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Sample records for abundance carbon isotope

  1. 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 composition (δ18O ≈ -9.25‰, and δ13C ≈ -21‰ or -8‰ for CO- or CH4-dominated systems, respectively) if the less altered CRs had higher mole fractions of CO2 in their fluids. Semarkona and Kaba carbonates have some of the lightest C isotopic compositions of the meteorites studied here, probably because they formed at higher temperatures and/or from more CO2-rich fluids. The fluids responsible for the alteration of chondrites and from which the carbonates formed were almost certainly accreted as ices. By analogy with cometary ices, CO2 and/or CO would have dominated the trapped volatile species in the ices. The chondrites studied are too oxidized for CO-dominated fluids to have formed in their parent bodies. If CH4 was the dominant C species in the fluids during carbonate formation, it would have to have been generated in the parent bodies from CO and/or CO2 when oxidation of metal by water created high partial pressures of H2. The fact that the chondrite carbonate C/H2O mole ratios are of the order predicted for CO/CO2-H2O ices that experienced temperatures of >50-100 K suggests that the chondrites formed at radial distances of <4-15 AU.

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

    NASA Technical Reports Server (NTRS)

    Wannier, P. G.; Sahai, R.

    1987-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Bird, Michael I.; Gröcke, Darren R.

    1997-08-01

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

  4. The Relative Abundances of Carbon and its Isotopes in Cataclysmic Variables

    NASA Astrophysics Data System (ADS)

    Harrison, Thomas E.; Osborne, Heather; Howell, Steve; Johnson, Joni

    2002-02-01

    We have an NSF-funded program to investigate the chemical and isotopic abundances of carbon in the photospheres of the secondary stars of cataclysmic variables. We propose to use OSIRIS on the CTIO 4 m to obtain medium resolution K-band spectra of a sample of ~ 15 cataclysmic variables (CVs). We will use these spectra to examine the chemical and isotopic abundances of carbon in the photospheres of their secondary stars. Models of close binary star evolution predict that both the abundance and isotopic ratio (^12C/^13C) decrease as the secondary star losses mass. Observations we have obtained using CRSP on the KPNO 2.1m confirm this scenario for a number of longer- period CV systems. We propose to observe a larger sample of CVs covering the entire observed range in orbital period to determine if the model predictions are correct. In addition, the chemical and isotopic abundances depend on the evolutionary history of the CV. Models by Marks & Sarna (1998) predict that if the CV accreted significant material from the common envelope phase, or from earlier classical novae eruptions, the chemical and isotopic abundances will be different from scenarios where this did not occur. To examine this, we will observe a few classical novae to investigate whether their secondary stars reveal evidence for this isotopic enrichment. Our program requires two nights with OSIRIS on the CTIO 4m in 2002A.

  5. Natural abundances of carbon isotopes in acetate from a coastal marine sediment

    NASA Technical Reports Server (NTRS)

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

    1987-01-01

    Measurements of the natural abundances of carbon isotopes were made in acetate samples isolated from the anoxic marine sediment of Cape Lookout Bight, North Carolina. The typical value of the total acetate carbon isotope ratio (delta 13C) was -16.1 +/- 0.2 per mil. The methyl and carboxyl groups were determined to be -26.4 +/- 0.3 and -6.0 +/- 0.3 per mil, respectively, for one sample. The isotopic composition of the acetate is thought to have resulted from isotopic discriminations that occurred during the cycling of that molecule. Measurements of this type, which have not been made previously in the natural environment, may provide information about the dominant microbial pathways in anoxic sediments as well as the processes that influence the carbon isotopic composition of biogenic methane from many sources.

  6. Carbon and nitrogen biogeochemistry in the ocean: A study using stable isotope natural abundance

    NASA Technical Reports Server (NTRS)

    Rau, G. H.; Desmarais, David J.

    1985-01-01

    Determining the biogeochemical pathways traveled by carbon and nitrogen in the ocean is fundamental to the understanding of how the ocean participates in the cycling of these elements within the biosphere. Because biological production, metabolism, and respiration can significantly alter the natural abundance of C-13 and N-15, these abundances can provide important information about the nature of these biological processes and their variability in the marine environment. The research initially seeks to characterize the spatial and temporal patterns of stable isotope abundances in organic matter, and to relate these abundances to C and N biogeochemical processes within selected areas of the northeastern Pacific Ocean.

  7. Investigating microbial carbon cycling using natural abundance isotope analysis of PLFA

    NASA Astrophysics Data System (ADS)

    Slater, G. G.; Brady, A.; Cowie, B.

    2008-12-01

    Understanding microbial carbon sources and cycling is fundamental to our conceptualization of microbial ecosystems and their role in biogeochemical cycling in natural systems. Achieving this understanding requires application of a wide range of approaches. Natural abundance isotope analysis of individual compounds, particularly cellular components such as Phospholipids Fatty Acids (PLFA) can provide insights into the carbon sources and metabolic activities of the in situ microbial community from environmental samples. This is primarily because specific PLFA can be well resolved by gas chromatography even from complex matrices where confounding biological/organic compound abound. These PLFA can then be attributed to the viable microbial community, in some cases to specific components of this community and due to characteristic biosynthetic fractionations of stable isotope ratios, δ13C analysis of PLFA can: differentiate isotopically distinct primary carbon sources of heterotrophic communities; identify isotopic patterns characteristic of autotrophic versus heterotrophic processes; and elucidate microbial biosynthetic pathways. In cases where there δ13C cannot provide resolution of carbon sources, new approaches in Δ14C of PLFA can be applied. The vast range in Δ14C of ancient and modern carbon provides an easily traceable signal that can differentiate uptake and utilization of these carbon sources. This is particularly useful in cases such as contaminated sites where petroleum based contamination has occurred, or in natural systems where microbial communities may be utilizing geologic versus recently photosynthetically fixed carbon. This talk will present several examples demonstrating the utility of this approach.

  8. Abundances in red giant stars - Nitrogen isotopes in carbon-rich molecular envelopes

    NASA Technical Reports Server (NTRS)

    Wannier, P. G.; Andersson, B.-G.; Olofsson, H.; Ukita, N.; Young, K.

    1991-01-01

    Results are presented of millimeter- and submillimeter-wave observations of HCN and HCCCN that were made of the circmustellar envelopes of eight carbon stars, including the two protoplanetary nebulae CRL 618 and CRL 2688. The observations yield a measure of the double ratio (N-14)(C-13)/(N-15)(C-12). Measured C-12/C-13 ratios are used to estimate the N-14/N-15 abundance ratio, with the resulting lower limits in all eight envelopes and possible direct determinations in two envelopes. The two determinations and four of the remaining six lower limits are found to be in excess of the terrestrial value of N-14/N-15 = 272, indicating an evolution of the nitrogen isotope ratio, which is consistent with stellar CNO processing. Observations of thermal SiO (v = 0, J = 2-1) emission show that the Si-29/Si-28 ratio can be determined in carbon stars, and further observations are indicated.

  9. Isotopic abundance ratios for carbon and nitrogen in Nova Herculis 1934

    NASA Technical Reports Server (NTRS)

    Sneden, C.; Lambert, D. L.

    1975-01-01

    Spectra of Nova Herculis 1934 taken during an episode of intense CN absorption are analyzed to determine the isotopic abundance ratios of C12/C13 and N14/N15. Synthetic spectrum analysis, based on the wavelengths, excitation potentials, and oscillator strengths for the CN lines, and radial velocity measurements indicate that C(12)N(14) was the dominant species in the Nova, and that the minimum abundance limit for C12/C13 is about 1.5, while the minimum for N14/N15 is about 2. The results are compared with predictions based on models of thermonuclear runaways in hydrogen-rich envelopes of white dwarfs. It is noted that the nova material may have been contaminated with C13-rich material prior to or during the eruption. Possible causes of this isotope enrichment are presented.

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

    NASA Technical Reports Server (NTRS)

    Kerridge, J. F.

    1985-01-01

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

  11. C, N, O abundances and carbon isotope ratios in evolved stars of the open clusters Collinder 261 and NGC 6253

    NASA Astrophysics Data System (ADS)

    Mikolaitis, Š.; Tautvaišienė, G.; Gratton, R.; Bragaglia, A.; Carretta, E.

    2012-05-01

    Context. Investigations of abundances of carbon and nitrogen in the atmospheres of evolved stars of open clusters may provide comprehensive information on chemical composition changes caused by stellar evolution. Aims: Our main aim is to increase the number of open clusters with determined carbon-to nitrogen and carbon isotope ratios. Methods: High-resolution spectra were analysed using a differential model atmosphere method. Abundances of carbon were derived using the C2 Swan (0, 1) band head at 5635.5 Å (FEROS spectra) and the C2 Swan (1, 0) band head at 4737 Å (UVES spectra). The wavelength interval 7980-8130 Å, with strong CN features was analysed to determine nitrogen abundances and 12C/13C isotope ratios. The oxygen abundances were determined from the [O i] line at 6300 Å. Results: The average value of 12C/13C isotope ratios of Cr 261 is equal to 18 ± 2 in four giants and to 12 ± 1 in two clump stars; it is equal to 16 ± 1 in four clump stars of the open cluster NGC 6253. The mean C/N ratios in Cr 261 and NGC 6253 are equal to 1.67 ± 0.06 and 1.37 ± 0.09, respectively. Conclusions: The 12C/13C and C/N values in Cr 261 and NGC 6253 within limits of uncertainties agree with the theoretical model of thermohaline-induced mixing as well as with the cool-bottom processing model. Based on observations collected at ESO telescopes under programmes 65.N-0286, 169.D-0473.

  12. Carbon, nitrogen and sulfur in lunar fines 15012 and 15013 - Abundances, distributions and isotopic compositions

    NASA Technical Reports Server (NTRS)

    Chang, S.; Lawless, J.; Romiez, M.; Kaplan, I. R.; Petrowski, C.; Sakai, H.; Smith, J. W.

    1974-01-01

    Lunar fines 15012,16 and 15013,3 were analyzed by stepwise pyrolysis and acid hydrolysis as well as complete combustion in oxygen to determine carbon, nitrogen and sulfur. In addition, hydrogen was analysed during pyrolysis as well as during hydrolysis. By comparison of the distribution frequencies of C, N, S, H2 and Fe with He-4, considered to have arisen from solar wind contribution, it is concluded that nitrogen and hydrogen have largely a solar origin. Carbon has a significant solar contribution, and metallic iron may have resulted from solar wind interaction with ferrous minerals on the lunar surface. Sulfur probably has a predominantly lunar origin. There is no direct evidence for meteorotic contribution to these samples. Solar wind interaction also has a marked effect on the stable isotope distribution of C-13/C-12, N-15/N-14, and S-34/S-32. In all cases, the heavy isotope was most enriched in the smallest grain-size fraction.

  13. Partitioning Respiration Between Plant and Microbial Sources Using Natural Abundance Stable Carbon Isotopes

    NASA Astrophysics Data System (ADS)

    Dawson, T. E.; Tu, K. P.

    2009-12-01

    Partitioning plant and microbial respiration is important for understanding the mechanistic basis of ecosystem respiration, as each can respond to changes in environmental conditions in different ways and at different timescales. In theory, natural abundance stable C isotopes can allow source partitioning when the isotopic difference between the sources can be resolved. The longstanding notion is that such differences do not exist, yet field measurements to support this conclusion are rare. The question remains as to how much isotopic difference exists between the plant and microbial respiration and whether or not this difference is sufficient for partitioning. We addressed this question by measuring the C isotope ratios (13C/12C) of plant, microbial, and whole ecosystem respiration from three contrasting ecosystems in California. We found significant variation in the 13C/12C ratios between plant and microbial sources. However, isotopic mass balance was not observed in more than half the cases. When isotopic mass balance was observed, the largest isotopic differences were always between CO2 evolved during leaf respiration and SOC decomposition, with leaf respiration more depleted by 1-8 per mil. Within plants, the leaf respiration was more depleted than rhizosphere respiration by 2-6 per mil. Among microbial sources, litter decomposition was more depleted than SOC decomposition by 1-5 per mil. The 13C/12C ratio of bulk C and respired CO2 exhibited similar trends, but bulk C values were clearly not a good surrogate for the 13C/12C ratios of respired CO2. Based on the 13C/12C ratios of respired CO2, belowground respiration accounted for 25% in the redwood forest, 37% in the grassland and 84% in the pine forest. Belowground respiration was further partitioned between rhizosphere, litter and SOC decomposition. Each contributed nearly equal amounts in the redwood forest (30/40/30) whereas litter respiration dominated in the grassland (20/70/10) and pine forest (15/65/20). Given that there were three sources and only one isotope, these estimates for belowground partitioning were only potential ranges. We also found large temporal variation in the 13C/12C ratios of plant respiration. At the pine forest, differences between night and day were as large as 4 per mil for leaf respiration and 2.5 per mil for rhizosphere respiration. Belowground respiration changed by less than 1 per mil, and this variation appeared to be driven entirely by rhizosphere respiration (r2= 94%). The fact that isotopic mass balance was not observed on many days may have been due to this temporal variability. For example, isotopic mass balance was observed in the redwood forest when all respiration samples were collected at the same time of day (pre-dawn), whereas isotopic mass balance was not observed when respiration samples were collected from different times of the day. Partitioning is therefore possible because of relatively large isotopic differences between leaf and SOC decomposition, but care must be taken to determine all source signatures at the same time due to large temporal variability.

  14. Temporal variation in mycorrhizal diversity and carbon and nitrogen stable isotope abundance in the wintergreen meadow orchid Anacamptis morio.

    PubMed

    Ercole, Enrico; Adamo, Martino; Rodda, Michele; Gebauer, Gerhard; Girlanda, Mariangela; Perotto, Silvia

    2015-02-01

    Many adult orchids, especially photoautotrophic species, associate with a diverse range of mycorrhizal fungi, but little is known about the temporal changes that might occur in the diversity and functioning of orchid mycorrhiza during vegetative and reproductive plant growth. Temporal variations in the spectrum of mycorrhizal fungi and in stable isotope natural abundance were investigated in adult plants of Anacamptis morio, a wintergreen meadow orchid. Anacamptis morio associated with mycorrhizal fungi belonging to Tulasnella, Ceratobasidium and a clade of Pezizaceae (Ascomycetes). When a complete growing season was investigated, multivariate analyses indicated significant differences in the mycorrhizal fungal community. Among fungi identified from manually isolated pelotons, Tulasnella was more common in autumn and winter, the pezizacean clade was very frequent in spring, and Ceratobasidium was more frequent in summer. By contrast, relatively small variations were found in carbon (C) and nitrogen (N) stable isotope natural abundance, A. morio samples showing similar (15)N enrichment and (13)C depletion at the different sampling times. These observations suggest that, irrespective of differences in the seasonal environmental conditions, the plant phenological stages and the associated fungi, the isotopic content in mycorrhizal A. morio remains fairly constant over time. PMID:25382295

  15. Tracing the source of cooking oils with an integrated approach of using stable carbon isotope and fatty acid abundance.

    PubMed

    Liu, Weiguo; Yang, Hong; Wang, Zheng; Liu, Jinzhao

    2012-08-15

    We report a new approach to identify swill-cooked oils that are recycled from tainted food and livestock waste from commercial vegetable and animal oils by means of carbon isotope values and relative abundance of fatty acids. We test this method using 40 cooking oil samples of different types with known sources. We found significant differences in both total organic carbon isotope as well as compound-specific isotope values and fatty acid C(14)/C(18) ratios between commercial vegetable oils refined from C(3) plants (from -35.7 to -27.0‰ and from 0 to 0.15) and animal oils (from -28.3 to -14.3‰ and from 0.1 to 0.6). Tested swill-cooked oils, which were generally refined by mixing with animal waste illegally, fall into a narrow δ(13)C/fatty acid ratio distribution: from -25.9 to -24.1‰ and from 0.1 to 0.2. Our data demonstrate that the index of a cross-plotting between fatty acid δ(13)C values and C(14)/C(18) ratios can be used to distinguish clean commercial cooking oils from illegal swill-cooked oils. PMID:22813234

  16. Isotopic abundance of CO in interstellar clouds

    NASA Technical Reports Server (NTRS)

    Langer, W. D.

    1977-01-01

    The fractional abundances of the isotopic species of carbon monoxide in interstellar clouds are calculated on a basis of gas-phase ion-molecule reactions. The (C-13)O/(C-12)O ratio varies significantly with extinction of the ultraviolet radiation field, and in the outer regions of dark dense clouds (C-13)O may be enhanced by a factor of 10. The observational interpretation of the CO to H2 or interstellar-reddening relation and the isotopic abundances of carbon are complicated by these effects.

  17. Isotopic abundances in interstellar clouds

    NASA Technical Reports Server (NTRS)

    Townes, C. H.

    1977-01-01

    Results of microwave measurements in dense interstellar clouds are discussed which pertain to determinations of relative isotopic abundances. Difficulties in deriving relative abundances from observations of the relative intensities of isotopic lines are examined, and measures available for coping with these complications are outlined. Results are presented concerning the relative abundances of C-13, O-17, O-18, N-15, Si-30, S-33, S-34, and D in a variety of interstellar clouds; the consistency of these results is evaluated. It is concluded that: (1) the relative abundances of C-13 and O-17 in interstellar clouds are generally higher than those in the solar system; (2) the abundances of N-15 and D are lower than the solar-system values; (3) the O-18 abundance is possibly higher than in the solar system; and (4) there are substantial variations in the isotopic abundances between different large interstellar clouds, with some of these variations not dependent on distance from the galactic center alone.

  18. Theory of interstellar abundances of the isotopes of carbon, nitrogen and oxygen.

    NASA Technical Reports Server (NTRS)

    Wollman, E. R.

    1973-01-01

    It is shown that CNO hydrogen burning in stars with a mass of 3 to 8 solar masses can account for both the likely abundances of C-13, N-14, and O-17 in the interstellar medium and the observed ratios C-12/C-13 O-16/O-17 in the atmospheres of evolved stars. A model which gives these abundances is shown to be consistent also with previously suggested mechanisms for the production of He-3, N-15, and O-18.

  19. Natural Carbon Isotope Abundance of Plasma Metabolites and Liver Tissue Differs between Diabetic and Non-Diabetic Zucker Diabetic Fatty Rats

    PubMed Central

    Godin, Jean-Philippe; Ross, Alastair B.; Cléroux, Marilyn; Pouteau, Etienne; Montoliu, Ivan; Moser, Mireille; Kochhar, Sunil

    2013-01-01

    Background ‘You are what you eat’ is an accurate summary for humans and animals when it comes to carbon isotope abundance. In biological material, natural13C/12C ratio is subject to minute variations due to diet composition (mainly from ingestion of C3 and C4 metabolism plants) and to the discrimination between ‘light’ and ‘heavy’ isotopes during biochemical reactions (isotope effects and isotopic fractionation). Methodology/Principal Findings Carbon isotopic abundance was measured in ZDF (fa/+) and ZDF (fa/fa), (lean and obese-diabetic rats respectively) fed the same diet. By analysing plasma metabolites (glucose and non-esterified fatty acids), breath and liver tissue by high-precision isotope ratio mass spectrometry, we demonstrate for the first time statistically distinguishable metabolic carbon isotope abundance between ZDF (fa/+) and ZDF (fa/fa) rats based on plasma glucose, palmitic, oleic, linoleic, arachidonic acids and bulk analysis of liver tissue (P<0.005) resulting into clear isotopic fingerprints using principal component analysis. We studied the variation of isotopic abundance between both groups for each metabolite and through the metabolic pathways using the precursor/product approach. We confirmed that lipids were depleted in 13C compared to glucose in both genotypes. We found that isotopic abundance of linoleic acid (C18: 2n-6), even though both groups had the same feed, differed significantly between both groups. The likely reason for these changes between ZDF (fa/+) and ZDF (fa/fa) are metabolic dysregulation associated with various routing and fluxes of metabolites. Conclusion/Significance This work provides evidence that measurement of natural abundance isotope ratio of both bulk tissue and individual metabolites can provide meaningful information about metabolic changes either associated to phenotype or to genetic effects; irrespective of concentration. In the future measuring the natural abundance δ13C of key metabolites could be used as endpoints for studying in vivo metabolism, especially with regards to metabolic dysregulation, and development and progression of metabolic diseases. PMID:24086387

  20. Millimeter-scale variations of stable isotope abundances in carbonates from banded iron-formations in the Hamersley Group of Western Australia

    NASA Technical Reports Server (NTRS)

    Baur, M. E.; Hayes, J. M.; Studley, S. A.; Walter, M. R.

    1985-01-01

    Several diamond drill cores from formations within the Hamersley Group of Western Australia have been studied for evidence of short-range variations in the isotopic compositions of the carbonates. For a set of 32 adjacent microbands analyzed in a specimen from the Marra Mamba Iron Formation, carbon isotope compositions of individual microbands ranged from -2.8 to -19.8 per mil compared to PDB and oxygen isotope compositions ranged from 10.2 to 20.8 per mil compared to SMOW. A pattern of alternating abundances was present, with the average isotopic contrasts between adjacent microbands being 3.0 per mil for carbon and 3.1 per mil for oxygen. Similar results were obtained for a suite of 34 microbands (in four groups) from the Bruno's Band unit of the Mount Sylvia Formation. Difficulties were experienced in preparing samples of single microbands from the Dales Gorge Member of the Brockman Iron Formation, but overall isotopic compositions were in good agreement with values reported by previous authors. Chemical analyses showed that isotopically light carbon and oxygen were correlated with increased concentrations of iron. The preservation of these millimeter-scale variations in isotopic abundances is interpreted as inconsistent with a metamorphic origin for the isotopically light carbon in the BIF carbonates. A biological origin is favored for the correlated variations in 13C and Fe, and it is suggested that the 13C-depleted carbonates may derive either from fermentative metabolism or from anaerobic respiration. A model is presented in which these processes occur near the sediment-water interface and are coupled with an initial oxidative precipitation of the iron.

  1. Abundance and isotope systematics of carbon in subglacial basalts, geothermal gases and fluids from Iceland's rift zones

    NASA Astrophysics Data System (ADS)

    Barry, P. H.; Hilton, D. R.; Fueri, E.; Halldorsson, S. A.; Fischer, T. P.; Gronvold, K.

    2010-12-01

    P. H. BARRY1*, D. R. HILTON1, E. FÜRI1, S.A. HALLDÓRSON1, T.P. FISCHER2, K. GRONVOLD3 1 Scripps Institution of Oceanography, UCSD, La Jolla, California 92093, USA (*Correspondence: pbarry@ucsd.edu). 2University of New Mexico, Albuquerque, NM 87131, USA. 3University of Iceland, Askja, Sturlugata 7, IS-101, Reykjavik, Iceland Carbon dioxide (CO2) is the dominant non-aqueous volatile species found in oceanic basalts and geothermal fluids and serves as the carrier gas for trace volatiles such as He and other noble gases. The aim of this study is to identify the superimposed effects of degassing and crustal contamination on the CO2 systematics of the Icelandic hotspot in order to reveal and characterize the carbon abundance and isotopic features of the underlying mantle source. Our approach involves coupling CO2 with He, utilizing the sensitivity of 3He/4He ratios to reveal mantle and crustal inputs. We report new C-isotope (δ13C) and abundance characteristics for a suite of 47 subglacial basalts and 50 geothermal gases and fluids from Iceland. CO2 contents in hyaloclastite glasses are extremely low (10-100 ppm) and likely residual following extensive degassing whereas geothermal fluids are dominated by CO2 (>90 %). C-isotopes range from -27.2 to -3.6 ‰ (vs. PDB) for basalts and from -18.8 to 2.86 ‰ (vs. PDB) for geothermal samples (mean = -4.2 ± 3.6 ‰). CO2/3He ratios range from 108 to 1012 for basalts and from 105 to 1012 for geothermal samples: In both cases, our results extend He-CO2 relationships over a much broader range than reported previously [1]. Taken together, these data suggest that several processes including mixing, degassing, and/or syn- or post-eruptive crustal contamination may act to modify CO2 source characteristics. Equilibrium degassing models are compatible with ~75 % of the basalt data, and preliminary results indicate that initial Icelandic source characteristics are ~500 ppm CO2 and δ13C ~ -5 ‰ (vs. PDB). These values are high compared to N-MORB mantle source estimates (72-134 ppm) based upon CO2/Nb ratios [2, 3]; however, they are in good agreement with those from submarine glasses on adjacent segments from the Reykjanes and Kolbeinsey ridges [4,5]. Significantly, the model-derived δ13C estimate is close to the mean Icelandic geothermal value, implying that fluids closely resemble source values, i.e. they likely represent the exsolved component. Integrating the estimated source CO2 content with magma production values of 0.079 km3/yr [6] yields a CO2 flux of ~1.2 x 1011 mol CO2 yr-1for Iceland, representing ~ 5.4 % of the total carbon ridge flux of 2.2 x 1012 mol CO2 yr-1 [7]. Thus, the average CO2 flux estimate for Iceland is ~2.2 x 108 mol CO2 yr-1km-1 strike of ridge axis, which compares to an overall ridge flux (including Iceland) of ~2.9 x 107 mol CO2 yr-1km-1. This difference highlights both heterogeneity in source volatile contents and magma production rates as important controls for determining mantle CO2 fluxes. [1] Poreda et al., 1992 [2] Saal et al., 2002. [3] Shaw et al., 2010. [4] de Leeuw, 2007 [5] Macpherson et al., 2005. [6] Thordarson et al., 2007 [7] Marty et al., 1998.

  2. Abundances of isotopes in planetary atmospheres

    NASA Technical Reports Server (NTRS)

    Owen, T.

    1978-01-01

    Carbon and oxygen isotopes show no large anomalies on Venus (no more than 10-15%) or Mars (less than 5%); the high value of N-15/N-14 found on Mars is explained by nonthermal escape of nitrogen. The isotopes of nonradiogenic noble gases in the atmosphere of Mars exhibit abundance patterns similar to those in the primordial component of meteoritic gases and in the earth's atmosphere. This implies that gas fractionation took place in the inner solar nebula prior to planet formation. The relatively high value of Xe-129 on Mars emphasizes its deficiency on earth, implying a difference in accretion histories of volatiles for the two planets. In the outer solar system, normal isotope ratios for nitrogen and carbon on Jupiter, and for carbon on Saturn are found, but precision is low (+ or - 15% at best). Controversy exists about the correct value of D/H, with current estimates ranging from 2.3 plus or minus 1.1 to 5.1 plus or - 0.7 times 10 to the minus 5th. Planetary missions planned for the next few years should add considerably to the quantity and quality of these data.

  3. Stellar Isotopic Abundances in the Milky Way: Insights into the Origin of Carbon and Neutron-Capture Elements

    NASA Astrophysics Data System (ADS)

    Guo, Michelle; Zhang, A.; Kirby, E. N.; Guhathakurta, P.

    2014-01-01

    Elements heavier than iron are formed by the capture of neutrons onto lighter nuclei. Neutron capture happens via two separate processes: the rapid neutron capture process (r-process) that occurs in supernovae, and slow neutron capture process (s-process) that occurs in less-massive stars. This work used high-resolution spectroscopy, synthetic model spectra, and a least-squares fit to show that the ratio of 12C to 13C increases proportionally with [Fe/H]. The new results agree with the conclusions of Lucatello et al. (2006) and Frebel (2008), and show significant improvement that contains less scattering of data points. Analysis of the obtained isotope ratios suggests that the carbon in most stars of the sample originated in supernovae. This paper also presents a method to calculate the europium isotope ratio by modeling the shapes of absorption lines. The range of europium isotopic ratios agrees with previous theoretical predictions about the classical model of heavy element nucleosynthesis, and the work presents new insight into the origins of life in the universe. We thank the US National Science Foundation, the UCSC Science Internship Program, and the Lick Observatory where the spectra were obtained.

  4. [Effects of intensive agricultural production on farmland soil carbon and nitrogen contents and their delta13C and delta15N isotope abundances].

    PubMed

    Yang, Guang-Rong; Hao, Xiying; Li, Chun-Li; Wang, Zi-Lin; Li, Yong-Mei

    2012-03-01

    Farmland soil carbon and nitrogen contents under intensive agricultural production are the important indices for the assessment of the soil fertility sustainability. This paper measured the soil pH, electrical conductivity (EC), organic carbon (SOC), total nitrogen (TN), and delta13C and delta15N isotope abundances of four types of farmland, i.e., conventional rice-broad bean rotation field, open vegetable field, 3-year plastic covered greenhouse field, and > 10-year plastic covered greenhouse field, aimed to understand the effects of intensive agricultural production degree on soil properties. In the open vegetable field, 3-year plastic covered greenhouse field, and > 10-year plastic covered greenhouse field, the soil (0-20 cm) pH decreased by 1.1, 0.8, and 0.7, and the soil EC was 4.2, 4.9, and 5.2 folds of that in conventional rice-broad bean rotation field, respectively. With the increasing year of plastic covered greenhouse production, the soil SOC and TN contents decreased after an initial increase. Comparing with those under rice-broad bean rotation, the SOC content in 0-20, 20-40, 40-60, 60-80 and 80-100 cm soil layers in >10-year plastic covered greenhouse decreased by 54%, 46%, 60%, 63%, and 59%, and the TN content decreased by 53%, 53%, 71%, 82%, and 85%, respectively. Intensive agricultural production degree had significant effects on the soil SOC and TN contents and delta13C and delta15N abundances. The delta13C abundance was significantly negatively correlated with the soil SOC, suggesting that the soil delta13C abundance could be regarded as an index for the assessment of carbon cycle in farmland soils under effects of human activities. PMID:22720621

  5. Simultaneous analysis of abundance and isotopic composition of nitrogen, carbon, and noble gases in lunar basalts: Insights into interior and surface processes on the Moon

    NASA Astrophysics Data System (ADS)

    Mortimer, J.; Verchovsky, A. B.; Anand, M.; Gilmour, I.; Pillinger, C. T.

    2015-07-01

    Simultaneous static-mode mass spectrometric measurements of nitrogen, carbon, helium, neon, and argon extracted from the same aliquot of sample by high-resolution stepped combustion have been made for a suite of six lunar basalts. Collecting abundance and isotopic data for several elements simultaneously from the same sample aliquot enables more detailed identification of different volatile components present in the basalts by comparing release patterns for volatiles across a range of temperature steps. This approach has yielded new data, from which new insights can be gained regarding the indigenous volatile inventory of the Moon. By taking into account N and C data for mid-temperature steps, unaffected by terrestrial contamination or cosmogenic additions, it is possible to determine the indigenous N and C signatures of the lunar basalts. With an average δ15N value of around +0.35‰, the indigenous N component seen in these samples is similar within error to other (albeit limited in number) isotopic measurements of indigenous lunar N. Average C/N ratios for indigenous volatiles in these six basalt samples are much lower than those of the terrestrial depleted mantle, or bulk silicate Earth, possibly suggesting much less C in the lunar interior, relative to N, than on Earth. Cosmogenic isotopes in these samples are well-correlated with published sample exposure ages, and record the rate of in situ production of spallogenic volatiles within material on the lunar surface.

  6. Absolute isotopic abundances of Ti in meteorites

    NASA Technical Reports Server (NTRS)

    Niederer, F. R.; Papanastassiou, D. A.; Wasserburg, G. J.

    1985-01-01

    A general formalism is presented for determining possible isotope compositions of exotic Ti, and illustrated with results from Ti isotope abundances measured in Ca-Al-rich inclusions of the Allende and Leoville meteorites and samples of other meteorites. Previously identified correlations between Ti-50 and Ca-48 in FUN (isotope fractionation effects and unknown nucleosynthetic effects) inclusions is shown to hold true, thereby supporting contributions from a neutron-rich equilibrium or nucleosynthetic equilibrium during formation of the meteorites. Extension of the study to carbonaceous meteorites indicated that condensation, volatilization and recondensation occurred during formation, although the isotope fractionation observed cannot yet be explained.

  7. Stable Carbon Isotope Ratios of Individual Pollen Grains as a Proxy for C3- Versus C4-Grass Abundance in Paleorecords: A Validation Study

    NASA Astrophysics Data System (ADS)

    Nelson, D. M.; Hu, F.; Pearson, A.

    2007-12-01

    C3 and C4 grasses have distinct influences on major biogeochemical processes and unique responses to important environmental controls. Difficulties in distinguishing between these two functional groups of grasses have hindered paleoecological studies of grass-dominated ecosystems. We recently developed a technique to analyze the stable carbon isotope composition of individual grass-pollen grains using a spooling- wire microcombustion device interfaced with an isotope-ratio mass spectrometer (Nelson et al. 2007). This technique holds promise for improving C3 and C4 grass reconstructions. It requires ~90% fewer grains than typical methods and avoids assumptions associated with mixing models. However, our previous work was based on known C3 and C4 grasses from herbarium specimens and field collections and the technique had not been test using geological samples. To test the ability of this technique to reproduce the abundance of C3 and C4 grasses on the landscape, we measured δ13C values of >1500 individual grains of grass pollen isolated from the surface sediments of 10 North American lakes that span a large gradient of C3 and C4 grass abundance. Results indicate a strong positive correlation (r=0.94) between % C4-grass pollen (derived from classifying δ13C values from single grains as C3 and C4) and the literature-reported abundance of C4 grasses on the landscape. However, the measured % C4-grass pollen shows some deviation from the actual abundance at sites with high proportions of C4 grasses. This is likely caused by uncertainty in the magnitude, composition, and variability of the analytical blank associated with these measurements. Correcting for this deviation using regression analysis improves the estimation of the abundance of C4 grasses on the landscape. Comparison of the % C4-grass pollen with C/N and δ13C measurements of total organic matter in the same lake-sediment samples illustrates the distinct advantage of grass-pollen δ13C as a proxy for distinguishing C3 and C4 shifts. At 9 of the 10 sites C/N values indicate that surface-sediment organic matter was derived primarily from aquatic production. At the one site where organic matter was produced primarily by vascular plants the δ13C value (-29.3°) suggests organic matter derived exclusively from C3 plants. However, ~80% of the grasses on the landscape at this site are C4 grasses. The C3- like bulk-sediment δ13C value likely represents woody species, which comprise >90% of the pollen spectra. Thus δ13C analysis of single grains of grass pollen offers a new tool to classify grass pollen into two major functional groups and promises to advance our understanding of grassland ecology and evolution. Reference Nelson, D.M., Hu, F.S., Mikucki, J., Tian, J., and Pearson, A., 2007, Carbon isotopic analysis of individual pollen grains from C3 and C4 grasses using a spooling wire microcombustion interface: Geochimica et Cosmochimica Acta, v. 71, p. 4005-4014.

  8. Helium and Carbon Isotope and Relative Abundance Relationships in Lau Basin Basalts: Resolving Mantle Source Composition from Degassing and Contamination Effects

    NASA Astrophysics Data System (ADS)

    Vukajlovich, D. J.; Hilton, D. R.; Castillo, P. R.; Hawkins, J. W.

    2005-12-01

    The Lau Basin has multiple mantle source components including contributions from the Indian and Pacific MORB sources, Tonga-Kermadec Arc and Samoan plume. In order to characterize the volatile systematics of these various sources and to map their spatial distribution, we have sampled basaltic glasses from over 50 dredge sites covering all known spreading centers in the basin as well as many off-axis seamounts. Here, we report He abundance and isotope results obtained by crushing, in addition to CO2 released through stepped heating, from sites at the Mangatolu Triple Junction (MTJ), Rochambeau Bank (RB), Peggy Ridge, and the Northern, Eastern and Central Lau Spreading Centers. High 3He/4He ratios from RB (up to 23 RA, where RA = air 3He/4He) confirm the presence of a plume component in the northwestern Lau Basin (Poreda, EPSL, 1985). Central and Eastern Lau Spreading Center basalts have 3He/4He ratios between 8.3 and 9.4 RA, consistent with a depleted, MORB-like mantle source with little influence from slab or crustal helium. In contrast, the large range in helium isotope ratios of MTJ samples (0.85 to 7.9 RA) and the correlation between low He abundances (~2 - 3 × 10-9 cm3/g) and low helium isotope ratios suggests the volatiles in this region have been severely affected by degassing and additions of radiogenic (crustal) He. CO2 abundances and carbon isotopes for samples from RB vary from 70 to 119 ppm ([CO2]total) with δ13Cvesicle falling between -12.3 to -14.8 ‰ and δ13Cdissolved lying between -9.3 to -10.7 ‰. In the MTJ, low helium concentration samples have δ13C as low as -27.4 ‰ and [CO2]total as low as 7.6ppm; interestingly, this region also has samples with the highest measured values (up to -6.3 ‰ and 132ppm total C). Combining the carbon and helium data, CO2/3He ratios in the MTJ range from arc-like values (~1010) to sediment or crustal values (~1013) showing the superimposition of degassing and/or contamination effects on a predominant slab-like signature. High 3He/4He samples from RB have CO2 /3He ratios similar to the upper mantle value (2 × 109), as at other back-arc localities exhibiting a high 3He/4He (plume) component (e.g. the Manus Basin; Shaw et al., GCA, 2004). Continuing analytical work will complete our He-C survey of the Lau Basin, identifying samples suitable for further effort involving Ne, Ar, H2O plus other tracers of interest. Presently, we are modeling degassing/contamination effects to identify the nature and distribution of mantle source components throughout the Lau Basin. The volatile characteristics of the high 3He/4He samples are of particular interest as they provide insight into the different recycling and storage histories of volatiles between distinct mantle reservoirs.

  9. Variation in soil organic carbon abundance and isotopic composition mediated by landslide activity in the Sierra de Las Minas, Guatemala

    NASA Astrophysics Data System (ADS)

    Restrepo, C.

    2013-12-01

    Tropical mountains play an important role in biogeochemical cycles worldwide due to complex interaction between geomorphic and ecosystem processes. The strength of these interactions, however, is likely to vary along the steep environmental gradients found in mountainous terrain. Here we focus on soil organic carbon and ask how landsliding alters soil organic carbon density, C:N ratios and ?13C and ?15N along the broad climatic gradients observed in the Sierra de Las Minas (SLM) of eastern Guatemala. Soils were sampled in intact forest and 14 year-old landside sites underlain by gneiss in the southern dry to mesic (Motagua) and northern wet (Polochic) aspects of the SLM along wide elevation, temperature, and precipitation gradients. Soils samples (10 cm depth increments down to 30 cm) from each site were processed to estimate soil bulk density and obtain total carbon and nitrogen, and ?13C and ?15N. Soil organic carbon density exhibited a greater variability in forests of the Motagua (10-170 MgC ha-1) than the Polochic (40-160 MgC ha-1) whereas the opposite was true in landslides (5-40 MgC ha-1 versus10-90 MgC ha-1 in the Motagua and Polochic, respectively). Soil organic carbon density was related non-linearly with mean annual temperature (MAT) and mean total annual precipitation (MAP) but the strength and sign of the interactions differed with aspect and habitats which suggests that landsliding has different potentials to mobilize and fix carbon along the complex environmental gradients of the SLM. Similarly, the C:N ratios and ?13C and ?15N values varied between forests and landslides of the Motagua and Polochic sides of the SLM suggesting important differences in the carbon cycle and thus functioning of montane ecosystems mediated by landslide activity. Results of our work are critical both for characterizing the size of soil organic carbon stocks and pinpointing the source of carbon mobilized by landsliding in the SLM.

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

    NASA Technical Reports Server (NTRS)

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

    1983-01-01

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

  11. Helium isotopic abundance variation in nature

    SciTech Connect

    Holden, N.E.

    1993-08-01

    The isotopic abundance of helium in nature has been reviewed. This atomic weight value is based on the value of helium in the atmosphere, which is invariant around the world and up to a distance of 100,000 feet. Helium does vary in natural gas, volcanic rocks and gases, ocean floor sediments, waters of various types and in radioactive minerals and ores due to {alpha} particle decay of radioactive nuclides.

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

    USGS Publications Warehouse

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

    1983-01-01

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

  13. Isotope-abundance variations of selected elements (IUPAC technical report)

    USGS Publications Warehouse

    Coplen, T.B.; Böhlke, J.K.; De Bievre, P.; Ding, T.; Holden, N.E.; Hopple, J.A.; Krouse, H.R.; Lamberty, A.; Peiser, H.S.; Revesz, K.; Rieder, S.E.; Rosman, K.J.R.; Roth, E.; Taylor, P.D.P.; Vocke, R.D., Jr.; Xiao, Y.K.

    2002-01-01

    Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic-weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic-weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope-abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope-abundance variations potentially are large enough to result in future expansion of their atomic-weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope variations in materials of natural terrestrial origin are too small to have a significant effect on their standard atomic-weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio.

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

    SciTech Connect

    Piper, Stephen C; Keeling, Ralph F

    2012-01-03

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

  15. Raman scattering method and apparatus for measuring isotope ratios and isotopic abundances

    DOEpatents

    Harney, Robert C.; Bloom, Stewart D.

    1978-01-01

    Raman scattering is used to measure isotope ratios and/or isotopic abundances. A beam of quasi-monochromatic photons is directed onto the sample to be analyzed, and the resulting Raman-scattered photons are detected and counted for each isotopic species of interest. These photon counts are treated mathematically to yield the desired isotope ratios or isotopic abundances.

  16. Carbon isotope and abundance systematics of Icelandic geothermal gases, fluids and subglacial basalts with implications for mantle plume-related CO2 fluxes

    NASA Astrophysics Data System (ADS)

    Barry, P. H.; Hilton, D. R.; Füri, E.; Halldórsson, S. A.; Grönvold, K.

    2014-06-01

    We report new carbon dioxide (CO2) abundance and isotope data for 71 geothermal gases and fluids from both high-temperature (HT > 150 °C at 1 km depth) and low-temperature (LT < 150 °C at 1 km depth) geothermal systems located within neovolcanic zones and older segments of the Icelandic crust, respectively. These data are supplemented by CO2 data obtained by stepped heating of 47 subglacial basaltic glasses collected from the neovolcanic zones. The sample suite has been characterized previously for He-Ne (geothermal) and He-Ne-Ar (basalt) systematics (Füri et al., 2010), allowing elemental ratios to be calculated for individual samples. Geothermal fluids are characterized by a wide range in carbon isotope ratios (δ13C), from -18.8‰ to +4.6‰ (vs. VPDB), and CO2/3He values that span eight orders of magnitude, from 1 × 104 to 2 × 1012. Extreme geothermal values suggest that original source compositions have been extensively modified by hydrothermal processes such as degassing and/or calcite precipitation. Basaltic glasses are also characterized by a wide range in δ13C values, from -27.2‰ to -3.6‰, whereas CO2/3He values span a narrower range, from 1 × 108 to 1 × 1012. The combination of both low δ13C values and low CO2 contents in basalts indicates that magmas are extensively and variably degassed. Using an equilibrium degassing model, we estimate that pre-eruptive basaltic melts beneath Iceland contain ∼531 ± 64 ppm CO2 with δ13C values of -2.5 ± 1.1‰, in good agreement with estimates from olivine-hosted melt inclusions (Metrich et al., 1991) and depleted MORB mantle (DMM) CO2 source estimates (Marty, 2012). In addition, pre-eruptive CO2 compositions are estimated for individual segments of the Icelandic axial rift zones, and show a marked decrease from north to south (Northern Rift Zone = 550 ± 66 ppm; Eastern Rift Zone = 371 ± 45 ppm; Western Rift Zone = 206 ± 24 ppm). Notably, these results are model dependent, and selection of a lower δ13C fractionation factor will result in lower source estimates and larger uncertainties associated with the initial δ13C estimate. Degassing can adequately explain low CO2 contents in basalts; however, degassing alone is unlikely to generate the entire spectrum of observed δ13C variations, and we suggest that melt-crust interaction, involving a low δ13C component, may also contribute to observed signatures. Using representative samples, the CO2 flux from Iceland is estimated using three independent methods: (1) combining measured CO2/3He values (in gases and basalts) with 3He flux estimates (Hilton et al., 1990), (2) merging basaltic emplacement rates of Iceland with pre-eruptive magma source estimates of ∼531 ± 64 ppm CO2, and (3) combining fluid CO2 contents with estimated regional fluid discharge rates. These methods yield CO2 flux estimates from of 0.2-23 × 1010 mol a-1, which represent ∼0.1-10% of the estimated global ridge flux (2.2 × 1012 mol a-1; Marty and Tolstikhin, 1998).

  17. Carbon isotopic fractionation in heterotrophic microbial metabolism

    SciTech Connect

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

    1985-10-01

    Differences in the natural-abundance carbon stable isotopic compositions between products from aerobic cultures of Escherichia coli K-12 were measured. Respired CO2 was 3.4 percent depleted in C-13 relative to the glucose used as the carbon source, whereas the acetate was 12.3 percent enriched in C-13. The acetate C-13 enrichment was solely in the carboxyl group. Even though the total cellular carbon was only 0.6 percent depleted in C-13, intracellular components exhibited a significant isotopic heterogeneity. The protein and lipid fractions were -1.1 and -2.7 percent, respectively. Aspartic and glutamic acids were -1.6 and +2.7 percent, respectively, yet citrate was isotopically identical to the glucose. Probable sites of carbon isotopic fractionation include the enzyme, phosphotransacetylase, and the Krebs cycle. 38 references.

  18. 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.

  19. THE ATOMIC WEIGHTS COMMISSION AND ISOTOPIC ABUNDANCE RATIO DETERMINATIONS.

    SciTech Connect

    HOLDEN, N.E.

    2005-08-07

    Following Thomson's discovery of stable isotopes in non-radioactive chemical elements, the derivation of atomic weight values from mass spectrometric measurements of isotopic abundance ratios moved very slowly. Forty years later, only 3 1/2 % of the recommended values were based on mass spectrometric measurements and only 38% in the first half century. It might be noted that two chemical elements (tellurium and mercury) are still based on chemical measurements, where the atomic weight value calculated from the relative isotopic abundance measurement either agrees with the value from the chemical measurement or the atomic weight value calculated from the relative isotopic abundance measurement falls within the uncertainty of the chemical measurement of the atomic weight. Of the 19 chemical elements, whose atomic weight is based on non-corrected relative isotopic abundance measurements, five of these are two isotope systems (indium, iridium, lanthanum, lutetium and tantalum) and one is a three-isotope system (oxygen).

  20. Climatic/Hydrologic Oscillations since 155,000 yr B.P. at Owens Lake, California, Reflected in Abundance and Stable Isotope Composition of Sediment Carbonate

    USGS Publications Warehouse

    Menking, K.M.; Bischoff, J.L.; Fitzpatrick, J.A.; Burdette, J.W.; Rye, R.O.

    1997-01-01

    Sediment grain size, carbonate content, and stable isotopes in 70-cm-long (???1500-yr) channel samples from Owens Lake core OL-92 record many oscillations representing climate change in the eastern Sierra Nevada region since 155,000 yr B.P. To first order, the records match well the marine ??18O record. At Owens Lake, however, the last interglaciation appears to span the entire period from 120,000 to 50,000 yr B.P., according to our chronology, and was punctuated by numerous short periods of wetter conditions during an otherwise dry climate. Sediment proxies reveal that the apparent timing of glacial-interglacial transitions, notably the penultimate one, is proxy-dependent. In the grain-size and carbonate-content records this transition is abrupt and occurs at ??? 120,000 yr B.P. In contrast, in the isotopic records the transition is gradual and occurs between 145,000 and 120,000 yr B. P. Differences in timing of the transition are attributed to variable responses by proxies to climate change. ?? 1997 University of Washington.

  1. 238U series isotopes and 232Th in carbonates and black shales from the Lesser Himalaya: implications to dissolved uranium abundances in Ganga-Indus source waters.

    PubMed

    Singh, S K; Dalai, Tarun K; Krishnaswami, S

    2003-01-01

    238U and (232)Th concentrations and the extent of (238)U-(234)U-(230)Th radioactive equilibrium have been measured in a suite of Precambrian carbonates and black shales from the Lesser Himalaya. These measurements were made to determine their abundances in these deposits, their contributions to dissolved uranium budget of the headwaters of the Ganga and the Indus in the Himalaya and to assess the impact of weathering on (238)U-(234)U-(230)Th radioactive equilibrium in them. (238)U concentrations in Precambrian carbonates range from 0.06 to 2.07 microg g(-1). The 'mean' U/Ca in these carbonates is 2.9 ng U mg(-1) Ca. This ratio, coupled with the assumption that all Ca in the Ganga-Indus headwaters is of carbonate origin and that U and Ca behave conservatively in rivers after their release from carbonates, provides an upper limit on the U contribution from these carbonates, to be a few percent of dissolved uranium in rivers. There are, however, a few streams with low uranium concentrations, for which the carbonate contribution could be much higher. These results suggest that Precambrian carbonates make only minor contributions to the uranium budget of the Ganga-Indus headwaters in the Himalaya on a basin wide scale, however, they could be important for particular streams. Similar estimates of silicate contribution to uranium budget of these rivers using U/Na in silicates and Na* (Na corrected for cyclic and halite contributions) in river waters show that silicates can contribute significantly (approximately 40% on average) to their U balance. If, however, much of the uranium in these silicates is associated with weathering resistant minerals, then the estimated silicate uranium component would be upper limits. Uranium concentration in black shales averages about 37 microg g(-1). Based on this concentration, supply of U from at least approximately 50 mg of black shales per liter of river water is needed to balance the average river water U concentration, 1.7 microg L(-1) in the Ganga-Indus headwaters. Data on the abundance and distribution of black shales in their drainage basin are needed to test if this requirement can be met. (234)U/(238)U activity ratios in both carbonates and black shales are at or near equilibrium, thus preferential mobilization of (234)U from these deposits, if any, is within analytical uncertainties. (230)Th is equivalent to or in excess of (238)U in most of the carbonates. (230)Th/(238)U>1 indicates that during weathering, uranium is lost preferentially over Th. (232)Th concentrations in carbonates are generally quite low, <0.5 microg g(-1), though with a wide range, 0.01-4.8 microg g(-1). The variation in its concentrations seem to be regulated by aluminosilicate content of the carbonates as evident from the strong positive correlation between (232)Th and Al. PMID:12634002

  2. A large area experiment to determine cosmic ray isotopic abundances

    NASA Technical Reports Server (NTRS)

    Mauger, B. G.; Balasubrahmanyan, V. K.; Ormes, J. F.; Streitmatter, R. E.; Heinrich, W.; Simon, M.; Tittel, H. O.

    1983-01-01

    Measurements of the isotopic composition of cosmic rays have shown that the cosmic ray isotope ratios, Ne-22/Ne-20 and (Mg-25 + Mg-26)/Mg-24, exceed the solar abundance ratios by factors of 2.7 and 1.8, respectively. There are several processes which could be responsible for the observed excess of neutron-rich isotopes. The considered models imply neutron enrichment in the case of other, less abundant species, and a measurement of the involved isotopic abundances could provide a basis for the determination of the dominating processes occurring in cosmic ray sources. However, an experiment utilizing special equipment is necessary to conduct the required measurements. Such an experiment, the Aluminum Isotopic Composition Experiment (Alice), is being designed in a joint effort involving NASA and a West German university. Alice uses a Cherenkov-range technique to determine the isotopic composition of elements from oxygen through argon.

  3. 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.

  4. 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.

  5. Isotopic abundance in atom trap trace analysis

    DOEpatents

    Lu, Zheng-Tian; Hu, Shiu-Ming; Jiang, Wei; Mueller, Peter

    2014-03-18

    A method and system for detecting ratios and amounts of isotopes of noble gases. The method and system is constructed to be able to measure noble gas isotopes in water and ice, which helps reveal the geological age of the samples and understand their movements. The method and system uses a combination of a cooled discharge source, a beam collimator, a beam slower and magneto-optic trap with a laser to apply resonance frequency energy to the noble gas to be quenched and detected.

  6. LITERATURE SURVEY ON ISOTOPIC ABUNDANCE RATIO MEASUREMENTS - 2001-2005

    SciTech Connect

    HOLDEN, N.E.

    2005-08-13

    Along with my usual weekly review of the published literature for new nuclear data, I also search for new candidates for best measurements of isotopic abundances from a single source. Most of the published articles, that I previously had found in the Research Library at the Brookhaven Lab, have already been sent to the members of the Atomic Weights Commission, by either Michael Berglund or Thomas Walczyk. In the last few days, I checked the published literature for any other articles in the areas of natural variations in isotopic abundance ratios, measurements of isotopic abundance ratios on samples of extra-terrestrial material and isotopic abundance ratio measurements performed using ICPMS instruments. Hopefully this information will be of interest to members of the Commission, the sub-committee on isotopic abundance measurements (SIAM), members of the former sub-committee on natural isotopic fractionation (SNIF), the sub-committee on extra-terrestrial isotope ratios (SETIR), the RTCE Task Group and the Guidelines Task Group, who are dealing with ICPMS and TIMS comparisons. In the following report, I categorize the publications in one of four areas. Measurements performed using either positive or negative ions with Thermal Ionization Mass Spectrometer, TIMS, instruments; measurements performed on Inductively Coupled Plasma Mass Spectrometer, ICPMS, instruments; measurements of natural variations of the isotopic abundance ratios; and finally measurements on extra-terrestrial samples with instrumentation of either type. There is overlap in these areas. I selected out variations and ET results first and then categorized the rest of the papers by TIMS and ICPMS.

  7. Some isotopic abundances in the cosmic radiation

    NASA Technical Reports Server (NTRS)

    Young, J. S.; Freier, P. S.; Waddington, C. J.

    1980-01-01

    Cosmic ray nuclei with Z not less than 10 have been observed in a detector which measures charge with a double scintillator-Cherenkov array and mass by combining the Cherenkov signal with residual range measured in nuclear emulsions. Results are presented for the isotopic analyses of Al, Ca, Sc, Mn, Fe, Co, Ni and Cu in the energy range 300-800 MeV/amu.

  8. 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.

  9. Clumped isotopes in soil carbonate

    NASA Astrophysics Data System (ADS)

    Quade, J.; Eiler, J. M.; Daeron, M.

