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Sample records for carbon isotopic signatures

  1. 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.

  2. Carbon Reservoir History of Mars Constrained by Atmospheric Isotope Signatures

    NASA Astrophysics Data System (ADS)

    Hu, Renyu; Kass, David M.; Ehlmann, Bethany L.; Yung, Yuk

    2014-11-01

    The evolution of the atmosphere on Mars is one of the most intriguing problems in the exploration of the Solar System, and the climate of Mars may have evolved from a warmer, wetter early state to the cold, dry current state. Because CO2 is the major constituent of Mars’s atmosphere, its isotopic signatures offer a unique window to trace the evolution of climate on Mars. Here we use a box model to trace the evolution of the carbon reservoir and its iso-topic signature on Mars, with carbonate deposition and atmospheric escape as the two sinks and magmatic activity as the sole source. We derive new quantitative constraints on the amount of carbonate deposition and the atmospher-ic pressure of Mars through time, extending into the Noachian, ~3.8 Gyr before present. This determination is based on recent Mars Science Laboratory (MSL) isotopic measurements of Mars’s atmosphere, recent orbiter, lander, and rover measurements of Mars’s surface, and a newly identified mechanism (photodissociation of CO) that efficiently enriches the heavy carbon isotope. In particular, we find that escape via CO photodissociation on Mars has a frac-tionation factor of 0.6 and hence, photochemical escape processes can effectively enrich 13C in the Mars’s atmos-phere during the Amazonian. As a result, modest carbonate deposition must have occurred early in Mars’s history to compensate the enrichment effects of photochemical processes and also sputtering, even when volcanic outgassing up to 200 mbar occurred during the Hesperian. For a photochemical escape flux that scales as the square of the solar EUV flux or more, at least 0.1 bar of CO2 must have been deposited as carbonates in the Noachian and Hesperian. More carbonate deposition would be required if carbonate deposition only occurred in the Noachian or with low fractionation factors.

  3. Carbon Reservoir History of Mars Constrained by Atmospheric Isotope Signatures

    NASA Astrophysics Data System (ADS)

    Hu, R.; Kass, D. M.; Ehlmann, B. L.; Yung, Y. L.

    2014-12-01

    The evolution of the atmosphere on Mars is one of the most intriguing problems in the exploration of the Solar System, and the climate of Mars may have evolved from a warmer, wetter early state to the cold, dry current state. Because CO2 is the major constituent of Mars's atmosphere, its isotopic signatures offer a unique window to trace the evolution of climate on Mars. Here we use a box model to trace the evolution of the carbon reservoir and its isotopic signature on Mars, with carbonate deposition and atmospheric escape as the two sinks and magmatic activity as the sole source. We derive new quantitative constraints on the amount of carbonate deposition and the atmospheric pressure of Mars through time, extending into the Noachian, ~3.8 Gyr before present. This determination is based on recent Mars Science Laboratory (MSL) isotopic measurements of Mars's atmosphere, recent orbiter, lander, and rover measurements of Mars's surface, and a newly identified mechanism (photodissociation of CO) that efficiently enriches the heavy carbon isotope. In particular, we find that escape via CO photodissociation on Mars has a fractionation factor of 0.6 and hence, photochemical escape processes can effectively enrich 13C in the Mars's atmosphere during the Amazonian. As a result, modest carbonate deposition must have occurred early in Mars's history to compensate the enrichment effects of photochemical processes and also sputtering, even when volcanic outgassing up to 200 mbar occurred during the Hesperian. For a photochemical escape flux that scales as the square of the solar EUV flux or more, at least 0.1 bar of CO2 must have been deposited as carbonates in the Noachian and Hesperian. More carbonate deposition would be required if carbonate deposition only occurred in the Noachian or with low fractionation factors.

  4. Analysis of isotope and organic carbon signatures in hillslope hydrographs

    NASA Astrophysics Data System (ADS)

    Dusek, Jaromir; Vogel, Tomas; Dohnal, Michal; Jankovec, Jakub; Sanda, Martin; Votrubova, Jana

    2015-04-01

    Headwater catchments are among the most important areas for investigation of isotope and carbon fluxes because their small sizes best enable separation of above- and below ground compartments for improved understanding of the respective transport mechanisms. So far, only few studies utilized stable isotope information in modeling and even fewer linked dissolved carbon fluxes to mixing or transport models. Stable isotopes of water and dissolved organic carbon provide basis for studying transport processes ranging from soil profile scale to hillslope and catchment scale. In this study, stormflow dynamics of oxygen-18 and dissolved organic carbon was analyzed using a physically based modeling approach. One-dimensional dual-continuum vertical flow and transport model, based on Richards and advection-dispersion equations, was used to simulate the subsurface processes during significant rainfall-runoff episodes of a summer season. Water flow and transport of solutes were assumed to take place in two mutually communicating continua, the soil matrix and the network of preferential pathways. Oxygen-18 and dissolved organic carbon were observed in soil water, stormflow discharge in the experimental hillslope trench, and stream discharge at the catchment outlet. In the present study, we analyzed the transformation of input solute signals into signatures observed in the stormflow discharge. The research was supported by the Czech Science Foundation Project No. 14-15201J.

  5. Stable Carbon and Nitrogen Isotope Ratios of Sodium and Potassium Cyanide as a Forensic Signature

    SciTech Connect

    Kreuzer, Helen W.; Horita, Juske; Moran, James J.; Tomkins, Bruce; Janszen, Derek B.; Carman, April J.

    2012-01-03

    Sodium and potassium cyanide are highly toxic, produced in large amounts by the chemical industry, and linked to numerous high-profile crimes. The U.S. Centers for Disease Control and Prevention has identified cyanide as one of the most probable agents to be used in a future chemical terrorism event. We investigated whether stable C and N isotopic content of sodium and potassium cyanide could serve as a forensic signature for sample matching, using a collection of 65 cyanide samples. A few of these samples displayed non-homogeneous isotopic content associated with degradation to a carbonate salt and loss of hydrogen cyanide. Most samples had highly reproducible isotope content. Of these, >95% could be properly matched based on C and N isotope ratios, with a false match rate <3%. These results suggest that stable C and N isotope ratios are a useful forensic signature for matching cyanide samples.

  6. Stable Carbon and Nitrogen Isotope Ratios of Sodium and Potassium Cyanide as a Forensic Signature

    SciTech Connect

    Kruzer, Helen W; Horita, Juske; Moran, James J; Tomkins, Bruce A; Janszen, Derek B; Carman, April

    2012-01-01

    Sodium and potassium cyanide are highly toxic, produced in large amounts by the chemical industry, and linked to numerous high-profile crimes. The U.S. Centers for Disease Control and Prevention has identified cyanide as one of the most probable agents to be used in a future chemical terrorism event. We investigated whether stable C and N isotopic content of sodium and potassium cyanide could serve as a forensic signature for sample matching, using a collection of 65 cyanide samples. A few of these samples displayed non-homogeneous isotopic content associated with degradation to a carbonate salt and loss of hydrogen cyanide. Most samples had highly reproducible isotope content. Of these, >95% could be properly matched based on C and N isotope ratios, with a false match rate <3%. These results suggest that stable C and N isotope ratios are a useful forensic signature for matching cyanide samples.

  7. Seasonal variations in the stable carbon isotopic signature of biogenic methane in a coastal sediment

    NASA Technical Reports Server (NTRS)

    Martens, C. S.; Green, C. D.; Blair, N. E.; Des Marais, D. J.

    1986-01-01

    Systematic seasonal variations in the stable carbon isotopic signature of methane gas occur in the anoxic sediments of Cape Lookout Bight, a lagoonal basin on North Carolina's Outer Banks. Values for the carbon isotope ratio of methane range from -57.3 per mil during summer to -68.5 per mil during winter in gas bubbles with an average methane content of 95 percent. The variations are hypothesized to result from changes in the pathways of microbial methane production and cycling of key substrates including acetate and hydrogen. The use of stable isotopic signatures to investigate the global methane cycle through mass balance calculations, involving various sediment and soil biogenic sources, appears to require seasonally averaged data from individual sites.

  8. Stable Carbon Isotopic Signatures of Abiotic Organics from Hydrothermal Synthesis Experiments

    NASA Technical Reports Server (NTRS)

    Stern, Jennifer C.; Summers, David P.; Kubo, Mike; Yassar, Saima

    2006-01-01

    Stable carbon isotopes can be powerful biogeochemical markers in the study of life's origins. Biogenic carbon fixation produces organics that are depleted in C-13 by about -20 to -30%0. Less attention has been paid to the isotopic signatures of abiotic processes. The possibility of abiotic processes producing organics with morphologies and isotopic signatures in the biogenic range has been at the center of recent debate over the Earth's earliest microfossils. The abiotic synthesis of organic compounds in hydrothermal environments is one possible source of endogenous organic matter to the prebiotic earth. Simulated hydrothermal settings have been shown to synthesize, among other things, single chain amphiphiles and simple lipids from a mix of CO, CO2, and H2. A key characteristic of these amphiphilic molecules is the ability to self-assemble in aqueous phases into more organized structures called vesicles, which form a selectively permeable boundary and serve the function of containing and concentrating other organic molecules. The ability to form cell like structures also makes these compounds more likely to be mistaken for biogenic. Hydrothermal simulation experiments were conducted from oxalic or formic acid in water at 175 C for 72 hr. The molecular and isotopic composition of the products of these reactions were determined and compared to biogenic fractionations . Preliminary results indicate isotopic fractionation during abiotic hydrocarbon synthesis in hydrothermal environments is on par with biological carbon fixation.

  9. Carbonate "clumped" isotope signatures in aragonitic scleractinian and calcitic gorgonian deep-sea corals

    NASA Astrophysics Data System (ADS)

    Kimball, J.; Tripati, R. E.; Dunbar, R.

    2015-12-01

    Deep-sea corals are a potentially valuable archive of the temperature and ocean chemistry of intermediate and deep waters. Living in near constant temperature, salinity and pH, and having amongst the slowest calcification rates observed in carbonate-precipitating biological organisms, deep-sea corals can provide valuable constraints on processes driving mineral equilibrium and disequilibrium isotope signatures. Here we report new data to further develop "clumped" isotopes as a paleothermometer in deep-sea corals as well as to investigate mineral-specific, taxon-specific, and growth-rate related effects. Carbonate clumped isotope thermometry is based on measurements of the abundance of the doubly-substituted isotopologue 13C18O16O2 in carbonate minerals, analyzed in CO2 gas liberated on phosphoric acid digestion of carbonates and reported as Δ47 values. We analyzed Δ47 in live-collected aragonitic scleractinian (Enallopsammia sp.) and calcitic gorgonian (Isididae and Coralliidae) deep-sea corals, and compared results to published data for other aragonitic scleractinian taxa. Measured Δ47 values were compared to in situ temperatures and the relationship between Δ47 and temperature was determined for each group to investigate taxon-specific effects. We find that aragonitic scleractinian deep-sea corals exhibit higher values than calcitic gorgonian corals and the two groups of coral produce statistically different relationship between Δ47-temperature calibrations. These data are significant in the interpretation of all carbonate "clumped" isotope calibration data as they show that distinct Δ47-temperature calibrations can be observed in different materials recovered from the same environment and analyzed using the same instrumentation, phosphoric acid composition, digestion temperature and technique, CO2 gas purification apparatus, and data handling. There are three possible explanations for the origin of these different calibrations. The offset between the

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

    PubMed

    Pearson, Scott F; Levey, Douglas J; Greenberg, Cathryn H; Martínez Del Rio, Carlos

    2003-05-01

    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 delta15N and delta13C turnover rates for blood, delta15N and delta13C 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 delta13C and from 0.5 to 1.7 days for delta15N . Half-life did not differ among diets. Whole blood half-life for delta13C 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 on diets 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 require use of mixing models that incorporate elemental concentration. PMID:16228250

  11. 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

  12. Distinct iron isotope signatures in suspended matter in the northern Baltic Sea; implications for cycling of organic carbon and phosphorus

    NASA Astrophysics Data System (ADS)

    Ingri, Johan; Conrad, Sarah

    2015-04-01

    Two distinct groups of iron isotope signatures can be identified both in river water and in the Bothnian Bay, northern Baltic Sea. Particles and colloids with negative iron isotope signatures (enriched in the light isotope) are mobilised in the riparian zone during high discharge. Due to high concentration of DOC the oxidation of Fe(II) is incomplete, and un-oxidised Fe(II) is associated with Fe(III)-OH and OC (organic carbon), forming Fe(II,III)-OC colloids, and particles, with a negative iron isotope signature. Colloidal iron with a negative signature is a labile fraction that transforms during freshwater transport. Photo reduction of Fe(II,III)-OC particles and colloids will release Fe(II) and reduce Fe(III) to Fe(II), and formed Fe(II) is oxidised forming Fe(III)-OH colloids with a heavy iron isotope signature. Phosphorus and organic carbon are to different extent associated to these two suspended iron complexes during transport and early diagenesis. Flocculation of negative Fe(II,III)-OC colloids produce negative Fe(II,III)-OC particles, without changes in the isotopic composition. Most of the suspended iron is rapidly removed below 1.0 psu, due to flocculation and sedimentation. Negative Fe(II,III)-OC particles may serve as an efficient 'rusty sink' for organic carbon, when deposited in the coastal zone.

  13. 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

  14. Nitrogen and Carbon Isotopes in Presolar Diamond Samples with Known Noble Gas Isotope Signature

    NASA Astrophysics Data System (ADS)

    Verchovsky, A. B.; Huss, G. R.; Pillinger, C. T.

    1994-07-01

    the noble gas results are described in detail elsewhere [7]. It should be noted that sample purity is supposed to be an important condition affecting release pattern of noble gases and N due to chemical reaction between coexisting minerals (for further discussion see [10]. Therefore we expected the influence of the reactions to be eliminated or significantly reduced for the samples studied here compared to those (OU samples) analyzed [6,8] before. Surprisingly we did not find any particular difference in C and N isotope systematics for the CT and OU samples. In particular they have the same carbon and N release profiles and isotope systematics (Figs. 1,2) although OU samples were measured without any attempt to remove spinel, SiC, or other oxidizing acid resistant phases. At low temperature pyrolysis steps, the CT samples have a similar peak of C, which we have previously correlated with P3 noble gases [11]. More important, release temperature of the light nitrogen from the CT samples (Fig. 2) is now confirmed to be significantly lower than that for HL noble gases supporting the hypothesis [11,12] of different carriers for the components or an entirely different release mechanism. Perhaps the most surprising outcome of our investigation was that none of the CT samples measured appeared to be 100% carbon; the reason for this apparent discrepancy ;the at present not clear. References: [1] Swart P. K. et al. (1983) Science, 220, 406-410. [2] Lewis R. S. et a1. (1983) Nature, 305, 767-771. [3] Pillinger C. T. (1993) Phil. Trans. Roy. Soc. Lond. A, 343, 73-76. [4] Anders E. and Zinner E. (1993) Meteoritics, 28, 490-514. [5] Ott U. (1993) Nature, 364, 25-33. [6] Russell S. S. et al. (1991) Science, 254, 1188-1191. [7] Huss G. R. and Lewis R. S. (1994) Meteoritics, in press. [8] Verchovsky A. B. et al. (1993) LPS XXV, 1435-1436. [9] Clayton D. D. et al. (1994) Astrophysics J., in press. [10] Verchovsky A. B. et al. (1994) Meteoritics, this volume. [11] Verchovsky A. B. et al

  15. Statistical clumped isotope signatures

    PubMed Central

    Röckmann, T.; Popa, M. E.; Krol, M. C.; Hofmann, M. E. G.

    2016-01-01

    High precision measurements of molecules containing more than one heavy isotope may provide novel constraints on element cycles in nature. These so-called clumped isotope signatures are reported relative to the random (stochastic) distribution of heavy isotopes over all available isotopocules of a molecule, which is the conventional reference. When multiple indistinguishable atoms of the same element are present in a molecule, this reference is calculated from the bulk (≈average) isotopic composition of the involved atoms. We show here that this referencing convention leads to apparent negative clumped isotope anomalies (anti-clumping) when the indistinguishable atoms originate from isotopically different populations. Such statistical clumped isotope anomalies must occur in any system where two or more indistinguishable atoms of the same element, but with different isotopic composition, combine in a molecule. The size of the anti-clumping signal is closely related to the difference of the initial isotope ratios of the indistinguishable atoms that have combined. Therefore, a measured statistical clumped isotope anomaly, relative to an expected (e.g. thermodynamical) clumped isotope composition, may allow assessment of the heterogeneity of the isotopic pools of atoms that are the substrate for formation of molecules. PMID:27535168

  16. Statistical clumped isotope signatures.

    PubMed

    Röckmann, T; Popa, M E; Krol, M C; Hofmann, M E G

    2016-01-01

    High precision measurements of molecules containing more than one heavy isotope may provide novel constraints on element cycles in nature. These so-called clumped isotope signatures are reported relative to the random (stochastic) distribution of heavy isotopes over all available isotopocules of a molecule, which is the conventional reference. When multiple indistinguishable atoms of the same element are present in a molecule, this reference is calculated from the bulk (≈average) isotopic composition of the involved atoms. We show here that this referencing convention leads to apparent negative clumped isotope anomalies (anti-clumping) when the indistinguishable atoms originate from isotopically different populations. Such statistical clumped isotope anomalies must occur in any system where two or more indistinguishable atoms of the same element, but with different isotopic composition, combine in a molecule. The size of the anti-clumping signal is closely related to the difference of the initial isotope ratios of the indistinguishable atoms that have combined. Therefore, a measured statistical clumped isotope anomaly, relative to an expected (e.g. thermodynamical) clumped isotope composition, may allow assessment of the heterogeneity of the isotopic pools of atoms that are the substrate for formation of molecules. PMID:27535168

  17. Isotopic Signature of Carbon Dioxide Efflux as Affected by Vegetation Recovery in Peatland.

    NASA Astrophysics Data System (ADS)

    Epron, D.; Bortoluzzi, E.; Buttler, A.

    2005-12-01

    Peatlands are widespread ecosystems in all climatic areas of the world and provide services of global significance such as long-term storage of organic carbon. The rehabilitation of degraded peatlands as a carbon sink is a considerable challenge in the context of climate change and issues such as capability of ecosystems for carbon sequestration and mitigating greenhouse gas emissions. Our aim was to study the isotopic composition of peatland CO2 efflux at various stages of development of mire vegetation and new peat accumulation on the top of the old drained peat, in order to quantify the contribution of vegetation respiration to the whole CO2 efflux of the ecosystem. The study site is located in the Jura mountains at the altitude of 870m and belongs to the European project RECIPE (reconciling commercial exploitation of peat with biodiversity in peatland ecosystems). It exhibited various regeneration stages with patches of bare peat, patches recently recolonised with cottongrass ( Eriophorum angustifolium) and areas covered with a deep layer of Sphagnum plants and litter (advanced regeneration). Keeling plots were realized on collars located in various vegetation patches by accumulating respired CO2 into a dark chamber. δ13C of the respired CO2 was measured using a mass-spectrometer. The isotopic signature of respired CO2 was lower in the advanced regeneration than it was in recent regeneration, and the latter was lower than it was on bare peat. This difference agrees with the higher δ13C of the old peat than of the actual vegetation (both vascular plants and mosses, and their litters), suggesting a decreasing contribution of old peat mineralization to ecosystem CO2 efflux with the progression of the regeneration of the cutover bog. Discrepancies between isotopic compositions of bulk organic matter and respired CO2 suggest an apparent discrimination during respiration.

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

    Stable carbon isotopes provide a powerful tool to assess carbon pools and their dynamics. Dissolved organic carbon (DOC) has been recognized to play an important role in ecosystem functioning and carbon cycling and has therefore gained increased research interest. However, direct measurement of 13C isotopic signature of carbon in the dissolved phase is technically challenging particularly using high temperature combustion. Until recently, mainly custom-made systems existed which were modified for coupling of TOC instruments with IRMS for simultaneous assessment of C content and isotopic signature. The variety of coupled systems showed differences in their analytical performances. For analysis of DOC high temperature combustion is recognized as best performing method, owing to its high efficiency of conversion to CO2 also for highly refractory components (e.g. humic, fulvic acids) present in DOC and soil extracts. Therefore, we tested high temperature combustion TOC coupled to IRMS (developed by Elementar Group) for bulk measurements of DOC concentration and 13C signature. The instruments are coupled via an Interface to exchange the carrier gas from O2 to He and to concentrate the derived CO2 for the isotope measurement. Analytical performance of the system was assessed for a variety of organic compounds characterized by different stability and complexity, including humic acid and DOM. We tested injection volumes between 0.2-3 ml, thereby enabling measurement of broad concentration ranges. With an injection volume of 0.5 ml (n=3, preceded by 1 discarded injection), DOC and 13C signatures for concentrations between 5-150 mg C/L were analyzed with high precision (standard deviation (SD) predominantly <0.1‰), good accuracy and linearity (overall SD <0.9‰). For the same settings, slightly higher variation in precision was observed among the lower concentration range and depending upon specific system conditions. Differences in 13C signatures of about 50‰ among

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

    PubMed

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

    2016-03-01

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

  20. Joint Application of Concentrations and Isotopic Signatures to Investigate the Global Atmospheric Carbon Monoxide Budget: Inverse Modeling Approach

    NASA Astrophysics Data System (ADS)

    Park, K.; Mak, J. E.; Emmons, L. K.

    2008-12-01

    Carbon monoxide is not only an important component for determining the atmospheric oxidizing capacity but also a key trace gas in the atmospheric chemistry of the Earth's background environment. The global CO cycle and its change are closely related to both the change of CO mixing ratio and the change of source strength. Previously, to estimate the global CO budget, most top-down estimation techniques have been applied the concentrations of CO solely. Since CO from certain sources has a unique isotopic signature, its isotopes provide additional information to constrain its sources. Thus, coupling the concentration and isotope fraction information enables to tightly constrain CO flux by its sources and allows better estimations on the global CO budget. MOZART4 (Model for Ozone And Related chemical Tracers), a 3-D global chemical transport model developed at NCAR, MPI for meteorology and NOAA/GFDL and is used to simulate the global CO concentration and its isotopic signature. Also, a tracer version of MOZART4 which tagged for C16O and C18O from each region and each source was developed to see their contributions to the atmosphere efficiently. Based on the nine-year-simulation results we analyze the influences of each source of CO to the isotopic signature and the concentration. Especially, the evaluations are focused on the oxygen isotope of CO (δ18O), which has not been extensively studied yet. To validate the model performance, CO concentrations and isotopic signatures measured from MPI, NIWA and our lab are compared to the modeled results. The MOZART4 reproduced observational data fairly well; especially in mid to high latitude northern hemisphere. Bayesian inversion techniques have been used to estimate the global CO budget with combining observed and modeled CO concentration. However, previous studies show significant differences in their estimations on CO source strengths. Because, in addition to the CO mixing ratio, isotopic signatures are independent tracers

  1. Environmental drivers of carbon and nitrogen isotopic signatures in peatland vascular plants along an altitude gradient.

    PubMed

    Gavazov, Konstantin; Hagedorn, Frank; Buttler, Alexandre; Siegwolf, Rolf; Bragazza, Luca

    2016-01-01

    Peatlands are important sinks of atmospheric carbon (C) that, in response to climate warming, are undergoing dynamic vegetation succession. Here we examined the hypothesis that the uptake of nutrients by different plant growth forms (PGFs) is one key mechanism driving changes in species abundance in peatlands. Along an altitude gradient representing a natural climate experiment, we compared the variability of the stable C isotope composition (δ(13)C) and stable nitrogen (N) isotope composition (δ(15)N) in current-year leaves of two major PGFs, i.e. ericoids and graminoids. The climate gradient was associated with a gradient of vascular plant cover, which was parallelled by different concentrations of organic and inorganic N as well as the fungal/bacterial ratio in peat. In both PGFs the (13)C natural abundance showed a marginal spatial decrease with altitude and a temporal decrease with progression of the growing season. Our data highlight a primary physical control of foliar δ(13)C signature, which is independent from the PGFs. Natural abundance of foliar (15)N did not show any seasonal pattern and only in the ericoids showed depletion at lower elevation. This decreasing δ(15)N pattern was primarily controlled by the higher relative availability of organic versus inorganic N and, only for the ericoids, by an increased proportion of fungi to bacteria in soil. Our space-for-time approach demonstrates that a change in abundance of PGFs is associated with a different strategy of nutrient acquisition (i.e. transfer via mycorrhizal symbiosis versus direct fine-root uptake), which could likely promote observed and predicted dwarf shrub expansion under climate change. PMID:26433961

  2. Methane seep carbonates yield clumped isotope signatures out of equilibrium with formation temperatures.

    PubMed

    Loyd, S J; Sample, J; Tripati, R E; Defliese, W F; Brooks, K; Hovland, M; Torres, M; Marlow, J; Hancock, L G; Martin, R; Lyons, T; Tripati, A E

    2016-01-01

    Methane cold seep systems typically exhibit extensive buildups of authigenic carbonate minerals, resulting from local increases in alkalinity driven by methane oxidation. Here, we demonstrate that modern seep authigenic carbonates exhibit anomalously low clumped isotope values (Δ47), as much as ∼0.2‰ lower than expected values. In modern seeps, this range of disequilibrium translates into apparent temperatures that are always warmer than ambient temperatures, by up to 50 °C. We examine various mechanisms that may induce disequilibrium behaviour in modern seep carbonates, and suggest that the observed values result from several factors including kinetic isotopic effects during methane oxidation, mixing of inorganic carbon pools, pH effects and rapid precipitation. Ancient seep carbonates studied here also exhibit potential disequilibrium signals. Ultimately, these findings indicate the predominance of disequilibrium clumped isotope behaviour in modern cold seep carbonates that must be considered when characterizing environmental conditions in both modern and ancient cold seep settings. PMID:27447820

  3. Methane seep carbonates yield clumped isotope signatures out of equilibrium with formation temperatures

    PubMed Central

    Loyd, S. J.; Sample, J.; Tripati, R. E.; Defliese, W. F.; Brooks, K.; Hovland, M.; Torres, M.; Marlow, J.; Hancock, L. G.; Martin, R.; Lyons, T.; Tripati, A. E.

    2016-01-01

    Methane cold seep systems typically exhibit extensive buildups of authigenic carbonate minerals, resulting from local increases in alkalinity driven by methane oxidation. Here, we demonstrate that modern seep authigenic carbonates exhibit anomalously low clumped isotope values (Δ47), as much as ∼0.2‰ lower than expected values. In modern seeps, this range of disequilibrium translates into apparent temperatures that are always warmer than ambient temperatures, by up to 50 °C. We examine various mechanisms that may induce disequilibrium behaviour in modern seep carbonates, and suggest that the observed values result from several factors including kinetic isotopic effects during methane oxidation, mixing of inorganic carbon pools, pH effects and rapid precipitation. Ancient seep carbonates studied here also exhibit potential disequilibrium signals. Ultimately, these findings indicate the predominance of disequilibrium clumped isotope behaviour in modern cold seep carbonates that must be considered when characterizing environmental conditions in both modern and ancient cold seep settings. PMID:27447820

  4. Methane seep carbonates yield clumped isotope signatures out of equilibrium with formation temperatures

    NASA Astrophysics Data System (ADS)

    Loyd, S. J.; Sample, J.; Tripati, R. E.; Defliese, W. F.; Brooks, K.; Hovland, M.; Torres, M.; Marlow, J.; Hancock, L. G.; Martin, R.; Lyons, T.; Tripati, A. E.

    2016-07-01

    Methane cold seep systems typically exhibit extensive buildups of authigenic carbonate minerals, resulting from local increases in alkalinity driven by methane oxidation. Here, we demonstrate that modern seep authigenic carbonates exhibit anomalously low clumped isotope values (Δ47), as much as ~0.2‰ lower than expected values. In modern seeps, this range of disequilibrium translates into apparent temperatures that are always warmer than ambient temperatures, by up to 50 °C. We examine various mechanisms that may induce disequilibrium behaviour in modern seep carbonates, and suggest that the observed values result from several factors including kinetic isotopic effects during methane oxidation, mixing of inorganic carbon pools, pH effects and rapid precipitation. Ancient seep carbonates studied here also exhibit potential disequilibrium signals. Ultimately, these findings indicate the predominance of disequilibrium clumped isotope behaviour in modern cold seep carbonates that must be considered when characterizing environmental conditions in both modern and ancient cold seep settings.

  5. Dynamics of carbon in deep soils inferred from carbon stable isotopes signatures : a worldwide meta-analysis

    NASA Astrophysics Data System (ADS)

    Balesdent, Jérôme; Basile-Doelsch, Isabelle; Chadoeuf, Joël; Cornu, Sophie; Derrien, Delphine; Fekiacova, Zuzana; Hatté, Christine

    2014-05-01

    The contribution of soil carbon deeper than 30 cm to the atmospheric carbon balance is still poorly understood. A very straightforward quantification of the gross exchange of carbon between the atmosphere and soil organic matter can be obtained at places where the 13C/12C signature of vegetation has been changed for known durations, due to switch of the photosynthetic metabolism (C3 or C4) or to Free Air Carbon Enrichment experiments. We compiled C and 13C profile data of 113 sites of this type, either gahered from the literature or from our own measurements. Each site comprised two profiles : one where the 13C/12C of the vegetation had been changed, and a reference profile with unchanged vegetation 13C/12C. An isotope mixing equation was used, which takes into account the natural isotope enrichments with depth and decay. Three main variables were calculated at any depth from 0 to 100 cm and in a few sites down to 200 cm : the carbon content, the proportion of new carbon (aged less than the duration of change t) and the amount of new carbon. The database concerned 23 countries, various climates (58% intertropical and 42% between 23° to 56° latitude) and various soil types and textures. Landuses and vegetation consisted in 26% of forests and woodlands, 35% of grasslands and 38% of cropped systems. The duration of the natural labelling t ranged from 2 years to ca. 4000 years. Peatlands, boreal, and desert environments were absent from the database. Non-linear regressions with time across the dataset yielded kinetic parameters of the age distribution on one hand and of the flux of new carbon incorporation (kg C m-2 yr-1) on the other, each calculated by 10 cm depth increments. On the average, the median ages of carbon increase from ca. 15 years at 0 cm to more than 1000 years at 100 cm. Turnover is on the average 2 to 3 times slower for the subsoil (30-100 cm) than for the topsoil (0-30 cm). Based on the incorporation of new C in the first decades, the carbon input

  6. Insect outbreaks produce distinctive carbon isotope signatures in defensive resins and fossiliferous ambers

    PubMed Central

    McKellar, Ryan C.; Wolfe, Alexander P.; Muehlenbachs, Karlis; Tappert, Ralf; Engel, Michael S.; Cheng, Tao; Sánchez-Azofeifa, G. Arturo

    2011-01-01

    Despite centuries of research addressing amber and its various inclusions, relatively little is known about the specific events having stimulated the production of geologically relevant volumes of plant resin, ultimately yielding amber deposits. Although numerous hypotheses have invoked the role of insects, to date these have proven difficult to test. Here, we use the current mountain pine beetle outbreak in western Canada as an analogy for the effects of infestation on the stable isotopic composition of carbon in resins. We show that infestation results in a rapid (approx. 1 year) 13C enrichment of fresh lodgepole pine resins, in a pattern directly comparable with that observed in resins collected from uninfested trees subjected to water stress. Furthermore, resin isotopic values are shown to track both the progression of infestation and instances of recovery. These findings can be extended to fossil resins, including Miocene amber from the Dominican Republic and Late Cretaceous New Jersey amber, revealing similar carbon-isotopic patterns between visually clean ambers and those associated with the attack of wood-boring insects. Plant exudate δ13C values constitute a sensitive monitor of ecological stress in both modern and ancient forest ecosystems, and provide considerable insight concerning the genesis of amber in the geological record. PMID:21429925

  7. Evolution of carbon isotope signatures during reactive transport of hydrocarbons in heterogeneous aquifers

    NASA Astrophysics Data System (ADS)

    Höyng, Dominik; Prommer, Henning; Blum, Philipp; Grathwohl, Peter; Mazo D'Affonseca, Fernando

    2015-03-01

    Compound-specific isotope analysis (CSIA) of organic pollutants has become a well-established tool for assessing the occurrence and extent of biodegradation processes in contaminated aquifers. However, the precision of CSIA is influenced by the degree to which assumptions underlying CSIA data interpretation hold under realistic field-scale conditions. For the first time this study demonstrates how aquifer analogs combined with reactive transport models offer an underexplored way to develop generic process understanding, evaluate monitoring and quantification strategies in highly heterogeneous subsurface settings. Data from high-resolution aquifer analogs were used in numerical experiments to track the propagation of a representative oxidizable organic compound (toluene) within a variety of realistic heterogeneous aquifers and to investigate its detailed fate. The simulations were used to analyze (1) the effects of physical aquifer heterogeneities on spatiotemporal patterns of contaminant concentrations and isotope signatures, (2) the performance of the commonly applied Rayleigh equation and (3) the applicability of an extension of the Rayleigh equation for complex hydrogeological conditions. The results indicate that if field-derived enrichment factors are applied without corrections for dilution, the conventional Rayleigh equation is inaccurate and estimates for biodegradation are typically overestimated and unreliable in heterogeneous aquifers. Underestimations can occur due to the partial source zone depletion. In contrast, if dilution can be accurately accounted for, field-derived enrichment factors comprise a suitable alternative to laboratory-derived and redox-specific enrichment factors. The study also examines to what extent variations in monitoring/sampling strategies influence the obtained results. Especially measurements from long-screened wells (> 1 m) reveal to be inappropriate for the application of the Rayleigh equation in the investigated aquifer

  8. Evolution of carbon isotope signatures during reactive transport of hydrocarbons in heterogeneous aquifers.

    PubMed

    Höyng, Dominik; Prommer, Henning; Blum, Philipp; Grathwohl, Peter; D'Affonseca, Fernando Mazo

    2015-03-01

    Compound-specific isotope analysis (CSIA) of organic pollutants has become a well-established tool for assessing the occurrence and extent of biodegradation processes in contaminated aquifers. However, the precision of CSIA is influenced by the degree to which assumptions underlying CSIA data interpretation hold under realistic field-scale conditions. For the first time this study demonstrates how aquifer analogs combined with reactive transport models offer an underexplored way to develop generic process understanding, evaluate monitoring and quantification strategies in highly heterogeneous subsurface settings. Data from high-resolution aquifer analogs were used in numerical experiments to track the propagation of a representative oxidizable organic compound (toluene) within a variety of realistic heterogeneous aquifers and to investigate its detailed fate. The simulations were used to analyze (1) the effects of physical aquifer heterogeneities on spatiotemporal patterns of contaminant concentrations and isotope signatures, (2) the performance of the commonly applied Rayleigh equation and (3) the applicability of an extension of the Rayleigh equation for complex hydrogeological conditions. The results indicate that if field-derived enrichment factors are applied without corrections for dilution, the conventional Rayleigh equation is inaccurate and estimates for biodegradation are typically overestimated and unreliable in heterogeneous aquifers. Underestimations can occur due to the partial source zone depletion. In contrast, if dilution can be accurately accounted for, field-derived enrichment factors comprise a suitable alternative to laboratory-derived and redox-specific enrichment factors. The study also examines to what extent variations in monitoring/sampling strategies influence the obtained results. Especially measurements from long-screened wells (>1 m) reveal to be inappropriate for the application of the Rayleigh equation in the investigated aquifer

  9. Carbon and nitrogen stable isotopes in fast food: signatures of corn and confinement.

    PubMed

    Jahren, A Hope; Kraft, Rebecca A

    2008-11-18

    Americans spend >100 billion dollars on restaurant fast food each year; fast food meals comprise a disproportionate amount of both meat and calories within the U.S. diet. We used carbon and nitrogen stable isotopes to infer the source of feed to meat animals, the source of fat within fries, and the extent of fertilization and confinement inherent to production. We sampled food from McDonald's, Burger King, and Wendy's chains, purchasing >480 servings of hamburgers, chicken sandwiches and fries within geographically distributed U.S. cities: Los Angeles, San Francisco, Denver, Detroit, Boston, and Baltimore. From the entire sample set of beef and chicken, only 12 servings of beef had delta(13)C < -21 per thousand; for these animals only was a food source other than corn possible. We observed remarkably invariant values of delta(15)N in both beef and chicken, reflecting uniform confinement and exposure to heavily fertilized feed for all animals. The delta(13)C value of fries differed significantly among restaurants indicating that the chains used different protocols for deep-frying: Wendy's clearly used only corn oil, whereas McDonald's and Burger King favored other vegetable oils; this differed from ingredient reports. Our results highlighted the overwhelming importance of corn agriculture within virtually every aspect of fast food manufacture. PMID:19001276

  10. Carbon and Nitrogen Stable Isotopes in Fastfood: Signatures of Corn and Confinement

    NASA Astrophysics Data System (ADS)

    Jahren, H.; Kraft, R.

    2008-12-01

    Americans spend more than one hundred billion dollars on restaurant fastfood each year; fastfood meals comprise a disproportionate amount of both meat and calories within the U.S. diet. Frustrated by futile attempts to gain information about the origin and production of fastfood from the companies themselves, we used carbon and nitrogen stable isotopes to infer the source of feed to meat animals, the source of fat within fries, and the extent of fertilization and confinement inherent to production. We sampled food from McDonald's, Burger King and Wendy's chains, purchasing more than 480 servings of hamburgers, chicken sandwiches and fries within geographically-distributed U.S. cities: Los Angeles, San Francisco, Denver, Detroit, Boston and Baltimore. From the entire sample set of beef and chicken, only 12 servings of beef had δ13C < -21 ‰; for these animals only was a food source other than corn possible. We observed remarkably invariant values of δ15N in both beef and chicken, reflecting uniform confinement and exposure to heavily fertilized feed for all animals. The δ13C value of fries differed significantly among restaurants indicating that the chains employed different protocols for deep- frying: Wendy's clearly employed only corn oil, while McDonald's and Burger King favored other vegetable oils; this differed from ingredient reports. Our results highlighted the overwhelming importance of corn agriculture within virtually every aspect of fastfood manufacture.

  11. 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

  12. 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.

  13. DETERMINING CARBON ISOTOPE SIGNATURES FROM MICROMETEOROLOGICAL MEASUREMENTS: IMPLICATIONS FOR STUDYING BIOSPHERE-ATMOSPHERE EXCHANGE PROCESSES

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In recent years considerable effort has been focused on combining micrometeorological and stable isotope techniques to elucidate and study biosphere-atmosphere exchange processes. At the ecosystem scale, these methods are increasingly being used to address a number of challenging problems, including...

  14. Non-linear dynamics of stable carbon and hydrogen isotope signatures based on a biological kinetic model of aerobic enzymatic methane oxidation.

    PubMed

    Vavilin, Vasily A; Rytov, Sergey V; Shim, Natalia; Vogt, Carsten

    2016-06-01

    The non-linear dynamics of stable carbon and hydrogen isotope signatures during methane oxidation by the methanotrophic bacteria Methylosinus sporium strain 5 (NCIMB 11126) and Methylocaldum gracile strain 14 L (NCIMB 11912) under copper-rich (8.9 µM Cu(2+)), copper-limited (0.3 µM Cu(2+)) or copper-regular (1.1 µM Cu(2+)) conditions has been described mathematically. The model was calibrated by experimental data of methane quantities and carbon and hydrogen isotope signatures of methane measured previously in laboratory microcosms reported by Feisthauer et al. [ 1 ] M. gracile initially oxidizes methane by a particulate methane monooxygenase and assimilates formaldehyde via the ribulose monophosphate pathway, whereas M. sporium expresses a soluble methane monooxygenase under copper-limited conditions and uses the serine pathway for carbon assimilation. The model shows that during methane solubilization dominant carbon and hydrogen isotope fractionation occurs. An increase of biomass due to growth of methanotrophs causes an increase of particulate or soluble monooxygenase that, in turn, decreases soluble methane concentration intensifying methane solubilization. The specific maximum rate of methane oxidation υm was proved to be equal to 4.0 and 1.3 mM mM(-1) h(-1) for M. sporium under copper-rich and copper-limited conditions, respectively, and 0.5 mM mM(-1) h(-1) for M. gracile. The model shows that methane oxidation cannot be described by traditional first-order kinetics. The kinetic isotope fractionation ceases when methane concentrations decrease close to the threshold value. Applicability of the non-linear model was confirmed by dynamics of carbon isotope signature for carbon dioxide that was depleted and later enriched in (13)C. Contrasting to the common Rayleigh linear graph, the dynamic curves allow identifying inappropriate isotope data due to inaccurate substrate concentration analyses. The non-linear model pretty adequately described experimental

  15. Application of δ13C and δ15N isotopic signatures of organic matter fractions sequentially separated from adjacent arable and forest soils to identify carbon stabilization mechanisms

    NASA Astrophysics Data System (ADS)

    Kayler, Z. E.; Kaiser, M.; Gessler, A.; Ellerbrock, R. H.; Sommer, M.

    2011-03-01

    Identifying the chemical mechanisms behind soil carbon bound in organo-mineral complexes is necessary to determine the degree to which soil organic carbon is stabilized belowground. We used the δ13C and δ15N isotopic signatures from two organic matter (OM) fractions from soil to identify the likely binding mechanisms involved. We used OM fractions hypothesized to contain carbon stabilized through organo-mineral complexes: (1) OM separated chemically with sodium pyrophosphate (OM(PY)) and (2) OM stabilized in microstructures found in the chemical extraction residue (OM(ER)). Furthermore, because the OM fractions were separated from five different soils with paired forest and arable land use histories, we could address the impact of land use change on carbon binding and processing mechanisms within these soils. We used partial least squares regression to analyze patterns in the isotopic signature of OM with established proxies of different binding mechanisms. Parsing soil OM into different fractions is a systematic method of dissection, however, we are primarily interested in how OM is bound in soil as a whole, requiring a means of re-assembly. Thus, we implemented the recent zonal framework described by Kleber et al. (2007) to relate our findings to undisturbed soil. The δ15N signature of OM fractions served as a reliable indicator for microbial processed carbon in both arable and forest land use types. The δ13C signature of OM fractions in arable sites did not correlate well with proxies of soil mineral properties while a consistent pattern of enrichment was seen in the δ13C of OM fractions in the forest sites. We found a significant difference in δ13C of pooled OM fractions between the forest and arable land use type although it was relatively small (<1‰). We found different binding mechanisms predominate in each land use type. The isotopic signatures of OM fractions from arable soils were highly related to the clay and silt size particles amount while

  16. 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.

  17. Identification of Lichen Metabolism in an Early Devonian Terrestrial Fossil using Carbon Stable Isotope Signature

    NASA Astrophysics Data System (ADS)

    Porter, S.; Jahren, H.

    2002-05-01

    The fossil organismSpongiophyton minutissimum is commonly found in early terrestrial assemblages (Devonian age, 430-340 Ma). Suites of morphological descriptions of this fossil have been published, starting in 1954, and have led to two competing hypotheses: 1.) that this early colonizer of land was a primitive bryophyte, and therefore a precursor to modern plant organisms, and 2.) thatS. minutissimum was a lichen: a close association between an alga and a fungus. Because the ultimate mechanisms for carbon supply to the carboxylating enzyme in bryophytes and lichens differ fundamentally, we expect these two types of organisms to exhibit separate ranges of δ 13Ctissue value. In bryophytes, gaseous carbon dioxide diffuses through perforations in cuticle (resulting in δ 13Catmosphere - δ 13Cbryophyte = ~20 ‰ ). Within the lichen, carbon is supplied to the carboxylating enzyme of the photobiont as carbon dioxide dissolved in fungal cell fluids (resulting in δ 13Catmosphere - δ 13Clichen = ~15 ‰ ). By comparing the δ 13Ctissue value ofS. minutissimum (mean = -23 ‰ ;n = 75) with δ 13Ctissue values in twenty-five lichens, representative of the four different phylogenetic clades (mean = -23 ‰ ;n = 25) and thirty different genera of bryophytes including mosses, liverworts, and hornworts (mean = -28 ‰ ;n = 30), we conclude thatS. minutissimum was cycling carbon via processes that much more closely resembled those of lichens, and not bryophytes. We discuss the general strategies associated with lichen biology, such as the ability to withstand dessication during reproduction, and how they may have contributed to the successful colonization of terrestrial environments.

  18. Carbon and oxygen isotope signatures in conifers from the Swiss National Park

    NASA Astrophysics Data System (ADS)

    Churakova (Sidorova), Olga; Saurer, Matthias; Siegwolf, Rolf; Bryukhanova, Marina; Bigler, Christof

    2015-04-01

    Our study investigates the physiological response and plasticity of trees under climatic changes for larch (Larix decidua) and mountain pine (Pinus mugo var. uncinata) in the Swiss National Park.This research was done in the context of investigation tree mortality and their potential to survive under the harsh mountainous conditions. For the stable isotope analysis we selected four mountain pine and four larch trees from each a south- and north-facing slope. Oxygen isotope ratios can give insight into water sources and evaporative processes. To understand the differential response of mountain pine and larch to short-term climatic changes we measured 18O/16O in water extracted from twigs and needles as well as soil samples for each species at both sites. The seasonal variabilities in 18O/16O needles and twigs of mountain pine and larch trees as well as soil samples were related to changes in climate conditions from end of May until middle of October. To reveal the main climatic factors driving tree growth of pine and larch trees in the long-term, tree-ring width chronologies were built and bulk 18O/16O, 13C/12C wood chronologies were analyzed and correlated with climatic parameters over the last 100 years. The results indicate a strong influence of spring and summer temperatures for larch trees, while variation of spring and summer precipitations is more relevant for mountain pine trees. This work is supported by the Swiss National Science Foundation, Marie-Heim Vögtlin Program PMPDP-2 145507

  19. Interannual Variability in Carbon and Nitrogen Stable Isotopic Signatures of Size-Fractionated POM from the South Florida Coastal Zone

    NASA Astrophysics Data System (ADS)

    Evans, S. L.; Anderson, W. T.; Jochem, F. J.; Fourqurean, J. W.

    2004-12-01

    Environmental conditions in South Florida coastal waters have been of local and national concern over the past 15 years. Attention has focused on the ecosystem impacts of salinity increases, seagrass die-off, increased algal bloom frequency, waste water influence, groundwater discharge, and exchange between Florida Bay, the Gulf of Mexico, and the Atlantic Ocean. Changes in water quality and productivity levels may be reflected in the isotopic signatures of coastal zone primary producers. Recent work with seagrasses in South Florida has demonstrated high seasonal and spatial variability in C and N isotopic signatures and decoupling between the two isotopic systems as they vary. To better understand the sources of seasonal and spatial fluctuation, size fractionated POM (particulate organic matter) samples have been collected on a quarterly basis since Sept. 2002. Fractions collected include >150μ m, 50-150μ m, and 0.1-50μ m using Nitex mesh sieves and a portable pump system deployed from a small boat at 10 sites around the Florida Keys and Florida Bay. It was hypothesized that planktonic groups respond more quickly to changes in water quality then seagrasses, and thus variations may be more clearly attributed to environmental parameters. Significant spatial and temporal variability is evident both within site between size fractions and between sites. Seasonal oscillations of up to 4‰ were observed in N isotopic values and 6‰ in C isotopic values of the 50-150μ m size fraction, which is dominated by diatoms and dinoflagellates. δ 13C values are depleted in the late winter/early spring sampling period possibly reflecting decreased productivity stress on available C pools. 13C depletion is generally coincident with δ 15N enrichment in the late winter/early spring, possibly demonstrating changes in DIN pools (NO3- and NH4+ concentrations) or changes in decomposition or denitrification rates. Broad groupings appear to separate Atlantic coral reef sites

  20. The Lithium Isotopic Signature of Hawaiian Basalts

    NASA Astrophysics Data System (ADS)

    Harrison, L.; Weis, D.; Hanano, D. W.

    2013-12-01

    shield stage volcanoes or amongst individual volcanoes; 2) differences in degree of mantle melt and spatial structure of the mantle heterogeneity melting in the case of pre-shield, shield, and post-shield differences. In Hawaiian basalts, lithium isotopes help distinguish between 'enriched' Loa source components: Ko';olau Makapu';u shield stage lavas may have between 4-10% of a carbonate input and Hualalai post-shield and shield lavas may reflect incorporation of subduction eroded lower continental crust. Comparison of this dataset with worldwide OIB published lithium isotopic data indicates that the lithium isotopic system behaves systematically on a mantle-wide scale. Hawai'i is generally characterized as EM-I like, with Hualalai post-shield lavas exhibiting both the lightest lithium isotopic signature and the most extreme EM-I characteristics. Lithium isotopes thus provide an additional insight into the nature of EM-I type mantle. [1] Weis, D. et al. (2011) Nature Geoscience 4, doi:10.1038/NGEO1328. [2] Nobre Silva, I.G. et al. (2013) Geochem. Geophy. Geosys. 14(3), doi: doi:10.1002/ggge.20047. [3] Chan, L.H., and Frey, F.A. (2003) Geochem. Geophy. Geosys. 4(3), doi: 10.1029/2002GC000365.

  1. Leaf oxygen and Carbon Isotopic Signatures Reflect Drought Resistance and Water Use Efficiency in the C4 Grass, Setaria viridis

    NASA Astrophysics Data System (ADS)

    Ellsworth, P.; Cousins, A. B.

    2014-12-01

    Low water availability is a major constraint in crop production, especially as agriculture is pushed to marginal lands. Therefore, improving drought resistance such as increasing water use efficiency (WUE) through plant breeding is needed to expand the range of soil water availability adequate for food production. With the goal of finding the genomic basis for WUE in C4 grasses, Setaria viridis makes an ideal model species because of its small size, short lifespan, and sequenced genome. Also it is part of the panicoid grass clade, which is one of the most important clades for food and biofuel production. In plant breeding programs, large numbers of genotypes must be quickly screened for drought resistance traits, but there is no well-defined method of screening for WUE in C4 grasses. However, bulk leaf oxygen (Δ18OBL) and carbon (δ13C) isotopic signatures have shown potential as recorders of transpiration rate (E) and stomatal conductance (gs), and combined with biomass production potentially serve as a measure of WUE. Values of Δ18OBL record differences in transpiration rate because leaf water becomes more enriched as transpiration rate decreases, and leaf tissue records the isotopic composition of leaf water in which it is synthesized. Additionally, in C4 plants δ13C values decrease as gs decreases but the change in δ13C in response to gs may not be adequate to tease apart differences in WUE. In this study, we grew S. viridis plants under well-watered and water-limited conditions to determine if Δ18OBL and δ13C could be used as proxies for E and gs, and be used to screen S. viridis for differences in WUE in breeding programs. The Δ18OBL and δ13C were significantly different between well-watered and water-limited plants and correlated with each other and with E, gs, and instantaneous water use efficiency (Anet/gs). Therefore, Δ18OBL and δ13C can be useful proxies to screen genotypes for drought resistance by recording differences in E, gs, and WUE

  2. Evaluating Carbon Isotope Signature of Bulk Organic Matter and Plant Wax Derived n-alkanes from Lacustrine Sediments as Climate Proxies along the Western Side of the Andes

    NASA Astrophysics Data System (ADS)

    Contreras, S.; Werne, J. P.; Araneda, A.; Conejero, C. A.

    2015-12-01

    Sedimentary carbon isotope values (δ13C) of bulk organic matter and long chain (C25 to C35) n-alkanes are among the most long-lived and widely utilized proxies of organic matter and vegetation source. The carbon distribution (e.g. average carbon chain length, ACL) and isotope signature from long chain n-alkanes had been intensively used on paleoclimate studies because they are less influenced by diagenesis, differential preservation of compound classes, and changes in the sources of organic matter than bulk δ13C values. Recently, studies of modern plant n-alkanes have challenged the use of carbon distribution and carbon isotope signature from sedimentary n-alkanes as reliable indicators of vegetation and climate change. The climate in central-south western South America (SA) is projected to become significantly warmer and drier over the next several decades to centuries in response to anthropogenically driven warming. Paleolimnological studies along western SA are critical to obtain more realistic and reliable regional reconstructions of past climate and environments, including vegetation and water budget variability. Here we discuss bulk δ13C, distribution and δ13C in long chain n-alkanes from a suite of ~40 lake surface sediment (core-top) samples spanning the transition from a Mediterranean climate with a patchwork of cultivated vegetation, pastureland, conifers in central Chile to a rainy temperate climate dominated by broadleaf deciduous and evergreen forest. Data are compared to the latitudinal and orographic climatic trends of the Andes based on the climatology (e.g. precipitation and temperature) of the locations of all lakes involved in this study, using monthly gridded reanalysis products of the Climate Forecast System Reanalysis (CFSR), based on the NCEP global forecast model and meteorological stations available in the region, from January 1979 to December 2010 with a 0.5° horizontal resolution.

  3. Measurement of Histone Methylation Dynamics by One-Carbon Metabolic Isotope Labeling and High-energy Collisional Dissociation Methylation Signature Ion Detection

    PubMed Central

    Tang, Hui; Tian, Bing; Brasier, Allan R.; Sowers, Lawrence C.; Zhang, Kangling

    2016-01-01

    Accumulating evidence suggests that cellular metabolites and nutrition levels control epigenetic modifications, including histone methylation. However, it is not currently possible to measure the metabolic control of histone methylation. Here we report a novel detection method to monitor methyl transfer from serine to histones through the one-carbon metabolic pathway, using stable-isotope labeling and detection of lysine methylation signature ions generated in high-energy-dissociation (HCD) tandem mass spectrometry. This method is a long-needed tool to study the metabolic control of histone methylation. PMID:27530234

  4. Interpretation of the origin of massive replacive dolomite within atolls and submerged carbonate platforms: strontium isotopic signature ODP Hole 866A, Resolution Guyot, Mid-Pacific Mountains

    NASA Astrophysics Data System (ADS)

    Flood, P. G.; Fagerstrom, J. A.; Rougerie, F.

    1996-01-01

    Endo-upwelling is a geothermally driven convective process operating within the upper part of the volcanic foundation and overlying carbonate pile, in atolls and guyots. By this process deep oceanic water, rich in CO 2 and dissolved nitrates, phosphates and silicates is drawn into the pile, circulates slowly upward through the porous-permeable carbonate interior and emerges at either the reef crest or lagoon on atolls to support the primary productivity of the surficial communities, or towards the interior of the platform surface on guyots. Continuous operation of the endo-upwelling process requires: (a) heat from the volcanic foundation; (b) an external impermeable apron on the submerged flanks to confine the convective flow within the pile; and (c) a porous cap from which water exiting the plumbing system returns to the ocean. At ODP Hole 866A on Resolution Guyot, Mid-Pacific Mountains, the Sr isotopic signature of massive white-coloured, coarsely crystalline dolomite indicates a considerable time delay of approximately 100 Ma between carbonate deposition and dolomitization. This time delay is determined by comparing the Sr isotopic value of the dolomite and the time that ocean seawater displayed a similar Sr isotopic value. This interpretation of the Sr isotopic values assumes that all of the Sr is viewed as coming from seawater and none from any precursor limestone. The massive white replacement dolomite from Resolution Guyot possibly provides confirmation of the origin of dolomite by way of thermally driven convective flow within submerged carbonate platforms. Endo-upwelling seawater probably enters the carbonate pile at some depth, thermally circulates upwards, and produces carbonate dissolution and could conceivably produce massive dolomite replacement.

  5. Isotopic signatures by bulk analyses

    SciTech Connect

    Efurd, D.W.; Rokop, D.J.

    1997-12-01

    Los Alamos National Laboratory has developed a series of measurement techniques for identification of nuclear signatures by analyzing bulk samples. Two specific applications for isotopic fingerprinting to identify the origin of anthropogenic radioactivity in bulk samples are presented. The first example is the analyses of environmental samples collected in the US Arctic to determine the impact of dumping of radionuclides in this polar region. Analyses of sediment and biota samples indicate that for the areas sampled the anthropogenic radionuclide content of sediments was predominantly the result of the deposition of global fallout. The anthropogenic radionuclide concentrations in fish, birds and mammals were very low. It can be surmised that marine food chains are presently not significantly affected. The second example is isotopic fingerprinting of water and sediment samples from the Rocky Flats Facility (RFP). The largest source of anthropogenic radioactivity presently affecting surface-waters at RFP is the sediments that are currently residing in the holding ponds. One gram of sediment from a holding pond contains approximately 50 times more plutonium than 1 liter of water from the pond. Essentially 100% of the uranium in Ponds A-1 and A-2 originated as depleted uranium. The largest source of radioactivity in the terminal Ponds A-4, B-5 and C-2 was naturally occurring uranium and its decay product radium. The uranium concentrations in the waters collected from the terminal ponds contained 0.05% or less of the interim standard calculated derived concentration guide for uranium in waters available to the public. All of the radioactivity observed in soil, sediment and water samples collected at RFP was naturally occurring, the result of processes at RFP or the result of global fallout. No extraneous anthropogenic alpha, beta or gamma activities were detected. The plutonium concentrations in Pond C-2 appear to vary seasonally.

  6. Lipid Biomarkers and Carbon Isotope Signatures of a Microbial (Beggiatoa) Mat Associated with Gas Hydrates in the Gulf of Mexico

    PubMed Central

    Zhang, Chuanlun L.; Huang, Zhiyong; Cantu, James; Pancost, Richard D.; Brigmon, Robin L.; Lyons, Timothy W.; Sassen, Roger

    2005-01-01

    White and orange mats are ubiquitous on surface sediments associated with gas hydrates and cold seeps in the Gulf of Mexico. The goal of this study was to determine the predominant pathways for carbon cycling within an orange mat in Green Canyon (GC) block GC 234 in the Gulf of Mexico. Our approach incorporated laser-scanning confocal microscopy, lipid biomarkers, stable carbon isotopes, and 16S rRNA gene sequencing. Confocal microscopy showed the predominance of filamentous microorganisms (4 to 5 μm in diameter) in the mat sample, which are characteristic of Beggiatoa. The phospholipid fatty acids extracted from the mat sample were dominated by 16:1ω7c/t (67%), 18:1ω7c (17%), and 16:0 (8%), which are consistent with lipid profiles of known sulfur-oxidizing bacteria, including Beggiatoa. These results are supported by the 16S rRNA gene analysis of the mat material, which yielded sequences that are all related to the vacuolated sulfur-oxidizing bacteria, including Beggiatoa, Thioploca, and Thiomargarita. The δ13C value of total biomass was −28.6‰; those of individual fatty acids were −29.4 to −33.7‰. These values suggested heterotrophic growth of Beggiatoa on organic substrates that may have δ13C values characteristic of crude oil or on their by-products from microbial degradation. This study demonstrated that integrating lipid biomarkers, stable isotopes, and molecular DNA could enhance our understanding of the metabolic functions of Beggiatoa mats in sulfide-rich marine sediments associated with gas hydrates in the Gulf of Mexico and other locations. PMID:15812044

  7. Lipid biomarkers and carbon isotope signatures of a microbial (Beggiatoa) mat associated with gas hydrates in the gulf of Mexico.

    PubMed

    Zhang, Chuanlun L; Huang, Zhiyong; Cantu, James; Pancost, Richard D; Brigmon, Robin L; Lyons, Timothy W; Sassen, Roger

    2005-04-01

    White and orange mats are ubiquitous on surface sediments associated with gas hydrates and cold seeps in the Gulf of Mexico. The goal of this study was to determine the predominant pathways for carbon cycling within an orange mat in Green Canyon (GC) block GC 234 in the Gulf of Mexico. Our approach incorporated laser-scanning confocal microscopy, lipid biomarkers, stable carbon isotopes, and 16S rRNA gene sequencing. Confocal microscopy showed the predominance of filamentous microorganisms (4 to 5 mum in diameter) in the mat sample, which are characteristic of Beggiatoa. The phospholipid fatty acids extracted from the mat sample were dominated by 16:1omega7c/t (67%), 18:1omega7c (17%), and 16:0 (8%), which are consistent with lipid profiles of known sulfur-oxidizing bacteria, including Beggiatoa. These results are supported by the 16S rRNA gene analysis of the mat material, which yielded sequences that are all related to the vacuolated sulfur-oxidizing bacteria, including Beggiatoa, Thioploca, and Thiomargarita. The delta13C value of total biomass was -28.6 per thousand; those of individual fatty acids were -29.4 to -33.7 per thousand. These values suggested heterotrophic growth of Beggiatoa on organic substrates that may have delta13C values characteristic of crude oil or on their by-products from microbial degradation. This study demonstrated that integrating lipid biomarkers, stable isotopes, and molecular DNA could enhance our understanding of the metabolic functions of Beggiatoa mats in sulfide-rich marine sediments associated with gas hydrates in the Gulf of Mexico and other locations. PMID:15812044

  8. Does avian malaria infection affect feather stable isotope signatures?

    PubMed

    Yohannes, Elizabeth; Palinauskas, Vaidas; Valkiūnas, Gediminas; Lee, Raymond W; Bolshakov, Casimir V; Bensch, Staffan

    2011-12-01

    It is widely accepted that stable isotope ratios in inert tissues such as feather keratin reflect the dietary isotopic signature at the time of the tissue synthesis. However, some elements such as stable nitrogen isotopes can be affected by individual physiological state and nutritional stress. Using malaria infection experiment protocols, we estimated the possible effect of malaria parasite infections on feather carbon (δ(13)C) and nitrogen (δ(15)N) isotope signatures in juvenile common crossbills Loxia curvirostra. The birds were experimentally infected with Plasmodium relictum (lineage SGS1) and P. ashfordi (GRW2), two widespread parasites of passerines. Experimental birds developed heavy parasitemia of both parasites and maintained high levels throughout the experiment (33 days). We found no significant difference between experimental and control birds in both δ(13)C and δ(15)N values of feathers re-grown. The study shows that even heavy primary infections of malaria parasites do not affect feather δ(13)C and δ(15)N isotopic signatures. The results of this experiment demonstrate that feather isotope values of wild-caught birds accurately reflect the dietary isotopic sources at the time of tissue synthesis even when the animal's immune system might be challenged due to parasitic infection. PMID:21671039

  9. Oxygen isotopic signature of CO2 from combustion processes

    NASA Astrophysics Data System (ADS)

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

    2008-11-01

    For a comprehensive understanding of the global carbon cycle precise knowledge of all processes is necessary. Stable isotope (13C and 18O) abundances provide information for the qualification and the quantification of the diverse source and sink processes. This study focuses on the δ18O signature of CO2 from combustion processes, which are widely present both naturally (wild fires), and human induced (fossil fuel combustion, biomass burning) in the carbon cycle. All these combustion processes use atmospheric oxygen, of which the isotopic signature is assumed to be constant with time throughout the whole atmosphere. The combustion is generally presumed to take place at high temperatures, thus minimizing isotopic fractionation. Therefore it is generally supposed that the 18O signature of the produced CO2 is equal to that of the atmospheric oxygen. This study, however, reveals that the situation is much more complicated and that important fractionation effects do occur. From laboratory studies fractionation effects in the order of about 26‰ became obvious, a clear differentiation of about 7‰ was also found in car exhausts which were sampled directly under ambient atmospheric conditions. We investigated a wide range of materials (both different raw materials and similar materials with different inherent 18O signature), sample geometries (e.g. texture and surface-volume ratios) and combustion circumstances. We found that the main factor influencing the specific isotopic signatures of the combustion-derived CO2 and of the concomitantly released oxygen-containing side products, is the case-specific rate of combustion. This points firmly into the direction of (diffusive) transport of oxygen to the reaction zone as the cause of the isotope fractionation. The original 18O signature of the material appeared to have little or no influence.

