement of δ 13C in CO2. Using a set of reference gases of known CO2 concentration and carbon isotopic composition, we evaluated the precision, long-term stability, temperature sensitivity and concentration dependence of the analyser. Despite good precision calculated from Allan variance (5.0 ppm for CO2 concentration, and 0.05 ‰ for δ 13C at 60 s averaging), real performances are altered by two main sources of error: temperature sensitivity and dependence of δ 13C on CO2 concentration. Data processing is required to correct for these errors. Following application of these corrections, we achieve an accuracy of 8.7 ppm for CO2 concentration and 1.3 ‰ for δ 13C, which is worse compared to mass spectrometry performance, but still allowing field applications. With this portable analyser we measured CO2 flux degassed from rock in an underground tunnel. The obtained carbon isotopic composition agrees with IRMS measurement, and can be used to identify the carbon source.

  20. Aspect of human food ecology; Development of carbon and nitrogen isotope method

    Energy Technology Data Exchange (ETDEWEB)

    Minagawa, Masao (Hokkaido Univ., Sapporo (Japan))

    1994-01-01

    The isotopic dietary analysis was applied for some prehistoric human populations from East Asia, Latin America, and Oceania region. Most samples were from archeological sites from 1000 to 6000 year's bp. Some modern ethnological groups including Tibet, Kurud, Shelpa and Tlingit were also studied for evaluating prehistoric human food habit. Carbon and nitrogen isotope compositions of gelatin fractions have been analyzed for prehistoric bone samples. Analytical procedure for isotopes and data analyses for reconstructing dietary composition was developed and tested by a modern human food system. A stochastic method based on the Monte Carlo model was applied to estimate dependency of major food resources having unique isotope compositions in carbon and nitrogen, and has showed consistent results to the statistic food consumption record in Japan. Carbon and nitrogen isotope composition of human tissues showed distinct difference among human groups in both prehistoric and modern samples. These data were evaluated by difference of dietary patterns: contributions of marine food, terrestrial food, meat, C3 and C4 plant, which are characterized by the difference of [sup 13]C and [sup 15]N content. On the basis of the stochastic feeding simulation, dietary consumption patterns were estimated for Jomon fisher-hunter-gatherers, historic Ainu, prehistoric east Siberian, prehistoric Latin American farmers in Mexico and Peru, and prehistoric fisheres in Cook island. Results showed a remarkable relationship between animal protein dependence and marine food usage. This result will be discussed from following two possibilities; the human adaptation on marine resources would be one of the important direction to upgrade animal protein uptake, or marine food could be used as alternative protein source for terrestrial game animals. (author).

  1. Upper Campanian–Maastrichtian nannofossil biostratigraphy and high-resolution carbon-isotope stratigraphy of the Danish Basin

    DEFF Research Database (Denmark)

    Thibault, Nicolas Rudolph; Harlou, Rikke; Schovsbo, Niels

    2012-01-01

    High-resolution carbon isotope stratigraphy of the upper Campanian – Maastrichtian is recorded in the Boreal Realm from a total of 1968 bulk chalk samples of the Stevns-1 core, eastern Denmark. Isotopic trends are calibrated by calcareous nannofossil bio-events and are correlated with a lower-res...

  2. Variation of carbon isotope fractionation in hydrogenotrophic methanogenic microbial cultures and environmental samples at different energy status

    NARCIS (Netherlands)

    Penning, H.; Plugge, C.M.; Galand, P.E.; Conrad, R.

    2005-01-01

    Methane is a major product of anaerobic degradation of organic matter and an important greenhouse gas. Its stable carbon isotope composition can be used to reveal active methanogenic pathways, if associated isotope fractionation factors are known. To clarify the causes that lead to the wide variatio

  3. Shale gas plays, Neuquén Basin, Argentina: chemostratigraphy and mud gas carbon isotopes insights

    Directory of Open Access Journals (Sweden)

    Héctor Adolfo Ostera

    Full Text Available ABSTRACT: In order to enhance the knowledge of shale objectives from Vaca Muerta and Los Molles Formations in the Neuquén Basin, Argentina, chemostratigraphic and mud gas carbon isotope analyses were performed in two wells from Agua del Cajón and Salitral oilfields (ADC-1016 and NqSa-1148. Geochemical data show restricted levels in both cases to perforate and produce. In ADC-1016 well, Lower Los Molles Formation looks like the most suitable play to be produced. At El Salitral oilfield (NqSa-1148, the best remarkable Vaca Muerta-Quintuco objectives are associated with authigenic elements, in limited horizons. Enhancement of the Quintuco reservoir by deep circulating fluids (thermobaric reservoir is suggested. Carbon isotope analysis reveals complex processes that affected the gas composition. Addition of microbial methane, biodegradation of ethane-propane and mixing of gases has been recognized. Isotope reversals and presumed water reforming of hydrocarbons have been registered associated with overpressure for Lower Los Molles Formation in the ADC-1016 well, which is pointed out as the most promising shale play in the area. Vaca Muerta gases at Agua del Cajon ADC- 1016 well are associated with the homonymous source. El Salitral 1148 well shows that primary isotope composition in gases from Vaca Muerta shale play and Quintuco reservoir could be associated with a Lower Los Molles source, an aloctonous charge related with the main structures of the area.

  4. Carbon isotopic characterization of cider CO2 by isotope ratio mass spectrometry: a tool for quality and authenticity assessment.

    Science.gov (United States)

    Cabañero, Ana I; Rupérez, Mercedes

    2012-08-30

    The cider market is an important sector of the food industry in certain regions. Adulteration of cider can happen in several ways: for example, by the addition of sugar, or of exogenous CO(2) to certain types of cider. Because such practices are not allowed by either Spanish legislation or the legislation of other countries, it is essential to study possible methods to detect these unauthorized practices. For this purpose a procedure was required to study the stable carbon isotopic composition of CO(2) in cider. A liquid sample of cider was transferred to a vial and CO(2) from the headspace of the vial was analyzed using a peripheral device interfaced to an isotope ratio mass spectrometer. Separation of the CO(2) from water and ethanol was achieved using a gas chromatography column located in the peripheral device. The values for repeatability and reproducibility obtained indicated the robustness of the method, which is required for routine analysis. Ninety cider samples from various origins were analyzed, most of which showed a (13)C content consistent with the declared origin. The δ(13)C ranged from -24.80‰ to -20.89‰ for ciders with endogenous carbon dioxide (-22.74 ± 0.79‰) and -37.13‰ to -26.00‰ if industrial CO(2) was added. Several samples were also suspected of C4 sugar addition prior to the fermentation. A fast, accurate and simple method for cider adulteration detection was developed. The addition of exogenous CO(2) as well as C4 sugar addition prior to fermentation could be detected. The method showed advantages over existing methods in term of simplicity (no sample preparation and very long-term stability of the sample), speed (less than 10 min/sample) and precision ((r ≤0.32 and R ≤0.42). Copyright © 2012 John Wiley & Sons, Ltd.