    2011-12-01

    We are monitoring soil temperature and measuring clumped isotopes from modern soil carbonate in North and South America, Hawaii, and Tibet. Clumped isotopes from 50-200 cm soil depth show a strong and systematic bias toward formation in the warmest summer months. For example, soil carbonate as these depths exceed local mean annual temperature by 10-15°C in soils from India and Tibet. Clumped isotope temperatures from modern carbonate increase very regularly (r2 = 0.90) with elevation gain from lowland India to Tibet. Here carbonate forms largely in May-June, just prior to the arrival of the soil-cooling monsoon rains. In this regard, clumped isotopes hold great promise as a paleoaltimeter on the plateau. The question is whether these patterns from a monsoonal climate can be generalized (and they probably can't be) to other climate regimes when soil carbonate forms at a different time of year than the pre-monsoon. For example, in winter-dominated rainfall regimes soil carbonate may form as soils dewater in the spring and soil temperature is closer to mean annual temperature. These are open questions. Diurnal temperature information is also archived in the upper 30 cm of soils. Modern carbonate in Tibet appears to form in very late morning through afternoon, when the surface soil is warmest. Shade and aspect also strongly influence measured soil and clumped isotope temperatures. Both variables will have to be controlled for to correctly interpret clumped isotopes from the paleosol record. Clumped isotope values correlate with δ13C values in soil carbonate from shallowly buried (<1 km) paleosols from Nepal and Pakistan. This makes sense since δ13C values in the sub-tropics are determined the fraction of tree (C3) to grass (C4) cover, and soils under tree-covered areas are cooler. Finally, clumped isotopes from carbonates are reset to higher temperatures at burial depths roughly >2-3 km or >50-75°C. This was reproduced from paleosol and lake carbonates from three Asian sections. If representative, this greatly limits the utility of clumped isotopes for reconstruction of primary surface temperatures in deep time, but makes them a potential low-temperature carbonate thermochronometer.

  10. (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.

  11. Comprehensive study of carbon and oxygen isotopic compositions, trace element abundances, and cathodoluminescence intensities of calcite in the Murchison CM chondrite

    NASA Astrophysics Data System (ADS)

    Fujiya, Wataru; Sugiura, Naoji; Marrocchi, Yves; Takahata, Naoto; Hoppe, Peter; Shirai, Kotaro; Sano, Yuji; Hiyagon, Hajime

    2015-07-01

    We have performed in situ analyses of C and O isotopic compositions, trace element concentrations, and cathodoluminescence (CL) intensities on calcite in Murchison, a weakly altered CM chondrite. We found that the trace element (Mg, Mn, and Fe) concentrations are heterogeneous within single calcite grains. Grain to grain heterogeneity is even more pronounced. The analyzed calcite grains can be separated into two distinct types with respect to their C isotopic ratios, trace element concentrations, and CL characteristics: Calcite grains with higher δ13CPDB values (∼75‰) have low trace element concentrations and uniformly dark CL, while grains with lower δ13C values (∼35‰) have higher trace element concentrations and CL zoning. In contrast to the C isotopic ratios, O isotopic ratios are similar for both types of calcites (δ18OSMOW ∼ 34‰). The O isotopic ratios, trace element concentrations, and CL characteristics provide no evidence for C-isotope evolution in fluids from a single C reservoir by Rayleigh-type isotope fractionation (i.e., removal of C-bearing gaseous species). Also, it seems difficult to explain the O and C isotopic compositions of the two types of calcites by their formation at different temperatures from a single fluid. Instead, the δ13C variation suggests the presence of at least two C reservoirs with different isotopic ratios in the aqueous fluids from which the calcites precipitated. The C reservoirs with lower δ13C values are likely to be organic matter. The same holds for the C reservoirs with higher δ13C values which might have significant contributions from the 13C-enriched grains identified in meteoritic insoluble organic matter. Thermodynamic calculations show that calcite with lower Fe concentrations formed under more reduced conditions than calcite with higher Fe concentrations. If this is the case, the 13C-rich organic grains may have been destroyed and dissolved in the fluids under more reduced conditions than other organic components. The fact that the two types of calcites were found in different domains in the same thin section suggests that microenvironments with diverse physicochemical conditions such as redox states were present at scales of 100's μm.

  12. Elemental, isotopic and molecular abundances in comets

    NASA Technical Reports Server (NTRS)

    Delsemme, A. H.

    1986-01-01

    The chemical composition of comet nuclei and the factors affecting it are discussed, summarizing the results of recent theoretical, experimental, and observational investigations. Consideration is given to the evidence supporting the view that the nucleus is radially differentiation (except for a thin outer layer), surface differentiation by heat processing and outgassing, and mantle buildup on an undifferentiated core. The nature of the refractory and volatile components is examined, and the elemental and isotopic compositions are given in tables and characterized. The uncertain (except for H2O) molecular composition of the volatile fraction is considered, and it is suggested that some oxides or aldehydes (such as CO, CO2, and H2CO), but no large amounts of fully hydrogenated compounds (such as CH4 and NH3) are included.

  13. Literature survey of isotopic abundance data for 1987-1989

    SciTech Connect

    Holden, N.E. )

    1989-08-09

    I have compiled all of the data on isotopic abundance measurements and their variation in nature for the time period since the last General Assembly. Most of the data deals with the variations in the abundances as given by per mil deviations from some standard. As such, they are not of major interest to the Atomic Weights Commission. However, there were some measurements which are of general interest in this list.

  14. Carbon-13 isotopic abundance and concentration of atmospheric methane for background air in the Southern and Northern Hemispheres from 1978 to 1989

    SciTech Connect

    Stevens, C.M.; Sepanski; Morris, L.J.

    1995-03-01

    Atmospheric methane (CH{sub 4}) may become an increasingly important contributor to global warming in future years. Its atmospheric concentration has risen, doubling over the past several hundred years, and additional methane is thought to have a much greater effect on climate, on a per molecule basis, than additional C0{sub 2} at present day concentrations (Shine et al. 1990). The causes of the increase of atmospheric CH{sub 4} have been difficult to ascertain because of a lack of quantitative knowledge of the fluxes (i.e., net emissions) from the numerous anthropogenic and natural sources. The goal of CH{sub 4} isotopic studies is to provide a constraint (and so reduce the uncertainties) in estimating the relative fluxes from the various isotopically distinct sources, whose combined fluxes must result in the measured atmospheric isotopic composition, after the fractionating effect of the atmospheric removal process is considered. In addition, knowledge of the spatial and temporal changes in the isotopic composition of atmospheric CH{sub 4}, along with estimates of the fluxes from some of the major sources, makes it possible to calculate growth rates for sources whose temporal emissions trends would be difficult to measure directly.

  15. Carbon and nitrogen stable isotopic inventory of the most abundant demersal fish captured by benthic gears in southwestern Iceland (North Atlantic)

    NASA Astrophysics Data System (ADS)

    Sarà, Gianluca; de Pirro, Maurizio; Sprovieri, Mario; Rumolo, Paola; Halldórsson, Halldór Pálmar; Svavarsson, Jörundur

    2009-12-01

    Stable isotopes (δ13C and δ15N) were used to examine the origin of organic matter for the most representative demersal species of the SW Icelandic fishery, accounting for over 70% of landings of those species in the North Atlantic. Samples were collected during a 2-week period in early September 2004 from landings and directly during fishing cruises. Stable isotopes showed that particulate organic matter and sedimentary organic matter were at the base of the food web and appeared to fill two different compartments: the pelagic and the benthic. The pelagic realm was composed of only capelin and sandeel; krill and redfish occupied an intermediate position between pelagic and benthic realms; while anglerfish, haddock, cod and ling resulted as the true demersal species while tusk, rays and plaice were strongly linked to the benthic habitat.

  16. Developing Model Constraints on Northern Extra-Tropical Carbon Cycling Based on measurements of the Abundance and Isotopic Composition of Atmospheric CO2

    SciTech Connect

    Keeling, Ralph

    2014-12-12

    The objective of this project was to perform CO2 data syntheses and modeling activities to address two central questions: 1) how much has the seasonal cycle in atmospheric CO2 at northern high latitudes changed since the 1960s, and 2) how well do prognostic biospheric models represent these changes. This project also supported the continuation of the Scripps time series of CO2 isotopes and concentration at ten baseline stations distributed globally.

  17. The abundance and isotopic composition of water in eucrites

    NASA Astrophysics Data System (ADS)

    Barrett, T. J.; Barnes, J. J.; TartèSe, R.; Anand, M.; Franchi, I. A.; Greenwood, R. C.; Charlier, B. L. A.; Grady, M. M.

    2016-05-01

    Volatile elements play a key role in the dynamics of planetary evolution. Extensive work has been carried out to determine the abundance, distribution, and source(s) of volatiles in planetary bodies such as the Earth, Moon, and Mars. A recent study showed that the water in apatite from eucrites has similar hydrogen isotopic compositions compared to water in terrestrial rocks and carbonaceous chondrites, suggesting that water accreted very early in the inner solar system given the ancient crystallization ages (~4.5 Ga) of eucrites. Here, the measurements of water (reported as equivalent H2O abundances) and the hydrogen isotopic composition (δD) of apatite from five basaltic eucrites and one cumulate eucrite are reported. Apatite H2O abundances range from ~30 to ~3500 ppm and are associated with a weighted average δD value of -34 ± 67‰. No systematic variations or correlations are observed in H2O abundance or δD value with eucrite geochemical trend or metamorphic grade. These results extend the range of previously published hydrogen isotope data for eucrites and confirm the striking homogeneity in the H-isotopic composition of water in eucrites, which is consistent with a common source for water in the inner solar system.

  18. Report on carbon and nitrogen abundance studies

    NASA Technical Reports Server (NTRS)

    Boehm-Vitense, Erika

    1991-01-01

    The aim of the proposal was to determine the nitrogen to carbon abundance ratios from transition layer lines in stars with different T(sub eff) and luminosities. The equations which give the surface emission line fluxes and the measured ratio of the NV to CIV emission line fluxes are presented and explained. The abundance results are compared with those of photospheric abundance studies for stars in common with the photospheric investigations. The results show that the analyses are at least as accurate as the photospheric determinations. These studies can be extended to F and early G stars for which photospheric abundance determinations for giants are hard to do because molecular bands become too weak. The abundance determination in the context of stellar evolution is addressed. The N/C abundance ratio increases steeply at the point of evolution for which the convection zone reaches deepest. Looking at the evolution of the rotation velocities v sin i, a steep decrease in v sin i is related to the increasing depth of the convection zone. It is concluded that the decrease in v sin i for T(sub eff) less than or approximately = 5800 K is most probably due to the rearrangement of the angular momentum in the stars due to deep convective mixing. It appears that the convection zone is rotating with nearly depth independent angular momentum. Other research results and ongoing projects are discussed.

  19. Solar-type xenon - Isotopic abundances in Pesyanoe

    NASA Technical Reports Server (NTRS)

    Kim, J. S.; Marti, K.

    1992-01-01

    Elemental and isotopic abundances of Ar and Xe were measured in three grain-size separates in the dark phase of the enstatite achondrite Pesyanoe by stepwise heating, using a combination of pyrolysis and combustion steps. The data reveal a low-temperature gas fraction with Ar/Xe ratios close to the solar ratio and isotopically similar to solar-type Ar and Xe observed in lunar samples. The gas released at intermediate temperature steps shows that Ar and Xe are isotopically fractionated, compared to the low-temperature components. Pesyanoe does not have excess Ar-40 and fission Xe, which means its parent body was too small for ion reimplantation. It is concluded that solar-type Xe isotopic abundances can be inferred from the low-temperature component. A comparison of Pesyanoe and lunar data shows that isotopic signatures of solar-wind Xe, as sampled at two different points in solar system space and time, are identical within experimental error.

  20. The carbon monoxide abundance in interstellar clouds

    NASA Technical Reports Server (NTRS)

    Langer, W.

    1976-01-01

    The steady-state abundance of carbon monoxide in interstellar clouds is calculated as a function of optical depth, density, and temperature. The molecular reactions which lead to CO can be initiated by the following ion-molecule reactions: H(+) + O yields O(+) + H, C(+) + H2 yields CH2(+) + a photon, and H3(+) + C and O. As the ultraviolet radiation field is attenuated, C(+) is transformed primarily into CO and C I. There are characteristic column densities for the transition to CO corresponding to the optical depths for attenuating this field at different wavelengths. For thick, low-temperature clouds the attenuation of the fields which ionize carbon, sulfur, and heavy metals is important for CO production initiated by H3(+). Complete conversion to CO does not necessarily occur, and considerable neutral carbon may be expected even in optically thick clouds. Comparison of integrated column densities of CO with extinction are in reasonable agreement with observations.

  1. Nitrogen abundances and isotopic compositions in stony meteorites

    NASA Technical Reports Server (NTRS)

    Kung, C.-C.; Clayton, R. N.

    1978-01-01

    Nitrogen contents range from a few parts per million in ordinary chondrites and achondrites to several hundred parts per million in enstatite chondrites and carbonaceous chondrites. Four major isotopic groups are recognized: (1) C1 and C2 carbonaceous chondrites, (2) enstatite chondrites, (3) C3 chondrites, and (4) ordinary chondrites. The major variations are primary, representing isotopic abundances established at the time of condensation and accretion. Secondary processes, such as spallation reactions, solar wind implantation and metamorphic loss may cause small but observable isotopic variations in particular cases. The large isotopic difference between enstatite chondrites and carbonaceous chondrites cannot be accounted for by equilibrium condensation from a homogeneous nebular gas, and requires either unusually large kinetic effects, or a temporal or spatial variation of isotopic composition of the nebula. Nitrogen isotopic heterogeneity in the nebula due to nuclear processes has not been firmly established, but may be required to account for the large variations found within the Allende and Leoville meteorites. The unique carbonaceous chondrite, Renazzo, also requires a special source. It is not yet possible, from the meteoritic data, to establish the mode of accretion of nitrogen onto the primitive earth.

  2. The Abundance and Isotopic Composition of Hg in Extraterrestrial Materials

    NASA Technical Reports Server (NTRS)

    Lauretta, D. S.

    2004-01-01

    During the past three year grant period we made excellent progress in our study of the abundances and isotopic compositions of Hg and other volatile trace elements in extraterrestrial materials. As part of my startup package I received funds to construct a state-of-the-art experimental facility to study gas-solid reaction kinetics. Much of our effort was spent developing the methodology to measure the abundance and isotopic composition of Hg at ultratrace levels in solid materials. In our first study, the abundance and isotopic composition of Hg was determined in bulk samples of the Murchison (CM) and Allende (CV) carbonaceous chondrites. We have continued our study of mercury in primitive meteorites and expanded the suite of meteorites to include other members of the CM and CV chondrite group as well as CI and CO chondrites. Samples of the CI chondrite Orgueil, the CM chondrites Murray, Nogoya, and Cold Bokkeveld, the CO chondrites Kainsaz, Omans, and Isna, and the CV chondrites Vigarano, Mokoia, and Grosnaja were tested. We have developed a thermal analysis ICP-MS technique and applied it to the study of a suite of thermally labile elements (Zn, As, Se, Cd, In, Sn, Sb, Te, Hg, Au, Tl, Pb, and Bi) in geologic materials as well.

  3. Mass Spectrometric Measurement of Martian Krypton and Xenon Isotopic Abundance

    NASA Technical Reports Server (NTRS)

    Mahaffy, P.; Mauersberger, K.

    1993-01-01

    The Viking gas chromatograph mass spectrometer experiment provided significant data on the atmospheric composition at the surface of Mars, including measurements of several isotope ratios. However, the limited dynamic range of this mass spectrometer resulted in marginal measurements for the important Kr and Xe isotopic abundance. The Xe-129 to Xe-132 ratio was measured with an uncertainty of 70%, but none of the other isotope ratios for these species were obtained. Accurate measurement of the Xe and Kr isotopic abundance in this atmosphere provides an important data point in testing theories of planetary formation and atmospheric evolution. The measurement is also essential for a stringent test for the Martian origin of the SNC meteorites, since the Kr and Xe fractionation pattern seen in gas trapped in glassy nodules of an SNC (EETA 79001) is unlike any other known solar system resevoir. Current flight mass spectrometer designs combined with the new technology of a high-performance vacuum pumping system show promise for a substantial increase in gas throughput and the dynamic range required to accurately measure these trace species. Various aspects of this new technology are discussed.

  4. Bodily variability of zinc natural isotope abundances in sheep.

    PubMed

    Balter, Vincent; Zazzo, Antoine; Moloney, Aidan P; Moynier, Fred; Schmidt, Olaf; Monahan, Frank J; Albarède, Francis

    2010-03-15

    Evidence is growing that the range of zinc stable isotope compositions, represented by the deviation of (66)Zn in permil units relative to a standard and expressed as delta(66)Zn, is larger in organic matter than in inorganic material. This study reports the variations of delta(66)Zn in various organs of sheep raised on a controlled diet. Zinc was purified by anion-exchange chromatography. The Zn concentrations and Zn stable isotope compositions were determined by quadrupole inductively coupled plasma mass spectrometry and multi-collector inductively coupled plasma mass spectrometry, respectively. The data show that delta(66)Zn variability exceeds 1 per thousand, with bone, muscle, serum and urine enriched in the heavy isotopes, and feces, red blood cells, kidney and liver enriched in light isotopes, all relative to the diet value. The (66)Zn enrichment of the circulating serum reservoir is likely to take place in the digestive tract, probably through the preferential binding of lighter isotopes with phytic acid, which is known to control the uptake of metallic elements. Mass balance calculations suggest that the (66)Zn depletion between diet and feces, which is not balanced by any other outward flux, leads to a secular isotopic drift in serum. A simple time-dependent two-box model, involving the gastro-intestinal tract on the one hand and the muscle and bone on the other, predicts that the maximum (66)Zn enrichment, which equals the difference in delta(66)Zn between diet and bulk (approximately 0.25 per thousand), is reached after about ten years. Therefore, a better understanding of the variations of natural abundance of Zn isotopes in animals and humans will probably bring new perspectives for the assessment of their Zn status. PMID:20155761

  5. 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.

  6. The Abundance and Isotopic Composition of Hg in Extraterrestrial Materials

    NASA Technical Reports Server (NTRS)

    Blum, J. D.; Klaue, Bjorn

    2005-01-01

    During the three year grant period we made excellent progress in our study of the abundances and isotopic compositions of Hg and other volatile trace elements in extraterrestrial materials. At the time the grant started, our collaborating PI, Dante Lauretts, was a postdoctoral research associate working with Peter Buseck at Arizona State University. The work on chondritic Hg was done in collaboration with Dante Lauretta and Peter Buseck and this study was published in Lauretta et a1 (2001a). In July, 2001 Dante Lauretta accepted a position as an Assistant Professor in the Lunar and Planetary Laboratory at the University of Arizona. His funding was transferred and this grant has supported much of his research activities during his first two years at the U of A. Several other papers are in preparation and will be published soon. We presented papers on this topic at Goldschmidt Conferences, the Lunar and Planetary Science Conferences, and the Annual Meetings of the Meteoritical Society. The work done under this grant has spurred several new directions of inquiry, which we are still pursuing. Included in this paper are the studies of bulk abundances and isotopic compositions of metreoritic Mercury, and the development of a thermal analysis ICP-MS technique applied to thermally liable elements.

  7. Metallicity-Dependent Isotopic Abundances and the Impact of Helium Rate Uncertainties in Massive Stars

    NASA Astrophysics Data System (ADS)

    West, Christopher

    2013-03-01

    All stellar evolution models for nucleosynthesis require an initial isotopic abundance set to use as a starting point, because nuclear reactions occur between isotopes. Generally, our knowledge of isotopic abundances of stars is fairly incomplete except for the Solar System. We develop a first model for a complete average isotopic decomposition as a function of metallicity. Our model is based on the underlying nuclear astrophysics processes, and is fitted to observational data, rather than traditional forward galactic chemical evolution modeling which integrates stellar yields beginning from big bang nucleosynthesis. We first decompose the isotopic solar abundance pattern into contributions from astrophysical sources. Each contribution is then assumed to scale as a function of metallicity. The resulting total isotopic abundances are summed into elemental abundances and fitted to available halo and disk stellar data to constrain the model's free parameter values. This procedure allows us to use available elemental observational data to reconstruct and constrain both the much needed complete isotopic evolution that is not accessible to current observations, and the underlying astrophysical processes. Our model finds a best fit for Type Ia supernovae contributing ˜0.7 to the solar Fe abundance, and Type Ia onset occurring at [Fe/H]~1.2, in agreement with typical values. The completed model can be used in future nucleosynthesis studies. We also perform a preliminary analysis to assess the impact of our isotopic scaling model on the resulting nucleosynthesis of massive stars, compared to a linear interpolation method. Using these two input methods we compute a limited grid of stellar models, and compare the final nucleosynthesis to observations. The compactness parameter was first used to assess which models would likely explode as successful supernovae, and contribute explosive nucleosynthesis yields. We find a better agreement to solar observations using the scaling model compared to the linear interpolation method, for the six s--only isotopes along the weak s--process path. As a second project, we study the sensitivity of presupernova evolution and supernova nucleosynthesis yields of massive stars to variations of the helium-burning reaction rates within the range of their uncertainties. The current solar abundances from Lodders (2010) are used for the initial stellar composition. We compute a grid of 12 initial stellar masses and 176 models per stellar mass to explore the effects of independently varying the 12C(alpha,gamma)16O and 3alpha reaction rates, denoted Ralpha,12 and R3alpha, respectively. The production factors of both the intermediate-mass elements (A=16--40) and the s--only isotopes along the weak s--process path ( 70Ge, 76Se, 80Kr, 82Kr, 86Sr, and 87Sr) were found to be in reasonable agreement with predictions for variations of R3alpha and Ralpha,12 of +/-25%; the s--only isotopes, however, tend to favor higher values of R3alpha than the intermediate-mass isotopes. The experimental uncertainty (one standard deviation) in R3alpha(Ralpha,12 ) is approximately +/-10%(+/-25%). The results show that a more accurate measurement of one of these rates would decrease the uncertainty in the other as inferred from the present calculations. We also observe sharp changes in production factors and standard deviations for small changes in the reaction rates, due to differences in the convection structure of the star. The compactness parameter was used to assess which models would likely explode as successful supernovae, and hence contribute explosive nucleosynthesis yields. We also provide the approximate remnant masses for each model and the carbon mass fractions at the end of core-helium burning as a key parameter for later evolution stages.

  8. 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/T2-0.329124× 10 9/T3+0.0304160× 10 12/T4]× X1.5 The results of the computations were used together with previously published experimental vaporous CO 2-silicate melt fractionations to determine, at 1200°C, a relationship between melt-CO 213C fractionation and melt composition, expressed as molecular proportions of the cations Mg, Fe, Mn, Ca, Na, K and Si and Al: 1000 lnα Melt- CO2=5.14× Mg+ Fe+ Mn+ Ca+ Na+ K/Si+ Al+0.86 A conceptual model to understand this relationship was developed. The results of the computations approximate closely the experimentally determined vaporous CO 2-CaCO 3 fractionations at high temperatures. Empirically derived dolomite-calcite and calcite-graphite 13C isotope geothermometers agree with results of the present work.

  9. Elemental and isotopic abundances in the solar wind

    NASA Technical Reports Server (NTRS)

    Geiss, J.

    1972-01-01

    The use of collecting foils and lunar material to assay the isotopic composition of the solar wind is reviewed. Arguments are given to show that lunar surface correlated gases are likely to be most useful in studying the history of the solar wind, though the isotopic abundances are thought to give a good approximation to the solar wind composition. The results of the analysis of Surveyor material are also given. The conditions leading to a significant component of the interstellar gas entering the inner solar system are reviewed and suggestions made for experimental searches for this fraction. A critical discussion is given of the different ways in which the basic solar composition could be modified by fractionation taking place between the sun's surface and points of observation such as on the Moon or in interplanetary space. An extended review is made of the relation of isotopic and elemental composition of the interplanetary gas to the dynamic behavior of the solar corona, especially processes leading to fractionation. Lastly, connection is made between the subject of composition, nucleosynthesis and the convective zone of the sun, and processes leading to modification of initial accretion of certain gases on the Earth and Moon.

  10. Nitrogen isotope abundances in the recent solar wind.

    PubMed

    Kim, J S; Kim, Y; Marti, K; Kerridge, J F

    1995-06-01

    Although lunar crystalline rocks are essentially devoid of nitrogen, the same is not true of the lunar regolith. The nitrogen contents of individual regolith samples (which can be as high as 0.012% by mass) correlate strongly with abundances of noble gases known to be implanted in the lunar surface by solar radiation, indicating that lunar regolith nitrogen is also predominantly of solar origin. The large variability in 15N/14N ratios measured in different regolith samples may thus reflect long-term changes in the isotopic composition of the solar radiation. But attempts to explain these variations have been hampered by the lack of any firm constraint on 15N/14N in the present solar wind. Here we report measurements of nitrogen isotopes from two lunar samples that have had simple (and relatively recent) exposure histories. We find that nitrogen implanted in the lunar surface during the past 10(5) to 5 x 10(7) years has a 15N/14N ratio approximately 40% higher than that in the terrestrial atmosphere, which is substantially lower than most previous estimates. This isotopic signature probably represents the best measure of 15N/14N in the present-day solar wind. PMID:7760930

  11. 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.

  12. On the abundances of carbon dioxide isotopologues in the atmospheres of mars and earth

    NASA Astrophysics Data System (ADS)

    Shved, G. M.

    2016-03-01

    The isotopic composition of carbon dioxide in the Martian atmosphere from the measurements of Mars Science Laboratory have been used to estimate the relative abundances of CO2 isotopologues in the Martian atmosphere. Concurrently, this study has revealed long-standing errors in the amounts of some of low-abundance CO2 isotopologues in the Earth's atmosphere in the databases of spectroscopic parameters of gases (HITRAN, etc.).

  13. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

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

    1991-04-01

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

  14. 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.

  15. 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

  16. Carbon isotope effects associated with autotrophic acetogenesis

    USGS Publications Warehouse

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

    1989-01-01

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

  17. Carbon 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.

  18. 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.

  19. The abundances of elements and isotopes in the solar wind

    NASA Technical Reports Server (NTRS)

    Gloeckler, George; Geiss, Johannes

    1989-01-01

    Solar wind abundances have now been measured for eleven elements and the isotopes of the noble gases. Aside from solar wind protons and alpha particles, which have been studied extensively since the 1960's, information for heavier elements is limited. Nevertheless, two effects stand out. First is the enrichment of abundances of elements with low first ionization potential (FIP), most likely the combined result of an atom-ion separation process in the upper chromosphere, and a marginal coupling of low-charge-state heavy ions to protons and alphas during the acceleration of the solar wind. Second, there is variability in the solar wind composition over a whole range of time scales. Recent measurements carried out in the earth's magnetosheath during times that included high-speed coronal-hole-associated flows indicate a significantly lower overabundance of low FIP elements. Given the fact that the He/H ratio is remarkably constant in the coronal hole solar wind, this result suggests that both enrichment and variability are reduced in such flows.

  20. The carbon isotopic composition of ecosystem breath

    NASA Astrophysics Data System (ADS)

    Ehleringer, J.

    2008-05-01

    At the global scale, there are repeatable annual fluctuations in the concentration and isotopic composition of atmospheric carbon dioxide, sometimes referred to as the "breathing of the planet". Vegetation components within ecosystems fix carbon dioxide through photosynthesis into stable organic compounds; simultaneously both vegetation and heterotrophic components of the ecosystem release previously fixed carbon as respiration. These two-way fluxes influencing carbon dioxide exchange between the biosphere and the atmosphere impact both the concentration and isotopic composition of carbon dioxide within the convective boundary layer. Over space, the compounding effects of gas exchange activities from ecosystems become reflected in both regional and global changes in the concentration and isotopic composition of atmospheric carbon dioxide. When these two parameters are plotted against each other, there are significant linear relationships between the carbon isotopic composition and inverse concentration of atmospheric carbon dioxide. At the ecosystem scale, these "Keeling plots" intercepts of C3-dominated ecosystems describe the carbon isotope ratio of biospheric gas exchange. Using Farquhar's model, these carbon isotope values can be translated into quantitative measures of the drought-dependent control of photosynthesis by stomata as water availability changes through time. This approach is useful in aggregating the influences of drought across regional landscapes as it provides a quantitative measure of stomatal influence on photosynthetic gas exchange at the ecosystem-to-region scales. Multi-year analyses of the drought-dependent trends across terrestrial ecosystems show a repeated pattern with water stress in all but one C3-ecosystem type. Ecosystems that are dominated by ring-porous trees appear not to exhibit a dynamic stomatal response to water stress and therefore, there is little dependence of the carbon isotope ratio of gas exchange on site water balance. The mechanistic basis for this pattern is defined; the implications of climate change on ring-porous versus diffuse-porous vegetation and therefore on future atmospheric carbon dioxide isotope-concentration patterns is discussed.

  1. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

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

    1991-01-01

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

  2. Preliminary report on isotope abundance measurements in groundwater samples from the Talbert Injection Barrier Area, Orange County Water District

    SciTech Connect

    Hudson, G.B.; Davisson, M.L.; Velsko, C.; Niemeyer, S.; Esser, B.; Beiriger, J.

    1995-02-01

    This report discusses isotope abundance measurements made on a collection of groundwater samples from the Orange County Water District. The water samples were collected in May, 1994 as part of a preliminary study conducted by LLNL to assess the feasibility of tracing and dating reclaimed water used in the Talbert Injection Barrier. A set of samples were collected both near to and far from the barrier and also at different depths in available monitoring wells. A variety of elements were selected for isotopic analysis; hydrogen (tritium), helium, neon, carbon, chlorine and strontium. The tritium abundance combined with the {sup 3}He and {sup 20}Ne abundance provides a method for age dating young (< 40 yr.) groundwater. The abundance of {sup 14}C provides an age dating technique for older (1,000--50,000 yr.) groundwater. The concentrations of {sup 36}Cl and {sup 87}Sr/{sup 86}Sr give information on sea water mixing and water-rock chemical interactions.

  3. 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.

  4. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

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

    1991-01-01

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

  5. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

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

    1991-12-31

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

  6. Total carbon and sulfur abundances in Antarctic meteorites

    NASA Technical Reports Server (NTRS)

    Gibson, E. K., Jr.; Yanai, K.

    1979-01-01

    Total carbon and sulfur abundances have been measured in five Antarctic meteorites. Two C2 carbonaceous chondrites Yamato 74662 and Allan Hills 77306 have sulfur abundances (3.490 plus or minus .040% and 3.863 plus or minus 0.050% respectively) similar to other C2 chondrites but their carbon abundances (1.514 plus or minus 0.050% and 1.324 plus or minus .040% respectively) are lower than previously measured C2 chondrites. The decreased carbon abundances may reflect the effects of weathering in cold environments. Carbon and sulfur abundances for one C4 carbonaceous chondrite, one E4 enstatite chondrite and one ureilite are similar to values reported previously for meteorites of the same petrologic grades.

  7. 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.

  8. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

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

    1990-05-01

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

  9. Spatial isotopic heterogeneity during the Guttenberg isotopic carbon excursion: Mechanisms and implications for craton-wide isotope gradients

    NASA Astrophysics Data System (ADS)

    Metzger, J. G.; Fike, D. A.

    2012-12-01

    The carbon isotopic compositions of carbonate carbon (δ13Ccarb) and organic carbon (δ13Corg) in marine limestones are frequently used as paleoenvironmental proxies and as chemostratigraphic tools for aligning strata. These functions are predicated upon the assumption that isotopic variability in these strata reflects the secular variation in the marine reservoir of dissolved inorganic carbon (DIC). As such, the utility of these isotopic systems largely depends on the assumed spatial homogeneity of marine δ13CDIC. While other isotope systems such as sulfate and strontium have been shown to be extremely well mixed in the modern ocean, a 1-2‰ range in δ13CDIC exists over the entire depth and latitude range of the ocean. This variability in δ13CDIC is largely the result of differences in the local balance of organic carbon fixation and export (increasing δ13CDIC) and/or organic carbon oxidation (decreasing δ13CDIC). The preservation of such isotopic variability in the geologic record has been advocated on several occasions. In particular, previous workers have argued for an ocean-to-interior seaway isotopic gradient in δ13Ccarb, δ13Corg, and ɛNd across Laurentia during the Late Ordovician across the interval that spans the Guttenberg Isotopic Carbon Excursion (GICE). Here we examine two Late Ordovician-aged sections from Missouri, USA that contain the GICE. At first glace, our data showed high degree of stratigraphic and lateral variability. Detailed petrographic and geochemical (e.g., trace element abundance) screening reveals that the majority of the isotopic heterogeneity in our sections is the result of local syndepositional/diagenetic alteration - and not the result of primary gradients in δ13CDIC between the localities examined. Our 'least-altered' δ13Ccarb profile matches closely with previously published records from Iowa; however, sections adjacent both to our locations in Missouri and to the similar δ13Ccarb profile in Iowa are characterized by variable and more depleted δ13Ccarb profiles. This pattern of long-range reproducibility (several hundred km) and short-range (~10s of km) heterogeneity is not consistent with a craton-scale gradient in δ13CDIC. Rather, these observations suggest local depositional conditions and diagenetic alteration are the sources of substantial δ13Ccarb heterogeneity. Detailed petrographic and geochemical analyses are necessary to constrain the mechanisms that give rise to isotopic heterogeneity and, in particular to support interpretations of primary (i.e., water column) gradients in ocean chemistry.

  10. Isotope abundance of {sup 180}Ta{sup m} and p-process nucleosynthesis

    SciTech Connect

    Laeter, J.R. de; Bukilic, N.

    2005-08-01

    The p-process of stellar nucleosynthesis produces the stable neutron-deficient nuclides heavier than the iron peak elements. An accurate determination of the isotopic composition of tantalum is required to enable p-process nucleosynthetic calculations to be evaluated in terms of an accurate isotope abundance for {sup 180}Ta. This odd-odd nuclide has the remarkable property of having a long-lived isomeric state and a short-lived ground state, so that in reality one is measuring the isotope abundance of {sup 180}Ta{sup m}, which is a unique situation in nature. {sup 180}Ta{sup m} is the rarest isotope of nature's rarest element and is therefore an important isotope in deciphering the origin of the p-process. Because the isotopic composition of tantalum has only been measured on two occasions with relatively large uncertainties, an accurate determination is required to provide a better basis for p-process production calculations. A thermal ionization mass spectrometer was used to measure the isotope abundance of {sup 180}Ta{sup m} with high precision. The linearity of this instrument was verified by measuring the isotopically certified reference material for potassium (NIST 985), whose isotopes span a wide range of isotope ratios. The abundance sensitivity of the mass spectrometer for the measured ion beams has been examined to ensure the absence of tailing effects and interfering isotopes. These procedures are essential because of the extremely low isotope abundance of {sup 180}Ta{sup m}. The isotope fractionation of the tantalum isotopes was estimated by reference to the isotope fractionation of the isotopically certified reference material for rhenium (NIST 989). The isotopic composition of tantalum has been determined to be {sup 181}Ta/{sup 180}Ta{sup m}=8325 {+-} 43, which gives isotope abundances for {sup 180}Ta{sup m}=0.0001201 {+-} 0.0000008 and {sup 181}Ta=0.9998799 {+-} 0.0000008. This gives a Solar System abundance of {sup 180}Ta{sup m} of 2.49 x 10{sup -6} with reference to silicon=10{sup 6}. These isotope abundances, together with the relative atomic masses, give an atomic weight for tantalum of 180.947878 {+-} 0.000002.

  11. 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

  12. Clumped Isotopes Applied to Carbonate Diagenesis and High Temperature Systems

    NASA Astrophysics Data System (ADS)

    John, C. M.; Jourdan, A.; Kluge, T.; Dale, A.; Davis, S.; Vandeginste, V.

    2012-12-01

    The field of clumped isotopes is concerned with the state of ordering of natural substances and aims at constraining the abundance of 18O-13C bonds (i.e. a 'clump') within the lattice of carbonate minerals. Measuring the difference between the abundance of 18O-13C bonds in a sample relative to a stochastic distribution of isotopologues offers a single-phase paleothermometer applicable to all carbonate phases. Most of the applications of clumped isotopes to date have been in the field of paleoclimate, but applications to diagenetic systems are becoming more common. The independence of clumped isotopes from the isotopic composition of the diagenetic fluid reduces ambiguities when interpreting paragenesis, fluid flow history, and thermal history of basins. This presentation will synthesize the results of several projects within our group that collectively aim at understanding and applying clumped isotopes to diagenetic systems. One example of project including diagenesis and clumped isotope is a study of low-temperature diagenetic calcite in a salt dome in Oman (Jebel Madar). Jebel Madar is an ideal case study as large fracture-related crystals can be sampled for both clumped isotopes and fluid inclusions. Results show a good match between single-phase fluid inclusions suggesting temperature of precipitations below 90-50°C, and clumped isotope data measured on the same crystals. The low-temperature study reveals the history of gradual cooling and progressive mixing between two sources of diagenetic fluids in the fracture of Jebel Madar, and highlights the potential of clumped isotope for diagenetic studies. However, applications at high-temperatures are currently more challenging because of the lack of empirical calibrations above 50°C. A second project is thus focused on a series of high-temperature lab precipitation experiments for calibrations at high temperature, while a third project explores applicability of clumped isotopes to cemented siliciclastic units. The long-term aim of our research efforts is thus calibration at subsurface conditions, and application of clumped isotope to unravel the diagenetic history of both carbonate and siliciclastic sequences. We would like to acknowledge the financial support of QCCSRC (funded jointly by Qatar Petroleum, Shell and the Qatar Science & Technology Park) and a BP Case studentship from the EPSRC.

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

    PubMed

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

    1990-01-18

    The organic matter found in sedimentary rocks must derive from many sources; not only from ancient primary producers but also from consumers and secondary producers. In all of these organisms, isotope effects can affect the abundance and distribution of 13C in metabolites. Here, by using an improved form of a previously described technique in which the effluent of a gas chromatograph is continuously analysed isotopically, we report evidence of the diverse origins of sedimentary organic matter. The record of 13C abundances in sedimentary carbonate and total organic carbon can be interpreted in terms of variations in the global carbon cycle. Our results demonstrate, however, that isotope variations within sedimentary organic mixtures substantially exceed those observed between samples of total organic carbon. Resolution of isotope variations at the molecular level offers a new and convenient means of refining views both of localized palaeoenvironments and of control mechanisms within the global carbon cycle. PMID:11536462

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

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

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

  15. The abundance of carbon monoxide in Jupiter

    NASA Technical Reports Server (NTRS)

    Beer, R.; Taylor, F. W.

    1978-01-01

    Spectra of Jupiter in the 5-micron window region have been acquired. From these it is deduced that (1) the presence of CO in Jupiter is verified; (2) the column abundance is approximately 0.016 cm amagat (identical to 4.3 by 10 to the 17th power mol/sq cm); and (3) the CO is probably nonuniformly mixed in the atmosphere, being concentrated into the stratosphere.

  16. Carbon abundances of sdO stars from SPY

    NASA Astrophysics Data System (ADS)

    Hirsch, Heiko; Heber, Uli

    2009-06-01

    Ströer et al. (2007) recently suggested a classification of sdOs according to supersolar and subsolar helium abundances, with only the helium-enriched stars showing signes of carbon and/or nitrogen in their optical spectra. We aim to derive reliable carbon and nitrogen abundances by fitting synthetic spectra to data obtained with the UVES spectrograph at ESO. Here we present our first results of the analysis of carbon abundances in hot subdwarf O stars. By constructing a grid of model atmospheres consisting of hydrogen, helium and carbon we were able to derive atmospheric parameters of nine carbon rich sdOs. We find log(NC/Ntotal) up to ten times higher than the solar value, while the mean value for the effective temperature and the surface gravity is slightly lower than derived by helium-hydrogen models only. Surprisingly, we also find three fast rotators among our program stars.

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

    PubMed

    Hayes, J M; Popp, B N; Takigiku, R; Johnson, M 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 (Cenomanian-Turonian) from the Western Interior Seaway of North America. Results are considered in terms of variations in the processes of primary production (which led to the biosynthesis of the molecular precursors of the geoporphyrins) and in secondary processes (those mediating the transformation of primary organic material into sedimentary total organic carbon). 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 13C relative to its primary precursor by 0.6 to 2.8%. This enrichment is attributed to isotope effects within the consumer foodweb and is associated with respiratory heterotrophy. Variations in this secondary enrichment are correlated with variations in the isotopic composition of marine carbonate. This correlation is attributed to effects of environmental changes on the marine foodweb. These may have included increased atmospheric oxygen associated with the Cenomanian-Turonian oceanic anoxic event. The isotopic fractionation associated with fixation of carbon by primary producers is observed to have varied by 1.5% during the interval of deposition. It is suggested that this change is due to a variation in the makeup of the community of primary producers and/or to a decrease in the atmospheric abundance of CO2 during the oceanic anoxic event. PMID:11539781

  18. 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 sufficiently precise to answer many important questions in this area, making the investigation of sub-surface processes an excellent target for future investigations.

  19. 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.

  20. Nitrogen abundances and isotopic compositions in lunar samples

    NASA Technical Reports Server (NTRS)

    Becker, R. H.; Clayton, R. N.

    1975-01-01

    Isotopic analyses were carried out on soil separates as well as on bulk samples. Analyses of nitrogen fractions obtained by step-wise heating of the separates were also conducted. It was also attempted to obtain a value for the isotopic composition of indigenous lunar nitrogen from analyses of igneous rock samples. Several breccias were also analyzed for their nitrogen isotope ratios. The significance of the obtained results is discussed. Several lines of evidence point to the conclusion that the isotope ratio of the nitrogen being implanted into the lunar regolith has increased by some 15% over a period of at least 450 million years and possibly as long as 3,700 million years or more. This may be the result of changes in the nitrogen isotope ratio of the solar wind with time, or it may be due to outgassing and subsequent reimplantation of an isotopically light indigenous lunar nitrogen from the lunar interior in the early history of the moon.

  1. 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 as the deep ocean carbon isotopic variability recorded in co-occurring benthic foraminifera. These reinterpretations bear not only on the assumed venting of carbon through the high latitude surface ocean, but also on the "preformed" carbon isotopic variability throughout the interior of the Pleistocene oceans.

  2. P-Process nucleosynthesis and the abundances of the minor isotopes of tin

    NASA Astrophysics Data System (ADS)

    de Laeter, J. R.; Rosman, K. J. R.; Loss, R. D.

    1984-04-01

    Tin has 10 isotopes, and the mode of production of these isotopes span the range of nucleosynthetic processes first proposed by Burbidge et al. (1957). A number of isotopic anomalies in the solar system have to be interpreted as primordial inhomogeneities, produced by incomplete mixing of the solar nebula. The quantitative classification of the minor tin isotopes according to the nucleosynthetic processes described by Ward and Beer (1981) is considered to be an essential prerequisite for deciphering possible isotopic anomalies which may provide a unique insight into the stellar conditions responsible for their production. No anomalies were found in an analysis of whole rock samples, whereas isotopic anomalies are now known to exist in inclusions of certain carbonaceous chondrites. A table listing the accurate isotopic abundances for the minor isotopes in terrestrial sample is presented. The data provide the basis for a study of cosmochemical isotopic anomalies in meteoritic materials.

  3. Bulk Earth carbon and its isotopic value

    NASA Astrophysics Data System (ADS)

    Jones, A. P.; Mikhail, S.; Basugupta, S.

    2012-12-01

    The carbon isotope distribution in the Earth today is the net product of several primary processes, including planetary accretion, segregation of the core, the Moon-forming giant impact, magma oceans, crustal recycling, and biological processes. Therefore carbon isotope fractionation under mantle pressure and temperature conditions is one of the most important factors in deciphering the messages recorded in mantle samples and will assist towards the greater understanding the geodynamic carbon system. The largest and most powerful geochemical differentiation event during Earth's geologic history was core formation. The behaviour of 13C during this process is little constrained and needs to be investigated to understand the potential effects that it may have had on the carbon isotope composition of the silicate Earth. Isotopic fractionation of carbon at mantle pressure and temperatures in laboratory experiments and for natural terrestrial and extra-terrestrial samples between coexisting elemental carbon and carbides (reducing conditions) are higher than other systems previously investigated and can exceed 12 ‰ in the cores of celestial bodies and observed in Fe-meteorites (Deines and Wickman, 1975; Mikhail et al., 2010). First we review the mean values for carbon in ordinary chondrites and other solar system meteorites (from Mars, Vesta and the Moon) with a value of δ13C ≈ -20 +/- 4 ‰ (Grady et al 2004). Then we review the notion that the bulk Earth δ13C is around -5 ‰ similar to enstatite and carbonaceous chondrites and reflected in the majority of peridotitic mantle materials. Our modelling demonstrates that in order to understand the core/mantle carbon ratio we need to constrain the bulk Earth's initial δ13C value. We can constrain the relative proportion of carbon in the core/mantle by using simple isotopic mass balance and produce a range of carbon contents for the Earth then apply this to the maximum and minimums for the core using geophysical constraints. The mantle dominates the terrestrial carbon reservoir from an initial δ13C value of -5 ‰, but is dwarfed by the core with an initial δ13C value of -20 ‰. REFERENCES: S. Mikhail 2010 AGU U21A-001 abstract; Deines, P., Wickman, F.E., 1975. A contribution to the stable carbon isotope geochemistry of iron meteorites. Geochimica Et Cosmochimica Acta 39, 547-557. Grady, M. Verchovsky A, Wright, I. 2004 Magmatic carbon in Martian meteorites: attempts to constrain the carbon cycle on Mars. Int. J. Astrobiol. 2004;3:117-124.

  4. Dependence of tree ring stable isotope abundances and ring width on climate in Finnish oak.

    PubMed

    Hilasvuori, Emmi; Berninger, Frank

    2010-05-01

    We measured ring widths and isotopic abundances of carbon, oxygen and hydrogen (delta(13)C, delta(18)O and delta(2)H) from the latewood of tree rings of pedunculate oak (Quercus robur L.) in its distributional northern limit in Southern Finland. Ring width was observed to be related to precipitation and relative humidity but not significantly to temperature. delta(13)C and delta(18)O were significantly related to all studied climatic variables, most strongly to cloud cover. Variations in delta(2)H were discovered to be complex combinations of signals from biochemical and physical processes. The results suggest that oaks in Finland can be used as a source of climate information. delta(18)O was discovered to be especially promising as it showed the strongest climate signal and highest common signal between trees. The relationship between climate and ring width indicates that water availability is the main control of ring radial growth. This is supported by the isotope data. High correlation between delta(13)C and delta(18)O time series indicates that photosynthetic carbon assimilation is limited by stomatal control. Therefore, in contrast to the expected temperature limitation, our data indicate that drought limits oak growth more than cold temperatures on the border of its northernmost distribution range. PMID:20357343

  5. 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 propane and labeled propane (13CH3-12CH2-12CH3). Results are consistent with the expected relative fractionations between the two fragments, indicating limited 'scrambling' of carbon positions of less than 2% in the source. The limits of precision of this method are currently ~0.5 ‰, sufficient to resolve known or suspected position-specific isotope effects in propane. We have explored the expected temperature-dependent equilibrium isotopic distributions of propane using density functional theory and quantum mechanical models of vibrational isotope effects. These models predict the homogeneous isotope exchange equilibria among the various isotopologues of propane, which include several of a wide range of effects that should be measurable by our methods. At 300 K we predict that the central carbon site is 15‰ higher in δ13C and 95 ‰ higher in δD than the terminal carbon site; similarly the molecule containing both a 13C and D in the central site is enriched by ~120 ‰ relative to a random isotopic distribution at 300 K. These predictions present targets for future experimental and empirical studies of the temperature dependence of isotopic ordering in propane. More generally, the methods we are developing for the study of intramolecular isotopic distributions in propane will serve as a model for future study of similar effects in other organic compounds. [1]DeNiro, Epstein (1977) Science Volume 197, 261-263.

  6. Atmospheric Trace Gas Abundances and Stable Isotope Ratios via IR-LIF

    NASA Technical Reports Server (NTRS)

    Blake, Geoffrey A.

    2004-01-01

    We propose to develop new technologies with support provided by PIDDP that will enable the in situ measurements of abundances and stable isotope ratios in important radiatively and biogenically active gases such as carbon dioxide, carbon monoxide, water, methane, nitrous oxide, and hydrogen sulfide to very high precision (0.1 per mil or better for the isotopic ratios, for example). Such measurements, impossible at present, could provide pivotal new constraints on the global (bio)geochemical budgets of these critical species, and could also be used to examine the dynamics of atmospheric transport on Mars, Titan, and other solar system bodies. We believe the combination of solid state light sources with imaging of the IR laser induced fluorescence (IR-LIF) via newly available detector arrays will make such in situ measurements possible for the first time. Even under ambient terrestrial conditions, the LIF yield from vibrational excitation of species such as water and carbon dioxide should produce emission measures well in excess of ten billion photons/sec from samples volumes of order 1 c.c. These count rates can, in principle, yield detection limits into the sub-ppt range that are required for the in situ isotopic study of atmospheric trace gases. While promising, such technologies are relatively immature, but developing rapidly, and there are a great many uncertainties regarding their applicability to in situ IR-LIF planetary studies. We therefore feel PIDDP support will be critical to developing these new tools, and propose a three-year program to combine microchip near-IR lasers with low background detection axes and state-of-the-art HgCdTe detectors developed for astronomical spectroscopy to investigate the sensitivity of IR-LIF under realistic planetary conditions, to optimize the optical pumping and filtering schemes for important species, and to apply the spectrometer to the non-destructive measurement of stable isotopes in a variety of test samples. These studies form the necessary precursors to the development of compact, lightweight stable isotope/trace gas sensors for future planetary missions.

  7. Variations in Lead Isotopic Abundances in Sprague-Dawley Rat Tissues: Possible Reason of Formation

    PubMed Central

    Liu, Duojian; Wu, Jing; Ouyang, Li; Wang, Jingyu

    2014-01-01

    It has been reported in previous research that the lead isotopic composition of blood, urine and feces samples statistically differed from the given lead sources in Sprague-Dawley (SD) rats. However, the reason for this phenomenon is still unclear. An animal experiment was performed to investigate the lead isotope fractionation in diverse biological samples (i.e., lungs, liver, kidneys, bone) and to explore the possible reasons. SD rats were intratracheally instilled with lead acetate at the concentrations of 0, 0.02, 0.2, and 2 mg/kg body weight. Biological samples were collected for lead isotope analysis using an inductively coupled plasma mass spectrometry (ICP-MS). Significant differences are observed in lead isotope abundances among the diverse biological samples. The lead isotope abundances (206Pb, 207Pb and 208Pb) in diverse biological samples show different degrees and directions of departure from the given lead source. The results suggest that differences in enrichment or depletion capacity for each lead isotope in the various tissues might lead to the variation in lead isotopic abundances in tissues. Moreover, a nonlinear relationship between the blood lead level and the lead isotope abundances in liver and bone is observed. When the whole-blood level is higher than 50 ng/mL, the lead isotopic compositions of biological samples tend to be the same. Thus, the data support the speculation of a fractionation functional threshold. PMID:24587048

  8. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

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

    1990-07-01

    Consol R D is developing and demonstrating stable carbon isotope analysis as a method to quantitatively distinguish coal-derived and petroleum-derived carbon in products from coal/petroleum coprocessing. The approach taken is to develop the method, then demonstrate its application on authentic continuous-unit products. The significance of selective isotopic fractionation is being determined and, if necessary, corrections will be applied to account for it. Precision, accuracy and range of applicability are being defined. The value of accessory analytical techniques also is being assessed. The program is designed to address a substantial, demonstrated need of coprocessing research (both exploratory and development) for a technique to quantitatively distinguish the contributions of the individual coprocessing feedstocks to the various products. The carbon isotope technique currently is in routine use for other applications. Progress is discussed. 7 refs., 7 figs., 12 tabs.

  9. Fractionation of stable carbon isotopes during chemoautotrophic growth of sulfur-oxidizing bacteria

    SciTech Connect

    Ruby, E.G.; Jannasch, H.W.; Deuser, W.G.

    1987-08-01

    Laboratory-grown strains of chemoautotrophic Thiomicrospira sp. strain L-12 and Thiobacillus neapolitanus produced cell carbon that was 24.6 to 25.1 ppt (24.6 to 25.1 mg/g) lower in /sup 13/C isotope abundance than the ambient source of carbon dioxide and bicarbonate. This degree of /sup 13/C isotope depletion was comparable to that found in organic material produced in deep-sea hydrothermal-vent communities.

  10. STABLE CARBON ISOTOPE ANALYSIS OF NUCLEIC ACIDS TO TRACE SOURCES OF DISSOLVED SUBSTRATES USED BY ESTUARINE BACTERIA

    EPA Science Inventory

    The natural abundance of stable carbon isotopes measured in bacterial nucleic acids that were extracted from estuarine bacterial concentrates were used to trace sources of organic matter for bacteria in.aquatic environments. he stable carbon isotope ratios of P. aeruginosa and nu...

  11. Anatomy of a cluster IDP. Part 2: Noble gas abundances, trace element geochemistry, isotopic abundances, and trace organic chemistry of several fragments from L2008#5

    NASA Technical Reports Server (NTRS)

    Thomas, K. L.; Clemett, S. J.; Flynn, G. J.; Keller, L. P.; Mckay, David S.; Messenger, S.; Nier, A. O.; Schlutter, D. J.; Sutton, S. R.; Walker, R. M.

    1994-01-01

    The topics discussed include the following: noble gas content and release temperatures; trace element abundances; heating summary of cluster fragments; isotopic measurements; and trace organic chemistry.

  12. Stable carbon isotope measurements using laser spectroscopy

    NASA Technical Reports Server (NTRS)

    Sauke, T. B.; Becker, J. F.

    1991-01-01

    The 2300 cm(exp -1) spectral region is especially interesting because (12)CO2 and (13)CO2 bands overlap in such a way that their rotational lines have approximately equal absorbance at the anticipated isotopic ratio (approximately 90) of carbon on Earth and Mars. Pairs of rotational lines we have studied are separated by as little as 0.050 cm(exp -1), but are well resolved with a tunable diode laser. Using sophisticated sweep integration and signal averaging techniques, we have measured the stable isotope ratio in carbon dioxide to a precision of better than 1 percent.

  13. 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.

  14. 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.

  15. Determination of lithium isotopes at natural abundance levels by atomic absorption spectrometry

    USGS Publications Warehouse

    Meier, A.L.

    1982-01-01

    The relationships of the absorption of 6Li and 7Li hollow cathode lamp emissions are used to determine lithium isotopic composition in the natural abundance range of geologic materials. Absorption was found to have a nonlinear dependence upon total lithium concentration and isotopic composition. A method using nonlinear equations to describe the relationship of the absorption of 6Li and 7Li lamp radiation is proposed as a means of calculating isotopic composition that is independent of total lithium concentration.

  16. 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.

  17. Carbon isotopic exchange between dissolved inorganic and organic carbon

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

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

  18. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

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

    1991-03-01

    Research on coprocessing materials/products continued. Major topics reported here are described below. Microautoclave runs are described in which gases and insoluble organic matter produced from five coals and gases produced from three petroleum resids were analyzed to study feedstock/product selective isotopic fractionation. Selective isotopic fractionation was further explored through isotope analysis of the feed New Mexico coal and products from a continuous coal liquefaction run (HRI CC-10 or 227-68). Feeds (Texas lignite/Maya VSB) and products from two HRI continuous coprocessing runs (227-54 and 238-12) were analyzed. The results were corrected for selective isotopic fractionation and carbon sourcing was performed for the product fractions. {sup 1}H-NMR and phenolic -OH determinations are reported for all continuous unit samples obtained under this contract. 13 refs., 17 figs., 40 tabs.