  10. Oxygen isotopic signature of CO2 from combustion processes

    NASA Astrophysics Data System (ADS)

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

    2011-02-01

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

  11. Stable Isotope Signatures for Microbial Forensics

    SciTech Connect

    Kreuzer, Helen W.

    2012-01-03

    The isotopic distribution of the atoms composing the molecules of microorganisms is a function of the substrates used by the organisms. The stable isotope content of an organism is fixed so long as no further substrate consumption and biosynthesis occurs, while the radioactive isotopic content decays over time. The distribution of stable isotopes of C, N, O and H in heterotrophic microorganisms is a direct function of the culture medium, and therefore the stable isotope composition can be used to associate samples with potential culture media and also with one another. The 14C content depends upon the 14C content, and therefore the age, of the organic components of the culture medium, as well as on the age of the culture itself. Stable isotope signatures can thus be used for sample matching, to associate cultures with specific growth media, and to predict characteristics of growth media.

  12. Nitrogen isotopic signatures in the Acapulco meteorite

    NASA Technical Reports Server (NTRS)

    Sturgeon, G.; Marti, K.

    1991-01-01

    N isotopic abundances are reported for a bulk sample of the unique meteorite Acapulco. Although the mineral chemistry indicates a high degree of recrystallization under redox conditions between those of H and E chondrites (Palme et al., 1981), the presence of two distinct N isotopic signatures shows that the carriers of these N components were not equilibrated. In stepwise pyrolysis, the larger (65 percent) N component is released mostly below 1000 C and reveals a signature of delta(N-15) = 8.9 + or - 1.2 per mil, which is within the range observed in chondrites. A second 'light' component appears above 1000 C and has a signature of delta(N-15) less than or equal to -110.5 + or - 4.0 per mil (uncorrected for spallation N-15).

  13. Differences in hydrophyte life forms induce spatial heterogeneity of CH4 production and its carbon isotopic signature in a temperate bog peatland

    NASA Astrophysics Data System (ADS)

    Itoh, Masayuki; Shimamura, Tetsuya; Ohte, Nobuhito; Takemon, Yasuhiro

    2015-07-01

    To clarify the effect of differences in hydrophyte life forms on methane (CH4) production and its carbon stable isotopic signature (δ13C-CH4), we analyzed CH4 and carbon dioxide (CO2) concentrations, their stable carbon isotope values, and chemical constituents dissolved in pore water in a small floating peat bog in Japan. Because eutrophication has modified the surrounding water quality, the bog vegetation on the mat has been, in part, replaced by fen-type vegetation. We hypothesized that differences in hydrophyte habitats affect redox conditions, including dissolved oxygen (DO) in water and therefore the amounts and carbon isotopic values of CH4 and CO2 dissolved in pore water. Between the habitats of two Sphagnum species, DO was considerably higher, and CH4 concentrations were significantly lower in Sphagnum cuspidatum Ehrh. habitats in hollow (DO: 0.62 ± 0.20 mg/L (standard error (SE)) and CH4: 0.18 ± 0.02 mmol/L) than in Sphagnum palustre L. habitats in hummock (DO: 0.29 ± 0.08 and CH4: 0.82 ± 0.06) in pore water (10 cm depth). Both DO and CH4 concentrations in three vascular plant habitats (Rhynchospora fauriei Franch., Phragmites australis [reed], and Menyanthes trifoliata L.) in pore water (10 cm depth) were intermediate relative to the two Sphagnum species. However, CH4 flux in M. trifoliata site was significantly higher than that at both Sphagnum sites, suggesting that the type of gas transport (diffusive or convective via root and stem) affected the depth profile of CH4 concentrations and its flux. δ13C-CH4 values in pore water also varied among the vegetation types, even within Sphagnum species (e.g., at 10 cm depth, δ13C-CH4: R. fauriei, -55.3 ± 1.8‰ (SE); P. australis, -57.5 ± 1.6‰; M. trifoliata, -56.7 ± 1.5‰; S. cuspidatum, -71.2 ± 1.4‰; and S. palustre, -60.4 ± 0.6‰). Our results suggest that significant differences arise in CH4 concentration and δ13C-CH4 values among the hydrophyte habitats even within a small peat bog and

  14. Lipid biomarkers for anaerobic oxidation of methane and sulphate reduction in cold seep sediments of Nyegga pockmarks (Norwegian margin): discrepancies in contents and carbon isotope signatures

    NASA Astrophysics Data System (ADS)

    Chevalier, Nicolas; Bouloubassi, Ioanna; Stadnitskaia, Alina; Taphanel, Marie-Hélène; Sinninghe Damsté, Jaap S.

    2014-06-01

    Distributions and carbon isotopic compositions of microbial lipid biomarkers were investigated in sediment cores from the G11 and G12 pockmarks in the Nyegga sector of the Storegga Slide on the mid-Norwegian margin to explore differences in depth zonation, type and carbon assimilation mode of anaerobic methane-oxidizing archaea (ANMEs) and associated sulphate-reducing bacteria responsible for anaerobic oxidation of methane (AOM) in these cold seep environments. While the G11 site is characterised by black reduced sediments colonized by gastropods and Siboglinidae tubeworms, the G12 site has black reduced sediments devoid of fauna but surrounded by a peripheral occurrence of gastropods and white filamentous microbial mats. At both sites, bulk sediments contained abundant archaeal and bacterial lipid biomarkers substantially depleted in 13C, consisting mainly of isoprenoidal hydrocarbons and dialkyl glycerol diethers, fatty acids and non-isoprenoidal monoalkylglycerol ethers. At the G11 site, down-core profiles revealed that lipid biomarkers were in maximum abundance from 10 cm depth to the core bottom at 16 cm depth, associated with δ13C values of -57 to -136‰. At the G12 site, by contrast, lipid biomarkers were in high abundance in the upper 5 cm sediment layer, associated with δ13C values of -43 to -133‰. This suggests that, as expected from the benthic fauna characteristics of the sites, AOM takes place mainly at depth in the G11 pockmark but just below the seafloor in the G12 pockmark. These patterns can be explained largely by variable fluid flow rates. Furthermore, at both sites, a dominance of ANME-2 archaea accompanied by their bacterial partners is inferred based on lipid biomarker distributions and carbon isotope signatures, which is in agreement with recently published DNA analyses for the G11 pockmark. However, the present data reveal high discrepancies in the contents and δ13C values for both archaeal and bacterial lipid profiles, implying the

  15. Signature lipids and stable carbon isotope analyses of Octopus Spring hyperthermophilic communities compared with those of Aquificales representatives

    NASA Technical Reports Server (NTRS)

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

    2001-01-01

    The molecular and isotopic compositions of lipid biomarkers of cultured Aquificales genera have been used to study the community and trophic structure of the hyperthermophilic pink streamers and vent biofilm from Octopus Spring. Thermocrinis ruber, Thermocrinis sp. strain HI 11/12, Hydrogenobacter thermophilus TK-6, Aquifex pyrophilus, and Aquifex aeolicus all contained glycerol-ether phospholipids as well as acyl glycerides. The n-C(20:1) and cy-C(21) fatty acids dominated all of the Aquificales, while the alkyl glycerol ethers were mainly C(18:0). These Aquificales biomarkers were major constituents of the lipid extracts of two Octopus Spring samples, a biofilm associated with the siliceous vent walls, and the well-known pink streamer community (PSC). Both the biofilm and the PSC contained mono- and dialkyl glycerol ethers in which C(18) and C(20) alkyl groups were prevalent. Phospholipid fatty acids included both the Aquificales n-C(20:1) and cy-C(21), plus a series of iso-branched fatty acids (i-C(15:0) to i-C(21:0)), indicating an additional bacterial component. Biomass and lipids from the PSC were depleted in (13)C relative to source water CO(2) by 10.9 and 17.2 per thousand, respectively. The C(20-21) fatty acids of the PSC were less depleted than the iso-branched fatty acids, 18.4 and 22.6 per thousand, respectively. The biomass of T. ruber grown on CO(2) was depleted in (13)C by only 3.3 per thousand relative to C source. In contrast, biomass was depleted by 19.7 per thousand when formate was the C source. Independent of carbon source, T. ruber lipids were heavier than biomass (+1.3 per thousand). The depletion in the C(20-21) fatty acids from the PSC indicates that Thermocrinis biomass must be similarly depleted and too light to be explained by growth on CO(2). Accordingly, Thermocrinis in the PSC is likely to have utilized formate, presumably generated in the spring source region.

  16. Carbon isotope techniques

    SciTech Connect

    Coleman, D.C. ); Fry, B. )

    1991-01-01

    This book is a hands-on introduction to using carbon isotope tracers in experimental biology and ecology. It is a bench-top reference with protocols for the study of plants, animals, and soils. The {sup 11}C, {sup 12}C, {sup 13}C, and {sup 14}C carbon isotopes are considered and standard techniques are described by established authors. The compilation includes the following features: specific, well-established, user-oriented techniques; carbon cycles in plants, animals, soils, air, and water; isotopes in ecological research; examples and sample calculations.

  17. Linkages Between Upwelling and Shell Characteristics of Mytilus californianus: Morphology and Stable Isotope (δ13C, δ18O) Signatures of a Carbonate Archive from the California Current

    NASA Astrophysics Data System (ADS)

    Hosfelt, J. D.; Hill, T. M.; Russell, A. D.; Bean, J. R.; Sanford, E.; Gaylord, B.

    2014-12-01

    Many calcareous organisms are known to record the ambient environmental conditions in which they grow, and their calcium carbonate skeletons are often valuable archives of climate records. Mytilus californianus, a widely distributed species of intertidal mussel, experiences a spatial mosaic of oceanographic conditions as it grows within the California Current System. Periodic episodes of upwelling bring high-CO2 waters to the surface, during which California coastal waters are similar to projected conditions and act as a natural analogue to future ocean acidification. To examine the link between upwelling and shell characteristics of M. californianus, we analyzed the morphology and stable isotope (δ13C, δ18O) signatures of mussel specimens collected live from seven study sites within the California Current System. Morphometric analyses utilized a combination of elliptic Fourier analysis and shell thickness measurements to determine the influence of low pH waters on the growth morphology and ecological fitness of M. californianus. These geochemical and morphological analyses were compared with concurrent high-resolution environmental (T, S, pH, TA, DIC) records from these seven study sites from 2010-2013. With appropriate calibration, new archives from modern M. californianus shells could provide a valuable tool to enable environmental reconstructions within the California Current System. These archives could in turn be used to predict the future consequences of continuing ocean acidification, as well as reconstruct past (archeological) conditions.

  18. Microbial activity and carbonate isotope signatures as a tool for identification of spatial differences in methane advection: a case study at the Pacific Costa Rican margin

    NASA Astrophysics Data System (ADS)

    Krause, S.; Steeb, P.; Hensen, C.; Liebetrau, V.; Dale, A. W.; Nuzzo, M.; Treude, T.

    2014-01-01

    The forearc of the convergent margin offshore Costa Rica is a region characterized by strong advection of methane-charged fluids causing the formation of ubiquitous cold seeps (mounds). Presented here are the first measurements of microbial anaerobic oxidation of methane (AOM) and sulfate reduction (SR) rates in sediments from two mounds (11 and 12), applying radiotracer techniques in combination with numerical modelling. In addition, analysis of microbial, methane-dependent carbonate δ18O, δ13C, and 87Sr / 86Sr signatures constrained the origin of the carbonate-precipitating fluid. Average rates of microbial activities differed by a factor of ~5 to 6 between Mound 11 (AOM 140.71 (±40.84 SD) mmol m-2 d-1, SR 117.25 (±82.06 SD) mmol m-2 d-1) and Mound 12 (AOM 22.37 (±0.85 SD) mmol m-2 d-1, SR 23.99 (±5.79 SD) mmol m-2 d-1). Modelling results yielded upward fluid advection velocities of 200 cm yr-1 at Mound 11 and 15 cm yr-1 at Mound 12. Analysis of oxygen and carbon isotope variations of authigenic carbonates from the two locations revealed more enriched values for Mound 11 (δ18O : 3.18 to 6.15‰; δ13C: -14.14 to -29.56‰) compared to Mound 12 (δ18O : 3.09 to 4.48‰; δ13C : -39.53 to -48.98‰). The variation of carbonate 87Sr / 86Sr indicated considerable admixture of deep-source fluid at Mound 11, while seawater 87Sr / 86Sr characteristics prevailed at Mound 12 during precipitation. The present study is in accordance with previous work supporting considerable differences of methane flux between the two mounds. It also strengthens the hypothesis of a dominant deep fluid source with thermogenic methane at Mound 11 versus a shallow source of biogenic methane at Mound 12. The results demonstrate that measurements of methane-driven microbial activity in combination with numerical modelling are a valid tool for constraining recent methane fluxes in the study area. In addition, the analysis of methane-derived authigenic carbonates provides an independent

  19. Carbon isotope signature of environmental change found in fossil ratite eggshells from a South Asian Neogene sequence

    NASA Astrophysics Data System (ADS)

    Stern, Libby A.; Johnson, Gary D.; Page Chamberlain, C.

    1994-05-01

    A >10-m.y.-long sequence of ratite (e.g., ostrich) eggshells from Siwalik Group sedimentary deposits of northern Pakistan and India shows a dramatic (˜8‰) increase in the δ13C in biomineralogic calcite by ˜4 Ma. Values of δ13C from ratite eggshell carbonate older than 7 Ma are about the same as those from carbonate from contemporaneous fossil mammal tooth enamel and paleosols. However, after 4 Ma, the ratite eggshell carbonate δ13C values are ˜5‰ less than these coexisting materials. These findings are evidence of the development of a C3-C4 vegetative mosaic probably mirroring the sedimentologic-edaphic mosaic of the aggrading alluvial plain of the Siwalik depositional system.

  20. Isotopic signatures of traffic-emitted CO and CO2

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

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

  1. Carbon Isotope Ratiometer

    SciTech Connect

    Dr. Anthony O'Keefe

    2001-05-07

    This Report details the design of a optical analyzer capable of measuring and recording the carbon 13/12 isotope ratio in atmospheric carbon dioxide. The system can operate in remote modes for long duration and will transmit real-time data via wireless contact.

  2. Carbon cycling and carbon metabolism by soil fungi in a boreal forest: impacts of wildfire and permafrost on functional genes, isotope signatures, and ectomycorrhizae

    NASA Astrophysics Data System (ADS)

    Waldrop, M. P.; Harden, J. W.

    2006-12-01

    Understanding the mechanisms that control the stabilization and destabilization of soil carbon within boreal forest ecosystems is of great importance to the global carbon budget. Much is currently known about boreal soil carbon dynamics in relation to biophysical and landscape variables such as temperature, moisture, wildfire intensity, and stand age. We have less information regarding the controls on decomposition at the molecular scale, where interactions between microbial communities, their genetic `potential' for decomposition, functional genes, enzyme synthesis, and organic matter transformations occur. We have entered an age in which these connections can be made at the molecular scale, but what form do they take, and can they scale up to affect carbon dynamics at the level of the ecosystem? We examined these molecular scale processes in mature boreal forest soils and soils that had been impacted by wildfire near Delta Junction, Alaska. We also examined the interactive effect of permafrost presence, which reduces soil drainage, with wildfire. We focused on three themes: linking microbial communities and laccase functional genes to soil laccase enzyme activity and lignin decomposition, assessing substrate availability using the natural abundance δ13C isotope ratios of microbial biomass, and the influence of ectomycorrhizal mats on decomposition. Wildfire reduced fungal biomass, laccase functional gene abundance, laccase activity, and δ13C-lignin decomposition. Relationships between gene abundance and microbial activity were significant and logarithmic in form. Soil drainage, which is mediated by the presence of permafrost, had little effect on the abundance of fungi, functional genes, or potential process rates. Microbial biomass δ13C was always enriched relative to soil organic matter, and this difference was greater in control soils compared to wildfire-affected soils, indicating that ÄΔδ13C MB-SOIL may indicate the level of bioavailability of soil

  3. Stable isotope signatures confirm carbon and nitrogen gain through ectomycorrhizas in the ghost orchid Epipogium aphyllum Swartz.

    PubMed

    Liebel, H T; Gebauer, G

    2011-03-01

    Epipogium aphyllum is a rare Eurasian achlorophyllous forest orchid known to associate with fungi that form ectomycorrhizas, while closely related orchids of warm humid climates depend on wood- or litter-decomposer fungi. We conducted (13) C and (15) N stable isotope natural abundance analyses to identify the organic nutrient source of E. aphyllum from Central Norway. These data for orchid shoot tissues, in comparison to accompanying autotrophic plants, document C and N flow from ectomycorrhizal fungi to the orchid. DNA data from fungal pelotons in the orchid root cortex confirm the presence of Inocybe and Hebeloma, which are both fungi that form ectomycorrhizas. The enrichment factors for (13) C and (15) N of E. aphyllum are used to calculate a new overall average enrichment factor for mycoheterotrophic plants living in association with ectomycorrhizal fungi (ε(13) C ± 1 SD of 7.2 ± 1.6 ‰ and ε(15) N ± 1 SD of 12.8 ± 3.9 ‰). These can be used to estimate the fungal contribution to organic nutrient uptake by partially mycoheterotrophic plants where fully mycoheterotrophic plants are lacking. N concentrations in orchid tissue were unusually high and significantly higher than in accompanying autotrophic leaf samples. This may be caused by N gain of E. aphyllum from obligate ectomycorrhizal fungi. We show that E. aphyllum is an epiparasitic mycoheterotrophic orchid that depends on ectomycorrhizal Inocybe and Hebeloma to obtain C and N through a tripartite system linking mycoheterotrophic plants through fungi with forest trees. PMID:21309973

  4. Biomarker and stable carbon isotopic signatures for 100-200 year sediment record in the Chaihe catchment in southwest China.

    PubMed

    Wang, Yanhua; Yang, Hao; Zhang, Jixiang; Xu, Meina; Wu, Changbin

    2015-01-01

    Natural inputs and anthropogenic influences on lakes and their catchments are reflected in the sediment record. In the present study, the extractable organic compounds from sediments in the Chaihe catchment of the Dianchi watershed were analyzed to characterize source inputs. Results show that the sediments are dominated by odd numbered n-alkanes (n-C16-n-C33), maximizing at n-C17, n-C29 and n-C31. Aliphatic hydrocarbon may be composed of terrestrial plants and bacteria. The values of δ(13)C27, δ(13)C29 and δ(13)C31 of n-alkanes exhibit a range from -33.27‰ to -25.46‰, from -35.76‰ to -28.47‰ and from -33.67‰ to -27.42‰, respectively and three records strongly covary with depth, falling within the range of C3 plants in the study area. An isotopic model revealed C3 plant contribution to sedimentary organic matter (OM) ranging from 40.75% to 97.22%. The values of ACL27-33, CPI27-33, OEP, Paq, Pr/Ph, (C27+C29)/2C31, (C21+C23+C25)/3C17 and nC26(-)/nC27(+) are consistent with the C3 plant predominance. A constant CRS model gave the accumulation rates ranging from 2.69 to 8.46mma(-1) spanning 1885-2010. It was concluded that OM transport in the Chaihe catchment was influenced strongly by human activities resulting in enhanced eutrophication. PMID:25261816

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  6. Impact of diagenetic alteration on brachiopod magnesium isotope signatures

    NASA Astrophysics Data System (ADS)

    Riechelmann, Sylvia; Mavromatis, Vasileios; Buhl, Dieter; Dietzel, Martin; Immenhauser, Adrian

    2016-04-01

    Carbonate rocks are amongst the most commonly exploited archives in palaeo-environmental studies. However, diagenetic processes overprint these carbonate rocks to different degrees, thus, the interpretation of individual proxy data sets such as element concentrations and isotope signatures is hindered. Furthermore, the process of diagenesis is still insufficiently understood. In order to shed light on diagenetic processes alteration experiments under controlled conditions were performed. Therefor, recent brachiopods of the species Notosaria nigricans were collected at Friday Harbour, USA. These shells were artificially altered using different solutions representing meteoric, marine and burial conditions. All three solutions were spiked with 16O-enriched water. Half of the shells were altered under 100°C, whilst the other half experienced a temperature of 175°C. This resulted in six different experimental setups. The duration of the experiments varied for each shell. Eighteen shells were selected in total for the analyses. Furthermore, two unaltered shells and four fossil brachiopod shells were used for comparison with the artificially altered ones. The Magnesium concentration as well as the Mg isotopic composition of the fluids and the shells were measured, whilst carbon and oxygen isotopes were analysed only on the shells. The oxygen isotopic composition of the altered shells exhibit a change in their values only at 175°C and not at 100°C. The same pattern is observed for the Mg isotopic composition of the shells, which were altered in the marine and burial solutions. The meteoric solution, however, is an exception. The original solution was Mg free and both at 100°C and 175°C the altered brachiopod shells are enriched in the lighter isotope compared to the unaltered shell. Thus, the heavier Mg isotope is preferably leached under meteoric conditions. However, solutions (marine and burial at 175°C) with a higher isotopic composition than the brachiopod

  7. Isotopic Signature of the Ancient Biosphere

    NASA Technical Reports Server (NTRS)

    DesMarais, D. J.; Chang, Sherwood (Technical Monitor)

    1997-01-01

    The age distribution of 261 field localities, sampled for their well-preserved Archean and Proterozoic sedimentary rocks, revealed a 500-700 Ma episodicity. Assuming that the numbers of sites are a proxy for mass of sediments, the record of well-preserved sediments is more abundant in the intervals 3.5-3.3, 2.8-2.5, 2.1-1.8, 1.5-1.3, and 1.0-0.54 Ga than in the intervening intervals. It is proposed that the crustal inventory of photosynthetic organic carbon was modulated by the volume of sedimentation in sites favorable for the burial and long-term preservation of organic carbon. Tectonic processes controlled this sediment volume. Episodic increases in the organic inventory led to stepwise increases in oxidized reservoirs (e.g., O2, SO4(2-), Fe(3+). The interval 2.9-2.5 Ga recorded a large rise in seawater Sr-87/Sr-86, the oldest-known extensive banded iron formations, and the first evidence (C-13-depleted kerogens) of O2 use by methylotrophic bacteria. The interval 2.2-1.8 Ga has both carbon isotopic evidence for a stepwise increase in the organic reservoir and also paleosol evidence for an O2 increase. The interval 1.1-0.6 Ga shows isotopic evidence for another organic carbon increase. The interval 1.5-1.3 Ga revealed no such increases as yet, perhaps because incomplete rifting of the mid-Proterozoic supercontinent was associated with extensive sedimentation in oxidized continental basins, producing redbeds, coarse clastics, etc. Such sedimentation did not promote the burial of reduced carbon.

  8. Exploring the structural controls on helium, nitrogen and carbon isotope signatures in hydrothermal fluids along an intra-arc fault system

    NASA Astrophysics Data System (ADS)

    Tardani, Daniele; Reich, Martin; Roulleau, Emilie; Takahata, Naoto; Sano, Yuji; Pérez-Flores, Pamela; Sánchez-Alfaro, Pablo; Cembrano, José; Arancibia, Gloria

    2016-07-01

    There is a general agreement that fault-fracture meshes exert a primary control on fluid flow in both volcanic/magmatic and geothermal/hydrothermal systems. For example, in geothermal systems and epithermal gold deposits, optimally oriented faults and fractures play a key role in promoting fluid flow through high vertical permeability pathways. In the Southern Volcanic Zone (SVZ) of the Chilean Andes, both volcanism and hydrothermal activity are strongly controlled by the Liquiñe-Ofqui Fault System (LOFS), an intra-arc, strike-slip fault, and by the Arc-oblique Long-lived Basement Fault System (ALFS), a set of transpressive NW-striking faults. However, the role that principal and subsidiary fault systems exert on magma degassing, hydrothermal fluid flow and fluid compositions remains poorly constrained. In this study we report new helium, carbon and nitrogen isotope data (3He/4He, δ13C-CO2 and δ15N) of a suite of fumarole and hot spring gas samples from 23 volcanic/geothermal localities that are spatially associated with either the LOFS or the ALFS in the central part of the SVZ. The dataset is characterized by a wide range of 3He/4He ratios (3.39 Ra to 7.53 Ra, where Ra = (3He/4He)air), δ13C-CO2 values (-7.44‰ to -49.41‰) and δ15N values (0.02‰ to 4.93‰). The regional variations in 3He/4He, δ13C-CO2 and δ15N values are remarkably consistent with those reported for 87Sr/86Sr in lavas along the studied segment, which are strongly controlled by the regional spatial distribution of faults. Two fumaroles gas samples associated with the northern "horsetail" transtensional termination of the LOFS are the only datapoints showing uncontaminated MORB-like 3He/4He signatures. In contrast, the dominant mechanism controlling helium isotope ratios of hydrothermal systems towards the south appears to be the mixing between mantle-derived helium and a radiogenic component derived from, e.g., magmatic assimilation of 4He-rich country rocks or contamination during the

  9. Carbon isotopes in bulk carbonaceous chondrites

    NASA Technical Reports Server (NTRS)

    Halbout, J.; Mayeda, T. K.; Clayton, R. N.

    1985-01-01

    The chemical and physical processes involved in the formation of the solar system are examined. Primitive matter has been found on a microscopic scale in a variety of meteorites: fragments of small solar system bodies that were never part of a large planet. This primitive matter has, in most cases, been identified by the presence of anomalous abundances of some isotopes of the chemical elements. Of particular interest for carbon isotope studies are the primitive meteorites known as carbonaceous chondrites. Using a selective oxidation technique to sort out the carbon contained in different chemical forms (graphite, carbonates, and organic matter), four carbonaceous chondrites are analyzed. The presence of the (13) C-rich component was confirmed and additional carbon components with different, but characteristic, isotopic signatures were resolved.

  10. A menagerie of graphite morphologies in the Acapulco meteorite with diverse carbon and nitrogen isotopic signatures: Implications for the evolution history of acapulcoite meteorites

    NASA Astrophysics Data System (ADS)

    El Goresy, Ahmed; Zinner, Ernst; Pellas, Paul; Caillet, Catherine

    2005-09-01

    Morphologies, petrographic settings and carbon and nitrogen isotopic compositions of graphites in the Acapulco meteorite, the latter determined by secondary ionization mass spectrometry, are reported. Seven different graphite morphologies were recognized, the majority of which occur enclosed exclusively in kamacite. Individual graphite grains also rarely occur in the silicate matrix. Kamacite rims surrounding taenite cores of metal grains are separated from the Ni-rich metal cores by graphite veneers. These graphite veneers impeded or prevented Ni-Fe interdiffusion during cooling. In addition, matrix FeNi metal contains considerable amounts of phosphorous (≈ 700 ppm) and silicon (≈ 300 ppm) ( Pack et al., 2005 in preparation) thus indicating that results of laboratory cooling experiments in the Fe-Ni binary system are inapplicable to Acapulco metals. Graphites of different morphologies display a range of carbon and nitrogen isotopic compositions, indicating a diversity of source regions before accretion in the Acapulco parent body. The isotopic compositions point to at least three isotopic reservoirs from which the graphites originated: (1) A reservoir with heavy carbon, represented by graphite in silicates (δ 13C = 14.3 ± 2.4 ‰ and δ 15N = -103.4 ± 10.9 ‰), (2) A reservoir with isotopically light carbon and nitrogen, characteristic for the metals. Its C- and N-isotopic compositions are probably preserved in the graphite exsolutions that are isotopically light in carbon and lightest in nitrogen (δ 13C = -17 to -23 ‰ δ 15N = -141 to -159 ‰). (3) A reservoir with an assumed isotopic composition (δ 13C ˜ -5 ‰; δ 15N ˜ -50 ‰). A detailed three-dimensional tomography in reflected light microscopy of the decorations of metal-troilite spherules in the cores of orthopyroxenes and olivines and metal-troilite veins was conducted to clarify their origin. Metal and troilite veins are present only near the fusion crust. Hence, these veins are not

  11. Variable Carbon Isotopes in ALH84001 Carbonates

    NASA Astrophysics Data System (ADS)

    Niles, P. B.; Leshin, L. A.; Guan, Y.

    2002-12-01

    The Martian meteorite ALH84001 contains a small amount of carbonate that was deposited from aqueous fluids on the Martian surface approximately 3.9 Ga.. McKay et al. (1996) proposed evidence for the existence of life preserved within the carbonate grains. In order to determine the nature of the ancient Martian aqueous system we have combined previously collected oxygen isotopic data with new carbon isotopic measurements performed on the Cameca 6f ion microprobe at Arizona State University. Isotopic measurements were made at high mass resolution with a spot size of 10 microns. The measured carbon isotopic values range from 29.2‰ to 64.5‰ (PDB) with an average uncertainty of +/-1.6‰ (1σ ). These data agree very well with previous acid dissolution and stepped combustion experiments which range from a δ13C of +32‰ to +41‰ . As observed with the oxygen isotopic data, the carbon isotopic composition is correlated with the chemical composition of the carbonates. This allows us to establish that the earliest (Ca-rich) carbonates had the lightest carbon isotopic composition while the latest forming (Mg-rich) carbonates had the heaviest carbon isotopic composition. The large range of carbon isotopic compositions measured in this study cannot be explained by previously proposed models. Temperature change or a Rayleigh distillation process caused by progressive carbonate precipitation are insufficient to create the observed carbon isotopic compositions. Furthermore, processes such as evaporation or photosynthesis will not produce large carbon isotopic variations due to rapid isotopic equilibration with the atmosphere. We propose two possible models for the formation of the ALH84001 carbonates consistent with the isotopic data collected thus far. Carbonates could have formed from an evolving system where the carbon and oxygen isotopic composition of the carbonates reflects a mixing between magmatic hydrothermal fluids and fluids in equilibrium with an isotopically

  12. C and O stable isotopic signatures of fast-growing dripstones on alkaline substrates: reflection of growth mechanism, carbonate sources and environmental conditions.

    PubMed

    Zavadlav, Saša; Mazej, Darja; Zavašnik, Janez; Rečnik, Aleksander; Dominguez-Víllar, David; Cukrov, Neven; Lojen, Sonja

    2012-06-01

    Secondary carbonate precipitates (dripstones) formed on concrete surfaces in four different environments--Mediterranean and continental open-space and indoor environments (inside a building and in a karstic cave)--were studied. The fabric of dripstones depends upon water supply, pH of mother solution and carbonate-resulting precipitation rate. Very low δ(13)C (average-28.2‰) and δ(18)O (average-18.4‰) values showed a strong positive correlation, typical for carbonate precipitated by rapid dissolution of CO(2) in a highly alkaline solution and consequent disequilibrium precipitation of CaCO(3). The main source of carbon is atmospheric or biogenic CO(2) in the poorly ventilated karstic cave, which is reflected in even lower δ(13)C values. Statistical analysis of δ(13)C and δ(18)O values of the four groups of samples showed that the governing factor of isotope fractionation is not the temperature, but rather the precipitation rate. PMID:22316094

  13. Carbon and oxygen isotopic signature of tooth enamel as a proxy for the Pliocene paleoenvironment and paleoclimate from Mt. Galili Formation, Ethiopia

    NASA Astrophysics Data System (ADS)

    Bedaso, Z. K.; Wynn, J. G.; Hujer, W.

    2011-12-01

    Analyses of the isotope ratios of naturally existing materials have increasingly been used to reconstruct paleoenvironmental and paleoclimatic conditions. In this study carbon (C) and oxygen (O) isotopic composition of bioapatite from fossil tooth enamel is used to reconstruct Pliocene environmental and climatic changes at Galili, in the Awash valley of Ethiopia. Enamel samples were obtained from 15 different mammalian taxa. The samples were collected from multiple localities at different stratigraphic levels spanning between >5.29 Ma and ~3.6 Ma. The wide range of samples helps to develop both spatial and temporal framework of mammalian dietary adaptation, habitat distribution, and climate change and variability within the Galili Formation. The mammalian dietary adaptations at Galili indicate the presence of a variety of vegetation, which includes gallery forest, closed woodland, open woodland and grasslands with a heterogeneous habitat structure on the landscape. However, the temporal change indicates a general tendency towards more open habitat (i.e., grassland to wooded grassland). It is also worth noting the significance of C4 grasses on the paleolandscape by Late Miocene or early Pliocene at the latest as it could have an important implication on hominin morphological adaptation (e.g., bipedalism). The oxygen isotopic composition of tooth enamel indicates a variable temporal climatic condition, where the middle Pliocene (~4.38 Ma - ~3.6 Ma) was wetter than the early Pliocene (>5.29 Ma - ~4.38 Ma). Similarly, estimated δ18O of meteoric water based on the most 18O-depleted hippo tooth enamel, displays range of values between -1.8% (VSMOW) and -5.24% (VSMOW), which elucidate changes in the isotopic composition of source water and hence precipitation. In general, by comparing the result of this study with data from younger localities in the region, it is evident that there is a major shift in the isotopic composition of water at ~ 3.0 Ma, which was accompanied

  14. Ontogenetic changes in isotopic signatures of an omnivorous fish Cultrichthys erythropterus in East Lake Taihu, China

    NASA Astrophysics Data System (ADS)

    Li, Yunkai; Zhang, Miao

    2015-05-01

    The relationship between body size and stable isotopic signatures of the omnivorous Redfin Culter ( Cultrichthys erythropterus), commonly found in East Lake Taihu, was investigated. Previous analyses of C. erythropterus stomach contents have shown that this species undergoes a diet switch from being predominantly zooplanktivorous to piscivorous during its life history. This was confirmed by stable carbon isotopic signature (δ13C) in this study, in which δ13C was positively correlated with both standard length and weight. The importance of littoral-benthic resources in supporting C. erythropterus during its lifespan was also demonstrated using a two-source mixing model, the results of which showed a significant increasing trend in the contribution of littoral-benthic energy. However, the stable nitrogen isotopic signature (δ15N) exhibited an unusual pattern compared with previous studies. The δ15N of C. erythropterus showed no relationship with body size, even though dietary changes were observed. This indicated that δ15N alone cannot fully reflect a diet shift in a species and possible variability in isotopic signatures over its life history. This should be considered when using stable isotopic signatures to investigate intra-specific variations and the timing of life-history events, such as estimating the trophic positions of fish species.

  15. 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.

  16. (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.

  17. 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.

  18. Distinguishing Biotic from Abiotic Phosphate Oxygen Isotopic Signatures

    NASA Astrophysics Data System (ADS)

    Blake, R.; Moyer, C.; Colman, A.; Liang, Y.; Dogru, D.

    2006-05-01

    On earth, phosphate has a strong biological oxygen isotope signature due to its concentration and intense cycling by living organisms as an essential nutrient. Phosphate does not undergo oxygen isotope exchange with water at low temperature without enzymatic catalysis, making the oxygen isotope ratio (18O/16O) of phosphate, δ18OP, an attractive biosignature in the search for early and extraterrestrial life. Recent laboratory and field studies have demonstrated that the δ18OP value of dissolved inorganic phosphate (PO4) records specific microbial activity and enzymatic reaction pathways in both laboratory cultures and natural waters/sediments (Blake et al., 2005; Colman et al 2005; Liang and Blake, 2005). Phosphate oxygen isotope biosignatures may be distinguished from abiotic signatures by: (1) evaluating the degree of temperature-dependent PO4-water oxygen isotope exchange in aqueous systems and deviation from equilibrium; and (2) evolution from an abiotic P reservoir signature towards a biotic P reservoir signature. Important abiotic processes potentially affecting phosphate δ18OP values include dissolution/precipitation, adsorption/desorption, recrystallization of PO4 mineral phases, diagenesis and metamorphism. For most of these processes, the recording, retention and alteration of δ18OP biosignatures have not been evaluated. Deep-sea hydrothermal vent fields are an ideal system in which to study the preservation and alteration of δ18OP biosignatures, as well as potential look-alikes produced by heat-promoted PO4 -water oxygen isotope exchange. Results from recent studies of δ18OP biosignatures in hydrothermal deposits near 9 and 21 degrees N. EPR and at Loihi seamount will be presented.

  19. Isotopic signatures: An important tool in today`s world

    SciTech Connect

    Rokop, D.J.; Efurd, D.W.; Benjamin, T.M.; Cappis, J.H.; Chamberlin, J.W.; Poths, H.; Roensch, F.R.

    1995-12-01

    High-sensitivity/high-accuracy actinide measurement techniques developed to support weapons diagnostic capabilities at the Los Alamos National Laboratory are now being used for environmental monitoring. The measurement techniques used are Thermal Ionization Mass Spectrometry (TIMS), Alpha Spectrometry(AS), and High Resolution Gamma Spectrometry(HRGS). These techniques are used to address a wide variety of actinide inventory issues: Environmental surveillance, site characterizations, food chain member determination, sedimentary records of activities, and treaty compliance concerns. As little as 10 femtograms of plutonium can be detected in samples and isotopic signatures determined on samples containing sub-100 femtogram amounts. Uranium, present in all environmental samples, can generally yield isotopic signatures of anthropogenic origin when present at the 40 picogam/gram level. Solid samples (soils, sediments, fauna, and tissue) can range from a few particles to several kilograms in size. Water samples can range from a few milliliters to as much as 200 liters.

  20. Metal stable isotope signatures as tracers in environmental geochemistry.

    PubMed

    Wiederhold, Jan G

    2015-03-01

    The biogeochemical cycling of metals in natural systems is often accompanied by stable isotope fractionation which can now be measured due to recent analytical advances. In consequence, a new research field has emerged over the last two decades, complementing the traditional stable isotope systems (H, C, O, N, S) with many more elements across the periodic table (Li, B, Mg, Si, Cl, Ca, Ti, V, Cr, Fe, Ni, Cu, Zn, Ge, Se, Br, Sr, Mo, Ag, Cd, Sn, Sb, Te, Ba, W, Pt, Hg, Tl, U) which are being explored and potentially applicable as novel geochemical tracers. This review presents the application of metal stable isotopes as source and process tracers in environmental studies, in particular by using mixing and Rayleigh model approaches. The most important concepts of mass-dependent and mass-independent metal stable isotope fractionation are introduced, and the extent of natural isotopic variations for different elements is compared. A particular focus lies on a discussion of processes (redox transformations, complexation, sorption, precipitation, dissolution, evaporation, diffusion, biological cycling) which are able to induce metal stable isotope fractionation in environmental systems. Additionally, the usefulness and limitations of metal stable isotope signatures as tracers in environmental geochemistry are discussed and future perspectives presented. PMID:25640608

  1. Noble Gas Isotopic Signatures and X-Ray and Electron Diffraction Characteristics of Tagish Lake Carbonaceous Chondrite

    NASA Technical Reports Server (NTRS)

    Nakamura, T.; Noguchi, T.; Zolensky, M. E.; Takaoka, N.

    2001-01-01

    Noble gas isotopic signatures and X-ray and electron diffraction characteristics of Tagish Lake indicate that it is a unique carbonaceous chondrite rich in saponite, Fe-Mg-Ca carbonate, primordial noble gases, and presolar grains. Additional information is contained in the original extended abstract.

  2. Unraveling the nitrogen isotopic signature of symbiotic corals

    NASA Astrophysics Data System (ADS)

    Devlin, Q.; Swart, P. K.; Altabet, M. A.

    2013-12-01

    Coral reefs thrive in shallow, tropical, low nutrient waters. Nutrient inputs to a reef environment are often interpreted by measuring the nitrogen isotopic composition of reef organisms. The δ15N signature of scleractinian corals has been historically measured to assess the presence of anthropogenic influences such as sewage and fertilizer runoff. The majority of reef building corals form a symbiotic partnership with the dinoflagellate algae, Symbiodinium microadriaticum. The δ15N signature of symbiotic corals is complex as it is not only dependent on nitrogen acquisition by the coral, but also by the algal symbionts that reside within the gastrodermal tissue layer. The relationship between the δ15N of dissolved inorganic nitrogen (DIN) and the δ15N of coral tissue has not been established. The aim of this study is to identify considerations necessary when interpreting nitrogen sources based on δ15N of coral tissue. Incubations were carried out in order to measure isotopic fractionation associated with nitrate and ammonium incorporation by the Pacific branching coral, Pocillopora damicornis. We investigated the dependence of nitrogen isotope fractionation on species of DIN (nitrate or ammonium), concentration of DIN (range: 1-50 μM N), genetic diversity of algal symbionts (clade C or clade D) and light levels.

  3. Molybdenum isotope signatures from the Yangtze block continental margin and its indication to organic burial rate

    NASA Astrophysics Data System (ADS)

    Zhou, L.; Zhou, H. B.; Huang, J. H.

    2007-12-01

    The paper presents the molybdenum isotope data, along with the trace element content, to investigate the geochemical behavior of authigenic Mo during long-term burial in sediments in continental margin settings of the Yangtze block, as well as their indication to the burial of original organic carbon. The burial rate of original organic carbon were estimated on the basis of the amount of sedimentary sulfur (TS content), whilst the carbon loss by aerobic degradation was estimated according to calculated Mn contents. On these points, the original organic carbon flux was calculated, exhibiting a large range of variation (2.54-15.82 mmol/m2/day). The strong correlation between sedimentary Mo isotope values and organic carbon burial rates previously proposed on the basis of the investigations on modern ocean sediments was also used here to estimate the organic carbon burial rate. The data gained through this model showed that organic carbon burial rates have large variations, ranging from 0.43- 2.87mmol/m2/day. Although the two sets of data gained through different geochemical records in the Yangtze block show a deviation of one order of magnitude, they do display a strong correlation. It is thus tempting to speculate that the Mo isotope signature of sediments may serve as a tracer for the accumulation rate of original organic carbon in the continental margin sediments. Keywords: Molybdenum isotopes; organic carbon burial rate; ancient continental margin setting ACKNOWLEDGMENTS We thank Professor Xie Shucheng for his constructive review comments. This research is co-supported by the Program for Changjiang Scholars and Innovative Research Team in University (grants IRT0441), the SinoPec project (grant no. G0800-06-ZS-319) and the National Nature Science Foundation of China (grants 40673020).

  4. Carbon (δ13C) and Nitrogen (δ15N) Stable Isotope Signatures in Bat Fur Indicate Swarming Sites Have Catchment Areas for Bats from Different Summering Areas

    PubMed Central

    Segers, Jordi L.; Broders, Hugh G.

    2015-01-01

    Migratory patterns of bats are not well understood and traditional methods to study this, like capture-mark-recapture, may not provide enough detail unless there are many records. Stable isotope profiles of many animal species have been used to make inferences about migration. Each year Myotis lucifugus and M. septentrionalis migrate from summering roosts to swarming caves and mines in the fall, but the pattern of movement between them is not well understood. In this study, fur δ13C and δ15N values of 305 M. lucifugus and 200 M. septentrionalis were analyzed to make inferences about migration patterns between summering areas and swarming sites in Nova Scotia, Canada. We expected that there would be greater variability in δ13C and δ15N among individuals at swarming sites because it was believed that these sites are used by individuals originating from many summering areas. There was extensive overlap in the standard ellipse area, corrected for small sample sizes (SEAc), of bats at swarming sites and much less overlap in SEAc among groups sampled at summering areas. Meaningful inference could not be made on M. septentrionalis because their low variation in SEAc may have been the result of sampling only 3 summering areas. However, for M. lucifugus, swarming sites had larger SEAc than summering areas and predictive discriminant analysis assigned swarming bats to multiple summering areas, supporting the contention that swarming bats are mixed aggregations of bats from several summering areas. Together, these data support the contention that swarming sites have catchment areas for bats from multiple summering areas and it is likely that the catchment areas for swarming sites overlap. These data suggest that δ13C and δ15N profiling of bat fur offer some potential to make inferences about regional migration in bats. PMID:25923696

  5. Carbon and oxygen isotope microanalysis of carbonate.

    PubMed

    Velivetskaya, Tatiana A; Ignatiev, Alexander V; Gorbarenko, Sergey A

    2009-08-30

    Technical modification of the conventional method for the delta(13)C and delta(18)O analysis of 10-30 microg carbonate samples is described. The CO(2) extraction is carried out in vacuum using 105% phosphoric acid at 95 degrees C, and the isotopic composition of CO(2) is measured in a helium flow by gas chromatography/isotope ratio mass spectrometry (GC/IRMS). The feed-motion of samples to the reaction vessel provides sequential dropping of only the samples (without the sample holder) into the acid, preventing the contamination of acid and allowing us to use the same acid to carry out very large numbers of analyses. The high accuracy and high reproducibility of the delta(13)C and delta(18)O analyses were demonstrated by measurements of international standards and comparison of results obtained by our method and by the conventional method. Our method allows us to analyze 10 microg of the carbonate with a standard deviation of +/-0.05 per thousand for delta(13)C and delta(18)O. The method has been used successfully for the analyses of the oxygen and carbon isotopic composition of the planktonic and benthic foraminifera in detailed palaeotemperature reconstructions of the Okhotsk Sea. PMID:19603476

  6. Cadmium Isotope Fractionation in Seawater - A Signature of Nutrient Utilization

    NASA Astrophysics Data System (ADS)

    Wichtlhuber, S.; Rehkaemper, M.; Halliday, A. N.

    2005-12-01

    .0005. The isotopic variations observed for seawater are likely to reflect isotope fractionation during uptake of Cd by phytoplankton, as recently reported by Lacan et al. (2005), because inorganic geological processes (other than evaporation/condensation) do not appear to generate isotope effects as large as those observed in the present study (Wombacher et. al, 2003). These preliminary results suggest that Cd isotopes have the potential to become a useful proxy of nutrient utilization, which could supplement the Cd/Ca and δ13C records of previous studies, if suitable sedimentary archives can be identified that preserve the Cd isotope signatures of past seawater. References: Lacan F., Francois R., Ji Y. and Sherrell R., 2005. Does oceanic productivity production lead to a cadmium isotope fractionation? Geophys. Res. Abstr. 7, 07657. Wombacher F., Rehkämper M., Mezger K. and Münker C., 2003. Stable isotope compositions of cadmium in geological materials and meteorites determined by multiple collector-ICPMS. Geochim. Cosmochim. Acta, 67, 4639-4654.

  7. Aerosol isotopic ammonium signatures over the remote Atlantic Ocean

    NASA Astrophysics Data System (ADS)

    Lin, C. T.; Jickells, T. D.; Baker, A. R.; Marca, A.; Johnson, M. T.

    2016-05-01

    We report aerosol ammonium 15N signatures for samples collected from research cruises on the South Atlantic and Caribbean using a new high sensitivity method. We confirm a pattern of isotopic signals from generally light (δ15N -5 to -10‰), for aerosols with very low (<2  nmol m-3) ammonium concentrations from the remote high latitude ocean, to generally heavier values (δ15N +5 to +10‰), for aerosols collected in temperate and tropical latitudes and with higher ammonium concentrations (>2  nmol m-3). We discuss whether this reflects a mixing of aerosols from two end-members (polluted continental and remote marine emissions), or isotopic fractionation during aerosol transport.

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

    NASA Astrophysics Data System (ADS)

    Esposito, Mario

    2016-04-01

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

  9. Geochemical and sulfur isotope signatures of microbial activity in acidic and sulfuric hot springs, northern Taiwan

    NASA Astrophysics Data System (ADS)

    Wang, P.; Chen, K.; Cheng, T.; Hsieh, H.; Lin, L.

    2009-12-01

    Acidic and sulfuric hot springs are natural habitats for thermophilic sulfur-utilizing microorganisms. Integration of bioenergetic evaluation, molecular analysis and stable isotopic signatures may be able to exhibit a full view of microbial activity in such an extreme environment. Widely distributed hot springs hosted by the Tatung volcano group in northern Taiwan provide a chance to evaluate the interplay between geochemical variation and microbial metabolism especially for sulfur. Several hot spring ponds varying in sizes and geochemical characteristics were studied to reveal the possible control of fluid compositions on microbial metabolisms, and vice versa. Sulfate, sulfide, elemental sulfur and dissolved organic carbon were available in spring water and sediments in the ponds. Dominant microbial metabolisms inferred from the bioenergetic evaluation were aerobic oxidations of various reduced compounds, including elemental sulfur, pyrite, ferrous iron and organic carbon. Sulfate and sulfur reductions were thermodynamically favorable but provided less energy flux, while sulfur disproportionation was thermodynamically incapable. The analyses of 16S rRNA genes extracted from the spring water and sediments indicated that aerobic oxidation of sulfur, hydrogen or organic carbon and anaerobic elemental sulfur reduction were possible metabolisms. Since the major portion of 16S rRNA sequences were affiliated with unclassified environmental sequences, their potential metabolisms remained obscure. Sulfur isotopic compositions of dissolved sulfate, pyrite and elemental sulfur exhibited significant variations among the different hot spring ponds. Apparently, the microbial effects on the sulfur isotopic signatures were various. A disproportionation reaction of volcanic gas was required to account for high sulfur isotope difference between sulfate and reduced sulfur in the large hot ponds. In contrary, abiotic or microbial oxidation of reduced sulfur might be dominant in the

  10. Using Bathymodiolus tissue stable isotope signatures to infer biogeochemical process at hydrocarbon seeps

    NASA Astrophysics Data System (ADS)

    Feng, D.; Kiel, S.; Qiu, J.; Yang, Q.; Zhou, H.; Peng, Y.; Chen, D.

    2015-12-01

    Here we use stable isotopes of carbon, nitrogen and sulfur in the tissue of two bathymodiolin mussel species with different chemotrophic symbionts (methanotrophs in B. platifrons and sulfide-oxidizers in B. aduloides) to gain insights into the biogeochemical processes at an active site in 1120 m depth on the Formosa Ridge, called Site F. Because mussels with methanotrophic symbionts acquire the isotope signature of the used methane, the average δ13C values of B. platifrons (-70.3‰; n=36) indicates a biogenic methane source at Site F, consistent with the measured carbon isotope signature of methane (-61.1‰ to -58.7‰) sampled 1.5 m above the mussel beds. The only small offset between the δ13C signatures of the ascending methane and the authigenic carbonate at site F (as low as -55.3‰) suggests only minor mixing of the pore water with marine bicarbonate, which in turn may be used as an indicator for advective rather than diffusive seepage at this site. B. aduloides has much higher average δ13C values of -34.4‰ (n=9), indicating inorganic carbon (DIC) dissolved in epibenthic bottom water as its main carbon source. The DIC was apparently marine bicarbonate with a small contribution of 13C-depleted carbon from locally oxidized methane. The δ34S values of the two mussel species indicate that they used two different sulfur sources. B. platifrons (average δ34S = +6.4±2.6‰; n=36) used seawater sulfate mixed with isotopically light re-oxidized sulfide from the sulfate-dependent anaerobic oxidation of methane (AOM), while the sulfur source of B. aduloides (δ34S = -8.0±3.1‰; n=9) was AOM-derived sulfide used by its symbionts. δ15N values differed between the mussels, with B. platifrons having a wider range of on average slightly lower values (mean = +0.5±0.7‰, n=36) than B. aduloides (mean = +1.1±0.0‰). These values are significantly lower than δ15N values of South China Sea deep-sea sediments (+5‰ to +6‰), indicating that the organic nitrogen

  11. Effect of native and invasive cordgrass on Macoma petalum density, growth, and isotopic signatures

    NASA Astrophysics Data System (ADS)

    Brusati, Elizabeth D.; Grosholz, Edwin D.

    2007-02-01

    Ecosystem engineers can influence community and ecosystem dynamics by controlling resources, modifying the flow of energy or biomass, or changing physical characteristics of the habitat. Invasive hybrid cordgrass ( Spartina alterniflora × Spartina foliosa ) is an ecosystem engineer in salt marshes in San Francisco Bay, California, U.S.A. that raises intertidal elevations and may be either increasing C4 plant carbon input into food webs or tying up carbon in a form that is not usable by consumers. A manipulative experiment compared abundance, growth, and stable isotope (δ 13C and δ 15N) composition of the clam Macoma petalum (= M. balthica) among native marsh, hybrid Spartina, and mudflats in central San Francisco Bay. We found higher densities (individuals m -2) of M. petalum on mudflats compared to either native or hybrid Spartina ( p < 0.001). Macoma petalum shell growth was significantly greater in mudflats than in either vegetation type in 2002 ( p = 0.005) but not 2003. Differences in shell growth between native and hybrid Spartina were not significant. Stable isotope results showed differences between habitats in δ 13C but not δ 15N. Carbon signatures of M. petalum placed in Spartina were much more depleted than the isotopic signature of Spartina. Neither native nor hybrid Spartina appears to be a significant carbon source for M. petalum in San Francisco Bay, and we found no evidence that hybrid Spartina contributes carbon to M. petalum beyond what is provided by S. foliosa, despite the hybrid's much greater biomass. Our results show that loss of mudflat habitat, rather than increased input of C4 carbon, is the greatest effect of the invasion of hybrid Spartina on M. petalum.

  12. Stable isotope signatures for characterising the biological stability of landfilled municipal solid waste

    SciTech Connect

    Wimmer, Bernhard; Hrad, Marlies; Huber-Humer, Marion; Watzinger, Andrea; Wyhlidal, Stefan; Reichenauer, Thomas G.

    2013-10-15

    Highlights: ► The isotopic signature of δ{sup 13}C-DIC of leachates is linked to the reactivity of MSW. ► Isotopic signatures of leachates depend on aerobic/anaerobic conditions in landfills. ► In situ aeration of landfills can be monitored by isotope analysis in leachate. ► The isotopic analysis of leachates can be used for assessing the stability of MSW. ► δ{sup 13}C-DIC of leachates helps to define the duration of landfill aftercare. - Abstract: Stable isotopic signatures of landfill leachates are influenced by processes within municipal solid waste (MSW) landfills mainly depending on the aerobic/anaerobic phase of the landfill. We investigated the isotopic signatures of δ{sup 13}C, δ{sup 2}H and δ{sup 18}O of different leachates from lab-scale experiments, lysimeter experiments and a landfill under in situ aeration. In the laboratory, columns filled with MSW of different age and reactivity were percolated under aerobic and anaerobic conditions. In landfill simulation reactors, waste of a 25 year old landfill was kept under aerobic and anaerobic conditions. The lysimeter facility was filled with mechanically shredded fresh waste. After starting of the methane production the waste in the lysimeter containments was aerated in situ. Leachate and gas composition were monitored continuously. In addition the seepage water of an old landfill was collected and analysed periodically before and during an in situ aeration. We found significant differences in the δ{sup 13}C-value of the dissolved inorganic carbon (δ{sup 13}C-DIC) of the leachate between aerobic and anaerobic waste material. During aerobic degradation, the signature of δ{sup 13}C-DIC was mainly dependent on the isotopic composition of the organic matter in the waste, resulting in a δ{sup 13}C-DIC of −20‰ to −25‰. The production of methane under anaerobic conditions caused an increase in δ{sup 13}C-DIC up to values of +10‰ and higher depending on the actual reactivity of the MSW

  13. Isotopic signature of atmospheric phosphate emitted from coal combustion

    NASA Astrophysics Data System (ADS)

    Weinberger, Roi; Weiner, Tal; Angert, Alon

    2016-07-01

    Atmospheric deposition of phosphorus (P) serves as an important nutrient input for many terrestrial, marine and freshwater ecosystems, influencing their biogeochemistry and primary production. Fossil fuel combustion, principally coal, is estimated to be a major source of atmospheric-P in industrialized regions. In this research, we aim to find a distinct isotopic signature for fly coal ash, the by-product of coal combustion that is emitted to the atmosphere. This signature could be used to identify coal's contribution to atmospheric-P. For this aim, ten fly coal ash samples from different coal sources, collected by power station filters, were analyzed for P concentrations and stable oxygen isotopic composition (δ18OP). Two inorganic phosphate fractions were analyzed: HCl-extractable and resin-extractable (bioavailable P). High HCl-P concentrations of up to 3500 μg P/g ash were found with a distinct δ18OP range of 17.1-20.5‰. The resin-P concentrations were substantially lower (<8 μg/g) with a wider and significantly lower δ18OP range of 10.6-16.5‰. The ash samples were found to have HCl-P δ18OP higher in ∼0-∼9‰ relative to the source coal. Similar isotopic values were found for ash with the same coal source country, regardless of the power station. Despite the low bioavailable P concentrations, fly ash could still be an important atmospheric P source to the biosphere since these combustion products likely acidify in the atmosphere to become bioavailable. This is also supported by our finding that smaller particles, which are more indicative of the particles actually emitted to the atmosphere, are significantly P-richer. Natural dust sources' δ18OP overlap fly ash's range, complicating the assessment of coal's contribution. Nonetheless, our results provide a new tool for identification of fossil fuel combustion sources in local and global atmospheric P deposition.

  14. Isotopic Signatures of Some Anthropogenic Nitrous Oxide Sources

    NASA Astrophysics Data System (ADS)

    Wilson, S. R.; Griffith, D. W.; Menegazzo, J. M.; Naylor, T.; Turatti, F.

    2002-05-01

    The relative abundances of the four major isotopomers of N2O (14N14N16O, 14N15N16O, 15N14N16O, 14N14N18O) have been measured from sources at a series of sites in Australia. The measurements have been carried out by cryogenically extracting N2O from the air, and then analysing the sample using high resolution FTIR spectrometry. The isotopic signature of urban air in Wollongong shows significant variation in the nitrogen isotopes, over a range consistent with that observed by Yoshida and Toyoda [2000]. The average δ 15N shows an inverse correlation with N2O mixing ratio, consistent with 15N-depleting sources in the area. Samples have also been collected from two agricultural sites and two waste water sites. We observe δ 15N values in the range of --25 to 5‰ , but with less variation in the difference (δ (14N15N16O) - δ (15N14N16O)) in most samples. Under certain conditions a significant change in this 15N isotopic difference can be seen, consistent with differing production mechanisms of N2O.

  15. Biomarker and Carbon Isotope Signals from Leaf to Terrestrial Archive

    NASA Astrophysics Data System (ADS)

    Freeman, K. H.

    2012-12-01

    Biomarker and isotopic signatures of terrestrial organic matter are increasingly used to discern organic matter provenance in transport systems as well as to reconstruct environmental conditions of ancient landscapes. Such tools help scholars evaluate river transport and the influence of climate on terrestrial biomass and soil carbon, the largest reduced carbon inventories within the global surface environment. These signals reflect isotopic fractionation during photosynthesis and the abundance and composition of plant lipids, which are ultimately influenced by plant community, ecosystem structure and climate. Case studies and literature data for plants, biomarkers, litter carbon and soil organic matter refine the framework for evaluating and interpreting ancient terrestrial environments. Such studies reveal isotopic and biomarker patterns primarily track woody cover and moisture gradients in ancient landscapes. This emerging approach is currently limited by a lack of supporting and critical information about carbon isotopic differences between lipids and leaves, which appear to vary with environment as well as plant type. Environmental reconstructions and carbon-cycle studies are also limited by incomplete understanding of carbon isotopic relationships between modern litter, mineral soil, leaf waxes, and ancient archives of these properties. The net imprint of diagenesis on bulk carbon archives can potentially be constrained with companion biomarker studies, provided biomass production, litter delivery and lipid isotopic characteristics are constrained. Soil organic matter isotopic diagenesis is not fully understood, especially on geologic timescales, but appears to vary with both climate and ecosystem properties. This presentation will highlight recent findings and current knowledge gaps in understanding biomarker and ancient soil organic carbon as landscape tracers of past vegetation and climate.

  16. Impact of environmental curium on plutonium migration and isotopic signatures.

    PubMed

    Kurosaki, Hiromu; Kaplan, Daniel I; Clark, Sue B

    2014-12-01

    Plutonium (Pu), americium (Am), and curium (Cm) activities were measured in sediments from a former radioactive waste disposal basin located on the Savannah River Site, South Carolina, and in subsurface aquifer sediments collected downgradient from the basin. In situ Kd values (Pu concentration ratio of sediment/groundwater) derived from this field data and previously reported groundwater concentration data compared well to laboratory Kd values reported in the literature. Pu isotopic signatures confirmed multiple sources of Pu contamination. The ratio of (240)Pu/(239)Pu was appreciably lower for sediment samples compared to the associated groundwater. This isotopic ratio difference may be explained by the following: (1) (240)Pu produced by decay of (244)Cm may exist predominantly in high oxidation states (Pu(V)O2(+) and Pu(VI)O2(2+)) compared to Pu derived from the disposed waste effluents, and (2) oxidized forms of Pu sorb less to sediments than reduced forms of Pu. Isotope-specific Kd values calculated from measured Pu activities in the sediments and groundwater indicated that (240)Pu, which is derived primarily from the decay of (244)Cm, had a value of 10 ± 2 mL g(-1), whereas (239)Pu originating from the waste effluents discharged at the site had a value of 101 ± 8 mL g(-1). One possible explanation for the isotope-specific sorption behavior is that (240)Pu likely existed in the weaker sorbing oxidation states, +5 or +6, than (239)Pu, which likely existed in the +3 or +4 oxidation states. Consequently, remediation strategies for radioactively contaminated systems must consider not only the discharged contaminants but also their decay products. In this case, mitigation of Cm as well as Pu will be required to completely address Pu migration from the source term. PMID:25350948

  17. Carbon Isotopic Fractionation in Fischer-Tropsch Type Reactions and Relevance to Meteorite Organics

    NASA Technical Reports Server (NTRS)

    Johnson, Natasha M; Elsila, Jamie E.; Kopstein, Mickey; Nuth, Joseph A., III

    2012-01-01

    Fischer-Tropsch-Type (FTT) reactions have been hypothesized to contribute to the formation of organic compounds in the early solar system, but it has been difficult to identify a signature of such reactions in meteoritic organics. The work reported here examined whether temperature-dependent carbon isotopic fractionation of FTT reactions might provide such a signature. Analyses of bulk organic deposits resulting from FTT experiments show a slight trend towards lighter carbon isotopic ratios with increasing temperature. It is unlikely, however, that these carbon isotopic signatures could provide definitive provenance for organic compounds in solar system materials produced through FTT reactions, because of the small scale of the observed fractionations and the possibility that signatures from many different temperatures may be present in any specific grain.

  18. Carbon isotopic composition of Amazon shelf sediments

    SciTech Connect

    Showers, W.J.; Angle, D.G.; Nittrouer, C.A.; Demaster, D.J.

    1985-02-01

    The distribution of carbon isotopes in Amazon shelf sediment is controlled by the same processes that are forming the modern subaqueous delta. The terrestrial (-27 to -25 per thousand) isotopic carbon signal observed in surficial sediments near the river mouth extends over 400 km northwest along the shelf. Terrestrial carbon is associated with areas of rapid sediment accumulation (topset and foreset regions). A sharp boundary between terrestrial (-27 to -25 per thousand) and marine (-23 to -22 per thousand) isotopic carbon values in surficial sediments is associated with a change in depositional conditions (foreset to bottomset regions) and a decrease in sediment accumulation rate. POC water-column isotopic values (-27 per thousand) near the river mouth are similar to the underlying surficial-sediment TOC isotopic values, but POC water-column samples collected 20 km off the river mouth have marine carbon isotopic values (-22 to -19 per thousand) and differ from the underlying surficial-sediment TOC isotopic values. These water column observations are related to variations in turbidity and productivity. Down-core isotopic variation is only observed in cores taken in areas of lower sediment accumulation rates. These observations indicate that the organic carbon in Amazon shelf sediment is dominantly terrestrial in composition, and the location of deposition of this carbon is controlled by modern processes of sediment accumulation. The modern Amazon shelf is similar to large clinoform shale deposits of the Cretaceous in North America. Thus, the stratigraphic setting may help predict the isotopic variations of carbon in ancient deposits.