  5. Insights to PETM Terrestrial Records from Global Patterns in Carbon Isotope Fractionation by Modern Plants

    Science.gov (United States)

    Freeman, K. H.; Diefendorf, A. F.; Mueller, K. E.; Wing, S. L.; Koch, P. L.

    2009-12-01

    Global patterns in plant fractionation and δ13C values of leaves are potentially important for understanding and predicting ecologic impacts of climate change, yet clear, global patterns have not emerged from the copious, highly variable leaf δ13C values published to date. Understanding drivers in modern plant fractionation at large spatial scales has potential to strengthen understanding of isotopic variability in ancient terrestrial organic matter and how it encodes climate and ecological signals. We converted published leaf δ13C-leaf data into mean fractionation values for 334 woody C3 plant species at 105 globally distributed locations to evaluate the influence of environmental properties and plant functional type. Biome designation reflects both community composition and climate properties, so it is not unexpected that in our study it exerts the greatest predictive power on leaf fractionation values. Pulling apart the influences of different environmental factors, precipitation has the next strongest correlation with fractionation, consistent with limitations on photosynthesis and global patterns of ecosystem productivity due to water availability. Individual plant functional types exhibit similar relationships between fractionation and both biome designation and precipitation amount. However, mean fractionation values for evergreen gymnosperms are 1-2.7‰ lower than other woody plant types when environmental factors are constrained. Our results illustrate that both plant type and precipitation can independently result in differences in isotope fractionation of up to several permil. The predictive relationships from our study provide a framework for assessing models of plant fractionation at large spatial scales, and potentially enable predictive spatial mapping of carbon isotopic patterns, both for plants and soil organic carbon. We use these relationships to re-evaluate the 5 ‰ carbon isotope excursion of the PETM in the Bighorn Basin recorded in plant

  6. Carbon and oxygen isotopic composition of coal and carbon dioxide derived from laboratory coal combustion: A preliminary study

    Science.gov (United States)

    Warwick, Peter; Ruppert, Leslie F.

    2016-01-01

    The concentration of carbon dioxide (CO2) in the atmosphere has dramatically increased from the start of the industrial revolution in the mid-1700s to present levels exceeding 400 ppm. Carbon dioxide derived from fossil fuel combustion is a greenhouse gas and a major contributor to on-going climate change. Carbon and oxygen stable isotope geochemistry is a useful tool to help model and predict the contributions of anthropogenic sources of CO2 in the global carbon cycle. Surprisingly few studies have addressed the carbon and oxygen isotopic composition of CO2 derived from coal combustion. The goal of this study is to document the relationships between the carbon and oxygen isotope signatures of coal and signatures of the CO2 produced from laboratory coal combustion in atmospheric conditions.Six coal samples were selected that represent various geologic ages (Carboniferous to Tertiary) and coal ranks (lignite to bituminous). Duplicate splits of the six coal samples were ignited and partially combusted in the laboratory at atmospheric conditions. The resulting coal-combustion gases were collected and the molecular composition of the collected gases and isotopic analyses of δ13C of CO2, δ13C of CH4, and δ18O of CO2 were analysed by a commercial laboratory. Splits (~ 1 g) of the un-combusted dried ground coal samples were analyzed for δ13C and δ18O by the U.S. Geological Survey Reston Stable Isotope Laboratory.The major findings of this preliminary work indicate that the isotopic signatures of δ13C (relative to the Vienna Pee Dee Belemnite scale, VPDB) of CO2 resulting from coal combustion are similar to the δ13CVPDB signature of the bulk coal (− 28.46 to − 23.86 ‰) and are not similar to atmospheric δ13CVPDB of CO2 (~ − 8 ‰, see http://www.esrl.noaa.gov/gmd/outreach/isotopes/c13tellsus.html). The δ18O values of bulk coal are strongly correlated to the coal dry ash yields and appear to have little or no influence on the δ18O values of CO2

  7. Carbon and strontium isotope variations and responses tosea-level fluctuations in the Ordovician of the Tarim Basin

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Abstract In the Ordovician, a carbonate platform system grading from the platformal interioreastwards to basin was developed in the Tazhong area of the Tarim Basin, and the study column islocated in the place where the paleoslope occurred. The isotope compositions of the carbonatesthere are thus considered as having reflected those of simultaneous sea waters in view of its goodconnection with the open seas. The carbon and strontium isotope compositions of the Ordoviciancarbonates in the Tazhong area are analyzed, and their relationships to the sea-level fluctuationsare discussed as well. Studies have revealed that the carbon isotope composition is related posi-tively with the sea-level fluctuations, whereas an opposing situation occurs to the strontium isotopevariation. Similar responses of carbon and strontium isotope compositions to the sea-level fluctua-tions are reported elsewhere in the world, suggesting that the Ordovician sea-level fluctuations ofthe Tarim Basin were of eustatic implication.

  8. Stable carbon and radiocarbon isotope compositions of particle size fractions to determine origins of sedimentary organic matter in an estuary

    NARCIS (Netherlands)

    Megens, L; van der Plicht, J; de Leeuw, JW; Smedes, F; Altabet, M.

    2002-01-01

    Stable and radioactive carbon isotopic compositions of particle size fractions of a surface sediment from the Ems-Dollard estuary vary considerably with particle size. The organic material in the fine fractions (

  9. Stable carbon and radiocarbon isotope compositions of particle size fractions to determine origins of sedimentary organic matter in an estuary

    NARCIS (Netherlands)

    Megens, L; van der Plicht, J; de Leeuw, JW; Smedes, F; Altabet, M.

    2002-01-01

    Stable and radioactive carbon isotopic compositions of particle size fractions of a surface sediment from the Ems-Dollard estuary vary considerably with particle size. The organic material in the fine fractions (

  10. Carbon isotopic record of foraminifers in surface sediments from the South China Sea and its significance

    Institute of Scientific and Technical Information of China (English)

    CHENG Xinrong; WANG Pinxian; HUANG Baoqi; LIU Chuanlian; JIAN Zhimin; ZHAO Quanhong; LI Jianru; TIAN Jun; XU Jian

    2005-01-01

    The study is based on stable carbon isotopic measurements of 112 foraminiferal samples from surface sediments at 40 sites in the South China Sea (SCS).δ13C of foraminifers and △δ13C between planktonic and benthic foraminiferal species exhibit a low value area at the northeastern and southern ends of the SCS. It is correlated with the nutrient distributional pattern in the SCS and circumjacent area, the influence of the northeastern and southwestern monsoons on water flow and water chemistry in the SCS. The monsoons have not only brought nutrients to the upper part of the sea but also disturbed water and decreased difference between the surface and bottom water. Its influence is most obvious at both ends, which resulted in the low value areas in δ13C and △δ13C at the ends. The distributional pattern of the stable carbon isotope in the SCS is a reflection of the East Asian monsoons.