  19. Stable isotope analysis of carbon and nitrogen in angrites

    NASA Astrophysics Data System (ADS)

    Abernethy, F. A. J.; Verchovsky, A. B.; Starkey, N. A.; Anand, M.; Franchi, I. A.; Grady, Monica M.

    2013-09-01

    Angrites are a small group of ancient basaltic achondrites, notable for their unusual chemistry and extreme volatile depletion. No comprehensive study of indigenous light elements currently exists for the group. Measurement of the abundances and isotopic composition of carbon and nitrogen could provide information pertaining to the evolution of the angrite parent body. Bulk-sample stepped combustion analyses of five angrites and a glass separate from D'Orbigny were combined with earlier data and acid dissolution experiments of carbonates found in D'Orbigny to compile an inventory of indigenous carbon and nitrogen. Indigenous carbon combusted between 700 °C and 1200 °C, with abundances of 10-140 ppm and a mass-weighted δ13C of -25 to -20‰ with the exception of D'Orbigny (δ13C approximately -5‰). Nitrogen was released at 850-1200 ºC, 1-20 ppm with a δ15N -3‰ to +4‰; again, D'Orbigny (δ15N approximately +20 to +25‰) was an exception. We interpret these components as largely indigenous and decoupled; the carbon in graphitic or amorphous form, while the nitrogen is present as a dissolved component in the silicates. No relationship with the textural sub-classification of angrites is apparent. We suggest that the angrite parent body contains a reservoir of reduced carbon and thus may have undergone a change in redox conditions, although the timing and mechanism for this remain unclear.

  20. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

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

    1989-06-01

    The program is designed to address a substantial, demonstrated need of the coprocessing community (both exploratory and development) for a technique to quantitatively distinguish the contributions of the individual coprocessing feedstocks to the various products. The carbon isotope technique is currently in routine use for other applications. Results achieved this quarter include: Feed and product fractions from a Kentucky 9 coal/Kentucky tar sand bitumen coprocessing bench unit run at the Kentucky Center for Applied Energy Research (CAER) were analyzed for carbon isotope ratios. Corrections were made to the coal carbon recoveries and selectivities from the products of HRI Run 227-53. Feeds (Westerholt coal/Cold Lake VSB) and products from two periods of HRI coprocessing Run 238-1 were analyzed. Three petroleum samples and three coal samples were pyrolyzed at 800{degree}F for 30 min to determine the effect of pyrolysis on the isotopic homogeneity of each petroleum and coal sample. Products from each pyrolysis test were separated into five fractions; an additional set of coprocessing samples and a set of two-stage coal liquefaction samples were obtained from HRI for future work; work performed by the Pennsylvania State University show that microscopy is a promising method for distinguishing coal and petroleum products in residual coprocessing materials; and coal and petroleums that have large differences in carbon isotope ratios were identified for Auburn University. 7 refs., 2 figs., 12 tabs.

  1. Measurement of isotopic abundances in collected stratospheric ozone samples

    NASA Technical Reports Server (NTRS)

    Schueler, B.; Morton, J.; Mauersberger, K.

    1990-01-01

    Enrichment of heavy O3 isotopes has been measured in collected stratospheric samples. A balloon-borne cryogenic sampler was used to gather six O3 samples between 26 and 35 km in three flights. Subsequent laboratory mass spectrometer analysis of rare O3 isotopes at both mass 49 and 50 has resulted in more precise measurements than have previously been reported with in situ and ground-based techniques. In one flight, (O-50)3 was enriched by 12-16 percent and (O-49)3 by 9-11 percent, both increasing with altitude. In the remaining two flights, the isotope enrichment was nearly mass-independent at 8-9 percent. The enrichments in O3 at mass 50 are less than the large 40 percent value observed in some stratospheric measurements but similar to (O-49)3 and (O-50)3 fractionations produced in laboratory-generated ozone.

  2. Ion Mobility Mass Spectrometry Direct Isotope Abundance Analysis

    SciTech Connect

    Manuel J. Manard, Stephan Weeks, Kevin Kyle

    2010-05-27

    The nuclear forensics community is currently engaged in the analysis of illicit nuclear or radioactive material for the purposes of non-proliferations and attribution. One technique commonly employed for gathering nuclear forensics information is isotope analysis. At present, the state-of-the-art methodology for obtaining isotopic distributions is thermal ionization mass spectrometry (TIMS). Although TIMS is highly accurate at determining isotope distributions, the technique requires an elementally pure sample to perform the measurement. The required radiochemical separations give rise to sample preparation times that can be in excess of one to two weeks. Clearly, the nuclear forensics community is in need of instrumentation and methods that can expedite their decision making process in the event of a radiological release or nuclear detonation. Accordingly, we are developing instrumentation that couples a high resolution IM drift cell to the front end of a MS. The IM cell provides a means of separating ions based upon their collision cross-section and mass-to-charge ratio (m/z). Two analytes with the same m/z, but with different collision cross-sections (shapes) would exit the cell at different times, essentially enabling the cell to function in a similar manner to a gas chromatography (GC) column. Thus, molecular and atomic isobaric interferences can be effectively removed from the ion beam. The mobility selected chemical species could then be introduced to a MS for high-resolution mass analysis to generate isotopic distributions of the target analytes. The outcome would be an IM/MS system capable of accurately measuring isotopic distributions while concurrently eliminating isobaric interferences and laboratory radiochemical sample preparation. The overall objective of this project is developing instrumentation and methods to produce near real-time isotope distributions with a modular mass spectrometric system that performs the required gas-phase chemistry and separations. The system couples a high-resolution ion mobility (IM) drift cell to the front end of a mass spectrometer (MS) allowing for chemical separation prior to isotope distribution analyses. This will yield isotope ratio measurement capabilities with minimal sample preparation.

  3. Carbon Abundances on the M92 Giant Branch

    NASA Astrophysics Data System (ADS)

    Bellman, S.; Briley, M. M.; Smith, G. H.

    1999-05-01

    Star clusters provide a snapshot of a group of stars nearly homogeneous in age and composition spread over a wide range of evolutionary states. By comparing elemental abundances among the stars in a cluster, changes in composition due to internal stellar processes are illuminated. In this project, carbon abundances were determined for a number of red giant and subgiant stars in the very metal-poor globular cluster M92 (NGC 6341). Determination was accomplished by comparing the spectral index S(4243) of program stars to index values computed for synthetic spectra of stellar models. Analysis of these index values confirms a clear pattern of decreasing carbon abundance as a function of increasing evolutionary state among cluster members. Carbon depletion in more evolved stars is evidence of internal mixing thought to be connected with a discontinuity in the luminosity function. In M92, carbon depletion appears to onset at absolute magnitude approximately 0.4 mag. below the previously derived (by Fusi Pecci et al., 1990) bump for a generalized metal-poor cluster. This implies a time lag between the onset of carbon depletion and the occurrence of the bump, and that the mixing of carbon-poor material to the surface is taking place earlier than originally thought.

  4. 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.

  5. 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.

  6. The abundance of the radioactive isotope Al-26 in galactic cosmic rays

    NASA Technical Reports Server (NTRS)

    Wiedenbeck, M. E.

    1983-01-01

    Satellite observations of the isotopic composition of aluminum in low energy cosmic rays (E/M = 200 MeV/amu) have been used to determine the abundance of the unstable isotope Al-26 (T1/2 = 0.87 Myr). The observed abundance ratio, Al-26/Al-27 = 0.036 (+0.037, -0.022), is in good agreement with previous balloon observations and yields a cosmic ray confinement time consistent with values based on the abundance of Be-10.

  7. Abundance of carbon and magnesium in the Orion nebula

    SciTech Connect

    Perinotto, M.; Patriarchi, P.

    1980-01-01

    The Orion nebula has been observed in two positions with IUE (International Ultraviolet Explorer) in the low-resolution mode (approx.7 A) and in the spectral range 1150--3200 A. Emission lines of C II), C III), (O II), and He I have been measured and used to determine what is probably the first reliable abundance of carbon in H II regions. The logarithmic total abundance of carbon is found to be 8.4 close to the solar value. In contrast with the situation in the planetary nebula of similar excitation, IC 418, where the resonance Mg II lambda2800 line is observed to be relatively strong, in the Orion nebula the lambda2800 line is not detectable. an upper limit for the magnesium abundance of the order of 10 times smaller than in the Sun is suggested.

  8. 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.

  9. 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

  10. CARBON ISOTOPE AND ISOTOPOMER FRACTIONATION IN COLD DENSE CLOUD CORES

    SciTech Connect

    Furuya, Kenji; Aikawa, Yuri; Sakai, Nami; Yamamoto, Satoshi

    2011-04-10

    We construct a gas-grain chemical network model which includes carbon isotopes ({sup 12}C and {sup 13}C) with an emphasis on isotopomer-exchange reactions. Temporal variations of molecular abundances, the carbon isotope ratios ({sup 12}CX/{sup 13}CX), and the isotopomer ratios ({sup 12}C{sup 13}CX/{sup 13}C{sup 12}CX) of CCH and CCS in cold dense cloud cores are investigated by numerical calculations. We confirm that the isotope ratios of molecules, both in the gas phase and grain surfaces, are significantly different depending on whether the molecule is formed from the carbon atom (ion) or the CO molecule. Molecules formed from carbon atoms have CX/{sup 13}CX ratios greater than the elemental abundance ratio of [{sup 12}C/{sup 13}C]. On the other hand, molecules formed from CO molecules have CX/{sup 13}CX ratios smaller than the [{sup 12}C/{sup 13}C] ratio. We reproduce the observed C{sup 13}CH/{sup 13}CCH ratio in TMC-1, if the isotopomer-exchange reaction, {sup 13}CCH + H {r_reversible} C{sup 13}CH + H + 8.1 K, proceeds with the forward rate coefficient k{sub f} > 10{sup -11} cm{sup 3} s{sup -1}. However, the C{sup 13}CS/{sup 13}CCS ratio is lower than that observed in TMC-1. We then assume the isotopomer-exchange reaction catalyzed by the H atom, {sup 13}CCS + H {r_reversible} C{sup 13}CS + H + 17.4 K. In the model with this reaction, we reproduce the observed C{sup 13}CS/{sup 13}CCS, CCS/C{sup 13}CS, and CCS/{sup 13}CCS ratios simultaneously.

  11. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

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

    1991-02-01

    Consol R D is developing and demonstrating stable carbon isotope analysis as a method to quantitatively distinguish coal-derived and petroleum-derived carbon in products from coal/petroleum coprocessing. The approach taken is develop the method, then demonstrate its application on authentic continuous-unit products. The significance of selective isotopic fractionation is being determined and, when necessary, corrections are applied to account for it. Precision, accuracy and range of applicability are being defined. The value of accessory analytical techniques also is being assessed. Previously reported data on samples from HRI bench-scale coprocessing Runs 227-53 (Texas lignite/Maya ASB and Texas lignite/Maya VSB) and 238-1 (Westerholt coal/Cold Lake VSB) were corrected for selective isotopic fractionation. Carbon sourcing was performed on samples from HRI bench-scale coprocessing Run 227-60 (Texas lignite/Maya VSB) and samples from UOP bench-scale coprocessing Run 26 (Illinois 6 coal/Lloydminster vacuum resid); the latter data were corrected for isotopic fractionation, though the former could not be corrected. A paper presented at the 1990 DOE Direct Liquefaction Contractor's Review Meeting is appended. 15 refs., 21 figs., 22 tabs.

  12. 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 conclusively distinguished whether C is taken up only as CO2 by passive diffusion or also by active transport of CO2 or HCO^{3-} . In reality, the patterns of stable isotopic variations in coccoliths may provide more constraints for unraveling the cellular C transport and the calcification mechanisms. We will present latest findings on these issues, both from culture experiments and sediment traps located in the Bay of Bengal. Coccolith species separated from these sediment traps also show evidence of carbonate ion effects.

  13. Carbon chain abundance in the diffuse interstellar medium

    NASA Technical Reports Server (NTRS)

    Allamandola, L. J.; Hudgins, D. M.; Bauschlicher, C. W. Jr; Langhoff, S. R.

    1999-01-01

    Thanks to the mid-IR sensitivities of the ISO and IRTS orbiting spectrometers it is now possible to search the diffuse interstellar medium for heretofore inaccessible molecular emission. In view of the recent strong case for the presence of C(7-) (Kirkwood et al. 1998, Tulej et al. 1998),and the fact that carbon chains possess prominent infrared active modes in a very clean portion of the interstellar spectrum, we have analyzed the IRTS spectrum of the diffuse interstellar medium for the infrared signatures of these species. Theoretical and experimental infrared band frequencies and absolute intensities of many different carbon chain species are presented. These include cyanopolyynes, neutral and anionic linear carbon molecules, and neutral and ionized, even-numbered, hydrogenated carbon chains. We show that--as a family--these species have abundances in the diffuse ISM on the order of 10(-10) with respect to hydrogen, values consistent with their abundances in dense molecular clouds. Assuming an average length of 10 C atoms per C-chain implies that roughly a millionth of the cosmically available carbon is in the form of carbon chains and that carbon chains can account for a few percent of the visible to near-IR diffuse interstellar band (DIB) total equivalent width (not DIB number).

  14. s-process studies - Xenon and krypton isotopic abundances

    NASA Technical Reports Server (NTRS)

    Clayton, D. D.; Ward, R. A.

    1978-01-01

    We propose an analysis of the s-process contributions to the isotopes of xenon and krypton. The object is to aid studies of the possibility that meteorites may contain gas that was carried in presolar grains that were grown in stellar ejecta and that were not degassed prior to incorporation into parent bodies. That model suggests routine interstellar fractionation of s-isotopes from r-isotopes owing to differential incorporation into dust. We show that a deficiency of s-process nuclei cannot yield details of Xe-X, but the gross similarities are strong enough to lead one to think that such a deficiency may play a role in a more complicated explanation. We predict the existence of an s-rich complement somewhere if fractional separation of this type has played a role in Xe-X. We show that the analogous decomposition of krypton is more uncertain, and we call for measurements of neutron-capture cross sections to alleviate these uncertainties.

  15. Current and relic carbon using natural abundance carbon-13

    SciTech Connect

    layse,MF; Clapp,CE; Allmaras,RR; Linden,D.R; Molina, JAE.; Copeland,SM; Dowdy,RH

    2002-05-01

    The role of agricultural practices on soil carbon (C) dynamics is critical to improved soil management. The main objective was to examine the C interactions resulting from crop changes under different tillage and residue treatments.

  16. A Modern Analogue for Proterozoic Inverse Carbon Isotope Signatures

    NASA Astrophysics Data System (ADS)

    Close, H. G.; Diefendorf, A. F.; Freeman, K. H.; Pearson, A.

    2008-12-01

    The carbon isotope distribution preserved in sedimentary lipids changes near the Neoproterozoic-Cambrian boundary. In older samples, n-alkyl lipids contain more 13C than both isoprenoid lipids and kerogen [1]. In younger samples, the opposite prevails. Although extreme heterotrophy has been invoked as a mechanism to explain the enrichment in 13C [2], here we suggest another explanation. The switch may reflect a fundamental transition from an oligotrophic ocean dominated by prokaryotic biomass, to an ocean in which carbon fixation is more intensive and burial is dominated by eukaryotic biomass. An analogue for Proterozoic ordering is found in the modern, oligotrophic Pacific Ocean, where n-alkyl lipids of picoplankton (0.2-0.5 ?m particulate matter) contain excess 13C relative to the same lipids found in larger size classes (> 0.5 ?m). Picoplanktonic lipids are heavier isotopically (-18 ) than both the sterols of eukaryotes (-23 to -26 ) and the total organic matter (-20 ; TOM). The 0.2-0.5 ?m size class also has a distinct chain-length abundance profile. Although large particles must be the vehicle for total carbon export, paradoxically the lipid component of export production appears to be dominated by the 0.2-0.5 ?m source. The picoplanktonic chain lengths and isotopic composition dominate lipids of TOM at 670 meters. When the ratio of prokaryotic to eukaryotic production is high, as in the modern central Pacific Ocean, it appears that exported material has an inverse carbon isotope signature similar to that preserved in Precambrian samples. [1] Logan, G. A. et al., Nature 376:53-56 (1995). [2] Rothman, D. H. et al., PNAS 100:8124-8129 (2003).

  17. Carbon isotopic composition of individual Precambrian microfossils.

    PubMed

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

    2000-08-01

    Ion microprobe measurements of carbon isotope ratios were made in 30 specimens representing six fossil genera of microorganisms petrified in stromatolitic chert from the approximately 850 Ma Bitter Springs Formation, Australia, and the approximately 2100 Ma Gunflint Formation, Canada. The delta 13C(PDB) values from individual microfossils of the Bitter Springs Formation ranged from -21.3 +/- 1.7% to -31.9 +/- 1.2% and the delta 13C(PDB) values from microfossils of the Gunflint Formation ranged from -32.4 +/- 0.7% to -45.4 +/- 1.2%. With the exception of two highly 13C-depleted Gunflint microfossils, the results generally yield values consistent with carbon fixation via either the Calvin cycle or the acetyl-CoA pathway. However, the isotopic results are not consistent with the degree of fractionation expected from either the 3-hydroxypropionate cycle or the reductive tricarboxylic acid cycle, suggesting that the microfossils studied did not use either of these pathways for carbon fixation. The morphologies of the microfossils suggest an affinity to the cyanobacteria, and our carbon isotopic data are consistent with this assignment. PMID:11543502

  18. 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.

  19. Abundances and Isotope Ratios in the Magellanic Clouds: The Star-Forming Environment of N 113

    NASA Astrophysics Data System (ADS)

    Wang, M.; Chin, Y.-N.; Henkel, C.; Whiteoak, J. B.; Cunningham, M.

    2009-01-01

    With the goal of deriving the physical and chemical conditions of star-forming regions in the Large Magellanic Cloud (LMC), a spectral line survey of the prominent star-forming region N 113 is presented. The observations cover parts of the frequency range from 85 GHz to 357 GHz and include 63 molecular transitions from a total of 16 species, among them are the spectra of rare isotopologues. Maps of selected molecular lines as well as the 1.2 mm continuum distribution are also presented. Molecular abundances in the core of the complex are consistent with a photon-dominated region in a nitrogen deficient environment. While carbon monoxide (CO) shows optical depths of the order of τ ~ 10, 13CO is optically thin. The most prominent lines of carbon monosulfide (CS), HCN, and HCO+show signs of weak saturation (τ ~ 0.5). Densities range from 5 × 103 cm-3 for CO to almost 106 for CS, HCN, and a few other species, indicating that only the densest regions provide sufficient shielding, even for some of the most common species. An ortho- to para-formaldehyde (H2CO) ratio of ~ 3 hints at H2CO formation in a warm (gsim 40 K) environment. Isotope ratios are 12C/13C ~ 49 ± 5, 16O/18O ~2000 ± 250, 18O/17O ~ 1.7 ± 0.2, and 32S/34S ~ 15. Agreement with data from other star-forming clouds shows that the gas is well mixed in the LMC. The isotope ratios not only differ from those seen in the Galaxy, they also do not form a continuation of the trends observed with decreasing metallicity from the inner to the outer Galaxy. This implies that the outer Galaxy, even though showing an intermediate metallicity, is not providing a transition zone between the inner Galaxy and the metal-poor environment of the Magellanic Clouds. A part of this discrepancy is likely caused by differences in the age of the stellar populations in the outer Galaxy and the LMC. While, however, this scenario readily explains measured carbon and oxygen isotope ratios, nitrogen and sulfur still lack a self-consistent interpretation. Based on observations with the Swedish/ESO Submillimeter Telescope (SEST) at the European Southern Observatory (ESO; La Silla, Chile) and the Atacama Pathfinder EXperiment (APEX; Chajnantor, Chile) of the Max-Planck-Institut für Radioastronomie (MPIfR), ESO, and Onsala Space Observatory (OSO).

  20. Determining the isotopic abundance of a labeled compound by mass spectrometry and how correcting for natural abundance distribution using analogous data from the unlabeled compound leads to a systematic error.

    PubMed

    Schenk, David J; Lockley, William J S; Elmore, Charles S; Hesk, Dave; Roberts, Drew

    2016-04-01

    When the isotopic abundance or specific activity of a labeled compound is determined by mass spectrometry (MS), it is necessary to correct the raw MS data to eliminate ion intensity contributions, which arise from the presence of heavy isotopes at natural abundance (e.g., a typical carbon compound contains ~1.1% (13) C per carbon atom). The most common approach is to employ a correction in which the mass-to-charge distribution of the corresponding unlabeled compound is used to subtract the natural abundance contributions from the raw mass-to-charge distribution pattern of the labeled compound. Following this correction, the residual intensities should be due to the presence of the newly introduced labeled atoms only. However, this will only be the case when the natural abundance mass isotopomer distribution of the unlabeled compound is the same as that of the labeled species. Although this may be a good approximation, it cannot be accurate in all cases. The implications of this approximation for the determination of isotopic abundance and specific activity have been examined in practice. Isotopically mixed stable-atom labeled valine batches were produced, and both these and [(14) C6 ]carbamazepine were analyzed by MS to determine the extent of the error introduced by the approach. Our studies revealed that significant errors are possible for small highly-labeled compounds, such as valine, under some circumstances. In the case with [(14) C6 ]carbamazepine, the errors introduced were minor but could be significant for (14) C-labeled compounds with particular isotopic distributions. This source of systematic error can be minimized, although not eliminated, by the selection of an appropriate isotopic correction pattern or by the use of a program that varies the natural abundance distribution throughout the correction. PMID:26916110

  1. 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 as isotopic reference material for the calibration of IRMS instruments. The new CRDS spectrometer will provide researchers with a simplified option to accelerate the pace and breadth of carbonates-based research.

  2. Empirical Solar Abundance Scaling Laws of Supernova {gamma} Process Isotopes

    SciTech Connect

    Hayakawa, Takehito; Iwamoto, Nobuyuki; Kajino, Toshitaka; Shizum, Toshiyuki; Umeda, Hideyuki; Nomoto, Ken'Ichi

    2008-11-11

    Analyzing the solar system abundances, we have found two empirical abundance scaling laws concerning the p- and s-nuclei with the same atomic number. They are evidence that the 27 p-nuclei are synthesized by the supernova {gamma}-process. The scalings lead to a novel concept of 'universality of {gamma}-process' that the s/p and p/p ratios of nuclei produced by individual {gamma}-processes are almost constant, respectively. We have calculated the ratios of materials produced by the {gamma}-process based on core-collapse supernova explosion models under various astrophysical conditions and found that the scalings hold for individual {gamma}-processes independent of the conditions assumed. The results further suggest an extended universality that the s/p ratios in the {gamma}-process layers are not only constant but also centered on a specific value of 3. With this specific value and the scaling of the s/p ratios, we estimate that the ratios of the s-process abundance contributions from the AGB stars to the massive stars are almost 6.7 for the s-nuclei of A>90 in the solar system.

  3. Isotope Variations in Terrestrial Carbonates and Thermal Springs as Biomarkers: Analogs for Martian Processes

    NASA Technical Reports Server (NTRS)

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

    2006-01-01

    Stable isotope measurements of carbonate minerals contained within ALH84001 [1] suggest that fluids were present at 3.9 Gy on Mars [2, 3, 4, 5]. Both oxygen and carbon isotopes provide independent means of deciphering paleoenvironmental conditions at the time of carbonate mineral precipitation. In terrestrial carbonate rocks oxygen isotopes not only indicate the paleotemperature of the precipitating fluid, but also provide clues to environmental conditions that affected the fluid chemistry. Carbon isotopes, on the other hand, can indicate the presence or absence of organic compounds during precipitation (i.e. biogenically vs. thermogenically-generated methane), thus serving as a potential biomarker. We have undertaken a study of micro scale stable isotope variations measured in some terrestrial carbonates and the influence of organic compounds associated with the formation of these carbonates. Preliminary results indicate that isotope variations occur within narrow and discrete intervals, providing clues to paleoenvironmental conditions that include both biological and non-biological activity. These results carry implications for deciphering Martian isotope data and therefore potential biological prospecting on the planet Mars. Recently, Fourier Transform Spectrometer observations have detected methane occurring in the Martian atmosphere [6] that could be attributed to a possible biogenic source. Indeed, Mars Express has detected the presence of methane in the Martian atmosphere [7], with evidence indicating that methane abundances are greatest above those basins with high water concentrations.

  4. Variability of organic and elemental carbon, water soluble organic carbon, and isotopes in Hong Kong

    NASA Astrophysics Data System (ADS)

    Ho, K. F.; Lee, S. C.; Cao, J. J.; Li, Y. S.; Chow, J. C.; Watson, J. G.; Fung, K.

    2006-06-01

    To determine the levels and variations of carbonaceous aerosol in Hong Kong, PM2.5 and PM10 samples were collected by high volume (Hi-vol) samplers at three monitoring stations (representing middle-scale roadside, urban-, and regional-scale environments) during winter (November 2000 to February 2001) and summer (June 2001 to August 2001) periods. The highest concentrations of organic carbon (OC), elemental carbon (EC), and water-soluble organic carbon (WSOC) were found at the middle-scale roadside site with the lowest at the regional-scale site. The percentages of WSOC in total carbon at these sites were inversely correlated with their concentrations (i.e., the highest percentages of WSOC were observed at the regional-scale site). A high WSOC fraction may be associated with aged aerosol because of the secondary formation by photochemical oxidation of organic precursors of anthropogenic pollutants during transport. The annual average of isotope abundances (δ13C) of OC and EC were -26.9±0.5 and -25.6±0.1, respectively. There were no notable differences for seasonal distributions of carbon isotopic composition, consistent with motor vehicle emissions being the main source contributors of carbonaceous aerosol in Hong Kong. OC 13C abundances at the regional-scale site were higher than those at the middle-scale roadside and urban sites, consistent with secondary organic aerosols of biogenic origin.

  5. Variability of organic and elemental carbon, water soluble organic carbon, and isotopes in Hong Kong

    NASA Astrophysics Data System (ADS)

    Ho, K. F.; Lee, S. C.; Cao, J. J.; Li, Y. S.; Chow, J. C.; Watson, J. G.; Fung, K.

    2006-10-01

    To determine the levels and variations of carbonaceous aerosol in Hong Kong, PM2.5 and PM10 samples were collected by high volume (Hi-vol) samplers at three monitoring stations (representing middle-scale roadside, urban-, and regional-scale environments) during winter (November 2000 to February 2001) and summer (June 2001 to August 2001) periods. The highest concentrations of organic carbon (OC), elemental carbon (EC), and water-soluble organic carbon (WSOC) were found at the middle-scale roadside site with the lowest at the regional-scale site. The percentages of WSOC in total carbon at these sites were inversely correlated with their concentrations (i.e., the highest percentages of WSOC were observed at the regional-scale site). A high WSOC fraction may be associated with aged aerosol because of the secondary formation by photochemical oxidation of organic precursors of anthropogenic pollutants during transport. The annual average of isotope abundances (δ13C) of OC and EC were -26.9±0.5‰ and -25.6±0.1‰, respectively. There were no notable differences for seasonal distributions of carbon isotopic composition, consistent with motor vehicle emissions being the main source contributors of carbonaceous aerosol in Hong Kong. OC 13C abundances at the regional-scale site were higher than those at the middle-scale roadside and urban sites, consistent with secondary organic aerosols of biogenic origin.

  6. 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).

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  8. Isotopic abundances and line formation in the Orion Nebula

    NASA Technical Reports Server (NTRS)

    Wannier, P. G.; Encrenaz, P. J.; Wilson, R. W.; Penzias, A. A.

    1974-01-01

    Measurements of the spatial variation of HC-12N-14 and HC-13N-14 line emission from the molecular cloud associated with the Orion Nebula indicate that HC-12N-14 has a high central opacity. This result seems to contradict a recent suggestion that the observed hyperfine structure of the line indicates a low opacity, which in turn would yield a C-13/C-12 abundance significantly different from other determinations. The observed hyperfine structure can be understood in the high-opacity case if radiative trapping in the lines is considered.

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

    PubMed Central

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

    2007-01-01

    The isotopic composition of long-lived trace molecules provides a window into atmospheric transport and chemistry. Carbon dioxide is a particularly powerful tracer, because its abundance remains >100 parts per million by volume (ppmv) in the mesosphere. Here, we successfully reproduce the isotopic composition of CO2 in the middle atmosphere, which has not been previously reported. The mass-independent fractionation of oxygen in CO2 can be satisfactorily explained by the exchange reaction with O(1D). In the stratosphere, the major source of O(1D) is O3 photolysis. Higher in the mesosphere, we discover that the photolysis of 16O17O and 16O18O by solar Lyman-α radiation yields O(1D) 10–100 times more enriched in 17O and 18O than that from ozone photodissociation at lower altitudes. This latter source of heavy O(1D) has not been considered in atmospheric simulations, yet it may potentially affect the “anomalous” oxygen signature in tropospheric CO2 that should reflect the gross carbon fluxes between the atmosphere and terrestrial biosphere. Additional laboratory and atmospheric measurements are therefore proposed to test our model and validate the use of CO2 isotopic fractionation as a tracer of atmospheric chemical and dynamical processes. PMID:17190796

  10. Diurnal and Interannual Variation in Absorption Lines of Isotopic Carbon Dioxide in Mars Atmosphere

    NASA Astrophysics Data System (ADS)

    Livengood, Timothy A.; Kostiuk, Theodor; Hewagama, Tilak; Kolasinski, John R.; Henning, Wade G.

    2015-11-01

    Groundbased observations of Mars in 2003, 2007, 2012, and 2014 have detected transitions of carbon dioxide containing the stable minor isotopes of oxygen and carbon as well as the primary isotopes, using the ultrahigh resolution spectrometer HIPWAC at the NASA Infrared Telescope Facility. The most well characterized minor isotope is O-18, due to strong lines and observational opportunities. The average estimated O-18/O-16 isotope ratio is roughly consistent with other in situ and remote spectroscopic measurements but demonstrates an additional feature in that the retrieved ratio appears to increase with greater ground surface temperature. These conclusions primarily come from analyzing a subset of the 2007 data. Additional observations have been acquired over a broad range of local time and meridional position to evaluate variability with respect to ground surface temperature. These additional observations include one run of measurements with C-13. These observations can be compared to local in situ measurements by the Curiosity rover to narrow the uncertainty in absolute isotope ratio and extend isotopic measurements to other regions and seasons on Mars. The relative abundance of carbon dioxide heavy isotopes on Mars is central to estimating the primordial atmospheric inventory on Mars. Preferential freeze-distillation of heavy isotopes means that any measurement of the isotope ratio can be only a lower limit on heavy isotope enrichment due to past and current loss to space.

  11. On krypton isotopic abundances in the sun and in the solar wind

    NASA Technical Reports Server (NTRS)

    Marti, K.

    1980-01-01

    The Kr isotopic systematics in the meteorite Pesyanoe which is known to contain solar-type gases, are reported. Discrepancies in the isotopic data of fractions released at stepwise increasing temperatures cannot be reconciled with spallation Kr components, although spallation effects are significant. Fractionation mechanisms on the parent body and in the solar wind source region are considered and the implications for solar abundances discussed.

  12. The isotopic and elemental abundances of neon nuclei accelerated in solar flares

    NASA Technical Reports Server (NTRS)

    Dietrich, W. F.; Simpson, J. A.

    1979-01-01

    The relative isotopic abundances of Ne-20 and Ne-22 in seven solar flares were determined from measurements of the satellite IMP 8, yielding the ratio Ne-20/Ne-22 = 7.7 (+2.3, -1.5) for solar chromospheric matter. This value is in agreement with the ratio for the component neon-A (the 'primordial' component) found in carbonaceous chondrites. An elemental abundance ratio Ne/O = 0.14 + or - 0.01 also has been obtained which agrees closely with earlier reported measurements. It is shown that the effects of preferential acceleration relative to solar-system abundances with increasing charge number observed for some solar flares - though biasing the elemental ratio - does not appear to influence the neon isotopic abundances.

  13. Natural abundance variations in stable isotopes and their potential uses in animal physiological ecology.

    PubMed

    Gannes, L Z; Martínez del Rio, C; Koch, P

    1998-03-01

    Chemical, biological, and physical processes lead to distinctive "isotopic signatures" in biological materials that allow tracing of the origins of organic substances. Isotopic variation has been extensively used by plant physiological ecologists and by paleontologists, and recently ecologists have adopted the use of stable isotopes to measure ecosystem patterns and processes. To date, animal physiological ecologists have made minimal use of naturally occurring stable isotopes as tracers. Here we provide a review of the current and potential uses of naturally occurring stable isotopes in animal physiological ecology. We outline the physical and biological processes that lead to variation in isotopic abundance in plants and animals. We summarize current uses in animal physiological ecology (diet reconstruction and animal movement patterns), and suggest areas of research where the use of stable isotopes can be fruitful (protein balance and turnover and the allocation of dietary nutrients). We argue that animal physiological ecologists can benefit from including the measurement of naturally occurring stable isotopes in their battery of techniques. We also argue that animal physiologists can make an important contribution to the emerging field of stable isotopes in biology by testing experimentally the plethora of assumptions upon which the techniques rely. PMID:9683412

  14. Breath carbon stable isotope ratios identify changes in energy balance and substrate utilization in humans

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Rapid detection of shifts in substrate utilization and energy balance would provide a compelling biofeedback tool to enable individuals to lose weight. In a pilot study, we tested whether the natural abundance of exhaled carbon stable isotope ratios (breath d13C values) reflects shifts between negat...

  15. Equations for Lipid Normalization of Carbon Stable Isotope Ratios in Aquatic Bird Eggs

    PubMed Central

    Elliott, Kyle H.; Davis, Mikaela; Elliott, John E.

    2014-01-01

    Stable isotope ratios are biogeochemical tracers that can be used to determine the source of nutrients and contaminants in avian eggs. However, the interpretation of stable carbon ratios in lipid-rich eggs is complicated because 13C is depleted in lipids. Variation in 13C abundance can therefore be obscured by variation in percent lipids. Past attempts to establish an algebraic equation to correct carbon isotope ratios for lipid content in eggs have been unsuccessful, possibly because they relied partly on data from coastal or migratory species that may obtain egg lipids from different habitats than egg protein. We measured carbon, nitrogen and sulphur stable isotope ratios in 175 eggs from eight species of aquatic birds. Carbon, nitrogen and sulphur isotopes were enriched in lipid-extracted egg samples compared with non extracted egg samples. A logarithmic equation using the C∶N ratio and carbon isotope ratio from the non extracted egg tissue calculated 90% of the lipid-extracted carbon isotope ratios within ±0.5‰. Calculating separate equations for eggs laid by species in different habitats (pelagic, offshore and terrestrial-influenced) improved the fit. A logarithmic equation, rather than a linear equation as often used for muscle, was necessary to accurately correct for lipid content because the relatively high lipid content of eggs compared with muscle meant that a linear relationship did not accurately approximate the relationship between percent lipids and the C∶N ratio. Because lipid extraction alters sulphur and nitrogen isotope ratios (and cannot be corrected algebraically), we suggest that isotopic measurement on bulk tissue followed by algebraic lipid normalization of carbon stable isotope ratio is often a good solution for homogenated eggs, at least when it is not possible to complete separate chemical analyses for each isotope. PMID:24465384

  16. Calcium isotope evidence for suppression of carbonate dissolution in carbonate-bearing organic-rich sediments

    NASA Astrophysics Data System (ADS)

    Turchyn, Alexandra V.; DePaolo, Donald J.

    2011-11-01

    Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (δ 44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of δ 44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, δ 44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the δ 44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these sites (the actual rates could be significantly slower) because other processes that impact the calcium isotope composition of sedimentary pore fluid have not been included. The results provide direct geochemical evidence for the anecdotal observation that the best-preserved carbonate fossils are often found in clay or organic-rich sedimentary horizons. The results also suggest that the presence of clay minerals has a strong passivating effect on the surfaces of biogenic carbonate minerals, slowing dissolution dramatically even in relation to the already-slow rates typical of carbonate-rich sediments.

  17. Further carbon isotope measurements of LEW 88516

    NASA Astrophysics Data System (ADS)

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

    1993-03-01

    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.

  18. 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.

  19. Coprecipitation and isotopic fractionation of boron in modern biogenic carbonates

    NASA Astrophysics Data System (ADS)

    Vengosh, Avner; Kolodny, Yehoshua; Starinsky, Abraham; Chivas, Allan R.; McCulloch, Malcolm T.

    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 boron content of the biogenic skeletons is independent of mineralogical composition and is probably related to biological (vital) effects. The δ11B values of the carbonates range from 14.2 to 32.2%. (relative to NBS SRM 951) and overlap with the δ11B values of modern deep-sea carbonate sediments ( δ11B = 8.9 to 26.2%.). The variations of δ11B may be controlled by isotopic exchange of boron species in which 10B is preferentially partitioned into the tetrahedral species, and coprecipitation of different proportions of trigonal and tetrahedral species in the calcium carbonates. Carbonates with low δ11B values (~ 15%.) may indicate preferential incorporation of tetrahedral species, whereas the higher δ11B values (~30%.) may indicate (1) uptake of both boron species assuming equilibrium with seawater (2) preferential incorporation of B(OH) 4- from in situ high-pH internal fluids of organisms that are isolated from seawater. The B content and δ11B 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 ± 0.9 × 10 10 g/yr is calculated for carbonates. This is only slightly lower than the sink for desorbable B in marine sediments (10 × 10 10 g/yr) and approximately half that of altered oceanic crust (14 × 10 10 g/yr). Thus, carbonates are an important sink for B in the oceans being ~20% of the total sinks. The preferential incorporation of 10B into calcium carbonate results in oceanic 11B-enrichment, estimated as 1.2 ± 0.3 × 10 12 per mil · 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. The potential use of boron-isotope geochemistry in skeletons as a tracer for palaeoenvironments is demonstrated in Ostracoda and Foraminifera from the Gulf of Carpentaria, Australia. The δ11B values of glacial-age, buried skeletons (4.0 and 4.9%., respectively) are lower than that of their modern equivalents (17.6 and 13.3%., respectively). This may reflect a "terrestrial" boron-isotope signature of the water in the gulf during the Late Quaternary when it was isolated from the ocean.

  20. 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.

  1. The influence of carbon source on abiotic organic synthesis and carbon isotope fractionation under hydrothermal conditions

    NASA Astrophysics Data System (ADS)

    McCollom, Thomas M.; Lollar, Barbara Sherwood; Lacrampe-Couloume, Georges; Seewald, Jeffrey S.

    2010-05-01

    A series of laboratory experiments were performed to investigate the relative contributions of CO and other single-carbon compounds to abiotic synthesis of organic compounds in hydrothermal environments. Experiments were conducted by heating aqueous solutions of CO, CO 2, HCOOH, or CH 4 at 250 °C under reducing conditions, and observing production of CH 4 and other hydrocarbons. Native Fe was included in the experiments as a source of H 2 through reaction with water and as a potential catalyst. Experiments with CO or HCOOH as the carbon source resulted in rapid generation of CH 4 and other hydrocarbons that closely resembled typical products of Fischer-Tropsch organic synthesis. In contrast, experiments using CO 2 or CH 4 as the carbon source yielded no detectable hydrocarbon products. Carbon isotope measurements of reaction products from the CO experiments indicate that the CH 4 and other hydrocarbons were substantially depleted in 13C, with CH 4 δ 13C values 30 to 34‰ lighter than the initial CO. Most of the fractionation apparently occurs during attachment of CO to the catalyst surface and subsequent reduction to surface-bound methylene. The initial step in polymerization of these methylene units to form hydrocarbons involves a small, positive fractionation, so that ethane and ethene are slightly enriched in 13C relative to CH 4. However, subsequent addition of carbon molecules to the growing hydrocarbon chain proceeds with no net observable fractionation, so that the isotopic compositions of the C 3+ light hydrocarbons are controlled by isotopic mass balance. This result is consistent with a previously proposed model for carbon isotopic patterns of light hydrocarbons in natural samples. The abundance and isotopic composition of light hydrocarbons produced with HCOOH as the carbon source were similar to those generated with CO, but the isotopic compositions of non-volatile hydrocarbons diverged, suggesting that the higher hydrocarbons were formed by different mechanisms in the CO and HCOOH experiments. The experiments indicate that CO, and possibly HCOOH, may be critical intermediates in the abiotic formation of organic compounds in geologic environments, and suggest that the low levels of these compounds present in most hydrothermal systems could represent a bottleneck restricting the extent of abiotic organic synthesis in some circumstances.

  2. Isotopic abundances of Hg in mercury stars inferred from the Hg II line at 3984 A

    NASA Technical Reports Server (NTRS)

    White, R. E.; Vaughan, A. H., Jr.; Preston, G. W.; Swings, J. P.

    1976-01-01

    Wavelengths of the Hg II absorption feature at 3984 A in 30 Hg stars are distributed uniformly from the value for the terrestrial mix to a value that corresponds to nearly pure Hg-204. The wavelengths are correlated loosely with effective temperatures inferred from Q(UBV). Relative isotopic abundances derived from partially resolved profiles of the 3984-A line in iota CrB, chi Lup, and HR 4072 suggest that mass-dependent fractionation has occurred in all three stars. It is supposed that such fractionation occurs in all Hg stars, and a scheme whereby isotopic compositions can be inferred from a comparison of stellar wavelengths and equivalent widths with those calculated for a family of fractionated isotopic mixes. Theoretical profiles calculated for the derived isotopic composition agree well with high-resolution interferometric profiles obtained for three of the stars.

  3. Dramatic shifts in biomarker carbon isotopic compositions during the Late Ordovician: Evidence for lower than expected pCO2?

    NASA Astrophysics Data System (ADS)

    Pancost, R.; Freeman, K. H.; Patzkowsky, M. E.; Ainsaar, L.; Martma, T.

    2003-04-01

    Positive carbon isotope excursions (ca 1.5 permil) occur in North American and East European carbonates of Late Ordovician (Caradocian) age. However, bulk organic carbon isotope records in three North American localities (Iowa, Ontario and Pennsylvania) and one Estonian locality indicate that carbon isotope fractionation by marine photoautotrophs decreased during this event. Such a decrease is unexpected. During other parts of Earth history, carbon isotope excursions, typically ascribed to organic carbon burial events, are commonly associated with a decrease in carbon isotope fractionation. However, at predicted Ordovician pCO2 and O2 concentrations, marine photosynthesis is not expected to be carbon-limited and carbon isotope fractionation will be constant despite the inferred pCO2 decrease. To further evaluate whether this represents evidence for relatively lower pCO2 levels (<8 times modern pre-industrial level) than those predicted by geochemical models, we deconstructed the organic carbon isotopic records using compound-specific carbon isotope analysis. The most dramatic increase in bulk organic carbon isotopic compositions (8 permil) occurs in the Iowa Guttenberg Formation, while a 5 permil increase occurs in sediments from Southern Ontario. In both cases, the carbon isotope excursion is associated with a change in organic matter assemblage: from a predominance of amorphous, presumably algal and bacterial, marine organic matter to abundant remains of the organic-walled microfossil Gloeocapsomporpha prisca. Biomarker analyses reveal that this shift in organic matter assemblage has strongly influenced the bulk organic carbon isotope record, and biomarkers (steranes, high-molecular-weight n-alkanes) that do not derive from G. prisca exhibit only a 3 to 4 permil excursions, consistent with the bulk organic records from Pennsylvania and Estonia. However, even biomarker-based calculations indicate that carbon isotope fractionation decreased during the isotope event, consistent with a dramatic decrease in pCO2. Alternatively, doubling of phytoplankton growth rates could also account for the observed decrease. An increase in productivity, and thus growth rate, is consistent with proposed changes in ocean circulation and sedimentological evidence for an increase in terrigenous inputs. Moreover, dramatic changes in the distributions of algal and bacterial biomarkers in the Iowa section provide evidence for a change in oceanographic conditions associated with the event. In particular, a dramatic decrease in the abundance of cyanobacterial biomarkers across the boundary suggests that nitrate-limiting conditions could have prevailed prior to the carbon isotope excursion but ceased at that point due to increased nutrient inputs. If so, the productivity event must have been regionally widespread, potentially recording a significant input of terrigenous nutrients into marine settings during the Taconic orogeny.

  4. 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.

  5. 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 generally 2-3‰ enriched relative to angiosperm leaves, we project that the far more abundant angiosperm lipids will be about 4-6 ‰ depleted relative to small amounts of conifer n-alkanes in natural samples. In addition, we report carbon isotope values of the terpenoids from the MVA (triterpenoids) and MEP (diterpenoids) synthesis pathways for our plant sample set. Bulk leaf tissue-to-lipid fractionation factors for terpenoids are similar and generally small, -0.4 and -0.6‰, for MVA and MEP products, respectively. Estimates of precipitation from fossil leaves at the Fifteenmile site allow us to predict leaf fractionation values for different plant types (bulk) and for triterpenoid and diterpenoid compound classes. Our fractionation factors, when applied to an estimate for the δ13C value of late Eocene CO2, agree well with bulk and molecular data. An understanding of molecular production biases greatly improves our ability to reconstruct both paleovegetation and δ13C of atmospheric CO2.

  6. Mercury (Hg) in meteorites: Variations in abundance, thermal release profile, mass-dependent and mass-independent isotopic fractionation

    NASA Astrophysics Data System (ADS)

    Meier, Matthias M. M.; Cloquet, Christophe; Marty, Bernard

    2016-06-01

    We have measured the concentration, isotopic composition and thermal release profiles of Mercury (Hg) in a suite of meteorites, including both chondrites and achondrites. We find large variations in Hg concentration between different meteorites (ca. 10 ppb to 14,000 ppb), with the highest concentration orders of magnitude above the expected bulk solar system silicates value. From the presence of several different Hg carrier phases in thermal release profiles (150-650 °C), we argue that these variations are unlikely to be mainly due to terrestrial contamination. The Hg abundance of meteorites shows no correlation with petrographic type, or mass-dependent fractionation of Hg isotopes. Most carbonaceous chondrites show mass-independent enrichments in the odd-numbered isotopes 199Hg and 201Hg. We show that the enrichments are not nucleosynthetic, as we do not find corresponding nucleosynthetic deficits of 196Hg. Instead, they can partially be explained by Hg evaporation and redeposition during heating of asteroids from primordial radionuclides and late-stage impact heating. Non-carbonaceous chondrites, most achondrites and the Earth do not show these enrichments in vapor-phase Hg. All meteorites studied here have however isotopically light Hg (δ202Hg = ∼-7 to -1) relative to the Earth's average crustal values, which could suggest that the Earth has lost a significant fraction of its primordial Hg. However, the late accretion of carbonaceous chondritic material on the order of ∼2%, which has been suggested to account for the water, carbon, nitrogen and noble gas inventories of the Earth, can also contribute most or all of the Earth's current Hg budget. In this case, the isotopically heavy Hg of the Earth's crust would have to be the result of isotopic fractionation between surface and deep-Earth reservoirs.

  7. Primary and diagenetic controls of isotopic compositions of iron-formation carbonates

    NASA Technical Reports Server (NTRS)

    Kaufman, Alan J.; Hayes, J. M.; Klein, C.

    1990-01-01

    Results are presented on parallel analyses of carbonate and chert microbands in segments from the early Proterozoic Dales Gorge Member of the Brockman Iron Formation (western Australia), including data on isotopic, chemical, and mineralogic variations in microbanded carbonates, cherts, and coexisting minerals in four core segments from Paraburdoo and one from Wittenoom. It is shown that patterns of variation observed in isotopic abundance and mineral composition can be consistently explained in terms of diagenetic replacement of fine-grained primary precipitates by secondary ones, rather than by mineral-dependent fractionations, metamorphism, or the influence of large volumes of water in an open system.

  8. 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.

  9. The Oxygen Isotopic Composition of MIL 090001: A CR2 Chondrite with Abundant Refractory Inclusions

    NASA Technical Reports Server (NTRS)

    Keller, Lindsay P.; McKeegan, K. D.; Sharp, Z. D.

    2012-01-01

    MIL 090001 is a large (>6 kg) carbonaceous chondrite that was classified as a member of the CV reduced subgroup (CVred) that was recovered during the 2009-2010 ANSMET field season [1]. Based on the abundance of refractory inclusions and the extent of aqueous alteration, Keller [2] suggested a CV2 classification. Here we report additional mineralogical and petrographic data for MIL 090001, its whole-rock oxygen isotopic composition and ion microprobe analyses of individual phases. The whole rock oxygen isotopic analyses show that MIL 090001 should be classified as a CR chondrite.

  10. Field variability of carbon isotopes in soil organic carbon

    NASA Astrophysics Data System (ADS)

    Leavitt, S. W.; Pendall, E.; Paul, E. A.; Pinter, P. J., Jr.; Kimball, B. A.

    1997-03-01

    Free-air CO2 enrichment (FACE) plant-growth experiments conducted in Arizona have allowed a spinoff isotope tracer experiment (tank CO2 is 14C- and 13C-depleted) to follow the input of carbon into soil organic matter pools. Accurate assessment of the 14C and 13C inputs to soils by this pathway requires detailed knowledge of the isotopic composition of the soils before the experiments. We have examined the variability of δ13C in soil organic matter in 8 experimental plots prior to the beginning of the 1995-1996 FACE experiments with wheat. δ13C variability was higher immediately after harvest of a previous crop in June, but the plots were much more homogeneous five months later immediately before planting. Intervening field management, including disking, plowing and installation of irrigation drip tape likely contributed to mixing the soils.

  11. 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.

  12. A secondary tracer approach to the derivation of galactic cosmic-ray source isotopic abundances

    NASA Technical Reports Server (NTRS)

    Stone, E. C.; Wiedenbeck, M. E.

    1979-01-01

    A formalism has been developed for deriving cosmic-ray source isotopic abundances from observed local abundances using a purely secondary nuclide as a tracer of spallation production during propagation. Although the formalism is based on the leaky-box model of cosmic-ray propagation, it is shown that source abundances derived by the tracer technique are reasonably independent of detailed propagation models. The tracer formalism also permits a quantitative evaluation of the effects of observational uncertainties on deduced source abundances. It is shown that statistical errors in the observed abundances and uncertainties in the spallation cross sections are at present the dominant sources of uncertainty. The latter error can be reduced with increased detector size or exposure time, while the former can be minimized by measurements of the relative production cross sections. As a specific example, the tracer technique is applied to the isotopes of sulfur and calcium, and the level of uncertainties which must be achieved to distinguish evolutionary differences between solar-system material and cosmic ray-source material are established.

  13. 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 that are emerging from clumped isotope analyses.

  14. Biological control of calcium isotopic abundances in the global calcium cycle

    SciTech Connect

    Skulan, J.; DePaolo, D.J.; Owens, T.L.

    1997-06-01

    Measurements of {sup 44}Ca/{sup 40}Ca, expressed as {delta}{sup 44}Ca, were made on igneous rocks and on shell and bone material from modern organisms to investigate the magnitude and origins of calcium isotopic fractionation in nature. The results document a span of 4{per_thousand} in {delta}{sup 44}Ca, measured with the double spike technique to a precision of {+-}0.15{per_thousand}. Volcanic rocks, including basalt and rhyolite, show little variability and cluster near {delta}{sup 44}Ca = 0 {+-}0.2. Systematic analysis of biological samples indicates that biological processing of calcium discriminates against heavy isotopes, and that biological fractionation is the primary generator of calcium isotopic fractionation in nature. Preliminary data suggest that calcium becomes isotopically lighter as it moves through food chains. Calcium carbonate shells of marine microorganisms and deep-sea carbonate ooze have {delta}{sup 44}Ca about 1.0{per_thousand}, lower than seawater; this fractionation causes seawater to be enriched in heavy calcium ({delta}{sup 44}Ca = +0.9) relative to igneous rocks. Marine organisms consequently are isotopically heavier than their terrestrial counterparts at similar trophic level. The calcium isotopic composition of living and fossil organisms may record information on diet and environment. 22 refs., 3 figs., 2 tabs.

  15. Carbon allocation in plants and ecosystems - insights from stable isotope studies

    NASA Astrophysics Data System (ADS)

    Gessler, Arthur

    2014-05-01

    Trees are large global stores of carbon (C) that will be impacted by increased carbon dioxide levels and climate change. However, at present we cannot properly predict the carbon balance of forests in future as we lack knowledge on how plant physiological processes, the transfer of carbon within the plant, carbon storage, and remobilization in the plant tissues as well as the release of carbon from the roots to the soil interact with environmental drivers and ecosystem-scale processes. This paper will summarise how stable isotope techniques can give new insights in the fate of newly assimilated C in plants and ecosystems on time scales from hours to seasons and it will include studies either characterizing temporal and spatial variation in the natural abundance of carbon and oxygen isotopes or applying isotopically enriched tracers. It comprises the assessment of the mechanisms of C partitioning among specific metabolic pathways, between plant organs and into various ecosystem C pools with different residence times. Moreover stable isotopes are highly suitable tools to characterise the role of the phloem, which is the central long-distance conveyer distributing C from source to sinks and thus plays a central role in linking sites and structures of storage, growth and other metabolic activities. A deeper understanding of these processes and their interaction with environmental drivers is critical for predicting how trees and ecosystems will respond to coming global environmental changes, including increased temperature, altered precipitation, and elevated carbon dioxide concentrations.

  16. 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 primarily dominated by C3/C4 plant composition and then ancillary environmental conditions. Along latitude, plant and litter carbon pools in northern ecosystems have slower turnover rates (i.e., higher 14C/12C) than those in tropical ecosystems. However, humus carbon in northern ecosystems with very long mean residence times has lower 14C/12C ratio, most of bomb-derived radioactive carbon lingered still in plant biomass. Now, we are attempting to examine the model estimations by comparing with atmospheric measurements.

  17. Forward modeling of carbonate proxy data from planktonic foraminifera using oxygen isotope tracers in a global ocean model

    NASA Astrophysics Data System (ADS)

    Schmidt, Gavin A.

    1999-08-01

    The distribution and variation of oxygen isotopes in seawater are calculated using the Goddard Institute for Space Studies global ocean model. Simple ecological models are used to estimate the planktonic foraminiferal abundance as a function of depth, column temperature, season, light intensity, and density stratification. These models are combined to forward model isotopic signals recorded in calcareous ocean sediment. The sensitivity of the results to the changes in foraminiferal ecology, secondary calcification, and dissolution are also examined. Simulated present-day isotopic values for ecology relevant for multiple species compare well with core-top data. Hindcasts of sea surface temperature and salinity are made from time series of the modeled carbonate isotope values as the model climate changes. Paleoclimatic inferences from these carbonate isotope records are strongly affected by erroneous assumptions concerning the covariations of temperature, salinity, and δ18Ow. Habitat-imposed biases are less important, although errors due to temperature-dependent abundances can be significant.