  19. Carbon isotope effects in carbonate systems

    NASA Astrophysics Data System (ADS)

    Deines, Peter

    2004-06-01

    Global carbon cycle models require a complete understanding of the δ 13C variability of the Earth's C reservoirs as well as the C isotope effects in the transfer of the element among them. An assessment of δ 13C changes during CO 2 loss from degassing magmas requires knowledge of the melt-CO 2 carbon isotope fractionation. In order to examine the potential size of this effect for silicate melts of varying composition, 13C reduced partition functions were computed in the temperature range 275 to 4000 K for carbonates of varying bond strengths (Mg, Fe, Mn, Sr, Ba, Pb, Zn, Cd, Li, and Na) and the polymorphs of calcite. For a given cation and a given pressure the 13C content increases with the density of the carbonate structure. For a given structure the tendency to concentrate 13C increases with pressure. The effect of pressure (‰/10 kbar) on the size of the reduced partition function of aragonite varies with temperature; in the pressure range 1 to 10 5 bars the change is given by: Δ 13C p average=-0.01796+0.06635∗ 10 3/T+0.006875∗ 10 6/T2 For calcite III the pressure effect is on average 1.4× larger than that for aragonite at all temperatures. The nature of the cation in a given structure type has a significant effect on the carbon isotope fractionation properties. The tendency to concentrate 13C declines in the series magnesite, aragonite, dolomite, strontianite, siderite, calcite, smithonite, witherite, rhodochrosite, otavite, cerrusite. For divalent cations a general expression for an estimation of the reduced partition function (β) from the reduced mass (μ = [M Cation × M Carbonate]/[M Cation + M Carbonate]) is: 1000 lnβ=(0.032367-0.072563∗ 10 3/T-0.01073∗ 10 6/T2)∗μ-14.003+29.953∗ 10 3/T+9.4610∗ 10 6/T2 For Mg-calcite the 13C content varies with the Mg concentration. The fractionation between Mg-calcite (X = mole fraction of MgCO 3) and calcite is given by: 1000 ln(α MgCalite- Calcite)=[0.013702-0.10957× 10 3/T+1.35940× 10 6/T2

  20. Microscale carbon isotope variability in ALH84001 carbonates and a discussion of possible formation environments

    NASA Astrophysics Data System (ADS)

    Niles, P. B.; Leshin, L. A.; Guan, Y.

    2005-06-01

    The carbonates in martian meteorite ALH84001 preserve a record of aqueous processes on Mars at 3.9 Ga, and have been suggested to contain signatures of ancient martian life. The conditions of the carbonate formation environment are critical for understanding possible evidence for life on Mars, the history of water on Mars, and the evolution of the martian atmosphere. Despite numerous studies of petrographic relationships, microscale oxygen isotope compositions, microscale chemical compositions, and other minerals associated with the carbonates, formation models remain relatively unconstrained. Microscale carbon isotope analyses of ALH84001 carbonates reveal variable δ 13C values ranging from +27 to +64 ‰. The isotopic compositions are correlated with chemical composition and extent of crystallization such that the Mg-poor, early-formed carbonates are relatively 13C depleted and the Mg-rich, later forming carbonates, are 13C enriched. These data are inconsistent with many of the previously proposed environments for carbonate formation, and a new set of hypotheses are proposed. Specifically, two new models that account for the data involve low temperature (<100°C) aqueous processes: (1) the carbonates formed during mixing of two fluids derived from separate chemical and isotopic reservoirs; or (2) the carbonates formed from high pH fluids that are exposed to a CO 2-rich atmosphere and precipitate carbonate, similar to high pH springs on Earth.

  1. Oxygen and hydrogen isotope signatures of Northeast Atlantic water masses

    NASA Astrophysics Data System (ADS)

    Voelker, Antje H. L.; Colman, Albert; Olack, Gerard; Waniek, Joanna J.; Hodell, David

    2015-06-01

    Only a few studies have examined the variation of oxygen and hydrogen isotopes of seawater in NE Atlantic water masses, and data are especially sparse for intermediate and deep-water masses. The current study greatly expands this record with 527 δ18O values from 47 stations located throughout the mid- to low-latitude NE Atlantic. In addition, δD was analyzed in the 192 samples collected along the GEOTRACES North Atlantic Transect GA03 (GA03_e=KN199-4) and the 115 Iberia-Forams cruise samples from the western and southern Iberian margin. An intercomparison study between the two stable isotope measurement techniques (cavity ring-down laser spectroscopy and magnetic-sector isotope ratio mass spectrometry) used to analyze GA03_e samples reveals relatively good agreement for both hydrogen and oxygen isotope ratios. The surface (0-100 m) and central (100-500 m) water isotope data show the typical, evaporation related trend of increasing values equatorward with the exception for the zonal transect off Cape Blanc, NW Africa. Off Cape Blanc, surface water isotope signatures are modified by the upwelling of fresher Antarctic Intermediate Water (AAIW) that generally has isotopic values of 0.0 to 0.5‰ for δ18O and 0 to 2‰ for δD. Along the Iberian margin the Mediterranean Outflow Water (MOW) is clearly distinguished by its high δ18O (0.5-1.1‰) and δD (3-6‰) values that can be traced into the open Atlantic. Isotopic values in the NE Atlantic Deep Water (NEADW) are relatively low (δ18O: -0.1 to 0.5‰; δD: -1 to 4‰) and show a broader range than observed previously in the northern and southern convection areas. The NEADW is best observed at GA03_e Stations 5 and 7 in the central NE Atlantic basin. Antarctic Bottom Water isotope values are relatively high indicating modification of the original Antarctic source water along the flow path. The reconstructed δ18O-salinity relationship for the complete data set has a slope of 0.51, i.e., slightly steeper than the 0

  2. The zinc stable isotope signature of waste rock drainage in Arctic Canada

    NASA Astrophysics Data System (ADS)

    Matthies, Romy; Blowes, David

    2014-05-01

    Leachate emerging from a pilot-scale waste rock pile of the Diavik diamond mine, Northwest Territories, was monitored. The well-characterized waste rock consists of granite, pegmatitic granite and biotite schist with an average total sulfur and carbonate carbon concentration of 0.053 and 0.027 wt. %, respectively. During the field seasons of 2011 and 2012, the Zn stable isotope footprint was characterized alongside standard monitoring parameters. pH ranged between 4.3 and 6.8 and carbonate alkalinity was low or undetectable. Al and Fe concentrations averaged 6.78 mg L-1 and 175 µg L-1, respectively. The pH and metal mobility were governed by sulfide oxidation and sorption and co-precipitation onto iron and aluminium hydroxides. The main processes controlling zinc mobility in the range of 0.4 and 4.7 mg L-1 was the oxidative dissolution of sphalerite (ZnS) in the biotite schist and the attenuation of zinc onto secondary iron and aluminium hydroxides and desorption upon the pH declining below the pHpzc. The isotope ratios between -0.16 and +0.19 ‰ (δ66Zn, avg = +0.05 ‰, n = 43) are consistent with values reported from other sphalerite containing deposits. Zn isotope ratios and concentrations were largely uncorrelated suggesting that the processes affecting Zn mobility had little or no impact on the Zn isotope signature. Data indicate, that the Zn isotope ratios of the waste rock leachate may be used as a fingerprint to track anthropogenic, mine-derived Zn sources under varying environmental conditions.

  3. Towards the Tracing of NOx Sources by Isotopic Signature

    NASA Astrophysics Data System (ADS)

    Fibiger, D. L.; Hastings, M. G.

    2012-12-01

    Atmospheric NOx (NO and NO2) plays a significant role in both air quality (through the production of tropospheric ozone) and reactive N deposition (through production and deposition of nitric acid). NOx is released by both anthropogenic (fossil fuel combustion, biomass burning, aircraft emissions) and natural (lightning, biogenic production in soils, natural fires) sources. Global concentrations of NOx are rising because of increased anthropogenic emissions, while natural source emissions also contribute significantly to the global NOx burden. The contributions of both natural and anthropogenic sources and their considerable variability in space and time make it difficult to attribute local NOx concentrations and deposited nitric acid to a particular source or sources. Further, global atmospheric models typically use comparisons with nitric acid deposition to verify simulations that include assumptions about source magnitude and variability, chemistry, and transport. Several recent studies suggest that variability in the nitrogen isotopic composition (δ15N) of nitric acid is related to variability in the isotopic signatures of NOx emission sources. Nevertheless, considerable uncertainty remains regarding the isotopic composition of most NOx sources. We have refined a method in the laboratory that efficiently collects NOx from air, which is important for isotopic analysis, as incomplete capture can fractionate the sample NOx. The method (modeled after Margeson et al., 1984) uses a 0.5M NaOH/0.25M KMnO4 solution in a gas-washing bottle to scrub NOx from the air stream. Efficiency verification was conducted using a tank of known concentration under various conditions, including varying total flow rate, NOx concentration (by mixing with N2), solution volume and NaOH concentration. Efficient collection was achieved under a wide range of conditions. In addition to discussion of methodological details, strengths and weaknesses, our presentation will include measurements

  4. THE CD ISOTOPE SIGNATURE OF THE SOUTHERN OCEAN

    NASA Astrophysics Data System (ADS)

    Abouchami, W.; Galer, S. J.; Middag, R.; de Baar, H.; Andreae, M. O.; Feldmann, H.; Raczek, I.

    2009-12-01

    The availability of micronutrients can limit and control plankton ecosystems, notably in the Southern Ocean which plays a major role in regulating the CO2 biological pump. Cadmium has a nutrient-like distribution in seawater - it is directly incorporated into living plankton in the upper water column and re-mineralised at depth. The nutritional role of Cd (Price and Morel, 1990) makes it a potentially useful tracer of biological productivity. We report Cd concentration and Cd stable isotope data obtained using a double-spike TIMS method on seawater samples collected during the Zero and Drake Passage cruise (ANTXXIV-III, IPY-GEOTRACES 2008). Four vertical profiles were collected from 40 to 70°S across the Polar Front using the ultra-clean Titan frame (De Baar et al., 2008), providing a record of changes in biological productivity from the Subantarctic to the Antarctic region. Data from two profiles from the SE Atlantic (47.66°S, 4.28W) and Drake Passage (55.13°S, 65.53°W) obtained on 1 litre-sized samples are presented. Both profiles show a increase in Cd concentration with depth, with noticeably higher concentrations in the SE Atlantic. Cd and PO4 are positively correlated with distinct slopes for the two profiles. The Cd isotope data are expressed as ɛ112/110Cd relative to our JMC Mainz standard (± 8ppm, 2SD, N=17). ɛ112/110Cd values show a continuous decrease with increasing depth and a significant shift towards heavier values in the upper 400m at both stations resolvable outside analytical error (2SE ≤ 20ppm). The sense of Cd isotope fractionation confirms previous findings of uptake of “light” Cd by phytoplankton in the upper water column (Lacan et al., 2006; Ripperger et al., 2007; Schmidt et al., 2009). Most important is the evidence for a distinctive heavier Cd isotope signature in AASW relative to AAIW. This result demonstrates that different water masses carry distinct Cd isotopic compositions reflecting changes in Cd uptake by phytoplankton

  5. Nitrate loading and isotopic signatures in subsurface agricultural drainage systems.

    PubMed

    Smith, E L; Kellman, L M

    2011-01-01

    Artificially draining soils using subsurface tiles is a common practice on many agricultural fields. High levels of nitrate-nitrogen (NO-N) are often released from these systems; therefore, knowledge on the sources and processes controlling NO-N in drainage systems is needed. A dual isotope study (δN and δO) was used to investigate three subsurface drainage systems (shallow, conventional, and controlled) in Onslow, Nova Scotia, Canada. The objectives of this study were (i) to identify which drainage system more effectively reduced the NO-N loading, (ii) to examine differences in isotopic signatures under identical nutrient and cropping regimes for a fixed soil type, and (iii) to identify the utility of different drainage systems in controlling nutrient flows. Nitrate concentrations measured ranged from 0.92 to 11.8, from 2.3 to 17.3, and from 2.1 to 19.8 mg L for the shallow, conventional, and controlled drains, respectively. Total NO-N loading from shallow and controlled drains were 20 and 5.6 kg ha, respectively, lower than conventional (39.1 kg ha). The isotopic composition of NO-N for all drainage types appeared to be a mixture of two organic sources (manure and soil organic matter) via the process of nitrification. There was no evidence that denitrification played a significant role in removing NO-N during transport. Overall, shallow drainage reduced NO-N loading but offered no water conservation benefits. Combining the benefits of decreased NO-N loading from shallow systems with water control capability may offer the best solution to reducing nutrient loadings into water systems, achieving optimal crop yield, and decreasing drainage installation costs. PMID:21712595

  6. 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.

  7. Carbon isotope effects associated with aceticlastic methanogenesis.

    PubMed

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

    1994-02-01

    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. PMID:11536629

  8. Carbon isotope effects associated with aceticlastic methanogenesis.

    PubMed Central

    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. PMID:11536629

  9. Combining stable isotope isotope geochemistry and carbonic anhydrase activity to trace vital effect in carbonate precipitation experiments

    NASA Astrophysics Data System (ADS)

    Thaler, C.; Ader, M.; Menez, B.; Guyot, F. J.

    2013-12-01

    Carbonates precipitated by skeleton-forming eukaryotic organisms are often characterized by non-equilibrium isotopic signatures. This specificity is referred to as the "vital effect" and can be used as an isotopic evidence to trace life. Combining stable isotope geochemistry and enzymology (using the enzyme carbonic anhydrase) we aim to demonstrate that prokaryotes are also able to precipitate carbonate with a non-equilibrium d18OCaCO3. Indeed, if in an biomineralization experiment carbonates are precipitated with a vital effect, the addition of carbonic anhydrase should drive the system to isotope equilibrium, And provide a comparison point to estimate the vital effect range. This protocol allowed us to identify a -20‰ vital effect for the d18O of carbonates precipitated by Sporosarcina pasteurii, a bacterial model of carbonatogen metabolisms. This approach is thus a powerfull tool for the understanding of microbe carbonatogen activity and will probably bring new insights into the understanding of bacterial activity in subsurface and during diagenesis.

  10. 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.

  11. Carbon isotope effects associated with autotrophic acetogenesis.

    PubMed

    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 degrees 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 account. For the overall reaction, total carbonate --> total acetate, isotope effects measured in replicate experiments ranged from -59.0 +/- 0.9% to -57.2 +/- 2.3%. 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. PMID:11542159

  12. Carbon isotope effects associated with autotrophic acetogenesis

    NASA Technical Reports Server (NTRS)

    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 degrees 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 account. For the overall reaction, total carbonate --> total acetate, isotope effects measured in replicate experiments ranged from -59.0 +/- 0.9% to -57.2 +/- 2.3%. 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.

  13. The magnesium isotope (δ26Mg) signature of dolomites

    NASA Astrophysics Data System (ADS)

    Geske, A.; Goldstein, R. H.; Mavromatis, V.; Richter, D. K.; Buhl, D.; Kluge, T.; John, C. M.; Immenhauser, A.

    2015-01-01

    Dolomite precipitation models and kinetics are debated and complicated due to the complex and temporally fluctuating fluid chemistry and different diagenetic environments. Using well-established isotope systems (δ18O, δ13C, 87Sr/86Sr), fluid inclusions and elemental data, as well as a detailed sedimentological and petrographic data set, we established the precipitation environment and subsequent diagenetic pathways of a series of Proterozoic to Pleistocene syn-depositional marine evaporative (sabkha) dolomites, syn-depositional non-marine evaporative (lacustrine and palustrine) dolomites, altered marine ("mixing zone") dolomites and late diagenetic hydrothermal dolomites. These data form the prerequisite for a systematic investigation of dolomite magnesium isotope ratios (δ26Mgdol). Dolomite δ26Mg ratios documented here range, from -2.49‰ to -0.45‰ (δ26Mgmean = -1.75 ± 1.08‰, n = 42). The isotopically most depleted end member is represented by earliest diagenetic marine evaporative sabkha dolomites (-2.11 ± 0.54‰ 2σ, n = 14). In comparing ancient compositions to modern ones, some of the variation is probably due to alteration. Altered marine (-1.41 ± 0.64‰ 2σ, n = 4), and earliest diagenetic lacustrine and palustrine dolomites (-1.25 ± 0.86‰ 2σ, n = 14) are less negative than sabkha dolomites but not distinct in composition. Various hydrothermal dolomites are characterized by a comparatively wide range of δ26Mg ratios, with values of -1.44 ± 1.33‰ (2σ, n = 10). By using fluid inclusion data and clumped isotope thermometry (Δ47) to represent temperature of precipitation for hydrothermal dolomites, there is no correlation between fluid temperature (∼100 to 180 °C) and dolomite Mg isotope signature (R2 = 0.14); nor is there a correlation between δ26Mgdol and δ18Odol. Magnesium-isotope values of different dolomite types are affected by a complex array of different Mg sources and sinks, dissolution/precipitation and non

  14. Development of a Field-Deployable Methane Carbon Isotope Analyzer

    NASA Astrophysics Data System (ADS)

    Dong, Feng; Baer, Douglas

    2010-05-01

    Methane is a potent greenhouse gas, whose atmospheric surface mixing ratio has almost doubled compared with preindustrial values. Methane can be produced by biogenic processes, thermogenic processes or biomass, with different isotopic signatures. As a key molecule involved in the radiative forcing in the atmosphere, methane is thus one of the most important molecules linking the biosphere and atmosphere. Therefore precise measurements of mixing ratios and isotopic compositions will help scientists to better understand methane sources and sinks. To date, high precision isotope measurements have been exclusively performed with conventional isotope ratio mass spectrometry, which involves intensive labor and is not readily field deployable. Optical studies using infrared laser spectroscopy have also been reported to measure the isotopic ratios. However, the precision of optical-based analyses, to date, is typically unsatisfactory without pre-concentration procedures. We present characterization of the performance of a portable Methane Carbon Isotope Analyzer (MCIA), based on cavity enhanced laser absorption spectroscopy technique, that provides in-situ measurements of the carbon isotope ratio (13C/12C or del_13C) and methane mixing ratio (CH4). The sample is introduced to the analyzer directly without any requirement for pretreatment or preconcentration. A typical precision of less than 1 per mill (< 0.1%) with a 10-ppm methane sample can be achieved in a measurement time of less than 100 seconds. The MCIA can report carbon isotope ratio and concentration measurements over a very wide range of methane concentrations. Results of laboratory tests and field measurements will be presented.

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

    USGS Publications Warehouse

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

    2008-01-01

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

  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.

    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

  18. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2003-12-01

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

  20. 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.

  1. 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. PMID:25393769

  2. Modeling stable isotope and organic carbon in hillslope stormflow

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  3. Stable isotope deltas: tiny, yet robust signatures in nature.

    PubMed

    Brand, Willi A; Coplen, Tyler B

    2012-09-01

    Although most of them are relatively small, stable isotope deltas of naturally occurring substances are robust and enable workers in anthropology, atmospheric sciences, biology, chemistry, environmental sciences, food and drug authentication, forensic science, geochemistry, geology, oceanography, and paleoclimatology to study a variety of topics. Two fundamental processes explain the stable isotope deltas measured in most terrestrial systems: isotopic fractionation and isotope mixing. Isotopic fractionation is the result of equilibrium or kinetic physicochemical processes that fractionate isotopes because of small differences in physical or chemical properties of molecular species having different isotopes. It is shown that the mixing of radioactive and stable isotope end members can be modelled to provide information on many natural processes, including (14)C abundances in the modern atmosphere and the stable hydrogen and oxygen isotopic compositions of the oceans during glacial and interglacial times. The calculation of mixing fractions using isotope balance equations with isotope deltas can be substantially in error when substances with high concentrations of heavy isotopes (e.g. (13)C, (2)H, and (18)O ) are mixed. In such cases, calculations using mole fractions are preferred as they produce accurate mixing fractions. Isotope deltas are dimensionless quantities. In the International System of Units (SI), these quantities have the unit 1 and the usual list of prefixes is not applicable. To overcome traditional limitations with expressing orders of magnitude differences in isotope deltas, we propose the term urey (symbol Ur), after Harold C. Urey, for the unit 1. In such a manner, an isotope delta value expressed traditionally as-25 per mil can be written as-25 mUr (or-2.5 cUr or-0.25 dUr; the use of any SI prefix is possible). Likewise, very small isotopic differences often expressed in per meg 'units' are easily included (e.g. either+0.015 ‰ or+15 per meg

  4. Stable isotope deltas: Tiny, yet robust signatures in nature

    USGS Publications Warehouse

    Brand, Willi A.; Coplen, Tyler B.

    2012-01-01

    Although most of them are relatively small, stable isotope deltas of naturally occurring substances are robust and enable workers in anthropology, atmospheric sciences, biology, chemistry, environmental sciences, food and drug authentication, forensic science, geochemistry, geology, oceanography, and paleoclimatology to study a variety of topics. Two fundamental processes explain the stable isotope deltas measured in most terrestrial systems: isotopic fractionation and isotope mixing. Isotopic fractionation is the result of equilibrium or kinetic physicochemical processes that fractionate isotopes because of small differences in physical or chemical properties of molecular species having different isotopes. It is shown that the mixing of radioactive and stable isotope end members can be modelled to provide information on many natural processes, including 14C abundances in the modern atmosphere and the stable hydrogen and oxygen isotopic compositions of the oceans during glacial and interglacial times. The calculation of mixing fractions using isotope balance equations with isotope deltas can be substantially in error when substances with high concentrations of heavy isotopes (e.g. 13C, 2H, and 18O ) are mixed. In such cases, calculations using mole fractions are preferred as they produce accurate mixing fractions. Isotope deltas are dimensionless quantities. In the International System of Units (SI), these quantities have the unit 1 and the usual list of prefixes is not applicable. To overcome traditional limitations with expressing orders of magnitude differences in isotope deltas, we propose the term urey (symbol Ur), after Harold C. Urey, for the unit 1. In such a manner, an isotope delta value expressed traditionally as−25 per mil can be written as−25 mUr (or−2.5 cUr or−0.25 dUr; the use of any SI prefix is possible). Likewise, very small isotopic differences often expressed in per meg ‘units’ are easily included (e.g. either+0.015 ‰ or+15 per meg

  5. Gluconeogenesis from labeled carbon: estimating isotope dilution

    SciTech Connect

    Kelleher, J.K.

    1986-03-01

    To estimate the rate of gluconeogenesis from steady-state incorporation of labeled 3-carbon precursors into glucose, isotope dilution must be considered so that the rate of labeling of glucose can be quantitatively converted to the rate of gluconeogenesis. An expression for the value of this isotope dilution can be derived using mathematical techniques and a model of the tricarboxylic acid (TCA) cycle. The present investigation employs a more complex model than that used in previous studies. This model includes the following pathways that may affect the correction for isotope dilution: 1) flux of 3-carbon precursor to the oxaloacetate pool via acetyl-CoA and the TCA cycle; 2) flux of 4- or 5-carbon compounds into the TCA cycle; 3) reversible flux between oxaloacetate (OAA) and pyruvate and between OAA and fumarate; 4) incomplete equilibrium between OAA pools; and 5) isotope dilution of 3-carbon tracers between the experimentally measured pool and the precursor for the TCA-cycle OAA pool. Experimental tests are outlined which investigators can use to determine whether these pathways are significant in a specific steady-state system. The study indicated that flux through these five pathways can significantly affect the correction for isotope dilution. To correct for the effects of these pathways an alternative method for calculating isotope dilution is proposed using citrate to relate the specific activities of acetyl-CoA and OAA.

  6. 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

  7. Constraining the global bromomethane budget from carbon stable isotopes

    NASA Astrophysics Data System (ADS)

    Bahlmann, Enno; Wittmer, Julian; Greule, Markus; Zetzsch, Cornelius; Seifert, Richard; Keppler, Frank

    2016-04-01

    Despite intense research in the last two decades, the global bromomethane (CH3Br) budget remains unbalanced with the known sinks exceeding the known sources by about 25%. The reaction with OH is the largest sink for CH3Br. We have determined the kinetic isotope effects for the reactions of CH3Br with the OH and Cl radical in order to better constrain the global CH3Br budget from an isotopic perspective. The isotope fractionation experiments were performed at 20±1°C in a 3500 L Teflon smog-chamber with initial CH3Br mixing ratios of about 2 and 10 ppm and perflourohexane (25 ppb) as internal standard. Atomic chlorine (Cl) was generated via photolysis of molecular chlorine (Cl2) using a solar simulator with an actinic flux comparable to that of the sun in mid-summer in Germany. OH radicals were generated via the photolysis of ozone (O3) at 253.7 nm in the presence of water vapor (RH = 70%).The mixing ratios of CH3Br, and perflourohexane were monitored by GC-MS with a time resolution of 15 minutes throughout the experiments. From each experiment 10 to 15 sub samples were taken in regular time intervals for subsequent carbon isotope ratio determinations by GC-IRMS performed at two independent laboratories in parallel. We found a kinetic isotope effect (KIE) of 17.6±3.3‰ for the reaction of CH3Br with OH and a KIE of 9.8±1.4 ‰ for the reaction with Cl*. We used these fractionation factors along with new data on the isotopic composition of CH3Br in the troposphere (-34±7‰) and the surface ocean (-26±7‰) along with reported source signatures, to constrain the unknown source from an isotopic perspective. The largest uncertainty in estimating the isotopic composition of the unknown source arises from the soil sink. Microbial degradation in soils is the second largest sink and assigned with a large fractionation factors of about 50‰. However, field experiments revealed substantially smaller apparent fractionation factors ranging from 11 to 22‰. In addition

  8. Carbon Isotopic Studies of Assimilated and Ecosystem Respired CO2 in a Southeastern Pine Forest. Final Report and Conference Proceedings

    SciTech Connect

    Conte, Maureen H

    2008-04-10

    Carbon dioxide is the major “greenhouse” gas responsible for global warming. Southeastern pine forests appear to be among the largest terrestrial sinks of carbon dioxide in the US. This collaborative study specifically addressed the isotopic signatures of the large fluxes of carbon taken up by photosynthesis and given off by respiration in this ecosystem. By measuring these isotopic signatures at the ecosystem level, we have provided data that will help to more accurately quantify the magnitude of carbon fluxes on the regional scale and how these fluxes vary in response to climatic parameters such as rainfall and air temperature. The focus of the MBL subcontract was to evaluate how processes operating at the physiological and ecosystem scales affects the resultant isotopic signature of plant waxes that are emitted as aerosols into the convective boundary layer. These wax aerosols provide a large-spatial scale integrative signal of isotopic discrimination of atmospheric carbon dioxide by terrestrial photosynthesis (Conte and Weber 2002). The ecosystem studies have greatly expanded of knowledge of wax biosynthetic controls on their isootpic signature The wax aerosol data products produced under this grant are directly applicable as input for global carbon modeling studies that use variations in the concentration and carbon isotopic composition of atmospheric carbon dioxide to quantify the magnitude and spatial and temporal patterns of carbon uptake on the global scale.

  9. Examining the Role of Multiple Carbon Sources in Isoprene Synthesis in Plants Using Stable Isotope Techniques

    NASA Astrophysics Data System (ADS)

    Funk, J. L.; Mak, J. E.; Lerdau, M. T.

    2001-12-01

    The carbon source for phytogenc isoprene is an issue with important ramifications for both atmospheric and biological science because of its impact on the isotopic signature of isoprene and its oxidation products and because it lends insight into the function that isoprene serves within leaves. Although recently assimilated carbon is believed to be the primary carbon source for isoprene production in plants, variation in diurnal and seasonal isoprene fluxes that cannot be explained by temperature, light, and leaf development have led to the suggestion that alternative carbon sources may contribute. Stable isotopes of carbon can be used to identify changes in carbon partitioning into isoprene synthesis, and mixing models can assess the relative importance of each source. In preliminary studies, we document an additional 8-10 \\permil discrimination in isoprene emitted in the absence of photosynthesis. This change in signature suggests that the carbon source is switched from recently obtained photosynthate to a source more depleted in 13C. We propose that intermediates from carbohydrate degradation and/or re-fixation of CO2 from mitichondrial respiration and photorespiration can contribute to isoprene production. In addition, we expect alternative carbon sources to be most important when photosynthate is limiting (e.g. during water stress events). Photosynthesis, respiration, and isoprene emission measurements are used to calculate the isotopic signatures of the three potential carbon pools: photosynthate derived from ambient CO2, photosynthate derived from respired CO2, and carbohydrate-derived intermediates.

  10. 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

  11. Baseline shifts in coral skeletal oxygen isotopic composition: a signature of symbiont shuffling?

    NASA Astrophysics Data System (ADS)

    Carilli, J. E.; Charles, C. D.; Garren, M.; McField, M.; Norris, R. D.

    2013-06-01

    Decades-long records of the stable isotopic composition of coral skeletal cores were analyzed from four sites on the Mesoamerican Reef. Two of the sites exhibited baseline shifts in oxygen isotopic composition after known coral bleaching events. Changes in pH at the calcification site caused by a change in the associated symbiont community are invoked to explain the observed shift in the isotopic composition. To test the hypothesis that changes in symbiont clade could affect skeletal chemistry, additional coral samples were collected from Belize for paired Symbiodinium identification and skeletal stable isotopic analysis. We found some evidence that skeletal stable isotopic composition may be affected by symbiont clade and suggest this is an important topic for future investigation. If different Symbiodinium clades leave consistent signatures in skeletal geochemical composition, the signature will provide a method to quantify past symbiont shuffling events, important for understanding how corals are likely to respond to climate change.

  12. Shear heating and clumped isotope reordering in carbonate faults

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  13. Tracking diet preferences of bats using stable isotope and fatty acid signatures of faeces.

    PubMed

    Lam, Monika My-Y; Martin-Creuzburg, Dominik; Rothhaupt, Karl-Otto; Safi, Kamran; Yohannes, Elizabeth; Salvarina, Ioanna

    2013-01-01

    Stable isotope and fatty acid signatures of biomaterials can provide important information about the dietary niche of animals. Stable isotope and fatty acid signatures differ between aquatic and terrestrial food webs, and therefore can be used to assess the aquatic and terrestrial contributions to the diets of species. We studied faecal samples of three co-occurring bat species with known differences in feeding preferences. The aim was to assess whether stable isotope and fatty acid signatures of faeces can be used to determine feeding preferences. We used bat faeces because they can be easily and non-invasively collected. We hypothesised that faeces stable isotope and fatty acid signatures will reveal the terrestrial, aquatic and mixed feeding niches of Myotis myotis, M. daubentonii, and M. mystacinus, respectively. As predicted, the faeces of M. myotis were characterized by higher δ(13)C values and higher concentrations of linoleic acid and total ω6 polyunsaturated fatty acids (PUFAs), which are typically higher in terrestrial food webs. The faeces of M. daubentonii had higher δ(15)Ν values and higher concentrations of docosahexaenoic acid and total ω3 PUFAs, characteristic features of aquatic systems. Myotis mystacinus faeces had intermediate δ(15)Ν values and concentrations of both types of fatty acids. Our results show that analysing stable isotope and/or fatty acid signatures of faeces provides a promising, non-invasive tool to study the feeding ecology of bats and to assess aquatic-terrestrial interactions. PMID:24376703

  14. Tracking Diet Preferences of Bats Using Stable Isotope and Fatty Acid Signatures of Faeces

    PubMed Central

    Lam, Monika My-Y; Martin-Creuzburg, Dominik; Rothhaupt, Karl-Otto; Safi, Kamran; Yohannes, Elizabeth; Salvarina, Ioanna

    2013-01-01

    Stable isotope and fatty acid signatures of biomaterials can provide important information about the dietary niche of animals. Stable isotope and fatty acid signatures differ between aquatic and terrestrial food webs, and therefore can be used to assess the aquatic and terrestrial contributions to the diets of species. We studied faecal samples of three co-occurring bat species with known differences in feeding preferences. The aim was to assess whether stable isotope and fatty acid signatures of faeces can be used to determine feeding preferences. We used bat faeces because they can be easily and non-invasively collected. We hypothesised that faeces stable isotope and fatty acid signatures will reveal the terrestrial, aquatic and mixed feeding niches of Myotis myotis, M. daubentonii, and M. mystacinus, respectively. As predicted, the faeces of M. myotis were characterized by higher δ13C values and higher concentrations of linoleic acid and total ω6 polyunsaturated fatty acids (PUFAs), which are typically higher in terrestrial food webs. The faeces of M. daubentonii had higher δ15Ν values and higher concentrations of docosahexaenoic acid and total ω3 PUFAs, characteristic features of aquatic systems. Myotis mystacinus faeces had intermediate δ15Ν values and concentrations of both types of fatty acids. Our results show that analysing stable isotope and/or fatty acid signatures of faeces provides a promising, non-invasive tool to study the feeding ecology of bats and to assess aquatic-terrestrial interactions. PMID:24376703

  15. Carbonate abundances and isotopic compositions in chondrites

    NASA Astrophysics Data System (ADS)

    Alexander, C. M. O'd.; Bowden, R.; Fogel, M. L.; Howard, K. T.

    2015-04-01

    We report the bulk C abundances, and C and O isotopic compositions of carbonates in 64 CM chondrites, 14 CR chondrites, 2 CI chondrites, LEW 85332 (C2), Kaba (CV3), and Semarkona (LL3.0). For the unheated CMs, the total ranges of carbonate isotopic compositions are δ13C ≈ 25-75‰ and δ18O ≈ 15-35‰, and bulk carbonate C contents range from 0.03 to 0.60 wt%. There is no simple correlation between carbonate abundance and isotopic composition, or between either of these parameters and the extent of alteration. Unless accretion was very heterogeneous, the uncorrelated variations in extent of alteration and carbonate abundance suggests that there was a period of open system behavior in the CM parent body, probably prior to or at the start of aqueous alteration. Most of the ranges in CM carbonate isotopic compositions can be explained by their formation at different temperatures (0-130 °C) from a single fluid in which the carbonate O isotopes were controlled by equilibrium with water (δ18O ≈ 5‰) and the C isotopes were controlled by equilibrium with CO and/or CH4 (δ13C ≈ -33‰ or -20‰ for CO- or CH4-dominated systems, respectively). However, carbonate formation would have to have been inefficient, otherwise carbonate compositions would have resembled those of the starting fluid. A quite similar fluid composition (δ18O ≈ -5.5‰, and δ13C ≈ -31‰ or -17‰ for CO- or CH4-dominated systems, respectively) can explain the carbonate compositions of the CIs, although the formation temperatures would have been lower (~10-40 °C) and the relative abundances of calcite and dolomite may play a more important role in determining bulk carbonate compositions than in the CMs. The CR carbonates exhibit a similar range of O isotopes, but an almost bimodal distribution of C isotopes between more (δ13C ≈ 65-80‰) and less altered samples (δ13C ≈ 30-40‰). This bimodality can still be explained by precipitation from fluids with the same isotopic

  16. 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.

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

    NASA Astrophysics Data System (ADS)

    Nowak-Lovato, K.

    2014-12-01

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

  18. 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???.

  19. Groundwater chemistry and isotope signatures of potential CCS sites in Korea - A baseline study for leakage detection

    NASA Astrophysics Data System (ADS)

    Choi, H.; Jeong, T.; Woo, N. C.

    2013-12-01

    This research aimed at drawing a baseline of groundwater chemistry and its stable isotope signatures of hydrogen, oxygen and carbon from the deep groundwater above the CO2 sequestration layer, in which physico-chemical conditions are conceived as temperature over 40 degree Celcius and high total dissolved solids. Samples were collected from hot springs (at surface and from seep wells) and high-carbonate springs. Based on water compositions, three groups were identified as saline, alkali-carbonate and soda spring types. Saline type hot springs at the west coastline area contain -14.5‰ δ13C of CO2. Before and after rainfall events, δ13C value of samples shows no change. Hot springs at Suanbo region, located at the center are of the Korean Peninsular, were collected from deep wells of 750 m in depth, and they show the alkali-carbonate type water having δ13C values (-11.3~-10.9‰) and ECs (364~431μS/cm). Both saline and alkali-carbonate type waters show no significant change in composition, indicating that recharge by precipitation has no effect on these groundwater. All the high-carbonate springs were collected at ground surface, and enriched with Ca, Mg and HCO3., probably caused by the dissolution of CO2, and high EC values of 1,016 μS/cm. Soda springs located in Chungcheongbuk-do region have -6.8~-6.7‰ δ13C of CO2, indicating that the source of CO2 could be the upper mantle affected by the carbonate minerals in the Quaternary sedimentary bedrock. On the contrary, carbonate waters in the Gangwon-do region have -3.9~-3.7‰ δ13C of CO2, clearly indicating the source of CO2 being the upper mantle (Gerlach and Taylor, 1990). More detailed chemical and isotopic signatures of the sampled waters will be discussed in presentation.

  20. 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.

  1. Carbon isotopic fractionation of CFCs during abiotic and biotic degradation.

    PubMed

    Archbold, Marie E; Elliot, Trevor; Kalin, Robert M

    2012-02-01

    Carbon stable isotope ((13)C) fractionation in chlorofluorocarbon (CFC) compounds arising from abiotic (chemical) degradation using zero-valent iron (ZVI) and biotic (landfill gas attenuation) processes is investigated. Batch tests (at 25 °C) for CFC-113 and CFC-11 using ZVI show quantitative degradation of CFC-113 to HCFC-123a and CFC-1113 following pseudo-first-order kinetics corresponding to a half-life (τ(1/2)) of 20.5 h, and a ZVI surface-area normalized rate constant (k(SA)) of -(9.8 ± 0.5) × 10(-5) L m(-2) h(-1). CFC-11 degraded to trace HCFC-21 and HCFC-31 following pseudo-first-order kinetics corresponding to τ(1/2) = 17.3 h and k(SA) = -(1.2 ± 0.5) × 10(-4) L m(-2) h(-1). Significant kinetic isotope effects of ε(‰) = -5.0 ± 0.3 (CFC-113) and -17.8 ± 4.8 (CFC-11) were observed. Compound-specific carbon isotope analyses also have been used here to characterize source signatures of CFC gases (HCFC-22, CFC-12, HFC-134a, HCFC-142b, CFC-114, CFC-11, CFC-113) for urban (UAA), rural/remote (RAA), and landfill (LAA) ambient air samples, as well as in situ surface flux chamber (FLUX; NO FLUX) and landfill gas (LFG) samples at the Dargan Road site, Northern Ireland. The latter values reflect biotic degradation and isotopic fractionation in LFG production, and local atmospheric impact of landfill emissions through the cover. Isotopic fractionations of Δ(13)C ∼ -13‰ (HCFC-22), Δ(13)C ∼ -35‰ (CFC-12) and Δ(13)C ∼ -15‰ (CFC-11) were observed for LFG in comparison to characteristic solvent source signatures, with the magnitude of the isotopic effect for CFC-11 apparently similar to the kinetic isotope effect for (abiotic) ZVI degradation. PMID:22191586

  2. Triple oxygen isotopes in biogenic and sedimentary carbonates

    NASA Astrophysics Data System (ADS)

    Passey, Benjamin H.; Hu, Huanting; Ji, Haoyuan; Montanari, Shaena; Li, Shuning; Henkes, Gregory A.; Levin, Naomi E.

    2014-09-01

    The 17O anomaly (Δ17O) of natural waters has been shown to be sensitive to evaporation in a way analogous to deuterium excess, with evaporated bodies of water (e.g., leaf waters, lake waters, animal body waters) tending to have lower Δ17O than primary meteoric waters. In animal body water, Δ17O relates to the intake of evaporated waters, evaporative effluxes of water, and the Δ17O value of atmospheric O2, which itself carries signatures of global carbon cycling and photochemical reactions in the stratosphere. Carbonates have the potential to record the triple oxygen isotope compositions of parent waters, allowing reconstruction of past water compositions, but such investigations have awaited development of methods for high-precision measurement of Δ17O of carbonate. We describe optimized methods based on a sequential acid digestion/reduction/fluorination approach that yield Δ17O data with the high precision (∼0.010‰, 1σ) needed to resolve subtle environmental signals. We report the first high-precision Δ17O dataset for terrestrial carbonates, focusing on vertebrate biogenic carbonates and soil carbonates, but also including marine invertebrates and high-temperature carbonates. We determine apparent three-isotope fractionation factors between the O2 analyte derived from carbonate and the parent waters of the carbonate. These in combination with appropriate temperature estimates (from clumped isotope thermometry, or known or estimated body temperatures) are used to calculate the δ18O and Δ17O of parent waters. The clearest pattern to emerge is the strong 17O-depletion in avian, dinosaurian, and mammalian body water (from analyses of eggshell and tooth enamel) relative to meteoric waters, following expected influences of evaporated water (e.g., leaf water) and atmospheric O2 on vertebrate body water. Parent waters of the soil carbonates studied here have Δ17O values that are similar to or slightly lower than global precipitation. Our results suggest

  3. Isotopic signatures and origin of nitrogen in IIE and IVA iron meteorites

    NASA Astrophysics Data System (ADS)

    Mathew, K. J.; Palma, R. L.; Marti, K.; Lavielle, B.

    2000-02-01

    Nitrogen concentrations and isotopic signatures have been determined in groups IIE and IVA iron meteorites. Contrary to assumptions made in the literature, the present data show that spallation components significantly modify the N signatures of the metal. All 15N data are corrected for cosmic-ray produced spallation components using 21Ne concentrations measured in aliquots. A production-rate ratio 21Ne/ 15N = 0.80 is obtained, which can reliably be used for this correction, since it is not sensitive to shielding differences. The trapped N signatures in group IVA irons fall into two subgroups IVA (-26) with δ 15N = -26 ± 2 ‰ and IVA (-6) with δ 15N = -6 ± 1.4‰, respectively. Only the latter is close to values reported for metal of L-chondrites. Group IIE irons also define two distinct subgroups IIE (Y) with δ 15N = -7.5 ± 1.5‰ and IIE (O) with δ 15N = -2.3 ± 1‰. Therefore, the earlier proposed subdivision of IIE irons into "young" and "old" subgroups is substantiated by the different trapped N signatures. With regard to a possible relationship with H-chondrites as suggested by oxygen isotopes, only the young IIE subgroup overlaps the range of signatures reported in H-chondrite metal. Seymchan has a distinctly lighter signature (δ 15N = -54‰), consistent with its reclassification as an ungrouped iron. We observe no correlation of either nitrogen concentrations or isotopic signatures with abundances of Ga, Ge, Ir or Ni. The distinct N components in the so-called magmatic group IVA constrain the thermal history of the parent body, as these signatures need to be reconciled with the magmatic history. Implications for the origin of nitrogen components are discussed. Some of the spread in N isotopic data in the literature apparently is due to inclusions.

  4. Carbon isotope composition of Antarctic plants

    NASA Astrophysics Data System (ADS)

    Galimov, E. M.

    2000-05-01

    Carbon isotope compositions of Antarctic land plants are first reported. The most interesting feature is the isotope specificity of the species. For example Usnea antarctica from different locations shows relatively narrow range of the δ 13C-values from -22.44 to -21.29‰ (7 samples), Drepanocladus sp. from -24.86 to -23.49‰ (8 samples), and Andreaea depressincrvis from -23.87 to -23.23‰ (3 samples) etc. Usually, in inhabited lands and parts of the world with rich flora and developed soil, isotopic specificity of species is masked by variations of carbon isotope composition of CO 2. In Antarctic conditions influence of local sources of CO 2 on the isotope composition of CO 2 is appeared to be minimal. Therefore the δ 13C-variations inherent to individual plant physiology and biochemistry can be distinguished on the background of the stable level of the atmospheric CO 2 δ 13C-value. The latter is best to reflect the global state of the carbon cycle.

  5. 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

    Freezing of cave pool water that is increasingly oversaturated with dissolved carbonate leads to precipitation of a very specific type of speleothems known as cryogenic cave carbonates (CCC). At present, two different environments for their formation have been proposed, based on their characteristic carbon and oxygen isotope ratios. Rapidly freezing thin water films result in the fast precipitation of fine-grained carbonate powder (CCCfine). This leads to rapid physicochemical changes including CO2 degassing and CaCO3 precipitation, resulting in significantly 13C-enriched carbonates. Alternatively, slow carbonate precipitation in ice-covered cave pools results in coarse crystalline CCC (CCCcoarse) yielding strongly 18O-depleted carbonate. This is due to the formation of relatively 18O-enriched ice causing the gradual depletion of 18O in the water from which the CCC precipitates. Cryogenic carbonates from Central European caves were found to have been formed primarily during the last glacial period, specifically during times of permafrost thawing, based on the oxygen isotope ratios and U-Th dating. Information about the precise conditions of CCCcoarse formation, i.e. whether these crystals formed under equilibrium or disequilibrium conditions with the parent fluid, however, is lacking. An improved understanding of CCCcoarse formation will increase the predictive value of this paleo-permafrost archive. Here we apply clumped isotopes to investigate the formation conditions of cryogenic carbonates using well-studied CCCcoarse from five different cave systems in western Germany. Carbonate clumped isotope measurements yielded apparent temperatures between 3 and 18 °C and thus exhibit clear evidence of isotopic disequilibrium. Although the very negative carbonate δ18O values can only be explained by gradual freezing of pool water accompanied by preferential incorporation of 18O into the ice, clumped isotope-derived temperatures significantly above expected freezing

  6. 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.

  7. Nitrogen isotopic signatures in agglutinates from breccia 79035

    NASA Technical Reports Server (NTRS)

    Kerridge, John F.; Kim, Yoosook; Kim, Jin S.; Marti, Kurt

    1993-01-01

    Agglutinates in the size range 125-175 microns from regolith breccia 79035 are substantially depleted in N compared with bulk 79035. Isotopically, agglutinate N closely resembles that found previously in ilmenite separates. The minimum (delta)N-15 value found during stepwise pyrolysis of agglutinates is significantly heavier than that observed for bulk 79035. The major host phase for trapped N in 79035, and the host phase of the lightest isotopic component(s), remain unidentified.

  8. Through a temporal window, we see isotopic signatures

    SciTech Connect

    Mizutani, Hiroshi

    1995-12-31

    Stable isotope composition of bioelements is different between diet and assimilated tissues. Furthermore, the apparent fractionation factors from diet to tissues seem to differ among different tissues: each tissue of an organism reflects the isotope abundances of diet in a different manner. The turnover rate of a tissue, its biochemical composition, its immediate source, and distribution of available resources within an individuals body are among the possible factors that would affect the fractionation factor. Stable isotope composition of an animal tissue or particular biochemical molecules would give a glimpse of the animal itself and its environments only through a particular window, whose width and height are dependent on many factors including animal age. Some tissues that form in a relatively short period during which material exchanges in an animal body can be considered nearly in a steady state would give a clearly defined window frame. One example is feathers of adult birds: the change in the isotope composition from diet to the tissue has been shown stable with time. Tissues formed during a rapid growth of animal body or during a metamorphosis would be an example of another extreme, the window frame being subject to a rapid change with time in its shape. Isotopic knowledge on characteristics of the window is needed to extend the applicability of stable isotope study into researches in ecogeochemistry and environmental chemistry.

  9. Degradation and Volatilization of Chlorofluorocarbons in Contaminated Groundwater Explored by Stable Carbon Isotope Analysis

    NASA Astrophysics Data System (ADS)

    Horst, A.; Lacrampe-Couloume, G.; Sherwood Lollar, B.

    2015-12-01

    Chlorofluorocarbons (CFCs) are ozone depleting compounds whose production was phased out by the regulations of the Montreal Protocol (1987). Accidental release and disposal also led to contamination of groundwater at many locations, however, and this legacy persists. Although very stable, CFCs may degrade via abiotic and biotic pathways. Quantification of the degree of transformation of CFCs has been challenging due to other processes such as dilution, sorption and volatilization. Compound specific stable carbon isotope analysis (CSIA) has been successfully applied for a variety of priority pollutants to distinguish degradation from other processes and to quantify transformation rates. A Purge & Trap - CSIA method developed in our lab was applied to determine the stable carbon isotopic signature of CFCs and HCFCs (hydrochlorofluorocarbons) in groundwater samples from a contaminated site. Preliminary results suggest that degradation of CFCs and HCFCs may result in enriched δ13C values, consistent with fractionation during bond breakage as has been reported for many other hydrocarbon pollutants. The effect of volatile loss during sampling on the isotopic signatures of CFCs was examined in laboratory experiments. Volatilization from pure phase CFCs showed a small inverse isotope effect during open system volatilization, opposite to the normal isotope effect generally observed during biodegradation. For volatilization of CFCs dissolved in water a much smaller isotope effect was observed. An important result from this work is that any volatile loss may introduce only a small change in CFC isotopic signatures in groundwater, and importantly, due to the opposite direction of isotope effects associated with volatilization versus degradation, any effects of volatile loss on the isotopic signatures cannot be confused with transformation of CFCs. At most, volatilization might contribute to a conservative estimate of the extent of degradation.

  10. Degradation and Volatilization of Chlorofluorocarbons in Contaminated Groundwater Explored by Stable Carbon Isotope Analysis

    NASA Astrophysics Data System (ADS)

    Hangx, S.; Pijnenburg, R. P.; Niemeijer, A. R.; Bakker, E.; Samuelson, J. E.; Spiers, C. J.

    2014-12-01

    Chlorofluorocarbons (CFCs) are ozone depleting compounds whose production was phased out by the regulations of the Montreal Protocol (1987). Accidental release and disposal also led to contamination of groundwater at many locations, however, and this legacy persists. Although very stable, CFCs may degrade via abiotic and biotic pathways. Quantification of the degree of transformation of CFCs has been challenging due to other processes such as dilution, sorption and volatilization. Compound specific stable carbon isotope analysis (CSIA) has been successfully applied for a variety of priority pollutants to distinguish degradation from other processes and to quantify transformation rates. A Purge & Trap - CSIA method developed in our lab was applied to determine the stable carbon isotopic signature of CFCs and HCFCs (hydrochlorofluorocarbons) in groundwater samples from a contaminated site. Preliminary results suggest that degradation of CFCs and HCFCs may result in enriched δ13C values, consistent with fractionation during bond breakage as has been reported for many other hydrocarbon pollutants. The effect of volatile loss during sampling on the isotopic signatures of CFCs was examined in laboratory experiments. Volatilization from pure phase CFCs showed a small inverse isotope effect during open system volatilization, opposite to the normal isotope effect generally observed during biodegradation. For volatilization of CFCs dissolved in water a much smaller isotope effect was observed. An important result from this work is that any volatile loss may introduce only a small change in CFC isotopic signatures in groundwater, and importantly, due to the opposite direction of isotope effects associated with volatilization versus degradation, any effects of volatile loss on the isotopic signatures cannot be confused with transformation of CFCs. At most, volatilization might contribute to a conservative estimate of the extent of degradation.

  11. 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

  12. Ecologically and geologically relevant isotope signatures of C, N, and S: okenone producing purple sulfur bacteria Part I.

    PubMed

    Smith, D A; Steele, A; Bowden, R; Fogel, M L

    2015-05-01

    Purple sulfur bacteria (PSB) are known to couple the carbon, nitrogen, and sulfur cycling in euxinic environments. This is the first study with multiple strains and species of okenone-producing PSB to examine the carbon (C), nitrogen (N), and sulfur (S) metabolisms and isotopic signatures in controlled laboratory conditions, investigating what isotopic fractionations might be recorded in modern environments and the geologic record. PSB play an integral role in the ecology of euxinic environments and produce the unique molecular fossil okenane, derived from the diagenetic alteration of the carotenoid pigment okenone. Cultures of Marichromatium purpuratum 1591 (Mpurp1591) were observed to have carbon isotope fractionations ((13)ε biomass - CO2), via RuBisCO, ranging from -16.1 to -23.2‰ during exponential and stationary phases of growth. Cultures of Thiocapsa marina 5653 (Tmar5653) and Mpurp1591 had a nitrogen isotope fractionation ((15)ε biomass - NH 4) of -15‰, via glutamate dehydrogenase, measured and recorded for the first time in PSB. The δ(34) SVCDT values and amount of stored elemental sulfur for Mpurp1591 cells grown autotrophically and photoheterotrophically were dependent upon their carbon metabolic pathways. We show that PSB may contribute to the isotopic enrichments observed in modern and ancient anoxic basins. In a photoheterotrophic culture of Mpurp1591 that switched to autotrophy once the organic substrate was consumed, there were bulk biomass δ(13)C values that span a broader range than recorded across the Late Devonian, Permian-Triassic, Triassic-Jurassic, and OAE2 mass extinction boundaries. This finding stresses the complexities in interpreting and assigning δ(13)C values to bulk organic matter preserved in the geologic record. PMID:25857753

  13. Distinct iron isotopic signatures and supply from marine sediment dissolution

    PubMed Central

    Homoky, William B.; John, Seth G.; Conway, Tim M.; Mills, Rachel A.

    2013-01-01

    Oceanic iron inputs must be traced and quantified to learn how they affect primary productivity and climate. Chemical reduction of iron in continental margin sediments provides a substantial dissolved flux to the oceans, which is isotopically lighter than the crust, and so may be distinguished in seawater from other sources, such as wind-blown dust. However, heavy iron isotopes measured in seawater have recently led to the proposition of another source of dissolved iron from ‘non-reductive’ dissolution of continental margins. Here we present the first pore water iron isotope data from a passive-tectonic and semi-arid ocean margin (South Africa), which reveals a smaller and isotopically heavier flux of dissolved iron to seawater than active-tectonic and dysoxic continental margins. These data provide in situ evidence of non-reductive iron dissolution from a continental margin, and further show that geological and hydro-climatic factors may affect the amount and isotopic composition of iron entering the ocean. PMID:23868399

  14. 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.

  15. 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.

  16. Laser ablation molecular isotopic spectrometry of carbon isotopes

    SciTech Connect

    Bol'shakov, Alexander A.; Jain, Jinesh; Russo, Richard E.; McIntyre, Dustin; Mao, Xianglei

    2015-08-28

    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 spectrumyielded 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

  17. Atmospheric lead in urban Guiyang, Southwest China: Isotopic source signatures

    NASA Astrophysics Data System (ADS)

    Zhao, Zhi-Qi; Zhang, Wei; Li, Xiao-Dong; Yang, Zhou; Zheng, Hou-Yi; Ding, Hu; Wang, Qi-Lian; Xiao, Jun; Fu, Ping-Qing

    2015-08-01

    Total suspended particles (TSP) and their source-related samples from Guiyang, Southwest China, were collected and analyzed for their lead (Pb) concentrations and Pb isotopic compositions, to identify the sources of atmosphere lead in urban Guiyang. Coals from Guizhou Province had significantly high radiogenic Pb, different to those from North China. Local vehicle exhaust had similar Pb isotope ratios to those of other areas in China. Pb isotopic compositions of atmospheric aerosols, rainwaters, plant samples, and acid-soluble fraction of street dusts were similar to each other. The results clearly suggest that the Pb-Zn ore-related industrial emission, and/or vehicle exhaust, rather than the local coal combustion, are the main sources of atmospheric Pb in Guiyang. Furthermore, binary mixing model indicates that the contribution of coal combustion to the local atmospheric Pb decreased from about 40% in 1988 to about 10% in 2013.

  18. Stable carbon isotope fractionation by methanogens growing on different Mars regolith analogs

    NASA Astrophysics Data System (ADS)

    Sinha, Navita; Kral, Timothy A.

    2015-07-01

    In order to characterize stable carbon (13C/12C) isotope fractionation of metabolically produced methane by methanogens in martian settings, Methanothermobacter wolfeii, Methanosarcina barkeri, and Methanobacterium formicicum were cultured on four different Mars regolith analogs - JSC Mars-1, Artificial Mars Simulant, montmorillonite, and Mojave Mars Simulant - and also in their growth supporting media. These chemoautotrophic methanogens utilize CO2 for their carbon source and H2 for their energy source. When compared to the carbon isotope signature of methane when grown on their respective growth media, M. wolfeii and M. barkeri demonstrated variability in carbon isotope fractionation values during methanogenesis on the Mars analogs, while M. formicicum showed subtle or negligible difference in carbon isotope fractionation values. Interestingly, M. wolfeii and M. barkeri have shown relatively consistent enriched values of 12C on montmorillonite, a kind of clay found on Mars, compared to other Mars regolith analogs. In general, M. barkeri showed large carbon isotope fractionation compared to M. wolfeii and M. formicicum during methanognesis on various kinds of analogs. Stable carbon isotope fractionation is one of the techniques used to infer different origins, environments, and pathways of methanogensis. The results obtained in this novel research can provide clues to determine ambiguous sources of methane on Mars.

  19. Extreme crustal oxygen isotope signatures preserved in coesite in diamond.

    PubMed

    Schulze, Daniel J; Harte, Ben; Valley, John W; Brenan, James M; Channer, Dominic M De R

    2003-05-01

    The anomalously high and low oxygen isotope values observed in eclogite xenoliths from the upper mantle beneath cratons have been interpreted as indicating that the parent rock of the eclogites experienced alteration on the ancient sea floor. Recognition of this genetic lineage has provided the foundation for a model of the evolution of the continents whereby imbricated slabs of oceanic lithosphere underpin and promote stabilization of early cratons. Early crustal growth is thought to have been enhanced by the addition of slab-derived magmas, leaving an eclogite residuum in the upper mantle beneath the cratons. But the oxygen isotope anomalies observed in eclogite xenoliths are small relative to those in altered ocean-floor basalt and intermediate-stage subduction-zone eclogites, and this has hindered acceptance of the hypothesis that the eclogite xenoliths represent subducted and metamorphosed ocean-floor basalts. We present here the oxygen isotope composition of eclogitic mineral inclusions, analysed in situ in diamonds using an ion microprobe/secondary ion mass spectrometer. The oxygen isotope values of coesite (a polymorph of SiO2) inclusions are substantially higher than previously reported for xenoliths from the subcratonic mantle, but are typical of subduction-zone meta-basalts, and accordingly provide strong support for the link between altered ocean-floor basalts and mantle eclogite xenoliths. PMID:12721625

  20. Carbonate Ion Effects on Coccolith Carbon and Oxygen Isotopes

    NASA Astrophysics Data System (ADS)

    Ziveri, P.; Probert, I.; Stoll, H. M.

    2006-12-01

    The stable oxygen and carbon isotopic composition of biogenic calcite constitutes one of the primary tools used in paleoceanographic reconstructions. The δ18O of shells of ocean floor microfossils and corals reflects the composition of the paleo-seawater as they use the oxygen to build up their calcite and aragonite shells. The δ13C is used to reconstruct variations in the carbon isotopic composition of dissolved inorganic carbon in the ocean, which is controlled by biological productivity through the removal of isotopically light carbon in organic matter. To be effective and sensitive tools for understanding photic zone processes it is first necessary to understand the various biological fractionations associated with carbonate precipitation. To date, isotopic fractionation models are mainly based on foraminifera and corals but not on coccoliths, tiny plates produced by coccolithophore algae, which are often the most dominant carbonate contributors to pelagic sediments. As photosynthetic organisms, their chemistry can provide a sensitive tool for understanding photic zone processes. Coccoliths may be the most important carbonate phase for geochemical analysis in sediments where foraminifera are less common and/or core material is limited, such as in subpolar regions and for Early Cenozoic and Mesozoic sediments. Here we report experimental results on a common living coccolithophore species showing that the 13C/12C and 18O/16O ratios decrease with the increase of HCO^{3-} (CO32-). The selected species are among the heaviest calcifying extant coccolithophores and are major contributors to present coccolith carbonate export production. Because coccolithophores are photosynthetic organisms that calcify intracellularly in specialized vesicles, the challenge lies in ascertaining how kinetic and thermodynamic processes of isotopic fractionation are linked to cellular carbon "transport" and carbonate precipitation. This is a daunting challenge since studies have not

  1. Carbon isotopic composition of individual Precambrian microfossils

    NASA Astrophysics Data System (ADS)

    House, Christopher H.; Schopf, J. William; McKeegan, Kevin D.; Coath, Christopher D.; Harrison, T. Mark; Stetter, Karl 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 ˜850 Ma Bitter Springs Formation, Australia, and the ˜2100 Ma Gunflint Formation, Canada. The δ13CPDB values from individual microfossils of the Bitter Springs Formation ranged from -21.3 ± 1.7‰ to -31.9 ± 1.2‰, and the δ13CPDB 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.

  2. 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.

  3. Carbon Reservoir History of Mars Constrained by Atmospheric Isotopic Measurements and Carbonate Remote Sensing

    NASA Astrophysics Data System (ADS)

    Hu, R.; Kass, D. M.; Ehlmann, B. L.; Yung, Y. L.

    2015-12-01

    The evolution of the atmosphere on Mars is one of the most intriguing problems in the exploration of the Solar System, and the climate of Mars may have evolved from a warmer, wetter early state to the cold, dry current state. Because CO2 is the major constituent of Mars's atmosphere, its isotopic signatures offer a unique window to trace the evolution of climate on Mars. We derive new quantitative constraints on the amount of carbonate deposition and the atmospheric pressure of Mars through time, extending into the Noachian, ~3.8 Gyr before present. This determination is based on recent Mars Science Laboratory (MSL) isotopic measurements of Mars's atmosphere, recent orbiter, lander, and rover measurements of Mars's surface, and a newly identified mechanism (photodissociation of CO) that efficiently enriches the heavy carbon isotope. In particular, we find that escape via CO photodissociation on Mars has a fractionation factor of 0.6 and hence, photochemical escape processes can effectively enrich 13C in the Mars's atmosphere during the Amazonian. This enrichment is partially compensated by moderate carbonate precipitation during the late Noachian and/or Hesperian. The current atmospheric 13C/12C and rock and soil carbonate measurements indicate an early atmosphere with a surface pressure less than 1 bar. Only scenarios with large amounts of carbonate formation in open lakes permit higher values up to 1.8 bars. The evolutionary scenarios are fully testable with data from the MAVEN mission and further studies of the isotopic composition of carbonate in the Martian rock record through time.