  11. Isotopic evidence of magmatism and a sedimentary carbon source at the Endeavour hydrothermal system

    Energy Technology Data Exchange (ETDEWEB)

    Brown, T A; Proskurowski, G; Lilley, M D

    2004-01-07

    Stable and radiocarbon isotope measurements made on CO{sub 2} from high temperature hydrothermal vents on the Endeavour Segment of the Juan de Fuca Ridge indicate both magmatic and sedimentary sources of carbon to the hydrothermal system. The Endeavour segment is devoid of overlying sediments and has shown no observable signs of surficial magmatic activity during the {approx}20 years of ongoing studies. The appearance of isotopically heavy, radiocarbon dead CO{sub 2} after a 1999 earthquake swarm requires that this earthquake event was magmatic in origin. Evidence for a sedimentary organic carbon source suggests the presence of buried sediments at the ridge axis. These findings, which represent the first temporally coherent set of radiocarbon measurements from hydrothermal vent fluids, demonstrate the utility of radiocarbon analysis in hydrothermal studies. The existence of a sediment source at Endeavour and the occurrence of magmatic episodes illustrate the extremely complex and evolving nature of the Endeavour hydrothermal system.

  12. Sinemurian–Pliensbachian calcareous nannofossil biostratigraphy and organic carbon isotope stratigraphy in the Paris Basin

    DEFF Research Database (Denmark)

    Peti, Leonie; Thibault, Nicolas Rudolph; Clemence, Marie-Emilie

    2017-01-01

    carbon isotope excursions are identified and defined in the Paris Basin including the well-documented Sinemurian–Pliensbachian boundary event. One positive excursion is further defined in the Pliensbachian interval. Our calibration of high-resolution calcareous nannofossil biostratigraphy to ammonite...... organic carbon isotope curve based on 385 data points. The main bioevents, i.e. the first occurrences of Parhabdolithus liasicus, Crepidolithus pliensbachensis, Crepidolithus crassus, Mitrolithus lenticularis, Similiscutum cruciulus sensu lato, Lotharingius hauffii, Crepidolithus cavus and Lotharingius...... sigillatus as well as the last occurrence of Parhabdolithus robustus, have been identified. However, we show that a large number of standard biostratigraphic markers show inconsistent occurrences at the base and top of their range, possibly accounting for some of the significant discrepancies observed...

  13. Sr isotopic chemostratigraphy of Precambrian carbonate rocks in the Amderma Rise, Pai-Khoi Ridge

    Science.gov (United States)

    Kuznetsov, A. B.; Starikova, E. V.; Maslov, A. V.; Konstantinova, G. V.

    2016-08-01

    The Sr and C isotopic compositions of Precambrian carbonate rocks are determined for Amderma Rise, in the northeastern margin of Pai-Khoi Ridge. Based on the Sr isotopic chemostratigraphy, it is established for the first time that the Amderma Formation is referred to the Early Vendian, while the Morozovsk Formation is Late Riphean in age. This conclusion along with detailed mapping proves that the Precambrian "section" of the Amderma Rise is a series of tectonic plates combined in a nonchronostratigraphic order. Volcanic and sedimentary rocks of the Morozovsk and Sokolninsk formations make up the allochthon proper, while carbonate rocks of the Amderma Formation make up the para-autochthon. The high values of δ13C (up to +9.5‰) identified in limestones of both formations suggest a considerable distance of the Pai-Khoi paleobasin from the passive margin of the Baltic Region upon facies similarity to the Laurentia active margins.

  14. Methane Production Pathways in a California Rice Paddy: Isotopic Evidence for Substantial CO2 Reduction as Cause for Isotopically Light Emitted CH4 Carbon

    Science.gov (United States)

    Tyler, S. C.; McMillan, A. M.; Bearden, K.; Chidthaisong, A.; Macalady, J.

    2003-12-01

    We report measurements of δ 13C of emitted CH4 and sediment CH4 and CO2 during the 1999 rice-growing season near Maxwell, CA. Two treatments, one with rice straw incorporated from the previous season and one without rice straw were studied. The δ 13C value of emitted CH4 was consistently lighter isotopically (-67‰ to -83‰ throughout the season) in both straw incorporated and straw removed (burned) plots than in fields we have studied in Texas, Kenya, and Japan. Measured isotopic values of the production zone CH4 were compared to a two-point mixing curve representative of isotopic CH4 produced from either pure methyl-group fermentation or CO2 reduction pathways to partition the production pathways and to track seasonal changes in the production processes. Our sediment CH4 and CO2 isotope data indicate that fermentation was rarely the dominant methanogenic pathway - on the contrary CO2 reduction with H2 was more prevalent than fermentation methanogenesis throughout most of the season. The relatively isotopically light CH4 emitted by the paddy fields is also a product of oxidation and stem-transport processes which have isotopic effects of their own. These effects are discussed in context with the methanogenic isotope effects to provide a complete picture of the paddy field CH4 carbon isotope system.

  15. Environmental and biosynthetic influences on carbon and hydrogen isotope ratios of leaf wax n-alkanes

    Science.gov (United States)

    McInerney, F. A.; Freeman, K. H.; Polissar, P. J.; Feakins, S. J.

    2013-12-01

    Both carbon and hydrogen isotope ratios of leaf-wax n-alkanes are influenced by the availability of water in a plant's growth environment. Carbon isotope ratios of bulk tissues in C3 plants demonstrate a strong inverse relationship with measures of available moisture (e.g. mean annual precipitation and precipitation/evaporation). Similarly, hydrogen isotope ratios of leaf wax n-alkanes (δDl) can be enriched relative to precipitation (δDw) by transpiration, which is related to relative humidity and the leaf-to-air vapor pressure deficit. Thus, D-enrichment of leaf-wax n-alkanes relative to precipitation, termed the apparent fractionation (2ɛl/w), becomes more positive with increasing aridity. In theory, more positive values of leaf-wax δ13C (δ13Cl) and 2ɛl/w of leaf-wax n-alkanes should both correspond to more arid conditions in C3 plants. Here we review published and unpublished data on over 100 plants to examine this relationship. Contrary to expectations, C3 dicots show no clear relationship between δ13Cl and 2ɛl/w. This global lack of correlation is surprising given our understanding of aridity related isotopic effects in C3 plants. One possibility is that the implicit assumption of constant fractionation between lipid and bulk tissue is flawed due to the effects of different biosynthetic carriers and reaction pathways. We explore this possibility by examining the offset of leaf-wax carbon isotopes from the bulk leaf tissue (13ɛl/bulk). Different offsets would indicate additional biosynthetic processes are affecting δ13Cl in addition to any direct effects from aridity. We find that 13ɛl/bulk is highly variable, ranging from -1 to -16‰, which could explain the lack of correlation between δ13Cl and 2ɛl/w. In addition, 13ɛl/bulk values for C3 and C4 monocots (averages of -10.6 and -11.4‰ respectively) represent significantly greater offset between leaf wax and bulk tissue than in C3 dicots (average of -4.3‰), which is consistent with previous