  18. Carbon Isotope Stratigraphy of the Triassic-Jurassic Boundary, Northern Calcareous Alps, Southern Bavaria.

    NASA Astrophysics Data System (ADS)

    Blom, Vincent P. C.; Prave, Anthony R.; Raub, Timothy D.

    2014-05-01

    The end Triassic is recognized as a period of increased marine biotic turnover, culminating in one of the five major mass extinction events of the Phanerozoic at the Triassic-Jurassic boundary. Carbon isotope excursions have been reported globally that may be in response to a perturbation to the earth system. Here we present findings from a succession of early Mesozoic Tethyan carbonate strata from the Northern Calcareous Alps (NCA) of southern Bavaria, Germany. The succession ranges from Carnian to Middle Jurassic in age and is part of the Bavarian Syncline, which trends East-West along the northern extent of the NCA. The two field areas studied, Wallberg and Buchstein, contain the Tr-J boundary, which is marked by an abrupt change from underlying reefal carbonate rocks to a deeper basinal setting dominated by marls, as well as the disappearance of abundant brachiopod, bivalve and colonial coral populations. The boundary is also characterized by a carbonate carbon isotope excursion. Carbonate C isotope values in the underlying reefal carbonate rocks are marked by values of 2.0 to 2.5‰. Above the contact, the carbonate C isotopes show a 1.5 - 2.0‰ decline, which coincides with the change from shallow to deeper marine carbonate sedimentation. Following the excursion, and whilst the succession maintains a basinal palaeoenvironmental setting, the C isotopes return to values similar to those present beneath the Tr-J boundary ranging from 2.0 - 2.5‰. The negative excursion may be recording a global perturbation to the carbon cycle, however the change from a shallow to deep marine depositional environment must also be considered as a possible influence on isotopic composition. Cross-plots of C and O isotopes show no correlation hence we prefer to interpret the carbonate C isotopic data to record original seawater values. Post-depositional diagenetic and lithification processes, however, likely modified the O isotope values. Our results urge caution in identifying C isotopic excursions as global until potential palaeoenvironmental-related changes can be excluded.

  19. 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 the accordance of carbon isotopic data.

  20. A Comparison of Oxidized Carbon Abundances among Comets

    NASA Astrophysics Data System (ADS)

    DiSanti, Michael A.; Mumma, M. J.; Bonev, B. P.; Villanueva, G. L.; Magee-Sauer, K.; Gibb, E. L.; Anderson, W. M.; Radeva, Y. L.

    2007-10-01

    Comets contain relatively primitive icy material remaining from the epoch of Solar System formation, however the extent to which they are modified from their initial state is a fundamental question in cometary science. One means of assessing the degree to which ices were processed prior to their incorporation into the nucleus is to measure the relative abundances of chemically related parent volatiles. For example, formation of C2H6 by hydrogen atom addition reactions (e.g., to C2H2) on surfaces of icy-mantled grains prior to their incorporation into the nucleus was proposed to explain the high C2H6 to CH4 abundance observed first in C/1996 B2 (Hyakutake)1 and then in subsequent comets. Comparing the abundance ratio C2H6/C2H2 among comets can provide information on the efficiency of this process. CO should also be hydrogenated on grain surfaces. Laboratory irradiation experiments on interstellar ice analogs have shown this process to be efficient only at very low temperatures, the resulting yields of H2CO and CH3OH being highly dependent both on hydrogen density (i.e., fluence) and on temperature in the range 10-25 K.2,3 Here, we compare the oxidation sequence of carbon in comets observed with NIRSPEC at Keck-2 and CSHELL at the NASA-IRTF. Their compositions are used to assess the efficiency of H-atom addition. Possible implications regarding formation conditions will be discussed. This work is supported by the NASA Astrobiology Program under RTOP 344-53-51, and by the NASA Planetary Astronomy Program under RTOPs 344-32-30-07 and 344-32-98. References: 1Mumma et al. 1996 Science 272:1310 2Hiraoka et al. 2002 Astrophys. J. 577:265 3Watanabe et al. 2004 Astrophys. J. 616:638

  1. LITHIUM ABUNDANCES IN CARBON-ENHANCED METAL-POOR STARS

    SciTech Connect

    Masseron, Thomas; Johnson, Jennifer A.; Lucatello, Sara; Karakas, Amanda; Plez, Bertrand; Beers, Timothy C.; Christlieb, Norbert E-mail: jaj@astronomy.ohio-state.edu

    2012-05-20

    Carbon-enhanced metal-poor (CEMP) stars are believed to show the chemical imprints of more massive stars (M {approx}> 0.8 M{sub Sun }) that are now extinct. In particular, it is expected that the observed abundance of Li should deviate in these stars from the standard Spite lithium plateau. We study here a sample of 11 metal-poor stars and a double-lined spectroscopic binary with -1.8 < [Fe/H] < -3.3 observed with the Very Large Telescope/UVES spectrograph. Among these 12 metal-poor stars, there are 8 CEMP stars for which we measure or constrain the Li abundance. In contrast to previous arguments, we demonstrate that an appropriate regime of dilution permits the existence of 'Li-Spite plateau and C-rich' stars, whereas some of the 'Li-depleted and C-rich' stars call for an unidentified additional depletion mechanism that cannot be explained by dilution alone. We find evidence that rotation is related to the Li depletion in some CEMP stars. Additionally, we report on a newly recognized double-lined spectroscopic binary star in our sample. For this star, we develop a new technique from which estimates of stellar parameters and luminosity ratios can be derived based on a high-resolution spectrum alone, without the need for input from evolutionary models.

  2. The abundances of carbon and nitrogen in I Zw 18

    NASA Technical Reports Server (NTRS)

    Dufour, Reginald J.; Garnett, Donald R.; Shields, Gregory A.

    1988-01-01

    The first measurements of the semiforbidden C III 1909 A and forbidden N II 6583 A emission lines in I Zw 18 are reported. These data are combined with previously published spectrophotometry in order to derive the carbon and nitrogen abundances in I Zw 18 with the aid of a nebular model. The CNO abundances in I Zw 18 are found to exceed those found in the Magellanic Clouds and other well-observed oxygen-poor irregular galaxies and are more similar to those in the sun and nearby Galactic H II regions. It is argued that I Zw 18 may be older and more chemically evolved than previously believed, and that its extremely low O/H results from escape of O-rich supernova ejecta from the Galaxy or from dilution by accretion of primordial gas. Alternatively, I Zw 18 may have formed from a preenriched intergalactic medium. Spectroscopic diagnostics for composite photoionization models to fit the spectrum of I Zw 18 are discussed.

  3. Enzymatic passaging of human embryonic stem cells alters central carbon metabolism and glycan abundance.

    PubMed

    Badur, Mehmet G; Zhang, Hui; Metallo, Christian M

    2015-10-01

    To realize the potential of human embryonic stem cells (hESCs) in regenerative medicine and drug discovery applications, large numbers of cells that accurately recapitulate cell and tissue function must be robustly produced. Previous studies have suggested that genetic instability and epigenetic changes occur as a consequence of enzymatic passaging. However, the potential impacts of such passaging methods on the metabolism of hESCs have not been described. Using stable isotope tracing and mass spectrometry-based metabolomics, we have explored how different passaging reagents impact hESC metabolism. Enzymatic passaging caused significant decreases in glucose utilization throughout central carbon metabolism along with attenuated de novo lipogenesis. In addition, we developed and validated a method for rapidly quantifying glycan abundance and isotopic labeling in hydrolyzed biomass. Enzymatic passaging reagents significantly altered levels of glycans immediately after digestion but surprisingly glucose contribution to glycans was not affected. These results demonstrate that there is an immediate effect on hESC metabolism after enzymatic passaging in both central carbon metabolism and biosynthesis. HESCs subjected to enzymatic passaging are routinely placed in a state requiring re-synthesis of biomass components, subtly influencing their metabolic needs in a manner that may impact cell performance in regenerative medicine applications. PMID:26289220

  4. Enzymatic passaging of human embryonic stem cells alters central carbon metabolism and glycan abundance

    PubMed Central

    Badur, Mehmet G.; Zhang, Hui; Metallo, Christian M.

    2016-01-01

    To realize the potential of human embryonic stem cells (hESCs) in regenerative medicine and drug discovery applications, large numbers of cells that accurately recapitulate cell and tissue function must be robustly produced. Previous studies have suggested that genetic instability and epigenetic changes occur as a consequence of enzymatic passaging. However, the potential impacts of such passaging methods on the metabolism of hESCs have not been described. Using stable isotope tracing and mass spectrometry-based metabolomics, we have explored how different passaging reagents impact hESC metabolism. Enzymatic passaging caused significant decreases in glucose utilization throughout central carbon metabolism along with attenuated de novo lipogenesis. In addition, we developed and validated a method for rapidly quantifying glycan abundance and isotopic labeling in hydrolyzed biomass. Enzymatic passaging reagents significantly altered levels of glycans immediately after digestion but surprisingly glucose contribution to glycans was not affected. These results demonstrate that there is an immediate effect on hESC metabolism after enzymatic passaging in both central carbon metabolism and biosynthesis. HESCs subjected to enzymatic passaging are routinely placed in a state requiring re-synthesis of biomass components, subtly influencing their metabolic needs in a manner that may impact cell performance in regenerative medicine applications. PMID:26289220

  5. Absolute and Relative Isotope Abundances Measured by Tunable Diode Laser Spectroscopy

    NASA Astrophysics Data System (ADS)

    Tucker, George Franklin

    The potential for measuring absolute and relative isotope abundances by high resolution spectroscopy with tunable diode lasers as sources was studied. In order to achieve the sensitivity necessary to determine the absolute abundances of molecules containing long-lived radionuclides such as ('14)C an ('129)I, a resonant spectrophone based on the photoacoustic effect was used for detection. For safety, NH(,3) was used as a sample with air as a buffer gas when characterizing the performance of the TDL-spectrophone system. Frequency modulation of the TDL was employed. The optimum operating pressure was found to be 6.6 kPa(50 Torr). Substitution of Kr as a buffer gas yielded a fourfold increase in signal. It is estimated that with currently available TDLs a photoacoustic spectrometer should be capable of detecting ('14)CO(,2) and CH('129)I at the levels present in nuclear reactor containment gases. An isotope shift of CH(,3)('129) I relative to CH(,3)('127)I in the (nu)(,6) band of (0.0135 (+OR-) 0.0006) cm('-1) was measured by TDL linear absorption spectroscopy. To perform relative isotope abundance measurements a TDL was tuned over two adjacent, but well-resolved, rotation -vibration absorption lines, one of each isotopic species, while the transmitted radiation was monitored with a HgCdTe detector. The P(26) line of the (nu)(,1) band of N(,2)('18)O at 1225.3671 cm('-1) and the P(63) line of the (nu)(,1) band of N(,2)('16)O at 1225.4879 cm('-1) were chosen, for their line strength ratio is inversely proportional to the ratio of their natural abundances, and thereby yielded approximately equal absorbance for each isotopic species. A double-beam, single-detector spectrometer with wavelength modulation to minimize the effects of laser power and cell temperature fluctuations, has been adapted for use with a TDL. After samples of known ('18)O enrichment were used to calibrate the spectrometer, the (delta)('18)O of tropospheric N(,2)O was measured to be (8.05 (+OR-) 0.17)('o)/oo relative to a laboratory standard, or approximately 42('o)/oo relative to standard mean ocean water. After 190 days at 24(DEGREES)C no oxygen isotope exchange was observed between N(,2)('16)O and H(,2)('18)O.

  6. Mercury Abundances and Isotopic Compositions in the Murchison (CM) and Allende (CV)Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    Lauretta, D. S.; Klaue, B.; Blum, J. D.; Buseck, P. R.

    2001-01-01

    The abundance and isotopic composition of Hg was determined in bulk samples of both the Murchison (CM) and Allende (CV) carbonaceous chondrites using single- and multi-collector inductively coupled plasma mass spectrometry (ICP-MS). The bulk abundances of Hg are 294 6 15 ng/g in Murchison and 30.0 6 1.5 ng/g in Allende. These values are within the range of previous measurements of bulk Hg abundances by neutron activation analysis (NAA). Prior studies suggested that both meteorites contain isotopically anomalous Hg, with d l 96/202Hg values for the anomalous, thermal-release components from bulk samples ranging from 2260 %o to 1440 9/00 in Murchison and from 2620 9/00 to 1540 9/00 in Allende (Jovanovic and Reed, 1976a; 1976b; Kumar and Goel, 1992). Our multi-collector ICP-MS measurements suggest that the relative abundances of all seven stable Hg isotopes in both meteorites are identical to terrestrial values within 0.2 to 0.5 9/00m. On-line thermal-release experiments were performed by coupling a programmable oven with the singlecollector ICP-MS. Powdered aliquots of each meteorite were linearly heated from room temperature to 900 C over twenty-five minutes under an Ar atmosphere to measure the isotopic composition of Hg released fiom the meteorites as a h c t i o n of temperature. In separate experiments, the release profiles of S and Se were determined simultaneously with Hg to constrain the Hg distribution within the meteorites and to evaluate the possibility of Se interferences in previous NAA studies. The Hg-release patterns differ between Allende and Murchison. The Hg-release profile for Allende contains two distinct peaks, at 225" and 343"C, whereas the profile for Murchison has only one peak, at 344 C. No isotopically anomalous Hg was detected in the thermal-release experiments at a precision level of 5 to 30 9/00, depending on the isotope ratio. In both meteorites the Hg peak at ;340"C correlates with a peak in the S-release profile. This correlation suggests that Hg is associated with S-bearing phases and, thus, that HgS is a major Hg-bearing phase in both meteorites. The Hg peak at 225 C for Allende is similar to release patterns of physically adsorbed Hg on silicate and metal grains.

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

    USGS Publications Warehouse

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

    1978-01-01

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

  8. Abundances of carbon-enhanced metal-poor stars as constraints on their formation

    NASA Astrophysics Data System (ADS)

    Hansen, C. J.; Nordström, B.; Hansen, T. T.; Kennedy, C. R.; Placco, V. M.; Beers, T. C.; Andersen, J.; Cescutti, G.; Chiappini, C.

    2016-04-01

    Context. An increasing fraction of carbon-enhanced metal-poor (CEMP) stars is found as their iron abundance, [Fe/H], decreases below [Fe/H] =-2.0. The CEMP-s stars have the highest absolute carbon abundances, [C/H], and are thought to owe their enrichment in carbon and the slow neutron-capture (s-process) elements to mass transfer from a former asymptotic giant branch (AGB) binary companion. The most Fe-poor CEMP stars are normally single, exhibit somewhat lower [C/H] than CEMP-s stars, but show no s-process element enhancement (CEMP-no stars). Abundance determinations of CNO offer clues to their formation sites. Aims: Our aim is to use the medium-resolution spectrograph X-Shooter/VLT to determine stellar parameters and abundances for C, N, Sr, and Ba in several classes of CEMP stars in order to further classify and constrain the astrophysical formation sites of these stars. Methods: Atmospheric parameters for our programme stars were estimated from a combination of V-K photometry, model isochrone fits, and estimates from a modified version of the SDSS/SEGUE spectroscopic pipeline. We then used X-Shooter spectra in conjunction with the 1D local thermodynamic equilibrium spectrum synthesis code MOOG, 1D ATLAS9 atmosphere models to derive stellar abundances, and, where possible, isotopic 12C/13C ratios. Results: Abundances (or limits) of C, N, Sr, and Ba are derived for a sample of 27 faint metal-poor stars for which the X-Shooter spectra have sufficient signal-to-noise ratios (S/N). These moderate resolution, low S/N (~10-40) spectra prove sufficient to perform limited chemical tagging and enable assignment of these stars into the CEMP subclasses (CEMP-s and CEMP-no). According to the derived abundances, 17 of our sample stars are CEMP-s and 3 are CEMP-no, while the remaining 7 are carbon-normal. For four CEMP stars, the subclassification remains uncertain, and two of them may be pulsating AGB stars. Conclusions: The derived stellar abundances trace the formation processes and sites of our sample stars. The [C/N] abundance ratio is useful for identifying stars with chemical compositions unaffected by internal mixing, and the [Sr/Ba] abundance ratio allows us to distinguish between CEMP-s stars with AGB progenitors and the CEMP-no stars. Suggested formation sites for the latter include faint supernovae with mixing and fallback and/or primordial, rapidly-rotating, massive stars (spinstars). X-Shooter spectra have thus proved to be valuable tools in the continued search for their origin. Based on observations obtained at ESO Paranal Observatory, programmes 084.D-0117(A) and 085.D-0041(A).

  9. Carbon isotopes of hydrocarbons and carbon dioxide in natural gases in China

    NASA Astrophysics Data System (ADS)

    Sheng, Xu; Nakai, Shun'ichi; Wakita, Hiroshi; Yongchang, Xu; Wang, Xianbin

    1997-02-01

    130 natural gases in the continent of China were determined for the abundance and carbon isotopes of hydrocarbons and carbon dioxide. The δ13C (PDB) values of methane range from -68 to - 24.4%, and the largest isotopic variability for hydrocarbons is of δ13C 1 < δ13C; < δ13C; < δ13C 4 < δ13C 5. These characteristics suggest that the gaseous hydrocarbons originated principally from thermal and or microbial decomposition of organic matter. The wide variations of δ13C 0 distribution patterns (n = 1, 2, 3, 4 and 5) can be explained by (1) extensive mixture between thermogenic and microbial gases, or between thermogenic gases produced during different thermal stage, and or (2) preferential microbial oxidation. There is no direct evidence for the presence of abiogenic hydrocarbon in natural gases in China. One sample from Songliao basin shows a heavier δ13C 1 ( - 24‰) and reverse isotopic distribution pattern ( δ13C 1 > δ13C 2 > δ13C 3). Concerning the occurrence of mantle-derived He, Ne, Ar and Xe in the south Songliao basin, we propose that the methane mantle derived and heavy hydrocarbons (ethane, propane, butane, etc.) formed from polymerization of the mantle-derived methane. The δ13C values for carbon dioxide range from - 13.9 to + 13.5‰ suggesting the multiple origins. Gases with CO 2 concentrations greater than 10% have a narrow range of δ13C values, from - 8 to - 2‰, and show higher 1He 4He ratios ( > 0.1 times the atmospheric value), suggesting that a mantle-derived component is diluted by CO 2 derived from carbonate and or organic matter. Positive δ13C values ( + 4 - + 14‰) indicate CO 2 reduction to CH 2, CO 2 with trace concentration in CH 4-rich gases can be attributed to microbial decomposition of organic matter in sedimentary rocks.

  10. Stable carbon and sulfur isotopes as records of the early biosphere

    NASA Technical Reports Server (NTRS)

    Desmarais, David J.

    1989-01-01

    The abundance ratios of the stable isotopes of light elements such as carbon and sulfur can differ between various naturally-occurring chemical compounds. If coexisting compounds have achieved mutual chemical and isotopic equilibrium, then the relative isotopic composition can record the conditions at which equilibrium was last maintained. If coexisting chemical compounds indeed formed simultaneously but had not achieved mutual equilibrium, then their relative isotopic compositions often reflect the conditions and mechanisms associated with the kinetically controlled reactions responsible for their production. In the context of Mars, the stable isotopic compositions of various minerals might record not only the earlier environmental conditions of the planet, but also whether or not the chemistry of life ever occurred there. Two major geochemical reservoirs occur in Earth's crust, both for carbon and sulfur. In rocks formed in low temperature sedimentary environments, the oxidized forms of these elements tend to be enriched in the isotope having the larger mass, relative to the reduced forms. In sediments where the organics and sulfides were formed by biological processes, these isotopic contrasts were caused by the processes of biological CO2 fixation and dissimilatory sulfate reduction. Such isotopic contrasts between oxidized and reduced forms of carbon and sulfur are permitted by thermodynamics at ambient temperatures. However, nonbiological chemical reactions associated with the production of organic matter and the reduction of organics and sulfides are extremely slow at ambient temperatures. Thus the synthesis of organics and sulfides under ambient conditions illustrates life's profound role as a chemical catalyst that has altered the chemistry of Earth's crust. Because the stable isotopes of carbon and sulfur can reflect their chemistry, they are useful probes of the Martian surface.

  11. Isotopic disequilibrium in Globigerina bulloides and carbon isotope response to productivity increase in Southern Ocean

    NASA Astrophysics Data System (ADS)

    Prasanna, K.; Ghosh, Prosenjit; Bhattacharya, S. K.; Mohan, K.; Anilkumar, N.

    2016-02-01

    Oxygen and carbon isotope ratios in planktonic foraminifera Globigerina bulloides collected from tow samples along a transect from the equatorial Indian ocean to the Southern Ocean (45°E and 80°E and 10°N to 53°S) were analysed and compared with the equilibrium δ18O and δ13C values of calcite calculated using the temperature and isotopic composition of the water column. The results agree within ~0.25‰ for the region between 10°N and 40°S and 75-200 m water depth which is considered to be the habitat of Globigerina bulloides. Further south (from 40°S to 55°S), however, the measured δ18O and δ13C values are higher than the expected values by ~2‰ and ~1‰ respectively. These enrichments can be attributed to either a ‘vital effect’ or a higher calcification rate. An interesting pattern of increase in the δ13C(DIC) value of the surface water with latitude is observed between 35°S and~ 60°S, with a peak at~ 42°S. This can be caused by increased organic matter production and associated removal. A simple model accounting for the increase in the δ13C(DIC) values is proposed which fits well with the observed chlorophyll abundance as a function of latitude.

  12. Isotopic disequilibrium in Globigerina bulloides and carbon isotope response to productivity increase in Southern Ocean

    PubMed Central

    Prasanna, K.; Ghosh, Prosenjit; Bhattacharya, S. K.; Mohan, K.; Anilkumar, N.

    2016-01-01

    Oxygen and carbon isotope ratios in planktonic foraminifera Globigerina bulloides collected from tow samples along a transect from the equatorial Indian ocean to the Southern Ocean (45°E and 80°E and 10°N to 53°S) were analysed and compared with the equilibrium δ18O and δ13C values of calcite calculated using the temperature and isotopic composition of the water column. The results agree within ~0.25‰ for the region between 10°N and 40°S and 75–200 m water depth which is considered to be the habitat of Globigerina bulloides. Further south (from 40°S to 55°S), however, the measured δ18O and δ13C values are higher than the expected values by ~2‰ and ~1‰ respectively. These enrichments can be attributed to either a ‘vital effect’ or a higher calcification rate. An interesting pattern of increase in the δ13C(DIC) value of the surface water with latitude is observed between 35°S and~ 60°S, with a peak at~ 42°S. This can be caused by increased organic matter production and associated removal. A simple model accounting for the increase in the δ13C(DIC) values is proposed which fits well with the observed chlorophyll abundance as a function of latitude. PMID:26903274

  13. Isotopic disequilibrium in Globigerina bulloides and carbon isotope response to productivity increase in Southern Ocean.

    PubMed

    Prasanna, K; Ghosh, Prosenjit; Bhattacharya, S K; Mohan, K; Anilkumar, N

    2016-01-01

    Oxygen and carbon isotope ratios in planktonic foraminifera Globigerina bulloides collected from tow samples along a transect from the equatorial Indian ocean to the Southern Ocean (45°E and 80°E and 10°N to 53°S) were analysed and compared with the equilibrium δ(18)O and δ(13)C values of calcite calculated using the temperature and isotopic composition of the water column. The results agree within ~0.25‰ for the region between 10°N and 40°S and 75-200 m water depth which is considered to be the habitat of Globigerina bulloides. Further south (from 40°S to 55°S), however, the measured δ(18)O and δ(13)C values are higher than the expected values by ~2‰ and ~1‰ respectively. These enrichments can be attributed to either a 'vital effect' or a higher calcification rate. An interesting pattern of increase in the δ(13)C(DIC) value of the surface water with latitude is observed between 35°S and~ 60°S, with a peak at~ 42°S. This can be caused by increased organic matter production and associated removal. A simple model accounting for the increase in the δ(13)C(DIC) values is proposed which fits well with the observed chlorophyll abundance as a function of latitude. PMID:26903274

  14. Stable carbon isotope depth profiles and soil organic carbon dynamics in the lower Mississippi Basin

    USGS Publications Warehouse

    Wynn, J.G.; Harden, J.W.; Fries, T.L.

    2006-01-01

    Analysis of depth trends of 13C abundance in soil organic matter and of 13C abundance from soil-respired CO2 provides useful indications of the dynamics of the terrestrial carbon cycle and of paleoecological change. We measured depth trends of 13C abundance from cropland and control pairs of soils in the lower Mississippi Basin, as well as the 13C abundance of soil-respired CO2 produced during approximately 1-year soil incubation, to determine the role of several candidate processes on the 13C depth profile of soil organic matter. Depth profiles of 13C from uncultivated control soils show a strong relationship between the natural logarithm of soil organic carbon concentration and its isotopic composition, consistent with a model Rayleigh distillation of 13C in decomposing soil due to kinetic fractionation during decomposition. Laboratory incubations showed that initially respired CO 2 had a relatively constant 13C content, despite large differences in the 13C content of bulk soil organic matter. Initially respired CO2 was consistently 13C-depleted with respect to bulk soil and became increasingly 13C-depleted during 1-year, consistent with the hypothesis of accumulation of 13C in the products of microbial decomposition, but showing increasing decomposition of 13C-depleted stable organic components during decomposition without input of fresh biomass. We use the difference between 13C / 12C ratios (calculated as ??-values) between respired CO 2 and bulk soil organic carbon as an index of the degree of decomposition of soil, showing trends which are consistent with trends of 14C activity, and with results of a two-pooled kinetic decomposition rate model describing CO2 production data recorded during 1 year of incubation. We also observed inconsistencies with the Rayleigh distillation model in paired cropland soils and reasons for these inconsistencies are discussed. ?? 2005 Elsevier B.V. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

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

    2012-05-01

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

  16. Molecular and stable carbon isotopic compositions of hopanoids in seep carbonates from the South China Sea continental slope

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

    The lipid biomarkers of hopanoids in cold seep carbonates from the South China Sea continental slope were investigated by gas chromatography-mass spectrometer (GC-MS) and gas chromatography-isotope ratio-mass spectrometer (GC-ir-MS). The distribution of hopanes/hopenes shows a preference for the ‘biological’ 17β(H), 21β(H)-over the ‘geological’ 17α(H), 21β(H)-configuration. This interpretation is in agreement with the strong odd-even preference of long-chain n-alkanes in those samples, suggesting that the ββ hopanes may be the early diagenetic products of biohopanoids and the αβ, βα configurations of hopanes were mainly derived from allochthonous sources contributing to the organic matter of the carbonates. In terms of hopanoid acids, the C30 to C33 17β(H), 21β(H)-hopanoid acids were detected with C32 17β(H), 21β(H)-hopanoid acid being the most abundant. However, there is a significant difference in stable carbon isotopic compostions of the C32 17β(H), 21β(H)-hopanoic acid among samples (-30.7‰ to -69.8‰). The δ13C values match well with the carbon isotopic compositions of SRB-derived iso-/anteiso-C15:0 fatty acids in the samples, which strongly depend on the carbon utilization types by microbe. The most abundant compound of hopanols detected in the samples, C30-17β(H), 21β(H)-hopanol, may be a good indicator of diagenetic product of type I methanotrophs. The molecular and carbon isotopic compositions of hopanoids demonstrate clearly that there is a combination contribution of both SRB and type I or type X methanotrophs to the source organism in the seep carbonates from the South China Sea continental slope.

  17. Chemical and Isotopic Study of Lab-formed Carbonates Under Cryogenic and Hydrothermal Conditions

    NASA Technical Reports Server (NTRS)

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

    2004-01-01

    Aqueous environments on early Mars were probably relatively short-lived and localized, as evidenced by the lack of abundant secondary minerals detected by the TES instrument. In order to better understand the aqueous history of early Mars we need to be able to interpret the evidence preserved in secondary minerals formed during these aqueous events. Carbonate minerals, in particular, are important secondary minerals for interpreting past aqueous environments as illustrated by the carbonates preserved in ALH84001. Carbonates formed in short-lived, dynamic aqueous events often preserve kinetic rather than equilibrium chemical and isotopic processes, and predicting the behavior of such systems is facilitated by empirical data.

  18. Carbon isotopic characterisation of dissolved organic matter during water treatment.

    PubMed

    Bridgeman, John; Gulliver, Pauline; Roe, Jessie; Baker, Andy

    2014-01-01

    Water treatment is a series of physio-chemical processes to aid organic matter (OM) removal, which helps to minimise the formation of potentially carcinogenic disinfection by-products and microbial regrowth. Changes in OM character through the treatment processes can provide insight into the treatment efficiency, but radiogenic isotopic characterisation techniques have yet to be applied. Here, we show for the first time that analysis of (13)C and (14)C of dissolved organic carbon (DOC) effectively characterises dissolved OM through a water treatment works. At the sites investigated: post-clarification, DOC becomes isotopically lighter, due to an increased proportion of relatively hydrophilic DOC. Filtration adds 'old' (14)C-DOC from abrasion of the filter media, whilst the use of activated carbon adds 'young' (14)C-DOC, most likely from the presence of biofilms. Overall, carbon isotopes provide clear evidence for the first time that new sources of organic carbon are added within the treatment processes, and that treated water is isotopically lighter and typically younger in (14)C-DOC age than untreated water. We anticipate our findings will precipitate real-time monitoring of treatment performance using stable carbon isotopes, with associated improvements in energy and carbon footprint (e.g. isotopic analysis used as triggers for filter washing and activated carbon regeneration) and public health benefits resulting from improved carbon removal. PMID:24075722

  19. 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.

  20. An investigation of techniques for the measurement and interpretation of cosmic ray isotopic abundances. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    Wiedenbeck, M. E.

    1977-01-01

    An instrument, the Caltech High Energy Isotope Spectrometer Telescope was developed to measure isotopic abundances of cosmic ray nuclei by employing an energy loss - residual energy technique. A detailed analysis was made of the mass resolution capabilities of this instrument. A formalism, based on the leaky box model of cosmic ray propagation, was developed for obtaining isotopic abundance ratios at the cosmic ray sources from abundances measured in local interstellar space for elements having three or more stable isotopes, one of which is believed to be absent at the cosmic ray sources. It was shown that the dominant sources of uncertainty in the derived source ratios are uncorrelated errors in the fragmentation cross sections and statistical uncertainties in measuring local interstellar abundances. These results were applied to estimate the extent to which uncertainties must be reduced in order to distinguish between cosmic ray production in a solar-like environment and in various environments with greater neutron enrichments.

  1. Isotopic exchange of carbon-bound hydrogen over geologic timescales

    NASA Astrophysics Data System (ADS)

    Sessions, Alex L.; Sylva, Sean P.; Summons, Roger E.; Hayes, John M.

    2004-04-01

    The increasing popularity of compound-specific hydrogen isotope (D/H) analyses for investigating sedimentary organic matter raises numerous questions about the exchange of carbon-bound hydrogen over geologic timescales. Important questions include the rates of isotopic exchange, methods for diagnosing exchange in ancient samples, and the isotopic consequences of that exchange. This article provides a review of relevant literature data along with new data from several pilot studies to investigate such issues. Published experimental estimates of exchange rates between organic hydrogen and water indicate that at warm temperatures (50-100°C) exchange likely occurs on timescales of 10 4 to 10 8 yr. Incubation experiments using organic compounds and D-enriched water, combined with compound-specific D/H analyses, provide a new and highly sensitive method for measuring exchange at low temperatures. Comparison of δD values for isoprenoid and n-alkyl carbon skeletons in sedimentary organic matter provides no evidence for exchange in young (<1 Ma), cool sediments, but strong evidence for exchange in ancient (>350 Ma) rocks. Specific rates of exchange are probably influenced by the nature and abundance of organic matter, pore-water chemistry, the presence of catalytic mineral surfaces, and perhaps even enzymatic activity. Estimates of equilibrium fractionation factors between organic H and water indicate that typical lipids will be depleted in D relative to water by ˜75 to 140‰ at equilibrium (30°C). Thus large differences in δD between organic molecules and water cannot be unambiguously interpreted as evidence against hydrogen exchange. A better approach may be to use changes in stereochemistry as a proxy for hydrogen exchange. For example, estimated rates of H exchange in pristane are similar to predicted rates for stereochemical inversion in steranes and hopanes. The isotopic consequences of this exchange remain in question. Incubations of cholestene with D 2O indicate that the number of D atoms incorporated during structural rearrangements can be far less than the number of C-H bonds that are broken. Sample calculations indicate that, for steranes in immature sediments, the D/H ratio imparted by biosynthesis may be largely preserved in spite of significant structural changes.

  2. Measurement of natural carbon isotopic composition of acetone in human urine.

    PubMed

    Yamada, Keita; Ohishi, Kazuki; Gilbert, Alexis; Akasaka, Mai; Yoshida, Naohiro; Yoshimura, Ryoko

    2016-02-01

    The natural carbon isotopic composition of acetone in urine was measured in healthy subjects using gas chromatography-combustion-isotope ratio mass spectrometry combined with headspace solid-phase microextraction (HS-SPME-GC-C-IRMS). Before applying the technique to a urine sample, we optimized the measurement conditions of HS-SPME-GC-C-IRMS using aqueous solutions of commercial acetone reagents. The optimization enabled us to determine the carbon isotopic compositions within ±0.2 ‰ of precision and ±0.3‰ of error using 0.05 or 0.2 mL of aqueous solutions with acetone concentrations of 0.3-121 mg/L. For several days, we monitored the carbon isotopic compositions and concentrations of acetone in urine from three subjects who lived a daily life with no restrictions. We also monitored one subject for 3 days including a fasting period of 24 h. These results suggest that changes in the availability of glucose in the liver are reflected in changes in the carbon isotopic compositions of urine acetone. Results demonstrate that carbon isotopic measurement of metabolites in human biological samples at natural abundance levels has great potential as a tool for detecting metabolic changes caused by changes in physiological states and disease. Graphical abstract The natural carbon isotopic composition of acetone in urine can be determined using HS-SPME-GCC-IRMS and can provide information on changes in the availability of glucose in the liver. PMID:26718914

  3. Stepwise atmospheric carbon-isotope excursion during the Toarcian Oceanic Anoxic Event (Early Jurassic, Polish Basin)

    NASA Astrophysics Data System (ADS)

    Hesselbo, Stephen P.; Pieńkowski, Grzegorz

    2011-01-01

    During the Mesozoic (250-64 Ma) intervals of about 0.5 Myr were subject to severe environmental changes, including high sea-surface temperature and very low oxygen content of marine water. These Oceanic Anoxic Events, or OAEs, occurred simultaneously with profound disturbance to the carbon cycle. The carbon-isotope anomaly in the Early Jurassic that marks the Toarcian Oceanic Anoxic Event (T-OAE) at ~ 182 Ma is characterized in marine sections by a series of dramatic steps towards lighter values. Herein we present new carbon-isotope data from terrestrial organic matter (phytoclast separates), collected through a Late Pliensbachian-Middle Toarcian coastal and marginal marine succession in the Polish Basin, a setting where hinterland climate and sea-level change are well recorded. The results show that the shift to light carbon-isotope values in the woody organic matter, and therefore also in atmospheric carbon dioxide, similarly occurred in major steps. The steps are here correlated with those identified from marine organic matter, where they have previously been attributed to 100 kyr eccentricity forcing of climate. The results provide strong support for orbitally and climatically controlled release of isotopically light carbon from gas hydrates into the ocean-atmosphere system in a series of rapid bursts. Additionally, a link between the carbon-isotope steps and shoreline movements can be demonstrated. Individual peaks of the negative excursion are mostly associated with facies indicative of sea-level rise (flooding surfaces). However, at the same time inferred higher atmospheric carbon-dioxide content may be expected to have resulted in increased rainfall and temperature, leading to accelerated weathering and erosion, and consequently increased sediment supply, progradation and regression, causing some mismatches between isotope shifts and inferred sea-level changes. Enhanced abundance of megaspores derived from hydrophilic plant groups, and marked increase in kaolinite, are coincident with the overall development of the negative isotope excursion. The combined data suggest that each 100-kyr cycle in carbon-isotope values was characterized by increasingly severe palaeoclimatic change, culminating in extremely hot and humid conditions co-incident with the peak of the final most negative carbon-isotope excursion. The chemostratigraphic correlation allows very precise dating of the Late Pliensbachian-Middle Toarcian coastal and marginal marine sedimentary succession in the Polish Basin.

  4. Carbon Isotopic Ratios of Amino Acids in Stardust-Returned Samples

    NASA Technical Reports Server (NTRS)

    Elsila, Jamie E.; Glavin, Daniel P.; Dworkin, Jason P.

    2009-01-01

    NASA's Stardust spacecraft returned to Earth samples from comet 81P/Wild 2 in January 2006. Preliminary examinations revealed the presence of a suite of organic compounds including several amines and amino acids, but the origin of these compounds could not be identified. Here. we present the carbon isotopic ratios of glycine and E-aminocaproic acid (EACH), the two most abundant amino acids observed, in Stardust-returned foil samples measured by gas chromatography-combustion-isotope ratio crass spectrometry coupled with quadrupole mass spectrometry (GC-QMS/IRMS).

  5. Carbon Isotopic Measurements of Amino Acids in Stardust-Returned Samples

    NASA Technical Reports Server (NTRS)

    Elsila, Jamie

    2009-01-01

    NASA's Stardust spacecraft returned to Earth samples from comet 81P/Wild 2 in January 2006. Preliminary examinations revealed the presence of a suite of organic compounds including several amines and amino acids, but the origin of these compounds could not be identified. Here, we present the carbon isotopic ratios of glycine and e-aminocaproic acid (EACA), the two most abundant amino acids, in Stardust-returned foil samples measured by gas chromatography-combustion-isotope ratio mass spectrometry coupled with quadrupole mass spectrometry (GC-CAMS/IRMS).

  6. The carbon isotope biogeochemistry of methane production in anoxic sediments. 1: Field observations

    NASA Technical Reports Server (NTRS)

    Blair, Neal E.; Boehme, Susan E.; Carter, W. Dale, Jr.

    1993-01-01

    The natural abundance C-13/C-12 ratio of methane from anoxic marine and freshwater sediments in temperate climates varies seasonally. Carbon isotopic measurements of the methanogenic precursors, acetate and dissolved inorganic carbon, from the marine sediments of Cape Lookout Bight, North Carolina were used to determine the sources of the seasonal variations at that site. Movement of the methanogenic zone over an isotopic gradient within the dissolved CO2 pool appears to be the dominant control of the methane C-13/C-12 ratio from February to June. The onset of acetoclastic methane-production is a second important controlling process during mid-summer. An apparent temperature dependence on the fractionation factor for CO2-reduction may have a significant influence on the isotopic composition of methane throughout the year.

  7. ISO/GUM UNCERTAINTIES AND CIAAW (UNCERTAINTY TREATMENT FOR RECOMMENDED ATOMIC WEIGHTS AND ISOTOPIC ABUNDANCES)

    SciTech Connect

    HOLDEN,N.E.

    2007-07-23

    The International Organization for Standardization (ISO) has published a Guide to the expression of Uncertainty in Measurement (GUM). The IUPAC Commission on Isotopic Abundance and Atomic Weight (CIAAW) began attaching uncertainty limits to their recommended values about forty years ago. CIAAW's method for determining and assigning uncertainties has evolved over time. We trace this evolution to their present method and their effort to incorporate the basic ISO/GUM procedures into evaluations of these uncertainties. We discuss some dilemma the CIAAW faces in their present method and whether it is consistent with the application of the ISO/GUM rules. We discuss the attempt to incorporate variations in measured isotope ratios, due to natural fractionation, into the ISO/GUM system. We make some observations about the inconsistent treatment in the incorporation of natural variations into recommended data and uncertainties. A recommendation for expressing atomic weight values using a tabulated range of values for various chemical elements is discussed.

  8. Changes of natural isotopic abundances in the KOSI comet simulation experiments

    NASA Astrophysics Data System (ADS)

    Roessler, K.; Eich, G.; Klinger, J.; Trimborn, P.

    1992-04-01

    Results are presented of the KOSI-7 comet simulation experiment in which samples were taken from the analog body at 90-110 K in a liquid nitrogen-cooled glove box. The H2O phase was analyzed for its D and O-18 abundances. An enrichment of both isotopes (from delta(D) of -47.7 per mil in the unirradiated sample to delta(D) of -35.7 per mil in the insolated and delta(O-18) of -6.40 per mil to delta(O-18) of -4.27 per mil) was observed for the crustal region formed via sintering near the surface. The interior did not exhibit isotopic anomalies, not even at the CO2 zone of recrystallization.

  9. Abundance and isotopic composition of gases in the martian atmosphere from the Curiosity rover.

    PubMed

    Mahaffy, Paul R; Webster, Christopher R; Atreya, Sushil K; Franz, Heather; Wong, Michael; Conrad, Pamela G; Harpold, Dan; Jones, John J; Leshin, Laurie A; Manning, Heidi; Owen, Tobias; Pepin, Robert O; Squyres, Steven; Trainer, Melissa

    2013-07-19

    Volume mixing and isotope ratios secured with repeated atmospheric measurements taken with the Sample Analysis at Mars instrument suite on the Curiosity rover are: carbon dioxide (CO2), 0.960(±0.007); argon-40 ((40)Ar), 0.0193(±0.0001); nitrogen (N2), 0.0189(±0.0003); oxygen, 1.45(±0.09) × 10(-3); carbon monoxide, < 1.0 × 10(-3); and (40)Ar/(36)Ar, 1.9(±0.3) × 10(3). The (40)Ar/N2 ratio is 1.7 times greater and the (40)Ar/(36)Ar ratio 1.6 times lower than values reported by the Viking Lander mass spectrometer in 1976, whereas other values are generally consistent with Viking and remote sensing observations. The (40)Ar/(36)Ar ratio is consistent with martian meteoritic values, which provides additional strong support for a martian origin of these rocks. The isotopic signature δ(13)C from CO2 of ~45 per mil is independently measured with two instruments. This heavy isotope enrichment in carbon supports the hypothesis of substantial atmospheric loss. PMID:23869014

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  11. 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.

  12. On the volatile inventory of Titan from isotopic abundances in nitrogen and methane.

    PubMed

    Lunine, J I; Yung, Y L; Lorenz, R D

    1999-01-01

    We analyze recently published nitrogen and hydrogen isotopic data to constrain the initial volatile abundances on Saturn's giant moon Titan. The nitrogen data are interpreted in terms of a model of non-thermal escape processes that lead to enhancement in the heavier isotope. We show that these data do not, in fact, strongly constrain the abundance of nitrogen present in Titan's early atmosphere, and that a wide range of initial atmospheric masses (all larger than the present value) can yield the measured enhancement. The enrichment in deuterated methane is now much better determined than it was when Pinto et al. (1986. Nature 319, 388-390) first proposed a photochemical mechanism to preferentially retain the deuterium. We develop a simple linear theory to provide a more reliable estimate of the relative dissociation rates of normal and deuterated methane. We utilize the improved data and models to compute initial methane reservoirs consistent with the observed enhancement. The result of this analysis agrees with an independent estimate for the initial methane abundance based solely on the present-day rate of photolysis and an assumption of steady state. This consistency in reservoir size is necessary but not sufficient to infer that methane photolysis has proceeded steadily over the age of the solar system to produce large quantities of less volatile organics. Our analysis indicates an epoch of early atmospheric escape of nitrogen, followed by a later addition of methane by outgassing from the interior. The results also suggest that Titan's volatile inventory came in part or largely from a circum-Saturnian disk of material more reducing than the surrounding solar nebula. Many of the ambiguities inherent in the present analysis can be resolved through Cassini-Huygens data and a program of laboratory studies on isotopic and molecular exchange processes. The value of, and interest in, the Cassini-Huygens data can be greatly enhanced if such a program were undertaken prior to the prime phase of the mission. PMID:11543194

  13. 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,...

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

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

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

  15. Hot bottom burning in asymptotic giant branch stars and its effect on oxygen isotopic abundances

    NASA Technical Reports Server (NTRS)

    Boothroyd, Arnold I.; Sackmann, I.-JULIANA; Wasserburg, G. J.

    1995-01-01

    A self-consistent calculation of asymptotic giant branch (AGB) evolution was carried out, including nucleosynthesis at the base of the convective envelope (hot bottom burning). Hot bottom burning was found to occur for stars between approximately 4.5 and approximately 7 solar mass, producing envelopes with O-18/O-16 less than or equal to 10(exp -6) and 10(exp -3) approximately less than or equal O-17/O-16 approximately less than or equal to 10(exp -1). The O-17 abundance depends sensitively on the nuclear O-17-destruction rate; this rate is only loosely constrained by the requirement that first and second dredge-up models match O-isotope observations of red giant branch (RGB) stars (Boothroyd, Sackmann, & Wasserburg 1994). In some cases, high mass-loss rates can terminate hot bottom burning before further O-17 enrichment takes place or even before all O-18 is destroyed. These predictions are in accord with the very limited stellar observations of J type carbon stars on the AGB and with some of the circumstellar Al2O3 grains from meteorites. In contrast, precise data from a number of grains and data from most low-mass S and C AGB stars (approximately less than 1.7 solar mass) lie in a region of the O-18/O-16 versus O-17/O-16 diagram that is not accessible by first and second dredge-up or by hot bottom burning. We conclude that for AGB stars, the standard models of stellar evolution are not in accord with these observations. We surmise that an additional mixing mechanism must exist that transports material from the cool bottom of the stellar convective envelope to a depth at which O-18 is destroyed. This 'cool bottom processing' mechanism on the AGB is similar to extra mixing mechanisms proposed to explain the excess C-13 (and depleted C-12) observed in the earlier RGB stage of evolution and the large Li-7 depletion observed in low-mass main-sequence stars.

  16. Oxygen isotopic abundances in the atmospheres of seven red giant stars

    SciTech Connect

    Harris, M.J.; Lambert, D.L.

    1984-10-15

    Abundances ratios of the oxygen isotopes have been measured in ..cap alpha.. Tau, ..beta.. And, ..mu.. Gem, ..cap alpha.. Her, ..beta.. Peg, ..gamma.. Dra, and ..cap alpha.. Boo. In all the stars the /sup 16/O//sup 18/O ratios are similar; the mean value is 475, which is consistent with the solar system value /sup 16/O//sup 18/O = 490. The /sup 16/O//sup 17/O ratios range from approx.1000 for ..beta.. Peg and ..cap alpha.. Boo to /sup 16/O//sup 17/O = 160 for ..beta.. And.

  17. The isotopic abundances of neon, magnesium and silicon nuclei accelerated in solar flares

    NASA Technical Reports Server (NTRS)

    Dietrich, W. F.; Simpson, J. A.

    1980-01-01

    Direct measurements of the relative abundance of the isotopes Ne-20 and Ne-22 are reported along with a preliminary value for the Mg-26/Mg-24 ratio and an upper limit to the abundance of Si-30 in solar flare accelerated nuclei. A Ne-20/Ne-22 ratio of 7.7 plus 2.3 or minus 1.7 is in agreement with the ratio for the component Neon-A found in carbonaceous chondrites, while a preliminary value of 0.22 plus or minus 0.07 for Mg-26/Mg-24 is larger by approximately one standard deviation than the expected ratio of 0.14 given by Cameron (1973).

  18. 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 it feasible to observe its less common isotopologues. As a step in our investigation of C-13 fractionation patterns in the ISM, we here present comparisons between observations of the C-13 fraction in formaldehyde, and chemical fractionation models.

  19. 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.

  20. Sims Analysis of Water Abundance and Hydrogen Isotope in Lunar Highland Plagioclase

    NASA Technical Reports Server (NTRS)

    Hui, Hejiu; Guan, Yunbin; Chen, Yang; Peslier, Anne H.; Zhang, Youxue; Liu, Yang; Rossman, George R.; Eiler, John M.; Neal, Clive R.

    2015-01-01

    The detection of indigenous water in mare basaltic glass beads has challenged the view established since the Apollo era of a "dry" Moon. Since this discovery, measurements of water in lunar apatite, olivine-hosted melt inclusions, agglutinates, and nominally anhydrous minerals have confirmed that lunar igneous materials contain water, implying that some parts of lunar mantle may have as much water as Earth's upper mantle. The interpretation of hydrogen (H) isotopes in lunar samples, however, is controversial. The large variation of H isotope ratios in lunar apatite (delta Deuterium = -202 to +1010 per mille) has been taken as evidence that water in the lunar interior comes from the lunar mantle, solar wind protons, and/or comets. The very low deuterium/H ratios in lunar agglutinates indicate that solar wind protons have contributed to their hydrogen content. Conversely, H isotopes in lunar volcanic glass beads and olivine-hosted melt inclusions being similar to those of common terrestrial igneous rocks, suggest a common origin for water in both Earth and Moon. Lunar water could be inherited from carbonaceous chondrites, consistent with the model of late accretion of chondrite-type materials to the Moon as proposed by. One complication about the sources of lunar water, is that geologic processes (e.g., late accretion and magmatic degassing) may have modified the H isotope signatures of lunar materials. Recent FTIR analyses have shown that plagioclases in lunar ferroan anorthosite contain approximately 6 ppm H2O. So far, ferroan anorthosite is the only available lithology that is believed to be a primary product of the lunar magma ocean (LMO). A possible consequence is that the LMO could have contained up to approximately 320 ppm H2O. Here we examine the possible sources of water in the LMO through measurements of water abundances and H isotopes in plagioclase of two ferroan anorthosites and one troctolite from lunar highlands.

  1. Eocene-Miocene carbon-isotope and floral record from brown coal seams in the Gippsland Basin of southeast Australia

    NASA Astrophysics Data System (ADS)

    Holdgate, Guy R.; McGowran, Brian; Fromhold, Tom; Wagstaff, Barbara E.; Gallagher, Stephen J.; Wallace, Malcolm W.; Sluiter, Ian R. K.; Whitelaw, Michael

    2009-01-01

    The carbon-isotope and palynological record through 580 m thick almost continuous brown coal in southeast Australia's Gippsland Basin is a relatively comprehensive southern hemisphere Middle Eocene to Middle Miocene record for terrestrial change. The carbon isotope δ 13C coal values of these coals range from - 27.7‰ to - 23.2. This isotopic variability follows gymnosperm/angiosperm fluctuations, where higher ratios coincide with heavier δ13C values. There is also long-term variability in carbon isotopes through time. From the Eocene greenhouse world of high gymnosperm-heavier δ13C coal values, there is a progressive shift to lighter δ13C coal values that follows the earliest (Oi1?) glacial events around 33 Ma (Early Oligocene). The overlying Oligocene-Early Miocene brown coals have lower gymnosperm abundance, associated with increased % Nothofagus (angiosperm), and lightening of isotopes during Oligocene cooler conditions. The Miocene palynological and carbon-isotope record supports a continuation to the Oligocene trends until around the late Early Miocene (circa 19 Ma) when a warming commenced, followed by an even stronger isotope shift around 16 Ma that peaked in the Middle Miocene when higher gymnosperm abundance and heavier isotopes prevailed. The cycle between the two major warm peaks of Middle Eocene and Middle Miocene was circa 30 Ma long. This change corresponds to a fall in inferred pCO 2 levels for the same period. The Gippsland data suggest a link between gymnosperm abundance, long-term plant δ13C composition, climatic change, and atmospheric pCO 2. Climatic deterioration in the Late Miocene terminated peat accumulation in the Gippsland Basin and no further significant coals formed in southeast Australia. The poor correspondence between this terrestrial isotope data and the marine isotope record is explained by the dominant control on δ13C by the gymnosperm/angiosperm abundance, although in turn this poor correspondence may reflect palaeoclimate control. From the brown coal seam dating, the coal appears to have accumulated during a considerable part of the allocated 30 Ma Cenozoic time period. These brown coal carbon isotope and palynological data appear to record a more gradual atmospheric carbon isotope change compared to the marine record.

  2. Isotopic anomalies from neutron reactions during explosive carbon burning

    NASA Technical Reports Server (NTRS)

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

    1979-01-01

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

  3. Paleodietary reconstruction using stable isotopes and abundance analysis of bovids from the Shungura Formation of South Omo, Ethiopia.

    PubMed

    Negash, Enquye W; Alemseged, Zeresenay; Wynn, Jonathan G; Bedaso, Zelalem K

    2015-11-01

    Preservation of the stable carbon isotopic composition of fossil tooth enamel enables us to estimate the relative proportion of C3 versus C4 vegetation in an animal's diet, which, combined with analysis of faunal abundance, may provide complementary methods of paleoenvironmental reconstruction. To this end, we analyzed stable carbon isotopic composition (δ(13)C values) of tooth enamel from four bovid tribes (Tragelaphini, Aepycerotini, Reduncini, and Alcelaphini) derived from six members of the Shungura Formation (Members B, C, D, F, G, and L; ages from ca. 2.90-1.05 Ma (millions of years ago) in the Lower Omo Valley of southwestern Ethiopia. The bovids show a wide range of δ(13)C values within taxa and stratigraphic members, as well as temporal changes in the feeding strategies of taxa analyzed throughout the middle to late Pliocene and early Pleistocene. Such variation suggests that the use of actualistic approaches for paleoenvironmental reconstruction may not always be warranted. Alcelaphini was the only taxon analyzed that retained a consistent dietary preference throughout the sequence, with entirely C4-dominated diets. Reduncini had a mixed C3/C4 to C4-dominated diet prior to 2.4 Ma, after which this taxon shifted to a largely C4-dominated diet. Aepycerotini generally showed a mixed C3/C4 diet, with a period of increased C4 diet from 2.5 to 2.3 Ma. Tragelaphini showed a range of mixed C3/C4 diets, with a median value that was briefly nearer the C4 end member from 2.9 to 2.4 Ma but was otherwise towards the C3 end member. These isotopic results, combined with relative abundance data for these bovids, imply that the environment of the Lower Omo Valley consisted of a mosaic of closed woodlands, with riverine forests and open grasslands. However, our data also signify that the overall environment gradually became more open, and that C4 grasses became more dominant. Finally, these results help document the range and extent of environments and potential diets that were available to the four hominin species encountered in the Shungura sequence. PMID:26341031

  4. The evolution of the global selenium cycle: Secular trends in Se isotopes and abundances

    NASA Astrophysics Data System (ADS)

    Stüeken, E. E.; Buick, R.; Bekker, A.; Catling, D.; Foriel, J.; Guy, B. M.; Kah, L. C.; Machel, H. G.; Montañez, I. P.; Poulton, S. W.