  4. Monsoonal influence on variation of hydrochemistry and isotopic signatures: Implications for associated arsenic release in groundwater

    NASA Astrophysics Data System (ADS)

    Majumder, Santanu; Datta, Saugata; Nath, Bibhash; Neidhardt, Harald; Sarkar, Simita; Roman-Ross, Gabriela; Berner, Zsolt; Hidalgo, Manuela; Chatterjee, Debankur; Chatterjee, Debashis

    2016-04-01

    The present study examines the groundwater and surface water geochemistry of two different geomorphic domains within the Chakdaha block, West Bengal, in an attempt to decipher potential influences of groundwater abstraction on the hydrochemical evolution of the aquifer, the effect of different water inputs (monsoon rain, irrigation and downward percolation from surface water impoundments) to the groundwater system and concomitant As release. A low-land flood plain and a natural levee have been selected for this purpose. Although the stable isotopic signatures of oxygen (δ18O) and hydrogen (δ2H) are largely controlled by local precipitation, the isotopic composition falls sub-parallel to the Global Meteoric Water Line (GMWL). The Cl/Br molar ratio indicates vertical recharge into the wells within the flood plain area, especially during the post-monsoon season, while influences of both evaporation and vertical mixing are visible within the natural levee wells. Increase in mean DOC concentrations (from 1.33 to 6.29 mg/L), from pre- to post-monsoon season, indicates possible inflow of organic carbon to the aquifer during the monsoonal recharge. Concomitant increase in AsT, Fe(II) and HCO3- highlights a possible initial episode of reductive dissolution of As-rich Fe-oxyhydroxides. The subsequent sharp increase in the mean As(III) proportions (by 223%), particularly in the flood plain samples during the post-monsoon season, which is accompanied by a slight increase in mean AsT (7%) may refer to anaerobic microbial degradation of DOC coupled with the reduction of As(V) to As(III) without triggering additional As release from the aquifer sediments.

  5. Geochemical and isotopic signatures for the identification of seawater intrusion in an alluvial aquifer

    NASA Astrophysics Data System (ADS)

    Nair, Indu S.; Rajaveni, S. P.; Schneider, M.; Elango, L.

    2015-08-01

    Seawater intrusion is one of the alarming processes that reduces the water quality and imperils the supply of freshwater in coastal aquifers. The region, north of the Chennai city, India is one such site affected by seawater intrusion. The objective of this study is to identify the extent of seawater intruded area by major geochemical and isotopic signatures. A total of 102 groundwater samples were collected and analysed for major and minor ions. Groundwater samples with electrical conductivity (EC) greater than 5000 μS/cm and a river mouth sample were analyzed for Oxygen-18 (δ 18O) and Deuterium (δ 2H) isotopes to study their importance in monitoring seawater intrusion. The molar ratio of geochemical indicators and isotopic signatures suggests an intrusion up to a distance of 13 km from the sea as on March 2012 and up to 14.7 km during May 2012.

  6. Stable isotope signatures in bulk samples from two soils with contrasting characteristics. What do they tell about ongoing pedogenic processes?

    NASA Astrophysics Data System (ADS)

    Jiménez-Morillo, Nicasio T.; dos Anjos Leal, Otávio; Knicker, Heike; Pinheiro Dick, Deborah; González-Vila, Francisco J.; González-Pérez, José A.

    2014-05-01

    Isotopic ratio mass spectrometry (IRMS) has been proven as a promising tool for the monitoring of biogeochemical processes in soil. In this work, stable isotope signatures of light elements δ15N, δ13C, δ18O and δD were determined for two soils with contrasting characteristics in terms of climate, vegetation, land use and management. The studied soils were a Cambisol from a subtropical area (Paraná region, South Brazil) and an Arenosol from a Mediterranean climate (Andalusia, South Spain). A Flash 2000 HT (N, C, S, H and O) elemental analyzer (Thermo Scientific) coupled to a Delta V Advantage IRMS (Thermo Scientific) was used. Isotopic ratios are reported as parts per thousand (o ) deviations from appropriate standards recognized by the international atomic energy agency (IAEA). In a first approach we took advantage of the well-known different δ13C signature between plants using either the C4 or C3 carbon fixation pathway (O'Leary, 1981). The Arenosol (Spain) revealed a δ13C signature which is clearly in the range of C3 plants (-26 to -30 o ). Different plant canopies (tree, shrubs or ferns) caused only slight variations δ13C (STD= 0.98). In contrast, the Cambisol (Brazil) showed less depletion of the heavier carbon isotope corresponding to C4 predominant vegetation. In addition an increase from -19 o in the soil surface (0 - 5 cm) to -16 o in the subsoil (20 - 30 cm) was observed in line with a recent (2 years old) shift of the land use from the predominant C4 grassland to eucalypt (C3) cultivation. Crossplots of δ15N vs. δ18O may provide information about nitrate (NO3-) sources and N cycling (Kendall, 1998). In the Mediterranean Arenosol this signal (δ18O = 30o δ15N = 2o ) was found compatible with a predominant nitrate atmospheric deposition, whereas the signal in the Brazilian Cambisol pointed to the use of a mineral N fertilization with signs of denitrification processes (δ18O = 13o δ15N = 9o ). No conclusive results could be obtained from the

  7. 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).

  8. Small-scale studies of roasted ore waste reveal extreme ranges of stable mercury isotope signatures

    NASA Astrophysics Data System (ADS)

    Smith, Robin S.; Wiederhold, Jan G.; Jew, Adam D.; Brown, Gordon E.; Bourdon, Bernard; Kretzschmar, Ruben

    2014-07-01

    Active and closed Hg mines are significant sources of Hg contamination to the environment, mainly due to large volumes of mine waste material disposed of on-site. The application of Hg isotopes as source tracer from such contaminated sites requires knowledge of the Hg isotope signatures of different materials potentially released to the environment. Previous work has shown that calcine, the waste residue of the on-site ore roasting process, can exhibit distinct Hg isotope signatures compared with the primary ore. Here, we report results from a detailed small-scale study of Hg isotope variations in calcine collected from the closed New Idria Hg mine, San Benito County, CA, USA. The calcine samples exhibited different internal layering features which were investigated using optical microscopy, micro X-ray fluorescence, micro X-ray absorption spectroscopy (μ-XAS), and stable Hg isotope analysis. Significant Fe, S, and Hg concentration gradients were found across the different internal layers. Isotopic analyses revealed an extreme variation with pronounced isotopic gradients across the internal layered features. Overall, δ202Hg (±0.10‰, 2 SD) describing mass-dependent fractionation (MDF) ranged from -5.96 to 14.49‰, which is by far the largest range of δ202Hg values reported for any environmental sample. In addition, Δ199Hg (±0.06‰, 2 SD) describing mass-independent fractionation (MIF) ranged from -0.17 to 0.21‰. The μ-XAS analyses suggested that cinnabar and metacinnabar are the dominant Hg-bearing phases in the calcine. Our results demonstrate that the incomplete roasting of HgS ores in Hg mines can cause extreme mass-dependent Hg isotope fractionations at the scale of individual calcine pieces with enrichments in both light and heavy Hg isotopes relative to the primary ore signatures. This finding has important implications for the application of Hg isotopes as potential source tracers for Hg released to the environment from closed Hg mines and

  9. Carbon Isotope Chemistry in Molecular Clouds

    NASA Technical Reports Server (NTRS)

    Robertson, Amy N.; Willacy, Karen

    2012-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  11. Nitrate denitrification with nitrite or nitrous oxide as intermediate products: Stoichiometry, kinetics and dynamics of stable isotope signatures.

    PubMed

    Vavilin, V A; Rytov, S V

    2015-09-01

    A kinetic analysis of nitrate denitrification by a single or two species of denitrifying bacteria with glucose or ethanol as a carbon source and nitrite or nitrous oxide as intermediate products was performed using experimental data published earlier (Menyailo and Hungate, 2006; Vidal-Gavilan et al., 2013). Modified Monod kinetics was used in the dynamic biological model. The special equations were added to the common dynamic biological model to describe how isotopic fractionation between N species changes. In contrast to the generally assumed first-order kinetics, in this paper, the traditional Rayleigh equation describing stable nitrogen and oxygen isotope fractionation in nitrate was derived from the dynamic isotopic equations for any type of kinetics. In accordance with the model, in Vidal-Gavilan's experiments, the maximum specific rate of nitrate reduction was proved to be less for ethanol compared to glucose. Conversely, the maximum specific rate of nitrite reduction was proved to be much less for glucose compared to ethanol. Thus, the intermediate nitrite concentration was negligible for the ethanol experiment, while it was significant for the glucose experiment. In Menyailo's and Hungate's experiments, the low value of maximum specific rate of nitrous oxide reduction gives high intermediate value of nitrous oxide concentration. The model showed that the dynamics of nitrogen and oxygen isotope signatures are responding to the biological dynamics. Two microbial species instead of single denitrifying bacteria are proved to be more adequate to describe the total process of nitrate denitrification to dinitrogen. PMID:25989520

  12. A highly unradiogenic lead isotopic signature revealed by volcanic rocks from the East Pacific Rise.

    PubMed

    Mougel, Berengere; Agranier, Arnaud; Hemond, Christophe; Gente, Pascal

    2014-01-01

    Radiogenic isotopes in oceanic basalts provide a window into the different geochemical components defining the composition of Earth's mantle. Here we report the discovery of a novel geochemical signature in volcanic glasses sampled at a sub-kilometre scale along the East Pacific Rise between 15°37'N and 15°47'N. The most striking aspect of this signature is its unradiogenic lead ((206)Pb/(204)Pb=17.49, (207)Pb/(204)Pb=15.46 and (208)Pb/(204)Pb=36.83). In conjunction with enriched Sr, Nd and Hf signatures, Pb isotopes depict mixing lines that trend away from any known mantle end-members. We suggest that this unradiogenic lead component sampled by magmatic melts corresponds to a novel upper mantle reservoir that should be considered in the Pb isotope budget of the bulk silicate Earth. Major, trace element and isotope compositions are suggestive of an ancient and lower continental origin for this unradiogenic lead component, possibly sulphide-bearing pyroxenites that were preserved even after prolonged stirring within the ambient upper mantle. PMID:25027032

  13. Carbonate clumped isotope bond reordering and geospeedometry

    NASA Astrophysics Data System (ADS)

    Passey, Benjamin H.; Henkes, Gregory A.

    2012-10-01

    Carbonate clumped isotope thermometry is based on the preference of 13C and 18O to form bonds with each other. At elevated temperatures such bond ordering is susceptible to resetting by diffusion of C and O through the solid mineral lattice. This type of bond reordering has the potential to obscure primary paleoclimate information, but could also provide a basis for reconstructing shallow crustal temperatures and cooling rates. We determined Arrhenius parameters for solid-state reordering of C-O bonds in two different calcites through a series of laboratory heating experiments. We find that the calcites have different susceptibilities to solid-state reordering. Reaction progress follows a first order rate law in both calcites, but only after an initial period of non-first order reaction that we suggest relates to annealing of nonequilibrium defects when the calcites are first heated to experimental temperature. We show that the apparent equilibrium temperature equations (or "closure temperature" equations) for carbonate clumped isotope reordering are analogous Dodson's equations for first order loss of daughter isotopes. For each calcite, the sensitivity of apparent equilibrium temperature to cooling rate is sufficiently high for inference of cooling rates within a factor of ˜5 or better for cooling rates ranging from tens of degrees per day to a few degrees per million years. However, because the calcites have different susceptibilities to reordering, each calcite defines its own cooling rate-apparent equilibrium temperature relationship. The cooling rates of Carrara marble inferred from carbonate clumped isotope geospeedometry are 10-6-10-3 degrees per annum and are in broad agreement with rates inferred from thermochronometric methods. Cooling rates for 13C-depleted calcites from the late Neoproterozoic Doushantou cap carbonates in south China are on the order of 102-104 degrees per annum, consistent with rapid cooling following formation of these calcites by a

  14. Rapid Cenozoic ingrowth of isotopic signatures simulating "HIMU" in ancient lithospheric mantle: Distinguishing source from process

    NASA Astrophysics Data System (ADS)

    McCoy-West, Alex J.; Bennett, Vickie C.; Amelin, Yuri

    2016-08-01

    Chemical and isotopic heterogeneities in the lithospheric mantle are increasingly being recognised on all scales of examination, although the mechanisms responsible for generating this variability are still poorly understood. To investigate the relative behaviour of different isotopic systems in off-cratonic mantle, and specifically the origin of the regional southwest Pacific "HIMU" (high time integrated 238U/204Pb) Pb isotopic signature, we present the first U-Th-Pb, Rb-Sr, Sm-Nd and Re-Os isotopic dataset for spinel peridotite xenoliths sampling the subcontinental lithospheric mantle (SCLM) beneath Zealandia. Strongly metasomatised xenoliths converge to a restricted range of Sr and Nd isotopic compositions (87Sr/86Sr = 0.7028-0.7033; εNd ≈ +3-+6) reflecting pervasive overprinting of their original melt depletion signatures by carbonatite-rich melts. In contrast, rare, weakly metasomatised samples possess radiogenic Nd isotopic compositions (εNd > +15) and unradiogenic Sr isotopic compositions (87Sr/86Sr < 0.7022). This is consistent with melt extraction at ca. 2.0 Ga and in accord with widespread Paleoproterozoic Re-Os model ages from both weakly metasomatised and the more numerous, strongly metasomatised xenoliths. The coupling of chalcophile (Os), and lithophile (Sr and Nd) melt depletion ages from peridotite xenoliths on a regional scale under Zealandia argues for preservation of a significant mantle keel (⩾2 million km3) associated with a large-scale Paleoproterozoic melting event. Lead isotopic compositions are highly variable with 206Pb/204Pb = 17.3-21.3 (n = 34) and two further samples with more extreme compositions of 22.4 and 25.4, but are not correlated with other isotopic data or U/Pb and Th/Pb ratios in either strongly or weakly metasomatised xenoliths; this signature is thus a recent addition to the lithospheric mantle. Lead model ages suggest that this metasomatism occurred in the last 200 m.y., with errorchrons from individual localities

  15. Isotopic evidence of enhanced carbonate dissolution at a coal mine drainage site in Allegheny County, Pennsylvania, USA

    SciTech Connect

    Sharma, Shikha; Sack, Andrea; Adams, James P.; Vesper, Dorothy; J Capo, Rosemary C.; Hartsock, Angela; Edenborn, Harry M.

    2013-01-01

    Stable isotopes were used to determine the sources and fate of dissolved inorganic C (DIC) in the circumneutral pH drainage from an abandoned bituminous coal mine in western Pennsylvania. The C isotope signatures of DIC (δ{sup 13}C{sub DIC}) were intermediate between local carbonate and organic C sources, but were higher than those of contemporaneous Pennsylvanian age groundwaters in the region. This suggests a significant contribution of C enriched in {sup 13}C due to enhanced carbonate dissolution associated with the release of H{sub 2}SO{sub 4} from pyrite oxidation. The Sr isotopic signature of the drainage was similar to other regional mine waters associated with the same coal seam and reflected contributions from limestone dissolution and cation exchange with clay minerals. The relatively high δ{sup 34}S{sub SO4} and δ{sup 18}O{sub SO4} isotopic signatures of the mine drainage and the presence of presumptive SO{sub 4}-reducing bacteria suggest that SO{sub 4} reduction activity also contributes C depleted in {sup 13}C isotope to the total DIC pool. With distance downstream from the mine portal, C isotope signatures in the drainage increased, accompanied by decreased total DIC concentrations and increased pH. These data are consistent with H{sub 2}SO{sub 4} dissolution of carbonate rocks, enhanced by cation exchange, and C release to the atmosphere via CO{sub 2} outgassing.

  16. Isotopic Signatures of Meteorolgoical Drivers of Inflow Variability in Apline Areas of the Snowy Mountains, Australia

    NASA Astrophysics Data System (ADS)

    Callow, J. N.; McGowan, H. A.; Denholm, J.

    2011-12-01

    Hydrometeorological instrument records in Australia are particularly short, rarely spanning more than 100-150 years. Analysis of these records has revealed the impact of short term climate variability cycles such as the El Niño - Southern Oscillation (ENSO) on drought and flood frequency. The impacts of longer-term climate cycles not repetitively recorded in the instrument record are less well understood. Palaeoclimate archives have begun to reveal the significance of cycles such as the Pacific Decadal Oscillation (PDO) and their interaction with ENSO as a driver of flood and drought. Our research is focused on field data collection and atmospheric modelling studies to build an archive of distinctive meteorological events and their characteristic precipitation stable oxygen isotope signature. Characteristic isotope signatures of particular weather systems were identified from analysis of real time precipitation and snowpack samples. Together with water vapour trajectory modelling, this study has shown strong agreement of with conventional models of isotopic behaviour associated with temperature/uplift and circulatory isotopic fractionation. More depleted signatures have been associated with "East-Coast Lows" and neutral signatures with localised convective activity associated with warm air masses originating in central Australia. Cold fronts are associated with cool air masses and water vapour trajectories from higher latitudes the Southern Ocean and have an intermediate signature. The overall objective of this research is to understand dominant drivers of precipitation variability such as ENSO-PDO (and other) cycles and their impacts on the hydrology of the Snowy Mountains region. Development of this capability would provide for better informed water resource planning and decision making in the Snowy Mountains region. As we continue to build our database of isotopic signatures of distinct precipitation events, we will build our capacity to interpret dominant

  17. Unique Hg stable isotope signatures of compact fluorescent lamp-sourced Hg.

    PubMed

    Mead, Chris; Lyons, James R; Johnson, Thomas M; Anbar, Ariel D

    2013-03-19

    The recent widespread adoption of compact fluorescent lamps (CFL) has increased their importance as a source of environmental Hg. Stable isotope analysis can identify the sources of environmental Hg, but the isotopic composition of Hg from CFL is not yet known. Results from analyses of CFL with a range of hours of use show that the Hg they contain is isotopically fractionated in a unique pattern during normal CFL operation. This fractionation is large by comparison to other known fractionating processes for Hg and has a distinctive, mass-independent signature, such that CFL Hg could be uniquely identified from other sources. The fractionation process described here may also explain anomalous fractionation of Hg isotopes in precipitation. PMID:23373764

  18. Mercury isotope signatures in contaminated sediments as a tracer for local industrial pollution sources.

    PubMed

    Wiederhold, Jan G; Skyllberg, Ulf; Drott, Andreas; Jiskra, Martin; Jonsson, Sofi; Björn, Erik; Bourdon, Bernard; Kretzschmar, Ruben

    2015-01-01

    Mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) may cause characteristic isotope signatures of different mercury (Hg) sources and help understand transformation processes at contaminated sites. Here, we present Hg isotope data of sediments collected near industrial pollution sources in Sweden contaminated with elemental liquid Hg (mainly chlor-alkali industry) or phenyl-Hg (paper industry). The sediments exhibited a wide range of total Hg concentrations from 0.86 to 99 μg g(-1), consisting dominantly of organically-bound Hg and smaller amounts of sulfide-bound Hg. The three phenyl-Hg sites showed very similar Hg isotope signatures (MDF δ(202)Hg: -0.2‰ to -0.5‰; MIF Δ(199)Hg: -0.05‰ to -0.10‰). In contrast, the four sites contaminated with elemental Hg displayed much greater variations (δ(202)Hg: -2.1‰ to 0.6‰; Δ(199)Hg: -0.19‰ to 0.03‰) but with distinct ranges for the different sites. Sequential extractions revealed that sulfide-bound Hg was in some samples up to 1‰ heavier in δ(202)Hg than organically-bound Hg. The selectivity of the sequential extraction was tested on standard materials prepared with enriched Hg isotopes, which also allowed assessing isotope exchange between different Hg pools. Our results demonstrate that different industrial pollution sources can be distinguished on the basis of Hg isotope signatures, which may additionally record fractionation processes between different Hg pools in the sediments. PMID:25437501

  19. 13CH3D kinetic isotope effects for methane oxidation by OH - predicting the "clumped" isotopic signature of atmospheric methane

    NASA Astrophysics Data System (ADS)

    Whitehill, A. R.; Joelsson, L. M. T.; Wang, D. T.; Johnson, M. S.; Ono, S.

    2015-12-01

    Methane is a significant long-lived greenhouse gas, but the tropospheric methane budget is not entirely constrained. "Clumped" isotopologues of methane, including 13CH3D, can provide additional constraints on the atmospheric methane cycle. Interpretation of these novel isotope tracers requires an understanding of the "clumped" isotopic signature of various methane sources, as well as the kinetic isotope effects of the methane sink reactions. We performed a series of photochemical experiments to measure the isotopic fractionation during the CH4+OH reaction. Experiments were carried out in a 100 L quartz photochemical reactor. Photolysis of ozone (O3) in the presence of water (H2O) was used to produce OH radicals. Experiments were performed in a helium bath gas. Fourier transform infrared spectroscopy (FTIR) was used to monitor reaction progress. At various intervals during the reaction, methane was sampled from the cell and analyzed for isotope ratios by tunable infrared laser direct absorption spectroscopy (TILDAS). By simultaneously measuring four different isotopologues of methane (12CH4,12CH3D, 13CH4, 13CH3D), we were able to constrain the kinetic isotope effects for 12CH3D, 13CH4, and the doubly-substitued isotopologue 13CH3D. These results are combined with published clumped isotope data from different methane sources to model the Δ13CH3D (i.e. deviation from "stochastic" distribution of isotopes) of tropospheric methane and its sensitivity to different sources. The Δ13CH3D value of tropospheric methane does not strongly depend upon isotope fractionation during the OH sink reaction. Rather, the Δ13CH3D value of tropospheric methane reflects a mixing of different source signatures. Due to nonlinearity in mixing of Δ13CH3D, the Δ13CH3D value of tropospheric methane will be larger than the weighted average of the Δ13CH3D value of the sources. A first order interpretation of variations in the Δ13CH3D value of tropospheric methane is that it reflects changes

  20. Mg Isotopic Compositions of Modern Marine Carbonates

    NASA Astrophysics Data System (ADS)

    Krogstad, E.; Bizzarro, M.; Hemming, N.

    2003-12-01

    We have used a MC-ICP-MS to measure the isotopic composition of magnesium in a number of samples of modern marine carbonate. Due to the large mass difference between 26Mg and 24Mg (similar to that between 13C and 12C), there is potential for mass fractionation during geologic and biologic processes that may make this isotope system useful for geochemical studies. These samples are from the study of Hemming and Hanson (1992, GCA 56: 537-543). The carbonate minerals analyzed include aragonite, low-Mg calcite, and high-Mg calcite. The samples include corals, echinoderms, ooids, etc., from subtropical to Antarctic settings. Mg purification was accomplished by ion-exchange chromatography, using Bio-Rad AG50W-X12 resin on which greater than 99 percent recovery of Mg is achieved. Samples were introduced into the MC-ICP-MS (VG Axiom) using a Cetac MCN-6000 nebuliser. We use a standard-sample-standard bracketing technique, and samples are analysed at least three times. For lab standards we find that the reproducibility on the 26Mg/24Mg to be about ñ 0.12 permil (2 s.d.). We monitored our separated samples for Na and Ca, as we have found that high Ca/Mg and Na/Mg produce variable magnesium isotopic fractionation during mass spectrometry due to as yet unclear matrix effects. We have normalized our results to our measured values for seawater. We observed a d26Mg(s.w.) range of -1.4 to -2.4 permil in our modern carbonate samples relative to present day seawater. Due to the long residence time of Mg in the oceans (ca. 50 my), this must be due to kinetic or biologic effects. Our d25Mg(s.w.) variations as a function of d26Mg(s.w.) plot along the terrestrial fractionation trend. With an average d26Mg(s.w.) of ca. +0.5 permil in all samples of mantle lithologies and mantle-derived igneous rocks (Bizzarro et al., Goldschmidt abs., 2003), we can assume that the Mg isotopic composition of Earth's river water lies between ca. -2.4 and +0.5 permil (relative to seawater). The actual

  1. Predicting isotopic signatures resulting from melting in global mantle models

    NASA Astrophysics Data System (ADS)

    van Heck, Hein; Davies, Huw; Elliott, Tim; Porcelli, Don

    2014-05-01

    Many outstanding problems in Earth science relate to the geodynamical explanation of geochemical observations. Nowadays, extensive geochemical databases of surface observations exist, but satisfying explanations of underlying processes are lacking. Longstanding problems such as; the possible existence and sustainability of chemically distinct reservoirs in the Earth's mantle; the possible need of layered convection through much of Earth's history to explain chemical observations; and the heat flow paradox remain unsolved. One way to address these problems is through numerical modeling of mantle convection while tracking chemical information throughout the convective mantle. In the past decade, both numerical mantle convection codes and computer power have grown sufficiently to begin to grasp much of the full problem of the complex interlocking physics, chemistry and thermodynamics of the convecting mantle, lithosphere, continents and atmosphere. We implemented a new way to track both bulk composition and concentration of trace elements in the well-developed mantle convection code TERRA. Our approach is to track bulk composition and trace element abundance via particles. One value on each particle represents bulk composition; it can be interpreted as the basalt component. The system is set up to track both radioactive isotopes (in the U, Th, K system) and noble gases (He, Ar). In our model, chemical separation on bulk composition and trace elements happens at self-consistent, evolving melting zones. Melting is defined via a composition dependent solidus, such that the amount of melt generated depends on pressure, temperature and bulk composition of each particle. A novel aspect is that we do not move particles that undergo melting; instead we transfer the chemical information carried by the particle to other particles. Molten material is instantaneously transported to the surface, thereby increasing the basalt component carried by the particles close to the surface

  2. Methane and its Stable Isotope Signature Across Pennsylvania: Assessing the Potential Impacts of Natural Gas Development and Agriculture

    NASA Astrophysics Data System (ADS)

    Ramos-Garcés, F.; Fuentes, J. D.; Grannas, A. M.; Martins, D. K.

    2012-12-01

    Methane is an important greenhouse gas with a global warming potential 72 times that of carbon dioxide (20 year time horizon). Many recent efforts have been focused on improving our understanding of methane sources to the atmosphere and better quantifying the atmospheric methane budget. Increased natural gas exploration, particularly associated with shale gas drilling, has been hypothesized to be a potential source of atmospheric methane during well development and also due to fugitive emissions from operational well sites and pipelines. For a six-day period in June 2012, measurements of methane and its stable isotope signature were obtained from a mobile measurement platform using cavity ringdown spectroscopy. Transects from southwestern to northeastern Pennsylvania were studied, with samples obtained in rural, forested, urban, farm-impacted and well-impacted sites. Particular emphasis was placed on performing air sampling in the vicinity of natural gas wells under development, just completed, and in full operation. In the rural atmosphere, away from cattle farms and natural gas systems, the ambient levels of methane were around 1.75 ppm. Near and around gas wells under development, ambient methane levels resembled those found in the rural atmosphere. In some cases, the atmosphere was enriched with methane (up to 2.2 ppm) in areas near old wells and existing pipelines. Ambient methane levels around cattle farms were significantly enhanced, with mixing ratios reaching about 4 ppm. We will discuss here the impact of both gas well development and agricultural activities on observed methane concentrations and stable isotope signatures.

  3. Food sources of macro-invertebrates in an important mangrove ecosystem of Vietnam determined by dual stable isotope signatures

    NASA Astrophysics Data System (ADS)

    Tue, Nguyen Tai; Hamaoka, Hideki; Sogabe, Atsushi; Quy, Tran Dang; Nhuan, Mai Trong; Omori, Koji

    2012-08-01

    Dual stable isotope signatures (δ13C and δ15N) were applied to determine the contribution of mangrove materials and other organic carbon sources to the invertebrate community in an ecologically important mangrove ecosystem of Vietnam. We have analyzed 181 specimens of 30 invertebrate species and found δ13C and δ15N ranging from - 14.5 to - 26.8‰ and from 1.3 to 12.1‰, respectively. From taxa measured for stable isotopes, polychaete, gastropods, bivalves, and grapsid crabs living in mangrove forest showed relative low δ13C values, while fiddler crabs inhabiting in the land-water ecotone showed the highest δ13C values. The δ13C showed that just a few mangrove inhabitants directly relied on the mangrove materials. The wide ranges of δ13C and δ15N signatures indicated that the invertebrates utilized heterogeneous diets, comprising benthic microalgae, marine phytoplankton, particulate organic matter, sediment organic matter, mangrove detritus, and meiofauna and rotten animal tissues as the supplemental nutrient food sources. Moreover, the significant correlation between δ13C values and body sizes of invertebrates showed that snails Littoraria melanostoma and Terebralia sulcata, bivalve Glauconome virens, and portunid crab Scylla serrata exhibited ontogenetic shifts in diets. The present study showed that adjacent habitats such as tidal flat and mangrove creeks seem to contribute an important microalgal food resource for invertebrates and highlighted the need for conservations of mangrove forests and the adjacent habitats.

  4. 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

  5. Investigation of Isotopic Signatures for Sources of Groundwater Contamination at the Hanford Site

    SciTech Connect

    Dresel, P Evan; Evans, John C.; Farmer, Orville T.

    2002-01-25

    The Hanford Site Groundwater Monitoring Project at Pacific Northwest National Laboratory (PNNL) investigated selected isotopic signature techniques to aid interpretation of contaminant plumes in Hanford Site groundwater. The main approach was to select groundwater samples expected to exhibit a variety of contaminant characteristics and then develop inductively coupled plasma mass spectrometry (ICP-MS) analytical methods for the groundwater matrix. Initial broad scans were used to identify interferences and to focus the method development on isotopes showing the greatest promise of practical application. In addition, earlier work characterizing chlorine-36 in Hanford Site groundwater by accelerator mass spectrometry (AMS) will be discussed.

  6. Carbon Isotope Chemostratigraphy, the Baby and the Bathwater

    NASA Astrophysics Data System (ADS)

    Arthur, M. A.

    2008-12-01

    Secular variations in the carbon isotopic values of carbonate sediments and rocks and their individual components have been applied successfully to problems of stratigraphic correlation and for interpretation of past changes in the global carbon cycle. However, this methodology is not without problems. A major tenet of stable isotope chemostratigraphy involves sampling and analyzing multiple, widely separated sequences, and, if possible, multiple carbon-bearing components (e.g., carbonate and organic carbon) in order to demonstrate a global signal. In some cases, this methodology has been short-circuited in the zeal to reveal a new event or excursion, particularly for time intervals for which adequate sequences are somewhat rare. Likewise, although most carbonate researchers are quite aware of the possible importance of diagenesis, particularly in organic-carbon rich sequences or in shoal-water carbonate sequences with longer-term subaerial exposure events, such overprints commonly go unrecognized or are considered of minor impact. Studies of stable isotope variations in carbonate sequences should always employ textural and geochemical methodologies for detecting and even quantifying diagenesis, if possible. Although some diagenetically overprinted or misinterpreted geochemical data have undoubtedly appeared in the literature, there are many excellent examples of global carbon isotope variations in records expressed in pelagic biogenic carbonate, marine organic carbon, platform carbonates, and terrestrial organic matter. Arguably, one of the best-documented examples is the Cenomanian-Turonian (ca. 93 Ma) positive carbon isotope excursion. The amplitude of the Cenomanian-Turonian carbon isotope excursion is similar among all types of records, but there are subtle pattern differences that arise from differences in sedimentation rate among and within sequences. Organic carbon and carbonate carbon isotope signals also may differ in phasing and amplitude for certain

  7. Isotopic signatures of CH 4 and higher hydrocarbon gases from Precambrian Shield sites: A model for abiogenic polymerization of hydrocarbons

    NASA Astrophysics Data System (ADS)

    Sherwood Lollar, B.; Lacrampe-Couloume, G.; Voglesonger, K.; Onstott, T. C.; Pratt, L. M.; Slater, G. F.

    2008-10-01

    Previous studies of methane and higher hydrocarbon gases in Precambrian Shield rocks in Canada and the Witwatersrand Basin of South Africa identified two major gas types. Paleometeoric waters were dominated by hydrocarbon gases with compositional and isotopic characteristics consistent with production by methanogens utilizing the CO 2 reduction pathway. In contrast the deepest, most saline fracture waters contained gases that did not resemble the products of microbial methanogenesis and were dominated by both high concentrations of H 2 gas, and CH 4 and higher hydrocarbon gases with isotopic signatures attributed to abiogenic processes of water-rock reaction in these high rock/water ratio, hydrogeologically-isolated fracture waters. Based on new data obtained for the higher hydrocarbon gases in particular, a model is proposed to account for carbon isotope variation between CH 4 and the higher hydrocarbon gases (specifically ethane, propane, butane, and pentane) consistent with abiogenic polymerization. Values of δ 13C for CH 4 and the higher hydrocarbon gases predicted by the model are shown to match proposed abiogenic hydrocarbon gas end-members identified at five field sites (two in Canada and three in South Africa) suggesting that the carbon isotope patterns between the hydrocarbon homologs reflect the reaction mechanism. In addition, the δ 2H isotope data for these gases are shown to be out of isotopic equilibrium, suggesting the consistent apparent fractionation observed between the hydrocarbon homologs may also reflect reaction mechanisms involved in the formation of the gases. Recent experimental and field studies of proposed abiogenic hydrocarbons such as those found at mid-ocean spreading centers and off-axis hydrothermal fields such as Lost City have begun to focus not only on the origin of CH 4, but on the compositional and isotopic information contained in the higher hydrocarbon gases. The model explored in this paper suggests that while the extent of

  8. Compound-specific carbon isotopic fractionation during transport of phthalate esters in sandy aquifer.

    PubMed

    Liu, Hui; Li, YanXi; He, Xi; Sissou, Zakari; Tong, Lei; Yarnes, Chris; Huang, Xianyu

    2016-02-01

    The present paper aims to evaluate the carbon isotopic fractionation of phthalate esters (PAEs) during transport in an sandy aquifer. Breakthrough curves of di-methyl phthalate (DMP), di-ethyl phthalate (DEP), and di-n-butyl phthalate (DBP) in mixed solution were determined by miscible displacement experiment, and simulated using HYDRUS-1D software. The stable carbon isotopes (δ(13)C) of 3 PAEs in effluent were analyzed at different times. Results showed that, in the transport process in sandy sediment, PAEs are mainly trapped into the pore space instead of being adsorbed on the surface of particles. At the initial stage of transport, PAEs with lighter carbon tend to run faster in the sandy sediment, and PAEs with heavier carbon run after. However, there is no priority for the transport of PAEs with different carbon isotopes at Stage Ⅱ with mainly time-limited sorption. So the transport-based isotope fractionation occurs in the front area of contaminant plume. This effect may be relevant for interpreting carbon isotope signatures in the real contaminant site. PMID:26539707

  9. Oxygen isotope fractionation in divalent metal carbonates

    USGS Publications Warehouse

    O'Neil, J.R.; Clayton, R.N.; Mayeda, T.K.

    1969-01-01

    Equilibrium fractionation factors for the distribution of 18O between alkaline-earth carbonates and water have been measured over the temperature range 0-500??C. The fractionation factors ?? can be represented by the equations CaCO3-H2O, 1000 ln??=2.78(106 T-2)-3.39, SrCO3-H 2O, 1000 ln??=2.69(106 T-2)-3.74, BaCO3-H2O, 1000 ln??=2.57(106 T -2)-4.73. Measurements on MnCO3, CdCO3, and PbCO3 were made at isolated temperatures. A statistical-mechanical calculation of the isotopic partition function ratios gives reasonably good agreement with experiment. Both cationic size and mass are important in isotopic fractionation, the former predominantly in its effect on the internal vibrations of the anion, the latter in its effect on the lattice vibrations.

  10. 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.

  11. Spatio-temporal variability in isotopic signatures of atmospheric NOx emissions from vehicles

    NASA Astrophysics Data System (ADS)

    Miller, D. J.; Wojtal, P.; O'Connor, M.; Clark, S.; Hastings, M. G.

    2015-12-01

    Atmospheric nitrogen oxides (NOx = NO + NO2) play key roles in atmospheric chemistry and radiative forcing. Their oxidation products, nitric acid or nitrate, have significant contributions to nitrogen (N) deposition, with implications for ecosystem health. On-road vehicle NOx sources currently dominate U.S. anthropogenic emission budgets, yet vehicle NOx emissions contributions to local and regional N deposition patterns are highly uncertain. NOx isotopic signatures offer a potentially valuable observational tool to trace source contributions to N deposition. We characterize the spatio-temporal variability of vehicle NOx emission isotopic signatures with a field and laboratory-verified technique for actively capturing NOx in solution to quantify the nitrogen isotopic composition (δ15N-NOx) to within ±1.5‰ (1σ) precision. We present a novel combination of on-road mobile and stationary urban δ15N-NOx measurements at minutes to hourly resolution along with NOx and CO2 concentration measurements. We evaluate spatial gradients of δ15N-NOx on U.S. Northeast and Midwest highways, including six urban metropolitan areas and rural interstate highways during summer and autumn. We also assess on-road diurnal δ15N-NOx variations over ~800 km driving distance in Providence, RI by targeting the upwind footprint of urban background measurements to distinguish background and source NOx. We observe on-road δ15N-NOx signatures range from -3 to -10‰ under different traffic conditions in the U.S. Northeast and Midwest. On-road δ15N-NOx daytime variations from -3 to -6‰ agree well with simultaneous urban background sampling in Providence, RI, suggesting that vehicles dominate NOx emissions in this region. We use these datasets to estimate the range of representative δ15N-NOx source signatures for U.S. vehicle fleet-integrated emission plumes. Our novel approach suggests that previously reported isotopic signatures for vehicle NOx are not necessarily representative. These

  12. Mercury isotope signatures as tracers for Hg cycling at the New Idria Hg mine.

    PubMed

    Wiederhold, Jan G; Smith, Robin S; Siebner, Hagar; Jew, Adam D; Brown, Gordon E; Bourdon, Bernard; Kretzschmar, Ruben

    2013-06-18

    Mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) of Hg isotopes provides a new tool for tracing Hg in contaminated environments such as mining sites, which represent major point sources of Hg pollution into surrounding ecosystems. Here, we present Hg isotope ratios of unroasted ore waste, calcine (roasted ore), and poplar leaves collected at a closed Hg mine (New Idria, CA, U.S.A.). Unroasted ore waste was isotopically uniform with δ(202)Hg values from -0.09 to 0.16‰ (± 0.10‰, 2 SD), close to the estimated initial composition of the HgS ore (-0.26‰). In contrast, calcine samples exhibited variable δ(202)Hg values ranging from -1.91‰ to +2.10‰. Small MIF signatures in the calcine were consistent with nuclear volume fractionation of Hg isotopes during or after the roasting process. The poplar leaves exhibited negative MDF (-3.18 to -1.22‰) and small positive MIF values (Δ(199)Hg of 0.02 to 0.21‰). Sequential extractions combined with Hg isotope analysis revealed higher δ(202)Hg values for the more soluble Hg pools in calcines compared with residual HgS phases. Our data provide novel insights into possible in situ transformations of Hg phases and suggest that isotopically heavy secondary Hg phases were formed in the calcine, which will influence the isotope composition of Hg leached from the site. PMID:23662941

  13. Isotopic signatures of H2 and CO uptake and emissions by soil

    NASA Astrophysics Data System (ADS)

    Popa, Maria Elena; Chen, Qianjie; Röckmann, Thomas

    2016-04-01

    We performed soil chamber experiments in order to determine the isotopic signatures of the exchange of H2 and CO between soil and atmosphere. The experiments took place at two sites in the Netherlands, a forest (Speuld) and a grass field (Cabauw). Flask samples were filled from the soil chamber, and then analyzed in the laboratory for δD in H2 and δ13C and δ18O in CO. The isotope results prove that, for both species, uptake and emission occur simultaneously regardless of the direction of the net flux. We were able to determine separately the isotopic effects of the two fluxes. For both H2 and CO, soil uptake is associated with a small positive fractionation (the lighter molecule is taken up faster). The soil uptake fractionation (α = kheavy/klight) was 0.945 ± 0.004 for H2; for CO, the fractionation was 0.992 for 13C and 0.985 for 18O. The isotopic composition of the H2 emitted from the grassland was -530 ± 40 ‰, less depleted that what is expected from the isotopic equilibrium of H2 with water. For CO, the isotopic composition of the soil emission is depleted in 13C compared to atmospheric CO, and lower than the average isotopic composition of plant or soil organic matter.

  14. Biotic and abiotic experimental identification of bacterial influence on calcium isotopic signatures.

    PubMed

    Cobert, Florian; Schmitt, Anne-Désirée; Calvaruso, Christophe; Turpault, Marie-Pierre; Lemarchand, Damien; Collignon, Christelle; Chabaux, François; Stille, Peter

    2011-10-15

    In this study, we tested experimentally the influence of plant and bacterial activities on the calcium (Ca) isotope distribution between soil solutions and plant organs. Abiotic apatite weathering experiments were performed under two different pH conditions using mineral and organic acids. Biotic experiments were performed using either apatite or Ca-enriched biotite substrates in the presence of Scots pines, inoculated or not with the rhizosphere bacterial strain Bulkholderia glathei PML1(12), or the B. glathei PML1(12) alone. For each experiment, the percolate was collected every week and analyzed for Ca concentrations and Ca isotopic ratios. No Ca isotopic fractionation was observed for the different abiotic experimental settings. This indicates that no Ca isotopic fractionation occurs during apatite dissolution, whatever the nature of the acid (mineral or organic). The main result of the biotic experiments is the 0.22 ‰ (44)Ca enrichment recorded for a solution in contact with Scots pines grown on the bacteria-free apatite substrate. In contrast, the presence of bacteria did not cause Ca isotopic fractionation of the solution collected after 14 weeks of the experiments. These preliminary results suggest that bacteria influence the Ca isotopic signatures by dissolving Ca from apatite more efficiently. Therefore, Ca isotopes might be suitable for detecting bacteria-mediated processes in soils. PMID:21913253

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

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

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

  16. Synthetic isotope mixtures for the calibration of isotope amount ratio measurements of carbon

    NASA Astrophysics Data System (ADS)

    Russe, K.; Valkiers, S.; Taylor, P. D. P.

    2004-07-01

    Synthetic isotope mixtures for the calibration of carbon isotope amount ratio measurements have been prepared by mixing carbon tetrafluoride highly enriched in 13C with carbon tetrafluoride depleted in 13C. Mixing procedures based on volumetry and gravimetry are described. The mixtures served as primary measurement standards for the calibration of isotope amount ratio measurements of the Isotopic Reference Materials PEF1, NBS22 and USGS24. Thus SI-traceable measurements of absolute carbon isotope amount ratios have been performed for the first time without any hypothesis needed for a correction of oxygen isotope abundances, such as is the case for measurements on carbon dioxide. As a result, "absolute" carbon isotope amount ratios determined via carbon tetrafluoride have smaller uncertainties than those published for carbon dioxide. From the measurements of the Reference Materials concerned, the absolute carbon isotope amount ratio of Vienna Pee Dee Belemnite (VPDB)--the hypothetical material upon which the scale for relative carbon isotope ratio measurements is based--was calculated to be R13(VPDB) = (11 101 +/- 16) × 10-6.

  17. Isotopic signatures of N2O produced by ammonia-oxidizing archaea from soils.

    PubMed

    Jung, Man-Young; Well, Reinhard; Min, Deullae; Giesemann, Anette; Park, Soo-Je; Kim, Jong-Geol; Kim, So-Jeong; Rhee, Sung-Keun

    2014-05-01

    N2O gas is involved in global warming and ozone depletion. The major sources of N2O are soil microbial processes. Anthropogenic inputs into the nitrogen cycle have exacerbated these microbial processes, including nitrification. Ammonia-oxidizing archaea (AOA) are major members of the pool of soil ammonia-oxidizing microorganisms. This study investigated the isotopic signatures of N2O produced by soil AOA and associated N2O production processes. All five AOA strains (I.1a, I.1a-associated and I.1b clades of Thaumarchaeota) from soil produced N2O and their yields were comparable to those of ammonia-oxidizing bacteria (AOB). The levels of site preference (SP), δ(15)N(bulk) and δ(18)O -N2O of soil AOA strains were 13-30%, -13 to -35% and 22-36%, respectively, and strains MY1-3 and other soil AOA strains had distinct isotopic signatures. A (15)N-NH4(+)-labeling experiment indicated that N2O originated from two different production pathways (that is, ammonia oxidation and nitrifier denitrification), which suggests that the isotopic signatures of N2O from AOA may be attributable to the relative contributions of these two processes. The highest N2O production yield and lowest site preference of acidophilic strain CS may be related to enhanced nitrifier denitrification for detoxifying nitrite. Previously, it was not possible to detect N2O from soil AOA because of similarities between its isotopic signatures and those from AOB. Given the predominance of AOA over AOB in most soils, a significant proportion of the total N2O emissions from soil nitrification may be attributable to AOA. PMID:24225887

  18. Natural Radionuclides and Isotopic Signatures for Determining Carbonaceous Aerosol Sources, Aerosol Lifetimes, and Washout Processes

    SciTech Connect

    Gaffney, Jeffrey

    2012-12-12

    This is the final technical report. The project description is as follows: to determine the role of aerosol radiative forcing on climate, the processes that control their atmospheric concentrations must be understood, and aerosol sources need to be determined for mitigation. Measurements of naturally occurring radionuclides and stable isotopic signatures allow the sources, removal and transport processes, as well as atmospheric lifetimes of fine carbonaceous aerosols, to be evaluated.

  19. Isotopic signatures of N2O produced by ammonia-oxidizing archaea from soils

    PubMed Central

    Jung, Man-Young; Well, Reinhard; Min, Deullae; Giesemann, Anette; Park, Soo-Je; Kim, Jong-Geol; Kim, So-Jeong; Rhee, Sung-Keun

    2014-01-01

    N2O gas is involved in global warming and ozone depletion. The major sources of N2O are soil microbial processes. Anthropogenic inputs into the nitrogen cycle have exacerbated these microbial processes, including nitrification. Ammonia-oxidizing archaea (AOA) are major members of the pool of soil ammonia-oxidizing microorganisms. This study investigated the isotopic signatures of N2O produced by soil AOA and associated N2O production processes. All five AOA strains (I.1a, I.1a-associated and I.1b clades of Thaumarchaeota) from soil produced N2O and their yields were comparable to those of ammonia-oxidizing bacteria (AOB). The levels of site preference (SP), δ15Nbulk and δ18O -N2O of soil AOA strains were 13–30%, −13 to −35% and 22–36%, respectively, and strains MY1–3 and other soil AOA strains had distinct isotopic signatures. A 15N-NH4+-labeling experiment indicated that N2O originated from two different production pathways (that is, ammonia oxidation and nitrifier denitrification), which suggests that the isotopic signatures of N2O from AOA may be attributable to the relative contributions of these two processes. The highest N2O production yield and lowest site preference of acidophilic strain CS may be related to enhanced nitrifier denitrification for detoxifying nitrite. Previously, it was not possible to detect N2O from soil AOA because of similarities between its isotopic signatures and those from AOB. Given the predominance of AOA over AOB in most soils, a significant proportion of the total N2O emissions from soil nitrification may be attributable to AOA. PMID:24225887

  20. Determining Clumped Isotope (Δ47) Signatures of CO2 During Ion-Molecule Isotopic Exchange Reactions

    NASA Astrophysics Data System (ADS)

    Sarna, J.; Priyadarshi, A.; Pourmorady, P.; Tripati, A.; Estaris, J.

    2015-12-01

    The abundance of multiply-substituted isotopologues such as 13C16O18O can be used to understand fundamental mechanisms that controls isotopic fractionation in chemical reactions. Knowledge of the energy-dependent ion-molecule isotopic exchange rate for 13C16O18O may also provide important insights into the CO2 ion-molecular exchange that occurs in the source of the mass spectrometer. It may offer an explanation for the recently observed nonlinearities associated with clumped isotope measurements. We designed a controlled set of laboratory experiments to investigate variations in the abundance of 13C16O18O associated with different ion-molecular isotopic exchange reactions. In our experiments, we characterize the effects of changing ionization energy, reaction time, CO2 amount, the presence of different compounds, and reaction chamber temperature on the clumped isotopic composition of CO2.

  1. Identifying sources of nitrogen to Hanalei Bay, Kauai, utilizing the nitrogen isotope signature of macroalgae

    USGS Publications Warehouse

    Derse, E.; Knee, K.L.; Wankel, Scott D.; Kendall, C.; Berg, C.J., Jr.; Paytan, A.

    2007-01-01

    Sewage effluent, storm runoff, discharge from polluted rivers, and inputs of groundwater have all been suggested as potential sources of land derived nutrients into Hanalei Bay, Kauai. We determined the nitrogen isotopic signatures (??15N) of different nitrate sources to Hanalei Bay along with the isotopic signature recorded by 11 species of macroalgal collected in the Bay. The macroalgae integrate the isotopic signatures of the nitrate sources over time, thus these data along with the nitrate to dissolved inorganic phosphate molar ratios (N:P) of the macroalgae were used to determine the major nitrate source to the bay ecosystem and which of the macro-nutrients is limiting algae growth, respectively. Relatively low ??15N values (average -0.5???) were observed in all algae collected throughout the Bay; implicating fertilizer, rather than domestic sewage, as an important external source of nitrogen to the coastal water around Hanalei. The N:P ratio in the algae compared to the ratio in the Bay waters imply that the Hanalei Bay coastal ecosystem is nitrogen limited and thus, increased nitrogen input may potentially impactthis coastal ecosystem and specifically the coral reefs in the Bay. Identifying the major source of nutrient loading to the Bay is important for risk assessment and potential remediation plans. ?? 2007 American Chemical Society.

  2. Identifying sources of nitrogen to Hanalei Bay, Kauai, utilizing the nitrogen isotope signature of macroalgae.

    PubMed

    Derse, Elizabeth; Knee, Karen L; Wankel, Scott D; Kendall, Carol; Berg, Carl J; Paytan, Adina

    2007-08-01

    Sewage effluent, storm runoff, discharge from polluted rivers, and inputs of groundwater have all been suggested as potential sources of land derived nutrients into Hanalei Bay, Kauai. We determined the nitrogen isotopic signatures (delta(15)N) of different nitrate sources to Hanalei Bay along with the isotopic signature recorded by 11 species of macroalgal collected in the Bay. The macroalgae integrate the isotopic signatures of the nitrate sources over time, thus these data along with the nitrate to dissolved inorganic phosphate molar ratios (N:P) of the macroalgae were used to determine the major nitrate source to the bay ecosystem and which of the macro-nutrients is limiting algae growth, respectively. Relatively low delta(15)N values (average -0.5% per hundred) were observed in all algae collected throughout the Bay; implicating fertilizer, rather than domestic sewage, as an important external source of nitrogen to the coastal water around Hanalei. The N:P ratio in the algae compared to the ratio in the Bay waters imply that the Hanalei Bay coastal ecosystem is nitrogen limited and thus, increased nitrogen input may potentially impact this coastal ecosystem and specifically the coral reefs in the Bay. Identifying the major source of nutrient loading to the Bay is important for risk assessment and potential remediation plans. PMID:17822082

  3. Investigation into nitrogen attenuation in groundwater pathways in Irish RBDs through the use of stable isotopic signature analysis

    NASA Astrophysics Data System (ADS)

    Orr, Alison; Ofterdinger, Ulrich; Flynn, Raymond

    2010-05-01

    Nitrogen has been identified by the Water Framework Directive as a major pollutant of concern in terms of water quality. Nitrogen contamination can pose a threat to human health and excessive loading into surface waters can lead to eutrophication. This research aims to investigate groundwater pathways from diffuse sources of nitrogen contamination and attenuation processes in various geological settings in Ireland. As part of the EPA Strive Pathways Project, the overall purpose of this research is to improve the understanding of nitrogen attenuation processes in groundwater for the development of a catchment management tool to assess the risk posed by diffuse contamination to surface and groundwater receptors. This will be undertaken through examining nitrogen attenuation pathways in various geological settings in distinctly different catchments in Ireland. These catchments include Gortinlieve in Co. Donegal and Mattock in Co. Louth which are both poorly drained catchments and Nuenna in Co. Kilkenny which is a well drained limestone catchment. This research will be useful to develop further ongoing research carried out into the natural chemistry of the Gortinlieve catchment. The research will focus mainly on characterising the fractionation of stable nitrogen isotopes in groundwater. The use of the stable isotopes δ15N and δ18O in the study of denitrification has been well documented in literature. In addition, the isotopes δ13C and δ34S have also been shown to be useful in evaluating the influence of sulphur and carbon as electron donors in denitrification. For example FeS2 produced as a result of denitrification has a different isotopic signature than FeS2 produced from other processes. This research aims to apply these established stable isotope signatures to a new context in terms of the catchment geology and the broader integrated approach of the Pathways project. Furthermore factors influencing the rate of attenuation will be explored, such as: strata

  4. Why do Different Anthropogenic Sources of Atmospheric Nitrate have Distinctive Isotopic Signatures?

    NASA Astrophysics Data System (ADS)

    Kendall, C.; Elliott, E. M.; Wankel, S. W.; Boyer, E. W.; Burns, D. A.

    2007-12-01

    Do different sources of atmospheric nitrate (power plants, vehicles, agricultural emissions) have distinctive isotopic signatures? To answer this question, we conducted a national survey of nitrate isotopes in wet deposition samples collected throughout the USA from 156 NADP sites. Archived samples from the year 2000 were pooled into bimonthly composites and analyzed for d15N and d18O, with a subset analyzed for D17O. In this presentation, we present our current thoughts about why the different sources have distinctive isotopic signatures, focusing mainly on oxygen isotopes of nitrate. Our original conceptual model was based largely on (1) Heaton's 1990 paper that showed that NOx emissions from power plants in South Africa had d15N values significantly higher than exhaust from vehicles, and (2) anecdotal data from several studies showing higher d15N and/or d18O values of nitrate in precipitation downwind of areas dominated by power plants. Our model proposed that atmospheric nitrate derived from near- surface sources (e.g., vehicle and biogenic emissions) would obtain d18O and D17O signatures predominantly from near-surface O2 produced by photosynthesis (averaging +23 permil), whereas NOx exiting power plant stacks would circulate higher into the atmosphere and obtain nitrate d18O and D17O signatures predominantly from tropospheric O3 (+95 and +35 permil, respectively). We speculated that the source discrimination seen in NOx emissions would be maintained in the atmospheric nitrate ultimately derived from it, despite potential isotopic fractionation during conversion to nitrate. Furthermore, because of the likelihood of temporal and spatial variation in the compositions of NOx exiting individual combustion engines due to changes in temperature, fuel types, and other operating conditions, we suspected that source signatures would best be determined after the NOx had been converted to nitrate. Hence, we proposed to determine source signatures primarily from

  5. Radiogenic Carbon Isotopes in Authigenic Carbonate from Lake Neusiedl, Austria

    NASA Astrophysics Data System (ADS)

    Neuhuber, Stephanie; Steier, Peter; Gier, Susanne; Draganits, Erich; Kogelbauer, Ilse

    2015-04-01

    Formation of authigenic carbonate in Lake Neusiedl, Austia, has been reported since the 1960ies. The reaction pathways resulting in carbonate precipitation (protodolomite and high magnesium calcite) have yet to be identified. Lake Neusiedl is a shallow lake without significant sediment accumulation but constant reworking of sediment due to its shallow depth (1.8m) and influence by wind. The sediments are water-saturated silts and clays that overly Neogene sediments. The age of Lake Neusiedl is unknown due to its low sedimentation rate and constant remixing of sediment. Dating of authigenic minerals is an alternative method to determine the minimum age of water present - even episodically - at the location. We characterize the sediments mineralogy in different size fractions by X-Ray Diffractometry (XRD), Simultaneous Themo Analysis (STA) and Fourier Transform Infra Red Spectroscopy, stable carbon and oxygen isotopes as well as radiogenic carbon. To describe the authigenic carbonates and find the fractions with highest authigenic carbonate minerals we investigate the size fractions <4 µm, <3 µm, <2 µm, <1 µm, 0.5 µm and <0.2 µm. The "coarser" fractions (4 µm to 2 µm) contain detrital minerals such as chlorite, muscovite, quartz, feldspar, stoichiometric calcite and stoichiometric dolomite as well as authigenic high Mg calcite. Radiogenic carbon ages increase with increasing grain size from 850 years before present to 2300 years before present and indicate a very slow growth rate or episodic growth of authigenic carbonate phases.

  6. The "Flood of the Century" as Isotopic Fingerprint in Canopy d18O Signatures

    NASA Astrophysics Data System (ADS)

    Seibt, U.; Wingate, L.; Berry, J. A.

    2006-12-01

    The d18O composition of water and CO2 exchange at smaller scales (leaf and ecosystem) can be affected by changes in environmental conditions at larger (regional) scales. During a sampling campaign in a beech forest in Germany in August 2002, we encountered such a large scale change when dry sunny weather was followed by a large storm system with heavy rains leading to floods across Europe. During the first, sunny period, bulk leaf water d18O was -1 permil at night and 7 permil at mid-day. Foliage CO2 exchange had positive values of 18O discrimination during photosynthesis (10-30 permil) and nocturnal respiration (11 permil). The second period had frequent rains and mostly diffuse light, with reduced foliage water fluxes but similar carbon fluxes. Canopy vapour d18O decreased at least 2 permil, and leaf water then reflected isotopic exchange with this depleted vapour due to the high humidity. Hence, bulk leaf water was substantially more depleted at night (-8 permil) and showed virtually no evaporative enrichment during the day (-5 permil). Values of 18O discrimination during CO2 exchange were small or even negative for photosynthesis (-2 to 6 permil) but larger for nocturnal respiration (23-39 permil). Model simulations indicated that the small positive foliage isoflux during the day was offset by the negative isoflux at night. As a consequence, the d18O of CO2 in canopy air decreased from -0.3 permil during the sunny period to -3 permil during the wet period. The d18O signatures of canopy water and CO2 thus reflected the transition from local water to the regional regime of depleted water deposited across the area by the storm.

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

    PubMed

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

    2010-11-23

    The debate of life on Mars centers around the source of the globular, micrometer-sized mineral carbonates in the ALH84001 meteorite; consequently, the identification of Martian processes that form carbonates is critical. This paper reports a previously undescribed carbonate formation process that occurs on Earth and, likely, on Mars. We identified micrometer-sized carbonates in terrestrial aerosols that possess excess (17)O (0.4-3.9‰). The unique O-isotopic composition mechanistically describes the atmospheric heterogeneous chemical reaction on aerosol surfaces. Concomitant laboratory experiments define the transfer of ozone isotopic anomaly to carbonates via hydrogen peroxide formation when O(3) reacts with surface adsorbed water. This previously unidentified chemical reaction scenario provides an explanation for production of the isotopically anomalous carbonates found in the SNC (shergottites, nakhlaites, chassignites) Martian meteorites and terrestrial atmospheric carbonates. The anomalous hydrogen peroxide formed on the aerosol surfaces may transfer its O-isotopic signature to the water reservoir, thus producing mass independently fractionated secondary mineral evaporites. The formation of peroxide via heterogeneous chemistry on aerosol surfaces also reveals a previously undescribed oxidative process of utility in understanding ozone and oxygen chemistry, both on Mars and Earth. PMID:21059939

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

    PubMed Central

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

    2010-01-01

    The debate of life on Mars centers around the source of the globular, micrometer-sized mineral carbonates in the ALH84001 meteorite; consequently, the identification of Martian processes that form carbonates is critical. This paper reports a previously undescribed carbonate formation process that occurs on Earth and, likely, on Mars. We identified micrometer-sized carbonates in terrestrial aerosols that possess excess 17O (0.4–3.9‰). The unique O-isotopic composition mechanistically describes the atmospheric heterogeneous chemical reaction on aerosol surfaces. Concomitant laboratory experiments define the transfer of ozone isotopic anomaly to carbonates via hydrogen peroxide formation when O3 reacts with surface adsorbed water. This previously unidentified chemical reaction scenario provides an explanation for production of the isotopically anomalous carbonates found in the SNC (shergottites, nakhlaites, chassignites) Martian meteorites and terrestrial atmospheric carbonates. The anomalous hydrogen peroxide formed on the aerosol surfaces may transfer its O-isotopic signature to the water reservoir, thus producing mass independently fractionated secondary mineral evaporites. The formation of peroxide via heterogeneous chemistry on aerosol surfaces also reveals a previously undescribed oxidative process of utility in understanding ozone and oxygen chemistry, both on Mars and Earth. PMID:21059939

  9. Stable carbon and oxygen isotopes as an indicator for soil degradation

    NASA Astrophysics Data System (ADS)

    Alewell, C.; Schaub, M.; Seth, B.

    2009-04-01

    Analyses of soil organic carbon content (SOC) and stable carbon and oxygen isotope signatures (^13C) of soils were assessed for their suitability to detect early stage soil erosion. Results were validated with Cs-137 measurements. We investigated the soils in the alpine Urseren Valley (Southern Central Switzerland) which are highly impacted by soil erosion. Hill slope transects from uplands (cambisols) to adjacent wetlands (histosols and histic to mollic gleysols) differing in their intensity of visual soil erosion and reference wetlands without erosion influence were sampled. Carbon isotopic signature and SOC content of soil depth profiles were determined. A close correlation of ^13C and carbon content (r > 0.80) is found for upland soils not affected by soil erosion, indicating that depth profiles of ^13C of these upland soils mainly reflect decomposition of SOC. Long term disturbance of an upland soil is indicated by decreasing correlation of ^13C and SOC (r ? 0.80) which goes parallel to increasing (visual) damage at the site. Early stage soil erosion in hill slope transects from uplands to adjacent wetlands is documented as an intermediate ^13C value (27.5 ) for affected wetland soil horizons (0 - 12 cm) between upland (aerobic metabolism, relatively heavier ^13C of 26.6 ) and wetland isotopic signatures (anaerobic metabolism, relatively lighter ^13C of 28.6 ). Cs-137 measurements confirmed stable isotope analysis. Stable oxygen isotope signature (^18O) of soil is the result of a mixture of the components within the soil with varying ^18O signatures. Thus, ^18O of soils should provide information about the soil's substrate, especially about the relative contribution of organic matter versus minerals. As there is no standard method available for measuring soil ^18O, the method for measurement of single components using High Temperature Conversion Elemental Analyzer (TC/EA) was adapted. We measured ^18O in standard materials (IAEA 601, IAEA 602, Merck Cellulose

  10. 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.

  11. Stable Hg isotope signatures in creek sediments impacted by a former Hg mine.

    PubMed

    Smith, Robin S; Wiederhold, Jan G; Jew, Adam D; Brown, Gordon E; Bourdon, Bernard; Kretzschmar, Ruben

    2015-01-20

    The goal of this study was to investigate the Hg stable isotope signatures of sediments in San Carlos Creek downstream of the former Hg mine New Idria, CA, USA and to relate the results to previously studied Hg isotope signatures of unroasted ore waste and calcine materials in the mining area. New Idria unroasted ore waste was reported to have a narrow δ(202)Hg range (−0.09 to 0.16‰), while roasted calcine materials exhibited a very large variability in δ(202)Hg (−5.96 to 14.5‰). In this study, creek sediment samples were collected in the stream bed from two depths (0–10 and 10–20 cm) at 10 locations between the mine adit and 28 km downstream. The sediment samples were size-fractionated into sand, silt, and (if possible) clay fractions as well as hand-picked calcine pebbles. The sediment samples contained highly elevated Hg concentrations (8.2 to 647 μg g(–1)) and displayed relatively narrow mass-dependent fractionation (MDF, δ(202)Hg; ± 0.08‰, 2SD) ranges (−0.58 to 0.24‰) and little to no mass-independent fractionation (MIF, Δ(199)Hg; ± 0.04‰, 2SD) (0.00 to 0.10‰), similar to what was observed previously for the unroasted ore waste. However, due to the highly variable and overlapping δ(202)Hg signatures of the calcines, they could not be ruled out as source of Hg to the creek sediments. Overall, our results suggest that analyzing creek sediments downstream of former Hg mines can provide a more reliable Hg isotope source signature for tracing studies at larger spatial scales, than analyzing the isotopically highly heterogeneous tailing piles typically found at former mining sites. Creek sediments carry an integrated isotope signature of Hg transported away from the mine with runoff into the creek, eventually affecting ecosystems downstream. PMID:25489982

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

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

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

  13. The Oxygen Isotopic Signature of Nitrous Oxide is Determined by Oxygen Exchange

    NASA Astrophysics Data System (ADS)

    Kool, D. M.; Wrage, N.; Oenema, O.; Harris, D.; van Groenigen, J.

