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Sample records for carbon isotopic composition

  1. Soil Carbon: Compositional and Isotopic Analysis

    SciTech Connect

    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.

  2. Carbon isotopic composition of individual Precambrian microfossils.

    PubMed

    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.

  3. Carbon isotopic composition of individual Precambrian microfossils

    NASA Technical Reports Server (NTRS)

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

    2000-01-01

    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.

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

    NASA Technical Reports Server (NTRS)

    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.

  5. Factors affecting the isotopic composition of organic matter. (1) Carbon isotopic composition of terrestrial plant materials.

    PubMed

    Yeh, H W; Wang, W M

    2001-07-01

    The stable isotope composition of the light elements (i.e., H, C, N, O and S) of organic samples varies significantly and, for C, is also unique and distinct from that of inorganic carbon. This is the result of (1) the isotope composition of reactants, (2) the nature of the reactions leading to formation and post-formational modification of the samples, (3) the environmental conditions under which the reactions took place, and (4) the relative concentration of the reactants compared to that of the products (i.e., [products]/[reactants] ratio). This article will examine the carbon isotope composition of terrestrial plant materials and its relationship with the above factors. delta13C(PDB) values of terrestrial plants range approximately from -8 to -38%, inclusive of C3-plants (-22 to -38%), C4-plants (-8 to -15%) and CAM-plants (-13 to -30%). Thus, the delta13C(PDB) values largely reflect the photosynthesis pathways of a plant as well as the genetics (i.e., species difference), delta13C(PDB) values of source CO2, relevant humidity, CO2/O2 ratios, wind and light intensity etc. Significant variations in these values also exist among different tissues, different portions of a tissue and different compounds. This is mainly a consequence of metabolic reactions. Animals mainly inherit the delta13C(PDB) values of the foods they consume; therefore, their delta13C(PDB) values are similar. The delta13C(PDB) values of plant materials, thus, contain information regarding the inner workings of the plants, the environmental conditions under which they grow, the delta13C(PDB) values of CO2 sources etc., and are unique. Furthermore, this uniqueness is passed on to their derivative matter, such as animals, humus etc. Hence, they are very powerful tools in many areas of research, including the ecological and environmental sciences.

  6. The Li isotope composition of modern biogenic carbonates

    NASA Astrophysics Data System (ADS)

    Dellinger, M.; West, A. J.; Adkins, J. F.; Paris, G.; Eagle, R.; Freitas, P. S.; Bagard, M. L.; Ries, J. B.; Corsetti, F. A.; Pogge von Strandmann, P.; Ullmann, C. V.

    2015-12-01

    The lithium stable isotope composition (δ7Li) of sedimentary carbonates has great potential to unravel weathering rates and intensity in the past, with implications for understanding the carbon cycle over geologic time. However, so far very little is known about the potential influence of fractionation of the stable Li isotope composition of biogenic carbonates. Here, we investigate the δ7Li of various organisms (particularly mollusks, echinoderms and brachiopods) abundant in the Phanerozoic record, in order to understand which geologic archives might provide the best targets for reconstructing past seawater composition. The range of measured samples includes (i) modern calcite and aragonite shells from variable natural environments, (ii) shells from organisms grown under controlled conditions (temperature, salinity, pCO2), and (iii) fossil shells from a range of species collected from Miocene deposits. When possible, both the inner and outer layers of bivalves were micro-sampled to assess the intra-shell heterogeneity. For calcitic shells, the measured δ7Li of bivalve species range from +32 to +41‰ and is systematically enriched in the heavy isotope relative to seawater (31 ‰) and to inorganic calcite, which is characterized by Δ7Licalcite-seawater = -2 to -5‰ [1]. The Li isotope composition of aragonitic bivalves, ranging from +16 to +22‰, is slightly fractionated to both high and low δ7Li relative to inorganic aragonite. The largest intra-shell Li isotope variability is observed for mixed calcite-aragonite shells (more than 20‰) whereas in single mineralogy shells, intra-shell δ7Li variability is generally less than 3‰. Overall, these results suggest a strong influence of vital effects on Li isotopes during bio-calcification of bivalve shells. On the contrary, measured brachiopods systematically exhibit fractionation that is very similar to inorganic calcite, with a mean δ7Li of 27.0±1.5‰, suggesting that brachiopods may provide good

  7. Behaviour of Structural Carbonate Stable Carbon and Oxygen Isotope Compositions in Bioapatite During Burning of Bone

    NASA Astrophysics Data System (ADS)

    Munro, L. E.; Longstaffe, F. J.; White, C. D.

    2003-12-01

    Bioapatite, the principal inorganic phase comprising bone, commonly contains a small fraction of carbonate, which has been substituted into the phosphate structure during bone formation. The isotopic compositions of both the phosphate oxygen and the structural carbonate oxygen are now commonly used in palaeoclimatological and bioarchaeological investigations. The potential for post-mortem alteration of these isotopic compositions, therefore, is of interest, with the behaviour of structural carbonate being of most concern. In bioarchaeological studies, alteration of bone isotopic compositions has the potential to occur not only during low-temperature processes associated with burial but also during food preparation involving heating (burning, boiling). Here, we examine the stable isotopic behaviour of structural carbonate oxygen and carbon, and coexisting phosphate oxygen during the burning of bone. Freshly deceased (6<8 months) white-tailed deer leg bones (Odocoileus virginianus) were collected from Pinery Provincial Park, Ontario, Canada. Each long bone was sectioned and incrementally heated from 25 to 900° C, in 25° intervals. The samples were then ground to a standardized grain-size (45<63μ m), and changes in bioapatite crystallinity (CI) were determined using powder X-ray diffraction (pXRD), and Fourier transform infra-red spectroscopy (FTIR). Combined differential thermal and thermogravimetric analyses (DTA/TG) were used to evaluate weight loss and associated reactions during heating. Stable carbon isotope compositions of the bioapatite remain relatively constant (+/-1‰ ) during heating to 650° C. A 4‰ increase in stable carbon isotopic composition then occurs between 650-750° C, accompanied by an increase in CI, followed by a 10‰ decline at temperatures above 800° C, as carbonate carbon is lost. Carbonate and phosphate oxygen isotopic compositions are correlated over the entire heating range, with carbonate being enriched relative to phosphate by

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

    PubMed

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

    2007-01-02

    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 CO(2) in the middle atmosphere, which has not been previously reported. The mass-independent fractionation of oxygen in CO(2) can be satisfactorily explained by the exchange reaction with O((1)D). In the stratosphere, the major source of O((1)D) is O(3) photolysis. Higher in the mesosphere, we discover that the photolysis of (16)O(17)O and (16)O(18)O by solar Lyman-alpha radiation yields O((1)D) 10-100 times more enriched in (17)O and (18)O than that from ozone photodissociation at lower altitudes. This latter source of heavy O((1)D) has not been considered in atmospheric simulations, yet it may potentially affect the "anomalous" oxygen signature in tropospheric CO(2) that should reflect the gross carbon fluxes between the atmosphere and terrestrial biosphere. Additional laboratory and atmospheric measurements are therefore proposed to test our model and validate the use of CO(2) isotopic fractionation as a tracer of atmospheric chemical and dynamical processes.

  9. Magnesium isotopic compositions of the Mesoproterozoic dolostones: Implications for Mg isotopic systematics of marine carbonates

    NASA Astrophysics Data System (ADS)

    Huang, Kang-Jun; Shen, Bing; Lang, Xian-Guo; Tang, Wen-Bo; Peng, Yang; Ke, Shan; Kaufman, Alan J.; Ma, Hao-Ran; Li, Fang-Bing

    2015-09-01

    Available Mg isotope data indicate that dolostones of different ages have overlapping range of Mg isotopic composition (δ26Mg) and there is no systematic difference among different types of dolomites. To further explore the Mg isotopic systematics of dolomite formation, we measured Mg isotopic compositions of Mesoproterozoic dolostones from the Wumishan Formation in North China Block, because dolomite formation in Mesoproterozoic might have been fundamentally different from the younger counterparts. Based on petrographic observations, three texturally-different dolomite phases (dolomicrite, subhedral dolomite and anhedral dolomite) are recognized in the Wumishan dolostones. Nevertheless, these three types of dolomites have similar δ26Mg values, ranging from -1.35‰ to -1.72‰, which are indistinguishable from Neoproterozoic and Phanerozoic dolostones. To explain δ26Mg values of dolostones, we simulate the Mg isotopic system during dolomite formation by applying the one-dimensional Diffusion-Advection-Reaction (1D-DAR) model, assuming that the contemporaneous seawater is the Mg source of dolostone. The 1D-DAR modeling results indicate that the degree of dolomitization is controlled by sedimentation rate, seawater Mg concentration, temperature, and reaction rate of dolomite formation, whereas Mg isotopic composition of dolostone is not only dependent on these factors, but also affected by δ26Mg of seawater and isotope fractionation during dolomite formation. Moreover, the 1D-DAR model predicts that dolomite formation within sediments has limited range of variation in δ26Mg with respect to limestones. Furthermore, the modeling results demonstrate that dolostone is always isotopically heavier than Ca-carbonate precipitated from seawater, explaining the systematic isotopic difference between dolostones and limestones. Finally, we can infer from the 1D-DAR model that early-formed dolostone at shallower depth of sediments is always isotopically lighter than that

  10. The carbon isotopic composition of Novo Urei diamonds

    NASA Technical Reports Server (NTRS)

    Fisenko, A. V.; Semjenova, L. F.; Verchovsky, A. B.; Russell, S. S.; Pillinger, C. T.

    1993-01-01

    The carbon isotopic composition of diamond grains isolated from the Novo Urei meteorite are discussed. A diamond separate was obtained from 2g of whole rock using the chemical treatments described aimed at obtaining very pure diamond. X ray diffraction of the residue, which represented 5000 ppm of the parent mass, indicated only the presence of the desired mineral. The diamond crystals were 1-30 microns in diameter, and some grains had a yellow color. The chemical treatments were followed by a size separation to give a 1-10 microns and a 5-30 microns fraction, which were named DNU-1 and DNU-2, respectively.

  11. Terrestrial and Meteorite Carbon Appear to Have the Same Isotopic Composition

    PubMed Central

    Libby, W. F.

    1971-01-01

    The carbon-isotope ratio recently obtained for the carbon found in the Murchison meteorite, which has been shown (by the racemic nature of twelve component amino acids) to be free of terrestrial contamination, agrees with that for average terrestrial sediments. This finding indicates that the earth and the stony meteorites contain carbon of the same isotopic composition. PMID:16591904

  12. Seasonality of Leaf Carbon Isotopic Composition and Leaf Water Isotopic Enrichment in a Mixed Evergreen Forest in Southern California

    NASA Astrophysics Data System (ADS)

    Santiago, L. S.; Sickman, J. O.; Goulden, M.; DeVan, C.; Pasquini, S. C.; Pivovaroff, A. L.

    2011-12-01

    Leaf carbon isotopic composition and leaf water isotopic enrichment reflect physiological processes and are important for linking local and regional scale processes to global patterns. We investigated how seasonality affects the isotopic composition of bulk leaf carbon, leaf sugar carbon, and leaf water hydrogen under a Mediterranean climate. Leaf and stem samples were collected monthly from four tree species (Calocedrus decurrens, Pinus lambertiana, Pinus ponderosa, and Quercus chrysolepis) at the James San Jacinto Mountain Reserve in southern California. Mean monthly bulk leaf carbon isotopic composition varied from -34.5 % in P. ponderosa to -24.7 % in P. lambertiana and became more depleted in 13C from the spring to the summer. Mean monthly leaf sugar varied from -29.3 % in P. ponderosa to -21.8 % in P. lambertiana and was enriched in 13C during the winter, spring and autumn, but depleted during the mid-summer. Leaf water hydrogen isotopic composition was 28.4 to 68.8 % more enriched in deuterium than source water and this enrichment was greater as seasonal drought progressed. These data indicate that leaf carbon and leaf water hydrogen isotopic composition provide sensitive measures that connect plant physiological processes to short-term climatic variability.

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

    NASA Astrophysics Data System (ADS)

    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

  14. Calcium and Oxygen Isotopic Composition of Calcium Carbonates

    NASA Astrophysics Data System (ADS)

    Niedermayr, Andrea; Eisenhauer, Anton; Böhm, Florian; Kisakürek, Basak; Balzer, Isabelle; Immenhauser, Adrian; Jürgen Köhler, Stephan; Dietzel, Martin

    2016-04-01

    Different isotopic systems are influenced in multiple ways corresponding to the crystal structure, dehydration, deprotonation, adsorption, desorption, isotope exchange and diffusion processes. In this study we investigated the structural and kinetic effects on fractionation of stable Ca- and O-isotopes during CaCO3 precipitation. Calcite, aragonite and vaterite were precipitated using the CO2 diffusion technique[1]at a constant pH of 8.3, but various temperatures (6, 10, 25 and 40° C) and precipitation rates R (101.5 to 105 μmol h-1 m-2). The calcium isotopic fractionation between solution and vaterite is lower (Δ44/40Ca= -0.10 to -0.55 ‰) compared to calcite (-0.69 to -2.04 ‰) and aragonite (-0.91 to -1.55 ‰). In contrast the fractionation of oxygen isotopes is highest for vaterite (32.1 ‰), followed by aragonite (29.2 ‰) and calcite (27.6 ‰) at 25° C and equilibrium. The enrichment of 18O vs. 16O in all polymorphs decreases with increasing precipitation rate by around -0.7 ‰ per log(R). The calcium isotopic fractionation between calcite/ vaterite and aqueous Ca2+ increases with increasing precipitation rate by ˜0.45 ‰ per log(R) and ˜0.1 ‰ per log(R) at 25° C and 40° C, respectively. In contrast the fractionation of Ca-isotopes between aragonite and aqueous Ca2+ decreases with increasing precipitation rates. The large enrichment of 18O vs. 16O isotopes in carbonates is related to the strong bond of oxygen to the small and highly charged C4+-ion. In contrast equilibrium isotopic fractionation between solution and calcite or vaterite is nearly zero as the Ca-O bond length is similar for calcite, vaterite and the hydrated Ca. Aragonite incorporates preferentially the lighter 40Ca isotope as it has very large Ca-O bonds in comparison to the hydrated Ca. At the crystal surface the lighter 40Ca isotopes are preferentially incorporated as dehydration and diffusion of lighter isotopes are faster. Consequently, the surface becomes enriched in 40

  15. Isotope composition of carbon in the carbonates of the Gumbeykan scheelite deposits in the southern Urals

    SciTech Connect

    Korzhinskii, A.F.; Mamchur, G.P.; Yarynych, O.A.

    1980-10-01

    Through investigations of the isotope composition of carbon of various generations and carbonates from marbles, skarns, and nested and vein scheelite orebodies, the probable source of carbon of these carbonates has been established as a mixture of sedimentary carbonates, carbon dioxide with carbonic acid that was formed by oxidation of the organic matter from sedimentary terrane (..delta..C/sup 13/ - 0.05 to -0.62%). In the calcite and dolomite phenocrysts of marble and the coarse-grained dolostone, containing scheelite, the carbon was lighter (..delta..C/sup 13/ from -0.60 to -0.87%). For the dolomite and ankerite from scheelite pockets of the Balkan deposit and quartz veins of the Buranovo, ..delta..C/sup 13/ varied from -0.44 to -0.87%. The lightest carbon found in strontianite (..delta..C/sup 13/ = -1.32%), located near the coating of the organic matter (..delta..C/sup 13/ = -1.26%) in fractures of the quartz vein of the Buranovo deposit. In the section through the orebodies and near-ore diffusion-metasomatic zones of the Balkan deposit, the lessening of carbon in the carbonates was observed, with increasing distance away from the fracture. ..delta..C/sup 13/ in the altered granitoids ranged from -0.44 to -1.03%; while in the diopside-wollastonite hornfels, from -0.89 to 1.13%. The lessening in weight of the carbon is explained by diffusional fractionation of the isotopes caused apparently by the differential movement of volatile mixtures of carbon during ore-forming processes and the formation of their diffusion-metasomatic zones.

  16. Soil drying effects on the carbon isotope composition of soil respiration

    EPA Science Inventory

    Stable isotopes are used widely as a tool for determining sources of carbon (C) fluxes in ecosystem C studies. Environmental factors that change over time, such as moisture, can create dynamic changes in the isotopic composition of C assimilated by plants, and offers a unique opp...

  17. Determination of the abundance and carbon isotope composition of elemental carbon in sediments

    NASA Astrophysics Data System (ADS)

    Bird, Michael I.; Gröcke, Darren R.

    1997-08-01

    We report measurements of the susceptibility of a variety of elemental and organic carbon samples to oxidative degradation using both acid dichromate and basic peroxide reagents. Organic carbon is rapidly oxidized using either reagent, or both reagents sequentially. Elemental carbon exhibits a wide range of susceptibilities to oxidation related both to the degree to which the precursor plant material was carbonized during pyrolysis and to the surface area available for oxidation. Despite a range of susceptibilities, a component of oxidation-resistant elemental carbon has been identified which can be reproducibly separated from organic contaminants. The carbon isotope composition (δ 13C value) of the precursor plant materials underwent a 0-1.6‰ decrease during the production of the elemental carbon by pyrolysis, while the subsequent oxidative degradation of the samples resulted in only small (generally < 0.5%o) changes in the δ 13C value of the remaining elemental carbon. The results suggest that the technique can be used to obtain records of elemental carbon abundance in marine sediment cores, and thus a record of the intensity of biomass burning on adjacent continental land masses in the geologic past. In addition, the δ 13C value of the elemental carbon can provide an indication of the type of vegetation being burnt.

  18. Concentration and isotopic composition of carbon and sulfur in apollo 11 lunar samples.

    PubMed

    Kaplan, I R; Smith, J W

    1970-01-30

    The concentration of carbon and sulfur in six samples ranged between 20 to 200 and 650 to 2300 parts per million, respectively. Carbon was present in gaseous, volatilizable, and nonvolatile forms, and terrestrial contaminants were recognized. Sulfur appeared to exist only as acid-volatile sulfide. The bulk fines contain a high concentration of carbon and a low concentration of sulfur. They are always enriched in the heavier isotope carbon-13 or sulfur-34. The fine-grained basaltic rocks show the reverse relation; lowest carbon, highest sulfide concentrations, and no apparent enrichment in heavy isotopes. The breccias are of intermediate composition.

  19. Carbon-isotopic composition of soil-respired carbon dioxide in static closed chambers at equilibrium.

    PubMed

    Mora, Germán; Raich, James W

    2007-01-01

    The carbon-isotopic composition (delta13C) of soil-respired CO2 has been employed to evaluate soil carbon-cycling processes and the contribution of soil CO2 emissions to canopy and tropospheric air. These evaluations can be successful only when accurate isotope values of soil-respired CO2 are available. Here, we tested the robustness of delta13C values of soil-respired CO2 obtained after long incubations in static closed chambers that were initially flushed with soil air. The rationale of this approach is that the equilibrium carbon-isotope values of chamber-headspace CO2 are theoretically equal to those of CO2 produced within the soil. Static closed chambers were installed in replicated grass monocultures, and measurements of headspace CO2 concentrations and delta13C values were performed at regular time intervals for 24 h in July 2005. The results revealed no significant effects of grass species on headspace CO2 concentrations or delta13C values (repeated measures analysis of variance (ANOVA), P>0.1). As predicted by theory, isotope values asymptotically approached equilibrium conditions, which in our experimental setting occurred after 10 h. This good match between model predictions and our results suggests that an accurate determination of delta13C values of CO2 produced within soils is obtained through the isotopic measurement of chamber-headspace CO2 once equilibrium conditions have been reached with the underlying soils. An additional advantage of this approach is that only one sample per chamber is required, which, combined with the low uncertainties of these measurements, facilitates the investigation of the spatial (landscape) variability of soil-respired CO2.

  20. The Suess Effect and Additional Impacts on the Carbon Isotope Composition of a Belizean Coral

    NASA Astrophysics Data System (ADS)

    Greer, L.; Bunn, S.; Humston, R.; Swart, P. K.; Curran, H.; Rose, L. E.

    2011-12-01

    Recent work has shown that the geochemistry of coral skeletons can reflect large-scale changes in the ocean carbon isotope budget as influenced by the anthropogenic influx of fossil fuel carbon to the atmosphere (the Suess Effect). Yet not all coral carbon records reflect just atmospheric controls on carbon. This study assesses the relative influence of the Suess Effect on carbon chemistry within a Belizean Montastrea faveolota colony and interprets deviations from the Suess Effect signal. The coral sample used for this study was collected off Wee Wee Caye, in South-Central Belize offshore of the Sittee River, Stann Creek District in 2003. Coral carbonate was sampled at an average resolution of 15 samples per coral year. Carbon isotope data from the Belizean coral were compared with mean annual carbon isotope data from Atlantic corals in a study by Swart et. al (2010) to analyze the relative contribution of the Suess Effect and competing controls on the carbon isotope composition of Belizean waters. The observed pattern in the Belize coral suggested two distinct trends in carbon isotopic composition, and segmented regression analysis indicated a significant breakpoint occurs in this record in approximately 1965. Deforestation rates in Belize after the 1960's have been almost double that for the rest of Central America (2.3% vs. 1.2% annually) corresponding with a general shift from rural farming to large scale agriculture in Belize. Consequently, increased rates of deforestation in Belize may have been an important factor in carbon isotope budgets of the area over the last several decades. Compared with data averaged from Atlantic coral samples, annual carbon isotope values in Belizean coral declined more rapidly since the 1960's. We attribute this sharper decline in the Belizean coral to enhanced influx of terrestrial 'light' organic carbon to the reef over the study period.

  1. Natural gas constituent and carbon isotopic composition in petroliferous basins, China

    NASA Astrophysics Data System (ADS)

    Zhu, Guangyou; Wang, Zhengjun; Dai, Jinxing; Su, Jing

    2014-02-01

    There are abundant gas resources in petroliferous basins of China. Large to midsize gas fields are found in Eastern, central and Western of China. However, origin, constituents and isotopic composition of natural gas in different gas fields are varied distinctly, and some present strong chemical secondary alteration and show variation both in age and space. Based on the systematic analysis of constituents and carbon isotope of a large number of gas samples, combined with the geological characteristics, this paper classifies the origins of the gases, explores the gas isotope characteristics and evolutionary regulation with the variation time and space, and further discusses the distinctive geochemistry of the gases in China. These gases are dominated by dry gas, its methane carbon isotope values range from -10‰ to -70‰, ethane from -16‰ to -52‰, propane from -13‰ to -43‰, and butane from -18‰ to -34‰. The carbon isotopes of most gases show the characteristics of humic-derived gas and crude oil cracked gas. In addition, large primary biogenic gas fields have been discovered in the Qaidam basin; inorganic-derived alkane gases have been discovered in deep of the Songliao Basin. Half of these gas fields are characterized by the alkane carbon isotope reversal in different degrees. Research indicates there are several reasons can result in carbon isotope reversal. Firstly, gas charge of different genetic types or different source in one gas reservoir may cause carbon isotope reversal. Besides, high-over mature evolution of gas can also lead to the carbon isotopic reversal of alkanes. Thirdly, secondary alteration of hydrocarbons may also result in abnormal distribution of carbon isotope, isotope transforms to unusual light and heavy.

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

    PubMed

    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.

  3. Triple oxygen isotope composition of tropospheric carbon dioxide and terrestrial carbonates

    NASA Astrophysics Data System (ADS)

    Hofmann, M. E.; Horváth, B.; Pack, A.

    2011-12-01

    The triple oxygen isotope composition of tropospheric CO2 is a potential new tracer in urban air studies and for biosphere-atmosphere interactions [1]. In this study, we are analyzing CO2 from different provenances in order to trace the influx of anthropogenic CO2 to urban air and to test predictions on the stratosphere-troposphere exchange flux. Since July 2010, we are monitoring the triple oxygen isotope composition of CO2 in urban air in a two-week interval. For this purpose, carbon dioxide was extracted from ~450L of ambient air on the campus of the University of Göttingen using a Russian Doll type cryogenic trap [2]. The CO2 was analyzed by CO2-CeO2 equilibration at 685°C and subsequent IR laser fluorination of CeO2 and CF-irmMS [3]. All triple oxygen isotope data are reported as Δ17OTFL values relative to the terrestrial fractionation line (TFL) with a slope βTFL=0.5251 and an intercept γTFL=-0.014%. On average, the Δ17OTFL value of ambient CO2 was -0.11±0.05% (SD) with a seasonal cycle of 0.04±0.01%. Lower Δ17O values were observed during wintertime. In order to test the potential of Δ17O as a tracer for anthropogenic CO2, we analyzed CO2 from different combustion processes. Our results showed that the Δ17O anomaly of tropospheric O2 [4] is passed on fully, or partially to the combustion CO2 [5]. We estimate that elevated anthropogenic emission during wintertime could be responsible for a decrease in Δ17O of urban air CO2 of -0.02±0.01%. In order to predict the triple oxygen isotope composition of tropospheric CO2 on a global scale, we revised the box model calculation from Hoag et al. [1]. For the exponent β for CO2-water equilibrium, we assume that βCO2-water=0.522±0.001 [6]. Furthermore, we took into account that the Δ17OTFL value of CO2 released from soils is affected by kinetic fractionation. Thus, we obtained a Δ17OTFL value for global tropospheric CO2 of -0.13%. The model calculation agrees well with the Δ17OTFL value determined for

  4. Soil moisture effects on the carbon isotopic composition of soil respiration

    EPA Science Inventory

    The carbon isotopic composition ( 13C) 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 13C of soil respiration, which suggests indir...

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

    NASA Technical Reports Server (NTRS)

    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.

  6. Modelling carbon isotope composition of dissolved inorganic carbon and methane in marine porewaters

    NASA Astrophysics Data System (ADS)

    Meister, Patrick; Liu, Bo; Khalili, Arzhang; Barker Jørgensen, Bo

    2014-05-01

    Carbon isotope compositions of dissolved inorganic carbon (DIC) and methane (CH4) in marine sedimentary porewaters at near surface temperatures show extremely large variation in apparent fractionation covering a range from -100 ‰ to +30 ‰. This fractionation is essentially the result of microbial activity, but the mechanisms and factors controlling this fractionation are still incompletely understood. This study provides a reaction transport model approach to evaluate the effects of the most important processes and factors on carbon isotope distribution with the goal to better understand carbon isotope distribution in modern sediment porewaters and in the geological record. Our model results show that kinetic fractionation during methanogenesis, both through the acetoclastic and autotrophic pathways, results in a nearly symmetrical distribution of δ13C values in DIC and CH4 with respect to the isotope value of buried organic matter. An increased fractionation factor during methanogenesis leads to a larger difference between δ13CDIC and δ13CCH4. Near the sulphate methane transition zone, DIC is more depleted in 13C due to diffusive mixing with DIC produced by anaerobic oxidation of methane (AOM) and organoclastic sulphate reduction. The model also shows that an upward decrease in δ13CCH4 near the SMT can only be caused by equilibrium fractionation during AOM including a backward "leakage" of carbon from DIC to CH4 through the enzymatic pathway. However, this effect of reversibility has no influence on the DIC pool as long as methane is completely consumed at the SMT. Only a release of methane at the sediment-water interface, due to a fraction of the methane escaping re-oxidation, results in a small shift towards more positive δ13CDIC values. Methane escape at the SMT is possible if either the methane flux is too high to be entirely oxidized by AOM, or if bubbles of methane gas by-pass the sulphate reduction zone and escape episodically into the water column

  7. Carbon and hydrogen isotopic compositions of algae and bacteria from hydrothermal environments, Yellowstone National Park

    NASA Astrophysics Data System (ADS)

    Estep, Marilyn L. F.

    1984-03-01

    Stromatolites forming today on a small scale in hydrothermal environments are chemical and biological analogues of much larger Precambrian formations. Carbon isotopic composition varied as a function of CO 2 concentration, pH, and species composition. Stratiform, layered stromatolites grew in silica-depositing springs at 55° to 70°C; they consisted mainly of a unicellular alga, Synechococcus, and a filamentous, photosynthetic bacterium, Chloroflexus. These thermophiles become enriched in 12C as the concentration of carbon dioxide in the effluent waters increases. At a concentration of 40 ppm total inorganic C, and δ 13C of organic carbon was ˜ -12%., whereas at 900 ppm total inorganic C, the δ 13C of similar species was ˜ -25%.. Conical stromatolites or conophytons (principally a filamentous, blue-green alga Phormidium and Chloroflexus) grew at 40°-55°C. In older, broader conophytons, Chloroflexus was the dominant organism. Their δ 13C values were ˜ -18%. in a variety of hot springs. In carbonate-depositing springs, i.e., carbon dioxide saturated, conophytons and stromatolites consisting of a variety of blue-green algae and photosynthetic bacteria had the most negative δ 13C values (to -30%.). These carbon isotope ratios are directly comparable to carbon isotope ratios of kerogen from Precambrian stromatolites. The presence and activity of methanogenic bacteria or heterotrophic, aerobic and anaerobic bacteria did not alter significantly the δ 13C of the original organic matter. The hydrogen isotopic fractionation between thermophilic organisms and water is 0 to -74 for temperatures of 85° to 46°C, respectively. Acidophilic algae fractionated hydrogen isotopes to a lesser extent than did the photosynthetic organisms inhabiting neutral pH springs. Because organic matter retains some of its original isotopic signature, relationships of CO 2 levels, pH, temperature, and species composition between modern stromatolites and their environment and those of

  8. Monitoring of carbon isotope composition of snow cover for Tomsk region

    NASA Astrophysics Data System (ADS)

    Akulov, P. A.; Volkov, Y. V.; Kalashnikova, D. A.; Markelova, A. N.; Melkov, V. N.; Simonova, G. V.; Tartakovskiy, V. A.

    2016-11-01

    This article shows the potential of using δ13C values of pollutants in snow pack to study the human impact on the environment of Tomsk and its surroundings. We believe that it is possible to use a relation between the isotope compositions of a fuel and black carbon for establishing the origin of the latter. The main object of our investigation was dust accumulated by the snow pack in the winter of 2015-2016. The study of dust samples included the following steps: determination of the total carbon content in snow pack samples of Tomsk and its surroundings, extraction of black carbon from the dust, as well as the determination of δ13C values of the total and black carbon accumulated in the snow pack. A snow survey was carried out on the 26th of January and on the 18th of March. The relative carbon content in the dust samples was determined by using an EA Flash 2000 element analyzer. It varied from 3 to 24%. The maximum carbon content was in the dust samples from areas of cottage building with individual heating systems. The δ13C values of the total and black carbon were determined by using a DELTA V Advantage isotope mass spectrometer (TomTsKP SB RAS). The isotope composition of black carbon corresponded to that of the original fuel. This fact allowed identifying the origin of black carbon in some areas of Tomsk.

  9. Carbon isotopic composition of graphite grains in the EL Taco IAB iron meteorite

    NASA Astrophysics Data System (ADS)

    Zipfel, J.; Hutcheon, I. D.; Marti, K.

    1997-03-01

    Carbon isotopes have been analyzed in individual graphite grains of the El Taco iron meteorite. Graphite is present in four distinct petrographic associations and a total of 28 grains has been analyzed from all areas. The C isotopic composition varies from delta-C-13 = +4 to -29 percent and exhibits well-defined correlations with graphite morphology. The El Taco graphites contain much less N, with CN/C ratios of 0.0027 to 0.005, than graphites from Acapulco or unequilibrated ordinary chondrites. Graphite appears to retain an isotopic record of precursor materials despite high peak temperatures and may be an important tracer of early solar system proceses.

  10. Factors that control the stable carbon isotopic composition of methane produced in an anoxic marine sediment

    NASA Astrophysics Data System (ADS)

    Alperin, M. J.; Blair, N. E.; Albert, D. B.; Hoehler, T. M.; Martens, C. S.

    1992-09-01

    The carbon isotopic composition of methane produced in anoxic marine sediment is controlled by four factors: (1) the pathway of methane formation, (2) the isotopic composition of the methanogenic precursors, (3) the isotope fractionation factors for methane production, and (4) the isotope fractionation associated with methane oxidation. The importance of each factor was evaluated by monitoring stable carbon isotope ratios in methane produced by a sediment microcosm. Methane did not accumulate during the initial 42-day period when sediment contained sulfate, indicating little methane production from "noncompetitive" substrates. Following sulfate depletion, methane accumulation proceeded in three distinct phases. First, CO2 reduction was the dominant methanogenic pathway and the isotopic composition of the methane produced ranged from -80 to -94‰. The acetate concentration increased during this phase, suggesting that acetoclastic methanogenic bacteria were unable to keep pace with acetate production. Second, acetate fermentation became the dominant methanogenic pathway as bacteria responded to elevated acetate concentrations. The methane produced during this phase was progressively enriched in 13C, reaching a maximum δ13C value of -42‰. Third, the acetate pool experienced a precipitous decline from >5 mM to <20 μM and methane production was again dominated by CO2 reduction. The δ13C of methane produced during this final phase ranged from -46 to -58‰. Methane oxidation concurrent with methane production was detected throughout the period of methane accumulation, at rates equivalent to 1 to 8% of the gross methane production rate. Thus methane oxidation was too slow to have significantly modified the isotopic signature of methane. A comparison of microcosm and field data suggests that similar microbial interactions may control seasonal variability in the isotopic composition of methane emitted from undisturbed Cape Lookout Bight sediment.

  11. Factors that control the stable carbon isotopic composition of methane produced in an anoxic marine sediment

    NASA Technical Reports Server (NTRS)

    Alperin, M. J.; Blair, Neal E.; Albert, D. B.; Hoehler, T. M.; Martens, C. S.

    1993-01-01

    The carbon isotopic composition of methane produced in anoxic marine sediment is controlled by four factors: (1) the pathway of methane formation, (2) the isotopic composition of the methanogenic precursors, (3) the isotope fractionation factors for methane production, and (4) the isotope fractionation associated with methane oxidation. The importance of each factor was evaluated by monitoring stable carbon isotope ratios in methane produced by a sediment microcosm. Methane did not accumulate during the initial 42-day period when sediment contained sulfate, indicating little methane production from 'noncompetitive' substrates. Following sulfate depletion, methane accumulation proceeded in three distinct phases. First, CO2 reduction was the dominant methanogenic pathway and the isotopic composition of the methane produced ranged from -80 to -94 per thousand. The acetate concentration increased during this phase, suggesting that acetoclastic methanogenic bacteria were unable to keep pace with acetate production. Second, acetate fermentation became the dominant methanogenic pathway as bacteria responded to elevated acetate concentrations. The methane produced during this phase was progressively enriched in C-13, reaching a maximum delta(C-13) value of -42 per thousand. Third, the acetate pool experienced a precipitous decline from greater than 5 mM to less than 20 micro-M and methane production was again dominated by CO2 reduction. The delta(C-13) of methane produced during this final phase ranged from -46 to -58 per thousand. Methane oxidation concurrent with methane production was detected throughout the period of methane accumulation, at rates equivalent to 1 to 8 percent of the gross methane production rate. Thus methane oxidation was too slow to have significantly modified the isotopic signature of methane. A comparison of microcosm and field data suggests that similar microbial interactions may control seasonal variability in the isotopic composition of methane

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

    NASA Technical Reports Server (NTRS)

    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.

  13. Global synchronous changes in the carbon isotopic composition of carbonate sediments unrelated to changes in the global carbon cycle.

    PubMed

    Swart, Peter K

    2008-09-16

    The carbon isotopic (delta(13)C) composition of bulk carbonate sediments deposited off the margins of four carbonate platforms/ramp systems (Bahamas, Maldives, Queensland Plateau, and Great Australian Bight) show synchronous changes over the past 0 to 10 million years. However, these variations are different from the established global pattern in the delta(13)C measured in the open oceans over the same time period. For example, from 10 Ma to the present, the delta(13)C of open oceanic carbonate has decreased, whereas platform margin sediments analyzed here show an increase. It is suggested that the delta(13)C patterns in the marginal platform deposits are produced through admixing of aragonite-rich sediments, which have relatively positive delta(13)C values, with pelagic materials, which have lower delta(13)C values. As the more isotopically positive shallow-water carbonate sediments are only produced when the platforms are flooded, there is a connection between changes in global sea level and the delta(13)C of sediments in marginal settings. These data indicate that globally synchronous changes in delta(13)C can take place that are completely unrelated to variations in the global carbon cycle. Fluctuations in the delta(13)C of carbonate sediments measured during previous geological periods may also be subject to similar processes, and global synchroniety of delta(13)C can no longer necessarily be considered an indicator that such changes are related to, or caused by, variations in the burial of organic carbon. Inferences regarding the interpretation of changes in the cycling of organic carbon derived from delta(13)C records should be reconsidered in light of the findings presented here.

  14. Global synchronous changes in the carbon isotopic composition of carbonate sediments unrelated to changes in the global carbon cycle

    PubMed Central

    Swart, Peter K.

    2008-01-01

    The carbon isotopic (δ13C) composition of bulk carbonate sediments deposited off the margins of four carbonate platforms/ramp systems (Bahamas, Maldives, Queensland Plateau, and Great Australian Bight) show synchronous changes over the past 0 to 10 million years. However, these variations are different from the established global pattern in the δ13C measured in the open oceans over the same time period. For example, from 10 Ma to the present, the δ13C of open oceanic carbonate has decreased, whereas platform margin sediments analyzed here show an increase. It is suggested that the δ13C patterns in the marginal platform deposits are produced through admixing of aragonite-rich sediments, which have relatively positive δ13C values, with pelagic materials, which have lower δ13C values. As the more isotopically positive shallow-water carbonate sediments are only produced when the platforms are flooded, there is a connection between changes in global sea level and the δ13C of sediments in marginal settings. These data indicate that globally synchronous changes in δ13C can take place that are completely unrelated to variations in the global carbon cycle. Fluctuations in the δ13C of carbonate sediments measured during previous geological periods may also be subject to similar processes, and global synchroniety of δ13C can no longer necessarily be considered an indicator that such changes are related to, or caused by, variations in the burial of organic carbon. Inferences regarding the interpretation of changes in the cycling of organic carbon derived from δ13C records should be reconsidered in light of the findings presented here. PMID:18772393

  15. Assessment of the clumped isotope composition of fossil bone carbonate as a recorder of subsurface temperatures

    NASA Astrophysics Data System (ADS)

    Suarez, Marina B.; Passey, Benjamin H.

    2014-09-01

    Bone is susceptible to early diagenesis, and its carbon and oxygen isotopic compositions have been suggested to reflect conditions in the soil environment and shallow subsurface during fossilization. This implies open-system recrystallization involving mass exchange of carbon and oxygen among bioapatite, soil water, and DIC. Such recrystallization would also redistribute isotopic clumping (including 13C-18O bonds), leading to the possibility that the carbonate clumped isotope compositions of fossil bone record ground temperature during early diagenesis. We assess this possibility by studying Quaternary mammalian fossil bone from subtropical to polar latitudes: if recrystallization is early and pervasive, clumped isotope derived temperatures, T(Δ47), should closely mirror latitudinal gradients in ground temperature. Excluding results from a mummified specimen yielding T(Δ47) = 38 °C (that is, indistinguishable from mammalian body temperature), we find that T(Δ47) values are intermediate between mammalian body temperature and ground temperature, suggesting partial recrystallization of bone carbonate. XRD analyses show that the nature and extent of diagenesis varies among the samples and does not relate in a straightforward manner to T(Δ47). No clear correlation exists between T(Δ47) and mean annual temperature or mean warm season temperature. Furthermore, bone tends to retain the 18O-enriched signature of body water, suggesting incomplete oxygen isotope exchange with meteoric waters. Incomplete carbon and oxygen isotope exchange between bone carbonate and soil waters is also indicated for a set of late Miocene bone-enamel pairs from a sequence of stacked paleosols in northern China. Analysis of bone as old as Early Cretaceous shows that bone carbonate is susceptible to later diagenesis at elevated burial temperatures, although T(Δ47) does not closely conform to maximum burial temperature, again suggesting partial recrystallization, or recrystallization during

  16. Analysis of the site-specific carbon isotope composition of propane by gas source isotope ratio mass spectrometer

    NASA Astrophysics Data System (ADS)

    Piasecki, Alison; Sessions, Alex; Lawson, Michael; Ferreira, A. A.; Neto, E. V. Santos; Eiler, John M.

    2016-09-01

    Site-specific isotope ratio measurements potentially provide valuable information about the formation and degradation of complex molecules-information that is lost in conventional bulk isotopic measurements. Here we discuss the background and possible applications of such measurements, and present a technique for studying the site-specific carbon isotope composition of propane at natural abundance based on mass spectrometric analysis of the intact propane molecule and its fragment ions. We demonstrate the feasibility of this approach through measurements of mixtures of natural propane and propane synthesized with site-specific 13C enrichment, and we document the limits of precision of our technique. We show that mass balance calculations of the bulk δ13C of propane based on our site-specific measurements is generally consistent with independent constraints on bulk δ13C. We further demonstrate the accuracy of the technique, and illustrate one of its simpler applications by documenting the site-specific carbon isotope signature associated with gas phase diffusion of propane, confirming that our measurements conform to the predictions of the kinetic theory of gases. This method can be applied to propane samples of moderate size (tens of micromoles) isolated from natural gases. Thus, it provides a means of studying the site-specific stable isotope systematics of propane at natural isotope abundances on sample sizes that are readily recovered from many natural environments. This method may also serve as a model for future techniques that apply high-resolution mass spectrometry to study the site-specific isotopic distributions of larger organic molecules, with potential applications to biosynthesis, forensics and other geochemical subjects.

  17. The carbon isotopic compositions of individual compounds from ancient and modern depositional environments

    SciTech Connect

    Freeman, K.H.

    1991-01-01

    This work examines factors influencing the isotopic compositions of individual compounds and, consequently, that of preserved sedimentary organic matter. Specifically, isotope effects associated with reactions resulting in the production and degradation of organic matter in the water column and reactions affecting preservation during diagenesis are considered in three projects. The first documents the preservation of the isotopic compositions of hydrocarbons altered by diagenetic reaction. Isotopic compositions of structurally-related polycyclic aromatic hydrocarbons (PAH) from the Messel Shale show little variation with increased unsaturation. The influence of environmental conditions on the isotopic composition of sedimentary organic carbon is documented by a comparison of the {delta}{sup 13}C of hydrocarbons in the marine Julia Creek Oil Shale and the lacustrine Condor Oil Shale. A model is proposed for identifying relative degrees of oxygenation and productivity within a paleoenvironment based on the observed {sup 13}C contents of biomarkers. Effects of processes proposed in the environmental model are documented by an examination of hydrocarbons from the waters and sediments of the Black Sea and of the Cariaco Trench. Sources of individual compounds are identified by comparison of their {sup 13}C content with that predicted for autotrophic biomass calculated from the concentration and {sup 13}C content of CO{sub 2}(aq) in the surface waters.

  18. Relationship between carbon isotope composition and crystal morphology of coated and polycrystalline diamonds

    NASA Astrophysics Data System (ADS)

    Janson, G. F.; Muehlenbachs, K.; Stachel, T.

    2009-12-01

    The carbon isotope composition of diamond coats from Diavik Mine, Canada was measured by secondary ion mass spectrometry (SIMS). In most cases, carbon isotope ratio increases outwards from approximately -8.5 to approximately -6.5‰. Although it has not been widely noted in the literature due to sparse data coverage, this trend is consistent with measurements by other researchers at other sampling localities and therefore represents a unique insight into fluid evolution during the formation of diamond coat. We model the outwards increase in carbon isotope ratio by Rayleigh fractionation during growth of diamond coat in a closed system from an oxidized, carbon supersaturated fluid with a mantle-like carbon isotope signature. The carbon may have been exsolved as a volatile-rich fluid from upwelling kimberlite magma at depths greater than 120 km. The fluid either encountered preexisting diamond ‘seed’ crystals which served as nuclei for the coats or, in the absence of such seeds, precipitated opaque cuboid crystals. Reduction of oxidized carbon to diamond would be driven by the reduced character of the depleted lithosphere (Haggerty and Tompkins, 1983). Several polycrystalline diamonds were also studied by SIMS. These are homogeneous with respect to δ13C and therefore show no isotopic evidence of fluid evolution during their growth. The degree of supersaturation of a fluid commonly determines the crystal habit of minerals precipitated from the fluid. In the case of diamonds, dendritic coat is interpreted as a product of conditions intermediate between the low degree carbon supersaturation that produces polyhedral and hopper morphologies, and the very high supersaturation responsible for the growth of polycrystalline diamond. During closed system growth, precipitation of diamond depletes the fluid reservoir of carbon, resulting in isotopic profiles consistent with Rayleigh fractionation. This depletion necessarily reduces the chemical potential between fluid and

  19. [Quantitative estimation source of urban atmospheric CO2 by carbon isotope composition].

    PubMed

    Liu, Wei; Wei, Nan-Nan; Wang, Guang-Hua; Yao, Jian; Zeng, You-Shi; Fan, Xue-Bo; Geng, Yan-Hong; Li, Yan

    2012-04-01

    To effectively reduce urban carbon emissions and verify the effectiveness of currently project for urban carbon emission reduction, quantitative estimation sources of urban atmospheric CO2 correctly is necessary. Since little fractionation of carbon isotope exists in the transportation from pollution sources to the receptor, the carbon isotope composition can be used for source apportionment. In the present study, a method was established to quantitatively estimate the source of urban atmospheric CO2 by the carbon isotope composition. Both diurnal and height variations of concentrations of CO2 derived from biomass, vehicle exhaust and coal burning were further determined for atmospheric CO2 in Jiading district of Shanghai. Biomass-derived CO2 accounts for the largest portion of atmospheric CO2. The concentrations of CO2 derived from the coal burning are larger in the night-time (00:00, 04:00 and 20:00) than in the daytime (08:00, 12:00 and 16:00), and increase with the increase of height. Those derived from the vehicle exhaust decrease with the height increase. The diurnal and height variations of sources reflect the emission and transport characteristics of atmospheric CO2 in Jiading district of Shanghai.

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

    NASA Astrophysics Data System (ADS)

    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

  1. The carbon isotope composition of atmospheric CO 2 in Paris

    NASA Astrophysics Data System (ADS)

    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.

  2. Carbon isotopic composition of deep carbon gases in an ombrogenous peatland, northwestern Ontario, Canada

    SciTech Connect

    Aravena, R. . Center for Groundwater Research and Wetlands Research Center); Warner, B.G. . Wetlands Research Center and Dept. of Geography); Charman, D.J. . Dept. of Geographical Sciences); Belyea, L.R. . School of Biological Sciences); Mathur, S.P. ); Dinel, H. )

    1993-01-01

    Radiocarbon dating and carbon isotope analyses of deep peat and gases in a small ombrogenous peatland in northwestern Ontario reveals the presence of old gases at depth that are 1000-2000 yr younger than the enclosing peat. The authors suggest that the most likely explanation to account for this age discrepancy is the downward movement by advection of younger dissolved organic carbon for use by fermentation and methanogens bacteria. This study identifies a potentially large supply of old carbon gases in peatlands that should be considered in global carbon models of the terrestrial biosphere.

  3. Carbon isotope composition of carbonaceous matter from the precambrian of the witwatersrand system.

    PubMed

    Hoefs, J; Schidlowski, M

    1967-03-03

    Polymerized hydrocarbons occurring in the gold-uranium conglomerates of the Witwatersrand System (South Africa) show deltaC(13) values between -22.4 and -32.8 per mille, their isotopic composition thus falling into the range of sedimentary organic carbon. Accordingly, organic derivation of the material seems very probable. This conclusion is consistent with a model of the existence of organic evolution and biologic activity in times certainly older than 2.15 x 10(9) years.

  4. Microscale determination of the spectral characteristics and carbon-isotopic compositions of porphyrins

    NASA Technical Reports Server (NTRS)

    Popp, B. N.; Hayes, J. M.; Boreham, C. J.

    1993-01-01

    Molar extinction coefficients for band III of Ni porphyrins are calculated from results of spectrophotometric and manometric analyses of individual etioporphyrins, DPEP, cyclic, and diDPEP porphyrins known to initially be pure from mass spectrometry, 1H NMR, and analytical HPLC studies. A method for determining carbon-isotopic compositions and purity of micromolar quantities of individual porphyrins using combined spectrophotometric and manometric techniques is presented.

  5. Composition of Hydrothermal Vent Microbial Communities as Revealed by Analyses of Signature Lipids, Stable Carbon Isotopes and Aquificales Cultures

    NASA Technical Reports Server (NTRS)

    Jahnke, L. L.; Eder, W.; Huber, Robert; Hinrichs, K-U.; Hayes, J. M.; DesMarais, D. J.; Cady, S. L.; Hope, J. M.; Summons, R. E.

    2001-01-01

    This paper describes a study of lipid biomarker composition and carbon isotopic fractionation in cultured Aquificales and natural analogues from Yellowstone National Park. Additional information is contained in the original extended abstract.

  6. Re-calculating the pH record from boron isotopic composition of biogenic carbonates

    NASA Astrophysics Data System (ADS)

    Paris, G.; Gaillardet, J.; Louvat, P.

    2010-12-01

    The boron isotopic composition of marine carbonates (δ11Bcarb, ‰) has been proposed as a seawater paleo-acidity proxy (Hemming and Hanson, 1992; Vengosh et al., 1991). This proxy has been extensively used to reconstruct seawater paleo-pH and eventually atmospheric pCO2 during recent times or over short time-scales. However, it requires the knowledge of seawater δ11B value. Boron has a residence time of 10-20 My in seawater, longer than the mixing time of the ocean. The boron isotopic composition of seawater (δ11Bsw) is thus homogeneous in the modern ocean, yet it is not known in the past even though reconstruction and modeling have been attempted that rely on many hypotheses (Lemarchand et al., 2002; Pearson and Palmer, 2000). The boron isotopic composition of Cenozoic evaporites has been recently reconstructed using the direct record of Cenozoic evaporites (Paris et al., 2010). This reconstruction suggests that δ11Bsw has significantly changed along the last 40 Ma, in agreement with other parameters of the oceanic chemical composition. The δ11Bsw change amplitude appears to be stronger than suggested by models. In this presentation, we explore the consequences of this reconstruction on paleo-pH calculation for the late Cenozoic from published boron isotope record in biogenic carbonates (Pearson and Palmer, 2000; Pearson et al., 2009; Seki et al., 2010; Spivack et al., 1993). It points out the inconsistency between different dataset, due to the techniques used for boron isotopic measurement. In conclusion, we suggest that the seawater pH variations are not known with a sufficient precision over the last 35 My and that seawater surface pH could have likely remained constant. Hemming, N.G., and Hanson, G.N. (1992), Boron isotopic composition and concentration in modern marine carbonates: Geochimica et Cosmochimica Acta, v. 56, p. 537-543. Lemarchand, D., et al. (2002), Boron isotope systematics in large rivers: implications for the marine boron budget and

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

    SciTech Connect

    Taviani, M. ); Reid, D.E.; Anderson, J.B. )

    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).

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

    NASA Astrophysics Data System (ADS)

    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

    2015-10-01

    "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 natural systems. The two

  9. Stable isotopic composition of pedogenic carbonate in soils of Minusinsk Hollow

    NASA Astrophysics Data System (ADS)

    Vasil'chuk, Jessica; Krechetov, Pavel; Budantseva, Nadine; Chizhova, Julia; Vasil'chuk, Yurij

    2016-04-01

    The purpose of the research is to characterize the isotopic composition of carbonate neoformations in soils and estimate its correlation with isotopic composition of water and parent material. The study site is located in the Minusinsk Hollow that is situated among Kuznetsk Alatau and Sayan Mountains. Three key-sites with in different parts of hollow, under mainly steppe vegetation with calciphilic grasses and diverse parent material were studied including: 1) Kazanovka Khakass state national reserve in foothills of Kuznetsk Alatau 2) Hankul salt lake that is considered as natural monument 3) region of Sayanogorsk aluminum smelter on a left bank of the Yenisei river. The samples of pedogenic and lithogenic carbonates as well as water samples were analyzed using the Delta-V mass spectrometer with a standard option of a gas bench according to standard methods. Carbonate coatings (also called pendants or cutans) is one of the most common types of carbonate neoformations occurring in the region. Fine coatings' layers one over another usually can be found on the bottom sides of rubble and gravel inside the soil profile colour varies from white to brownish and yellowish (probably depending on the impurities of organic matter). In Petric Calcisols, Chernozems and Kastanozems δ18O values of coatings vary in a rather small range from - 8.9 to - 10.1 ‰ PDB. This probably shows that their forming took place approximately in the same climatic conditions. While δ18O values of carbonate parent rocks are close to them and are vary from - 11.1 to - 11.9 ‰ PDB. Also, δ13C values of coatings strongly decrease from inner (older) to outer (younger) layers, that can indicate differences connected with the diffusion of organic material. River waters' δ18O values also show a small range from - 16.62 to - 17.66‰ SMOW, while salt lakes' waters due to the fractionation evaporation effects demonstrate much heavier values from - 4.73 to - 9.22‰ SMOW. The groundwater shows δ18O

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

    USGS Publications Warehouse

    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

  11. Temporal Variability in Carbon Isotope Composition of Leaf-Respired Carbon Dioxide

    NASA Astrophysics Data System (ADS)

    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

  12. Carbon and nitrogen isotopic compositions of alkyl porphyrins from the Triassic Serpiano oil shale.

    PubMed

    Chicarelli, M I; Hayes, J M; Popp, B N; Eckardt, C B; Maxwell, J R

    1993-01-01

    The carbon and nitrogen isotopic compositions of seven of the most abundant alkylporphyrins from the Serpiano oil shale (marine, Triassic) were determined. For the C31 and C32 butanoporphyrins, values of delta 13CPDB and delta 15NAIR averaged -24.0% and -3.1%. In contrast, the C31 and C32 methylpropanoporphyrins, DPEP, and a C30 13-nor etioporphyrin had delta 13C and delta 15N values averaging -27.5 and -3.3%, respectively. Carbon and nitrogen isotopic values for kerogen averaged -30.8 and -0.9, whereas those for total extract averaged -31.6, and -4.0%. The butanoporphyrins apparently derive from a biological source different from that giving rise to the other porphyrins, their 13C enrichment not being related to carbon isotopic fractionation accompanying diagenetic reactions. The delta 15N values for all the porphyrins indicate that the depletion of 15N observed in the kerogen is of primary origin. Consistent with the very high abundance of hopanoids and methyl hopanoids in the aliphatic hydrocarbon fraction, it is suggested that cyanobacterial fixation of N2 may have been the main cause of 15N depletion.

  13. Carbon and nitrogen isotopic compositions of alkyl porphyrins from the Triassic Serpiano oil shale

    NASA Technical Reports Server (NTRS)

    Chicarelli, M. I.; Hayes, J. M.; Popp, B. N.; Eckardt, C. B.; Maxwell, J. R.

    1993-01-01

    The carbon and nitrogen isotopic compositions of seven of the most abundant alkylporphyrins from the Serpiano oil shale (marine, Triassic) were determined. For the C31 and C32 butanoporphyrins, values of delta 13CPDB and delta 15NAIR averaged -24.0% and -3.1%. In contrast, the C31 and C32 methylpropanoporphyrins, DPEP, and a C30 13-nor etioporphyrin had delta 13C and delta 15N values averaging -27.5 and -3.3%, respectively. Carbon and nitrogen isotopic values for kerogen averaged -30.8 and -0.9, whereas those for total extract averaged -31.6, and -4.0%. The butanoporphyrins apparently derive from a biological source different from that giving rise to the other porphyrins, their 13C enrichment not being related to carbon isotopic fractionation accompanying diagenetic reactions. The delta 15N values for all the porphyrins indicate that the depletion of 15N observed in the kerogen is of primary origin. Consistent with the very high abundance of hopanoids and methyl hopanoids in the aliphatic hydrocarbon fraction, it is suggested that cyanobacterial fixation of N2 may have been the main cause of 15N depletion.

  14. Carbon elemental and isotopic composition in mantle xenoliths from Spain: Insights on sources and petrogenetic processes

    NASA Astrophysics Data System (ADS)

    Bianchini, G.; Natali, C.

    2017-02-01

    The carbon elemental concentration (C wt%) and isotopic (δ13C ‰) composition of mantle xenoliths from the Tallante and Calatrava volcanic occurrences (in South-East and Central Spain, respectively) have been investigated to identify carbon sources and processes occurring in distinct geodynamic settings of the Iberian Peninsula. The peridotitic mantle xenoliths from Calatrava show elemental C ranging from 0.11 to 2.87 wt% which is coupled with a continuous isotopic variation from very negative values (δ13C - 26.1‰) to typical mantle values (δ13C - 5.9‰). On the other hand, the Tallante mantle xenolith suite displays lower C contents (0.06-0.15 wt%) showing a tighter variation with 13C-depleted values ranging between - 20.1 and - 23.7‰; higher elemental C up to 0.41 wt% displaying distinctly less negative isotopic values (δ13C between - 13.8 and - 11.9‰) have been recorded in veins crosscutting Tallante peridotites, plausibly representing the product of metasomatic reactions. The data from the two investigated xenolith suites invariably display a good correlation between elemental and isotopic composition, suggesting a mantle origin for carbon and Rayleigh-type fractionation as the process responsible for the observed C-δ13C variation. However, the correlation between the carbon isotopic data with other isotopic tracers (e.g. 87Sr/86Sr, 3He/4He) used to identify distinct mantle components and metasomatic reactions, indicates systematic differences between the two xenolith suites suggesting that beneath the Betic Cordillera (where Tallante is located) the deep C-cycle involves recycling, via subduction preceding/accompanying continental collision, of crustal components back in the mantle. Coherently, geochemical trends observed in the Tallante xenoliths seem to be influenced by metasomatic agents generated by melting of crustal lithologies that according to the analysis of a metasedimentary xenolith can contain C up to 1.2 wt% having δ13C of ca. - 18

  15. A review of volatile compounds in tektites, and carbon content and isotopic composition of moldavite glass

    NASA Astrophysics Data System (ADS)

    Žák, Karel; SkáLA, Roman; Šanda, Zdeněk.; Mizera, Jiří.

    2012-06-01

    Tektites, natural silica-rich glasses produced during impact events, commonly contain bubbles. The paper reviews published data on pressure and composition of a gas phase contained in the tektite bubbles and data on other volatile compounds which can be released from tektites by either high-temperature melting or by crushing or milling under vacuum. Gas extraction from tektites using high-temperature melting generally produced higher gas yield and different gas composition than the low-temperature extraction using crushing or milling under vacuum. The high-temperature extraction obviously releases volatiles not only from the bubbles, but also volatile compounds contained directly in the glass. Moreover, the gas composition can be modified by reactions between the released gases and the glass melt. Published data indicate that besides CO2 and/or CO in the bubbles, another carbon reservoir is present directly in the tektite glass. To clarify the problem of carbon content and carbon isotopic composition of the tektite glass, three samples from the Central European tektite strewn field—moldavites—were analyzed. The samples contained only 35-41 ppm C with δ13C values in the range from -28.5 to -29.9‰ VPDB. This indicates that terrestrial organic matter was a dominant carbon source during moldavite formation.

  16. Soil Drying Effects on the Carbon Isotope Composition of Soil Respiration

    NASA Astrophysics Data System (ADS)

    Phillips, C. L.; Nickerson, N.; Risk, D.; Kayler, Z. E.; Rugh, W.; Mix, A. C.; Bond, B. J.

    2008-12-01

    Stable isotopes are used widely as a tool for determining sources of carbon (C) fluxes in ecosystem C studies. Environmental factors that change over time, such as moisture, can create dynamic changes in the isotopic composition of C assimilated by plants, and offers a unique opportunity to distinguish fast- responding plant C from slower-responding soil C pools, which under steady-state conditions may be too similar isotopically to partition. Monitoring the isotopic composition of soil respiration over a period of changing moisture conditions is potentially a useful approach for characterizing plant contributions to soil respiration. But this partitioning hinges on the assumption that any change in the isotopic signature of soil respiration is solely due to recent photosynthetic discrimination, and that post-photosynthetic processes, such as microbial respiration, do not discriminate as moisture decreases. The purpose of the present study is to test the assumption that δ13CO2 from microbial respiration remains static as soil dries. We conducted a series of greenhouse experiments employing different techniques to isolate microbial respiration from root respiration. The first involves removing roots from soil, and showed that when roots are present, respiration from dry soil is enriched in 13C relative to moist soil, but when roots are absent, respiration is isotopically similar from moist and dry soils. This indicates that rhizospheric respiration changes isotopically with moisture whereas soil microbial respiration does not. In contrast, a second experiment in which soil columns without plants were monitored as they dried, showed respiration from very dry soil to be enriched by 8‰ relative to moist soil. However, simulations with an isotopologue-based soil gas diffusion model demonstrate that at least a portion of the apparent enrichment is due to non-steady state gas transport processes. Careful sampling methodologies which prevent or account for non

  17. Stable isotope composition of land snail body water and its relation to environmental waters and shell carbonate

    NASA Astrophysics Data System (ADS)

    Goodfriend, Glenn A.; Magaritz, Mordeckai; Gat, Joel R.

    1989-12-01

    Day-to-day and within-day (diel) variations in δD and δ18O of the body water of the land snail, Theba pisana, were studied at a site in the southern coastal plain of Israel. Three phases of variation, which relate to isotopic changes in atmospheric water vapor, were distinguished: 1) on rain days, snail water becomes isotopically depleted approximately in the direction of the rain isotope values, but always less depleted in D as is atmospheric water vapor; 2) during the 1-3 days following a rain, the snail water becomes isotopically enriched along a line with slope < 8, in δD vs. δ18O space (this relates to an increasing influence of humidity derived from the Mediterranean Sea); 3) a period of relative stability of the isotopic composition persists until the next rain event. The isotopic variations can be explained by isotopic equilibration with atmospheric water vapor and/or uptake of dew derived therefrom. During the winter, when the snails are active, there is only very minor enrichment in 18O relative to equilibrium with water vapor or dew, apparently as a result of metabolic activity. But this enrichment becomes pronounced after long periods of inactivity. Within-day variation in body water isotopic composition is minor on non-rain days. Shell carbonate is enriched in 18O by ca. 1-2%. relative to equilibrium with body water. In most regions, the isotopic composition of atmospheric water vapor (or dew) is a direct function of that of rain. Because the isotopic composition of snail body water is related to that of atmospheric water vapor and the isotopic composition of shell carbonate in turn is related to that of body water, land snail shell carbonate 18O should provide a reliable indication of rainfall 18O. However, local environmental conditions and the ecological properties of the snail species must be taken into account.

  18. Environmental inputs that can influence carbon isotopic compositions of hot spring biofilms

    NASA Astrophysics Data System (ADS)

    Donatelli, J. L.; Havig, J. R.; Shock, E.

    2011-12-01

    The carbon isotopic compositions of hydrothermal biofilms are influenced by microbial carbon cycling, and can be correlated with the presence or absence of specific genes in environmental genomic analyses (Havig et al., 2011, JGR). Additional isotopic data on potential environmental sources of carbon will enable further tests of the specific pathways of carbon assimilation and cycling throughout hydrothermal ecosystems. Hot springs at Yellowstone National Park (YNP) are often located in open meadows or forested areas with varying amounts of vegetation and exposed soil surrounding the pools. These pools are open systems which have the potential to accumulate allochthonous materials via physical and biogenic processes. These inputs may affect the δ13C signatures of the hot spring waters and the biofilms associated with them. In the YNP hot springs we have studied since 2003, biofilms range in δ13C from -1.2 to -30.7%. Dissolved inorganic carbon (DIC) in coexisting fluids ranges from 4.3 to -3.9%. The heaviest biofilms typically show minimal isotopic fractionation from the DIC in coexisting fluids. DIC values are strongly influenced by inputs from magma degassing, water-rock reactions in the hydrothermal system, and the atmosphere. Dissolved organic carbon (DOC) values for the coexisting fluids range from -16.5 to -26.8%, which are within the range of biofilm δ13C values. DOC values will also be affected by diverse processes as precipitation infiltrates, reacts, and eventually returns to the surface as hydrothermal fluids, but may also be influenced by biologically derived inputs from the local environments where hot springs occur. In an effort to characterize the environmental context of hot springs, we have collected isotopic data on lodgepole pine needles, grasses, soils, insects and bison feces. Of these, the δ13C data for bison feces (-27.7 to -29.6%) are lighter than any of the DOC data. Pine needles (-26.3 to -29.1%) and soils (-24.8 to -27.1%) overlap with

  19. Interpreting bryophyte stable carbon isotope composition: Plants as temporal and spatial climate recorders

    NASA Astrophysics Data System (ADS)

    Royles, Jessica; Horwath, Aline B.; Griffiths, Howard

    2014-04-01

    are unable to control tissue water content although physiological adaptations allow growth in a wide range of habitats. Carbon isotope signals in two mosses (Syntrichia ruralis and Chorisodontium aciphyllum) and two liverworts (Conocephalum conicum and Marchantia polymorpha), whether instantaneous (real time, Δ13C), or organic matter (as δ13COM), provide an assimilation-weighted summary of bryophyte environmental adaptations. In mosses, δ13COM is within the measured range of Δ13C values, which suggests that other proxies, such as compound-specific organic signals, will be representative of historical photosynthetic and growth conditions. The liverworts were photosynthetically active over a wider range of relative water contents (RWC) than the mosses. There was a consistent 5‰ offset between Δ13C values in C. conicum and M. polymorpha, suggestive of greater diffusion limitation in the latter. Analysis of a C. aciphyllum moss-peat core showed the isotopic composition over the past 200 years reflects recent anthropogenic CO2 emissions. Once corrected for source-CO2 inputs, the seasonally integrated Δ13COM between 1350 and 2000 A.D. varied by 1.5‰ compared with potential range of the 12‰ measured experimentally, demonstrating the relatively narrow range of conditions under which the majority of net assimilation takes place. Carbon isotope discrimination also varies spatially, with a 4‰ shift in epiphytic bryophyte organic matter found between lowland Amazonia and upper montane tropical cloud forest in the Peruvian Andes, associated with increased diffusion limitation.

  20. Stable isotope composition of land snail body water and its relation to environmental waters and shell carbonate

    SciTech Connect

    Goodfriend, G.A.; Magaritz, M.; Gat, J.R. )

    1989-12-01

    Day-to-day and within-day (diel) variations in {delta}D and {delta}{sup 18}O of the body water of the land snail, Theba pisana, were studied at a site in the southern coastal plain of Israel. Three phases of variation, which relate to isotopic changes in atmospheric water vapor, were distinguished. The isotopic variations can be explained by isotopic equilibration with atmospheric water vapor and/or uptake of dew derived therefrom. During the winter, when the snails are active, there is only very minor enrichment in {sup 18}O relative to equilibrium with water vapor or dew, apparently as a result of metabolic activity. But this enrichment becomes pronounced after long periods of inactivity. Within-day variation in body water isotopic composition is minor on non-rain days. Shell carbonate is enriched in {sup 18}O by ca. 1-2% relative to equilibrium with body water. In most regions, the isotopic composition of atmospheric water vapor (or dew) is a direct function of that of rain. Because the isotopic composition of snail body water is related to that of atmospheric water vapor and the isotopic composition of shell carbonate in turn is related to that of body water, land snail shell carbonate {sup 18}O should provide a reliable indication of rainfall {sup 18}O. However, local environmental conditions and the ecological properties of the snail species must be taken into account.

  1. The origin of particulate organic carbon in the marine atmosphere as indicated by its stable carbon isotopic composition

    NASA Astrophysics Data System (ADS)

    Chesselet, R.; Fontugne, M.; Buat-Ménard, P.; Ezat, U.; Lambert, C. E.

    1981-04-01

    Organic carbon concentration and isotopic composition were determined in samples of atmospheric particulate matter collected in 1979 at remote marine locations (Enewetak atoll, Sargasso Sea) during the SEAREX (Sea-Air Exchange) program field experiments. Atmospheric Particulate Organic Carbon (POC) concentrations were found to be in the range of 0.3 to 1.2µg.m-3, in agreement with previous literature data. The major mass of POC was found on the smallest particles (r<0.5µm). The 13C/12C of the small particles is close to the one expected (δ13C = 26 ± 2‰) for atmospheric POC of continental origin. For all the samples analysed so far, it appears that more than 80% of atmospheric POC over remote marine areas is of continental origin. This can be explained either by long-range transport of small sized continental organic aerosols or by the production of POC in the marine atmosphere from a vapor phase organic carbon pool of continental origin. The POC in the large size fraction of marine aerosols (<20% of the total concentration) is likely to have a direct marine origin since its carbon isotopic composition is close to the expected value (δ13C = -21 ± 2‰) for POC associated with sea-salt droplets transported to the marine atmosphere.