    2015-08-01

    The Earth's surface has undergone major transitions in its redox state over the past three billion years, which have affected the mobility and distribution of many elements. Here we use Se isotopic and abundance measurements of marine and non-marine mudrocks to reconstruct the evolution of the biogeochemical Se cycle from ∼3.2 Gyr onwards. The six stable isotopes of Se are predominantly fractionated during redox reactions under suboxic conditions, which makes Se a potentially valuable new tool for identifying intermediate stages from an anoxic to a fully oxygenated world. δ82/78Se shows small fractionations of mostly less than 2‰ throughout Earth's history and all are mass-dependent within error. In the Archean, especially after 2.7 Gyr, we find an isotopic enrichment in marine (+0.37 ± 0.27‰) relative to non-marine samples (-0.28 ± 0.67‰), paired with increasing Se abundances. Student t-tests show that these trends are statistically significant. Although we cannot completely rule out the possibility of volcanic Se addition, these trends may indicate the onset of oxidative weathering on land, followed by non-quantitative reduction of Se oxyanions during fluvial transport. The Paleoproterozoic Great Oxidation Event (GOE) is not reflected in the marine δ82/78Se record. However, we find a major inflection in the secular δ82/78Se trend during the Neoproterozoic, from a Precambrian mean of +0.42 ± 0.45‰ to a Phanerozoic mean of -0.19 ± 0.59‰. This drop probably reflects the oxygenation of the deep ocean at this time, stabilizing Se oxyanions throughout the water column. Since then, reduction of Se oxyanions has likely been restricted to anoxic basins and diagenetic environments in sediments. In light of recent Cr isotope data, it is likely that oxidative weathering before the Neoproterozoic produced Se oxyanions in the intermediate redox state SeIV, whereas the fully oxidized species SeVI became more abundant after the Neoproterozoic rise of atmospheric oxygen.

  5. Locations of marine animals revealed by carbon isotopes

    PubMed Central

    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

  6. 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

  7. The Palaeocene-Eocene carbon isotope excursion: constraints from individual shell planktonic foraminifer records.

    PubMed

    Zachos, James C; Bohaty, Steven M; John, Cedric M; McCarren, Heather; Kelly, Daniel C; Nielsen, Tina

    2007-07-15

    The Palaeocene-Eocene thermal maximum (PETM) is characterized by a global negative carbon isotope excursion (CIE) and widespread dissolution of seafloor carbonate sediments. The latter feature supports the hypothesis that the PETM and CIE were caused by the rapid release of a large mass (greater than 2000Gt C) of 12C-enriched carbon. The source of this carbon, however, remains a mystery. Possible sources include volcanically driven thermal combustion of organic-rich sediment, dissociation of seafloor methane hydrates and desiccation and oxidation of soil/sediment organics. A key constraint on the source(s) is the rate at which the carbon was released. Fast rates would be consistent with a catastrophic event, e.g. massive methane hydrate dissociation, whereas slower rates might implicate other processes. The PETM carbon flux is currently constrained by high-resolution marine and terrestrial records of the CIE. In pelagic bulk carbonate records, the onset of the CIE is often expressed as a single- or multiple-step excursion extending over 10(4) years. Individual planktonic shell records, in contrast, always show a single-step CIE, with either pre-excursion or excursion isotope values, but no transition values. Benthic foraminifera records, which are less complete owing to extinction and diminutive assemblages, show a delayed excursion. Here, we compile and evaluate the individual planktonic shell isotope data from several localities. We find that the most expanded records consistently show a bimodal isotope distribution pattern regardless of location, water depth or depositional facies. This suggests one of several possibilities: (i) the isotopic composition of the surface ocean/atmosphere declined in a geologic instant (<500yr), (ii) that during the onset of the CIE, most shells of mixed-layer planktonic foraminifera were dissolved, or (iii) the abundances or shell production of these species temporarily declined, possibly due to initial pH changes. PMID:17513259

  8. Carbon isotope systematics of a mantle ``hotspot'': a comparison of Loihi Seamount and MORB glasses

    NASA Astrophysics Data System (ADS)

    Exley, R. A.; Mattey, D. P.; Clague, D. A.; Pillinger, C. T.

    1986-06-01

    The carbon isotope geochemistry of glasses from Loihi Seamount has been compared with that of MORB glasses. Stepped heating shows two carbon components in both sample suites: (1) isotopically light carbon ( avg. δ 13C = -26.3‰ ) released < 600°C, ascribed to surficial contamination, and (2) isotopically heavy carbon released > 600°C, regarded as indigenous. The high-temperature component in MORB samples varied from 52 to 169 ppm C, average δ 13C = -6.6‰ , consistent with previous studies (overall MORD average δ 13C = -6.4 ± 0.9‰ ), and new results for Indian Ocean glasses are similar to Atlantic and Pacific Ocean samples. Carbon release profiles produced by stepped heating may be typical of locality, but there are no significant differences in δ 13C values between MORB samples from different areas. Lower yields (17-110 ppm C) correlated with depth in the Loihi samples suggest that they are partially degassed. This degassing has not affected δ 13C values significantly (avg. -5.8‰). Loihi tholeiites have higher δ 13C (avg. -5.6‰) than the alkali basalts (avg. -7.1‰). Carbon abundances correlate well with He concentration data. Comparison of the δ 13C values with trace element and He, Sr, Nd, and Pb isotope data from the literature suggests that the Loihi samples with highest δ 13C have high 3He/ 4He and possibly the least depleted 143Nd/ 144Nd and 87Sr/ 86Sr. The carbon isotope data are consistent with previous models for Loihi involving several mantle sources, lithospheric contamination, and mixing. The slightly higher δ 13C of Loihi tholeiites suggests that the undegassed "plume" component manifested by high 3He/ 4He values might have δ 13C about 1‰ higher than the MORB average.

  9. Measurement of stable carbon isotope ratios of non-methane hydrocarbons and halocarbons

    NASA Astrophysics Data System (ADS)

    Zuiderweg, A. T.

    2012-09-01

    Within the realm of volatile organic compounds, hydrocarbons and halocarbons form a sizable proportion of carbon input to the atmosphere. Within these compound categories, the light non-methane hydrocarbons (NMHC, two to seven carbon atoms) and monocarbon halocarbons have a special place as these have strong, if not exclusive, anthropogenic (human-caused) sources. With common atmospheric molar mixing ratios in the parts-per-trillion (10-12 mole/mole) to parts-per-billion (10-9 mole/mole) range, these trace gases, though decidedly minor constituants of the atmosphere, have diverse consequences due to their atmospheric presence and their removal processes. Effects range from causing ground level air pollution and resulting hazards to health, to contributing to anthropogenic climate change and the destruction of the ozone layer in the stratosphere, among many others. The existance of stable isotopes (otherwise identical atoms with varying amounts of neutrons that do not spontaneously disintegrate) in several elements relevant to atmospheric chemistry and physics is a boon to research. Their presence in molecules is detectable by mass and cause small intra- and intermolecular property changes. These changes range from the physical (e.g. boiling point variation) to the chemical (reaction rate variation) and can influence external interactions as well. The measurement of the ratio of a minor stable isotope of an element to the major one (the stable isotope ratio) can be used to establish source fingerprints, trace the interaction dynamics, and refine the understanding of the relative contribution of sources and sinks to the atmosphere as a whole. The stable minor stable isotope of carbon, 13C, has a natural abundance of approximately 1.1 %. It has a sufficient fractional mass difference from its major isotope as to cause significant effects, making it ideal for measuring the ratios and properties of hydro- and halocarbons. In order to enable a better understanding of the behavior of these compounds in terms of their sources, sinks, inter- and intramolecular processes, it was decided in 2006 to develop an instrument capable of selectively measuring NMHC mixing ratios and stable carbon isotope ratios for use in the laboratory of the Atmospheric Physics and Chemistry Group at Universiteit Utrecht. This thesis documents the successful development, construction, testing and first applications of this stable carbon isotope ratio instrument. It is divided into five chapters, representing the content of three publications and additional material: an introduction; a method section; and applications: analysis of NMHC stable carbon isotopes in urban ambient air, laboratory measurments of the isotope effects in UV degradation of monocarbon chlorofluorocarbons, isotope analysis of diverse gases from firn air samples from Greenland, plus a section on future perspectives

  10. Variations in carbon and nitrogen stable isotopes of cryoconite

    NASA Astrophysics Data System (ADS)

    Takeuchi, N.

    2012-12-01

    Cryoconite is biogenic surface dust on snow and ice, and is commoly observed on glaciers worldwide. Because of their dark coloration, cryoconite substantially reduce surface albedo and accelerate melting of glaciers. Therefore, it is important to understand formation process of cryoconite to evaluate its effect on glacier melting. Although cryoconite consists of mineral particles and organic matter, organic fraction is more important in terms of albedo effect because it is usually darker color and accounts for major part of cryoconite in volume. The organic matter is derived from photosynthetic microbes such as cyanobacteria, and/or from windblown organic matter from ground soil around glaciers. Carbon (C) and nitrogen (N) stable isotopes of the organic matter could be useful to know their sources and to understand their cycles on glaciers. In this study, I analyzed carbon and nitrogen stable isotopes of cryoconite collected from 6 sites of different elevation from May to September on an Alaska glacier (Gulkana Glacier) to know their spatial and seasonal variations. I also analyze those collected from glaciers in Asia and Arctic to compare them among different geographical locations. Results on the Alaska glacier show that C and N stable isotopes of cryoconite organic mater significantly varied among elevations and seasons. C isotope was generally higher in lower elevation, probably due to higher photosynthetic activity in the lower elevation. In contrast, N isotope was constant on the ice area, but was lower in the snow area where the red snow algae were blooming. N isotope may be reflective of nitrogen availavility on the glacier surface. Geograpical comparison shows large variations in C and N isotopes among regions: higher C and N isotopes on Asian glaciers, lower C and N isotopes in Alaska, and lower C and higher N isotopes on Arctic glaciers. The isotope values suggest that algal production is a major carbon source on most of glaciers, but their productivity and nirotogen cycle largely varied among the regions.

  11. 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.

  12. [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.

  13. Abundance, stable isotopic composition, and export fluxes of DOC, POC, and DIC from the Lower Mississippi River during 2006-2008

    NASA Astrophysics Data System (ADS)

    Cai, Yihua; Guo, Laodong; Wang, Xuri; Aiken, George

    2015-11-01

    Sources, abundance, isotopic compositions, and export fluxes of dissolved inorganic carbon (DIC), dissolved and colloidal organic carbon (DOC and COC), and particulate organic carbon (POC), and their response to hydrologic regimes were examined through monthly sampling from the Lower Mississippi River during 2006-2008. DIC was the most abundant carbon species, followed by POC and DOC. Concentration and δ13C of DIC decreased with increasing river discharge, while those of DOC remained fairly stable. COC comprised 61 ± 3% of the bulk DOC with similar δ13C abundances but higher percentages of hydrophobic organic acids than DOC, suggesting its aromatic and diagenetically younger status. POC showed peak concentrations during medium flooding events and at the rising limb of large flooding events. While δ13C-POC increased, δ15N of particulate nitrogen decreased with increasing discharge. Overall, the differences in δ13C between DOC or DIC and POC show an inverse correlation with river discharge. The higher input of soil organic matter and respired CO2 during wet seasons was likely the main driver for the convergence of δ13C between DIC and DOC or POC, whereas enhanced in situ primary production and respiration during dry seasons might be responsible for their isotopic divergence. Carbon export fluxes from the Mississippi River were estimated to be 13.6 Tg C yr-1 for DIC, 1.88 Tg C yr-1 for DOC, and 2.30 Tg C yr-1 for POC during 2006-2008. The discharge-normalized DIC yield decreased during wet seasons, while those of POC and DOC increased and remained constant, respectively, implying variable responses in carbon export to the increasing discharge.

  14. Isotope analyses of molecular and total organic carbon from Miocene sediments

    NASA Astrophysics Data System (ADS)

    Pagani, Mark; Freeman, Katherine H.; Arthur, Michael A.

    2000-01-01

    Carbon-isotope compositions of n-alkanes, pristane and phytane, and total organic carbon were measured and compared against isotopic trends of coeval alkadienones from Miocene sediments containing very low organic-carbon contents. Compound-specific isotope analysis of n-alkanes and isoprenoid lipids, in conjunction with abundance distributions of n-alkanes reveal the influence of terrestrially derived organic carbon at all sites analyzed. In general, n-alkanes are derived from allochthonous sources with the exception of n-C 37 from site 516, which appears genetically related to coeval alkadienones. Further, pristane and phytane from pelagic sites 608 and 516 apparently derive from terrestrial sources as well, although a marine origin cannot be excluded. δ TOC values lack a coherent relationship to %TOC and δ 13C 37:2. Differential alteration and mixing of diverse isotopic signals most likely contribute to temporal variation and spatial differences in δ TOC. Therefore, when working with sediments from oligotrophic settings, we do not recommend δ TOC as an indicator of phytoplankton δ 13C values.

  15. Carbon Abundances for Metal-Poor Stars Based on Medium-Resolution Spectra

    NASA Astrophysics Data System (ADS)

    Rossi, Silvia; Beers, Timothy C.; Sneden, Chris

    Several recent papers have pointed out that the frequency of carbon-enhanced stars in the Galaxy appears to increase at the lowest metal abundances, which may provide an important clue to the early chemical evolution of the Milky Way. The large objective-prism survey of Beers and collaborators has discovered numerous additional carbon-rich stars at extremely low metallicity. First estimates of the carbon abundances for these stars can be obtained by application of spectral-synthesis techniques in combination with moderate-resolution spectra collected during the course of the survey. We calibrate our carbon abundance estimates by comparison with previous determinations for metal-deficient dwarf and giant stars reported in the literature. Using this approach, we are able to reproduce the literature carbon abundances with an accuracy of ~0.15 dex. We then apply this technique to estimate the abundance of carbon in a sample of 56 stars identified as carbon-rich, relative to stars of similar metal abundance, in the sample of strong G-band stars discussed by Beers, Preston, & Shectman. We combine our new measurements with other data for metal-deficient stars to study the range of carbon abundances in stars over the metallicity interval -4.0 <= feh <= 0.0.

  16. Stable carbon isotope fractionations of the hyperthermophilic crenarchaeon Metallosphaera sedula.

    PubMed

    van der Meer, M T; Schouten, S; Rijpstra, W I; Fuchs, G; Sinninghe Damsté, J S

    2001-03-01

    The stable carbon isotopic compositions of the inorganic carbon source, bulk cell material, and isoprenoid lipids of the hyperthermophilic crenarchaeon Metallosphaera sedula, which uses a 3-hydroxypropionate-like pathway for autotrophic carbon fixation, have been measured. Bulk cell material was approximately 3 per thousand enriched in 13C relative to the dissolved inorganic carbon, and 2 per thousand depleted in 13C relative to isoprenoid membrane lipids. The isotope data suggested that M. sedula uses mainly bicarbonate rather than CO(2) as inorganic carbon source, which is in accordance with a 3-hydroxypropionate-like carbon fixation pathway. To the best of our knowledge this is the first report of 13C fractionation effects of such a hyperthermophilic crenarchaeon. PMID:11257550

  17. Paleogene plants fractionated carbon isotopes similar to modern plants

    NASA Astrophysics Data System (ADS)

    Diefendorf, Aaron F.; Freeman, Katherine H.; Wing, Scott L.; Currano, Ellen D.; Mueller, Kevin E.

    2015-11-01

    The carbon isotope composition (δ13 C) of terrestrial plant biomarkers, such as leaf waxes and terpenoids, provides insights into past carbon cycling. The δ13 C values of modern plant biomarkers are known to be sensitive to climate and vegetation type, both of which influence fractionation during lipid biosynthesis by altering plant carbon supply and its biochemical allocation. It is not known if fractionation observed in living plants can be used to interpret fossil lipids because plant biochemical characteristics may have evolved during the Cenozoic in response to changes in global climate and atmospheric CO2. The goal of this study was to determine if fractionation during photosynthesis (Δleaf) in the Paleogene was consistent with expectations based on living plants. To study plant fractionation during the Paleogene, we collected samples from eight stratigraphic beds in the Bighorn Basin (Wyoming, USA) that ranged in age from 63 to 53 Ma. For each sample, we measured the δ13 C of angiosperm biomarkers (triterpenoids and n-alkanes) and, abundance permitting, conifer biomarkers (diterpenoids). Leaf δ13 C values estimated from different angiosperms biomarkers were consistently 2‰ lower than leaf δ13 C values for conifers calculated from diterpenoids. This difference is consistent with observations of living conifers and angiosperms and the consistency among different biomarkers suggests ancient εlipid values were similar to those in living plants. From these biomarker-based δ13Cleaf values and independent records of atmospheric δ13 C values, we calculated Δleaf. These calculated Δleaf values were then compared to Δleaf values modeled by applying the effects that precipitation and major taxonomic group in living plants have on Δleaf values. Calculated and modeled Δleaf values were offset by less than a permil. This similarity suggests that carbon fractionation in Paleogene plants changed with water availability and major taxonomic group to about the same degree it does today. Further, paleoproxy data suggest at least two of the stratigraphic beds were deposited at times when pCO2 levels were higher than today. Biomarker data from these beds are not consistent with elevated Δleaf values, possibly because plants adapted carbon uptake and assimilation characteristics to pCO2 changes over long timescales.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  19. Submicron Measurements of Mg Isotopes in Biogenic Carbonates Using Laser Ablation-MC-ICPMS: New Window into Biomineralisation

    NASA Astrophysics Data System (ADS)

    Sadekov, A.; Lloyd, N. S.; Misra, S.; Funcke, A.; Shuttleworth, S.; Langer, G.; Bijma, J.; Elderfield, H.

    2014-12-01

    Magnesium is one of the most abundant elements in the earth's crust and in seawater. Fractionation of its stable isotopes has been shown to be useful indicators of many geological, chemical and biological processes. For example, biogenic carbonates display ~5‰ range of d26Mg values, which is attributed to variable degree of biological control on Mg ions during biomineralisation. Understanding this biological control is essential for developing proxies based on biogenic carbonates. Current methods of magnesium isotope measurements in carbonates are often time consuming and require relatively large volumes of samples. In this work, we present a new approach of measuring Mg isotopes in biogenic carbonates using Laser Ablation MC-ICP-MS. We will show that this microanalytical approach provides accurate and relatively fast measurements of Mg isotopes in biological carbonate with precision down to 0.2‰ (1sd). We will also present examples on how this new method can provide additional information about foraminiferal biomineralisation. For example, we will demonstrate submicron variation in Mg isotopes across shells of Orbulina universa, which are linked to high and low Mg/Ca layers in this species. We will also report changes in Mg isotope composition of benthic foraminifera Amphistegina sp. cultured in seawater with different Mg/Ca values. Both examples will be used to draw attention to the complexity and possibilities of multiple mechanisms of Mg incorporation into biogenic carbonates during biomineralisation.

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

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

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

  1. The early Cretaceous carbon- and oxygen-isotope record

    NASA Astrophysics Data System (ADS)

    Grocke, D. R.; Coccioni, R.; Price, G. D.; Arthur, M. A.

    2003-04-01

    Bulk-carbonate carbon- and oxygen-isotope analyses have been conducted on marlstones from a biostratigraphically-continuous section (Berriasian-Aptian) from Ro Argos, SE Spain. The stratigraphic succession at Ro Argos consists of rhythmic limestones with a bed thickness between 0.5-75cm that are inter-bedded with marlstones with a thickness between 0.005-1m. The limestone beds through the succession are considered to be the result of differential dissolution and cementation during diagenesis, and so only the marlstones have been analyzed for isotopic ratios. Carbon- and oxygen-isotope ratios through the entire section show both short- and long-term variation, although only the major shifts will be discussed in this abstract. Carbon-isotope ratios fluctuate between -1 ppm and +1.2 ppm during the Berriasian and Lower Valanginian, with a rapid positive excursion at the base of the Upper Valanginian to +2.6 ppm. Values subsequently decline gradually towards background values (+0.4 ppm to +1.6 ppm) during the Hauterivian. From the mid-Barremian carbon-isotope ratios fluctuate in two major cycles between -1 ppm to +2.2 ppm. The Lower Aptian records a major negative excursion from a background of +1.8 ppm to -2.5 ppm (that is equivalent to OAE1a), followed by a rapid shift to +3.3 ppm. No correlation is found between carbon- and oxygen-isotope ratios and although there may be some diagenetic overprint we interpret the oxygen-isotope curve in terms of temporal shifts in palaeotemperature; the oxygen-isotope range for the entire stratigraphic section is between -4.6 ppm to -1.8 ppm. The Berriasian has relatively positive oxygen-isotope ratios (cool), although by the Lower Valanginian the values become more negative (warm) peaking in the Upper Valanginian. Oxygen-isotope ratios gradually increase throughout the remainder of the stratigraphic section to a peak in the mid-Barremian (cool), followed by a rapid drop to more negative (warm) ratios and increase once again to more positive ratios (cool) in the Lower Aptian. Although global sea-level changes may also affect oxygen-isotope ratios it is intriguing to note that both warm periods coincide with the initiation of large igneous provinces (Paran-Etendeka, Valanginian; Ontong Java Plateau, Late Barremian).

  2. Detection of exogenous hydrocortisone in horse urine by gas chromatography-combustion-carbon isotope ratio mass spectrometry.

    PubMed

    Aguilera, R; Becchi, M; Mateus, L; Popot, M A; Bonnaire, Y; Casabianca, H; Hatton, C K

    1997-11-21

    A gas chromatography-combustion-isotope ratio mass spectrometry method for confirmation of hydrocortisone abuse in horseracing and equine sports is proposed. Urinary hydrocortisone was converted to a bismethylenedioxy derivative which presents good gas chromatographic properties and brings an extra carbon contribution of only two carbon atoms. Synthetic hydrocortisone has a different 13C abundance from that of natural urinary horse hydrocortisone and the difference is significant, therefore exogenous and endogenous hydrocortisone can be distinguished. PMID:9449559

  3. Carbon and oxygen isotope composition of carbonates from an L6 chondrite: Evidence for terrestrial weathering from the Holbrook meteorite

    NASA Technical Reports Server (NTRS)

    Socki, R. A.; Gibson, E. K.; Jull, A. J. T.; Karlsson, H. R.

    1991-01-01

    Terrestrial weathering in meteorites is an important process which alters pristine elemental and isotopic abundances. The Holbrook L6 chondrite fell in 1912. Material was recovered at the time of the fall, in 1931, and 1968. The weathering processes operating on the freshly fallen meteorite in a semi-arid region of northeastern Arizona have been studied after a ground residence of 19 and 56 years. It has been shown that a large portion of the carbonate material in 7 Antarctic ordinary chondrites either underwent extensive isotopic exchange with atmospheric CO2, or formed recently in the Antarctic environment. In fact it has been demonstrated that hydrated Mg-carbonates, nesquehonite and hydromagnesite, formed in less than 40 years on LEW 85320. In order to help further constrain the effects of terrestrial weathering in meteorites, the carbon and oxygen isotopes extracted from carbonates of three different samples of Holbrook L6: a fresh sample at the time of the fall in 1912, a specimen collected in 1931, and a third specimen collected at the same site in 1968.

  4. Carbon and Hydrogen Stable Isotope Fractionation Associated with the Aerobic and Anaerobic Degradation of Saturated and Alkylated Aromatic Hydrocarbons.

    PubMed

    Musat, Florin; Vogt, Carsten; Richnow, Hans H

    2016-01-01

    Saturated hydrocarbons (alkanes) and alkylated aromatic hydrocarbons are abundant environmental compounds. Hydrocarbons are primarily removed from the environment by biodegradation, a process usually associated with moderate carbon and significant hydrogen isotope fractionation allowing monitoring of biodegradation processes in the environment. Here, we review the carbon and hydrogen stable isotope fractionation associated with the cleavage of C-H bonds at alkyl chains of hydrocarbons. Propane, n-butane and ethylbenzene were used as model components for alkyl moieties of aliphatic and aromatic hydrocarbons with emphasis on the cleavage of the C-H bond without the involvement of molecular oxygen. The carbon and hydrogen isotope fractionation factors were further used to explore the diagnostic potential for characterizing the mode of bond cleavage under oxic and anoxic conditions. x039B; factors, calculated to correlate carbon and hydrogen fractionation, allowed to distinguish between aerobic and anaerobic biodegradation processes in the environment. PMID:26959878

  5. Isotopic variation of carbonate cements sampled by different techniques

    NASA Astrophysics Data System (ADS)

    Psomiadis, D.; Dotsika, E.; Albanakis, K.; Zisi, N.

    2009-04-01

    Several studies have been carried out using the isotopic signature of carbonate cements in the marine-phreatic environment. This study aims to compare the isotopic composition of specific levels inside a carbonate formation like beachrock. In particular, samples from the same level were analyzed, differing from each other on the sampled material. Bulk rock sample, macroscopic and microscopic selection, stirred and dried material are some of the selected methods of sample extraction for isotopic analysis. The results are plotted on diagrams and compared, in order to evaluate the reliability and suitability of sampling methods for isotopic analysis. Samples were taken from the same level of the formation in order to avoid differences of values originated in different precipitation conditions.

  6. Does burial diagenesis reset pristine isotopic compositions in paleosol carbonates?

    NASA Astrophysics Data System (ADS)

    Bera, M. K.; Sarkar, A.; Tandon, S. K.; Samanta, A.; Sanyal, P.

    2010-11-01

    Sedimentological study of early Oligocene continental carbonates from the fluvial Dagshai Formation of the Himalayan foreland basin, India resulted in the recognition of four different types namely, soil, palustrine, pedogenically modified palustrine and groundwater carbonates. Stable oxygen and carbon isotopic ( δ18O and δ13C) analyses of fabric selective carbonate microsamples show that although the pristine isotopic compositions are largely altered during deep-burial diagenesis, complete isotopic homogenization does not occur. δ18O and δ13C analyses of ~ 200 calcrete and palustrine carbonates from different stratigraphic horizons and comparison with δ18O of more robust bioapatite (fossil vertebrate tooth) phase show that dense micrites (~ > 70% carbonate) invariably preserve the pristine δ18O value (mean) of ~ - 9.8‰, while altered carbonates show much lower δ18O value ~ - 13.8‰. Such inhomogeneity causes large intra-sample and intra-soil profile variability as high as > 5‰, suggesting that soils behave like a closed system where diagenetic overprinting occurs in local domains. A simple fluid-rock interaction model suggests active participation of clay minerals to enhance the effect of fluid-rock ratio in local domains during diagenesis. This places an upper limit of 70% micrite concentration above which the effect of diagenetic alteration is minimal. Careful sampling of dense micritic part of the soil carbonate nodules, therefore, does provide pristine isotopic composition and it is inappropriate, as proposed recently, to reject the paleoclimatic potential of all paleosol carbonates affected by burial diagenesis. Based on pristine δ13C value of - 8.8 ± 0.2‰ in soil carbonates an atmospheric CO 2 concentration between ~ 764 and ~ 306 ppmv is estimated for the early Oligocene (~ 31 Ma) Dagshai time. These data show excellent agreement between two independent proxy records (viz. soil carbonate and marine alkenone) and support early Oligocene survival of the Antarctic ice sheet.

  7. 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 Proterozoic seawater. Within the Damara basin, carbon-isotopic compositions of carbonates provide a potentially useful tool for the correlation of units between the Kalahari and Congo cratons. Carbonates depleted in 13C were deposited during and immediately following three separate glacial episodes in Namibia. The correspondence between ice ages and negative delta 13C excursions may reflect the effects of lowered sea levels; enhanced circulation of deep, cold, O2-rich seawater; and/or the upwelling of 13C-depleted deep water. Iron-formation is additionally associated with one of the glacial horizons, the Chuos tillite. Carbon-13 enriched isotopic abundances in immediately pre-glacial carbonates suggest that oceanographic conditions favored high rates of organic burial. It is likely that marine waters were stratified, with deep waters anoxic. A prolonged period of ocean stratification would permit the build-up of ferrous iron, probably from hydrothermal sources. At the onset of glaciation, upwelling would have brought 13C-depleted and iron-rich deep water onto shallow shelves where contact with cold, oxygenated surface waters led to the precipitation of ferric iron. PMID:11538647

  8. 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 Proterozoic seawater. Within the Damara basin, carbon-isotopic compositions of carbonates provide a potentially useful tool for the correlation of units between the Kalahari and Congo cratons. Carbonates depleted in 13C were deposited during and immediately following three separate glacial episodes in Namibia. The correspondence between ice ages and negative delta 13C excursions may reflect the effects of lowered sea levels; enhanced circulation of deep, cold, O2-rich seawater; and/or the upwelling of 13C-depleted deep water. Iron-formation is additionally associated with one of the glacial horizons, the Chuos tillite. Carbon-13 enriched isotopic abundances in immediately pre-glacial carbonates suggest that oceanographic conditions favored high rates of organic burial. It is likely that marine waters were stratified, with deep waters anoxic. A prolonged period of ocean stratification would permit the build-up of ferrous iron, probably from hydrothermal sources. At the onset of glaciation, upwelling would have brought 13C-depleted and iron-rich deep water onto shallow shelves where contact with cold, oxygenated surface waters led to the precipitation of ferric iron.

  9. Investigation of tubular handling of bicarbonate in man. A new approach utilizing stable carbon isotope fractionation.

    PubMed Central

    Burbea, Z H; Luz, B; Lazar, B; Winaver, J; Better, O S

    1983-01-01

    Two alternative mechanisms have been proposed for tubular reabsorption of bicarbonate: (a) H+ secretion and CO2 reabsorption and (b) direct reabsorption of HCO-3. In an attempt to differentiate between the two mechanisms, the present study utilized the natural abundance of stable carbon isotopes (13C, 12C) in the urinary total CO2. This novel methodology used mass spectrometric analysis of 13C/12C ratios in urinary total CO2 under normal conditions and during acetazolamide treatment. Blood and respiratory CO2 were analyzed to yield reference values. The results demonstrate that alkaline urine is preferentially enriched with 13C relative to the blood. It is suggested that this fractionation results from reaction out of isotopic equilibrium in which HCO-3 converts to CO2 during the reabsorption process in the distal nephron. The presence of carbonic anhydrase in the proximal nephron results in rapid isotopic exchange between CO2 and HCO-3 and keeps them in isotopic equilibrium. The ratio of urinary 13C/12C increases strikingly after acetazolamide administration and consequent inhibition of carbonic anhydrase in the proximal tubule. Although it is possible that in the latter case high HCO-3 generates the CO2 (ampholyte effect), the isotope fractionation indicates that CO2 rather than HCO-3 is reabsorbed. In contrast, at low urinary pH and total CO2 values, the carbon isotope composition approaches that of blood CO2. This indicates rapid CO2 exchange between urine and blood, through luminal membrane highly permeable to CO2. These results could be anticipated by a mathematical model constructed to plot 13C concentration of urinary total CO2. It is concluded that the mechanism of HCO-3 reclamation in man (and, by inference, in other mammals as well) works by conversion of HCO-3 to CO2 and reabsorption of CO2. PMID:6417168

  10. The evolution of carbon, sulphur and titanium isotopes from high redshift to the local Universe

    NASA Astrophysics Data System (ADS)

    Hughes, G. L.; Gibson, B. K.; Carigi, L.; Snchez-Blzquez, P.; Chavez, J. M.; Lambert, D. L.

    2008-11-01

    Recent observations of carbon, sulphur and titanium isotopes at redshifts z~1 and in the local stellar disc and halo have opened a new window into the study of isotopic abundance patterns and the origin of the chemical elements. Using our Galactic chemical evolution code GETOOL, we have examined the evolution of these isotopes within the framework of a Milky Way-like system. We have three aims in this work: first, to test the claim that novae are required, in order to explain the carbon isotope patterns in the Milky Way; secondly, to test the claim that sulphur isotope patterns at high redshift require an initial mass function (IMF) biased towards massive stars; and thirdly, to test extant chemical evolution models against new observations of titanium isotopes that suggest an anti-correlation between trace-to-dominant isotopes with metallicity. Based upon our dual-infall galactic chemical evolution modelling of a Milky Way-like system and the subsequent comparison with these new and unique data sets, we conclude the following: novae are not required to understand the evolution of 12C/13C in the solar neighbourhood; a massive star-biased IMF is consistent with the low ratios of 12C/13C and 32S/34S seen in one high-redshift late-type spiral, but the consequent super-solar metallicity prediction for the interstellar medium in this system seems highly unlikely; and deficient isotopes of titanium are predicted to correlate positively with metallicity, in apparent disagreement with the new data sets; if confirmed, classical chemical evolution models of the Milky Way (and the associated supernovae nucleosynthetic yields) may need a substantial overhaul to be made consistent.

  11. The Carboniferous carbon isotope record from sedimentary organic matter: can we disentangle the carbon cycle?

    NASA Astrophysics Data System (ADS)

    Davies, S. J.; Bennett, C. E.; Leng, M. J.; Kearsey, T.; Marshall, J. E.; Millward, D.; Reeves, E. J.; Snelling, A.; Sherwin, J. E.

    2014-12-01

    A comprehensive analysis of the δ13C composition of sedimentary organic matter from Euramerican Carboniferous successions indicates there are significant shifts in δ13C through this key time interval. Our studies have revealed that, at an individual location, the source and delivery mechanism of the sediment contribute to the type of organic matter preserved and, in turn this influences the measured δ13C values from bulk sedimentary organic matter of organic matter. In general, where marine-derived organic matter is dominant in these Carboniferous successions then δ13C values are characteristically lower compared to the higher values encountered where terrestrial plant-derived material is most abundant. The implication of these observations is that an apparent carbon isotope excursion identified from the bulk organic matter may reflect a change in transport processes, or depositional environment, rather than a perturbation in the global carbon cycle. In our most recent studies, however, we compare δ13C values from specific wood fragments and bulk sedimentary organic matter from non-marine, marine basinal, and marine shelfal successions from the earliest Mississippian through to the early Pennsylvanian. These data indicate that early Mississippian δ13C of organic matter is far less negative (around -22%0) than material of Late Mississippian age (around -26%0), however by the early Pennsylvanian, δ13C values return to -22%0. There are some δ13C data from brachiopod carbonate from this time interval and similar shifts are indicated. Our data are beginning to address whether we can identify a primary carbon cycle signal from the Carboniferous record using δ13C from a range of sedimentary environments. If we can, there are still questions around what the record is telling us about the global carbon cycle during a period when plant groups, including lycopods and seed ferns, rapidly diversified.

  12. Major and trace element abundances, and Sr and Nd isotopic composition of Carbonatites from Amba Dongar, Gujarat, India

    NASA Astrophysics Data System (ADS)

    Chandra, Jyoti; Paul, Debajyoti; Viladkar, Shrinivas G.; Sensarma, Sarajit

    2015-04-01

    Despite significant progress during the last decade, the petrogenesis of carbonatites is still highly debated regarding the exact mechanism of carbonatite magma generation (fractional crystallization of carbonated-silicate magmas, liquid immiscibility of carbonated-silicate magmas, partial melting of carbonated mantle peridotite or carbonated lherzolitic mantle) and its evolution. The Amba Dongar carbonatite complex in Chhota Udaipur district, Gujarat is the youngest Indian carbonatite complex, which intruded into the ~ 90 Ma Bagh sandstones and limestone and 68-65 Ma Deccan flood basalts. The emplacement age (40Ar/39Ar age of 65±0.3 Ma; Ray and Pande, 1999) coincides with the age of main pulse of Deccan flood basalts at ca. 65 Ma. We report new geochemical data (major oxide and trace element abundances, and Sr and Nd isotopic ratios) on 23 carbonatite samples from Amba Dongar. The Amba Dongar carbonatite complex consists of carbonatite (sövite, and ankerite), and associated nephelinite, phonolite, and both pre- and post-carbonatite basalts. Detailed minerology of carbonatite include dominant calcite along with pyrochlore, apatite, magnetite, aegirine-augite and accessory phases. Apatite crystals are observed in carbonatite as well as in nephelinite. In sövites, apatite occur in various forms including cumulus, clusters and scattered within and along the boundary of calcite crystals. Two generation of apatite crystals are commonly observed in sövite and nephelinite; textural changes suggest presence of different five pulses of sövitic magma during the emplacement of the sövite ring dike. Bulk major oxides and trace element (including REEs) compositions of carbonatites and associated silicate rocks are determined by WD-XRF and ICP-MS, respectively. Major oxides abundances are consistent with the already available data on the Amba Dongar carbonatite complex. Trace element concentrations for the sövite reveals high concentrations of Sr (929-7476 ppm), Ba (344-52072 ppm) and Nb (35-2115 ppm). The ankeritic carbonatites are extremely enriched in the incompatible trace elements (e.g., ~7-32 times higher Ba, highest REE ~40,000 ppm and ~600 ppm of Th). Chondrite-normalized REE patterns show high degree of LREE enrichment suggesting low-degree partial melting of the source. The chondrite normalized La/Yb ratio of sövite and ankeritic carbonatite vary in the range 70-411. The radiogenic Sr-Nd isotopic composition of sövites (87Sr/86Sr: 0.7055-0.7066; ɛNd: -6.0 to -2.2) and ankerites (0.7058-0.7081; -3.8 to -1.9) reveal more isotopic variability compared to the available data (sövites 0.7054-0.706; -2.5 to -1.5; ankerites 0.7056-0.7065; -2.5 to -1.5). It is likely that EM I and II type sources are involved in the generation of Amba Dongar carbonatite complex. More data on carbonatites and associated silicate rocks will be helpful to establish the composition of parental carbonatite melts, depth of generation (lithosphere vs asthenosphere), their spatial relation with associated silicate rocks, and the evolution of the primary carbonatite melt over time.

  13. Isotopic composition of carbon and nitrogen in ureilitic fragments of the Almahata Sitta meteorite

    NASA Astrophysics Data System (ADS)

    Downes, H.; Abernethy, F. A. J.; Smith, C. L.; Ross, A. J.; Verchovsky, A. B.; Grady, M. M.; Jenniskens, P.; Shaddad, M. H.

    2015-02-01

    This study characterizes carbon and nitrogen abundances and isotopic compositions in ureilitic fragments of Almahata Sitta. Ureilites are carbon-rich (containing up to 7 wt% C) and were formed early in solar system history, thus the origin of carbon in ureilites has significance for the origin of solar system carbon. These samples were collected soon after they fell, so they are among the freshest ureilite samples available and were analyzed using stepped combustion mass spectrometry. They contained 1.2-2.3 wt% carbon; most showed the major carbon release at temperatures of 600-700 °C with peak values of δ13C from -7.3 to +0.4‰, similar to literature values for unbrecciated ("monomict") ureilites. They also contained a minor low temperature (≤500 °C) component (δ13C = ca -25‰). Bulk nitrogen contents (9.4-27 ppm) resemble those of unbrecciated ureilites, with major releases mostly occurring at 600-750 °C. A significant lower temperature release of nitrogen occurred in all samples. Main release δ15N values of -53 to -94‰ fall within the range reported for diamond separates and acid residues from ureilites, and identify an isotopically primordial nitrogen component. However, they differ from common polymict ureilites which are more nitrogen-rich and isotopically heavier. Thus, although the parent asteroid 2008TC3 was undoubtedly a polymict ureilite breccia, this cannot be deduced from an isotopic study of individual ureilite fragments. The combined main release δ13C and δ15N values do not overlap the fields for carbonaceous or enstatite chondrites, suggesting that carbon in ureilites was not derived from these sources.

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

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

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

  15. The link between assimilation and below-ground processes - stable isotopes as tools to assess carbon transfer

    NASA Astrophysics Data System (ADS)

    Gessler, A.; Wingate, L.; Ogeé, J.; Offermann, C.; Kodama, N.

    2011-12-01

    At present, there is lack of knowledge on how plant physiological processes, the transfer of carbon within the plant, carbon storage and remobilization in the plant tissues as well as the release of carbon from the roots to the soil interact with ecosystem-scale processes. On the background of global climate change, we need to mechanistically link plant physiology, CO2 net exchange between ecosystems and the atmosphere and plant biomass accumulation. This is the basis for predicting productivity of forests as well as their carbon sequestration potential in future. This paper will give an overview on how stable isotope studies can give insights into the fate of newly assimilated carbon transported within trees and transferred to the soil and atmosphere. The paper includes assessments characterizing temporal and spatial variation in the natural abundance of carbon and oxygen isotopes or applying isotopically enriched tracers. In addition, it highlights the fact that the stable isotope composition of assimilates transported within the plant contains important time integrated information on environmental conditions, leaf physiology, and post-photosynthetic metabolism. The paper on the one hand focuses on the fast turn over carbon pools, which fuel plant respiration and soil microbial activity and on the other hand explores the transfer of the isotope information to long-lived compounds in plant archives such as tree rings.

  16. 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.

  17. Carbon and oxygen abundances across the Hertzsprung gap

    SciTech Connect

    Adamczak, Jens; Lambert, David L. E-mail: dll@astro.as.utexas.edu

    2014-08-10

    We derived atmospheric parameters and spectroscopic abundances for C and O for a large sample of stars located in the Hertzsprung gap in the Hertzsprung-Russell diagram in order to detect chemical peculiarities and get a comprehensive overview of the population of stars in this evolutionary state. We have observed and analyzed high-resolution spectra (R = 60,000) of 188 stars in the mass range 2-5 M{sub ☉} with the 2.7 m Harlan J. Smith Telescope at the McDonald Observatory including 28 stars previously identified as Am/Ap stars. We find that the C and O abundances of the majority of stars in the Hertzsprung gap are in accordance with abundances derived for local lower-mass dwarfs but detect expected peculiarities for the Am/Ap stars. The C and O abundances of stars with T{sub eff} < 6500 K are slightly lower than for the hotter objects but the C/O ratio is constant in the analyzed temperature domain. No indication of an alteration of the C and O abundances of the stars by mixing during the evolution across the Hertzsprung gap could be found before the homogenization of their atmospheres by the first dredge-up.

  18. 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

  19. Temperature dependence of carbon isotope fractionation in CAM plants

    SciTech Connect

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

    1985-09-01

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

  20. A robust method for ammonium nitrogen isotopic analysis in freshwater and seawater at natural abundance levels

    NASA Astrophysics Data System (ADS)

    Zhang, L.; Altabet, M. A.; Wu, T.; Hadas, O.

    2006-12-01

    Natural ammonium N isotopic abundance has been increasingly used in studies of marine and freshwater biogeochemistry. However, current methods are time-consuming, subject to interference from DON, and not reliable at low concentrations. Our new method for determining the δ15N of ammonium overcomes these difficulties by employing the oxidation of ammonium to nitrite followed by conversion of nitrite to nitrous oxide. In the first step, ammonium is quantitatively oxidized by hypobromite at pH~12. After the addition of sodium arsenite to consume excess hypobromite, yield is verified by colorimetric NO2-measurement using sulfanilamide and naphthyl ethylenediamine (NED). Nitrite is further reduced to N2O by a 1:1 sodium azide and acetic acid buffer solution using previously established procedures. Buffer concentration can be varied according to sample matrix to ensure that a reaction pH between 2 and 4 is reached. The product nitrous oxide is then isotopically analyzed using a continuous flow purge and cryogenic trap system coupled to an isotope ratio mass spectrometer. Reliable δ15N values (±0.31‰) are obtained over a concentration range of 0.5 μM to 20 μM using 20 ml volumes of either fresh or seawater samples. Reagent blanks are very low, about 0.05 μM. There is no interference from any of the nitrogen containing compounds tested except short chain aliphatic amino acid (i.e. glycine) which typically are not present at sufficiently high environmental concentrations to pose a problem.

  1. Abundance and isotopic composition of noble gases in metal and graphite of the Bohumilitz IAB iron meteorite

    NASA Astrophysics Data System (ADS)

    Maruoka, Teruyuki; Matsuda, Jun-Ichi; Kurat, Gero

    2001-05-01

    Abundances and isotopic compositions of noble gases in metal and graphite of the Bohumilitz IAB iron meteorite were measured. The abundance ratios of spallogenic components in metal reveal a 3He deficiency which is due to the diffusive loss of parent isotopes, i.e., tritium (Tilles, 1963; Schultz, 1967). The diffusive loss likely has been induced by thermal heating by the Sun during cosmic ray exposure (( 160 My; Lavielle et al., 1999). Thermal process such as impact-induced partial loss may have affected the isotopic composition of spallogenic Ne. The 129Xe/131Xe ratio of cosmogenic components in the metal indicates an enhanced production of epi-thermal neutrons. The abundance ratios of spallogenic components in the graphite reveal that it contained small amounts of metal and silicates. The isotopic composition of heavy noble gases in graphite itself was obtained from graphite treated with HF/HCl. The isotopic composition of the etched graphite shows that it contains two types of primordial Xe, i.e., Q-Xe and El Taco Xe. The isotopic heterogeneity preserved in the Bohumilitz graphite indicates that the Bohumilitz graphite did not experience any high(temperature event and, consequently, must have been emplaced into the metal at subsolidus temperatures. This situation is incompatible with an igneous model as well as the impact melting models for the IAB-IIICD iron meteorites as proposed by Choi et al. (1995) and Wasson et al. (1980).

  2. Carbon Abundance Plateaus among Carbon-Enhanced Metal-Poor Stars

    NASA Astrophysics Data System (ADS)

    Yoon, Jinmi; He, Siyu; Placco, Vinicius; Carollo, Daniela; Beers, Timothy C.

    2016-01-01

    A substantial fraction of low-metallicity stars in the Milky Way, the Carbon-Enhanced Metal-Poor (CEMP) stars, exhibit enhancements of their carbon-to-iron relative to the solar value ([C/Fe] > +0.7). They can be divided into several sub-classes, depending on the nature and degree of the observed enhancements of their neutron-capture elements, providing information on their likely progenitors. CEMP-s stars (which exhibit enhanced s-process elements) are thought to be enhanced by mass transfer from an evolved AGB companion, while CEMP-no stars (which exhibit no over-abundances of neutron-capture elements) appear to be associated with explosions of the very first generations of stars. High-resolution spectroscopic analyses are generally required in order to make these sub-classifications.Several recent studies have suggested the existence of bimodality in the distribution of absolute carbon abundances among CEMP stars -- most CEMP-no stars belong to a low-C band ((A(C) ˜ 6.5), while most CEMP-s stars reside on a high-C band (A(C) ˜ 8.25). The number of CEMP stars considered by individual studies is, however, quite small, so we have compiled all available high-resolution spectroscopic data for CEMP stars, in order to further investigate the existence of the claimed carbon bi-modality, and to consider what can be learned about the progenitors of CEMP-s and CEMP-no stars based on the observed distribution of A(C) on the individual plateaus.We acknowledge partial support from the grant PHY 14-30152; Physics Frontier Center/JINA Center for the Evolution of the Elements (JINA-CEE), awarded by the US National Science Foundation.

  3. ANALYSIS OF RICIN TOXIN PREPARATIONS FOR CARBOHYDRATE AND FATTY ACID ABUNDANCE AND ISOTOPE RATIO INFORMATION

    SciTech Connect

    Wunschel, David S.; Kreuzer-Martin, Helen W.; Antolick, Kathryn C.; Colburn, Heather A.; Moran, James J.; Melville, Angela M.

    2009-12-01

    This report describes method development and preliminary evaluation for analyzing castor samples for signatures of purifying ricin. Ricin purification from the source castor seeds is essentially a problem of protein purification using common biochemical methods. Indications of protein purification will likely manifest themselves as removal of the non-protein fractions of the seed. Two major, non-protein, types of biochemical constituents in the seed are the castor oil and various carbohydrates. The oil comprises roughly half the seed weight while the carbohydrate component comprises roughly half of the remaining “mash” left after oil and hull removal. Different castor oil and carbohydrate components can serve as indicators of specific toxin processing steps. Ricinoleic acid is a relatively unique fatty acid in nature and is the most abundant component of castor oil. The loss of ricinoleic acid indicates a step to remove oil from the seeds. The relative amounts of carbohydrates and carbohydrate-like compounds, including arabinose, xylose, myo-inositol fucose, rhamnose, glucosamine and mannose detected in the sample can also indicate specific processing steps. For instance, the differential loss of arabinose relative to mannose and N-acetyl glucosamine indicates enrichment for the protein fraction of the seed using protein precipitation. The methods developed in this project center on fatty acid and carbohydrate extraction from castor samples followed by derivatization to permit analysis by gas chromatography-mass spectrometry (GC-MS). Method descriptions herein include: the source and preparation of castor materials used for method evaluation, the equipment and description of procedure required for chemical derivatization, and the instrument parameters used in the analysis. Two types of derivatization methods describe analysis of carbohydrates and one procedure for analysis of fatty acids. Two types of GC-MS analysis is included in the method development, one employing a quadrupole MS system for compound identification and an isotope ratio MS for measuring the stable isotope ratios of deuterium and hydrogen (D/H) in fatty acids. Finally, the method for analyzing the compound abundance data is included. This study indicates that removal of ricinoleic acid is a conserved consequence of each processing step we tested. Furthermore, the stable isotope D/H ratio of ricinoleic acid distinguished between two of the three castor seed sources. Concentrations of arabinose, xylose, mannose, glucosamine and myo-inositol differentiated between crude or acetone extracted samples and samples produced by protein precipitation. Taken together these data illustrate the ability to distinguish between processes used to purify a ricin sample as well as potentially the source seeds.

  4. 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).

  5. Hydrocarbon analogs of cosmic dust to trace the solid carbon abundance in the interstellar medium

    NASA Astrophysics Data System (ADS)

    Gadallah, Kamel A. K.

    2015-01-01

    The spectral changes of hydrogenated amorphous carbon (HAC) could show variable distributions of solid carbon abundance in the interstellar medium (ISM). The variable optical properties of HAC analogs, produced by the laser ablation in a high vacuum, depends on the variation in its atomic and electronic structures. The fraction of hydrogen atoms in HAC increases proportionally with the laser's power. The available solid carbon tied up in the interstellar HAC, being the carrier of the interstellar 3.4 ? m and 4.6 ? m-1 bands, is indicated by the strength of these bands. Comparing the strength of these bands with those of laboratory data indicates that the amount of carbon in HAC analogs is not inherently sufficient. The lack in the solid carbon (locked solid carbon) in these analogs can be analytically estimated to facilitate the simulation of cosmic carbon dust. The results show a reduction in the locked solid carbon when the fraction of hydrogen atoms in HAC analogs increases. When this fraction becomes approximately 0.52 relative to the total number of hydrogen and carbon atoms, there is no lack of carbon in HAC analogs. The interstellar distribution of variable solid carbon abundance is attributed to the modification of cosmic HAC, which occurs as a result of the variation in its hydrogen atom fraction and the UV processing taking place in the interstellar environments. This distribution reveals more solid carbon abundances reside in the dust phase and may assist in resolving the carbon crisis.

  6. 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 types of experiments yielded statistically indistinguishable results, and these measurements yield a calibration that overlaps with our theoretical predictions for calcite at equilibrium. The slow-growing Devils Hole calcite exhibits Δ47 and δ18O values consistent with lattice equilibrium. Factors influencing DIC speciation (pH, salinity) and the timescale for DIC equilibration, as well as reactions at the mineral-solution interface, have the potential to influence clumped-isotope signatures and the δ18O of carbonate minerals. In fast-growing carbonate minerals, solution chemistry may be an important factor, particularly over extremes of pH and salinity. If a crystal grows too rapidly to reach an internal equilibrium (i.e., achieve the value for the temperature-dependent mineral lattice equilibrium), it may record the clumped-isotope signature of a DIC species (e.g., the temperature-dependent equilibrium of HCO3-) or a mixture of DIC species, and hence record a disequilibrium mineral composition. For extremely slow-growing crystals, and for rapidly-grown samples grown at a pH where HCO3- dominates the DIC pool at equilibrium, effects of solution chemistry are likely to be relatively small or negligible. In summary, growth environment, solution chemistry, surface equilibria, and precipitation rate may all play a role in dictating whether a crystal achieves equilibrium or disequilibrium clumped-isotope signatures.

  7. 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.

  8. 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 account, other Lower Aptian negative excursions reported in the literature and assigned to the OAE 1a, perhaps, must be reconsidered to distinguish among the two Lower Aptian negative excursions.; Figure 1: Isotopic curve of the FZD section compared with one section of Spain. The sharp negative peak in the Mexican section is compared with the Spanish section (see the arrow).

  9. 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.

  10. Contrasting the CO2-He Isotope and Relative Abundance Systematics of the Central American and IBM Arcs

    NASA Astrophysics Data System (ADS)

    Hilton, D. R.; Fischer, T. P.; Shaw, A. M.; Hauri, E.; Walker, J.

    2006-12-01

    We report CO2 and He isotope and relative abundance data obtained utilizing high-T fumaroles, geothermal wells, boiling mud pots, hot springs and phenocryst-bearing lavas from both MARGINS-targeted regions. In Central America, we collected ~140 fluid and ~30 lava samples covering a total of 41 volcanic centers in Costa Rica (7), Nicaragua (8), El Salvador (10), Honduras (9) and Guatemala (7). Along the IBM arc, we sampled the islands of Uracas, Agrigan, Pagan and Alamagan in the CNMI and Oshima, Niijima, Shikinajima, Hachijojima and Aogashima in the Izu islands. Helium isotope ratios (3He/4He) reach a maximum of 8RA (where RA = air 3He/4He) with most values > 5 RA. The majority of samples have CO2/3He ratios between 1010 and 1011, as at other arcs. The δ13C of the CO2 for the majority of samples fall between -5 and 0 ‰ (PDB) consistent with a major slab input to the carbon inventory. The entire database has been assessed to identify samples unmodified by localised crustal processes (~75% of total), thereby defining the He and C systematics of the underlying mantle source. At both arcs, we utilize along-strike He-C variations to consider the relative influence of various subduction zone forcing functions on the output C-flux. We show that subducted sediment lithology, particularly down-hole C distribution and the nature (oxidized/reduced) of the C, is a major control on the output as opposed to other factors such as angle of slab dip, convergence rate, and thickness of overlying arc crust.