  16. Cerium anomaly across the mid-Tournaisian carbon isotope excursion (TICE)

    Science.gov (United States)

    Jiang, G.; Morales, D. C.; Maharjan, D. K.

    2015-12-01

    The Early Mississippian (ca. 359-345 Ma) represents one of the most important greenhouse-icehouse climate transitions in Earth history. Closely associated with this critical transition is a prominent positive carbon isotope excursion (δ13C ≥ +5‰) that has been documented from numerous stratigraphic successions across the globe. This δ13C excursion, informally referred to as the TICE (mid-Tournaisian carbon isotope excursion) event, has been interpreted as resulting from enhanced organic carbon burial, with anticipated outcomes including the lowering of atmospheric CO2 and global cooling, the growth of continental ice sheets and sea-level fall, and the increase of ocean oxygenation and ocean redox changes. The casual relationship between these events has been addressed from various perspectives but not yet clearly demonstrated. To document the potential redox change associated with the perturbation of the carbon cycle, we have analyzed rare earth elements (REE) and trace elements across the TICE in two sections across a shallow-to-deep water transect in the southern Great Basin (Utah and Nevada), USA. In both sections, the REE data show a significant positive cerium (Ce) anomaly (Ce/Ce* = Ce/(0.5La+0.5Pr)). Prior to the positive δ13C shift, most Ce/Ce* values are around 0.3 (between 0.2 and 0.4). Across the δ13C peak, Ce/Ce* values increase up to 0.87, followed by a decrease back to 0.2~0.3 after the δ13C excursion (Figure 1). The positive Ce anomaly is best interpreted as recording expansion of oxygen minimum zone and anoxia resulted from increased primary production. This is consistent with a significant increase of nitrogen isotopes (δ15N) across the δ13C peak. Integration of the carbon, nitrogen, and REE data demonstrates a responsive earth systems change linked to the perturbation of the Early Mississippian carbon cycle.

  17. Stable Carbon Isotope Ratios in Atmospheric VOC across the Asian Summer Monsoon Anticyclone obtained during the OMO-ASIA campaign

    Science.gov (United States)

    Krebsbach, Marc; Koppmann, Ralf; Meisehen, Thomas

    2017-04-01

    The automated high volume air sampling system (MIRAH) has been deployed during the atmospheric measurement campaign OMO-ASIA (Oxidation Mechanism Observations) with the German High Altitude - Long-range research aircraft (HALO) in July and August 2015. The intensive measurement period with base stations in Paphos (Cyprus) and Gan (Maldives) focussed on oxidation processes and air pollution chemistry downwind of the South Asia summer monsoon anticyclone, a pivot area critical for air quality and climate change, both regionally and worldwide. The measurement region covered the Eastern Mediterranean region, the Arabian Peninsula, Egypt, and the Arabian Sea. In total 194 air samples were collected on 17 flights in a height region from 3 km up to 15 km. The air samples were analysed for stable carbon isotope ratios in VOC with GC-C-IRMS in the laboratory afterwards. We determined stable carbon isotope ratios and mixing ratios of several aldehydes, ketones, alcohols, and aromatics. The large extent of the investigated area allowed for encountering air masses with different origin, characteristic, and atmospheric processing, e.g. Mediterranean air masses, crossing of polluted filaments and remnants of the Asian monsoon outflow, split of the Asian monsoon anticyclone. In this presentation we will show first results and interpretations supported by HYSPLIT backward trajectories.

  18. Tracing paleo-ocean redox using Cr isotopes in carbonates spanning the Great Oxidation Event

    Science.gov (United States)

    Holmden, C. E.; Bekker, A.

    2013-12-01

    Cr is an element whose isotopes are fractionated by redox reactions in the Earth's exogenic system, such as those occuring during oxidative weathering on the continents and scavenging into reduced marine sediments. Frei et al. (2009) proposed that the range of Cr isotope fractionation in exogenic materials in the absence of molecular oxygen would likely not extend beyond the range in igneous rocks, which is quite small (δ53Cr = -0.1 ×0.1‰). They tested their hypothesis on iron formations spanning the Great Oxidation Event (GOE) and found small fractionations that predated the GOE, but no permil level fractionation until the Neoproterozoic. We tested whether δ53Cr values in shallow-water carbonates spanning the GOE might record steps in the rise of atmospheric oxygen between 2.45 and 2.06 Ga. Carbonates representing 15 formations were chosen with depositonal ages ranging between 2.5 Ga and 1.9 Ga. We find very little Cr isotope fractionation recorded in carbonates deposited during this time with the exception of those corresponding to the peak of the Lomagundi Event at ca. 2.15 Ga. A defining characterisitic of the Lomagundi Event is the widespread prevalance of shallow-water carbonate platforms with abundant stromatolites, making their deposits an ideal lithology to record the state of the seawater Cr cycle. Five formations deposited during this time yield δ53Cr values with permil level fractionation recorded in some examples, in both positive and negative directions with respect to the igenous rock baseline. The data suggests that although the oxidative part of the Cr cycle started at least during the peak of the Lomagundi Event, the Cr(VI) reservoir and its residence time remained small, making it susceptible to local processes. 1. Frei et al. (2009) Fluctuations in Precambrian atmospheric oxygen recorded by Cr isotopes, Nature, v. 461, 250-253.