  2. Origin of particulate organic carbon in the marine atmosphere as indicated by it stable carbon isotopic composition

    SciTech Connect

    Chesselet, R.; Fontugne, M.; Buat-Menard, P.; Ezat, U.; Lambert, C.E.

    1981-04-01

    Organic carbon concentration and isotopic composition were determined in samples of atmospheric particulate matter collected in 1979 at remote marine locations (Enewetak atoll, Sargasso Sea) during the SEAREX (Sea-Air Exchange) program field experiments. Atmospheric Particulate Organic Carbon (POC) concentrations were found to be in the range of 0.3 to 1.2 mg. m/sup -3/, in agreement with previous literature data. The major mass of POC was found on the smallest particles (r<0.5 mm). The /sup 13/C//sup 12/C of the small particles is close to the one expected (d/sup 13/C = 26 +- 2/sup 0///sub infinity/) for atmospheric POC of continental origin. For all the samples analysed so far, it appears that more than 80% of atmospheric POC over remote marine areas is of continental origin. This can be explained either by long-range transport of small sized continental organic aserosols or by the production of POC in the marine atmosphere from a vapor phase organic carbon pool of continental origin. The POC in the large size fraction of marine aerosols (<20% of the total concentration) is likely to have a direct marine origin since its carbon isotopic composition is close to the expected value (d/sup 13/C = -21 +- 2/sup 0///sub 00/) for POC associated with sea-salt droplets transported to the marine atmosphere.

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

    PubMed Central

    Horita, Juske; Polyakov, Veniamin B.

    2015-01-01

    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 δ13C ≈ −5 ± 3‰ with a very broad distribution to lower values (∼−40‰). The processes that have produced the wide δ13C distributions to the observed low δ13C 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 13C 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 δ13C values. The sharp contrast in the δ13C 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 δ13C values and that an average δ13C value of the bulk Earth could be much lower than ∼−5‰, consistent with those of chondrites and other planetary body. The heterogeneous and depleted δ13C 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. PMID:25512520

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

    PubMed

    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.

  5. Carbon isotope geochemistry and geobiology

    NASA Technical Reports Server (NTRS)

    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.

  6. Effects of Land Use on Stable Carbon Isotopic Composition and Concentration of Dissolved Organic Carbon (DOC) and Dissolved Inorganic Carbon (DIC) in Southeastern US Piedmont Headwater Streams

    EPA Science Inventory

    Stable carbon isotopic composition (delta 13C) and concentrations of DOC and DIC were measured in stream water samples collected monthly in 15 headwater streams from an area with extensive poultry and cattle production and a rapidly growing human population. Linear regression te...

  7. Unsaturated zone carbon dioxide flux, mixing, and isotopic composition at the USGS Amargosa Desert Research Site

    NASA Astrophysics Data System (ADS)

    Conaway, C. H.; Thordsen, J. J.; Thomas, B.; Haase, K.; Moreo, M. T.; Walvoord, M. A.; Andraski, B. J.; Stonestrom, D. A.

    2015-12-01

    Elevated concentrations of tritium, radiocarbon, and volatile organic compounds at the USGS Amargosa Desert Research Site, adjacent to a low-level radioactive waste disposal facility, have stimulated research on factors affecting transport of these contaminants. This research includes an examination of unsaturated zone carbon dioxide (CO2) fluxes, mixing, and isotopic composition, which can help in understanding these factors. In late April 2015 we collected 76 soil-gas samples in multi-layer foil bags from existing 1.5-m deep tubes, both inside and outside the low-level waste area, as well as from two 110-m-deep multilevel gas-sampling boreholes and a distant background site. These samples were analyzed for carbon dioxide concentration and isotopic composition by direct injection into a cavity ring-down spectrometer. Graphical analysis of results indicates mixing of CO2 characteristic of the root zone (δ13C -18 ‰ VPDB), deep soil gas of the capillary fringe (-20‰), and CO2 produced by microbial respiration of organic matter disposed in the waste area trenches (-28‰). Land-surface boundary conditions are being constrained by the application of a novel non-dispersive infrared sensor and traditional concentration and flux measurements, including discrete CO2 flux data using a gas chamber method to complement continuous data from surface- and tower-based CO2 sensors. These results shed light on radionuclide and VOC mobilization and transport mechanisms from this and similar waste disposal facilities.

  8. The carbon-isotopic composition of Proterozoic carbonates: Riphean successions from northwestern Siberia (Anabar Massif, Turukhansk Uplift)

    NASA Technical Reports Server (NTRS)

    Knoll, A. H.; Kaufman, A. J.; Semikhatov, M. A.

    1995-01-01

    Thick carbonate-dominated successions in northwestern Siberia document secular variations in the C-isotopic composition of seawater through Mesoproterozoic and early Neoproterozoic (Early to early Late Riphean) time. Mesoproterozoic dolomites of the Billyakh Group, Anabar Massif, have delta 13C values that fall between 0 and -1.9 permil versus PDB, with values in the upper part of the succession (Yusmastakh Formation) consistently higher than those of the lower (Ust'-Il'ya and Kotuikan formations). Consistent with available biostratigraphic and radiometric data, delta 13C values for Billyakh carbonates compare closely with those characterizing early Mesoproterozoic carbonates (about 1600-1200 Ma) worldwide. In contrast, late Mesoproterozoic to early Neoproterozoic limestones and dolomites in the Turukhansk Uplift exhibit moderate levels of secular variation. Only the lowermost carbonates in the Turukhansk succession (Linok Formation) have delta 13C values that approximate Billyakh values. Higher in the Turukhansk succession, delta 13C values vary from -2.7 to +4.6 permil (with outliers as low as -5.0 permil interpreted as diagentically altered). Again, consistent with paleontological and radiometric data, these values compare well with isotopic values from 1200 to 850 Ma successions elsewhere. Five sections measured in different parts of the Turukhansk basin show nearly identical patterns of variation, confirming that carbonate delta 13C correlates primarily with time and not facies. The Siberian sections illustrate the potential of integrated biostratigraphic and chemostratigraphic data in the intra- and interbasinal correlation of Mesoproterozoic and early Neoproterozoic rocks.

  9. Lead isotopic composition of paleozoic and late proterozoic marine carbonate rocks in the vicinity of Yucca Mountain, Nevada

    USGS Publications Warehouse

    Zartman, Robert E.; Kwak, Loretta M.

    1993-01-01

    Paleozoic and Late Proterozoic marine carbonate rocks (limestones, dolomites, and their metamorphic equivalents) cropping out in the vicinity of Yucca Mountain contain lead with an isotopic composition strongly suggesting them to be a major source of the lead observed at Trench 14 in the carbonate phase of carbonate-silica veins and nearby surficial calcrete deposits. Six whole-rock samples of marine carbonate rocks yield 206Pb/204Pb = 19.21-29.06, 207Pb/204Pb = 15.74-16.01, and 208Pb/204Pb = 37.90-39.25, and leachate and residue fractions of the rocks reveal additional isotopic heterogeneity within individual samples. Two samples of eolian dust also have isotopic compositions lying along a 'carbonate' to 'silicate' mixing trend that appears to arise entirely from pedogenic processes. The tendency for the marine carbonate rocks to evolve highly uranogenic, but no thorogenic, lead results in a distinctive isotopic composition that serves as a tracer in eolian dust and secondary carbonate minerals derived from the marine carbonate rocks.

  10. Carbon and oxygen isotopic composition of coal and carbon dioxide derived from laboratory coal combustion: A preliminary study

    USGS Publications Warehouse

    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

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

    PubMed

    Pang, Jiaping; Wen, Xuefa; Sun, Xiaomin

    2016-01-01

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

  12. Dissolved inorganic carbon isotopic composition of the Gulf of Mexico deep-water masses.

    NASA Astrophysics Data System (ADS)

    Quintanilla-Terminel, J. G.; Herguera, J. C.; Ferreira-Bartrina, V.; Hernández-Ayón, J. M.; Camacho-Ibar, V.

    2014-12-01

    This study provides new data for the establishment of a carbon biogeochemical dynamics baseline in the deep Gulf of Mexico (GM) based on carbon isotopes in dissolved inorganic carbon. Water samples from 40 deep-water stations south of 25˚N were collected during XIXIMI-2 cruise, July 2011, aboard BO/Justo Sierra. Vertical profiles of temperature, salinity and dissolved oxygen (DO) were further measured in each station. In the Stable Isotopes Laboratory at CICESE we determined the carbon isotopic composition of the dissolved inorganic carbon (DIC) (δ13CDIC). Remarkably, density, DO and δ13CCID profiles showed a clear difference between the Loop current and the deep-waters of the GM south of 25˚N. We found the following average δ13CCID values in the Loop current and in the deep-waters of the Gulf: subtropical underwater (SUW): 0.73±0.06‰ and 0.86±0.04‰; 18 degree water (18W): 0.76 ± 0.08‰ and 0.58± 0.06‰; North Atlantic central water (NACW): 0.77 ± 0.05‰ and 0.71 ± 0.09‰; South Atlantic central water (SACW): 0.80 ± 0.08‰ and 0.77 ± 0.07‰; Antartic intermediate water (AAIW): 1.00 ± 0.06‰ and 0.90 ± 0.08‰; North Atlantic deep water (NADW): 1.03 ± 0.06‰ and 1.01 ± 0.10‰. We will discuss how the biological component, δ13CCID-BIO, of subsurface water masses match very closely the apparent oxygen utilization relation described by Kroopnick, 1985, with the exception of SUW, and as a consequence the 18W is probably the water mass most affected by organic carbon remineralization processes in the GM south of 25˚N. We further show how these waters seem to store a larger proportion of anthropogenic carbon than the deeper water masses.

  13. Unusual carbon isotope compositions of biomarker hydrocarbons in a Permian tasmanite

    SciTech Connect

    Simoneit, B.R.T. ); Schoell, M.; Dias, R.F. ); De Aquino Neto, F.R. )

    1993-09-01

    The Permian oil shale sample of this study is from a deposit in Tasmania in which the only recognizable structures are large, thick-walled, unicellular specimens of the green algae Tasmanites. The fossils are so densely packed that this shale is termed tasmanite. The carbon isotopic composition of bulk kerogen carbon ([sigma]C[sup 13]C[sub org] = [minus]16.6[per thousand], vs. PDB) is unusually enriched in [sup 13]C compared to marine Permian organic carbon ([minus]25 to [minus]30[per thousand]). This [sup 13]C enrichment suggests specific environmental conditions (CO[sub 2] draw down) and/or physiological specialties (cell size and growth rate) of Tasmanites which, in modern environments, are known to cause [sup 13]C enrichment in marine phytoplankton. Isotope signatures of extractable organic species, unlike in normal immature oil shales, are considerably enriched in [sup 13]C compared to the kerogen. The isotopic similarity of all the cyclic terpanes in the sample, together with their occurrence in the free lipids and kerogen, suggests that they have a common origin and are biosynthesis products of the marine unicellular green algae Tasmanites. The tetracyclic terpanes, therefore, are not des-A-oleananes derived from land plants but are possibly monoaromatic des-A-gammaceranes or other des-A-triterpenoids derived from marine sources. The unusual enrichment in [sup 13]C in the cyclic hydrocarbons is hypothesized to result from the special growth conditions of the algae. Isoprenoids and n-alkanes are also likely biosynthesis products of Tasmanites, possibly during the spore formation stage when physiological and environmental conditions were different than during planktonic biosynthesis.

  14. Pyrogenic carbon from tropical savanna burning: production and stable isotope composition

    NASA Astrophysics Data System (ADS)

    Saiz, G.; Wynn, J. G.; Wurster, C. M.; Goodrick, I.; Nelson, P. N.; Bird, M. I.

    2015-03-01

    Widespread burning of mixed tree-grass ecosystems represents the major natural locus of pyrogenic carbon (PyC) production. PyC is a significant, pervasive and yet poorly understood "slow-cycling" form of carbon present in the atmosphere, hydrosphere, soils and sediments. We conducted 16 experimental burns on a rainfall transect through northern Australian savannas with C4 grasses ranging from 35 to 99% of total biomass. Residues from each fire were partitioned into PyC and further into recalcitrant (HyPyC) components, with each of these fluxes also partitioned into proximal components (>125 μm), likely to remain close to the site of burning, and distal components (<125 μm), likely to be transported from the site of burning. The median (range) PyC production across all burns was 16.0 (11.5) % of total carbon exposed (TCE), with HyPyC accounting for 2.5 (4.9) % of TCE. Both PyC and HyPyC were dominantly partitioned into the proximal flux. Production of HyPyC was strongly related to fire residence time, with shorter duration fires resulting in higher HyPyC yields. The carbon isotope (δ13C) compositions of PyC and HyPyC were generally lower by 1-3‰ relative to the original biomass, with marked depletion up to 7‰ for grasslands dominated by C4 biomass. δ13C values of CO2 produced by combustion were computed by mass balance and ranged from ~0.4 to 1.3‰. The depletion of 13C in PyC and HyPyC relative to the original biomass has significant implications for the interpretation of δ13C values of savanna soil organic carbon and of ancient PyC preserved in the geologic record, as well as for global 13C isotopic disequilibria calculations.

  15. The carbon isotopic composition of catalytic gas: A comparative analysis with natural gas

    SciTech Connect

    Mango, F.D.; Elrod, L.W.

    1999-04-01

    Tee idea that natural gas is the thermal product of organic decomposition has persisted for over half a century. Crude oil is thought to be an important source of gas, cracking to wet gas above 150 C, and dry gas above 200 C. But there is little evidence to support this view. For example, crude oil is proving to be more stable than previously thought and projected to remain intact over geologic time at typical reservoir temperature. Moreover, when oil does crack, the products do not resemble natural gas. Oil to gas could be catalytic, however, promoted by the transition metals in carbonaceous sediments. This would explain the low temperatures at which natural gas forms, and the high amounts of methane. This idea gained support recently when the natural progression of oil to dry gas was duplicated in the laboratory catalytically. The authors report here the isotopic composition of catalytic gas generated from crude oil and pure hydrocarbons between 150 and 200 C. {delta}{sup 13}C for C{sub 1} through C{sub 5} was linear with 1/n (n = carbon number) in accordance with theory and typically seen in natural gases. Over extended reaction, isobutane and isopentane remained lighter than their respective normal isomers and the isotopic differentials were constant as all isomers became heavier over time. Catalytic methane, initially {minus}51.87{per_thousand} (oil = {minus}22.5{per_thousand}), progressed to a final composition of {minus}26.94{per_thousand}, similar to the maturity trend seen in natural gases: {minus}50{per_thousand} to {minus}20{per_thousand}. Catalytic gas is thus identical to natural gas in molecular and isotopic composition adding further support to the view that catalysis by transition metals may be a significant source of natural gas.

  16. Seasonal cycle of carbon dioxide and its isotopic composition in an urban atmosphere: Anthropogenic and biogenic effects

    NASA Astrophysics Data System (ADS)

    Pataki, D. E.; Bowling, D. R.; Ehleringer, J. R.

    2003-12-01

    Atmospheric CO2 mixing ratios and carbon and oxygen isotope composition were measured at 18 m above the ground in Salt Lake City, Utah, United States, for a one-year period. Mixing ratios were highest in the wintertime with maximum values approaching 600 μmol.mol-1 during atmospheric inversions. Nighttime carbon and oxygen isotope ratios of source CO2 showed a seasonal pattern with isotopically depleted values in the wintertime and isotopically enriched values in the spring and summer. The effects of gasoline combustion, natural gas combustion, and biogenic respiration of plants and soils on CO2 mixing ratio were quantified with a mass balance calculation using dual carbon and oxygen isotopic tracers. The calculations showed large contributions of natural gas combustion in the winter and significant nighttime biogenic respiration in the spring and late summer/early fall. The isotope-tracer technique used shows promise for quantifying the impacts of urban processes on the isotopic composition of the atmosphere and partitioning urban CO2 sources into their component parts.

  17. Factors controlling carbon isotopic composition of land snail shells estimated from lab culturing experiment

    NASA Astrophysics Data System (ADS)

    Zhang, Naizhong; Yamada, Keita; Yoshida, Naohiro

    2014-05-01

    Carbon isotopic composition (δ13C) of land snail shell carbonate is widely applied in reconstructing the C3/C4 vegetation distribution of paleo-environment, which is considered to reflect variations of some environmental parameters [1][2][3]. Land snail shell carbon has three potential sources: diet, atmospheric CO2 and ingested carbonate (limestone) [4]. However, their relative contributions to shell carbonate have not been understood well yet [4][5][6][7][8]. More researches are necessary before we could apply this tool in paleo-environment reconstruction, especially inter-lab culturing experiment. A kind of land snail species, Acusta despecta sieboldiana, was collected at Yokohama, Japan and cultured under suitable environment to lay eggs. The second generations were growing up from eggs to adults around 6-12 months at the temperature of 20°, 25° and 30°, respectively. All of the snails at 25° and 30° and most of those at 20° were fed by cabbage (C3 plant) during their life span while others were fed by corn (C4 plant). To investigate the effect of ingested carbonate, some of them were fed by Ca3(PO4)2 powder while others were fed by CaCO3 powder. δ13C of shells were analyzed by an Isotope Ratio Mass Spectrometry (Thermo Finnigan MAT 253); δ13C of food and snail tissue were measured by a Cavity Ring-Down Spectroscopy (Picarro G1121-i). At the same time, δ13C of eggshell and new born snails were analyzed by a Continuous Flow Isotope Ratio Mass Spectrometry (GasBench II). We confirmed that diet, atmospheric CO2 and ingested limestone could be important sources controlling shell δ13C values. And the temperature could affect shell carbonate δ13C values, too. A simple but credible frame was raised to discuss the mechanism of how each possible source and environmental parameter could affect shell carbonate δ13C values based on previous works [4][6][8] and this study. According to this frame and some reasonable assumptions, we have estimated the

  18. Stable carbon isotopic compositions of organic acids in total suspended particles and dusts from Guangzhou, China

    NASA Astrophysics Data System (ADS)

    Ma, Shexia; Peng, Ping'an; Song, Jianzhong; Zhao, Jinping; He, Lulu; Sheng, Guoying; Fu, Jiamo

    2010-10-01

    Stable carbon isotopic compositions of individual organic acids were determined in total suspended particles and dusts from Guangzhou. The δ 13C values of high molecular weight n-alkanoic acids (C 20-C 28) varied from -34.1‰ to -32.4‰ and tended to be heavier in summer and lighter in winter. These δ 13C values indicate that high molecular weight n-alkanoic acids were derived mainly from emission by C 3 plants. Reduced biological synthesis of high molecular weight n-alkanoic acids in winter may be the reason for the light carbon isotopic composition. The δ 13C values of low molecular weight n-alkanoic acids (C 10-C 18) changed from -31.7‰ to -30.3‰ and exhibited a reverse seasonal trend, i.e., heavier in winter and lighter in summer. Slightly heavier δ 13C values of low molecular weight n-alkanoic acids than those of high molecular weight n-alkanoic acids suggested that they may be emitted from blended sources, e.g., anthropogenic sources and vegetation waxes. Lighter δ 13C values in summer may be attributed to relatively low anthropogenic sources and high botanic sources in summer. Dicarboxylic acids and aromatic acids have been proposed as secondary products from photochemical degradation. The average δ 13C values of dicarboxylic acids and aromatic acids were heavier, and ranged from -25.2‰ to -22.9‰ and from -30.0‰ to -27.6‰, respectively. Both dicarboxylic acids and aromatic acids displayed the same temporal variations in the δ 13C values, i.e., negative δ 13C in the summer samples and positive in the winter samples, which may be controlled by photochemical reactions; they are generally severe in winter in Guangzhou under the monsoon weather system. The heaviest δ 13C values were observed in dicarboxylic acids, indicating that dicarboxylic acids were formed by fast and more complete oxidation reactions. These results indicate that the stable carbon isotopic composition of organic acids may provide important information about sources and

  19. The effects of early diagenesis on the chemical and stable carbon isotopic composition of wood

    USGS Publications Warehouse

    Spiker, E. C.; Hatcher, P.G.

    1987-01-01

    Studies of modern and ancient buried wood show that there is a linear correlation between carbohydrate content and the stable carbon isotope composition as carbohydrates are preferentially degraded during early diagenesis. As the carbohydrate content decreases, the ??13C value of the degraded wood decreases 1 to 2 per mil, approaching the value of the residual lignin. These results indicate that carbohydrate degradation products are lost and not incorporated into the aromatic structure as lignin is selectively preserved during early diagenesis of wood. These results also indicate that attempts to quantify terrestrial inputs to modern sedimentary organic matter based on ??13C values should consider the possibility of a 1 to 2 per mil decrease in the ??13C value of degraded wood. ?? 1987.

  20. Atmospheric pCO2 control on speleothem stable carbon isotope compositions

    NASA Astrophysics Data System (ADS)

    Breecker, Daniel O.

    2017-01-01

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

  1. Precise determination of U isotopic compositions in low concentration carbonate samples by MC-ICP-MS.

    PubMed

    Wang, Ruo-Mei; You, Chen-Feng

    2013-03-30

    We developed a fast and simple analytical procedure for precise determination of U isotopic compositions in low concentration natural samples. The main advantage of the new method is that it requires only 12ng U and can obtain all U isotopic ratios without using spike. Five carbonate reference materials (JCp-1, RKM-4, RKM-5, GBW04412 and GBW04413) and 3 international standards with different matrices (IAPSO, IRMM-3184 and CRM-U010) were analyzed for ((234)U/(238)U) and (238)U/(235)U ratios by MC-ICPMS. Using our method, the results for these standards are in close agreement with the certified values, 1.144 ± 0.004, 0.966 ± 0.004 and 0.990 ± 0.003 for ((234)U/(238)U) and 137.72 ± 0.13, 137.64 ± 0.15 and 98.63 ± 0.04 for (238)U/(235)U, in IAPSO, IRMM-3184 and CRM-U010, respectively. The long-term reproducibility of ((234)U/(238)U) and (238)U/(235)U is 0.970 ± 0.002 and 137.56 ± 0.09; 1.144 ± 0.004 and 137.72 ± 0.13, respectively, for in-house U solution and IAPSO. The new ((234)U/(238)U) results for carbonates show much better precision than previous studies and also reflect their age variability. The obtained (238)U/(235)U ratios, representing the first measurements in these carbonate specimens, are rather constant. The method described here requires only 12 ng of U for analysis and can be completed in 5.2 min. The approach provides a fast method to measure ((234)U/(238)U) and (238)U/(235)U ratios in sample matrices commonly encountered in studies of chemical weathering, oceanography and paleoclimatology.

  2. Correction of ground-water chemistry and carbon isotopic composition for effects of CO2 outgassing

    USGS Publications Warehouse

    Pearson, F.J.; Fisher, D.W.; Plummer, L.N.

    1978-01-01

    Direct Pco2 measurements on water samples from several CO2-charged warm springs are significantly higher than Pco2 values calculated from field pH and alkalinity (and other constituents). In addition, calcite saturation indices calculated from field pH and solution composition indicated supersaturation in samples which, on the basis of hydrogeologic concepts, should be near saturation or undersaturated. We attribute these discrepancies to uncertainties in field pH, resulting from CO2 outgassing during pH measurement. Because samples for direct Pco2 measurement can be taken with minimal disturbance to the water chemistry, we have used the measured Pco2 to back calculate an estimate of the field pH and the carbon isotopic composition of the water before outgassing. By reconstructing water chemistry in this way, we find generally consistent grouping of ??13C, pH, and degree of calcite saturation in samples taken from the same source at different times, an observation which we expect based on our understanding of the hydrogeology and geochemistry of the ground-water systems. This suggests that for very careful geochemical work, particularly on ground-waters much above ambient temperature, Pco2 measurements may provide more information on the system and a better estimate of its state of saturation with respect to carbonate minerals than can field measurements of pH. ?? 1978.

  3. The Hydrological Cycle on Mars as Inferred from the Multi O-isotopic Composition of Carbonates in ALH84001

    NASA Astrophysics Data System (ADS)

    Shaheen, R.; Niles, P. B.; Chong, K.; Thiemens, M. H.

    2011-12-01

    Carbonate minerals provide valuable record of the atmosphere in which they are formed. This work utilizes C and O triple isotopic compositions of the carbonate minerals found in ALH84001 to explore the interaction between atmosphere-hydrosphere and lithosphere. The origin of carbonates found in the Martian meteorite ALH84001 (<1%) is heavily debated with low temperature aqueous precipitation, biogenic production, evaporative processes, high temperature reactions, and impact induced melting and reprecipitation are all candidate processes. These carbonates are heterogeneous chemically (Mg, Ca and Fe-Mn rich) and isotopically (δ13CPDB = +27 to 46 %; δ18OVSMOW = +9.5 to 20.6%) on micrometer scales. Our stepped phosphoric acid dissolution experiments released CO2 from multiple phases of Martian carbonate in the rock (12h acid digestion at 25o C for Ca rich phase and 3h acid digestion at 150oC for Mg rich phase). Both Ca and Mg rich phases showed 0.7% excess 17O (Δ17O = δ17O - 0.52δ18O) in contrast to terrestrial carbonate minerals formed by surficial weathering of the meteorite with no oxygen isotopic anomaly Δ17O ≈ 0 (one hour acid digestion at 25o C). The newly identified Ca-rich carbonate phase is 18O enriched (δ18O = +25%) in contrast to all of the other Ca-rich carbonates previously described. It also contains excess 17O (Δ17O = 0.7%) indicating incorporation of oxygen from an atmospheric source of Martian origin. These oxygen isotope characteristics differentiate this phase from the more commonly described carbonate globules or rosettes and suggest formation from separate aqueous event. This is confirmed by the carbon isotope composition of this new carbonate phase (δ13C= +20%) which differs from the other Martian carbonates in the meteorite and from terrestrial sources. This difference may be an evidence of the long term evolution of carbon isotopes in the atmosphere of Mars. The discovery of highly enriched (O isotopes) Ca-rich phase of Martian

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

    NASA Astrophysics Data System (ADS)

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

    2010-12-01

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

  5. Bulk and Stable Isotopic Compositions of Carbonate Minerals in Martian Meteorite Allan Hills 84001: No Proof of High Formation Temperature

    NASA Technical Reports Server (NTRS)

    Treiman, Allan H.; Romanek, Christopher S.

    1998-01-01

    Understanding the origin of carbonate minerals in the Martian meteorite Allan Hills (ALH) 84001 is crucial to evaluating the hypothesis that they contain traces of ancient Martian life. Using arguments based on chemical equilibria among carbonates and fluids, an origin at greater than 650 C (inimical to life) has been proposed. However, the bulk and stable isotopic compositions of the carbonate minerals are open to multiple interpretations and so lend no particular support to a high-temperature origin. Other methods (possibly less direct) will have to be used to determine the formation temperature of the carbonates in ALH 84001.

  6. Carbon and hydrogen isotopic composition of bacterial methane in a shallow freshwater lake

    SciTech Connect

    Woltemate, I.; Whiticar, M.J.; Schoell, M.

    1984-09-01

    Anoxic sediments from freshwater environments such as bogs, swamps, and lakes undergoing early diagenesis are frequently characterized by the formation of biogenic methane. Freshwater biogenic methanes exhibit carbon and hydrogen isotopic values strongly depleted in C-13 and deuterium relative to the respective values for carbon dioxide and formation water. The percentages of methane generated by fermentation and carbon dioxide reduction can be estimated by comparison of hydrogen isotopes in the formation water and methane. On the basis of these hydrogen isotope data, about 75% of the methane formation in Wurmsee comes from acetate reduction. Fermentation is thus the dominant although not exclusive process. Carbon dioxide reduction contributed the balance of the bacterial methane generated. 35 references, 5 figures, 1 table.

  7. Origin of sub-lithospheric diamonds from the Juina-5 kimberlite (Brazil): constraints from carbon isotopes and inclusion compositions

    NASA Astrophysics Data System (ADS)

    Thomson, A. R.; Kohn, S. C.; Bulanova, G. P.; Smith, C. B.; Araujo, D.; Walter, M. J.

    2014-12-01

    Forty-one diamonds sourced from the Juina-5 kimberlite pipe in Southern Brazil, which contain optically identifiable inclusions, have been studied using an integrated approach. The diamonds contain <20 ppm nitrogen (N) that is fully aggregated as B centres. Internal structures in several diamonds revealed using cathodoluminescence (CL) are unlike those normally observed in lithospheric samples. The majority of the diamonds are composed of isotopically light carbon, and the collection has a unimodal distribution heavily skewed towards δ13C ~ -25 ‰. Individual diamonds can display large carbon isotope heterogeneity of up to ~15 ‰ and predominantly have isotopically lighter cores displaying blue CL, and heavier rims with green CL. The light carbon isotopic compositions are interpreted as evidence of diamond growth from abiotic organic carbon added to the oceanic crust during hydrothermal alteration. The bulk isotopic composition of the oceanic crust, carbonates plus organics, is equal to the composition of mantle carbon (-5 ‰), and we suggest that recycling/mixing of subducted material will replenish this reservoir over geological time. Several exposed, syngenetic inclusions have bulk compositions consistent with former eclogitic magnesium silicate perovskite, calcium silicate perovskite and NAL or CF phases that have re-equilibrated during their exhumation to the surface. There are multiple occurrences of majoritic garnet with pyroxene exsolution, coesite with and without kyanite exsolution, clinopyroxene, Fe or Fe-carbide and sulphide minerals alongside single occurrences of olivine and ferropericlase. As a group, the inclusions have eclogitic affinity and provide evidence for diamond formation at pressures extending to Earth's deep transition zone and possibly the lower mantle. It is observed that the major element composition of inclusions and isotopic compositions of host Juina-5 diamonds are not correlated. The diamond and inclusion compositions are

  8. Variability in magnesium, carbon and oxygen isotope compositions, and trace element contents of brachiopod shells: implications for paleoceanographic studies

    NASA Astrophysics Data System (ADS)

    Rollion-Bard, Claire; Saulnier, Ségolène; Vigier, Nathalie; Schumacher, Aimryc; Chaussidon, Marc; Lécuyer, Christophe

    2016-04-01

    Magnesium content in the ocean is ≈ 1290 ppm and is one of the most abundant elements. It is involved in the carbon cycle via the dissolution and precipitation of carbonates, especially Mg-rich carbonates as dolomites. The Mg/Ca ratio of the ocean is believed to have changed through time. The causes of these variations, i.e. hydrothermal activity change or enhanced precipitation of dolomite, could be constrained using the magnesium isotope composition (δ26Mg) of carbonates. Brachiopods, as marine environmental proxies, have the advantage to occur worldwide in a depth range from intertidal to abyssal, and have been found in the geological record since the Cambrian. Moreover, as their shell is in low-Mg calcite, they are quite resistant to diagenetic processes. Here we report δ26Mg, δ18O, δ13C values along with trace element contents of one modern brachiopod specimen (Terebratalia transversa) and one fossil specimen (Terebratula scillae, 2.3 Ma). We combined δ26Mg values with oxygen and carbon isotope compositions and trace element contents to look for possible shell geochemical heterogeneities in order to investigate the processes that control the Mg isotope composition of brachiopod shells. We also evaluate the potential of brachiopods as a proxy of past seawater δ26Mg values. The two investigated brachiopod shells present the same range of δ26Mg variation (up to 2 ‰)). This variation cannot be ascribed to changes in environmental parameters, i.e. temperature or pH. As previously observed, the primary layer of calcite shows the largest degree of oxygen and carbon isotope disequilibrium relative to seawater. In contrast, the δ26Mg value of this layer is comparable to that of the secondary calcite layer value. In both T. scillae and T. transversa, negative trends are observable between magnesium isotopic compositions and oxygen and carbon isotopic compositions. These trends, combined to linear relationships between δ26Mg values and REE contents, are best

  9. Effects of elemental composition on the incorporation of dietary nitrogen and carbon isotopic signatures in an omnivorous songbird

    SciTech Connect

    Pearson, Scott, F.; Levey, Douglas, J.; Greenberg, Catheryn, H.; Martinez del Rio, Carlos

    2003-02-28

    Pearson, S.F., D.J. Levey, C.H. Greenberg, and C.M. del Rio. 2003. Effects of elemental composition on the incorporation of dietary nitrogen and carbon isotopic signatures in an omnivorous songbird. Oecologia. 135:516-523. The use of stable isotopes to infer diet requires quantifying the relationship between diet and tissues and, in particular, knowing of how quickly isotopes turnover in different tissues and how isotopic concentrations of different food components change (discriminate) when incorporated into consumer tissues. We used feeding trials with wild-caught yellow-rumped warblers (Dendroica coronata) to determine d15N and d13C turnover rates for blood, d15N and d13C diet-tissue discrimination factors, and diet-tissue relationships for blood and feathers. After 3 weeks on a common diet, 36 warblers were assigned to one of four diets differing in the relative proportion of fruit and insects. Plasma half-life estimates ranged from 0.4 to 0.7 days for d13C and from 0.5 to 1.7 days for d15N. Half-life did not differ among diets. Whole blood half-life for d13C ranged from 3.9 to 6.1 days. Yellow-rumped warbler tissues were enriched relative to diet by 1.7.3.6% for nitrogen isotopes and by 1.2 to 4.3% for carbon isotopes, depending on tissue and diet. Consistent with previous studies, feathers were the most enriched and whole blood and plasma were the least enriched or, in the case of carbon, slightly depleted relative to diet. In general, tissues were more enriched relative to diet for birds with high percentages of insects. For all tissues, carbon and nitrogen isotope discrimination factors increased with carbon and nitrogen concentrations of diets. The isotopic signature of plasma increased linearly with the sum of the isotopic signature of the diet and the discrimination factor. Because the isotopic signature of tissues depends on both elemental concentration and isotopic signature of the diet, attempts to reconstruct diet from stable isotope signatures

  10. Factors controlling shell carbon isotopic composition of land snail Acusta despecta sieboldiana estimated from laboratory culturing experiment

    NASA Astrophysics Data System (ADS)

    Zhang, N.; Yamada, K.; Suzuki, N.; Yoshida, N.

    2014-10-01

    The carbon isotopic composition (δ13C) of land snail shell carbonate derives from three potential sources: diet, atmospheric CO2, and ingested carbonate (limestone). However, their relative contributions remain unclear. Under various environmental conditions, we cultured one land snail subspecies, Acusta despecta sieboldiana, collected from Yokohama, Japan, and confirmed that all of these sources affect shell carbonate δ13C values. Herein, we consider the influences of metabolic rates and temperature on the carbon isotopic composition of the shell carbonate. Based on results obtained from previous works and this study, a simple but credible framework is presented to illustrate how each source and environmental parameter affects shell carbonate δ13C values. According to this framework and some reasonable assumptions, we estimated the contributions of different carbon sources for each snail individual: for cabbage-fed (C3 plant) groups, the contributions of diet, atmospheric CO2, and ingested limestone vary in the ranges of 66-80, 16-24, and 0-13%, respectively. For corn-fed (C4 plant) groups, because of the possible food stress (less ability to consume C4 plants), the values vary in the ranges of 56-64, 18-20, and 16-26%, respectively. Moreover, according to the literature and our observations, the subspecies we cultured in this study show preferences towards different plant species for food. Therefore, we suggest that the potential food preference should be considered adequately for some species in paleoenvironment studies. Finally, we inferred that only the isotopic exchange of the calcite-HCO3--aragonite equilibrium during egg laying and hatching of our cultured snails controls carbon isotope fractionation.

  11. Factors controlling shell carbon isotopic composition of land snail Acusta despecta sieboldiana estimated from lab culturing experiment

    NASA Astrophysics Data System (ADS)

    Zhang, N.; Yamada, K.; Suzuki, N.; Yoshida, N.

    2014-05-01

    The carbon isotopic composition (δ13C) of land snail shell carbonate derives from three potential sources: diet, atmospheric CO2, and ingested carbonate (limestone). However, their relative contributions remain unclear. Under various environmental conditions, we cultured one land snail species, Acusta despecta sieboldiana collected from Yokohama, Japan, and confirmed that all of these sources affect shell carbonate δ13C values. Herein, we consider the influences of metabolic rates and temperature on the carbon isotopic composition of the shell carbonate. Based on previous works and on results obtained in this study, a simple but credible framework is presented for discussion of how each source and environmental parameter can affect shell carbonate δ13C values. According to this framework and some reasonable assumptions, we have estimated the contributions of different carbon sources for each snail individual: for cabbage (C3 plant) fed groups, the contributions of diet, atmospheric CO2 and ingested limestone respectively vary as 66-80%, 16-24%, and 0-13%. For corn (C4 plant) fed groups, because of the possible food stress (lower consumption ability of C4 plant), the values vary respectively as 56-64%, 18-20%, and 16-26%. Moreover, we present new evidence that snails have discrimination to choose C3 and C4 plants as food. Therefore, we suggest that food preferences must be considered adequately when applying δ13C in paleo-environment studies. Finally, we inferred that, during egg laying and hatching of our cultured snails, carbon isotope fractionation is controlled only by the isotopic exchange of the calcite-HCO3--aragonite equilibrium.

  12. [Study on the content and carbon isotopic composition of water dissolved inorganic carbon from rivers around Xi'an City].

    PubMed

    Guo, Wei; Li, Xiang-Zhong; Liu, Wei-Guo

    2013-04-01

    In this study, the content and isotopic compositions of water dissolved inorganic carbon (DIC) from four typical rivers (Chanhe, Bahe, Laohe and Heihe) around Xi'an City were studied to trace the possible sources of DIC. The results of this study showed that the content of DIC in the four rivers varied from 0.34 to 5.66 mmol x L(-1) with an average value of 1.23 mmol x L(-1). In general, the content of DIC increased from the headstream to the river mouth. The delta13C(DIC) of four rivers ranged from -13.3 per thousand to -7.2 per thousand, with an average value of -10.1 per thousand. The delta13C(DIC) values of river water were all negative (average value of -12.6 per thousand) at the headstream of four rivers, but the delta13C(DIC) values of downstream water were more positive (with an average value of -9.4 per thousand). In addition, delta13C(DIC) of river water showed relatively negative values (the average value of delta13C(DIC) was -10.5 per thousand) near the estuary of the rivers. The variation of the DIC content and its carbon isotope suggested that the DIC sources of the rivers varied from the headstream to the river mouth. The negative delta13C(DIC) value indicated that the DIC may originate from the soil CO2 at the headstream of the rivers. On the other hand, the delta13C(DIC) values of river water at the middle and lower reaches of rivers were more positive, and it showed that soil CO2 produced by respiration of the C4 plants (like corn) and soil carbonates with positive delta13C values may be imported into river water. Meanwhile, the input of pollutants with low delta13C(DIC) values may result in a decrease of delta13C(DIC) values in the rivers. The study indicated that the DIC content and carbon isotope may be used to trace the sources of DIC in rivers around Xi'an City. Our study may provide some basic information for tracing the sources of DIC of rivers in the small watershed area in the Loess Plateau of China.

  13. Distribution and Carbon-Isotope Composition of Lipid Biomarkers in Lake Sediments on the Tibetan Plateau, China

    NASA Astrophysics Data System (ADS)

    Tuo, J.; Li, Q.; Li, Y.; Jiang, H.; Dong, H.; Zhang, C. L.

    2005-12-01

    The goal of this study was to determine the carbon source and microbial community structure in different lake environments on the Tibetan Plateau using carbon isotopes and lipid biomarkers. Microbial mats and sediments were collected from Erhai-, Qinghai-, Gahai-, and Chaka-lakes, which have different pHs (7.4-9.5) and salinities (0.1-21%). Phospholipid fatty acids (PLFA) have different distribution patterns in algal mats, sandy mud, and salt deposits, which may reflect changes in microbial community structure in different environments. For example, terminally branched fatty acids reflect heterotrophic bacteria and varied from less than 1% in a brown algal mat in Lake Gahai to 23% in a salt deposit in Lake Chaka. The cyclopropyl fatty acids may reflect stress conditions under different salinities. These compounds varied from 0% in algal mats living on the bank of the lake, which received freshwater run off, to 12% in grey mud in the saline lake water. On the other hand, long-chain n-alkanes in these samples reflect contributions of a mixture of epicuticular waxes of higher plants and submerged or floating aquatic macrophytes. Carbon isotopes of lipid biomarkers indicate different sources of organic carbon in different lake sediments. For example, carbon isotopes of total organic carbon and lipid biomarkers averaged -23.9 ± 1.5‰ (n = 2) and -26.0 ± 3.1‰ (n = 18), respectively, in Lake Erhai, and averaged -30.0 ± 1.5‰ (n = 4) and -33.5 ± 3.3‰ (n = 92), respectively, in Lake Gahai. These results suggest that a relatively heavy carbon source is going into Lake Erhai compared to carbon sources going into Lake Gahai. This study indicates that the distribution patterns of the lipid biomarkers and theirs carbon-isotope compositions can be used to evaluate the community structure and the source of carbon that supports microbial growth in lake sediments on the Tibetan Plateau.

  14. [Effect of processes in the earth's crust on evolution of photosynthesis (as indicated by data on carbon isotopic composition)].

    PubMed

    Ivlev, A A

    2010-01-01

    model, data on isotope composition of carbon of carbonate and organic substance in rocks are used and its ability to explain several known natural regularities and empirical correlations. The model is used for analysis of some key stages of evolution of photosynthesis.

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

    NASA Technical Reports Server (NTRS)

    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

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

    PubMed

    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. Landscape variability of the stable carbon isotope composition of soil CO2 concentrations and flux in complex terrain

    NASA Astrophysics Data System (ADS)

    Riveros-Iregui, Diego; Liang, Liyin; Risk, David

    2015-04-01

    Stable isotopes are commonly used to understand how physical and biological processes mediate the exchange of carbon between terrestrial ecosystems and the atmosphere. Numerous studies have described fundamental relationships between environmental variables, the carbon isotopic composition (δ13C) of recently assimilated sugars in plants, litter, soil carbon, or recently respired CO2. However, studies that examine the landscape scale variability of the 13C content of forest soils are lacking. We report on measurements of the carbon isotopic composition of soil CO2 concentrations (δ13CC) and flux (δ13CJ) across a subalpine forest of the northern Rocky Mountains of Montana, United States. Our analysis demonstrates that soil moisture and the lateral redistribution of soil water are strong predictors of the spatial variability of both δ13CC and δ13CJ at the watershed scale. Our analysis suggests that there are concomitant yet independent effects of soil water on physical (i.e., soil gas diffusivity) and biological (i.e., photosynthetic activity) processes that mediate the 13C composition of forest soils. We show systematic spatial variability in the δ13C of forest soils at the landscape scale that can be useful to accurately predict and model land-atmosphere CO2 exchange over complex terrain.

  18. USE OF THE COMPOSITION AND STABLE CARBON ISOTOPE RATIO OF MICROBIAL FATTY ACIDS TO STUDY CARBON CYCLING

    EPA Science Inventory

    We use measurements of the concentration and stable carbon isotopic ratio (Gamma 13C) of individual microbial phospholipid fatty acids (PLFAS) in soils and sediments as indicators of live microbial biomass levels and microbial carbon source. For studies of soil organic matter (SO...

  19. Alkane distribution and carbon isotope composition in fossil leaves: An interpretation of plant physiology in the geologic past

    NASA Astrophysics Data System (ADS)

    Graham, H. V.; Freeman, K. H.

    2014-12-01

    The relative chain-length distribution and carbon-isotope composition of n-alkanes extracted from sedimentary rocks are important geochemical tools for investigating past terrestrial ecosystems. Alkanes preserved in ancient sediments are assumed to be contemporaneous, derived from the same ecosystem, and integrated from the biomass present on the landscape at the time of deposition. Further, there is an underlying assumption that ancient plants exhibited the same metabolic and physiological responses to climate conditions that are observed for modern plants. Interpretations of alkane abundances and isotopic signatures are complicated by the strong influence of phylogenetic affiliation and ecological factors, such as canopy structure. A better understanding of how ecosystem and taxa influence alkane properties, including homologue abundance patterns and leaf-lipid carbon isotope fractionation would help strengthen paleoecological interpretations based on these widely employed plant biomarkers. In this study, we analyze the alkane chain-length distribution and carbon-isotope composition of phytoleim and alkanes (d13Cleaf and d13Clipid) extracted from a selection of Cretaceous and Paleocene fossil leaves from the Guaduas and Cerrejon Formations of Colombia. These data were compared with data for the same families in a modern analogue biome. Photosynthetic and biosynthetic fractionation (∆leaf and elipid) values determined from the fossil material indicate carbon metabolism patterns were similar to modern plants. Fossil data were incorporated in a biomass-weighted mixing model to represent the expected lipid complement of sediment arising from this ecosystem and compared with alkane measurements from the rock matrix. Modeled and observed isotopic and abundance patterns match well for alkane homologs most abundant in plants (i.e., n-C27 to n-C33). The model illustrates the importance of understanding biases in litter flux and taphonomic pressures inherent in the

  20. Alteration of the Carbon and Nitrogen Isotopic Composition in the Martian Surface Rocks Due to Cosmic Ray Exposure

    NASA Technical Reports Server (NTRS)

    Pavlov, A. A.; Pavlov, A. K.; Ostryakov, V. M.; Vasilyev, G. I.; Mahaffy, P.; Steele, A.

    2014-01-01

    C-13/C-12 and N-15/N-14 isotopic ratios are pivotal for our understanding of the Martian carbon cycle, history of the Martian atmospheric escape, and origin of the organic compounds on Mars. Here we demonstrate that the carbon and nitrogen isotopic composition of the surface rocks on Mars can be significantly altered by the continuous exposure of Martian surface to cosmic rays. Cosmic rays can effectively produce C-13 and N-15 isotopes via spallation nuclear reactions on oxygen atoms in various Martian rocks. We calculate that in the top meter of the Martian rocks, the rates of production of both C-13 and N-15 due to galactic cosmic rays (GCRs) exposure can vary within 1.5-6 atoms/cm3/s depending on rocks' depth and chemical composition. We also find that the average solar cosmic rays can produce carbon and nitrogen isotopes at a rate comparable to GCRs in the top 5-10 cm of the Martian rocks. We demonstrate that if the total carbon content in a surface Martian rock is <10 ppm, then the "light," potentially "biological" C-13/C-12 ratio would be effectively erased by cosmic rays over 3.5 billion years of exposure. We found that for the rocks with relatively short exposure ages (e.g., 100 million years), cosmogenic changes in N-15/N-14 ratio are still very significant. We also show that a short exposure to cosmic rays of Allan Hills 84001 while on Mars can explain its high-temperature heavy nitrogen isotopic composition (N-15/N-14). Applications to Martian meteorites and the current Mars Science Laboratory mission are discussed.

  1. Genetic architecture of carbon isotope composition and growth in Eucalyptus across multiple environments.

    PubMed

    Bartholomé, Jérôme; Mabiala, André; Savelli, Bruno; Bert, Didier; Brendel, Oliver; Plomion, Christophe; Gion, Jean-Marc

    2015-06-01

    In the context of climate change, the water-use efficiency (WUE) of highly productive tree varieties, such as eucalypts, has become a major issue for breeding programmes. This study set out to dissect the genetic architecture of carbon isotope composition (δ(13) C), a proxy of WUE, across several environments. A family of Eucalyptus urophylla × E. grandis was planted in three trials and phenotyped for δ(13) C and growth traits. High-resolution genetic maps enabled us to target genomic regions underlying δ(13) C quantitative trait loci (QTLs) on the E. grandis genome. Of the 15 QTLs identified for δ(13) C, nine were stable across the environments and three displayed significant QTL-by-environment interaction, suggesting medium to high genetic determinism for this trait. Only one colocalization was found between growth and δ(13) C. Gene ontology (GO) term enrichment analysis suggested candidate genes related to foliar δ(13) C, including two involved in the regulation of stomatal movements. This study provides the first report of the genetic architecture of δ(13) C and its relation to growth in Eucalyptus. The low correlations found between the two traits at phenotypic and genetic levels suggest the possibility of improving the WUE of Eucalyptus varieties without having an impact on breeding for growth.

  2. Carbon Isotope Composition of Ecosystem Respired Carbon Dioxide in Three Boreal Forest Ecosystems: Measurements and Model Calculations

    NASA Astrophysics Data System (ADS)

    Cai, T.; Flanagan, L. B.

    2007-12-01

    We conducted measurements of seasonal and inter-annual variation in the carbon isotope composition of ecosystem respired CO2 (δR) in aspen, black spruce and jack pine dominated ecosystems in northern Saskatchewan during 2004-2006 as part of the Fluxnet-Canada Research Network. All three sites showed relatively small variation (approximately -26 to -29 per mil) in δR values during the entire study. The measurements were strongly correlated with modeled δ13C values of ecosystem respired CO2. The model calculated leaf CO2 assimilation, stomatal conductance and chloroplast CO2 concentration separately for sunlit and shaded leaves within multiple canopy layers, and, therefore, allowed us to estimate canopy photosynthetic 13C discrimination. All three sites showed variation in canopy 13C discrimination in response to environmental conditions in a manner consistent with well-known leaf-level studies. Specifically, 13C discrimination was positively correlated with soil moisture and negatively correlated with photon flux density, air temperature and vapor pressure deficit. As a consequence a strong diurnal pattern was observed for 13C discrimination. The measured δR values also varied in response to environmental conditions in a manner consistent with well-known leaf-level studies of photosynthetic 13C discrimination, but with a dampened response caused by the contribution of heterotrophic respiration, which had a constant δ13C value. These results indicate that the stable isotope composition of respired CO2 is a useful ecosystem-scale tool to study constraints to photosynthesis and acclimation of ecosystems to environmental stress.

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

    PubMed

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

    2013-10-29

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

  4. Carbon and Noble Gas Isotope Banks in Two-Phase Flow: Changes in Gas Composition During Migration

    NASA Astrophysics Data System (ADS)

    Sathaye, K.; Larson, T.; Hesse, M. A.

    2015-12-01

    In conjunction with the rise of unconventional oil and gas production, there has been a recent rise in interest in noble gas and carbon isotope changes that can occur during the migration of natural gas. Natural gas geochemistry studies use bulk hydrocarbon composition, carbon isotopes, and noble gas isotopes to determine the migration history of gases from source to reservoir, and to trace fugitive gas leaks from reservoirs to shallow groundwater. We present theoretical and experimental work, which helps to explain trends observed in gas composition in various migration scenarios. Noble gases are used as tracers for subsurface fluid flow due to distinct initial compositions in air-saturated water and natural gases. Numerous field studies have observed enrichments and depletions of noble gases after gas-water interaction. A theoretical two-phase gas displacement model shows that differences in noble gas solubility will cause volatile gas components will become enriched at the front of gas plumes, leaving the surrounding residual water stripped of dissolved gases. Changes in hydrocarbon gas composition are controlled by gas solubility in both formation water and residual oil. In addition to model results, we present results from a series of two-phase flow experiments. These results demonstrate the formation of a noble gas isotope banks ahead of a main CO2 gas plume. Additionally, we show that migrating hydrocarbon gas plumes can sweep biogenic methane from groundwater, significantly altering the isotope ratio of the gas itself. Results from multicomponent, two-phase flow experiments qualitatively agree with the theoretical model, and previous field studies. These experimentally verified models for gas composition changes can be used to aid source identification of subsurface gases.

  5. Stable isotopic compositions of carbon in vegetation and soil organic matter along the bioclimatic transect, North Caucasus

    NASA Astrophysics Data System (ADS)

    Kovda, Irina; Morgun, Evgeny; Golubeva, Natalia

    2010-05-01

    Stable isotopic composition of carbon in plant species and soil organic matter was investigated along the bioclimatic transect in the North Caucasus. The aim of this research was to find the possible shift of stable isotopic composition of carbon reflecting the gradual successive changes of landscapes connected with the changes of climatic conditions (temperature, precipitation, air humidity) at a various absolute heights above sea level i.e. along the vertical zonation. The study site was located in the North Caucasus near Arkhiz, Big Zelentchuk valley (43o33-40'N; 41o16-27'E). Soil and vegetation samples were collected along Precaucasus and Caucasus slopes at an absolute heights interval of 1280 - 2065 m. Soils are formed at eluvo-deluvium of noncarbonated silicate massive rocks under warm temperate climate with MAT 4-5oC and MAP ~ 860 mm and more. Samples of vegetation (whole grasses and tree leaves) represented several altitudinal vegetation belts including forest and subalpine belts with coniferous (pine, spruce, fir), mixed coniferous-deciduous (fir + beech), broad-leaved (beech, maple), small-leaved (birch, aspen) forests, elfin birch wood and subalpine meadows. Stable isotope composition of carbon was determined using IRMS Finnigan Delta V+. Stable isotopic composition of vegetal species ranges from -33.04 to -27.29 o/oo with the general trend of lighter δ13С with the decreasing of absolute heights. The most heavier δ13С = ~ -27o/oo were found in subalpine meadow plants, while at a smaller altitudes in the forest belt δ13С shifts to ~ 30-31, and up to ~ - 32-33o/oo. More clear regularities were found for vegetation specimens grouped into three categories such as "trees", "grasses" and "litter". δ13С of each category clearly shifts to the lighter values with the decrease of absolute heights i.e from subalpine meadows to spruce-broad-leaved forests. δ13С shift is about 2,49o/oo for trees, 1,75-4,92 o/oo for grasses and ~ 1,8 o/oo for the litter. The

  6. Triple Isotopic Composition of Atmospheric Carbonates: A Novel Technique to Identify Heterogeneous Chemistry on Aerosol Surfaces in Polluted Environment

    NASA Astrophysics Data System (ADS)

    Shaheen, R.; Horn, J.; Dominguez, G.; Masterson, A.; Ivanov, A. V.; Thiemens, M. H.

    2009-12-01

    In the ambient atmosphere, the physical and chemical properties of aerosol vary greatly between location and time due to various heterogeneous and photochemical reactions in the atmosphere. In polluted urban environments, the aerosol and gaseous mixtures interact to produce new compounds and particulates; consequently humans are exposed to many as yet undetected species. Studies of actual chemically-active, airborne particulates can better address the interaction of complex particulate and gaseous pollutant mixtures, however, it is notoriously difficult to measure chemical transformations of aerosols. Here we describe a new technique that can be used to understand the chemical transformation occurring on the surface of aerosols and thus to quantify the interaction of gaseous species and aerosol in the atmosphere. Fine and coarse aerosol samples were collected on filter papers in La Jolla, CA, USA for one week. The aerosol samples were digested with phosphoric acid and CO2 released was purified chromatographically and analyzed for 13 C. To obtain independent measurements of oxygen isotopes, the CO2 was fluorinated and oxygen gas obtained was analyzed using Mat253 Isotope Ratio Mass Spectrometer. The data indicated an excess 17O (0.6 to 4‰) in atmospheric carbonates. The oxygen isotope anomaly in atmospheric carbonates has been observed for the first time and it showed a highly significant correlation (r2 = 0.90) with urban index; an indirect measure of ozone chemistry. The δ13C in atmospheric carbonates was found to vary from -18 to -40‰. Controlled laboratory experiments to understand the origin and variation in the C and O isotopic composition of atmospheric carbonates were conducted using various mineral surfaces. Isotopic measurements of in-situ formed carbonated on CaOH, CaO, MgO, SiO2,Cu, CuO, Ni and Fe2O3 due to chemisorbed CO2 in the presence of thin water films were performed and we found that the δ13C in these carbonates ranged from -12 to -24

  7. Carbon, hydrogen and nitrogen in carbonaceous chondrites Abundances and isotopic compositions in bulk samples

    NASA Technical Reports Server (NTRS)

    Kerridge, J. F.

    1985-01-01

    Whole-rock samples of 25 carbonaceous chondrites were analyzed for contents of C, H and N and delta C-13, delta D and delta N-15. Inhomogeneous distribution of these isotopes within individual meteorites is pronounced in several cases. Few systematic intermeteorite trends were observed; N data are suggestive of isotopic inhomogeneity in the early solar system. Several chondrites revealed unusual compositions which would repay further, more detailed study. The data are also useful for classification of carbonaceous chondrites; N abundance and isotopic compositions can differentiate existing taxonomic groups with close to 100 percent reliability; Al Rais and Renazzo clearly constitute a discrete 'grouplet', and there are hints that both CI and CM groups may each be divisible into two subgroups.

  8. Influence of diagenesis on the stable isotopic composition of biogenic carbonates from the Gulf of Tehuantepec oxygen minimum zone

    NASA Astrophysics Data System (ADS)

    Blanchet, C. L.; Kasten, S.; Vidal, L.; Poulton, S. W.; Ganeshram, R.; Thouveny, N.

    2012-04-01

    In order to evaluate the influence of diagenetic and post-sampling processes on the stable oxygen and carbon isotope compositions of biogenic carbonates, we conducted a multiproxy study of organic-rich sediments from the eastern Pacific oxygen minimum zone. Core MD02-2520, which was retrieved from the Gulf of Tehuantepec (Mexico), has seasonal laminations and covers the last 40 kyr. Together with the presence of gypsum crystals and inorganic calcite aggregates, the occurrence of large excursions in the stable oxygen and carbon isotope records of both planktonic and benthic foraminifera (as large as +3‰ in δ18O and -5‰ in δ13C) point to significant secondary transformations. Storage-related gypsum precipitation was ruled out since it implies sulfide reoxidation by oxygen that triggers biogenic calcite dissolution, which proved to be of minor importance here. Instead, precipitation of authigenic calcite during early diagenesis appears to be the most likely process responsible for the observed isotopic excursions. The δ13C composition for inorganic calcite aggregates (-5 to -7‰) suggests a major contribution from anaerobic oxidation of organic matter. The δ34S composition for gypsum crystals (-10 to +15‰) suggests a major contribution from anaerobic reoxidation of authigenic sulfides, potentially involving reactions with metal oxides and sulfur disproportionation. A minor part of the gypsum might possibly have formed as a result of local pore water salinity increases induced by gas hydrate formation.

  9. Carbon and nitrogen isotope composition of core catcher samples from the ICDP deep drilling at Laguna Potrok Aike (Patagonia, Argentina)

    NASA Astrophysics Data System (ADS)

    Luecke, Andreas; Wissel, Holger; Mayr*, Christoph; Oehlerich, Markus; Ohlendorf, Christian; Zolitschka, Bernd; Pasado Science Team

    2010-05-01

    The ICDP project PASADO aims to develop a detailed paleoclimatic record for the southern part of the South American continent from sediments of Laguna Potrok Aike (51°58'S, 70°23'W), situated in the Patagonian steppe east of the Andean cordillera and north of the Street of Magellan. The precursor project SALSA recovered the Holocene and Late Glacial sediment infill of Laguna Potrok Aike and developed the environmental history of the semi-arid Patagonian steppe by a consequent interdisciplinary multi-proxy approach (e.g. Haberzettl et al., 2007). From September to November 2008 the ICDP deep drilling took place and successfully recovered in total 510 m of sediments from two sites resulting in a composite depth of 106 m for the selected main study Site 2. A preliminary age model places the record within the last 50.000 years. During the drilling campaign, the core catcher content of each drilled core run (3 m) was taken as separate sample to be shared and distributed between involved laboratories long before the main sampling party. A total of 70 core catcher samples describe the sediments of Site 2 and will form the base for more detailed investigations on the palaeoclimatic history of Patagonia. We here report on the organic carbon and nitrogen isotope composition of bulk sediment and plant debris of the core catcher samples. Similar investigations were performed for Holocene and Late Glacial sediments of Laguna Potrok Aike revealing insights into the organic matter dynamics of the lake and its catchment as well as into climatically induced hydrological variations with related lake level fluctuations (Mayr et al., 2009). The carbon and nitrogen content of the core catcher fine sediment fraction (<200 µm) is low to very low (around 1 % and 0.1 %, respectively) and requires particular attention in isotope analysis. The carbon isotope composition shows comparably little variation around a value of -26.0 per mil. The positive values of the Holocene and the Late

  10. The formation of weathering products on the LEW 85320 ordinary chondrite: evidence from carbon and oxygen stable isotope compositions and implications for carbonates in SNC meteorites.

    PubMed

    Grady, M M; Gibson, E K; Wright, I P; Pillinger, C T

    1989-01-01

    Isotopic analysis of nesquehonite recovered from the surface of the LEW 85320 H5 ordinary chondrite shows that the delta 13C and delta 18O values of the two generations of bicarbonate (Antarctic and Texas) are different: delta 13C = +7.9% and +4.2%; delta 18O = +17.9% and 12.1% respectively. Carbon isotopic compositions are consistent with equilibrium formation from atmospheric carbon dioxide at -2 +/- 4 degrees C (Antarctic) and +16 +/- 4 degrees C (Texas). Oxygen isotopic data imply that the water required for nesquehonite precipitation was derived from atmospheric water vapour or glacial meltwater which had locally exchanged with silicates, either in the meteorite or in underlying bedrock. Although carbonates with similar delta 13C values have been identified in the SNC meteorites EETA 79001 and Nakhla, petrographic and temperature constraints argue against their simply being terrestrial weathering products.

  11. The formation of weathering products on the LEW 85320 ordinary chondrite - Evidence from carbon and oxygen stable isotope compositions and implications for carbonates in SNC meteorites

    NASA Technical Reports Server (NTRS)

    Grady, Monica M.; Wright, I. P.; Pillinger, C. T.; Gibson, E. K., Jr.

    1989-01-01

    Isotopic analysis of nesquehonite recovered from the surface of the LEW 85320 H5 ordinary chondrite shows that the delta C-13 and delta O-18 values of the two generations of bicarbonate (Antarctic and Texas) are different: delta C-13 = + 7.9 per mil and + 4.2 per mil; delta O-18 = + 17.9 per mil and + 12.1 per mil, respectively. Carbon isotopic compositions are consistent with equilibrium formation from atmospheric carbon dioxide at - 2 + or - 4 C (Antarctic) and + 16 + or - 4 C (Texas). Oxygen isotopic data imply that the water required for nesquehonite precipitation was derived from atmospheric water vapor or glacial meltwater which had locally exchanged with silicates, either in the meteorite or in underlying bedrock. Although carbonates with similar delta C-13 values have been identified in the SNC meteorites EETA 79001 and Nakhla, petrographic and temperature constraints argue against their simply being terrestrial weathering products.

  12. Isotopic compositions of elemental carbon in smoke and ash derived from crop straw combustion

    NASA Astrophysics Data System (ADS)

    Liu, Gang; Li, Jiuhai; Xu, Hui; Wu, Dan; Liu, Yan; Yang, Hui

    2014-08-01

    Six cultivars of straw for rice, maize and wheat, respectively, were burned under flaming and smoldering conditions, and carbon isotopic ratio values of elemental carbon (EC) in smoke and ash determined. The results showed that mean carbon isotopic fractionation (Δ13C) between EC in flaming and smoldering smoke from rice straw, and the starting material was -2.7‰ and -3.0‰, respectively. Moreover, the corresponding Δ13C values for EC in flaming and smoldering smoke from wheat straw were -0.1‰ and +0.4‰, respectively. Δ13C for EC in the two types of smoke from maize straw were -3.4‰ and +0.2‰, respectively. Δ13C for EC in flaming and smoldering ash from rice straw were -1.8‰ and -1.6‰ in turn. Δ13C for EC in flaming and smoldering ash from wheat straw were +0.9‰ and +2.4‰, respectively. Additionally, the ones for EC in the two types of ash from maize straw were -1.2‰ and -1.0‰, respectively. If δ13CEC values for pollutants, such as straw smoke, soot from coal and diesel-powered vehicles, and ambient PM2.5 in a region, are determined in summer and autumn, the contribution of straw burning to ambient EC is likely to be estimated with the approach of carbon isotopic mass balance.

  13. Stable Carbon and Oxygen Isotope Composition of Soil and Shell from an Archeological Site in Kimble County, Texas

    NASA Astrophysics Data System (ADS)

    Salazar, K. K.; Paul, D.; Skrzypek, G.; Tomka, S. A.

    2007-12-01

    We report stable carbon (δ13C) and oxygen (δ18O) isotopic composition of inorganic carbonates, soil organic matter (SOM), and terrestrial gastropod shells present in a 130cm soil profile (radiocarbon date of 2340-2120 B.P) recovered from archeological site 41KM69, Kimble County, Texas. Prior to soil carbonate and SOM analyses, samples were treated with 5% sodium hypochlorite to remove organic matter and treated with 4% HCl to remove inorganic carbonate, respectively. Isotopic compositions of samples were obtained utilizing a Gasbench II (for carbonate-acid reaction technique) and a CHNS Elemental Analyzer (for SOM) coupled with a DeltaPlus XP Isotope Ratio Mass Spectrometer in continuous-flow. δ13C of carbonates in the soil profile varies in the range -2.15 to -4.63 ‰. δ18O of carbonates (ranging from -3.22 to -3.92‰) show little variation within the profile. δ13C of SOM (-25.61‰ to -22.83‰) suggests that C3 plants were predominant in the study area. There is ~3‰ enrichment in 13C of SOM at the bottom of profile relative to the top. Previous studies have shown that δ13C of modern soil carbonates are higher by 14-16‰ than SOM, whereas our results show about 20‰ difference. δ13C of land snail shells ( Rabdotus, Polygyra, Helicina) recovered from the soil show strong linear correlation with depth (R2= 0.88): -9.46‰ at 60cm to -5.4‰ at 112cm. δ18O of shells show no correlation with depth and range from - 3.34‰ to 0.62‰. Excluding one shell analysis, δ13C of shells and SOM exhibit good correlation (R2= 0.80). Previous studies of variation in δ13C in land snail shell document that carbon isotopic composition in shell are primarily a function of snail diet. Balakrishnan et al. (2005) have shown that δ13C of shells in C3 vegetation regimes range from -10.0‰ to -8.8‰, which is consistent with our results. Although, the interpretation of δ18O values in land snails is not straightforward, values are probably related to several different

  14. Contribution of Organic Material to the Stable Isotope Composition of Some Terrestrial Carbonates as Analogs for Martian Processes

    NASA Technical Reports Server (NTRS)

    Socki, Richard A.; Gibson, Everett K., Jr.; Bissada, K. K.

    2005-01-01

    Understanding the isotopic geochemistry of terrestrial carbonate formation is essential to understanding the evolution of the Martian atmosphere, hydrosphere, and potential biosphere. Carbonate minerals, in particular, are important secondary minerals for interpreting past aqueous environments, as illustrated by the carbonates present in ALH84001 [1]. Models for the history of Mars suggest that the planet was warmer, wetter, and possessed a greater atmospheric pressure within the first billion years as compared to present conditions [2],[3],[4], and likely had an active hydrologic cycle. Morse and Marion [5] point out that associated with this hydrologic cycle would be the active chemical weathering of silicate minerals and thus consumption of atmospheric CO2 and deposition of carbonate and silica. It is during this warmer and wetter period of Martian history that surface and/or near-surface conditions would be most favorable for harboring possible microbiological life. Carbonates within ALH84001 offer evidence that fluids were present at 3.9 Gy on Mars [6]. A more through understanding of the effects of aqueous weathering and the potential contribution of organic compounds on the isotopic composition of Martian carbonate minerals can be gained by studying some terrestrial occurrences of carbonate rocks.