  11. Stable carbon isotope analysis of nucleic acids to trace sources of dissolved substrates used by estuarine bacteria.

    PubMed Central

    Coffin, R B; Velinsky, D J; Devereux, R; Price, W A; Cifuentes, L A

    1990-01-01

    The natural abundance of stable carbon isotopes measured in bacterial nucleic acids extracted from estuarine bacterial concentrates was used to trace sources of organic matter for bacteria in aquatic environments. The stable carbon isotope ratios of Pseudomonas aeruginosa and nucleic acids extracted from cultures resembled those of the carbon source on which bacteria were grown. The carbon isotope discrimination between the substrate and total cell carbon from bacterial cultures averaged 2.3% +/- 0.6% (n = 13). Furthermore, the isotope discrimination between the substrate and nucleic acids extracted from bacterial cultures was 2.4% +/- 0.4% (n = 10), not significantly different from the discrimination between bacteria and the substrate. Estuarine water samples were prefiltered through 1-micron-pore-size cartridge filters. Bacterium-sized particles in the filtrates were concentrated with tangential-flow filtration and centrifugation, and nucleic acids were then extracted from these concentrates. Hybridization with 16S rRNA probes showed that approximately 90% of the nucleic acids extracted on two sample dates were of eubacterial origin. Bacteria and nucleic acids from incubation experiments using estuarine water samples enriched with dissolved organic matter from Spartina alterniflora and Cyclotella caspia had stable carbon isotope values similar to those of the substrate sources. In a survey that compared diverse estuarine environments, stable carbon isotopes of bacteria grown in incubation experiments ranged from -31.9 to -20.5%. The range in isotope values of nucleic acids extracted from indigenous bacteria from the same waters was similar, -27.9 to -20.2%. Generally, the lack of isotope discrimination between bacteria and nucleic acids that was noted in the laboratory was observed in the field.(ABSTRACT TRUNCATED AT 250 WORDS) Images PMID:2389930

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

    NASA Astrophysics Data System (ADS)

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

    2003-12-01

    Bioapatite, the principal inorganic phase comprising bone, commonly contains a small fraction of carbonate, which has been substituted into the phosphate structure during bone formation. The isotopic compositions of both the phosphate oxygen and the structural carbonate oxygen are now commonly used in palaeoclimatological and bioarchaeological investigations. The potential for post-mortem alteration of these isotopic compositions, therefore, is of interest, with the behaviour of structural carbonate being of most concern. In bioarchaeological studies, alteration of bone isotopic compositions has the potential to occur not only during low-temperature processes associated with burial but also during food preparation involving heating (burning, boiling). Here, we examine the stable isotopic behaviour of structural carbonate oxygen and carbon, and coexisting phosphate oxygen during the burning of bone. Freshly deceased (6<8 months) white-tailed deer leg bones (Odocoileus virginianus) were collected from Pinery Provincial Park, Ontario, Canada. Each long bone was sectioned and incrementally heated from 25 to 900° C, in 25° intervals. The samples were then ground to a standardized grain-size (45<63μ m), and changes in bioapatite crystallinity (CI) were determined using powder X-ray diffraction (pXRD), and Fourier transform infra-red spectroscopy (FTIR). Combined differential thermal and thermogravimetric analyses (DTA/TG) were used to evaluate weight loss and associated reactions during heating. Stable carbon isotope compositions of the bioapatite remain relatively constant (+/-1‰ ) during heating to 650° C. A 4‰ increase in stable carbon isotopic composition then occurs between 650-750° C, accompanied by an increase in CI, followed by a 10‰ decline at temperatures above 800° C, as carbonate carbon is lost. Carbonate and phosphate oxygen isotopic compositions are correlated over the entire heating range, with carbonate being enriched relative to phosphate by about 8-10‰ below 500° C, 5-6‰ between 500-700° C, and 8-10‰ above 700° C. CI and oxygen isotopic compositions of carbonate and phosphate are not well correlated. Only modest CI changes are recorded from 25-675° C, compared with much larger changes in oxygen isotopic composition, especially above 300° C. On average, original isotopic compositions are largely preserved for both phosphate (+/-1‰ ) and carbonate (+/-2‰ ) oxygen at <300° C. At higher temperatures, however, both phosphate and carbonate oxygen in the bioapatite are systematically depleted of oxygen-18 relative to original values.

  13. Carbon isotope systematics of a mantle "hotspot": a comparison of Loihi Seamount and MORB glasses

    USGS Publications Warehouse

    Exley, R.A.; Mattey, D.P.; Clague, D.A.; Pillinger, C.T.

    1986-01-01

    The carbon isotope geochemistry of glasses from Loihi Seamount has been compared with that of MORB glasses. Stepped heating shows two carbon components in both sample suites: (1) isotopically light carbon (avg. ??13C = -26.3???) released 600??C, regarded as indigenous. The high-temperature component in MORB samples varied from 52 to 169 ppm C, average ??13C = -6.6???, consistent with previous studies (overall MORD average ??13C = -6.4 ?? 0.9???), and new results for Indian Ocean glasses are similar to Atlantic and Pacific Ocean samples. Carbon release profiles produced by stepped heating may be typical of locality, but there are no significant differences in ??13C values between MORB samples from different areas. Lower yields (17-110 ppm C) correlated with depth in the Loihi samples suggest that they are partially degassed. This degassing has not affected ??13C values significantly (avg. -5.8???). Loihi tholeiites have higher ??13C (avg. -5.6???) than the alkali basalts (avg. -7.1???). Carbon abundances correlate well with He concentration data. Comparison of the ??13C values with trace element and He, Sr, Nd, and Pb isotope data from the literature suggests that the Loihi samples with highest ??13C have high 3He/4He and possibly the least depleted 143Nd/144Nd and 87Sr/86Sr. The carbon isotope data are consistent with previous models for Loihi involving several mantle sources, lithospheric contamination, and mixing. The slightly higher ??13C of Loihi tholeiites suggests that the undegassed "plume" component manifested by high 3He/4He values might have ??13C about 1??? higher than the MORB average. ?? 1986.

  14. 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.

  15. 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 ...

  16. Siderophile and chalcophile element abundances in oceanic basalts, Pb isotope evolution and growth of the earth's core

    NASA Technical Reports Server (NTRS)

    Newsom, H. E.; White, W. M.; Jochum, K. P.; Hofmann, A. W.

    1986-01-01

    The hypothesis that the mantle Pb isotope ratios reflect continued extraction of Pb into the earth's core over geologic time is evaluated by studying the depeletion of chalcophile and siderophile elements in the mantle. Oceanic basalt samples are analyzed in order to determine the Pb, Sr, and Nd isotropic compositions and the abundances of siderophile and chalcophile elements and incompatible lithophile elements. The data reveal that there is no systematic variation of siderophile or chalcophile element abundances relative to abundances of lithophile elements and the Pb/Ce ratio of the mantle is constant. It is suggested that the crust formation involves nonmagmatic and magmatic processes.

  17. Carbon and nitrogen abundances in red giant stars in the globular cluster 47 Tucanae

    NASA Technical Reports Server (NTRS)

    Dickens, R. J.; Bell, R. A.; Gustafsson, B.

    1979-01-01

    The effects of changes in temperature, gravity, overall metal abundance, and carbon and nitrogen abundances have been investigated for model stellar spectra and colors representing globular-cluster giants of moderate metal deficiency. The results are presented in the form of spectral atlases and theoretical color-color diagrams. Using these results, approximate abundances of carbon and nitrogen have been derived for some red giant stars in 47 Tuc, from intermediate- and low-dispersion spectra and from intermediate- and narrow-band photometry. In all the normal giants studied, nitrogen is overabundant by up to about a factor of 5 (the precise value depends on the adopted carbon abundance), with different enhancements for different giants. The observational material is not sufficient to distinguish between a normal carbon abundance and a slight carbon depletion for the giant-branch stars, but carbon appears to be somewhat depleted in stars on the asymptotic giant branch. A most probable value of M/H = -0.8 for the overall cluster metal abundance is suggested from analysis of Stromgren photometry of red horizontal-branch stars.

  18. 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.

  19. 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.

  20. A Comparison of Oxidized Carbon Abundances among Comets

    NASA Technical Reports Server (NTRS)

    DiSanti, M. A.; Mumma, M. J.; Bonev, B. P.; Villanueva, G. L.; Radeva, Y. L.; Magee-Sauer, K.; Gibb, E. L.

    2010-01-01

    Comets contain relatively well preserved icy material remaining from the epoch of Solar System formation, however the extent to which these ices are modified from their initial state remains a fundamental question in cometary science. As a comet approaches the Sun, sublimation of the ices contained in its nucleus (termed " native ices") releases parent volatiles into the coma, where they can be measured spectroscopically. One means of assessing the degree to which interstellar ices were processed prior to their incorporation into cometary nuclei is to measure the relative abundances of chemically-related parent volatiles. For example, formation of C2H6 by hydrogen atom addition (e.g., to C2H2) on surfaces of ice-mantled grains was proposed to explain the high C2H6 to CH4 abundance observed in C/1996 B2 (Hyakutake) [1]. The large C2H6/CH4 abundance ratios measured universally in comets, compared with those predicted by gas phase production of C2H6, establishes H-atom addition as an important and likely ubiquitous process. CO should also be hydrogenated on grain surfaces. Laboratory irradiation experiments on interstellar ice analogs indicate this to require very low temperatures (T approx. 10-25 K), the resulting yields of H2CO and CH3OH being highly dependent both on hydrogen density (i.e., fluence) and on temperature ([2],[3]). This relatively narrow range in temperature reflects a lack of mobility below 8-10 K on the one hand, and reduced sticking times for H-atoms as grain surfaces are warmed above 20 K on the other. The relative abundances of these three chemically-related molecules in comets provides one measure of the efficiency of H-atom addition to CO on pre-cometary grains (Fig. 1).

  1. The Determination of the Natural Abundance of the Isotopes of Chlorine: An Introductory Experiment in Mass Spectrometry.

    ERIC Educational Resources Information Center

    O'Malley, Rebecca M.

    1982-01-01

    Describes a laboratory experiment which introduces basic principles and experimental techniques of mass spectrometry for fourth year undergraduate (B.Sc.) students. Laboratory procedures, background information, and discussion of results are provided for the experiment in which the natural isotopic abundance of chlorine is determined. (Author/JN)

  2. Carbon and Oxygen Isotopic Ratios for Miras

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

    We have measured vibration-rotation first and second overtone 12C16O, 13C16O, 12C17O, 12C18O lines in 1.5 to 2.5 micron spectra of 41 Mira and SRa stars. These measurements have been used to derive 12C/13C, 16O/17O, and 16O/18O isotopic ratios. The ratios are compared to available literature values for the individual stars and the ratios are compared to isotopic ratios for various samples of evolved stars. Models for solar composition AGB stars of different initial masses are compared to the results. We find that the majority of the M stars had main sequence masses <1.5 solar mass and have not experienced the third dredge up. The progenitors of the S and C Miras in the sample were more massive but no stars in the sample show evidence of hot bottom burning.

  3. 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, equilibrium carbon isotope fractionation relations dictate that shell carbonate should be preferentially enriched in C-13 by 3 to 5 per mill (from 30° to 0°C) compared to EPF at a pH of 7.5. Anomalous positive excursions are rarely, if ever, observed in shell carbonate and they have yet to be associated with growth cessation markers in bivalves. The most likely explanation for the lack of anomalous positive values is that the percentage of metabolic carbon increases in EPF when bivalves experience stressful condition. This influx of metabolic carbon is balanced to a measureable extent by the enhanced fractionation of carbon isotopes during shell deposition from EPF at relatively low pH. These two processes may be combined in a quantitative model to extract a historical record of metabolic activity from the carbon isotope profiles of bivalve shells.

  4. Hydropyrolysis as a preparative method for the compound-specific carbon isotope analysis of fatty acids.

    PubMed

    Sephton, Mark A; Meredith, Will; Sun, Cheng-Gong; Snape, Colin E

    2005-01-01

    Compound-specific stable carbon isotope analysis by gas chromatography/combustion/isotope ratio mass spectrometry is an effective and risk-free means of investigating fatty acid metabolism. Straightforward analysis, however, leads to poor chromatographic resolution, while derivatization adds carbon thereby corrupting the starting stable isotopic composition. Hydropyrolysis is a new approach which defunctionalizes fatty acids to yield the corresponding n-alkanes thus retaining the carbon skeleton intact and improving chromatography, allowing the faithful measurement of carbon isotope ratios. PMID:15645412

  5. Carbon-13 and carbon-14 abundances in alaskan aquatic organisms: delayed production from peat in arctic food webs.

    PubMed

    Schell, D M

    1983-03-01

    Inputs of terrestrial peat carbon to the nearshore Alaskan Beaufort Sea from erosion and fluvial transport are of the same magnitude as in situ primary production within 10 kilometers of shore. Nevertheless, carbon-13/carbon-12 ratios and carbon-14 abundances in marine organisms show that only small amounts of the terrestrial carbon are transferred beyond the microbial level. Freshwater organisms, however, are heavily dependent on peat, as shown by pronounced seasonal radiocarbon depressions in resident fish and ducks. Tundra ponds and lakes are areas where accumulated terrestrial peat carbon is apparently transferred to aquatic insect larvae and passed on to higher organisms. The lack of functionally analogous abundant marine prey organisms may explain why peat carbon is not efficiently transferred to apical food web species in the marine environment. PMID:17811748

  6. Carbon-13 and Carbon-14 Abundances in Alaskan Aquatic Organisms: Delayed Production from Peat in Arctic Food Webs

    NASA Astrophysics Data System (ADS)

    Schell, Donald M.

    1983-03-01

    Inputs of terrestrial peat carbon to the nearshore Alaskan Beaufort Sea from erosion and fluvial transport are of the same magnitude as in situ primary production within 10 kilometers of shore. Nevertheless, carbon-13/carbon-12 ratios and carbon-14 abundances in marine organisms show that only small amounts of the terrestrial carbon are transferred beyond the microbial level. Freshwater organisms, however, are heavily dependent on peat, as shown by pronounced seasonal radiocarbon depressions in resident fish and ducks. Tundra ponds and lakes are areas where accumulated terrestrial peat carbon is apparently transferred to aquatic insect larvae and passed on to higher organisms. The lack of functionally analogous abundant marine prey organisms may explain why peat carbon is not efficiently transferred to apical food web species in the marine environment.

  7. Carbon and hydrogen isotope fractionation by moderately thermophilic methanogens

    NASA Astrophysics Data System (ADS)

    Valentine, David L.; Chidthaisong, Amnat; Rice, Andrew; Reeburgh, William S.; Tyler, Stanley C.

    2004-04-01

    A series of laboratory studies were conducted to increase understanding of stable carbon ( 13C/ 12C) and hydrogen (D/H) isotope fractionation arising from methanogenesis by moderately thermophilic acetate- and hydrogen-consuming methanogens. Studies of the aceticlastic reaction were conducted with two closely related strains of Methanosaeta thermophila. Results demonstrate a carbon isotope fractionation of only 7 (? = 1.007) between the methyl position of acetate and the resulting methane. Methane formed by this process is enriched in 13C when compared with other natural sources of methane; the magnitude of this isotope effect raises the possibility that methane produced at elevated temperature by the aceticlastic reaction could be mistaken for thermogenic methane based on carbon isotopic content. Studies of H 2/CO 2 methanogenesis were conducted with Methanothermobacter marburgensis. The fractionation of carbon isotopes between CO 2 and CH 4 was found to range from 22 to 58 (1.023 ? ? ? 1.064). Greater fractionation was associated with low levels of molecular hydrogen and steady-state metabolism. The fractionation of hydrogen isotopes between source H 2O and CH 4 was found to range from 127 to 275 (1.16 ? ? ? 1.43). Fractionation was dependent on growth phase with greater fractionation associated with later growth stages. The maximum observed fractionation factor was 1.43, independent of the ?D-H 2 supplied to the culture. Fractionation was positively correlated with temperature and/or metabolic rate. Results demonstrate significant variability in both hydrogen and carbon isotope fractionation during methanogenesis from H 2/CO 2. The relatively small fractionation associated with deuterium during H 2/CO 2 methanogenesis provides an explanation for the relatively enriched deuterium content of biogenic natural gas originating from a variety of thermal environments. Results from these experiments are used to develop a hypothesis that differential reversibility in the enzymatic steps of the H 2/CO 2 pathway gives rise to variability in the observed carbon isotope fractionation. Results are further used to constrain the overall efficiency of electron consumption by way of the hydrogenase system in M. marburgensis, which is calculated to be less than 55%.

  8. 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 but no adequate assessment is possible based on current data. References Tcherkez G., Farquhar G.D., Badeck F.-W. & Ghashghaie J. (2004) Theoretical considerations about carbon isotope distribution in glucose of C3 plants, Functional Plant Biology 31, 857-877

  9. The Distribution of Carbon Abundances in Stars in the Milky Ways Satellite Galaxies

    NASA Astrophysics Data System (ADS)

    Guo, Michelle; Zhang, A.

    2013-01-01

    There is evidence that the Milky Way halo is comprised in part of disrupted dwarf satellite galaxies; however, the extent to which they contribute to the halos formation is unclear. To further examine the role of dwarf galaxies in building the halo, we compared the degrees of carbon enhancement of the dwarf spheroidal (dSph) galaxies and field halo populations. We generated a grid of high-resolution synthetic spectra for hypothetical stars of specific effective temperature, surface gravity, metallicity, alpha element abundance, and carbon abundance for comparison with medium-resolution observed spectra of dSph stars of unmeasured [C/Fe] but otherwise known properties. After smoothing, rebinning, and normalizing the two data sets, we varied carbon abundance to find the best carbon abundance by determining the synthetic spectrum that gave the minimal deviation. We found a lower Carbon-Enhanced Metal-Poor (CEMP) fraction in the dSph galaxies, which suggests that they have evolved over time. Whereas star formation and chemical evolution stopped for accreted galaxies, the surviving galaxies evolved to became less carbon enhanced and more metal rich. The variation in carbon abundances supports prior knowledge of dSph stars and provide a deeper understanding the formation of stars such as those of the Milky Way halo. We thank the US National Science Foundation, the UCSC Science Internship Program, and the W. M. Keck Observatory where the spectra were obtained.

  10. Optimizing sample pretreatment for compound-specific stable carbon isotopic analysis of amino sugars in marine sediment

    NASA Astrophysics Data System (ADS)

    Zhu, R.; Lin, Y.-S.; Lipp, J. S.; Meador, T. B.; Hinrichs, K.-U.

    2014-09-01

    Amino sugars are quantitatively significant constituents of soil and marine sediment, but their sources and turnover in environmental samples remain poorly understood. The stable carbon isotopic composition of amino sugars can provide information on the lifestyles of their source organisms and can be monitored during incubations with labeled substrates to estimate the turnover rates of microbial populations. However, until now, such investigation has been carried out only with soil samples, partly because of the much lower abundance of amino sugars in marine environments. We therefore optimized a procedure for compound-specific isotopic analysis of amino sugars in marine sediment, employing gas chromatography-isotope ratio mass spectrometry. The whole procedure consisted of hydrolysis, neutralization, enrichment, and derivatization of amino sugars. Except for the derivatization step, the protocol introduced negligible isotopic fractionation, and the minimum requirement of amino sugar for isotopic analysis was 20 ng, i.e., equivalent to ~8 ng of amino sugar carbon. Compound-specific stable carbon isotopic analysis of amino sugars obtained from marine sediment extracts indicated that glucosamine and galactosamine were mainly derived from organic detritus, whereas muramic acid showed isotopic imprints from indigenous bacterial activities. The δ13C analysis of amino sugars provides a valuable addition to the biomarker-based characterization of microbial metabolism in the deep marine biosphere, which so far has been lipid oriented and biased towards the detection of archaeal signals.

  11. Optimizing sample pretreatment for compound-specific stable carbon isotopic analysis of amino sugars in marine sediment

    NASA Astrophysics Data System (ADS)

    Zhu, R.; Lin, Y.-S.; Lipp, J. S.; Meador, T. B.; Hinrichs, K.-U.

    2014-01-01

    Amino sugars are quantitatively significant constituents of soil and marine sediment, but their sources and turnover in environmental samples remain poorly understood. The stable carbon isotopic composition of amino sugars can provide information on the lifestyles of their source organisms and can be monitored during incubations with labeled substrates to estimate the turnover rates of microbial populations. However, until now, such investigation has been carried out only with soil samples, partly because of the much lower abundance of amino sugars in marine environments. We therefore optimized a procedure for compound-specific isotopic analysis of amino sugars in marine sediment employing gas chromatography-isotope ratio mass spectrometry. The whole procedure consisted of hydrolysis, neutralization, enrichment, and derivatization of amino sugars. Except for the derivatization step, the protocol introduced negligible isotopic fractionation, and the minimum requirement of amino sugar for isotopic analysis was 20 ng, i.e. equivalent to ~ 8 ng of amino sugar carbon. Our results obtained from δ13C analysis of amino sugars in selected marine sediment samples showed that muramic acid had isotopic imprints from indigenous bacterial activities, whereas glucosamine and galactosamine were mainly derived from organic detritus. The analysis of stable carbon isotopic compositions of amino sugars opens a promising window for the investigation of microbial metabolisms in marine sediments and the deep marine biosphere.

  12. Sediment Tracking Using Carbon and Nitrogen Stable Isotopes

    NASA Astrophysics Data System (ADS)

    Fox, J. F.; Papanicolaou, A.

    2002-12-01

    As landscapes are stripped of valuable, nutrient rich topsoils and streams are clouded with habitat degrading fine sediment, it becomes increasingly important to identify and mitigate erosive surfaces. Particle tracking using vegetative derived carbon (C) and nitrogen (N) isotopic signatures and carbon/nitrogen (C/N) atomic ratios offer a promising technique to identify such problematic sources. Consultants and researchers successfully use C, N, and other stable isotopes of water for hydrologic purposes, such as quantifying groundwater vs. surface water contribution to a hydrograph. Recently, C and N isotopes and C/N atomic ratios of sediment were used to determine sediment mass balance within estuarine environments. The current research investigates C and N isotopes and C/N atomic ratios of source sediment for two primary purposes: (1) to establish a blueprint methodology for estimating sediment source and erosion rates within a watershed using this isotopic technology coupled with mineralogy fingerprinting techniques, radionuclide transport monitoring, and erosion-transport models, and (2) to complete field studies of upland erosion processes, such as, solifluction, mass wasting, creep, fluvial erosion, and vegetative induced erosion. Upland and floodplain sediment profiles and riverine suspended sediment were sampled on two occasions, May 2002 and August 2002, in the upper Palouse River watershed of northern Idaho. Over 300 samples were obtained from deep intermountain valley (i.e. forest) and rolling crop field (i.e. agriculture) locations. Preliminary sample treatment was completed at the Washington State University Water Quality Laboratory where samples were dried, removed of organic constituents, and prepared for isotopic analysis. C and N isotope and C/N atomic ratio analyses was performed at the University of Idaho Natural Resources Stable Isotope Laboratory using a Costech 4010 Elemental Combustion System connected with a continuous flow inlet system to the Finnigan MAT Delta Plus isotope ratio mass spectrometer. Results indicate distinct N isotopic signatures and C/N atomic ratios for forest and agriculture sediment sources. In addition, unique C and N isotopic signatures and C/N atomic ratios exist within floodplain and upland surfaces, and within the 10 centimeter profiles of erosion and deposition locations. Suspended sediment analyses are preliminary at this time. Conclusions indicate that sediment C and N isotopic signature and C/N atomic ratio are dependent upon land use and soil moisture conditions, and will serve as a useful technique in quantifying erosive source rates and understanding upland erosion processes.

  13. 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.

  14. 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 groundwater ages. The DIC calculated groundwater ages were compared with DOC calculated groundwater ages and both of these ages were compared to travel times developed in ground-water flow and transport models. If nuclear waste is stored in Yucca Mountain, the saturated zone is the final barrier against the release of radionuclides to the environment. The most recent rendition of the TSPA takes little credit for the presence of the saturated zone and is a testament to the inadequate understanding of this important barrier. If radionuclides reach the saturated zone beneath Yucca Mountain, then there is a travel time before they would leave the Yucca Mountain area and flow down gradient to the Amargosa Valley area. Knowing how long it takes groundwater in the saturated zone to flow from beneath Yucca Mountain to down gradient areas is critical information for potential radionuclide transport. Radionuclide transport in groundwater may be the quickest pathway for radionuclides in the proposed Yucca Mountain repository to reach land surface by way of groundwater pumped in Amargosa Valley. An alternative approach to ground-water flow and transport models to determine the travel time of radionuclides from beneath Yucca Mountain to down gradient areas in the saturated zone is by carbon-14 dating of both inorganic and organic carbon dissolved in the groundwater. A standard method of determining ground-water ages is to measure the carbon-13 and carbon-14 of DIC in the groundwater and then correct the measured carbon-14 along a flow path for geochemical reactions that involve carbon containing phases. These geochemical reactions are constrained by carbon-13 and isotopic fractionations. Without correcting for geochemical reactions, the ground-water ages calculated from only the differences in carbon-14 measured along a flow path (assuming the decrease in carbon-14 is due strictly to radioactive decay) could be tens of thousands of years too old. The computer program NETPATH, developed by the USGS, is the best geochemical program for correcting carbon-14 activities for geochemical reactions. The DIC carbon-14 corrected ages can be further constrained by measuring the carbon isotopes of DOC. Because the only source of organic carbon in aquifers is almost always greater than 40,000 years old, any organic carbon that may be added to the groundwater would contain no carbon-14. Thus, ground-water ages determined by carbon isotopes of DOC should be maximum ages that can be used to constrain DIC corrected ages.

  15. 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.

  16. Changing carbon isotope ratio of atmospheric carbon dioxide: implications for food authentication.

    PubMed

    Peck, William H; Tubman, Stephanie C

    2010-02-24

    Carbon isotopes are often used to detect the addition of foreign sugars to foods. This technique takes advantage of the natural difference in carbon isotope ratio between C(3) and C(4) plants. Many foods are derived from C(3) plants, but the low-cost sweeteners corn and sugar cane are C(4) plants. Most adulteration studies do not take into account the secular shift of the carbon isotope ratio of atmospheric carbon dioxide caused by fossil fuel burning, a shift also seen in plant tissues. As a result statistical tests and threshold values that evaluate authenticity of foods based on carbon isotope ratios may need to be corrected for changing atmospheric isotope values. Literature and new data show that the atmospheric trend in carbon isotopes is seen in a 36-year data set of maple syrup analyses (n = 246), demonstrating that published thresholds for cane or corn sugar adulteration in maple syrup (and other foods) have become progressively more lenient over time. PMID:20121108

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  18. 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.

  19. Carbon and sulfur isotopes as tracers of fluid-fluid and fluid-rock interaction in geothermal systems

    NASA Astrophysics Data System (ADS)

    Stefansson, A.; Keller, N. S.; Gunnarsson Robin, J.; Kjartansdottir, R.; Ono, S.; Sveinbjörnsdottir, A. E.

    2014-12-01

    Carbon and sulfur are among major components in geothermal systems. They are found in various oxidation state and present in solid phases and fluids (water and vapor). In order to study the reactions and mass movement within multiphase geothermal systems, we have combined geochemical fluid-fluid and fluid-rock modelling with sulfur and carbon isotope fractionation modelling and compared the results with measured carbon and sulfur isotopes in geothermal fluids (water and vapor) for selected low- and high-enthalpy geothermal systems in Iceland. In this study we have focused on δ34S for H2S in vapor and water and SO4 in water as well as δ13C for CO2 in vapor and water phases. Isotope fractionations for CO2 and H2S between vapor and liquid water, upon aqueous speciation and upon carbonate and sulfide mineral formation were revised. These were combined with reaction modelling involving closed system boiling and progressive water-rock interaction to constrain the mass movement and isotope abundance between various phases. The results indicate that for a closed system, carbon and sulfur isotope abundance is largely dependent on progressive fluid-fluid and fluid-rock interaction and the initial total δ34S and δ13C value of the system. Initially, upon progressive fluid rock interaction the δ34S and δ13C values for the bulk aqueous phase approach that of the host rocks. Secondary mineral formation may alter these values, the exact isotope value of the mineral and resulting aqueous phase depending on aqueous speciation and isotope fractionation factor. In turn, aqueous speciation and mineral saturation depends on progressive fluid-rock interaction, fluid-fluid interaction, temperature and acid supply to the system. Depressurization boiling also results in isotope fractionation, the exact isotope value of the vapor and aqueous phase depending on aqueous speciation and isotope fractionation fractor. In this way, carbon and sulfur isotopes may be used combined with measured values for natural fluids to constrain mass movement upon fluid-fluid and fluid-rock interaction in geothermal systems.

  20. Can Mg isotopes be used to trace cyanobacteria-mediated magnesium carbonate precipitation in alkaline lakes?

    NASA Astrophysics Data System (ADS)

    Shirokova, L. S.; Mavromatis, V.; Bundeleva, I.; Pokrovsky, O. S.; Bénézeth, P.; Pearce, C.; Gérard, E.; Balor, S.; Oelkers, E. H.

    2011-07-01

    The fractionation of Mg isotopes was determined during the cyanobacterial mediated precipitation of hydrous magnesium carbonate precipitation in both natural environments and in the laboratory. Natural samples were obtained from Lake Salda (SE Turkey), one of the few modern environments on the Earth's surface where hydrous Mg-carbonates are the dominant precipitating minerals. This precipitation was associated with cyanobacterial stromatolites which were abundant in this aquatic ecosystem. Mg isotope analyses were performed on samples of incoming streams, groundwaters, lake waters, stromatolites, and hydromagnesite-rich sediments. Laboratory Mg carbonate precipitation experiments were conducted in the presence of purified Synechococcus sp cyanobacteria that were isolated from the lake water and stromatolites. The hydrous magnesium carbonates nesquehonite (MgCO3·3H2O) and dypingite (Mg5(CO3)4(OH)25(H2O)) were precipitated in these batch reactor experiments from aqueous solutions containing either synthetic NaHCO3/MgCl2 mixtures or natural Lake Salda water, in the presence and absence of live photosynthesizing Synechococcus sp. Bulk precipitation rates were not to affected by the presence of bacteria when air was bubbled through the system. In the stirred non-bubbled reactors, conditions similar to natural settings, bacterial photosynthesis provoked nesquehonite precipitation, whilst no precipitation occurred in bacteria-free systems in the absence of air bubbling, despite the fluids achieving a similar or higher degree of supersaturation. The extent of Mg isotope fractionation (Δ26Mgsolid-solution) between the mineral and solution in the abiotic experiments was found to be identical, within uncertainty, to that measured in cyanobacteria-bearing experiments, and ranges from -1.4 to -0.7 ‰. This similarity refutes the use of Mg isotopes to validate microbial mediated precipitation of hydrous Mg carbonates.

  1. Mars regolith versus SNC meteorites: Evidence for abundant crustal carbonates

    NASA Technical Reports Server (NTRS)

    Warren, Paul H.

    1987-01-01

    Viking XRF analyses are compared with those for terrestrial and lunar basalt samples, and eucritic meteorites (of possible Mars origin). The comparison indicates depletion of Ca relative to Si in the Mars regolith. It is suggested that carbonate formation during a warmer, wetter epoch early in Mars' history could have been responsible.

  2. 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 corals of different mineralogy is in the same direction as published theoretical predictions for the offset between calcite and aragonite, although the magnitude of the offset is different. One possibility is that the deep-sea coral results reflect that crystals may attain nominal mineral equilibrium clumped isotope signatures only under conditions of extremely slow growth. In that case, a possible explanation for the attainment of disequilibrium bulk isotope signatures and equilibrium clumped isotope signatures by deep-sea corals is that extraordinarily slow growth rates can promote the occurrence of isotopic reordering in the interfacial region of growing crystals. We also cannot rule out a component of a biological "vital-effect" influencing clumped isotope signatures in one or both orders of coral. Based on published experimental data and theoretical calculations, these biological "vital" effects could arise from kinetic isotope effects due to the source of carbon used for calcification, temperature- and pH-dependent rates of CO2 hydration and/or hydroxylation, calcifying fluid pH, the activity of carbonic anhydrase, the residence time of dissolved inorganic carbon in the calcifying fluid, and calcification rate. A third possible explanation is the occurrence of variable acid digestion fractionation factors. Although a recent study has suggested that dolomite, calcite, and aragonite may have similar clumped isotope acid digestion fractionation factors, the influence of acid digestion kinetics on Δ47 is a subject that warrants further investigation.

  3. Silicon and carbon abundances in the Orion nebula

    NASA Technical Reports Server (NTRS)

    Rubin, Robert H.; Dufour, Reginald J.; Walter, Donald K.

    1993-01-01

    We assess the gas-phase abundances of Si and C from our recent measurements of Si(2+), C(2+), and C(+) in the Orion Nebula by expanding on our earlier 'blister' models. The C and Si abundances are derived from new IUE high-dispersion spectra of the C(2+) 1907, 1909 A and Si(2+) 1883, 1892 A lines and archival IUE data. Gas-phase Si/C = 0.016 in the Orion ionized volume and is particularly insensitive to uncertainties in extinction and temperature structure. The solar value is 0.098. Gas-phase C/H = 2.8 x 10 exp -4 and Si/H = 4.5 x 10 exp -6. Compared to solar, Si is depleted by a factor of about 8 in the ionized region, while C is much less depleted (factor of 1.3), if depleted at all. This suggests that most Si resides in dust grains even in the ionized volume. Thus, most of the observed forbidden Si II 34.8-micron emission in Orion does not arise in the H II region.

  4. 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.

  5. How much do carbon isotope measurements constrain glacial ocean circulation?

    NASA Astrophysics Data System (ADS)

    Schmittner, A.; Mix, A. C.

    2010-12-01

    Reconstructions of the isotopic composition of dissolved inorganic carbon in seawater (d13DIC) are often interpreted as a ventilation or circulation proxy in paleoceanography. The modern deep-sea distribution of d13C in dissolved inorganic carbon (d13DIC) is highly anti-correlated to macronutrient (PO4, NO3) and apparent oxygen utilization (AOU) patterns due to fractionation during photosynthetic carbon uptake by phytoplankton. Nutrient and AOU concentrations in freshly ventilated North Atlantic Deep Water, for example, are low (d13DIC is high), whereas older water masses contain more respired nutrients and (isotopically light) carbon and have high AOU. However, d13DIC is also influenced by fractionation during air sea gas exchange - a process that decouples d13DIC from changes in nutrients and AOU. Moreover, biological fractionation is not constant but spatially and temporally variable. Here we are using a new global three-dimensional model of stable carbon isotope cycling that includes variable biological and air-sea gas exchange fractionation effects in conjunction with modern and glacial d13C observations to reconstruct ocean circulation patterns. Model versions with different rates and patterns of ocean circulation are produced and the resulting d13C patterns are compared to a compilation of measurements from ocean sediment cores in a probabilistic approach. The method allows us to quantify the uncertainty of deep ocean mass fluxes given available d13C observations/reconstructions and provide a quantitative test of the assumption of d13C as a ventilation proxy.

  6. A survey of methane isotope abundance (14C, 13C, 2H) from five nearshore marine basins that reveals unusual radiocarbon levels in subsurface waters

    NASA Astrophysics Data System (ADS)

    Kessler, J. D.; Reeburgh, W. S.; Valentine, D. L.; Kinnaman, F. S.; Peltzer, E. T.; Brewer, P. G.; Southon, J.; Tyler, S. C.

    2008-12-01

    Methane (CH4) in the subsurface ocean is often supersaturated compared to equilibrium with the modern atmosphere. In order to investigate sources of CH4 to the subsurface ocean, isotope surveys (14C-CH4,δ13C-CH4, δ2H-CH4) were conducted at five locations: Skan Bay (SB), Santa Barbara Basin (SBB), Santa Monica Basin (SMB), Cariaco Basin (CB), and the Guaymas Basin (GB). Depth distributions of CH4 concentration and isotopic abundance were determined for both the sediment and water column at the SB, SBB, SMB, and CB sites; CH4 emitted from seeps on the continental shelf adjacent to the SBB as well as seeps and decomposing clathrate hydrates in the GB was also collected, purified, and analyzed. Methane isotope distributions in the sediments were consistent with known methanogenic and methanotrophic activity; seep- and clathrate-hydrate-derived CH4 was found to be depleted in radiocarbon. However, surprising results were obtained in the water column at all sites investigated. In SB the radiocarbon content of the subsurface CH4 concentration maximum was on average 41% less than its suspected sediment CH4 source, suggesting CH4 seepage in the bay. In the SBB, SMB, and CB, the 14C-CH4 contents in the subsurface ocean were 1.2 to 3.6 times greater than modern carbon quantities suggesting a source of 14C from atmospheric nuclear weapons testing, nuclear power plant effluents, or cosmogenic isotope production.

  7. Biosynthetic effects on the stable carbon isotopic compositions of algal lipids: implications for deciphering the carbon isotopic biomarker record

    NASA Astrophysics Data System (ADS)

    Schouten, Stefan; Klein Breteler, Wim C. M.; Blokker, Peter; Schogt, Nelleke; Rijpstra, W. Irene C.; Grice, Kliti; Baas, Marianne; Sinninghe Damsté, Jaap S.

    1998-04-01

    Thirteen species of algae covering an extensive range of classes were cultured and stable carbon isotopic compositions of their lipids were analysed in order to assess carbon isotopic fractionation effects during their biosynthesis. The fatty acids were found to have similar stable carbon isotopic compositions to each other in all the algae with the exceptions of the C 28 fatty acid in Scenedesmus communis and the polyunsaturated fatty acids in Ampidinium sp. and Gymnodinium simplex which are 3.5‰ more depleted in 13C and up to 8‰ more enriched in 13C, compared to the C 16 fatty acid, respectively. Phytol is consistently enriched in 13C by 2-5‰ compared with the C 16 fatty acid in all algae. The sterols are, however, enriched in 13C by 0-8‰ compared to the C 16 fatty acid, possibly due to a different pool of isopentenyl diphosphate in the cytosol. These large ranges in carbon isotopic compositions of compounds biosynthesized by the same eukaryotes can significantly complicate the interpretation of δ 13C values of sedimentary biomarkers.

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

    PubMed

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

    2014-10-01

    Natural stable isotopes of carbon and nitrogen ((12)C, (13)C, (14)N, (15)N) have abundances unique to each living creature. Therefore, measurement of the stable isotope ratio of carbon and nitrogen (δ(13)C=(13)C/(12)C, δ(15)N=(15)N/(14)N) in milk provides a reliable method to determine organic milk (OM) authenticity. In the present study, the mean δ(13)C value of OM was higher than that of conventional milk (CM), whereas the mean δ(15)N value of OM was lower than that of CM; nonetheless both δ(13)C and δ(15)N values were statistically different for the OM and CM (P<0.05). Furthermore, the values of δ(13)C and δ(15)N were found to differ statistically with the collection date and the milk brand (P<0.05). The combination of δ(13)C and δ(15)N values was more effective than either value alone in distinguishing between OM and CM. The results of the present study, which is based on preliminary data from a limited sample size and sampling period, could be highly valuable and helpful for consumers, the food industry, and/or government regulatory agencies as it can prevent fraudulent labelling of organic food. Further studies include additional analyses of other milk brands and analyses over longer time periods in order to accurately determine OM authenticity using stable isotopes of carbon and nitrogen. PMID:24799230

  9. 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). Geomicrobiol. J. 20, 85-98.

  10. The isotope geochemistry of carbon in groundwater at Stripa

    SciTech Connect

    Fritz, P.; Frape, S.K. ); Fontes, J.Ch.; Louvat, D.; Michelot, J.L. ); Balderer, W. )

    1989-08-01

    The carbon isotopic composition of the total dissolved inorganic carbon in groundwater associated with a granitic pluton at Stripa (Sweden) reflects both inorganic and organic carbon sources. Following the uptake of soil carbon-dioxide, calcite dissolution dominates the geochemical evolution of shallow groundwater. Calcite saturation is reached at a depth of about 100 m. In deeper waters geochemical release of Ca and increasing pH cause calcite precipitation. Radiocarbon contents suggest carbon (and water ) ages in excess of 20,000 years for waters 300-400 m depth. In deep ground waters with enhanced salinities organic carbon is added to the dissolved inorganic carbon either through bacterial activity (e.g. sulfate reducing bacteria) or the oxidation of organic compounds such as methane. The lowest radiocarbon contents were measured at the 300-400 meter levels and not in the deepest fluids. The distribution of {sup 13}C in the deep ground waters suggests the existence of well-defined flow systems with limited active hydraulic interaction. Isotope analyses on fracture calcites substantiate the complex geochemical history of the pluton.

  11. 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.

  12. 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.

  13. 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...

  14. 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 that Δ17O will have useful application to paleoenvironmental studies of continental environments where the effects of evaporation are important, and where vertebrate body water may record an isotopic signal of evaporated water sources and atmospheric oxygen.

  15. Atmospheric Parameters and Carbon Abundance for Hot DB White Dwarfs

    NASA Astrophysics Data System (ADS)

    Koester, Detlev; Provencal, Judi; Gänsicke, Boris T.

    2015-06-01

    Accurate atmospheric parameters for DB (helium atmosphere) white dwarfs near 25000 K are difficult to determine, but are needed to help or confirm the asteroseismic analysis of these objects. Another important aspect is the new class of white dwarfs - the hot DQ - whose spectra are dominated by carbon lines. The origin of these stars is not yet understood, but they may have an evolutionary link with the hotter DBs as studied here. We use absolutely calibrated high-resolution UV spectra of five DBs in addition to available optical spectroscopy. We find photospheric C and no other heavy elements - with extremely high limits on the C/Si ratio - in two of the five objects. We compare various explanations for this unusual composition that have been proposed in the literature: accretion of interstellar or circumstellar matter, radiative levitation, carbon dredge-up from the deeper interior below the helium layer, and a residual stellar wind. None of these explanations is completely satisfactory, and the problem of the origin of the hot DQ remains an open question.

  16. Tracing paleo-ocean redox using Cr isotopes in carbonates spanning the Great Oxidation Event

    NASA Astrophysics Data System (ADS)

    Holmden, C. E.; Bekker, A.

    2013-12-01

    Cr is an element whose isotopes are fractionated by redox reactions in the Earth's exogenic system, such as those occuring during oxidative weathering on the continents and scavenging into reduced marine sediments. Frei et al. (2009) proposed that the range of Cr isotope fractionation in exogenic materials in the absence of molecular oxygen would likely not extend beyond the range in igneous rocks, which is quite small (δ53Cr = -0.1 ×0.1‰). They tested their hypothesis on iron formations spanning the Great Oxidation Event (GOE) and found small fractionations that predated the GOE, but no permil level fractionation until the Neoproterozoic. We tested whether δ53Cr values in shallow-water carbonates spanning the GOE might record steps in the rise of atmospheric oxygen between 2.45 and 2.06 Ga. Carbonates representing 15 formations were chosen with depositonal ages ranging between 2.5 Ga and 1.9 Ga. We find very little Cr isotope fractionation recorded in carbonates deposited during this time with the exception of those corresponding to the peak of the Lomagundi Event at ca. 2.15 Ga. A defining characterisitic of the Lomagundi Event is the widespread prevalance of shallow-water carbonate platforms with abundant stromatolites, making their deposits an ideal lithology to record the state of the seawater Cr cycle. Five formations deposited during this time yield δ53Cr values with permil level fractionation recorded in some examples, in both positive and negative directions with respect to the igenous rock baseline. The data suggests that although the oxidative part of the Cr cycle started at least during the peak of the Lomagundi Event, the Cr(VI) reservoir and its residence time remained small, making it susceptible to local processes. 1. Frei et al. (2009) Fluctuations in Precambrian atmospheric oxygen recorded by Cr isotopes, Nature, v. 461, 250-253.

  17. 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

  18. 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.

  19. {sup 39}Ar Detection at the 10{sup -16} Isotopic Abundance Level with Atom Trap Trace Analysis

    SciTech Connect

    Jiang, W.; Williams, W.; Bailey, K.; O'Connor, T. P.; Mueller, P.; Davis, A. M.; Hu, S.-M.; Sun, Y. R.; Lu, Z.-T.; Purtschert, R.; Sturchio, N. C.

    2011-03-11

    Atom trap trace analysis, a laser-based atom counting method, has been applied to analyze atmospheric {sup 39}Ar (half-life=269 yr), a cosmogenic isotope with an isotopic abundance of 8x10{sup -16}. In addition to the superior selectivity demonstrated in this work, the counting rate and efficiency of atom trap trace analysis have been improved by 2 orders of magnitude over prior results. The significant applications of this new analytical capability lie in radioisotope dating of ice and water samples and in the development of dark matter detectors.

  20. In situ analysis of carbon isotopes in North American diamonds

    NASA Astrophysics Data System (ADS)

    van Rythoven, A. D.; Hauri, E. H.; Wang, J.; McCandless, T.; Shirey, S. B.; Schulze, D. J.

    2010-12-01

    Diamonds from three North American kimberlite occurrences were investigated with cathodoluminescence (CL) and secondary ion mass spectrometry (SIMS) to determine their growth history and carbon isotope composition. Diamonds analyzed include fourteen from Lynx (Quebec), twelve from Kelsey Lake (Colorado) and eleven from A154 South (Diavik mine, Northwest Territories). Growth histories for the diamonds vary from simple to highly complex based on their CL images and depending on the individual stone. Deformation laminae are evident in CL images of the Lynx diamonds that typically are brownish in color. Two to five points per diamond were analyzed by SIMS for carbon isotope composition. Sample heterogeneity is minimal in terms of δ13C (vs. PDB) values. Points within single diamond had a maximum range of approximately 1 ‰. The results for the A154 South (-6.4 to -3 ‰) and Kelsey Lake (-11.2 to -2.6 ‰) stones were in accordance with earlier reported values. The Lynx kimberlite stones have anomalously high ratios and range from -3.5 to +0.2 ‰ (average: -1.4 ‰). No previous carbon isotope analyses on diamonds from Lynx or any other eastern Superior craton occurrence have been published. The diamonds possess carbon isotope ratios higher than those for the only other reported analyses of Superior craton diamonds at Wawa, Ontario (-5.5 to -1.1 ‰). In global terms, the only published analyses of diamonds that consistently contain even higher values are those from New South Wales (Australia). However, these diamonds are alluvial and contain eclogitic and/or exotic mineral inclusions. The Lynx diamonds are entirely peridotitic and from a primary deposit. The unusually low (i.e. >-5‰) δ13C values of the Lynx (and Wawa) diamonds may indicate a different carbon reservoir for the Superior craton mantle as compared to other cratons.

  1. 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

  2. Testing the ``Wildfire Hypothesis:'' Terrestrial Organic Carbon Burning as the Cause of the Paleocene-Eocene Boundary Carbon Isotope Excursion

    NASA Astrophysics Data System (ADS)

    Moore, E. A.; Kurtz, A. C.

    2005-12-01

    The 3‰ negative carbon isotope excursion (CIE) at the Paleocene-Eocene boundary has generally been attributed to dissociation of seafloor methane hydrates. We are testing the alternative hypothesis that the carbon cycle perturbation resulted from wildfires affecting the extensive peatlands and coal swamps formed in the Paleocene. Accounting for the CIE with terrestrial organic carbon rather than methane requires a significantly larger net release of fossil carbon to the ocean-atmosphere, which may be more consistent with the extreme global warming and ocean acidification characteristic of the Paleocene-Eocene Thermal Maximum (PETM). While other researchers have noted evidence of fires at the Paleocene-Eocene boundary in individual locations, the research presented here is designed to test the "wildfire hypothesis" for the Paleocene-Eocene boundary by examining marine sediments for evidence of a global increase in wildfire activity. Such fires would produce massive amounts of soot, widely distributed by wind and well preserved in marine sediments as refractory black carbon. We expect that global wildfires occurring at the Paleocene-Eocene boundary would produce a peak in black carbon abundance at the PETM horizon. We are using the method of Gelinas et al. (2001) to produce high-resolution concentration profiles of black carbon across the Paleocene-Eocene boundary using seafloor sediments from ODP cores, beginning with the Bass River core from ODP leg 174AX and site 1209 from ODP leg 198. This method involves the chemical and thermal extraction of non-refractory carbon followed by combustion of the residual black carbon and measurement as CO2. Measurement of the δ 13C of the black carbon will put additional constraints on the source of the organic material combusted, and will allow us to determine if this organic material was formed prior to or during the CIE.

  3. Using the Carbon Isotope Ratios of Bison Tooth Enamel and Bone Collagen as a Quantitative Proxy for Reconstructing Grassland Vegetation and Paleotemperatures

    NASA Astrophysics Data System (ADS)

    Hoppe, K. A.; Paytan, A.; Chamberlain, P.

    2005-12-01

    The carbon isotope ratios of tissues from grazing herbivores reflect the average carbon isotope ratios of local grasslands, which vary with the abundance of cool-season (C-3) versus warm-season (C-4) grasses. Since the C-3/C-4 ratios of grasslands correlate with climate, the carbon isotope ratios of fossil grazers may serve as a proxy for reconstructing paleovegetation and paleoclimatic conditions. Analyses of fossil and subfossil bison hold particular promise for use as a proxy for paleoenvironmental conditions in North America because bison remains are abundant in Holocene and Pleistocene deposits across most of the continent. However, the accuracy and precision of paleoenvironmental reconstructions based on bison is currently uncertain because the relationship between bison isotope and the abundance of C-3 and C-4 grasses has not been precisely quantified across different environments. We have analyzed the carbon isotope ratios of tooth enamel carbonate and bone collagen from 88 modern free ranging bison ( Bison bison) from ten locations in the Central United States. The C-4 biomass at these locations ranged from less than 1 percent to 95 percent of the total grass biomass. The mean carbon isotope ratios of enamel for each population correlated well with the local abundance of C-4 grasses (R2 = 0.93, p = 0.0001) and with variations in mean annual temperatures (R2 = 0.83, p = 0.001). The mean carbon isotope ratios of collagen for each population also correlated well with the C-4 grass abundance (R2 = 0.97, p = 0.0001) and mean annual temperature (R2 = 0.84, p = 0.0002). Enamel and collagen display similar variability (mean standard deviation = 0.7 per mil), and the variability does not change with climate, habitat, or C-4 abundance. These results demonstrate that analyses of the carbon isotope ratios of fossil bison can be used as a quantitative proxy for reconstructing grassland C-3/C-4 ratios and paleotemperatures, and they will serve as a baseline for interpreting isotopic analyses of fossil bison and other large herbivores from North America.

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

    NASA Astrophysics Data System (ADS)

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

    2012-07-01

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

  5. Clumped isotope thermometry of modern and early Cretaceous molluscan carbonate from high-latitude seas (Invited)

    NASA Astrophysics Data System (ADS)

    Henkes, G. A.; Price, G. D.; Ambrose, W. G.; Carroll, M. L.; Passey, B. H.

    2010-12-01

    The carbonate clumped isotope thermometer is based on the temperature sensitivity of the relative abundance of carbonate ion groups containing 13C-18O bonds. One application of clumped isotope thermometry is to determine the temperature of ancient seawater from the skeletal material of calcium carbonate-secreting marine organisms. The relationship between Δ47, a parameter describing isotopic clumping, and the temperature of carbonate biomineralization has been well-defined for fish otoliths, corals, foraminifera, and coccolithophore tests, but few data have been published for brachiopods and bivalve mollusks. A comprehensive evaluation of the Δ47-temperature relationship for mollusks is required for paleotemperature interpretations from the marine fossil record. Here we present a more comprehensive calibration for modern mollusks, including bivalves, cephalopods, and gastropods. Further, we focus on a subset of cold water, high-latitude species collected in the northern Barents Sea. The observed Δ47-temperature relationship is similar to the theoretical relationship presented by Guo et al. (2009) but deviates at low temperatures from the original Ghosh et al. (2007) calibration curve. This divergence could be related to methodological differences or unaccounted differences in the biomineralization of mollusks versus that of other carbonate-secreting organisms at low temperature. One advantage of clumped isotope thermometry over traditional oxygen isotope thermometry is that it does not require assumptions about the isotopic composition of the water in which the carbonate formed. This may be particularly useful in Mesozoic paleoceanography where the oxygen isotope value of seawater is uncertain. Using clumped isotope thermometry applied to early Cretaceous (Valangian) belemnite carbonate from the Yatria River, sub-polar Urals, Siberia, we find shell growth temperatures of 20-26°C at a paleolatitude of ~60-65°N. Our data imply average seawater δ18O values of 0.5-1.5‰ when used in conjunction with published temperature-δ18Ocarb-δ18Osw calibrations. This δ18O range is higher than is traditionally assumed for high-latitude Cretaceous seawater. We argue, however, that such values are plausible and may be related to different basin- or global-scale hydrologies or belemnite body fluid that was in isotopic disequilibrium with the seawater. The paired Δ47 and δ18O from the fossils rule out isotopic exchange with high temperature fluids or later diagenesis in 18O-depleted meteoric waters. We observe no textual or chemical evidence of recrystallization, and we hypothesize that these shells faithfully record early Cretaceous high-latitude seawater temperatures. The inferred temperature range of 20-26°C is substantially higher than 60-70°N modern mean annual sea surface temperature (˜-1.0 to 10.0°C) and mean summer surface temperatures (˜-0.5 to 14.5°C), implying a substantially shallower latitudinal temperature gradient during the early Cretaceous.

  6. 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???.

  7. 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.

  8. Titan Aerosol Formation as a Sink for Stable Carbon and Nitrogen Isotopes

    NASA Astrophysics Data System (ADS)

    Trainer, Melissa G.; Stern, Jennifer C.; Sebree, Joshua A.; Gautier, Thomas J.; Fuentes, Javier A.; Domagal-Goldman, Shawn D.; Mandt, Kathleen E.

    2015-11-01

    Stable isotope ratios of major elements can be used to infer much about local- and global-scale processes on a planet. On Titan, aerosol production is a significant sink of carbon and nitrogen in the atmosphere, and isotopic fractionation of these elements may be introduced during the advanced organic chemistry that leads to the condensed phase products. Several stable isotope pairs, including 12C/13C and 14N/15N, have been measured in situ or probed spectroscopically by Cassini-borne instruments, space telescopes, or through ground-based observations. However, the effect of a potentially critical pathway for isotopic fractionation - organic aerosol formation and subsequent deposition onto the surface of Titan - has not been considered due to insufficient data regarding fractionation during aerosol formation. To better understand the nature of this process, we have measured the isotopic fractionation associated with the formation of Titan aerosol analogs via far-UV irradiation of several methane (CH4) and nitrogen (N2) mixtures.Our initial results probed the fractionation of the aerosol product, relative to the reactant gases, as a function of CH4 abundance [1]. Our results show that the direction of carbon isotope fractionation during aerosol formation is in contrast to the expected result if the source of the fractionation is a kinetic isotope effect. The resultant fractionation in nitrogen favored the light (14N) isotope in the aerosol, with N/C ratios varying from 0.13 - 0.31. Ongoing work includes probing the effects of pressure and temperature on the direction and magnitude of the stable isotope fractionation. We will present results alongside interpretation of the driving processes, as well as implications for Titan if similar fractionation occurred during aerosol formation in the atmosphere.[1] Sebree, J.A., Stern, J.C., Mandt, K.E., Domagal-Goldman, S.D., and Trainer, M.G.: 13C and 15N Fractionation of CH4/N2 Mixtures during Photochemical Aerosol Formation: Relevance to Titan, Icarus, in press, 2015, doi:10.1016/j.icarus.2015.04.016.