  19. Altitude effect on leaf wax carbon isotopic composition in humid tropical forests

    Science.gov (United States)

    Wu, Mong Sin; Feakins, Sarah J.; Martin, Roberta E.; Shenkin, Alexander; Bentley, Lisa Patrick; Blonder, Benjamin; Salinas, Norma; Asner, Gregory P.; Malhi, Yadvinder

    2017-06-01

    The carbon isotopic composition of plant leaf wax biomarkers is commonly used to reconstruct paleoenvironmental conditions. Adding to the limited calibration information available for modern tropical forests, we analyzed plant leaf and leaf wax carbon isotopic compositions in forest canopy trees across a highly biodiverse, 3.3 km elevation gradient on the eastern flank of the Andes Mountains. We sampled the dominant tree species and assessed their relative abundance in each tree community. In total, 405 sunlit canopy leaves were sampled across 129 species and nine forest plots along the elevation profile for bulk leaf and leaf wax n-alkane (C27-C33) concentration and carbon isotopic analyses (δ13C); a subset (76 individuals, 29 species, five forest plots) were additionally analyzed for n-alkanoic acid (C22-C32) concentrations and δ13C. δ13C values display trends of +0.87 ± 0.16‰ km-1 (95% CI, r2 = 0.96, p families, suggesting the biochemical response to environment is robust to taxonomic turnover. We calculate fractionations and compare to adiabatic gradients, environmental variables, leaf wax n-alkane concentrations, and sun/shade position to assess factors influencing foliar chemical response. For the 4 km forested elevation range of the Andes, 4-6‰ higher δ13C values are expected for upland versus lowland C3 plant bulk leaves and their n-alkyl lipids, and we expect this pattern to be a systematic feature of very wet tropical montane environments. This elevation dependency of δ13C values should inform interpretations of sedimentary archives, as 13C-enriched values may derive from C4 grasses, petrogenic inputs or upland C3 plants. Finally, we outline the potential for leaf wax carbon isotopes to trace biomarker sourcing within catchments and for paleoaltimetry.

  20. Laws of the oxidation of carbon isotopes in plasma processes under magnetic field

    Science.gov (United States)

    Myshkin, V. F.; Bespala, E. V.; Khan, V. A.; Makarevich, S. V.

    2016-06-01

    From law of quantum mechanics it follows that spin precession phase of unpaired electron in external magnetic field cannot be determined. It uncertainty necessary take into account in different physical and chemical processes. The expression of the rate constant of a chemical reaction based on the number of discrete spin states was obtained. The equations of chemical kinetics of plasma oxidation of carbon isotopes in the magnetic field were given.

  1. Stable carbon isotopes as indicators for micro-geomorphic changes in palsa peats

    Directory of Open Access Journals (Sweden)

    C. Alewell

    2011-01-01

    Full Text Available Palsa peats are unique northern ecosystems formed under an arctic climate and characterized by an unique biodiversity and ecology. The stability of the palsas are seriously threatened by climate warming which will change the permafrost dynamic and results in degradation of the mires. We used stable carbon isotope depth profiles in two palsa mires of Northern Sweden to track environmental change during the formation of the mires. Carbon isotope13C depth profile of the yet undisturbed mire Storflaket indicated very low to no degradation of the peat in the water saturated depressions (hollows but increased rates of anaerobic degradation at the Stordalen site. The latter might be induced by degradation of the permafrost cores in the uplifted areas (hummocks and subsequent braking and submerging of the hummock peat into the hollows due to climate warming. Carbon isotope depth profiles of hummocks indicated a turn from aerobic mineralisation to anaerobic degradation at a peat depth between 4 to 25 cm. The age of these turning point was 14C dated between 150 and 670 years and could thus not be caused by anthropogenically induced climate change. We found the uplifting of the hummocks due to permafrost heave the most likely explanation for our findings. We thus concluded that differences in carbon isotope profiles of the hollows might point to the disturbance of the mires due to climate warming or due to differences in hydrology. The characteristic profiles of the hummocks are indicators for micro-geomorphic change during permafrost up heaving.

  2. Charge-changing cross section measurement of neutron-rich carbon isotopes at 50 AMeV

    Directory of Open Access Journals (Sweden)

    Tran D.T.

    2016-01-01

    Full Text Available Charge Changing Cross Sections (CCCS or σCC of neutron-rich carbon isotopes on carbon target were measured at low energy (50A MeV for the first time. The consistency between Glauber calculation and experimental σCC of 12C isotope at low energy region shows that proton distribution radii can be derived from CCCS at low energy.

  3. Mantle CO2 degassing through the Icelandic crust: Evidence from carbon isotopes in groundwater

    Science.gov (United States)

    Stefánsson, Andri; Sveinbjörnsdóttir, Árný E.; Heinemeier, Jan; Arnórsson, Stefán; Kjartansdóttir, Ríkey; Kristmannsdóttir, Hrefna

    2016-10-01

    Carbon isotopes of groundwater in Iceland were studied in order to determine the source and reactions of carbon at divergent plate boundaries not associated with active volcanic systems. All the waters were of meteoric origin, with temperatures of 1-130 °C, pH of ∼4.5-10.5 and dissolved inorganic carbon (∑CO2) between 1.8 and 4100 ppm. The measured range of δ13CO2 and 14CO2 in these waters was large, -27.4 to +2.0‰ and 0.6-118 pMC, respectively. The sources and reactions of dissolved inorganic carbon were studied by comparing the measured chemical and isotope composition with those simulated using isotope geochemical models. Three major sources of CO2 were identified: (1) dissolution of partially degassed basaltic rocks formed at the surface or shallow depths, (2) atmospheric CO2 through air-water exchange at surface, and (3) input of gas at depth into the groundwater systems that has similar carbon and isotope composition as the pre-erupted melt of the upper mantle and lower crust beneath Iceland. In the groundwater systems the CO2 chemistry and isotope content are modified due to carbonate mineral precipitation and changes in aqueous species distribution upon progressive water-rock interaction; these changes needed to be quantified in order to reveal the various CO2 sources. The CO2 flux of the Icelandic crust was estimated to be ∼5-10 · 1010 mol/yr with as high as 50% of the flux not associated with active volcanic centers but placed off-axis where a significant proportion of the CO2 may originate from the mantle. The mantle input of the groundwater off-axis corresponds to CO2 partial pressures of ∼10-6-1 bar and to a mantle CO2 flux of <5 · 105 mol/km2/yr for most areas and up to 125 · 105 and 1600 · 105 for the Southern Lowlands and Snæfellsnes Peninsula, respectively. The CO2 flux from active volcanic geothermal systems in Iceland was estimated to be ∼500-3000 · 105 mol CO2/km2/yr, considerably greater than the highest values observed off-axis.

  4. Time-dependent properties of liquid water isotopes adsorbed in carbon nanotubes

    Science.gov (United States)

    Martí, J.; Gordillo, M. C.

    2001-06-01

    Dynamics of liquid water and its isotopes when adsorbed inside carbon nanotubes of different radii is studied by means of molecular dynamics simulations. Water molecules have been modeled with a flexible simple point charged (SPC) potential while carbon forces were accounted for with Lennard-Jones-type potentials. Diffusive behavior and the librational, rotational, intra- and intermolecular motions of the constrained molecules have been investigated by means of the spectral densities computed from atomic velocity autocorrelation functions. The results show in all cases significant new vibrational bands and frequency shifts absent in bulk water.