  15. Oxygen isotopic composition of fruit carbonate in Lithospermeae and its potential for paleoclimate research in the Mediterranean

    NASA Astrophysics Data System (ADS)

    Pustovoytov, Konstantin; Riehl, Simone; Hilger, Hartmut H.; Schumacher, Erich

    2010-04-01

    Calcareous pericarps of the tribe Lithospermeae (fam. Boraginaceae) are a common component of archaeobotanical macroremain assemblages in the Mediterranean region. In this study, the relationship between oxygen isotopic composition of fruit biogenic carbonate and climatic conditions was examined. δ18O and δ13C values of biogenic carbonate were measured in modern Lithospermeae fruits from seven Eurasian sites (Berlin, Kirchentellinsfurt, Göttingen, Athens, Ankara, Tbilisi, and Almaty) and in fossil fruits from three archaeological sites in the eastern Mediterranean (Troy, Kumtepe, and Hirbet ez-Zeraqon). Additionally, three 14C measurements were performed on ancient fruit carbonate from Hirbet ez-Zeraqon. The δ18O and δ13C values varied from - 9 to 5‰ PDB and between - 35 and - 7‰ PDB respectively. In modern fruits, δ18O of biogenic carbonate was correlated to local summer precipitation amounts (inversely proportional) and summer air temperatures (proportional). In fossil fruits, the δ18O values of carbonate from Troy and Kumtepe were significantly lower than that from Hirbet ez-Zeraqon (ca. - 5 vs. 2‰ PDB respectively). The vertical distribution of stable isotopic values and 14C dates in cultural layers of Hirbet ez-Zeraqon indicate that fruit biogenic carbonate can persist in sediment without appreciable diagenetic alteration. These findings suggest that biogenic carbonate of Lithospermeae fruits can be useful as a paleoclimate proxy at least in the Mediterranean.

  16. Correlating genetic variation in carbon isotopic composition with complex climatic gradients.

    PubMed Central

    Comstock, J P; Ehleringer, J R

    1992-01-01

    Genetic variation in both carbon isotope discrimination and the proportions of leaf and photosynthetic twig tissues were observed in ecotypes of Hymenoclea salsola T.G., a common shrub in the deserts of the western United States, when grown under common garden conditions. These variations were correlated with climatic conditions in the habitats of origin through a model that described the leaf-to-air water vapor gradients experienced by plants during the growing season. Both carbon isotope discrimination and the proportion of leaves in the canopy were lower in plants derived from habitats with higher leaf-to-air vapor gradients, despite the fact that some of these sites received relatively high amounts of annual precipitation. These patterns were consistent with the notion that plants are able to maintain substantial control of water-use efficiency over large environmental gradients of temperature and moisture availability. PMID:1502194

  17. Effect of thermal decarbonation on the stable isotope composition of carbonates

    SciTech Connect

    Durakiewicz, T.; Sharp, Z. D.; Papike, J. J. ,

    2001-01-01

    The unusual texture and stable isotope variability of carbonates in AH84001 have been used as evidence for early life on Mars (Romanek et al., 1994; McKay et al., 1996). Oxygen and carbon isotope variability is most commonly attributed to low-temperature processes, including Rayleigh-like fractionation associated with biological activity. Another possible explanation for the isotopic variability in meteoritic samples is thermal decarbonation. In this report, different carbonates were heated in a He-stream until decomposition temperatures were reached. The oxygen and carbon isotope ratios ({delta}{sup 18}O and {delta}{sup 13}C values) of the resulting gas were measured on a continuous flow isotope ratio mass spectrometer. The aim of this work is to evaluate the possibility that large isotopic variations can be generated on a small scale abiogenically, by the process of thermal decarbonation. Oxygen isotope fractionations of >4{per_thousand} have been measured during decarbonation of calcite at high temperatures (McCrea, 1950), and in excess of 6{per_thousand} for dolomite decarbonated between 500 and 600 C (Sharma and Clayton, 1965). Isotopic fractionations of this magnitude, coupled with Rayleigh-like distillation behavior could result in very large isotopic variations on a small scale. To test the idea, calcite, dolomite and siderite were heated in a quartz tube in a He-stream in excess of 1 atmosphere. Simultaneous determinations of {delta}{sup 13}C and {Delta}{sup 18}O values were obtained on 250 {micro}l aliquots of the CO{sub 2}-bearing He gas using an automated 6-way switching valve system (Finnigan MAT GasBench II) and a Finnigan MAT Delta Plus mass spectrometer. It was found that decarbonation of calcite in a He atmosphere begins at 720 C, but the rate significantly increases at temperatures of 820 C. After an initial light {delta}{sup 18}O value of -14.1{per_thousand} at 720 C associated with very early decarbonation, {delta}{sup 18}0 values increase to a

  18. Compositional and stable carbon isotopic fractionation during non-autocatalytic thermochemical sulfate reduction by gaseous hydrocarbons

    USGS Publications Warehouse

    Xia, Xinyu; Ellis, Geoffrey S.; Ma, Qisheng; Tang, Yongchun

    2014-01-01

    The possibility of autocatalysis during thermochemical sulfate reduction (TSR) by gaseous hydrocarbons was investigated by examination of previously reported laboratory and field data. This reaction was found to be a kinetically controlled non-autocatalytic process, and the apparent lack of autocatalysis is thought to be due to the absence of the required intermediate species. Kinetic parameters for chemical and carbon isotopic fractionations of gaseous hydrocarbons affected by TSR were calculated and found to be consistent with experimentally derived values for TSR involving long-chain hydrocarbons. Model predictions based on these kinetic values indicate that TSR by gaseous hydrocarbon requires high-temperature conditions. The oxidation of C2–5 hydrocarbons by sulfate reduction is accompanied by carbon isotopic fractionation with the residual C2–5 hydrocarbons becoming more enriched in 13C. Kinetic parameters were calculated for the stable carbon isotopic fractionation of gaseous hydrocarbons that have experienced TSR. Model predictions based on these kinetics indicate that it may be difficult to distinguish the effects of TSR from those of thermal maturation at lower levels of hydrocarbon oxidation; however, unusually heavy δ13C2+ values (>−10‰) can be diagnostic of high levels of conversion (>50%). Stoichiometric and stable carbon isotopic data show that methane is stable under the investigated reaction conditions and is likely a product of TSR by other gaseous hydrocarbons rather than a significant reactant. These results indicate that the overall TSR reaction mechanism for oxidation of organic substrates containing long-chain hydrocarbons involves three distinct phases as follows: (1) an initial slow and non-autocatalytic stage characterized by the reduction of reactive sulfate by long-chain saturated hydrocarbons; (2) a second autocatalytic reaction phase dominated by reactions involving reduced sulfur species and partially oxidized hydrocarbons; (3

  19. Compositional and stable carbon isotopic fractionation during non-autocatalytic thermochemical sulfate reduction by gaseous hydrocarbons

    NASA Astrophysics Data System (ADS)

    Xia, Xinyu; Ellis, Geoffrey S.; Ma, Qisheng; Tang, Yongchun

    2014-08-01

    The possibility of autocatalysis during thermochemical sulfate reduction (TSR) by gaseous hydrocarbons was investigated by examination of previously reported laboratory and field data. This reaction was found to be a kinetically controlled non-autocatalytic process, and the apparent lack of autocatalysis is thought to be due to the absence of the required intermediate species. Kinetic parameters for chemical and carbon isotopic fractionations of gaseous hydrocarbons affected by TSR were calculated and found to be consistent with experimentally derived values for TSR involving long-chain hydrocarbons. Model predictions based on these kinetic values indicate that TSR by gaseous hydrocarbon requires high-temperature conditions. The oxidation of C2-5 hydrocarbons by sulfate reduction is accompanied by carbon isotopic fractionation with the residual C2-5 hydrocarbons becoming more enriched in 13C. Kinetic parameters were calculated for the stable carbon isotopic fractionation of gaseous hydrocarbons that have experienced TSR. Model predictions based on these kinetics indicate that it may be difficult to distinguish the effects of TSR from those of thermal maturation at lower levels of hydrocarbon oxidation; however, unusually heavy δ13C2+ values (>-10‰) can be diagnostic of high levels of conversion (>50%). Stoichiometric and stable carbon isotopic data show that methane is stable under the investigated reaction conditions and is likely a product of TSR by other gaseous hydrocarbons rather than a significant reactant. These results indicate that the overall TSR reaction mechanism for oxidation of organic substrates containing long-chain hydrocarbons involves three distinct phases as follows: (1) an initial slow and non-autocatalytic stage characterized by the reduction of reactive sulfate by long-chain saturated hydrocarbons; (2) a second autocatalytic reaction phase dominated by reactions involving reduced sulfur species and partially oxidized hydrocarbons; (3) and

  20. The concentration and isotopic composition of carbon in basaltic glasses from the Juan de Fuca Ridge, Pacific Ocean

    NASA Technical Reports Server (NTRS)

    Blank, Jennifer G.; Delaney, John R.; Des Marais, David J.

    1993-01-01

    The abundance and C-13/C-12 ratios of carbon were analyzed in basaltic glass from twenty locations along the Juan de Fuca Ridge using a 3-step combustion/extraction technique. Carbon released during the first two combustion steps at 400-500 C and 600-650 C is interpreted to be secondary, and only the carbon recovered during a final combustion step at about 1200 C is thought to be indigenous to the samples. For carbon released at about 1200 C, glasses analyzed as 1-2 mm chips contained 23-146 ppm C with delta C-13 values of -4.8 to -9.3 per mil, whereas samples crushed to 38-63 microns or 63-90 microns yielded 56-103 ppm C with delta C-13 values of -6.1 to -9.2 per mil. The concentrations and isotopic compositions of the primary carbon dissolved in the glasses and present in the vesicles are similar to those previously reported for other ocean-ridge basalts. The Juan de Fuca basaltic magmas were not in equilibrium with respect to carbon when they erupted and quenched on the sea floor. Evidence of disequilibrium includes (1) a large range of carbon contents among glasses collected at similar depths, (2) a highly variable calculated carbon isotopic fractionation between melt and vapor determined by comparing crushed and uncrushed splits of the same sample, and (3) a lack of correlation between vesicle abundance, carbon concentration, and depth of eruption. Variations in carbon concentration and delta C-13 ratios along the ridge do not correlate with major element chemistry. The observed relationship between carbon concentrations and delta C-13 values may be explained by late-stage, variable degrees of open-system (Rayleigh-like) degassing.

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

    NASA Astrophysics Data System (ADS)

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

    2002-05-01

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

  2. Hydrogen isotopic compositions of organic compounds in plants reflect the plant's carbon metabolism

    NASA Astrophysics Data System (ADS)

    Cormier, M. A.; Kahmen, A.; Werner, R. A.

    2015-12-01

    The main factors controlling δ2H of plant organic compounds are generally assumed to be the plant's source water and the evaporative deuterium enrichment of leaf water. Hydrogen isotope analyses of plant compounds from sediments or tree rings are therefore mainly applied to assess hydrological conditions at different spatial and temporal scales. However, the biochemical hydrogen isotope fractionation occurring during biosynthesis of plant organic compounds (ɛbio) also accounts for a large part of the variability observed in the δ2H values. Nevertheless, only few studies have directly addressed the physiological basis of this variability and even fewer studies have thus explored possible applications of hydrogen isotope variability in plant organic compounds for plant physiological research. Here we show two datasets indicating that the plant's carbon metabolism can have a substantial influence on δ2H values of n-alkanes and cellulose. First, we performed a controlled experiment where we forced plants into heterotrophic and autotrophic C-metabolism by growing them under four different light treatments. Second, we assessed the δ2H values of different parasitic heterotrophic plants and their autotrophic host plants. Our two datasets show a systematic shift in ɛbio of up to 80 ‰ depending on the plant's carbon metabolism (heterotrophic or autotrophic). Differences in n-alkane and cellulose δ2H values in plants with autotrophic vs. heterotrophic metabolisms can be explained by different NADPH pools that are used by the plants to build their compounds either with assimilates that originate directly from photosynthesis or from stored carbohydrates. Our results have significant implications for the calibration and interpretation of geological records. More importantly, as the δ2H values reflect the plant's carbon metabolism involved during the tissue formation, our findings highlight the potential of δ2H values as new tool for studying plant and ecosystem carbon

  3. Distribution of dicarboxylic acids and carbon isotopic compositions in aerosols from 1997 Indonesian forest fires

    NASA Astrophysics Data System (ADS)

    Narukawa, M.; Kawamura, K.; Takeuchi, N.; Nakajima, T.

    Fine aerosol particles collected in Southeast Asia during 1997 Indonesian forest fires were studied for the concentrations of total carbon (TC), water-soluble organic carbon (WSOC) and low molecular weight dicarboxylic acids (C2-C12) as well as carbon isotopic ratios of TC (δ13CTC). TC and WSOC showed a large increase during the heavy forest fire event. At the same period, dicarboxylic acids, dominated by oxalic (C2) followed by succinic (C4) and malonic (C3) acids, also showed a concentration increase. Furthermore, the δ13CTC showed a decrease from ca. -25.5 to -27.5‰ during an intensified forest fire event, suggesting an addition of organic aerosols derived from C3 plants whose δ13C are lighter. These results indicate that the aerosol particles in Southeast Asia were significantly affected by the combustion processes of vegetations during the 1997 Indonesian forest fires that were extensively induced by El Ninõ event.

  4. Effect of trans-reservoir water supply on carbon and nitrogen stable isotope composition in hydrologically connected reservoirs in China

    NASA Astrophysics Data System (ADS)

    Zhang, Huajun; Peng, Liang; Gu, Binhe; Han, Bo-Ping

    2016-10-01

    Dajingshan, Fenghuangshan and Meixi reservoirs are located in Zhuhai, a coastal city in southern China, and they function to supply drinking water to Zhuhai and Macau. For effectively supplying waster, they are hydrologically connected and Dajingshan Reservoir first receives the water pumped from the river at Guangchang Pumping Station, and then feeds Fenghuangshan Reservoir, and the two well-connected reservoirs are mesotrophic. Meixi Reservoir is a small and oligotrophic water body and feeds Dajingshan Reservoir only in wet seasons when overflow occurs. Particulate organic matter (POM) was collected from three hydrologically connected water supply reservoirs, and seasonal variations of POM were ascertained from stable carbon and nitrogen isotopes in wet and dry seasons, and the effects of pumping water and reservoir connectivity on POM variations and composition were demonstrated by the relationships of the stable isotope ratios of POM. Seasonality and similarity of stable carbon and nitrogen isotopes of POM varied with hydrodynamics, connectivity and trophic states of the four studied water bodies. The two well-connected reservoirs displayed more similar seasonality for δ13CPOM than those between the river station and the two reservoirs. However, the opposite seasonality appeared for δ15NPOM between the above waters and indicates different processes affecting the stable carbon and nitrogen isotopes of POM. δ13CPOM and δ15NPOM changed little between wet and dry seasons in Meixi Reservoir-a low productive and rain-driven system, suggesting little POM response to environmental changes in that water system. As expected, connectivity enhanced the similarity of the stable isotope ratios of POM between the water bodies.

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

    NASA Astrophysics Data System (ADS)

    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.

  6. Origin of epigenetic calcite in coal from Antarctica and Ohio based on isotope compositions of oxygen, carbon and strontium

    USGS Publications Warehouse

    Faure, G.; Botoman, G.

    1984-01-01

    Isotopic compositions of oxygen, carbon and strontium of calcite cleats in coal seams of southern Victoria Land, Antarctica, and Tuscarawas County, Ohio, contain a record of the conditions a the time of their formation. The Antarctic calcites (?? 18O(SMOW) = +9.14 to +11.82%0) were deposited from waters enriched in 16O whose isotopic composition was consistent with that of meteoric precipitation at low temperature and high latitude. The carbon of the calcite cleats (?? 13C(PDB) = -15.6 to -16.9%0) was derived in part from the coal (?? 13C(PDB) = -23.5 to -26.7%0) as carbon dioxide and by oxidation of methane or other hydrocarbon gases. The strontium ( 87Sr 86Sr = 0.71318-0.72392) originated primarily from altered feldspar grains in the sandstones of the Beacon Supergroup. Calcite cleats in the Kittaning No. 6 coal seam of Ohio (?? 18O(SMOW) = +26.04 to +27.79%0) were deposited from waters that had previously exchanged oxygen, possibly with marine carbonate at depth. The carbon (?? 13C(PDB) = 0.9 to +2.4%0) is enriched in 13C even though that cleats were deposited in coal that is highly enriched in 12C and apparently originated from marine carbonates. Strontium in the cleats ( Sr 87 0.71182-0.71260) is not of marine origin but contains varying amounts of radiogenic 87Sr presumably derived from detrital Rb-bearing minerals in the adjacent sedimentary rocks. The results of this study suggest that calcite cleats in coal of southern Victoria Land, Antarctica, were deposited after the start of glaciation in Cenozoic time and that those in Ohio precipitated from formation waters derived from the underlying marine carbonate rocks, probably in the recent geologic past. ?? 1984.

  7. Soils at the hyperarid margin: The isotopic composition of soil carbonate from the Atacama Desert, Northern Chile

    USGS Publications Warehouse

    Quade, Jay; Rech, Jason A.; Latorre, Claudio; Betancourt, Julio L.; Gleeson, Erin; Kalin, Mary T.K.

    2007-01-01

    We evaluate the impact of exceptionally sparse plant cover (0–20%) and rainfall (2–114 mm/yr) on the stable carbon and oxygen composition of soil carbonate along elevation transects in what is among the driest places on the planet, the Atacama Desert in northern Chile. δ13C and δ18O values of carbonates from the Atacama are the highest of any desert in the world. δ13C (VPDB) values from soil carbonate range from -8.2% at the wettest sites to +7.9% at the driest. We measured plant composition and modeled respiration rates required to form these carbonate isotopic values using a modified version of the soil diffusion model of [Cerling (1984) Earth Planet. Sci. Lett.71, 229–240], in which we assumed an exponential form of the soil CO2 production function, and relatively shallow (20–30 cm) average production depths. Overall, we find that respiration rates are the main predictor of the δ13C value of soil carbonate in the Atacama, whereas the fraction C3 to C4 biomass at individual sites has a subordinate influence. The high average δ13C value (+4.1%) of carbonate from the driest study sites indicates it formed&mdahs;perhaps abiotically—in the presence of pure atmospheric CO2. δ18O (VPDB) values from soil carbonate range from -5.9% at the wettest sites to +7.3% at the driest and show much less regular variation with elevation change than δ13C values. δ18O values for soil carbonate predicted from local temperature and δ18O values of rainfall values suggest that extreme (>80% in some cases) soil dewatering by evaporation occurs at most sites prior to carbonate formation. The effects of evaporation compromise the use of δ18O values from ancient soil carbonate to reconstruct paleoelevation in such arid settings.

  8. Isotopic composition and speciation of sedimentary nitrogen and carbon in the Okinawa Trough over the past 30 ka

    NASA Astrophysics Data System (ADS)

    Zheng, Li-Wei; Hsiao, Silver Sung-Yun; Ding, Xiao-Dong; Li, Dawei; Chang, Yuan-Pin; Kao, Shuh-Ji

    2015-10-01

    Total organic carbon to total nitrogen ratios (C/N) and their isotopic compositions (δ13CTOC and δ15NTN) are oft-applied proxies to discern terrigenous from marine-sourced organics and to unravel ancient environmental information. In high depositional Asian marginal seas, the inclusion of N-bearing minerals in the bulk sediment dilutes or masks signals sought after in δ15N and δ13C analyses, thus leading to incorrect and even contradictory interpretations. We used KOH-KOBr to separate operationally defined total organic matter into oxidizable (labile) and residual fractions for content and isotope measurements. In a sediment core in the Okinawa Trough, significant amounts of carbon and nitrogen existed in the residual phase, in which the C/N ratio was ~9, resembling most documented sedimentary bulk C/N ratios in the China marginal seas. The residual carbon, which was included in operationally defined total organic carbon (TOC), displayed a δ13C range (-22.7 to -18.9‰, mean -20.7‰) similar to the oft-used marine end-member. After removing the interference from the residual fraction, we found that the temporal pattern of δ13CLOC (LOC denotes labile organic carbon) was more variable. The residual nitrogen content was associated with illite, suggesting a terrestrial origin. Additionally, δ15N in the residual fraction likely reflected the climatic controls (e.g., precipitation) on lithogenic source materials. Further studies are required to explore the controlling factors for carbon and nitrogen isotopic speciation and to retrieve the information locked in the residual fraction.

  9. Stable Carbon Isotope Composition and Dynamics of Particulate Organic Carbon in the Basin of the Ganga-Brahmaputra River

    NASA Astrophysics Data System (ADS)

    Aucour, A.; France-Lanord, C.; Pedoja, K.; Piersson-Wickmann, A.; Sheppard, S.

    2004-05-01

    The Ganga-Brahmaputra River ranks first for sediment transport among world rivers, with high erosion rates in the Himalayan range driving the high suspended flux. The organic carbon (OC) burial flux in the Bengal fan has been estimated to be around 1.1 x 1012 molC yr-1 for the Neogene and could represent about 10% of the global burial flux of OC in continental margins. This stresses the importance of assessing the sources of the organic matter in the Himalayan watersheds and the chemical processing of organic matter on the flood-plain. To follow the dynamics of particulate OC, we used natural 13C-labelling of OC, which is essentially linked to the variable proportion of C3- and C4- plants on the watersheds, together with the mineralogical, chemical and isotopic (ɛ Nd) data of the associated silicates. The stable isotope compositions of OC were measured (1) in bedrocks, soils, and river sediments from an Himalayan watershed (Narayani River, Nepal), (2) in river sediments at several outflows of the range, and (3) in soils and river sediments on the Bangladeshi flood-plain. In the watershed of the Narayani River, the δ 13C values of OC range from 26.3 to 22‰ for the bank sediments and from 24.2 to 22‰ for the suspended sediments. They present a narrow range of values around 24‰ at the outflow of the Himalayan range. They are less negative than those of OC in forest soils, hence indicating a significant contribution from the deforested, subtropical zone. On the Bangladesh flood-plain, sediments from the Ganga and Brahmaputra Rivers are enriched in 13C (with δ 13C values around 22.5‰ ) relative to those collected at the range's outflow. This indicates addition of organic matter derived from the mixed C3-C4 biomass on the flood-plain. In sediments of the Ganga and Brahmaputra Rivers, the clay-size fraction is depleted in 13C relative to the bulk sediment. A possible explanation is that the organic matter associated with the clay-size fraction is essentially

  10. Quantification of Aridity Changes During the Late Holocene From the Carbon Isotope Composition of Fossil Charcoal

    NASA Astrophysics Data System (ADS)

    Voltas, J.; Ferrio, P.; Espinar, C.

    2006-12-01

    Climate dynamics during the Holocene can be characterized by a variety of proxies that provide information at a different scale and accuracy. In seasonally dry climates, the carbon isotope composition of tree-rings has been related to variables such as rainfall or evaporative demand. Extensive tree-ring records, however, are not always available owing to factors such as human-induced deforestation or harsh conditions for most long-lived trees to thrive. An illustrative example concerns the Mediterranean region. In this work, we aim to show that the original climate signal of wood δ13C is preserved in fossil charcoal (recovered from archaeological sites), and thus can be used to quantify past changes in water availability. We present two case studies on climate reconstruction at the temporal and spatial dimensions from Eastern Spain. We first describe, for a restricted area, the evolution of aridity during the last 4000 years using charcoals ranging from the Bronze Age (ca. 2100 BCE) to the Modern Age (XVIII ca. CE) (1). Further, we characterize, for a larger region, the transition between Bronze and Iron Ages, the so called Cold Iron Age Epoch (ca. 700-500 BCE), using remains from a set of contemporary sites (2). Climatic inferences were obtained after calibration of quantitative models predicting rainfall from wood δ13C. For case (1), charcoals of Mediterranean trees (Aleppo pine, several oaks, mastic) were analysed for δ13C. We found similar trends for the time course of changes in this parameter regardless of the species. Estimated rainfall in the past was 25% to 40% higher than present, with phases of greater water availability (1500-900 BCE; 300 BCE-300 CE) alternating with drier periods (900-300 BCE; 900-1100 CE). For case (2), we combined data from Aleppo pine and Holm oak, which exhibit differential responses to changes in climate seasonality, to provide information on intra-annual rainfall dynamics. The divergence in δ13C between pines and oaks can be

  11. Variation in the Carbon Isotope Composition of a Plant with Crassulacean Acid Metabolism

    PubMed Central

    Lerman, J. C.; Deleens, Eliane; Nato, Aimé; Moyse, Alexis

    1974-01-01

    The content of 13C varies in plants with Crassulacean acid metabolism. Differences up to 3.5‰ in the 13C/12C ratios were observed between leaves of different age in the same plant of Bryophyllum daigremontianum. Soluble and insoluble carbon in the same leaf differed up to 8‰, the largest difference occurring in the leaves with the highest Crassulacean acid metabolism activity. Models to account for the isotope discrimination by C3, C4, and Crassulacean acid metabolism plants are proposed. PMID:16658746

  12. Chemical and Strontium, Oxygen, and Carbon Isotopic Compositions of Carbonates from the Lesser Himalaya: Implications to the Strontium Isotope Composition of the Source Waters of the Ganga, Ghaghara, and the Indus Rivers

    NASA Astrophysics Data System (ADS)

    Singh, Sunil K.; Trivedi, J. R.; Pande, K.; Ramesh, R.; Krishnaswami, S.

    1998-03-01

    Samples of Precambrian carbonate (mostly dolomite) outcrops collected across the Lesser Himalaya have been analysed for their mineralogy, chemical composition, and isotope ratios of Sr, O, and C to assess the extent of their preservation and their role in contributing to the high radiogenic strontium isotope composition of the source waters of the Ganga, Ghaghara, and the Indus. Their Sr concentrations range from 20 to 363 ppm, δ 18O PDB -1.4 to -12.8‰ and Mn 11-2036 ppm. The petrography of the samples, their low Sr concentrations, and wide range of δ 18O values are suggestive of their postdepositional alteration. The 87Sr/ 86Sr of the bulk samples and their carbonate fractions are similar to one another with values ranging from 0.7064 to 0.8935 and are generally more radiogenic than that of contemporaneous seawater. Comparison of the 87Sr/ 86Sr and Sr/Ca ratios among the carbonates and silicates from the Lesser Himalaya and the source waters of the Ganga, Ghaghara, and the Indus shows that the values for the source waters overlap with those of the silicates but are much higher than those in carbonates. An upper limit of carbonate Sr in the various source waters is calculated to be between 6% and 43%, assuming that all the Ca in the rivers is of carbonate origin. The results show that on the average, weathering of the Precambrian carbonates is unlikely to be a major contributor to the highly radiogenic strontium isotope composition of these source waters; however, they can be a dominant supplier of radiogenic Sr to some rivers on a regional scale. The silicate Sr component in some of the source waters of the Ganga (Bhagirathi, Bhilangna, Alaknanda, and Ganga), Ghaghara (Kali and Sarju), and the Indus (Sutlej) was calculated from the Ca/Na, Sr/Na ratios, and strontium isotope compositions of these rivers and the silicate endmember. These calculations suggest that 33-89% of Sr in the Bhagirathi, Bhilangna, Alaknanda, Ganga, and Sarju rivers is of silicate origin

  13. Soil carbon isotopic composition and soil carbon content in an agroecosystem during six years of Free Air Carbon dioxide Enrichment (FACE).

    PubMed

    Giesemann, Anette; Weigel, Hans-Joachim

    2008-12-01

    The Free Air Carbon dioxide Enrichment (FACE) experiment conducted at the Federal Agricultural Research Centre (FAL) in Braunschweig in an arable crop rotation (total duration six years) allowed us to trace carbon (C) input in the soil C pool, as the CO(2), used in the experiment to increase the atmospheric CO(2) concentration, was depleted in (13)C. Accurate assessment of the C input by means of stable C isotope analysis requires detailed knowledge on the spatial distribution of both the C isotopic composition and the C content in the soil C. Assumed changes in these parameters were examined. CO(2) enrichment treatment over a six year period resulted in a clear trend towards an increase of soil C content in the uppermost 10 cm of soil. About 4.9% of the soil C present under ambient air conditions, and 10.7% present under elevated CO(2) conditions were determined as new input. However, the results are not statistically significant yet.

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

    NASA Astrophysics Data System (ADS)

    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

  15. Impact of contamination and pre-treatment on stable carbon and nitrogen isotopic composition of charred plant remains

    PubMed Central

    Vaiglova, Petra; Snoeck, Christophe; Nitsch, Erika; Bogaard, Amy; Lee-Thorp, Julia

    2014-01-01

    Rationale Stable isotope analysis of archaeological charred plants has become a useful tool for interpreting past agricultural practices and refining ancient dietary reconstruction. Charred material that lay buried in soil for millennia, however, is susceptible to various kinds of contamination, whose impact on the grain/seed isotopic composition is poorly understood. Pre-treatment protocols have been adapted in distinct forms from radiocarbon dating, but insufficient research has been carried out on evaluating their effectiveness and necessity for stable carbon and nitrogen isotope analysis. Methods The effects of previously used pre-treatment protocols on the isotopic composition of archaeological and modern sets of samples were investigated. An archaeological sample was also artificially contaminated with carbonates, nitrates and humic acid and subjected to treatment aimed at removing the introduced contamination. The presence and removal of the contamination were investigated using Fourier transform infrared spectroscopy (FTIR) and δ13C and δ15N values. Results The results show a ca 1‰ decrease in the δ15N values of archaeological charred plant material caused by harsh acid treatments and ultra-sonication. This change is interpreted as being caused by mechanical distortion of the grains/seeds rather than by the removal of contamination. Furthermore, specific infrared peaks have been identified that can be used to detect the three types of contaminants studied. We argue that it is not necessary to try to remove humic acid contamination for stable isotope analysis. The advantages and disadvantages of crushing the grains/seeds before pre-treatment are discussed. Conclusions We recommend the use of an acid-only procedure (0.5 M HCl for 30 min at 80°C followed by three rinses in distilled water) for cleaning charred plant remains. This study fills an important gap in plant stable isotope research that will enable future researchers to evaluate potential

  16. The effects of biomanipulation on the biogeochemistry, carbon isotopic composition and pelagic food web relations of a shallow lake

    NASA Astrophysics Data System (ADS)

    Bontes, B. M.; Pel, R.; Ibelings, B. W.; Boschker, H. T. S.; Middelburg, J. J.; Van Donk, E.

    2006-03-01

    In this study we investigated the effects of experimental biomanipulation on community structure, ecosystem metabolism, carbon biogeochemistry and stable isotope composition of a shallow eutrophic lake in the Netherlands. Three different biomanipulation treatments were applied. In two parts of the lake, isolated from the rest, fish was removed and one part was used as a reference treatment in which no biomanipulation was applied. Stable isotopes have proved useful to trace trophic interactions at higher food web levels but until now methodological limitations have restricted species specific isotope analysis in the plankton community. We applied a new approach based on the combination of fluorescence activated cell sorting (FACS) and isotope ratio mass spectrometry (IRMS) to trace carbon flow through the planktonic food web. With this method we aimed at obtaining group specific δ13C signatures of phytoplankton and to trace possible shifts in δ13C resulting from fish removal.

    Biomanipulation led to an increase in transparency and macrophyte biomass and decrease in phytoplankton abundance, but zooplankton numbers did not increase. Fish removal also resulted in high pH, high O2, low CO2 and more negative δ13CDIC values than expected, which is attributed to chemical enhanced diffusion with large negative fractionation. Despite high temporal variation we detected differences between the isotopic signatures of the primary producers and between the different treatments. The fractionation values of green algae (~21) and diatoms (~23) were similar and independent of treatment, while fractionation factors of filamentous cyanobacteria were variable between the treatments that differed in CO2 availability. 13C-labeling of the phytoplankton groups showed that biomanipulation led to increased growth rates of green algae and diatoms at the expense of cyanobacteria. Finally, consumers seemed generalists to the available food sources.

  17. Effect of forest and savanna vegetation on the carbon-isotope composition of sediments from the Sanaga River, Cameroon

    SciTech Connect

    Bird, M.I.; Chivas, A.R.; Giresse, P.

    1994-12-01

    The carbon-isotope composition {delta}{sup 13}C values of around -22{per_thousand}. After the river passes through extensively forested regions, the {delta}{sup 13}C values of the sediments closest to the mouth of the river decrease to -25{per_thousand}. Samples collected from rivers with entirely forested catchment had low {delta}{sup 13}C values (from -27 to -29{per_thousand}) consistent with a pure C{sub 3} vegetation source. The downriver carbon-isotope trends are consistent with the hypothesis that observed variations are due to changes in the relative proportions of C{sub 3} and C{sub 4} carbon in the sediments, which are derived from terrestrial vegetation in the river catchment. Some sediments from the Mbam River, the principal tributary of the Sanaga River, have extremely high {delta}{sup 13}C values (up to -16.7{per_thousand}). These high values may be the result of severe erosion in the densely populated and intensively farmed Bamileke region in the headwaters of the Mbam. An underrepresentation of C{sub 4{minus}}derived carbon in the upper reaches of the Sanaga is possibly due to the damming of the Djerem River at Mbakaou. Since the dam was constructed <25 yr ago, this suggests that the {delta}{sup 13}C value of river sediments responds rapidly to changes in the basin. 19 refs., 5 figs., 3 tabs.

  18. Precipitation source inferred from stable isotopic composition of Pleistocene groundwater and carbonate deposits in the western desert of Egypt.

    SciTech Connect

    Sultan, M.; Sturchio, N.; Hassan, F. A.; Abdel, M.; Hamdan, R.; Mahmood, A. M.; Alfy, Z. E.; Stein, T.; Environmental Research; Univ. Coll. London; Cairo Univ.; Ain Shams Univ.; Egyptian Geological survey and Mining Authority; Washington Univ.

    1997-01-01

    An Atlantic source of precipitation can be inferred from stable isotopic data (H and O) for fossil groundwaters and uranium-series-dated carbonate spring deposits from oases in the Western Desert of Egypt. In the context of available stable isotopic data for fossil groundwaters throughout North Africa, the observed isotopic depletions ({delta}D -72 to -81{per_thousand}; {delta}{sup 18}O -10.6 to -11.5{per_thousand}) of fossil ({ge}32,000 yr B.P.) groundwaters from the Nubian aquifer are best explained by progressive condensation of water vapor from paleowesterly wet oceanic air masses that traveled across North Africa and operated at least as far back as 450,000 yr before the present. The values of {delta}{sup 18}O (17.1 to 25.9{per_thousand}) for 45,000- to >450,000-yr-old tufas and vein-filling calcite deposits from the Kharga and Farafra Oases are consistent with deposition from groundwaters having oxygen isotopic compositions similar to those of fossil groundwaters sampled recently at these locations.

  19. Atomic Weights and Isotopic Compositions

    National Institute of Standards and Technology Data Gateway

    SRD 144 Atomic Weights and Isotopic Compositions (Web, free access)   The atomic weights are available for elements 1 through 111, and isotopic compositions or abundances are given when appropriate.

  20. Climate controls on the carbon isotopic composition of soil organic matter and its regional variability in grasslands and savannas

    NASA Astrophysics Data System (ADS)

    Cotton, J. M.; Still, C. J.; Cerling, T. E.; Sheldon, N. D.

    2013-12-01

    Future environmental changes driven by anthropogenic CO2 emissions are of increasing importance to human society. Among those changes, the balance between economically and ecologically important C3 and C4 vegetation is of particular significance. There is considerable disagreement in recent predictions of changing distribution of grasses due to anthropogenic climate change because increasing temperature and atmospheric pCO2 have opposing effects on the relative productivity of C3 vegetation. In order to forecast future changes to vegetation composition in grasslands, we must first better constrain the modern relationship between climate and the distribution of C3 and C4 grasses. Due to the isotopic differences between the two photosynthetic pathways, the carbon isotopic composition of soil organic matter (δ13Corg) is a proxy for the relative abundance and productivity of overlying C3 and C4 vegetation. Here, we have compiled an extensive dataset through literature review of δ13Corg to determine the relationships between the distribution of C3 and C4 vegetation in grasslands with climate. We find that the best predictor of δ13Corg variation is growing season average air temperature, and that there are unique relationships between growing season average temperature and δ13Corg for different regions of the world, including North America, South America and Australia. These results imply that the response of C4 grasses to anthropogenic climate warming may not be uniform across different species and grassland communities. We also use this dataset to create an 'isoscape', or a predictive spatial model for the isotopic composition of soil organic carbon for temperate grasslands and savannas worldwide.

  1. Carbon-isotope composition of Lower Cretaceous fossil wood: Ocean-atmosphere chemistry and relation to sea-level change

    SciTech Connect

    Groecke, D.R.; Hesselbo, S.P.; Jenkyns, H.C.

    1999-02-01

    The carbon-isotope composition of fossil wood fragments, collected through a biostratigraphically well-constructed Aptian (Lower Cretaceous) shallow-marine siliciclastic succession on the Isle of Wight, southern Britain, shows distinct variations with time. The results indicate that the stratigraphic signature of {delta}{sup 13}C{sub wood} through the Aptian was influenced primarily by fluctuations in the isotopic composition of CO{sub 2} in the global ocean-atmosphere system, as registered in marine carbonates elsewhere, and was not governed by local paleoenvironmental and/or paleoecological factors. Negative and positive excursions in {delta}{sup 13}C{sub wood} through the lower Aptian occur in phase with inferred transgressions and regressions, respectively -- a pattern that contrasts with that observed in many previous studies for different time intervals. The relationship between {delta}{sup 13}C variations and relative sea-level change is tentatively interpreted as a response to various climatic and eustatic factors, relating to rapid sea-floor spreading, thermal uplift of ocean floor, emplacement of plateaus, volcanic CO{sub 2} emissions, weathering, and sedimentary rate.

  2. Isotopic composition of river waters and early stage carbonates crusts along an elevation transect at 33 degrees south latitude, southern central Andes

    NASA Astrophysics Data System (ADS)

    Hoke, G. D.; Williams, K.; Garzione, C. N.; Araneo, D.; Strecker, M. R.

    2008-12-01

    We assess the quality of the transfer of elevation specific isotopic information into the rock record by comparing the stable isotopic composition of Quaternary to recent authigenic carbonates and river waters along a 3000 m elevation transect across the Andes at 33°S. Carbonate and water samples are from the Río Aconcagua (Chile) and Río Mendoza (Argentina) watersheds. Isotopic data from small tributaries of these rivers show similar elevation gradients on both sides of the range despite different initial moisture sources. The δ18O of authigenic carbonates correlate well with elevation and yield an elevation gradient which is shallower than that of the rivers. These data confirm that carbonate material is indeed an accurate recorder of information about elevation, and show that in some instances, different moisture sources do not result in drastically different isotope-elevation gradients.

  3. Carbon isotope effects associated with aceticlastic methanogenesis

    NASA Technical Reports Server (NTRS)

    Gelwicks, J. T.; Risatti, J. B.; Hayes, J. M.

    1994-01-01

    The carbon isotope effects associated with synthesis of methane from acetate have been determined for Methanosarcina barkeri 227 and for methanogenic archaea in sediments of Wintergreen Lake, Michigan. At 37 degrees C, the 13C isotope effect for the reaction acetate (methyl carbon) --> methane, as measured in replicate experiments with M. barkeri, was - 21.3% +/- 0.3%. The isotope effect at the carboxyl portion of acetate was essentially equal, indicating participation of both positions in the rate-determining step, as expected for reactions catalyzed by carbon monoxide dehydrogenase. A similar isotope effect, - 19.2% +/- 0.3% was found for this reaction in the natural community (temperature = 20 degrees C). Given these observations, it has been possible to model the flow of carbon to methane within lake sediment communities and to account for carbon isotope compositions of evolving methane. Extension of the model allows interpretation of seasonal fluctuations in 13C contents of methane in other systems.

  4. Dynamic behavior of hydrogen isotopes in tungsten-carbon composite materials

    NASA Astrophysics Data System (ADS)

    Horikawa, T.; Tsuchiya, B.; Morita, K.

    The thermal re-emission of hydrogen isotopes from WC layers on graphite, implanted with 5 keV H +2 and D +2 ion beams up to saturation at room temperature, has been studied by means of the elastic recoil detection (ERD) technique. It is found on isochronal annealing for 10 min that the re-emission takes place in three stages: the first stage occurs for retained fraction of 1.0-0.6, the second stage for retained fractions of 0.6-0.2 and the third stage below the retained fraction of 0.2, which is ascribed to re-emission from carbon segregated in the grain boundaries of the WC layers. It is also found on isothermal annealing that the concentration of retained hydrogen decreases rapidly in the beginning and hereafter very gradually with increasing the annealing time. The isothermal re-emission curves have been analyzed by taking into account the two trapping sites and the mass balance equations with two kinds of thermal detrapping ( Σd 1, Σd 2), retrapping (Σ t) and local molecular recombination ( K1) between free hydrogen atoms. The isotope difference of the rate constants for elementary processes determined by best fitting of the solution to the experimental re-emission profiles is discussed with relevance to the nature of two trapping sites.

  5. Isotopic inferences of ancient biochemistries - Carbon, sulfur, hydrogen, and nitrogen

    NASA Technical Reports Server (NTRS)

    Schidlowski, M.; Hayes, J. M.; Kaplan, I. R.

    1983-01-01

    In processes of biological incorporation and subsequent biochemical processing sizable isotope effects occur as a result of both thermodynamic and kinetic fractionations which take place during metabolic and biosynthetic reactions. In this chapter a review is provided of earlier work and recent studies on isotope fractionations in the biogeochemical cycles of carbon, sulfur, hydrogen, and nitrogen. Attention is given to the biochemistry of carbon isotope fractionation, carbon isotope fractionation in extant plants and microorganisms, isotope fractionation in the terrestrial carbon cycle, the effects of diagenesis and metamorphism on the isotopic composition of sedimentary carbon, the isotopic composition of sedimentary carbon through time, implications of the sedimentary carbon isotope record, the biochemistry of sulfur isotope fractionation, pathways of the biogeochemical cycle of nitrogen, and the D/H ratio in naturally occurring materials.

  6. An episode of widespread ocean anoxia during the latest Ediacaran Period revealed by light U isotope compositions in carbonates

    NASA Astrophysics Data System (ADS)

    Zhang, F.

    2015-12-01

    Reconstruction of ocean redox chemistry during the Ediacaran Period is important for understanding the causal relationship between environmental oxygen levels and early metazoan evolution. Geochemical data (e.g., high Mo and U concentrations and/or heavy Mo and U isotope compositions from sedimentary rocks) provide evidence of extensive ocean oxygenation shortly after the Marinoan glaciation at ca. 632 Ma [1], during the late Ediacaran Period at ca. 560-551 Ma [2], and multiple times during the early Cambrian Period [3, 4]. These episodes of oxygenation may have been separated by intervals of less oxygenated conditions [1, 2]. However, the global redox state of the ocean during the terminal Ediacaran period (ca. 551-541 Ma) is poorly constrained. We address this knowledge gap by measuring carbonate U isotope compositions (δ238U) - a novel global ocean redox proxy - of the Gaojiashan Member of the late Ediacaran Dengying Formation (ca. 551-541 Ma) in South China. An abrupt negative shift in δ238U from values scattering around -0.45‰ to values averaging -0.95‰ (±0.20‰, 2sd) was observed in the middle Gaojiashan Member, suggesting a globally widespread expansion of ocean anoxia during the terminal Ediacaran Period. The negative δ238U shift coincides with the onset of a pronounced positive carbon isotope excursion (from 0‰ to +6‰), suggesting that ocean anoxia is the major driving force behind enhanced organic carbon burial that led to the carbon isotope excursion. The widespread anoxia recorded by the Gaojiashan Member is bracketed by known intervals of extensive ocean oxygenation, thus indicating that the Precambrian-Phanerozoic transition was characterized by oscillating ocean redox conditions. The Ediacara biota (ca. 541 Ma) [5] disappeared shortly after the widespread ocean anoxia, suggesting that an expansion of ocean anoxia may have triggerred the onset of a mass extinction in the latest Ediacaran time. References: [1] Sahoo, et al. (2012), Nature

  7. Emission rate, isotopic composition and origin(s) of magmatic carbon dioxide at Merapi volcano, Indonesia

    NASA Astrophysics Data System (ADS)

    Allard, P.

    2012-12-01

    (iii) other Javanese volcanoes whose lavas do not contain calc-silicate xenoliths emit CO2 with identical δ13C values of -4‰. Based on the above observations and on typical arc-type isotopic ratios for water, sulphur and nitrogen in Merapi magmatic gases [2], I rather propose that 80% of CO2 emitted by the volcano ultimately derives from a subducted sediment contribution, in agreement with Sr-Nd-Pb isotope data for bulk lavas [9]. The CO2/HCl ratio of Merapi magmatic gases, normalized to the bulk mass fraction of outgassed Cl inferred from analysis of melt inclusions in clinopyroxene and the matrix glasses, points to a maximum CO2 content of ~1 wt% in the undegassed magma [3], 0.8 wt% of which derived from subducted carbon. [1] Allard, 1980, C.R. Acad Sciences Paris; [2] Allard, 1986, Ph.D thesis, Paris 7 Univ.; [3] Allard et al., 1995, and submitted (JVGR, 2012); [4] Toutain et al., Bull. Volcanol. 2009; [5] Clocchiatti et al., 1982, C.R. Acad. Sciences Paris; [6] Chadwick et al., 2007, J. Petrol.; [7] Deegan et al., 2010, J. Petrol.; [8] Troll et al., 2012, Geophys. Res. Lett.; [9] Gertisser and Keller, 2003, J. Petrol..

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

    NASA Astrophysics Data System (ADS)

    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

  9. The first investigation of Wilms' tumour atomic structure-nitrogen and carbon isotopic composition as a novel biomarker for the most individual approach in cancer disease

    PubMed Central

    Taran, Katarzyna; Frączek, Tomasz; Sikora-Szubert, Anita; Sitkiewicz, Anna; Młynarski, Wojciech; Kobos, Józef; Paneth, Piotr

    2016-01-01

    The paper describes a novel approach to investigating Wilms' tumour (nephroblastoma) biology at the atomic level. Isotope Ratio Mass Spectrometry (IRMS) was used to directly assess the isotope ratios of nitrogen and carbon in 84 Wilms' tumour tissue samples from 28 cases representing the histological spectrum of nephroblastoma. Marked differences in nitrogen and carbon isotope ratios were found between nephroblastoma histological types and along the course of cancer disease, with a breakout in isotope ratio of the examined elements in tumour tissue found between stages 2 and 3. Different isotopic compositions with regard to nitrogen and carbon content were observed in blastemal Wilms' tumour, with and without focal anaplasia, and in poorly- and well-differentiated epithelial nephroblastoma. This first assessment of nitrogen and carbon isotope ratio reveals the previously unknown part of Wilms' tumour biology and represents a potential novel biomarker, allowing for a highly individual approach to treating cancer. Furthermore, this method of estimating isotopic composition appears to be the most sensitive tool yet for cancer tissue evaluation, and a valuable complement to established cancer study methods with prospective clinical impact. PMID:27732932

  10. The first investigation of Wilms' tumour atomic structure-nitrogen and carbon isotopic composition as a novel biomarker for the most individual approach in cancer disease.

    PubMed

    Taran, Katarzyna; Frączek, Tomasz; Sikora-Szubert, Anita; Sitkiewicz, Anna; Młynarski, Wojciech; Kobos, Józef; Paneth, Piotr

    2016-11-22

    The paper describes a novel approach to investigating Wilms' tumour (nephroblastoma) biology at the atomic level. Isotope Ratio Mass Spectrometry (IRMS) was used to directly assess the isotope ratios of nitrogen and carbon in 84 Wilms' tumour tissue samples from 28 cases representing the histological spectrum of nephroblastoma. Marked differences in nitrogen and carbon isotope ratios were found between nephroblastoma histological types and along the course of cancer disease, with a breakout in isotope ratio of the examined elements in tumour tissue found between stages 2 and 3. Different isotopic compositions with regard to nitrogen and carbon content were observed in blastemal Wilms' tumour, with and without focal anaplasia, and in poorly- and well-differentiated epithelial nephroblastoma. This first assessment of nitrogen and carbon isotope ratio reveals the previously unknown part of Wilms' tumour biology and represents a potential novel biomarker, allowing for a highly individual approach to treating cancer. Furthermore, this method of estimating isotopic composition appears to be the most sensitive tool yet for cancer tissue evaluation, and a valuable complement to established cancer study methods with prospective clinical impact.

  11. Stable carbon isotopic composition of methane from some natural and anthropogenic sources

    SciTech Connect

    Stevens, C.M.; Engelkemeir, A.

    1988-01-20

    The results of delta/sup 13/C measurements of several types of major sources of methane are as follows: rice paddies, -67%; the peat bogs of the Lake Agassiz region of northern Minnesota, -67 +- 5%; swamps of the Florida Everglades, -55 +- 3% and biomass burning, -24 to -32%. In addition, results are presented of a study of the delta/sup 13/C of CH/sub 4/ released from a slough, compared to the CH/sub 4/ in the bottom sediment. These isotopic values are used, together with previously published data, to make up a tentative budget of the fluxes of the major sources for atmospheric methane with an averge isotopic composition matching the measured value for atmospheric CH/sub 4/, taking into account the fractionation effect of the sink processes. This budget requires the existence of a significant flux from an anthropogenic source of heavy CH/sub 4/, calculated to be 45 +- 15 Tg yr/sup -1/ if attributed to CH/sub 4/ from biomass burning, with deltaC = -25%. copyright American Geophysical Union 1988

  12. Carbon isotope composition of ambient CO2 and recycling: a matrix simulation model

    USGS Publications Warehouse

    da Silveira Lobo Sternberg, Leonel; DeAngelis, Donald L.

    2002-01-01

    The relationship between isotopic composition and concentration of ambient CO2 in a canopy and its associated convective boundary layer was modeled. The model divides the canopy and convective boundary layer into several layers. Photosynthesis, respiration, and exchange between each layer can be simulated by matrix equations. This simulation can be used to calculate recycling; defined here as the amount of respired CO2 re-fixed by photosynthesis relative to the total amount of respired CO2. At steady state the matrix equations can be solved for the canopy and convective boundary layer CO2 concentration and isotopic profile, which can be used to calculate a theoretical recycling index according to a previously developed equation. There is complete agreement between simulated and theoretical recycling indices for different exchange scenarios. Recycling indices from a simulation of gas exchange between a heterogeneous vegetation canopy and the troposphere also agreed with a more generalized form of the theoretical recycling equation developed here.

  13. Stable carbon isotopic composition of methane from some natural and anthropogenic sources

    NASA Astrophysics Data System (ADS)

    Stevens, Charles M.; Engelkemeir, Antoinette

    1988-01-01

    The results of δ13C measurements of several types of major sources of atmospheric methane are as follows: rice paddies, -67‰; the peat bogs of the Lake Agassiz region of northern Minnesota, -67±5‰; swamps of the Florida Everglades, -55±3‰ and biomass burning, -24 to -32‰. In addition, results are presented of a study of the δ13C of CH4 released from a slough, compared to the CH4 in the bottom sediment. These isotopic values are used, together with previously published data, to make up a tentative budget of the fluxes of the major sources for atmospheric methane with an average isotopic composition matching the measured value for atmospheric CH4, taking into account the fractionation effect of the sink processes. This budget requires the existence of a significant flux from an anthropogenic source of heavy CH4, calculated to be 45±15 Tg yr-1 if attributed to CH4 from biomass burning, with δC = -25‰.

  14. Carbon and nitrogen isotopic compositions of particulate organic matter in four large river systems across the United States

    USGS Publications Warehouse

    Kendall, C.; Silva, S.R.; Kelly, V.J.

    2001-01-01

    Riverine particulate organic matter (POM) samples were collected bi-weekly to monthly from 40 sites in the Mississippi, Colorado, Rio Grande, and Columbia River Basins (USA) in 1996-97 and analysed for carbon and nitrogen stable isotopic compositions. These isotopic compositions and C : N ratios were used to identify four endmember sources of POM: Plankton, fresh terrestrial plant material, aquatic plants, and soil organic material. This large-scale study also incorporated ancillary chemical and hydrologic data to refine and extend the interpretations of POM sources beyond the source characterizations that could be done solely with isotopic and elemental ratios. The ancillary data were especially useful for differentiating between seasonal changes in POM source materials and the effects of local nutrient sources and in-stream biogeochemical processes. Average values of ??13 C and C : N for all four river systems suggested that plankton is the dominant source of POM in these rivers, with higher percentages of plankton downstream of reservoirs. Although the temporal patterns in some rivers are complex, the low ??13C and C : N values in spring and summer probably indicate plankton blooms, whereas relatively elevated values in fall and winter are consistent with greater proportions of decaying aquatic vegetation and/or terrestrial material. Seasonal shifts in the ??13C of POM when the C : N remains relatively constant probably indicate changes in the relative rates of photosynthesis and respiration. Periodic inputs of plant detritus are suggested by C : N ratios >15, principally on the Columbia and Ohio Rivers. The ??15N and ??13C also reflect the importance of internal and external sources of dissolved carbon and nitrogen, and the degree of in-stream processing. Elevated ??15N values at some sites probably reflect inputs from sewage and/or animal waste. This information on the spatial and temporal variation in sources of POM in four major river systems should prove

  15. Methane flux and stable hydrogen and carbon isotope composition of sedimentary methane from the Florida Everglades

    NASA Astrophysics Data System (ADS)

    Burke, Roger A., Jr.; Barber, Timothy R.; Sackett, William M.

    1988-12-01

    Methane flux and the stable isotopic composition of sedimentary methane were measured at four locations in the Florida Everglades system. Individual estimates of methane flux ranged over more than 3 orders of magnitude, from about 0.001 to 2.6 g CH4 m-2 d-1. Significant interstation differences in total methane flux were also observed and are judged most likely attributable to differences in the size and spacing of emergent aquatic vegetation, and possibly differences in the type (i.e., vascular plant versus algal) of organic matter incorporated into the sediments. On the basis of measurements presented here and by other investigators, the Everglades system appears to be a relatively weak source of atmospheric methane, probably contributing less than 0.5 Tg CH4 yr-1. Emergent aquatic plants appear to be capable of indirectly affecting the stable isotopic composition of sedimentary methane by stimulating methane oxidation via root aeration. A significant positive correlation between δD-CH4 and δ13C-CH4 was observed for samples collected from sediments covered by tall, dense stands of emergent plants. In contrast, a significant negative correlation between the δD and δ13C of sedimentary methane was observed for samples collected at an open water site where ebullition dominated methane transfer to the atmosphere. The mean δ13C of sedimentary methane samples measured in the Everglades system (mean δ13C =-61.7‰, s.d. = 3.6‰, n = 51) is not significantly different from the estimated average δ13C of all natural sources (-58.3‰). The mean δD of Everglades sedimentary methane (mean δ D = -293‰, s.d. = 14‰, n = 50) appears to be slightly less D-depleted than the estimated average methane (δD =-360 ± 30‰) from all sources.

  16. Carbon isotope effects associated with autotrophic acetogenesis

    USGS Publications Warehouse

    Gelwicks, J.T.; Risatti, J.B.; Hayes, J.M.

    1989-01-01

    The carbon kinetic isotope effects associated with synthesis of acetate from CO2 and H2 during autotrophic growth of Acetobacterium woodii at 30??C have been measured by isotopic analyses of CO2, methyl-carbon, and total acetate. Closed systems allowing construction of complete mass balances at varying stages of growth were utilized, and the effects of the partitioning of carbon between CO2 and HCO3- were taken into account. For the overall reaction, total carbonate ??? total acetate, isotope effects measured in replicate experiments ranged from -59.0 ?? 0.9% to - 57.2 ?? 2.3z%. Taking into account all measurements, the weighted mean and standard deviation are -58.6 ?? 0.7%. There is no evidence for intramolecular ordering in the acetate. The carbon isotopic composition of sedimentary acetate, otherwise expected to be near that of sedimentary organic carbon, is likely to be depleted in environments in which autotrophic acetogenesis is occurring. ?? 1989.

  17. Carbon isotope compositions of terrestrial C3 plants as indicators of (paleo)ecology and (paleo)climate.

    PubMed

    Kohn, Matthew J

    2010-11-16

    A broad compilation of modern carbon isotope compositions in all C3 plant types shows a monotonic increase in δ(13)C with decreasing mean annual precipitation (MAP) that differs from previous models. Corrections for temperature, altitude, or latitude are smaller than previously estimated. As corrected for altitude, latitude, and the δ(13)C of atmospheric CO(2), these data permit refined interpretation of MAP, paleodiet, and paleoecology of ecosystems dominated by C3 plants, either prior to 7-8 million years ago (Ma), or more recently at mid- to high latitudes. Twenty-nine published paleontological studies suggest preservational or scientific bias toward dry ecosystems, although wet ecosystems are also represented. Unambiguous isotopic evidence for C4 plants is lacking prior to 7-8 Ma, and hominid ecosystems at 4.4 Ma show no isotopic evidence for dense forests. Consideration of global plant biomass indicates that average δ(13)C of C3 plants is commonly overestimated by approximately 2‰.

  18. Carbon isotope compositions of terrestrial C3 plants as indicators of (paleo)ecology and (paleo)climate

    PubMed Central

    Kohn, Matthew J.

    2010-01-01

    A broad compilation of modern carbon isotope compositions in all C3 plant types shows a monotonic increase in δ13C with decreasing mean annual precipitation (MAP) that differs from previous models. Corrections for temperature, altitude, or latitude are smaller than previously estimated. As corrected for altitude, latitude, and the δ13C of atmospheric CO2, these data permit refined interpretation of MAP, paleodiet, and paleoecology of ecosystems dominated by C3 plants, either prior to 7–8 million years ago (Ma), or more recently at mid- to high latitudes. Twenty-nine published paleontological studies suggest preservational or scientific bias toward dry ecosystems, although wet ecosystems are also represented. Unambiguous isotopic evidence for C4 plants is lacking prior to 7–8 Ma, and hominid ecosystems at 4.4 Ma show no isotopic evidence for dense forests. Consideration of global plant biomass indicates that average δ13C of C3 plants is commonly overestimated by approximately 2‰. PMID:21041671

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

    NASA Astrophysics Data System (ADS)

    Saltzman, Matthew R.; Edwards, Cole T.

    2017-04-01

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

  20. Carbon isotope composition of individual amino acids in the Murchison meteorite

    SciTech Connect

    Engel, M.H.; Macko, S.A.; Silter, J.A.

    1996-07-01

    A SIGNIFICANT parties of prebiotic organic matter on the early Earth may have been introduced by carbonaceous asteroids and comets.{sup 1} The distribution and stable-isotope composition of individual organic compounds in carbonaceous meteorites, which are thought to be derived from asteroidal parent bodies, may therefore provide important information concerning mechanistic pathways for prebiotic synthesis{sup 2} and the composition of organic matter on Earth before living systems developed.{sup 3} Previous studies{sup 11,12} have shown that meteorite amino acids are enriched in {sup 13}C relatives to their terrestrial counterparts, but individual species were not distinguished. Here we report the {sup 13}C contents of individual amino acids in the Murchison meteorite. The amino acids are enriched in {sup 13}C, indicating an extraterrestrial origin. Alanine is not racemic, and the {sup 13}C enrichment of its D- and L-enantiomers implies that the excess of the L-enantiomer is indigenous rather than terrestrial contamination, suggesting that optically active materials were present in the early Solar System before life began. {copyright} {ital 1996 American Institute of Physics.}

  1. A balloon measurement of the isotopic composition of galactic cosmic ray boron, carbon and nitrogen. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    Zumberge, J. F.

    1981-01-01

    The isotopic compositions of galactic cosmic ray boron, carbon, and nitrogen were measured at energies near 300 MeV amu, using a balloon-borne instrument at an atmospheric depth of approximately 5 g/sq cm. The calibrations of the detectors comprising the instrument are described. The saturation properties of the cesium iodide scintillators used for measurement of particle energy are studied in the context of analyzing the data for mass. The achieved rms mass resolution varies from approximately 0.3 amu at boron to approximately 0.5 amu at nitrogen, consistent with a theoretical analysis of the contributing factors. Corrected for detector interactions and the effects of the residual atmosphere the results are B-10/B=0.33 (+0.17, -0.11), C-13/C=0.06 (+0.13, -0.11), and N-15/N=0.42 (+0.19, -0.17). A model of galactic propagation and solar modulation is described. Assuming a cosmic ray source composition of solar-like isotopic abundances, the model predicts abundances near Earth consistent with the measurements.

  2. Organismal versus Environmental Control of the Carbon Isotope Composition of Dicot Angiosperm Pollen: Implications for Paleoenvironmental Reconstruction

    NASA Astrophysics Data System (ADS)

    King, D. P.; Schubert, B.; Foelber, K.; Jahren, H.

    2011-12-01

    The prevalence and diagenetic resilience of palynomorphs in Proterozoic and Phanerozoic sediments has led researchers to investigate its potential as an environmental proxy based on its stable isotope composition. Towards this, Loader and Hemming (2001), noted that the carbon isotope composition (δ13C) of modern Pinus sylvestris pollen exine correlates with the developmental period temperature (°C) of the pollen (R2=0.68), implying that the δ13C of gymnosperm pollen could be quantitatively utilized as a paleotemperature proxy. However, the majority of pollen-producing organisms during the last ~120 million years have been angiosperms, which are subject to complex internal signaling for reproduction, in addition to environmental triggers. Because these internal signals control the relative proportion of lipids, long-chain fatty acids, and polysaccharides within pollen grains, we hypothesized that the δ13C variability in pollen (δ13Cpollen) from several plants subject to the same external environmental parameters is of the same magnitude as the amount attributed to the environment for gymnosperms. Within growth chambers, the test organism (Brassica rapa) was cultivated under constant light, water, pCO2, and nutrient supply, but exhibited average δ13Cpollen variability = 4.35% within any chamber (n = 6 to 8 plants per chamber). Field experiments were also conducted in which the pollen from the test organism (Hibiscus spp.) was sampled from several botanical gardens within the state of Hawaii. Pollen collected from any one botanical garden exhibited an average δ13Cpollen variability = 4.5% (up to 5 plants per garden). Upon comparing chambers operating at different temperatures (17°C to 32°C), we discovered no correlation (R2=0.01) between the developmental period temperature (°C) and the δ13C of B. rapa pollen; similarly, no correlation was found between the δ13C of Hibiscus pollen and its developmental period temperature (°C) (R2=0.12). This work

  3. The Carbon and Hydrogen Stable Isotope Composition of Methane Released from Natural Wetlands and Ruminants

    NASA Astrophysics Data System (ADS)

    Lansdown, John Malcolm

    The delta^{13} {rm C} of CH_4 emitted from the tropical Amazon river floodplain, temperate peat bogs in Washington and Minnesota, and the arctic Alaskan tundra was -59, -73, -66, and -65perthous, respectively. The deltaD of CH_4 from these sites was -294, -308, -339, and -391perthous, respectively, and a linear relationship was observed between the deltaD of CH_4 and soil water. A ^{13} C balance between CH_4, CO _2 and soil organic matter indicated a higher percentage of CH_4 production via methyl conversion at the Amazon floodplain than at the other wetland sites and that the anoxic CO _2 flux was 1.5 to 2.0 times the CH _4 flux. The ^{13} C balance provided greater constraint on the anoxic CO_2 flux than calculations based on soil water gradients. An in situ value of 0.774 for the hydrogen kinetic isotope effect during microbial CH _4 oxidation was estimated from the increase in the delta^{13} {rm C} and deltaD of CH_4 in flux samples from the Amazon site. The average delta^{13 }{rm C} of CH_4 released from an acidic peat bog in Washington state (pH = 3.5) was -73perthous, lower than previously measured at freshwater wetland sites. Soil incubations with ^{14 }C-labeled CO_2 and acetate substrates showed that CO_2 reduction accounted for essentially all methane production in the bog. An in situ value of 0.933 for the carbon kinetic isotope effect for CO_2 reduction was calculated from the delta^{13 }{rm C} of the CH_4 flux and soil water CO_2.. The delta^{13} {rm C} and deltaD of CH_4 emitted from ruminants was measured and averaged -63 and -404perthous, respectively. CO _2 reduction accounted for ~70% of rumen CH_4 production based on the change in the delta ^{13}{rm C} and deltaD of rumen CH_4 vs. time during normal conditions and after the addition of deuterated water to the rumen. These results contrast the dogma in the literature that CO_2 reduction accounts for essentially all CH _4 production in the rumen. A global budget for the deltaD of CH_4 was

  4. Woody Plant Invasion of Grassland: Lignin and Aliphatic Biopolymer Chemistry and Carbon Isotope Composition in Physical Fractions

    NASA Astrophysics Data System (ADS)

    Gamblin, D.; Boutton, T.; Liao, J.; Jastrow, J.; Filley, T.

    2003-12-01

    Significant changes in the apportionment of organic carbon in grassland and savanna soils have been document as a result of woody plant encroachment. In the Rio Grande Plains of Texas, C4 grasslands (d13C = -14 0/00) have undergone succession to trees and shrubs of a subtropical thorn woodland (d13C = -27 0/00) over the past 150 y which has resulted in increased soil organic carbon storage. Large differences in the turnover times of physical fractions in this system indicate selective preservation mechanisms which may include physical protection or inherent biochemical recalcitrance. To elucidate mechanisms of SOC sequestration during woody plant succession in this system, we are investigating the chemistry and compound-specific stable carbon isotope composition of lignin and aliphatic biopolymers in specific physical (size, density) soil fractions within a chronosequence that includes remnant grasslands (Time 0) and woody plant stands ranging in age from 10-130 y. The soil fraction data is being compared to biopolymer and isotope chemistry of the root, stem and/or leaf tissue of 20 of the dominant genus of plants in the system. Lignin phenols and suberin and cutin-derived hydroxyfatty acids are being isolated using alkaline CuO oxidation and tetramethylammonium hydroxide thermochemolysis. A comparison of the macroaggregate (greater than 250 um), microaggregate (53-250 um), and free silt and clay fractions in the oldest stand indicates that lignin is the most concentrated (organic carbon normalized values) in macroaggregates and is significantly less degraded, as determined by relative yields of oxidized and reduced lignin phenols. Additionally, the intra-aggregate silt and clay fraction from the macroaggregates contains less than half of the organic carbon normalized lignin phenols and is relatively more oxidized than what is found in the total macroaggregate pool. From these preliminary results it appears that the bulk macroaggregate pool contains the least

  5. Short-term changes in carbon isotope composition of soluble carbohydrates and starch: from canopy leaves to the root system.

    PubMed

    Göttlicher, Sabine; Knohl, Alexander; Wanek, Wolfgang; Buchmann, Nina; Richter, Andreas

    2006-01-01

    Changes in the 13C discrimination of current leaf photosynthesis might have profound impacts on root respiratory substrates. Therefore, the aim of this study was (1) to refine a method for the isolation of root and leaf starch and soluble sugars (neutral fraction) for stable carbon isotope analysis and (2) to assess the short-term temporal variability of the C isotope composition (delta13C) of starch and of the neutral fraction of beech roots and leaves at different canopy heights. An existing method for isolating starch for stable C isotope analysis based on enzymatic hydrolysis was modified to account for the low starch content of the samples. This was achieved by removing the enzyme (alpha-amylase) by ultrafiltration after the hydrolysis, resulting in very low carbon blanks. The neutral fraction was separated from organic acids and cations by ion-exchange chromatography. An anion-exchange resin in the [HCO3]--form was chosen that ensured high precision of C blanks. Beech leaves at 5, 10 and 20 m above the forest floor as well as roots were sampled six times during a day/night cycle in July 2003. Delta13C values of bulk material, starch and the neutral fraction increased from the lower to the higher canopy with mean differences between 5 and 20 m of 3.8, 3.4 and 2.7 per thousand for the delta13C values of starch, neutral fraction and bulk foliage, respectively. The delta13C value of foliar starch increased from the morning to the afternoon and decreased during the night, but diurnal differences (up to 3.1 per thousand) were only statistically significant for leaves sampled at 5 and 10 m height. In roots, no diurnal variation in the delta13C of starch was observed during the short time frame of one day and the delta13C of the neutral fraction did not differ between samples taken at 16:30 and 22:00. Calculated delta13C values of starch, which was mobilised during the night, were more positive than the total starch (all sampling times pooled) in leaves. Furthermore

  6. Leaf wax composition and carbon isotopes vary among major conifer groups

    NASA Astrophysics Data System (ADS)

    Diefendorf, Aaron F.; Leslie, Andrew B.; Wing, Scott L.