  9. Rapid Analysis of Carbon Isotopic Compositions of Sedimentary Algal Sterols

    NASA Astrophysics Data System (ADS)

    Ménot-Combes, G.; Sessions, A. L.; Hayes, J. M.; Altabet, M. A.; Higginson, M. J.

    2002-12-01

    We are developing a new procedure to produce highly resolved records of the carbon isotopic composition of algal sterols. The procedure includes: (i) recovery of geolipids from dry sediments by extraction in organic solvents; (ii) chromatographic fractionation of the extract on silica gel; and (iii) removal of n-alcohols with Silicalite. Simplifications allow processing of 24 samples per day. Miniaturization has reduced the amount of sediment required to 300 mg. The carbon isotopic composition of the extract is measured using a moving-wire combustion system initially developed to accept the effluent of a liquid chromatograph (Brand and Dobberstein, Isotopes Environ. Health Stud. 32, 275-283, 1996). Analyses are made at 25-sec intervals with an average standard error of 0.15‰ for samples ranging from 200 to 900 ngC. Comparison of the resulting records of the isotopic composition of algal lipids to parallel analyses of inorganic carbon allows calculation of the isotopic fractionation associated with primary production and thus provides information about conditions in the photic zone. It serves also to identify samples in which more detailed, compound-specific analysis would be worthwhile. A highly-resolved record of 13C in polar lipids from a sediment core collected on the Oman Margin (ODP 723B) indicates fractionations between 20 and 25‰ . Events occurring on timescales of a few hundred years have caused variations as large as 4‰ . Increases in the fractionation could be caused by slowed rates of growth, an increase of the surface area/volume ratio of the community or an increase in the concentration of CO2. Such changes could be related to varying strengths of upwelling, supplies of key nutrients, or to changes in the dominant population in the producer community. Characterization of the lipids present at selected depths, as well as the comparison of our profile with existing paleoceanographic records from the Oman Margin, should allow refinement of these possibilities.

  10. Using natural isotopic abundances to determine the source of nitrous oxide (N2O) emissions

    NASA Astrophysics Data System (ADS)

    Mothet, A.; Sebilo, M.; Laverman, A. M.; Vaury, V.; Mariotti, A.

    2012-04-01

    Numerous greenhouse gas studies have focused on carbon dioxide (CO2), whereas nitrous oxide (N2O) also plays a major role in global warming. Indeed, while nitrous oxide is 1000 times less concentrated than CO2 in the atmosphere, it is 300 times more efficient in terms of global warming potential. In addition, its atmospheric concentration increases with 0,3 % per year. According to the literature, nitrous oxide is produced, in soils and sediments, by two major processes: (1) Nitrification, mediated by autotrophic nitrifying bacteria under oxic conditions; (2) Denitrification, mediated by heterotrophic denitrifying bacteria under anoxic conditions. Denitrification induces intensive, localized and instantaneous fluxes. N2O emissions can be easily measured and modeled. In contrast, nitrification induces weak emissions, but spatially and temporally extended. Therefore, this process could represent a large potential of N2O emissions from soils and sediments. The study of isotopomer's isotopic composition of N2O, i.e. the intramolecular distribution or site preference (SP) determined by 15N measurement allows the determination of the origin of N2O emissions (nitrification vs. denitrification). Recent studies on pure cultures have showed that SP associated with nitrification is 35 ‰ while SP associated with denitrification is 0 ‰. The aim of this study was to determine SP associated with denitrification in soils and sediments, taking into account the environmental denitrifying bacterial communities, and under different environmental variables. To this end, flow-through reactors were used to determine denitrification rates at different temperatures and varying substrate (nitrate) concentrations. Site preference was measured for the different experiments. Different experiments of denitrification were realized in sediment flow through reactors under denitrifying conditions (anoxia, presence of organic matter and nitrate). We used acetylene (25°C) to block the enzyme nitrous oxide reductase, resulting in accumulation of N2O originating only from denitrification. Despite the fact that the isotopic composition of the produced N2O (15N and 18O) varies, the SP did not change significantly (SP = 6 ‰). These results compared to those of chemical denitrification show that despite very different isotopic compositions, the SP value is independent of the type of denitrification. Different nitrate concentrations (5 mM, 3 mM, 1,5 mM and 1 mM) at ambient temperature (25°C). The results of N2O production kinetics were not related to nitrate concentrations. SP of N2O are currently being analyzed. Different temperatures (35°C, 25°C and 12°C) and a nitrate concentration of 5 mM. The results of N2O production kinetics at different temperatures show an increase in N2O emissions with increasing temperature. SP of N2O are currently being analyzed. The goal for future work is to study the SP in these systems relative to salinity, pH and carbon organic concentration in denitrifying conditions but also in nitrifying conditions.

  11. Abundance and Characterization of Dissolved Organic Carbon in Suburban Streams of Baltimore, Maryland, USA

    NASA Astrophysics Data System (ADS)

    Mora, G.; Fazekas, M.

    2014-12-01

    The contribution of streams and rivers to the carbon cycle is significant, transporting to the oceans ~1.4 Pg C/yr, with dissolved carbon corresponding to as much as 0.7 Pg C/yr. Changes in land use have the potential effect of modifying this flux, particularly in urban areas where impervious areas are common. To investigate the effect of urbanization on riverine carbon transport, we studied four first-order streams in Towson, a suburb of Baltimore, Maryland, USA. The watersheds from the studied streams exhibit different levels of urbanization as measured by the percentage of impervious areas. Samples from these four streams were taken weekly, and several chemical constituents were measured either in the field or in the laboratory. These constituents included nitrate, dissolved organic nitrogen, pH, dissolved organic carbon (DOC), total carbon, dissolved inorganic carbon (DIC), phosphate, the carbon isotopic compositions of DOC and DIC, and fluorescence intensity of the DOC. Results show that DOC concentrations were consistently below 5 mg C/L regardless of the level of imperviousness of the watershed. Similarly, carbon isotope ratios were consistent across the studied streams, with values centered around -26.4 per mil, thus suggesting a significant influx of soil-derived organic carbon originated from C3 plants that are common in the watersheds. Confirming this interpretation, fluorescence spectroscopy data suggest a humic-like origin for the DOC of the streams, thus pointing to the heterotrophic nature of the streams. The combined results suggest that the studied streams exhibit similar DOC concentrations, carbon isotopic values, and fluorescence spectra, despite their level of impervious surfaces in their watersheds.

  12. Forward Modeling of Carbonate Proxy Data from Planktonic Foraminifera using Oxygen Isotope Tracers in a Global Ocean Model

    NASA Technical Reports Server (NTRS)

    Schmidt, Gavin A.

    1999-01-01

    The distribution and variation of oxygen isotopes in seawater are calculated using the Goddard Institute for Space Studies global ocean model. Simple ecological models are used to estimate the planktonic foraminiferal abundance as a function of depth, column temperature, season, light intensity, and density stratification. These models are combined to forward model isotopic signals recorded in calcareous ocean sediment. The sensitivity of the results to the changes in foraminiferal ecology, secondary calcification, and dissolution are also examined. Simulated present-day isotopic values for ecology relevant for multiple species compare well with core-top data. Hindcasts of sea surface temperature and salinity are made from time series of the modeled carbonate isotope values as the model climate changes. Paleoclimatic inferences from these carbonate isotope records are strongly affected by erroneous assumptions concerning the covariations of temperature, salinity, and delta (sup 18)O(sub w). Habitat-imposed biases are less important, although errors due to temperature-dependent abundances can be significant.

  13. Stable Carbon Isotope Fractionation by Methylotrophic Methanogenic Archaea

    PubMed Central

    Penger, Jörn; Conrad, Ralf

    2012-01-01

    In natural environments methane is usually produced by aceticlastic and hydrogenotrophic methanogenic archaea. However, some methanogens can use C1 compounds such as methanol as the substrate. To determine the contributions of individual substrates to methane production, the stable-isotope values of the substrates and the released methane are often used. Additional information can be obtained by using selective inhibitors (e.g., methyl fluoride, a selective inhibitor of acetoclastic methanogenesis). We studied stable carbon isotope fractionation during the conversion of methanol to methane in Methanosarcina acetivorans, Methanosarcina barkeri, and Methanolobus zinderi and generally found large fractionation factors (−83‰ to −72‰). We further tested whether methyl fluoride impairs methylotrophic methanogenesis. Our experiments showed that even though a slight inhibition occurred, the carbon isotope fractionation was not affected. Therefore, the production of isotopically light methane observed in the presence of methyl fluoride may be due to the strong fractionation by methylotrophic methanogens and not only by hydrogenotrophic methanogens as previously assumed. PMID:22904062

  14. 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.

  15. Ion-microprobe measurements of H, C, O, Mg, and Si isotopic abundances in individual interplanetary-dust particles

    SciTech Connect

    McKeegan, K.D.

    1987-01-01

    This thesis reports the isotopic abundances of H, C, O, Mg, and/or Si measured by means of secondary ion mass spectrometry in 48 individual approx. 10-..mu..m-diameter particles collected from the Earth's stratosphere. Thirty-one of these are chondritic interplanetary dust particles (IDPs). The results of a search for previously unrecognized types of IDPs are also reported. The D/H ratios measured in individual fragments of 34 IDPs give deltaD values ranging from -386 to 2705 per thousand relative to SMOW. Fourteen particles exhibit significant D excesses, and 4 particles have D depletions. The hydrogen isotopic compositions are heterogeneous on a several micron size scale. Carbonaceous material is the primary carrier of the D enrichments. The D-rich molecules in the IDPs were probably produced by isotope-exchange reactions between ions and molecules at low temperatures in dark interstellar clouds. Most of the IDPs have isotopically normal C, Mg, and Si. No correlations between deltaD and C,O, Mg, or Si isotopic compositions are observed. Isotopic anomalies that can be attributed to incomplete mixing of distinct nucleosynthetic components are found in a few particles.

  16. 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.

  17. On the Stability and Abundance of Single Walled Carbon Nanotubes

    PubMed Central

    Hedman, Daniel; Reza Barzegar, Hamid; Rosén, Arne; Wågberg, Thomas; Andreas Larsson, J.

    2015-01-01

    Many nanotechnological applications, using single-walled carbon nanotubes (SWNTs), are only possible with a uniform product. Thus, direct control over the product during chemical vapor deposition (CVD) growth of SWNT is desirable, and much effort has been made towards the ultimate goal of chirality-controlled growth of SWNTs. We have used density functional theory (DFT) to compute the stability of SWNT fragments of all chiralities in the series representing the targeted products for such applications, which we compare to the chiralities of the actual CVD products from all properly analyzed experiments. From this comparison we find that in 84% of the cases the experimental product represents chiralities among the most stable SWNT fragments (within 0.2 eV) from the computations. Our analysis shows that the diameter of the SWNT product is governed by the well-known relation to size of the catalytic nanoparticles, and the specific chirality is normally determined by the product’s relative stability, suggesting thermodynamic control at the early stage of product formation. Based on our findings, we discuss the effect of other experimental parameters on the chirality of the product. Furthermore, we highlight the possibility to produce any tube chirality in the context of recent published work on seeded-controlled growth. PMID:26581125

  18. On the Stability and Abundance of Single Walled Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Hedman, Daniel; Reza Barzegar, Hamid; Rosén, Arne; Wågberg, Thomas; Andreas Larsson, J.

    2015-11-01

    Many nanotechnological applications, using single-walled carbon nanotubes (SWNTs), are only possible with a uniform product. Thus, direct control over the product during chemical vapor deposition (CVD) growth of SWNT is desirable, and much effort has been made towards the ultimate goal of chirality-controlled growth of SWNTs. We have used density functional theory (DFT) to compute the stability of SWNT fragments of all chiralities in the series representing the targeted products for such applications, which we compare to the chiralities of the actual CVD products from all properly analyzed experiments. From this comparison we find that in 84% of the cases the experimental product represents chiralities among the most stable SWNT fragments (within 0.2 eV) from the computations. Our analysis shows that the diameter of the SWNT product is governed by the well-known relation to size of the catalytic nanoparticles, and the specific chirality is normally determined by the product’s relative stability, suggesting thermodynamic control at the early stage of product formation. Based on our findings, we discuss the effect of other experimental parameters on the chirality of the product. Furthermore, we highlight the possibility to produce any tube chirality in the context of recent published work on seeded-controlled growth.

  19. 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.

  20. A Large Velocity Gradient Model for Formaldehyde Spectra in Dark Clouds with Applications to Galactic Isotopic Abundance Ratios.

    NASA Astrophysics Data System (ADS)

    Massano, William Joseph

    1982-03-01

    Dark Nebula provide radio astronomers with a wealth of information. Many molecules present in these clouds have transitions which are easily seen with today's equipment. One such molecule is the ortho species of formaldehyde. The 6-cm transition is particularly interesting as it appears in absorption despite the low kinetic temperatures (10 - 50(DEGREES)K) of the clouds. This absorption makes formaldehyde a useful probe of cloud dynamics as the cooling effects are sensitive to the conditions present in the clouds. Initial attempts to model cloud dynamics relied on ad hoc assumptions concerning the cloud's temperature. Principally the assumption of thermal equilibrium was made. With the advent of high-speed computers, more realistic models, known as non-LTE (non Local Thermal Equilibrium), have emerged. These make the less stringent assumption of statistical equilibrium. The non-LTE models divide roughly into two classes. The microturbulent and Large Velocity Gradient (LVG) models. It is one of the latter class of models that will be developed here. LVG allows the simplest explanation for the linewidths and has none of the other potential problems of the other class of models. The model developed here encompassess the first 22 energy levels (in order of increasing energy) of ortho-formaldehyde and is shown to be consistent with observed spectra. As an application, the LVG model is used to generate theoretical corrections for radiative-trapping effects in dark clouds. These corrections are used to modify observational results to obtain the isotopic abundance ratio of ('12)C/('13)C in the galactic center and plane. The calculations show that the LVG model gives a straightforward method of generating theoretical profiles which fit quite well to experimental observations. In fact, the theoretical profiles match well with very general input parameters. Applying this model to the optically thin species H(,2)('13)CO and H(,2)C('18)O demonstrates that using even such thin species requires a radiative -trapping correction factor of about 8%. With this factor, the ('12)C/('13)C ratio is determined to be nearly terrestrial in the galactic plane, and approximately half terrestrial in the center. This indicates that formaldehyde in the galactic center may be undergoing some sort of chemical fractionation in the carbon isotope.

  1. 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.

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

    SciTech Connect

    Magdas, D. A. Cristea, G. Bot, A. Mirel, V.

    2013-11-13

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

  3. Mass Accuracy and Isotopic Abundance Measurements for HR-MS Instrumentation: Capabilities for Non-Targeted Analyses

    NASA Astrophysics Data System (ADS)

    Knolhoff, Ann M.; Callahan, John H.; Croley, Timothy R.

    2014-07-01

    The development of automated non-targeted workflows for small molecule analyses is highly desirable in many areas of research and diagnostics. Sufficient mass and chromatographic resolution is necessary for the detectability of compounds and subsequent componentization and interpretation of ions. The mass accuracy and relative isotopic abundance are critical in correct molecular formulae generation for unknown compounds. While high-resolution instrumentation provides accurate mass information, sample complexity can greatly influence data quality and the measurement of compounds of interest. Two high-resolution instruments, an Orbitrap and a Q-TOF, were evaluated for mass accuracy and relative isotopic abundance with various concentrations of a standard mixture in four complex sample matrices. The overall average ± standard deviation of the mass accuracy was 1.06 ± 0.76 ppm and 1.62 ± 1.88 ppm for the Orbitrap and the Q-TOF, respectively; however, individual measurements were ± 5 ppm for the Orbitrap and greater than 10 ppm for the Q-TOF. Relative isotopic abundance measurements for A + 1 were within 5% of the theoretical value if the intensity of the monoisotopic peak was greater than 1E7 for the Orbitrap and 1E5 for the Q-TOF, where an increase in error is observed with a decrease in intensity. Furthermore, complicating factors were found in the data that would impact automated data analysis strategies, including coeluting species that interfere with detectability and relative isotopic abundance measurements. The implications of these findings will be discussed with an emphasis on reasonable expectations from these instruments, guidelines for experimental workflows, data analysis considerations, and software design for non-targeted analyses.

  4. The Zn abundance and isotopic composition of diatom frustules, a proxy for Zn availability in ocean surface seawater

    NASA Astrophysics Data System (ADS)

    Andersen, Morten B.; Vance, Derek; Archer, Corey; Anderson, Robert F.; Ellwood, Michael J.; Allen, Claire S.

    2011-01-01

    We have developed cleaning methods for extracting diatomopal from bulk marine sediment samples, for measurement of both zinc (Zn) abundance and isotope composition. This cleaning technique was then applied to a set of Holocene core-top samples from the Southern Ocean. The measured δ66Zn (reported relative to the JMCLyon standard) and Zn/Si ratios from the Southern Ocean diatomopal samples range from 0.7 to 1.5‰, and from 14 to 0.9 μmol/mol, respectively. The Zn abundance and isotope composition data show a clear correlation with opal burial rates and other oceanographic parameters. In common with previous work, we interpret the systematic changes in the Zn/Si ratio to be linked to the variability in the concentrations of bioavailable Zn in the ambient surface seawater where the diatom opal is formed. This variability is likely to be primarily controlled by the degree to which Zn is taken up into phytoplankton biomass. The observed systematic pattern in the δ66Zn compositions of the diatomopal core-top samples is, similarly, likely to reflect changes in the δ66Zn composition of the ambient Zn in the surface waters above the core-top sites, which is progressively driven towards isotopically heavier values by preferential incorporation of the lighter isotopes into phytoplankton organic material. Thus, the systematic relationship between Zn isotopes and abundance observed in the core-top diatomopal samples suggests a potential tool for investigating the biogeochemical cycling of Zn in the past surface ocean for down-core diatomopal material. In this respect, it may be possible to test hypotheses that attribute variations in atmospheric CO2 on glacial-interglacial timescales to the degree to which trace metals limited primary productivity in HNLC zones.

  5. 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 separate local, regional and even global environment condition impact to isotopic values in the past. 1. Hammarlund, Dan, et al. "Climate and environment during the Younger Dryas (GS-1) as reflected by composite stable isotope records of lacustrine carbonates at Torreberga, southern Sweden." Journal of Quaternary Science 14.1 (1999): 17-28. 2. Makhnach, N., et al. "Stable oxygen and carbon isotopes in Late Glacial-Holocene freshwater carbonates from Belarus and their palaeoclimatic implications." Palaeogeography, Palaeoclimatology, Palaeoecology 209.1 (2004): 73-101.

  6. Stable carbon and nitrogen isotope enrichment in primate tissues.

    PubMed

    Crowley, Brooke E; Carter, Melinda L; Karpanty, Sarah M; Zihlman, Adrienne L; Koch, Paul L; Dominy, Nathaniel J

    2010-11-01

    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. PMID:20628886

  7. 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

  8. Regional Atmospheric Circulation Change in the North Pacific During the Holocene Inferred from Lacustrine Carbonate Oxygen Isotopes, Yukon Territory, Canada

    NASA Astrophysics Data System (ADS)

    Anderson, L.; Abbott, M. B.; Finney, B. P.; Burns, S. J.

    2004-12-01

    Analyses of sediment cores from Jellybean Lake, a small, hydrologically-open groundwater-fed lake, provide a record of changes in North Pacific atmospheric circulation for the last 7500 years at twenty to thirty-year resolution. A regional isotope hydrology study in the southern Yukon indicates that the oxygen isotope composition of water from Jellybean Lake reflects the oxygen isotope composition of mean annual precipitation. Thus, the oxygen isotope history of Jellybean Lake inferred from sedimentary carbonate oxygen isotope ratios suggests multi-decadal shifts in the oxygen isotope composition of mean annual precipitation superimposed on century and millennial trends. Recent fluctuations of Jellybean oxygen isotopes correlate well with changes in the North Pacific Index, a measure of the intensity and position of the Aleutian Low. We propose that oxygen isotope variability of precipitation in the interior of the Yukon is related to the degree of fractionation during moisture transport from the Gulf of Alaska across the St Elias Mountains that is ultimately controlled by the position and strength of the Aleutian Low. Following this model, Aleutian Low intensity during the early to middle Holocene was relatively reduced and increasing intensity coincided with the initial onset of Neoglacial advances. Rapid shifts during the last two millennia corresponds with glacial activity, changes in North Pacific salmon abundance, and shifts in atmospheric circulation over the Beaufort Sea.

  9. Carbon and nitrogen isotope studies in an arctic ecosystem. Final report

    SciTech Connect

    Schell, D.M.

    1994-06-01

    The dynamics of carbon fixation and storage in tundra soils has received considerable attention with respect to global carbon cycling. Recent findings by investigators using chamber measurements of fixation/respiration rates in arctic tundra have led to the conclusion that tundra is no longer storing carbon but is instead a source of carbon dioxide to the atmosphere. The author has sought to test these conclusions and to determine methods by which the long-term accumulation or loss of carbon in tundra can be determined. Little is known, however, of the processes that control storage and the current rates of carbon fixation and peat formation in arctic Alaska. This project focused on several aspects of carbon dynamics and the roles of decomposition and herbivory at the DOE research site at Imnavait Creek, Alaska. Through the use of natural abundance stable and radioisotope techniques, several conclusions emerged. Peat carbon continues to accumulate in wetter areas of foothill valleys and on the coastal plain of arctic Alaska. Radiocarbon profiles of bomb {sup 14}C were used to date layers of vegetation and litter to obtain decomposition rates and to extrapolate these values to intersection with the permafrost horizon where further decomposition is assumed to cease. Carbon storage in riparian moss at Imnavait Creek was estimated at 3 g C/m{sup 2}-yr. Profiles of {sup 137}Cs closely matched those of {sup 14}C and may provide a more expeditious means of assessing recent carbon accumulation rates in tundra. Carbon and nitrogen stable isotope ratios in tundra vegetation vary markedly over hydrologic gradients in apparent response to changing growth rates and sources of nitrogenous nutrients. Within a taxon, {delta}{sup 15}N values varied by several {per_thousand} over a tens of meters distance.

  10. A stable carbon isotope and biological marker study of Polish bituminous coals and carbonaceous shales

    USGS Publications Warehouse

    Kotarba, M.J.; Clayton, J.L.

    2003-01-01

    Biological marker and carbon isotopic compositions of coals and carbonaceous shales from the Upper Carboniferous strata of the Upper Silesian (USCB), Lower Silesian (LSCB), and Lublin (LCB) coal basins were determined to assess depositional conditions and sources of the organic matter. n-Alkane, sterane, and isoprenoid distribution, and carbon isotope ratios are consistent with an origin from higher plants. In some cases, pristane/phytane (Pr/Ph) ratios of carbonaceous shales (roof and floor shales) are < 1.0, while the associated coals have high ratios (??? 1.0). This suggests that reducing conditions prevailed during deposition of the shales, but a period of oxidizing conditions accompanied deposition of the coals. Steranes present in coal extracts are dominated by the 14??(H)17??(H)20R C29 stereoisomers, typical, but not conclusive, of higher plant origin. Carbonaceous shales exhibit a wider range of sterane composition, suggesting local, significant input of algal organic matter. Significant amounts of benzohopanes and gammacerane are present in some coals. Although benzohopanes are present at least in small amounts in samples from many different environments, they have been reported to occur most commonly in marine environments. The present study seems to provide the first example where benzohopanes have been reported in significant amounts in terrestrial organic matter. Gammacerane is abundant in rocks or sediments deposited in carbonate or highly saline marine environments. The finding of high gammacerane concentrations in the coals expands the depositional settings in which it has been observed and questions its utility as an independent indicator of hypersaline carbonate environments. Stable carbon isotope composition of coals, and type III kerogen in carbonaceous shales as well as correlation of stable carbon isotope composition of saturated and aromatic hydrocarbons in carbonaceous shales from both the USCB and the LSCB indicate terrigenous origin. Bitumens are always co-genetic with associated coals and kerogens. Isotopic data reveal that Sofer's genetic classification of oils is not applicable to organic matter in coals. ?? 2003 Elsevier B.V. All rights reserved.

  11. Maturation of Green River Shale Kerogen with Hydrous Pyrolysis: Characterization of Geochemical Biomarkers and Carbon Isotopes

    NASA Astrophysics Data System (ADS)

    Fu, Q.; Darnell, M.; Bissada, K. K.

    2014-12-01

    To fully understand controlling factors of organic compound generation during oil shale maturation, and systematically assess associated carbon isotope values, a series of hydrous pyrolysis experiments are performed. Kerogen was isolated from Green River shale by a set of acid treatment. Experiments are conducted at 350 °C and 300 bars of total pressure with running time of 24, 48 and 72 hours, respectively. In each experiment, the reactor contains 1.5 grams of kerogen and 30 grams of deionized water. After experiments, gaseous products are removed under cryogenic conditions for chemical and carbon isotope analyses (GC-IRMS). The bitumen product is retrieved and separated into saturated hydrocarbons, aromatics, resins, and asphaltenes (SARA) by HPLC before subsequent analyses (GC, GC-MS, and IRMS). The gaseous compounds from experiments consisted of CO2 and C1 to C4 hydrocarbons. Semiquantitative analysis indicates the yield of n-alkanes decreases with carbon number, with CO2 being more abundant than all alkanes. The δ13C value of alkanes increases with molecular weight, with CO2 having the highest value. Methane and ethane become enriched in 13C with time. In bitumen products, gravimetric analysis has shown that the abundance of aromatics increases with time, while that of asphaltenes decreases. After 72 hours, the weight percentages of saturated hydrocarbons, aromatics, resins and asphaltenes are 2.6, 42.3, 40.1, and 15.0, respectively. High resolution GC-MS results indicate low kerogen maturation after 72 hours using saturated biomarker compounds as thermal maturity indicator, such as 22S/(22S + 22R) of C31 to C35 homohopanes, tricyclics/17(H)-hopanes, and Ts/(Ts + Tm). Bulk carbon isotope value of bitumen decreases with time, with 2.5‰ lighter than original kerogen after 72 hours. In terms of different groups, saturated hydrocarbons and resins become depleted in 13C with longer reaction time, while aromatics and asphaltenes become enriched in 13C. Experiments with longer reaction time and under different physicochemical conditions are underway. That would facilitate a better understanding of oil and gas generation and carbon isotope systematics during kerogen maturation processes for effective conventional and unconventional exploration.

  12. The clumped isotope geothermometer in soil and paleosol carbonate

    NASA Astrophysics Data System (ADS)

    Quade, J.; Eiler, J.; Daëron, M.; Achyuthan, H.

    2013-03-01

    We studied both modern soils and buried paleosols in order to understand the relationship of temperature (T°C(47)) estimated from clumped isotope compositions (Δ47) of soil carbonates to actual surface and burial temperatures. Carbonates from modern soils with differing rainfall seasonality were sampled from Arizona, Nevada, Tibet, Pakistan, and India. T°C(47) obtained from these soils shows that soil carbonate forms in the warmest months of the year, in the late morning to afternoon, and probably in response to intense soil dewatering. T°C(47) obtained from modern soil carbonate ranges from 10.8 to 39.5 °C. On average, T°C(47) exceeds mean annual temperature by 10-15 °C due to summertime bias in soil carbonate formation, and to summertime ground heating by incident solar radiation. Secondary controls on T°C(47) are soil depth and shading. Site mean annual air temperature (MAAT) across a broad range (0-30 °C) of site temperatures is highly correlated with T°C(47) from soils, following the equation: MAAT(°C)=1.20(T°C(47)0)-21.72(r2=0.92) where T°C(47)0 is the effective air temperature at the site estimated from T°C(47). The effective air temperature represents the air temperature required to account for the T°C(47) at each site, after consideration of variations in T°C(47) with soil depth and ground heating. The highly correlated relationship in this equation should now permit mean annual temperature in the past to be reconstructed from T°C(47) in paleosol carbonate, assuming one is studying paleosols that formed in environments generally similar in seasonality and ground cover to our calibration sites. T°C(47)0 decreases systematically with elevation gain in the Himalaya, following the equation: elevation(m)=-229(T°C(47)0)+9300(r2=0.95) Assuming that temperature varied similarly with elevation in the past, this equation can be used to reconstruct paleoelevation from clumped isotope analysis of ancient soil carbonates. We also measured T°C(47) from long sequences of deeply buried (⩽5 km) paleosol carbonate in the Himalayan foreland in order to evaluate potential diagenetic resetting of clumped isotope composition. We found that paleosol carbonate faithfully records plausible soil T°C(47) down to 2.5-4 km burial depth, or ˜90-125 °C. Deeper than this and above this temperature, T°C(47) in paleosol carbonate is reset to temperatures >40 °C. We observe ˜40 °C as the upper limit for T°C(47) in modern soils from soil depths >25 cm, and therefore that T°C(47) >40 °C obtained from ancient soil carbonate indicates substantially warmer climate regimes compared to the present, or non-primary temperatures produced by resetting during diagenesis. If representative, this limits the use of T°C(47) to reconstruct ancient surface temperature to modestly buried (<3-4 km) paleosol carbonates. Despite diagenetic resetting of Δ47 values, δ18O and δ13C values of the same deeply buried paleosol carbonate appear unaltered. We conclude that solid-state reordering or recrystallization of clumping of carbon and oxygen isotopes can occur in the absence of open-system exchange of paleosol carbonate with significant quantities of water or other phases.

  13. Carbon and Nitrogen Isotope Variation in Peat Bogs in the Midwestern US: Implications for Holocene Climate Reconstruction

    NASA Astrophysics Data System (ADS)

    Wong, D.; Paytan, A.; Jackson, S.

    2008-12-01

    A peat core, from near the center of Minden Bog in Michigan, representing about 3500 years of accumulation was previously analyzed for plant macrofossils, colorimetric humification, and testate amoebae to yield three independent climate proxies (Booth and Jackson, 2003). The plant macrofossil data show the site to be sensitive to bog water table fluctuations. The data suggest that this may be related to regional climatic changes. We analyzed the carbon and nitrogen isotopes, as well as the carbon-nitrogen ratios in the bulk peat samples to determine if fluctuations of these records correspond to climate events as seen in the plant microfossil and amoebae records. The degree to which peat-based carbon and nitrogen isotope records reflect changes in the relative distribution of vegetation and, in turn, reflect temperature changes in effective precipitation (precipitation minus evapotranspiration) will be assessed. Peat carbon and nitrogen isotope records will be compared with existing proxy climate records and with a temperature reconstruction based on testate amoebae in bogs. We expect that climate-related changes, in the relative abundance of vegetation remains accumulating in the peat bogs, will be recorded in the organic matter in forms of carbon and nitrogen isotopes.

  14. Abundance Anomaly of the 13C Isotopic Species of c-C3H2 in the Low-mass Star Formation Region L1527

    NASA Astrophysics Data System (ADS)

    Yoshida, Kento; Sakai, Nami; Tokudome, Tomoya; López-Sepulcre, Ana; Watanabe, Yoshimasa; Takano, Shuro; Lefloch, Bertrand; Ceccarelli, Cecilia; Bachiller, Rafael; Caux, Emmanuel; Vastel, Charlotte; Yamamoto, Satoshi

    2015-07-01

    The rotational spectral lines of c-C3H2 and two kinds of the 13C isotopic species, c-{}13{{CCCH}}2 ({C}2v symmetry) and c-{{CC}}13{{CH}}2 (Cs symmetry), have been observed in the 1-3 mm band toward the low-mass star-forming region L1527. We have detected 7, 3, and 6 lines of c-C3H2, c-{}13{{CCCH}}2, and c-{{CC}}13{{CH}}2, respectively, with the Nobeyama 45 m telescope and 34, 6, and 13 lines, respectively, with the IRAM 30 m telescope, where seven, two, and two transitions, respectively, are observed with both telescopes. With these data, we have evaluated the column densities of the normal and 13C isotopic species. The [c-C3H2]/[c-{}13{{CCCH}}2] ratio is determined to be 310 ± 80, while the [c-C3H2]/[c-{{CC}}13{{CH}}2] ratio is determined to be 61 ± 11. The [c-C3H2]/[c-{}13{{CCCH}}2] and [c-C3H2]/[c-{{CC}}13{{CH}}2] ratios expected from the elemental 12C/13C ratio are 60-70 and 30-35, respectively, where the latter takes into account the statistical factor of 2 for the two equivalent carbon atoms in c-C3H2. Hence, this observation further confirms the dilution of the 13C species in carbon-chain molecules and their related molecules, which are thought to originate from the dilution of 13C+ in the gas-phase C+ due to the isotope exchange reaction: {}13{{{C}}}++{CO}\\to {}13{CO}+{{{C}}}+. Moreover, the abundances of the two 13C isotopic species are different from each other. The ratio of c-{}13{{CCCH}}2 species relative to c-{{CC}}13{{CH}}2 is determined to be 0.20 ± 0.05. If 13C were randomly substituted for the three carbon atoms, the [c-{}13{{CCCH}}2]/[c-{{CC}}13{{CH}}2] ratio would be 0.5. Hence, the observed ratio indicates that c-{{CC}}13{{CH}}2 exists more favorably. Possible origins of the different abundances are discussed. Based on observations carried out with the IRAM 30 m Telescope and the NRO 45 m Telescope. IRAM is supported by INSU/CNRS (France), MPG (Germany), and IGN (Spain). NRO is a branch of the National Astronomical Observatory of Japan, National Institutes of Natural Sciences, Japan.

  15. Trace sulfate in mid-Proterozoic carbonates and the sulfur isotope record of biospheric evolution

    NASA Astrophysics Data System (ADS)

    Gellatly, Anne M.; Lyons, Timothy W.

    2005-08-01

    Concentrations of oceanic and atmospheric oxygen have varied over geologic time as a function of sulfur and carbon cycling at or near the Earth's surface. This balance is expressed in the sulfur isotope composition of seawater sulfate. Given the near absence of gypsum in pre-Phanerozoic sediments, trace amounts of carbonate-associated sulfate (CAS) within limestones or dolostones provide the best available constraints on the isotopic composition of sulfate in Precambrian seawater. Although absolute CAS concentrations, which range from those below detection to ˜120 ppm sulfate in this study, may be compromised by diagenesis, the sulfur isotope compositions can be buffered sufficiently to retain primary values. Stratigraphically controlled δ 34S measurements for CAS from three mid-Proterozoic carbonate successions (˜1.2 Ga Mescal Limestone, Apache Group, Arizona, USA; ˜1.45-1.47 Ga Helena and Newland formations, Belt Supergroup, Montana, USA; and ˜1.65 Ga Paradise Creek Formation, McNamara Group, NW Queensland, Australia) show large isotopic variability (+9.1‰ to +18.9‰, -1.1‰ to +27.3‰, and +14.1‰ to +37.3‰, respectively) over stratigraphic intervals of ˜50 to 450 m. This rapid variability, ranging from scattered to highly systematic, and overall low CAS abundances can be linked to sulfate concentrations in the mid-Proterozoic ocean that were substantially lower than those of the Phanerozoic but higher than values inferred for the Archean. Results from the Belt Supergroup specifically corroborate previous arguments for seawater contributions to the basin. Limited sulfate availability that tracks the oxygenation history of the early atmosphere is also consistent with the possibility of extensive deep-ocean sulfate reduction, the scarcity of bedded gypsum, and the stratigraphic δ 34S trends and 34S enrichments commonly observed for iron sulfides of mid-Proterozoic age.

  16. 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 0.20 ‰ for JCp-1 and 0.15 ‰ for JCt-1, hence within uncertainty of the reported values. With the exception of one MC-ICPMS lab that provided significantly lower JCp-1 δ11B data for unoxidised material (1.7 ‰ below median), the remaining JCp-1 results reproduced within ± 0.54 ‰ for unoxidised (n=21) and ± 0.37 ‰ for oxidised standards (n=21). The JCt-1 standards did not reproduce as well, resulting in a 2 s.d. of 1.0 ‰ for both unoxidised and oxidised powders (n=21) and in places the effect of oxidation appeared to be laboratory dependent. Exclusion of one MC-ICPMS lab resulted in an improved reproducibility of 0.52 ‰ (n=18) for oxidised JCt-1 material. The mean difference for the two standard materials in the respective labs (i.e., Δδ11B = mean δ11B(JCp-1) - mean δ11B(JCt-1)) was 7.9 ± 0.9 ‰ for unoxidised (n=7) and 8.1 ± 0.7 ‰ for oxidised standards (n=7). In this presentation emphasis will also be placed on distinguishing factors leading to increased/decreased interlaboratory consistency during the preparation and analysis of biogenic carbonates for other isotopic systems. References [1] Foster, G.L. et al. (2013) Chemical Geology 358: p. 1-14. [2] Okai, T. et al. (2002) Geostandards Newsletter 26: p. 95-99. [3] Inoue, M. et al. (2004) Geostandards and Geoanalytical Research 28: p. 411-416.

  17. CNO ABUNDANCES OF HYDROGEN-DEFICIENT CARBON AND R CORONAE BOREALIS STARS: A VIEW OF THE NUCLEOSYNTHESIS IN A WHITE DWARF MERGER

    SciTech Connect

    Garcia-Hernandez, D. A.; Lambert, David L.; Eriksson, K. E-mail: hinkle@noao.edu E-mail: Kjell.Eriksson@astro.uu.se

    2009-05-10

    We present high-resolution (R {approx} 50, 000) observations of near-IR transitions of CO and CN of the five known hydrogen-deficient carbon (HdC) stars and four R Coronae Borealis (RCB) stars. We perform an abundance analysis of these stars by using spectrum synthesis and state-of-the-art MARCS model atmospheres for cool hydrogen-deficient stars. Our analysis confirms reports by Clayton and colleagues that those HdC stars exhibiting CO lines in their spectrum and the cool RCB star S Aps are strongly enriched in {sup 18}O (with {sup 16}O/{sup 18}O ratios ranging from 0.3 to 16). Nitrogen and carbon are in the form of {sup 14}N and {sup 12}C, respectively. Elemental abundances for CNO are obtained from C I, C{sub 2}, CN, and CO lines. Difficulties in deriving the carbon abundance are discussed. Abundances of Na from Na I lines and S from S I lines are obtained. Elemental and isotopic CNO abundances suggest that HdC and RCB stars may be related objects, and that they probably formed from a merger of an He white dwarf with a C-O white dwarf.

  18. Biogeochemistry of a mesotrophic lake and it's carbon isotope geochemistry

    NASA Astrophysics Data System (ADS)

    Cheng, S.; Ehresman, W.; Sadurski, S. E.

    2010-12-01

    Crystal Lake, located in west-central Ohio, is the main lake of a series of 4 interconnected lakes. The location and orientation indicate that they are most likely moulin-induced glacial lakes. Crystal Lake is about 5 hectares (12.5 acres). The maximum depth and mean depth are about 11.9 meters and 3.8 meters, respectively. As a result of this high depth-to-surface area ratio, it creates a strong thermal stratification during warm season. The lake was classified as eutrophic lake. However, the water quality has improved in the past decades. The chlorophyll in the epillimnion and upper metalimlion is about 4 μg/l and the Secchi disk depth is about 3.0 meters (10 feet). It is therefore reclassified as mesotrophic lake. Dissolved oxygen maximum (15.6 ppm) and pH peak (8.6) existed at 4.1 meter on August 16, 2010. At around 7.3 meter, where redox potential reading shows a sudden change from oxidizing to reducing , a ~half meter layer of dense purple sulfur bacteria coincides with turbidity, chlorophyll, and sulfate maxima. The chemical depth profiles are a result of thermal stratification, oxygenic photosynthesis by algae, non-oxygenic photosynthesis by purple sulfur bacteria, and respiration in the hypolimnion. Precipitation of calcium carbonate in the epilimnion and metalimnion is coupled by it’s dissolution in the hypolimnion. The purpose of the current project is to present extensive background study to form the framework for quantifying the carbon isotope evolution with multiple reaction pathways. Carbon isotope composition of dissolved inorganic carbon is being analyzed. Wigley-Plummer-Pearson mass transfer model will be used for the quantification of carbon isotope reaction pathways.

  19. Coupling Organic Carbon and Nitrogen Isotope with Carbonate Carbon Isotope Excursion Across the Early Mississippian Kinderhookian-Osagean Boundary in Great Basin, Western USA

    NASA Astrophysics Data System (ADS)

    Maharjan, D. K.; Jiang, G.; Peng, Y.; Sahoo, S. K.; Henry, R. A.

    2014-12-01

    The Early Mississippian Kinderhookian-Osagean (K-O) boundary transition represents one of the largest global perturbations of carbon cycle during Phanerozoic. This interval is characterized by large positive carbonate carbon isotope anomaly (δ13Ccarb) enriched to more than + 5‰ that has been globally recognized. Controversies exit regarding the origin and nature of this carbon isotope excursion. Here we report that a primary preservation of the K-O δ13Ccarb excursion was coupled by organic carbon isotope (δ13Corg) and organic nitrogen isotope (δ15Norg) from carbonate successions of Great Basin in Western USA. Our samples were obtained from Mountain Home (MH) and Alamo (AL) sections, represent shallow and deeper depositional environment, respectively. The values of δ13Ccarb covaried with δ13Corg in both sections, indicating photosynthetic origin of organic carbon isotope excursion during K-O. δ13Ccarb values from AL records 1-1.5‰ higher than MH, possibly related to locally higher production. Carbonate-organic carbon isotope differences (Δ13C = δ13Ccarb - δ13Corg) increase across the peak of δ13Ccarb excursion in AL section but remain invariant ∆δ13C in MH, suggesting that δ13Corg values in AL may have been imprinted with signature from secondary (chemo- and methanotrophic) biomass contribution as anoxia was developed in the distal carbonate platform. The contrasting ∆δ13C profiles in time-equivalent sections questioned the general concept that increase in ∆δ13C records elevated O2/CO2 ratios, as have been suggested for Late Cambrian and Permo-Carboniferous. Only when the temporal depositional environments did not change, the ∆δ13C may have implications for changes in O2/CO2 ratios. Nitrogen isotopes values increased to 4‰ across the K-O δ13C excursion indicating increased pelagic denitrification in response to the development of oxygen minimum zone as a result of enhanced organic carbon production, global cooling and sea-level fall. The integrated δ13Ccarb, δ13Corg, and δ15Norg data across the K-O transition support an organic carbon burial event associated with global cooling/oxygenation occurred during the Early Mississippian.

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

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

    The Paleocene-Eocene Thermal Maximum (PETM), a period of abrupt, transient, and large-scale global warming fueled by a large release of isotopically light carbon, is a relevant analogue for episodes of rapid global warming and recovery. The PETM is recorded in pedogenic carbonate, bulk organic matter, and n-alkanes as a prominent negative carbon isotope excursion (CIE) in paleosols exposed in the Bighorn Basin, WY. Here we present a composite stable carbon isotope record from n-alkanes and dispersed soil organic δ13C records from five individual sections that span the PETM in the southeastern Bighorn Basin. Four sections are from a 10km transect in the Cabin Fork area and one section was collected at Sand Creek Divide. These five new dispersed organic carbon (DOC) isotope records are compared to the previously published Polecat Bench (Magioncalda et al. 2004) and Honeycombs (Yans et al. 2006) isotope records. The high-resolution n-alkane curve shows an abrupt, negative shift in δ13C values, an extended CIE body, and a rapid recovery to more positive δ13C values. Although the five DOC records show similarly abrupt negative shifts in δ13C values, the DOC CIEs are compressed, smaller in magnitude, and return to more positive δ13C values more gradually relative to the n-alkane record. Moreover, the stratigraphic thickness of the body of the excursion and the pattern of the recovery phase are not consistent among the five DOC records. We modeled predicted DOC δ13C values from the n-alkane record by applying enrichment factors based on modern plants to the n-alkane δ13C values. The anomaly, difference between the expected and observed DOC δ13C values, was calculated for the PETM records and compared to weight percent carbon and grain size. There is no correlation between pre- and post-PETM anomaly values and grain size or weight percent carbon. PETM anomaly values, however, do trend with both grain size and weight percent carbon. The largest PETM anomaly values correspond to the highest grain sizes and lowest weight percent carbon. We hypothesize that the difference between the n-alkane and DOC δ13C records is due to contamination of the DOC δ13C signal by weathering of older, refractory Jurassic-Cretaceous carbon. According to this hypothesis, before and after the CIE the difference in the isotopic composition of autochthonous (Cenozoic) and allochthonous (Jurassic-Cretaceous) organic matter would have been small because C3 plants in the Jurassic-Cretaceous and pre- and post-PETM had relatively similar values. Thus, the ratio of autochthonous: allochthonous organic matter would be uncorrelated with isotopic composition. During the CIE, the isotopic composition of autochthonous organic carbon decreased dramatically. Therefore, autochthonous and allochthonous carbon pools were isotopically distinct and a correlation between weight percent carbon and isotopic composition is expected: the lower the weight percent carbon, the higher the proportion of allochthonous carbon, the larger the anomaly.

  1. Carbonate concretions as a significant component of ancient marine carbon cycles: Insights from paired organic and inorganic carbon isotope analyses of a Cretaceous shale

    NASA Astrophysics Data System (ADS)

    Loyd, S. J.

    2014-12-01

    Carbonate concretions often occur within fine-grained, organic-rich sedimentary rocks. This association reflects the common production of diagenetic minerals through biologic cycling of organic matter. Chemical analysis of carbonate concretions provides the rare opportunity to explore ancient shallow diagenetic environments, which are inherently transient due to progressive burial but are an integral component of the marine carbon cycle. The late Cretaceous Holz Shale (~80 Ma) contains abundant calcite concretions that exhibit textural and geochemical characteristics indicative of relatively shallow formation (i.e., near the sediment-water interface). Sampled concretions contain between 5.4 and 9.8 wt.% total inorganic carbon (TIC), or ~45 and 82 wt.% CaCO3, compared to host shale values which average ~1.5 wt.% TIC. Organic carbon isotope compositions (δ13Corg) are relatively constant in host and concretion samples ranging from ­-26.3 to -24.0‰ (VPDB). Carbonate carbon isotope compositions (δ13Ccarb) range from -22.5 to -3.4‰, indicating a significant but not entirely organic source of carbon. Concretions of the lower Holz Shale exhibit considerably elevated δ13Ccarb values averaging -4.8‰, whereas upper Holz Shale concretions express an average δ13Ccarb value of -17.0‰. If the remaining carbonate for lower Holz Shale concretions is sourced from marine fluids and/or dissolved marine carbonate minerals (e.g., shells), a simple mass balance indicates that ~28% of concretion carbon was sourced from organic matter and ~72% from late Cretaceous marine inorganic carbon (with δ13C ~ +2.5‰). Upper Holz Shale calculations indicate a ~73% contribution from organic matter and a ~27% contribution from inorganic carbon. When normalized for carbonate, organic contents within the concretions are ~2-13 wt.% enriched compared to host contents. This potentially reflects the protective nature of cementation that acts to limit permeability and chemical destruction of organic material. These data imply that concretion growth in shallow sediments can act as a significant and long-term sink for both marine inorganic and organic carbon.

  2. Anomalous Oxygen Isotopic Fractionation in Vacuum Ultraviolet Photodissociation of Carbon Monoxide and Test of Self-Shielding: Relevance for Meteorite Oxygen Isotopes

    NASA Astrophysics Data System (ADS)

    Chakraborty, S.; Ahmed, M.; Jackson, T. L.; Thiemens, M. H.

    2008-12-01

    Oxygen is the predominant elemental constituent of rocky planets and asteroids. It is the third most abundant element in the solar system after hydrogen and helium. The isotopic compo-sition of oxygen in three-isotope space (δ18O vs. δ17O plot) exhibits large heterogeneity among different bodies formed from the same primordial gas and dust mixture, termed the solar nebula. It is not possible to fully understand the formation and evolution of our own planetary system, unless we resolve the source of the oxygen isotopes. At present, there are two models: self shielding photochemistry in the solar nebula, and symmetry driven gas-phase and/or surface chemistry in the solar nebula, which can also involve photochemistry, but isn't required. Photochemistry is a dominant process at the outer layers of the nebular disk and isotopically selective photodissociation (a process known as isotopic self-shielding) of carbon monoxide, the most abundant nebular oxygen bearing molecule, has been suggested as a source of isotopically anomalous oxygen in the solar reservoir [1-3]. However, these models have had no experimental verification of the relevant isotopic fractionation associated with VUV-CO photodissociation at the relevant wavelengths. Recently, we have performed a series of CO photodissociation experiment with a windowless flow chamber at the Advanced Light Source (LBNL) synchrotron at Berkeley. These experiments demonstrate an anomalously enriched atomic oxygen reservoir is generated through CO photo-dissociation, but, without requiring isotopic self shielding [4]. These results emphasize the importance of chemistry in the solar nebula as we have previously demonstrated through recent laboratory experiments [5]. It is clear that the mass- independent oxygen isotopic composition, as observed in some of the first condensed solids in the solar system (Calcium-Aluminum rich Inclusions- CAIs, Chondrules etc.), can be generated through symmetry driven gas-phase chemical reactions. We will present new oxygen isotope data of VUV photodissociation of CO and discuss the relevance of this data to address the anomalous oxygen isotopic compositions of meteorites. References: [1] Clayton R. N. (2002) Nature, 415, 860-861. [2] Yurimoto H. and Kuramoto K. (2004) Science, 305, 1763-1766. [3] Lyons J. R. and Young E. D. and (2005) Nature, 435, 317-320. [4] Chakraborty S., Ahmed M., Jackson, T. L. and Thiemens M.H. (2008) Science, 321, 1328-1331. [5] Kimura Y., Nuth J. A., Chakraborty S., and Thiemens M. H. (2007) Meteoritics and Planetary Science, 42, 1429-1439.

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

    SciTech Connect

    Guy, R.D. ); Fogel, M.L.; Berry, J.A. )

    1993-01-01

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

  4. STABLE ISOTOPIC EVIDENCE OF CARBON AND NITROGEN USE IN CULTURED ECTOMYCORRHIZAL AND SAPROTROPHIC FUNGI

    EPA Science Inventory

    Stable isotopes in sporocarps have proven useful for inferring ectomycorrhizal or saprotrophic status and understanding carbon (C) and nitrogen (N) utilization. However, greater understanding of processes producing isotopic concentrations is needed. We measured natural abundanc...

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

    SciTech Connect

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

    1993-01-01

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

  6. Combined carbonate carbon isotopic and cellular ultrastructural studies of individual benthic foraminifera: Method description

    NASA Astrophysics Data System (ADS)

    Martin, Jonathan B.; Bernhard, Joan M.; Curtis, Jason; Rathburn, Anthony E.

    2010-06-01

    Carbon isotopes of foraminiferal tests provide a widely used proxy for past oceanographic environmental conditions. This proxy can be calibrated using live specimens, which are reliably identified with observations of cell ultrastructure. Observations of ultrastructures can also be used for studies of biological characteristics such as diet and presence of symbionts. Combining biological and isotopic studies on individual foraminifera could provide novel information, but standard isotopic methods destroy ultrastructures by desiccating specimens and observations of ultrastructure require removal of carbonate tests, preventing isotope measurements. The approach described here preserves cellular ultrastructure during isotopic analyses by keeping the foraminifera in an aqueous buffer (Phosphate Buffered Saline (PBS)). The technique was developed and standardized with 36 aliquots of NBS-19 standard of similar weight to foraminiferal tests (5 to 123 μg). Standard errors ranged from ± 0.06 to ± 0.85‰ and were caused by CO2 contaminants dissolved in the PBS. The technique was used to measure δ13C values of 96 foraminifera, 10 of which do not precipitate carbonate tests. Calcareous foraminiferal tests had corrected carbon isotope ratios of -8.5 to +3.2‰. This new technique allows comparisons of isotopic compositions of tests made by foraminifera known to be alive at the time of collection with their biological characteristics such as prey composition and presence or absence of putative symbionts. The approach may be applied to additional biomineralizing organisms such as planktonic foraminifera, pteropods, corals, and coccolithophores to elucidate certain biological controls on their paleoceanographic proxy signatures.

  7. Abundance anomalies of carbon and nitrogen in the IUE spectra of Algol-type interacting binaries

    NASA Technical Reports Server (NTRS)

    Mccluskey, Carolina P. S.

    1990-01-01

    There are two primary ways in which the products of nucleosynthesis in stellar interiors may appear at the surface of a star. These are mixing and/or loss of the original unburned stellar envelope. In interacting binaries, overflow can contribute dramatically to envelope loss. The simplest abundance anomalies to be expected from nuclear burning of hydrogen, helium, or carbon would be under or over abundances H, He, C, O, Ne, and Mg. In addition, it is expected that carbon is initially severely depleted, while nitrogen is enhanced during hydrogen burning via the CNO cycle in stars above two solar masses. Other, more subtle anomalies are also expected, and elements heavier than magnesium can be created during very late evolution by nuclear burning in massive stars. Consequently, it is expected that abundance anomalies of various kinds should occur in interacting binaries where one or both stars have lost significant amounts of mass.

  8. On strontium isotopic anomalies and odd-A p-process abundances. [in solar system

    NASA Technical Reports Server (NTRS)

    Clayton, D. D.

    1978-01-01

    Several aspects of the nucleosynthesis of Sr isotopes are considered in an attempt to shed light on the problem of the Sr isotopic anomalies discovered in an inclusion of the Allende meteorite. Decomposition of the Sr isotopes into average r-, s-, and p-process nucleosynthetic classes is performed. It is suggested that the Allende inclusion most likely has an excess of s-process Sr and that the initial Sr-87/Sr-86 isotopic ratio is probably slightly more primitive than basaltic achondrites. The results also show that Sn-115 is mostly due to the r-process and that odd-A yields are very small. It is concluded that if the Sr anomaly in the inclusion is an average s enhancement, it argues somewhat in favor of a model of gas/dust fractionation of s and r isotopes during accumulation of the inclusion parent in the protosolar cloud.

  9. Lithium isotopes and light lithophile element abundances in shergottites: Evidence for both magmatic degassing and subsolidus diffusion

    NASA Astrophysics Data System (ADS)

    Udry, Arya; McSween, Harry Y.; Hervig, Richard L.; Taylor, Lawrence A.