    2008-12-01

    In order to derive accurate budget estimations and effective mitigation strategies for the greenhouse gas nitrous oxide (N2O), it is essential to identify the processes involved in its production. Analyses of the isotopic composition of N2O are increasingly used to characterize the importance of these processes. However, we argue that the reliability of results based on oxygen (O) isotopic analysis of N2O may be questioned due to insufficient consideration of O exchange between H2O and nitrogen oxides. We studied the process of O exchange in 12 widely varying soils using a novel combination of 18O and 15N tracing experiments. Incorporation of O from 18O-enriched H2O into N2O exceeded theoretical maxima based on reaction stoichiometry, revealing the presence of O exchange. Novel methodology based on the retention of the 18O:15N-enrichment ratio of NO3- in N2O allowed to quantify O exchange during denitrification: up to 97% of N2O-O originated from H2O instead of NO3-. Our results show that in soil, the main source of N2O, the conventional assumption that the O isotopic composition of N2O is determined by reaction stoichiometry and isotopic fractionation during its production does not hold. In all cases, the O isotopic signature of N2O was found to be dominated by the effect of O exchange between nitrogen oxides and water. We speculate that the implications of O exchange will extend across terrestrial and aquatic ecosystems, and possibly to other nitrogen oxides as well. Especially, a potential effect of O exchange on the O isotopic signature of NO3- needs to be studied, as this is routinely used for NO3- source determination. Our results may facilitate the development of improved methodology to study and understand the global N cycle.

  14. 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.

  15. Carbon isotope fractionation in synthetic magnesian calcite

    NASA Astrophysics Data System (ADS)

    Jimenez-Lopez, Concepción; Romanek, Christopher S.; Caballero, Emilia

    2006-03-01

    Mg-calcite was precipitated at 25 °C in closed system, free-drift experiments, from solutions containing NaHCO 3, CaCl 2 and MgCl 2. The carbon stable isotope composition of bulk solid and solution were analyzed from subsamples collected during time course experiments of 24 h duration. Considering only the Mg-content and δ 13C values for the bulk solid, the carbon isotope fractionation factor for the Mg-calcite-HCO 3(aq)- system (as 103lnα) increased with average mol percentage of Mg (X Mg) in the solid at a rate of (0.024 ± 0.011) per mol% MgCO 3. Extrapolation of this relationship to the pure calcite end member yields a value of 0.82 ± 0.09, which is similar to published values for the calcite-HCO 3(aq)- system. Although 103lnα did not vary for precipitation rates that ranged from 10 3.21 to 10 4.60 μmol m -2 h -1, it was not possible to hold Mg-content of the solid constant, so kinetic effect on 10 3 ln α could not be evaluated from these experiments.

  16. Isotopic and Geochemical signatures of different aged drained thaw lake basins (DTLBs) and drainage channels in Arctic Alaska

    NASA Astrophysics Data System (ADS)

    Throckmorton, H.; Perkins, G.; Rearick, M.; Altmann, G. L.; Cohen, L. R.; Hudak, M.; Gard, M.; Newman, B. D.; Heikoop, J. M.; Wilson, C. J.

    2013-12-01

    associated with large drainage channels had highly reducing conditions, relative to less distinct, smaller internal drainages. Dissolved inorganic carbon (DIC) concentrations ranged from 0-734ppm HCO3-, and exhibited a trend of greater concentration with depth for nearly all sites. The 13C DIC isotope signature ranged widely, from -2.2 to -25.1, with the lightest values at the shallow subsurface depth for all sites relative to the surface and deeper subsurface. Additional results will discuss concentrations and isotope signatures of dissolved CH4 (C13 and H2) and organic C at the selected sites; as well as geochemistry (anions and metals).

  17. Compound-Specific Stable Carbon Isotope Analysis of Chlorofluorocarbons in Groundwater.

    PubMed

    Horst, Axel; Lacrampe-Couloume, Georges; Sherwood Lollar, Barbara

    2015-10-20

    Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), controlled substances due to their role in stratospheric ozone loss, also occur as dissolved contaminants in groundwaters. Stable carbon isotopic signatures may provide valuable new information on the fate of these compounds as has been seen for other priority hydrocarbon contaminants, but to date no method for extraction and isotopic analysis of dissolved CFCs from groundwaters has been developed. Here we describe a cryogenic purge and trap system coupled to continuous flow compound-specific stable carbon isotope analysis mass spectrometry for concentrations as low as 35 μg/L. The method is validated by comparing isotopic signatures from water extracted CFCs against a new suite of isotopic CFC standards. Fractionation of CFCs in volatilization experiments from pure-phase CFC-11 and CFC-113 resulted in enrichment factors (ε) of +1.7 ± 0.1‰ and +1.1 ± 0.1‰, respectively, indicating that such volatile loss, if significant, would produce a more (13)C depleted signature in the remaining CFCs. Importantly, no significant fractionation was observed during volatile extraction of dissolved CFCs from aqueous solutions. δ(13)C values for groundwaters from a CFC-contaminated site were, on average, more enriched than δ(13)C values for pure compounds. Such enriched δ(13)C values have been seen in other hydrocarbon contaminants such as chlorinated ethenes and ethanes due to in situ degradation, but definitive interpretation of such enriched signatures in field samples requires additional experiments to characterize fractionation of CFCs during biodegradation. The establishment of a robust and sensitive method of extraction and analysis, as described here, provides the foundation for such future directions. PMID:26383531

  18. Geological controls on isotopic signatures of streamflow: results from a nested catchment experiment in Luxembourg (Europe)

    NASA Astrophysics Data System (ADS)

    Pfister, Laurent; McDonnell, Jeffrey J.; Hissler, Christophe; Martinez-Carreras, Nuria; Gourdol, Laurent; Klaus, Julian; François Iffly, Jean; Barnich, François; Stewart, Mike K.

    2014-05-01

    Controls of geology and topography on hydrological metrics, like summer low flow (Grant and Tague, 2004) or dynamic storage (Sayama et al., 2011), have been identified in nested catchment experiments. However, most tracer-based studies on streamflow generation have been carried out in small (10 km2) homogenous catchments (Klaus and McDonnell, 2013). The controlling effects of catchment physiography on how catchments store and release water, and how this eventually controls stream isotope behaviour over a large range of scale are poorly understood. Here, we present results from a nested catchment analysis in the Alzette River basin (Luxembourg, Europe). Our hydro-climatological network consists of 16 recording streamgauges and 21 pluviographs. Catchment areas range from 0.47 to 285 km2, with clean and mixed combinations of distinct geologies ranging from schists to marls, sandstone, dolomite and limestone. Our objective was to identify geological controls on (i) winter runoff ratios, (ii) maximum storage and (iii) isotopic signatures in streamflow. For each catchment we determined average runoff ratios from winter season precipitation-discharge double-mass curves. Maximum catchment storage was based on the dynamic storage change approach of Sayama et al. (2011). Changes in isotopic signatures of streamflow were documented along individual catchment flow duration curves. We found strong correlations between average winter runoff ratios, maximum storage and the prevailing geological settings. Catchments with impermeable bedrock (e.g. marls or schists) were characterised by small storage potential and high average filling ratios. As a consequence, these catchments also exhibited the highest average runoff ratios. In catchments underlain by permeable bedrock (e.g. sandstone), storage potential was significantly higher and runoff ratios were considerably smaller. The isotopic signatures of streamflow showed large differences between catchments. In catchments dominated by

  19. Oxygen and carbon isotope disequilibria in Galapagos corals: isotopic thermometry and calcification physiology

    SciTech Connect

    McConnaughey, T.A.

    1986-01-01

    Biological carbonate skeletons are built largely from carbon dioxide, which reacts to form carbonate ion within thin extracellular solutions. The light isotopes of carbon and oxygen react faster than the heavy isotopes, depleting the resulting carbonate ions in /sup 13/C and /sup 18/O. Calcium carbonate precipitation occurs sufficiently fast that the skeleton remains out of isotopic equilibrium with surrounding fluids. This explanation for isotopic disequilibrium in biological carbonates was partially simulated in vitro, producing results similar to those seen in non-photosynthetic corals. Photosynthetic corals have higher /sup 13/C//sup 12/C ratios due to the preferential removal of /sup 12/C (as organic carbon) from the reservoir of dissolved inorganic carbon. The oxygen isotopic variations in corals can be used to reconstruct past sea surface temperatures to an accuracy of about 0.5/sup 0/C. The carbon isotopic content of photosynthetic corals provides an indication of cloudiness. Using isotopic data from Galapagos corals, it was possible to construct proxy histories of the El Nino phenomenon. The physiology of skeletogenesis appears to be surprisingly similar in calcium carbonate, calcium phosphate, and silica precipitating systems.

  20. A Clumped Isotope Calibration for Lacustrine Carbonates

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  1. Nutrient cycling in the Atlantic basin: The evolution of nitrate isotope signatures in water masses

    NASA Astrophysics Data System (ADS)

    Tuerena, R. E.; Ganeshram, R. S.; Geibert, W.; Fallick, A. E.; Dougans, J.; Tait, A.; Henley, S. F.; Woodward, E. M. S.

    2015-10-01

    A basin-wide transect of nitrate isotopes (δ15NNO3, δ18ONO3), across the UK GEOTRACES 40°S transect in the South Atlantic is presented. This data set is used to investigate Atlantic nutrient cycling and the communication pathways of nitrogen cycling processes in the global ocean. Intermediate waters formed in the subantarctic are enriched in δ15NNO3 and δ18ONO3 from partial utilization of nitrate by phytoplankton and distant denitrification processes, transporting heavy isotope signatures to the subtropical Atlantic. Water mass modification through the Atlantic is investigated by comparing data from 40°S (South Atlantic) and 30°N (North Atlantic). This reveals that nitrate in the upper intermediate waters is regenerated as it transits through the subtropical Atlantic, as evidenced by decreases in δ18ONO3. We document diazotrophy-producing high N:P particle ratios (18-21:1) for remineralization, which is further confirmed by a decrease in δ15NNO3 through the subtropical Atlantic. These modifications influence the isotopic signatures of the North Atlantic Deep Water (NADW) which is subsequently exported from the Atlantic to the Southern Ocean. This study reveals the dominance of recycling processes and diazotrophy on nitrate cycling in the Atlantic. These processes provide a source of low δ15NNO3 to the Southern Ocean via the NADW, to counteract enrichment in δ15NNO3 from water column denitrification in the Indo/Pacific basins. We hence identify the Southern Ocean as a key hub through which denitrification and N2 fixation communicate in the ocean through deepwater masses. Therefore, the balancing of the oceanic N budget and isotopic signatures require time scales of oceanic mixing.

  2. Isotopic noble gas signatures released from medical isotope production facilities - Simulations and measurements

    SciTech Connect

    Saey, Paul R.; Bowyer, Ted W.; Ringbom, Anders

    2010-09-09

    Journal article on the role that radioxenon isotopes play in confirming whether or not an underground explosion was nuclear in nature. Radioxenon isotopes play a major role in confirming whether or not an underground explosion was nuclear in nature. It is then of key importance to understand the sources of environmental radioxenon to be able to distinguish civil sources from those of a nuclear explosion. Based on several years of measurements, combined with advanced atmospheric transport model results, it was recently shown that the main source of radioxenon observations are strong and regular batch releases from a very limited number of medical isotope production facilities. This paper reviews production processes in different medical isotope facilities during which radioxenon is produced. Radioxenon activity concentrations and isotopic compositions are calculated for six large facilities. The results are compared with calculated signals from nuclear explosions. Further, the outcome is compared and found to be consistent with radioxenon measurements recently performed in and around three of these facilities. Some anomalies in measurements in which {sup 131m}Xe was detected were found and a possible explanation is proposed. It was also calculated that the dose rate of the releases is well below regulatory values. Based on these results, it should be possible to better understand, interpret and verify signals measured in the noble gas measurement systems in the International Monitoring of the Comprehensive Nuclear-Test-Ban Treaty.

  3. Variations of Carbon Isotopes during Shale Gas Production from the Horn River Basin, British Columbia, Canada

    NASA Astrophysics Data System (ADS)

    Norville, G.; Muehlenbachs, K.

    2014-12-01

    Chemical and stable isotope compositions of natural gases are key parameters for characterizing gas and hydrocarbon reservoirs. Produced gases were obtained from eight wells at multi-well pad sites located in the Horn River Basin (HRB), NE British Columbia. Shale gas wells were drilled and completed in the Devonian Muskwa, Otter Park and Evie Formations of the HRB, and gases collected as time series over short term (~50 days) and long term periods (~ 1250 days). δ13C of gases from HRB formations confirm high thermal maturity and the shale gases frequently showed partial or full isotope reversals among hydrocarbon components. A 10‰ variation in δ13C values of methane was observed during production. In general, during early phases of production shale gases appear enriched in 12C compared to gases sampled at later stages and δ13Cmethane values were approximately between -38‰ and -35‰ during times up to 50 days. The majority of cases of carbon isotope reversals between methane and ethane components of gases (δ13Cmethane > δ13Cethane) were observed at times greater than 100 days, while ethane and propane reversals were common throughout production. Gas production rates differed significantly among the sampled wells from ~ 50 to 400 e3m3/d. Higher rates were frequently associated with gases showing 12Cmethane enrichment. Subsequent to periods of well 'shut in' a change in the carbon isotope composition was detected with enrichment in 13Cmethane of gases. Carbon isotope signatures of produced gases likely reflect a combination of both the in-situ shale gas isotope signature as well as effects of isotope fractionation which may occur during transport through pores and fractures of the shale.

  4. Genetic Effect on Carbon-Isotope Composition of a Plant

    NASA Astrophysics Data System (ADS)

    Yeh, H.

    2005-05-01

    Stable carbon isotopes of organic sediments are potential tools in investigating a wide spectrum of geological problems. These include paleoclimate, paleoecology, and the origin of life. The quality of the information the tools provides depends largely on our knowledge on the factors determining the isotopic composition of a plant. This is because most biogenic organic sediments are derived from plants. The factors can be grouped into internal and external. The internal factors are ultimately attributable to the genetic make-up of a plant. The most well known internal factor is the photosynthetic pathway. Others include structure of the leave tissue and metabolic characteristics of a plant. External factors are concentration and the isotopic composition of the source CO2 and the physical and chemical conditions of the plant's growth environments. This study addresses primarily the genetic effect, the internal factors. Based on the results of two suites of natural plant samples, it is concluded that the difference in photosynthetic pathway entails about 20.0 % of spread in terms of ä13CPDB values. Genetic effect is also accountable for up to 7.0 to 8.0 % spread in ä13CPDB values within a single category of photosynthetic pathway (i.e. the Calvin cycle). With constrains from the relevant known knowledge, it is concluded that the ä13CPDB values of terrestrial plants are probably ranging from - 8.0 to equal or less than -44.9 %. This range of ä13CPDB values may also be considered the bio-signature of organic sediments of great antiquity.

  5. Systematic AMD+GCM Study of Structure of Carbon Isotopes

    SciTech Connect

    Thiamova, G.; Itagaki, N.; Otsuka, T.; Ikeda, K.

    2004-02-27

    The structure of low-lying states of the carbon isotopes is investigated using the extended version of the Antisymmetrized Molecular Dynamics (AMD) Multi-Slater Determinant model. We can reproduce reasonably well many experimental data for carbon isotopes 12C-22C. A special approach is adopted for 15C to better describe the tail of the wave function.

  6. Preservation of carbonate clumped isotopes in sedimentary paleoclimate archives

    NASA Astrophysics Data System (ADS)

    Henkes, G. A.; Passey, B. H.; Grossman, E. L.; Shenton, B.; Perez-Huerta, A.

    2014-12-01

    Carbonate clumped isotope thermometry is increasingly used to reconstruct paleotemperatures of ancient terrestrial environments. One promising application is elucidating paleoelevation from carbonate archives such as paleosols, lacustrine marls, and fossil freshwater shells. Unlike conventional stable isotope approaches (e.g., mineral δ18O or δD), clumped isotope thermometry is independent of the isotopic composition of the precipitating waters and can therefore be used to reconstruct elevation by both the temperature-altitude relationship and the rainfall δ18O-altitude relationship. However, interpretation of clumped isotope data is not without its own complications. Like conventional stable isotopes, clumped isotope paleotemperatures can be effectively reset to warmer values by dissolution/reprecipitation-type diagenesis during sedimentary burial. It is also known that carbonate clumped isotope bonds (i.e., 13C-18O) are susceptible to 'reordering' in the solid mineral lattice at warmer burial temperatures, with laboratory studies of natural carbonates indicating activation of this phenomenon at temperatures as low as 100 °C over geologic timescales. A challenge in applying carbonate clumped isotope thermometry to natural samples is now evaluating terrestrial archives with respect to both types of alteration: 'open-system' alteration and 'closed-system' bond reordering. In this talk we will review our experimental efforts to constrain the kinetics of clumped isotope reordering, with relevance to low-temperature carbonates like fossil shells and early diagenetic minerals, and present new laboratory data that further inform our theoretical framework for the mechanism(s) of 13C-18O bond reordering. Together with traditional analytical and petrographic screening for recrystallization, empirical and laboratory studies of carbonate clumped isotope reordering represent the next steps in evaluating isotopic records of paleoclimate, paleobiology, and paleoelevation

  7. 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.

  8. Carbon isotope stratigraphy of the upper Kharaib and Shuaiba formations: Implications for the Early Cretaceous evolution of the Arabian Gulf Region

    SciTech Connect

    Vahrenkamp, V.C.

    1996-05-01

    The carbon isotope profiles of shallow-marine carbonates from the Barremian-Aptian Kharaib and Shuaiba formations of the Arabian Gulf region range between 0.5 and 7{per_thousand} {delta}{sup 13}C PDB (Peedee belemnite). Systematic variations can be correlated with isotope profiles reported from Tethyan pelagic limestone sequences. The detailed correspondence between the isotopic signature of the relatively well-dated pelagic limestones and the poorly dated shallow-water limestones from the Arabian Gulf region suggests that global marine carbon isotope changes apparently affected deep-sea and shallow-water carbonate sediments similarly and at a similar time resolution. Although oxygen isotopes have been reset during diagenesis, carbon isotopes appear to have maintained their primary marine signature through time. No evidence has been found to connect carbon isotope trends to subaerial exposure or later meteoric diagenesis. In combination with other data, the investigated carbon isotope profiles can be used for basin-to-platform and regional correlations beyond the current resolution of biostratigraphy in shallow-water limestones. Carbon isotope stratigraphy confirms significant hiatuses in the investigated shallow-water carbonate sequences. Using carbon isotope trends as a proxy for sea level fluctuations, the carbon isotope cycles of the late Early Cretaceous of the Arabian Gulf region may represent four cycles of rising and falling sea level with a duration corresponding to that of third-order sea level fluctuations. Regional correlations derived from isotope trends provide a scenario for the larger scale stratigraphic evolution of the Arabian peninsula during the end of the Early Cretaceous.

  9. Mg and Ca isotope signatures of authigenic dolomite in siliceous deep-sea sediments

    NASA Astrophysics Data System (ADS)

    Blättler, Clara L.; Miller, Nathaniel R.; Higgins, John A.

    2015-06-01

    Authigenic carbonates in marine sediments frequently have carbon isotope ratios that reflect local organic carbon processing rather than the δ13C of the global DIC (dissolved inorganic carbon) reservoir, but their contributions to ancient sedimentary sections are difficult to assess. In this study of authigenic dolomite from the Miocene-age Monterey Formation of offshore California, Mg and Ca isotopes are shown to vary with stratigraphic depth as a result of early diagenetic processes. The dolomite is a pre-compaction authigenic phase that occurs as beds and nodules with δ13C ranging from -16 to + 9 ‰. Light δ13C values were likely acquired from the sedimentary zone of microbial sulfate reduction, while heavy δ13C values were acquired from the zone of methanogenesis. Mg and Ca isotopes are roughly anti-correlated, with intervals of negative δ13C associated with low δ26Mg and higher δ 44/40Ca values. The variability is observed over a wide range of length-scales, from 10-2 meters within individual authigenic beds/nodules, to 102 meters over the entire stratigraphic column, and can be understood as the consequence of dolomite precipitation in pore fluids where Mg supply is limited by diffusive transport. The relationship of δ26Mg and δ 44/40Ca to the more common stable isotope measurements of δ13C and δ18O represents a new, diagenetically robust, geochemical fingerprint for identifying synsedimentary authigenic carbonates in the geological record.

  10. Chromium-isotope signatures in scleractinian corals from the Rocas Atoll, Tropical South Atlantic.

    PubMed

    Pereira, N S; Voegelin, A R; Paulukat, C; Sial, A N; Ferreira, V P; Frei, R

    2016-01-01

    Chromium-isotope compositions (expressed as δ(53) Cr) of recent and ancient skeletal and non-skeletal carbonates are currently explored as a (paleo-) redox-proxy for shallow seawater. The idea behind this approach is that biogenic and non-biogenic carbonates could potentially be used as archives recording the Cr-isotope composition of seawater in which they formed, and with this contribute to the reconstruction of past paleo-environmental changes in the marine realm, and potentially to climate changes on land. However, investigations addressing the behavior and uptake mechanism of Cr, and the potential isotope fractionations between seawater and biogenic carbonates are scarce. Here, we present a study of Cr-isotope variations in three species of corals and contemporary seawater from the Rocas Atoll, NE, Brazil. Cr-isotope values of the studied coral species (Siderastrea stellata, Porites sp., and Montastrea cavernosa) vary from -0.5 to +0.33‰ and point to significant isotopic disequilibrium with coexisting seawater characterized by a Cr-isotope value of +0.92 ± 0.2‰. This isotopic offset requires reduction of hexavalent Cr(VI) in the sequestration process of all the studied coral species. Cr-isotope values in a profile across an S. stellata colony returned homogeneous, slightly positively fractioned δ(53) Cr values of +0.07 ± 0.08‰ (n = 8, 2σ), which we interpret to reflect a constant reductive uptake during the 20-year growth period recorded in this coral. In contrast, samples across a 12-year growth profile from Porites sp. display rather heterogeneous Cr-isotope values with δ(53) Cr varying from -0.50 to +0.10‰, indicating Cr incorporation under changing redox processes during its growth intervals. We propose a mechanism whereby initial photoreduction of isotopically heavy Cr(VI) to isotopically lighter Cr(III) in the endodermal layer of corals must be followed by efficient and effective re-oxidation of reduced Cr species to favor subsequent

  11. Oxygen isotope signature of P i regeneration from organic compounds by phosphomonoesterases and photooxidation

    NASA Astrophysics Data System (ADS)

    Liang, Y.; Blake, R. E.

    2006-08-01

    Phosphomonoesters are an important source of dissolved inorganic orthophosphate (PO 4 or P i), the preferred form of P utilized by microbiota and aquatic plants in marine and freshwater ecosystems. Two enzymes involved in phosphomonoester metabolism and commonly detected in natural waters (alkaline phosphatase and 5'-nucleotidase) have been studied to determine the oxygen isotope signature of P i-regeneration from phosphomonoesters by enzymatic degradation. Oxygen (O) isotope ratios of water and P i released from phosphomonoesters during enzyme hydrolysis experiments demonstrate that released P i incorporates one oxygen atom from water. The isotopic fractionation between this incorporated water O and ambient water O is -30 (±8)‰ for alkaline phosphatase and -10 (±1)‰ for 5'-nucleotidase, with very weak dependence on temperature. The result of these enzyme-specific isotopic fractionations at one of the four O sites in PO 4 is that the δ 18O value of P i regenerated by 5'-nucleotidase is 5‰ higher than P i regenerated by alkaline phosphatase from the same phosphomonoester substrate. The δ 18O value of regenerated P i also reflects inheritance of 75% of O from the phosphomonoester substrate, thus making the δ 18O of phosphomonoester-derived P i a potential tracer of organophosphorous compound sources. Phosphomonoesterase-regenerated P i has a distinct phosphate oxygen isotope signature that is different and distinguishable from that of biologically recycled and subsequently equilibrated P i and P i regenerated from photooxidation of organic matter. The δ 18O value of regenerated P i will correlate positively with the δ 18O value of bulk water and the fractionation, α, between regenerated P i and water, αregen Pi-water , should converge toward equilibrium αPi-water values with increased biological cycling of P i.

  12. Isotopic noble gas signatures released from medical isotope production facilities--simulations and measurements.

    PubMed

    Saey, Paul R J; Bowyer, Theodore W; Ringbom, Anders

    2010-09-01

    Radioxenon isotopes play a major role in confirming whether or not an underground explosion was nuclear in nature. It is then of key importance to understand the sources of environmental radioxenon to be able to distinguish civil sources from those of a nuclear explosion. Based on several years of measurements, combined with advanced atmospheric transport model results, it was recently shown that the main source of radioxenon observations are strong and regular batch releases from a very limited number of medical isotope production facilities. This paper reviews production processes in different medical isotope facilities during which radioxenon is produced. Radioxenon activity concentrations and isotopic compositions are calculated for six large facilities. The results are compared with calculated signals from nuclear explosions. Further, the outcome is compared and found to be consistent with radioxenon measurements recently performed in and around three of these facilities. Some anomalies in measurements in which (131m)Xe was detected were found and a possible explanation is proposed. It was also calculated that the dose rate of the releases is well below regulatory values. Based on these results, it should be possible to better understand, interpret and verify signals measured in the noble gas measurement systems in the International Monitoring of the Comprehensive Nuclear-Test-Ban Treaty. PMID:20447828

  13. 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

  14. Use of stable isotope signatures to determine mercury sources in the Great Lakes

    USGS Publications Warehouse

    Lepak, Ryan F.; Yin, Runsheng; Krabbenhoft, David P.; Ogorek, Jacob M.; DeWild, John F.; Holsen, Thomas M.; Hurley, James P.

    2015-01-01

    Sources of mercury (Hg) in Great Lakes sediments were assessed with stable Hg isotope ratios using multicollector inductively coupled plasma mass spectrometry. An isotopic mixing model based on mass-dependent (MDF) and mass-independent fractionation (MIF) (δ202Hg and Δ199Hg) identified three primary Hg sources for sediments: atmospheric, industrial, and watershed-derived. Results indicate atmospheric sources dominate in Lakes Huron, Superior, and Michigan sediments while watershed-derived and industrial sources dominate in Lakes Erie and Ontario sediments. Anomalous Δ200Hg signatures, also apparent in sediments, provided independent validation of the model. Comparison of Δ200Hg signatures in predatory fish from three lakes reveals that bioaccumulated Hg is more isotopically similar to atmospherically derived Hg than a lake’s sediment. Previous research suggests Δ200Hg is conserved during biogeochemical processing and odd mass-independent fractionation (MIF) is conserved during metabolic processing, so it is suspected even is similarly conserved. Given these assumptions, our data suggest that in some cases, atmospherically derived Hg may be a more important source of MeHg to higher trophic levels than legacy sediments in the Great Lakes.

  15. Distal and proximal controls on the silicon stable isotope signature of North Atlantic Deep Water

    NASA Astrophysics Data System (ADS)

    de Souza, Gregory F.; Slater, Richard D.; Hain, Mathis P.; Brzezinski, Mark A.; Sarmiento, Jorge L.

    2015-12-01

    It has been suggested that the uniquely high δ30Si signature of North Atlantic Deep Water (NADW) results from the contribution of isotopically fractionated silicic acid by mode and intermediate waters that are formed in the Southern Ocean and transported to the North Atlantic within the upper limb of the meridional overturning circulation (MOC). Here, we test this hypothesis in a suite of ocean general circulation models (OGCMs) with widely varying MOCs and related pathways of nutrient supply to the upper ocean. Despite their differing MOC pathways, all models reproduce the observation of a high δ30Si signature in NADW, as well showing a major or dominant (46-62%) contribution from Southern Ocean mode/intermediate waters to its Si inventory. These models thus confirm that the δ30Si signature of NADW does indeed owe its existence primarily to the large-scale transport of a distal fractionation signal created in the surface Southern Ocean. However, we also find that more proximal fractionation of Si upwelled to the surface within the Atlantic Ocean must also play some role, contributing 20-46% of the deep Atlantic δ30Si gradient. Finally, the model suite reveals compensatory effects in the mechanisms contributing to the high δ30Si signature of NADW, whereby less export of high-δ30Si mode/intermediate waters to the North Atlantic is compensated by production of a high-δ30Si signal during transport to the NADW formation region. This trade-off decouples the δ30Si signature of NADW from the pathways of deep water upwelling associated with the MOC. Thus, whilst our study affirms the importance of cross-equatorial transport of Southern Ocean-sourced Si in producing the unique δ30Si signature of NADW, it also shows that the presence of a deep Atlantic δ30Si gradient does not uniquely constrain the pathways by which deep waters are returned to the upper ocean.

  16. Isotope Dependence of Chemical Erosion of Carbon

    SciTech Connect

    Reinhold, Carlos O; Krstic, Predrag S; Stuart, S. J.; Zhang, Hengda; Harris, Peter R; Meyer, Fred W

    2010-01-01

    We study the chemical erosion of hydrogen-supersaturated carbon due to bombardment by hydrogen isotopes H, D, and T at energies of 1 30 eV using classical molecular dynamics simulations. The chemical structure at the hydrogen-saturated interface (the distribution of terminal hydrocarbon moieties, in particular) shows a weak dependence on the mass of the impinging atoms. However the sputtering yields increase considerably with increasing projectile mass. We analyze the threshold energies of chemical sputtering reaction channels and show that they are nearly mass independent, as expected from elementary bond-breaking chemical reactions involving hydrocarbons. Chemical sputtering yields for D impact are compared with new experimental data. Good agreement is found for small hydrocarbons but the simulations overestimate the production of large hydrocarbons for energies larger than 15 eV. We present a thorough analysis of the dependence of our simulations on the parameters of the bombardment schemes and discuss open questions and possible avenues for development.

  17. Burial Diagenesis Effects on Clumped Isotope Signatures of Coexisting Dolomites and Calcites

    NASA Astrophysics Data System (ADS)

    Winkelstern, I. Z.; Lohmann, K. C.

    2014-12-01

    Carbonate clumped isotope paleothermometry is a promising method for diagenetic and deep time paleoclimate studies, but original clumped isotope (Δ47) compositions can be altered by fluid and thermal diagenetic processes. Previous work shows Δ47 resetting of calcite occurs at temperatures exceeding 100°C over time periods of millions of years, but such thermally-driven effects have not been considered for dolomite. Differences between calcite and dolomite temperature calibrations are also largely unquantified, and the effect of burial diagenesis on dolomite Δ47 has not been measured. Coexisting calcites and dolomites in a ~4500 meter core from Andros Island, Bahamas, offer a unique opportunity to address these questions. These dolomites and calcites formed over a time span from the Cretaceous to Pleistocene under near-surface temperature conditions. Clumped isotope analysis of this material reveals that where these carbonate phases are buried to depths greater than ~3000 meters, realistic surface temperatures (~25 °C) are not preserved. Moreover, these phases do not record reasonable geothermal conditions (> 80 °C), but rather record temperatures between 40 and 60°C. Here we evaluate whether this Δ47 "error" is due to solid-state resetting of clumped isotopes, emplacement of minor burial cements, fabric retentive recrystallization, or some combination thereof. Our results show that clumped isotope compositions of both calcite and dolomite respond similarly to diagenetic resetting of primary values under conditions of burial. These data further emphasize the need to constrain the diagenetic history of samples used for clumped isotope work. The similar Δ47 temperatures recorded by each carbonate type suggest that dolomites and calcites are equally viable temperature proxy sources under shallow burial conditions, yet both seem equally susceptible to "resetting" of their primary clumped isotope abundances.

  18. Carbon Isotopic Constraints on Arctic Methane Sources, 2008-2010

    NASA Astrophysics Data System (ADS)

    Fisher, R. E.; Lowry, D.; Lanoiselle, M.; Sriskantharajah, S.; Nisbet, E. G.

    2010-12-01

    Arctic methane source strengths are particularly vulnerable to large changes with year-to year meteorological variations and with climatic change. A global increase in methane seen in 2007 (Dlugokencky et al., 2009) may have been in part be due to elevated wetland emissions caused by a warm, wet summer over large parts of Siberia. In 2010 wildfires over large areas of Russia will have added methane to the Arctic atmosphere. Carbon isotopic composition of methane in air from the Arctic arriving at a measurement station can be used to identify sources of the gas. Measurement of methane δ13C in air close to sources, including wetlands, permafrost, pine forest and submarine methane clathrate has extended the available data of source signatures of methane from northern sources. Keeling plot analysis of diurnal records from field campaigns in Arctic wetlands show that bulk wetland methane emissions are typically close to δ13CCH4 -69±1 ‰. Air samples from Zeppelin (Spitsbergen, Norway), Pallas (Finland) and Barra (Outer Hebrides, Scotland) have been regularly analysed for methane δ13C. Summer campaigns at Zeppelin point to a 13C depleted bulk Arctic source of dominantly biogenic origin, at -67‰. In spring, while the wetlands are still frozen, the source signature is more enriched, -53‰, with trajectory analysis implying a large contribution from onshore gas fields. Arctic methane emissions respond rapidly to warming with strong positive feedbacks. With rapid warming there is the potential to release large stores of carbon from permafrost and methane hydrates. Isotopic data are powerful discriminants of sources. High frequency, ideally continuous, monitoring of methane δ13C from a number of Arctic sites, onshore and offshore, coupled with back-trajectory analysis and regional modelling, will be important if future changes in Arctic source strengths are to be quantified. Reference: Dlugokencky, E. J., et al. (2009), Observational constraints on recent increases

  19. Atmospheric mercury inputs in montane soils increase with elevation: evidence from mercury isotope signatures

    PubMed Central

    Zhang, Hua; Yin, Run-sheng; Feng, Xin-bin; Sommar, Jonas; Anderson, Christopher W. N.; Sapkota, Atindra; Fu, Xue-wu; Larssen, Thorjørn

    2013-01-01

    The influence of topography on the biogeochemical cycle of mercury (Hg) has received relatively little attention. Here, we report the measurement of Hg species and their corresponding isotope composition in soil sampled along an elevational gradient transect on Mt. Leigong in subtropical southwestern China. The data are used to explain orography-related effects on the fate and behaviour of Hg species in montane environments. The total- and methyl-Hg concentrations in topsoil samples show a positive correlation with elevation. However, a negative elevation dependence was observed in the mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) signatures of Hg isotopes. Both a MIF (Δ199Hg) binary mixing approach and the traditional inert element method indicate that the content of Hg derived from the atmosphere distinctly increases with altitude. PMID:24270081

  20. Isotopic signature of N(2)O produced by marine ammonia-oxidizing archaea.

    PubMed

    Santoro, Alyson E; Buchwald, Carolyn; McIlvin, Matthew R; Casciotti, Karen L

    2011-09-01

    The ocean is an important global source of nitrous oxide (N(2)O), a greenhouse gas that contributes to stratospheric ozone destruction. Bacterial nitrification and denitrification are thought to be the primary sources of marine N(2)O, but the isotopic signatures of N(2)O produced by these processes are not consistent with the marine contribution to the global N(2)O budget. Based on enrichment cultures, we report that archaeal ammonia oxidation also produces N(2)O. Natural-abundance stable isotope measurements indicate that the produced N(2)O had bulk δ(15)N and δ(18)O values higher than observed for ammonia-oxidizing bacteria but similar to the δ(15)N and δ(18)O values attributed to the oceanic N(2)O source to the atmosphere. Our results suggest that ammonia-oxidizing archaea may be largely responsible for the oceanic N(2)O source. PMID:21798895

  1. Signatures of shape transitions in odd-A neutron-rich rubidium isotopes

    SciTech Connect

    Rodriguez-Guzman, R.; Sarriguren, P.; Robledo, L. M.

    2010-12-15

    The isotopic evolution of the ground-state nuclear shapes and the systematics of one-quasiproton configurations are studied in odd-A Rubidium isotopes. We use a self-consistent Hartree-Fock-Bogoliubov formalism based on the Gogny energy density functional with two parametrizations, D1S and D1M, and implemented with the equal-filling approximation. We find clear signatures of a sharp shape transition at N=60 in both the charge radii and spin parity of the ground states, which are robust, consistent with each other, and in agreement with experiment. We point out that the combined analysis of these two observables could be used to predict unambiguously new regions where shape transitions might develop.

  2. Study of medical isotope production facility stack emissions and noble gas isotopic signature using automatic gamma-spectra analysis platform

    NASA Astrophysics Data System (ADS)

    Zhang, Weihua; Hoffmann, Emmy; Ungar, Kurt; Dolinar, George; Miley, Harry; Mekarski, Pawel; Schrom, Brian; Hoffman, Ian; Lawrie, Ryan; Loosz, Tom

    2013-04-01

    The nuclear industry emissions of the four CTBT (Comprehensive Nuclear-Test-Ban Treaty) relevant radioxenon isotopes are unavoidably detected by the IMS along with possible treaty violations. Another civil source of radioxenon emissions which contributes to the global background is radiopharmaceutical production companies. To better understand the source terms of these background emissions, a joint project between HC, ANSTO, PNNL and CRL was formed to install real-time detection systems to support 135Xe, 133Xe, 131mXe and 133mXe measurements at the ANSTO and CRL 99Mo production facility stacks as well as the CANDU (CANada Deuterium Uranium) primary coolant monitoring system at CRL. At each site, high resolution gamma spectra were collected every 15 minutes using a HPGe detector to continuously monitor a bypass feed from the stack or CANDU primary coolant system as it passed through a sampling cell. HC also conducted atmospheric monitoring for radioxenon at approximately 200 km distant from CRL. A program was written to transfer each spectrum into a text file format suitable for the automatic gamma-spectra analysis platform and then email the file to a server. Once the email was received by the server, it was automatically analysed with the gamma-spectrum software UniSampo/Shaman to perform radionuclide identification and activity calculation for a large number of gamma-spectra in a short period of time (less than 10 seconds per spectrum). The results of nuclide activity together with other spectrum parameters were saved into the Linssi database. This database contains a large amount of radionuclide information which is a valuable resource for the analysis of radionuclide distribution within the noble gas fission product emissions. The results could be useful to identify the specific mechanisms of the activity release. The isotopic signatures of the various radioxenon species can be determined as a function of release time. Comparison of 133mXe and 133Xe activity

  3. Carbon-Isotopic Dynamics of Streams, Taylor Valley, Antarctica: Biological Effects

    NASA Technical Reports Server (NTRS)

    Neumann, K.; DesMarais, D. J.

    1998-01-01

    We have investigated the role of biological processes in the C-isotopic dynamics of the aquatic ecosystems in Taylor Valley, Antarctica. This cold desert ecosystem is characterized by the complete lack of vascular plants, and the presence of algal mats in ephemeral streams and perennially ice covered lakes. Streams having abundant algal mats and mosses have very low sigma CO2 concentrations, as well as the most depleted delta C-13 values (-4%). Previous work has shown that algal mats in these streams have delta C-13 values averaging -7.01%. These values are similar to those observed in the algal mats in shallow areas of the lakes in Taylor Valley, where CO2 is thought to be colimiting to growth. These low Sigma CO2 concentrations, and delta C(13) signatures heavier than the algal mats, suggest that CO2 may be colimiting in the streams, as well. Streams with little algal growth, especially the longer ones in Fryxell Basin, have higher Sigma CO2 concentrations and much more enriched isotopic signatures (as high as +8%). In these streams, the dissolution of isotopically enriched, cryogenic CaCO3 is probably the major source of dissolved carbonate. The delta C(13) geochemistry of Antarctic streams is radically different from the geochemistry of more temperate streams, as it is not affected by terrestrially produced, isotopically depleted Sigma CO2. These results have important implications for the understanding of "biogenic" carbonate that might have been produced from aquatic ecosystems in the past on Mars.

  4. From the Arctic Lake to the Arctic Ocean: Radiogenic Isotope Signature of Transitional Sediments

    NASA Astrophysics Data System (ADS)

    Poirier, A.; Hillaire-Marcel, C.; Veron, A. J.; Stevenson, R.; Carignan, J.

    2011-12-01

    The Arctic Ocean was once an enclosed basin with fresh surface water conditions during the Paleocene and most of the Eocene epochs (e.g. Moran et al. 2004), until a readjustment in high latitude plate tectonics allowed North Atlantic marine water to flow into the Arctic basin some 36 Ma ago (Poirier and Hillaire-Marcel, 2011). This first input was sufficient to overprint the earlier osmium isotopic composition in the basin (ibid.) and deposit marine sediments on the Lomonosov Ridge between 36 Ma and present day. Here, we present Sr and Pb isotope signatures in the transitional layers of the same ACEX sequence from Lomonosov Ridge (ca. 190 to 210 mcd). Bulk sediment samples were leached prior to total dissolution in order to remove the hydrogeneous Sr fraction of the sediment. The Sr isotopic signature of the residual fraction is thought to reflect the origin of the sedimentary load that was deposited before, during, and after the transition (source tracing). Leaching was not required for the Pb isotope analyses as leached residues and bulk sediments yielded similar isotopic composition for the oxic sediments. Moreover, correction for in-situ production is needed within the anoxic lacustrine section (see below), so bulk sediments were measured. Above and below the lacustrine/marine boundary, we note relatively constant source provenances (or mixture of sources). This implies that the relative contributions from regional detrital sedimentary sources, and thus relative erosion rates over surrounding continents, did not change much on the long term scale. On the other hand, a sharp change in the isotopic compositions highlights the transition level itself, with an abrupt shift to low 87Sr/88Sr isotope compositions and by a smaller excursion in all three 204Pb-normalised lead isotopes compositions (corrected for in-situ decay of U). In the light of the recently revised age of the transitional layer (~36 Ma at the lacustrine/marine transition), this isotopic excursion

  5. A New Method to Quantify the Isotopic Signature of Leaf Transpiration: Implications for Landscape-Scale Evapotranspiration Partitioning Studies

    NASA Astrophysics Data System (ADS)

    Wang, L.; Good, S. P.; Caylor, K. K.

    2010-12-01

    Characterizing the constituent components of evapotranspiration is crucial to better understand ecosystem-level water budgets and water use dynamics. Isotope based evapotranspiration partitioning methods are promising but their utility lies in the accurate estimation of the isotopic composition of underlying transpiration and evaporation. Here we report a new method to quantify the isotopic signature of leaf transpiration under field conditions. This method utilizes a commercially available laser-based isotope analyzer and a transparent leaf chamber, modified from Licor conifer leaf chamber. The method is based on the water mass balance in ambient air and leaf transpired air. We verified the method using “artificial leaves” and glassline extracted samples. The method provides a new and direct way to estimate leaf transpiration isotopic signatures and it has wide applications in ecology, hydrology and plant physiology.

  6. Searching for isovector signatures in the neutron-rich oxygen and calcium isotopes

    NASA Astrophysics Data System (ADS)

    Chen, Wei-Chia; Piekarewicz, J.

    2015-09-01

    We search for potential isovector signatures in the neutron-rich oxygen and calcium isotopes within the framework of a relativistic mean-field theory with an exact treatment of pairing correlations. To probe the isovector sector we calibrate a few relativistic density functionals using the same isoscalar constraints but with one differing isovector assumption. It is found that under certain conditions, the isotopic chain in oxygen can be made to terminate at the experimentally observed 24O isotope and in the case of the calcium isotopes at 60Ca. To produce such behavior, the resulting symmetry energy must be soft, with predicted values for the symmetry energy and its slope at saturation density being J = (30.92 ± 0.47) MeV and L = (51.0 ± 1.5) MeV, respectively. As a consequence, the neutron-skin thickness of 208Pb is rather small: Rskin208 = (0.161 ± 0.011) fm. This same model-labeled "FSUGarnet"-predicts R1.4 = (13.0 ± 0.1) km for the radius of a "canonical" 1.4M⊙ neutron star, yet is also able to support a two-solar-mass neutron star.

  7. Searching for signatures of life on Mars: an Fe-isotope perspective

    PubMed Central

    Anand, M; Russell, S.S; Blackhurst, R.L; Grady, M.M

    2006-01-01

    Recent spacecraft and lander missions to Mars have reinforced previous interpretations that Mars was a wet and warm planet in the geological past. The role of liquid water in shaping many of the surface features on Mars has long been recognized. Since the presence of liquid water is essential for survival of life, conditions on early Mars might have been more favourable for the emergence and evolution of life. Until a sample return mission to Mars, one of the ways of studying the past environmental conditions on Mars is through chemical and isotopic studies of Martian meteorites. Over 35 individual meteorite samples, believed to have originated on Mars, are now available for lab-based studies. Fe is a key element that is present in both primary and secondary minerals in the Martian meteorites. Fe-isotope ratios can be fractionated by low-temperature processes which includes biological activity. Experimental investigations of Fe reduction and oxidation by bacteria have produced large fractionation in Fe-isotope ratios. Hence, it is considered likely that if there is/were any form of life present on Mars then it might be possible to detect its signature by Fe-isotope studies of Martian meteorites. In the present study, we have analysed a number of Martian meteorites for their bulk-Fe-isotope composition. In addition, a set of terrestrial analogue material has also been analysed to compare the results and draw inferences. So far, our studies have not found any measurable Fe-isotopic fractionation in bulk Martian meteorites that can be ascribed to any low-temperature process operative on Mars. PMID:17008212

  8. Searching for signatures of life on Mars: an Fe-isotope perspective.

    PubMed

    Anand, M; Russell, S S; Blackhurst, R L; Grady, M M

    2006-10-29

    Recent spacecraft and lander missions to Mars have reinforced previous interpretations that Mars was a wet and warm planet in the geological past. The role of liquid water in shaping many of the surface features on Mars has long been recognized. Since the presence of liquid water is essential for survival of life, conditions on early Mars might have been more favourable for the emergence and evolution of life. Until a sample return mission to Mars, one of the ways of studying the past environmental conditions on Mars is through chemical and isotopic studies of Martian meteorites. Over 35 individual meteorite samples, believed to have originated on Mars, are now available for lab-based studies. Fe is a key element that is present in both primary and secondary minerals in the Martian meteorites. Fe-isotope ratios can be fractionated by low-temperature processes which includes biological activity. Experimental investigations of Fe reduction and oxidation by bacteria have produced large fractionation in Fe-isotope ratios. Hence, it is considered likely that if there is/were any form of life present on Mars then it might be possible to detect its signature by Fe-isotope studies of Martian meteorites. In the present study, we have analysed a number of Martian meteorites for their bulk-Fe-isotope composition. In addition, a set of terrestrial analogue material has also been analysed to compare the results and draw inferences. So far, our studies have not found any measurable Fe-isotopic fractionation in bulk Martian meteorites that can be ascribed to any low-temperature process operative on Mars. PMID:17008212

  9. Stable Carbon Isotope Record in a Palau Sclerosponge

    NASA Astrophysics Data System (ADS)

    Grottoli, A. G.

    2002-12-01

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

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

    SciTech Connect

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

    1994-12-31

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

  11. Carbon pools and isotopic trends in a hypersaline cyanobacterial mat.

    PubMed

    Wieland, A; Pape, T; Möbius, J; Klock, J-H; Michaelis, W

    2008-03-01

    The fine-scale depth distribution of major carbon pools and their stable carbon isotopic signatures (delta(13)C) were determined in a cyanobacterial mat (Salin-de-Giraud, Camargue, France) to study early diagenetic alterations and the carbon preservation potential in hypersaline mat ecosystems. Particular emphasis was placed on the geochemical role of extracellular polymeric substances (EPS). Total carbon (C(tot)), organic carbon (C(org)), total nitrogen (N(tot)), total hydrolysable amino acids (THAA), carbohydrates, cyanobacteria-derived hydrocarbons (8-methylhexadecane, n-heptadec-5-ene, n-heptadecane) and EPS showed highest concentrations in the top millimetre of the mat and decreased with depth. The hydrocarbons attributed to cyanobacteria showed the strongest decrease in concentration with depth. This correlated well with the depth profiles of oxygenic photosynthesis and oxygen, which were detected in the top 0.6 and 1.05 mm, respectively, at a high down-welling irradiance (1441 micromol photons m(-2) s(-1)). At depths beneath the surface layer, the C(org) was composed mainly of amino acids and carbohydrates. A resistance towards microbial degradation could have resulted from interactions with diverse functional groups present in biopolymers (EPS) and with minerals deposited in the mat. A (13)C enrichment with depth for the total carbon pool (C(tot)) was observed, with delta(13)C values ranging from -16.3 per thousand at the surface to -11.3 per thousand at 9-10 mm depth. Total lipids depicted a delta(13)C value of -17.2 per thousand in the top millimetre and then became depleted in (13)C with depth (-21.7 to -23.3 per thousand). The delta(13)C value of EPS varied only slightly with depth (-16.1 to -17.3 per thousand) and closely followed the delta(13)C value of C(org) at depths beneath 4 mm. The EPS represents an organic carbon pool of preservation potential during early stages of diagenesis in recent cyanobacterial mats as a result of a variety of possible

  12. Carbon Biogeochemistry: A Stable Isotope Approach to Trophic Dynamics in an Indian Coastal Ecosystem

    NASA Astrophysics Data System (ADS)

    Mathukumalli, B.; Alagappan, R.

    2005-12-01

    Stable isotope(δ13C & δ15N) approach was applied to understand carbon biogeochemistry and trophic dynamics in an Indian coastal mangrove wetland. The δ13C and δ15N values of potential nutrient sources (mangrove plant leaves, lichen, sediment and suspended material) and in seven species of consumers (invertebrates) were measured. The value of δ13C and δ15N isotopes of different potential nutrient sources and the consumers determine the sources of nutrients for the invertebrate consumer community of the mangrove. There is a significant variation in the stable carbon in the nutrient sources; however, δ15N signatures were not significantly different among the different potential nutrient sources. Organic matter in the sediments under the mangrove vegetation was characterized by relatively negatively fractionated and moderately high C:N ratios, indicating that mangrove derived organic matter was the principal diet source for the invertebrate consumer communities in the mangrove ecosystem. Invertebrates in the mangrove showed a wide range of δ13C signatures and are enriched relative to the mangrove leaf stable isotope values. Micro-environmental differences certainly drive the variability in the nutrient sources and consumable nature among the different regions of the ecosystem. Therefore, further research is needed to determine whether carbon assimilation is different from one zone to another.

  13. Isotope composition of carbon in amino acids of solid bitumens

    NASA Astrophysics Data System (ADS)

    Shanina, S. N.; Bushnev, D. A.

    2014-06-01

    Primary data are presented on the isotope composition of carbon in individual amino acids from solid bitumens and several biological objects. The amino acids of biological objects are characterized by wide variations of the isotope composition of carbon. This fact occurs owing to the difference in biochemical paths of metabolism resulting in the synthesis of individual amino acids. The δ13C values are somewhat decreased for individual amino acids in asphaltenes, varying from -7.7 to -31.7‰. The carbon of amino acids is weighted in kerits from Bad'el' compared to asphaltenes. All the natural bitumens retain the characteristic trend for natural substances: the isotopically heavy and light amino acids by carbon are glycine and leucine, respectively. The isotope composition of amino-acid carbon is lightened compared to natural bitumens in the samples formed under a pronounced thermal impact (asphalt-like crust and kirishite).

  14. Biomarker and molecular isotope approaches to deconvolve the terrestrial carbon isotope record: modern and Eocene calibrations

    NASA Astrophysics Data System (ADS)

    Diefendorf, A. F.; Freeman, K. H.; Wing, S.; Currano, E. D.

    2010-12-01

    Climate, biome, and plant community are important predictors of carbon isotope patterns recorded in leaves and leaf waxes. However, signatures recorded by terrestrial organic carbon and lipids that have mixed floral sources (e.g., n-alkanes) potentially reflect both plant community changes and climate. More taxonomically specific proxies for plants (i.e., di- and tri-terpenoids for conifers and angiosperms, respectively), can help to resolve the relative influences of changing community and climate, provided differences in biomarker production and lipid biosynthetic fractionation among plants can be better constrained. We present biomarker abundance and carbon isotope values for lipids from leaves, branches and bark of 44 tree species, representing 21 families including deciduous and evergreen conifers and angiosperms. n-alkane production differs greatly between conifer and angiosperm leaves. Both deciduous and evergreen angiosperms make significantly more n-alkanes than conifers, with n-alkanes not detected in over half of the conifers in our study. Terpenoid abundances scale strongly with leaf habit: evergreen species have significantly higher abundances. We combine these relative differences in lipid production with published estimates of fluxes for leaf litter from conifer and angiosperm trees to develop a new proxy approach for estimating paleo plant community inputs to ancient soils and sediments. To test our modern calibration results, we have evaluated n-alkanes and terpenoids from laterally extensive (~18 km) carbonaceous shales and mudstones in Eocene sediments (52.6 Ma) at Fifteenmile Creek in the Bighorn Basin (WY, USA). Our terpenoid-based proxy predicts on average a 40% conifer community, which is remarkably close in agreement with a fossil-based estimate of 36%. n-alkane carbon isotope fractionation (leaf-lipid) differs among plant types, with conifer n-alkanes about 2-3‰ 13C enriched relative to those in angiosperms. Since conifer leaves are

  15. Ancient carbonate sedimentary signature in the Hawaiian plume: Evidence from Mahukona volcano, Hawaii

    NASA Astrophysics Data System (ADS)

    Huang, Shichun; Abouchami, Wafa; Blichert-Toft, Janne; Clague, David A.; Cousens, Brian L.; Frey, Frederick A.; Humayun, Munir

    2009-08-01

    Lavas from Mahukona, a small Hawaiian volcano on the Loa trend, exhibit major and trace element abundance variations exceeding those in lavas from large Hawaiian shields, such as Mauna Loa and Mauna Kea. Mahukona lavas define three geochemically distinct groups of tholeiitic shield basalt and a transitional group of postsshield basalt. At 10% MgO the tholeiitic groups range from 9 to 12% CaO; such differences in CaO can reflect partial melts derived from garnet pyroxenite (low CaO) and peridotite (high CaO), but the negative CaO-Yb (both at 10% MgO) trend formed by Mahukona lavas is inconsistent with this explanation. Within Mahukona lavas, radiogenic Nd-Hf-Pb isotopic ratios are highly correlated with each other; however, 87Sr/86Sr is decoupled from these radiogenic isotopic ratios. Rather, 87Sr/86Sr is correlated with trace element abundance ratios involving Sr, and importantly, Mahukona lavas define a negative Rb/Sr-87Sr/86Sr trend, implying that a Sr-rich source component characterized by high 87Sr/86Sr is important in the petrogenesis of Mahukona lavas. We infer that this Sr-rich source component is recycled ancient carbonate-rich sediments. Intershield heterogeneity among Hawaiian shields also shows a negative Rb/Sr-87Sr/86Sr trend. For example, Makapuu-stage Koolau lavas have higher 87Sr/86Sr but lower Rb/Sr than Mauna Kea lavas. Consequently, we infer that a recycled ancient carbonate-rich sedimentary source component is important in the Hawaiian plume. Although most lavas from Loa and Kea trend volcanoes define distinct fields in isotopic ratios of Sr, Nd, Hf, and Pb, the majority of Mahukona lavas have isotopic ratios at the boundary between the fields defined by Loa and Kea trend lavas. However, a subgroup of Mahukona shield lavas have Kea-like isotopic and trace element signatures, an observation that can be explained by vertical heterogeneity in a bilaterally asymmetrical plume.

  16. The origin of groundwater in Zhangye Basin, northwestern China, using isotopic signature

    NASA Astrophysics Data System (ADS)

    Chen, Jiansheng; Liu, Xiaoyan; Sun, Xiaoxu; Su, Zhiguo; Yong, Bin

    2014-03-01

    Zhangye Basin, in arid northwestern China, has recently been repeatedly flooded by rising groundwater. Isotope signatures of sampled waters gained insight into the recharge source of the groundwater. The summer Heihe River water and most of the spring water in Zhangye and Yongchang basins plotted above the global meteoric water line (GMWL) on the δ18O-δD plot. The spring water had R/Ra ratio >1, low TDS and high tritium, which indicates origin from Qilian Mountain glacier meltwater. The groundwater of Qilian Mountains was transported to the Hexi Corridor (in which Zhangye Basin is located) through underground fault zones. Additionally, some of the groundwater in the alluvial plain, and all spring water surrounding Zhangye Basin, plotted below the GMWL on the δ18O-δD plot along an evaporation line, and had R/Ra ratio < 1 and high TDS. It is proposed that the Tibetan rivers or lakes source the Hexi Corridor groundwater through either the NE-trending or NW-trending buried fault zones. The isotopic signatures presented as part of this study rule out the conventional viewpoint that groundwater of the Zhangye Basin was recharged by local precipitation and infiltration of Heihe River water on the alluvial plain.

  17. 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.

  18. Mercury isotope signatures of seawater discharged from a coal-fired power plant equipped with a seawater flue gas desulfurization system.

    PubMed

    Lin, Haiying; Peng, Jingji; Yuan, Dongxing; Lu, Bingyan; Lin, Kunning; Huang, Shuyuan

    2016-07-01

    Seawater flue gas desulfurization (SFGD) systems are commonly used to remove acidic SO2 from the flue gas with alkaline seawater in many coastal coal-fired power plants in China. However, large amount of mercury (Hg) originated from coal is also transferred into seawater during the desulfurization (De-SO2) process. This research investigated Hg isotopes in seawater discharged from a coastal plant equipped with a SFGD system for the first time. Suspended particles of inorganic minerals, carbon residuals and sulfides are enriched in heavy Hg isotopes during the De-SO2 process. δ(202)Hg of particulate mercury (PHg) gradually decreased from -0.30‰ to -1.53‰ in study sea area as the distance from the point of discharge increased. The results revealed that physical mixing of contaminated De-SO2 seawater and uncontaminated fresh seawater caused a change in isotopic composition of PHg isotopes in the discharging area; and suggested that both De-SO2 seawater and local background contributed to PHg. The impacted sea area predicted with isotopic tracing technique was much larger than that resulted from a simple comparison of pollutant concentration. It was the first attempt to apply mercury isotopic composition signatures with two-component mixing model to trace the mercury pollution and its influence in seawater. The results could be beneficial to the coal-fired plants with SFGD systems to assess and control Hg pollution in sea area. PMID:27155100

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    Tibetan Plateau is located at a mountain region isolated from direct anthropogenic sources. Mercury concentrations and stable isotopes of carbon, nitrogen, and mercury were analyzed in sediment and biota for Nam Co and Yamdrok Lake. Biotic mercury concentrations and high food web magnification factors suggested that Tibetan Plateau is no longer a pristine site. The primary source of methylmercury was microbial production in local sediment despite the lack of direct methylmercury input. Strong ultraviolet intensity led to extensive photochemical reactions and up to 65% of methylmercury in water was photo-demethylated before entering the food webs. Biota displayed very high Δ199Hg signatures, with some highest value (8.6%) ever in living organisms. The δ202Hg and Δ199Hg in sediment and biotic samples increased with trophic positions (δ15N) and %methylmercury. Fish total length closely correlated to δ13C and Δ199Hg values due to dissimilar carbon sources and methylmercury pools in different living waters. This is the first mercury isotope study on high altitude lake ecosystems that demonstrated specific isotope fractionations of mercury under extreme environmental conditions.

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

    PubMed

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

    2016-01-01

    Tibetan Plateau is located at a mountain region isolated from direct anthropogenic sources. Mercury concentrations and stable isotopes of carbon, nitrogen, and mercury were analyzed in sediment and biota for Nam Co and Yamdrok Lake. Biotic mercury concentrations and high food web magnification factors suggested that Tibetan Plateau is no longer a pristine site. The primary source of methylmercury was microbial production in local sediment despite the lack of direct methylmercury input. Strong ultraviolet intensity led to extensive photochemical reactions and up to 65% of methylmercury in water was photo-demethylated before entering the food webs. Biota displayed very high Δ(199)Hg signatures, with some highest value (8.6%) ever in living organisms. The δ(202)Hg and Δ(199)Hg in sediment and biotic samples increased with trophic positions (δ(15)N) and %methylmercury. Fish total length closely correlated to δ(13)C and Δ(199)Hg values due to dissimilar carbon sources and methylmercury pools in different living waters. This is the first mercury isotope study on high altitude lake ecosystems that demonstrated specific isotope fractionations of mercury under extreme environmental conditions. PMID:27151563

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

    PubMed Central

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

    2016-01-01

    Tibetan Plateau is located at a mountain region isolated from direct anthropogenic sources. Mercury concentrations and stable isotopes of carbon, nitrogen, and mercury were analyzed in sediment and biota for Nam Co and Yamdrok Lake. Biotic mercury concentrations and high food web magnification factors suggested that Tibetan Plateau is no longer a pristine site. The primary source of methylmercury was microbial production in local sediment despite the lack of direct methylmercury input. Strong ultraviolet intensity led to extensive photochemical reactions and up to 65% of methylmercury in water was photo-demethylated before entering the food webs. Biota displayed very high Δ199Hg signatures, with some highest value (8.6%) ever in living organisms. The δ202Hg and Δ199Hg in sediment and biotic samples increased with trophic positions (δ15N) and %methylmercury. Fish total length closely correlated to δ13C and Δ199Hg values due to dissimilar carbon sources and methylmercury pools in different living waters. This is the first mercury isotope study on high altitude lake ecosystems that demonstrated specific isotope fractionations of mercury under extreme environmental conditions. PMID:27151563

  2. Carbon Monoxide Isotopes: On the Trail of Galactic Chemical Evolution

    NASA Technical Reports Server (NTRS)

    Langer, W.

    1995-01-01

    From the early days of the discovery of radio emission from carbon monoxide it was realized that it offered unusual potential for under- standing the chemical evolution of the Galaxy and external galaxies through measurements of molecular isotopes. These results bear on stellar nucleosynthesis, star formation, and gases in the interstellar medium. Progress in isotopic radio measurements will be reviewed.

  3. Probing the Isotopic Composition of Surface Waters Across Isotopic Extremes of Cryogenian Carbonates

    NASA Astrophysics Data System (ADS)

    Bosak, T.; Matys, E. D.; Bird, L. R.; Macdonald, F. A.; Freeman, K. H.