    2015-12-01

    Leaf waxes (e.g. n-alkanes, n-alkanoic acids) and their carbon isotopes (δ13C) are commonly used to track past changes in the carbon cycle, water availability, and plant ecophysiology. Previous studies indicated that conifers have lower n-alkane concentrations than angiosperms and that 13C fractionation during n-alkane synthesis (εn-alkane) is smaller than in angiosperms. These prior studies, however, sampled a limited phylogenetic and geographic subset of conifers, leaving out many important subtropical and Southern Hemisphere groups that were once widespread and common components of fossil assemblages. To expand on previous work, we collected 43 conifer species (and Ginkgo biloba) from the University of California Botanical Garden at Berkeley, sampling all extant conifer families and almost two-thirds of extant genera. We find that Pinaceae, including many North American species used in previous studies, have very low or no n-alkanes. However, other conifer groups have significant concentrations of n-alkanes, especially Southern Hemisphere Araucariaceae and Podocarpaceae (monkey puzzles, Norfolk Island pines, and yellowwoods), and many species of Cupressaceae (junipers and relatives). Within the Cupressaceae, we find total n-alkane concentrations are high in subfamilies Cupressoideae and Callitroideae, but significantly lower in the early diverging taxodioid lineages (including bald cypress and redwood). Individual n-alkane chain lengths have a weak phylogenetic signal, except for n-C29 alkane, but when combined using average chain length (ACL), a strong phylogenetic signal emerges. The strong phylogenetic signal in ACL, observed in the context of a common growth environment for all plants we sampled, suggests that ACL is strongly influenced by factors other than climate. An analysis of εn-alkane indicates a strong phylogenetic signal in which the smallest biosynthetic fractionation occurs in Pinaceae and the largest in Taxaceae (yews and relatives). The

  7. Effect of Salinity on the Stable Carbon Isotopic Composition of Microbial Mats and Associated Lipid Biomarkers

    NASA Astrophysics Data System (ADS)

    Jahnke, L. L.; Parenteau, M. N.; Kubo, M. D.; Des Marais, D. J.

    2014-12-01

    Modern microbial mats are commonly used as analogs for understanding early ecosystem evolution. A primary feature of benthic ecosystems is the fixation of CO2 in the photic zone and transfer and/or mineralization of organic carbon through a diverse tropic structure. Generally, the resulting δ13C values for organic matter relative to DIC is small which indicates that these mats are CO2-limited. Microcoleus mat flux measurements indicate that small amounts of CO2 fixed during the day are lost to the overlying water at night as C13-enriched DIC (Des Marais and Canfield 1994). This loss results in depletion in mat organic matter and is thought to occur as a result of remineralized DIC fixation by chemo- and/or photoautotrophs. We have examined the fate of fixed carbon in hypersaline mats by analysis of the stable C-isotopes of bulk organic carbon and lipid compounds in a laminated-Microcoleus mat (90 ‰, pH 8.6) and in a gypsum-endoevaporitic, Halothece mat (163‰, pH 7.4). In the surface photic zone of Microcoleus mat, the δ13C TOC was -10.0 ‰ with membrane fatty acids (i-15, n-16, n-18, cy-19) ranging from -17.2 to -18.0‰. Cyanobacterial alkanes were similarly depleted (n-17 = -19.5‰). Eurkaryotic sterols and bacterial hopanoids were somewhat enriched with δ13C values ~-15‰. For Microcoleus mat, little variation occurred over 70 mm of core depth. The TOC and FA values for surface, endoevaporitic Halothece mat were generally similar to those of Microcoleus. However, below the surface gypsum crust, discrimination increased. Mass balance calculations for surface FA = -18.5‰ while the FA from layers below the crust = -25.2‰. The δ13C values for cyanobacterial alkanes (~-20‰) were similar from all layers while hopanoids from below crust were slightly depleted relative to those from surface. An apparent increased discrimination during fixation of remineralized DIC presumably by anoxygenic phototrophs present below the surface gypsum crust (Jahnke et al

  8. Attempts to comprehend Martian surface processes through interpretation of the oxygen isotopic compositions of carbonates in SNC meteorites

    NASA Technical Reports Server (NTRS)

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

    1992-01-01

    The SNC meteorites are known to contain trace quantities of a variety of secondary minerals such as carbonates, sulfates, and aluminosilicates. Since these constituents are thought to be mostly preterrestrial in origin, their study has the potential to provide rigorous constraints on the nature of martian weathering processes. However, this line of investigation is potentially complicated by the presence within the meteorite samples of any additional weathering products produced by terrestrial processes. Examination of such terrestrial components is important since weathering processes that affect meteorite samples following their fall to Earth might have some bearing on the nature of analogous processes at the surface of Mars. It is obviously necessary to try and distinguish which secondary components in SNC meteorites are terrestrial in origin from those that are preterrestrial. Herein consideration is made of the stable isotopic compositions of weathering products in two SNC meteorites: EET A79001 (a sample collected from Antarctica) and Nakhla (a fall from Egypt, 1911).

  9. Different carbon reservoirs of auriferous fluids in African Archean and Proterozoic gold deposits? Constraints from stable carbon isotopic compositions of quartz-hosted CO2-rich fluid inclusions

    NASA Astrophysics Data System (ADS)

    Lüders, Volker; Klemd, Reiner; Oberthür, Thomas; Plessen, Birgit

    2015-04-01

    Stable carbon (and when present, nitrogen) isotope ratios of fluid inclusions in quartz from selected gold deposits in Ghana and Zimbabwe have been analyzed using a crushing device interfaced to an isotopic ratio mass spectrometer (IRMS) in order to constrain possible sources of the auriferous fluids. The study revealed a striking difference in stable carbon isotopic compositions of CO2 in quartz-hosted fluid inclusions from Archean and Paleoproterozoic orogenic gold deposits and points to diverse sources of CO2 in the studied deposits. Whether this finding can be generalized for other Archean and Proterozoic orogenic gold deposits worldwide remains open. However, a significant CO2 contribution by mantle degassing can be ruled out for every deposit studied. Devolatilization of greenstone belt rocks is the most likely source for CO2 in some Archean Au deposits in Zimbabwe, whereas CO2 in Proterozoic vein-type Au deposits in the West African Craton is most likely derived from Corg-bearing metasedimentary rocks. The δ13CCO2 values of high-density CO2-rich, water-poor inclusions hosted in quartz pebbles from the world-class Au-bearing conglomerate deposits at Tarkwa (Ghana) differ considerably from the δ13CCO2 values of similar high-density CO2-rich inclusions in vein quartz from the giant Ashanti deposit (Ghana) and disprove the idea of derivation of the Tarkwaian quartz (and gold?) from an older equivalent to the Ashanti vein-type gold deposit.

  10. Oxygen and carbon isotopic composition of limestones and dolomites, bikini and eniwetok atolls.

    PubMed

    Gross, M G; Tracey, J I

    1966-03-04

    Aragonitic, unconsolidated sediments from the borings on the Eniwetok and Bikini atolls are isotopically identical with unaltered skeletal fragments, whereas the recrystallized limestones exhibit isotopic variations resulting from alteration in meteoric waters during periods of emergence. Dolomites and associated calcites are enriched in O(18), perhaps because of interaction with hypersaline brines.

  11. Stable isotopic compositions of carbonates from the Mesoproterozoic Bangemall Group, northwestern Australia

    NASA Technical Reports Server (NTRS)

    Buick, R.; Des Marais, D. J.; Knoll, A. H.

    1995-01-01

    Marine carbonate rocks from the Mesoproterozoic Bangemall Group of northwestern Australia show little deviation (+/-1.3%) in whole-rock delta 13C(carb)-values about a mean of -0.5%. This narrow range persists despite close sampling (every 10-20 m) through long sections (up to 2500 m) that are geographically widespread (up to 250 km apart), over many depositional environments (supralittoral to outer shelf), sediment sources (stromatolitic bioherms to detrital calcilutites) and rock types (pure limestones to dolomitic shales). The only major excursions from the norm seem related to unusual environmental or post-depositional processes, as they are correlated with large enrichments (to -3%) or depletions (to -16%) in 18O. Relatively heavy delta 13C-values, up to +2.5%, occur in a single bed of brecciated ferruginous dolostone at a single locality; these abnormal values may result from local evaporitic conditions. Limey and shaley nodular dolostones have delta 13C-values as low as -4.3%, probably caused by remineralization of organic matter during late and patchy dolomitization. Most notably, sharp negative excursions in delta 13C, up to -8.4%, occur in bleached kerogen-free rocks with mineral assemblages of dolomite + quartz + calcite +/- tremolite + talc, reflecting isotopic re-equilibration in thick metamorphic aureoles around dolerite intrusions. General environmental variations are minor, with delta 13C-values of peritidal facies tending to be slightly positive whereas those of subtidal facies are slightly negative. There are no strong secular trends, but subtle fluctuations within the range -2 to +l% can be correlated along the northwestern margin of the basin. This resembles the pattern seen in other Mesoproterozoic successions, but is markedly unlike the heavy background (> +5%) and extreme variations (up to l0%) in delta 13C evident in Neoproterozoic successions of similar thickness and environmental setting. Hence, in contrast to the Neoproterozoic, the global

  12. Stable isotopic compositions of carbonates from the Mesoproterozoic Bangemall Group, northwestern Australia.

    PubMed

    Buick, R; Des Marais, D J; Knoll, A H

    1995-06-20

    Marine carbonate rocks from the Mesoproterozoic Bangemall Group of northwestern Australia show little deviation (+/-1.3%) in whole-rock delta 13C(carb)-values about a mean of -0.5%. This narrow range persists despite close sampling (every 10-20 m) through long sections (up to 2500 m) that are geographically widespread (up to 250 km apart), over many depositional environments (supralittoral to outer shelf), sediment sources (stromatolitic bioherms to detrital calcilutites) and rock types (pure limestones to dolomitic shales). The only major excursions from the norm seem related to unusual environmental or post-depositional processes, as they are correlated with large enrichments (to -3%) or depletions (to -16%) in 18O. Relatively heavy delta 13C-values, up to +2.5%, occur in a single bed of brecciated ferruginous dolostone at a single locality; these abnormal values may result from local evaporitic conditions. Limey and shaley nodular dolostones have delta 13C-values as low as -4.3%, probably caused by remineralization of organic matter during late and patchy dolomitization. Most notably, sharp negative excursions in delta 13C, up to -8.4%, occur in bleached kerogen-free rocks with mineral assemblages of dolomite + quartz + calcite +/- tremolite + talc, reflecting isotopic re-equilibration in thick metamorphic aureoles around dolerite intrusions. General environmental variations are minor, with delta 13C-values of peritidal facies tending to be slightly positive whereas those of subtidal facies are slightly negative. There are no strong secular trends, but subtle fluctuations within the range -2 to +l% can be correlated along the northwestern margin of the basin. This resembles the pattern seen in other Mesoproterozoic successions, but is markedly unlike the heavy background (> +5%) and extreme variations (up to l0%) in delta 13C evident in Neoproterozoic successions of similar thickness and environmental setting. Hence, in contrast to the Neoproterozoic, the global

  13. Composition of Hydrothermal Vent Microbial Communities as Revealed by Analyses of Signature Lipids, Stable Carbon Isotopes and Aquificales Cultures

    NASA Technical Reports Server (NTRS)

    Jahnke, Linda L.; Edger, Wolfgang; Huber, Robert; Hinrichs, Kai-Uwe; Hayes, John M.; DesMarais, David J.; Cady, Sherry; Hope, Janet M.; Summons, Roger E.; DeVincenzi, Donald L. (Technical Monitor)

    2001-01-01

    Extremely thermophilic microbial communities associated with the siliceous vent walls and outflow channel of Octopus Spring, Yellowstone National Park, have been examined for lipid biomarkers and carbon isotopic signatures. These data were compared with that obtained from representatives of three Aquificales genera. Thermocrinis ruber. "Thermocrinis sp. HI", Hydrogenobacter thermophilus TK-6, Aquifex pyrophilus and Aquifex aeolicus all contained phospholipids composed not only of the usual ester-linked fatty acids, but also ether-linked alkyls. The fatty acids of all cultured organisms were dominated by a very distinct pattern of n-C-20:1 and cy-C-21 compounds. The alkyl glycerol ethers were present primarily as CIS() monoethers with the expection of the Aquifex spp. in which dialkyl glycerol ethers with a boarder carbon-number distribution were also present. These Aquificales biomarker lipids were the major constituents in the lipid extracts of the Octopus Spring microbial samples. Two natural samples, a microbial biofilm growing in association with deposition of amorphous silica on the vent walls at 92 C, and the well-known 'pink-streamers community' (PSC), siliceous filaments of a microbial consortia growing in the upper outflow channel at 87 C were analyzed. Both the biofilm and PSC samples contained mono and dialkyl glycerol ethers with a prevalence of C-18 and C-20 alkyls. Phospholipid fatty acids were comprised of both the characteristic Aquificales n-C-20:1 and cy-C-21, and in addition, a series of iso-branched fatty acids from i-C-15:0 to i-C-21:0, With i-C-17:0 dominant in the PSC and i-C-19:0 in the biofilm, suggesting the presence of two major bacterial groups. Bacteriohopanepolyols were absent and the minute quantities of archaeol detected showed that Archaea were only minor constituents. Carbon isotopic compositions of the PSC yielded information about community structure and likely physiology. Biomass was C-13-depleted (10.9%) relative to available

  14. An attempt to compare variations of carbon stable isotopes composition in two replicate cores from a Baltic bog in N Poland

    NASA Astrophysics Data System (ADS)

    Pawlyta, Jacek; Lamentowicz, Mariusz; Goslar, Tomasz

    2010-05-01

    Two one-meter long monolith cores were taken from Stążki mire. Stążki mire is well preserved Baltic type raised bog with a very small evidence of exploitation. Stable isotopic composition of carbon (13C) was investigated in the bulk organic matter of Sphagnum. One centimetre resolution sampling was chosen for the investigation. Only carefully selected, leaf-free Sphagnum stems were collected for the study. Isotopic composition was determined using elemental analyser coupled to isotopic ratio mass spectrometer. For the correlation purposes age-depth models were established for both monoliths. Radiocarbon dating and 210Pb dating results were used to obtain the age-depth model for one monolith. Age-depth model for the second monolith was based on radiocarbon dating only. Both cores covered the last 1200 years of Stążki mire history. We will present a detailed comparison of correlate isotopic signal from Sphagnum in both cores.

  15. Carbon isotopic fractionation in heterotrophic microbial metabolism.

    PubMed Central

    Blair, N; Leu, A; Muñoz, 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% depleted in 13C relative to the glucose used as the carbon source, whereas the acetate was 12.3% enriched in 13C. The acetate 13C enrichment was solely in the carboxyl group. Even though the total cellular carbon was only 0.6% depleted in 13C, intracellular components exhibited a significant isotopic heterogeneity. The protein and lipid fractions were -1.1 and -2.7%, respectively. Aspartic and glutamic acids were -1.6 and +2.7%, respectively, yet citrate was isotopically identical to the glucose. Probable sites of carbon isotopic fractionation include the enzyme, phosphotransacetylase, and the Krebs cycle. PMID:2867741

  16. Carbon isotopic fractionation in heterotrophic microbial metabolism

    NASA Technical Reports Server (NTRS)

    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.

  17. Carbon isotopic fractionation in heterotrophic microbial metabolism

    SciTech Connect

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

    1985-10-01

    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. 38 references.

  18. Isotopic composition of carbon dioxide from a boreal forest fire: Inferring carbon loss from measurements and modeling

    USGS Publications Warehouse

    Schuur, E.A.G.; Trumbore, S.E.; Mack, M.C.; Harden, J.W.

    2003-01-01

    Fire is an important pathway for carbon (C) loss from boreal forest ecosystems and has a strong effect on ecosystem C balance. Fires can range widely in severity, defined as the amount of vegetation and forest floor consumed by fire, depending on local fuel and climatic conditions. Here we explore a novel method for estimating fire severity and loss of C from fire using the atmosphere to integrate ecosystem heterogeneity at the watershed scale. We measured the ??13C and ??14C isotopic values of CO2 emitted from an experimental forest fire at the Caribou-Poker Creek Research Watershed (CPCRW), near Fairbanks, Alaska. We used inverse modeling combined with dual isotope near measurements of C contained in aboveground black spruce biomass and soil organic horizons to estimate the amount of C released by this fire. The experimental burn was a medium to severe intensity fire that released, on average, about 2.5 kg Cm-2, more than half of the C contained in vegetation and soil organic horizon pools. For vegetation, the model predicted that approximately 70-75% of pools such as needles, fine branches, and bark were consumed by fire, whereas only 20-30% of pools such as coarse branches and cones were consumed. The fire was predicted to have almost completely consumed surface soil organic horizons and burned about half of the deepest humic horizon. The ability to estimate the amount of biomass combusted and C emission from fires at the watershed scale provides an extensive approach that can complement more limited intensive ground-based measurements.

  19. [Relationship of intramolecular carbon isotopes in pyruvate decarboxylation].

    PubMed

    Ivlev, A A; Kniazev, D A; Kaloshin, A G

    1982-01-01

    Relationships were obtained which made possible to calculate isotope content of carbon atoms in the products and reaction compound in the course of piruvate decarboxilation. Isotope composition was determined from kinetic isotope effect accompanying the destruction of carbon bonds. Some applications of the expressions obtained are presented.

  20. Problem of soot aggregates separation and purification for Carbon isotopic composition analyses - burning experiment and real black layers from speleothems examples

    NASA Astrophysics Data System (ADS)

    Hercman, Helena; Zawidzki, Pawel; Majewska, Agata

    2015-04-01

    Burning products are often used as an indicator of fire or prehistoric men activities. When it consists of macroscopically visible black layer it may be studied by different methods. When it is dispersed within sediment it is necessary to apply method for burning product separation. Soot aggregates as a result of incomplete combustion of organic materials are most reliable indication of burning. Size of soot particles is too small to observe by optical microscopy. There are two main advantages of application of transmission electron microscopy (TEM) for investigations of samples formed as a result of organic materials (like wood) combustion. First, it makes possible to investigate not only morphology but also its interior structure. The carbon layers arrangement is characteristic for particles obtained from combustion processes, and it directly confirm that these particles were formed that way. And second, analysis of chemical composition using of EDS spectroscopy in transmission microscope are precise and it spatial resolution is about a few nanometers. Burning chamber for wood burning experiments was constructed. It allows wood burning with controlling of burning temperature, carbon isotopic composition in carbon dioxide of burning atmosphere and carbon dioxide originated during burning. Burning products are collected on the plates with controlling of plates material, temperature and distance from flame. Two types of samples were studied. The first type of samples consisted the products of recent wood burning. The second type of samples consisted of black layers collected from speleothems. Soot aggregates were chemically separated from other burning products collected on plates. Process of chemical separation and purity of soot material were tested by TEM observations. Isotopic carbon composition at each step of soot separation as well as original wood fragments was analysed at the Isotopic Laboratory for Dating and Palaeoenvironment Studies, Polish Academy of

  1. Pliocene-Early Pleistocene climatic trends in the Italian Peninsula based on stable oxygen and carbon isotope compositions of rhinoceros and gomphothere tooth enamel

    NASA Astrophysics Data System (ADS)

    Szabó, Péter; Kocsis, László; Vennemann, Torsten; Pandolfi, Luca; Kovács, János; Martinetto, Edoardo; Demény, Attila

    2017-02-01

    The Pliocene and Early Pleistocene (5.2-1 Ma) palaeoclimate for localities in Italy is evaluated using stable carbon and oxygen isotope compositions of tooth enamel of fossil specimens from Rhinocerotidae (Stephanorhinus sp.) and Gomphotheriidae (Anancus sp.) taxa. Carbon isotope composition was measured in the structural carbonate (δ13C), while oxygen isotope values were determined both in the structural carbonate (δ18OCO3) and the phosphate (δ18OPO4) of bioapatite. The δ13CCO3 values indicate that the taxa were grazers-browsers of a pure C3 vegetation. Low δ13CCO3 values for Central and North Italy indicate a humid climate with woodlands and forest cover in the Pliocene. For northern localities the δ13C values increase between MN16a and MNQ16b biozones most likely linked to the Northern Hemisphere Glaciation at 2.7 Ma after the "Mid-Pliocene Warm Period". For Central Italy the values have a wide range with a long term increasing trend in the Early Pleistocene, indicating more arid climate and/or more open vegetation. Overall, the δ18OPO4 values in Central Italy change together with the δ13CCO3 values and are taken to reflect the warmer/wetter interglacials and cooler/more arid glacial phases. The δ18OPO4 values in North Italy are lower than those in Central Italy and show no clear temporal trend. One explanation for the low values especially in MN14-15 biozone is that these δ18OPO4 values do not reflect entirely the isotopic composition of local precipitation but river waters from the Alps with 18O-depleted isotopic compositions or a N-S directed rain-shadow effect on the precipitation. In general the new isotope data agree well with palaeoclimate reconstructions based on palynological and other proxies.

  2. Intraspecific variations in carbon-isotope and oxygen-isotope compositions of a brachiopod Basiliola lucida collected off Okinawa-jima, southwestern Japan

    NASA Astrophysics Data System (ADS)

    Takayanagi, Hideko; Asami, Ryuji; Abe, Osamu; Miyajima, Toshihiro; Kitagawa, Hiroyuki; Sasaki, Keiichi; Iryu, Yasufumi

    2013-08-01

    This study presents intraspecific variations in carbon-isotope (δ13C) and oxygen-isotope (δ18O) compositions of nine specimens of a subtropical brachiopod, Basiliola lucida, collected west of Okinawa-jima, Ryukyu Islands, southwestern Japan. The δ13C values of samples collected along the maximum growth axis (ontogenetic samples) from two modern and seven older (pre-1945 cal AD) shells show no seasonal changes. The modern shells, which were collected from comparable depths, have similar δ13C values that fall within the range of calcite precipitated in isotopic equilibrium with ambient seawater (equilibrium calcite) (δ13CEC values), and their mean δ13C values are ˜1.1-1.6‰ less than those from the older shells. This decrease in δ13C values is similar in magnitude to the decreases in atmospheric CO2 and the oceanic dissolved inorganic carbon at the sea surface in recent years (13C Suess effect), suggesting that the effect can even be detected at water depths of 200-300 m in the subtropical northwestern Pacific Ocean. The δ18O values fluctuate within a narrow range (0.26-0.41‰) with no seasonal changes, and they exhibit small (0.14-0.51‰) offsets from those of equilibrium calcite (δ18OEC values). A statistically significant negative linear relationship is established between seawater temperature and mean δ18O values of the nine shells, but the slope (-0.31‰/°C) is steeper than those of equilibrium calcite (-0.23‰/°C) and other calcareous organisms (-0.15‰ to -0.26‰/°C). The cross-plots of the δ13C and δ18O values suggest that the degree of the vital effect varies among individuals in this species. The δ13C and δ18O values of B. lucida are potentially useful for reconstructing the δ13C and δ18O evolution of ancient oceans, because both values show small intraspecific variations, the former is identical to the δ13CEC values, and the latter shows small within-shell variations and small, nearly constant offsets from the δ18OEC values.

  3. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Burke, F.P.; Winschel, R.A.; Lancet, M.S.

    1990-05-01

    Consol R D is developing and demonstrating stable carbon isotope analysis as a method quantitatively distinguish coal-derived and petroleum-derived carbon in products from coal/petroleum coprocessing. The approach taken is to develop the method, then demonstrate its application on authentic continuous-unit products. The significance of selective isotopic fractionation is being determined and, if necessary, corrections will be applied to account for it. Activities for this quarter include: method development -- investigation of selective fractionation. Three petroleum atmospheric still bottoms (ASBs) were separated by distillation and solubility fractionation to determine the homogeneity of the carbon isotope ratios of the separated fractions. These same three petroleum ASBs and three geographically distinct coals were pyrolyzed at 800{degree}F for 30 min and hydrogenated over a CoMo catalyst at 750{degree}F for 60 min to determine the effects of these treatments on the isotopic compositions of the produce fractions. Twelve coal liquefaction oils were analyzed for carbon isotope ratios. These oils were derived from subbituminous and bituminous coals from the first- and second-stage reactors in the thermal/catalytic and modes; validation and application, analysis. Carbon isotope analyses of samples from HRI bench unit coprocessing run 238-2 (Taiheiyo coal/Maya VSB) were analyzed. A method to correct for selective isotopic fractionation was developed and applied to the data. Five coprocessing samples were analyzed at the request of SRI International. 12 refs., 15 figs., 24 tabs.

  4. Stable isotopic compositions of elemental carbon in PM1.1 in north suburb of Nanjing Region, China

    NASA Astrophysics Data System (ADS)

    Guo, Zhaobing; Jiang, Wenjuan; Chen, Shanli; Sun, Deling; Shi, Lei; Zeng, Gang; Rui, Maoling

    2016-02-01

    Stable isotopic compositions (δ13C) of elemental carbon (EC) in PM1.1 in north suburb of Nanjing region were determined in order to quantitatively evaluate the carbon sources of atmospheric fine particles during different seasons. Besides, δ13C values from potential sources such as coal combustion, vehicle exhaust, biomass burning, and dust were synchronously measured. The results showed that the average δ13C values of EC in PM1.1 in winter and summer were - 23.89 ± 1.6‰ and - 24.76 ± 0.9‰, respectively. Comparing with δ13C values from potential sources, we concluded that the main sources of EC in PM1.1 were from the emission of coal combustion and vehicle exhaust. The higher δ13C values in winter than those in summer were chiefly attributed to the more coal consumption. Combining with the concentrations of SO42 - and K+ in PM1.1, the high δ13C values of EC on 24 December and 27 December 2013 were ascribed to extra input of corn straw burning in addition to coal combustion and vehicle exhaust.

  5. Molecular distributions and compound-specific stable carbon isotopic compositions of lipids in wintertime aerosols from Beijing.

    PubMed

    Ren, Lujie; Fu, Pingqing; He, Yue; Hou, Juzhi; Chen, Jing; Pavuluri, Chandra Mouli; Sun, Yele; Wang, Zifa

    2016-06-08

    Molecular distributions and stable carbon isotopic compositions (δ(13)C) of n-alkanes, fatty acids and n-alcohols were investigated in urban aerosols from Beijing, northern China to better understand the sources and long-range atmospheric transport of terrestrial organic matter during polluted and clear days in winter. n-Alkanes (C19-C36), fatty acids (C8-C32) and n-alcohols (C16-C32) detected in Beijing aerosols are characterized by the predominance of C23, C16 and C28, respectively. Carbon preference index (CPI) values of n-alkanes, the ratios of the sum of odd-numbered n-alkanes to the sum of even-numbered n-alkanes, are close to 1, indicating a heavy influence of fossil fuel combustion. Relatively higher ratios of C(18:0+16:0)/C(18:n+16:1) (fatty acids) on clear days than polluted days indicate that long-distance transport and/or photochemical aging are more significant during clear days. δ(13)C values of n-alkanes and low molecular weight fatty acids (C16:0, C18:0) ranged from -34.1 to -24.7% and -26.9 to -24.6%, respectively, which are generally heavier on polluted days than those on clear days. Such a wide range suggests that atmospheric lipids in Beijing aerosols originate from multiple sources and encounter complicated atmospheric processes during long-range transport in North China.

  6. Temporal changes in the isotope composition of Sierra spring water: Implications for recent climatic changes and carbon cycling (Invited)

    NASA Astrophysics Data System (ADS)

    Clark, J. F.; Rademacher, L. K.; Manning, A. H.; Blumhagen, E. D.

    2013-12-01

    Springs are natural windows into groundwater systems, which are good archives of signals inherited at the time of recharge, as well as those gained during subsequent groundwater flow. These signals are influenced by water rock interactions and temporal variations of external forcing often related to climatic, anthropogenic, and ecological changes. Spring water piston flow ages as determined from environmental tracers (CFCs, tritium, SF6) range between <1 yr to 50 yr and differ depending on which tracer is used. Using a 13-yr data set, Manning et al. (J Hydro., 460/61, 13-28, 2012) found that a bimodal mixing model consisting of a new (<1 yr old) fraction and a fraction that is older, but still modern (<50 yr), best explained the age data. Here, we will present spring apparent ages using the CFC piston flow model. Many parameters, including major cations, stable isotopes of water, 14C, and caddisfly species diversity correlate with CFC apparent ages. Cation concentrations, pH, and caddisfly species diversity increase while stable isotope compositions and 14C contents decrease with increasing apparent CFC ages. From waters recharging in 1960 to waters recharging in 1990, there is a 1.2‰ and 11‰ increase in δ18O and δD, respectively. Historic temperature records from surrounding areas show about a 2°C mean winter temperature increase over the same period. This temperature change alone is not great enough to explain the observed increase in δ18O. We suggest that changes in atmospheric circulation patterns or changes in snow melt processes account for the remaining offset in δ18O. Spring 14C content ranged between 85 and 110 pmc and vary with apparent age, whereby the youngest groundwater has the highest radiocarbon values. The spring 14C is set by the soil pCO2 because the aquifer contains little carbonate, and its trend can be best described assuming the soil CO2 is composed of a 50:50 mix of young (15-25 years) and old (4000 years) soil carbon reservoir

  7. Summer precipitation influences the stable oxygen and carbon isotopic composition of tree-ring cellulose in Pinus ponderosa.

    PubMed

    Roden, John S; Ehleringer, James R

    2007-04-01

    The carbon and oxygen isotopic composition of tree-ring cellulose was examined in ponderosa pine (Pinus ponderosa Dougl.) trees in the western USA to study seasonal patterns of precipitation inputs. Two sites (California and Oregon) had minimal summer rainfall inputs, whereas a third site (Arizona) received as much as 70% of its annual precipitation during the summer months (North American monsoon). For the Arizona site, both the delta(18)O and delta(13)C values of latewood cellulose increased as the fraction of annual precipitation occurring in the summer (July through September) increased. There were no trends in latewood cellulose delta(18)O with the absolute amount of summer rain at any site. The delta(13)C composition of latewood cellulose declined with increasing total water year precipitation for all sites. Years with below-average total precipitation tended to have a higher proportion of their annual water inputs during the summer months. Relative humidity was negatively correlated with latewood cellulose delta(13)C at all sites. Trees at the Arizona site produced latewood cellulose that was significantly more enriched in (18)O compared with trees at the Oregon or California site, implying a greater reliance on an (18)O-enriched water source. Thus, tree-ring records of cellulose delta(18)O and delta(13)C may provide useful proxy information about seasonal precipitation inputs and the variability and intensity of the North American monsoon.

  8. Carbon and nitrogen composition and stable isotope as potential indicators of source and fate of organic matter in the salt marsh of the Changjiang Estuary, China.

    PubMed

    Zhou, Junli; Wu, Ying; Zhang, Jing; Kang, Qinshu; Liu, Zhengtao

    2006-10-01

    Elemental (TOC, TN, C/N) and stable carbon and nitrogen isotopic (delta(13)C, delta(15)N) compositions were measured for surface sediments, three sediment vibrocores, plants, and suspended particulate matter (SPM) collected from salt marsh of the Changjiang Estuary. The purpose of this study is to characterize the sources of organic matter in sediments and to further elucidate the factors influencing the isotope signature in the salt marsh. Our results indicate that organic matter preserved in the sediments is predominantly controlled by the particulate organic matter in the Changjiang Estuary. The in situ contribution of marsh plants carbon to sediment organic matter is clearest in the high marsh, where the low delta(13)C of the plants (-28.1 per thousand) is reflected by a sediment delta(13)C (-24.7 per thousand) lower than values found for the low marsh and bare flat sediments (-23.4 per thousand and -23.0 per thousand, respectively). The effect of grain size on the spatial difference of isotope composition in the marsh sediments is insignificant, based on the observation that similar isotope values are found in different size particles, both for delta(13)C and delta(15)N. Nutrient utilization by plant assimilation, however, shows great impact on the surface sediment delta(15)N composition, due to the isotope fractionation. With extensive plant coverage and the consequent low surface water nitrate concentration, delta(15)N values of the high marsh surface sediments show (15)N enrichment.

  9. Carbon isotopes in comets

    NASA Technical Reports Server (NTRS)

    Wehinger, Peter A.

    1990-01-01

    The progress is reported of high resolution spectra of selected bright comets with the aim of determining the carbon isotope abundance ratio, C-12/C-13. The ratio was determined for various Solar System objects (in the atmospheres of the giant planets, meteorites, the Earth, and the solar photosphere), where the C-12/C-13 = 89/1. In the interstellar medium, optical and radio observations give a range of C-12/C-13 = 43-67/1 depending on the observing techniques used and the specific interstellar cloud observed. The echelle spectra is presented of the CN(0,0) violet system in three comets: P/Brorsen-Metcalf, C/Okazaki-Levy-Rudenko, and C/Austin. P/Brorsen-Metcalf has a period of 70 y (prograde) compared with P/Halley which is 76 y (retrograde). The similar periods made P/Brorsen-Metcalf of special interest for comparison with P/Halley.

  10. Carbon isotope anomalies in carbonates of the Karelian series

    NASA Astrophysics Data System (ADS)

    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.

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

    SciTech Connect

    Piper, Stephen C; Keeling, Ralph F

    2012-01-03

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

  12. Carbon, nitrogen, magnesium, silicon, and titanium isotopic compositions of single interstellar silicon carbide grains from the Murchison carbonaceous chondrite

    NASA Technical Reports Server (NTRS)

    Hoppe, Peter; Amari, Sachiko; Zinner, Ernst; Ireland, Trevor; Lewis, Roy S.

    1994-01-01

    Seven hundred and twenty SiC grains from the Murchison CM2 chondrite, ranging in size from 1 to 10 micrometers, were analyzed by ion microprobe mass spectrometry for their C-isotopic compositions. Subsets of the grains were also analyzed for N (450 grains), Si (183 grains), Mg (179 grains), and Ti (28 grains) isotopes. These results are compared with previous measurements on 41 larger SiC grains (up to 15 x 26 micrometers) from a different sample of Murchison analyzed by Virag et al. (1992) and Ireland, Zinner, & Amari (1991a). All grains of the present study are isotopically anomalous with C-12/C-13 ratios ranging from 0.022 to 28.4 x solar, N-14/N-15 ratios from 0.046 to 30 x solar, Si-29/Si-28 from 0.54 to 1.20 x solar, Si-30/Si-28 from 0.42 to 1.14 x solar, Ti-49/Ti-48 from 0.96 to 1.95 x solar, and Ti-50/Ti-48 from 0.94 to 1.39 x solar. Many grains have large Mg-26 excesses from the decay of Al-26 with inferred Al-26/Al-27 ratios ranging up to 0.61, or 12,200 x the ratio of 5 x 10(exp -5) inferred for the early solar system. Several groups can be distinguished among the SiC grains. Most of the grains have C-13 and N-14 excesses, and their Si isotopic compositions (mostly excesses in Si-29 and Si-30) plot close to a slope 1.34 line on a Delta Si-29/Si-28 versus Delta Si-30/Si-28 three-isotope plot. Grains with small C-12/C-13 ratios (less than 10) tend to have smaller or no N-14 excesses and high Al-26/Al-27 ratios (up to 0.01). Grains with C-12/C-13 greater than 150 fall into two groups: grains X have N-15 excesses and Si-29 and Si-30 deficits and the highest (0.1 to 0.6) Al-26/Al-27 ratios; grains Y have N-14 excesses and plot on a slope 0.35 line on a Si three-isotope plot. In addition, large SiC grains of the Virag et al. (1992) study fall into three-distinct clusters according to their C-, Si-, and Ti-isotopic compositions. The isotopic diversity of the grains and the clustering of their isotopic compositions imply distinct and multiple stellar sources

  13. Determination of Cr isotopic composition in low-level carbonates by MC-ICP-MS: a sensitive proxy for redox changes?

    NASA Astrophysics Data System (ADS)

    Bonnand, Pierre; Parkinson, Ian; James, Rachael; Karjalainen, Anne-Mari; Fehr, Manuela; Fairchild, Ian

    2010-05-01

    Geochemical data suggest that atmospheric oxygen increased during two major steps: the Great oxidation event (~2.4 Ga) and the Neoproterozoic (~1Ga-545Ma). The O2 concentration in the atmosphere is strongly linked to the redox condition of the oceans. Therefore the study of redox sensitive elements in marine sediments can be used to evaluate the evolution of O2 concentrations in the atmosphere. Chromium is a redox sensitive element which significantly fractionates its isotopes during the reduction of Cr(VI) to Cr(III) (Ellis et al., 2002). Thus, Cr isotopes can be used to assess redox changes in the past oceans. Chromium isotopic compositions in sedimentary rocks (BIFs) have been used to determine the evolution of the O2 concentration in the atmosphere during the Proterozoic (Frei et al., 2009). We have developed a chemical procedure for the purification of Cr in carbonates by using a single cation column to separate the Cr from the matrix, Fe, Ti and V. Cr isotopic compositions are determined used a 50Cr-54Cr double spike method and analysed on a ThermoFisher Neptune MC-ICP-MS using HR and MR in order to be able to discriminate Ar interferences. Standards and samples are analysed as 50ppb Cr solutions and yield an external reproducibility 50 and 70ppm. This new method allowed us to analyse samples with a Cr concentrations as low as 1ppm. We have analysed a suite of Neoproterozoic carbonates from Australia, but also modern ooids and oolithic limestones through the Phanerozoic. The Cr isotopic data for carbonates record a range of δ53Cr between -0.1 and +1.7. This range indicates that some of these carbonates clearly reflect oxidising conditions in the ocean. By comparison, the Neoproterozoic samples have Cr isotopic compositions close to the continental crust value (-0.1 to 0.1), indicating the Neoproterozoic samples reflect deposition under more reducing conditions These data suggests that the redox condition during the deposition of shallow-water carbonates

  14. Stable carbon isotopic compositions of intact polar lipids reveal complex carbon flow patterns among hydrocarbon degrading microbial communities at the Chapopote asphalt volcano

    NASA Astrophysics Data System (ADS)

    Schubotz, Florence; Lipp, Julius S.; Elvert, Marcus; Hinrichs, Kai-Uwe

    2011-08-01

    Seepage of asphalt forms the basis of a cold seep system at 3000 m water depth at the Chapopote Knoll in the southern Gulf of Mexico. Anaerobic microbial communities are stimulated in the oil-impregnated sediments as evidenced by the presence of intact polar membrane lipids (IPLs) derived from archaea and Bacteria at depths up to 7 m below the seafloor. Detailed investigation of stable carbon isotope composition (δ 13C) of alkyl and acyl moieties derived from a range of IPL precursors with distinct polar head groups resolved the complexity of carbon metabolisms and utilization of diverse carbon sources by uncultured microbial communities. In surface sediments most of the polar lipid-derived fatty acids with phosphatidylethanolamine (PE), phosphatidylglycerol (PG) and diphosphatidylglycerol (DPG) head groups could be tentatively assigned to autotrophic sulfate-reducing bacteria, with a relatively small proportion involved in the anaerobic oxidation of methane. Derivatives of phosphatidyl-( N)-methylethanolamine (PME) were abundant and could be predominantly assigned to heterotrophic oil-degrading bacteria. Archaeal IPLs with phosphate-based hydroxyarchaeols and diglycosidic glyceroldibiphytanylglyceroltetraethers (GDGTs) were assigned to methanotrophic archaea of the ANME-2 and ANME-1 cluster, respectively, whereas δ 13C values of phosphate-based archaeols and mixed phosphate-based and diglycosidic GDGTs point to methanogenic archaea. At a 7 m deep sulfate-methane transition zone that is linked to the upward movement of gas-laden petroleum, a distinct increase in abundance of archaeal IPLs such as phosphate-based hydroxyarchaeols and diglycosidic archaeol and GDGTs is observed; their δ 13C values are consistent with their origin from both methanotrophic and methanogenic archaea. This study reveals previously hidden, highly complex patterns in the carbon-flow of versatile microbial communities involved in the degradation of heavy oil including hydrocarbon gases

  15. Molecular isotopic engineering (MIE): industrial manufacture of naproxen of predetermined stable carbon-isotopic compositions for authenticity and security protection and intellectual property considerations

    NASA Astrophysics Data System (ADS)

    Jasper, J. P.; Farina, P.; Pearson, A.; Mezes, P. S.; Sabatelli, A. D.

    2016-05-01

    Molecular Isotopic Engineering (MIE) is the directed stable-isotopic synthesis of chemical products for reasons of product identification and of product security, and also for intellectual property considerations. We report here a generally excellent correspondence between the observed and predicted stable carbon-isotopic (δ13C) results for a successful directed synthesis of racemic mixture from its immediate precursors. The observed results are readily explained by the laws of mass balance and isotope mass balance. Oxygen- and hydrogen isotopic results which require an additional assessment of the effects of O and H exchange, presumably due to interaction with water in the reaction solution, are addressed elsewhere. A previous, cooperative study with the US FDA-DPA showed that individual manufacturers of naproxen could readily be differentiated by their stable-isotopic provenance (δ13C, δ18O, and δD ref. 1). We suggest that MIE can be readily employed in the bio/pharmaceutical industry without alteration of present manufacturing processes other than isotopically selecting and/or monitoring reactants and products.

  16. Isotopic Composition of Carbonates in Antarctic Ordinary Chondrites and Miller Range Nakhlites: Insights into Martian Amazonian Aqueous Alteration

    NASA Technical Reports Server (NTRS)

    Evans, M. E.; Niles, P. B.; Chapman, P.

    2017-01-01

    The martian surface contains features of ancient fluvial systems. Stable isotope analysis of carbonates that form in aqueous systems can reveal their formation conditions. The Nakhlite meteorites originally formed on Mars 1.3 Ga and were later exposed to aqueous fluids that left behind carbonate minerals [1], thus analysis of these carbonates can provide data to understand Amazonian climate conditions on Mars. Carbonates found in the Nakhlite meteorites contain a range of delta(sup 13)C values, which may be either martian carbonates or terrestrial contamination. To better under-stand terrestrial weathering products and martian carbonate formation processes, we conducted a set of carbonate isotope analyses on Antarctic meteorites focusing on Miller Range (MIL) Nakhlites as well as Ordinary Chondrites (OCs) (Figure 1)[1-11] [12]. OCs of petrology type H, L, and LL 3-6 were selected since they are not expected to contain preterrestrial carbonates, yet they have visible evaporite minerals on the fusion crust indicating terrestrial alteration. These cryogenically formed terrestrial carbonates may also provide an analog for cryogenic carbonate formation on Mars.

  17. Evolution of stable carbon-isotope compositions for methane and carbon dioxide in freshwater wetlands and other anaerobic environments

    NASA Astrophysics Data System (ADS)

    Hornibrook, Edward R. C.; Longstaffe, Frederick J.; Fyfe, William S.

    2000-03-01

    Two types of distribution for α C values are observed in anaerobic environments when δ 13C-ΣCO 2 and δ 13C-CH 4 values are measured across gradients of depth or age of organic debris. The type-I distribution involves a systematic increase in α C values with depth as a result of decreasing δ 13C-CH 4 and increasing δ 13C-ΣCO 2 values. This behavior corresponds to a progressive increase in the prevalence of methanogenesis by the CO 2 reduction pathway relative to acetate fermentation. Utilization of autotrophically formed acetate by methanogens would also cause an increase in α C values. The type-II distribution occurs when both δ 13C-CH 4 and δ 13C-ΣCO 2 values decrease with depth, resulting in approximately constant α C values. This condition corresponds with a strong dependence of methanogens on porewater ΣCO 2 as a carbon source by way of either the CO 2 reduction pathway or utilization of autotrophically formed acetate. Freshwater wetlands possess both types of α C value distribution. Wetlands with type-I distributions exhibit curves with slopes that vary probably as a function of deposition and preservation of labile organic carbon. An abundance of labile substrates in anaerobic soils yields steeper curves because aceticlastic methanogenesis predominates and δ 13C-CH 4 and δ 13C-CO 2 values are high. Diminished transfer of labile carbon to the methanogenic zone results in an increased prevalence of the CO 2 reduction pathway, yielding low δ 13C-CH 4 values and shallowly sloping curves. Aerobic oxidation of organic matter or decay involving sulfate reduction produces CO 2 with low δ 13C values, which also will contribute to shallowly sloping curves. The size of the dissolved CO 2 pool can influence the sensitivity of δ 13C-CO 2 values to change during methanogenesis. Regression curves of δ 13C-CH 4 and δ 13C-ΣCO 2 values from four wetlands with type-I distributions intersect at δ 13C-CH 4 = -40.7 ± 6.1‰ (1σ) and δ 13C-ΣCO 2 = -23

  18. Carbon isotopic exchange between dissolved inorganic and organic carbon

    NASA Astrophysics Data System (ADS)

    Thomas, B.; Freeman, K. H.; House, C. H.; Arthur, M. A.

    2009-12-01

    The pools of inorganic and organic carbon are often considered to be separate and distinct. Isotopic exchange between the inorganic and organic carbon pools in natural waters is rarely considered plausible at low temperatures owing to kinetic barriers to exchange. In certain circumstances, however carboxyl carbon of dissolved organic matter (DOM) may be subject to exchange with the dissolved inorganic carbon (DIC) pool. We report results from an isotopic labeling experiment that resulted in rapid methanogen-catalyzed isotopic exchange between DIC and the carboxyl carbon of acetate. This exchange rapidly mixes the isotopic composition of the DIC pool into the dissolved organic carbon (DOC) acetate pool. This exchange is likely associated with the reversible nature of the carbon monoxide dehydrogenase enzyme. In nature, many decarboxylase enzymes are also reversible and some can be shown to facilitate similar exchange reactions. Those decarboxylase enzymes that are important in lignin decomposition and other organic carbon (OC) transformations may help to mask the isotopic composition of the precursor DOC with as much as 15% contribution from DIC. Though this dilution is unlikely to matter in soils where DOC and DIC are similar in composition, this exchange may be extremely important in systems where the stable or radioisotope composition of DOC and DIC differ significantly. As an example of the importance of this effect, we demonstrate that the stable and radiocarbon isotopic composition of fluvial DOC could be altered by mixing with marine DIC to produce a DOC composition similar to those observed in the deep marine DOC pool. We hypothesize that this exchange resolves the conundrum of apparently old (>5 kyr) marine-derived DOC. If most of the carboxyl carbon of pre-aged, terrestrial-derived DOC (15% of total carbon) is subject to exchange with marine DIC, the resulting carbon isotopic composition of deep DOC will be similar to that observed in deep marine studies

  19. Multiple sulfur and carbon isotope composition of the Mesoarchean Manjeri and Cheshire Formations (Belingwe Greenstone Belt, Zimbabwe): a window on the sulfur and carbon Mesoarchean biogeochemistry

    NASA Astrophysics Data System (ADS)

    Thomazo, C.; Strauss, H.; Grassineau, N.; Nisbet, E. G.

    2010-12-01

    In order to bring further insights into the biogeochemical conditions prevailing during the dampendown Mesoarchean Mass Independant Fractionation of Sulfur (MIF-S) attributed to changes in atmospheric and/or oceanic geochemistry, we report the results of a detailed carbon (12C, 13C) and multiple sulfur (32S, 33S, 34S) isotopic study through the ~2.7 Ga Manjeri and ~2.65 Ga Cheshire Formations (Belingwe Greenstone Belt, Zimbabwe). The studied rocks consist of low-grade metamorphic (sub-greenschist facies) black shales, laminated limestones, and stromatolites. In the Manjeri Fm. the stromatolites are a minor part of the succession, which mostly show organic rich black shales associated with sulfide-rich layers. In contrast, the Cheshire Fm. shows well preserved stromatolites and black shales. Organic δ13C values of the Manjeri Formation show a wide range of δ13Corg between -16.2 and -35.4‰ (average of -30.3 ± 6.0‰), while the Cheshire formation show a narrow range of isotopic composition of -41.3 ± 3.5‰. TOC (wt. %) vary from 0.06 to 3.31 (average of 1.28) and from 0.02 to 1.05 (average of 0.18) for the Manjeri and Cheshire Fm., respectively. The remarkable difference of carbon isotope signatures between these two formations argue for the occurrence of different biomass likely reflecting different metabolic pathways, including photosynthesis, methanogenesis and methanotrophy. The Manjeri Fm. δ34S values of sedimentary sulfides (Acid Volatile Sulfur and Chromium Reducible Sulfur) vary between -15.15 and 2.37‰ (average -1.71 ± 4.76‰) and show very small and mostly negative MIF-S varying from -0.58 to 0.87‰ (average 0.02 ± 0.43‰). The Cheshire Fm. is isotopically distinct with δ34S values ranging from -2.11 to 2.39‰ (average 0.25 ± 1.08‰) and show near zero but consistently positive Δ33S anomalies between 0.14 and 1.17 ‰ (average 0.56 ± 0.29‰). Sulfides S contents (wt. %) vary from 0.06 to 3.31 (average of 1.28) and from 0.02 to 1

  20. Interannual, seasonal, and diel variability in the carbon isotope composition of respiration in a C3/C4 agricultural ecosystem

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The stable carbon isotope ratio 13CO2/12CO2 is a valuable tool for understanding the processes controlling the autotrophic (FRa) and heterotrophic (FRh) contributions to ecosystem respiration (FR) as well as influences of photosynthesis on respiration. There is increasing interest in the temporal va...

  1. Partitioning of atmospheric carbon dioxide over Central Europe: insights from combined measurements of CO2 mixing ratios and their carbon isotope composition.

    PubMed

    Zimnoch, Miroslaw; Jelen, Dorota; Galkowski, Michal; Kuc, Tadeusz; Necki, Jaroslaw; Chmura, Lukasz; Gorczyca, Zbigniew; Jasek, Alina; Rozanski, Kazimierz

    2012-09-01

    Regular measurements of atmospheric CO (2) mixing ratios and their carbon isotope composition ((13)C/(12)C and (14)C/(12)C ratios) performed between 2005 and 2009 at two sites of contrasting characteristics (Krakow and the remote mountain site Kasprowy Wierch) located in southern Poland were used to derive fossil fuel-related and biogenic contributions to the total CO (2) load measured at both sites. Carbon dioxide present in the atmosphere, not coming from fossil fuel and biogenic sources, was considered 'background' CO (2). In Krakow, the average contribution of fossil fuel CO (2) was approximately 3.4%. The biogenic component was of the same magnitude. Both components revealed a distinct seasonality, with the fossil fuel component reaching maximum values during winter months and the biogenic component shifted in phase by approximately 6 months. The partitioning of the local CO (2) budget for the Kasprowy Wierch site revealed large differences in the derived components: the fossil fuel component was approximately five times lower than that derived for Krakow, whereas the biogenic component was negative in summer, pointing to the importance of photosynthetic sink associated with extensive forests in the neighbourhood of the station. While the presented study has demonstrated the strength of combined measurements of CO (2) mixing ratios and their carbon isotope signature as efficient tools for elucidating the partitioning of local atmospheric CO (2) loads, it also showed the important role of the land cover and the presence of the soil in the footprint of the measurement location, which control the net biogenic surface CO (2) fluxes.

  2. The stable carbon isotope composition of PM 2.5 and PM 10 in Mexico City Metropolitan Area air

    NASA Astrophysics Data System (ADS)

    López-Veneroni, D.

    The sources and distribution of carbon in ambient suspended particles (PM 2.5 and PM 10) of Mexico City Metropolitan Area (MCMA) air were traced using stable carbon isotopes ( 13C/ 12C). Tested potential sources included rural and agricultural soils, gasoline and diesel, liquefied-petroleum gas, volcanic ash, and street dust. The complete combustion of LP gas, diesel and gasoline yielded the lightest δ13C values (-27 to -29‰ vs. PDB), while street dust (PM 10) represented the isotopically heaviest endmember (-17‰). The δ13C values of rural soils from four geographically separated sites were similar (-20.7 ± 1.5‰). δ13C values of particles and soot from diesel and gasoline vehicle emissions and agricultural soils varied between -23 and -26‰. Ambient PM samples collected in November of 2000, and March and December of 2001 at three representative receptor sites of industrial, commercial and residential activities had a δ13C value centered around -25.1‰ in both fractions, resulting from common carbon sources. The predominant carbon sources to MCMA atmospheric particles were hydrocarbon combustion (diesel and/or gasoline) and particles of geological origin. The significantly depleted δ13C values from the industrial site reflect the input of diesel combustion by mobile and point source emissions. Based on stable carbon isotope mass balance, the carbon contribution of geological sources at the commercial and residential sites was approximately 73% for the PM 10 fraction and 54% for PM 2.5. Although not measured in this study, biomass-burning emissions from nearby forests are an important carbon source characterized by isotopically lighter values (-29‰), and can become a significant contributor (67%) of particulate carbon to MCMA air under the prevalence of southwesterly winds. Alternative sources of these 13C-depleted particles, such as cooking fires and municipal waste incineration, need to be assessed. Results show that stable carbon isotope

  3. Measurement and interpretation of the oxygen isotope composition of carbon dioxide respired by leaves in the dark.

    PubMed

    Cernusak, Lucas A; Farquhar, Graham D; Wong, S Chin; Stuart-Williams, Hilary

    2004-10-01

    We measured the oxygen isotope composition (delta(18)O) of CO(2) respired by Ricinus communis leaves in the dark. Experiments were conducted at low CO(2) partial pressure and at normal atmospheric CO(2) partial pressure. Across both experiments, the delta(18)O of dark-respired CO(2) (delta(R)) ranged from 44 per thousand to 324 per thousand (Vienna Standard Mean Ocean Water scale). This seemingly implausible range of values reflects the large flux of CO(2) that diffuses into leaves, equilibrates with leaf water via the catalytic activity of carbonic anhydrase, then diffuses out of the leaf, leaving the net CO(2) efflux rate unaltered. The impact of this process on delta(R) is modulated by the delta(18)O difference between CO(2) inside the leaf and in the air, and by variation in the CO(2) partial pressure inside the leaf relative to that in the air. We developed theoretical equations to calculate delta(18)O of CO(2) in leaf chloroplasts (delta(c)), the assumed location of carbonic anhydrase activity, during dark respiration. Their application led to sensible estimates of delta(c), suggesting that the theory adequately accounted for the labeling of CO(2) by leaf water in excess of that expected from the net CO(2) efflux. The delta(c) values were strongly correlated with delta(18)O of water at the evaporative sites within leaves. We estimated that approximately 80% of CO(2) in chloroplasts had completely exchanged oxygen atoms with chloroplast water during dark respiration, whereas approximately 100% had exchanged during photosynthesis. Incorporation of the delta(18)O of leaf dark respiration into ecosystem and global scale models of C(18)OO dynamics could affect model outputs and their interpretation.

  4. Molecular distributions and compound-specific stable carbon isotopic compositions of lipids in wintertime aerosols from Beijing

    PubMed Central

    Ren, Lujie; Fu, Pingqing; He, Yue; Hou, Juzhi; Chen, Jing; Pavuluri, Chandra Mouli; Sun, Yele; Wang, Zifa

    2016-01-01

    Molecular distributions and stable carbon isotopic compositions (δ13C) of n-alkanes, fatty acids and n-alcohols were investigated in urban aerosols from Beijing, northern China to better understand the sources and long-range atmospheric transport of terrestrial organic matter during polluted and clear days in winter. n-Alkanes (C19–C36), fatty acids (C8–C32) and n-alcohols (C16–C32) detected in Beijing aerosols are characterized by the predominance of C23, C16 and C28, respectively. Carbon preference index (CPI) values of n-alkanes, the ratios of the sum of odd-numbered n-alkanes to the sum of even-numbered n-alkanes, are close to 1, indicating a heavy influence of fossil fuel combustion. Relatively higher ratios of C(18:0+16:0)/C(18:n+16:1) (fatty acids) on clear days than polluted days indicate that long-distance transport and/or photochemical aging are more significant during clear days. δ13C values of n-alkanes and low molecular weight fatty acids (C16:0, C18:0) ranged from –34.1 to −24.7% and −26.9 to −24.6%, respectively, which are generally heavier on polluted days than those on clear days. Such a wide range suggests that atmospheric lipids in Beijing aerosols originate from multiple sources and encounter complicated atmospheric processes during long-range transport in North China. PMID:27270951

  5. Sources and accumulation of organic carbon in the Pearl River Estuary surface sediment as indicated by elemental, stable carbon isotopic, and carbohydrate compositions

    NASA Astrophysics Data System (ADS)

    He, B.; Dai, M.; Huang, W.; Liu, Q.; Chen, H.; Xu, L.

    2010-04-01

    Organic matter in surface sediments from the upper reach of the Pearl River Estuary and Lingdingyang Bay, as well as the adjacent northern South China Sea shelf was characterized by a variety of techniques, including elemental (C and N), stable carbon isotopic (δ 13C) composition, as well as molecular-level analyses. Total organic carbon (TOC) content was 1.61±1.20% in the upper reach down to 1.00±0.22% in Lingdingyang Bay and to 0.80±0.10% on the inner shelf and 0.58±0.06% on the outer shelf. δ13C values ranged from -25.11‰ to -21.28‰ across the studied area, with a trend of enrichment seaward. The spatial trend in C/N ratios mirrored that of δ13C, with a substantial decrease in C/N ratio from 10.9±1.3 in the Lingdingyang Bay surface sediments to 6.5±0.09 in the outer shelf surface sediments. Total carbohydrate yields ranged from 22.1 to 26.7 mg (100 mg OC)-1, and typically followed TOC concentrations in the estuarine and shelf sediments, suggesting that the relative abundance of total carbohydrate was fairly constant in TOC. Total neutral sugars as detected by the nine major monosaccharides (lyxose, rhamnose, ribose, arabinose, fucose, xylose, galactose, mannose, and glucose) yielded between 4.0 and 18.6 mg (100 mg OC)-1 in the same sediments, suggesting that a significant amount of carbohydrates were not neutral aldoses. The bulk organic matter properties, isotopic composition and C/N ratios, combined with molecular-level carbohydrate compositions were used to assess the sources and accumulation of terrestrial organic matter in the Pearl River Estuary and the adjacent northern South China Sea shelf. Results showed a mixture of terrestrial riverine organic carbon with in situ phytoplankton organic carbon in the areas studied. Using a two end-member mixing model based on δ13C values and C/N ratios, we estimated that the terrestrial organic carbon contribution to the surface sediment TOC was ca. 57±13% for Lingdingyang Bay, 19±2% for the inner shelf

  6. Understanding the historical trend in atmospheric methane using its carbon isotopic composition 1978 to 1998

    NASA Astrophysics Data System (ADS)

    Teama, D. G.; Rice, A. L.

    2010-12-01

    Methane (CH4) is one of the most important greenhouse gases with a global warming potential of 25 based on a 100 year time horizon. Its concentration has more than doubled since dawn of the industrial era, primarily due to anthropogenic practices such as fossil fuel production, rice cultivation, biomass burning and waste management. The rate of increase, however, is not constant and fluctuates on short and long timescales due to the dynamical interaction of CH4 sources and sinks. One powerful tool to identify changes in sources and sinks of atmospheric CH4 is the use of stable isotopes. By comparing trends in the 13C/12C (δ13C) and D/H (δD) content of atmospheric CH4 in time series to the isotopic signatures of sources, we can potentially disentangle trends in methane sources and sinks. In this work we focus on the period 1978-1998, a period that experienced a dramatic slow-down in the growth rate of atmospheric CH4. We present measurements of δ13C of CH4 from a unique archive of nearly 200 air samples collected at Cape Meares, Oregon (45.5oN, 124oW). The measurements indicate enrichment in δ13C of 0.017 (±.003) ‰ yr-1 over the whole time period. Deeper analysis, however, show that δ13C enrichment from 1978 through the end of 1988 has smaller rate of change (0.01 ‰ yr-1) than from 1988 to 1998 (0.02 ‰ yr-1). As it is integral to our work, sample stability of the archive is also investigated by comparing modern measurements of CH4 mixing ratio to the original determinations of archive samples. Finally, we discuss implications for CH4 sources over this time period and compare our results to findings in prior work.

  7. Stable carbon and nitrogen isotope composition of aquatic and terrestrial plants of the San Francisco Bay estuarine system

    USGS Publications Warehouse

    Cloern, J.E.; Canuel, E.A.; Harris, D.

    2002-01-01

    We report measurements of seasonal variability in the C-N stable isotope ratios of plants collected across the habitat mosaic of San Francisco Bay, its marshes, and its tributary river system. Analyses of 868 plant samples were binned into 10 groups (e.g., terrestrial riparian, freshwater phytoplankton, salt marsh) to determine whether C-N isotopes can be used as biomarkers for tracing the origins of organic matter in this river-marsh-estuary complex. Variability of ??13C and ??15N was high (???5-10???) within each plant group, and we identified three modes of variability: (1) between species and their microhabitats, (2) over annual cycles of plant growth and senescence, and (3) between living and decomposing biomass. These modes of within-group variability obscure any source-specific isotopic signatures, confounding the application of C-N isotopes for identifying the origins of organic matter. A second confounding factor was large dissimilarity between the ??13C-??15N of primary producers and the organic-matter pools in the seston and sediments. Both confounding factors impede the application of C-N isotopes to reveal the food supply to primary consumers in ecosystems supporting diverse autotrophs and where the isotopic composition of organic matter has been transformed and become distinct from that of its parent plant sources. Our results support the advice of others: variability of C-N stable isotopes within all organic-matter pools is high and must be considered in applications of these isotopes to trace trophic linkages from primary producers to primary consumers. Isotope-based approaches are perhaps most powerful when used to complement other tools, such as molecular biomarkers, bioassays, direct measures of production, and compilations of organic-matter budgets.

  8. Stable carbon isotopic composition of tree rings from a pine tree from Augustów Wilderness, Poland, as a temperature and local environment conditions indicator.

    PubMed

    Pawelczyk, Slawomira; Pazdur, Anna; Halas, Stanislaw

    2004-06-01

    Tree rings can be used as archives of climatic and environmental data with annual resolution. Tree rings widths, maximum late wood density and other parameters as stable composition in tree rings can be used for the reconstruction of past climatic and environmental changes. Stable carbon isotope ratios in tree rings may provide valuable information on past climatic conditions. 13C/12C ratios of plant organic matter can reflect corresponding 13C/12C ratio of atmospheric CO2 during formation of the rings. Investigations of isotopic carbon composition in tree rings from in the ecologically clean the Augustów Wilderness region in the north-eastern part of Poland (22 degrees 58'E, 53 degrees 51'N) (nowadays a sanctuary) were undertaken. Series of delta13C in alpha-cellulose and in wholewood were acquired. Those measurements constituted a part of more complex investigations of carbon isotope composition in tree rings including the measurements of radiocarbon concentration and tree ring widths. This article presents preliminary results. It is argued that contrary to the tree ring widths and delta13C in wholewood that do not reveal significant correlation with temperature, the variation of delta13C in the latewood alpha-cellulose is correlated with combined July and August temperatures.

  9. Mineralogy, Petrography, and Oxygen-Isotope Compositions of Carbonates and Olivines in Sutter"s Mill, CM Chondrite Breccia

    NASA Astrophysics Data System (ADS)

    Nagashima, K.; Yin, Q.-Z.; Krot, A. N.; Ogliore, R. C.

    2012-09-01

    Sutter's Mill sample we studied has two CM-like lithologies, CM2.0 and CM2.1. O-isotope compositions of chondrule and AOA olivines plot along CCAM line. Dolomites and calcites plot below TF line. Calcites show a spread in δ18O values, +13 to +39‰.

  10. Sources and accumulation of organic carbon in the Pearl River Estuary surface sediment as indicated by elemental, stable carbon isotopic, and carbohydrate compositions

    NASA Astrophysics Data System (ADS)

    He, B.; Dai, M.; Huang, W.; Liu, Q.; Chen, H.; Xu, L.

    2010-10-01

    Organic matter in surface sediments from the upper reach of the Pearl River Estuary and Lingdingyang Bay, as well as the adjacent northern South China Sea shelf was characterized using a variety of techniques, including elemental (C and N) ratio, bulk stable organic carbon isotopic composition (δ13C), and carbohydrate composition analyses. Total organic carbon (TOC) content was 1.21±0.45% in the upper reach, down to 1.00±0.22% in Lingdingyang Bay and to 0.80±0.10% on the inner shelf and 0.58±0.06% on the outer shelf. δ13C values ranged from -25.1‰ to -21.3‰ in Lingdingyang Bay and the South China Sea shelf, with a trend of enrichment seawards. The spatial trend in C/N ratios mirrored that of δ13C, with a substantial decrease in C/N ratio offshore. Total carbohydrate yields ranged from 22.1 to 26.7 mg (100 mg OC)-1, and typically followed TOC concentrations in the estuarine and shelf sediments. Total neutral sugars, as detected by the nine major monosaccharides (lyxose, rhamnose, ribose, arabinose, fucose, xylose, galactose, mannose, and glucose), were between 4.0 and 18.6 mg (100 mg OC)-1 in the same sediments, suggesting that significant amounts of carbohydrates were not neutral aldoses. Using a two end-member mixing model based on δ13C values and C/N ratios, we estimated that the terrestrial organic carbon contribution to the surface sediment TOC was ca. 78±11% for Lingdingyang Bay, 34±4% for the inner shelf, and 5.5±1% for the outer shelf. The molecular composition of the carbohydrate in the surface sediments also suggested that the inner estuary was rich in terrestrially derived carbohydrates but that their contribution decreased offshore. A relatively high abundance of deoxyhexoses in the estuary and shelf indicated a considerable bacterial source of these carbohydrates, implying that sediment organic matter had undergone extensive degradation and/or transformation during transport. Sediment budget based on calculated regional accumulation rates

  11. Infiltrated carbon foam composites

    NASA Technical Reports Server (NTRS)

    Lucas, Rick D. (Inventor); Danford, Harry E. (Inventor); Plucinski, Janusz W. (Inventor); Merriman, Douglas J. (Inventor); Blacker, Jesse M. (Inventor)

    2012-01-01

    An infiltrated carbon foam composite and method for making the composite is described. The infiltrated carbon foam composite may include a carbonized carbon aerogel in cells of a carbon foam body and a resin is infiltrated into the carbon foam body filling the cells of the carbon foam body and spaces around the carbonized carbon aerogel. The infiltrated carbon foam composites may be useful for mid-density ablative thermal protection systems.

  12. Carbonate clumped isotope thermometry in continental tectonics

    NASA Astrophysics Data System (ADS)

    Huntington, Katharine W.; Lechler, Alex R.

    2015-04-01

    Reconstructing the thermal history of minerals and fluids in continental environments is a cornerstone of tectonics research. Paleotemperature constraints from carbonate clumped isotope thermometry have provided important tests of geodynamic, structural, topographic and basin evolution models. The thermometer is based on the 13C-18O bond ordering in carbonates (mass-47 anomaly, Δ47) and provides estimates of the carbonate formation temperature independent of the δ18O value of the water from which the carbonate grew; Δ47 is measured simultaneously with conventional measurements of carbonate δ13C and δ18O values, which together constrain the isotopic composition of the parent water. Depending on the geologic setting of carbonate growth, this information can help constrain paleoenvironmental conditions or basin temperatures and fluid sources. This review examines how clumped isotope thermometry can shed new light on problems in continental tectonics, focusing on paleoaltimetry, basin evolution and structural diagenesis applications. Paleoaltimetry is inherently difficult, and the precision in carbonate growth temperature estimates is at the limit of what is useful for quantitative paleoelevation reconstruction. Nevertheless, clumped isotope analyses have enabled workers to address previously intractable problems and in many settings offer the best chance of understanding topographic change from the geologic record. The portion of the shallow crust residing at temperatures up to ca. 200 °C is important as host to economic resources and records of tectonics and climate, and clumped isotope thermometry is one of the few proxies that can access this critical range with sensitivity to temperature alone. Only a handful of studies to date have used clumped isotopes to investigate diagenesis and other sub-surface processes using carbonate crystallization temperatures or the sensitivity of Δ47 values to a sample's thermal history. However, the thermometer is

  13. Stable carbon isotopic compositions of total carbon, dicarboxylic acids and glyoxylic acid in the tropical Indian aerosols: Implications for sources and photochemical processing of organic aerosols

    NASA Astrophysics Data System (ADS)

    Pavuluri, Chandra Mouli; Kawamura, Kimitaka; Swaminathan, T.; Tachibana, Eri

    2011-09-01

    The tropical Indian aerosols (PM10) collected on day- and nighttime bases in winter and summer, 2007 from Chennai (13.04°N; 80.17°E) were studied for stable carbon isotopic compositions (δ13C) of total carbon (TC), individual dicarboxylic acids (C2-C9) and glyoxylic acid (ωC2). δ13C values of TC ranged from -23.9‰ to -25.9‰ (-25.0 ± 0.6‰; n = 49). Oxalic (C2) (-17.1 ± 2.5‰), malonic (C3) (-20.8 ± 1.8‰), succinic (C4) (-22.5 ± 1.5‰) and adipic (C6) (-20.6 ± 4.1‰) acids and ωC2 acid (-22.4 ± 5.5‰) were found to be more enriched with 13C compared to TC. In contrast, suberic (C8) (-29.4 ± 1.8‰), phthalic (Ph) (-30.1 ± 3.5‰) and azelaic (C9) (-28.4 ± 5.8‰) acids showed smaller δ13C values than TC. Based on comparisons of δ13C values of TC in Chennai aerosols to those (-24.7 ± 2.2‰) found in unburned cow-dung samples collected from Chennai and isotopic signatures of the particles emitted from point sources, we found that biofuel/biomass burning are the major sources of carbonaceous aerosols in South and Southeast Asia. The decrease in δ13C values of C9 diacid by about 5‰ from winter to summer suggests that tropical plant emissions also significantly contribute to organic aerosol in this region. Significant increase in δ13C values from C4 to C2 diacids in Chennai aerosols could be attributed for their photochemical processing in the tropical atmosphere during long-range transport from source regions.