  5. Carbon isotope fractionation in developing natural phototrophic biofilms

    Science.gov (United States)

    Staal, M.; Thar, R.; Kühl, M.; van Loosdrecht, M. C. M.; Wolf, G.; de Brouwer, J. F. C.; Rijstenbil, J. W.

    2007-01-01

    Natural phototrophic biofilms are influenced by a broad array of abiotic and biotic factors and vary over temporal and spatial scales. Different developmental stages can be distinguished and growth rates will vary due to the thickening of the biofilm, which are expected to lead to a limitation of light or mass transport. In this study it is shown that a variation of the availability of CO2 leads to a shift in fractionation, thereby affecting δ13C signatures during the successive developmental stages. For phototrophic freshwater biofilms it was found that the δ13C value became less negative with the thickening of the biofilm, while the opposite trend in δ13C values was found in marine biofilms. Modeling and pH profiling indicated that the change in the freshwater system was caused by an increase in CO2 limitation resulting in an increase of HCO3- as C-source. The opposite trend in the marine system could be explained by a higher heterotrophic biomass and activity causing a higher carbon recycling and thereby lower δ13C values. We conclude that δ13C was more related to the net areal photosynthesis rate and carbon recycling, rather than to the growth rate of the biofilms.

  6. Tracing carbon sources through aquatic and terrestrial food webs using amino acid stable isotope fingerprinting.

    Directory of Open Access Journals (Sweden)

    Thomas Larsen

    Full Text Available Tracing the origin of nutrients is a fundamental goal of food web research but methodological issues associated with current research techniques such as using stable isotope ratios of bulk tissue can lead to confounding results. We investigated whether naturally occurring δ(13C patterns among amino acids (δ(13CAA could distinguish between multiple aquatic and terrestrial primary production sources. We found that δ(13CAA patterns in contrast to bulk δ(13C values distinguished between carbon derived from algae, seagrass, terrestrial plants, bacteria and fungi. Furthermore, we showed for two aquatic producers that their δ(13CAA patterns were largely unaffected by different environmental conditions despite substantial shifts in bulk δ(13C values. The potential of assessing the major carbon sources at the base of the food web was demonstrated for freshwater, pelagic, and estuarine consumers; consumer δ(13C patterns of essential amino acids largely matched those of the dominant primary producers in each system. Since amino acids make up about half of organismal carbon, source diagnostic isotope fingerprints can be used as a new complementary approach to overcome some of the limitations of variable source bulk isotope values commonly encountered in estuarine areas and other complex environments with mixed aquatic and terrestrial inputs.

  7. Carbonate Chemistry and Isotope Characteristics of Groundwater of Ljubljansko Polje and Ljubljansko Barje Aquifers in Slovenia

    Science.gov (United States)

    2013-01-01

    Ljubljansko polje and Ljubljansko Barje aquifers are the main groundwater resources for the needs of Ljubljana, the capital of Slovenia. Carbonate chemistry and isotope analysis of the groundwater were performed to acquire new hydrogeological data, which should serve as a base for improvement of hydrogeological conceptual models of both aquifers. A total of 138 groundwater samples were collected at 69 sampling locations from both aquifers. Major carbonate ions and the stable isotope of oxygen were used to identify differences in the recharging areas of aquifers. Four groups of groundwater were identified: (1) Ljubljansko polje aquifer, with higher Ca2+values, as limestone predominates in its recharge area, (2) northern part of Ljubljansko Barje aquifer, with prevailing dolomite in its recharge area, (3) central part of Ljubljansko Barje aquifer, which lies below surface cover of impermeable clay and is poor in carbonate, and (4) Brest and Iški vršaj aquifer in the southern part of Ljubljansko Barje with higher Mg2+ in groundwater and dolomite prevailing in its recharge area. The radioactive isotope tritium was also used to estimate the age of groundwater. Sampled groundwater is recent with tritium activity between 4 and 8 TU and residence time of up to 10 years. PMID:24453928

  8. Tracing carbon sources through aquatic and terrestrial food webs using amino acid stable isotope fingerprinting.

    Science.gov (United States)

    Larsen, Thomas; Ventura, Marc; Andersen, Nils; O'Brien, Diane M; Piatkowski, Uwe; McCarthy, Matthew D

    2013-01-01

    Tracing the origin of nutrients is a fundamental goal of food web research but methodological issues associated with current research techniques such as using stable isotope ratios of bulk tissue can lead to confounding results. We investigated whether naturally occurring δ(13)C patterns among amino acids (δ(13)CAA) could distinguish between multiple aquatic and terrestrial primary production sources. We found that δ(13)CAA patterns in contrast to bulk δ(13)C values distinguished between carbon derived from algae, seagrass, terrestrial plants, bacteria and fungi. Furthermore, we showed for two aquatic producers that their δ(13)CAA patterns were largely unaffected by different environmental conditions despite substantial shifts in bulk δ(13)C values. The potential of assessing the major carbon sources at the base of the food web was demonstrated for freshwater, pelagic, and estuarine consumers; consumer δ(13)C patterns of essential amino acids largely matched those of the dominant primary producers in each system. Since amino acids make up about half of organismal carbon, source diagnostic isotope fingerprints can be used as a new complementary approach to overcome some of the limitations of variable source bulk isotope values commonly encountered in estuarine areas and other complex environments with mixed aquatic and terrestrial inputs.

  9. Carbonate Chemistry and Isotope Characteristics of Groundwater of Ljubljansko Polje and Ljubljansko Barje Aquifers in Slovenia

    Directory of Open Access Journals (Sweden)

    Sonja Cerar

    2013-01-01

    Full Text Available Ljubljansko polje and Ljubljansko Barje aquifers are the main groundwater resources for the needs of Ljubljana, the capital of Slovenia. Carbonate chemistry and isotope analysis of the groundwater were performed to acquire new hydrogeological data, which should serve as a base for improvement of hydrogeological conceptual models of both aquifers. A total of 138 groundwater samples were collected at 69 sampling locations from both aquifers. Major carbonate ions and the stable isotope of oxygen were used to identify differences in the recharging areas of aquifers. Four groups of groundwater were identified: (1 Ljubljansko polje aquifer, with higher Ca2+ values, as limestone predominates in its recharge area, (2 northern part of Ljubljansko Barje aquifer, with prevailing dolomite in its recharge area, (3 central part of Ljubljansko Barje aquifer, which lies below surface cover of impermeable clay and is poor in carbonate, and (4 Brest and Iški vršaj aquifer in the southern part of Ljubljansko Barje with higher Mg2+ in groundwater and dolomite prevailing in its recharge area. The radioactive isotope tritium was also used to estimate the age of groundwater. Sampled groundwater is recent with tritium activity between 4 and 8 TU and residence time of up to 10 years.