    2012-12-01

    Neoproterozoic carbonate strata record unusually large and positive carbon isotope values (δ13Ccarb from 4 to 10 per mil), and stratigraphically extensive large negative carbon isotope excursions (δ13Ccarb < -5 per mil). Mechanisms that account for the magnitude, the facies distribution and the global abundance of these isotopically extreme carbonates in Neoproterozoic successions remain poorly understood. Little is also known about organisms and metabolisms that cycled carbon in these carbonate strata, because they rarely contain well-preserved organic-rich fossils. To better understand the cycling of carbon during the deposition of the 715-635 Ma Tayshir member of the Tsagaan Oloom Formation, Mongolia, we analyzed δ13Cfossil of two types of organic fossils that occur in 13C- enriched carbonates (+ 5 to 9.9 per mil) and within 13C-depleted carbonates of the Tayshir anomaly (-3 to -6 per mil). Because these organic microfossils are remarkably similar to the tests of modern planktonic, herbivorous tintinnid ciliates and benthic macroscopic red algae, respectively, they can be used as tracers of organic matter production in surface waters. Fossil tests were extracted by acid maceration, cleaned and analyzed morphologically and microscopically. Their carbon isotopic composition was measured using a nano-scaled elemental analyzer inlet (nano-EA-IRMS), with ±1 per mil analytical precision. To date, we analyzed 12 samples of 100-150 organic tests, representing 3 different fossiliferous parts of the Tayshir anomaly (δ13Ccarb < -3 per mil) and 3 different strata predating the Tayshir anomaly (δ13Ccarb > +5 per mil), respectively. More samples, including those of fossil algae and tests from the carbonate strata overlying the Tayshir anomaly, are currently being analyzed. Initial data reveal a rather constant isotopic composition of organic carbon in fossil tests (δ13Cfossil), with values of -23 ±1 per mil both within 13C-enriched and 13C-depleted carbonates. The

  4. BIODEGRADATION OF FLUORANTHENE AS MONITORED USING STABLE CARBON ISOTOPES

    EPA Science Inventory

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

  5. Carbon Isotope Composition of Mysids at a Terrestrial-Marine Ecotone, Clayoquot Sound, British Columbia, Canada

    NASA Astrophysics Data System (ADS)

    Mulkins, L. M.; Jelinski, D. E.; Karagatzides, J. D.; Carr, A.

    2002-04-01

    The relative contribution of summertime terrestrial versus marine carbon to an estuary on coastal British Columbia, Canada was explored using stable carbon isotopic (δ 13C values) analysis of mysid crustaceans (Malacostraca: Peracarida: Mysidacea). We hypothesized that landscape linkages between the forested upland and adjacent inshore marine waters, via river, groundwater and overland flows, may influence carbon content and metabolism in the coastal zone. We sampled 14 stations spatially distributed in a grid and found δ 13C compositions of mysids ranged from -15·2 to -18·4‰. There was, however, no obvious spatial distribution of δ 13C values relative to the estuarine gradient in Cow Bay. Heavy tidal mixing is suggested to disperse marine and terrestrial carbon throughout the entire bay. From a temporal perspective however, mysid δ 13C signatures became enriched over the sampling period (mid-July to mid-August), which is representative of a stronger marine influence. This may arise because mysids are exposed to greater marine-derived carbon sources later in the summer, a decrease in freshwater input (and hence terrestrial carbon), changes in phytoplankton or macrophyte community structure, or that mysids preferentially feed on marine food sources. Overall, the recorded isotopic values are characteristic of marine organic carbon signatures suggesting that in summer, despite the proximity to shore, little or no terrestrial carbon penetrates the food web at the trophic level of mysids. This notwithstanding we believe there is a strong need for additional study of carbon flows at the marine-terrestrial interface, especially for disturbed watersheds.

  6. Integrating Ontogenetic Shift, Growth and Mortality to Determine a Species' Ecological Role from Isotopic Signatures

    PubMed Central

    Fontoura, Nelson F.; Rodrigues, Lúcia R.; Batista, Cibele B.; Persch, Tanilene S. P.; Janowicz, Mariola E.

    2015-01-01

    Understanding species linkages and energy transfer is a basic goal underlying any attempt at ecosystem analysis. Although the first food-web studies were based on gut contents of captured specimens, the assessment of stable isotopes, mainly δ13C and δ15N, has become a standard methodology for wide-range analyses in the last 30 years. Stable isotopes provide information on the trophic level of species, food-web length, and origin of organic matter ingested by consumers. In this study, we analyzed the ontogenetic variability of δ13C and δ15N obtained from samples of three Neotropical fish species: silver sardine (Lycengraulis grossidens, n=46), white lambari (Cyanocharax alburnus, n= 26), and the red-tail lambari (Astyanax fasciatus, n=23) in Pinguela Lagoon, southern Brazil. We developed a new metric, called the Weighted Isotopic Signature (φ 15N or φ 13C, ‰), that incorporates ontogenetic variability, body growth, and natural mortality into a single number. PMID:25996777

  7. Pushing back the frontiers of mercury speciation using a combination of biomolecular and isotopic signatures: challenge and perspectives.

    PubMed

    Pedrero, Zoyne; Donard, Olivier F X; Amouroux, David

    2016-04-01

    Mercury (Hg) pollution is considered a major environmental problem due to the extreme toxicity of Hg. However, Hg metabolic pathways in biota remain elusive. An understanding of these pathways is crucial to elucidating the (eco)toxic effects of Hg and its biogeochemical cycle. The development of a new analytical methodology based on both speciation and natural isotopic fractionation represents a promising approach for metabolic studies of Hg and other metal(loid)s. Speciation provides valuable information about the reactivity and potential toxicity of metabolites, while the use of natural isotopic signature analysis adds a complementary dynamic dimension that allows the life history of the target element to be probed, the source of the target element (i.e., the source of pollution) to be identified, and reactions to be tracked. The resulting combined (bio)molecular and isotopic signature affords precious insight into the behavior of Hg in biota and Hg detoxification mechanisms. In the long term, this highly innovative methodology could be used in life and environmental science studies of metal(loid)s to push back the frontiers of our knowledge in this field. This paper summarizes the current status of the application of Hg speciation and the isotopic signature of Hg at the biomolecular level in living organisms, and discusses potential future uses of this combination of techniques. Graphical Abstract Application of Hg speciation and the isotopic signature of Hg to enhance our understanding of the roles of Hg in metabolic, toxicological, and environmental processes. PMID:26753975

  8. Bulk Stable Isotope Analysis of Carbon from Solids and Liquids using an Elemental Analyzer Coupled to a Wavelength-Scanned Cavity Ring-Down Spectrophotometer

    NASA Astrophysics Data System (ADS)

    Saad, N.; Rella, C.; van Pelt, A.

    2009-04-01

    We report here on the novel employment of a small footprint Wavelength-Scanned Cavity Ring-Down Spectrometer (WS-CRDS) interfaced to an elemental analyzer for the measurement of the bulk isotopic carbon signature in plants and food products. The current system provides an inexpensive alternative with unparalleled ease-of-use as compared to standard methods using the more complex analytical instrumentation of isotope ratio mass spectrometry. A precision of carbon isotopic ratio measurements of less than 1 permil was achieved in minutes of measurement time. Such precision readily distinguishes the isotopic carbon signatures of a variety of environmental and agricultural products from different origins, providing information about food authenticity and climate changes effect on plant physiology.

  9. Sulfur and carbon isotope biogeochemistry of a rewetted brackish fen

    NASA Astrophysics Data System (ADS)

    Koebsch, Franziska; Gehre, Matthias; Winkel, Matthias; Koehler, Stefan; Koch, Marian; Jurasinski, Gerald; Spitzy, Alejandro; Liebner, Susanne; Sachs, Torsten; Schmiedinger, Iris; Kretzschmann, Lisett; Saborowski, Anke; Böttcher, Michael E.

    2015-04-01

    Coastal wetlands are at the interface between terrestrial freshwater and marine and exhibit very specific biogeochemical conditions. Intermittent sea water intrusion affects metabolic pathways, i. e. anaerobic carbon metabolism is progressively dominated by sulfate reduction with lower contribution of methanogenesis whilst methane production is increasingly shifted from acetoclastic to hydrogenotrophic. Due to expanding anthropogenic impact a large proportion of coastal ecosystems is degraded with severe implications for the biogeochemical processes. We use concentration patterns and stable isotope signatures of water, sulfate, dissolved carbonate, and methane (δ2H, δ13C, δ18O, δ34S) to investigate the S and C metabolic cycle in a rewetted fen close to the southern Baltic Sea border. Such studies are crucial to better predict dynamic ecosystem feedback to global change like organic matter (OM) decomposition or greenhouse gas emissions. Yet, little is known about the metabolic pathways in such environments. The study site is part of the TERENO Observatory "Northeastern German Lowlands' and measurements of methane emissions have run since 2009. High methane fluxes up to 800 mg m-2 hr-1 indicate that methanogenesis is the dominant C metabolism pathway despite of high sulfate concentrations (up to 37 mM). The presented data are part of a comprehensive biogeochemical investigation that we conducted in autumn 2014 and that comprises 4 pore water profiles and sediment samples within a transect of 300-1500 m distance to the Baltic Sea. Depth of organic layers ranged from 25 to 140 cm with high OM contents (up to 90 dwt.%). Sulfate/chloride ratios in the pore waters were lower than in the Baltic Sea for most sites and sediment depths indicated a substantial net sulfate loss. Sulfide concentrations were negligible at the top and increased parallel to the sulfate concentrations with depth to values of up to 0.3 mM. One pore water profiles situated 1150 m from the Baltic

  10. Isotopic fractionation of alkali earth metals during carbonate precipitation

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  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. Observations of Carbon Isotopic Fractionation in Interstellar Formaldehyde

    NASA Technical Reports Server (NTRS)

    Wirstrom, E. S.; Charnley, S. B.; Geppert, W. D.; Persson, C. M.

    2012-01-01

    Primitive Solar System materials (e.g. chondrites. IDPs, the Stardust sample) show large variations in isotopic composition of the major volatiles (H, C, N, and O ) even within samples, witnessing to various degrees of processing in the protosolar nebula. For ex ample. the very pronounced D enhancements observed in IDPs [I] . are only generated in the cold. dense component of the interstellar medium (ISM), or protoplanetary disks, through ion-molecule reactions in the presence of interstellar dust. If this isotopic anomaly has an interstellar origin, this leaves open the possibility for preservation of other isotopic signatures throughout the form ation of the Solar System. The most common form of carbon in the ISM is CO molecules, and there are two potential sources of C-13 fractionation in this reservoir: low temperature chemistry and selective photodissociation. While gas-phase chemistry in cold interstellar clouds preferentially incorporates C-13 into CO [2], the effect of self-shielding in the presence of UV radiation instead leads to a relative enhancement of the more abundant isotopologue, 12CO. Solar System organic material exhibit rather small fluctuations in delta C-13 as compared to delta N-15 and delta D [3][1], the reason for which is still unclear. However, the fact that both C-13 depleted and enhanced material exists could indicate an interstellar origin where the two fractionation processes have both played a part. Formaldehyde (H2CO) is observed in the gas-phase in a wide range of interstellar environments, as well as in cometary comae. It is proposed as an important reactant in the formation of more complex organic molecules in the heated environments around young stars, and formaldehyde polymers have been suggested as the common origin of chondritic insoluable organic matter (IOM) and cometary refractory organic solids [4]. The relatively high gas-phase abundance of H2CO observed in molecular clouds (10(exp- 9) - 10(exp- 8) relative to H2) makes

  13. 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.

  14. The stable isotopic signature of biologically produced molecular hydrogen (H2)

    NASA Astrophysics Data System (ADS)

    Walter, S.; Laukenmann, S.; Stams, A. J. M.; Vollmer, M. K.; Gleixner, G.; Röckmann, T.

    2011-12-01

    Biologically produced molecular hydrogen (H2) is characterized by a very strong depletion in deuterium. Although the biological source to the atmosphere is small compared to photochemical or combustion sources, it makes an important contribution to the global isotope budget of molecular hydrogen (H2). Large uncertainties exist in the quantification of the individual production and degradation processes that contribute to the atmospheric budget, and isotope measurements are a tool to distinguish the contributions from the different sources. Measurements of δD from the various H2 sources are scarce and for biologically produced H2 only very few measurements exist. Here the first systematic study of the isotopic composition of biologically produced H2 is presented. We investigated δD of H2 produced in a biogas plant, covering different treatments of biogas production, and from several H2 producing microorganisms such as bacteria or green algae. A Keeling plot analysis provides a robust overall source signature of δD = -712‰ (±13‰) for the samples from the biogas reactor (at 38 °C, δDH2O = 73.4‰), with a fractionation constant ϵH2-H2O of -689‰ (±20‰). The pure culture samples from different microorganisms give a mean source signature of δD = -728‰ (±39‰), and a fractionation constant ϵH2-H2O of -711‰ (±45‰) between H2 and the water, respectively. The results confirm the massive deuterium depletion of biologically produced H2 as was predicted by calculation of the thermodynamic fractionation factors for hydrogen exchange between H2 and water vapor. As expected for a thermodynamic equilibrium, the fractionation factor is largely independent of the substrates used and the H2 production conditions. The predicted equilibrium fractionation coefficient is positively correlated with temperature and we measured a change of 2.2‰/°C between 45 °C and 60 °C. This is in general agreement with the theoretical predictions. Our

  15. Hydrogen and carbon isotope systematics in hydrogenotrophic methanogenesis under H2-limited and H2-enriched conditions: implications for the origin of methane and its isotopic diagnosis

    NASA Astrophysics Data System (ADS)

    Okumura, Tomoyo; Kawagucci, Shinsuke; Saito, Yayoi; Matsui, Yohei; Takai, Ken; Imachi, Hiroyuki

    2016-12-01

    Hydrogen and carbon isotope systematics of H2O-H2-CO2-CH4 in hydrogenotrophic methanogenesis and their relation to H2 availability were investigated. Two H2-syntrophic cocultures of fermentatively hydrogenogenic bacteria and hydrogenotrophic methanogens under conditions of <102 Pa-H2 and two pure cultures of hydrogenotrophic methanogens under conditions of 105 Pa-H2 were tested. Carbon isotope fractionation between CH4 and CO2 during hydrogenotrophic methanogenesis was correlated with pH2, as indicated in previous studies. The hydrogen isotope ratio of CH4 produced during rapid growth of the thermophilic methanogen Methanothermococcus okinawensis under high pH2 conditions ( 105 Pa) was affected by the isotopic composition of H2, as concluded in a previous study of Methanothermobacter thermautotrophicus. This " {δ D}_{{H}_2} effect" is a possible cause of the diversity of previously reported values for hydrogen isotope fractionation between CH4 and H2O examined in H2-enriched culture experiments. Hydrogen isotope fractionation between CH4 and H2O, defined by (1000 + {δ D}_{{CH}_4} )/(1000 + {δ D}_{{H}_2O} ), during hydrogenotrophic methanogenesis of the H2-syntrophic cocultures was in the range 0.67-0.69. The hydrogen isotope fractionation of our H2-syntrophic dataset overlaps with those obtained not only from low- pH2 experiments reported so far but also from natural samples of "young" methane reservoirs (0.66-0.74). Conversely, such hydrogen isotope fractionation is not consistent with that of "aged" methane in geological samples (≥0.79), which has been regarded as methane produced via hydrogenotrophic methanogenesis from the carbon isotope fractionation. As a possible process inducing the inconsistency in hydrogen isotope signatures between experiments and geological samples, we hypothesize that the hydrogen isotope signature of CH4 imprinted at the time of methanogenesis, as in the experiments and natural young methane, may be altered by diagenetic hydrogen

  16. Abiogenic hydrocarbon isotopic signatures in granitic rocks: Identifying pathways of formation

    NASA Astrophysics Data System (ADS)

    Potter, Joanna; Salvi, Stefano; Longstaffe, Fred J.

    2013-12-01

    The stability and isotopic composition of hydrocarbons formed in the mantle are controversial subjects. Knowing the range in isotopic compositions of abiogenically-derived hydrocarbons is important for recognising biological signatures in ancient and extra-terrestrial materials. In an effort to enhance this database, stable isotope results are reported here for hydrocarbon-bearing fluid inclusions hosted in two peralkaline igneous complexes from Lovozero, Russia and Strange Lake, Canada. Based on the distribution of isotopic compositions, we propose three pathways for abiogenically-generated hydrocarbons. Type-1 (δ13CCH4 > δ13CCO2 and δ13CC2 +) represents mantle-derived hydrocarbons generated in equilibrium with hyperagpaitic magmas in the upper mantle, and suggests that mantle CH4 and C2H6δ13C and δ2H could have values of ~ - 5.3 and ~ - 112‰, and ~ - 10.8 and - 162‰, respectively. Type-2 (δ13CCO2 > δ13CCH4 > δ13CC2 +) represents Fischer-Tropsch-type hydrocarbon generation in quartz-bearing peralkaline rocks with CO2 as the initial magmatic gas phase. For Type-2, δ13CCO2 values are ~ - 2‰, whereas δ13CCH4 and δ2HCH4 values range from - 32 to - 20‰ and - 170 and - 160‰, respectively. The δ13CC2H6 values are slightly lower than associated δ13CCH4 values. Type-3 (δ13CCO2 > δ13CCH4 < δ13CC2 +) represents an overprint of Type-2, formed during low temperature alteration of quartz-bearing peralkaline rocks. Here, δ13CCO2 values are variable, - 14.0 to - 9.5‰, δ13CCH4 values range from - 30.8 to - 20.8‰ while δ13CC2H6 values are higher than associated δ13CCH4 values. Both Type-2 and Type-3 isotopic compositions mimic patterns normally considered to be thermogenic in origin, thus demonstrating that isotopic data alone cannot be used reliably to distinguish between hydrocarbons of abiogenic versus biogenic origin.

  17. Locations of marine animals revealed by carbon isotopes.

    PubMed

    MacKenzie, Kirsteen M; Palmer, Martin R; Moore, Andy; Ibbotson, Anton T; Beaumont, William R C; Poulter, David J S; Trueman, Clive N

    2011-01-01

    Knowing the distribution of marine animals is central to understanding climatic and other environmental influences on population ecology. This information has proven difficult to gain through capture-based methods biased by capture location. Here we show that marine location can be inferred from animal tissues. As the carbon isotope composition of animal tissues varies with sea surface temperature, marine location can be identified by matching time series of carbon isotopes measured in tissues to sea surface temperature records. Applying this technique to populations of Atlantic salmon (Salmo salar L.) produces isotopically-derived maps of oceanic feeding grounds, consistent with the current understanding of salmon migrations, that additionally reveal geographic segregation in feeding grounds between individual philopatric populations and age-classes. Carbon isotope ratios can be used to identify the location of open ocean feeding grounds for any pelagic animals for which tissue archives and matching records of sea surface temperature are available. PMID:22355540

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

    PubMed

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

    2012-03-01

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

  19. The carbon isotopes ratio and trace metals content determinations in some Transylvanian fruit juices

    NASA Astrophysics Data System (ADS)

    Dehelean, A.; Magdas, D. A.; Cristea, G.

    2012-02-01

    This work presents a preliminary study on the carbon isotope signature and trace metal content investigated on the soil-plant-fruit pulp chain. The samples were collected from two Transylvanian areas namely Alba and Salaj. The average value of the δ13C at the soil surface was around δ13C ≈ -27%° and important differences of the δ13C values between the two studied areas were not observed. Meanwhile, differences between fruit pulp of grape juice and the pulp of pear juice relived a difference of about 1.5%° for δ13C values.

  20. Carbon and oxygen isotope fractionation in dense interstellar clouds

    NASA Technical Reports Server (NTRS)

    Langer, W. D.; Graedel, T. E.; Frerking, M. A.; Armentrout, P. B.

    1984-01-01

    It is pointed out that isotope fractionation as a result of chemical reactions is due to the small zero-point energy differences between reactants and products of isotopically distinct species. Only at temperatures near absolute zero does this energy difference become significant. Favorable conditions for isotope fractionation on the considered basis exist in space within dense interstellar clouds. Temperatures of approximately 10 K may occur in these clouds. Under such conditions, ion-molecule reactions have the potential to distribute isotopes of hydrogen, carbon, oxygen unequally among the interstellar molecules. The present investigation makes use of a detailed model of the time-dependent chemistry of dense interstellar clouds to study cosmological isotope fractionation. Attention is given to fractionation chemistry and the calculation of rate parameters, the isotope fractionation results, and a comparison of theoretical results with observational data.

  1. [Carbon isotope fractionation inplants]. Final report

    SciTech Connect

    O`Leary, M.H.

    1990-12-31

    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.

  2. A carbon and nitrogen isotope study of carbonaceous vein material in ureilite meteorites

    NASA Technical Reports Server (NTRS)

    Russell, S. S.; Arden, J. W.; Franchi, I. A.; Pillinger, C. T.

    1993-01-01

    The ureilite meteorite group is known to be rich in carbon in the form of graphite/diamond veins that are associated with planetary type noble gases. This paper reports preliminary data from a systematic study of the carbon and nitrogen isotopic composition of this carbonaceous vein material. A previous study focused on the whole rock signatures and reported that the carbon inventory appeared to be dominated by the graphitic/diamond intergrowths, whereas the nitrogen was clearly composed of several distinct components including one that was isotopically light, possibly associated with the carbonaceous material. Recent studies have demonstrated that diamonds in the solar system formed in many different environments. C and N measurements from ureilitic diamond made in a similar way would be a useful addition to this overall study. The methods used for isolating diamonds of possible presolar origin from primitive meteorites are equally applicable to the processing of carbon bearing components in the ureilite group so that their stable isotopic composition can be determined. Herein we discuss conjoint C and N stepped combustion measurements made on crushed whole rock ureilite samples that have been treated with 1M HCl/9M HF to dissolve silicate and free metal. In addition, two samples have been further treated with oxidizing acids to leave a diamond rich residue.

  3. Textural and Carbon Isotopic Analyses of Modern Carbonate Microbialites: Possible Ancient and Martian Analogs

    NASA Technical Reports Server (NTRS)

    Thompson, Joel B.

    1998-01-01

    Many modem and ancient carbonate deposits around the world have been recognized as microbial buildups or microbialites. Ancient microbialite structures have been divided into two basic categories based on their internal fabric or texture. They include stromatolites which have a predominantly laminated internal fabric and thrombolites which have an open-porous clotted fabric, that lacks laminae. The origin of these two basic microbial fabrics is still being debated in the literature. Understanding the origin and the various microorganisms involved in forming these modem fabrics is the key to the interpretation of similar fabrics in ancient and possibly Martian rocks. Therefore, detailed studies are needed on the microbiological makeup and origin of the fabrics in modem microbialites. Such studies may serve as analogs for ancient and Martian microbialites in the future. The purpose of this study is to examine the textures and carbon isotopic signatures of the following modem microbialites from the Bahamas: 1) a modem subtidal microbialite from Iguana Cay, Bahamas and 2) a modem microbial mat (stromatolite) from a hypersaline pond on Lee Stocking Island, Bahamas.

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

    NASA Astrophysics Data System (ADS)

    Simoneit, Bernd R. T.; Schoell, Martin; Dias, Robert F.; de Aquino Neto, F. Radler

    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 alga Tasmanites. The fossils are so densely packed that this shale is termed tasmanite. The carbon isotopic composition of bulk kerogen carbon ( δC13Corg = -16.6%., vs. PDB) is unusually enriched in 13C compared to marine Permian organic carbon (-25 to -30%.). This 13C enrichment suggests specific environmental conditions (CO 2 draw down) and/or physiological specialties (cell size and growth rate) of Tasmanites which, in modern environments, are known to cause 13C enrichment in marine phytoplankton. Isotope signatures of extractable organic species, unlike in normal immature oil shales, are considerably enriched in 13C compared to the kerogen. The bitumen (-10.9%.) is composed predominantly of extended saturated C 18-C 25 tricyclic terpane hydrocarbons (-9.9 to -12.2%. total range, with an average of -10.8%.). These tricyclics are not only found as free lipids in the extract but also in pyrolysates with similar isotopic signatures and are therefore likely biosynthesis products of Tasmanites. The monoaromatic and diaromatic tricyclic terpane hydrocarbons (C 17-C 19) have similar isotopic signatures (-9.3 to -12.8%. total range, with an average of -10.6%.). Two monoaromatic tetracyclic hydrocarbons (C 23 and C 24), a quantitatively minor but biogenetically interesting group, average at -10.2%.. In contrast, pristane and phytane, as well as n-alkanes (-18 to -22%.), are depleted in 13C compared to kerogen carbon. The isotopic similarity of all the cyclic terpanes in this 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

  5. 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.

  6. Strontium, Lead, and Oxygen Isotopic Signatures of Mid-Miocene Silicic Volcanism in Eastern Oregon

    NASA Astrophysics Data System (ADS)

    Hess, Emily Nancy

    Widespread, mid-Miocene rhyolite volcanism of eastern Oregon that are coeval or slightly postdate flood basalts of the Columbia River Basalt Province allows for mapping crustal domains using radiogenic and stable isotopes. Rhyolites are thought to be derived in large part by partial melting of the crust and thus yield direct information on the composition of the crust. Silicic volcanism is expressed in the form of numerous domes and tuffs exposed over a wide area (~300 km in N-S dimension and ~200 km in E-W dimension) west of the presumed craton boundary, which runs parallel but mostly east of the Oregon-Idaho state border as delineated by geophysical characteristics and isotopic transitions, including the 87Sr/86Sri =0.7060 line (MSL) and 87Sr/86Sri =0.7040 line (CSL). 87Sr/86Sri of twenty-seven silicic units are variable and some are high. Sr isotopic ratios are inconsistent with the location of the traditional MSL and CSL boundaries. A primary control on the 87Sr/86Sri isotope variations may reflect changes in the crustal make-up of Paleozoic accreted terranes of a particular area rather than arising from a westward-dipping decollement that moved cratonic lithosphere below accreted terranes in eastern Oregon. A secondary control on observed isotopic ratios may be related to the amount and composition of basalt involved in the generation of rhyolites. This could lead to higher or lower 87Sr/86Sri relative to the surrounding crust because de facto coeval mafic magmas of the Columbia River Basalt Group have a wide range of Sr isotopic signatures. While Pb isotope data is incomplete for all samples of this study, the available data indicate a significant range in Pb isotopes. Yet, data of individual regions tend to plot close to one another relative to the entire data distribution. Comparison of samples from this study in a more regional view indicates the samples generally fall within the previously defined lead isotope boundaries of the main-phase Columbia River

  7. Hg speciation and stable isotope signatures in human hair as a tracer for dietary and occupational exposure to mercury.

    PubMed

    Laffont, Laure; Sonke, Jeroen E; Maurice, Laurence; Monrroy, Selma Luna; Chincheros, Jaime; Amouroux, David; Behra, Philippe

    2011-12-01

    Exposure of humans and wildlife to various inorganic and organometallic forms of mercury (Hg) may induce adverse health effects. While human populations in developed countries are mainly exposed to marine fish monomethylmercury (MMHg), this is not necessarily the case for developing countries and diverse indigenous people. Identification of Hg exposure sources from biomonitor media such as urine or hair would be useful in combating exposure. Here we report on the Hg stable isotope signatures and Hg speciation in human hair across different gold miner, indigenous and urban populations in Bolivia and France. We found evidence for both mass-dependent isotope fractionation (MDF) and mass-independent isotope fractionation (MIF) in all hair samples. Three limiting cases of dominant exposure to inorganic Hg (IHg), freshwater fish MMHg, and marine fish MMHg sources are used to define approximate Hg isotope source signatures. Knowing the source signatures, we then estimated Hg exposure sources for the Bolivian gold miner populations. Modeled IHg levels in hair correspond well to measured IHg concentrations (R = 0.9), demonstrating that IHg exposure sources to gold miners can be monitored in hair samples following either its chemical speciation or isotopic composition. Different MMHg and inorganic exposure levels among gold miners appear to correspond to living and working conditions, including proximity to small towns, and artisanal vs large scale mining activity. PMID:22003970

  8. Whisker isotopic signature depicts migration patterns and multi-year intra- and inter-individual foraging strategies in fur seals

    PubMed Central

    Cherel, Y.; Kernaléguen, L.; Richard, P.; Guinet, C.

    2009-01-01

    The movement and dietary history of individuals can be studied using stable isotope records in archival keratinous tissues. Here, we present a chronology of temporally fine-scale data on the trophic niche of otariid seals by measuring the isotopic signature of serially sampled whiskers. Whiskers of male Antarctic fur seals breeding at the Crozet Islands showed synchronous and regular oscillations in both their δ13C and δ15N values that are likely to represent their annual migrations over the long term (mean 4.8 years). At the population level, male Antarctic fur seals showed substantial variation in both δ13C and δ15N values, occupying nearly all the ‘isotopic space’ created by the diversity of potential oceanic habitats (from high Antarctica to the subtropics) and prey (from Antarctic krill to subantarctic and subtropical mesopelagic fishes). At the individual level, whisker isotopic signatures depict a large diversity of foraging strategies. Some seals remained in either subantarctic or Antarctic waters, while the migratory cycle of most animals encompassed a wide latitudinal gradient where they fed on different prey. The isotopic signature of whiskers, therefore, revealed new multi-year foraging strategies of male Antarctic fur seals and is a powerful tool for investigating the ecological niche during cryptic stages of mammals' life. PMID:19793740

  9. Lost cold Antarctic deserts inferred from unusual sulfate formation and isotope signatures.

    PubMed

    Sun, Tao; Socki, Richard A; Bish, David L; Harvey, Ralph P; Bao, Huiming; Niles, Paul B; Cavicchioli, Ricardo; Tonui, Eric

    2015-01-01

    The Antarctic ice cap significantly affects global ocean circulation and climate. Continental glaciogenic sedimentary deposits provide direct physical evidence of the glacial history of the Antarctic interior, but these data are sparse. Here we investigate a new indicator of ice sheet evolution: sulfates within the glaciogenic deposits from the Lewis Cliff Ice Tongue of the central Transantarctic Mountains. The sulfates exhibit unique isotope signatures, including δ(34)S up to +50‰ for mirabilite evaporites, Δ(17)O up to +2.3‰ for dissolved sulfate within contemporary melt-water ponds, and extremely negative δ(18)O as low as -22.2‰. The isotopic data imply that the sulfates formed under environmental conditions similar to today's McMurdo Dry Valleys, suggesting that ice-free cold deserts may have existed between the South Pole and the Transantarctic Mountains since the Miocene during periods when the ice sheet size was smaller than today, but with an overall similar to modern global hydrological cycle. PMID:26119082

  10. Measurement of the Isotopic Signatures of Water on Mars: Implications for Studying Methane

    NASA Technical Reports Server (NTRS)

    Novak, R. E.; Mumma, M. J.; Villanueva, G. L.

    2010-01-01

    The recent discovery of methane on Mars has led to much discussion concerning its origin. On Earth, the isotopic signatures of methane vary with the nature of its production. Specifically, the ratios among 12CH4, 13CH4, and 12CH3D differ for biotic and abiotic origins. On Mars, measuring these ratios would provide insights into the origins of methane and measurements of water isotopologues co-released with methane would assist in testing their chemical relationship. Since 1997, we have been measuring HDO and H2O in Mars atmosphere and comparing their ratio to that in Earth s oceans. We recently incorporated a line-by-line radiative transfer model (LBLRTM) into our analysis. Here, we present a map for [HDO]/[H2O] along the central meridian (1541W) for Ls 501. From these results, we constructed models to determine the observational conditions needed to quantify the isotopic ratios of methane in Mars atmosphere. Current ground-based instruments lack the spectral resolution and sensitivity needed to make these measurements. Measurements of the isotopologues of methane will likely require in situ sampling.

  11. Paleoceanographic Implications of the Terrestrial Carbon-Isotope Record of the Early Toarcian (Jurassic) Oceanic Anoxic Event

    NASA Astrophysics Data System (ADS)

    Hesselbo, S.; Jenkyns, H. C.; Duarte, L. V.

    2005-12-01

    Macrofossil wood in two European sections representing the Toarcian (Early Jurassic) Oceanic Anoxic Event (OAE) have previously been shown to exhibit a large (~ -6 to -7 %) shift in d13C values which has been interpreted as a massive and geologically short-lived perturbation to the global carbon cycle. This interpretation has recently been challenged on the basis of a compilation of carbon-isotope data from belemnites collected from sections in northern Europe that exhibit carbon isotope values that are heavier than expected at the peak of the OAE. Here we present new carbon isotope measurements from wood collected from a marine record of the early Toarcian at Peniche, Portugal, a section currently under consideration as a GSSP for the base of the Toarcian. A large negative excursion (~ -7%) is confirmed for the OAE in these samples. These cannot have been severely impregnated by hydrocarbons of marine origin and the ages are well defined by ammonite biostratigraphy and by Sr-isotope stratigraphy. Carbon-isotope data is also presented for an early diagenetic silica nodule that formed within jet from the Toarcian of the Yorkshire coast, northeast England; values are indistinguishable from those of stratigraphically equivalent jet samples from which solvent extractable hydrocarbons had been removed. Thus, the early Toarcian negative carbon-isotope excursion is confirmed as a phenomenon of the global shallow-ocean, biosphere and atmosphere. It is likely that the anomalously heavy values obtained from belemnites from the OAE interval derive their isotopic signature from localized and possibly seasonal water masses characterized by dissolved inorganic carbon strongly enriched in heavy carbon by very high organic productivity.

  12. Vertical Stratification Changes During the Last Deglaciation Based on Foraminiferal Neodymium and Carbon Isotopes

    NASA Astrophysics Data System (ADS)

    Piotrowski, A. M.; Noble, T. L.; Roberts, N. L.; Yu, J.

    2011-12-01

    consistent with water mass mixing changes. However, deep records from both the Atlantic and Pacific-sector Southern Ocean are marked by very large deglacial changes in carbon isotopes, which are not supported as being related to water mass mixing by their ~2 to 3 epsilon unit Nd isotope changes, and suggests that a strong negative carbon isotope signature was confined to the deep glacial Southern Ocean. In contrast, north-eastern North Atlantic sites from the BOFS transect on the Rockall Bank show little vertical difference in Nd isotopes at intermediate and abyssal depths during the glacial through Holocene, despite significant differences between them in the carbon isotopes and other proxy records. A new Nd isotope record from intermediate-depth Caribbean core VM28-122 is similar to and parallels changes in the BOFS NE Atlantic cores. The apparent homogeneity of the glacial North Atlantic, in terms of Nd isotopes, may have been caused by a NADW endmember change, or by greater boundary exchange in a more stagnant glacial North Atlantic.

  13. Hydrologic functions of wetlands in a discontinuous permafrost basin indicated by isotopic and chemical signatures

    NASA Astrophysics Data System (ADS)

    Hayashi, Masaki; Quinton, William L.; Pietroniro, Alain; Gibson, John J.

    2004-08-01

    The hydrology of subarctic, discontinuous permafrost regions is sensitive to the effects of climatic warming, because pronounced changes in water storage and runoff pathways could occur with small additional ground heating. The objective of this study is to understand the hydrologic functions of unique land-cover types in this region (channel fens, flat bogs, and peat plateaus) using isotopic and chemical signatures of surface and subsurface water, as well as hydrometric measurements. The study was conducted in a 152-km 2 basin of Scotty Creek, located in the central part of the Mckenzie River basin in northern Canada. The headwater of Scotty Creek, Goose Lake had a strongly enriched isotopic composition due to evaporation. The stream water composition changed downstream, as the lateral drainage from the active layer of peat plateaus contributed isotopically light and chemically dilute water to channel fens that are part of the drainage network. Flat bogs received drainage from peat plateau in addition to direct precipitation, and were internally drained or drained water to adjacent channel fens. Average evapotranspiration estimated from the chloride-balance method was 280-300 mm/yr, which was consistent with the hydrometric estimate (precipitation minus runoff) of 275 mm/yr indicating a potential applicability of this method to ungauged basins. Tracer-based hydrograph separation showed that the direct snowmelt contribution to spring runoff was less than half of total discharge, suggesting an importance of the water stored over winter in lakes and wetlands. The total amount of water stored over winter in the basin was estimated to be 140-240 mm, which was comparable to the average annual basin discharge (149 mm).

  14. Shear heating and solid state diffusion: Constraints from clumped isotope thermometry in carbonate faults

    NASA Astrophysics Data System (ADS)

    Siman-Tov, S.; Affek, H. P.; Matthews, A.; Aharonov, E.; Reches, Z.

    2015-12-01

    Natural faults are expected to heat rapidly during seismic slip and to cool quite quickly after the event. Here we examine clumped isotope thermometry for its ability to identify short duration elevated temperature events along frictionally heated carbonate faults. This method is based on measured Δ47 values that indicate the relative atomic order of oxygen and carbon stable isotopes in the calcite lattice, which is affected by heat and thus can serve as a thermometer. We examine three types of calcite rock samples: (1) samples that were rapidly heated and then cooled in static laboratory experiments, simulating the temperature cycle experienced by fault rock during earthquake slip; (2) limestone samples that were experimentally sheared to simulate earthquake slip events; and (3) samples taken from principle slip zones of natural carbonate faults that likely experienced earthquake slip. Experimental results show that Δ47 values decrease rapidly (in the course of seconds) and systematically both with increasing temperature and shear velocity. On the other hand, carbonate shear zone from natural faults do not show such Δ47 reduction. We propose that the experimental Δ47 response is controlled by the presence of high-stressed nano-grains within the fault zone that can reduce the activation energy for diffusion by up to 60%, and thus lead to an increased rate of solid-state diffusion in the experiments. However, the lowering of activation energy is a double-edged sword in terms of clumped isotopes: In laboratory experiments, it allows for rapid disordering so that isotopic signal appears after very short heating, but in natural faults it also leads to relatively fast isotopic re-ordering after the cessation of frictional heating, thus erasing the high temperature signature in Δ47 values within relatively short geological times (<1 Ma).

  15. Stable isotopic signatures of diachronous Andean mountain building from volcanic glass, Condoroma Basin, northern Altiplano, Peru

    NASA Astrophysics Data System (ADS)

    Saylor, J.; Horton, B. K.; Stockli, D. F.

    2012-12-01

    Recent stable isotopic analyses of pedogenic carbonates from the central Altiplano (~18S) suggest that the plateau may have uplifted rapidly between 10 and 6 Ma possibly in response to removal of mantle lithosphere. Climate modeling, however, suggests that gradual uplift may have produced a similar magnitude effect in the stable isotopic system of the central Altiplano in response to attainment of a critical elevation. We present the results of new stable isotope (δD) analyses of volcanic glass from the Condoroma Basin in southern Peru (~15S). Nonmarine sedimentation in this hinterland basin extended from ~20 to ~5 Ma. The basin fill is composed primarily of lacustrine and lake-margin lithofacies but, critically, contains records of multiple volcanic eruptions. Samples of volcanic glass, which hydrates in the presence of surface water within ~10 kyr following eruption, were separated from multiple volcanic levels in two stratigraphic sections. Analysis of the deuterium isotopic composition of the volcanic glass reveals an abrupt and pronounced decrease of approximately 50-70‰ in both stratigraphic sections. Analyses of multiple grain size fractions yield consistent δD values, providing additional confidence in the robustness of the data. (U-Th)/He analysis of zircons separated from volcanic strata indicate that this shift occurred at ~18-14 Ma; earlier than in the central Altiplano. Applying the modern lapse rate implies an elevation increase of ~2.5 km. However, the isotopic shift could be the result of attainment of a threshold elevation, rather than representing a rapid, large-magnitude uplift event. Nevertheless, temporal variations suggest that uplift was not a single, plateau-wide event but rather, that the northern Altiplano was rapidly uplifted or attained the critical elevation prior to the central Altiplano. The possible effects of a diachronous rise in the Andes have not fully been incorporated into climate models. These data point to a diachronous

  16. Nd and Pb isotopic Mediterranean overflow water signature in the Gulf of Cadiz over the Mio-Pliocene boundary.

    NASA Astrophysics Data System (ADS)

    van der Schee, Marlies; Gutjahr, Marcus; Sierro, Francisco Javier; Flecker, Rachel; Jiménez Espejo, Francisco; Hodell, David; Abel Flores, Jose

    2014-05-01

    Marine gateways play a major role in ocean circulation and therefore climate. Currently, it is thought that there was no significant Mediterranean Overflow Water (MOW) in the Gulf of Cadiz during the Messinian Salinity Crisis (MSC) in the Late Miocene. However, a connection has supplied the Mediterranean with enough salt to precipitate the extensive evaporates preserved across the basin. After the MSC, the Mediterranean overflow was re-established through the Straits of Gibraltar. Today, MOW follows the continental slope of the Iberian Peninsula at a depth of 500-800 m in the Gulf of Cadiz northwards. In this study, lead and neodymium isotopes are used as water mass tracers for Mio-Pliocene MOW and NE Atlantic water in the Gulf of Cadiz. Complementary biostratigraphic data, carbon and oxygen isotopes and trace elements are presented alongside to corroborate our findings. Here we present a detailed authigenic Fe-Mn oxyhydroxide-derived Pb and Nd isotope records extracted from ~5.85 - 4.0 million year old bulk sediments recovered in IODP Core U1387C in the Gulf of Cadiz (current water depth 559 m). MOW and NE Atlantic waters have different Nd and Pb isotopic characteristics allowing for the identification of bottom water mass provenance changes and mixing proportions at the core site. The properties of the water bodies during the given time period are defined by Fe-Mn crust and marine sediment signatures. We also examine the natural variability within a single precession cycle. In order to confirm that the bulk sediment data indeed reliably reflects the primary composition of the bottom water masses, several bulk sediment samples are compared to foraminifera-derived Nd isotopic compositions. Results from the Messinian show a trend from isotope compositions that are more typical for MOW towards compositions more typical for the NE Atlantic. Subsequently, this trend reverses. After this, around 5.6 Ma an abrupt shift from MOW to more NE Atlantic characteristics is

  17. Stable carbon isotope ratios of toluene in the boundary layer and the lower free troposphere

    NASA Astrophysics Data System (ADS)

    Wintel, J.; Hösen, E.; Koppmann, R.; Krebsbach, M.; Hofzumahaus, A.; Rohrer, F.

    2013-11-01

    During the field campaign ZEPTER-2 in autumn 2008 whole air samples were collected on board a Zeppelin NT airship in the planetary boundary layer (PBL) and the lower free troposphere (LFT) over south-west Germany using the ZEppelin Based Isotope Sampler (ZEBIS). These samples were analysed with respect to volatile organic compound (VOC) mixing ratios and stable carbon isotope ratios using a gas chromatograph combustion isotope ratio mass spectrometer (GC-C-IRMS). In this study we present results for toluene, one of the major anthropogenic pollutants, which emphasise the viability of isotope ratio measurements in VOC for atmospheric research, especially to study VOC sources or to track both dynamical and chemical processes. In situ measurements of CO mixing ratios on board the Zeppelin NT were used to allocate the air samples either to the PBL or the LFT. In the PBL we observed rather fresh emissions mixing into the background air. We estimated a toluene source isotope ratio of δ13C = -28.2 ± 0.5‰. Samples from the PBL and the LFT were clearly distinguishable by means of their mixing ratio and isotope ratio signatures. Using the concept of the effective kinetic isotope effect, we were able to separate the effects of dilution processes and photochemical degradation in the free troposphere. We calculated the photochemical age of toluene in the atmosphere in two different ways using isotope ratios and mixing ratios. The results differ strongly in the PBL, probably due to mixing processes, but are compatible with each other in the LFT. Here, they correlate with a slope of 0.90±0.31.

  18. Yucca Mountain Area Saturated Zone Dissolved Organic Carbon Isotopic Data

    SciTech Connect

    Thomas, James; Decker, David; Patterson, Gary; Peterman, Zell; Mihevc, Todd; Larsen, Jessica; Hershey, Ronald

    2007-06-25

    Groundwater samples in the Yucca Mountain area were collected for chemical and isotopic analyses and measurements of water temperature, pH, specific conductivity, and alkalinity were obtained at the well or spring at the time of sampling. For this project, groundwater samples were analyzed for major-ion chemistry, deuterium, oxygen-18, and carbon isotopes of dissolved inorganic carbon (DIC) and dissolved organic carbon (DOC). The U.S. Geological Survey (USGS) performed all the fieldwork on this project including measurement of water chemistry field parameters and sample collection. The major ions dissolved in the groundwater, deuterium, oxygen-18, and carbon isotopes of dissolved inorganic carbon (DIC) were analyzed by the USGS. All preparation and processing of samples for DOC carbon isotopic analyses and geochemical modeling were performed by the Desert Research Institute (DRI). Analysis of the DOC carbon dioxide gas produced at DRI to obtain carbon-13 and carbon-14 values was conducted at the University of Arizona Accelerator Facility (a NSHE Yucca Mountain project QA qualified contract facility). The major-ion chemistry, deuterium, oxygen-18, and carbon isotopes of DIC were used in geochemical modeling (NETPATH) to determine groundwater sources, flow paths, mixing, and ages. The carbon isotopes of DOC were used to calculate groundwater ages that are independent of DIC model corrected carbon-14 ages. The DIC model corrected carbon-14 calculated ages were used to evaluate groundwater travel times for mixtures of water including water beneath Yucca Mountain. When possible, groundwater travel times were calculated for groundwater flow from beneath Yucca Mountain to down gradient sample sites. DOC carbon-14 groundwater ages were also calculated for groundwaters in the Yucca Mountain area. When possible, groundwater travel times were estimated for groundwater flow from beneath Yucca Mountain to down gradient groundwater sample sites using the DOC calculated

  19. The stable isotopic signature of biologically produced molecular hydrogen (H2)

    NASA Astrophysics Data System (ADS)

    Walter, S.; Laukenmann, S.; Stams, A. J. M.; Vollmer, M. K.; Gleixner, G.; Röckmann, T.

    2012-10-01

    Biologically produced molecular hydrogen (H2) is characterised by a very strong depletion in deuterium. Although the biological source to the atmosphere is small compared to photochemical or combustion sources, it makes an important contribution to the global isotope budget of H2. Large uncertainties exist in the quantification of the individual production and degradation processes that contribute to the atmospheric budget, and isotope measurements are a tool to distinguish the contributions from the different sources. Measurements of δ D from the various H2 sources are scarce and for biologically produced H2 only very few measurements exist. Here the first systematic study of the isotopic composition of biologically produced H2 is presented. In a first set of experiments, we investigated δ D of H2 produced in a biogas plant, covering different treatments of biogas production. In a second set of experiments, we investigated pure cultures of several H2 producing microorganisms such as bacteria or green algae. A Keeling plot analysis provides a robust overall source signature of δ D = -712‰ (±13‰) for the samples from the biogas reactor (at 38 °C, δ DH2O= +73.4‰), with a fractionation constant ϵH2-H2O of -689‰ (±20‰) between H2 and the water. The five experiments using pure culture samples from different microorganisms give a mean source signature of δ D = -728‰ (±28‰), and a fractionation constant ϵH2-H2O of -711‰ (±34‰) between H2 and the water. The results confirm the massive deuterium depletion of biologically produced H2 as was predicted by the calculation of the thermodynamic fractionation factors for hydrogen exchange between H2 and water vapour. Systematic errors in the isotope scale are difficult to assess in the absence of international standards for δ D of H2. As expected for a thermodynamic equilibrium, the fractionation factor is temperature dependent, but largely independent of the substrates used and

  20. Drivers of carbon isotopic fractionation in a coral reef lagoon: Predominance of demand over supply

    NASA Astrophysics Data System (ADS)

    Carvalho, Matheus C.; Santos, Isaac R.; Maher, Damien T.; Cyronak, Tyler; McMahon, Ashly; Schulz, Kai G.; Eyre, Bradley D.

    2015-03-01

    The carbon isotopic signature (δ13C) of coral skeletons is influenced by isotopic fractionation (εorg) during photosynthetic dissolved inorganic carbon (DIC) fixation, but only a few direct εorg measurements are available in coral communities. In particular, observations of εorg at the ecosystem scale are lacking. Here we present high frequency (hourly) measurements of DIC and its δ13C in the water column and benthic chambers in a highly productive coral reef lagoon (Heron Island, Great Barrier Reef, Australia) and apply simple molar balance calculations to infer community εorg. Variation in εorg was between 3.7‰ and 25.2‰ in the open lagoon, with lower values during the mid-afternoon and higher values in early morning and evening. The εorg range was broader (0.3-30.1‰) in enclosed benthic chambers with a similar diel pattern. There was a strong correlation between carbon uptake rates and εorg in closed incubations, suggesting that C demand largely controlled εorg. Benthic chamber incubations revealed increased εorg as water circulation increased, implying that C supply to photosynthesizing algae on the sediment also influenced εorg. Hysteresis in carbon uptake through the day complicated the expected straightforward influence of irradiance on C demand, and consequently on εorg. These results highlight the need for more in depth understanding on carbon uptake rates to fully understand δ13C variation in coral paleo-records.

  1. Stable Isotope Signatures of Middle Palaeozoic Ahermatypic Rugose Corals – Deciphering Secondary Alteration, Vital Fractionation Effects, and Palaeoecological Implications

    PubMed Central

    Jakubowicz, Michal; Berkowski, Blazej; López Correa, Matthias; Jarochowska, Emilia; Joachimski, Michael; Belka, Zdzislaw

    2015-01-01

    This study investigates stable isotope signatures of five species of Silurian and Devonian deep-water, ahermatypic rugose corals, providing new insights into isotopic fractionation effects exhibited by Palaeozoic rugosans, and possible role of diagenetic processes in modifying their original isotopic signals. To minimize the influence of intraskeletal cements on the observed signatures, the analysed specimens included unusual species either devoid of large intraskeletal open spaces ('button corals': Microcyclus, Palaeocyclus), or typified by particularly thick corallite walls (Calceola). The corals were collected at four localities in the Holy Cross Mountains (Poland), Mader Basin (Morocco) and on Gotland (Sweden), representing distinct diagenetic histories and different styles of diagenetic alteration. To evaluate the resistance of the corallites to diagenesis, we applied various microscopic and trace element preservation tests. Distinct differences between isotopic compositions of the least-altered and most-altered skeleton portions emphasise a critical role of material selection for geochemical studies of Palaeozoic corals. The least-altered parts of the specimens show marine or near-marine stable isotope signals and lack positive correlation between δ13C and δ18O. In terms of isotopic fractionation mechanisms, Palaeozoic rugosans must have differed considerably from modern deep-water scleractinians, typified by significant depletion in both 18O and 13C, and pronounced δ13C-δ18O co-variance. The fractionation effects exhibited by rugosans seem similar rather to the minor isotopic effects typical of modern non-scleractinian corals (octocorals and hydrocorals). The results of the present study add to growing evidence for significant differences between Scleractinia and Rugosa, and agree with recent studies indicating that calcification mechanisms developed independently in these two groups of cnidarians. Consequently, particular caution is needed in using

  2. Dissolved black carbon in Antarctic lakes: Chemical signatures of past and present sources

    NASA Astrophysics Data System (ADS)

    Khan, Alia L.; Jaffé, Rudolf; Ding, Yan; McKnight, Diane M.

    2016-06-01

    The perennially ice-covered, closed-basin lakes in the McMurdo Dry Valleys, Antarctica, serve as sentinels for understanding the fate of dissolved black carbon from glacial sources in aquatic ecosystems. Here we show that dissolved black carbon can persist in freshwater and saline surface waters for thousands of years, while preserving the chemical signature of the original source materials. The ancient brines of the lake bottom waters have retained dissolved black carbon with a woody chemical signature, representing long-range transport of black carbon from wildfires. In contrast, the surface waters are enriched in contemporary black carbon from fossil fuel combustion. Comparison of samples collected 25 years apart from the same lake suggests that the enrichment in anthropogenic black carbon is recent. Differences in the chemical composition of dissolved black carbon among the lakes are likely due to biogeochemical processing such as photochemical degradation and sorption on metal oxides.

  3. Stable carbon isotope biogeochemistry of lakes along a trophic gradient

    NASA Astrophysics Data System (ADS)

    de Kluijver, A.; Schoon, P. L.; Downing, J. A.; Schouten, S.; Middelburg, J. J.

    2014-11-01

    The stable carbon (C) isotope variability of dissolved inorganic and organic C (DIC and DOC), particulate organic carbon (POC), glucose and polar-lipid derived fatty acids (PLFAs) was studied in a survey of 22 North American oligotrophic to eutrophic lakes. The δ13C of different PLFAs were used as proxy for phytoplankton producers and bacterial consumers. Lake pCO2 was primarily determined by autochthonous production (phytoplankton biomass), especially in eutrophic lakes, and governed the δ13C of DIC. All organic-carbon pools showed overall higher isotopic variability in eutrophic lakes (n = 11) compared to oligo-mesotrophic lakes (n = 11) because of the high variability in δ13C at the base of the food web (both autochthonous and allochthonous carbon). Phytoplankton δ13C was negatively related to lake pCO2 over all lakes and positively related to phytoplankton biomass in eutrophic lakes, which was also reflected in a large range in photosynthetic isotope fractionation (ϵCO2-phyto, 8-25‰). The carbon isotope ratio of allochthonous carbon in oligo-mesotrophic lakes was rather constant, while it varied in eutrophic lakes because of maize cultivation in the watershed.

  4. Stable carbon isotope biogeochemistry of lakes along a trophic gradient

    NASA Astrophysics Data System (ADS)

    de Kluijver, A.; Schoon, P. L.; Downing, J. A.; Schouten, S.; Middelburg, J. J.

    2014-05-01

    The stable carbon (C) isotope variability of dissolved inorganic and organic C (DIC and DOC), particulate organic carbon (POC), glucose and polar-lipid derived fatty acids (PLFA) were studied in a survey of 22 North American oligotrophic to eutrophic lakes. The δ13C of different PLFA were used as proxy for phytoplankton producers and bacterial consumers. Lake pCO2 was primarily determined by autochthonous production (phytoplankton biomass), especially in eutrophic lakes, and governed the δ13C of DIC. All organic-carbon pools showed larger isotopic variability in eutrophic lakes compared to oligo-mesotrophic lakes because of the high variability in δ13C at the base of the food web (both autochthonous and allochthonous carbon). Phytoplankton δ13C was negatively related to lake pCO2 over all lakes and positively related to phytoplankton biomass in eutrophic lakes, which was also reflected in a large range in photosynthetic isotope fractionation (ϵCO2-phyto, 8-25 ‰). The carbon isotope ratio of allochthonous carbon in oligo-mesotrophic lakes was rather constant, while it varied in eutrophic lakes because of maize cultivation in the watershed.

  5. Carbon and its isotopes in mid-oceanic basaltic glasses

    USGS Publications Warehouse

    Des Marais, D.J.; Moore, J.G.

    1984-01-01

    Three carbon components are evident in eleven analyzed mid-oceanic basalts: carbon on sample surfaces (resembling adsorbed gases, organic matter, or other non-magmatic carbon species acquired by the glasses subsequent to their eruption), mantle carbon dioxide in vesicles, and mantle carbon dissolved in the glasses. The combustion technique employed recovered only reduced sulfur, all of which appears to be indigenous to the glasses. The dissolved carbon concentration (measured in vesicle-free glass) increases with the eruption depth of the spreading ridge, and is consistent with earlier data which show that magma carbon solubility increases with pressure. The total glass carbon content (dissolved plus vesicular carbon) may be controlled by the depth of the shallowest ridge magma chamber. Carbon isotopic fractionation accompanies magma degassing; vesicle CO2 is about 3.8??? enriched in 13C, relative to dissolved carbon. Despite this fractionation, ??13CPDB values for all spreading ridge glasses lie within the range -5.6 and -7.5, and the ??13CPDB of mantle carbon likely lies between -5 and -7. The carbon abundances and ??13CPDB values of Kilauea East Rift glasses apparently are influenced by the differentiation and movement of magma within that Hawaiian volcano. Using 3He and carbon data for submarine hydrothermal fluids, the present-day mid-oceanic ridge mantle carbon flux is estimated very roughly to be about 1.0 ?? 1013 g C/yr. Such a flux requires 8 Gyr to accumulate the earth's present crustal carbon inventory. ?? 1984.

  6. Distinct carbon isotope fractionation during anaerobic degradation of dichlorobenzene isomers.

    PubMed

    Liang, Xiaoming; Mundle, Scott O C; Nelson, Jennifer L; Passeport, Elodie; Chan, Calvin C H; Lacrampe-Couloume, Georges; Zinder, Stephen H; Sherwood Lollar, Barbara

    2014-05-01

    Chlorinated benzenes are ubiquitous organic contaminants found in groundwater and soils. Compound specific isotope analysis (CSIA) has been increasingly used to assess natural attenuation of chlorinated contaminants, in which anaerobic reductive dechlorination plays an essential role. In this work, carbon isotope fractionation of the three dichlorobenzene (DCB) isomers was investigated during anaerobic reductive dehalogenation in methanogenic laboratory microcosms. Large isotope fractionation of 1,3-DCB and 1,4-DCB was observed while only a small isotope effect occurred for 1,2-DCB. Bulk enrichment factors (εbulk) were determined from a Rayleigh model: -0.8 ± 0.1 ‰ for 1,2-DCB, -5.4 ± 0.4 ‰ for 1,3-DCB, and -6.3 ± 0.2 ‰ for 1,4-DCB. εbulk values were converted to apparent kinetic isotope effects for carbon (AKIE) in order to characterize the carbon isotope effect at the reactive positions for the DCB isomers. AKIE values are 1.005 ± 0.001, 1.034 ± 0.003, and 1.039 ± 0.001 for 1,2-DCB, 1,3-DCB, and 1,4-DCB, respectively. The large difference in AKIE values between 1,2-DCB and 1,3-DCB (or 1,4-DCB) suggests distinct reaction pathways may be involved for different DCB isomers during microbial reductive dechlorination by the methanogenic cultures. PMID:24758692

  7. Tracking variations in wetland use by breeding flamingos using stable isotope signatures of feather and blood

    NASA Astrophysics Data System (ADS)

    Yohannes, Elizabeth; Arnaud, Antoine; Béchet, Arnaud

    2014-01-01

    This study tracks temporal variations in the habitat use of breeding adult greater flamingos (Phoenicopterus roseus) in the Camargue (southern France) using simultaneous sampling of δ15N, δ13C and δ34S from feather and blood of chicks at fledging. Camargue flamingos forage in a heterogeneous complex of saltpans, permanent and temporary brackish lagoons, freshwater and euryhaline marshes to provision their chicks over a two month period. Using Bayesian mixing models with diet- and tissue-specific discrimination factors and invertebrates collected from 23 locations, we investigated whether blood and feather isotopes indicated temporal variations in habitat use relative to salinity and hydroperiod. We also tested whether fledgling body condition could be explained by the isotopic signatures of their tissues. While δ13C and δ15N values did not differ significantly between blood and feather, marked differences were apparent in the δ34S values obtained from these tissues. Saltpans (38%) and freshwater marshes (33%) appeared to be the main habitats visited by adult birds in the early phase of parental care with use of saline wetlands increasing later in the season (54%). This habitat shift may be related to the peak of resources in saltpans and the drying up of freshwater and brackish marshes by mid-summer. Habitat shift (as expressed in individual shifts in isotope values between feather and blood) was not correlated with offspring age, and differed between individuals. A negative relationship was observed between offspring body condition and feather δ15N, indicating that chicks fed from temporary flooded marshes fare better than those provisioned from permanent marshes. Foraging strategies of greater flamingos during parental care were heterogeneous, possibly tracking changes in resource availability as the season progressed and reflecting differences in the competitive ability of parent birds. Given that the Camargue saltpans face closure and the region

  8. Temperature Dependence of Carbon Isotope Fractionation in CAM Plants.

    PubMed

    Deleens, E; Treichel, I; O'leary, M H

    1985-09-01

    The carbon isotope fractionation associated with nocturnal malic acid synthesis in Kalanchoë 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 degrees C nights, 23 degrees C days), the isotope fractionation for both plants is -4 per thousand (that is, malate is enriched in (13)C relative to the atmosphere). For K. daigremontiana, the isotope fractionation decreases with increasing temperature, becoming approximately 0 per thousand at 27 degrees C/33 degrees 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. PMID:16664371

  9. 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.

    1978-01-01

    The possibility that the newly discovered correlated isotopic anomalies for heavy elements in the Allende meteorite were synthesized in the secondary neutron capture episode during the explosive carbon burning, the possible source of the O-16 and Al-26 anomalies, is examined. Explosive carbon burning calculations under typical conditions were first performed to generate time profiles of temperature, density, and free particle concentrations. These quantities were inputted into a general neutron capture code which calculates the resulting isotopic pattern from exposing the preexisting heavy seed nuclei to these free particles during the explosive carbon burning conditions. The interpretation avoids the problem of the Sr isotopic data and may resolve the conflict between the time scales inferred from 1-129, Pu-244, and Al-26.

  10. Carbon and Hydrogen Isotopic Fractionation during Anaerobic Biodegradation of Benzene

    PubMed Central

    Mancini, Silvia A.; Ulrich, Ania C.; Lacrampe-Couloume, Georges; Sleep, Brent; Edwards, Elizabeth A.; Sherwood Lollar, Barbara

    2003-01-01

    Compound-specific isotope analysis has the potential to distinguish physical from biological attenuation processes in the subsurface. In this study, carbon and hydrogen isotopic fractionation effects during biodegradation of benzene under anaerobic conditions with different terminal-electron-accepting processes are reported for the first time. Different enrichment factors (ɛ) for carbon (range of −1.9 to −3.6‰) and hydrogen (range of −29 to −79‰) fractionation were observed during biodegradation of benzene under nitrate-reducing, sulfate-reducing, and methanogenic conditions. These differences are not related to differences in initial biomass or in rates of biodegradation. Carbon isotopic enrichment factors for anaerobic benzene biodegradation in this study are comparable to those previously published for aerobic benzene biodegradation. In contrast, hydrogen enrichment factors determined for anaerobic benzene biodegradation are significantly larger than those previously published for benzene biodegradation under aerobic conditions. A fundamental difference in the previously proposed initial step of aerobic versus proposed anaerobic biodegradation pathways may account for these differences in hydrogen isotopic fractionation. Potentially, C-H bond breakage in the initial step of the anaerobic benzene biodegradation pathway may account for the large fractionation observed compared to that in aerobic benzene biodegradation. Despite some differences in reported enrichment factors between cultures with different terminal-electron-accepting processes, carbon and hydrogen isotope analysis has the potential to provide direct evidence of anaerobic biodegradation of benzene in the field. PMID:12513995

  11. Isotopic mass independent signature of black crusts: a proxy for atmospheric aerosols formation in the Paris area (France).

    NASA Astrophysics Data System (ADS)

    Genot, Isabelle; Martin, Erwan; Yang, David Au; De Rafelis, Marc; Cartigny, Pierre; Wing, Boswell; Le Gendre, Erwann; Bekki, Slimane

    2016-04-01

    In view of the negative forcing of the sulfate aerosols on climate, a more accurate understanding of the formation of these particles is crucial. Indeed, despite the knowledge of their effects, uncertainties remain regarding the formation of sulfate aerosols, particularly the oxidation processes of S-bearing gases. Since the discovery of oxygen and sulfur mass independent fractionation (O- and S-MIF) processes on Earth, the sulfate isotopic composition became essential to investigate the atmospheric composition evolution and its consequences on the climate and the biosphere. Large amount of S-bearing compounds (SO2 mainly) is released into the atmosphere by anthropogenic and natural sources. Their oxidation in the atmosphere generates sulfate aerosols, H2SO4, which precipitate on the earth surface mainly as acid rain. One consequence of this precipitation is the formation of black crust on buildings made of carbonate stones. Indeed the chemical alteration of CaCO3 by H2SO4 leads to gypsum (CaSO4·2H2O) concretions on building walls. Associated to other particles, gypsum forms black-crusts. Therefore, black crusts acts as 'sulfate aerosol traps', meaning that their isotopic composition reveals the composition and thus the source and formation processes of sulfate aerosols in the atmosphere in a specific region. In this study we collected 37 black crusts on a 300km NW-SE profile centered on Paris (France). In our samples, sulfate represent 40wt.% and other particles 60wt.% of the black crusts. After sulfate extraction from each samples we measured their O- and S-isotopes composition. Variations of about 10‰ in δ18O and δ34S are observed and both O-MIF (Δ17O from 0 to 1.4‰) and S-MIF (Δ33S from 0 to -0.3‰) compositions have been measured. In regards to these compositions we can discuss the source and formation (oxidation pathways) of the sulfate aerosols in troposphere above the Paris region that covers urban, rural and coastal environments. Furthermore

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

  13. 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.