  14. Preservation and detection of microstructural and taxonomic correlations in the carbon isotopic compositions of individual Precambrian microfossils

    NASA Astrophysics Data System (ADS)

    Williford, Kenneth H.; Ushikubo, Takayuki; Schopf, J. William; Lepot, Kevin; Kitajima, Kouki; Valley, John W.

    2013-03-01

    Here we present techniques for, and new data from, in situ carbon isotope (δ13C) analysis of Precambrian permineralized microscopic fossils with a reproducibility of 1-2‰ using secondary ion mass spectrometry (SIMS). Individual microfossils, selected for their excellent preservation, were analyzed in petrographic thin sections of stromatolitic cherts from the Proterozoic Gunflint (˜1880 Ma), Bitter Springs (˜830 Ma), Min'yar (˜740 Ma), and Chichkan (˜775 Ma) Formations. The range of δ13C values (-34.6‰ to -22.1‰ VPDB) among the 46 individuals analyzed falls within that expected for photoautotrophic carbon fixation by ribulose bisphosphate carboxylase (RuBisCO), consistent with morphology-based taxonomic assignments for these specimens. Microfossils classified as cyanobacteria from the Gunflint, Bitter Springs, and Min'yar Formations (for which published carbonate carbon isotope data can be used to estimate the δ13C of the original dissolved inorganic carbon substrate) exhibit a consistent ˜19‰ total fractionation (δ13C of dissolved inorganic carbon - δ13C of biomass) similar to that observed in living cyanobacteria, over a wide range of δ13Ccarb values (-2.9‰ to 3.4‰). In stromatolitic chert of the Min'yar Formation, morphologically diverse microfossils preserved in a ˜1 mm2 part of a microbial mat exhibit systematic isotopic differences among and within taxa that correlate with their morphologically inferred biological affinities and suggest that isotopic signatures of their original biosynthetic processes (e.g., lipid and peptidoglycan synthesis) are preserved. Isotopic offsets consistent with the different RuBisCO-based fractionations typical of cyanobacteria and photosynthetic eukaryotes are documented by the differing δ13C values of a colonial cyanobacterium (-22.6 ± 0.5‰) and a phytoplanktonic protistan acritarch (-28.9 ± 1.0‰) situated <1 cm apart in the stromatolitic Chichkan chert. These findings show for the first time the

  15. Clumped isotope thermometry of cryogenic cave carbonates

    NASA Astrophysics Data System (ADS)

    Kluge, Tobias; Affek, Hagit P.; Zhang, Yi Ge; Dublyansky, Yuri; Spötl, Christoph; Immenhauser, Adrian; Richter, Detlev K.

    2014-02-01

    ) leads to an enrichment in 13C and 18O in DIC and depletion in Δ47. Oxygen isotope exchange between DIC and water drives δ18O and Δ47 back towards equilibrium (Mühlinghaus et al., 2009; Affek, 2013). The progressive precipitation of carbonate minerals further leads to δ13C and δ18O values higher than at equilibrium (Scholz et al., 2009; Dreybrodt and Scholz, 2011).The influence of carbonate precipitation conditions on the isotopic ratios of CCCcoarse is not well known. The isotope exchange reaction between water and DIC at the freezing point is much slower (τex ˜ 126,000 s) than chemical reactions and the process of carbonate mineral precipitation (τp ˜ 2000 s; Dreybrodt and Scholz, 2011). Thus, isotopic values reflecting disequilibrium induced by CO2 escape from the pool water take a long time to return to isotopic equilibrium (3 * τex ˜ 4.4 d) and are therefore expected to be recorded in the carbonate minerals.The aims of this study is to test the applicability of the clumped isotope thermometry (Ghosh et al., 2006; Eiler, 2007, 2011) to CCCcoarse precipitated in ice-covered pools. Furthermore, the known CCCcoarse formation temperature (˜0 °C) can be used together with clumped isotope analyses to assess potential disequilibrium effects in order to improve our understanding of the mode of CCCcoarse formation. This is essential in order to extract the potential information of the CCCcoarse stable isotopic composition, e.g., for calculation of the water δ18O value during carbonate formation.

  16. Magnesium isotopic composition of achondrites

    NASA Astrophysics Data System (ADS)

    Sedaghatpour, Fatemeh; Teng, Fang-Zhen

    2016-02-01

    Magnesium isotopic compositions of 22 well-characterized differentiated meteorites including 7 types of achondrites and pallasite meteorites were measured to estimate the average Mg isotopic composition of their parent bodies and evaluate Mg isotopic heterogeneity of the solar system. The δ26Mg values are -0.236‰ and -0.190‰ for acapulcoite-lodranite and angrite meteorites, respectively and vary from -0.267‰ to -0.222‰ in the winonaite-IAB-iron silicate group, -0.369‰ to -0.292‰ in aubrites, -0.269‰ to -0.158‰ in HEDs, -0.299‰ to -0.209‰ in ureilites, -0.307‰ to -0.237‰ in mesosiderites, and -0.303‰ to -0.238‰ in pallasites. Magnesium isotopic compositions of most achondrites and pallasite meteorites analyzed here are similar and reveal no significant isotopic fractionation. However, Mg isotopic compositions of D‧Orbigny (angrite) and some HEDs are slightly heavier than chondrites and the other achondrites studied here. The slightly heavier Mg isotopic compositions of angrites and some HEDs most likely resulted from either impact-induced evaporation or higher abundance of clinopyroxene with the Mg isotopic composition slightly heavier than olivine and orthopyroxene. The average Mg isotopic composition of achondrites (δ26Mg = -0.246 ± 0.082‰, 2SD, n = 22) estimated here is indistinguishable from those of the Earth (δ26Mg = -0.25 ± 0.07‰; 2SD, n = 139), chondrites (δ26Mg = -0.28 ± 0.06‰; 2SD, n = 38), and the Moon (δ26Mg = -0.26 ± 0.16‰; 2SD, n = 47) reported from the same laboratory. The chondritic Mg isotopic composition of achondrites, the Moon, and the Earth further reflects homogeneity of Mg isotopes in the solar system and the lack of Mg isotope fractionation during the planetary accretion process and impact events.

  17. (Carbon isotope fractionation inplants)

    SciTech Connect

    O'Leary, M.H.

    1990-01-01

    The objectives of this research are: To develop a theoretical and experimental framework for understanding isotope fractionations in plants; and to develop methods for using this isotope fractionation for understanding the dynamics of CO{sub 2} fixation in plants. Progress is described.

  18. Measurements of the stable carbon isotope composition of dissolved inorganic carbon in the Northeastern Atlantic and Nordic Seas during summer 2012

    NASA Astrophysics Data System (ADS)

    Humphreys, M. P.; Achterberg, E. P.; Griffiths, A. M.; McDonald, A.; Boyce, A. J.

    2015-01-01

    The stable carbon isotope composition of dissolved inorganic carbon (δ13CDIC) in seawater was measured in samples collected during two cruises in the Northeastern Atlantic and Nordic Seas from June to August 2012. One cruise was part of the UK Ocean Acidification research programme, and the other was a repeat hydrographic transect of the Extended Ellett Line. In combination with measurements made of various other variables on these and other cruises, these data can be used to constrain the anthropogenic component of DIC in the interior ocean, and also assist in determining the influence of biological carbon uptake on surface ocean carbonate chemistry. The measurements have been processed, quality-controlled and submitted to an in-preparation global compilation of seawater δ13CDIC data, and are available from the British Oceanographic Data Centre. The observed δ13CDIC values fall in a range from -0.58 to +2.37‰, relative to the Vienna Peedee Belemnite standard. From duplicate samples collected during both cruises, the precision for the 552 results is 0.07‰, which is similar to other published studies of this kind. Data doi:10.5285/09760a3a-c2b5-250b-e053-6c86abc037c0 (Northeastern Atlantic), doi:10.5285/09511dd0-51db-0e21-e053-6c86abc09b95 (Nordic Seas).

  19. The stable isotopic compositions of indigenous carbon-bearing components in EETA 79001

    NASA Technical Reports Server (NTRS)

    Hartmetz, C. P.; Wright, I. P.; Pillinger, C. T.

    1992-01-01

    It is now widely accepted that the most likely source of SNC meteorites is Mars. An oblique impact on Mars, or vaporization of permafrost, by an impactor seem to be the most likely ejection mechanisms capable of accelerating material to the 5 km/s velocity needed to overcome the gravitational field of Mars. These ejection mechanisms involve a large shock event in the SNC class, the shergottites EETA 79001 and ALHA 77055 are the most likely shocked samples, in which whole rock pressures of 35 to 45 GPa have been estimated. Martian weathering products have also been identified in EETA 79001. Here, the author started a series of analyses of EETA 79001 using a high-sensitivity static mass spectrometer capable of measuring sub-nanogram quantities of carbon. Recent measurements of lithology C confirm that the shock-implanted atmospheric CO2 is released during the 1100 to 1200 C step.

  20. Isotopic composition of dissolved inorganic carbon in subsurface sediments of gas hydrate-bearing mud volcanoes, Lake Baikal: implications for methane and carbonate origin

    NASA Astrophysics Data System (ADS)

    Krylov, Alexey A.; Khlystov, Oleg M.; Hachikubo, Akihiro; Minami, Hirotsugu; Nunokawa, Yutaka; Shoji, Hitoshi; Zemskaya, Tamara I.; Naudts, Lieven; Pogodaeva, Tatyana V.; Kida, Masato; Kalmychkov, Gennady V.; Poort, Jeffrey

    2010-06-01

    We report on the isotopic composition of dissolved inorganic carbon (DIC) in pore-water samples recovered by gravity coring from near-bottom sediments at gas hydrate-bearing mud volcanoes/gas flares (Malenky, Peschanka, Peschanka 2, Goloustnoe, and Irkutsk) in the Southern Basin of Lake Baikal. The δ13C values of DIC become heavier with increasing subbottom depth, and vary between -9.5 and +21.4‰ PDB. Enrichment of DIC in 13C indicates active methane generation in anaerobic environments near the lake bottom. These data confirm our previous assumption that crystallization of carbonates (siderites) in subsurface sediments is a result of methane generation. Types of methanogenesis (microbial methyl-type fermentation versus CO2-reduction) were revealed by determining the offset of δ13C between dissolved CH4 and CO2, and also by using δ13C and δD values of dissolved methane present in the pore waters. Results show that both mechanisms are most likely responsible for methane generation at the investigated locations.

  1. Carbon isotopes in mollusk shell carbonates

    NASA Astrophysics Data System (ADS)

    McConnaughey, Ted A.; Gillikin, David Paul

    2008-10-01

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

  2. NanoSIMS Determination of Carbon and Oxygen Isotopic Compositions of Presolar Graphites from the Murchison Meteorite

    NASA Technical Reports Server (NTRS)

    Stadermann, F. J.; Croat, T. K.; Bernatowicz, T.

    2004-01-01

    Graphite from the Murchison density separate KFC1 (2.15 - 2.20 g/cu cm) has previously been studied by combined SEM/EDX and ion microprobe analysis. These studies found several distinct morphological types of graphites and C isotopic compositions that vary over more than 3 orders of magnitude, clearly establishing their presolar origin. Subsequent TEM measurements of a subset of these particles found abundant embedded crystals of metal (Zr, Mo, Ti, Ru) carbides which were incorporated during the growth of the graphites. A new TEM study of a large set of KFC1 graphites led to the discovery of another type of presolar material, Ru-Fe metal. Here we report results of the C and O isotopic measurements in the same graphite sections, which makes it possible for the first time to directly correlate isotopic and TEM data of KFC1 grains.

  3. Environmental regulation of carbon isotope composition and crassulacean acid metabolism in three plant communities along a water availability gradient

    PubMed Central

    Ricalde, M. Fernanda; Durán, Rafael; Dupuy, Juan Manuel; Simá, J. Luis; Us-Santamaría, Roberth; Santiago, Louis S.

    2010-01-01

    Expression of crassulacean acid metabolism (CAM) is characterized by extreme variability within and between taxa and its sensitivity to environmental variation. In this study, we determined seasonal fluctuations in CAM photosynthesis with measurements of nocturnal tissue acidification and carbon isotopic composition (δ13C) of bulk tissue and extracted sugars in three plant communities along a precipitation gradient (500, 700, and 1,000 mm year−1) on the Yucatan Peninsula. We also related the degree of CAM to light habitat and relative abundance of species in the three sites. For all species, the greatest tissue acid accumulation occurred during the rainy season. In the 500 mm site, tissue acidification was greater for the species growing at 30% of daily total photon flux density (PFD) than species growing at 80% PFD. Whereas in the two wetter sites, the species growing at 80% total PFD had greater tissue acidification. All species had values of bulk tissue δ13C less negative than −20‰, indicating strong CAM activity. The bulk tissue δ13C values in plants from the 500 mm site were 2‰ less negative than in plants from the wetter sites, and the only species growing in the three communities, Acanthocereus tetragonus (Cactaceae), showed a significant negative relationship between both bulk tissue and sugar δ13C values and annual rainfall, consistent with greater CO2 assimilation through the CAM pathway with decreasing water availability. Overall, variation in the use of CAM photosynthesis was related to water and light availability and CAM appeared to be more ecologically important in the tropical dry forests than in the coastal dune. PMID:20652592

  4. Environmental regulation of carbon isotope composition and crassulacean acid metabolism in three plant communities along a water availability gradient.

    PubMed

    Ricalde, M Fernanda; Andrade, José Luis; Durán, Rafael; Dupuy, Juan Manuel; Simá, J Luis; Us-Santamaría, Roberth; Santiago, Louis S

    2010-12-01

    Expression of crassulacean acid metabolism (CAM) is characterized by extreme variability within and between taxa and its sensitivity to environmental variation. In this study, we determined seasonal fluctuations in CAM photosynthesis with measurements of nocturnal tissue acidification and carbon isotopic composition (δ(13)C) of bulk tissue and extracted sugars in three plant communities along a precipitation gradient (500, 700, and 1,000 mm year(-1)) on the Yucatan Peninsula. We also related the degree of CAM to light habitat and relative abundance of species in the three sites. For all species, the greatest tissue acid accumulation occurred during the rainy season. In the 500 mm site, tissue acidification was greater for the species growing at 30% of daily total photon flux density (PFD) than species growing at 80% PFD. Whereas in the two wetter sites, the species growing at 80% total PFD had greater tissue acidification. All species had values of bulk tissue δ(13)C less negative than -20‰, indicating strong CAM activity. The bulk tissue δ(13)C values in plants from the 500 mm site were 2‰ less negative than in plants from the wetter sites, and the only species growing in the three communities, Acanthocereus tetragonus (Cactaceae), showed a significant negative relationship between both bulk tissue and sugar δ(13)C values and annual rainfall, consistent with greater CO(2) assimilation through the CAM pathway with decreasing water availability. Overall, variation in the use of CAM photosynthesis was related to water and light availability and CAM appeared to be more ecologically important in the tropical dry forests than in the coastal dune.

  5. Variations in growth, survival and carbon isotope composition (delta(13)C) among Pinus pinaster populations of different geographic origins.

    PubMed

    Correia, Isabel; Almeida, Maria Helena; Aguiar, Alexandre; Alía, Ricardo; David, Teresa Soares; Pereira, João Santos

    2008-10-01

    To evaluate differences in growth and adaptability of maritime pine (Pinus pinaster Ait.), we studied growth, polycyclism, needle tissue carbon isotope composition (delta(13)C) as an estimate of water-use efficiency (WUE) and survival of seven populations at 10 years of age growing in a performance trial at a provenance test site in Escaroupim, Portugal. Six populations were from relatively high rainfall sites in Portugal and southwestern France (Atlantic group), and one population was from a more arid Mediterranean site in Spain. There were significant differences between some populations in total height, diameter at breast height, delta(13)C of bulk needle tissue, polycyclism and survival. A population from central Portugal (Leiria, on the Atlantic coast) was the tallest and had the lowest delta(13)C. Overall, the variation in delta(13)C was better explained by the mean minimum temperatures of the coldest month than by annual precipitation at the place of origin. Analyses of the relationships between delta(13)C and growth or survival revealed a distinct pattern for the Mediterranean population, with low delta(13)C (and WUE) associated with the lowest growth potential and reduced survival. There were significant negative correlations between delta(13)C and height or survival in the Atlantic group. Variation in polycyclism was correlated with annual precipitation at the place of origin. Some Atlantic populations maintained a high growth potential while experiencing moderate water stress. A detailed knowledge of the relationships between growth, survival and delta(13)C in contrasting environments will enhance our ability to select populations for forestry or conservation.

  6. Lipid Biomarkers and Carbon Isotopic Composition from Authigenic Carbonates and Seep Sediments from the US Mid-Atlantic Margin

    NASA Astrophysics Data System (ADS)

    Campbell, P.; Prouty, N.; Demopoulos, A. W.; Roark, B.; Coykendall, K.

    2015-12-01

    Anaerobic oxidation of methane (AOM), mediated by Archaea and sulfate-reducing bacteria, is common in continental margin sediment and can result in authigenic carbonate precipitation. A lipid biomarker study was undertaken in Mid-Atlantic submarine canyons, focusing specifically on Baltimore and Norfolk canyons, to determine biomarker variability of carbonate rock and the associated sediment in cold seep communities dominated by chemosynthetic mussels, Bathymodiolus childressi. Preliminary 16S metagenomic results confirm the presence of free-living sulfur-reducing bacteria and methantrophic endosymbiotic bacteria in the mussels. Depleted d13C values in both the mussel tissue (-63 ‰) and authigenic carbonates (-48 ‰) support methanotrophy as the dominant nutritional pathway and AOM as the main driver of carbonate precipitation. In addition, paired 14C and 230Th dates are highly discordant, reflecting dilution of the 14C pool with fossil hydrocarbon derived carbon. Seep and canyon sediment, as well as authigenic carbonates, were collected and analyzed for a suite of biomarkers, including sterols, alcohols, alkanes and fatty acids, as well as δ13C values of select biomarkers, to elucidate pathways of organic matter cycling. A comparison of terrestrial biomarker signatures (e.g., n-alkane carbon preference index and C23 / (C23 + C29) values, HMW n-alkanes and C29 sterols) suggests that terrestrial inputs dominate the submarine canyon surface sediment, whereas seep sediment is predominantly marine autochthonous (i.e., cholesterol and 5α-cholestanol). Lipid biomarker profiles (e.g., n-alkanes in the C15 to C33 range) from authigenic carbonates mirror those found in the seep sediment, suggesting that the organisms mediating carbonate precipitation on the seafloor are characteristic of the assemblages present in the sediment at these sites. With widespread methane leakage recently discovered along the Atlantic Margin, the presence of AOM-mediated carbonate

  7. A carbon isotope mass balance for an anoxic marine sediment: Isotopic signatures of diagenesis

    NASA Technical Reports Server (NTRS)

    Boehme, Susan E.

    1993-01-01

    A carbon isotope mass balance was determined for the sediments of Cape Lookout Bight, NC to constrain the carbon budgets published previously. The diffusive, ebullitive and burial fluxes of sigma CO2 and CH4, as well as the carbon isotope signatures of these fluxes, were measured. The flux-weighted isotopic signature of the remineralized carbon (-18.9 plus or minus 2.7 per mil) agreed with the isotopic composition of the remineralized organic carbon determined from the particulate organic carbon (POC) delta(C-13) profiles (-19.2 plus or minus 0.2), verifying the flux and isotopic signature estimates. The measured delta(C-13) values of the sigma CO2 and CH4 diffusive fluxes were significantly different from those calculated from porewater gradients. The differences appear to be influenced by methane oxidation at the sediment-water interface, although other potential processes cannot be excluded. The isotope mass balance provides important information concerning the locations of potential diagenetic isotope effects. Specifically, the absence of downcore change in the delta(C-13) value of the POC fraction and the identical isotopic composition of the POC and the products of remineralization indicate that no isotopic fractionation is expressed during the initial breakdown of the POC, despite its isotopically heterogeneous composition.

  8. Carbon-carbon composites

    NASA Technical Reports Server (NTRS)

    Maahs, Howard G.

    1992-01-01

    The current applications of C-C composites extend to aircraft brakes, rocket nozzles, missile nosetips, and leading edges of the Space Shuttle. More advanced, secondary and even primary structure applications in cyclic, high-temperature oxidizing environments depend on effective oxidation protection for repeated missions. Accounts are presently given of state-of-the-art methods in substrate fabrication, carbon deposition, and SiC and Si3N4 protective coatings. Attention is given to current levels of high temperature oxidation protection for various mission and vehicle types, as well as to performance projections for C-C composites used by a representative National Aerospace Plane airframe structure. Future technology requirements in C-C composites are projected.

  9. [Composition and seasonal variations of carbon isotopes in aerosols of Lhasa, Tibet].

    PubMed

    Huang, Jie; Kang, Shi-chang; Shen, Cheng-de; Cong, Zhi-yuan; Liu, Ke-xin; Liu, Li-chao

    2010-05-01

    A total of 30 samples of total suspended particles were collected at an urban site in western of Lhasa city, Tibet from August 2006 to July 2007 for investigating carbonaceous aerosol features. 14C was taken as a reference to quantitatively distinguish the fossil and biogenic-derived origins along with the characteristics of seasonal variations of all carbonaceous materials in Lhasa are discussed. The results showed that the f(c) values in Lhasa ranged from 0.357 to 0.702, with an average of 0.493, which is higher than Beijing and Tokyo, but are far lower than that of remote/rural regions such as Launceston, indicating a major biogenic influence in Lhasa. Values of f(c) displayed clear seasonal variations with higher mean value in winter, a decreasing trend in spring, while relatively lower values in summer and autumn. Higher f(C) values in winter demonstrate that carbonaceous aerosol is mainly dominated by wood burning and incineration of agricultural wastes during the winter. The lower f(c) values in summer and autumn might be caused by increased diesel engines, motor vehicles emissions, which are related to the tourism in Lhasa. delta13C values ranged from -26.40% per hundred to approximately -25.10% per hundred, with an average of -25.8% per hundred, and showed no clear seasonal variation. The relative higher values in summer reflected the increment of fossil carbon emissions. 13C(TC) values are relatively homogeneous at -25.8% per hundred, considering the characteristics of seasonal variations of f(c) values, it can be concluded that carbonaceous aerosol of Lhasa was mainly influenced by a constant mixing of several pollution sources such as motor vehicles and wood burning emissions.

  10. Assessing the Origins of Aliphatic Amines in the Murchison Meteorite from their Compound-Specific Carbon Isotopic Ratios and Enantiomeric Composition

    NASA Technical Reports Server (NTRS)

    Aponte, Jose; Dworkin, Jason; Elsila, Jamie E.

    2014-01-01

    The study of meteoritic organic compounds provides a unique window into the chemical inventory of the early Solar System and prebiotic chemistry that may have been important for the origin of life on Earth. Multiple families of organic compounds have been extracted from the Murchison meteorite, which is one of the most thoroughly studied carbonaceous chondrites. The amino acids extracted from Murchison have been extensively analyzed, including measurements of non-terrestrial stable isotopic ratios and discoveries of L-enantiomeric excesses for alpha-dialkyl amino acids, notably isovaline. However, although the isotopic signatures of bulk amine-containing fractions have been measured, the isotopic ratios and enantiomeric composition of individual aliphatic amines, compounds that are chemically related to amino acids, remain unknown. Here, we report a novel method for the extraction, separation, identification and quantitation of aliphatic monoamines extracted from the Murchison meteorite. Our results show a complete suite of structural isomers, with a larger concentration of methylamine and ethylamine and decreasing amine concentrations with increasing carbon number. The carbon isotopic compositions of fourteen meteoritic aliphatic monoamines were measured, with delta C-13 values ranging from +21% to +129%, showing a decrease in C-13 with increasing carbon number, a relationship that may be consistent with the chain elongation mechanism under kinetic control previously proposed for meteoritic amino acids. We also found the enantiomeric composition of sec-butylamine, a structural analog to isovaline, was racemic within error, while the isovaline extracted from the same Murchison piece showed an L-enantiomeric excess of 9.7; this result suggested that processes leading to enantiomeric excess in the amino acid did not affect the amine. We used these collective data to assess the primordial synthetic origins of these meteoritic aliphatic amines and their potential

  11. A First Look at Graphite Grains from Orgueil: Morphology, Carbon, Nitrogen and Neon Isotopic Compositions of Individual, Chemically Separated Grains

    NASA Technical Reports Server (NTRS)

    Pravdivtseva, O.; Zinner, E.; Meshik, A. P.; Hohenberg, C. M.; Walker, R. W.

    2004-01-01

    Presolar graphite in Murchison has been extensively studied. It is characterized by a unique Ne isotopic composition, known as the Ne-E(L) component. According to studies by Huss and Lewis, the concentration of Ne-E(L) in Orgueil is about one order of magnitude higher than in Murchison, when normalized to the matrix. This could be due to a higher presolar graphite abundance in Orgueil, or due to a higher Ne-E concentrations per grain. The Ne isotopic compositions in individual presolar graphite grains from Murchison have been measured before. It was shown, that a third of the grains have detectable excesses in 22Ne, characteristic of the Ne-E(L) component. One grain in a hundred had a Ne-22 concentration two orders of magnitude higher than blank.

  12. Carbon Isotope Composition as an Indicator of DOC Sources to a Stream During Events in a Temperate Forested Catchment

    NASA Astrophysics Data System (ADS)

    Doctor, D. H.; Sebestyen, S. D.; Aiken, G. R.; Shanley, J. B.; Kendall, C.; Boyer, E. W.

    2006-12-01

    Increased DOC flux in streams and rivers is commonly observed during high runoff regimes, however DOC concentrations alone do not provide information about multiple sources or pathways of DOC to streams. In an effort to gain this information, we measured DOC concentrations and stable carbon isotope composition (δ13C-DOC) on samples collected at high-frequency during events at Sleepers River Research Watershed in Vermont, USA. During snowmelt and storm events, peaks in stream DOC concentration (up to 10.5 mg/L) were coincident with peaks in flow. Stream water δ13C-DOC measurements ranged between -23.7‰ and - 28.9‰ and indicated changing sources of DOC during events; the highest δ13C-DOC values occurred consistently at the lowest flows, and the lowest δ13C-DOC values occurred with peaks in discharge. Water samples collected from shallow wells and stacked soil lysimeters showed the highest DOC concentrations in the most shallow (<0.5 m) lysimeter waters, and the lowest concentrations in the deeper (>1.5 m) well waters. Wells and lysimeters exhibited a range of δ13C-DOC values similar to those observed in the stream; however, samples collected from shallow horizons at nested wells and lysimeters consistently showed lower δ13C-DOC values than those from greater depths. Maple leaf litter collected from across the watershed provided an end-member of fresh organic material, with average δ13C composition of -31.3±0.7‰ (n=57), which is lower than the lowest measured DOC values in any of the stream, well, or lysimeter waters. A subset of stream waters were fractionated onto XAD4 and XAD8 resins; the hydrophobic acid fraction (XAD8) had consistently lower δ13C values than the transphilic acid fraction (XAD4), and both of these were lower than those of the bulk DOC. Samples with lower δ13C-DOC values also exhibited higher SUVA-254 values, i.e. greater aromaticity. Thus, lower δ13C-DOC values are interpreted as an indicator of relatively "fresh", more aromatic

  13. He, Ar, N and C isotope compositions in Tatun Volcanic Group (TVG), Taiwan: Evidence for an important contribution of pelagic carbonates in the magmatic source

    NASA Astrophysics Data System (ADS)

    Roulleau, Emilie; Sano, Yuji; Takahata, Naoto; Yang, Frank T.; Takahashi, Hiroshi A.

    2015-09-01

    The Tatun Volcanic Group (TVG), Northeastern Taiwan, is considered to be the extension of the Ryukyu arc, and belongs to the post-collisional collapse Okinawa Trough. Strong hydrothermal activity is concentrated along the Chinshan fault, and Da-you-keng (DYK) represents the main fumarolic area where the most primitive isotopic and chemical composition is observed. In this study, we present chemical and He, Ar, C and N isotopic compositions of fumaroles, bubbling gas and water from hot springs sampled in 2012 and 2013. High 3He/4He ratios from DYK fumaroles (≈ 6.5 Ra) show a typical arc-like setting, whereas other sampling areas show a strong dependence of 3He/4He and CH4/3He ratios with the distance from the main active hydrothermal area (DYK). This could mean strong crustal contamination and thermal decomposition of organic matter from local sediments. Carbon isotope compositions of DYK range from - 6.67‰ to - 5.85‰, and indicate that carbon contribution comes mainly from pelagic carbonates from the slab (limestone, mantle and sediment contributions are 63%, 19% and 18%, respectively). This is consistent with the negative δ15N values (- 1.4 ± 0.5‰) observed for DYK, implying a strong nitrogen-mantle contribution, and an absence of contribution from nitrogen-pelagic carbonates. These results have important consequences related to the Ryukyu subducted slab. In fact, the Ryukyu margin presents little in off scraping the sedimentary cover to the subducting plate that does not permit any nitrogen contribution in magma from TVG.

  14. Carbon Isotopic Composition of CO2, Evolved During Perchlorate-Induced Reactions in Mars Analog Materials: Interpreting SAM/MSL Rocknest Data

    NASA Technical Reports Server (NTRS)

    Stern, J. C.; McAdam, A. C.; Archer, P. D., Jr.; Bower, H.; Buch, A.; Eigenbrode, J.; Freissinet, C.; Franz, H. B.; Glavin, D.; Jones, J. H.; Mahaffy, P. R.; Ming, D. W.; Niles, P. B.; Steele, A.; Sutter, B.

    2013-01-01

    The Sample Analysis at Mars (SAM) Instrument Suite on the Mars Science Laboratory (MSL) Rover Curiosity made its first solid sample evolved gas analysis of unconsolidated material at aeolian bedform Rocknest in Gale Crater. The magnitude of O2 evolved in each run as well as the chlorinated hydrocarbons detected by SAM gas chromatograph/ mass spectrometer (GCMS) [1] suggest a chlorinated oxidant such as perchlorate in Rocknest materials [2]. Perchlorate induced combustion of organics present in the sample would contribute to the CO2 volatile inventory, possibly overlapping with CO2 from inorganic sources. The resulting carbon and oxygen isotopic composition of CO2 sent to the Tunable Laser Spectrometer (TLS) for analysis would represent mixed sources. This work was undertaken to better understand a) how well the carbon isotopic composition ( 13C) of CO2 from partially combusted products represents their source and b) how the 13C of combusted products can be deconvolved from other carbon sources such as thermal decomposition of carbonate.

  15. Trophic Relationships and Habitat Preferences of Delphinids from the Southeastern Brazilian Coast Determined by Carbon and Nitrogen Stable Isotope Composition

    PubMed Central

    Bisi, Tatiana Lemos; Dorneles, Paulo Renato; Lailson-Brito, José; Lepoint, Gilles; Azevedo, Alexandre de Freitas; Flach, Leonardo; Malm, Olaf; Das, Krishna

    2013-01-01

    To investigate the foraging habitats of delphinids in southeastern Brazil, we analyzed stable carbon (δ13C) and nitrogen (δ15N) isotopes in muscle samples of the following 10 delphinid species: Sotalia guianensis, Stenella frontalis, Tursiops truncatus, Steno bredanensis, Pseudorca crassidens, Delphinus sp., Lagenodelphis hosei, Stenella attenuata, Stenella longirostris and Grampus griseus. We also compared the δ13C and δ15N values among four populations of S. guianensis. Variation in carbon isotope results from coast to ocean indicated that there was a significant decrease in δ13C values from estuarine dolphins to oceanic species. S. guianensis from Guanabara Bay had the highest mean δ13C value, while oceanic species showed significantly lower δ13C values. The highest δ15N values were observed for P. crassidens and T. truncatus, suggesting that these species occupy the highest trophic position among the delphinids studied here. The oceanic species S. attenuata, G. griseus and L. hosei had the lowest δ15N values. Stable isotope analysis showed that the three populations of S. guianensis in coastal bays had different δ13C values, but similar δ15N results. Guiana dolphins from Sepetiba and Ilha Grande bays had different foraging habitat, with specimens from Ilha Grande showing more negative δ13C values. This study provides further information on the feeding ecology of delphinids occurring in southeastern Brazil, with evidence of distinctive foraging habitats and the occupation of different ecological niches by these species in the study area. PMID:24358155

  16. Sedimentary process control on carbon isotope composition of sedimentary organic matter in an ancient shallow-water shelf succession

    NASA Astrophysics Data System (ADS)

    Davies, S. J.; Leng, M. J.; Macquaker, J. H. S.; Hawkins, K.

    2012-11-01

    Source and delivery mechanisms of organic matter are rarely considered when interpreting changing δ13C through sedimentary successions even though isotope excursions are widely used to identify and correlate global perturbations in the carbon cycle. Combining detailed sedimentology and geochemistry we demonstrate how organic carbon abundance and δ13C values from sedimentary organic matter from Carboniferous-aged mudstones are influenced by the proportion of terrestrial versus water column-derived organic matter. Silt-bearing clay-rich shelf mudstones that were deposited by erosive density flows are characterized by 1.8-2.4% organic carbon and highδ13C values (averaging -22.9 ± 0.3‰, n = 12). Typically these mudstones contain significant volumes of terrestrial plant-derived material. In contrast, clay-rich lenticular mudstones, with a marine macrofauna, are the products of the transport of mud fragments, eroded from pre-existing water-rich shelfal muds, when shorelines were distant and biological productivity in the water column was high. Higher organic carbon (2.1-5.2%) and lowerδ13C values (averaging -24.3 ± 0.5‰, n = 11) characterize these mudstones and are interpreted to reflect a greater contribution by (isotopically more negative) amorphous organic matter derived from marine algae. Differences in δ13C between terrestrial and marine organic matter allow the changing proportions from different sources to be tracked through this succession. Combining δ13C values with zirconium (measured from whole rock), here used as a proxy for detrital silt input, provides a novel approach to distinguishing mudstone provenance and ultimately using δ13C to identify oil-prone organic matter in potential source rocks. These results have important implications for using bulk organic matter to identify and characterize global C-isotope excursions.

  17. Carbon and oxygen isotope composition of Pb-, Cu- and Bi-carbonates of the Schwarzwald mining district: Carbon sources, first data on bismutite and the discovery of an oxidation zone formed by ascending thermal water

    NASA Astrophysics Data System (ADS)

    Haßler, Kathrin; Taubald, Heinrich; Markl, Gregor

    2014-05-01

    The carbon and oxygen isotope composition of cerussite, bismutite, malachite and azurite samples from the Schwarzwald mining district, SW Germany, was analyzed in order to evaluate carbon sources and conditions of formation. We deliberately chose samples showing various textures and coming from deposits at various altitudes and geological settings. δ13C values vary from +1.0‰ to -21.0‰ VPDB, cerussite, bismutite, malachite and azurite δ18O values show a variation from +11.2‰ to +17.9‰, +16.8‰ to +21.0‰, +23.0‰ to +28.1‰ and +26.3‰ to +30.2‰ VSMOW2, respectively. In accordance with earlier studies, the δ13C values indicate carbon partially derived from biogenic (vegetation-respired or from heterotrophic degradation of organic matter) soil CO2 combined with carbon from an isotopically heavier reservoir (e.g. atmospheric CO2, carbonate rocks, hydrothermal calcite from the ore vein) in varying proportions.

  18. Carbon stable isotopic composition of soluble sugars in Tillandsia epiphytes varies in response to shifts in habitat.

    PubMed

    Goode, Laurel K; Erhardt, Erik B; Santiago, Louis S; Allen, Michael F

    2010-07-01

    We studied C stable isotopic composition (delta(13)C) of bulk leaf tissue and extracted sugars of four epiphytic Tillandsia species to investigate flexibility in the use of crassulacean acid metabolism (CAM) and C(3) photosynthetic pathways. Plants growing in two seasonally dry tropical forest reserves in Mexico that differ in annual precipitation were measured during wet and dry seasons, and among secondary, mature, and wetland forest types within each site. Dry season sugars were more enriched in (13)C than wet season sugars, but there was no seasonal difference in bulk tissues. Bulk tissue delta(13)C differed by species and by forest type, with values from open-canopied wetlands more enriched in (13)C than mature or secondary forest types. The shifts within forest habitat were related to temporal and spatial changes in vapor pressure deficits (VPD). Modeling results estimate a possible 4% increase in the proportional contribution of the C(3) pathway during the wet season, emphasizing that any seasonal or habitat-mediated variation in photosynthetic pathway appears to be quite moderate and within the range of isotopic effects caused by variation in stomatal conductance during assimilation through the C(3) pathway and environmental variation in VPD. C isotopic analysis of sugars together with bulk leaf tissue offers a useful approach for incorporating short- and long-term measurements of C isotope discrimination during photosynthesis.

  19. Carbon stable isotopic composition of soluble sugars in Tillandsia epiphytes varies in response to shifts in habitat

    PubMed Central

    Erhardt, Erik B.; Santiago, Louis S.; Allen, Michael F.

    2010-01-01

    We studied C stable isotopic composition (δ13C) of bulk leaf tissue and extracted sugars of four epiphytic Tillandsia species to investigate flexibility in the use of crassulacean acid metabolism (CAM) and C3 photosynthetic pathways. Plants growing in two seasonally dry tropical forest reserves in Mexico that differ in annual precipitation were measured during wet and dry seasons, and among secondary, mature, and wetland forest types within each site. Dry season sugars were more enriched in 13C than wet season sugars, but there was no seasonal difference in bulk tissues. Bulk tissue δ13C differed by species and by forest type, with values from open-canopied wetlands more enriched in 13C than mature or secondary forest types. The shifts within forest habitat were related to temporal and spatial changes in vapor pressure deficits (VPD). Modeling results estimate a possible 4% increase in the proportional contribution of the C3 pathway during the wet season, emphasizing that any seasonal or habitat-mediated variation in photosynthetic pathway appears to be quite moderate and within the range of isotopic effects caused by variation in stomatal conductance during assimilation through the C3 pathway and environmental variation in VPD. C isotopic analysis of sugars together with bulk leaf tissue offers a useful approach for incorporating short- and long-term measurements of C isotope discrimination during photosynthesis. PMID:20155286

  20. Measurements of the stable carbon isotope composition of dissolved inorganic carbon in the northeastern Atlantic and Nordic Seas during summer 2012

    NASA Astrophysics Data System (ADS)

    Humphreys, M. P.; Achterberg, E. P.; Griffiths, A. M.; McDonald, A.; Boyce, A. J.

    2015-06-01

    The stable carbon isotope composition of dissolved inorganic carbon (δ13CDIC) in seawater was measured in a batch process for 552 samples collected during two cruises in the northeastern Atlantic and Nordic Seas from June to August 2012. One cruise was part of the UK Ocean Acidification research programme, and the other was a repeat hydrographic transect of the Extended Ellett Line. In combination with measurements made of other variables on these and other cruises, these data can be used to constrain the anthropogenic component of dissolved inorganic carbon (DIC) in the interior ocean, and to help to determine the influence of biological carbon uptake on surface ocean carbonate chemistry. The measurements have been processed, quality-controlled and submitted to an in-preparation global compilation of seawater δ13CDIC data, and are available from the British Oceanographic Data Centre. The observed δ13CDIC values fall in a range from -0.58 to +2.37 ‰, relative to the Vienna Pee Dee Belemnite standard. The mean of the absolute differences between samples collected in duplicate in the same container type during both cruises and measured consecutively is 0.10 ‰, which corresponds to a 1σ uncertainty of 0.09 ‰, and which is within the range reported by other published studies of this kind. A crossover analysis was performed with nearby historical δ13CDIC data, indicating that any systematic offsets between our measurements and previously published results are negligible. Data doi:10.5285/09760a3a-c2b5-250b-e053-6c86abc037c0 (northeastern Atlantic), doi:10.5285/09511dd0-51db-0e21-e053-6c86abc09b95 (Nordic Seas).

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  2. Calcium isotopic compositions of chondrites

    NASA Astrophysics Data System (ADS)

    Huang, Shichun; Jacobsen, Stein B.

    2017-03-01

    We report mass-dependent and mass-independent Ca isotopic variations in nine chondrites from three groups: carbonaceous, ordinary and enstatite chondrites. There is about 0.25‰ per amu, i.e., ∼1‰ in 44Ca/40Ca, variation in chondrites: carbonaceous chondrites have the lightest Ca isotopes, enstatite chondrites have modeled bulk Earth like Ca isotopes, and ordinary chondrites are in between. The correlations between mass-dependent Ca isotopic variation and chemical variations in chondrites may reflect variable contributions from different endmembers, including refractory inclusions, in different chondrite groups. In detail, enstatite chondrites and the Earth share similar isotopic characteristics, but are very different in chemical compositions. At the ±1 and ±2 ε-unit levels, respectively, there is no measurable 40Ca or 43Ca anomaly in bulk chondrites. Carbonaceous chondrites show several ε-units of 48Ca excess. That is, Ca exhibits both mass-dependent and mass-independent isotopic variations in chondrites, similar to O isotopes. The 48Ca anomaly in bulk chondrites is positively correlated with 50Ti anomaly, but does not form simple correlation with 54Cr anomaly, implying multiple supernova sources for these neutron-rich isotopes in the Solar System. Finally, all meteorites with negative Δ17O have either 48Ca deficits (differentiated meteorites) or 48Ca excess (carbonaceous chondrites), implying that the Sun with a very negative Δ17O is probably also characterized by 48Ca anomaly compared to the Earth. CAIs cannot be taken as representative of the initial isotopic compositions of refractory elements like Ca for the Earth-Moon system.

  3. Global simulation of the carbon isotope exchange of terrestrial ecosystems

    NASA Astrophysics Data System (ADS)

    Ito, A.; Terao, Y.; Mukai, H.

    2009-12-01

    There remain large uncertainties in our quantification of global carbon cycle, which has close interactions with the climate system and is subject to human-induced global environmental change. Information on carbon isotopes is expected to reduce the uncertainty by providing additional constraints on net atmosphere-ecosystem exchange. This study attempted to simulate the dynamics of carbon isotopes at the global scale, using a process-based terrestrial ecosystem model: Vegetation Integrative SImulator for Trace gases (VISIT). The base-model of carbon cycle (Sim-CYCLE, Ito 2003) has already considered stable carbon isotope composition (13C/12C), and here radioactive carbon isotope (14C) was included. The isotope ratios characterize various aspects of terrestrial carbon cycle, which is difficult to be constrained by sole mass balance. For example, isotopic discrimination by photosynthetic assimilation is closely related with leaf stomatal conductance and composition of C3 and C4 plant in grasslands. Isotopic disequilibrium represents mean residence time of terrestrial carbon pools. In this study, global simulations (spatial resolution 0.5-deg, time-step 1-month) were conducted during the period 1901 to 2100 on the basis of observed and projected atmospheric CO2, climate, and land-use conditions. As anthropogenic CO2 accumulates in the atmosphere, heavier stable carbon isotope (13C) was diluted, while radioactive carbon isotope (14C) is strongly affected by atomic bomb experiments mainly in the 1950s and 1960s. The model simulated the decadal change in carbon isotope compositions. Leaf carbon with shorter mean residence time responded rapidly to the atmospheric change, while plant stems and soil humus showed substantial time-lag, leading to large isotopic disequilibrium. In the future, the isotopic disequilibrium was estimated to augment, due to accelerated rate of anthropogenic CO2 accumulation. Spatial distribution of stable isotope composition (12C/13C, or d13C) was

  4. Origin of petroporphyrins. 2. Evidence from stable carbon isotopes

    NASA Technical Reports Server (NTRS)

    Boreham, C. J.; Fookes, C. J.; Popp, B. N.; Hayes, J. M.

    1990-01-01

    Compared with the carbon-13 isotopic composition of the ubiquitous C32DPEP (DPEP, deoxophylloerythroetioporphyrin) the heavy but equivalent carbon-13 isotopic composition for the porphyrin structures 15(2)-methyl-15,17-ethano-17-nor-H-C30DPEP and 15,17-butano-, 13,15-ethano-13(2),17-propano-, and 13(1)-methyl-13,15-ethano-13(2),17-propanoporphyrin suggests a common precursor, presumably chlorophyll c, for these petroporphyrins isolated from the marine Julia Creek oil shale and the lacustrine Condor oil shale. Similarly, the heavy but variable carbon-13 isotopic composition of 7-nor-H-C31DPEP compared with C32DPEP is consistent with an origin from both chlorophyll b and chlorophyll c3. The equivalent carbon-13 isotopic composition for 13(2)-methyl-C33DPEP compared with C32DPEP suggests a common origin resulting from a weighted average of chlorophyll inputs.

  5. An isotopic study of biogeochemical relationships between carbonates and organic carbon in the Greenhorn Formation

    NASA Technical Reports Server (NTRS)

    Hayes, J. M.; Popp, Brian N.; Takigiku, Ray; Johnson, Marcus W.

    1989-01-01

    Carbon-isotopic compositions of total carbonate, inoceramid carbonate, micritic carbonate, secondary cements, total organic carbon, and geoporphyrins have been measured in 76 different beds within a 17-m interval of a core through the Greenhorn Formation, an interbedded limestone and calcareous shale unit of Cretaceous age from the Western Interior Seaway of North America. Results are considered in terms of variations in the processes of primary production and in secondary processes. It is shown that the porphyrin isotopic record reflects primary isotopic variations more closely than the TOC isotopic record and that, in these sediments, TOC is enriched in C-13 relative to its primary precursor by 0.6 to 2.8 percent. This enrichment is attributed to isotope effects within the consumer foodweb and is associated with respiratory heterotrophy. Variation in this secondary enrichment are correlated with variations in the isotopic composition of marine carbonate.

  6. Growth factor controls on the distribution and carbon isotope composition of n-alkanes in leaf wax

    NASA Astrophysics Data System (ADS)

    Jia, C.; Xie, S.; Huang, X.

    2012-12-01

    Cuticular wax plays pivotal physiological and ecological roles in the interactions between plants and the environments in which they grow. Plant-derived long-chain alkanes are more resistant to decay than other biochemical polymers. n-Alkane distributions (Carbon Preference Index (CPI) values and Average Chain Length (ACL) values) and carbon isotopic values are used widely in palaeoenvironmental reconstruction. However, there is little information available on how growth stages of the plant might influence the abundance of n-alkanes in the natural environment. In this study, we analyzed n-alkane distributions and carbon isotope data from two tree species (Cinnamomum camphora (L.) Presl. and Liquidambar formosana Hance) collected monthly from 2009 to 2011 in Nanwang Shan, Wuhan, Hubei Province. CPI values for n-alkanes from C. camphora remained stable in autumn and winter but fluctuated dramatically during spring and autumn each year. Positive correlations between CPI values and the relative content of (C27+C29) were observed in both sun and shade leaves of C. camphora from April to July. In L. formosana, CPI values decreased gradually from April to December. A similar trend was observed in all three years suggesting that growth stages rather than temperature or relative humidity affected the CPI values on a seasonal timescale. In the samples of L. formosana ACL values were negatively correlated with CPI values in the growing season (from April to July) and positively correlated with CPI values in the other seasons. The δ13C values of C29 and C31 n-alkanes displayed more negative carbon isotopic values in autumn and winter compared with leaves sampled at the start of the growing season from both trees. The δ13C values of C29 and C31 n-alkanes of L. formosana decreased from April to December. These results demonstrate the importance of elucidating the growing factors that influence the distribution and δ13C values of alkanes in modern leaves prior to using CPI

  7. Carbon isotopes in biological carbonates: Respiration and photosynthesis

    USGS Publications Warehouse

    McConnaughey, T.A.; Burdett, J.; Whelan, J.F.; Paull, C.K.

    1997-01-01

    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 CO2/O2 ratios appear to be the major controlling variable. Atmospheric CO2/O2 ratios are about thirty times lower than in most natural waters, hence air breathing animals absorb less environmental CO2 in the course of obtaining O2. Tissue CO2 therefore, does not isotopically equilibrate with environmental CO2 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 CO2 in their tissues. Photosynthetic corals calcify mainly during the daytime when photosynthetic CO2 uptake is several times faster than respiratory CO2 release. Photosynthesis, therefore, affects skeletal ??13C 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. Copyright ?? 1997 Elsevier Science Ltd.

  8. Organic chemistry of Murchison meteorite: Carbon isotopic fractionation

    NASA Technical Reports Server (NTRS)

    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. Carbon isotope fractionation during microbial methane oxidation

    NASA Astrophysics Data System (ADS)

    Barker, James F.; Fritz, Peter

    1981-09-01

    Methane, a common trace constituent of groundwaters, occasionally makes up more than 20% of the total carbon in groundwaters1,2. In aerobic environments CH4-rich waters can enable microbial food chain supporting a mixed culture of bacteria with methane oxidation as the primary energy source to develop3. Such processes may influence the isotopic composition of the residual methane and because 13C/12C analyses have been used to characterize the genesis of methanes found in different environments, an understanding of the magnitude of such effects is necessary. In addition, carbon dioxide produced by the methane-utilizing bacteria can be added to the inorganic carbon pool of affected groundwaters. We found carbon dioxide experimentally produced by methane-utilizing bacteria to be enriched in 12C by 5.0-29.6‰, relative to the residual methane. Where methane-bearing groundwaters discharged into aerobic environments microbial methane oxidation occurred, with the residual methane becoming progressively enriched in 13C. Various models have been proposed to explain the 13C/12C and 14C content of the dissolved inorganic carbon (DIC) of groundwaters in terms of additions or losses during flow in the subsurface4,5. The knowledge of both stable carbon isotope ratios in various pools and the magnitude of carbon isotope fractionation during various processes allows geochemists to use the 13C/12C ratio of the DIC along with water chemistry to estimate corrected 14C groundwater ages4,5. We show here that a knowledge of the carbon isotope fractionation between CH4 and CO2 during microbial methane-utilization could modify such models for application to groundwaters affected by microbial methane oxidation.

  10. Influences of heterotrophic and autotrophic resource use on carbon and hydrogen isotopic compositions of tropical tree leaves.

    PubMed

    Terwilliger, V J; Kitajima, K; Le Roux-Swarthout, D J; Mulkey, S; Wright, S J

    2001-01-01

    The delta13C and SD values of newly emerging to senescing tree leaves produced during a rainy season were obtained in dry seasonal and moist forest in Panamá. Newly emerging leaves had less negative delta13C values than older leaves yet instantaneous pi/pa was never lowest in the youngest leaves. Furthermore, isotopic enrichment during early growth may have a detectable influence on the delta13C values of mature leaves. The deltaD values of cellulose nitrate were only related to deltaD values of leaf water if leaf age was also considered so that, for a given deltaD of leaf water, deltaD values were highest in the youngest leaves (R2 = 98%). There was no correlation between leaf age and deltaD values of leaf water. Investment of translocated organic carbon is a factor likely to be associated with both 13C and deuterium enrichment effects in new leaves. A coarse, mass balance approach can estimate the proportional heterotrophic investment in leaf growth and improve estimates of integrated pi/pa by approximating delta13C for the most autotrophic phase of leaf growth. Delta13C values of the predominantly sucrose mobile organic fraction in new leaves were less negative than in older leaves, thereby suggesting that the enrichment did not occur at the original site of production of the substrate for new leaf growth. Although the delta values of early leaf growth must be influenced by inputs of translocated organic carbon, enrichment effects, per se, are apparently caused by other mechanisms such as, for carbon, de novo sucrose synthesis and anaplerotic replenishment. Better recognition of metabolic causes of isotopic enrichment in leaves promises to increase the power and accuracy of inferences about carbon and water use of tropical trees from delta analyses.

  11. [Stable isotopes of carbon and nitrogen in soil ecological studies].

    PubMed

    Tiunov, A V

    2007-01-01

    The development of stable isotope techniques is one of the main methodological advances in ecology of the last decades of the 20th century. Many biogeochemical processes are accompanied by changes in the ratio between stable isotopes of carbon and nitrogen (12C/13C and 14N/15N), which allows different ecosystem components and different ecosystems to be distinguished by their isotopic composition. Analysis of isotopic composition makes it possible to trace matter and energy flows through biological systems and to evaluate the rate of many ecological processes. The main concepts and methods of stable isotope ecology and patterns of stable isotope fractionation during organic matter decomposition are considered with special emphasis on the fractionation of isotopes in food chains and the use of stable isotope studies of trophic relationships between soil animals in the field.

  12. Carbon and nitrogen isotopic composition of PM2.5 at a periurban Mt. Taehwa near Seoul and over the Yellow Sea

    NASA Astrophysics Data System (ADS)

    LIM, S.; Joo, T.; Lee, M.; Czimczik, C. I.; Holden, S. R.; Mouteva, G.; Santos, G.; Xu, X.; Kim, S.; Cho, G.; Park, J.; Shin, B.; Ryoo, S. B.

    2015-12-01

    Fine particular matter (PM2.5) is a major contributor to poor air quality in East Asia, with detrimental effects on air quality and climate. The elemental and isotopic composition of PM2.5 is powerful proxy for identifying emission sources, understanding atmospheric processing, and mitigating emissions of PM2.5. Here, we present a time-series of the elemental and isotopic composition of PM2.5 in East Asia, sampled at a periurban site (Mt. Taehwa, South Korea, August - October 2014) and over the Yellow Sea (onboard RV Gisang 1, November 2014). We measured the radiocarbon (14C) content of total carbon (TC) and elemental carbon (EC) with accelerator mass spectrometry and the carbon and nitrogen elemental and stable isotopic composition of bulk PM2.5 with isotope ratio mass spectrometry. At Mt. Taehwa, EC was depleted in 14C (fM-EC=0.224±0.071 (ave±SD, n=6)). The bulk PM2.5 was enriched in 14C above natural levels (fM-TC=1.19±0.47, n=9), with a δ13C of -25.6±0.5 (n=7), and a δ15N of 14.6±3.8 (n=4), and was strongly enriched in nitrogen (C:N=2.8±1.4, n=16). Over the Yellow Sea, bulk PM2.5 was depleted in 14C (fM-TC=0.57±0.07, n=5), with a δ13C of -24.2±0.8 (n=3), and a δ15N of 5.2±4.3 (n=3); EC was too small for 14C analysis. Our results confirm that periurban Mt. Taehwa site is exposed to combustion plumes of fossil fuels, especially from on-road sources. PM2.5 over the Yellow Sea turned out to be a mixture of fossil and biogenic emissions and experience more intense atmospheric processes. This isotope-based source apportionment of PM2.5 is a first step to characterize major sources of aerosols at Taehwa Research Forest, which was established to examine interactions of megacity and biogenic emissions and their impact on air quality.

  13. Controls on the stable carbon isotopic composition of biogenic methane produced in a tidal freshwater estaurine sediment

    SciTech Connect

    Avery, G.B. Jr.; Martens, C.S.

    1999-04-01

    The {delta}{sup 13}C value of methane in sediments from a tidal freshwater site in the White Oak River Estuary, North Carolina, exhibited a relatively small, but consistent, seasonal variation ({approximately}3{per_thousand}) with isotopically heavier values occurring during the warmer months ({minus}66.1{per_thousand} summer, {minus}69.2{per_thousand} winter). These isotopic shifts could have resulted from changes in: (1) isotopic compositions of precursor molecules; (2) kinetic isotope effects associated with methane production; or (3) pathways of methane production. Methane production rate and isotopic data from sediment incubation experiments and field measurements were used to determine the relative contributions of these factors to the observed seasonal variations. Although changes in {delta}{sup 13}C values of biogenic methane are typically thought to result from changes in pathways of methane production, this study showed that a significant amount (36 {+-} 22%) of the seasonal variations between the {delta}{sup 13}C value of methane produced in sediment incubation experiments could be attributed to changes in the {delta}{sup 13}C value of the {Sigma}CO{sub 2} pool. This was due to increased methane production rates and removal of {sup 12}CO{sub 2} with increasing temperature, a prevalent feature of methanogenic systems that may account for some of the frequently observed {sup 13}C enrichment in methane during warmer months. Combining the change in the {delta}{sup 13}C value of the {Sigma}CO{sub 2} pool with temperature-controlled changes in fractionation ({alpha}) resulting from kinetic isotope effects accounted for (53 {+-} 22%) of the {sup 13}C enrichment observed during summer sediment incubation experiments. Although large pathway changes were not observed in sediment incubation experiments, the remaining differences in {delta}{sup 13}C values could have resulted from smaller, undetectable changes in the percentage of methane production from acetate

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

    USGS Publications Warehouse

    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.

  15. Stable carbon isotopic compositions of low-molecular-weight dicarboxylic acids, oxocarboxylic acids, α-dicarbonyls, and fatty acids: Implications for atmospheric processing of organic aerosols

    NASA Astrophysics Data System (ADS)

    Zhang, Yan-Lin; Kawamura, Kimitaka; Cao, Fang; Lee, Meehye

    2016-04-01

    Stable carbon isotopic compositions (δ13C) were measured for 23 individual organic species including 9 dicarboxylic acids, 7 oxocarboxylic acids, 1 tricarboxylic acid, 2 α-dicarbonyls, and 4 fatty acids in the aerosols from Gosan background site in East Asia. δ13C values of particle phase glyoxal and methylglyoxal are significantly larger than those previously reported for isoprene and other precursors. The values are consistently less negative in oxalic acid (C2, average -14.1‰), glyoxylic acid (-13.8‰), pyruvic acid (-19.4‰), glyoxal (-13.5‰), and methylglyoxal (-18.6‰) compared to other organic species (e.g., palmitic acid, -26.3‰), which can be explained by the kinetic isotope effects during atmospheric oxidation of pre-aged precursors (e.g., isoprene) and the subsequent gas-particle partitioning after the evaporation of clouds or wet aerosols. The δ13C values of C2 is positively correlated with C2 to organic carbon ratio, indicating that photochemical production of C2 is more pronounced than its degradation during long-range atmospheric transport. The isotopic results also suggest that aqueous phase oxidation of glyoxal and methylglyoxal is a major formation process of oxalic acid via the intermediates such as glyoxylic acid and pyruvic acid. This study provides evidence that organic aerosols are intensively photochemically aged in the western North Pacific rim.

  16. Stable carbon isotopic compositions of low-molecular-weight dicarboxylic acids, oxocarboxylic acids, α-dicarbonyls, and fatty acids: implications for atmospheric processing of organic aerosols

    NASA Astrophysics Data System (ADS)

    Zhang, Y.; Kawamura, K.; Cao, F.; Lee, M.

    2015-12-01

    Stable carbon isotopic compositions (δ13C) were measured for 23 individual organic species including 9 dicarboxylic acids, 7 oxocarboxylic acids, 1 tricarboxylic acid, 2 α-dicarbonyls and 4 fatty acids in the aerosols from Gosan background site in East Asia. δ13C of particle-phase glyoxal and methylglyoxal are significantly higher than those previously reported for isoprene and other precursors, associated with isotope fractionation during atmospheric oxidation. 13C is consistently more enriched for oxalic acid (C2), glyoxylic acid, pyruvic acid, glyoxal and methylglyoxal compared to other organic compounds identified, which can be explained by the kinetic isotope effects during aqueous-phase processing and the subsequent gas-particle partitioning after clouds or wet aerosols evaporation δ13C of C2 is positively correlated with C2 and organic carbon ratio, indicating that a photochemical production of C2 is more pronounced than its degradation process during long-range transport. The 13C results also suggest that aqueous-phase oxidation of glyoxal and methylglyoxal is major formation process of oxalic acid production via the major intermediates glyoxylic acid and pyruvic acid. This study provides evidence that organic aerosols are intensively photo-chemically aged in this region.

  17. Tracking Movement of Plant Carbon Through Soil to Water by Lignin Phenol Stable Carbon Isotope Composition in a Small Agricultural Watershed

    NASA Astrophysics Data System (ADS)

    Crooker, K.; Filley, T.; Six, J.; Frey, J.

    2005-12-01

    Few studies integrate land cover, soil physical structure, and aquatic physical fractions when investigating the fate of agricultural carbon in watersheds. In crop systems that involve rotations of soy (a C3 plant) and corn (a C4 plant) the large intrinsic differences in stable carbon isotope values and lignin plus cutin chemistry enable tracking of plant carbon movement from soil fractions to DOM and overland flow during precipitation events. In a small (~3Km2) agricultural basin in central Indiana, we studied plant carbon dynamics in a soy/corn agricultural rotation (2004-2005) to determine the relative inputs of these two plants to soil fractions and the resultant contributions to dissolved, colloidal, and particulate organic matter when mobilized. Using bulk isotope values the fraction of carbon derived from corn in macroaggregates (>250 micron), microaggregates (53-250 mm), and silts plus clays (<53 mm) ranged from 39, 49, to 42%, respectively. Unlike bulk analyses, compound specific isotope analysis of lignin in the soil fractions revealed a wide range of relative inputs among the monomers with cinnamyl phenols being almost exclusively (~ 93%) derived from corn. Syringyl phenols ranged from 75-56% corn and vanillyl phenols ranged from 37-40% corn carbon. The relative input among the fractions mirrors closely the comparative plant chemistry abundances between soy and corn. During export of DOM from the land to the stream the relative abundance of plant source varied with discharge (0.05-1.8 m3/sec) as increases in flow increased the relative export of corn-derived C from the fields. Over the full range of flows lignin phenols varied from 0.05 to 82% corn-derived with the greatest relative corn input for cinnamyl and syringyl carbon. The trend with stream discharge indicates a progressive movement of particulate corn residues with overland flow. Ongoing studies look to resolve contributions of algae, bacteria and terrestrial plants to soil fractions and their

  18. Planktonic foraminiferal shell weight and boron isotopic composition as proxies for carbonate system parameters: Insight from sediment trap studies in the Cariaco Basin, Venezuela

    NASA Astrophysics Data System (ADS)

    Marshall, B. J.; Thunell, R.; Henehan, M. J.; McConnell, M. C.; Astor, Y.

    2012-12-01

    The area-normalized shell weight (ANSW) and boron isotopic compositions of planktonic foraminifera collected from Cariaco Basin, Venezuela sediment traps were used as proxies for seawater carbonate ion concentrations ([CO32-]) and pH respectively. Three species of planktonic forams: G. ruber (pink), G. sacculifer, and O. universa were used in conjunction with known hydrographic data to calibrate the relationship between carbonate ion concentration and area-normalized shell weight. Individuals of each species were picked from sediment trap samples collected between January 2005 and September 2008, then weighed and photographed for size analysis. The individual foraminiferal ANSW were averaged for each sample (n > 10) and compared to the concurrent [CO32-] calculated from time-equivalent hydrographic data (pH, alkalinity, temperature, salinity, nutrient concentrations). The results of this study revealed strong positive-linear relationships between [CO32-] and the ANSW of G. ruber (r2 = 0.84), G. sacculifer (r2 = 0.90), and O. universa (r2 = 0.52) for broad size fractions. The results also suggest that the relationship between [CO32-] and ANSW is variable amongst species and thus species-specific equations are necessary when using foraminiferal ANSW during down-core paleo-oceanographic reconstructions. The relationship between pH and the boron isotopic composition of sediment trap foraminiferal calcite was also assessed. Trap samples containing 3-5 mg of O. universa were prepared for boron isotopic analysis on the Neptune MC-ICP-MS using a micro-sublimation method following oxidative cleaning and dissolution via nitric acid. The results of these sediment trap calibration studies were then compared to previously published calibration equations. The determination of seawater [CO32-] and pH using the proxies above will allow for the derivation of all other carbonate parameters during down-core paleo-climatic and paleo-oceanographic studies.

  19. The separation of stable isotopes of carbon

    NASA Astrophysics Data System (ADS)

    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.

  20. BOREAS TE-5 Leaf Carbon Isotope Data

    NASA Technical Reports Server (NTRS)

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

    2000-01-01

    The BOREAS TE-5 team collected measurements in the NSA and SSA on gas exchange, gas composition, and tree growth. This documentation describes leaf carbon isotope data that were collected in 1993 and 1994 at the NSA and SSA OJP sites, the SSA OBS site, and the NSA UBS site. In addition, leaf carbon isotope data were collected in 1994 only at the NSA and SSA OA sites. These data was collected to provide seasonal integrated physiological information for 10 to 15 common species at these 6 BOREAS sites. The data are stored 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).

  1. Asynchronous evolution of the isotopic composition and amount of precipitation in north China during the Holocene revealed by a record of compound-specific carbon and hydrogen isotopes of long-chain n-alkanes from an alpine lake

    NASA Astrophysics Data System (ADS)

    Rao, Zhiguo; Jia, Guodong; Li, Yunxia; Chen, Jianhui; Xu, Qinghai; Chen, Fahu

    2016-07-01

    Both the timing of the maximum East Asian summer monsoon (EASM) intensity in monsoonal China and the environmental significance of the Chinese stalagmite oxygen isotopic record (δ18O) have been debated. Here, we present a ca. 120-year-resolution compound-specific carbon (δ13C) and hydrogen (δD) isotopes of terrestrial long-chain n-alkanes extracted from a well-dated sediment core from an alpine lake in north China. Our δ13C data, together with previously reported pollen data from a parallel core, demonstrate a humid mid-Holocene from ca. 8-5 ka BP. Assuming that the climatic humidity of north China is an indicator of the EASM intensity, then the maximum EASM intensity occurred in the mid-Holocene. Our δD data reveal a similar long-term trend to the δ18O record from nearby Lianhua Cave, indicating that the synchronous δD and δ18O records faithfully record the δD and δ18O of precipitation, respectively. The most negative δD and δ18O values occur in the early-mid Holocene, from ca. 11-5 ka BP. This contrast in the timing of isotopic variations demonstrates a complex relationship between the isotopic composition of precipitation and precipitation amount, or EASM intensity. Further comparisons indicate a possible linkage between the precipitation amount in north China and the west-east thermal gradient in the equatorial Pacific. In addition, the temperature of the moisture source area may play an important role in determining the isotopic composition of precipitation in monsoonal China.

  2. Carbon and Sulfur Isotopic Composition of Yellowknife Bay Sediments: Measurements by the Sample Analysis at Mars (SAM) Quadrupole Mass Spectrometer

    NASA Technical Reports Server (NTRS)

    Franz, H. B.; Mahaffy, P. R.; Stern, J. C.; Eigenbrode, J. L.; Steele, A.; Ming, D. W.; McAdam, A. C.; Freissinet, C.; Glavin, D. P.; Archer, P. D.; Brunner, A. E.; Grotzinger,J. P.; Jones, J. H.; Leshin, L. A.; Miller, K.; Morris, R. V.; Navarro-Gonzalez, R.; Niles, P. B.; Owen, T. C.; Summons, R. E.; Sutter, B.; Webster, C. R.