  10. Carbonate chemistry and isotope characteristics of groundwater of Ljubljansko polje and Ljubljansko Barje aquifers in Slovenia.

    Science.gov (United States)

    Cerar, Sonja; Urbanc, Janko

    2013-01-01

    Ljubljansko polje and Ljubljansko Barje aquifers are the main groundwater resources for the needs of Ljubljana, the capital of Slovenia. Carbonate chemistry and isotope analysis of the groundwater were performed to acquire new hydrogeological data, which should serve as a base for improvement of hydrogeological conceptual models of both aquifers. A total of 138 groundwater samples were collected at 69 sampling locations from both aquifers. Major carbonate ions and the stable isotope of oxygen were used to identify differences in the recharging areas of aquifers. Four groups of groundwater were identified: (1) Ljubljansko polje aquifer, with higher Ca(2+)values, as limestone predominates in its recharge area, (2) northern part of Ljubljansko Barje aquifer, with prevailing dolomite in its recharge area, (3) central part of Ljubljansko Barje aquifer, which lies below surface cover of impermeable clay and is poor in carbonate, and (4) Brest and Iški vršaj aquifer in the southern part of Ljubljansko Barje with higher Mg(2+) in groundwater and dolomite prevailing in its recharge area. The radioactive isotope tritium was also used to estimate the age of groundwater. Sampled groundwater is recent with tritium activity between 4 and 8 TU and residence time of up to 10 years.

  11. Carbon isotope fractionation during permanganate oxidation of chlorinated ethylenes (cDCE, TCE, PCE).

    Science.gov (United States)

    Poulson, Simon R; Naraoka, Hiroshi

    2002-08-01

    Permanganate oxidation of chlorinated ethylenes is an attractive technique to effect remediation of these important groundwater contaminants. Stable carbon isotope fractionation associated with permanganate oxidation of trichloroethylene (TCE), tetrachloroethylene (PCE), and cis-1,2-dichloroethylene (cDCE) has been measured, to study the possibility of applying stable carbon isotope analysis as a technique to assess the efficacy of remediation implemented by permanganate oxidation. Average carbon isotope fractionation factors of alphaTCE = 0.9786, alphaPCE = 0.9830, and alphacDCE = 0.9789 were obtained, although the fractionation factor for PCE may be interpreted to change from a value of 0.9779-0.9871 during the course of the reaction. The fractionation factors for all three compounds are quite similar, in contrast to the variation of fractionation factors vs degree of chlorination observed for other degradative processes, such as microbial dechlorination. This may be due to a common rate-determining step for permanganate oxidation of all three compounds studied. The large fractionation factors and the relative lack of dependence of the fractionation factors upon other environmental factors (e.g. oxidation rate, presence of multiple contaminants, incomplete oxidation, presence of chloride in solution) indicate that monitoring delta13C values of chlorinated ethylenes during oxidation with permanganate may be a sensitive, and potentially quantitative, technique to investigate the extent of degradation.

  12. Carbon isotope excursions and the oxidant budget of the Ediacaran atmosphere and ocean

    Science.gov (United States)

    Bristow, Thomas F.; Kennedy, Martin J.

    2008-11-01

    A possible global drop in marine carbon isotope values to aslow as -12 Peedee belemnite (PDB), recorded in the EdiacaranShuram Formation of Oman, has been attributed to the non-steady-stateoxidation of oceanic dissolved organic carbon (DOC) resultingfrom the rise in atmospheric oxygen to near modern values atthe end of the Precambrian. Geologic constraints indicate thatthe excursion lasted between 25 and 50 m.y., requiring a DOCpool thousands of times to 10,000 times the modern inventoryto conform with carbon isotope mass balance calculations fora -12 excursion. At the consequent rates of DOC oxidation,oceanic sulfate and oxygen in the atmosphere and oceans areexhausted on a time scale of 800 k.y. Oxidant depletion isincompatible with independent geochemical and biological indicatorsthat show oceanic sulfate and oxygen levels were maintainedor increased during the Shuram excursion. Furthermore, a DOC-drivenexcursion does not explain strong covariation between the carbonand oxygen isotope record. These indicators show that negativeisotope excursions recorded in the Shuram and other Ediacaransections are unlikely to represent a global ocean signal.

  13. Hydrogen and carbon isotope systematics in hydrogenotrophic methanogenesis under H2-limited and H2-enriched conditions: implications for the origin of methane and its isotopic diagnosis

    Science.gov (United States)

    Okumura, Tomoyo; Kawagucci, Shinsuke; Saito, Yayoi; Matsui, Yohei; Takai, Ken; Imachi, Hiroyuki

    2016-12-01

    Hydrogen and carbon isotope systematics of H2O-H2-CO2-CH4 in hydrogenotrophic methanogenesis and their relation to H2 availability were investigated. Two H2-syntrophic cocultures of fermentatively hydrogenogenic bacteria and hydrogenotrophic methanogens under conditions of pure cultures of hydrogenotrophic methanogens under conditions of 105 Pa-H2 were tested. Carbon isotope fractionation between CH4 and CO2 during hydrogenotrophic methanogenesis was correlated with pH2, as indicated in previous studies. The hydrogen isotope ratio of CH4 produced during rapid growth of the thermophilic methanogen Methanothermococcus okinawensis under high pH2 conditions ( 105 Pa) was affected by the isotopic composition of H2, as concluded in a previous study of Methanothermobacter thermautotrophicus. This " {δ D}_{{H}_2} effect" is a possible cause of the diversity of previously reported values for hydrogen isotope fractionation between CH4 and H2O examined in H2-enriched culture experiments. Hydrogen isotope fractionation between CH4 and H2O, defined by (1000 + {δ D}_{{CH}_4} )/(1000 + {δ D}_{{H}_2O} ), during hydrogenotrophic methanogenesis of the H2-syntrophic cocultures was in the range 0.67-0.69. The hydrogen isotope fractionation of our H2-syntrophic dataset overlaps with those obtained not only from low- pH2 experiments reported so far but also from natural samples of "young" methane reservoirs (0.66-0.74). Conversely, such hydrogen isotope fractionation is not consistent with that of "aged" methane in geological samples (≥0.79), which has been regarded as methane produced via hydrogenotrophic methanogenesis from the carbon isotope fractionation. As a possible process inducing the inconsistency in hydrogen isotope signatures between experiments and geological samples, we hypothesize that the hydrogen isotope signature of CH4 imprinted at the time of methanogenesis, as in the experiments and natural young methane, may be altered by diagenetic hydrogen isotope exchange