  14. Sources of Variation in the Carbon Isotopic Composition of Root Respiration

    NASA Astrophysics Data System (ADS)

    Carrillo, Y.; Pendall, E.

    2008-12-01

    Soil CO2 efflux is comprised of CO2 from root respiration, rhizosphere microbes and heterotrophic respiration from soil organic matter. Isotopic approaches at partitioning autotrophic and heterotrophic respiration require determining source signatures. The signature of root tissue has been commonly used as the root end-member. However, this signature corresponds to all cellular constituents, which are not expected to be part of root respiration. Also, there is some evidence of fractionation during dark respiration so that the use of dried bulk roots may not accurately represent respired CO2. Incubation of excised roots and subsequent isotope analysis offers a simple alternative that can be of use for experimental purposes. To assess the applicability of this approach we measured respiration rates and 13C signatures of the respiration of excised roots from an ongoing field experiment studying the effects of warming and elevated CO2 concentrations and their interactions on soil organic matter dynamics. The experiment uses Free-Air CO2 enrichment and generates continuous labeling with 13C depleted CO2 in the elevated CO2 treatments. Roots were collected from two different depths in the spring and summer seasons and isotopic analyses of respiration and whole tissue were performed. Analyses to date have found no differences in the respiration rates of roots from any treatment at any date. d13C (delta Carbon 13) values of respiration were lower under elevated CO2 and there was no effect of warming or root depth. There was a greater difference between the respiration signatures of roots from elevated CO2 and ambient CO2 in the samples collected in the summer than in the samples collected in the spring because values in the ambient CO2 treatment were higher in the summer. d13C values became significantly more positive with time since collection in all treatments. We hypothesize that root metabolism immediately after excision utilizes labile C (sugars and starch) that

  15. Factors Controlling Respiration Rates and Respired Carbon Dioxide Signatures in Riverine Ecosystems of the Amazon Basin

    NASA Astrophysics Data System (ADS)

    Ellis, E. E.; Richey, J. E.; Aufdenkampe, A. K.; Quay, P. D.; Krusche, A. V.; Alin, S. R.

    2006-12-01

    =0.76), suggesting that the fuel for respiration is either C4 vegetation or an isotopically enriched pool of C3 based organic matter that is selectively respired. Given that the <5 kDa pool of organic matter is positively correlated with respiration, we hypothesize that this pool may be isotopically enriched and derived from autochthonous material, leading to a heavy isotopic signature of the respired CO2. Autochthonous carbon production may play a larger role in riverine carbon cycling in the Amazon than previously thought during the dry season.

  16. Preliminary identification of ground-water nitrate sources using nitrogen and carbon stable isotopes, Kansas

    USGS Publications Warehouse

    Townsend, M.A.; Macko, S.A.

    2007-01-01

    Increasing nitrate-N in ground water is a problem in areas with limited ground-water supplies, such as central Kansas. Nitrate-N concentrations in ground water in the study area in Ellis County range from 0.9 to 26 mg/L. Calculated mean values observed in soil cores are 1.2-15 mg/kg. The ??15N signatures of the ground waters are more enriched (+16.8 to +28.7???) than those of the soils (+8.4 to +1 3.7???), strongly suggesting that nitrate-N sources are not from mineralized and labile nitrogen present in the unsaturated zone. Soil cores were collected near municipal wells to determine if soil nitrogen was a contributing source to the ground water. Increased ??15N of total nitrogen with depth suggests that microbial mineralization processes and possible denitrification or volatilization isotope enrichments have affected the observed ?? 15N signatures in the soil. However, the observed soil-nitrogen values are not of sufficient magnitude to explain the nitrate-N concentrations or associated ??15N values observed in the ground water. Stable carbon isotopes provide some supporting evidence that soils are not a major contributor to the observed nitrate-N concentration in the ground water. ?? 13C values of the dissolved organic carbon (DOC) in soils generally become more enriched with depth while corresponding ground-water ??13C (DOC) values are more depleted than in the overlying soils. Carbon isotope values of the soils are indicative of a C4 plant source that is enriched by microbial processes. The ??13C (DOC) of ground water indicates C3 values that may reflect impacts from animal-waste sources.

  17. Aptian Carbon Isotope Stratigraphy in Sierra del Rosario, Northeastern Mexico

    NASA Astrophysics Data System (ADS)

    Barragan-Manzo, R.; Moreno-Bedmar, J.; Nuñez, F.; Company, M.

    2013-05-01

    In most recent years Aptian carbon isotope stratigraphy has been widely studied in Europe where isotopic stages have been developed to correlate global events. Two negative excursions have been recorded in the Lower Aptian, the older is OAE 1a in the middle part, and a younger negative excursion labeled "Aparein level", which occurs in the uppermost part of the Lower Aptian. In Mexico previous works reported a carbon isotope negative excursion in the lowermost part of the La Peña Formation that was assigned to the onset of Oceanic Anoxic Event 1a (=OAE 1a). In this work we study the isotopic record of the δ13Ccarb of 32 bulk rock samples of limestone from the uppermost part of the Cupido Formation and the lower part of the La Peña Formation at the Francisco Zarco Dam Section (=FZD), Durango State, northeastern Mexico. The isotopic data are calibrated using the latest ammonite biostratigraphic biozonation of the Aptian. This age calibration allows us to make a precise correlation between the carbon isotopic record of Mexico and several European sections (e.g. Spain and France). In the studied Francisco Zarco Dam section we recognize a negative carbon isotopic excursion in the Dufrenoyia justinae ammonite Zone that corresponds to the "Aparein level", which we correlate using the ammonite zonation of others European sections (Figure 1). This correlation allows us to see how the negative excursion that characterizes the "Aparein level" is consistent with the C7 segment. Thus, our recent stratigraphic study allows us to conclude that the ammonite record in the lowermost part of the La Peña Formation is regionally isochronous, and correlates with the Dufrenoyia justinae Zone and Lower Aptian isotope interval C7. In agreement to these biostratigraphic data, the supposed record of the OAE 1a in the lowermost part of the La Peña Formation is not correct, and the carbon isotope negative excursion must be assigned to the younger event "Aparein level". Taking this into

  18. Sequential Isotopic Signature Along Gladius Highlights Contrasted Individual Foraging Strategies of Jumbo Squid (Dosidicus gigas)

    PubMed Central

    Lorrain, Anne; Argüelles, Juan; Alegre, Ana; Bertrand, Arnaud; Munaron, Jean-Marie; Richard, Pierre; Cherel, Yves

    2011-01-01

    Background Cephalopods play a major role in marine ecosystems, but knowledge of their feeding ecology is limited. In particular, intra- and inter-individual variations in their use of resources has not been adequatly explored, although there is growing evidence that individual organisms can vary considerably in the way they use their habitats and resources. Methodology/Principal Findings Using δ13C and δ15N values of serially sampled gladius (an archival tissue), we examined high resolution variations in the trophic niche of five large (>60 cm mantle length) jumbo squids (Dosidicus gigas) that were collected off the coast of Peru. We report the first evidence of large inter-individual differences in jumbo squid foraging strategies with no systematic increase of trophic level with size. Overall, gladius δ13C values indicated one or several migrations through the squid's lifetime (∼8–9 months), during which δ15N values also fluctuated (range: 1 to 5‰). One individual showed an unexpected terminal 4.6‰ δ15N decrease (more than one trophic level), thus indicating a shift from higher- to lower-trophic level prey at that time. The data illustrate the high diversity of prey types and foraging histories of this species at the individual level. Conclusions/Significance The isotopic signature of gladii proved to be a powerful tool to depict high resolution and ontogenic variations in individual foraging strategies of squids, thus complementing traditional information offered by stomach content analysis and stable isotopes on metabolically active tissues. The observed differences in life history strategies highlight the high degree of plasticity of the jumbo squid and its high potential to adapt to environmental changes. PMID:21779391

  19. Stable Isotope and Signature Fatty Acid Analyses Suggest Reef Manta Rays Feed on Demersal Zooplankton

    PubMed Central

    Couturier, Lydie I. E.; Rohner, Christoph A.; Richardson, Anthony J.; Marshall, Andrea D.; Jaine, Fabrice R. A.; Bennett, Michael B.; Townsend, Kathy A.; Weeks, Scarla J.; Nichols, Peter D.

    2013-01-01

    Assessing the trophic role and interaction of an animal is key to understanding its general ecology and dynamics. Conventional techniques used to elucidate diet, such as stomach content analysis, are not suitable for large threatened marine species. Non-lethal sampling combined with biochemical methods provides a practical alternative for investigating the feeding ecology of these species. Stable isotope and signature fatty acid analyses of muscle tissue were used for the first time to examine assimilated diet of the reef manta ray Manta alfredi, and were compared with different zooplankton functional groups (i.e. near-surface zooplankton collected during manta ray feeding events and non-feeding periods, epipelagic zooplankton, demersal zooplankton and several different zooplankton taxa). Stable isotope δ15N values confirmed that the reef manta ray is a secondary consumer. This species had relatively high levels of docosahexaenoic acid (DHA) indicating a flagellate-based food source in the diet, which likely reflects feeding on DHA-rich near-surface and epipelagic zooplankton. However, high levels of ω6 polyunsaturated fatty acids and slightly enriched δ13C values in reef manta ray tissue suggest that they do not feed solely on pelagic zooplankton, but rather obtain part of their diet from another origin. The closest match was with demersal zooplankton, suggesting it is an important component of the reef manta ray diet. The ability to feed on demersal zooplankton is likely linked to the horizontal and vertical movement patterns of this giant planktivore. These new insights into the habitat use and feeding ecology of the reef manta ray will assist in the effective evaluation of its conservation needs. PMID:24167562

  20. Carbon isotope effects associated with Fenton-like degradation of toluene: potential for differentiation of abiotic and biotic degradation.

    PubMed

    Ahad, Jason M E; Slater, Greg F

    2008-08-15

    Hydrogen peroxide (H(2)O(2))-mediated oxygenation to enhance subsurface aerobic biodegradation is a frequently employed remediation technique. However, it may be unclear whether observed organic contaminant mass loss is caused by biodegradation or chemical oxidation via hydroxyl radicals generated during catalyzed Fenton-like reactions. Compound-specific carbon isotope analysis has the potential to discriminate between these processes. Here we report laboratory experiments demonstrating no significant carbon isotope fractionation during Fenton-like hydroxyl radical oxidation of toluene. This implies that observation of significant isotopic fractionation of toluene at a site undergoing H(2)O(2)-mediated remediation would provide direct evidence of biodegradation. We applied this approach at a field site that had undergone 27 months of H(2)O(2)-mediated subsurface oxygenation. Despite substantial decreases (>68%) in groundwater toluene concentrations carbon isotope signatures of toluene (delta(13)C(tol)) showed no significant variation (mean=-27.5+/-0.3 per thousand, n=13) over a range of concentrations from 11.1 to 669.0 mg L(-1). Given that aerobic degradation by ring attack has also been shown to result in no significant isotopic fractionation during degradation, at this site we were unable to discern the mechanism of degradation. However, such differentiation is possible at sites where aerobic degradation by methyl group attack results in significant isotopic fractionation. PMID:18466958

  1. Multiple sulfur isotope signatures of sulfite and thiosulfate reduction by the model dissimilatory sulfate-reducer, Desulfovibrio alaskensis str. G20

    PubMed Central

    Leavitt, William D.; Cummins, Renata; Schmidt, Marian L.; Sim, Min S.; Ono, Shuhei; Bradley, Alexander S.; Johnston, David T.

    2014-01-01

    Dissimilatory sulfate reduction serves as a key metabolic carbon remineralization process in anoxic marine environments. Sulfate reducing microorganisms can impart a wide range in mass-dependent sulfur isotopic fractionation. As such, the presence and relative activity of these organisms is identifiable from geological materials. By extension, sulfur isotope records are used to infer the redox balance of marine sedimentary environments, and the oxidation state of Earth's oceans and atmosphere. However, recent work suggests that our understanding of microbial sulfate reduction (MSRs) may be missing complexity associated with the presence and role of key chemical intermediates in the reductive process. This study provides a test of proposed metabolic models of sulfate reduction by growing an axenic culture of the well-studied MSRs, Desulfovibrio alaskensis strain G20, under electron donor limited conditions on the terminal electron acceptors sulfate, sulfite or thiosulfate, and tracking the multiple S isotopic consequences of each condition set. The dissimilatory reduction of thiosulfate and sulfite produce unique minor isotope effects, as compared to the reduction of sulfate. Further, these experiments reveal a complex biochemistry associated with sulfite reduction. That is, under high sulfite concentrations, sulfur is shuttled to an intermediate pool of thiosulfate. Site-specific isotope fractionation (within thiosulfate) is very large (34ε ~ 30‰) while terminal product sulfide carries only a small fractionation from the initial sulfite (34ε < 10‰): a signature similar in magnitude to sulfate and thiosulfate reduction. Together these findings show that microbial sulfate reduction (MSR) is highly sensitive to the concentration of environmentally important sulfur-cycle intermediates (sulfite and thiosulfate), especially when thiosulfate and the large site-specific isotope effects are involved. PMID:25505449

  2. Biochemical and physiological bases for the use of carbon and nitrogen isotopes in environmental and ecological studies

    NASA Astrophysics Data System (ADS)

    Ohkouchi, Naohiko; Ogawa, Nanako O.; Chikaraishi, Yoshito; Tanaka, Hiroyuki; Wada, Eitaro

    2015-12-01

    We review the biochemical and physiological bases of the use of carbon and nitrogen isotopic compositions as an approach for environmental and ecological studies. Biochemical processes commonly observed in the biosphere, including the decarboxylation and deamination of amino acids, are the key factors in this isotopic approach. The principles drawn from the isotopic distributions disentangle the complex dynamics of the biosphere and allow the interactions between the geosphere and biosphere to be analyzed in detail. We also summarize two recently examined topics with new datasets: the isotopic compositions of individual biosynthetic products (chlorophylls and amino acids) and those of animal organs for further pursuing the basis of the methodology. As a tool for investigating complex systems, compound-specific isotopic analysis compensates the intrinsic disadvantages of bulk isotopic signatures. Chlorophylls provide information about the particular processes of various photoautotrophs, whereas amino acids provide a precise measure of the trophic positions of heterotrophs. The isotopic distributions of carbon and nitrogen in a single organism as well as in the whole biosphere are strongly regulated, so that their major components such as amino acids are coordinated appropriately rather than controlled separately.

  3. 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

  4. Estimation of lake water - groundwater interactions in meromictic mining lakes by modelling isotope signatures of lake water.

    PubMed

    Seebach, Anne; Dietz, Severine; Lessmann, Dieter; Knoeller, Kay

    2008-03-01

    A method is presented to assess lake water-groundwater interactions by modelling isotope signatures of lake water using meteorological parameters and field data. The modelling of delta(18)O and deltaD variations offers information about the groundwater influx into a meromictic Lusatian mining lake. Therefore, a water balance model is combined with an isotope water balance model to estimate analogies between simulated and measured isotope signatures within the lake water body. The model is operated with different evaporation rates to predict delta(18)O and deltaD values in a lake that is only controlled by weather conditions with neither groundwater inflow nor outflow. Comparisons between modelled and measured isotope values show whether the lake is fed by the groundwater or not. Furthermore, our investigations show that an adaptation of the Craig and Gordon model [H. Craig, L.I. Gordon. Deuterium and oxygen-18 variations in the ocean and the marine atmosphere. In Stable Isotopes in Oceanographic Studies and Paleotemperature, Spoleto, E. Tongiorgi (Ed.), pp. 9-130, Consiglio Nazionale delle Ricerche, Laboratorio di Geologia Nucleare, Pisa (1965).] to specific conditions in temperate regions seems necessary. PMID:18320431

  5. Soil properties, strontium isotopic signatures and multi-element profiles to authenticate the origin of vegetables from small-scale regions: illustration with early potatoes from southern Italy.

    PubMed

    Zampella, Mariavittoria; Quétel, Christophe R; Paredes, Eduardo; Goitom Asfaha, Daniel; Vingiani, Simona; Adamo, Paola

    2011-10-15

    We propose a method for the authentication of the origin of vegetables grown under similar weather conditions, in sites less than 10 km distance from the sea and distributed over a rather small scale area (58651 km(2)). We studied how the strontium (Sr) isotopic signature and selected elemental concentrations ([Mn], [Cu], [Zn], [Rb], [Sr] and [Cd]) in early potatoes from three neighbouring administrative regions in the south of Italy were related to the geological substrate (alluvial sediments, volcanic substrates and carbonate rocks) and to selected soil chemical properties influencing the bioavailability of elements in soils (pH, cation exchange capacity and total carbonate content). Through multiple-step multivariate statistics (PLS-DA) we could assign 26 potatoes (including two already commercialised samples) to their respective eight sites of production, corresponding to the first two types of geological substrates. The other 12 potatoes from four sites of production had similar characteristics in terms of the geological substrate (third type) and these soil properties could be grouped together. In this case, more discriminative parameters would be required to allow the differentiation between sites. The validation of our models included external prediction tests with data of potatoes harvested the year before and a study on the robustness of the uncertainties of the measurement results. Annual variations between multi-elemental and Sr isotopic fingerprints were observed in potatoes harvested from soils overlying carbonate rocks, stressing the importance of testing long term variations in authentication studies. PMID:21913249

  6. Evolution of carbon isotopes, agglutinates, and the lunar regolith

    NASA Technical Reports Server (NTRS)

    Desmarais, D. J.; Basu, A.; Hayes, J. M.; Meinschein, W. G.

    1975-01-01

    Apollo 17 light-mantle soils and Apollo 15 Apennine Front soils are compared with respect to isotopic enrichment of C-13 and the maturity of the site. Analyses of soil-size fractions indicate that while the carbon concentration on particle surfaces remains relatively constant with increasing soil maturity, total surface-correlated carbon increases due to increasing total soil surface area. The role of agglutinates in the incorporation of surface-correlated carbon into aggregate grains is examined; agglutinates contain a major percentage of the carbon found in mature soil, and the volume-correlated carbon component in agglutinates apparently continues to increase after the surface-correlated carbon concentrations have reached a constant value. Constraints that may limit the carbon concentration in lunar soils to a value not greater than 300 micrograms/g are considered.

  7. CARBON ISOTOPE DISCRIMINATION AND GROWTH RESPONSE TO STAND DENSITY REDUCTIONS IN OLD PINUS PONDEROSA TREES

    EPA Science Inventory

    Carbon isotope ratios ( 13C) of tree rings are commonly used for paleoclimatic reconstruction and for inferring canopy water-use efficiency (WUE). However, the responsiveness of carbon isotope discrimination ( ) to site disturbance and resource availability has only rarely been ...

  8. Stable and radioactive carbon in forest soils of Chhattisgarh, Central India: Implications for tropical soil carbon dynamics and stable carbon isotope evolution

    NASA Astrophysics Data System (ADS)

    Laskar, A. H.; Yadava, M. G.; Ramesh, R.

    2016-06-01

    Soils from two sites viz. Kotumsar and Tirathgarh, located ∼5 km apart in a tropical reserve forest (18°52‧N, 81°56‧E) in central India, have been explored for soil organic carbon (SOC) content, its mean residence time (MRT) and the evolution of stable carbon isotopic composition (δ13C). SOC stocks in the upper 30 cm of soil layers are ∼5.3 kg/m2 and ∼3.0 kg/m2; in the upper 110 m are ∼10.7 kg/m2 and ∼7.8 kg/m2 at Kotumsar and Tirathgarh, respectively. SOC decreases with increasing depth. Bomb carbon signature is observed in the upper ∼10 cm. Organic matters in the top soil layers (0-10 cm) have MRTs of the order of a century which increases gradually with depths, reaching 3500-5000 yrs at ∼100 cm. δ13C values of SOC increase with depth, the carbon isotopic fractionation is obtained to be -1.2‰ and -3‰ for soils at Kotumsar and Tirathgarh, respectively, confirmed using Rayleigh isotopic fractionation model. The evolution of δ13C in soils was also studied using a modified Rayleigh fractionation model incorporating a continuous input into the reservoir: the depth profiles of δ13C for SOC show that the input organic matter from surface into the deeper soil layers is either insignificant or highly labile and decomposes quite fast in the top layers, thus making little contribution to the residual biomasses of the deeper layers. This is an attempt to understand the distillation processes that take place in SOC, assess the extent of decomposition by microbes and effect of percolation of fresh organic matter into dipper soil layers which are important for stable isotope based paleoclimate and paleovegetation reconstruction and understanding the dynamics of organic carbon in soils.

  9. Mercury deposition and re-emission pathways in boreal forest soils investigated with Hg isotope signatures.

    PubMed

    Jiskra, Martin; Wiederhold, Jan G; Skyllberg, Ulf; Kronberg, Rose-Marie; Hajdas, Irka; Kretzschmar, Ruben

    2015-06-16

    Soils comprise the largest terrestrial mercury (Hg) pool in exchange with the atmosphere. To predict how anthropogenic emissions affect global Hg cycling and eventually human Hg exposure, it is crucial to understand Hg deposition and re-emission of legacy Hg from soils. However, assessing Hg deposition and re-emission pathways remains difficult because of an insufficient understanding of the governing processes. We measured Hg stable isotope signatures of radiocarbon-dated boreal forest soils and modeled atmospheric Hg deposition and re-emission pathways and fluxes using a combined source and process tracing approach. Our results suggest that Hg in the soils was dominantly derived from deposition of litter (∼90% on average). The remaining fraction was attributed to precipitation-derived Hg, which showed increasing contributions in older, deeper soil horizons (up to 27%) indicative of an accumulation over decades. We provide evidence for significant Hg re-emission from organic soil horizons most likely caused by nonphotochemical abiotic reduction by natural organic matter, a process previously not observed unambiguously in nature. Our data suggest that Histosols (peat soils), which exhibit at least seasonally water-saturated conditions, have re-emitted up to one-third of previously deposited Hg back to the atmosphere. Re-emission of legacy Hg following reduction by natural organic matter may therefore be an important pathway to be considered in global models, further supporting the need for a process-based assessment of land/atmosphere Hg exchange. PMID:25946594

  10. Influence of environmental factors on dissolved nitrate stable isotopes under denitrifying conditions - carbon sources and water isotopes

    NASA Astrophysics Data System (ADS)

    Wunderlich, A.; Meckenstock, R.; Einsiedl, F.

    2012-04-01

    Stable isotopes in dissolved nitrate are regularly used to identify sources of nitrate contamination in aquifers and water bodies. A dual isotope plot of 15N and 18O in nitrate can provide good evidence of the origin of such pollution as various sources have different isotopic signatures. Microbial denitrification changes both isotopic values by removing nitrate with lighter isotopes first, thereby increasing δ18O as well as δ15N. This change can distort the determination of sources but also has the potential to be used to identify and quantify microbial denitrification. Previous studies found a wide range of enrichment factors (ɛ) that did not allow conclusions towards the extent of microbial denitrification. However, it was found that during denitrification at each respective field site or laboratory experiment, there was a constant ratio in increase of the values of δ18O in relation to δ15N. That ratio was, however, not constant across field sites and the values published range from below 0.5 to more than 1.0. The reasons for these variations in enrichment factors and relative enrichment of oxygen compared to nitrogen are yet unknown. We conducted microcosm experiments with three different bacterial species to elucidate possible influences of environmental factors on these parameters. As a result we conclude that the type of carbon source available to denitrifying bacteria can play a role in the value of the enrichment factors, but not in the relative enrichment of the two isotopes. Specifically we found that complex hydrocarbons (toluene, benzoate) produce significantly different enrichment factors in nitrate than a simple hydrocarbon substrate (acetate). The relative enrichment of δ18O compared to δ15N was 0.86. We hypothesise that this influence is based on a variation in process kinetics of cross-membrane nitrate transport in relation to intracellular nitrate reduction. The core of the hypothesis is that nitrate transport into the cell becomes rate

  11. 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

  12. Comparing isotope signatures of prey fish: does gut removal affect δ13C or δ15N?

    USGS Publications Warehouse

    Chipps, Steven R.; Fincel, Mark J.; VanDeHey, Justin A.; Wuestewald, Andrew

    2011-01-01

    Stable isotope analysis is a quick and inexpensive method to monitor the effects of food web changes on aquatic communities. Traditionally, whole specimens have been used when determining isotope composition of prey fish or age-0 recreational fishes. However, gut contents of prey fish could potentially alter isotope composition of the specimen, especially when recent foraging has taken place or when the gut contains non-assimilated material that would normally pass through fishes undigested. To assess the impacts of gut content on prey fish isotope signatures, we examined the differences in isotopic variation of five prey fish species using whole fish, whole fish with the gut contents removed, and dorsal muscle only. We found significant differences in both δ15N and δ13C between the three tissue treatments. In most cases, muscle tissue was enriched compared to whole specimens or gut-removed specimens. Moreover, differences in mean δ15N within a species were up to 2‰ among treatments. This would result in a change of over half a trophic position (TP) based on a 3.4‰ increase per trophic level. However, there were no apparent relationships between tissue isotope values in fish with increased gut fullness (more prey tissue present). We suggest that muscle tissue should be used as the standard tissue for determining isotope composition of prey fish or age-0 recreational fishes, especially when determining enrichment for mixing models, calculating TP, or constructing aquatic food webs.

  13. The oxygen isotope signature of sulfate derived from abiotic sulfite oxidation under different pH conditions

    NASA Astrophysics Data System (ADS)

    Mueller, I.; Brunner, B.; Ferdelman, T. G.

    2011-12-01

    The oxygen isotope composition of sulfate serves as an archive of past oxidative sulfur cycling. It carries information about the oxidants as well as the biochemical pathway involved in the oxidation of reduced sulfur compounds, because oxygen sources can be traced by their distinct oxygen isotope composition. Studies on the aerobic oxidation of pyrite determined varying relative contributions of oxygen from dissolved molecular oxygen (O2) and water (H2O). These discrepancies were assumed to be due to slight differences in the production and consumption of sulfur intermediates which can exchange oxygen isotopes with water. Additionally, changing pH conditions influence the oxidation rate of sulfur intermediates to sulfate as well as the rate of oxygen exchange between sulfur intermediates and water. Consequently, this affects the oxygen isotope signature of produced sulfate. However, very little is known about the oxygen isotope effects during the oxidation of sulfur intermediates. We performed experiments to assess the abiotic oxidation of sulfite to sulfate under different pH conditions, as sulfite is assumed to be an intermediate during the oxidation of reduced sulfur compounds. Dissolved sulfite was oxidized with differently isotopically labeled O2, as well as in differently labeled H2O. The relative contribution of oxygen from O2 and water in produced sulfate was determined, along with the respective oxygen isotope fractionation. Our results provide a more detailed mechanistic understanding of the aerobic oxidation of reduced sulfur species.

  14. Using the clumped isotope signature in to constrain diagenetic temperature in oceanic and periplatform sediments

    NASA Astrophysics Data System (ADS)

    Staudigel, P. T.; Swart, P. K.

    2014-12-01

    Carbonate platform margins provide a rare insight into the chemistry of the ancient oceans. As subduction destroys most pelagic sediments, periplatform sediments, mixtures of platform and oceanic derived carbonates, often are the only extant records of ancient ocean conditions. During times when the Mg/Ca ratio of the oceans is elevated, such as during the present day, metastable aragonite is the favored form of calcium carbonate produced on the platform top. Consequently periplatform sediments formed during these times initially possess high amounts of aragonite and as such have a significantly higher diagenetic potential than periplatform sediments formed during calcite seas. The rate and extent of diagenesis can be ascertained by petrographic, chemical and isotopic examination of the sediments. Numerous models can be employed to interpret the porewater and sediment chemistry. One such model involves the modeled loss of strontium over time compared to the amount available from sediment recrystallization. The degree of equilibration between sediments and their corresponding porewaters can also provide an estimate for recrystallization. Reactive transport models examine changes in the concentration of elements such as Sr and its isotopes (87Sr/86Sr) or calcium (44Ca/40Ca) in the pore fluids and the sediments. The d18O of the sediments and pore water provides an additional mechanism with which to understand diagenesis as during burial the temperatures increases while the pore waters become evolved in response to the higher temperatures and mineral-water reactions. For example, in the case of the Bahamas, the pore waters from sites drilled during ODP 166 show a dramatic increase in the d18O with depth below the sea floor. This has been interpreted as being a result of carbonate dissolution and precipitation and increasingly higher temperatures. The d18O of the carbonates decrease over the same interval, presumably as a result of higher formation temperatures at depth

  15. Partitioning water and carbon fluxes in a Mediterranean oak woodland using stable oxygen isotopes

    NASA Astrophysics Data System (ADS)

    Dubbert, Maren; Piayda, Arndt; Cuntz, Matthias; Correia, Alexandra; Silva, Filipe Costa e.; Pereira, Joao; Werner, Christiane

    2014-05-01

    Water is a key factor driving ecosystem productivity, especially in water-limited ecosystems. A separation of the component fluxes is needed to gain a functional understanding on the development of net ecosystem water fluxes and their coupling with biogeochemical cycles. Oxygen isotope signatures are valuable tracers for water movements within the ecosystem because of the distinct isotopic compositions of water in soil and vegetation. In the past, determination of isotopic signatures of evaporative or transpirational fluxes has been challenging since measurements of water vapor isotopes were difficult to obtain using cold-trap methods, delivering data with low time resolution. Recent developments in laser spectroscopy now enable direct high frequency measurements of the isotopic composition of atmospheric water vapor (δv), evapotranspiration (δET), and its components and allow validations of common modeling approaches for estimating δE and δT based on Craig and Gordon (1965). Here, a novel approach was used, combining a custom build flow-through gas-exchange branch chamber with a Cavity Ring-Down Spectrometer in a Mediteranean cork-oak woodland where two vegetation layers respond differently to drought: oak-trees (Quercus suber L.) avoid drought due to their access to ground water while herbaceous plants survive the summer as seeds. We aimed at 1) testing the Craig and Gordon equation for soil evaporation against directly measured δE and 2) quantifying the role of non-steady-state transpiration under natural conditions. Thirdly, we used this approach to quantify the impact of the understory herbaceous vegetation on ecosystem carbon and water fluxes throughout the year and disentangle how ET components of the ecosystem relate to carbon dioxide exchange. We present one year data comparing modeled and measured stable oxygen isotope signatures (δ18O) of soil evaporation, confirming that the Craig and Gordon equation leads to good agreement with measured δ18O of

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

    NASA Astrophysics Data System (ADS)

    Romanek, C.

    2010-12-01

    The stable carbon isotope composition of bivalve shells is a valuable archive of paleobiological and paleoenvironmental information. Previous work has shown that the carbon isotope composition of the shell is related to the carbon isotope composition of dissolved inorganic carbon (DIC) in the ambient water in which a bivalve lives, as well as metabolic carbon derived from bivalve respiration. The contribution of metabolic carbon varies among organisms, but it is generally thought to be relatively low (e.g., <10%) in shells from aquatic organism and high (>90%) in the shells from terrestrial organisms. Because metabolic carbon contains significantly more C-12 than DIC, negative excursions from the expected environmental (DIC) signal are interpreted to reflect an increased contribution of metabolic carbon in the shell. This observation contrasts sharply with modeled carbon isotope compositions for shell layers deposited from the inner extrapallial fluid (EPF). Previous studies have shown that growth lines within the inner shell layer of bivalves are produced during periods of anaerobiosis when acidic metabolic byproducts (e.g., succinic acid) are neutralized (or buffered) by shell dissolution. This requires the pH of EPF to decrease below ambient levels (~7.5) until a state of undersaturation is achieved that promotes shell dissolution. This condition may occur when aquatic bivalves are subjected to external stressors originating from ecological (predation) or environmental (exposure to atm; low dissolved oxygen; contaminant release) pressures; normal physiological processes will restore the pH of EPF when the pressure is removed. As a consequence of this process, a temporal window should also exist in EPF at relatively low pH where shell carbonate is deposited at a reduced saturation state and precipitation rate. For example, EPF chemistry should remain slightly supersaturated with respect to aragonite given a drop of one pH unit (6.5), but under closed conditions

  17. 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.

  18. 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.

  19. 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

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

    NASA Astrophysics Data System (ADS)

    Price, Gregory; Grimes, Stephen

    2015-04-01

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

  1. Carbon dioxide gasification of carbon black: isotope study of carbonate catalysis

    SciTech Connect

    Saber, J.M.; Falconer, J.L.; Brown, L.F.

    1984-11-01

    Temperature-programmed reaction was used with labeled isotopes (/sup 13/C and /sup 18/O) to study interactions between carbon black and potassium carbonate in pure He and 10% CO/sub 2//90% He atmospheres. Catalytic gasification precursor complexes were observed. Carbon and oxygen-bearing carbon surface groups interacted with the carbonate above 500 K to form surface complexes. Between 500 and 950 K, and in the presence of gaseous CO/sub 2/, the complexes participated in C and O exchange with the gas phase while oxygen atoms within the complexes also exchanged with those on the carbon surface. As the temperature rose, the complexes decomposed, with CO/sub 2/ the initial product. Decomposition started around 500 K in pure He, and around 950 K in CO/sub 2//He. Catalytic gasification began only after decomposition of significant portions of the complexes. Elemental potassium formed, and the active catalyst appears to alternate between being potassium metal and a potassium-oxygen-carbon complex. Potassium carbonate is not part of the catalytic cycle. 20 references, 10 figures.

  2. The chromium isotopic composition of seawater and marine carbonates

    NASA Astrophysics Data System (ADS)

    Bonnand, P.; James, R. H.; Parkinson, I. J.; Connelly, D. P.; Fairchild, I. J.

    2013-11-01

    Chromium isotopes are fractionated during redox reactions and have the potential to provide a record of changes in the oxygenation levels of the oceans in the geological past. However, Cr is a trace metal in seawater and its low concentrations make isotopic measurements challenging. Here we report the first determinations of δCr53 for seawater from open ocean (Argentine Basin) and coastal (Southampton Water) settings, using a double-spike technique. The total chromium concentration in seawater from Southampton Water is 1.85 nM, whereas the Cr content of Argentine Basin samples is 5.8-6.6 nM. The δCr53 value of seawater from the Argentine Basin is 0.491-0.556‰ in intermediate and deep waters, and varies between 0.412 and 0.664‰ in surface waters (<150 m). The δCr53 value of Southampton Water seawater is 1.505‰, which may reflect in situ reduction of Cr(VI) to Cr(III). All of our seawater samples have higher δCr53 than crustal and mantle silicates, and mass balance modelling demonstrates that river water must also be enriched in heavy Cr isotopes, indicating that Cr isotopes are fractionated during weathering and/or during transport to the oceans. We also show that the Cr isotopic composition of modern non-skeletal marine carbonates (0.640- 0.745‰) encompasses the range that we measure for Argentine Basin seawater. Thus, fractionation of Cr isotopes during precipitation of these marine carbonates is likely to be small (<0.2‰), and they have the potential to provide a record of the Cr isotopic composition of ancient seawater. Phanerozoic carbonates are also characterised by heavy δCr53 and a correlation between δCr53 and Ce/Ce* suggests that the Cr and Ce cycles in the ocean are linked.

  3. Isotope tracers of organic carbon during artificial recharge

    SciTech Connect

    Davisson, M.L.

    1998-02-09

    This project developed an analytical technique for measuring the isotope abundance for 14C and 13C in total organic carbon (TOC) in order to test whether these measurements can trace TOC interaction with sedimentary material at the bottom of rivers and lakes, soils, and subsurface aquifer rocks.

  4. Large amplitude carbon isotope excursion during the Late Silurian Lau Event

    NASA Astrophysics Data System (ADS)

    Schoenmaker, N. R.; Reichart, G. J.; Nierop, K. G. J.; Mann, U.; White, T.; Sancay, R. H.

    2010-05-01

    High magnitude excursions in the stable carbon isotope record reveal that the Silurian greenhouse world (443.7-416.0 Ma) represents a period of globally unstable environmental conditions. Fundamental changes in the global carbon cycle were more frequent and had a larger impact during the Silurian compared to any other period of the Phanerozoic [1]. The late Silurian "Lau event" is the largest of four major positive d13Ccarb excursions. The carbon isotope excursion associated with the "Lau event" is recognized globally and reaches values ranging from +6‰ from the Eastern Baltic, +8.5‰ on Gotland, 11‰ from southern Sweden and even up to 12‰ in Australia, Queensland. This makes the "Lau event" the strongest d13C excursion of the entire Phanerozoic, comparable in amplitude to Precambrian events. However, the mechanism underlying the Silurian stable isotope excursions is ill understood. Scenarios proposed include enhanced carbon burial due to anoxic conditions [2] and/or enhanced productivity [3]. Alternative hypotheses range from alternating wet and humid periods influencing global ocean circulation [4], weathering of carbonates [5] to changes in the primary producer community [6]. Evaluating these different scenarios critically relies on establishing the true magnitude of the isotopic excursions and rates of change. Existing stable carbon isotope studies of the Lau event were based on analyses of bulk carbonates or bulk organic matter. Both signal carriers are subject to admixing of organic matter or carbonates from various sources. Moreover, preferential preservation of some organic moieties, e.g. lipids, over other potentially offsets isotopic records, since the carbon isotopic signatures between these moieties substantially differ. A stable organic geochemical composition over the isotope events is thus crucial to ensure capturing the true amplitude of the excursion. Here we therefore investigate, using Curie point pyrolysis GC-MS, the composition of the

  5. Isotopic signatures and distribution of nitrogen and trapped and radiogenic xenon in the Acapulco and FRO90011 meteorites

    NASA Technical Reports Server (NTRS)

    Kim, Y.; Marti, K.

    1993-01-01

    Acapulco metal and silicate show distinct N isotopic signatures. Trapped heavy noble gases are carried by 'magnetic' opx and radiogenic Xe-129 excesses are observed in phosphate and in minor surficial phases on metal grains. N and Xe isotopic signatures in FRO90011 do not agree with those observed in Acapulco. The Acapulco meteorite is unique in having achondritic texture and chondritic composition. Its mineralogical study shows the record of high temperature (1100 C) recrystallization. However, this meteorite shows abundances of volatile elements close to the levels observed in carbonaceous chondrites and concentrations of heavy noble gases comparable to those observed in type 4 ordinary chondrites, not expected for a presumed highly equilibrated object. Nitrogen measurements in bulk Acapulco revealed two different isotopic signatures, in apparent conflict with evidence for a high degree of recrystallization. N and Xe were studied in separated mineral phases to search for the carriers in order to better understand the formation and thermal history of the Acapulco parent body.

  6. Strontium isotopic signatures of oil-field waters: Applications for reservoir characterization

    USGS Publications Warehouse

    Barnaby, R.J.; Oetting, G.C.; Gao, G.

    2004-01-01

    The 87Sr/86Sr compositions of formation waters that were collected from 71 wells producing from a Pennsylvanian carbonate reservoir in New Mexico display a well-defined distribution, with radiogenic waters (up to 0.710129) at the updip western part of the reservoir, grading downdip to less radiogenic waters (as low as 0.708903 to the east. Salinity (2800-50,000 mg/L) displays a parallel trend; saline waters to the west pass downdip to brackish waters. Elemental and isotopic data indicate that the waters originated as meteoric precipitation and acquired their salinity and radiogenic 87Sr through dissolution of Upper Permian evaporites. These meteoric-derived waters descended, perhaps along deeply penetrating faults, driven by gravity and density, to depths of more than 7000 ft (2100 m). The 87 Sr/86Sr and salinity trends record influx of these waters along the western field margin and downdip flow across the field, consistent with the strong water drive, potentiometric gradient, and tilted gas-oil-water contacts. The formation water 87Sr/86Sr composition can be useful to evaluate subsurface flow and reservoir behavior, especially in immature fields with scarce pressure and production data. In mature reservoirs, Sr Sr isotopes can be used to differentiate original formation water from injected water for waterflood surveillance. Strontium isotopes thus provide a valuable tool for both static and dynamic reservoir characterization in conjunction with conventional studies using seismic, log, core, engineering, and production data. Copyright ??2004. The American Association of Petroleum Geologist. All rights reserved.

  7. Carbon Isotope Fractionation Effects During Degradation of Methyl Halides in Agricultural Soils

    NASA Astrophysics Data System (ADS)

    Miller, L. G.; Baesman, S. M.; Oremland, R. S.; Bill, M.; Goldstein, A. H.

    2001-12-01

    fractionation factors comparable to live soil. Loss of MeCl during the same time was lower (<10%) however isotope fractionation was comparable to live soil. Our results indicate that bacterial oxidation in soil rapidly consumes methyl halides but only partly controls the fractionation of carbon isotopes. Two chemical processes also act to remove MeBr in soil, hydrolysis and nucleophilic exchange with Cl-, both of which result in fractionation of carbon isotopes. Hydrolysis does not remove MeCl. It seems likely that fractionation in soil could result from a combination of biological and chemical processes, but since they all have sizeable fractionation factors associated with the removal of methyl halides, the relative rate of each process may not be as important as the total amount of methyl halide degraded. Attempts to constrain our understanding of atmospheric methyl halide budgets using stable isotope signatures of sources and sinks will have to rely on this type of information regarding the net isotopic impact of methyl halide uptake by soils. Miller, L.G., Kalin, R.M., McCauley, S.E., Hamilton, J.T.G., Harper, D.B., Millet, D.B., Oremland, R.S., and Goldstein, A.H. (2001) Large carbon isotope fractionation associated with oxidation of methyl halides by methylotrophic bacteria, PNAS, vol. 98, 5833-5837.

  8. Constraining recharge and groundwater flow processes in hard-rock aquifers in temperate maritime climate using stable isotope signatures.

    NASA Astrophysics Data System (ADS)

    Pilatova, Katarina; Ofterdinger, Ulrich

    2015-04-01

    Recharge estimates and in understanding flow process in hard rock aquifers pose significant challenges. These arise from structural complexities of the hardrock aquifers and are further complicated by variability of the superficial cover. A comparative study of three metamorphic catchments situated in the North of Ireland is presented in this study, each with contrasting geology, glaciation history and consequently superficial cover. The presented study focusses on two main strains. Firstly, due to lack of existing records, stable water isotopes in precipitation (δ18O and δ2H) were monitored at the research sites and their temporal and spatial variability was examined. Secondly, flow processes and dynamics of groundwater recharge based on continuous records of stable isotopes in groundwater, collected along catchment transects from various depths, and its variability in relation to the acquired precipitation signal were studied. Each precipitation station exhibited distinct isotopic signatures, where weather effect and proximity to coastline are the main controlling factors governing the isotope signatures. Moreover, in each of the stations the isotopic signature varied seasonally and thus stable isotopes proved a useful tool for assessing the dynamics of groundwater recharge. The analysis of isotope signatures in precipitation and groundwater from various depths within the hard rock aquifers allowed to evaluate the timescale of recharge, with rapid responses varying from few days up to several months. In general, the recharge appeared continuous over the hydrological year within wetter catchments with higher annual precipitation amounts purging the hardrock aquifers throughout the year. However, within comparatively dryer catchments recharge has a more seasonal character, predominantly taking place during the winter half of the year. Spatially, the recharge is highly localised within the elevated catchment areas, where superficial deposits are scarce and the

  9. Recent planktic foraminifers in the Fram Strait (Arctic Ocean): carbon and oxygen stable isotope composition

    NASA Astrophysics Data System (ADS)

    Pados, T.; Spielhagen, R. F.; Bauch, D.; Meyer, H.; Segl, M.

    2012-12-01

    In paleoceanographic reconstructions the carbon isotopic compositions (δ13C) of fossil foraminifers refer to, e.g., paleoproductivity and stratification, while oxygen isotopic (δ18O) records provide information about variations in sea surface temperatures and salinities in the past. However, for a correct interpretation of the fossil data it is important to improve our understanding of the correlation between recent oceanic variability and the composition of shells of living calcareous microorganisms. For this, the upper water column and sediment surface in the Fram Strait (Arctic Ocean, 78°50'N, 5°W-8°E) were sampled for planktic foraminifer species Neogloboquadrina pachyderma (sin.) and Turborotalita quinqueloba with a large-diameter multinet and a multicorer, respectively. The δ13C and δ18O values of the shells are compared to the stable isotope composition of the ambient water and to equilibrium calcite values to define the preferred calcification depths of the foraminifers and to determine the factors controlling the isotopic signature of these calcareous microorganisms. The study area was chosen because of its high oceanographic variability: in the eastern Fram Strait the northward flowing West Spitsbergen Current (WSC) carries Atlantic Water, with a thin mixed layer on top, while in the west the upper 200 m consists of cold, low-saline Arctic outflow waters of the East Greenland Current (EGC) and warmer, saline waters of Atlantic origin underneath. Despite this variable oceanographic regime along the studied transect, the stable carbon isotope ratios of the shells do not show major differences according to their horizontal but to their vertical distribution: the δ13C values of N. pachyderma (sin.) from plankton tow samples vary roughly between -1 and -0.1‰ depending on the water depth, while the δ18O values of the tests differ more between the stations.

  10. Lipid Biomarkers and Stable Isotope Signatures of Microbial Mats in Hot Springs of Kamchatka, Russia

    NASA Astrophysics Data System (ADS)

    Romanek, C. S.; Mills, G. L.; Jones, M. E.; Paddock, L.; Li, Y.; Zhang, C. L.; Wiegel, J.

    2004-12-01

    Various hot springs of the Uzon Caldera, Kamchatka, were analyzed for their chemical and stable isotope composition to better understand the relationship(s) between thermophilic microorganisms and the environments in which they live. The springs had water temperatures ranging from 40-90\\deg C and pH ranging from 5.6-5.9. Gases that emanated from the springs were composed predominantly of CO2 (20 to 90%), with lesser amounts of CH4, (< 20%), H2, NH3 and SO2. Because the springs were acidic, they contained little dissolved inorganic carbon (DIC: millimol L-1) and sulfide (< 200 ppb), yet in some cases where microbial activity was relatively high, these constituents reached the millimol L-1 and ppm range, respectively. Total biomass displayed a relatively large range of carbon isotope compositions that ranged from -5.7 to -22.4 per mil, which may reflect the large range of carbon sources, varied CO2 fixation pathways, or other unknown mechanisms. Microbial mats were freeze-dried and extracted for lipid biomarker analysis. The lipids were separated into hydrocarbon, sterol, ether lipid, free fatty acid, and phospholipid fatty acid (PLFA) fractions. Among these fractions, PLFA indicated the community structure and abundance for Bacteria while the ether lipid fraction provided analogous information for Archaea. Results of PLFA showed 16:0 as the most abundant fatty acid (33-44%), which is universal in all living organisms. Other significant biomarkers included 18:1ω (19 to 24%), 18:2ω (5 to 13%), 16:1ω (3 to 12%), and 18:0 (2 to 7%). These biomarkers are characteristic of cyanobacteria, green-sulfur bacteria, and green non-sulfur bacteria, respectively, which are common autotrophic organisms in terrestrial hot springs. On the other hand, biomarkers of heterotrophic bacteria, such as iso- and anteiso-15:0 were low (2-8%), indicating that the bacterial carbon cycle was dominated by autotrophic organisms. Analogous archaeal constituents were present in significant

  11. The UV signature of carbon in the solar system

    NASA Astrophysics Data System (ADS)

    Hendrix, Amanda R.; Vilas, Faith; Li, Jian-Yang

    2016-01-01

    Carbon compounds are ubiquitous in the solar system but are challenging to study using remote sensing due to the mostly bland spectral nature of these species in the traditional visible-near-infrared regime. In contrast, carbonaceous species are spectrally active in the ultraviolet (UV) but have largely not been considered for studies of solar system surfaces. We compile existing UV data of carbon compounds—well-studied in contemplation of the ISM extinction "bump"—to review trends in UV spectral behavior. Thermal and/or irradiation processing of carbon species results in the loss of H and ultimately graphitization. Graphitization is shown to produce distinct spectral features in the UV, which are predicted to be more readily detected in the inner solar system, whereas outer solar system bodies are expected to be more dominated by less-processed carbon compounds. Throughout the solar system, we can thus consider a "carbon continuum" where the more evolved carbons in the inner solar system exhibit a stronger UV absorption feature and associated far-UV rise. We compare carbon spectral models with spacecraft data of two bodies from different points in the carbon continuum, Ceres and Iapetus. We find that the apparent strong far-UV upturn in Ceres' spectrum (in the 150-200 nm range) can be explained by an anthracite-like species while Iapetus' spectrum features a reflectance peak consistent with polycyclic aromatic hydrocarbons. We make generalized predictions for UV spectral characteristics in other regions of the solar system.

  12. Improved quantification of microbial CH4 oxidation efficiency in arctic wetland soils using carbon isotope fractionation

    NASA Astrophysics Data System (ADS)

    Preuss, I.; Knoblauch, C.; Gebert, J.; Pfeiffer, E.-M.

    2013-04-01

    Permafrost-affected tundra soils are significant sources of the climate-relevant trace gas methane (CH4). The observed accelerated warming of the arctic will cause deeper permafrost thawing, followed by increased carbon mineralization and CH4 formation in water-saturated tundra soils, thus creating a positive feedback to climate change. Aerobic CH4 oxidation is regarded as the key process reducing CH4 emissions from wetlands, but quantification of turnover rates has remained difficult so far. The application of carbon stable isotope fractionation enables the in situ quantification of CH4 oxidation efficiency in arctic wetland soils. The aim of the current study is to quantify CH4 oxidation efficiency in permafrost-affected tundra soils in Russia's Lena River delta based on stable isotope signatures of CH4. Therefore, depth profiles of CH4 concentrations and δ13CH4 signatures were measured and the fractionation factors for the processes of oxidation (αox) and diffusion (αdiff) were determined. Most previous studies employing stable isotope fractionation for the quantification of CH4 oxidation in soils of other habitats (such as landfill cover soils) have assumed a gas transport dominated by advection (αtrans = 1). In tundra soils, however, diffusion is the main gas transport mechanism and diffusive stable isotope fractionation should be considered alongside oxidative fractionation. For the first time, the stable isotope fractionation of CH4 diffusion through water-saturated soils was determined with an αdiff = 1.001 ± 0.000 (n = 3). CH4 stable isotope fractionation during diffusion through air-filled pores of the investigated polygonal tundra soils was αdiff = 1.013 ± 0.003 (n = 18). Furthermore, it was found that αox differs widely between sites and horizons (mean αox = 1.017 ± 0.009) and needs to be determined on a case by case basis. The impact of both fractionation factors on the quantification of CH4 oxidation was analyzed by considering both the

  13. Improved quantification of microbial CH4 oxidation efficiency in Arctic wetland soils using carbon isotope fractionation

    NASA Astrophysics Data System (ADS)

    Preuss, I.; Knoblauch, C.; Gebert, J.; Pfeiffer, E.-M.

    2012-12-01

    Permafrost-affected tundra soils are significant sources of the climate-relevant trace gas methane (CH4). The observed accelerated warming of the Arctic will cause a deeper permafrost thawing followed by increased carbon mineralization and CH4 formation in water saturated tundra soils which might cause a positive feedback to climate change. Aerobic CH4 oxidation is regarded as the key process reducing CH4 emissions from wetlands, but quantification of turnover rates has remained difficult so far. The application of carbon stable isotope fractionation enables the in situ quantification of CH4 oxidation efficiency in arctic wetland soils. The aim of the current study is to quantify CH4 oxidation efficiency in permafrost-affected tundra soils in Russia's Lena River Delta based on stable isotope signatures of CH4. Therefore, depth profiles of CH4 concentrations and δ13CH4-signatures were measured and the fractionation factors for the processes of oxidation (αox) and diffusion (αdiff) were determined. Most previous studies employing stable isotope fractionation for the quantification of CH4 oxidation in soils of other habitats (e.g. landfill cover soils) have assumed a gas transport dominated by advection (αtrans = 1). In tundra soils, however, diffusion is the main gas transport mechanism, aside from ebullition. Hence, diffusive stable isotope fractionation has to be considered. For the first time, the stable isotope fractionation of CH4 diffusion through water-saturated soils was determined with an αdiff = 1.001 ± 0.000 (n = 3). CH4 stable isotope fractionation during diffusion through air-filled pores of the investigated polygonal tundra soils was αdiff = 1.013 ± 0.003 (n = 18). Furthermore, it was found that αox differs widely between sites and horizons (mean αox, = 1.017 ± 0.009) and needs to be determined individually. The impact of both fractionation factors on the quantification of CH4 oxidation was analyzed by considering both the potential diffusion

  14. Carbon isotopes in three SNC meteorites

    NASA Astrophysics Data System (ADS)

    Carr, R. H.; Wright, I. P.; Pillinger, C. T.

    1985-02-01

    The presence of several carbonaceous components in SNC meteorites has been inferred from the analyses of samples of three SNC meteorites, Shergotty, Chassigny, and Elephant Moraine. The identification of the actual species involved, however, has not been possible except for that of the terrestrial materials known to contaminate extraterrestrial samples. Above 700 C, there is evidence of the presence of isotropically heavy and light components in all three meteorites, although there are notable differences in their isotopic compositions. The similarities observed may indicate a common origin for the meteorites, but the possibility that magmatic processes on different parent bodies have produced these features must be more fully explored.

  15. Trawling disturbance on the isotopic signature of a structure-building species, the sea urchin Gracilechinus acutus (Lamarck, 1816)

    NASA Astrophysics Data System (ADS)

    González-Irusta, José M.; Preciado, Izaskun; López-López, Lucia; Punzón, Antonio; Cartes, Joan E.; Serrano, Alberto

    2014-08-01

    Bottom trawling is one of the main sources of anthropogenic disturbance in benthic habitats with important direct and indirect effects on the ecosystem functional diversity. In this study, the effect of this impact on a structure-building species, the sea urchin Gracilechinus acutus, was studied in the Central Cantabrian Sea (southern Bay of Biscay) comparing its isotopic signature and additional population descriptors across different trawling pressures. Trawling disturbance had a significant effect on the studied descriptors. In trawling areas, this urchin showed significantly lower values of biomass and mean size and significantly higher values of fullness index. Moreover, the trawling disturbance effect was also significant in the isotopic signature of G. acutus. Urchins inhabiting untrawled areas showed significant lower values of δ15N than urchins dwelling areas under trawling pressure. The urchins' isotopic enrichment increased along the species ontogeny regardless of the trawling effort level. Stable isotope analyses are a suitable tool to detect trawling disturbance on the trophic pathways but do not suffice to explain these changes, especially if there is a lack of baseline information.

  16. Carbon Isotopes of Alkanes in Hydrothermal Abiotic Organic Synthesis Processes at High Temperatures and Pressures: An Experimental Study

    NASA Technical Reports Server (NTRS)

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

    2010-01-01

    Observation of methane in the Martian atmosphere has been reported by different detection techniques [1-4]. With more evidence showing extensive water-rock interaction in Martian history [5-7], abiotic formation by Fischer-Tropsch Type (FTT) synthesis during serpentization reactions may be one possible process responsible for methane generation on Mars [8, 9]. While the experimental studies performed to date leave little doubt that chemical reactions exist for the abiotic synthesis of organic compounds by mineral surface-catalyzed reactions [10-12], little is known about the reaction pathways by which CO2 and/or CO are reduced under hydrothermal conditions. Carbon and hydrogen isotope measurements of alkanes have been used as an effective tool to constrain the origin and reaction pathways of hydrocarbon formation. Alkanes generated by thermal breakdown of high molecular weight organic compounds have carbon and hydrogen isotopic signatures completely distinct from those formed abiotically [13-15]. Recent experimental studies, however, showed that different abiogenic hydrocarbon formation processes (e.g., polymerization vs. depolymerization) may have different carbon and hydrogen isotopic patterns [16]. Results from previous experiments studying decomposition of higher molecular weight organic compounds (lignite) also suggested that pressure could be a crucial factor affecting fractionation of carbon isotopes [17]. Under high pressure conditions, no experimental data are available describing fractionation of carbon isotope during mineral catalyzed FTT synthesis. Thus, hydrothermal experiments present an excellent opportunity to provide the requisite carbon isotope data. Such data can also be used to identify reaction pathways of abiotic organic synthesis under experimental conditions.

  17. Spatially resolved analysis of plutonium isotopic signatures in environmental particle samples by laser ablation-MC-ICP-MS.

    PubMed

    Konegger-Kappel, Stefanie; Prohaska, Thomas

    2016-01-01

    Laser ablation-multi-collector-inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) was optimized and investigated with respect to its performance for determining spatially resolved Pu isotopic signatures within radioactive fuel particle clusters. Fuel particles had been emitted from the Chernobyl nuclear power plant (ChNPP) where the 1986 accident occurred and were deposited in the surrounding soil, where weathering processes caused their transformation into radioactive clusters, so-called micro-samples. The size of the investigated micro-samples, which showed surface alpha activities below 40 mBq, ranged from about 200 to 1000 μm. Direct single static point ablations allowed to identify variations of Pu isotopic signatures not only between distinct fuel particle clusters but also within individual clusters. The resolution was limited to 100 to 120 μm as a result of the applied laser ablation spot sizes and the resolving power of the nuclear track radiography methodology that was applied for particle pre-selection. The determined (242)Pu/(239)Pu and (240)Pu/(239)Pu isotope ratios showed a variation from low to high Pu isotope ratios, ranging from 0.007(2) to 0.047(8) for (242)Pu/(239)Pu and from 0.183(13) to 0.577(40) for (240)Pu/(239)Pu. In contrast to other studies, the applied methodology allowed for the first time to display the Pu isotopic distribution in the Chernobyl fallout, which reflects the differences in the spent fuel composition over the reactor core. The measured Pu isotopic signatures are in good agreement with the expected Pu isotopic composition distribution that is typical for a RBMK-1000 reactor, indicating that the analyzed samples are originating from the ill-fated Chernobyl reactor. The average Pu isotope ratios [(240)Pu/(239)Pu = 0.388(86), (242)Pu/(239)Pu = 0.028(11)] that were calculated from all investigated samples (n = 48) correspond well to previously published results of Pu analyses in contaminated samples from

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

    NASA Astrophysics Data System (ADS)

    Hesselbo, S. P.; Korte, C.

    2010-12-01

    The Jurassic comprises some 55 million years of Earth history. However, within the Jurassic, only one major environmental change (hyperthermal) event is really well known - the Early Toarcian Oceanic Anoxic Event (OAE) at ~183 Ma - and until very recently the extent to which the accompanying environmental changes were global has been strongly debated. Nevertheless, partly as a result of the international effort to define Global Stratotype Sections and Points (GSSPs), much more is now being discovered about environmental changes taking place at and around the other Jurassic Age (Stage) boundaries, to the extent that meaningful comparisons between these events can begin to be made. Here we present new carbon and oxygen isotope data from mollusks (bivalves and belemnites) and brachiopods collected through the marine Early Jurassic succession of NE England, including the Sinemurian-Plienbachian boundary GSSP. All materials have been screened by chemical analysis and scanning electron microscopy to check for diagenetic alteration. Analysis of carbon isotopes from marine calcite is supplemented by analysis of carbon-isotope values from fossil wood collected through the same section. It is demonstrated that both long-term and short-term carbon-isotope shifts from the UK Early Jurassic represent global changes in carbon cycle balances. The Sinemurian-Pliensbachian boundary event is an event of global significance and shows several similarities to the Toarcian OAE (relative sea-level change, carbon-isotope signature), but also some significant contrasts (oxygen-isotope based paleotemperatures which provide no evidence for warming). Significant contrast in oxygen- and carbon-isotope co-variation also occurs on a long timescale. There appear to be two modes in the co-variation of carbon and oxygen isotopes through this time interval: mode 1 shows positive correlation and may be explained by conventional sources and sinks for carbon-dioxide; mode 2, representing negative

  19. 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

  20. 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.

  1. Magnesium isotope fractionation in bacterial mediated carbonate precipitation experiments

    NASA Astrophysics Data System (ADS)

    Parkinson, I. J.; Pearce, C. R.; Polacskek, T.; Cockell, C.; Hammond, S. J.

    2012-12-01

    Magnesium is an essential component of life, with pivotal roles in the generation of cellular energy as well as in plant chlorophyll [1]. The bio-geochemical cycling of Mg is associated with mass dependant fractionation (MDF) of the three stable Mg isotopes [1]. The largest MDF of Mg isotopes has been recorded in carbonates, with foraminiferal tests having δ26Mg compositions up to 5 ‰ lighter than modern seawater [2]. Magnesium isotopes may also be fractionated during bacterially mediated carbonate precipitation and such carbonates are known to have formed in both modern and ancient Earth surface environments [3, 4], with cyanobacteria having a dominant role in carbonate formation during the Archean. In this study, we aim to better constrain the extent to which Mg isotope fractionation occurs during cellular processes, and to identify when, and how, this signal is transferred to carbonates. To this end we have undertaken biologically-mediated carbonate precipitation experiments that were performed in artificial seawater, but with the molar Mg/Ca ratio set to 0.6 and with the solution spiked with 0.4% yeast extract. The bacterial strain used was marine isolate Halomonas sp. (gram-negative). Experiments were run in the dark at 21 degree C for two to three months and produced carbonate spheres of various sizes up to 300 μm in diameter, but with the majority have diameters of ~100 μm. Control experiments run in sterile controls (`empty` medium without bacteria) yielded no precipitates, indicating a bacterial control on the precipitation. The carbonate spheres are produced are amenable to SEM, EMP and Mg isotopic analysis by MC-ICP-MS. Our new data will shed light on tracing bacterial signals in carbonates from the geological record. [1] Young & Galy (2004). Rev. Min. Geochem. 55, p197-230. [2] Pogge von Strandmann (2008). Geochem. Geophys. Geosys. 9 DOI:10.1029/2008GC002209. [3] Castanier, et al. (1999). Sed. Geol. 126, 9-23. [4] Cacchio, et al. (2003

  2. Using carbon isotope fractionation for an improved quantification of CH4 oxidation efficiency in Arctic peatlands

    NASA Astrophysics Data System (ADS)

    Preuss, I.; Knoblauch, C.; Gebert, J.; Pfeiffer, E.-M.