    2014-01-01

    Since landing at Gale Crater in Au-gust 2012, the Sample Analysis at Mars (SAM) instru-ment suite on the Mars Science Laboratory (MSL) “Curiosity” rover has analyzed solid samples from the martian regolith in three locations, beginning with a scoop of aeolian deposits from the Rocknest (RN) sand shadow. Curiosity subsequently traveled to Yellowknife Bay, where SAM analyzed samples from two separate holes drilled into the Sheepbed Mudstone, designated John Klein (JK) and Cumberland (CB). Evolved gas analysis (EGA) of all samples revealed the presence of H2O as well as O-, C- and S-bearing phas-es, in most cases at abundances below the detection limit of the CheMin instrument. In the absence of definitive mineralogical identification by CheMin, SAM EGA data can help provide clues to the mineralogy of volatile-bearing phases through examination of tem-peratures at which gases are evolved from solid sam-ples. In addition, the isotopic composition of these gas-es may be used to identify possible formation scenarios and relationships between phases. Here we report C and S isotope ratios for CO2 and SO2 evolved from the JK and CB mudstone samples as measured with SAM’s quadrupole mass spectrometer (QMS) and draw com-parisons to RN.

  3. By-products of the serpentinization process on the Oman ophiolite : chemical and isotopic composition of carbonate deposits in alkaline springs, and associated secondary phases

    NASA Astrophysics Data System (ADS)

    Sissmann, O.; Martinez, I.; Deville, E.; Beaumont, V.; Pillot, D.; Prinzhofer, A.; Vacquand, C.; Chaduteau, C.; Agrinier, P.; Guyot, F. J.

    2014-12-01

    The isotopic compositions (d13C, d18O) of natural carbonates produced by the alteration of basic and ultrabasic rocks on the Oman ophiolite have been measured in order to better understand their formation mechanisms. Fossil carbonates developed on altered peridotitic samples, mostly found in fractures, and contemporary carbonates were studied. The samples bear a large range of d13C. Those collected in veins are magnesian (magnesite, dolomite) and have a carbon signature reflecting mixing of processes and important fractionation (-11‰ to 8‰). Their association with talc and lizardite suggests they are by-products of a serpentinization process, that must have occurred as a carbon-rich fluid was circulating at depth. On the other hand, the carbonates are mostly calcic when formed in alkaline springs, most of which are located in the vicinity of lithological discontinuities such as the peridotite-gabbro contact (Moho). Aragonite forms a few meters below the surface of the ponds in Mg-poor water, and is systematically associated with brucite (Mg(OH)2). This suggests most of the Mg dissolved at depth has reprecipitated during the fluid's ascension through fractures or faults as carbonates and serpentine. Further up, on the surface waters of the ponds (depleted in Mg and D.I.C.), thin calcite films precipitate and reach extremely negative d13C values (-28‰), which could reflect either a biological carbon source, or kinetic fractionation from pumping atmospheric CO2. Their formation represent an efficient and natural process for carbon dioxide mineral sequestration. The d18O signature from all samples confirm the minerals crystallized from a low-temperature fluid. The hyperalkaline conditions (pH between 11 and 12) allowing for these fast precipitation kinetics are generated by the serpentinization process occurring at depth, as indicated by the measured associated H2-rich gas flows (over 50%) seeping out to the surface.

  4. Distribution, abundance and carbon isotopic composition of gaseous hydrocarbons in Big Soda Lake, Nevada - An alkaline, meromictic lake

    NASA Technical Reports Server (NTRS)

    Oremland, R. S.; Des Marais, D. J.

    1983-01-01

    The study of the distribution and isotopic composition of low molecular weight hydrocarbon gases at the Big Soda Lake, Nevada, has shown that while neither ethylene nor propylene were found in the lake, ethane, propane, isobutane and n-butane concentrations all increased with water column depth. It is concluded that methane has a biogenic origin in both the sediments and the anoxic water column, and that C2-C4 alkanes have biogenic origins in the monimolimnion water and shallow sediments. The changes observed in delta C-13/CH4/ and CH4/(C2H6 + C3H8) with depth in the water column and sedimeents are probably due to bacterial processes, which may include anaerobic methane oxidation and different rates of methanogenesis, and C2-to-C4 alkane production by microorganisms.

  5. Within-shell variations in carbon and oxygen isotope compositions of two modern brachiopods from a subtropical shelf environment off Amami-o-shima, southwestern Japan

    NASA Astrophysics Data System (ADS)

    Yamamoto, Kazuyuki; Asami, Ryuji; Iryu, Yasufumi

    2010-10-01

    This study examines the fidelity of carbon (δ13C) and oxygen (δ18O) isotope compositions of two modern brachiopod species (Kikaithyris hanzawai and Basiliola lucida) to use as proxies of δ13C values of total dissolved inorganic carbon and temperature and/or δ18O values of seawater, respectively. Well-preserved shells of K. hanzawai and living individuals of B. lucida were collected from a subtropical shelf environment off Amami-o-shima, southwestern Japan. Some portions of the shells are in isotopic equilibrium with the ambient seawater, while other portions are not. The degree of disequilibrium differs between the two species and between different portions of each shell. Statistically significant positive correlations are recognized between the δ13C and δ18O values of these samples, which can be ascribed to a kinetic fractionation effect. Far from the posterior shell edge and along the axis of shell growth, the δ18O values of the secondary shell layer of K. hanzawai mostly fall within the expected range of equilibrium calcite. The δ13C values from the inner surface of the secondary shell layer in both species are relatively constant and are equivalent to or very close to equilibrium calcite. Therefore, these portions of the shells are most suitable for collecting reliable environmental proxy data. Although the δ13C and δ18O values of modern brachiopod shells are predominantly controlled by a kinetic fractionation effect, the appropriate selection of species and shell portions that reflect the isotopic composition of ambient seawater can facilitate the reconstruction of secular variations in oceanic δ13C or δ18O values.

  6. Composition of Hydrothermal Vent Microbial Communities as Revealed by Analyses of Signature Lipids, Stable Carbon Isotopes and Aquificales Cultures

    NASA Technical Reports Server (NTRS)

    Jahnke, Linda L.; Eder, Wolfgang; Huber, Robert; Hinrichs, Kai-Uwe; Hayes, John M.; Cady, Sherry L.; DesMarais, David J.; Hope, Janet M.; Summons, Roger E.

    2001-01-01

    Extremely thermophilic microbial communities associated with the siliceous vent walls and outflow channel of Octopus Spring, Yellowstone National Park, have been examined for lipid biomarker and carbon isotopic signatures. These data were compared with that obtained from representatives of three Aquificales genera. Thermocrinis ruber, Thermocrinis sp. HI, Hydrogenobacter thermophilus, Aquifex pyrophilus and Aquifex aeolicus all contained phospholipids composed not only of the usual ester-linked fatty acids, but also ether-linked alkyl moieties. The fatty acids of all cultured organisms were dominated by very distinct pattern of n-C-20:1 and cy-C-21 compounds. The alkyl glycerol ethers were present primarily as C-18:0 monoethers with the exception of the Aquifex spp. in which dialkyl glycerol ethers with a boarder carbon-number distribution were also present. These Aquificales biomarker lipids were the major constituents in the lipid extracts of the Octopus Spring microbial samples. Two natural samples, a microbial biofilm growing in association with deposition of amorphous silica on the vent walls at 92 C, and the well-known "pink-streamer community" (PSC), siliceous filaments of a microbial consortia growing in the outflow channel at 87 C were analyzed. Both the biofilm and PSC samples contained mono- and dialkyl glycerol ethers with a prevalence of C-18 and C-20 alkyls. Phospholipid fatty acids were comprised of both the characteristic. Additional information is contained in the original extended abstract.

  7. Chemical and stable carbon isotopic composition of PM2.5 from on-road vehicle emissions in the PRD region and implications for vehicle emission control policy

    NASA Astrophysics Data System (ADS)

    Dai, S.; Bi, X.; Chan, L. Y.; He, J.; Wang, B.; Wang, X.; Peng, P.; Sheng, G.; Fu, J.

    2015-03-01

    Vehicle emissions are a major source of urban air pollution. In recent decade, the Chinese government has introduced a range of policies to reduce vehicle emissions. In order to understand the chemical characteristics of PM2.5 from on-road vehicle emissions in the Pearl River Delta (PRD) region and to evaluate the effectiveness of control policies on vehicle emissions, the emission factors of PM2.5 mass, elemental carbon (EC), organic carbon (OC), water-soluble organic carbon (WSOC), water-soluble inorganic ions (WSII), metal elements, organic compounds and stable carbon isotopic composition were measured in the Zhujiang tunnel of Guangzhou, in the PRD region of China in 2013. Emission factors of PM2.5 mass, OC, EC and WSOC were 92.4, 16.7, 16.4 and 1.31 mg vehicle-1 km-1 respectively. Emission factors of WSII were 0.016 (F-) ~ 4.17 (Cl-) mg vehicle-1 km-1, contributing about 9.8% to the PM2.5 emissions. The sum of 27 measured metal elements accounted for 15.2% of PM2.5 emissions. Fe was the most abundant metal element, with an emission factor of 3.91 mg vehicle-1 km-1. Emission factors of organic compounds including n-alkanes, polycyclic aromatic hydrocarbons, hopanes and steranes were 91.9, 5.02, 32.0 and 7.59 μg vehicle-1 km-1, respectively. Stable carbon isotopic composition δ13C value was -25.0‰ on average. An isotopic fractionation of 3.2‰ was found during fuel combustion. Compared to a previous study in Zhujiang tunnel in 2004, emission factors of PM2.5mass, EC, OC, WSII except Cl- and organic compounds decreased by 16.0 ~ 93.4%, which could be attributed to emission control policy from 2004 to 2013. However, emission factors of most of the metal elements increased significantly, which could be partially attributed to the changes in motor oil additives and vehicle conditions. There are no mandatory national standards to limit metal content from vehicle emissions, which should be a concern of the government. A snapshot of the 2013 characteristic

  8. Molecular and Stable Carbon Isotope Composition of Organic Compounds from Particles Sampled from the Lower Fraser Valley, BC Urban and Regional Air Shed

    NASA Astrophysics Data System (ADS)

    Whiticar, M. J.; Gray, S. L.

    2001-12-01

    This study examines the character of specific non-volatile organic compounds (N-VOCs) extracted from total suspended particulates. Aerosols are collected on filters by HiVol samplers on monthly intervals, at well-characterized meteorological sites throughout the Lower Fraser Valley. Filters are solvent-extracted , then separated into different compound classes by Silica-gel Chromatography. Selected fractions are analysed for their individual compound molecular compositions by Gas Chromatography-Mass Spectrometry (GC/MS) and by Continuous Flow-Isotope Ratio Mass Spectrometry (CF-IRMS) for their stable carbon isotope ratio. The purpose is to identify spatial and temporal variations in N-VOCs, with the long-term goal of understanding their sources, transport processes and atmospheric chemistry. This Health Canada, Toxic Substance Research Initiative offers insights into the levels and signatures of N-VOCs exposed to humans in congested urban settings. The program is also part of the Pacific 2001 field study. This paper presents the initial year's results on our N-VOCs, including alkanes, organic acids, in comparison with bulk isotope analyses.

  9. Large regional-scale variation in C3/C4 distribution pattern of Inner Mongolia steppe is revealed by grazer wool carbon isotope composition

    NASA Astrophysics Data System (ADS)

    Auerswald, K.; Wittmer, M. H. O. M.; Männel, T. T.; Bai, Y. F.; Schäufele, R.; Schnyder, H.

    2009-05-01

    This work explored the spatial variation of C3/C4 distribution in the Inner Mongolia, P. R. China, steppe by geostatistical analysis of carbon isotope data of vegetation and sheep wool. Standing community biomass (n=118) and sheep wool (n=146) were sampled in a ~0.2 Mio km2 area. Samples from ten consecutive years (1998-2007) were obtained. Community biomass samples represented the carbon isotopic composition of standing vegetation on about 1000 m2 ("community-scale"), whereas the spatio-temporal scale of wool reflected the isotope composition of the entire area grazed by the herd during a 1-yr period (~5-10 km2, "farm-scale"). Pair wise sampling of wool and vegetation revealed a 13C-enrichment of 2.7±0.7‰ (95% confidence interval) in wool relative to vegetation, but this shift exhibited no apparent relationships with environmental parameters or stocking rate. The proportion of C4 plants in above-ground biomass (PC4, %) was estimated with a two-member mixing model of 13C discrimination by C3 and C4 vegetation (13Δ3 and 13Δ4, respectively), in accounting for the effects of changing 13C in atmospheric CO2 on sample isotope composition, and of altitude and aridity on 13Δ3. PC4 averaged 19%, but the variation was enormous: full-scale (0% to 100%) at community-scale, and 0% to 85% at farm-scale. The farm-scale variation of PC4 exhibited a clear regional pattern over a range of ~250 km. Importantly PC4 was significantly higher above the 22°C isotherm of the warmest month, which was obtained from annual high-resolution maps and averaged over the different sampling years. This is consistent with predictions from C3/C4 crossover temperature of quantum yield or light use efficiency in C3 and C4 plants. Still, temperature gradients accounted for only 10% of the farm-scale variation of PC4, indicating that additional factors control PC4 on this scale.

  10. Large regional-scale variation in C3/C4 distribution pattern of Inner Mongolia steppe is revealed by grazer wool carbon isotope composition

    NASA Astrophysics Data System (ADS)

    Auerswald, K.; Wittmer, M. H. O. M.; Männel, T. T.; Bai, Y. F.; Schäufele, R.; Schnyder, H.

    2009-01-01

    This work explored the spatial variation of C3/C4 distribution in the Inner Mongolia, China, steppe by geostatistical analysis of carbon isotope data of vegetation and sheep wool. Standing community biomass (n=118) and sheep wool (n=146) were sampled in a ~0.2 Mio km2 area. Samples from ten consecutive years (1998-2007) were obtained. Community biomass samples represented the carbon isotopic composition of standing vegetation on about 1000 m2 ("community-scale"), whereas the spatio-temporal scale of wool reflected the isotope composition of the entire area grazed by the herd during a 1-yr period (~5-10 km2, "farm-scale"). Pair wise sampling of wool and vegetation revealed a 13C-enrichment of 2.7‰ in wool relative to vegetation, but this shift exhibited no apparent relationships with environmental parameters or stocking rate. The proportion of C4 plants in above-ground biomass (PC4, %) was estimated with a two-member mixing model of C3 and C4 13C discrimination (13Δ3 and 13Δ4, respectively), in accounting for the effects of changing 13C in atmospheric CO2 on sample isotope composition, and of altitude and aridity on 13Δ3. PC4 averaged 19%, but the variation was enormous: full-scale (0% to 100%) at community-scale, and 0% to 85% at farm-scale. The farm-scale variation of PC4 exhibited a clear regional pattern over a range of ~250 km. Importantly PC4 was significantly higher above and lower below the 22°C isotherm of the warmest month, which was averaged from high-resolution maps of the sample years. This is consistent with predictions from C3/C4 crossover temperature of quantum yield in C3 and C4 plants. Still, temperature gradients accounted for only 10% of the farm-scale variation of PC4, indicating that additional factors control PC4 on this scale.

  11. Oxygen Isotopic Compositions of Fulgurites

    NASA Astrophysics Data System (ADS)

    Robert, F.; Javoy, M.

    1992-07-01

    Two occurrences of vitreous rocks (fulgurites) that have resulted from the fusion of Etnean lavas, have been ascribed to the result of lightning striking the basalts and melting fresh volcanic rocks [1]. Rapidly quenched melts appear as tubular cavities that preserve the path of the discharge. Glass droplets (D <= 500 micrometers) are always dispersed around the fused lava tube and show several petrographic similarities with chondrules found in ordinary chondrites (presence of melilite, radiating skeletal fassaite, etc). In this process, high temperatures (T>1800 K) have probably been reached during timescales <=10 sec. Because it has been suggested that lightning discharges may have played an important role in the formation of chondrules [2], we have analyzed the oxygen isotope compositions of these fulgurites (our experimental protocol is described elsewhere [3]). The glass (free from any contamination from the unmelted basalt) is 1.5o/oo depleted in ^18O relative to its measured initial isotopic composition (delta^18O = +5.6o/oo); most of the data define a mass-dependent fractionation relationship (i.e. delta^17O = 0.52 x delta^18O). Therefore the data clearly do not reproduce the oxygen isotope anomaly defined for meteorites, which has a slope of 1 in the diagram delta^17O versus delta^18O (i.e. delta^17O = 1.0 x delta^18O). Nevertheless, it should be noted that some glass samples scatter around this canonical value of 0.52 with minor departures from a purely mass-dependent fractionation. If these results are confirmed by additional determinations (now in progress) on the separated glassy droplets, the following conclusions can be proposed: 1) lightning discharges do not yield oxygen isotope anomalies similar to those measured in chondrules and 2) an isotope exchange between hot chondrules and their parent nebular gas--presumably "anomalous" in its oxygen isotopes-- seems difficult to achieve within the duration of the rapid cooling of the melt. This last point

  12. Effect of Feeding On The Carbon and Oxygen Isotopic Composition In The Tissues and Skeleton of The Zooxanthellate Coral Stylophora Pistillata

    NASA Astrophysics Data System (ADS)

    Reynaud-Vaganay, S.; Ferrier-Pagès, C.; Sambrotto, R.; Juillet-Leclerc, A.; Jaubert, J.

    and J.-P. Gattuso4 1Centre Scientifique de Monaco, Avenue Saint Martin, MC-98000, Principality of Monaco 2Lamont-Doherty Earth Observatory, 61 Rt. 9W/ P.O. Box 1000, Palisades, NY 10964 U.S.A 3Laboratoire des Sciences du Climat et de l'Environnement, Laboratoire mixte CNRS- CEA, F-91180 Gif-sur-Yvette Cedex, France 4Observatoire Océanologique, Laboratoire d'Océanographie, CNRS-UPMC, BP 28, F- 06234 Villefranche-sur-mer Cedex, France The effect of feeding on the carbon isotopic composition of zooxanthellae, animal tissue and skeleton was investigated in the scleractinian coral Stylophora pistillata. Two sets of corals were grown with filtered seawater under controlled conditions. One group of colonies was fed with Artemia nauplii and compared to a control group that was starved. Fed corals exhibited higher concentrations of chlorophyll protein calcification rates than starved colonies. The net photosynthetic rate was higher in starved than in fed corals, whereas dark respiration was not significantly different. The average ? C value of Artemia nauplii used for feeding was -12. ? C was 13 13 significantly heavier in zooxanthellae than in animal tissues, for both fed (-10.1vs. -11.7) and starved colonies (-10.9vs. -13.2). Isotopic data reflected the incorporation of Artemia carbon into the coral tissue in that the ? C was 13 significantly heavier in fed than in starved colonies (-11.7 to -13.2 respectively), although there was no difference in the ? C of the zooxanthellae fraction. Skeletal 13 ? C was similar in fed and starved colonies (mean = -4.6). Skeletal ? O 13 18 composition was, however, significantly different between the two treatments (-4.24 to -4.05 for fed and starved colonies respectively). These data are used to establish a conceptual model of the carbon flow between the various compartments of a symbiotic coral.

  13. Carbon isotopic composition of forest soil respiration in the decade following bark beetle and stem girdling disturbances in the Rocky Mountains.

    PubMed

    Maurer, Gregory E; Chan, Allison M; Trahan, Nicole A; Moore, David J P; Bowling, David R

    2016-07-01

    Bark beetle outbreaks are widespread in western North American forests, reducing primary productivity and transpiration, leading to forest mortality across large areas and altering ecosystem carbon cycling. Here the carbon isotope composition (δ(13) C) of soil respiration (δJ ) was monitored in the decade after disturbance for forests affected naturally by mountain pine beetle infestation and artificially by stem girdling. The seasonal mean δJ changed along both chronosequences. We found (a) enrichment of δJ relative to controls (<1 ‰) in near-surface soils in the first 2 years after disturbance; (b) depletion (1‰ or no change) during years 3-7; and (c) a second period of enrichment (1-2‰) in years 8-10. Results were consistent with isotopic patterns associated with the gradual death and decomposition of rhizosphere organisms, fine roots, conifer needles and woody roots and debris over the course of a decade after mortality. Finally, δJ was progressively more (13) C-depleted deeper in the soil than near the surface, while the bulk soil followed the well-established pattern of (13) C-enrichment at depth. Overall, differences in δJ between mortality classes (<1‰) and soil depths (<3‰) were smaller than variability within a class or depth over a season (up to 6‰).

  14. Black carbon aerosol dynamics and isotopic composition in Alaska linked with boreal fire emissions and depth of burn in organic soils

    NASA Astrophysics Data System (ADS)

    Mouteva, G. O.; Czimczik, C. I.; Fahrni, S. M.; Wiggins, E. B.; Rogers, B. M.; Veraverbeke, S.; Xu, X.; Santos, G. M.; Henderson, J.; Miller, C. E.; Randerson, J. T.

    2015-11-01

    Black carbon (BC) aerosol emitted by boreal fires has the potential to accelerate losses of snow and ice in many areas of the Arctic, yet the importance of this source relative to fossil fuel BC emissions from lower latitudes remains uncertain. Here we present measurements of the isotopic composition of BC and organic carbon (OC) aerosols collected at two locations in interior Alaska during the summer of 2013, as part of NASA's Carbon in Arctic Reservoirs Vulnerability Experiment. We isolated BC from fine air particulate matter (PM2.5) and measured its radiocarbon (Δ14C) content with accelerator mass spectrometry. We show that fires were the dominant contributor to variability in carbonaceous aerosol mass in interior Alaska during the summer by comparing our measurements with satellite data, measurements from an aerosol network and predicted concentrations from a fire inventory coupled to an atmospheric transport model. The Δ14C of BC from boreal fires was 131 ± 52‰ in the year 2013 when the Δ14C of atmospheric CO2 was 23 ± 3‰, corresponding to a mean fuel age of 20 years. Fire-emitted OC had a similar Δ14C (99 ± 21‰) as BC, but during background (low fire) periods OC (45 to 51‰) was more positive than BC (-354 to -57‰). We also analyzed the carbon and nitrogen elemental and stable isotopic composition of the PM2.5. Fire-emitted aerosol had an elevated carbon to nitrogen (C/N) ratio (29 ± 2) and δ15N (16 ± 4‰). Aerosol Δ14C and δ13C measurements were consistent with a mean depth of burning in organic soil horizons of 20 cm (and a range of 8 to 47 cm). Our measurements of fire-emitted BC and PM2.5 composition constrain the end-member of boreal forest fire contributions to aerosol deposition in the Arctic and may ultimately reduce uncertainties related to the impact of a changing boreal fire regime on the climate system.

  15. A deep-time CO2 barometer based on triple oxygen isotope compositions of dinosaurian eggshell carbonate

    NASA Astrophysics Data System (ADS)

    Hu, H.; Passey, B. H.; Montanari, S.; Levin, N.; Li, S.

    2013-12-01

    Photochemical reactions in the stratosphere lead to mass independent fractionation of oxygen isotopes: oxygen exchange among O2, O3, and CO2 produces 17O-enriched O3 and CO2, and 17O-depleted O2. This effect increases with increasing atmospheric CO2 concentration, and thus the 17O anomaly of O2, Δ17O (O2), is reflective of pCO2. Animals incorporate this signal into body water via respiration, and minerals such as bioapatite and eggshell calcite forming in equilibrium with body water can preserve the signal for millions of years. We contribute to the development of this new pCO2 barometer by developing analytical methods for high-precision triple oxygen isotope analysis of carbonates, by developing an ecophysiological model of body water triple oxygen isotopes, and by applying the method to eggshell from modern birds and late Cretaceous (Campanian and Maastrichtian) dinosaur eggshells. Our findings include the following: (1) If animal ecophysiology and climatic context are perfectly known, the sensitivity of Δ17O (body water) to atmospheric CO2 is on the order of 0.01 ‰ per 100 ppm CO2; our analytical precision is ~ 0.01 ‰, thus ultimately permitting sub -100 ppm - level pCO2 reconstructions. (2) However, the effect of ecophysiology and climate can lead to a range in Δ17O (body water) of about 0.15 ‰ for animals living under the same Δ17O (O2); this prediction, confirmed by analyses of eggshells and body water of modern birds, translates to an apparent pCO2 range of about 1500 ppm. (3) Animals that are highly dependent on unevaporated free surface water ('drinking water') and live in humid climates have Δ17O (body water) signals that mimic low pCO2, whereas animals that consume primarily evaporated water (e.g., leaf water) and living in arid environments have Δ17O (body water) signals that mimic high pCO2. (4) There is an upper limit to this 'evaporation / aridity' effect mimicking high pCO2, so Δ17O (fossil eggshell) can be modeled assuming such upper

  16. The Effects of Trimethylamine and Organic Matter Additions on the Stable Carbon Isotopic Composition of Methane Produced in Hypersaline Microbial Mat Environments

    NASA Astrophysics Data System (ADS)

    Kelley, C. A.; Nicholson, B. E.; Beaudoin, C. S.; Detweiler, A. M.; Bebout, B.

    2014-12-01

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

  17. Compound-specific stable carbon isotopic composition of petroleum hydrocarbons as a tool for tracing the source of oil spills.

    PubMed

    Li, Yun; Xiong, Yongqiang; Yang, Wanying; Xie, Yueliang; Li, Siyuan; Sun, Yongge

    2009-01-01

    With the increasing demand for and consumption of crude oils, oil spill accidents happen frequently during the transportation of crude oils and oil products, and the environmental hazard they pose has become increasingly serious in China. The exact identification of the source of spilled oil can act as forensic evidence in the investigation and handling of oil spill accidents. In this study, a weathering simulation experiment demonstrates that the mass loss of crude oils caused by short-term weathering mainly occurs within the first 24h after a spill, and is dominated by the depletion of low-molecular weight hydrocarbons (carbon isotope profile of n-alkanes can be a useful tool for tracing the source of an oil spill, particularly for weathered oils or those with a relatively low concentration or absence of sterane and terpane biomarkers.

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

    NASA Astrophysics Data System (ADS)

    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

  19. Carbon isotope fractionation during calcium carbonate precipitation induced by ureolytic bacteria

    NASA Astrophysics Data System (ADS)

    Millo, Christian; Dupraz, S.; Ader, M.; Guyot, F.; Thaler, C.; Foy, E.; Ménez, B.

    2012-12-01

    Ureolytic bacteria have been proposed as model organisms to investigate the potential of subsurface microorganisms to enhance carbon capture and storage through solubility- and mineral-trapping of CO2 induced by bacterial ureolysis and carbonate formation. Ideally, CO2 incorporation into carbonates can be readily traced using carbon isotope measurements. However, the carbon isotope systematics of bacterial ureolysis and associated carbonate precipitation is still poorly known. We determined the carbon isotope fractionations expressed during ureolysis and carbonate precipitation induced by Sporosarcina pasteurii at 30 °C. Our results indicate that bacterial ureolysis proceeds as a Rayleigh distillation characterized by a 13C-enrichment factor equal to -12.5‰. As precipitation proceeds, the δ13C value of CaCO3, initially 1-2.1‰ lower than that of dissolved inorganic carbon (DIC), evolves progressively until it is 0.5‰ higher than that of the DIC, i.e. close to the value predicted for isotopic equilibrium. The minor isotope disequilibrium at the onset of precipitation and its rapid evolution towards isotopic equilibrium point to bacterial carbonates as reliable recorders of the carbon isotope composition of DIC. This corroborates the potential utility of 13C-tracing for the quantification of microbially-induced CO2 sequestration into solid carbonates and DIC.

  20. Vertical distributions of bound saturated fatty acids and compound-specific stable carbon isotope compositions in sediments of two lakes in China: implication for the influence of eutrophication.

    PubMed

    Wang, Lifang; Xiong, Yongqiang; Wu, Fengchang; Li, Qiuhua; Lin, Tian; Giesy, John P

    2014-11-01

    Lakes Dianchi (DC) and Bosten (BST) were determined to be at different stages of eutrophication, by use of total organic carbon content, bulk carbon isotopic composition, bulk nitrogen isotopic composition, and bound saturated fatty acid (BSFA) concentrations in sediment cores. A rapid increase in the supply of organic matter (OM) to DC began after the 1950s, while the environment and trophic status of BST remained constant as indicated by characteristics of OM input to sediments. The BSFA ratios of nC14 + nC16 + nC18/nC24 + nC26 + nC28 increase upward from 7 to 13 in the DC core, which are significantly greater than those from BST (2 to 3). This result is consistent with algae or bacteria being the dominant contribution of the OM increase induced by eutrophication in DC. The positive shift of nC16 compound-specific δ (13)C in the upper section might be an indicator of excess algal productivity, which was observed in the two lakes. The positive shifts of compound-specific δ (13)C of other BSFAs were also observed in the upper section of the core only from DC. The observed trends of compound-specific δ(13)C of BSFA originated from different sources became more consistent, which reflected the intensified eutrophication had profoundly affected production and preservation of OM in DC. The results observed for BST indicated that accumulation of algae did not affect the entire aquatic ecosystem until now.

  1. Spatial and temporal variations in stable carbon (δ(13)C) and nitrogen (δ(15)N) isotopic composition of symbiotic scleractinian corals.

    PubMed

    Nahon, Sarah; Richoux, Nicole B; Kolasinski, Joanna; Desmalades, Martin; Ferrier Pages, Christine; Lecellier, Gael; Planes, Serge; Berteaux Lecellier, Véronique

    2013-01-01

    Tropical scleractinian corals are considered autotrophic as they rely mainly on photosynthesis-derived nutrients transferred from their photosymbionts. Corals are also able to capture and ingest suspended particulate organic matter, so heterotrophy can be an important supplementary trophic pathway to optimize coral fitness. The aim of this in situ study was to elucidate the trophic status of 10 coral species under contrasted environmental conditions in a French Polynesian lagoon. Carbon (δ(13)C) and nitrogen (δ(15)N) isotopic compositions of coral host tissues and photosymbionts were determined at 3 different fringing reefs during wet and dry seasons. Our results highlighted spatial variability in stable isotopic compositions of both coral host tissues and photosymbionts. Samples from the site with higher level of suspended particulate matter were (13)C-depleted and (15)N-enriched relative to corals and photosymbionts from less turbid sites. However, differences in both δ(13)C and δ(15)N between coral host tissues and their photosymbionts (Δ(host-photosymbionts 13)C and Δ(host-photosymbionts 15)N) were small (0.27 ± 0.76‰ and 1.40 ± 0.90‰, respectively) and similar at all sites, thus indicating no general increases in the heterotrophic pathway. Depleted δ(13)C and enriched δ(15)N values of coral host tissues measured at the most turbid site were explained by changes in isotopic composition of the inorganic nutrients taken up by photosymbionts and also by changes in rate of isotopic fractionation with environmental conditions. Our results also highlighted a lack of significant temporal variations in δ(13)C and δ(15)N values of coral host and photosymbiont tissues and in Δ(host-photosymbionts 13)C and Δ(host-photosymbionts 15)N values. This temporal stability indicated that corals remained principally autotrophic even during the wet season when photosymbiont densities were lower and the concentrations of phytoplankton were higher. Increased coral

  2. Isotopic anomalies from neutron reactions during explosive carbon burning

    NASA Technical Reports Server (NTRS)

    Lee, T.; Schramm, D. N.; Wefel, J. P.; Blake, J. B.

    1979-01-01

    The heavy isotopic anomalies observed recently in the fractionation and unknown nuclear inclusions from the Allende meteorite are explained by neutron reactions during the explosive carbon burning (ECB). This model produces heavy anomalies in the same zone where Al-26 and O-16 are produced, thus reducing the number of source zones required for the isotopic anomalies. Unlike the classical r-process, the ECB n-process avoids the problem with the Sr anomaly and may resolve the problem of conflicting time scales between Al-26 and the r-process isotopes I-129 and Pu-244. Experimental studies of Zr and Ce isotopic composition are proposed to test this model.

  3. Carbon isotope controlled molecular switches

    NASA Astrophysics Data System (ADS)

    Foster, Brian K.

    Single molecules represent one fundamental limit to the downscaling of electronics. As a prototype element for carbon-based nanoscale science and technology, the detailed behavior of carbon monoxide (CO) on the copper surface Cu(111) has been investigated. These investigations span from individual carbon isotope resolution, to single molecules, to compact clusters assembled by molecular manipulation via a homemade scanning tunneling microscope (STM). Sub-nanoscale devices, composed of only a few molecules, which exploit both lone CO properties and molecule-molecule interaction, have been designed and assembled. The devices function as bi-stable switches and can serve as classical bits with densities > 50 Tbits/cm2. Operated in the nuclear mass sensitive regime, each switch can also function as a molecular "centrifuge" capable of identifying the isotope of a single carbon atom in real-time. A model, based on electron-vibron couping and inelastic tunneling, has been developed and explains the dynamic behavior of the switch. The interaction between pairs of switches was also explored and it was found that their behavior ranges from completely independent to strongly coupled. Larger nanostructures, which were composed of many sub-switches organized to leverage the fully coupled interaction, link two spatially separated "bits" on the surface. Such a linked system can set or read a state non-locally, which is equivalent to bidirectional information transfer. The linked system has also exhibited logic functionality. These experiments demonstrate scalable molecular cells for information storage, and for information processing through cellular automata logic schemes.

  4. Variability in the carbon isotopic composition of foliage carbon pools (soluble carbohydrates, waxes) and respiration fluxes in southeastern U.S. pine forests

    NASA Astrophysics Data System (ADS)

    Mortazavi, Behzad; Conte, Maureen H.; Chanton, Jeffrey P.; Weber, J. C.; Martin, Timothy A.; Cropper, Wendell P., Jr.

    2012-06-01

    We measured the δ13C of assimilated carbon (foliage organic matter (δCOM), soluble carbohydrates (δCSC), and waxes (δCW)) and respiratory carbon (foliage (δCFR), soil (δCSR) and ecosystem 13CO2 (δCER)) for two years at adjacent ecosystems in the southeastern U.S.: a regenerated 32 m tall mature Pinus palustrisforest, and a mid-rotation 13 m tallPinus elliottii stand. Carbon pools and foliage respiration in P. palustris were isotopically enriched by 2‰ relative to P. elliottii. Despite this enrichment, mean δCER values of the two sites were nearly identical. No temporal trends were apparent in δCSC, δCFR, δCSR and δCER. In contrast, δCOM and δCW at both sites declined by approximately 2‰ over the study. This appears to reflect the adjustment in the δ13C of carbon storage reserves used for biosynthesis as the trees recovered from a severe drought prior to our study. Unexpectedly, the rate of δ13C decrease in the secondary C32-36 n-alkanoic acid wax molecular cluster was twice that observed forδCOM and the predominant C22-26 compound cluster, and provides new evidence for parallel but separate wax chain elongation systems utilizing different carbon precursor pools in these species. δCFR and δCER were consistently enriched relative to assimilated carbon but, in contrast to previous studies, showed limited variations in response to changes in vapor pressure deficit (D). This limited variability in respiratory fluxes and δCSC may be due to the shallow water table as well as the deep taproots of pines, which limit fluctuations in photosynthetic discrimination arising from changes in D.

  5. Effects of mistletoe removal on growth, N and C reserves, and carbon and oxygen isotope composition in Scots pine hosts.

    PubMed

    Yan, Cai-Feng; Gessler, Arthur; Rigling, Andreas; Dobbertin, Matthias; Han, Xing-Guo; Li, Mai-He

    2016-05-01

    Most mistletoes are xylem-tapping hemiparasites, which derive their resources from the host's xylem solution. Thus, they affect the host's water relations and resource balance. To understand the physiological mechanisms underlying the mistletoe-host relationship, we experimentally removed Viscum album ssp. austriacum (Wiesb.) Vollmann from adult Pinus sylvestris L. host trees growing in a Swiss dry valley. We analyzed the effects of mistletoe removal over time on host tree growth and on concentrations of nonstructural carbohydrates (NSC) and nitrogen (N) in needles, fine roots and sapwood. In addition, we assessed the δ(13)C and δ(18)O in host tree rings. After mistletoe removal, δ(13)C did not change in newly produced tree rings compared with tree rings in control trees (still infected with mistletoe), but δ(18)O values increased. This pattern might be interpreted as a decrease in assimilation (A) and stomatal conductance (gs), but in our study, it most likely points to an inadequacy of the dual isotope approach. Instead, we interpret the unchanged δ(13)C in tree rings upon mistletoe removal as a balanced increase in A and gs that resulted in a constant intrinsic water use efficiency (defined as A/gs). Needle area-based concentrations of N, soluble sugars and NSC, as well as needle length, single needle area, tree ring width and shoot growth, were significantly higher in trees from which mistletoe was removed than in control trees. This finding suggests that mistletoe removal results in increased N availability and carbon gain, which in turn leads to increased growth rates of the hosts. Hence, in areas where mistletoe is common and the population is large, mistletoe management (e.g., removal) may be needed to improve the host vigor, growth rate and productivity, especially for relatively small trees and crop trees in xeric growth conditions.

  6. Carbon and oxygen stable isotope compositions of late Pleistocene mammal teeth from dolines of Ajoie (Northwestern Switzerland)

    NASA Astrophysics Data System (ADS)

    Scherler, Laureline; Tütken, Thomas; Becker, Damien

    2014-09-01

    Fossils of megaherbivores from eight late Pleistocene 14C- and OSL-dated doline infillings of Ajoie (NW Switzerland) were discovered along the Transjurane highway in the Swiss Jura. Carbon and oxygen analyses of enamel were performed on forty-six teeth of large mammals (Equus germanicus, Mammuthus primigenius, Coelodonta antiquitatis, and Bison priscus), coming from one doline in Boncourt (~ 80 ka, marine oxygen isotope stage MIS5a) and seven in Courtedoux (51-27 ka, late MIS3), in order to reconstruct the paleoclimatic and paleoenvironmental conditions of the region. Similar enamel δ13C values for both periods, ranging from - 14.5 to - 9.2‰, indicate that the megaherbivores lived in a C3 plant-dominated environment. Enamel δ18OPO4 values range from 10.9 to 16.3‰ with a mean of 13.5 ± 1.0‰ (n = 46). Mean air temperatures (MATs) were inferred using species-specific δ18OPO4-δ18OH2O-calibrations for modern mammals and a present-day precipitation δ18OH2O-MAT relation for Switzerland. Similar average MATs of 6.6 ± 3.6°C for the deposits dated to ~ 80 ka and 6.5 ± 3.3°C for those dated to the interval 51-27 ka were estimated. This suggests that these mammals in the Ajoie area lived in mild periods of the late Pleistocene with MATs only about 2.5°C lower than modern-day temperatures.

  7. Carbon and hydrogen isotope composition of plant biomarkers as proxies for precipitation changes across Heinrich Events in the subtropics

    NASA Astrophysics Data System (ADS)

    Arnold, T. E.; Freeman, K.; Brenner, M.; Diefendorf, A. F.

    2014-12-01

    Lake Tulane is a relatively deep (~23 m) solution lake in south-central Florida. Its depth and location on a structural high, the Lake Wales Ridge, enabled continuous lacustrine sediment accumulation over the past >60,000 years. Pollen in the lake sediments indicate repeated major shifts in the vegetation community, with six peaks in Pinus (pine) abundance that coincide with the most intense cold phases of Dansgaard-Oeschger cycles and the Heinrich events that terminate them. Alternating with Pinus peaks are zones with high relative percentages of Quercus (oak), Ambrosia (ragweed), Lyonia (staggerbush) and Ceratiola (rosemary) pollen, genera that today occupy the most xeric sites on the Florida landscape. This suggests the pollen record indicates the Pinus phases, and therefore Heinrich Events, were wetter than the intervening Quercus phases. To test the connection between Heinrich Events and precipitation in Florida, we analyzed the carbon (δ13C) and hydrogen (δD) isotope signatures of plant biomarkers extracted from the Lake Tulane sediment core as proxies of paleohydrology. The δ13C of plant biomarkers, such as n-alkanes and terpenoids, are determined, in part, by changes in water-use efficiency (WUE = Assimilation/Transpiration) in plant communities, which changes in response to shifts in mean annual precipitation. Plant δ13C values can, therefore, provide a rough indication of precipitation changes when other factors, such as plant community, are relatively stable throughout time. Paleohydrology is also recorded in the δD of plant leaf waxes, which are strongly controlled by precipitation δD. In this region, precipitation δD is negatively correlated with rainfall amount (i.e. the "amount" effect) and positively correlated with aridity. Thus, the δ13C and δD signatures of molecular plant biomarkers provide relative indicators of precipitation change, and when combined, provide a test of our hypothesis that vegetation changes in this region are driven

  8. Effect of temperature on the oxygen isotope composition of carbon dioxide (δ18O) prepared from carbonate minerals by reaction with polyphosphoric acid: An example of the rhombohedral CaCO 3-MgCO 3 group minerals

    NASA Astrophysics Data System (ADS)

    Crowley, Stephen F.

    2010-11-01

    Measurement of the ratio of 18O to 16O in CO 2(δ18O) produced from rhombohedral carbonate minerals in the compositional range CaCO 3-MgCO 3 by reaction with polyphosphoric acid (PPA), at temperatures of between 25 and 110 °C, shows that values of δ18O are linearly correlated ( r o > 0.99) with the reciprocal of absolute reaction temperature (K/ T). This observation is consistent with earlier studies documenting the effect of temperature on the kinetic fractionation of oxygen isotopes between parent carbonate and product CO 2 and H 2O during acid decomposition. However, analysis of the resultant data reveals: (1) a progressive increase in dδ18O/dT-1 with increasing Mg content, and (2) a significant variation in dδ18O/dT-1 between individual samples of carbonate of identical lattice symmetry and similar chemical composition. The overall increase in gradient with increasing Mg content is assumed to reflect cation radius dependent factors that control the bonding environment at the interface between the metal cation exposed at the surface of the reacting carbonate solid and a H 2CO 3 transitional species during disproportionation of H 2CO 3 to CO 2 and H 2O ("cluster model" of Guo et al., 2009). Phase-specific variations in dδ18O/dT-1 might result from differences in lattice structure variables (e.g., degree of lattice distortion, extent of positional disorder, and non-ideal mixing of substituent cations where carbonates depart from end-member compositions). Lattice structure variables may be dependent on geochemical conditions pertaining at the time of carbonate precipitation (e.g., biosynthetic versus inorganic precipitates) and suggests that dδ18O/dT-1 has the potential to vary, within limits, in response to both the chemical composition and structure of each carbonate sample. Because the oxygen isotope composition of carbonate minerals (δ18O) measured on the VPDB scale is defined by the oxygen isotope composition of CO 2 prepared from NBS19 (calcite) by

  9. Diurnal and seasonal variation in the carbon isotope composition of leaf dark-respired CO(2) in velvet mesquite (Prosopis velutina).

    PubMed

    Sun, Wei; Resco, Víctor; Williams, David G

    2009-10-01

    We evaluated diurnal and seasonal patterns of carbon isotope composition of leaf dark-respired CO(2) (delta(13)C(l)) in the C(3) perennial shrub velvet mesquite (Prosopis velutina) across flood plain and upland savanna ecosystems in the south-western USA. delta(13)C(l) of darkened leaves increased to maximum values late during daytime periods and declined gradually over night-time periods to minimum values at pre-dawn. The magnitude of the diurnal shift in delta(13)C(l) was strongly influenced by seasonal and habitat-related differences in soil water availability and leaf surface vapour pressure deficit. delta(13)C(l) and the cumulative flux-weighted delta(13)C value of photosynthates were positively correlated, suggesting that progressive (13)C enrichment of the CO(2) evolved by darkened leaves during the daytime mainly resulted from short-term changes in photosynthetic (13)C discrimination and associated shifts in the delta(13)C signature of primary respiratory substrates. The (13)C enrichment of dark-respired CO(2) relative to photosynthates across habitats and seasons was 4 to 6 per thousand at the end of the daytime period (1800 h), but progressively declined to 0 per thousand by pre-dawn (0300 h). The origin of night-time and daytime variations in delta(13)C(l) is discussed in terms of the carbon source(s) feeding respiration and the drought-induced changes in carbon metabolism.

  10. A process-based model for non-equilibrium clumped isotope effects in carbonates

    NASA Astrophysics Data System (ADS)

    Watkins, J. M.; Hunt, J. D.

    2015-12-01

    The equilibrium clumped isotope composition of carbonate minerals is independent of the composition of the aqueous solution. However, many carbonate minerals grow at rates that place them in a non-equilibrium regime with respect to carbon and oxygen isotopes with unknown consequences for clumped isotopes. We develop a process-based model that allows one to calculate the oxygen, carbon, and clumped isotope composition of calcite as a function of temperature, crystal growth rate, and solution pH. In the model, carbon and oxygen isotope fractionation occurs through the mass-dependent attachment/detachment kinetics of the isotopologues of HCO-3 and CO2-3 to and from the calcite surface, which in turn, influence the clumped isotope composition of calcite. At experimental and biogenic growth rates, the mineral is expected to inherit a clumped isotopic composition that is similar to that of the DIC pool, which helps to explain (1) why different organisms share the same clumped isotope versus temperature calibration curves, (2) why many inorganic calibration curves are slightly different from one another, and (3) why foraminifera, coccoliths, and deep sea corals can have near-equilibrium clumped isotope compositions but far-from-equilibrium carbon and oxygen isotope compositions. Some aspects of the model can be generalized to other mineral systems and should serve as a useful reference in future efforts to quantify kinetic clumped isotope effects.

  11. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Winschel, R.A.; Lancet, M.S.; Burke, F.P.

    1991-04-01

    This is the final report which was a thirty-four month project conducted to develop and demonstrate stable carbon isotope analysis as a method to quantitatively distinguish the source of carbon in products of coal/petroleum coprocessing. The work included assessing precision, accuracy, the range of application and the significance of selective isotopic fractionation effects. A method was devised to correct for selective isotopic fractionation errors. The method was demonstrated through application with samples from twelve continuous-unit coprocessing tests. A data base of carbon isotope analyses is appended. 21 refs.

  12. Modelling environmental controls on ecosystem photosynthesis and the carbon isotope composition of ecosystem-respired CO2 in a coastal Douglas-fir forest.

    PubMed

    Cai, Tiebo; Flanagan, Lawrence B; Jassal, Rachhpal S; Black, T Andrew

    2008-04-01

    We developed and applied an ecosystem-scale model that calculated leaf CO2 assimilation, stomatal conductance, chloroplast CO2 concentration and the carbon isotope composition of carbohydrate formed during photosynthesis separately for sunlit and shaded leaves within multiple canopy layers. The ecosystem photosynthesis model was validated by comparison to leaf-level gas exchange measurements and estimates of ecosystem-scale photosynthesis from eddy covariance measurements made in a coastal Douglas-fir forest on Vancouver Island. A good agreement was also observed between modelled and measured delta13C values of ecosystem-respired CO2 (deltaR). The modelled deltaR values showed strong responses to variation in photosynthetic photon flux density (PPFD), air temperature, vapour pressure deficit (VPD) and available soil moisture in a manner consistent with leaf-level studies of photosynthetic 13C discrimination. Sensitivity tests were conducted to evaluate the effect of (1) changes in the lag between the time of CO2 fixation and the conversion of organic matter back to CO2; (2) shifts in the proportion of autotrophic and heterotrophic respiration; (3) isotope fractionation during respiration; and (4) environmentally induced changes in mesophyll conductance, on modelled delta(R) values. Our results indicated that deltaR is a good proxy for canopy-level C(c)/C(a) and 13C discrimination during photosynthetic gas exchange, and therefore has several applications in ecosystem physiology.

  13. Changes in soil C-isotopic composition in an agroecosystem under Free Air Carbon dioxide Enrichment (FACE) treatment during a crop rotation period.

    PubMed

    Giesemann, Anette

    2005-01-01

    FACE (Free Air Carbon dioxide Enrichment) has been used since 1999 to evaluate the effects of future atmospheric CO(2) concentrations on an arable crop agroecosystem. The experiment conducted at the Institute of Agroecology at the Federal Research Centre in Braunschweig consists of a typical local crop rotation of winter barley, a cover crop, sugar beet and winter wheat. The atmospheric CO2 concentration of ambient air is about 375 ppm with a delta13C value of -7 to -9 per thousand, and 550 ppm (delta13C value = -20.2 per thousand) during daylight hours in the rings fumigated with additional CO2. Thus, the surplus C can be traced in the agricultural system. Over the course of the first experimental period (3-year crop rotation period), the C-isotopic composition and the C concentration in soil were monitored monthly. Plant samples were analysed according to the relevant developmental stages of the crop under cultivation. A 13C depletion was observed in plant parts, as well as in soil samples from the FACE rings under CO2 enrichment, indicating that labelled C has reached both respective ecosystem compartments. Albeit farming management practice (especially ploughing) leads to a mixing of 'old' and 'new' C compounds throughout all soil horizons down to the end of the ploughing layer and resulted in a heterogeneous distribution of newly formed C compounds in the soil, isotope analysis of soil C reflected where the surplus C went.

  14. Further carbon isotope measurements of LEW 88516

    NASA Technical Reports Server (NTRS)

    Wright, I. P.; Douglas, C.; Pillinger, C. T.

    1993-01-01

    Douglas et al. have previously analyzed the carbon content and isotopic composition of a crushed sample (sub-sample 13) of the shergottite, LEW 88516. The powder, which was from a relatively large portion of the meteorite in order to obtain a representative sample, was distributed amongst the scientific community. However, it is probable that the preparation procedure was not optimized for the purposes of carbon measurements. Indeed, it was found that LEW 88516,13 contained over 1200 ppm carbon, a concentration which is greater than that present in any other SNC meteorite. That a close relative, ALH A77005, contains only 141 ppm carbon seems to implicate the preparation procedure as being responsible for the apparently high carbon content of LEW 88516. However, it may also be the nature of the fine powder which has resulted in contamination. The observation of high carbon content in LEW 88516,13 highlights the extreme difficulty of trying to obtain representative samples of whole meteorites for this kind of investigation. Presented herein are some further measurements of LEW 88516 which should serve to clarify some of the issues raised by the previous investigation.

  15. Molecular and stable carbon isotopic compositions of saturated fatty acids within one sedimentary profile in the Shenhu, northern South China Sea: Source implications

    NASA Astrophysics Data System (ADS)

    Zhu, Xiaowei; Mao, Shengyi; Wu, Nengyou; Sun, Yongge; Guan, Hongxiang

    2014-10-01

    This study examined the distributions and stable carbon isotopic compositions of saturated fatty acids (SaFAs) in one 300 cm long sedimentary profile, which was named as Site4B in Shenhu, northern South China Sea. The concentrations of total SaFAs in sediments ranged from 1.80 to 10.16 μg/g (μg FA/g dry sediment) and showed an even-over-odd predominance in the carbon chain of C12 to C32, mostly with n-C16 and n-C18 being the two major components. The short-chain fatty acids (ScFAs; n-C12 to n-C18) mainly from marine microorganisms had average δ13C values of -26.7‰ to -28.2‰, whereas some terrigenous-sourced long-chain fatty acids (LcFAs; n-C21 to n-C32) had average δ13C values of -29.6‰ to -34.1‰. The other LcFAs (n-C24 & n-C26 ∼ n-C28; average δ13C values are -26.1‰ to -28.0‰) as well as n-C19 and n-C20 SaFAs (average δ13C values are -29.1‰ and -29.3‰, respectively) showed a mixed signal of carbon isotope compositions. The relative bioproductivity calculation (marine vs. terrigenous) demonstrated that most of organic carbon accumulation throughout the sedimentary profile was contributed by marine organism. The high marine productivity in Shenhu, South China Sea may be related to the hydrocarbon seepage which evidenced by diapiric structures. Interestingly, there is a sever fluctuation of terrigenous inputs around the depth of 97 cm below the seafloor (bsf), probably resulting from the influence of the Dansgaard-Oeschger events and the Younger Dryas event as revealed by 14C age measurements.

  16. Reprint of "Stable hydrogen and carbon isotopic compositions of long-chain (C21-C33) n-alkanes and n-alkenes in insects"

    NASA Astrophysics Data System (ADS)

    Chikaraishi, Yoshito; Kaneko, Masanori; Ohkouchi, Naohiko

    2013-06-01

    We report the molecular and stable isotopic (δD and δ13C) compositions of long-chain n-alkanes in common insects including the cabbage butterfly, swallowtail, wasp, hornet, grasshopper, and ladybug. Insect n-alkanes are potential candidates of the contamination of soil and sedimentary n-alkanes that are believed to be derived from vascular plant waxes. Long-chain n-alkanes (range C21-33; maximum C23-C29) are found to be abundant in the insects (31-781 μg/dry g), with a carbon preference index (CPI) of 5.1-31.5 and an average chain length (ACL) of 24.9-29.3. The isotopic compositions (mean ± 1σ, n = 33) of the n-alkanes are -195 ± 16‰ for hydrogen and -30.6 ± 2.4‰ for carbon. The insect n-alkanes are depleted in D by approximately 30-40‰ compared with wax n-alkanes from C3 (-155 ± 25‰) and C4 vascular plants (-167 ± 13‰), whereas their δ13C values fall between those of C3 (-36.2 ± 2.4‰) and C4 plants (-20.3 ± 2.4‰). Thus, the contribution of insect-derived n-alkanes to soil and sediment could potentially shift δD records of n-alkanes toward more negative values and potentially muddle the assumed original C3/C4 balance in the δ13C records of the soil and sedimentary n-alkanes. n-Alkenes are also found in three insects (swallowtail, wasp and hornet). They are more depleted in D relative to the same carbon numbered n-alkanes (δDn-alkene - δDn-alkane = -17 ± 16‰), but the δ13C values are almost identical to those of the n-alkanes (δ13Cn-alkene - δ13Cn-alkane = 0.1 ± 0.2‰). These results suggest that these n-alkenes are desaturated products of the same carbon numbered n-alkanes.

  17. Stable hydrogen and carbon isotopic compositions of long-chain (C21-C33) n-alkanes and n-alkenes in insects

    NASA Astrophysics Data System (ADS)

    Chikaraishi, Yoshito; Kaneko, Masanori; Ohkouchi, Naohiko

    2012-10-01

    We report the molecular and stable isotopic (δD and δ13C) compositions of long-chain n-alkanes in common insects including the cabbage butterfly, swallowtail, wasp, hornet, grasshopper, and ladybug. Insect n-alkanes are potential candidates of the contamination of soil and sedimentary n-alkanes that are believed to be derived from vascular plant waxes. Long-chain n-alkanes (range C21-33; maximum C23-C29) are found to be abundant in the insects (31-781 μg/dry g), with a carbon preference index (CPI) of 5.1-31.5 and an average chain length (ACL) of 24.9-29.3. The isotopic compositions (mean ± 1σ, n = 33) of the n-alkanes are -195 ± 16‰ for hydrogen and -30.6 ± 2.4‰ for carbon. The insect n-alkanes are depleted in D by approximately 30-40‰ compared with wax n-alkanes from C3 (-155 ± 25‰) and C4 vascular plants (-167 ± 13‰), whereas their δ13C values fall between those of C3 (-36.2 ± 2.4‰) and C4 plants (-20.3 ± 2.4‰). Thus, the contribution of insect-derived n-alkanes to soil and sediment could potentially shift δD records of n-alkanes toward more negative values and potentially muddle the assumed original C3/C4 balance in the δ13C records of the soil and sedimentary n-alkanes. n-Alkenes are also found in three insects (swallowtail, wasp and hornet). They are more depleted in D relative to the same carbon numbered n-alkanes (δDn-alkene - δDn-alkane = -17 ± 16‰), but the δ13C values are almost identical to those of the n-alkanes (δ13Cn-alkene - δ13Cn-alkane = 0.1 ± 0.2‰). These results suggest that these n-alkenes are desaturated products of the same carbon numbered n-alkanes.

  18. The isotopic characterization of carbon monoxide in the troposphere

    NASA Astrophysics Data System (ADS)

    Conny, Joseph M.

    The distributions of stable isotopes in trace atmospheric species are controlled mainly by the isotopic compositions of precursor molecules and isotope fractionation effects during production and removal of the species. Distributions of radioactive isotopes are controlled mainly by the isotopic compositions of precursor molecules and radioactive decay processes. As a result, through their isotopic compositions, atmospheric species are traceable to sources and sinks. Thus, isotopic compositions provide useful information for estimating source strengths and for understanding the importance of removal processes in the cycling of the species. The use of radioactive 14C and the stable isotopes ( 13C and 18O) are reviewed here for understanding production and removal processes of CO in the troposphere. Carbon monoxide is a critical component in atmospheric chemistry because of its large effect on levels of OH, the principal oxidant in the atmosphere. In the troposphere, this is due to relatively high concentrations of CO and a short lifetime (2-4 months). Initially, 14CO measurements were instrumental in estimating accurately the tropospheric lifetime. Since seasonal 14CO variation is controlled largely by OH, 14CO serves as an important surrogate measure of tropospheric OH. Global 14CO measurements have also been used to estimate the biogenic component of the global CO budget, specifically contributions from biomass burning, oxidized non-methane hydrocarbon (NMHC) emissions, oceans and plants. Research using 14CO measurements is also active in quantifying fossil and non-fossil urban emissions. Kinetic isotopic fractionation during production of 13CO and C 18O from reduced precursors allows one to distinguish, at least qualitatively, different varieties of CO based on seasonal tropospheric isotopic measurements. Difficulties in interpreting the stable isotopic record arise from large fractionation effects that obscure source isotopic signatures (in particular the oxygen

  19. Grosnaja ABCs: Magnesium isotope compositions

    NASA Technical Reports Server (NTRS)

    Goswami, J. N.; Srinivasan, G.; Ulyanov, A. A.

    1993-01-01

    Three CAI's from the Grosnaja CV3 chondrite were analyzed for their magnesium isotopic compositions by the ion microprobe. The selected CAI's represent three distinct types: GR4(compact Type A), GR7(Type B) and GR2(Type C). Petrographic studies indicate that all three Grosnaja inclusions were subjected to secondary alterations. The Type A CAI GR4 is primarily composed of melilite with spinel and pyroxene occurring as minor phases. The rim of the inclusion does not exhibit distinct layered structure and secondary alteration products (garnet, Fe-rich olivine and Na-rich plagioclase) are present in some localized areas near the rim region. The average major element compositions of different mineral phases in GR4 are given. Preliminary REE data suggest a depletion of HREE relative to LREE by about a factor of 3 without any clear indication of interelement fractionation. The CAI GR7 has textural and minerological characteristics similar to Type B inclusions. The REE data show a pattern that is similar to Group 6 with enrichment in Eu and Yb. In addition, a depletion of HREE compared to LREE is also evident in this object. Melilite composition shows a broad range of akermanite content (Ak(sub 15-55)). Detailed petrographic study is in progress. GR2 is a anorthite-rich Type C inclusion with large plagioclase laths intergrown with Ti-rich pyroxene. The average plagioclase composition is close to pure anorthite (An99).

  20. Carbon-isotopic analysis of dissolved acetate

    NASA Technical Reports Server (NTRS)

    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.

  1. Carbon-isotopic analysis of dissolved acetate.

    PubMed

    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.

  2. Impact of Mountaintop Mining/Valley Fill on the Stable Carbon Isotopic Composition and Concentration of Dissolved Organic Carbon and Dissolved Inorganic Carbon in Headwater Streams

    EPA Science Inventory

    Headwater streams are the dominant land-water interface across much of the landscape and provide many important ecological services. Cycling and transport of various carbon fractions, which serve as important food sources for downstream aquatic ecosystems, are among the important...

  3. Influence of Land Use on the Stable Carbon Isotopic Composition and Concentration of Dissolved Organic Carbon and Dissolved Inorganic Carbon in Georgia Piedmont Headwater Streams

    EPA Science Inventory

    Headwater streams are the dominant land-water interface across much of the landscape and provide many important ecological services. Cycling and transport of various carbon fractions, which serve as important food sources for downstream aquatic ecosystems, are among the important...

  4. PHOTOCHEMICALLY-INDUCED ALTERATION OF STABLE CARBON ISOTOPE RATIOS (DELTA C-13) IN TERRIGENOUS DISSOLVED ORGANIC CARBON

    EPA Science Inventory

    Exposure of riverine waters to natural sunlight initiated alterations in stable carbon isotope ratios (delta C-13) of the associated dissolved organic carbon (DOC). Water samples were collected from two compositionally distinct coastal river systems in the southeastern United Sta...

  5. Tracing the Fate of Enhanced Organic Carbon Production during a Southern Ocean Fe Fertilization Experiment using Natural Variations in Carbon and Nitrogen Isotopic Composition

    SciTech Connect

    Altabet, M.A.

    2005-02-05

    This project focused on the N and C natural stable isotope response during SOFeX--a purposeful iron (Fe) addition experiment in the Fe limited Southern Ocean. One purpose of the study was to determine if relief of phytoplankton Fe stress would increase productivity sufficiently to enhance C export from surface to deep waters. We proposed that N and C stable isotopes would be useful for tracing this export. Iron was added to waters north and south of the Antarctic Polar Front in waters to the southwest of New Zealand. While both sites have high-nutrient, low chlorophyll conditions (HNLC) typical of Fe limitation, [SiO4] a required nutrient for diatoms was low at the northerly site and high at the southern location. The most extensive coverage occurred at the southern site. Here, FeSO4 was added four different times over an {approx}two week period. We found that: (1) Particulate organic nitrogen and carbon in the mixed layer increased by a factor of 2-3 in response to the Fe addition in the southern patch. (2) PN accumulation and NO3- drawdown were both 1-2 {micro}M during the occupation of the bloom, suggesting retention of particulates within the mixed layer of the southern patch. (3) {sub 15}N of PN and of NO{sub 3}{sup -} increased by 1-2{per_thousand} as [NO{sub 3}{sup -}] decreased, and there is a clear contrast between in- and out-patch stations with respect to particulate {sub 15}N. The isotopic fractionation factor for NO{sub 3}{sup -} was near 5-6{per_thousand} and appears to have been unaffected by Fe fertilization. In contrast, there was little change in {delta}{sup 13}C. (4) The > 54 {micro}m size fraction was typically lighter than the 1-54 {micro}m size fraction by about 0.5 {per_thousand} in {delta}{sup 13}C. In the south patch, this difference increased as the bloom progressed, and with increasing PN concentration. This result may have been caused by large chain-forming diatoms responded to the Fe addition and were likely isotopically lighter than

  6. The carbon isotopic composition of soil respiration in the decade following disturbance by bark beetle or stem girdling

    NASA Astrophysics Data System (ADS)

    Chan, A.; Maurer, G. E.; Bowling, D. R.

    2013-12-01

    Recent outbreaks of mountain pine beetle have caused large-scale tree mortality in western North America, which can lead to fundamental changes in carbon cycling. When a tree is infested, the flow of photosynthate is disrupted. This causes the roots and their symbionts to die, eliminating the autotrophic component of soil respiration. Mycorrhizal fungi are enriched in 13C compared to plant tissues. As the dead fungal biomass is consumed by soil heterotrophs, the δ13C of CO2 in heterotrophic soil respiration may become more enriched as the fungal biomass is consumed. We investigated this response by measuring soil respiration in chronosequences of stem-girdled plots at the Niwot Ridge AmeriFlux site, and beetle-killed plots at the Fraser Experimental Forest, both in Colorado. Stem girdling was used to simulate beetle attack because it kills trees by a similar mechanism. Plots at Niwot Ridge included live trees and 7 years of girdled plots extending back to 2002. Plots at Fraser included live trees and three age classes of beetle-killed trees, within a similar chronosequence. We used manual soil-gas sampling at three depths, during the summers of 2011 and 2012, to determine if there is an isotopic effect associated with disturbance. Consistent with our expectations, in 2011, we found an enrichment in δ13C of approximately 1‰ in the two years following girdling which was absent in subsequent years. Although this pattern was also evident in 2012, the enrichment in δ13C during the same time period was about half that in 2011. At both Niwot and Fraser, in 2011, seasonal mean δ13C decreased by about 1‰ at all depths 3-4 years after disturbance, but returned to values close to control plots in the following 4-6 years. While we found a similar pattern at Fraser in 2012, we measured an enrichment of 1-1.5‰ at the OA interface at Niwot 8-10 years after disturbance, which was not found in 2011. It is possible this is due to the decomposition of woody biomass. At both

  7. Composite carbon foam electrode

    DOEpatents

    Mayer, S.T.; Pekala, R.W.; Kaschmitter, J.L.

    1997-05-06

    Carbon aerogels used as a binder for granulated materials, including other forms of carbon and metal additives, are cast onto carbon or metal fiber substrates to form composite carbon thin film sheets. The thin film sheets are utilized in electrochemical energy storage applications, such as electrochemical double layer capacitors (aerocapacitors), lithium based battery insertion electrodes, fuel cell electrodes, and electrocapacitive deionization electrodes. The composite carbon foam may be formed by prior known processes, but with the solid particles being added during the liquid phase of the process, i.e. prior to gelation. The other forms of carbon may include carbon microspheres, carbon powder, carbon aerogel powder or particles, graphite carbons. Metal and/or carbon fibers may be added for increased conductivity. The choice of materials and fibers will depend on the electrolyte used and the relative trade off of system resistivity and power to system energy. 1 fig.

  8. Composite carbon foam electrode

    DOEpatents

    Mayer, Steven T.; Pekala, Richard W.; Kaschmitter, James L.

    1997-01-01

    Carbon aerogels used as a binder for granularized materials, including other forms of carbon and metal additives, are cast onto carbon or metal fiber substrates to form composite carbon thin film sheets. The thin film sheets are utilized in electrochemical energy storage applications, such as electrochemical double layer capacitors (aerocapacitors), lithium based battery insertion electrodes, fuel cell electrodes, and electrocapacitive deionization electrodes. The composite carbon foam may be formed by prior known processes, but with the solid particles being added during the liquid phase of the process, i.e. prior to gelation. The other forms of carbon may include carbon microspheres, carbon powder, carbon aerogel powder or particles, graphite carbons. Metal and/or carbon fibers may be added for increased conductivity. The choice of materials and fibers will depend on the electrolyte used and the relative trade off of system resistivty and power to system energy.

  9. A Negative Relationship between Foliar Carbon Isotope Composition and Mass-Based Nitrogen Concentration on the Eastern Slope of Mount Gongga, China

    PubMed Central

    Li, Jiazhu; Wang, Guoan; Zhang, Runan; Li, Li

    2016-01-01

    Plants adopt ecological strategy to resist environmental changes and increase their resource-use efficiency. The ecological strategy includes changes in physiological traits and leaf morphology, which may result in simultaneous variations in foliar N concentration and the ratio of intercellular CO2 concentration to ambient CO2 concentration (ci/ca). This in turn links to foliar carbon isotope discrimination, and thus, a relationship between foliar N concentration and foliar carbon isotope composition (δ13C) is expected. To understand how plants integrate their structural and physiological resistance to environmental changes, the relationship between foliar N concentration and foliarδ13C has been assessed intensively, especially the correlation between area-based N concentration (Narea) and δ13C.Less effort has been dedicated to the examination of the relationship between mass-based N concentration(Nmass) and δ13C. Studies on the Nmass–δ13C relationship, especially those including a large amount of data and species, will enhance our understanding of leaf economics and benefit ecological modeling. The present study includes an intensive investigation into this relationship by measuring foliar Nmass and δ13C in a large number of plant species grown on the eastern slope of Mount Gongga, China. This study shows that foliar Nmass decreases with increasing δ13C, which is independent of functional group, vegetation type, and altitude. This suggests that a negative correlation between Nmass and δ13C may be a general pattern for plants grown not only on Mount Gongga, but also in other areas. PMID:27870885

  10. The Oxygen Isotopic Composition of the Sun

    NASA Astrophysics Data System (ADS)

    McKeegan, K. D.; Kallio, A.; Heber, V. S.; Jarzebinski, G.; Mao, P.; Coath, C.; Kunihiro, T.; Wiens, R. C.; Judith, A.; Burnett, D. S.