  14. Boron isotopic fractionation in laboratory inorganic carbonate precipitation: Evidence for the incorpora-tion of B(OH)3 into carbonate

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    A laboratory inorganic carbonate precipitation experiment at high pH of 8.96 to 9.34 was conducted, and the boron isotopic fractionations of the precipitated carbonate were measured. The data show that boron isotopic fractionation factors (αcarb-3) between carbonate and B(OH)3 in seawater range 0.937 and 0.965, with an average value of 0.953. Our results together with those reported by Sanyal and collabo-rators show that the αcarb-3 values between carbonate and B(OH)3 in solution are not constant but are negatively correlated with the pH of seawater. The measured boron isotopic compositions of carbonate precipitation (δ11Bcarb) do not exactly lie on the best-fit theoretical δ 11B4-pH curves and neither do they exactly parallel any theoretical δ 11B4-pH curves. Therefore, it is reasonable to argue that a changeable proportion of B(OH)3 with pH of seawater should also be incorporated into carbonate except for the dominant incorporation of B(OH)4- in carbonate . Hence, in the reconstruction of the paleo-pH of sea-water from boron isotopes in marine biogenic carbonates, the use of theoretical boron isotopic frac-tionation factor (α4-3) between B(OH)4- and B(OH)3 is not suitable. Instead, an empirical equation should be established.

  15. Mechanisms controlling the carbon stable isotope composition of phytoplankton in karst reservoirs

    Directory of Open Access Journals (Sweden)

    Baoli Wang

    2013-02-01

    Full Text Available In order to systematically understand the mechanisms controlling the carbon stable isotope composition of phytoplankton (δ13CPHYin freshwater ecosystems, seasonal changes in δ13CPHY and related environmental factors were determined in karst reservoirs from the Wujiang river basin, China. Substantial and systematic differences within seasons and reservoirs were observed for δ13CPHY, which ranged from -39.2‰ to -15.1‰. An increase in water temperature triggered fast growth of phytoplankton which assimilated more dissolved inorganic carbon (DIC, resulting in the increase of δ13CPHY, δ13CDIC and pH. When the concentration of dissolved carbon dioxide (CO2 was less than 10 mmol L–1, phytoplankton shifted to using HCO3– as a carbon source. This resulted in the sharp increase of δ13CPHY. The carbon stable isotope composition of phytoplankton tended to decrease with the increase of Bacillariophyta, which dominated in January and April, but tended to increase with the increase of Chlorophyta and Dinophyta, which dominated in July. Multiple regression equations suggested that the influence of biological factors such as taxonomic difference on δ13CPHY could be equal or more important than that of physical and chemical factors. Thus, the effect of taxonomic differences on δ13CPHY must be considered when explaining the δ13C of organic matter in lacustrine ecosystem.

  16. Evolution of Sulfur Isotopes and Oceanic Oxygenation Recorded in a Neoproterozoic Cap Carbonate From the Chaidam Block, China

    Science.gov (United States)

    Shen, B.; Xiao, S.; Kaufman, A.; Zhou, C.

    2006-12-01

    Neoproterozoic successions in the Chaidam Block, northwestern China, include the Hongtiegou Formation, which consists of a 20-meter thick, reddish diamictite with widespread dropstones and outsized clasts. The age of the Hongtiegou diamictite is unknown, but recent biostratigraphic correlations support a Neoproterozoic assignment. The glacial deposit is immediately overlain by a 5-meter thick carbonate of the basal Zhoujieshan Formation, which we interpret as a classic post-glacial cap carbonate. However, carbon isotope compositions of samples from this unit are near zero or slightly positive (up to ~ 2‰), which contrasts with the strongly negative (ca. -5‰) values recorded in the basal portions of most other post-glacial Neoproterozoic caps. Trace sulfate concentrations in samples of the carbonate are notably high, with an average of 366 ± 266 ppm. In the lower 2.5 meters of the Zhoujieshan cap (stage I) sulfur isotope compositions of both carbonate associated sulfate (CAS) and sulfides isolated from the same sample are indistinguishable from each other, and rise in concert by over 10% to values around +22‰. Above this level (stage II), 34S abundances of sulfides continue to increase to a peak of +27‰, but CAS values fall back to ~15‰. As a result isotopic differences between sulfides and sulfates are near zero in stage I and around 10% in stage II. The evolution of both systems in the lower half of the deposit suggests that seawater sulfate must have evolved to progressively heavier 34S compositions, and that sulfate in pore waters ¨C where sulfate reducing bacteria were active ¨C was quantitatively reduced to pyrite. This might result from the progressive distillation of sulfate from seawater by an enhanced rain of carbonate, in addition to bacterial reduction of sulfate, in the glacial aftermath. The anomalous isotope systematics of stage II are difficult to model, but might signal a new source and higher abundances of oceanic sulfate, based on

  17. Testing of an automated online EA-IRMS method for fast and simultaneous carbon content and stable isotope measurement of aerosol samples

    Science.gov (United States)

    Major, István; Gyökös, Brigitta; Túri, Marianna; Futó, István; Filep, Ágnes; Hoffer, András; Molnár, Mihály

    2016-04-01

    Comprehensive atmospheric studies have demonstrated that carbonaceous aerosol is one of the main components of atmospheric particulate matter over Europe. Various methods, considering optical or thermal properties, have been developed for quantification of the accurate amount of both organic and elemental carbon constituents of atmospheric aerosol. The aim of our work was to develop an alternative fast and easy method for determination of the total carbon content of individual aerosol samples collected on prebaked quartz filters whereby the mass and surface concentration becomes simply computable. We applied the conventional "elemental analyzer (EA) coupled online with an isotope ratio mass spectrometer (IRMS)" technique which is ubiquitously used in mass spectrometry. Using this technique we are able to measure simultaneously the carbon stable isotope ratio of the samples, as well. During the developing process, we compared the EA-IRMS technique with an off-line catalytic combustion method worked out previously at Hertelendi Laboratory of Environmental Studies (HEKAL). We tested the combined online total carbon content and stable isotope ratio measurement both on standard materials and real aerosol samples. Regarding the test results the novel method assures, on the one hand, at least 95% of carbon recovery yield in a broad total carbon mass range (between 100 and 3000 ug) and, on the other hand, a good reproducibility of stable isotope measurements with an uncertainty of ± 0.2 per mill. Comparing the total carbon results obtained by the EA-IRMS and the off-line catalytic combustion method we found a very good correlation (R2=0.94) that proves the applicability of both preparation method. Advantages of the novel method are the fast and simplified sample preparation steps and the fully automated, simu