    2012-04-01

    Much research effort is focused on identifying global CH4 sources and sinks to estimate their current and potential strength in response to land-use change and global warming. Aerobic CH4 oxidation is regarded as the key process reducing the strength of CH4 emissions in wetlands, but is hitherto difficult to quantify. Recent studies quantify the efficiency of CH4 oxidation based on CH4 stable isotope signatures. The approach utilizes the fact that a significant isotope fractionation occurs when CH4 is oxidized. Moreover, it also considers isotope fractionation by diffusion. For field applications the 'open-system equation' is applied to determine the CH4 oxidation efficiency: fox = (δE - δP)/ (αox - αtrans) where fox is the fraction of CH4 oxidized; δE is δ13C of emitted CH4; δP is δ13C of produced CH4; αox is the isotopic fractionation factor of oxidation; αtrans is the isotopic fractionation factor of transport. We quantified CH4 oxidation in polygonal tundra soils of Russia's Lena River Delta analyzing depth profiles of CH4 concentrations and stable isotope signatures. Therefore, both fractionation factors αox and αtrans were determined for three polygon centers with differing water table positions and a polygon rim. While most previous studies on landfill cover soils have assumed a gas transport dominated by advection (αtrans = 1), other CH4 transport mechanisms as diffusion have to be considered in peatlands and αtrans exceeds a value of 1. At our study we determined αtrans = 1.013 ± 0.003 for CH4 when diffusion is the predominant transport mechanism. Furthermore, results showed that αox differs widely between sites and horizons (αox = 1.013 ± 0.012) and has to be determined for each case. The impact of both fractionation factors on the quantification of CH4 oxidation was estimated by considering both the potential diffusion rate at different water contents and potential oxidation rates. Calculations for a water saturated tundra soil

  3. Systematic analysis of reaction cross sections of carbon isotopes

    SciTech Connect

    Horiuchi, W.; Suzuki, Y.; Abu-Ibrahim, B.; Kohama, A.

    2007-04-15

    We systematically analyze total reaction cross sections of carbon isotopes with N= 6-16 on a {sup 12}C target for wide range of incident energy. The intrinsic structure of the carbon isotope is described by a Slater determinant generated from a phenomenological mean-field potential, which reasonably well reproduces the ground-state properties for most of the even N isotopes. We need separate studies not only for odd nuclei but also for {sup 16}C and {sup 22}C to improve their wave functions. The density of the carbon isotope is constructed by eliminating the effect of the center-of-mass motion. For the calculations of the cross sections, we take two schemes, the Glauber approximation and the eikonal model using a global optical potential. Both the reaction models successfully reproduce low and high incident energy data on the cross sections of {sup 12}C, {sup 13}C, and {sup 16}C on {sup 12}C. The calculated reaction cross sections of {sup 15}C are found to be considerably smaller than the empirical values observed at low energy. We find a consistent parametrization of the nucleon-nucleon scattering amplitude, differently from previous ones. Finally, we predict the total reaction cross section of {sup 22}C on {sup 12}C.

  4. Fingerprints of carbon, nitrogen, and silicon isotopes in small interstellar SiC grains from the Murchison meteorite

    NASA Technical Reports Server (NTRS)

    Hoppe, Peter; Geiss, Johannes; Buehler, Fritz; Neuenschwander, Juerg; Amari, Sachiko; Lewis, Roy S.

    1993-01-01

    We report ion microprobe determinations of the carbon, nitrogen, and silicon isotopic compositions of small SiC grains from the Murchison CM2 chondrite. Analyses were made on samples containing variable numbers of grains and on 14 individual grains. In some cases the multiple-grain sample compositions were probably dominated by only one or two grains. Total ranges observed are given. Only a few grains show values near the range limits. Both the total ranges of carbon and nitrogen isotopic compositions, and even the narrower ranges typical for the majority of the grains, are similar to those observed for larger SiC grains. Two rare components appear to be present in the smaller-size fraction, one characterized by C-12/C-13 about 12-16 and the other by very heavy nitrogen. The carbon and nitrogen isotopic compositions qualitatively may reflect hydrostatic H-burning via the CNO cycle and He-burning in red giants, as well as explosive H-burning in novae. The silicon isotopic compositions of most grains qualitatively show what is the signature of He-burning. The silicon isotopic composition of one grain, however, suggests a different process.

  5. Carbonate clumped isotope constraints on Silurian ocean temperature and seawater δ18O

    NASA Astrophysics Data System (ADS)

    Cummins, Renata C.; Finnegan, Seth; Fike, David A.; Eiler, John M.; Fischer, Woodward W.

    2014-09-01

    Much of what we know about the history of Earth’s climate derives from the chemistry of carbonate minerals in the sedimentary record. The oxygen isotopic compositions (δ18O) of calcitic marine fossils and cements have been widely used as a proxy for past seawater temperatures, but application of this proxy to deep geologic time is complicated by diagenetic alteration and uncertainties in the δ18O of seawater in the past. Carbonate clumped isotope thermometry provides an independent estimate of the temperature of the water from which a calcite phase precipitated, and allows direct calculation of the δ18O of the water. The clumped isotope composition of calcites is also highly sensitive to recrystallization and can help diagnose different modes of diagenetic alteration, enabling evaluation of preservation states and identification of the most pristine materials from within a sample set-critical information for assessing the quality of paleoproxy data generated from carbonates. We measured the clumped isotope composition of a large suite of calcitic fossils (primarily brachiopods and corals), sedimentary grains, and cements from Silurian (ca. 433 Ma) stratigraphic sections on the island of Gotland, Sweden. Substantial variability in clumped isotope temperatures suggests differential preservation with alteration largely tied to rock-buffered diagenesis, complicating the generation of a stratigraphically resolved climate history through these sections. Despite the generally high preservation quality of samples from these sections, micro-scale observations of calcite fabric and trace metal composition using electron backscatter diffraction and electron microprobe analysis suggest that only a subset of relatively pristine samples retain primary clumped isotope signatures. These samples indicate that Silurian tropical oceans were likely warm (33 ± 7 °C) and similar in oxygen isotopic composition to that estimated for a “modern” ice-free world (δ18OVSMOW of -1

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

    NASA Technical Reports Server (NTRS)

    Eigenbrode, Jennifer L.

    2012-01-01

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

  7. Isotopic Hg in an Allende carbon-rich residue

    NASA Technical Reports Server (NTRS)

    Reed, G. W., Jr.; Jovanovic, S.

    1990-01-01

    A carbon-rich residue from Allende subjected to stepwise heating yielded two isotopically resolvable types of Hg: one with an (Hg-196)/(Hg-202) concentration ratio the same as terrestrial (monitor) Hg; the other enriched in Hg-196 relative to Hg-202 by about 60 percent. Hg with the 202 isotope enriched relative to 196, as is found in bulk Allende, was not observed. Whether the result of mass fractionation or nucleosynthesis, the distinct types of Hg entered different carrier phases and were not thermally mobilized since the accretion of the Allende parent body.

  8. Comparison of DNA and Carbon and Nitrogen Stable Isotope-based Techniques for Identification of Prior Vertebrate Hosts of Ticks.

    PubMed

    Hamer, Sarah A; Weghorst, Alex C; Auckland, Lisa D; Roark, E Brendan; Strey, Otto F; Teel, Pete D; Hamer, Gabriel L

    2015-09-01

    Identification of the vertebrate hosts upon which hematophagous arthropods feed provides key information for understanding the ecology and transmission of vector-borne diseases. Bloodmeal analysis of ticks presents unique challenges relative to other vectors, given the long interval between bloodmeal acquisition and host-seeking, during which DNA degradation occurs. This study evaluates DNA-based and stable isotope-based bloodmeal analysis methodologies for the lone star tick, Amblyomma americanum (Linneaus, 1758), in an experimental study with chicken as the known host. We subjected ticks of different ages and environmental rearing conditions to three DNA-based approaches and a stable isotopic analysis, which relies on the natural variation of nitrogen ((15)N/(14)N) and carbon ((13)C/(12)C) isotopes. While all three DNA-based approaches were successful in identifying the bloodmeal host of the engorged nymphs, only the probe-based RT-PCR was able to detect host DNA in aged ticks, the success of which was low and inconsistent across age and rearing treatments. In contrast, the stable isotope analysis showed utility in determining the host across all ages of ticks when isotopic values of ticks were compared with a panel of candidate vertebrate species. There was a positive shift in both δ(13)C and δ(15)N in adult A. americanum until 34 wk postnymphal bloodmeal. Through analyzing the isotopic signatures of eight potential vertebrate host species, we determined that the magnitude of this isotopic shift that occurred with tick age was minor compared with the heterogeneity in the δ(15)N and δ(13)C signatures among species. These results suggest that stable isotopes are a useful tool for understanding tick-host interactions. PMID:26336205

  9. Monitoring crude oil mineralization in salt marshes: Use of stable carbon isotope ratios

    SciTech Connect

    Jackson, A.W.; Pardue, J.H.; Araujo, R.

    1996-04-01

    In laboratory microcosms using salt marsh soils and in field trials, it was possible to monitor and quantify crude oil mineralization by measuring changes in CO{sub 2} {delta}{sup 13}C signatures and the rate of CO{sub 2} production. These values are easy to obtain and can be combined with simple isotope mass balance equations to determine the rate of mineralization from both the crude oil and indigenous carbon pool. Hydrocarbon degradation was confirmed by simultaneous decreases in alkane-, isoprenoid-, and PAH-hopane ratios. Additionally, the pseudo-first-order rate constants of alkane degradation (0.087 day{sup -1}) and CO{sub 2} production (0.082 day{sup -1}) from oil predicted by the {delta}{sup 13}C signatures were statistically indistinguishable. The addition of inorganic nitrogen and phosphate increased the rate of mineralization of crude oil in aerated microcosms but had no clear effect on in situ studies. This procedure appears to offer a means of definitively quantifying crude oil mineralization in a sensitive, inexpensive, and simple manner in environments with appropriate background {delta}{sup 13}C signatures. 23 refs., 5 figs., 1 tab.

  10. Trophic interactions in the benthic boundary layer of the Beaufort Sea shelf, Arctic Ocean: Combining bulk stable isotope and fatty acid signatures

    NASA Astrophysics Data System (ADS)

    Connelly, Tara L.; Deibel, Don; Parrish, Christopher C.

    2014-01-01

    The food web structure and diets of 26 taxa of benthic boundary layer (BBL) zooplankton on the Beaufort Sea shelf were studied using carbon and nitrogen stable isotopes and fatty acids. Mean δ15N values ranged from 7.3‰ for the amphipod Melita formosa to 14.9‰ for an unidentified polychaete, suggesting that taxa sampled came from three trophic levels. For 8 taxa, the lightest carbon signature occurred near the mouth of the Mackenzie River. Stable isotope ratios helped clarify the origin of signature fatty acids. Levels of certain polyunsaturated fatty acids (PUFA) were negatively correlated with δ15N, with the exception of 22:6ω3, which was positively correlated with δ15N, suggesting that this essential PUFA was retained through the food web. Discriminant analysis proved to be a powerful tool, predicting taxa from fatty acid profiles with 99% accuracy, and revealing strong phylogenetic trends in fatty acid profiles. The amphipod Arrhis phyllonyx had higher levels of ω6 PUFA, especially 20:4ω6 with several possible sources, than other peracarid crustaceans. The holothurian had high levels of odd numbered and branched chain fatty acids, indicative of bacterial consumption, while fatty acids of phytoplankton origin were important discriminants for Calanus hyperboreus and the chaetognaths Eukrohnia hamata and Parasagitta elegans. This relationship indicates that the conventional phytoplankton-copepod-chaetognath food web found in the water column also exists in the BBL. This observation, as well as generally low δ15N and high levels of certain PUFA in samples with lower δ15N, strongly suggests that BBL zooplankton on the Beaufort Sea shelf have access to fresh material of phytoplankton origin either by feeding on sedimenting matter or by active migration to surface waters.

  11. Impact of feeding and short-term temperature stress on the content and isotopic signature of fatty acids, sterols, and alcohols in the scleractinian coral Turbinaria reniformis

    NASA Astrophysics Data System (ADS)

    Tolosa, I.; Treignier, C.; Grover, R.; Ferrier-Pagès, C.

    2011-09-01

    This study assesses the combined effect of feeding and short-term thermal stress on various physiological parameters and on the fatty acid, sterol, and alcohol composition of the scleractinian coral Turbinaria reniformis. The compound-specific carbon isotope composition of the lipids was also measured. Under control conditions (26°C), feeding with Artemia salina significantly increased the symbiont density and chlorophyll content and the growth rates of the corals. It also doubled the concentrations of almost all fatty acid (FA) compounds and increased the n-alcohol and sterol contents. δ13C results showed that the feeding enhancement of FA concentrations occurred either via a direct pathway, for one of the major polyunsaturated fatty acid (PUFA) compounds of the food (18:3n-3 FA), or via an enhancement of photosynthate transfer (indirect pathway), for the other coral FAs. Cholesterol (C27Δ5) was also directly acquired from the food. Thermal stress (31°C) affected corals, but differently according to their feeding status. Chlorophyll, protein content, and maximal photosynthetic efficiency of photosystem II (PSII) decreased to a greater extent in starved corals. In such corals, FA concentrations were reduced by 33%, (especially C16, C18 FAs, and n-3 PUFA) and the sterol content by 27% (especially the C28∆5,22 and C28∆5). The enrichment in the δ13C signature of the storage and structural FAs suggests that they were the main compounds respired during the stress to maintain the coral metabolism. Thermal stress had less effect on the lipid concentrations of fed corals, as only FA levels were reduced by 13%, with no major changes in their isotope carbon signatures. In conclusion, feeding plays an essential role in sustaining T. reniformis metabolism during the thermal stress.

  12. Emission sources and atmospheric processing of carbonaceous aerosols in India and China: Insights from dual carbon isotope techniques

    NASA Astrophysics Data System (ADS)

    Andersson, A.; Kirillova, E. N.; Bosch, C.; Suresh, T.; Lee, M.; Du, K.; Sheesley, R. J.; Budhavant, K.; Gustafsson, O. M.

    2013-12-01

    The large emissions of carbonaceous aerosols, e.g., black carbon (BC), in India and China have detrimental effects on both human health and the regional climate. However, mitigation efforts as well as accurate modeling of these effects are currently hampered by large uncertainties regarding the contributions from different emission sources, including both primary and secondary processes. Here, we present dual carbon isotope constraints on emissions sources and atmospheric processing from multiple sites capturing the outflow from India and China. Radiocarbon (14C) studies of elemental carbon (EC) - a tracer for BC - show larger relative fossil contributions than expected from bottom-up emission inventories, for both India (49+-5) and China (80 +-6%). Similarly to EC, radiocarbon constraints of water soluble organic carbon (WSOC) shows substantially larger relative fossil contributions in Chinese outflow (30-50%) as compared with India, but also compared to Europe and USA (10-20%). In contrast to the radiocarbon data, stable carbon (d13C) analysis of WSOC shows substantial variability for different sites capturing the Indian outflow. Strong enrichment of heavy isotopes in WSOC is coupled to expected transport time from sources, indicating the influence of photochemical aging during transport. Such trends in the d13C signature are not observed for the EC fraction. Taken together this work show that carbon isotope techniques provide firm constraints on emission sources of different fractions of carbonaceous aerosols, and may also offer insights into atmospheric processing of these constituents during air mass transport.

  13. Carbon and nitrogen isotope studies in an arctic ecosystem

    SciTech Connect

    Schell, D.M.

    1989-12-31

    This proposal requests funding for the completion of our current ecological studies at the MS-117 research site at Toolik Lake, Alaska. We have been using a mix of stable and radioisotope techniques to assess the fluxes of carbon and nitrogen within the ecosystem and the implications for long-term carbon storage or loss from the tundra. Several tentative conclusions have emerged from our study including: Tundra in the foothills is no longer accumulating carbon. Surficial radiocarbon abundances show little or no accumulation since 1000--2500 yrs BP. Coastal plain tundra is still accumulating carbon, but the rate of accumulation has dropped in the last few thousand years. Carbon export from watersheds in the Kuparuk and Imnavait Creek drainages are in excess of that expected from estimated primary productivity; and Nitrogen isotope abundances vary between species of plants and along hydrologic gradients.

  14. Carbon and nitrogen isotope studies in an arctic ecosystem

    SciTech Connect

    Schell, D.M.

    1989-01-01

    This proposal requests funding for the completion of our current ecological studies at the MS-117 research site at Toolik Lake, Alaska. We have been using a mix of stable and radioisotope techniques to assess the fluxes of carbon and nitrogen within the ecosystem and the implications for long-term carbon storage or loss from the tundra. Several tentative conclusions have emerged from our study including: Tundra in the foothills is no longer accumulating carbon. Surficial radiocarbon abundances show little or no accumulation since 1000--2500 yrs BP. Coastal plain tundra is still accumulating carbon, but the rate of accumulation has dropped in the last few thousand years. Carbon export from watersheds in the Kuparuk and Imnavait Creek drainages are in excess of that expected from estimated primary productivity; and Nitrogen isotope abundances vary between species of plants and along hydrologic gradients.

  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. Investigating the Formation of Pedogenic Carbonate Using Stable Isotopes

    NASA Astrophysics Data System (ADS)

    Breecker, D. O.; Sharp, Z. D.; McFadden, L.

    2006-12-01

    The stable isotope composition of pedogenic carbonate has been used as a paleoenvironmental proxy because it is thought to form in isotopic equilibrium with soil CO2 and soil water, which are influenced by vegetation type and atmospheric circulation patterns, respectively. However, the isotopic composition of soil CO2 and soil water change seasonally and it is not known what portion of this variability is recorded by the isotopic composition of pedogenic carbonate. It is generally believed that carbonate precipitation in soils is driven by evaporative concentration of Ca ions and/or decreasing soil pCO2. We seek to improve the proxy by determining the seasonality of pedogenic carbonate formation, in particular whether pedogenic carbonate forms during the wet season after individual rainstorms or during seasonal drying following the wet season. This was done by comparing the variations in carbon and oxygen isotope composition of soil CO2 with the isotopic composition of proximally located, newly-formed carbonates. Soil CO2 and incipient pedogenic carbonate coatings were collected in a very young (< 500yrs) soil developing in an inset terrace on the piedmont of the Sandia Mountains, central New Mexico. We also measure soil temperatures at the same site. In May 2006, at the end of the driest 6-month period on record in central New Mexico, soil CO2 profiles displayed a 2‰ decrease in δ13C values with depth from 9 to 100 cm. In August 2006, the shapes of the profiles were similar, but the δ13C values were 3-4‰ lower at each depth than in May. These results can be explained by an increase in respiration rate during the latter half of the summer (the wettest on record) when monsoon rainfall maintained high moisture contents in soils across New Mexico. Calculated δ13C values of calcite in equilibrium with May (but not August) soil CO2 agree with measured carbonate δ13C values below 20 cm depth. Very shallow carbonate has anomalously high δ13C values. Measurements

  18. USE OF FATTY ACID STABLE CARBON ISOTOPE RATIO TO INDICATE MICROBIAL CARBON SOURCE IN TROPICAL SOILS

    EPA Science Inventory


    We use measurements of the concentration and stable carbon isotope ratio of individual microbial phospholipid fatty acids (PLFAs) in soils as indicators of live microbial biomass levels, broad microbial community structure, and microbial carbon source. For studies of soil o...

  19. Isotopic Signature Transfer and Mass Pattern Prediction (IsoStamp): An Enabling Technique for Chemically-Directed Proteomics

    PubMed Central

    2011-01-01

    Directed proteomics applies mass spectrometry analysis to a subset of information-rich proteins. Here we describe a method for targeting select proteins by chemical modification with a tag that imparts a distinct isotopic signature detectable in a full-scan mass spectrum. Termed isotopic signature transfer and mass pattern prediction (IsoStamp), the technique exploits the perturbing effects of a dibrominated chemical tag on a peptide’s mass envelope, which can be detected with high sensitivity and fidelity using a computational method. Applying IsoStamp, we were able to detect femtomole quantities of a single tagged protein from total mammalian cell lysates at signal-to-noise ratios as low as 2.5:1. To identify a tagged-peptide’s sequence, we performed an inclusion list-driven shotgun proteomics experiment where peptides bearing a recoded mass envelope were targeted for fragmentation, allowing for direct site mapping. Using this approach, femtomole quantities of several targeted peptides were identified in total mammalian cell lysate, while traditional data-dependent methods were unable to identify as many peptides. Additionally, the isotopic signature imparted by the dibromide tag was detectable on a 12-kDa protein, suggesting applications in identifying large peptide fragments, such as those containing multiple or large posttranslational modifications (e.g., glycosylation). IsoStamp has the potential to enhance any proteomics platform that employs chemical labeling for targeted protein identification, including isotope coded affinity tagging, isobaric tagging for relative and absolute quantitation, and chemical tagging strategies for posttranslational modification. PMID:21604797

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

    PubMed

    Nilsson, Roland; Jain, Mohit

    2016-05-24

    Stable isotope tracing is a powerful method for interrogating metabolic enzyme activities across the metabolic network of living cells. However, most studies of mammalian cells have used (13)C-labeled tracers only and focused on reactions in central carbon metabolism. Cellular metabolism, however, involves other biologically important elements, including nitrogen, hydrogen, oxygen, phosphate and sulfur. Tracing stable isotopes of such elements may help shed light on poorly understood metabolic pathways. Here, we demonstrate the use of high-resolution mass spectrometry to simultaneously trace carbon and nitrogen metabolism in human cells cultured with (13)C- and (15)N-labeled glucose and glutamine. To facilitate interpretation of the complex isotopomer data generated, we extend current methods for metabolic flux analysis to handle multivariate mass isotopomer distributions (MMIDs). We find that observed MMIDs are broadly consistent with known biochemical pathways. Whereas measured (13)C MIDs were informative for central carbon metabolism, (15)N isotopes provided evidence for nitrogen-carrying reactions in amino acid and nucleotide metabolism. This computational and experimental methodology expands the scope of metabolic flux analysis beyond carbon metabolism, and may prove important to understanding metabolic phenotypes in health and disease. PMID:27098229

  1. Pore fluid chemistry and spectral induced polarization signatures of calcium carbonate

    NASA Astrophysics Data System (ADS)

    Wu, Y.; Hubbard, S. S.; Ajo Franklin, J. B.; Williams, K. H.

    2010-12-01

    Calcium carbonate (CaCO3) minerals are a key family of compounds that frequently precipitate during natural and engineered subsurface processes. They play important roles in elemental cycling within geosystems and can be utilized in the context of environmental remediation (such as metal sequestration through co-precipitation) and in geotechnical engineering (such as improving soil strength or decreasing rock permeability). Characterizing the spatial extent and temporal dynamics of carbonate mineral precipitation is critical for these studies. Our previous research has indicated the potential of geophysical methods, particularly spectral induced polarization (SIP) for tracking the onset and evolution of mineral precipitates, including calcite. Here, we experimentally document the significant role of pore fluid chemistry and surface charge structure on the SIP signature of calcium carbonates. Our column studies revealed that the SIP signature of calcium carbonate is dictated by surface charge structure that relies heavily on surface complexation properties, such as charge density and speciation. For calcium carbonate, the primary potential determining ions (PDIs) are calcium and carbonate ions and the SIP signatures of calcium carbonate are primarily controlled by the concentrations of these species. Our data show that calcium carbonates in thermodynamic equilibrium with pore fluid produce a negligible SIP response due to very small (if any) surface charges. In contrast, systems that are over saturated with respect to calcium carbonate (i.e., far from equilibrium) produce significant SIP responses, which is consistent with high surface charge densities shown by high zeta potential values in previous studies. Our studies reveal that a closed system that transitions from over-saturation to equilibrium conditions is accompanied by significant decrease of SIP signals (and vice-versa). The studies also show that the effect of pH on SIP signature of calcium carbonate is

  2. The Late Miocene Carbon Isotope Shift and Marine Biological Productivity.

    NASA Astrophysics Data System (ADS)

    Diester-Haass, L.; Billups, K.; Emeis, K. C.

    2004-12-01

    The late Miocene global carbon isotope shift of approximately 1 per mil is not well understood. Is it linked to ocean-related processes such as the AƒAøAøâ_sA¬A.â_oBiologic BloomAƒAøAøâ_sA¬ \\(Farrell et al., 1995\\), or to changes in type \\(C3/C4 plants\\) or cover of terrestrial vegetation? Here we examine the evolution of marine biological productivity during the isotope shift at ODP Site 846 \\(Pacific equatorial upwelling, where the AƒAøAøâ_sA¬A.â_oBiologic BloomAƒAøAøâ_sA¬ has been first described, Farrell al, 1995\\) and at Indian Ocean Site 721 \\(monsoon-driven upwelling\\), and compare their productivity history with non upwelling locations in the Atlantic Ocean. The onset of the carbon isotope shift is accompanied at all locations by an increase in paleoproductivity derived from benthic foraminiferal accumulation rates \\(expressed as gC/cm2 * ky; Huerguera, 2000\\) and increased abundance of Uvigerina spp.. At the equatorial upwelling sites the increase is comparable to half present-day values to present-day values; in the Atlantic Ocean paleoproductivity increases from present-day up to 3 times present-day values. But the productivity maxima are not concurrent. The carbon isotope shift is accompanied by severe carbonate dissolution and reduced ventilation of bottom waters, as reflected in the occurrence of pyrite and good preservation of cartilageous fish debris. Carbonate preservation is good since about 6 Ma despite high productivity. We discuss changing deep water circulation patterns, increased weathering and continental nutrient delivery, as well as erosion of terrestrial vegetation as possible factors to explain our findings.

  3. Boron isotope fractionation in magma via crustal carbonate dissolution

    PubMed Central

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

    2016-01-01

    Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ11B values down to −41.5‰, reflecting preferential partitioning of 10B into the assimilating melt. Loss of 11B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports 11B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ11B melt values in arc magmas could flag shallow-level additions to the subduction cycle. PMID:27488228

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

    PubMed

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

    2016-01-01

    Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ(11)B values down to -41.5‰, reflecting preferential partitioning of (10)B into the assimilating melt. Loss of (11)B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports (11)B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ(11)B melt values in arc magmas could flag shallow-level additions to the subduction cycle. PMID:27488228

  5. Boron isotope fractionation in magma via crustal carbonate dissolution

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

    Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ11B values down to ‑41.5‰, reflecting preferential partitioning of 10B into the assimilating melt. Loss of 11B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports 11B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ11B melt values in arc magmas could flag shallow-level additions to the subduction cycle.

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

    NASA Astrophysics Data System (ADS)

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

    1990-12-01

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

  7. Emissions of molecular hydrogen (H2) and its isotopic signature from residential heaters and waste incinerators

    NASA Astrophysics Data System (ADS)

    Vollmer, M. K.; Walter, S.; Mohn, J.; Steinbacher, M.; Bond, S. W.; Roeckmann, T.; Reimann, S.

    2011-12-01

    Atmospheric molecular hydrogen (H2) has recently received increased interest in the scientific community because of a potential shift to a global hydrogen energy economy which could potentially alter the atmospheric budget of H2 due to substantial leakage. This calls for an improved understanding of the present day's atmospheric H2 budget. One of the major sources of H2 are emissions from incomplete combustion of fossil fuel. While emissions of H2 from car exhaust have been studied extensively, those from fossil fuel based heating systems have remained a matter of speculation. Here we present results from measurements of a variety of residential heating systems covering oil, gas, and wood heating with various burner capacities. For oil and gas heating systems we surprisingly find no net H2 emissions, i.e. the exhaust air contains H2 at or below the mole fractions of the intake air (approx. 0.5 ppm). While H2 emissions are virtually absent, those of carbon monoxide (CO) are not. As a consequence, caution has to be exercised when modeling H2 emissions based on assumed H2/CO ratios and using CO emission inventories. We also find that the molecular hydrogen in the approx. 0.5 ppm exhaust air is isotopically strongly depleted (-20 permil to -200 permil) compared to the ambient air (+130 permil). This suggests that H2 is involved in the combustion processes, and therefore the H2 of the intake air is not the same H2 in the exhaust air. Exhausts from waste incinerator plants are generally also depleted in H2 mole fractions and in their H/D isotopic composition.

  8. Organic matter dynamics and stable isotope signature as tracers of the sources of suspended sediment

    NASA Astrophysics Data System (ADS)

    Schindler Wildhaber, Y.; Liechti, R.; Alewell, C.

    2012-06-01

    Suspended sediment (SS) and organic matter in rivers can harm brown trout Salmo trutta by affecting the health and fitness of free swimming fish and by causing siltation of the riverbed. The temporal and spatial dynamics of sediment, carbon (C), and nitrogen (N) during the brown trout spawning season in a small river of the Swiss Plateau were assessed and C isotopes as well as the C/N atomic ratio were used to distinguish autochthonous and allochthonous sources of organic matter in SS loads. The visual basic program IsoSource with 13Ctot and 15N as input isotopes was used to quantify the temporal and spatial sources of SS. Organic matter concentrations in the infiltrated and suspended sediment were highest during low flow periods with small sediment loads and lowest during high flow periods with high sediment loads. Peak values in nitrate and dissolved organic C were measured during high flow and high rainfall, probably due to leaching from pasture and arable land. The organic matter was of allochthonous sources as indicated by the C/N atomic ratio and δ13Corg. Organic matter in SS increased from up- to downstream due to an increase of pasture and arable land downstream of the river. The mean fraction of SS originating from upper watershed riverbed sediment decreased from up to downstream and increased during high flow at all measuring sites along the course of the river. During base flow conditions, the major sources of SS are pasture, forest and arable land. The latter increased during rainy and warmer winter periods, most likely because both triggered snow melt and thus erosion. The measured increase in DOC and nitrate concentrations during high flow support these modeling results. Enhanced soil erosion processes on pasture and arable land are expected with increasing heavy rain events and less snow during winter seasons due to climate change. Consequently, SS and organic matter in the river will increase, which will possibly affect brown trout negatively.

  9. Carbon isotope fractionation during experimental crystallisation of diamond from carbonate fluid at mantle conditions

    NASA Astrophysics Data System (ADS)

    Reutsky, Vadim; Borzdov, Yuri; Palyanov, Yuri; Sokol, Alexander; Izokh, Olga

    2015-12-01

    We report first results of a systematic study of carbon isotope fractionation in a carbonate fluid system under mantle PT conditions. The system models a diamond-forming alkaline carbonate fluid using pure sodium oxalate (Na2C2O4) as the starting material, which decomposes to carbonate, CO2 and elementary carbon (graphite and diamond) involving a single source of carbon following the reaction 2Na2C2O4 → 2Na2CO3 + CO2 + C. Near-liquidus behaviour of carbonate was observed at 1300 °C and 6.3 GPa. The experimentally determined isotope fractionation between the components of the system in the temperature range from 1300 to 1700 °C at 6.3 and 7.5 GPa fit the theoretical expectations well. Carbon isotope fractionation associated with diamond crystallisation from the carbonate fluid at 7.5 GPa decreases with an increase in temperature from 2.7 to 1.6 ‰. This trend corresponds to the function ΔCarbonate fluid-Diamond = 7.38 × 106 T-2.

  10. Carbon and nitrogen isotope fractionation during possible organic aerosol formation in Titan and the early Earth

    NASA Astrophysics Data System (ADS)

    Imanaka, H.

    2012-12-01

    Abiotic formation of complex organic macromolecule aerosols is important not only for the potential for prebiotic chemical evolution, but also in the global elemental cycle. The direct clues of the habitable environment and biosphere on the early Earth are mostly obtained from geological records, such as isotope signatures and biomarkers in the ancient organic sediments. The recent Cassini-Huygens mission revealed the generation of complex organic aerosols in Titan's upper atmosphere, and similar processes could have lead to the formation of organic aerosols in the early Earth atmosphere. Understanding the formation reaction network and accompanying isotope fractionation processes of the organic aerosols is necessary to constrain the active organic environment on the early Earth from the available geological evidence. We have investigated the abiotic formation of organic aerosols in simulated atmospheres of Titan and the early, with particular focus on carbon and nitrogen isotope fractionation. Laboratory aerosol analogues, termed tholins, are generated with cold plasma irradiation of reduced gas mixtures, such as N2/CH4 and N2/H2/CO. Stable isotopic ratios of 15N/14N and 13C/12C for the generated tholins are measured with an elemental analysis-isotope ratio mass spectrometer (EA-IR-MS). Our preliminary data for tholins generated from an equivalent N2/CH4 (=90/10) gas mixture at various pressures suggests the 15N isotopic fractionation up to δ15N = -20~25 permil during tholin formation, while 13C isotopic fractionation seems almost negligible. This negative δ15N is even lighter than those observed in kerogens in the Archean sediments (Beaumont and Robert, 1999; Pinti et al., 2001), and the organic haze could have contributed to the source of 15N-depleted kerogens. Furthermore, the δ15N vary with deposition pressure. Previous works demonstrated that the resulted two types of tholin are very different in chemical structure and optical properties (Imanaka et al

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

    PubMed Central

    KŁUSEK, MARZENA; PAWEŁCZYK, SŁAWOMIRA

    2015-01-01

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

  12. Stable carbon isotope fractionation during aerobic biodegradation of chlorinated ethenes

    SciTech Connect

    Chu, Kung-Hui; Mahendra, Shaily; Song, Donald L.; Conrad, Mark E.; Alvarez-Cohen, Lisa

    2003-06-01

    Stable isotope analysis is recognized as a powerful tool for monitoring, assessing, and validating in-situ bioremediation processes. In this study, kinetic carbon isotope fractionation factors () associated with the aerobic biodegradation of vinyl chloride (VC), cis-1,2-dichloroethylene (cDCE), and trichloroethylene (TCE) were examined. Of the three solvents, the largest fractionation effects were observed for biodegradation of VC. Both metabolic and cometabolic VC degradation were studied using Mycobacterium aurum L1 (grown on VC), Methylosinus trichosporium OB3b (grown on methane), Mycobacterium vaccae JOB 5 (grown on propane), and two VC enrichment cultures seeded from contaminated soils of Alameda Point and Travis Air Force Base, CA. M. aurum L1 caused the greatest fractionation (= -5.7) while for the cometabolic cultures, values ranged from -3.2 to -4.8. VC fractionation patterns for the enrichment cultures were within the range of those observed for the metabolic and cometabolic cultures (= -4.5 to -5.5). The fractionation for cometabolic degradation of TCE by Me. trichosporium OB3b was low (= -1.1), while no quantifiable carbon isotopic fractionation was observed during the cometabolic degradation of cDCE. For all three of the tested chlorinated ethenes, isotopic fractionation measured during aerobic degradation was significantly smaller than that reported for anaerobic reductive dechlorination. This study suggests that analysis of compound-specific isotopic fractionation could assist in determining whether aerobic or anaerobic degradation of VC and cDCE predominates in field applications of in-situ bioremediation. In contrast, isotopic fractionation effects associated with metabolic and cometabolic reactions are not sufficiently dissimilar to distinguish these processes in the field.

  13. Disequilibrium in Clumped Isotopes Caused by Diagenesis in Tertiary Carbonates

    NASA Astrophysics Data System (ADS)

    Murray, S.; Swart, P. K.

    2015-12-01

    This work examines the clumped isotopes and carbonate associated sulfate (CAS) within a system which is being altered from aragonite to calcite and being subjected to partial dolomitization within the marine realm. Samples were collected from Clino, a ≈670m long core which represents slope carbonates composed of varying percentages of aragonite, low-magnesium calcite (LMC), and dolomite. The concentrations of these endmembers differ dramatically over short distances and are associated with varying degrees of marine diagenesis. In the deeper water portion of the core, previous work has shown no evidence of exposure throughout nor is there any evidence for hydrothermal fluids existing in the Bahamas. Bulk samples were collected from the portions of the core in which dolomite was most prominent. Samples were treated and measured for CAS and for their clumped isotope value. They were then subjected to a series of buffered acetic acid leaches to remove the aragonite and LMC portion of the sample. There were up to three treatments per sample with the resulting sediment measured on XRD to determine its % dolomite composition. These treatments were then also measured for clumped isotopes. The δ34S of the sediments yielded values of up to 10‰ more positive than contemporaneous sweater and implicate bacterial sulfate reduction in the formation of these dolomites. Clumped isotope results of the separates allowed for the calculation of end-member formation temperatures for the LMC and dolomite, whilst using a mixing model to account for non-linearity in ∆47 between end-member combinations and varying ∆47-temperature equations. In contrast to other dolomites in the Bahamas proposed to have formed by massive flow of normal seawater, the Clino temperatures values were significantly elevated compared to the presumed equilibrium values. These data suggest that BSR may result in carbonates with clumped isotopic values significant elevated to equilibrium.

  14. Can isotopic signatures reveal reactive nitrogen priming of soil organic matter decompostion ?

    NASA Astrophysics Data System (ADS)

    Hood-Nowotny, Rebecca; Msii Participants, Alter-Net

    2015-04-01

    The newest meta-data analyses and the model based hypotheses state that global soil C storage is controlled by microbial scale processes of fungal competition for available nitrogen (N). However, the details of these microbe-dependent feedback mechanisms on N and C dynamics in European soils are largely unknown and contentious. Given global trends of increasing atmospheric N deposition and the continuing use of inorganic N fertilizer, the function of soils as a carbon sink is potentially under threat. Therefore, further research is urgently required in order to be able to provide reliable information on soil microbial responses for predictive climate change models. Changes in nutrient status could result in a chain reaction of interacting microbial mechanisms which in turn could lead to the shifts in underlying ecosystem biogeochemical process rates. Recent meta-analysis has shown that plant fungal symbiont community structure, exerts a greater fundamental control over soil C storage than temperature, precipitation or net primary production. Based on the hypothesis that plant associated fungi effectively scavenge all available organic and inorganic N leaving little N for the growth of the free-living decomposer microbial community and preventing further breakdown of SOM To investigate these possible effects we have sampled natural grassland and forest soils across a trans European gradient (ALTER-net-MSII Network) which have received additional inputs of inorganic nitrogen for the last five years and studied the impacts of nitrogen on the concentrations and isotope ratios of bulk soil organic matter (SOM) in addition to particular organic matter (POM) fractions, as early indicators of SOM decomposition. Initial results suggest that isotope ratios combined with C:N ratios of SOM can be useful to tease out some underlying mechanisms of organic matter breakdown for example the impact of carbonate/pH on SOM decomposition. But more detailed analyses of specific soil

  15. 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.

  16. Precision performance of a Cavity Ring-down isotope spectrometer for carbon and oxygen isotopes of carbonate materials

    NASA Astrophysics Data System (ADS)

    Cunningham, K. L.; Hoffnagle, J.; He, Y.; Fleck, D.; Saad, N.; Dennis, K.

    2013-12-01

    We have developed a novel laser spectrometer intended specifically for the measurement of δ18O and δ13C in solid carbonate material. Carbonate carbon and oxygen isotopes provide key contributions into our understanding of climate, biogeochemical processes and the carbon cycle. For this reason, the isotopic measurements of carbonates are one of the most abundant measures made by Earth scientists today. Conventional measurement techniques using isotope ratio mass spectrometry (IRMS), although optimized and prevalent, require dedicated personnel and can be expensive to operate. Here we present a new laser-based technique that will simplify measurements of δ18Ocarb and δ13Ccarb without compromising precision. To date, there have been no laser-based instruments with a demonstrated ability to meet the requirements of the carbonates community -- typically better than 0.1 ‰ for δ13C and δ18O for CO2 evolved from 1 mg of pure CaCO3. We will present data showing that the new Picarro G2171-i spectrometer meets these requirements. The spectrometer uses the laser-based spectroscopy technique of Cavity Ring-Down Spectroscopy (CRDS), a technology that has been successfully applied to many other isotopic ratio measurements including δ13C of CO2, δ13C of CH4, and δ18O and δD of H2O. The spectrometer has been optimized to analyze the absorption spectra of concentrated CO2, specifically the isotopologues 12C16O16O, 13C16O16O, 12C16O18O, and 12C18O16O. We employ a new sample delivery technique that enables a longer integration time period, and hence more precise data. Long-term results for a run of 540 pulses of tank CO2 (90 hours) records a 1σ standard deviation precision for δ18O and δ13C of < 0.08 ‰ and < 0.055 ‰, respectively. We coupled the CRDS spectrometer to an optimized sample acidification system and analyzed standards to assess the accuracy of the CRDS. We will present an inter-comparison between CRDS and IRMS for carbonates using standards commonly used

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

    NASA Astrophysics Data System (ADS)

    Nowak, M. E.; Beulig, F.; von Fischer, J.; Muhr, J.; Küsel, K.; Trumbore, S. E.

    2015-09-01

    quantification of cbbL/cbbM marker genes encoding for RubisCO by quantitative polymerase chain reaction (qPCR) and by acetogenic and methanogenic microorganisms, shown present in the moffettes by previous studies. Combined Δ14C and δ13C isotope mass balances indicated that microbially derived carbon accounted for 8 to 27 % of bulk SOM in this soil layer. The findings imply that autotrophic organisms can recycle significant amounts of carbon in wetland soils and might contribute to observed reservoir effects influencing radiocarbon signatures in peat deposits.

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

    NASA Astrophysics Data System (ADS)

    Nowak, M. E.; Beulig, F.; von Fischer, J.; Muhr, J.; Küsel, K.; Trumbore, S. E.

    2015-12-01

    -Benson-Bassham (CBB) cycle, as indicated from quantification of cbbL/cbbM marker genes encoding for RubisCO by quantitative polymerase chain reaction (qPCR) and by acetogenic and methanogenic microorganisms, shown present in the mofettes by previous studies. Combined Δ14C and δ13C isotope mass balances indicated that microbially derived carbon accounted for 8-27 % of bulk SOM in this soil layer. The findings imply that autotrophic microorganisms can recycle significant amounts of carbon in wetland soils and might contribute to observed radiocarbon reservoir effects influencing Δ14C signatures in peat deposits.

  19. The influence of microclimates and fog on stable isotope signatures used in interpretation of regional hydrology: East Maui, Hawaii

    USGS Publications Warehouse

    Scholl, M.A.; Gingerich, S.B.; Tribble, G.W.

    2002-01-01

    Stable isotopes of precipitation, ground water and surface water measured on the windward side of East Maui from 0 to 3055 m altitude were used to determine recharge sources for stream flow and ground water. Correct interpretation of the hydrology using rainfall ??18O gradients with altitude required consideration of the influence of fog, as fog samples had isotopic signatures enriched by as much as 3??? in ??18O and 21??? in ??D compared to volume-weighted average precipitation at the same altitude. The isotopic analyses suggested that fog drip was a major component of stream flow and shallow ground water at higher altitudes in the watershed. 18O/altitude gradients in rainfall were comparable for similar microclimates on Maui (this study) and Hawaii Island (1990-1995 study), however, East Maui ??18O values for rain in trade-wind and high-altitude microclimates were enriched compared to those from Hawaii Island. Isotopes were used to interpret regional hydrology in this volcanic island aquifer system. In part of the study area, stable isotopes indicate discharge of ground water recharged at least 1000 m above the sample site. This deep-flowpath ground water was found in springs from sea level up to 240 m altitude, indicating saturation to altitudes much higher than a typical freshwater lens. These findings help in predicting the effects of ground water development on stream flow in the area. Published by Elsevier Science B.V.

  20. 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

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

    USGS Publications Warehouse

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

    1981-01-01

    Previous interest in light hydrocarbons from geothermal systems has focused principally on the origin of the methane1 and the estimation of subsurface temperatures from the carbon isotopic content of coexisting methane and carbon dioxide1-3. Higher molecular weight hydrocarbons were first reported in gases from Yellowstone National Park4, and have since been found to occur commonly in geothermal emanations in the western United States5. Isotopic measurements of individual geothermal hydrocarbons are now reported which help to explain the origin of these hydrocarbons. The thermal decomposition of sedimentary or groundwater organic matter is a principal source of hydrocarbons in four geothermal areas in western North America. ?? 1981 Nature Publishing Group.

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

    SciTech Connect

    Ismail, Atef; Cheong, Lee Yen; Yahya, Noorhana; Tammam, M.

    2014-10-24

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

  3. Low stable carbon isotope fractionation by coccolithophore RubisCO

    NASA Astrophysics Data System (ADS)

    Boller, Amanda J.; Thomas, Phaedra J.; Cavanaugh, Colleen M.; Scott, Kathleen M.

    2011-11-01

    The 13C/ 12C ratio of carbon compounds is used to identify sources and sinks in the global carbon cycle. However, the relatively enriched 13C content observed for marine organic carbon remains enigmatic. The majority of oceanic carbon is fixed by algae and cyanobacteria via the Calvin-Benson-Bassham cycle, yet isotopic discrimination by the CO 2 fixation enzyme, RubisCO (ribulose 1,5-bisphosphate carboxylase/oxygenase), has only been measured for a single marine cyanobacterium. Different forms of RubisCO occur in different phytoplankton species (overall amino acid identity varying by as much as ˜75%) and thus may vary in the degree to which they fractionate carbon. Here we measured isotope discrimination by RubisCO from the coccolithophore Emiliania huxleyi, a cosmopolitan species used as a marine algal model .E. huxleyi RubisCO discriminated substantially less ( ɛ = 11.1‰) against 13CO 2 than other RubisCO enzymes (18-29‰), despite having Michaelis-Menten kinetic parameters ( K = 72 μM; Vmax = 0.66 μmol min -1 mg -1 protein) similar to those measured for RubisCO enzymes from different organisms. If widespread, decreased isotope discrimination of 13C by phytoplankton RubisCO may be a major factor influencing the enriched 13C content of marine organic carbon. This finding emphasizes the necessity of (a) determining ɛ values for RubisCOs of other marine phytoplankton and (b) re-evaluation of δ13C values from physiological, environmental, and geological studies.

  4. 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.

  5. 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.

  6. Mechanistic insights into the formation of chloroform from natural organic matter using stable carbon isotope analysis

    NASA Astrophysics Data System (ADS)

    Breider, Florian; Hunkeler, Daniel

    2014-01-01

    Chloroform can be naturally formed in terrestrial environments (e.g. forest soils, peatland) by chlorination of natural organic matter (NOM). Recently, it was demonstrated that natural and anthropogenic chloroform have a distinctly different carbon isotope signature that makes it possible to identify its origin in soil and groundwater. In order to evaluate the contribution of different functional groups to chloroform production and factors controlling the isotopic composition of chloroform, carbon isotope trends during chlorination of model compounds, soil organic matter (SOM) and humic acids were evaluated, and apparent kinetic isotope effects (AKIEs) quantified. Phenol and propanone were selected as model compounds representing common functional groups in NOM. Chlorination was induced by hypochlorous acid to mimic natural chlorination. The pH ranged between 4 and 8 to cover typical soil conditions. For each model compound and pH, different AKIEs were observed. For phenol, the AKIE was normal at pH 4 (1.0156 ± 0.0012) and inverse at pH 8 (0.9900 ± 0.0007). For 2-propoanol, an opposite pH dependence was observed with an inverse AKIE at pH 4 (0.9935 ± 0.0007) and a normal AKIE at pH 8 (1.0189 ± 0.0016). The variations of the AKIE values suggest that the rate-limiting step of the reaction is either the re-hybridization of the carbon atom involved in chloroform formation or the hydrolysis of trichloroacetyl intermediates depending on the nature of functional group and pH. The chloroform formation from humic acid and SOM gives rise to small isotope variations. A comparison of the isotopic trends of chloroform formed from humic acid and SOM with those found for the model compounds suggest that opposed AKIE associated with the chlorination of phenolic and ketone moieties of NOM partly compensate each other during chlorination of NOM indicating that different types of functional groups contribute to chloroform formation.

  7. Terpane biomarkers and carbon isotopes in environmental geochemistry-application of a case study from Prince William Sound, Alaska

    SciTech Connect

    Kvenvolden, K.A.; Hostettler, F.D.; Rosenbauer, R.J.; Hostetter, D.E.; Castle, W.T.

    1996-12-31

    Geochemical studies in Prince William Sound, Alaska, following the 1989 Exxon Valdez oil spill have provided information that is being used to interpret preliminary environmental geochemical observations made in coastal California. Although the shorelines of Prince William Sound still retain traces of the 1989 oil spill, most of the flattened tar balls that can be found today on these shorelines are not residues of Exxon Valdez oil. Rather, the hydrocarbon-biomarker and carbon-isotopic signatures of these tar balls have remarkably similar characteristics that are consistent with those of oil products that originated from Monterey Formation source rocks of California. Some of these products were spilled into the sound during the 1964 Alaskan earthquake. Selected terpane biomarker ratios and carbon isotope composition of whole oil samples can geochemically distinguish Exxon Valdez residues from the tar balls. Results are discussed.

  8. The Robustness of Clumped Isotope Temperatures to Bond Reordering: Evidence from Deeply Buried Carbonate Reservoirs

    NASA Astrophysics Data System (ADS)

    MacDonald, J.; John, C. M.; Girard, J. P.

    2014-12-01

    Numerous studies have shown that clumped isotope thermometry records the temperature of precipitation for carbonate minerals in surface and near-surface environments. However, the ability of a mineral to retain its clumped isotope signature at deeper, hotter burial conditions is still debated. Dolomite has been shown to be more robust to clumped isotope bond reordering than calcite. In this contribution we measure clumped isotopes in calcite veins from Southern Europe that have been buried to up to 7 km to test the robustness of calcite and dolomite to bond reordering. First, we analysed finely crystalline dolostone matrix samples collected in industry wells from Southwest France and buried to between 2 and 5.5 km, Results indicated a temperatures of ~40-60 °C, interpreted to represent formation in an early burial environment. By contrast, coarser dolomite crystals that are petrographically distinct from the fine-grained dolomite record higher temperatures and are interpreted to reflect a deeper, hotter phase of dolomite formation. Preliminary analysis of a calcite vein from a Cretaceous dolostone in Southern Europe buried to 6.3 km records a temperature of 41±3 °C; the calcite matrix around this records a similarly low temperature. This is well below the present-day well temperature of 130-140 °C. Our results indicate that both calcite and dolomite are not affected by bond reordering at the range of depths and temperatures investigated here. Furthermore, this suggests that clumped isotope thermometry can be applied to deeply-buried samples (i.e. >5km).

  9. The relationship between needle sugar carbon isotope ratios and tree rings of larch in Siberia.

    PubMed

    Rinne, K T; Saurer, M; Kirdyanov, A V; Loader, N J; Bryukhanova, M V; Werner, R A; Siegwolf, R T W

    2015-11-01

    Significant gaps still exist in our knowledge about post-photosynthetic leaf level and downstream metabolic processes and isotopic fractionations. This includes their impact on the isotopic climate signal stored in the carbon isotope composition (δ(13)C) of leaf assimilates and tree rings. For the first time, we compared the seasonal δ(13)C variability of leaf sucrose with intra-annual, high-resolution δ(13)C signature of tree rings from larch (Larix gmelinii Rupr.). The trees were growing at two sites in the continuous permafrost zone of Siberia with different growth conditions. Our results indicate very similar low-frequency intra-seasonal trends of the sucrose and tree ring δ(13)C records with little or no indication for the use of 'old' photosynthates formed during the previous year(s). The comparison of leaf sucrose δ(13)C values with that in other leaf sugars and in tree rings elucidates the cause for the reported (13)C-enrichment of sink organs compared with leaves. We observed that while the average δ(13)C of all needle sugars was 1.2‰ more negative than δ(13)C value of wood, the δ(13)C value of the transport sugar sucrose was on an average 1.0‰ more positive than that of wood. Our study shows a high potential of the combined use of compound-specific isotope analysis of sugars (leaf and phloem) with intra-annual tree ring δ(13)C measurements for deepening our understanding about the mechanisms controlling the isotope variability in tree rings under different environmental conditions. PMID:26433019

  10. Carbon Isotope and Isotopomer Fractionation in Dense Molecular Cloud Cores

    NASA Astrophysics Data System (ADS)

    Furuya, K.; Aikawa, Y.; Sakai, N.; Yamamoto, S.

    2011-05-01

    Observations of 13C species would be useful to investigate chemistry of carbon-bearing species. Recent observations in TMC-1 indicate that the abundances are different among carbon isotopomers of the same species. For instance, Takano et al. (1998) found that HCC13CN is more abundant than HC13CCN and H13CCCN, which indicates the three carbon atoms are not equivalent in HC_3N. Sakai et al. (2007; 2010) reported the abundance ratios of C13CS/13CCS and CCH/13CCH to be 4.2 and 1.6, respectively. Again, two carbon atoms are not equivalent in CCS and CCH. Sakai et al. (2007; 2010) discussed an origin of these anomalies and pointed out two possibilities: (i) fractionation during the formation of the species and (ii) rearrangements of the 13C position after the formation of molecules by isotopomer-exchange reactions. We construct a gas-grain chemical network model which includes carbon isotopes (12C and 13C) and isotopomers in order to investigate the evolution of molecular abundances, the carbon isotope ratios (12CX/13CX) and the isotopomer ratios (12C13CX/13C12CX) of CCH and CCS in dense molecular cores. We confirm that the isotope ratios of molecules, both in the gas phase and on grain surfaces, mostly depend on whether the species is formed from the carbon atom (ion) or the CO molecule; the isotope ratio is larger than the elemental abundance ratio of 12C/13C if the species is formed from the carbon atom, while the ratio is smaller if the species is formed from the CO molecule (cf. Langer et al. 1984). We successfully reproduce the observed C13CH/13CCH ratio in TMC-1 by considering the isotopomer-exchange reaction, 13CCH + H rightleftharpoons C13CH + H + 8.1 K. However, the C13CS/13CCS ratio remains lower than observed in TMC-1. We then assume the isotopomer-exchange reaction catalyzed by the H atom, 13CCS + H rightleftharpoons C13CS + H + 17.4 K. In the model with this reaction, the observed C13CS/13CCS, CCS/C13CS and CCS/13CCS ratios can be reproduced simultaneously.

  11. Stable carbon and nitrogen isotope enrichment in primate tissues

    PubMed Central

    Carter, Melinda L.; Karpanty, Sarah M.; Zihlman, Adrienne L.; Koch, Paul L.; Dominy, Nathaniel J.

    2010-01-01

    Isotopic studies of wild primates have used a wide range of tissues to infer diet and model the foraging ecologies of extinct species. The use of mismatched tissues for such comparisons can be problematic because differences in amino acid compositions can lead to small isotopic differences between tissues. Additionally, physiological and dietary differences among primate species could lead to variable offsets between apatite carbonate and collagen. To improve our understanding of the isotopic chemistry of primates, we explored the apparent enrichment (ε*) between bone collagen and muscle, collagen and fur or hair keratin, muscle and keratin, and collagen and bone carbonate across the primate order. We found that the mean ε* values of proteinaceous tissues were small (≤1‰), and uncorrelated with body size or phylogenetic relatedness. Additionally, ε* values did not vary by habitat, sex, age, or manner of death. The mean ε* value between bone carbonate and collagen (5.6 ± 1.2‰) was consistent with values reported for omnivorous mammals consuming monoisotopic diets. These primate-specific apparent enrichment values will be a valuable tool for cross-species comparisons. Additionally, they will facilitate dietary comparisons between living and fossil primates. Electronic supplementary material The online version of this article (doi:10.1007/s00442-010-1701-6) contains supplementary material, which is available to authorized users. PMID:20628886

  12. STABLE ISOTOPE SIGNATURES OF MUCUS OF STEELHEAD TROUT IN A CONTROLLED DIET SWITCH EXPERIMENT

    EPA Science Inventory

    Our work has shown that fish mucus can serve as a very rapid indicator of diet switching in fish. We performed diet switching studies of steelhead trout in a controlled hatchery setting using specially formulated low delta 15N signature and high delta 15N signature diets. To ou...

  13. Local and regional oscillations of carbon and oxygen isotopes in terestrial carbonates

    NASA Astrophysics Data System (ADS)

    Skipitytė, Raminta; Stančikaitė, Miglė

    2014-05-01

    Stable isotope ratios of carbon and oxygen in sediment carbonates are used as a tool to identify climatic changes in the past [1], [2]. Carbon is more related to humidity whereas oxygen is thought to respond the temperature [2]. Nevertheless number of questions about local, regional and global scale impacts to these records is left. In this research work carbon and oxygen isotope ratios in lacustrine carbonates are used to identify palaeoenvironmental dynamics of different locations. Samples of lacutrine carbonates were obtained from 8 sequences of different sites in Lithuania (4), Poland (1), Belarus (1) and Kaliningrad (1). Every sequence was divided into 2 cm intervals. The study showed differences in average carbon and oxygen isotope ratios between Lithuania and other countries (Poland, Belarus and Kaliningrad). Carbon and oxygen isotope ratios in 4 sites in Lithuania are: ¯U la δ13C -4.72± 2.11, o and δ18O -9.46± 1.9, o ; Zervynos δ13C -4.79± 1.82, o and δ18O -9.57± 1.69, o ; Rudnia δ13C -4.94± 7.53, o and δ18O -9.3± 3.92, o ; Pauliai δ13C -4.15± 0.67, o and δ18O -9.94± 1.07, o : In other countries: Poland δ13C -1.07± 1.94, o and δ18O -7.69± 0.95, o ; Belarus δ13C 0.97± 1.94, o and δ18O -7.61± 1.42, o ; Kaliningrad δ13C -1.14± 1.43, o and δ18O -6.51± 1.00, o : Average stable carbon and oxygen isotope values from four sites in Lithuania were -4.65 o for carbon and -9.51 o for oxygen. Despite homogeneity of average isotope signals in these four sites there are relatively large oscillations of isotopic values in Rudnia and relatively small in Pauliai. These oscillations could be related to local characteristics of particular place such as environmental conditions, water balance, input of terrigenous materials into basin, etc. Total amount of CaCO3 could also play a significant role in reconstructing palaeoenvironment from stable isotopes and creating isomaps. The comparison of isotope records from different locations could enable to

  14. Microbial isotopic signatures in calcareous tufa from Punta Mita coastal vents, Mexico

    NASA Astrophysics Data System (ADS)

    Canet, C.; Prol-Ledesma, R. M.; Melgarejo, J. C.; Reyes, A.

    2002-12-01

    Numerous small calcareous mounds accompanied by Ba, Hg and Tl mineralization occur in shallow submarine hydrothermal manifestations on the sea bottom, at 10 m depth, in Punta Mita (Western coast of Mexico). The formation of calcite mounds in these coastal vents provides an uncommon example of calcareous tufa deposits in a submarine hydrothermal environment. The hydrothermal activity consists in water and gas (essentially nitrogen and methane) venting at 85°C, through a 100 m fissure hosted in basaltic rocks and partially covered by unconsolidated sediments. The mounds consist of travertine-like metre-sized calcite aggregates that develop around the main submarine hot springs. Barite, sulphides (mostly pyrite and cinnabar) and phosphates (carbonate-hydroxylapatite) are also present in these mounds. Two main calcite types are texturally distinguished: firstly an earlier radial-fibrous generation, and a later fine-grained calcite generation that cements the detrital grains and fills the pore spaces. Stable isotope analyses were performed in calcite from these mounds. The δ13C measured values show a strong depletion in 13C, with values as low as -39.2 per mil (PDB). These values agree with a microbially mediated calcite mineralization process, by means of bacterial oxidation of vent derived methane. In contrast to most known cases of microbial methane oxidation, in Punta Mita this process took place under hydrothermal conditions.

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

  16. 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.

  17. New high resolution geochemistry of Lower Jurassic marine sections in western North America: A global positive carbon isotope excursion in the Sinemurian?

    NASA Astrophysics Data System (ADS)

    Porter, Sarah J.; Smith, Paul L.; Caruthers, Andrew H.; Hou, Pengfei; Gröcke, Darren R.; Selby, David

    2014-07-01

    Recognising variations in the carbon isotope compositions of marine organic-rich sedimentary rocks can provide insight into changes in ocean chemistry throughout geological time. Further, identification of global excursions in the carbon isotope record has proved to be valuable as a chronostratigraphic correlation tool. This investigation presents new high-resolution organic carbon isotope data (δCorg13) for marine sediments from 2 regions in North America (Last Creek, British Columbia, Canada and Five Card Draw, Nevada, USA). The carbon isotope profiles demonstrate that there were significant differences between the carbon reservoirs at Five Card Draw and Last Creek, notably in the upper part of the Leslei Zone. The δCorg13 values show a gradual positive CIE (∼2‰) at Last Creek in the upper part of the Leslei Zone. This corresponds to a coeval positive CIE of similar duration in Dorset, UK (upper Turneri Zone; Jenkyns and Weedon, 2013), suggesting that this may be a global marine carbon isotope signature, and likely reflects a widespread increase in primary productivity during the Early Sinemurian. In addition, a brief negative CIE is observed in the uppermost Lower Sinemurian at Last Creek. This negative excursion is not recorded in the Dorset section, suggesting localised upwelling of 12C-rich bottom-waters at Last Creek. Further, the signals identified at Last Creek are not present in coeval sections at Five Card Draw, thus highlighting a significant difference between these localities. Osmium (Os) isotope data (initial 187Os/188Os values) provide a quantitative determination of the contrasting depositional environments of Five Card Draw and Last Creek (at least partially restricted with high levels of continental inundation and open-ocean, respectively). This demonstrates that basinal restriction may act as a major factor that controls isotopic stratigraphic signatures, thus preventing the identification of global or widespread regional excursions.

  18. C isotope fractionation during heterotrophic activity driven carbonate precipitation

    NASA Astrophysics Data System (ADS)

    Balci, Nurgul; Demirel, Cansu

    2016-04-01

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

  19. 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

  20. Boron Isotope Intercomparison Project (BIIP): Development of a new carbonate standard for stable isotopic analyses

    NASA Astrophysics Data System (ADS)

    Gutjahr, Marcus; Bordier, Louise; Douville, Eric; Farmer, Jesse; Foster, Gavin L.; Hathorne, Ed; Hönisch, Bärbel; Lemarchand, Damien; Louvat, Pascale; McCulloch, Malcolm; Noireaux, Johanna; Pallavicini, Nicola; Rodushkin, Ilia; Roux, Philippe; Stewart, Joseph; Thil, François; You, Chen-Feng

    2014-05-01

    Boron consists of only of two isotopes with a relatively large mass difference (~10 %). It is also volatile in acidic media and prone to contamination during analytical treatment. Nevertheless, an increasing number of isotope laboratories are successfully using boron isotope compositions (expressed in δ11B) in marine biogenic carbonates to reconstruct seawater pH. Recent interlaboratory comparison efforts [1] highlighted the existence of a relatively high level of disagreement between laboratories when measuring such material, so in order to further strengthen the validity of this carbonate system proxy, appropriate reference materials need to be urgently characterised. We describe here the latest results of the Boron Isotope Intercomparison Project (BIIP) where we aim to characterise the boron isotopic composition of two marine carbonates: Japanese Geological Survey carbonate standard materials JCp-1 (coral porites) [2] and JCt-1 (Giant Clam) [3]. This boron isotope interlaboratory comparison study has two aims: (i) to assess to what extent chemical pre-treatment, aimed at removing organic material, can influence the resulting carbonate δ11B; (ii) to determine the isotopic composition of the two reference materials with a number of analytical techniques to provide the community with reference δ11B values for JCp-1 and JCt-1 and to further explore any differences related to analytical technique. In total eight isotope laboratories participated, of which one determined δ11B via negative thermal ionisation mass spectrometry (NTIMS) and seven used multi collector inductively coupled plasma mass spectrometry (MC-ICPMS). For the latter several different introduction systems and chemical purification methods were used. Overall the results are strikingly consistent between the participating labs. The oxidation of organic material slightly lowered the median δ11B by ~0.1 ‰ for both JCp-1 and JCt-1, while the mean δ11B of all labs for both standards was lowered by 0