    2010-12-01

    An accurate and precise determination of the oxygen isotopic composition of the Sun is the highest priority scientific goal of the Genesis Mission [1] as such data would provide a baseline from which one could interpret the oxygen isotopic anomalies found at all spatial scales in inner solar system materials. We have measured oxygen isotope compositions of implanted solar wind in 40 spots along a radial traverse of the Genesis SiC target sample 60001 by depth profiling with the UCLA MegaSIMS [2]. Mass-dependent fractionation induced by the solar wind concentrator [3] ion optics was corrected by comparison of the concentrator 22Ne/20Ne with that measured in a bulk solar wind target (diamond-like carbon on Si, [4]). The solar wind captured at L1 has an isotopic composition of (δ18O, δ17O) ≈ (-99, -79)‰, a value which is far removed from the terrestrial mass fractionation line. Profiles from the central portion of the target, where solar concentrations are highest and background corrections minimal, yield a mean Δ17O = -28.3 ± 1.8 ‰ indicating that the Earth and other planetary materials from the inner solar system are highly depleted in 16O relative to the solar wind. A mass-dependent fractionation of ~ -20%/amu in the acceleration of solar wind is required if we hypothesize that the photospheric oxygen isotope value, which represents the bulk starting composition of the solar system, is on the 16O-mixing line characteristic of refractory phase in primitive meteorites [5]. With this assumption, our preferred value for the bulk solar oxygen isotope composition is δ18O ≈ δ17O ≈ -57‰. A mechanism is required to fractionate oxygen isotopes in a non-mass-dependent manner to deplete 16O by ~6 to 7% in the rocky materials of the solar nebula. As oxygen is the third most abundant element in the solar system, and the most abundant in the terrestrial planets, this mechanism must operate on a large scale. Isotope-selective photochemistry, for example as in

  11. Carbon isotopic studies of organic matter in Precambrian rocks.

    NASA Technical Reports Server (NTRS)

    Oehler, D. Z.; Schopf, J. W.; Kvenvolden, K. A.

    1972-01-01

    A survey has been undertaken of the carbon composition of the total organic fraction of a suite of Precambrian sediments to detect isotopic trends possibly correlative with early evolutionary events. Early Precambrian cherts of the Fig Tree and upper and middle Onverwacht groups of South Africa were examined for this purpose. Reduced carbon in these cherts was found to be isotopically similar to photosynthetically produced organic matter of younger geological age. Reduced carbon in lower Onverwacht cherts was found to be anomalously heavy; it is suggested that this discontinuity may reflect a major event in biological evolution.

  12. Nocturnal and seasonal patterns of carbon isotope composition of leaf dark-respired carbon dioxide differ among dominant species in a semiarid savanna.

    PubMed

    Sun, Wei; Resco, Víctor; Williams, David G

    2010-10-01

    The C isotope composition of leaf dark-respired CO(2) (δ(13)C(l)) integrates short-term metabolic responses to environmental change and is potentially recorded in the isotopic signature of ecosystem-level respiration. Species differences in photosynthetic pathway, resource acquisition and allocation patterns, and associated isotopic fractionations at metabolic branch points can influence δ(13)C(l), and differences are likely to be modified by seasonal variation in drought intensity. We measured δ(13)C(l) in two deep-rooted C(3) trees (Prosopis velutina and Celtis reticulata), and two relatively shallow-rooted perennial herbs (a C(3) dicot Viguiera dentata and a C(4) grass Sporobolus wrightii) in a floodplain savanna ecosystem in southeastern Arizona, USA during the dry pre-monsoon and wet monsoon seasons. δ(13)C(l) decreased during the nighttime and reached minimum values at pre-dawn in all species. The magnitude of nocturnal shift in δ(13)C(l) differed among species and between pre-monsoon and monsoon seasons. During the pre-monsoon season, the magnitude of the nocturnal shift in δ(13)C(l) in the deep-rooted C(3) trees P. velutina (2.8 ± 0.4‰) and C. reticulata (2.9 ± 0.2‰) was greater than in the C(3) herb V. dentata (1.8 ± 0.4‰) and C(4) grass S. wrightii (2.2 ± 0.4‰). The nocturnal shift in δ(13)C(l) in V. dentata and S. wrightii increased to 3.2 ± 0.1‰ and 4.6 ± 0.6‰, respectively, during the monsoon season, but in C(3) trees did not change significantly from pre-monsoon values. Cumulative daytime net CO(2) uptake was positively correlated with the magnitude of the nocturnal decline in δ(13)C(l) across all species, suggesting that nocturnal δ(13)C(l) may be controlled by (13)C/(12)C fractionations associated with C substrate availability and C metabolite partitioning. Nocturnal patterns of δ(13)C(l) in dominant plant species in the semiarid savanna apparently have predictable responses to seasonal changes in water

  13. Distribution, abundance and carbon isotopic composition of gaseous hydrocarbons in Big Soda Lake, Nevada: An alkaline, meromictic lake

    USGS Publications Warehouse

    Oremland, R.S.; Des Marais, D.J.

    1983-01-01

    Distribution and isotopic composition (??13C) of low molecular weight hydrocarbon gases were studied in Big Soda Lake (depth = 64 m), an alkaline, meromictic lake with permanently anoxic bottom waters. Methane increased with depth in the anoxic mixolimnion (depth = 20-35 m), reached uniform concentrations (55 ??M/l) in the monimolimnion (35-64 m) and again increased with depth in monimolimnion bottom sediments (>400 ??M/kg below 1 m sub-bottom depth). The ??13C[CH4] values in bottom sediment below 1 m sub-bottom depth (<-70 per mil) increased with vertical distance up the core (??13C[CH4] = -55 per mil at sediment surface). Monimolimnion ??13C[CH4] values (-55 to -61 per mil) were greater than most ??13C[CH4] values found in the anoxic mixolimnion (92% of samples had ??13C[CH4] values between -20 and -48 per mil). No significant concentrations of ethylene or propylene were found in the lake. However ethane, propane, isobutane and n-butane concentrations all increased with water column depth, with respective maximum concentrations of 260, 80, 23 and 22 nM/l encountered between 50-60 m depth. Concentrations of ethane, propane and butanes decreased with depth in the bottom sediments. Ratios of CH4 [C2H6 + C3H8] were high (250-620) in the anoxic mixolimnion, decreased to ~161 in the monimolimnion and increased with depth in the sediment to values as high as 1736. We concluded that methane has a biogenic origin in both the sediments and the anoxic water column and that C2-C4 alkanes have biogenic origins in the monimolimnion water and shallow sediments. The changes observed in ??13C[CH4] and CH4 (C2H6 + C3H8) with depth in the water column and sediments are probably caused by bacteria] processes. These might include anaerobic methane oxidation and different rates of methanogenesis and C2 to C4 alkane production by microorganisms. ?? 1983.

  14. Automated determination of the stable carbon isotopic composition (δ13C) of total dissolved inorganic carbon (DIC) and total nonpurgeable dissolved organic carbon (DOC) in aqueous samples: RSIL lab codes 1851 and 1852

    USGS Publications Warehouse

    Révész, Kinga M.; Doctor, Daniel H.

    2014-01-01

    The purposes of the Reston Stable Isotope Laboratory (RSIL) lab codes 1851 and 1852 are to determine the total carbon mass and the ratio of the stable isotopes of carbon (δ13C) for total dissolved inorganic carbon (DIC, lab code 1851) and total nonpurgeable dissolved organic carbon (DOC, lab code 1852) in aqueous samples. The analysis procedure is automated according to a method that utilizes a total carbon analyzer as a peripheral sample preparation device for analysis of carbon dioxide (CO2) gas by a continuous-flow isotope ratio mass spectrometer (CF-IRMS). The carbon analyzer produces CO2 and determines the carbon mass in parts per million (ppm) of DIC and DOC in each sample separately, and the CF-IRMS determines the carbon isotope ratio of the produced CO2. This configuration provides a fully automated analysis of total carbon mass and δ13C with no operator intervention, additional sample preparation, or other manual analysis. To determine the DIC, the carbon analyzer transfers a specified sample volume to a heated (70 °C) reaction vessel with a preprogrammed volume of 10% phosphoric acid (H3PO4), which allows the carbonate and bicarbonate species in the sample to dissociate to CO2. The CO2 from the reacted sample is subsequently purged with a flow of helium gas that sweeps the CO2 through an infrared CO2 detector and quantifies the CO2. The CO2 is then carried through a high-temperature (650 °C) scrubber reactor, a series of water traps, and ultimately to the inlet of the mass spectrometer. For the analysis of total dissolved organic carbon, the carbon analyzer performs a second step on the sample in the heated reaction vessel during which a preprogrammed volume of sodium persulfate (Na2S2O8) is added, and the hydroxyl radicals oxidize the organics to CO2. Samples containing 2 ppm to 30,000 ppm of carbon are analyzed. The precision of the carbon isotope analysis is within 0.3 per mill for DIC, and within 0.5 per mill for DOC.

  15. Carbon isotope compositions (δ(13) C) of leaf, wood and holocellulose differ among genotypes of poplar and between previous land uses in a short-rotation biomass plantation.

    PubMed

    Verlinden, M S; Fichot, R; Broeckx, L S; Vanholme, B; Boerjan, W; Ceulemans, R

    2015-01-01

    The efficiency of water use to produce biomass is a key trait in designing sustainable bioenergy-devoted systems. We characterized variations in the carbon isotope composition (δ(13) C) of leaves, current year wood and holocellulose (as proxies for water use efficiency, WUE) among six poplar genotypes in a short-rotation plantation. Values of δ(13) Cwood and δ(13) Cholocellulose were tightly and positively correlated, but the offset varied significantly among genotypes (0.79-1.01‰). Leaf phenology was strongly correlated with δ(13) C, and genotypes with a longer growing season showed a higher WUE. In contrast, traits related to growth and carbon uptake were poorly linked to δ(13) C. Trees growing on former pasture with higher N-availability displayed higher δ(13) C as compared with trees growing on former cropland. The positive relationships between δ(13) Cleaf and leaf N suggested that spatial variations in WUE over the plantation were mainly driven by an N-related effect on photosynthetic capacities. The very coherent genotype ranking obtained with δ(13) C in the different tree compartments has some practical outreach. Because WUE remains largely uncoupled from growth in poplar plantations, there is potential to identify genotypes with satisfactory growth and higher WUE.

  16. Isotopic Compositions of the Elements, 2001

    NASA Astrophysics Data System (ADS)

    Böhlke, J. K.; de Laeter, J. R.; De Bièvre, P.; Hidaka, H.; Peiser, H. S.; Rosman, K. J. R.; Taylor, P. D. P.

    2005-03-01

    The Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry completed its last review of the isotopic compositions of the elements as determined by isotope-ratio mass spectrometry in 2001. That review involved a critical evaluation of the published literature, element by element, and forms the basis of the table of the isotopic compositions of the elements (TICE) presented here. For each element, TICE includes evaluated data from the "best measurement" of the isotope abundances in a single sample, along with a set of representative isotope abundances and uncertainties that accommodate known variations in normal terrestrial materials. The representative isotope abundances and uncertainties generally are consistent with the standard atomic weight of the element Ar(E) and its uncertainty U[Ar(E)] recommended by CAWIA in 2001.

  17. Isotopic compositions of the elements, 2001

    USGS Publications Warehouse

    Böhlke, J.K.; De Laeter, J. R.; De Bievre, P.; Hidaka, H.; Peiser, H.S.; Rosman, K.J.R.; Taylor, P.D.P.

    2005-01-01

    The Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry completed its last review of the isotopic compositions of the elements as determined by isotope-ratio mass spectrometry in 2001. That review involved a critical evaluation of the published literature, element by element, and forms the basis of the table of the isotopic compositions of the elements (TICE) presented here. For each element, TICE includes evaluated data from the "best measurement" of the isotope abundances in a single sample, along with a set of representative isotope abundances and uncertainties that accommodate known variations in normal terrestrial materials. The representative isotope abundances and uncertainties generally are consistent with the standard atomic weight of the element A r(E) and its uncertainty U[Ar(E)] recommended by CAWIA in 2001. ?? 2005 American Institute of Physics.

  18. Carbon and hydrogen isotopic compositions of stratospheric methane: 1. High-precision observations from the NASA ER-2 aircraft

    NASA Astrophysics Data System (ADS)

    Rice, A. L.; Tyler, S. C.; McCarthy, M. C.; Boering, K. A.; Atlas, E.

    2003-08-01

    Measurements of δ13C and δD of atmospheric CH4 from whole air samples collected in the upper troposphere and lower stratosphere aboard the NASA ER-2 aircraft during the SOLVE (2000), POLARIS (1997), and STRAT (1996) campaigns are reported. Samples cover latitudes from 1°S to 89°N and altitudes from 11 to 21 km, providing CH4 mixing ratios that range from 1744 to 716 ppbv. Measurements of isotope ratios were made by continuous-flow gas chromatography isotope ratio mass spectrometry which provides high-precision analyses on 60 ml aliquots of air. These measurements comprise the first upper atmosphere isotopic CH4 data set to date using this technique and the most extensive with respect to latitude and season in any case. Values of δ13C-CH4 on the V-PDB scale range from -47.28‰ near the tropical tropopause to -34.05‰ in the high northern latitude stratosphere. Values of δD on the V-SMOW scale range from -90.9‰ to +26.4‰. Correlations of isotope ratios with CH4 mixing ratios show enrichment in the heavy isotopes as CH4 mixing ratios decrease due to kinetic isotope effects associated with oxidation by reaction with OH, Cl, and O(1D). Empirical fractionation factors are found to be highly dependent on the range of CH4 mixing ratio considered, increasing with decreasing mixing ratio. Systematic nonlinearity in a Rayleigh fractionation model suggests a range of stratospheric fractionation factors, αCstrat = 1.0108 ± 0.0004 to 1.0204 ± 0.0004 (2σ) and αHstrat = 1.115 ± 0.008 to 1.198 ± 0.008 (2σ), from high to low CH4 mixing ratio, respectively. The variation in α over the range in mixing ratios reflect changes in partitioning between CH4 sink reactions in different regions of the stratosphere. In Part 1, these new high-precision observations are discussed and compared with other stratospheric and tropospheric isotope measurements. In Part 2 [, 2003] the observations are compared with 2-D model results, and implications for the kinetic isotope effects

  19. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Lancet, M.S.; Winschel, R.A.; Burke, F.P.

    1991-01-01

    Consol R D is developing and demonstrating stable carbon isotope analysis as a method to quantitatively distinguish coal-derived and petroleum-derived carbon in products from coal/petroleum coprocessing. The approach taken is to develop the method, then demonstrate its application an authentic continuous-unit products. The experimental details used for stable carbon isotope analyses by the organization that performs most of those analyses under this contract are described. A method was developed previously under this contract to correct the carbon sourcing calculations performed from stable carbon isotope analyses for selective isotopic fractionation. The method relies on three assumptions. This quarter, a study was completed to define the sensitivity of the carbon sourcing results to errors in the assumptions. Carbon contents and carbon isotope ratios were determined for the available feeds and product fractions from HRI bench-scale coprocessing Run 238-10 (Texas lignite/Hondo vacuum still bottoms (VSB), Texas lignite/Cold Lake VSB and Westerholt coal/Cold Lake VSB). These data were used for carbon sourcing calculations and individual feedstock conversion calculations. A previously devised means for correcting for selective isotope fractionation was applied. 6 refs., 30 figs., 16 tabs.

  20. Diel variations in stream chemistry and isotopic composition of dissolved inorganic carbon, upper Clark Fork River, Montana, USA

    USGS Publications Warehouse

    Parker, Stephen R.; Gammons, Christopher H.; Poulson, Simon R.; DeGrandpre, Michael D.

    2007-01-01

    Many rivers undergo diel (24-h) concentration fluctuations of pH, dissolved gases, trace metals, nutrients, and other chemical species. A study conducted in 1994 documented such behavior in the upper Clark Fork River, Montana, a stream whose headwaters have been severely impacted by historic metal mining, milling, and smelting. The purpose of the present investigation was to expand on these earlier findings by conducting simultaneous diel samplings at two sites on the upper Clark Fork River separated by 2.5 h of stream travel time. By monitoring two stations, it was possible to more closely examine the processes that control temporal and spatial gradients in stream chemistry. Another objective was to examine diel changes in the δ13C composition of dissolved inorganic C (DIC) and their relationship to biological activity in the stream. The most important findings of this study include: (1) concentrations of dissolved and particulate heavy metals increased during the night and decreased during the day, in agreement with previous work; (2) these changes were positively correlated to diel changes in pH, dissolved O2, and water temperature; (3) dissolved concentrations increased during the night at the lower site, but showed the opposite behavior at the upper site; and (4) diel changes in δ13C-DIC were noted at both sites, although the timing and magnitudes of the cycles differed. Hypotheses to explain the first two observations include: cyclic co-precipitation of divalent metals with carbonate minerals; pH- and temperature-dependent sorption of metal cations onto the streambed and suspended particles; or photosynthetically enhanced oxidation and removal of Fe and Mn oxides at biofilm surfaces during the daytime. The latter model explains the majority of the field observations, including night-time increases in particulate forms of Fe and other elements.

  1. The origin and isotopic composition of dissolved sulfide in groundwater from carbonate aquifers in Florida and Texas

    USGS Publications Warehouse

    Rye, R.O.; Back, W.; Hanshaw, B.B.; Rightmire, C.T.; Pearson, F.J.

    1981-01-01

    The ??34S values of dissolved sulfide and the sulfur isotope fractionations between dissolved sulfide and sulfate species in Floridan ground water generally correlate with dissolved sulfate concentrations which are related to flow patterns and residence time within the aquifer. The dissolved sulfide derives from the slow in situ biogenic reduction of sulfate dissolved from sedimentary gypsum in the aquifer. In areas where the water is oldest, the dissolved sulfide has apparently attained isotopic equilibrium with the dissolved sulfate (??34S = 65 per mil) at the temperature (28??C) of the system. This approach to equilibrium reflects an extremely slow reduction rate of the dissolved sulfate by bacteria; this slow rate probably results from very low concentrations of organic matter in the aquifer. In the reducing part of the Edwards aquifer, Texas, there is a general down-gradient increase in both dissolved sulfide and sulfate concentrations, but neither the ??34S values of sulfide nor the sulfide-sulfate isotope fractionation correlates with the ground-water flow pattern. The dissolved sulfide species appear to be derived primarily from biogenic reduction of sulfate ions whose source is gypsum dissolution although upgradient diffusion of H2S gas from deeper oil field brines may be important in places. The sulfur isotope fractionation for sulfide-sulfate (about 38 per mil) is similar to that observed for modern oceanic sediments and probably reflects moderate sulfate reduction in the reducing part of the aquifer owing to the higher temperature and significant amount of organic matter present; contributions of isotopically heavy H2S from oil field brines are also possible. ?? 1981.

  2. The origin of the Maozu carbonate-hosted Pb-Zn deposit, southwest China: Constrained by C-O-S-Pb isotopic compositions and Sm-Nd isotopic age

    NASA Astrophysics Data System (ADS)

    Zhou, Jiaxi; Huang, Zhilong; Yan, Zaifei

    2013-09-01

    The Maozu Pb-Zn deposit, located on the western margin of the Yangtze Block, southwest China, is a typical carbonate-hosted deposit in the Sichuan-Yunnan-Guizhou Pb-Zn metallogenic province with Pb + Zn reserves of about 2.0 million tonnes grading 4.15 wt.% Pb and 7.25 wt.% Zn. Its ore bodies are hosted in Sinian (635-541 Ma) Dengying Formation dolostone and show stratiform, vein and irregular textures. Ores are composed of sphalerite, galena, pyrite, calcite, dolomite, quartz and fluorite with massive, banded, disseminated and veined structures. The C-O-Sm-Nd isotopic compositions of hydrothermal calcites and S-Pb isotopic compositions of sulfides were analyzed to constrain the origin of the Maozu deposit. δ13CPDB and δ18OSMOW values of hydrothermal calcites range from -3.7‰ to -2.0‰ and +13.8‰ to +17.5‰, respectively, and plot near the marine carbonate rocks field in a plot of δ13CPDB vs. δ18OSMOW, with a negative correlation. It suggests that CO2 in the hydrothermal fluids was mainly originated from marine carbonate rocks, with limited influence from sedimentary organic matter. δ34SCDT values of sulfides range from +9.9‰ to +19.2‰, similar to that of Cambrian to Triassic seawater sulfate (+15‰ to +35‰) and evaporate (+15‰ to +30‰) in the Cambrian to Triassic sedimentary strata. It suggests that reduced sulfur was derived from evaporate in sedimentary strata by thermo chemical sulfate reduction. Sulfides have low radiogenic Pb isotope compositions (206Pb/204Pb = 18.129-18.375, 207Pb/204Pb = 15.640-15.686 and 208Pb/204Pb = 38.220-38.577) that plot in the field between upper crust and the orogenic belt evolution curve in the plot of 207Pb/204Pb vs. 206Pb/204Pb, and similar to that of age corrected Proterozoic basement rocks (Dongchuan and Kunyang Groups). This indicates that ore-forming metals were mainly derived from basement rocks. Hydrothermal calcite yields a Sm-Nd isotopic age of 196 ± 13 Ma, possibly reflecting the timing of Pb

  3. Stable Carbon Isotope Composition and Stomatal Density of the Conifer Genus Frenelopsis: Effect of pCO2, Species and Soil Salinity

    NASA Astrophysics Data System (ADS)

    Aucour, A.; Gomez, B.; Thevenard, F.; Sheppard, S.

    2004-05-01

    Experimental studies indicate that some modern conifers adjust their stomatal numbers in response to variations of atmospheric pCO2, suggesting that fossil conifer leaves may provide a proxy of pCO2. The stable carbon isotope composition of plants provides an additional constraint on the conditions during plant growth as it is known to vary, for a single species, with the δ 13C of the source CO2, and environmental factors such as soil salinity and water content. Our objectives were to document the variation of the stable carbon isotope composition of the fossil Coniferale Frenelopsis through the Cretaceous and to decipher the effect of pCO2, environmental and genetic factors on the fossil record. The leaf cuticles of Frenelopsis present a large variation in δ 13C values from 27 ‰ for F. ugnaensis growing on freshwater lake shores to 21 ‰ for species growing on brackish to marine environments. The species growing on freshwater lake shore presents an increase in 13C through the Barremian that is consistent with an increase in aridity. It presents a low stomatal density (SD) and index (SI: stomates over stomates plus epidermal cells). Comparison of the SD and SI within a single population shows that the variability in SD essentially reflects that of the cellular size and growth rate. The δ 13C values of species growing in brackish to marine environment are all similar but higher than freshwater ones in the late Albian. They decrease in the Cenomanian, with a much larger intra-population variability. This shift can be related to a switch from marine to brackish conditions as well as to more global change. SD and SI are higher for the late Albian-Cenomanian cuticles and appear not sensitive to the environmental change (presumably a switch from marine to more brackish conditions) recorded in the δ 13C. The large variability in both SD and SI within the studied populations in the marine-brackish environment appears to be related to change in the stomates over

  4. Biosynthetic and environmental effects on the stable carbon isotopic compositions of anteiso- (3-methyl) and iso- (2-methyl) alkanes in tobacco leaves.

    PubMed

    Grice, Kliti; Lu, Hong; Zhou, Youping; Stuart-Williams, Hilary; Farquhar, Graham D

    2008-11-01

    Nicotiana tabacum is the only plant known to synthesise large quantities of anteiso- (3-methyl) alkanes and iso- (2-methyl) alkanes. We investigated the carbon isotope ratios of individual long-chain n-alkanes, anteiso- and iso-alkanes (in the C(29)-C(33) carbon number range) extracted from tobacco grown in chambers under controlled conditions to confirm the pathway used by the tobacco plant to synthesise these particular lipids and to examine whether environmental data are recorded in these compounds. Tobacco was grown under differing temperatures, water availabilities and light intensities in order to control its stable carbon isotope ratios and evaluate isotopic fractionations associated with the synthesis of these particular lipids. The anteiso-alkanes were found to have a predominant even-carbon number distribution (maximising at C(32)), whereas the iso-alkanes exhibit an odd-carbon number distribution (maximising at C(31)). Iso-alkanes were relatively more abundant than the anteiso-alkanes and only two anteiso-alkanes (C(30) and C(32)) were observed. The anteiso-alkanes and iso-alkanes were found to be enriched in (13)C by 2.8-4.3 per thousand and 0-1.8 per thousand compared to the n-alkanes, respectively, consistent with different biosynthetic precursors. The assumed precursor for the odd-carbon-numbered iso-alkanes is iso-butyryl-CoA (a C(4) unit derived from valine) followed by subsequent elongation of C(2) units and then decarboxylation. The assumed precursor for even-carbon-numbered anteiso-alkanes is alpha-methylbutyryl-CoA (a C(5) unit derived from isoleucine) and subsequent elongation by C(2) units followed by decarboxylation. The ratio of carbon atoms derived from alpha-methylbutyryl-CoA and subsequent C(2) units (from malonyl-CoA) is 1:5 for the biosynthesis of a C(30)anteiso-alkane. The ratio of carbon atoms derived from iso-butyryl-CoA and subsequent C(2) units (from malonyl-CoA) is 4:25 for the synthesis of a C(29)iso-alkane. An order of (13)C

  5. The Effect of the Interannual Variability of the OH Sink on the Interannual Variability of the Atmospheric Methane Mixing Ratio and Carbon Stable Isotope Composition

    NASA Astrophysics Data System (ADS)

    Guillermo Nuñez Ramirez, Tonatiuh; Houweling, Sander; Marshall, Julia; Williams, Jason; Brailsford, Gordon; Schneising, Oliver; Heimann, Martin

    2013-04-01

    The atmospheric hydroxyl radical concentration (OH) varies due to changes in the incoming UV radiation, in the abundance of atmospheric species involved in the production, recycling and destruction of OH molecules and due to climate variability. Variability in carbon monoxide emissions from biomass burning induced by El Niño Southern Oscillation are particularly important. Although the OH sink accounts for the oxidation of approximately 90% of atmospheric CH4, the effect of the variability in the distribution and strength of the OH sink on the interannual variability of atmospheric methane (CH4) mixing ratio and stable carbon isotope composition (δ13C-CH4) has often been ignored. To show this effect we simulated the atmospheric signals of CH4 in a three-dimensional atmospheric transport model (TM3). ERA Interim reanalysis data provided the atmospheric transport and temperature variability from 1990 to 2010. We performed simulations using time dependent OH concentration estimations from an atmospheric chemistry transport model and an atmospheric chemistry climate model. The models assumed a different set of reactions and algorithms which caused a very different strength and distribution of the OH concentration. Methane emissions were based on published bottom-up estimates including inventories, upscaled estimations and modeled fluxes. The simulations also included modeled concentrations of atomic chlorine (Cl) and excited oxygen atoms (O(1D)). The isotopic signal of the sources and the fractionation factors of the sinks were based on literature values, however the isotopic signal from wetlands and enteric fermentation processes followed a linear relationship with a map of C4 plant fraction. The same set of CH4emissions and stratospheric reactants was used in all simulations. Two simulations were done per OH field: one in which the CH4 sources were allowed to vary interannually, and a second where the sources were climatological. The simulated mixing ratios and

  6. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Lancet, M.S.; Winschel, R.A.; Burke, F.P.

    1991-01-01

    The purpose of obtaining stable carbon isotope analyses of coprocessing products is to determine the amount of coal (or petroleum) carbon that is present in any reaction product. This carbon-sourcing of distillate fractions, soluble resid, and insoluble organic matter, etc. is useful in modeling reactions, and evaluating synergistic effects if they exist.

  7. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Lancet, M.S.; Winschel, R.A.; Burke, F.P.

    1991-12-31

    The purpose of obtaining stable carbon isotope analyses of coprocessing products is to determine the amount of coal (or petroleum) carbon that is present in any reaction product. This carbon-sourcing of distillate fractions, soluble resid, and insoluble organic matter, etc. is useful in modeling reactions, and evaluating synergistic effects if they exist.

  8. Strontium Isotopic Composition of Paleozoic Carbonate Rocks in the Nevada Test Site Vicinity, Clark, Lincoln, and Nye Counties, Nevada and Inyo County, California.

    SciTech Connect

    James B. Paces; Zell E. Peterman; Kiyoto Futa; Thomas A. Oliver; and Brian D. Marshall.

    2007-08-07

    Ground water moving through permeable Paleozoic carbonate rocks represents the most likely pathway for migration of radioactive contaminants from nuclear weapons testing at the Nevada Test Site, Nye County, Nevada. The strontium isotopic composition (87Sr/86Sr) of ground water offers a useful means of testing hydrochemical models of regional flow involving advection and reaction. However, reaction models require knowledge of 87Sr/86Sr data for carbonate rock in the Nevada Test Site vicinity, which is scarce. To fill this data gap, samples of core or cuttings were selected from 22 boreholes at depth intervals from which water samples had been obtained previously around the Nevada Test Site at Yucca Flat, Frenchman Flat, Rainier Mesa, and Mercury Valley. Dilute acid leachates of these samples were analyzed for a suite of major- and trace-element concentrations (MgO, CaO, SiO2, Al2O3, MnO, Rb, Sr, Th, and U) as well as for 87Sr/86Sr. Also presented are unpublished analyses of 114 Paleozoic carbonate samples from outcrops, road cuts, or underground sites in the Funeral Mountains, Bare Mountain, Striped Hills, Specter Range, Spring Mountains, and ranges east of the Nevada Test Site measured in the early 1990's. These data originally were collected to evaluate the potential for economic mineral deposition at the potential high-level radioactive waste repository site at Yucca Mountain and adjacent areas (Peterman and others, 1994). Samples were analyzed for a suite of trace elements (Rb, Sr, Zr, Ba, La, and Ce) in bulk-rock powders, and 87Sr/86Sr in partial digestions of carbonate rock using dilute acid or total digestions of silicate-rich rocks. Pre-Tertiary core samples from two boreholes in the central or western part of the Nevada Test Site also were analyzed. Data are presented in tables and summarized in graphs; however, no attempt is made to interpret results with respect to ground-water flow paths in this report. Present-day 87Sr/86Sr values are compared to values

  9. Strontium Isotopic Composition of Paleozoic Carbonate Rocks in the Nevada Test Site Vicinity, Clark, Lincoln, and Nye Counties, Nevada, and Inyo County, California

    USGS Publications Warehouse

    Paces, James B.; Peterman, Zell E.; Futo, Kiyoto; Oliver, Thomas A.; Marshall, Brian D.

    2007-01-01

    Ground water moving through permeable Paleozoic carbonate rocks represents the most likely pathway for migration of radioactive contaminants from nuclear weapons testing at the Nevada Test Site, Nye County, Nevada. The strontium isotopic composition (87Sr/86Sr) of ground water offers a useful means of testing hydrochemical models of regional flow involving advection and reaction. However, reaction models require knowledge of 87Sr/86Sr data for carbonate rock in the Nevada Test Site vicinity, which is scarce. To fill this data gap, samples of core or cuttings were selected from 22 boreholes at depth intervals from which water samples had been obtained previously around the Nevada Test Site at Yucca Flat, Frenchman Flat, Rainier Mesa, and Mercury Valley. Dilute acid leachates of these samples were analyzed for a suite of major- and trace-element concentrations (MgO, CaO, SiO2, Al2O3, MnO, Rb, Sr, Th, and U) as well as for 87Sr/86Sr. Also presented are unpublished analyses of 114 Paleozoic carbonate samples from outcrops, road cuts, or underground sites in the Funeral Mountains, Bare Mountain, Striped Hills, Specter Range, Spring Mountains, and ranges east of the Nevada Test Site measured in the early 1990's. These data originally were collected to evaluate the potential for economic mineral deposition at the potential high-level radioactive waste repository site at Yucca Mountain and adjacent areas (Peterman and others, 1994). Samples were analyzed for a suite of trace elements (Rb, Sr, Zr, Ba, La, and Ce) in bulk-rock powders, and 87Sr/86Sr in partial digestions of carbonate rock using dilute acid or total digestions of silicate-rich rocks. Pre-Tertiary core samples from two boreholes in the central or western part of the Nevada Test Site also were analyzed. Data are presented in tables and summarized in graphs; however, no attempt is made to interpret results with respect to ground-water flow paths in this report. Present-day 87Sr/86Sr values are compared to values

  10. Carbon isotopic compositions of organic matter across continental Cretaceous-Tertiary (K-T) boundary sections: Implications for paleoenvironment after the K-T impact event

    USGS Publications Warehouse

    Maruoka, T.; Koeberl, C.; Bohor, B.F.

    2007-01-01

    To assess the environmental perturbation induced by the impact event that marks the Cretaceous-Tertiary (K-T) boundary, concentrations and isotopic compositions of bulk organic carbon were determined in sedimentary rocks that span the terrestrial K-T boundary at Dogie Creek, Montana, and Brownie Butte, Wyoming in the Western Interior of the United States. The boundary clays at both sites are not bounded by coals. Although coals consist mainly of organic matter derived from plant tissue, siliceous sedimentary rocks, such as shale and clay, may contain organic matter derived from microbiota as well as plants. Coals record ??13C values of plant-derived organic matter, reflecting the ??13C value of atmospheric CO2, whereas siliceous sedimentary rocks record the ??13C values of organic matter derived from plants and microbiota. The microbiota ??13C value reflects not only the ??13C value of atmospheric CO2, but also biological productivity. Therefore, the siliceous rocks from these sites yields information that differs from that obtained previously from coal beds. Across the freshwater K-T boundary at Brownie Butte, the ??13C values decrease by 2.6??? (from - 26.15??? below the boundary clay to - 28.78??? above the boundary clay), similar to the trend in carbonate at marine K-T sites. This means that the organic ??13C values reflect the variation of ??13C of atmospheric CO2, which is in equilibrium with carbon isotopes at the ocean surface. Although a decrease in ??13C values is observed across the K-T boundary at Dogie Creek (from - 25.32??? below the boundary clay to - 26.11??? above the boundary clay), the degree of ??13C-decrease at Dogie Creek is smaller than that at Brownie Butte and that for marine carbonate. About 2??? decrease in ??13C of atmospheric CO2 was expected from the ??13C variation of marine carbonate at the K-T boundary. This ??13C-decrease of atmospheric CO2 should affect the ??13C values of organic matter derived from plant tissue. As such a

  11. Temperature dependence of carbon isotope fractionation in CAM plants

    SciTech Connect

    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.

  12. Isotope Engineering of Carbon Nanotube Systems

    NASA Astrophysics Data System (ADS)

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

    2005-06-01

    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.

  13. Carbonized asphaltene-based carbon-carbon fiber composites

    DOEpatents

    Bohnert, George; Lula, James; Bowen, III, Daniel E.

    2016-12-27

    A method of making a carbon binder-reinforced carbon fiber composite is provided using carbonized asphaltenes as the carbon binder. Combinations of carbon fiber and asphaltenes are also provided, along with the resulting composites and articles of manufacture.

  14. Isotopic compositions of cometary matter returned by Stardust.

    PubMed

    McKeegan, Kevin D; Aléon, Jerome; Bradley, John; Brownlee, Donald; Busemann, Henner; Butterworth, Anna; Chaussidon, Marc; Fallon, Stewart; Floss, Christine; Gilmour, Jamie; Gounelle, Matthieu; Graham, Giles; Guan, Yunbin; Heck, Philipp R; Hoppe, Peter; Hutcheon, Ian D; Huth, Joachim; Ishii, Hope; Ito, Motoo; Jacobsen, Stein B; Kearsley, Anton; Leshin, Laurie A; Liu, Ming-Chang; Lyon, Ian; Marhas, Kuljeet; Marty, Bernard; Matrajt, Graciela; Meibom, Anders; Messenger, Scott; Mostefaoui, Smail; Mukhopadhyay, Sujoy; Nakamura-Messenger, Keiko; Nittler, Larry; Palma, Russ; Pepin, Robert O; Papanastassiou, Dimitri A; Robert, François; Schlutter, Dennis; Snead, Christopher J; Stadermann, Frank J; Stroud, Rhonda; Tsou, Peter; Westphal, Andrew; Young, Edward D; Ziegler, Karen; Zimmermann, Laurent; Zinner, Ernst

    2006-12-15

    Hydrogen, carbon, nitrogen, and oxygen isotopic compositions are heterogeneous among comet 81P/Wild 2 particle fragments; however, extreme isotopic anomalies are rare, indicating that the comet is not a pristine aggregate of presolar materials. Nonterrestrial nitrogen and neon isotope ratios suggest that indigenous organic matter and highly volatile materials were successfully collected. Except for a single (17)O-enriched circumstellar stardust grain, silicate and oxide minerals have oxygen isotopic compositions consistent with solar system origin. One refractory grain is (16)O-enriched, like refractory inclusions in meteorites, suggesting that Wild 2 contains material formed at high temperature in the inner solar system and transported to the Kuiper belt before comet accretion.

  15. Carbon isotopic composition (δ(13)C and (14)C activity) of plant samples in the vicinity of the Slovene nuclear power plant.

    PubMed

    Sturm, Martina; Vreča, Polona; Krajcar Bronić, Ines

    2012-08-01

    δ(13)C values of various plants (apples, wheat, and maize) collected in the vicinity of the Krško Nuclear Power Plant (Slovenia) during 2008 and 2009 were determined. By measuring dried samples and their carbonized counterparts we showed that no significant isotopic fractionation occurs during the carbonization phase of the sample preparation process in the laboratory. The measured δ(13)C values of the plants were used for δ(13)C correction of their measured (14)C activities.

  16. Carbon and Hydrogen Isotopic Composition of Plant Wax n-Alkanes: A Tool for Characterizing Soil Provenance in Forensic Science

    NASA Astrophysics Data System (ADS)

    Pedentchouk, N.; Wagner, T.; Jones, M.

    2009-04-01

    Forensic science is an integrative discipline that requires material evidence from diverse sources. Geochemical evidence derived from inorganic and organic substances is becoming increasingly popular among law enforcement agencies in industrialized countries. Previous investigations indicate that the relative distributions of individual plant-derived biomarkers found in soils are linked to the biomarker patterns found in the overlying vegetation. However, identification of soil provenance based on the distribution of plant-derived biomarkers for forensic purposes is inhibited by the fact that a significant number of terrestrial plant species have overlapping biomarker distributions. In order to enhance the resolving power of plant-derived biomarker signal, we propose to enhance the molecular approach by adding a stable isotope component, i.e. the delta13C/deltaD values of individual biomarkers. The first objective of this project is to determine the delta13C/deltaD signatures of n-alkanes derived from various higher plant types commonly growing in the UK. The second objective is to investigate whether the same species/plant types differ isotopically between two locations affected by different weather patterns in the UK: a relatively warmer and drier Norwich, Norfolk and a cooler and wetter Newcastle-upon-Tyne in NE England. The n-C29 alkane data from 14 tree species sampled during July 2007 and August 2008 in Newcastle show a clear negative trend between delta13C and deltaD values. When these data are plotted against each other, the six deciduous angiosperms (delta13C: c. -39 to -35 per mil; deltaD: c. -155 to -130 per mil) are completely separated from four evergreen angiosperms (delta13C: c. -33 to -28 per mil; deltaD: c. -195 to -165 per mil). The four gymnosperm species data plot between those of the deciduous and evergreen angiosperms. Because all 14 species in Newcastle experience the same environmental conditions, we suggest that the observed isotopic

  17. Carbon Isotope Discrimination in Leaves of C3 Plants

    NASA Astrophysics Data System (ADS)

    Cuntz, M.; Gleixner, G.

    2009-04-01

    Carbon isotope composition is regarded as a powerful tool in understanding carbon cycling, both as a tracer and as a process recorder. However, accurate predictions of, for example, partitioning the net carbon flux into its components or obtaining climate information from tree rings, requires a good understanding of plant metabolism and related isotopic fractionations. Mechanistic models have concentrated largely on photosynthetic pathways and their isotopic composition. This cannot be said for respiratory processes. The mechanistic models of leaf isotope discrimination hence do not describe dawn, dusk and night very realistically or not at all. A new steady-state approach of the carbon isotope distribution in glucose potentially addresses the time of twilight and night (Tcherkez et al. 2004). Here, a new model of 13C discrimination in leaves of C3 plants is presented. The model is based on the steady-state approach of Tcherkez et al. (2004) but with much reduced complexity while retaining its general characteristics. In addition, the model introduces some new concepts such as a day-length dependent starch synthesis, night-length dependent starch degradation, energy-driven biosynthesis rates, and continuous leaf discrimination calculation for the whole diel cycle. It is therefore well adapted for biosphere-atmosphere exchange studies. The model predicts enriched sucrose and starch pools in the leaf compared to assimilated CO2. Biosynthesis on the other hand acts as the sink of the remaining, depleted carbon. The model calculates slightly different absolute starch compositions from the Tcherkez et al. (2004) model but this depends on chosen fractionation factors. The greatest difference between the two models is during dawn, dusk and night. For example, while Tcherkez et al. has changing phloem sucrose isotope composition during night, the model here predicts constant sucrose export composition. Observations seem to support rather constant phloem isotope composition

  18. Stable isotope composition of human fingernails from Slovakia.

    PubMed

    Grolmusová, Zuzana; Rapčanová, Anna; Michalko, Juraj; Čech, Peter; Veis, Pavel

    2014-10-15

    Stable isotope composition of human fingernails has proven to be useful for documenting human dietary information and geographical patterns in archeological, forensic, anthropological and biological studies. Therefore, it is of interest to detect all factors influencing the stable isotopic composition in the certain regions in the world. Carbon and nitrogen isotope data of human fingernail keratin from 52 individuals from Slovakia were reported in this study. The online combustion and continuous flow isotope-ratio mass spectrometer Delta V Advantage was used for δ(13)C and δ(15)N analysis of fingernail keratin samples from 24 vegetarian and 28 omnivorous individuals. A group of people with frequent meat consumption showed enrichment in (13)C and (15)N isotopes in fingernails. A similar trend was observed with increasing seafood in an individual's diet. Moreover a significant difference was revealed between smokers and nonsmokers for both δ(13)C and δ(15)N values. These data were compared to previously published δ(13)C and δ(15)N fingernail values from across the globe. This study brings new information on the stable isotope signature of individuals from Slovakia and characterizes the Central European region for the first time. The stable isotope composition of fingernails is influenced by the frequency of meat and seafood consumption as well as smoking.

  19. Influence of Ozone on the Stable Carbon Isotope Composition, deltaC, of Leaves and Grain of Spring Wheat (Triticum aestivum L.).

    PubMed

    Saurer, M; Fuhrer, J; Siegenthaler, U

    1991-09-01

    The relative composition of stable carbon isotopes, delta(13)C, was determined in flag leaves and grain of spring wheat (Triticum aestivum L. cv Albis) grown in open-top field fumigation chambers and exposed to different O(3) levels during the growing season. The aim of the study was to establish exposure-response relationships for the radiation-weighted seasonal mean O(3) concentration and delta(13)C (relative deviation of the (13)C/(12)C ratio) values of the two plant parts. Samples were collected at harvest in 1986, 1987, and 1988. With increasing O(3) concentration, delta(13)C values increased (became less negative) proportionally. Year to year delta(13)C differences at equivalent O(3) concentrations were small. The shift in delta(13)C caused by O(3) was more pronounced in grain than in leaves. According to models of (13)C discrimination in C(3) plants, these results indicate increasing limitation of photosynthesis by CO(2) diffusion relative to limitation by carboxylation with increasing O(3) exposure. This conclusion is not in agreement with results from gas exchange analysis. Water use efficiency in green flag leaves tended to decrease with increasing O(3), indicating a dominating effect of O(3) on CO(2) carboxylation.

  20. Isotopic composition of carbonate-bound organic nitrogen in deep-sea scleractinian corals: A new window into past biogeochemical change

    NASA Astrophysics Data System (ADS)

    Wang, Xingchen T.; Prokopenko, Maria G.; Sigman, Daniel M.; Adkins, Jess F.; Robinson, Laura F.; Ren, Haojia; Oleynik, Sergey; Williams, Branwen; Haug, Gerald H.

    2014-08-01

    Over the last two decades, the skeletal remains of deep-sea corals have arisen as a geochemical archive of Pleistocene oceanographic change. Here we report the exploration of the isotopic composition of the carbonate-bound organic nitrogen (hereafter, CB-δ15N) in the deep-sea scleractinian coral Desmophyllum dianthus as a possible tool for reconstructing past changes in the ocean nitrogen cycle. The measurement protocol is adapted from a high-sensitivity method for foraminifera shell-bound δ15N. We explored the variability of CB-δ15N within specimens, among corals collected at different depths in a given ocean region, and among different ocean regions. Modern D. dianthus CB-δ15N is strongly correlated with the δ15N of N export as estimated from sediment traps, shallow subsurface nitrate, and surface sediments, suggesting that CB-δ15N is a reliable proxy for δ15N of N export. D. dianthus CB-δ15N is consistently 8-9‰ higher than δ15N of N export, indicating that D. dianthus acquires its nutrition primarily from suspended particulate organic matter (POM) that derives from sinking POM, not directly from sinking POM.

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

    NASA Technical Reports Server (NTRS)

    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.

  2. Interpreting the Ca isotope record of marine biogenic carbonates

    NASA Astrophysics Data System (ADS)

    Sime, Neil G.; De La Rocha, Christina L.; Tipper, Edward T.; Tripati, Aradhna; Galy, Albert; Bickle, Michael J.

    2007-08-01

    An 18 million year record of the Ca isotopic composition (δ 44/42Ca) of planktonic foraminiferans from ODP site 925, in the Atlantic, on the Ceara Rise, provides the opportunity for critical analysis of Ca isotope-based reconstructions of the Ca cycle. δ 44/42Ca in this record averages +0.37 ± 0.05 (1 σ SD) and ranges from +0.21‰ to +0.52‰. The record is a good match to previously published Neogene Ca isotope records based on foraminiferans, but is not similar to the record based on bulk carbonates, which has values that are as much as 0.25‰ lower. Bulk carbonate and planktonic foraminiferans from core tops differ slightly in their δ 44/42Ca (i.e., by 0.06 ± 0.06‰ ( n = 5)), while the difference between bulk carbonate and foraminiferan values further back in time is markedly larger, leaving open the question of the cause of the difference. Modeling the global Ca cycle from downcore variations in δ 44/42Ca by assuming fixed values for the isotopic composition of weathering inputs (δ 44/42Ca w) and for isotope fractionation associated with the production of carbonate sediments (Δ sed) results in unrealistically large variations in the total mass of Ca 2+ in the oceans over the Neogene. Alternatively, variations of ±0.05‰ in the Ca isotope composition of weathering inputs or in the extent of fractionation of Ca isotopes during calcareous sediment formation could entirely account for variations in the Ca isotopic composition of marine carbonates. Ca isotope fractionation during continental weathering, such as has been recently observed, could easily result in variations in δ 44/42Ca w of a few tenths of permil. Likewise a difference in the fractionation factors associated with aragonite versus calcite formation could drive shifts in Δ sed of tenths of permil with shifts in the relative output of calcite and aragonite from the ocean. Until better constraints on variations in δ 44/42Ca w and Δ sed have been established, modeling the Ca 2+ content

  3. Calcium isotopic compositions of mid-ocean ridge basalts

    NASA Astrophysics Data System (ADS)

    Zhu, H.; Zhang, Z.; Sun, W.; Wang, G. Q.

    2015-12-01

    Previous studies have demonstrated that Earth's mantle has heterogeneous calcium isotopic compositions. But the reason why mantle has its heterogeneity remains uncertain. In general, δ44/40Ca values of mantle xenolith samples have a variation of >0.45‰. While ultramafic rocks, especially dunites, have higher δ44/40Ca values than volcanic rocks, and there is a positive correlation between δ44/40Ca and Ca/Mg. These phenomena imply that the heterogeneity of Ca isotopic compositions of mantle xenolith samples might result from different degrees of melt extraction, as indicated by large Ca isotopic fractionation between co-existing clinopyroxene and orthopyroxene. However, because ancient marine carbonate has its own unique calcium isotopic characteristics, recycling of even a small amount of ancient marine carbonates into the mantle could also cause the heterogeneity of Ca isotopes in Earth's mantle. This could be the reason why oceanic island basalts (OIB) have lighter Ca isotopic compositions than the mantle xenolith. Thus, the lighter Ca isotopic compositions in the mantle source cannot only be ascribed to magmatic processes. Therefore, it is more important to know calcium isotopic characteristics during partial melting and oceanic crust contamination.Mid-ocean ridge basalts (MORB) are formed from the partial melts of the upper mantle and are rarely affected by crustal contamination. Different types of MORB, including D-MORB, N-MORB and E-MORB, have experienced different degrees of partial melting and contamination of enriched end-members. Here we report calcium isotopic characteristic of different types of MORB, we believe it will be very helpful to understand the behaviors of Ca isotopes during partial melting and it is possible to provide further information to discover the reason why calcium isotopic compositions is heterogeneous in Earth's mantle. This work was supported by Natural Science Foundation of China (No. 41373007, No. 41490632 and No. 91328204

  4. Differences in isotopic composition of carbonaceous components in enstatite chondrites

    NASA Astrophysics Data System (ADS)

    Grady, M. M.; Wright, I. P.; Carr, R. H.; Poths, J.; Pillinger, C. T.

    1988-02-01

    Carbon stable isotopic composition of the major carbonaceous component in enstatite chondrites varies with petrologic type. Investigation of a suite of HF/HCl-resistant residues has shown that this variation is due to an inherent difference in delta(C-13) of the carbon, and is not a result of the presence of small amounts of isotopically anomalous carbon-bearing components. These latter do occur in type EH3 and EH4 chondrites, in concentrations similar to those found in C1 and C2 carbonaceous chondrites. Combustion of the major carbon component (apparently elemental carbon, not necessarily graphite) occurs at relatively higher temperatures in enstatite chondrites of increasing petrologic type. This is considered to reflect an increase in crystallinity or ordering of the carbonaceous component, and is a measure of the degree of thermal processing to which the meteorites have been subjected during accretion and/or metamorphism.

  5. Pitch carbon microsphere composite

    NASA Technical Reports Server (NTRS)

    Price, H. L.; Nelson, J. B.

    1977-01-01

    Petroleum pitch carbon microspheres were prepared by flash heating emulsified pitch and carbonizing the resulting microspheres in an inert atmosphere. Microsphere composites were obtained from a mixture of microspheres and tetraester precursor pyrrone powder. Scanning electron micrographs of the composite showed that it was an aggregate of microspheres bonded together by the pyrrone at the sphere contact points, with voids in and among the microspheres. Physical, thermal, and sorption properties of the composite are described. Composite applications could include use as a honeycomb filler in elevated-temperature load-bearing sandwich boards or in patient-treatment tables for radiation treatment of tumors.

  6. Oxygen isotope fractionation in double carbonates.

    PubMed

    Zheng, Yong-Fei; Böttcher, Michael E

    2016-01-01

    Oxygen isotope fractionations in double carbonates of different crystal structures were calculated by the increment method. Synthesis experiments were performed at 60 °C and 100 °C to determine oxygen and carbon isotope fractionations involving PbMg[CO3]2. The calculations suggest that the double carbonates of calcite structure are systematically enriched in (18)O relative to those of aragonite and mixture structures. Internally consistent oxygen isotope fractionation factors are obtained for these minerals with respect to quartz, calcite and water at a temperature range of 0-1200 °C. The calculated fractionation factors for double carbonate-water systems are generally consistent with the data available from laboratory experiments. The experimentally determined fractionation factors for PbMg[CO3]2, BaMg[CO3]2 and CaMg[CO3]2 against H2O not only fall between fractionation factors involving pure carbonate end-members but are also close to the calculated fractionation factors. In contrast, experimentally determined carbon isotope fractionation factors between PbMg[CO3]2 and CO2 are much closer to theoretical predictions for the cerussite-CO2 system than for the magnesite-CO2 system, similar to the fractionation behavior for BaMg[CO3]2. Therefore, the combined theoretical and experimental results provide insights into the effects of crystal structure and exchange kinetics on oxygen isotope partitioning in double carbonates.

  7. Concentrations and stable carbon isotope compositions of oxalic acid and related SOA in Beijing before, during, and after the 2014 APEC

    NASA Astrophysics Data System (ADS)

    Wang, Jiayuan; Wang, Gehui; Gao, Jian; Wang, Han; Ren, Yanqin; Li, Jianjun; Zhou, Bianhong; Wu, Can; Zhang, Lu; Wang, Shulan; Chai, Fahe

    2017-01-01

    To ensure good air quality for the 2014 Asia-Pacific Economic Cooperation (APEC) summit, stringent emission controls were implemented in Beijing and its surrounding regions, leading to a significant reduction in PM2.5 loadings. To investigate the impact of the emission controls on aerosol chemistry, high-volume PM2.5 samples were collected in Beijing from 8 October to 24 November 2014 and determined for secondary inorganic aerosols (SIA, i.e., SO42-, NO3-, and NH4+), dicarboxylic acids, keto-carboxylic acid, and α-dicarbonyls, as well as stable carbon isotope composition of oxalic acid (C2). Our results showed that SIA, C2, and related secondary organic aerosols in PM2.5 during APEC were 2-4 times lower than those before APEC, which is firstly ascribed to the strict emission control measures and secondly attributed to the relatively colder and drier conditions during the event that are unfavorable for secondary aerosol production.C2 in the polluted air masses, which mostly occurred before APEC, are abundant and enriched in 13C. On the contrary, C2 in the clean air masses, which mostly occurred during APEC, is much less abundant but still enriched in 13C. In the mixed type of clean and polluted air masses, which mostly occurred after APEC, C2 is lower than that before APEC but higher than that during APEC and enriched in lighter 12C. A comparison on chemical composition of fine particles and δ13C values of C2 in two events that are characterized by high loadings of PM2.5 further showed that after APEC SIA and the total detected organic compounds (TDOC) are much less abundant and fine aerosols are enriched with primary organics and relatively fresh, compared with those before APEC.

  8. The temperature and carbonate ion influence on Pleistocene high latitude planktonic foraminiferal carbon isotopic records

    NASA Astrophysics Data System (ADS)

    Charles, C.; Foreman, A. D.; Munson, J.; Slowey, N. C.; Hodell, D. A.

    2014-12-01

    Establishing a credible record of the carbon isotopic composition of high latitude surface ocean DIC over ice ages has been an enormous challenge, because the possible archives of this important variable in deep sea sediments all incorporate complex effects of the biomineralization process. For example, culture experiments (by Spero and colleagues) demonstrate a strong temperature and carbonate ion effect on the carbon isotopic composition of G. bulloides--the taxon of planktonic foraminifera that is most abundant in the majority of subpolar sediment sequences. Here we capitalize on the fortuitous observation of exceptionally strong covariation between the oxygen and carbon isotopic composition of G. bulloides in multiple sediment sequences from the Benguela upwelling region. The covariation is most clear during Marine Isotopic Stage 3 (an interval when the isotopic composition of the seawater was least variable) and undoubtedly results from the precipitation of tests under variable conditions of temperature and carbonate ion. The unusually clear isotopic relationship in planktonic foraminifera observed off Namibia constitutes a field calibration of the biomineralization effects observed in culture, and we apply it to previously published high latitude carbon isotopic records throughout the Southern Ocean. We find that many of the excursions toward lower planktonic foraminiferal δ13C that have been interpreted previously as the upwelling of nutrient rich water during deglaciations are better explained as increases in upper ocean temperature and carbonate ion. Conversely, the excursions toward high δ13C during ice age intervals that have been interpreted previously as increased export production (purportedly stimulated by dust) are also better explained by temperature and carbonate ion variability. After removal of the inferred temperature and carbonate ion signal from the planktonic foraminiferal time series, the residual is essentially (but not exactly) the same

  9. Experimental evidence for diel variations of the carbon isotope composition in leaf, stem and phloem sap organic matter in Ricinus communis.

    PubMed

    Gessler, Arthur; Tcherkez, Guillaume; Peuke, Andreas D; Ghashghaie, Jaleh; Farquhar, Graham D

    2008-07-01

    Carbon isotope fractionation in metabolic processes following carboxylation of ribulose-1,5-bisphosphate (RuBP) is not as well described as the discrimination during photosynthetic CO(2) fixation. However, post-carboxylation fractionation can influence the diel variation of delta(13)C of leaf-exported organic matter and can cause inter-organ differences in delta(13)C. To obtain a more mechanistic understanding of post-carboxylation modification of the isotopic signal as governed by physiological and environmental controls, we combined the modelling approach of Tcherkez et al., which describes the isotopic fractionation in primary metabolism with the experimental determination of delta(13)C in leaf and phloem sap and root carbon pools during a full diel course. There was a strong diel variation of leaf water-soluble organic matter and phloem sap sugars with relatively (13)C depleted carbon produced and exported during the day and enriched carbon during the night. The isotopic modelling approach reproduces the experimentally determined day-night differences in delta(13)C of leaf-exported carbon in Ricinus communis. These findings support the idea that patterns of transitory starch accumulation and remobilization govern the diel rhythm of delta(13)C in organic matter exported by leaves. Integrated over the whole 24 h day, leaf-exported carbon was enriched in (13)C as compared with the primary assimilates. This may contribute to the well-known--yet poorly explained--relative (13)C depletion of autotrophic organs compared with other plant parts. We thus emphasize the need to consider post-carboxylation fractionations for studies that use delta(13)C for assessing environmental effects like water availability on ratio of mole fractions of CO(2) inside and outside the leaf (e.g. tree ring studies), or for partitioning of CO(2) fluxes at the ecosystem level.

  10. Exotic Structure of Carbon Isotopes

    NASA Astrophysics Data System (ADS)

    Suzuki, Toshio; Sagawa, Hiroyuki; Hagino, Kouichi

    2003-12-01

    Ground state properties of C isotopes, deformation and elecromagnetic moments, as well as electric dipole transition strength are investigated. We first study the ground state properties of C isotopes using a deformed Hartree-Fock (HF) + BCS model with Skyrme interactions. Isotope dependence of the deformation properties is investigated. Shallow deformation minima are found in several neutron-rich C isotopes. It is also shown that the deformation minima appear in both the oblate and the prolate sides in 17C and 19C having almost the same binding energies. Next, we carry out shell model calculations to study electromagnetic moments and electric dipole transitions of 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 deformation and spin-parities of the ground states of these nuclei. Electric dipole states of C isotopes are studied focusing on the interplay between low energy Pigmy strength and giant dipole resonances. Low peak energies, two-peak structure and large widths of the giant resonances show deformation effects. Calculated transition strength below dipole giant resonance in heavier C isotopes than 15C is found to exhaust 12 ~ 15% of the Thomas-Reiche-Kuhn sum rule value and 50 ~ 80% of the cluster sum rule value.

  11. The Stable Isotopic Composition of Atmospheric CO2

    NASA Astrophysics Data System (ADS)

    Yakir, D.

    2003-12-01

    When a bean leaf was sealed in a closed chamber under a lamp (Rooney, 1988), in two hours the atmospheric CO2 in the microcosm reached an isotopic steady state with a 13C abundance astonishingly similar to the global mean value of atmospheric CO2 at that time (-7.5‰ in the δ13C notation introduced below). Almost concurrently, another research group sealed a suspension of asparagus cells in a different type of microcosm in which within about two hours the atmospheric O2 reached an isotopic steady state with 18O enrichment relative to water in the microcosm that was, too, remarkably similar to the global-scale offset between atmospheric O2 and mean ocean water (21‰ versus 23.5‰ in the δ18O notation introduced below; Guy et al., 1987). These classic experiments capture some of the foundations underlying the isotopic composition of atmospheric CO2 and O2. First, in both cases the biological system rapidly imposed a unique isotopic value on the microcosms' atmosphere via their massive photosynthetic and respiratory exchange of CO2 and O2. Second, in both cases the biological system acted on materials with isotopic signals previously formed by the global carbon and hydrological cycles. That is, the bean leaf introduced its previously formed organic matter (the source of the CO2 respired into microcosm's atmosphere), and the asparagus cells were introduced complete with local tap water (from which photosynthesis released molecular oxygen). Therefore, while the isotopic composition of the biological system used was slave to long-term processes, intense metabolic processes centered on few specific enzymes (Yakir, 2002) dictated the short-term atmospheric composition.In a similar vein, on geological timescales of millions of years, the atmosphere and its isotopic composition are integral parts of essentially a single dynamic ocean-atmosphere-biosphere system. This dynamic system exchanges material, such as carbon and oxygen, with the sediments and the lithosphere via

  12. Carbon isotopes in xenoliths from the Hualalai Volcano, Hawaii, and the generation of isotopic variability

    SciTech Connect

    Pineau, F. ); Mathez, E.A. )

    1990-01-01

    The isotopic composition of carbon has been determined in a suite of xenoliths from lava of the 1800-1801 Kaupulehu eruption of Hualalai Volcano, Hawaii. Several lithologies are represented in the suite, including websterite, dunite, wehrlite, pyroxenite, and gabbro. In addition, there are composite xenoliths in which contacts between lithologies are preserved. Most of the xenoliths represent deformed cumulates. The contact relations in the composite samples indicate that the lithologies originated from the same source region, which, based on pressures determined from fluid inclusions, is estimated to be at a depth of {approx}20 km, or near the crust-mantle boundary. The observations and isotopic results demonstrate that isotopic variability can be generated by multistage fractionation processes such as degassing of CO{sub 2} from magma and precipitation of CO{sub 2}-rich fluids to form graphitic compounds. Such processes operated over regions the scales of which were determined by style and intensity of deformation and by lithology.

  13. Carbon and oxygen isotopes of Maastrichtian Danian shallow marine carbonates: Yacoraite Formation, northwestern Argentina

    NASA Astrophysics Data System (ADS)

    Marquillas, Rosa; Sabino, Ignacio; Nobrega Sial, Alcides; Papa, Cecilia del; Ferreira, Valderez; Matthews, Stephen

    2007-04-01

    The Maastrichtian-Danian limestones of the Yacoraite Formation (northwestern Argentina) show carbon and oxygen isotopic values consistent with shallow marine conditions. The members of the formation respond to different sedimentary environments and are characterised by distinctive stable isotopes and geochemistry. The basal Amblayo Member is composed of high-energy dolomitic limestones and limestones with positive isotopic values (+2‰ δ 13C, +2‰ δ 18O). The top of the member reveals an isotopic shift of δ 13C (-5‰) and δ 18O (-10‰), probably related to a descent in the sea level. The sandy Güemes Member has isotopically negative (-2‰ δ 13C, -1‰ δ 18O) limestones, principally controlled by water mixing, decreased organic productivity, and compositional changes in the carbonates. The isotopically lighter limestones are calcitic, with a greater terrigenous contribution and different geochemical composition (high Si-Mn-Fe-Na, low Ca-Mg-Sr). These isotopic and lithological changes relate to the Cretaceous-Palaeogene transition. The Alemanía Member, composed of dolomitic limestones and pelites, represents a return to marine conditions and shows a gradual increase in isotopic values, reaching values similar to those of the Amblayo Member. The Juramento Member, composed of stromatolite limestones, shows isotopic variations that can be correlated with the two well-defined, shallowing-upward sequences of the member.

  14. The Lithium Isotope Composition of Planktonic Foraminifera

    NASA Astrophysics Data System (ADS)

    Hathorne, E. C.; James, R. H.; Harris, N. B.

    2003-12-01

    The temporal record of the lithium isotopic composition of seawater has the potential to provide an important proxy of the relative rates of weathering and hydrothermal processes. One of the most powerful types of evidence for changes in ocean chemistry comes from analyses of foraminiferal calcium carbonate. Here, we explore the utility of foraminifera as recorders of the Li isotopic composition of seawater. The Li isotopic composition of foraminifera tests has been determined by multicollector inductively coupled plasma mass spectrometry (Nu Instruments) using a sample-standard bracketing technique. The external precision of this technique is +/- 0.3 ‰ (2σ ), based on fifteen analyses of seawater over a period of 9 months. Planktonic foraminifera ( ˜10 mg) have been picked from surface sediments of the equatorial Pacific and the North Atlantic. Samples from the equatorial Pacific are Holocene/Pleistocene in age; those from the North Atlantic are from the Holocene. The foraminifera were subject to; cleaning in methanol and water, oxidation (hydrogen peroxide and sodium hydroxide), and leaching in weak acid (0.001M nitric acid). Additional reductive and refractory-phase cleaning steps (respectively, hydrous hydrazine/ammonia and DTPA solutions) had no effect on δ 7Li or Li/Ca. The δ 7Li value of the foraminifera ranges from 27 to 31‰ ; slightly lighter than modern-day seawater (31.1 ‰ ). Different species have consistently different δ 7Li values; O. universa have δ 7Li values within error of seawater, while Gr. truncatulinoides record the lightest δ 7Li (27.1+/- 0.3‰ ). This indicates that there are species specific vital effects on foraminiferal δ 7Li. Samples of the same species from different latitudes in the North Atlantic have the same δ 7Li, suggesting that there is no temperature effect on foraminiferal δ 7Li. Furthermore, with the exception of G. sacculifer, there appears to be no variability in foraminiferal δ 7Li with test size

  15. The effects of biomanipulation on the biogeochemistry, carbon isotopic composition and pelagic food web relations of a shallow turf lake

    NASA Astrophysics Data System (ADS)

    Bontes, B. M.; Pel, R.; Ibelings, B. W.; Boschker, H. T. S.; Middelburg, J. J.; van Donk, E.

    2005-08-01

    The effects of fish removal on the biogeochemistry and lower-trophic level food web relations were studied in a shallow eutrophied turf lake. Biomanipulation led to an increase in transparency and macrophyte biomass and decrease in phytoplankton abundance, but zooplankton numbers did not increase. Moreover, fish removal resulted in high pH, high O2, low CO2, and more negative δ13CDIC values than expected, which is proposed to be the likely result of chemical enhanced diffusion with large negative fractionation (-13). By combining fluorescence activated cell sorting and isotope ratio mass spectrometry (IRMS) of fatty acids we were able to obtain group specific δ13C signatures and to trace possible shifts in δ13C resulting from fish removal. Fractionation values of green algae (20) and diatoms (22) were uniform and independent of treatment, while fractionation factors of filamentous cyanobacteria were variable between the treatments that differed in CO2 availability. 13C-labeling of the phytoplankton groups showed that biomanipulation led to increased growth rates of green algae and diatoms at the expense of cyanobacteria. Finally, the primary consumer Chydorus appeared to prefer cyanobacteria, whilst Asplanchna grazed predominantly upon eukaryotes.

  16. Unusual mercury isotopic compositions in aqueous environment

    NASA Astrophysics Data System (ADS)

    Chen, J.; Hintelmann, H.; Zheng, W.; Feng, X.; Cai, H.; Wang, Z.; Yuan, S.

    2014-12-01

    Preliminary studies have demonstrated both mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) of Hg isotopes in natural samples. Laboratory experiments showed that photochemical reduction of inorganic mercury (iHg) and methylmercury (MMHg) and liquid-vapour evaporation could produce MIF of odd Hg isotopes. This was thought to cause the MIF actually observed in aquatic organisms. Although isotopic measurements of Hg in aqueous environment would give direct evidence, little data was reported for surface water samples. Recent work reported, unexpectedly, positive MIF of odd Hg isotopes in both precipitation and ambient air, in contrast with the prediction of laboratory experiments and measurements of Hg accumulated in lichens . Intriguingly, MIF of even-mass Hg isotope (200Hg) was also recently determined in the atmosphere. In contrast with the now mainstream observation of odd Hg isotope anomaly that has several theoretical explanations, the hitherto mysterious even Hg isotope anomalies were neither reported in laboratory experiments, nor predicted by isotope fractionation mechanisms, highlighting the importance of further study on Hg isotopes in variable systems. Our measurements of lichens and lake water samples from different countries show for the first time significant Δ200Hg in surface terrestrial reservoirs, realizing a direct connection of even Hg isotope anomaly in the terrestrial reservoirs to the atmospheric deposition, and fulfilling the gap of Δ200Hg between the atmosphere and the terrestrial receptors. The specific odd Hg isotope compositions determined in lake waters also support the atmosphere contribution, and may be directly linked to the high Δ199Hg values largely determined and manifested on the top of aqueous food web. Our data show that the watershed Hg input is another contributing source, rather than the in-lake processes, to explain the lacustrine Hg isotope anomalies. Interestingly, lake sediments are isotopically

  17. Constraining paleotemperature and water isotope signals at Lake Bonneville using carbonate clumped isotopes

    NASA Astrophysics Data System (ADS)

    Mering, J. A.; Oviatt, C. G.; Petryshyn, V. A.; Canet, J.; Tripati, A.

    2013-12-01

    Lake Bonneville was the largest pluvial system in the Great Basin during the Last Glacial Maximum (23-19 ka BP), reaching nearly 50,000 square kilometers at its high stand. Carbonate clumped isotope paleothermometry provides a new avenue to evaluate lake and atmospheric conditions by constraining the temperature and oxygen isotope ratios of lake water. Here, we present estimates of lake temperature, the oxygen isotope composition of paleowater, and Mean Annual Air Temperature (MAAT) from LGM paleoshoreline sites in Utah and Eastern Nevada. Multiple phases of ancient carbonate were evaluated, including endogenic carbonate from the ubiquitous Bonneville marl stratigraphic unit, and aragonitic shells of two species of aquatic gastropods (genera Pyrgulopsis and Stagnicola) collected from littoral deposits adjacent to the marl. These phases should record surface water conditions. Preliminary results indicate that paleotemperature estimates from gastropods and marl are similar at any given site. However, the latitudinal water isotope gradient reconstructed using marls is steeper than that reconstructed from gastropods, indicating that perhaps carbonate precipitation in marl is more evaporation-driven than shell growth of aquatic snails. Comparison with recent climate data, and clumped isotope measurements of modern samples from the Great Salt Lake, supports moderate temperature change in the Great Basin from the Last Glacial Maximum to present.

  18. Determination of multiple organic matter sources in aerosol PM10 from Wrocław, Poland using molecular and stable carbon isotope compositions

    NASA Astrophysics Data System (ADS)

    Górka, Maciej; Rybicki, Maciej; Simoneit, Bernd R. T.; Marynowski, Leszek

    2014-06-01

    The natural and anthropogenic contributions of hydrocarbon groups (aliphatic and aromatic), as well as total organic carbon, in atmospheric PM10 dust (particulate matter <10 μm) collected from Wrocław (SW Poland) were assessed using combined molecular (gas chromatography-mass spectrometry - GC-MS) and stable carbon isotopic (isotope-ratio mass spectrometry - IR-MS) analyses. The PM10 samples were taken in the seasonal sampling program in 2007, and represent air pollution from all months of the year. The δ13C values of the total carbon varied seasonally from -27.6 to -25.3‰. The isotopic mass balance calculations confirmed greater coal burning input, reaching 70.5%, in the heating season and dominant transported sources 47.5% in the vegetative season. The data obtained for the aliphatic fractions: carbon preference index (CPI), carbon number maximum (Cmax), wax n-alkane contents (%WNA), and δ13C values of the aliphatic fractions (-36.6 to -29.4‰), indicated a dominant anthropogenic origin (gasoline/diesel/coal combustion) and a lesser biogenic input (biomass burning and natural organic matter). Petroleum and coal combustion emissions were confirmed by the presence of hopanes and moretanes. The molecular analysis of the concentrations and diagnostic ratios of the polycyclic aromatic hydrocarbons (PAHs) and the δ13C values of the aromatic fractions (-35.4 to -26.8‰) indicated that the main PAH sources were also collectively from combustion of liquid fuels and coal. Based on PAH discrimination diagrams it is also clear that the main organic carbon source is derived from coal, biomass and petroleum combustion in both seasons. However, taking into account the PAH concentrations during the vegetative and heating seasons, coal and biomass burning seem to be their major source. Additionally, the polar organic compounds (mainly levoglucosan) confirmed a significant contribution from biomass burning to the total anthropogenic input. The general conclusion derived

  19. Magnesium Isotopic Composition of Subducting Marine Sediments

    NASA Astrophysics Data System (ADS)

    Hu, Y.; Teng, F. Z.; Plank, T. A.; Huang, K. J.

    2015-12-01

    Subducted marine sediments have recently been called upon to explain the heterogeneous Mg isotopic composition (δ26Mg, ‰) found in mantle wehrlites (-0.39 to +0.09 [1]) in the context of a homogeneous mantle (-0.25 ± 0.07 [2]). However, no systematic measurements of δ26Mg on marine sediments are currently available to provide direct support to this model. To characterize the Mg inputs to global subduction zones, we measured δ26Mg data for a total of 90 marine sediments collected from 12 drill sites outboard of the world's major subduction zones. These sediments span a 1.73‰ range in δ26Mg. The detritus-dominated sediments have δ26Mg (-0.59 to +0.53) comparable to those of weathered materials on continents (e.g. -0.52 to +0.92 [3]), while the calcareous oozes yield δ26Mg (as light as -1.20) more similar to the seawater value (-0.83 [4]). The negative correlation between δ26Mg and CaO/Al2O3 in these sediments indicates the primary control of mineralogy over the Mg isotopic distribution among different sediment types, as carbonates are enriched in light Mg isotopes (-5.10 to -0.40 [5]) whereas clay-rich weathering residues generally have heavier δ26Mg (e.g. up to +0.65 in saprolite [6]). In addition, chemical weathering and grain-size sorting drive sediments to a heavier δ26Mg, as indicated by the broad positive trends between δ26Mg with CIA (Chemical Index of Alteration [7]) and Al2O3/SiO2, respectively. Collectively, the arc systems sampled in this study represent ~30% of global arc length and the extrapolated global Mg flux of subducting marine sediments accounts for ~9% of the yearly Mg riverine input with a flux-weighted average δ26Mg at -0.26. Subduction of these heterogeneous sediments may not cause significant mantle heterogeneity on a global scale, but the highly variable Mg fluxes and δ26Mg of sediments delivered to different trenches are capable of producing local mantle variations. Volcanic rocks sourced from these mantle domains are thus

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

    NASA Technical Reports Server (NTRS)

    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.

  1. Multiproxy Holocene paleoclimate records from the southern Peruvian Andes - what new can we learn from the stable carbon isotope composition of high altitude organic matter deposits?

    NASA Astrophysics Data System (ADS)

    Skrzypek, Grzegorz; Engel, Zbyněk

    2015-04-01

    Interpretation of the Central Andean paleoclimate over the last millennia still represents a research challenge demanding deeper studies [1,2]. Several high-resolution paleoclimate proxies for the last 10,000 years have been developed for the northern hemisphere. However, similar proxies are very limited for South America, particularly for high altitudes where, for example, tree-ring chronologies are not available and instrumental records are very limited. Consequently, our knowledge of high altitude climate changes in arid regions of the Peruvian Andes mainly relies on ice-core and lake deposit studies. In our study, we used a new alternative proxy for interpretation of palaeoclimate conditions based on a peat core taken from the Carhuasanta Valley at the foot of Nevado Mismi in the southern Peruvian Andes (15° 30'S, 71° 43'W, 4809m a.s.l.). The stable carbon isotope composition (δ13C) of Distichia peat reflects mainly the relative variation of the mean air temperature during subsequent growing seasons [3], and allows reconstructions of palaeotemperature changes. In contrast, peat organic carbon concentration (C % wt) records mainly wetness in the valley, directly corresponding to the changes in runoff in the upper part of the catchment. The most prominent climate changes recorded in the peat over last 4ka occurred between 3040 and 2750 cal. yrs BP. The initial warming turned to a very rapid cooling to temperatures at least 2° C lower than the mean for the Late Holocene. Initially drier conditions within this event turned to a short wet phase after 2780 cal. yrs BP, when the temperature increased again. This event coincides with significant changes in peat and ice core records in the Central Andes that match the timing of the global climate event around 2.8 cal. ka BP. Climatic conditions in the study area became relatively dry and stable after the event for about 800 years. Highly variable temperatures and humidity prevailed during the last 2000 years, when

  2. Photosynthesis, water use efficiency and stable carbon isotope composition are associated with anatomical properties of leaf and xylem in six poplar species.

    PubMed

    Cao, X; Jia, J B; Li, H; Li, M C; Luo, J; Liang, Z S; Liu, T X; Liu, W G; Peng, C H; Luo, Z B

    2012-07-01

    Although fast-growing Populus species consume a large amount of water for biomass production, there are considerable variations in water use efficiency (WUE) across different poplar species. To compare differences in growth, WUE and anatomical properties of leaf and xylem and to examine the relationship between photosynthesis/WUE and anatomical properties of leaf and xylem, cuttings of six poplar species were grown in a botanical garden. The growth performance, photosynthesis, intrinsic WUE (WUE(i) ), stable carbon isotope composition (δ(13) C) and anatomical properties of leaf and xylem were analysed in these poplar plants. Significant differences were found in growth, photosynthesis, WUE(i) and anatomical properties among the examined species. Populus cathayana was the clone with the fastest growth and the lowest WUE(i) /δ(13) C, whereas P. × euramericana had a considerable growth increment and the highest WUE(i) /δ(13) C. Among the analysed poplar species, the highest total stomatal density in P. cathayana was correlated with its highest stomatal conductance (g(s) ) and lowest WUE(i) /δ(13) C. Moreover, significant correlations were observed between WUE(i) and abaxial stomatal density and stem vessel lumen area. These data suggest that photosynthesis, WUE(i) and δ(13) C are associated with leaf and xylem anatomy and there are tradeoffs between growth and WUE(i) . It is anticipated that some poplar species, e.g. P. × euramericana, are better candidates for water-limited regions and others, e.g. P. cathayana, may be better for water-abundant areas.

  3. Relationships between C3 Plant Foliar Carbon Isotope Composition and Element Contents of Grassland Species at High Altitudes on the Qinghai-Tibet Plateau, China

    PubMed Central

    Zhou, Yong-Chun; Fan, Jiang-Wen; Harris, Warwick; Zhong, Hua-Ping; Zhang, Wen-Yan; Cheng, Xi-Lei

    2013-01-01

    Relationships of foliar carbon isotope composition (δ13C) with foliar C, N, P, K, Ca, Mg contents and their ratios of 219 C3 species leaf samples, obtained in August in 2004 to 2007 from 82 high altitude grassland sites on the Qinghai-Tibet Plateau China, were examined. This was done with reference to the proposition that foliar δ13C increases with altitude and separately for the life-form groups of graminoids, forbs and shrubs and for the genera Stipa and Kobresia. For all samples, foliar δ13C was negatively related to foliar K, P and ∑K+ Ca+ Mg, and positively correlated to foliar C, C/N and C/P. The significance of these correlations differed for the taxonomic and life-form groups. Lack of a relationship of foliar δ13C with foliar N was inconsistent with the majority of studies that have shown foliar δ13C to be positively related to foliar N due to a decrease of Ci/Ca (the ratio between intercellular and atmospheric concentration of CO2) and explained as a result of greater photosynthetic capacity at higher foliar N concentration. However this inconsistency relates to other high altitude studies that have found that photosynthetic capacity remains constant as foliar N increases. After accounting for the altitudinal relationship with foliar δ13C, of the elements only the K effect was significant and was most strongly expressed for Kobresia. It is concluded that factors critical to plant survival and growth at very high altitudes, such as low atmospheric pressure and low temperatures, may preclude expression of relationships between foliar δ13C and foliar elements that have been observed at lower altitudes. PMID:23565275

  4. Evolution of chemical and isotopic composition of inorganic carbon in a complex semi-arid zone environment: Consequences for groundwater dating using radiocarbon

    NASA Astrophysics Data System (ADS)

    Meredith, K. T.; Han, L. F.; Hollins, S. E.; Cendón, D. I.; Jacobsen, G. E.; Baker, A.

    2016-09-01

    Estimating groundwater age is important for any groundwater resource assessment and radiocarbon (14C) dating of dissolved inorganic carbon (DIC) can provide this information. In semi-arid zone (i.e. water-limited environments), there are a multitude of reasons why 14C dating of groundwater and traditional correction models may not be directly transferable. Some include; (1) the complex hydrological responses of these systems that lead to a mixture of different ages in the aquifer(s), (2) the varied sources, origins and ages of organic matter in the unsaturated zone and (3) high evaporation rates. These all influence the evolution of DIC and are not easily accounted for in traditional correction models. In this study, we determined carbon isotope data for; DIC in water, carbonate minerals in the sediments, sediment organic matter, soil gas CO2 from the unsaturated zone, and vegetation samples. The samples were collected after an extended drought, and again after a flood event, to capture the evolution of DIC after varying hydrological regimes. A graphical method (Han et al., 2012) was applied for interpretation of the carbon geochemical and isotopic data. Simple forward mass-balance modelling was carried out on key geochemical processes involving carbon and agreed well with observed data. High values of DIC and δ13CDIC, and low 14CDIC could not be explained by a simple carbonate mineral-CO2 gas dissolution process. Instead it is suggested that during extended drought, water-sediment interaction leads to ion exchange processes within the top ∼10-20 m of the aquifer which promotes greater calcite dissolution in saline groundwater. This process was found to contribute more than half of the DIC, which is from a mostly 'dead' carbon source. DIC is also influenced by carbon exchange between DIC in water and carbonate minerals found in the top 2 m of the unsaturated zone. This process occurs because of repeated dissolution/precipitation of carbonate that is dependent on

  5. Stable isotopic composition of bottled mineral waters from Romania

    NASA Astrophysics Data System (ADS)

    Bădăluţă, Carmen; Nagavciuc, Viorica; Perșoiu, Aurel

    2015-04-01

    Romania has a high potential of mineral waters resources, featuring one of the largest mineral resources at European and global level. In the last decade, due to increased in consumption of bottled water, numerous brands have appeared on the market, with equally numerous and variable sources of provenance. In this study we have analyzed the isotopic composition of bottled mineral waters from Romania in order to determine their source and authenticity. We have analysed 32 carbonated and 24 non-carbonated mineral waters from Romania. and the results were analysed in comparison with stable isotope data from precipitation and river waters. Generally, the isotopic values of the mineral waters follow those in precipitation; however, differences occur in former volcanic regions (due to deep circulation of meteoric waters and increased exchange with host rock and volcanic CO2), as well as in mountainous regions, where high-altitude recharge occurs.

  6. Site-Specific Carbon Isotopes in Organics

    NASA Astrophysics Data System (ADS)

    Piasecki, A.; Eiler, J. M.

    2012-12-01

    Natural organic molecules exhibit a wide range of internal site-specific isotope variation (i.e., molecules with same isotopic substitution type but different site). Such variations are generally unconstrained by bulk isotopic measurements. If known, site-specific variations might constrain temperatures of equilibrium, mechanisms of formation or consumption reactions, and possibly other details. For example, lipids can exhibit carbon isotope differences of up to 30‰ between adjacent carbon sites as a result of fractionations arising during decarboxylation of pyruvate and other steps in lipid biosynthesis(1). We present a method for site-specific carbon isotope analysis of propane, based on high-resolution, multi-collector gas source mass spectrometry, using a novel prototype instrument - the Thermo MAT 253 Ultra. This machine has an inlet system and electron bombardment ion source resembling those in conventional stable isotope gas source mass spectrometers, and the energy filter, magnet, and detector array resembling those in multi-collector ICPMS and TIMS. The detector array has 7 detector positions, 6 of which are movable, and each of which can collect ions with either a faraday cup (read through amplifiers ranging from 107-1012 ohms) or an SEM. High mass resolving power (up to 27,000, MRP = M/dM definition) is achieved through a narrow entrance slit, adjustable from 250 to 5 μm. Such resolution can cleanly separate isobaric interferences between isotopologues of organic molecules having the same cardinal mass (e.g., 13CH3 and 12CH2D). We use this technology to analyze the isotopologues and fragments of propane, and use such data to solve for the site-specific carbon isotope fractionation. By measuring isotopologues of both the one-carbon (13CH3) and the two-carbon (13C12CH4) fragment ion, we can solve for both bulk δ13C and the difference in δ13C between the terminal and central carbon position. We tested this method by analyzing mixtures between natural

  7. A Holocene record of endogenic iron and manganese precipitation, isotopic composition of endogenic carbonate, and vegetation history in a lake-fen complex in northwestern Minnesota

    USGS Publications Warehouse

    Dean, Walter E.; Doner, Lisa A.

    2011-01-01

    percent in the LSL-B core and 15.5 percent in the LSF-10 core. Values of delta18O in mollusk (Pisidium) and ostracode shells increase by only about 20 per mil from the bottom to the top of the LSL-B core (about 12600-2200 calendar years). The remarkably constant oxygen-isotope composition throughout the Holocene suggests that environmental conditions affecting values of delta18O (temperature, salinity, composition of the water, composition of precipitation) did not change greatly. Values of delta13C in carbonate shells generally decreased by about 2 per mil from 9000 calendar years to 6000 calendar years, but they did not increase in organic carbon. This mid-Holocene increase in delta13C in shells but not in organic carbon is likely due to an increase in residence time. A late Pleistocene forest dominated by spruce was replaced in the early Holocene by a pine forest. The pine forest migrated east during the middle Holocene and was replaced by an open sagebrush-oak savanna. The western migration of forests into northwestern Minnesota is marked first by a hardwood forest and finally a pine forest.

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

    PubMed Central

    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

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Nucleosynthesis and the Isotopic Composition of Stardust

    NASA Technical Reports Server (NTRS)

    Tielens, Alexander G. M.

    1997-01-01

    Various components have been isolated from carbonaceous meteorites with an isotopically anomalous elemental composition. Several of these are generally thought to represent stardust containing a nucleosynthetic record of their birthsites. This paper discusses the expected isotopic composition of stardust based upon astronomical observations and theoretical studies of their birthsites: red giants and supergiants, planetary nebulae, C-rich Wolf-Rayet stars, novae and supernovae. Analyzing the stardust budget, it is concluded that about 15% of the elements will be locked up in stardust components in the interstellar medium. This stardust will be isotopically heterogenous on an individual grain basis by factors ranging from 2 to several orders of magnitude. Since comets may have preserved a relatively unprocessed record of the stardust entering the solar nebula, isotopic studies of returned comet samples may provide valuable information on the nucleosynthetic processes taking place in the interiors of stars and the elemental evolution of the Milky Way.

  11. Diel variations in carbon isotopic composition and concentration of organic acids and their impact on plant dark respiration in different species.

    PubMed

    Lehmann, M M; Wegener, F; Werner, R A; Werner, C

    2016-09-01

    Leaf respiration in the dark and its C isotopic composition (δ(13) CR ) contain information about internal metabolic processes and respiratory substrates. δ(13) CR is known to be less negative compared to potential respiratory substrates, in particular shortly after darkening during light enhanced dark respiration (LEDR). This phenomenon might be driven by respiration of accumulated (13) C-enriched organic acids, however, studies simultaneously measuring δ(13) CR during LEDR and potential respiratory substrates are rare. We determined δ(13) CR and respiration rates (R) during LEDR, as well as δ(13) C and concentrations of potential respiratory substrates using compound-specific isotope analyses. The measurements were conducted throughout the diel cycle in several plant species under different environmental conditions. δ(13) CR and R patterns during LEDR were strongly species-specific and showed an initial peak, which was followed by a progressive decrease in both values. The species-specific differences in δ(13) CR and R during LEDR may be partially explained by the isotopic composition of organic acids (e.g., oxalate, isocitrate, quinate, shikimate, malate), which were (13) C-enriched compared to other respiratory substrates (e.g., sugars and amino acids). However, the diel variations in both δ(13) C and concentrations of the organic acids were generally low. Thus, additional factors such as the heterogeneous isotope distribution in organic acids and the relative contribution of the organic acids to respiration are required to explain the strong (13) C enrichment in leaf dark-respired CO2 .

  12. Improvement of 2,4-dinitrophenylhydrazine derivatization method for carbon isotope analysis of atmospheric acetone.

    PubMed

    Wen, Sheng; Yu, Yingxin; Guo, Songjun; Feng, Yanli; Sheng, Guoying; Wang, Xinming; Bi, Xinhui; Fu, Jiamo; Jia, Wanglu

    2006-01-01

    Through simulation experiments of atmospheric sampling, a method via 2,4-dinitrophenylhydrazine (DNPH) derivatization was developed to measure the carbon isotopic composition of atmospheric acetone. Using acetone and a DNPH reagent of known carbon isotopic compositions, the simulation experiments were performed to show that no carbon isotope fractionation occurred during the processes: the differences between the predicted and measured data of acetone-DNPH derivatives were all less than 0.5 per thousand. The results permitted the calculation of the carbon isotopic compositions of atmospheric acetone using a mass balance equation. In this method, the atmospheric acetone was collected by a DNPH-coated silica cartridge, washed out as acetone-DNPH derivatives, and then analyzed by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Using this method, the first available delta13C data of atmospheric acetone are presented.

  13. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Winschel, R.A.; Lancet, M.S.; Burke, F.P.

    1990-07-01

    Consol R D is developing and demonstrating stable carbon isotope analysis as a method to quantitatively distinguish coal-derived and petroleum-derived carbon in products from coal/petroleum coprocessing. The approach taken is to develop the method, then demonstrate its application on authentic continuous-unit products. The significance of selective isotopic fractionation is being determined and, if necessary, corrections will be applied to account for it. Precision, accuracy and range of applicability are being defined. The value of accessory analytical techniques also is being assessed. The program is designed to address a substantial, demonstrated need of coprocessing research (both exploratory and development) for a technique to quantitatively distinguish the contributions of the individual coprocessing feedstocks to the various products. The carbon isotope technique currently is in routine use for other applications. Progress is discussed. 7 refs., 7 figs., 12 tabs.

  14. Nickel isotopic composition of the mantle

    NASA Astrophysics Data System (ADS)

    Gall, Louise; Williams, Helen M.; Halliday, Alex N.; Kerr, Andrew C.

    2017-02-01

    This paper presents a detailed high-precision study of Ni isotope variations in mantle peridotites and their minerals, komatiites as well as chondritic and iron meteorites. Ultramafic rocks display a relatively large range in δ60 Ni (permil deviation in 60 Ni /58 Ni relative to the NIST SRM 986 Ni isotope standard) for this environment, from 0.15 ± 0.07‰ to 0.36 ± 0.08‰, with olivine-rich rocks such as dunite and olivine cumulates showing lighter isotope compositions than komatiite, lherzolite and pyroxenite samples. The data for the mineral separates shed light on the origin of these variations. Olivine and orthopyroxene display light δ60 Ni whereas clinopyroxene and garnet are isotopically heavy. This indicates that peridotite whole-rock δ60 Ni may be controlled by variations in modal mineralogy, with the prediction that mantle melts will display variable δ60 Ni values due to variations in residual mantle and cumulate mineralogy. Based on fertile peridotite xenoliths and Phanerozoic komatiite samples it is concluded that the upper mantle has a relatively homogeneous Ni isotope composition, with the best estimate of δ60Nimantle being 0.23 ± 0.06‰ (2 s.d.). Given that >99% of the Ni in the silicate Earth is located in the mantle, this also defines the Ni isotope composition of the Bulk Silicate Earth (BSE). This value is nearly identical to the results obtained for a suite of chondrites and iron meteorites (mean δ60 Ni 0.26 ± 0.12‰ and 0.29 ± 0.10‰, respectively) showing that the BSE is chondritic with respect to its Ni isotope composition, with little to no Ni mass-dependent isotope fractionation resulting from core formation.

  15. Identification and carbon isotope composition of a novel branched GDGT isomer in lake sediments: Evidence for lacustrine branched GDGT production

    NASA Astrophysics Data System (ADS)

    Weber, Yuki; De Jonge, Cindy; Rijpstra, W. Irene C.; Hopmans, Ellen C.; Stadnitskaia, Alina; Schubert, Carsten J.; Lehmann, Moritz F.; Sinninghe Damsté, Jaap S.; Niemann, Helge

    2015-04-01

    Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are bacterial membrane lipids that occur ubiquitously in soils and lacustrine sediments and have great potential as proxy indicators for paleotemperature and pH reconstructions. Initially, brGDGTs in lakes were thought to originate from soils of the watershed. The composition of the lacustrine brGDGT pool, however, often differs substantially from that in catchment soils, complicating the application of the brGDGT paleothermometer to lake sediments. This suggests that terrigenous brGDGT signals in lacustrine sedimentary archives may be affected by aquatic in situ production. In sediments of a Swiss mountain lake, we detected a novel hexamethylated brGDGT, which elutes between the known 5- and 6-methyl brGDGT isomers during HPLC-MS analysis. This novel isomer accounted for 8.5% of the total brGDGTs. Most remarkably, this brGDGT was not detected in soils collected from the catchment of the lake, providing circumstantial evidence for an in situ brGDGT source in the lake's water column or sediments. Isolation of the compound by preparative HPLC and subsequent GC-MS analysis of the alkyl chains revealed that the novel brGDGT comprises two structural isomers. One possesses a 5,13,16- and a 6,13,16-trimethyloctacosanyl moiety and constitutes 84% of the new brGDGT; the second contains a 13,16-dimethyloctacosanyl and a 5,13,16,23-tetramethyloctacosanyl moiety. The δ13C values of both the alkyl chains derived from the novel brGDGT (-46‰) and all other major brGDGTs (-43‰ to -44‰) were significantly lower than those of brGDGT-derived alkanes in catchment soils (-27‰ to -28‰) further attesting to in situ production of brGDGTs in the studied lake.

  16. Stable isotope mass balances versus concentration differences of dissolved inorganic carbon - implications for tracing carbon turnover in reservoirs.

    PubMed

    Barth, Johannes A C; Mader, Michael; Nenning, Franziska; van Geldern, Robert; Friese, Kurt

    2017-02-13

    The aim of this study was to identify sources of carbon turnover using stable isotope mass balances. For this purpose, two pre-reservoirs in the Harz Mountains (Germany) were investigated for their dissolved and particulate carbon contents (dissolved inorganic carbon (DIC), dissolved organic carbon, particulate organic carbon) together with their stable carbon isotope ratios. DIC concentration depth profiles from March 2012 had an average of 0.33 mmol L(-1). Increases in DIC concentrations later on in the year often corresponded with decreases in its carbon isotope composition (δ(13)CDIC) with the most negative value of -18.4 ‰ in September. This led to a carbon isotope mass balance with carbon isotope inputs of -28.5 ‰ from DOC and -23.4, -31.8 and -30.7 ‰ from algae, terrestrial and sedimentary matter, respectively. Best matches between calculated and measured DIC gains were achieved when using the isotope composition of algae. This shows that this type of organic material is most likely responsible for carbon additions to the DIC pool when its concentrations and δ(13)CDIC values correlate negatively. The presented isotope mass balance is transferable to other surface water and groundwater systems for quantification of organic matter turnover.

  17. Method of making carbon-carbon composites

    DOEpatents

    Engle, Glen B.

    1993-01-01

    A process for making 2D and 3D carbon-carbon composites having a combined high crystallinity, high strength, high modulus and high thermal and electrical conductivity. High-modulus/high-strength mesophase derived carbon fibers are woven into a suitable cloth. Layers of this easily graphitizible woven cloth are infiltrated with carbon material to form green composites. The carbonized composite is then impregnated several times with pitch by covering the composite with hot pitch under pressure. The composites are given a heat treatment between each impregnant step to crack up the infiltrated carbon and allow additional pitch to enter the microstructure during the next impregnation cycle. The impregnated composites are then given a final heat treatment in the range 2500.degree. to 3100.degree. C. to fully graphitize the fibers and the matrix carbon. The composites are then infiltrated with pyrolytic carbon by chemical vapor deposition in the range 1000.degree. C. to 1300.degree. C. at a reduced. pressure.

  18. Carbon and Carbon Isotope Cycling in the Western Canadian Arctic

    NASA Astrophysics Data System (ADS)

    Mol, Jacoba; Thomas, Helmuth

    2016-04-01

    Increasing carbon dioxide levels in the atmosphere are having drastic effects on the global oceans. The Arctic Ocean is particularly susceptible to change as warming, sea-ice loss and a weak buffering capacity all influence this complicated semi-enclosed sea. In order to investigate the inorganic carbon system in the Canadian Arctic, water samples were collected in the Beaufort Sea, on the Alaskan shelf, at the Mackenzie river delta, and in Amundsen Gulf during the summer of 2014 and were analyzed for dissolved inorganic carbon (DIC), total alkalinity (TA), DI13C and 18O isotopes. Carbon isotopes are used to investigate the role of biological production on the uptake and transfer of inorganic carbon to depth. A preferential uptake of the lighter 12C relative to the heavier 13C isotope during biological production leads to a fractionation of the 13C/12C isotopes in both the organic matter and the water column. This results in an enrichment of DI13C in the high productivity surface waters and a depletion of DI13C at depth. Physical processes including freshwater input, brine rejection, and water mass mixing are investigated through the measurement of oxygen isotopes. Differences in the carbon system across the study area due to both biological and physical processes are assessed using depth profiles of DI13C and related carbon system parameters.

  19. Controls on the stable isotope compositions of travertine from hyperalkaline springs in Oman: Insights from clumped isotope measurements

    NASA Astrophysics Data System (ADS)

    Falk, E. S.; Guo, W.; Paukert, A. N.; Matter, J. M.; Mervine, E. M.; Kelemen, P. B.

    2016-11-01

    Carbonate formation at hyperalkaline springs is typical of serpentinization in peridotite massifs worldwide. These travertines have long been known to exhibit large variations in their carbon and oxygen isotope compositions, extending from apparent equilibrium values to highly depleted values. However, the exact causes of these variations are not well constrained. We analyzed a suite of well-characterized fresh carbonate precipitates and travertines associated with hyperalkaline springs in the peridotite section of the Samail ophiolite, Sultanate of Oman, and found their clumped isotope compositions vary systematically with formation environments. Based on these findings, we identified four main processes controlling the stable isotope compositions of these carbonates. These include hydroxylation of CO2, partial isotope equilibration of dissolved inorganic carbon, mixing between isotopically distinct carbonate end-members, and post-depositional recrystallization. Most notably, in fresh crystalline films on the surface of hyperalkaline springs and in some fresh carbonate precipitates from the bottom of hyperalkaline pools, we observed large enrichments in Δ47 (up to ∼0.2‰ above expected equilibrium values) which accompany depletions in δ18O and δ13C, yielding about 0.01‰ increase in Δ47 and 1.1‰ decrease in δ13C for every 1‰ decrease in δ18O, relative to expected equilibrium values. This disequilibrium trend, also reflected in preserved travertines ranging in age from modern to ∼40,000 years old, is interpreted to arise mainly from the isotope effects associated with the hydroxylation of CO2 in high-pH fluids and agrees with our first-order theoretical estimation. In addition, in some fresh carbonate precipitates from the bottom of hyperalkaline pools and in subsamples of one preserved travertine terrace, we observed additional enrichments in Δ47 at intermediate δ13C and δ18O, consistent with mixing between isotopically distinct carbonate end

  20. Carbon isotope systematics of individual hydrocarbons in hydrothermal petroleum from Escanaba Trough, Northeastern Pacific Ocean

    USGS Publications Warehouse

    Simoneit, B.R.T.; Schoell, M.; Kvenvolden, K.A.

    1997-01-01

    We submitted individual aliphatic and polycyclic aromatic hydrocarbons in samples of hydrothermal petroleum from Escanaba trough to compound specific isotope analysis to trace their origins. The carbon isotope compositions of the alkanes and polycyclic aromatic hydrocarbons (means -27.5 and -24.7%, respectively) reflect a primarily terrestrial organic matter source.We submitted individual aliphatic and polycyclic aromatic hydrocarbons in samples of hydrothermal petroleum from Escanaba Trough to compound specific isotope analysis to trace their origins. The carbon isotope compositions of the alkanes and polycyclic aromatic hydrocarbons (means -27.5 and -24.7 per mill, respectively) reflect a primarily terrestrial organic matter source.

  1. Stable isotope compositions of carbonate and inclusion-hosted water of speleothems from the last interglacial - spatial patterns of climate fluctuations in Europe

    NASA Astrophysics Data System (ADS)

    Demény, Attila; Kern, Zoltán; Czuppon, György; Németh, Alexandra; Leél-Őssy, Szabolcs; Shen, Chuan-Chou; Vennemann, Torsten

    2016-04-01

    Studies on the last interglacial (LIG) can provide information on how our environment behaved in a period of slightly higher global temperatures at about 120 ka compared to the current climate conditions. This paper presents complex stable H-C-O isotope records obtained for carbonate and fluid inclusion hosted water of U-Th dated stalagmites from the Baradla Cave system in Central Europe. Comparing C and O isotope data with records reported for other speleothem (cave-hosted carbonate) deposits from Europe revealed the complex behavior of these climate proxies, with a concerted relative increase in 18O of carbonates from 128 to 120 ka and synchronized shifts in the opposite direction after 119 ka. The hydrogen isotope analyses of inclusion-hosted water extracted from the BAR-II stalagmite also correspond to the regional climate proxy records, with meaningful deviations from global temperature trends. Beside the well known 120 ka climate optimum and the subsequent cooling starting at about 118 ka, the δD values show a negative peak at about 124-125 ka that does not appear in the C-O isotope data. This negative peak fits well to temperature and humidity changes inferred from proxy records from the northern Atlantic to the eastern Mediterranean. Spatial distributions of these variables show, that while the northern Atlantic ocean experienced a cold phase (possibly also dry in NW Europe), the Mediterranean region was characterized by warm, humid conditions and enhanced seasonality, most probably related to a freshwater flux to the North Atlantic and consequent large-scale heat and moisture transport changes affecting the Mediterranean. The combined interpretation of H-C-O isotope data revealed that the Alpine and Mediterranean regions behaved differently again during Greenland Stadial 26 (GS26, ~119 to 115.5 ka). While the Alpine records fluctuated in close agreement with the Central Greenland ice core δ18O data, the BAR-II stalagmite and southern European records

  2. Isotope-based Fluvial Organic Carbon (ISOFLOC) Model: Model formulation, sensitivity, and evaluation

    NASA Astrophysics Data System (ADS)

    Ford, William I.; Fox, James F.

    2015-06-01

    Watershed-scale carbon budgets remain poorly understood, in part due to inadequate simulation tools to assess in-stream carbon fate and transport. A new numerical model termed ISOtope-based FLuvial Organic Carbon (ISOFLOC) is formulated to simulate the fluvial organic carbon budget in watersheds where hydrologic, sediment transport, and biogeochemical processes are coupled to control benthic and transported carbon composition and flux. One ISOFLOC innovation is the formulation of new stable carbon isotope model subroutines that include isotope fractionation processes in order to estimate carbon isotope source, fate, and transport. A second innovation is the coupling of transfers between carbon pools, including algal particulate organic carbon, fine particulate and dissolved organic carbon, and particulate and dissolved inorganic carbon, to simulate the carbon cycle in a comprehensive manner beyond that of existing watershed water quality models. ISOFLOC was tested and verified in a low-gradient, agriculturally impacted stream. Results of a global sensitivity analysis suggested the isotope response variable had unique sensitivity to the coupled interaction between fluvial shear resistance of algal biomass and the concentration of dissolved inorganic carbon. Model calibration and validation suggested good agreement at event, seasonal, and annual timescales. Multiobjective uncertainty analysis suggested inclusion of the carbon stable isotope routine reduced uncertainty by 80% for algal particulate organic carbon flux estimates.

  3. Stable carbon and nitrogen isotopic compositions of ambient aerosols collected from Okinawa Island in the western North Pacific Rim, an outflow region of Asian dusts and pollutants

    NASA Astrophysics Data System (ADS)

    Kunwar, Bhagawati; Kawamura, Kimitaka; Zhu, Chunmao

    2016-04-01

    Stable carbon (δ13C) and nitrogen (δ15N) isotope ratios were measured for total carbon (TC) and nitrogen (TN), respectively, in aerosol (TSP) samples collected at Cape Hedo, Okinawa, an outflow region of Asian pollutants, during 2009-2010. The averaged δ13C and δ15N ratios are -22.2‰ and +12.5‰, respectively. The δ13C values are similar in both spring (-22.5‰) and winter (-22.5‰), suggesting the similar sources and/or source regions. We found that δ13C from Okinawa aerosols are ca. 2‰ higher than those reported from Chinese megacities probably due to photochemical aging of organic aerosols. A strong correlation (r = 0.81) was found between nss-Ca and TSP, suggesting that springtime aerosols are influenced from Asian dusts. However, carbonates in the Asian dusts were titrated with acidic species such as sulfuric acid and oxalic acid during atmospheric transport although two samples suggested the presence of remaining carbonate. No correlations were found between δ13C and tracer compounds (levoglucosan, elemental carbon, oxalic acid, and Na+). During winter and spring, coal burning is significant source in China. Based on isotopic mass balance, contribution of coal burning origin particles to total aerosol carbon was estimated as ca. 97% in winter, which is probably associated with the high emissions in China. Contribution of NO3- to TN was on average 45% whereas that of NH4+ was 18%. These results suggest that vehicular exhaust is an important source of TN in Okinawa aerosols. Concentration of water-soluble organic nitrogen (WSON) is higher in summer, suggesting that WSON is more emitted from the ocean in warmer season whereas inorganic nitrogen is more emitted in winter and spring from pollution sources in the Asian continent.

  4. Mercury isotope compositions in North American forest soils and litters

    NASA Astrophysics Data System (ADS)

    Zheng, W.; Obrist, D.; Bergquist, B. A.

    2013-12-01

    (II), indicating that photochemical reduction (either on the surface of soils and vegetations, in surface water or in the atmosphere) is the plausible cause of the MIF in the soils. We are currently studying samples from the other three sites to determine the variation of Hg isotope composition in soils formed in different geological and climatic settings. We will also evaluate the correlation between Hg isotope composition in soils and organic carbon, precipitation and clay content in order to determine the key environmental factors that shape the Hg isotope composition in soils.

  5. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Lancet, M.S.; Winschel, R.A.; Burke, F.P.

    1991-03-01

    Research on coprocessing materials/products continued. Major topics reported here are described below. Microautoclave runs are described in which gases and insoluble organic matter produced from five coals and gases produced from three petroleum resids were analyzed to study feedstock/product selective isotopic fractionation. Selective isotopic fractionation was further explored through isotope analysis of the feed New Mexico coal and products from a continuous coal liquefaction run (HRI CC-10 or 227-68). Feeds (Texas lignite/Maya VSB) and products from two HRI continuous coprocessing runs (227-54 and 238-12) were analyzed. The results were corrected for selective isotopic fractionation and carbon sourcing was performed for the product fractions. {sup 1}H-NMR and phenolic -OH determinations are reported for all continuous unit samples obtained under this contract. 13 refs., 17 figs., 40 tabs.

  6. New Carbonate Standard Reference Materials for Boron Isotope Geochemistry

    NASA Astrophysics Data System (ADS)

    Stewart, J.; Christopher, S. J.; Day, R. D.

    2015-12-01

    The isotopic composition of boron (δ11B) in marine carbonates is well established as a proxy for past ocean pH. Yet, before palaeoceanographic interpretation can be made, rigorous assessment of analytical uncertainty of δ11B data is required; particularly in light of recent interlaboratory comparison studies that reported significant measurement disagreement between laboratories [1]. Well characterised boron standard reference materials (SRMs) in a carbonate matrix are needed to assess the accuracy and precision of carbonate δ11B measurements throughout the entire procedural chemistry; from sample cleaning, to ionic separation of boron from the carbonate matrix, and final δ11B measurement by multi-collector inductively coupled plasma mass spectrometry. To date only two carbonate reference materials exist that have been value-assigned by the boron isotope measurement community [2]; JCp-1 (porites coral) and JCt-1 (Giant Clam) [3]. The National Institute of Standards and Technology (NIST) will supplement these existing standards with new solution based inorganic carbonate boron SRMs that replicate typical foraminiferal and coral B/Ca ratios and δ11B values. These new SRMs will not only ensure quality control of full procedural chemistry between laboratories, but have the added benefits of being both in abundant supply and free from any restrictions associated with shipment of biogenic samples derived from protected species. Here we present in-house δ11B measurements of these new boron carbonate SRM solutions. These preliminary data will feed into an interlaboratory comparison study to establish certified values for these new NIST SRMs. 1. Foster, G.L., et al., Chemical Geology, 2013. 358(0): p. 1-14. 2. Gutjahr, M., et al., Boron Isotope Intercomparison Project (BIIP): Development of a new carbonate standard for stable isotopic analyses. Geophysical Research Abstracts, EGU General Assembly 2014, 2014. 16(EGU2014-5028-1). 3. Inoue, M., et al., Geostandards and

  7. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Burke, F.P.; Winschel, R.A.; Lancet, M.S.

    1989-06-01

    The program is designed to address a substantial, demonstrated need of the coprocessing community (both exploratory and development) for a technique to quantitatively distinguish the contributions of the individual coprocessing feedstocks to the various products. The carbon isotope technique is currently in routine use for other applications. Results achieved this quarter include: Feed and product fractions from a Kentucky 9 coal/Kentucky tar sand bitumen coprocessing bench unit run at the Kentucky Center for Applied Energy Research (CAER) were analyzed for carbon isotope ratios. Corrections were made to the coal carbon recoveries and selectivities from the products of HRI Run 227-53. Feeds (Westerholt coal/Cold Lake VSB) and products from two periods of HRI coprocessing Run 238-1 were analyzed. Three petroleum samples and three coal samples were pyrolyzed at 800{degree}F for 30 min to determine the effect of pyrolysis on the isotopic homogeneity of each petroleum and coal sample. Products from each pyrolysis test were separated into five fractions; an additional set of coprocessing samples and a set of two-stage coal liquefaction samples were obtained from HRI for future work; work performed by the Pennsylvania State University show that microscopy is a promising method for distinguishing coal and petroleum products in residual coprocessing materials; and coal and petroleums that have large differences in carbon isotope ratios were identified for Auburn University. 7 refs., 2 figs., 12 tabs.

  8. Coprecipitation and isotopic fractionation of boron in modern biogenic carbonates

    SciTech Connect

    Vengosh, A. Hebrew Univ., Jerusalem ); Chivas, A.R.; McCulloch, M.T. ); Kolodny, Y.; Starinsky, A. )

    1991-10-01

    The abundances and isotopic composition of boron in modern, biogenic calcareous skeletons from the Gulf of Elat, Israel, the Great Barrier Reef, Australia, and in deep-sea sediments have been examined by negative thermal-ionization mass spectrometry. The selected species (Foraminifera, Pteropoda, corals, Gastropoda, and Pelecypoda) yield large variations in boron concentration that range from 1 ppm in gastropod shells to 80 ppm in corals. The variations of {delta}{sup 11}B may be controlled by isotopic exchange of boron species in which {sup 10}B is preferentially partitioned into the tetrahedral species, and coprecipitation of different proportions of trigonal and tetrahedral species in the calcium carbonates. The B content and {delta}{sup 11}B values of deep-sea sediments, Foraminifera tests, and corals are used to estimate the global oceanic sink of elemental boron by calcium carbonate deposition. As a result of enrichment of B in corals, a substantially higher biogenic sink of 6.4 {plus minus} 0.9 {times} 10{sup 10} g/yr is calculated for carbonates. This is only slightly lower than the sink for desorbable B in marine sediments (10 {times} 10{sup 10} g/yr) and approximately half that of altered oceanic crust (14 {times} 10{sup 10} g/yr). Thus, carbonates are an important sink for B in the oceans being {approximately}20% of the total sinks. The preferential incorporation of {sup 10}B into calcium carbonate results in oceanic {sup 11}B-enrichment, estimated as 1.2 {plus minus} 0.3 {times} 10{sup 12} per mil {center dot} g/yr. The boron-isotope composition of authigenic, well-preserved carbonate skeletons may provide a useful tool to record secular boron-isotope variations in seawater at various times in the geological record.

  9. Carbon isotopes as indicators of peatland growth?

    NASA Astrophysics Data System (ADS)

    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

  10. Carbon isotope fractionation of methyl bromide during agricultural soil fumigations

    USGS Publications Warehouse

    Bill, M.; Miller, L.G.; Goldstein, Allen H.

    2002-01-01

    The isotopic composition of methyl bromide (CH3Br) has been suggested to be a potentially useful tracer for constraining the global CH3Br budget. In order to determine the carbon isotopic composition of CH3Br emitted from the most significant anthropogenic application (pre-plant fumigation) we directly measured the ??13C of CH3Br released during commercial fumigation. We also measured the isotopic fractionation associated with degradation in agricultural soil under typical field fumigation conditions. The isotopic composition of CH3Br collected in soil several hours after injection of the fumigant was -44.5??? and this value increased to -20.7??? over the following three days. The mean kinetic isotope effect (KIE) associated with degradation of CH3Br in agricultural soil (12???) was smaller than the reported value for methylotrophic bacterial strain IMB-1, isolated from previously fumigated agricultural soil, but was similar to methylotrophic bacterial strain CC495, isolated from a pristine forest litter zone. Using this fractionation associated with the degradation of CH3Br in agricultural soil and the mean ??13C of the industrially manufactured CH3Br (-54.4???), we calculate that the agricultural soil fumigation source has a carbon isotope signature that ranges from -52.8??? to -42.0???. Roughly 65% of industrially manufactured CH3Br is used for field fumigations. The remaining 35% is used for structural and post-harvest fumigations with a minor amount used during industrial chemical manufacturing. Assuming that the structural and post-harvest fumigation sources of CH3Br are emitted without substantial fractionation, we calculate that the ??13C of anthropogenically emitted CH3Br ranges from -53.2??? to -47.5???.

  11. Calcium isotopic composition of mantle peridotites

    NASA Astrophysics Data System (ADS)

    Huang, F.; Kang, J.; Zhang, Z.

    2015-12-01

    Ca isotopes are useful to decipher mantle evolution and the genetic relationship between the Earth and chondrites. It has been observed that Ca isotopes can be fractionated at high temperature [1-2]. However, Ca isotopic composition of the mantle peridotites and fractionation mechanism are still poorly constrained. Here, we report Ca isotope composition of 12 co-existing pyroxene pairs in 10 lherzolites, 1 harzburgite, and 1 wehrlite xenoliths collected from Hainan Island (South Eastern China). Ca isotope data were measured on a Triton-TIMS using the double spike method at the Guangzhou Institute of Geochemistry, CAS. The long-term external error is 0.12‰ (2SD) based on repeated analyses of NIST SRM 915a and geostandards. δ44Ca of clinopyroxenes except that from the wehrlite ranges from 0.85‰ to 1.14‰, while opx yields a wide range from 0.98‰ up to 2.16‰. Co-existing pyroxene pairs show large ∆44Caopx-cpx (defined as δ44Caopx-δ44Cacpx) ranging from 0 to 1.23‰, reflecting equilibrium fractionation controlled by variable Ca contents in the opx. Notably, clinopyroxene of wehrlite shows extremely high δ44Ca (3.22‰). δ44Ca of the bulk lherzolites and harzburgites range from 0.86‰ to 1.14‰. This can be explained by extracting melts with slightly light Ca isotopic compositions. Finally, the high δ44Ca of the wehrlite (3.22‰) may reflect metasomatism by melt which has preferentially lost light Ca isotopes due to chemical diffusion during upwelling through the melt channel. [1] Amini et al (2009) GGR 33; [2] Huang et al (2010) EPSL 292.

  12. Laser ablation molecular isotopic spectrometry of carbon isotopes

    NASA Astrophysics Data System (ADS)

    Bol‧shakov, Alexander A.; Mao, Xianglei; Jain, Jinesh; McIntyre, Dustin L.; Russo, Richard E.

    2015-11-01

    Quantitative determination of carbon isotopes using Laser Ablation Molecular Isotopic Spectrometry (LAMIS) is described. Optical emission of diatomic molecules CN and C2 is used in these measurements. Two quantification approaches are presented: empirical calibration of spectra using a set of reference standards and numerical fitting of a simulated spectrum to the experimental one. Formation mechanisms of C2 and CN in laser ablation plasma are briefly reviewed to provide insights for implementation of LAMIS measurements. A simulated spectrum of the 12C2 Swan system was synthesized using four constituents within 473.5-476.5 nm. Simulation included three branches of 12C2 (1-0), branches R(0-0) and R(1-1), and branch P(9-8) of 12C2. Spectral positions of the tail lines in R(0-0) and R(1-1) were experimentally measured, since they were not accurately known before. The Swan band (1-0) of the isotopologue 13C12C was also simulated. Fitting to the experimental spectrum yielded the ratio 13C/12C = 1.08% in a good agreement with measurements by isotope ratio mass spectrometry. LAMIS promises to be useful in coal, oil and shale exploration, carbon sequestration monitoring, and agronomy studies.

  13. Carbon dioxide emissions from fossil fuel consumption and cement manufacture, 1751-1991; and an estimate of their isotopic composition and latitudinal distribution

    SciTech Connect

    Andres, R.J.; Marland, G.; Boden, T.; Bischof, S.

    1994-10-01

    This work briefly discusses four of the current research emphases at Oak Ridge National Laboratory regarding the emission of carbon dioxide (CO{sub 2}) from fossil fuel consumption, natural gas flaring and cement manufacture. These emphases include: (1) updating the 1950 to present time series of CO{sub 2} emissions from fossil fuel consumption and cement manufacture, (2) extending this time series back to 1751, (3) gridding the data at 1{sup 0} by 1{sup 0} resolution, and (4) estimating the isotopic signature of these emissions. In 1991, global emissions of CO{sub 2} from fossil fuel and cement increased 1.5% over 1990 levels to 6188 {times} 10{sup 6} metric tonnes C. The Kuwaiti oil fires can account for all of the increase. Recently published energy data (Etemad et al., 1991) allow extension of the CO emissions time series back to 1751. Preliminary examination shows good agreement with two other, but shorter, energy time series. A latitudinal distribution of carbon emissions is being completed. A southward shift in the major mass of CO{sub 2} emissions is occurring from European-North American latitudes towards central-southeast Asian latitudes, reflecting the growth of population and industrialization at these lower latitudes. The carbon isotopic signature of these emissions has been re-examined. The emissions of the last two decades are approximately 1{per_thousand} lighter than previously reported (Tans, 1981). This lightening of the emissions signature is due to fossil fuel gases and liquids, including a revision of their {delta}{sup 13}C isotopic signature and an increased production rate.

  14. Stable carbon isotope fractionation by sulfate-reducing bacteria

    NASA Technical Reports Server (NTRS)

    Londry, Kathleen L.; Des Marais, David J.

    2003-01-01

    Biogeochemical transformations occurring in the anoxic zones of stratified sedimentary microbial communities can profoundly influence the isotopic and organic signatures preserved in the fossil record. Accordingly, we have determined carbon isotope discrimination that is associated with both heterotrophic and lithotrophic growth of pure cultures of sulfate-reducing bacteria (SRB). For heterotrophic-growth experiments, substrate consumption was monitored to completion. Sealed vessels containing SRB cultures were harvested at different time intervals, and delta(13)C values were determined for gaseous CO(2), organic substrates, and products such as biomass. For three of the four SRB, carbon isotope effects between the substrates, acetate or lactate and CO(2), and the cell biomass were small, ranging from 0 to 2 per thousand. However, for Desulfotomaculum acetoxidans, the carbon incorporated into biomass was isotopically heavier than the available substrates by 8 to 9 per thousand. SRB grown lithoautotrophically consumed less than 3% of the available CO(2) and exhibited substantial discrimination (calculated as isotope fractionation factors [alpha]), as follows: for Desulfobacterium autotrophicum, alpha values ranged from 1.0100 to 1.0123; for Desulfobacter hydrogenophilus, the alpha value was 0.0138, and for Desulfotomaculum acetoxidans, the alpha value was 1.0310. Mixotrophic growth of Desulfovibrio desulfuricans on acetate and CO(2) resulted in biomass with a delta(13)C composition intermediate to that of the substrates. The extent of fractionation depended on which enzymatic pathways were used, the direction in which the pathways operated, and the growth rate, but fractionation was not dependent on the growth phase. To the extent that environmental conditions affect the availability of organic substrates (e.g., acetate) and reducing power (e.g., H(2)), ecological forces can also influence carbon isotope discrimination by SRB.

  15. Interfaces in carbon-carbon composites

    SciTech Connect

    Peebles, L.H.; Meyer, R.A.; Jortner, J.

    1988-01-01

    Carbon-carbon composites, consisting of a carbon matrix reinforced with carbon fibers, have complex microstructures. Several types of interfaces, microcracks, and various degress of local anisotropy were observed. This paper provides examples of microstructures seen in carbon-carbon composites, with emphasis on the interfaces. Information relating to the degree of bonding at interfaces, and its effects on composite behavior, is reviewed. The causes and effects of the various observed microstructures are beginning to be understood, but there remain many questions deserving further study.

  16. The Chlorine Isotope Composition of Martian Meteorites

    NASA Astrophysics Data System (ADS)

    Sharp, Z. D.; Shearer, C. K.; Agee, C.; Burger, P. V.; McKeegan, K. D.

    2014-11-01

    The Cl isotope composition of martian meteorites range from -3.8 to +8.6 per mil. Ol-phyric shergottites are lightest; crustally contaminated samples are heaviest, basaltic shergottites are in-between. The system is explained as two component mixing.

  17. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Lancet, M.S.; Winschel, R.A.; Burke, F.P.

    1991-02-01

    Consol R D is developing and demonstrating stable carbon isotope analysis as a method to quantitatively distinguish coal-derived and petroleum-derived carbon in products from coal/petroleum coprocessing. The approach taken is develop the method, then demonstrate its application on authentic continuous-unit products. The significance of selective isotopic fractionation is being determined and, when necessary, corrections are applied to account for it. Precision, accuracy and range of applicability are being defined. The value of accessory analytical techniques also is being assessed. Previously reported data on samples from HRI bench-scale coprocessing Runs 227-53 (Texas lignite/Maya ASB and Texas lignite/Maya VSB) and 238-1 (Westerholt coal/Cold Lake VSB) were corrected for selective isotopic fractionation. Carbon sourcing was performed on samples from HRI bench-scale coprocessing Run 227-60 (Texas lignite/Maya VSB) and samples from UOP bench-scale coprocessing Run 26 (Illinois 6 coal/Lloydminster vacuum resid); the latter data were corrected for isotopic fractionation, though the former could not be corrected. A paper presented at the 1990 DOE Direct Liquefaction Contractor's Review Meeting is appended. 15 refs., 21 figs., 22 tabs.

  18. Deconvolving the Carbon Isotope Record

    NASA Astrophysics Data System (ADS)

    Cramer, B. S.

    2003-12-01

    The evolution of the whole-ocean δ 13C value, under an assumption of steady state with respect to mass, can be modeled as: \\[ {d \\over dt}\\delta_\\Sigma(t)+{\\delta_\\Sigma(t) \\over \\tau_C}={1 \\over \\tau_C}\\delta_F(t) \\] where δ Σ is the whole-ocean δ 13C value, τ C is the residence time of carbon and a net instantaneous δ 13C forcing function is defined: \\[ \\delta_F=\\delta_i-f_{carb}\\Delta_{carb}-\\(1-f_{carb}\\)\\Delta_{org} \\] where δ i is the δ 13C value of carbon input (e.g. weathering and volcanism), fcarb is the fraction of carbon removed through burial of carbonates as opposed to organic carbon, and Δ carb and Δ org are the differences between δ Σ and δ 13C values for buried carbonate and organic carbon. The solution to this differential equation is: \\[ \\delta_\\Sigma\\(t\\)={1 \\over \\tau_C}\\int_0^t{{\\delta_F\\(t^\\prime\\)}e^{\\(-{t-t^\\prime \\over \\tau_C}\\)}dt^\\prime} \\] which can be expressed as a convolution \\[ \\delta_\\Sigma\\(t\\)={1 \\over \\tau_C} {{\\delta_F\\(t^\\prime\\)} \\otimes e^{\\(-{t-t^\\prime \\over \\tau_C}\\)}} \\] revealing that the evolution of the whole ocean δ 13C value is determined by the instantaneous δ 13C forcing (δ F) subjected to a causal (i.e. phase-shifting) low-pass filter whose frequency response is dependent only on the carbon residence time. One consequence of this observation is that variance in δ 13C records should be concentrated at wavelengths >0.1 m.y., thereby explaining the persistent appearance of cyclicity dependent on orbital eccentricity ( ˜0.1~and ˜0.4 m.y.~periods) in δ 13C records. I demonstrate that an assumption of non-linear forcing of fcarb by orbitally-forced variations in insolation can explain most of the structure of high-resolution δ 13C records throughout the Cenozoic. A second consequence is that τ C and δ F should be separable by numerical manipulation of δ 13C records. Two applications are 1) estimation of the residence time of carbon at

  19. Isotopic composition of Silurian seawater

    SciTech Connect

    Knauth, L.P.; Kealy, S.; Larimer, S.

    1985-01-01

    Direct isotopic analyses of 21 samples of the Silurian hydrosphere preserved as fluid inclusions in Silurian halite deposits in the Michigan Basin Salina Group yield delta/sup 18/O, deltaD ranging from 0.2 to +5.9 and -26 to -73, respectively. delta/sup 18/O has the same range as observed for modern halite facies evaporite waters and is a few per thousand higher than 100 analyses of fluid inclusions in Permian halite. deltaD is about 20 to 30 per thousand lower than modern and Permian examples. The trajectory of evaporating seawater on a deltaD-delta/sup 18/O diagram initially has a positive slope of 3-6, but hooks strongly downward to negative values, the shape of the hook depending upon humidity. Halite begins to precipitate at delta values similar to those observed for the most /sup 18/O rich fluid inclusions. Subsequent evaporation yields progressively more negative delta values as observed for the fluid inclusions. The fluid inclusion data can be readily explained in terms of evaporating seawater and are consistent with the degree of evaporation deduced from measured bromide profiles. These data are strongly inconsistent with arguments that Silurian seawater was 5.5 per thousand depleted in /sup 18/O. delta/sup 18/O for evaporite waters is systematically related to that of seawater, and does not show a -5.5 per thousand shift in the Silurian, even allowing for variables which affect the isotope evaporation trajectory. The lower deltaD may indicate a component of gypsum dehydration waters or may suggest a D-depleted Silurian hydrosphere.

  20. Isotopic composition of formaldehyde in urban air.

    PubMed

    Rice, Andrew L; Quay, Paul

    2009-12-01

    The isotopic composition of atmospheric formaldehyde was measured in air samples collected in urban Seattle, Washington. A recently developed gas chromatography-isotope ratio mass spectrometry analytical technique was used to extract formaldehyde directly from whole air, separate it from other volatile organic compounds, and measure its (13)C/(12)C and D/H ratio. Measurements of formaldehyde concentration were also made concomitant with isotope ratio. Results of the analysis of nine discrete air samples for delta(13)C-HCHO have a relatively small range in isotopic composition (-31 to -25 per thousand versus VPDB [+/-1.3 per thousand]) over a considerable concentration range (0.8-4.4 ppb [+/-15%]). In contrast, analyses of 17 air samples for deltaD-HCHO show a large range (-296 to +210 per thousand versus VSMOW [+/-50 per thousand]) over the concentrations measured (0.5-2.9 ppb). Observations of deltaD are weakly anticorrelated with concentration. Isotopic data are interpreted using both source- and sink-based approaches. Results of delta(13)C-HCHO are similar to those observed previously for a number of nonmethane hydrocarbons in urban environments and variability can be reconciled with a simple sink-based model. The large variability observed in deltaD-HCHO favors a source-based interpretation with HCHO depleted in deuterium from primary sources of HCHO (i.e., combustion) and HCHO enriched in deuterium from secondary photochemical sources (i.e., hydrocarbon oxidation).

  1. In situ analysis of carbon isotopes in North American diamonds

    NASA Astrophysics Data System (ADS)

    van Rythoven, A. D.; Hauri, E. H.; Wang, J.; McCandless, T.; Shirey, S. B.; Schulze, D. J.

    2010-12-01

    Diamonds from three North American kimberlite occurrences were investigated with cathodoluminescence (CL) and secondary ion mass spectrometry (SIMS) to determine their growth history and carbon isotope composition. Diamonds analyzed include fourteen from Lynx (Quebec), twelve from Kelsey Lake (Colorado) and eleven from A154 South (Diavik mine, Northwest Territories). Growth histories for the diamonds vary from simple to highly complex based on their CL images and depending on the individual stone. Deformation laminae are evident in CL images of the Lynx diamonds that typically are brownish in color. Two to five points per diamond were analyzed by SIMS for carbon isotope composition. Sample heterogeneity is minimal in terms of δ13C (vs. PDB) values. Points within single diamond had a maximum range of approximately 1 ‰. The results for the A154 South (-6.4 to -3 ‰) and Kelsey Lake (-11.2 to -2.6 ‰) stones were in accordance with earlier reported values. The Lynx kimberlite stones have anomalously high ratios and range from -3.5 to +0.2 ‰ (average: -1.4 ‰). No previous carbon isotope analyses on diamonds from Lynx or any other eastern Superior craton occurrence have been published. The diamonds possess carbon isotope ratios higher than those for the only other reported analyses of Superior craton diamonds at Wawa, Ontario (-5.5 to -1.1 ‰). In global terms, the only published analyses of diamonds that consistently contain even higher values are those from New South Wales (Australia). However, these diamonds are alluvial and contain eclogitic and/or exotic mineral inclusions. The Lynx diamonds are entirely peridotitic and from a primary deposit. The unusually low (i.e. >-5‰) δ13C values of the Lynx (and Wawa) diamonds may indicate a different carbon reservoir for the Superior craton mantle as compared to other cratons.

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

    SciTech Connect

    Magdas, D. A. Cristea, G. Bot, A. Mirel, V.

    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.

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

    NASA Astrophysics Data System (ADS)

    Magdas, D. A.; Cristea, G.; Bot, A.; Mirel, V.

    2013-11-01

    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 δ13C 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.

  4. Multiple sulfur and carbon isotope composition of sediments from the Belingwe Greenstone Belt (Zimbabwe): A biogenic methane regulation on mass independent fractionation of sulfur during the Neoarchean?

    NASA Astrophysics Data System (ADS)

    Thomazo, Christophe; Nisbet, Euan G.; Grassineau, Nathalie V.; Peters, Marc; Strauss, Harald

    2013-11-01

    To explore the linkage between mass-independent sulfur isotope fractionation (MIF-S) and δ13Corg excursions during the Neoarchean, as well as the contemporary redox state and biogeochemical cycling of carbon and sulfur, we report the results of a detailed carbon and multiple sulfur (δ34S, δ33S, δ36S) isotopic study of the ∼2.7 Ga Manjeri and ∼2.65 Ga Cheshire formations of the Ngezi Group (Belingwe Greenstone Belt, Zimbabwe). Multiple sulfur isotope data show non-zero Δ33S and Δ36S values for sediments older than 2.4 Ga (i.e. prior to the Great Oxidation Event, GOE), indicating MIF-S thought to be associated with low atmospheric oxygen concentration. However, in several 2.7-2.5 Ga Neoarchean localities, small-scale variations in MIF-S signal (magnitude) seem to correlate with negative excursion in δ13Corg, possibly reflecting a global connection between the relative reaction rate of different MIF-S source reaction and sulfur exit channels and the biogenic flux of methane into the atmosphere during periods of localized, microbiologically mediated, shallow surface-water oxygenation. The Manjeri Formation black shales studied here display a wide range of δ13Corg between -35.4‰ and -16.2‰ (average of -30.3 ± 6.0‰, 1σ), while the Cheshire Formation shales have δ13Corg between -47.7‰ and -35.1‰ (average -41.3 ± 3‰, 1σ). The δ34S values of sedimentary sulfides from Manjeri Formation vary between -15.15‰ and +2.37‰ (average -1.71 ± 4.76‰, 1σ), showing very small and mostly negative Δ33S values varying from -0.58‰ to 0.87‰ (average 0.02 ± 0.43‰, 1σ). Cheshire Formation black shale sulfide samples measured in this study have δ34S values ranging from -2.11‰ to 2.39‰ (average 0.25 ± 1.08‰, 1σ) and near zero and solely positive Δ33S anomalies between 0.14‰ and 1.17‰ (average 0.56 ± 0.29‰, 1σ). Moreover, Δ36S/Δ33S in the two formations are comparable with a slope of -1.38 (Manjeri Formation) and -1.67 (Cheshire

  5. [Carbon stable isotope composition (delta 13C) of lichen thalli in the forests in the vicinity of the Chernobyl atomic power station].

    PubMed

    Biazrov, L G; Gongal'skiĭ, K B; Pel'gunova, L A; Tiunov, A V

    2010-01-01

    The stable isotope abundance of carbon in the lichens Cladina mitis, Cladonia crispata Hypogymnia physodes, Parmelia sulcata has been investigated in a study relating these values with known levels of 106Ru, 134Cs, 137Cs and 144Ce defined activity in their thalli in the pine forests of region within a 30-km radius of the Chernobyl atomic power station and beyond it (37 km). All 63 samples of the lichens were obtained from 7 different sites. Small effects on delta 13C values in the lichens Cladina mitis, Hypogymnia physodes were found to be associated with distance from CNPP, activity level of radionuclides in them thalli whereas at Cladonia crispata is observed weighting of carbon with increase in values of 134Cs and 137Cs activity in thalli. Values of delta 13C the investigated lichen species more depends on habitat conditions rather than from levels of thalli radioactivity. In our study we didn't reveal the isotope specificity of any one species as it was not possible to establish a correlation between values of delta 13C and a particular species.

  6. [Metabolic isotopic effects of carbon and production process in cultivated plants in light of oscillatory concept for photosynthesis].

    PubMed

    Ivlev, A A; Dubinskiĭ, A Iu; Pichuzhkin, V I

    2013-01-01

    Some perspectives on the use of stable carbon isotopes (13C/12C) in studying production processes are considered. It has been shown that the efficiency of the isotope technique depends on the adequacy of the chosen model. The model of isotope fractionation proposed based on the oscillatory concept of photosynthesis provides for more accurate and comprehensive description of the observed empirical correlations between the yield (bioproductivity) and carbon isotope composition in cereal cultures as compared with the widely used stationary model.

  7. Method of making carbon-carbon composites

    SciTech Connect

    Engle, G.B.

    1993-06-08

    A method for fabricating a high-strength, high-modulus and high thermal and electrical conducting 2D laminate carbon-carbon composite is described comprising the steps of: (a) forming a green laminate composite comprising: (1) graphitizible carbon cloth plies, (2) fine graphitizible pitch powder; said cloth plies comprising mesophase derived pitch fiber tow with moduli in a range of 25 to 140 Msi, and (3) thermal conductivity enhancers; (b) heating the green laminate composite to a temperature high enough to cause the pitch powder to soften and pressing the composite to form a pressed green laminate composite comprised of graphitizible carbon cloth, pitch matrix and thermal conductivity enhancers; (c) heating the pressed green composite to at least 500 C. to: (1) carbonize the pitch, (2) form a carbon matrix and (3) shrink and crack the matrix carbon; (d) impregnating the composite with additional graphitizible pitch by covering the composite with the pitch and heating the covered composite to at least 200 C. to melt the pitch and permit it to flow into the composite and then increasing the pressure to at least 15 Psi; (e) heating the composites to at least 900 C.; (f) repeating steps d and e at least once; (g) heating the composite to between 2,400 to 3,100 C to graphitize the fibers and the pitch matrix carbon in the composites to produce a graphitized composite having cracks and pores; and (h) reimpregnating the graphitized composites by infiltrating the cracks and pores of the composites with a hydrocarbon gas at a temperature in the range 982 to 1,490 C. and depositing pyrolytic carbon in the pores and cracks.

  8. High Thermal Conductivity Carbon/Carbon Composites.

    DTIC Science & Technology

    1995-09-30

    The objective of this project was to develop a lowcost, high thermal conductivity carbon/carbon composite with a mesophase pitch -based matrix. A low...carbonization technique and heat treatment of the mesophase pitch was utilized to enhance composite properties by increasing the composite density...Three different fibers, T300 PAN-based, P55 pitch -based, and an experimental high thermal conductivity mesophase pitch -based, were incorporated as the

  9. Carbon Fiber Composites

    NASA Technical Reports Server (NTRS)

    1997-01-01

    HyComp(R), Inc. development a line of high temperature carbon fiber composite products to solve wear problems in the harsh environment of steel and aluminum mills. WearComp(R), self-lubricating composite wear liners and bushings, combines carbon graphite fibers with a polyimide binder. The binder, in conjunction with the fibers, provides the slippery surface, one that demands no lubrication, yet wears at a very slow rate. WearComp(R) typically lasts six to ten times longer than aluminum bronze. Unlike bronze, Wea