    2016-01-01

    Degassed magmatic water was potentially the major source of surficial water on Mars. We measured Li, B, and Be abundances and Li isotope profiles in pyroxenes, olivines, and maskelynite from four compositionally different shergottites—Shergotty, QUE 94201, LAR 06319, and Tissint—using secondary ion mass spectrometry (SIMS). All three light lithophile elements (LLE) are incompatible: Li and B are soluble in H2O-rich fluids, whereas Be is insoluble. In the analyzed shergottites, Li concentration decreases and Be concentration increases from cores to rims in pyroxenes. However, B concentrations do not vary consistently with Li and Be abundances, except in QUE 94201 pyroxenes. Additionally, abundances of these three elements in olivines show a normal igneous-fractionation trend consistent with the crystallization of olivine before magma ascent and degassing. We expect that kinetic effects would lead to fractionation of 6Li in the vapor phase compared to 7Li during degassing. The Li isotope profiles, with increasing δ7Li from cores to rims, as well as Li and B profiles indicate possible degassing of hydrous fluids only for the depleted shergottite QUE 94201, as also supported by degassing models. Conversely, Shergotty, LAR 06319, and Tissint appear to have been affected by postcrystallization diffusion, based on their LLE and Li isotope profiles, accompanied by diffusion models. This process may represent an overlay on a degassing pattern. The LLE profiles and isotope profiles in QUE 94201 support the hypothesis that degassing of some basaltic shergottite magmas provided water to the Martian surface, although evidence may be obscured by subsolidus diffusion processes.

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

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

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

  11. A continuous 250,000 yr record of oxygen and carbon isotopes in ostracode and bulk-sediment carbonate from Bear Lake, Utah-Idaho

    USGS Publications Warehouse

    Bright, Jordon; Kaufman, D.S.; Forester, R.M.; Dean, W.E.

    2006-01-01

    Oxygen and carbon isotopes from a continuous, 120-m-long, carbonate-rich core from Bear Lake, Utah-Idaho, document dramatic fluctuations in the hydrologic budget of the lake over the last 250,000 yr. Isotopic analyses of bulk sediment samples capture millennial-scale variability. Ostracode calcite was analyzed from 78 levels, mainly from the upper half of the core where valves are better preserved, to compare the isotopic value of purely endogenic carbonate with the bulk sediment, which comprises both endogenic and detrital components. The long core exhibits three relatively brief intervals with abundant endogenic aragonite (50??10%) and enriched ??18O and ??13C. These intervals are interpreted as warm/dry periods when the lake retracted into a topographically closed basin. We correlate these intervals with the interglacial periods of marine oxygen-isotope stages 1, 5e, and 7a, consistent with the presently available geochronological control. During most of the time represented by the core, the lake was fresher than the modern lake, as evidenced by depleted ??18O and ??13C in bulk-sediment carbonate. ?? 2006 Elsevier Ltd. All rights reserved.

  12. Carbon and oxygen isotopes in apatite CO/sub 2/ and co-existing calcite

    SciTech Connect

    Kolodny, Y.; Kaplan, I. R.

    1981-04-01

    Carbon and oxygen isotopes were analyzed in carbonate apatite CO/sub 2/ and in co-existing calcite. Both C and O in apatite CO/sub 2/ are enriched in the respective light isotopes relative to calcite. These results confirm the proposition that carbonate is part of the apatite structure.

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

    EPA Science Inventory

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

  14. Oxygen isotopic abundances in calcium- aluminum-rich inclusions from ordinary chondrites: implications for nebular heterogeneity.

    PubMed

    McKeegan, K D; Leshin, L A; Russell, S S; MacPherson, G J

    1998-04-17

    The oxygen isotopic compositions of two calcium-aluminum-rich inclusions (CAIs) from the unequilibrated ordinary chondrite meteorites Quinyambie and Semarkona are enriched in 16O by an amount similar to that in CAIs from carbonaceous chondrites. This may indicate that most CAIs formed in a restricted region of the solar nebula and were then unevenly distributed throughout the various chondrite accretion regions. The Semarkona CAI is isotopically homogeneous and contains highly 16O-enriched melilite, supporting the hypothesis that all CAI minerals were originally 16O-rich, but that in most carbonaceous chondrite inclusions some minerals exchanged oxygen isotopes with an external reservoir following crystallization. PMID:9545215

  15. 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

  16. Determination of the natural abundance δ15N of taurine by gas chromatography-isotope ratio measurement mass spectrometry.

    PubMed

    Tea, Illa; Antheaume, Ingrid; Besnard, Jorick; Robins, Richard J

    2010-12-15

    The measurement of the nitrogen isotope ratio of taurine (2-aminoethanesulphonic acid) in biological samples has a large number of potential applications. Taurine is a small water-soluble molecule which is notoriously difficult to analyze due to its polarity and functionality. A method is described which allows the determination of the natural abundance δ(15)N values of taurine and structural analogues, such as 3-amino-1-propanesulphonic acid (APSA), by isotope ratio mass spectrometry interfaced to gas chromatography (GC-irm-MS). The one-step protocol exploits the simultaneous derivatization of both functionalities of these aminosulphonic acids by reaction with triethylorthoacetate (TEOA). Conditions have been established which ensure quantitative reaction thus avoiding any nitrogen isotope fractionation during derivatization and workup. The differences in the δ(15)N values of derivatized and non-derivatized taurine and APSA all fall within the working range of 0.4‰ (-0.02 to 0.39‰). When applied to four sources of taurine with various δ(15)N values, the method achieved excellent reproducibility and accuracy. The optimized method enables the determination of the natural abundance δ(15)N values of taurine over the concentration range 1.5-7.84 µmol.mL(-1) in samples of biological origin. PMID:21072793

  17. Carbon Isotope Ratios in Crassulacean Acid Metabolism Plants

    PubMed Central

    Szarek, Stan R.; Troughton, John H.

    1976-01-01

    A year round study of photosynthesis and carbon isotope fractionation was conducted with plants of Opuntia phaeacantha Engelm. and Yucca baccata Torr. occurring in natural stands at elevations of 525, 970, 1450 and 1900 m. Plant water potentials and the daytime pattern of 14CO2 photosynthesis were similar for all cacti along the elevational gradient, despite significant differences in temperature regime and soil water status. Carbon isotope ratios of total tissue and soluble extract fractions were relatively constant throughtout the entire year. Additionally, the σ13C values were similar in all plants of the same species along the elevational gradient, i.e. −12.5 ± 0.86 ‰ for O. phaeacantha and −15.7 ± 0.95 ‰ for Y. baccata. The results of this study indicate Crassulacean acid metabolism predominates as the major carbon pathway of these plants, which do not facultatively utilize the reductive pentose phosphate cycle of photosynthesis as the primary carboxylation reaction. PMID:16659680

  18. Reaction cross sections of carbon isotopes incident on a proton

    SciTech Connect

    Abu-Ibrahim, B.; Horiuchi, W.; Kohama, A.; Suzuki, Y.

    2008-03-15

    We systematically study total reaction cross sections of carbon isotopes with N=6-16 on a proton target for wide range of incident energies. An emphasis is put on the difference from the case of a carbon target. The calculations include the reaction cross sections of {sup 19,20,22}C at 40A MeV, the data of which have recently been measured at RIKEN. The Glauber theory is used to calculate the reaction cross sections. To describe the intrinsic structure of the carbon isotopes, we use a Slater determinant generated from a phenomenological mean-field potential, and construct the density distributions. To go beyond the simple mean-field model, we adopt two types of dynamical models: One is a core+n model for odd-neutron nuclei, and the other is a core+n+n model for {sup 16}C and {sup 22}C. We propose empirical formulas which are useful in predicting unknown cross sections.

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

    NASA Astrophysics Data System (ADS)

    Neumann, K.; Lyons, W. B.; 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 by Doran et al. has shown that algal mats in these streams have delta C-13 values averaging -7.0%. 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. Additional information is contained in the original.

  20. Physiological and environmental factors related to carbon isotopic variations in mollusc shell carbonate

    SciTech Connect

    Krantz, D.E.; Williams, D.F.; Jones, D.S.

    1985-01-01

    The carbon isotopic composition of mollusc shell carbonate has been used as a general environmental indicator in numerous studies, but relatively little is known of the factors which affect within-shell variation. Primary control of delta/sup 13/C values in shell carbonate comes from the dissolved bicarbonate source, particularly as related to marine versus fresh water. Present models explain cyclic variations in the delta/sup 13/C profiles of mollusc shells due to upwelling, phytoplankton productivity and stratification, disequilibrium with rapid shell growth, and infaunal versus epifaunal habitat. Carbon and oxygen isotopic profiles in this study were obtained from specimens of Spisula solidissima (surf clam) and Placopecten magellanicus (sea scallop) collected alive from 14 to 57 m water depths off the Virginia coast. Three main factors appear to affect the delta/sup 13/C profiles in these specimens. Isotopically light values commonly associated with the spring and occasionally the fall correspond with seasonal phytoplankton productivity. A significant negative delta/sup 13/C offset of the infaunal Spisula relative to the epifaunal Placopecten probably relates to the inclusion of isotopically more negative pore-water bicarbonate by Spisula. Additionally, occasional transient spikes in both the delta/sup 18/O and delta/sup 13/C profiles correspond to intrusion of reduced-salinity water.

  1. RAPID AND PRECISE METHOD FOR MEASURING STABLE CARBON ISOTOPE RATIOS OF DISSOLVED INORGANIC CARBON

    EPA Science Inventory

    We describe a method for rapid preparation, concentration and stable isotopic analysis of dissolved inorganic carbon (d13C-DIC). Liberation of CO2 was accomplished by placing 100 ?l phosphoric acid and 0.9 ml water in an evacuated 1.7-ml gas chromatography (GC) injection vial. Fo...

  2. Carbon isotope ratios and impurities in diamonds from Southern Africa

    NASA Astrophysics Data System (ADS)

    Kidane, Abiel; Koch-Müller, Monika; Morales, Luiz; Wiedenbeck, Michael; De Wit, Maarten

    2015-04-01

    We are investigating the sources of diamonds from southern Africa by studying both their carbon isotopic composition and chemical impurities. Our samples include macro-sized diamonds from River Ranch kimberlite in Zimbabwe and the Helam and Klipspringer kimberlitic deposits from South Africa, as well as micro-sized diamonds from Klipspringer and Premier kimberlites in South Africa. We have characterized the samples for their structurally bounded nitrogen, hydrogen and platelets defect using a Fourier Transmission Infrared Spectroscopy (FTIR). Using the DiaMap routine, open source software (Howell et al., 2012), IR spectra were deconvulated and quantified for their nitrogen (A, B and D components) and hydrogen contents. High to moderate nitrogen concentrations (1810 to 400 µg/g; 400 to 50 µg/g respectively) were found in diamonds from Klipspringer and Helam. Moderate to low (<50 µg/g) nitrogen concentrations were observed in diamonds from Premier and River Ranch. Type II diamonds, i.e. diamonds with no N impurities, which are presumed to have been derived from ultramafic sources, are found in the River Ranch deposit. The macro- and micro-size diamonds from the Klipspringer deposit display similar nitrogen defects, with higher nitrogen concentration and more frequent D components found in the macro-size diamonds. One of the first steps towards reliable carbon isotope studies is the development of calibration materials for SIMS carbon isotopic analyses. We have investigated candidate materials both from a polycrystalline synthetic diamond sheet and two natural gem quality diamonds from Juina (Brazil). Electron-based images of the synthetic diamond sheet, obtained using GFZ Potsdam's dual beam FIB instrument, show many diamond grains with diameters greater than 35 µm. SIMS testing of the isotopic homogeneity of the back and front sides of the synthetic sheets reveal similar 13C/12C ratio within a RSD of <1 ‰ . SIMS isotopic analyses of the two natural diamond RMs yield a constant 13C/12C ratio with RSD of better than 0.5 ‰ . Using the natural diamond as calibratrant, a preliminary result on a selected diamond from the four kimberlitic sample suites yields a δ13C in range between -3 to -7 ‰ . Reference: Howell, D., O'Neill, C. J., Grant, K. J., Griffin, W. L., Pearson, N. J., & O'Reilly, S. Y. (2012). μ-FTIR mapping: Distribution of impurities in different types of diamond growth. Diamond and Related Materials, 29, 29-36. doi:10.1016/j.diamond.2012.06.003.

  3. The source charge and isotopic abundances of cosmic rays with Z = 9-16 - A study using new fragmentation cross sections

    NASA Technical Reports Server (NTRS)

    Webber, W. R.; Gupta, M.; Soutoul, A.; Ferrando, P.

    1990-01-01

    The cosmic ray source charge and isotopic abundances for charges with Z = 9-16 are reexamined using newly measured fragmentation cross sections in a standard Galactic propagation model. Compared with earlier studies, the cosmic-ray data are now consistent with no excess of Si-29 and Si-30 in the source relative to the solar coronal abundances. The excess of Mg-25 and Mg-26 is now about 1 sigma or less relative to solar coronal isotopic abundances, leaving Ne-22 as the only clearly established neutron-rich isotopic excess in the cosmic ray source. Better estimates of the source abundances of elements obtained using the new cross sections permit the conclusion that high first ionization potential (FIP) elements have a wide spread of compositional differences in the cosmic-ray source relative to solar coronal abundances, whereas elements with a low FIP have a composition similar to the solar corona.

  4. Isotope-based Fluvial Organic Carbon (ISOFLOC) Model: Model formulation, sensitivity, and evaluation

    NASA Astrophysics Data System (ADS)

    Ford, William I.; Fox, James F.

    2015-06-01

    Watershed-scale carbon budgets remain poorly understood, in part due to inadequate simulation tools to assess in-stream carbon fate and transport. A new numerical model termed ISOtope-based FLuvial Organic Carbon (ISOFLOC) is formulated to simulate the fluvial organic carbon budget in watersheds where hydrologic, sediment transport, and biogeochemical processes are coupled to control benthic and transported carbon composition and flux. One ISOFLOC innovation is the formulation of new stable carbon isotope model subroutines that include isotope fractionation processes in order to estimate carbon isotope source, fate, and transport. A second innovation is the coupling of transfers between carbon pools, including algal particulate organic carbon, fine particulate and dissolved organic carbon, and particulate and dissolved inorganic carbon, to simulate the carbon cycle in a comprehensive manner beyond that of existing watershed water quality models. ISOFLOC was tested and verified in a low-gradient, agriculturally impacted stream. Results of a global sensitivity analysis suggested the isotope response variable had unique sensitivity to the coupled interaction between fluvial shear resistance of algal biomass and the concentration of dissolved inorganic carbon. Model calibration and validation suggested good agreement at event, seasonal, and annual timescales. Multiobjective uncertainty analysis suggested inclusion of the carbon stable isotope routine reduced uncertainty by 80% for algal particulate organic carbon flux estimates.

  5. Isotopic Ratios of Carbon and Oxygen in Titan’s CO using ALMA

    NASA Astrophysics Data System (ADS)

    Serigano, Joseph; Nixon, C. A.; Cordiner, M. A.; Irwin, P. G. J.; Teanby, N. A.; Charnley, S. B.; Lindberg, J. E.

    2016-04-01

    We report interferometric observations of carbon monoxide (CO) and its isotopologues in Titan’s atmosphere using the Atacama Large Millimeter/submillimeter Array (ALMA). The following transitions were detected: CO (J = 1-0, 2-1, 3-2, 6-5), 13CO (J = 2-1, 3-2, 6-5), C18O (J = 2-1, 3-2), and C17O (J = 3-2). Molecular abundances and the vertical atmospheric temperature profile were derived by modeling the observed emission line profiles using NEMESIS, a line-by-line radiative transfer code. We present the first spectroscopic detection of 17O in the outer solar system with C17O detected at >8σ confidence. The abundance of CO was determined to be 49.6 +/- 1.8 ppm, assumed to be constant with altitude, with isotopic ratios 12C/13C = 89.9 +/- 3.4, 16O/18O = 486 +/- 22, and 16O/17O = 2917 +/- 359. The measurements of 12C/13C and 16O/18O ratios are the most precise values obtained in Titan’s atmospheric CO to date. Our results are in good agreement with previous studies and suggest no significant deviations from standard terrestrial isotopic ratios.

  6. Hydropyrolysis of steroids: a preparative step for compound-specific carbon isotope ratio analysis.

    PubMed

    Sephton, Mark A; Meredith, Will; Sun, Cheng-Gong; Snape, Colin E

    2005-01-01

    Compound-specific stable carbon isotope analysis by gas chromatography/combustion/isotope ratio mass spectrometry is an important method for the detection of steroid abuse in athletes. However, steroids in their natural form exhibit poor chromatographic resolution, while derivatization adds carbon thereby corrupting the starting stable isotopic composition. Hydropyrolysis is a new approach, which defunctionalizes steroids but leaves their carbon skeleton intact. The process improves chromatography, allowing the faithful measurement of carbon isotope ratios and enabling a more effective apportionment for the source of steroids and their metabolites. PMID:16228967

  7. Variability in the carbon isotope composition of individual amino acids in plant proteins from different sources: 1 Leaves.

    PubMed

    Lynch, Anthony H; Kruger, Nicholas J; Hedges, Robert E M; McCullagh, James S O

    2016-05-01

    The natural carbon isotope composition of individual amino acids from plant leaf proteins has been measured to establish potential sources of variability. The plant leaves studied, taken from a range of plant groups (forbs, trees, grasses, and freshwater aquatic plants), showed no significant influence of either season or environment (water and light availability) on their Δδ(13)C values. Plant groups did, however, differ in carbon isotope composition, although no consistent differences were identified at the species level. A discriminant analysis model was constructed which allowed leaves from (1) nettles, (2) Pooideae, (3) other Poales, (4) trees and (5) freshwater higher plants to be distinguished from each other on the basis of their natural abundance (13)C/(12)C ratios of individual amino acids. Differences in carbon isotope composition are known to be retained, to some extent, in the tissues of their consumers, and hence an understanding of compound-specific variation in (13)C/(12)C fractional abundance in plants has the potential to provide dietary insights of value in archaeological and ecological studies. PMID:26948983

  8. Carbon amendment and soil depth affect the distribution and abundance of denitrifiers in agricultural soils.

    PubMed

    Barrett, M; Khalil, M I; Jahangir, M M R; Lee, C; Cardenas, L M; Collins, G; Richards, K G; O'Flaherty, V

    2016-04-01

    The nitrite reductase (nirS and nirK) and nitrous oxide reductase-encoding (nosZ) genes of denitrifying populations present in an agricultural grassland soil were quantified using real-time polymerase chain reaction (PCR) assays. Samples from three separate pedological depths at the chosen site were investigated: horizon A (0-10 cm), horizon B (45-55 cm), and horizon C (120-130 cm). The effect of carbon addition (treatment 1, control; treatment 2, glucose-C; treatment 3, dissolved organic carbon (DOC)) on denitrifier gene abundance and N2O and N2 fluxes was determined. In general, denitrifier abundance correlated well with flux measurements; nirS was positively correlated with N2O, and nosZ was positively correlated with N2 (P < 0.03). Denitrifier gene copy concentrations per gram of soil (GCC) varied in response to carbon type amendment (P < 0.01). Denitrifier GCCs were high (ca. 10(7)) and the bac:nirK, bac:nirS, bac:nir (T) , and bac:nosZ ratios were low (ca. 10(-1)/10) in horizon A in all three respective treatments. Glucose-C amendment favored partial denitrification, resulting in higher nir abundance and higher N2O fluxes compared to the control. DOC amendment, by contrast, resulted in relatively higher nosZ abundance and N2 emissions, thus favoring complete denitrification. We also noted soil depth directly affected bacterial, archaeal, and denitrifier abundance, possibly due to changes in soil carbon availability with depth. PMID:26762934

  9. Modeling Chemical and Isotopic Variations in Lab Formed Hydrothermal Carbonates

    NASA Technical Reports Server (NTRS)

    Niles, P. B.; Leshin, L. A.; Golden, D. C.; Socki, R. A.; Guan, Y.; Ming, D. W.

    2005-01-01

    Chemical and mineralogical data (e.g. [1]) from Mars suggest that the history of liquid water on the planet was more sporadic in nature than long-lived. The non-equilibrium chemical and isotopic compositions of the carbonates preserved in the martian meteorite ALH84001 are direct evidence of ancient secondary minerals that have not undergone significant diagenesis or stabilization processes typical of long-lived aqueous systems on Earth. Thus secondary minerals and sediments on Mars may primarily record the characteristics of the aqueous environment in which they formed without being significantly overprinted by subsequent diagenetic processes during burial.

  10. Ca isotope fractionation in modern and fossil bivalve shell carbonate

    NASA Astrophysics Data System (ADS)

    Hippler, D.; Witbaard, R.; Buhl, D.; Immenhauser, A.

    2009-04-01

    Ca isotopes of bivalve carbonate, used in combination with light stable isotopes and metal/Ca ratios may provide a useful archive of annual and seasonal parameters such as temperature, salinity or nutrient level, and therefore for high-resolution palaeoclimate reconstructions, but the reliability of these proxies remains questionable given potential vital/ontogenetic and microenvironmental effects. Furthermore, in order to test the applicability of bivalve-based environmental proxies on geological time-scales, it is of crucial importance to assess the sensitivity of shell geochemistry to early diagenesis. We investigated these potential effects, first by using field cultured, intertidal and subtidal bivalve species cultured in the Dutch Wadden Sea, and second by using selected fossil bivalve shells from Pleistocene (MIS 5e) uplifted marine terraces located in the SE Gulf of Corinth area, Greece. Cultured individuals offer the chance to compare time series of instrumental environmental data directly to growth rate and shell chemistry, whereas fossil samples, which were exposed to meteoric conditions for an extended period, are perfect for studying potential diagenetic influences on the Ca isotope system. Ca isotope signatures of both cultured bivalve species are positively correlated with ambient seawater temperature. The slope of the temperature-fractionation relation is similar to inorganic calcite and aragonite precipitates. However, the Ca isotope values are offset from the inorganic curves of about 0.5 permil. The most likely explanation for this offset is a biological induced fractionation, which can be attributed to the active transport of calcium through different cell layers to the site of calcification. In contrast, the studied fossil shells show little variations in Ca isotope composition. We observed that fossil biogenic aragonite from the same chronostratigraphic unit is considerably less fractionated than fossil biogenic calcite, which can be either explained by an implausible temperature effect of approximately 10 degree Celsius or by weak diagenetic overprinting. To summarize, these results provide new insights into biomineralization processes and indicate however a limited use of Ca isotopes in bivalves as temperature proxy.

  11. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  13. Barium isotope abundances in meteorites and their implications for early Solar System evolution

    NASA Astrophysics Data System (ADS)

    Bermingham, K. R.; Mezger, K.; Scherer, E. E.; Horan, M. F.; Carlson, R. W.; Upadhyay, D.; Magna, T.; Pack, A.

    2016-02-01

    Several nucleosynthetic processes contributed material to the Solar System, but the relative contributions of each process, the timing of their input into the solar nebula, and how well these components were homogenized in the solar nebula remain only partially constrained. The Ba isotope system is particularly useful in addressing these issues because Ba isotopes are synthesized via three nucleosynthetic processes (s-, r-, p-process). In this study, high precision Ba isotope analyses of 22 different whole rock chondrites and achondrites (carbonaceous chondrites, ordinary chondrites, enstatite chondrites, Martian meteorites, and eucrites) were performed to constrain the distribution of Ba isotopes on the regional scale in the Solar System. A melting method using aerodynamic levitation and CO2-laser heating was used to oxidize SiC, a primary carrier of Ba among presolar grains in carbonaceous chondrites. Destruction of these grains during the fusion process enabled the complete digestion of these samples. The Ba isotope data presented here are thus the first for which complete dissolution of the bulk meteorite samples was certain. Enstatite chondrites, ordinary chondrites, and all achondrites measured here possess Ba isotope compositions that are not resolved from the terrestrial composition. Barium isotope anomalies are evident in most of the carbonaceous chondrites analyzed, but the 135Ba anomalies are generally smaller than previously reported for similarly sized splits of CM2 meteorites. Variation in the size of the 135Ba anomaly is also apparent in fused samples from the same parent body (e.g., CM2 meteorites) and in different pieces from the same meteorite (e.g., Orgueil, CI). Here, we investigate the potential causes of variability in 135Ba, including the contribution of radiogenic 135Ba from the decay of 135Cs and incomplete homogenization of the presolar components on the <0.8 g sample scale.

  14. Ground penetrating radar measurements show a spatial relationship between coarse root biomass and soil carbon abundance

    NASA Astrophysics Data System (ADS)

    O'Donnell, F. C.; Caylor, K. K.; Gerlein, C.; Bhattachan, A.

    2013-05-01

    In savanna ecosystems, the dynamics of soil organic carbon are complicated by multiple sources of inputs, created by the coexistance of trees and grasses, and by spatial heterogeneity induced by a patchy vegetation structure. A previous study on the spatial pattern of soil carbon abundance on the Kalahari Transect in Southern Africa found that for savannas with sparse woody cover the semivariogram of soil carbon abundance demonstrates periodicity. It is hypothesized that the periodicity is induced by the patchy spatial distribution of the canopies and root systems of woody plants. We tested this by mapping the abundance of coarse woody roots with ground penetrating radar. Spatial patterns of soil carbon abundance were measured at our research site in a previous study. The site is on the Botswana portion of the Kalahari Transect, and has deep, homogeneous, sandy soil. We ran the ground penetrating radar over three 20 by 20 meter square plots in two perpendicular directions. We filtered the radar images to remove background noise and applied a Hilbert transform to reduce echoes. In each plot, we also dug 20 root biomass sampling pits. Using the sampling pit data, we were able to verify that there is a log-linear relationship (r2 = 0.80) between radar signal return and coarse root biomass in the upper 50 cm of soil. Semivariograms of coarse root biomass inferred from radar returns showed periodicity at similar spatial scales to the periodicity in soil carbon abundance. Our results suggest that the belowground components of woody plants, which may extend well beyond their canopies, exert a stronger influence on soil carbon cycling than the aboveground components, illustrating a key issue with the common practice of dividing arid and semiarid landscapes into "under canopy" and "inter-canopy" components in analyses of soil biogeochemistry. We were able to show that a relationship exists between ground penetrating radar returns and coarse root biomass for dry, sandy soils. However, the large amount of information needed to determine a predictive relationship suggests that ground penetrating radar may be more useful in investigating spatial patterns of root biomass than as a tool for quantifying absolute biomass abundance.

  15. Chemical and carbon isotopic composition of dissolved organic carbon in a regional confined methanogenic aquifer

    USGS Publications Warehouse

    Aravena, R.; Wassenaar, L.I.; Spiker, E. C.

    2004-01-01

    This study demonstrates the advantage of a combined use of chemical and isotopic tools to understand the dissolved organic carbon (DOC) cycle in a regional confined methanogenic aquifer. DOC concentration and carbon isotopic data demonstrate that the soil zone is a primary carbon source of groundwater DOC in areas close to recharge zones. An in-situ DOC source linked to organic rich sediments present in the aquifer matrix is controlling the DOC pool in the central part of the groundwater flow system. DOC fractions, 13C-NMR on fulvic acids and 14C data on DOC and CH4 support the hypothesis that the in-situ DOC source is a terrestrial organic matter and discard the Ordovician bedrock as a source of DOC. ?? 2004 Taylor and Francis Ltd.

  16. Abundances and isotopic compositions of rhenium and osmium in pyrite samples from the Huaibei coalfield, Anhui, China

    USGS Publications Warehouse

    Liu, Gaisheng; Chou, C.-L.; Peng, Z.; Yang, G.

    2008-01-01

    Two pyrite samples from the Shihezi Formation (Lower Permian), Huaibei coalfield, Anhui, China, have been analyzed for abundances and isotopic compositions of rhenium and osmium using negative thermal ion mass spectrometry. The Re-Os ages of the pyrites are 64.4 and 226 Ma, which are younger than the formation age of the coal seam. The pyrite samples may consist of pyrite formed at various stages during the history of coal formation. The ??Osvalues of the two pyrite samples are +17 and +18, respectively. Such high ??Osvalues are reported for the first time for recycles crustal materials from a sedimentary basin. ?? Springer-Verlag 2007.

  17. Carbon isotope fractionation of sapropelic organic matter during early diagenesis

    USGS Publications Warehouse

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

    1984-01-01

    Study of an algal, sapropelic sediment from Mangrove Lake, Bermuda shows that the mass balance of carbon and stable carbon isotopes in the major organic constituents is accounted for by a relatively straightforward model of selective preservation during diagenesis. The loss of 13C-enriched carbohydrates is the principal factor controlling the intermolecular mass balance of 13C in the sapropel. Results indicate that labile components are decomposed leaving as a residual concentrate in the sediment an insoluble humic substance that may be an original biochemical component of algae and associated bacteria. An overall decrease of up to about 4??? in the ?? 13C values of the organic matter is observed as a result of early diagenesis. ?? 1984.

  18. A molecular organic carbon isotope record of miocene climate changes.

    PubMed

    Schoell, M; Schouten, S; Damsté, J S; de Leeuw, J W; Summons, R E

    1994-02-25

    The difference in carbon-13 ((13)C) contents of hopane and sterane biomarkers in the Monterey formation (Naples Beach, California) parallels the Miocene inorganic record of the change in (18)O (delta(18)O), reflecting the Miocene evolution from a well-mixed to a highly stratified photic zone (upper 100 meters) in the Pacific. Steranes (delta(13)C = 25.4 +/- 0.7 per mil versus the Pee Dee belemnite standard) from shallow photic-zone organisms do not change isotopically throughout the Miocene. In contrast, sulfur-bound C(35) hopanes (likely derived from bacterial plankton living at the base of the photic zone) have systematically decreasing (13)C concentrations in Middle and Late Miocene samples (delta(13)C = -29.5 to -31.5 per mil), consistent with the Middle Miocene formation of a carbon dioxide-rich cold water mass at the base of the photic zone. PMID:17831625

  19. Reconstructing grassland vegetation and paleotemperatures using carbon isotope ratios of bison tooth enamel

    NASA Astrophysics Data System (ADS)

    Hoppe, Kathryn A.; Paytan, Adina; Chamberlain, Page

    2006-08-01

    Carbon isotope ratios (δ13C values) of herbivores reflect the δ13C values of dietary plants, and the δ13C values of grazers (animals that consume >90% grass) reflect the local abundance of C3 versus C4 grasses. Because grassland C3/C4 ratios correlate with climate, the δ13C of fossil grazers may serve as a proxy for reconstructing paleoclimates and paleovegetation patterns. However, the accuracy of environmental reconstructions based on herbivore δ13C values is often uncertain, because the relationship between the δ13C of many animals and the abundance of C4 and C3 grasses has not been precisely quantified. We analyzed the δ13C of tooth enamel carbonate from modern bison (Bison bison bison) from nine localities in the United States. The C4 grass biomass at these sites ranged from <1% to ˜95% of the total grass biomass. The mean δ13C of enamel for each population correlated well with the local abundance of C4 grasses and with variations in mean annual temperatures. The variability of enamel δ13C values did not differ among habitats and was not correlated with the abundance of C4 grasses. These results demonstrate that analyses of the δ13C values of fossil bison can be used as a quantitative proxy for reconstructing grassland C3/C4 ratios and paleotemperatures, and they will serve as a baseline for interpreting the δ13C of fossil bison and other large herbivores in North America.

  20. Kinetic fractionation of carbon and oxygen isotopes during hydration of carbon dioxide

    NASA Astrophysics Data System (ADS)

    Zeebe, Richard E.

    2014-08-01

    Kinetic isotope effects (KIEs) during the inorganic hydration of carbon dioxide (CO2) in aqueous solution cause reduced stable carbon and oxygen isotope ratios (13C/12C and 18O/16O) in the reaction product carbonic acid (H2CO3) or bicarbonate ion (HCO3-), relative to CO2. While such KIEs are of importance in various physicochemical, geochemical, and biological systems, very few experimental and theoretical studies have attempted to determine the magnitude of the carbon and oxygen kinetic isotope fractionation (KIF) during hydration of CO2. Here I use transition state theory (TST) and quantum chemistry calculations to investigate the reaction rates of isotopic reactants CO2+nH2O (n = 1-8) along the hydration pathway to H2CO3 or HCO3-. Locating transition states is difficult and the quantum chemistry calculations time-consuming at large n. My results suggest that the hydration mechanism for n = 1-3 is unlikely to be the dominant pathway producing KIFs during CO2 hydration in aqueous solution; hydration mechanisms for n ⩾ 4 appear more likely. For n = 4-8, the predicted KIF based on MP2/aug-cc-pVDZ calculations at 25 °C is ∼1.023-1.033 and ∼1.013-1.015, for carbon and oxygen, respectively. However, these values are uncertain and the results of the present study suggest that new experimental work is required to accurately determine the KIF of carbon and oxygen during CO2 hydration.

  1. CARBON ISOTOPE FRACTIONATION AND DEPLETION IN TMC1

    SciTech Connect

    Liszt, H. S.; Ziurys, L. M.

    2012-03-01

    {sup 12}C/{sup 13}C isotopologue abundance anomalies have long been predicted for gas-phase chemistry in molecules other than CO and have recently been observed in the Taurus molecular cloud (TMC) in several species hosting more than one carbon atom, i.e., CCH, CCS, CCCS, and HC{sub 3}N. Here we work to ascertain whether these isotopologic anomalies actually result from the predicted depletion of the {sup 13}C{sup +} ion in an oxygen-rich optically shielded dense gas, or from some other more particular mechanism or mechanisms. We observed {lambda}3mm emission from carbon-, sulfur-, and nitrogen-bearing isotopologues of HNC, CS, and H{sub 2}CS at three positions in Taurus (TMC1, L1527, and the NH{sub 3} peak) using the ARO 12 m telescope. We saw no evidence of {sup 12}C/{sup 13}C anomalies in our observations. Although the pool of C{sup +} is likely to be depleted in {sup 13}C, {sup 13}C is not depleted in the general pool of carbon outside CO, which probably exists mostly in the form of C{sup 0}. The observed isotopologic abundance anomalies are peculiar to those species in which they are found.

  2. Late Pleistocene Variability of the Carbon Isotopic Composition of Organic Matter in the Eastern Mediterranean: Monitor of Changes in Carbon Sources and Atmospheric CO2 Concentrations

    NASA Astrophysics Data System (ADS)

    Fontugne, M. R.; Calvert, S. E.

    1992-02-01

    The organic carbon isotopic record of the sapropels (S1 and S3-S10) and intercalated marl oozes has been determined in a 12-m piston core from the eastern Mediterranean. The ?13Corganic values are systematically lighter (mean=-21.00.82 ) in all sapropels and heavier (mean=-18.81.07) in the marl oozes. These differences are not due to variable marine and terrestrial organic matter mixtures because all values are heavier than modern plankton in the Mediterranean, there is no relationship between the Corganic/N ratios and the isotopic values, and published information on the abundance and distribution of organic biomarkers shows that terrestrial material constitutes a minor fraction of the total organic matter. Temperature effects on isotope fractionation are also discounted because the change in ?13Corganic values between glacial and interglacial horizons is in the opposite sense. Diagenesis, which can produce relatively small changes in the carbon isotopic composition of sedimentary organic matter under certain circumstances, is unlikely to have caused the observed differences because this mechanism would cause an enrichment in 12C, implying that all values were even heavier originally, and there is no secular trend in the ?13Corganic record. The observed differences in ?13Corganic between the two lithologies are probably produced by changes in the isotopic composition and the concentration of dissolved CO2. First, freshwater flooding during the formation of the sapropels caused the isotopic composition of the dissolved inorganic carbon in the surface waters of the Mediterranean to become lighter because of the 13C deficiency in fresh waters. Hence photosynthesis would have produced isotopically lighter organic material. Second, changes in atmospheric pCO2 between glacial and interglacial periods, as shown by the Vostok ice core, caused marked changes in the concentration of free dissolved CO2 in the mixed layer; lower values during glacial maxima caused a smaller fractionation of the carbon isotopes by phytoplankton, whereas levels were less limiting during the interglacials. Concentrations of dissolved CO2 could also have been much higher during the deposition of the sapropels because of the supply of regenerated CO2 to the mixed layer by upwelling, and this could have further lightened the ?13Corganic values in the sapropels themselves. Carbon isotope records may provide an alternative method for estimating atmospheric pCO2 levels over longer time periods than can be obtained from ice cores.

  3. Correlated isotopic effects near the Fe abundance peak. [in carbonaceous meteorites

    NASA Technical Reports Server (NTRS)

    Papanastassiou, D. A.

    1986-01-01

    A special class of refractory inclusions in carbonaceous meteorites show large isotopic anomalies in Ca, Ti, and Cr that are correlated by virtue of having been measured on the same samples. Large excesses in the neutron-rich isotopes Ca-48, Ti-50, and Cr-54 are comparable and consistent with theoretical calculations of the composition of materials produced during neutron-rich nuclear statistical equilibrium nucleosynthesis. This correlation suggests that materials from very near the core of an expoloding massive star may be injected into the interstellar medium.

  4. Uptake of dissolved sulfide by Spartina alterniflora: evidence from natural sulfur isotope abundance ratios

    SciTech Connect

    Carlson, P.R. Jr.; Forrest, J.

    1982-05-07

    The difference in the stable sulfur isotope ratios of sulfate and sulfide in marsh pore water was used to verify the uptake of hydrogen sulfide by the salt marsh cordgrass Spartina alterniflora in a North Carolina salt marsh. Most of the plant sulfur derived from pore-water sulfide was recovered as sulfate, an indication that the sulfide had been oxidized within the plant. The anaysis of the sulfur isotope ratios of other coastal halophytes may be a useful technique for determining whether sulfide is taken up by plants in saline wetlands.

  5. Plutonium isotopic abundance measurements on CBNM NRM 271 analyzed with the FRAM and MGA codes

    SciTech Connect

    Friar, R.J.; Sampson, T.E.

    1992-05-01

    We report results of gamma-ray spectroscopy measurements of the isotopic distributions of plutonium in the reference-material set CBNM NRM 271 as analyzed by the FRAM and MGA plutonium isotopic codes. We acquired high-quality spectral data under measurement conditions approximating field-use conditions recommended by the code developers. Bias and precision results from these measurements are presented for both codes. Both codes performed very well for these measurements. These standards have proven to be very useful for testing the Los Alamos FRAM code in the high-burnup region where well-characterized materials have been unavailable at Los Alamos.

  6. Linear-chain structure of alpha clusters in Carbon isotopes

    NASA Astrophysics Data System (ADS)

    Baba, Tomoyuki; Chiba, Yohei; Kimura, Masaaki

    2014-09-01

    The linear-chain structure of 12C in which three alpha particles are linearly aligned has long been interested and investigated since its proposal by Morinaga, but nowadays, its existence is doubt, because its instability was shown by fill-microscopic nuclear models. However, the possible existence of linear-chains in neutron-rich carbon isotopes assisted by the valence neutrons was recently suggested based on the cluster model. Therefore, it is of importance and interest to examine their stability and investigate the stabilization mechanism based on full-microscopic model. In this presentation, we will discuss the alpha cluster states of carbon isotopes including the linear-chains based on the antisymmetrized molecular dynamics (AMD) model. For, example, we will demonstrate two different types of the alpha cluster states, that are, triangular and linear-chain configurations. Four valence neutrons occupy the molecular-orbit surrounding the cluster cores, in particular, their orbits of the linear-chain structure are π-orbit and σ-orbit as suggested by the cluster calculation. In addition, we predict the excitation energies of two structures. We will show that the linear-chain states have very large moment of inertia and they appear near the 6He+10Be threshold energy.

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

    NASA Astrophysics Data System (ADS)

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

    2011-11-01

    The terrestrial carbon (C) cycle has received increasing interest over the past few decades, however, there is still a lack of understanding of the fate of newly assimilated C allocated within plants and to the soil, stored within ecosystems and lost to the atmosphere. Stable carbon isotope studies can give novel insights into these issues. In this review we provide an overview of an emerging picture of plant-soil-atmosphere C fluxes, as based on C isotope studies, and identify processes determining related C isotope signatures. The first part of the review focuses on isotopic fractionation processes within plants during and after photosynthesis. The second major part elaborates on plant-internal and plant-rhizosphere C allocation patterns at different time scales (diel, seasonal, interannual), including the speed of C transfer and time lags in the coupling of assimilation and respiration, as well as the magnitude and controls of plant-soil C allocation and respiratory fluxes. Plant responses to changing environmental conditions, the functional relationship between the physiological and phenological status of plants and C transfer, and interactions between C, water and nutrient dynamics are discussed. The role of the C counterflow from the rhizosphere to the aboveground parts of the plants, e.g. via CO2 dissolved in the xylem water or as xylem-transported sugars, is highlighted. The third part is centered around belowground C turnover, focusing especially on above- and belowground litter inputs, soil organic matter formation and turnover, production and loss of dissolved organic C, soil respiration and CO2 fixation by soil microbes. Furthermore, plant controls on microbial communities and activity via exudates and litter production as well as microbial community effects on C mineralization are reviewed. A further part of the paper is dedicated to physical interactions between soil CO2 and the soil matrix, such as CO2 diffusion and dissolution processes within the soil profile. Finally, we highlight state-of-the-art stable isotope methodologies and their latest developments. From the presented evidence we conclude that there exists a tight coupling of physical, chemical and biological processes involved in C cycling and C isotope fluxes in the plant-soil-atmosphere system. Generally, research using information from C isotopes allows an integrated view of the different processes involved. However, complex interactions among the range of processes complicate or currently impede the interpretation of isotopic signals in CO2 or organic compounds at the plant and ecosystem level. This review tries to identify present knowledge gaps in correctly interpreting carbon stable isotope signals in the plant-soil-atmosphere system and how future research approaches could contribute to closing these gaps.

  8. The abundances of atomic carbon and carbon monoxide compared with visual extinction in the Ophiuchus molecular cloud complex

    NASA Technical Reports Server (NTRS)

    Frerking, Margaret A.; Keene, Jocelyn; Blake, Geoffrey A.; Phillips, T. G.

    1989-01-01

    Emission from the 492 GHz lines of C I have been observed toward six positions in the Ophiuchus molecular cloud complex for which accurate visual extinctions are available. The column density of C I increases with A(V) to greater than 2 x 10 to the 17th/sq cm at 100 mag, the column-averaged fractional abundance reaches a peak of about 2.2 x 10 to the -5th for A(V) in the range 4-11 mag and the column-averaged abundance ratio of C I to CO decreases with A(V) from about 1 at 2 mag to greater that about 0.03 at 100 mag. These results imply that, while C I is not the primary reservoir of gaseous carbon even at cloud edges, its fractional abundance remains high for at least 10 mag into the cloud and may be significant at even greater depths.

  9. Genesis of carbonates within Abalak and Bazhenov formations (West Siberia), revealed from stable carbon and oxygen isotopes distribution

    NASA Astrophysics Data System (ADS)

    Yurchenko, A.; Blinova, V.; Kalmikov, G. A.; Balushkina, N. S.

    2013-12-01

    Upper Jurassic deposits of Bazhenov formation are the main source rocks of the West Siberia Basin. Now the Bazhenov suite is intensively investigated not only as a source rock, but as unconventional reservoir of oil due to its vertical and lateral heterogeneity. The rocks of Bazhenov formation are composed of four main units: silica minerals, clay (predominantly hydromica), kerogen and carbonates. To predict the distribution of different lithological units it is important to reveal their genesis and facial conditions during their formation. One of the reservoir types is presented by cavernous-porous carbonates. Stable carbon and oxygen isotopes investigations has been carried out to reveal origin of carbonate material in Late Abalak - Bazhenov time. Four genetic types of carbonates have been subdivided according to mineralogical composition and stable carbon and oxygen isotopes distribution: 1) belemnites and other faunal remains; 2) secondary dolomites of Bazhenov formation; 3) secondary calcite filling cracks and composing inclusions of Abalak deposits; 4) methane-derived authigenic carbonates of Abalak formation. The first three types are presented by normal marine carbonates according to their carbon isotopes composition. Light oxygen isotopes composition indicates high temperatures during their precipitation (diagenesis). The fourth type is characterized by light carbon isotopes composition, which indicates presence of isotopically light biogenic CO2 in the environment. According to oxygen isotopic composition the carbonate material is primary and precipitated in subsurface conditions. Such carbon and oxygen isotopes composition is characteristic for methane-derived carbonates formed in the areas of active fluids discharge to the seafloor (cold seeps) as a result of Anaerobic Oxidation of Methane (AOM). Thus in Late Jurassic time active fluid escape to the sea floor took place in the West Siberia Basin.

  10. Position-specific carbon isotope analysis of trichloroacetic acid by gas chromatography/isotope ratio mass spectrometry.

    PubMed

    Breider, Florian; Hunkeler, Daniel

    2011-12-30

    Trichloroacetic acid (TCAA) is an important environmental contaminant present in soils, water and plants. A method for determining the carbon isotope signature of the trichloromethyl position in TCAA using gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) was developed and tested with TCAA from different origins. Position-specific isotope analysis (PSIA) can provide direct information on the kinetic isotope effect for isotope substitution at a specific position in the molecule and/or help to distinguish different sources of a compound. The method is based on the degradation of TCAA into chloroform (CF) and CO₂ by thermal decarboxylation. Since thermal decarboxylation is associated with strong carbon isotope fractionation (ε = -34.6 ± 0.2‰) the reaction conditions were optimized to ensure full conversion. The combined isotope ratio of CF and CO₂ at the end of the reaction corresponded well to the isotope ratio of TCAA, confirming the reliability of the method. A method quantification limit (MQL) for TCAA of 18.6 µg/L was determined. Samples of TCAA produced by enzymatic and non-enzymatic chlorination of natural organic matter (NOM) and some industrially produced TCAA were used as exemplary sources. Significant different PSIA isotope ratios were observed between industrial TCAA and TCAA samples produced by chlorination of NOM. This highlights the potential of the method to study the origin and the fate of TCAA in the environment. PMID:22468322

  11. Modeling whole-tree carbon assimilation rate using observed transpiration rates and needle sugar carbon isotope ratios.

    PubMed

    Hu, Jia; Moore, David J P; Riveros-Iregui, Diego A; Burns, Sean P; Monson, Russell K

    2010-03-01

    *Understanding controls over plant-atmosphere CO(2) exchange is important for quantifying carbon budgets across a range of spatial and temporal scales. In this study, we used a simple approach to estimate whole-tree CO(2) assimilation rate (A(Tree)) in a subalpine forest ecosystem. *We analysed the carbon isotope ratio (delta(13)C) of extracted needle sugars and combined it with the daytime leaf-to-air vapor pressure deficit to estimate tree water-use efficiency (WUE). The estimated WUE was then combined with observations of tree transpiration rate (E) using sap flow techniques to estimate A(Tree). Estimates of A(Tree) for the three dominant tree species in the forest were combined with species distribution and tree size to estimate and gross primary productivity (GPP) using an ecosystem process model. *A sensitivity analysis showed that estimates of A(Tree) were more sensitive to dynamics in E than delta(13)C. At the ecosystem scale, the abundance of lodgepole pine trees influenced seasonal dynamics in GPP considerably more than Engelmann spruce and subalpine fir because of its greater sensitivity of E to seasonal climate variation. *The results provide the framework for a nondestructive method for estimating whole-tree carbon assimilation rate and ecosystem GPP over daily-to weekly time scales. PMID:20100209

  12. Sources of carbon isotope variation in kangaroo bone collagen and tooth enamel

    NASA Astrophysics Data System (ADS)

    Murphy, Brett P.; Bowman, David M. J. S.; Gagan, Michael K.

    2007-08-01

    The stable carbon isotopic composition (expressed as δ 13C) of herbivore remains is commonly used to reconstruct past changes in the relative abundance of C 4 versus C 3 grass biomass (C 4 relative abundance). However, the strength of the relationship between herbivore δ 13C and C 4 relative abundance in extant ecosystems has not been thoroughly examined. We determined sources of variation in δ 13C of bone collagen and tooth enamel of kangaroos ( Macropus spp.) collected throughout Australia by measuring δ 13C of bone collagen (779 individuals) and tooth enamel (694 individuals). An index of seasonal water availability, i.e. the distribution of rainfall in the C 4 versus C 3 growing seasons, was used as a proxy for C 4 relative abundance, and this variable explained a large proportion of the variation in both collagen δ 13C (68%) and enamel δ 13C (68%). These figures increased to 78% and 77%, respectively, when differences between kangaroo species were accounted for. Vegetation characteristics, such as woodiness and the presence of an open forest canopy, had no effect on collagen or enamel δ 13C. While there was no relationship between collagen δ 13C and kangaroo age at death, tooth enamel produced later in life, following weaning, was enriched in 13C by 3.5‰ relative to enamel produced prior to weaning. From the observed relationships between seasonal water availability and collagen and enamel δ 13C, enrichment factors ( ɛ∗) for collagen-diet and enamel-diet (post-weaning) were estimated to be 5.2‰ ± 0.5 (95% CI) and 11.7‰ ± 0.6 (95% CI), respectively. The findings of this study confirm that at a continental scale, collagen and enamel δ 13C of a group of large herbivores closely reflect C 4 relative abundance. This validates a fundamental assumption underpinning the use of isotopic analysis of herbivore remains to reconstruct changes in C 4 relative abundance.

  13. Method for the identification and elimination of contamination during carbon isotopic analyses of extraterrestrial samples

    SciTech Connect

    Swart, P.K.; Grady, M.M.; Pillinger, C.T.

    1983-06-30

    A stepped combustion method for the elimination of carbon-containing contamination and weathering products from meteorite and lunar samples is presented. Samples of the Allende CV3 chondrite, the Sharps and Weston ordinary chondrite falls, one ordinary and five Antarctic finds, and lunar soils from Apollo 11 were oxidized in pure O2 at increasing temperatures, from 200 to 1200 C in 100-C, 30-min steps and C yield and delta-(C-13) were measured after each step. It is found that some C contamination is present in all samples and can adversely affect C-isotopic-abundance measurements. Except for C1 and C2 carbonaceous chondrites, C combustion below 425 + or - 25 C is limited to the terrestrial contaminants, demonstrating the usefulness of stepped combustion in removing them. Graphs and tables of the results are presented and discussed. 34 references.

  14. Unusually high stable carbon isotopic values of methane from low organic carbon Mars analog hypersaline environments

    NASA Astrophysics Data System (ADS)

    Kelley, C. A.; Poole, J. A.; Tazaz, A.; Chanton, J.; Bebout, B.

    2010-12-01

    Motivated by the Mars rovers’ findings of past hypersaline environments and the discovery of methane in the atmosphere of Mars, we examined methanogenesis in hypersaline ponds in Baja California Sur and in the Don Edwards National Wildlife Refuge in northern California. Methane-rich bubbles were observed to be released from below gypsum/halite crusts in these environments. The stable carbon isotopic composition of these bubbles ranged from about -30 to -40 ‰. Methane with these relatively high isotopic values would typically be considered non-biogenic, however incubations of crust and sediments samples over time resulted in the production of methane. We therefore undertook a series of measurements aimed at understanding the isotopic composition of methane in these environments. The concentrations and isotopic composition of the particulate organic carbon (POC) in these environments were measured. POC content was low (relative to most methane-producing sedimentary environments), generally less than 1%, and always less than 2% of the total mass. The isotopic composition of the POC ranged from -13 to -22 ‰. To determine the substrates used by the methanogens, 13C-labeled trimethylamine (TMA), monomethylamine, methanol, acetate and bicarbonate were added to incubation vials and the methane produced was monitored for 13C content. The main substrates used by the methanogens in these hypersaline environments were the non-competitive substrates, the methylamines and methanol. When unlabeled, but isotopically known, TMA was added to incubation vials in varying concentrations, the isotopic composition of the methane produced also varied. Little, if any, difference in the isotopic composition between the TMA and methane occurred at the lowest TMA concentration (10 µM final concentration). The lowest methane δ13C values (and so greatest fractionation between methane and TMA) occurred when the most TMA was added (1000 µM final concentration). This change in the isotopic composition of the methane produced with varying TMA concentrations, along with the high in situ methane δ13C values, suggest that the methanogens in these environments are operating at low substrate concentrations. Apparently, substrate limitation decreases isotopic fractionation during methanogenesis, which results in the abnormally high biogenic methane δ13C values.

  15. Oxygen-18 Carbon Dioxide Isotope Ratio in Mars Atmosphere

    NASA Astrophysics Data System (ADS)

    Kostiuk, T.; Livengood, T. A.; Hewagama, T.; Smith, R.; Fast, K. E.; Annen, J.; Sonnabend, G.; Sornig, M.

    2012-09-01

    The determination of isotopic ratios on Mars is important to the study of atmospheric evolution [1]. The relative abundance of isotopes of CO2 provides insight into the loss of Mars' primordial atmosphere. Isotopic ratios also provide markers in the study of geochemistry of Mars meteorites and future returned samples formed in equilibrium with ambient atmosphere, and are probes of biogenic and abiotic chemistry, which differ in isotope fractionation. Due to its lesser gravity and relatively thin residual atmosphere, Mars' atmosphere should be enriched in heavy isotopes [1]. However Viking [2] results indicated an Earth-like singly substituted oxygen-18 CO2 isotopic ratio, 18OCO/OCO, with δ18O = 0±50‰ relative to Vienna Standard Mean Ocean Water (VSMOW). By comparison, isotopic ratios in Earth atmospheric CO2 are not uniquely defined due to seasonal and biotic variability, but have a range 0-41‰ relative to VSMOW [3, 4]. Phoenix lander TEGA [3] measurements found a modest enrichment of δ18O = 31.0±5.7‰. Only the Viking and Phoenix landers have carried a mass spectrometer to Mars, so far, until the arrival of Mars Science Laboratory in August 2012. Using ground-based spectroscopic techniques Krasnopolsky et al. [5] also found modest enrichment δ18O = 18±18‰. We present results from fully resolved spectroscopic measurements near 10.6 μm of both the normal and singly substituted oxygen- 18 CO2 lines, taken with the Goddard Space Flight Center Heterodyne Instrument for Planetary Winds And Composition (HIPWAC) at the NASA Infrared Telescope Facility on Mauna Kea, Hawaii. Measurements with spectral resolving power λ/Δλ=107 were obtained in October 2007 with an instantaneous field-of-view on the planet of ~1 arcsec, at the locations shown in Fig. 1 as open squares. The solid and broken line tracks show Mars SPICAM measurements of ozone corresponding to ozone measurements also obtained with HIPWAC and shown as hatched and solid regions [6]. Figure 1: Locations of measured 18O12C16O fractional abundance on Mars (open squares). The colored tracks are Mars Express SPICAM measurements of ozone; the solid and hatched areas show contemporaneous HIPWAC measurements of ozone [6]. Figure 2 illustrates the CO2 normal-isotope and O-18 isotopologue lines measured on Mars at ~1 MHz (0.0003 cm-1) spectral resolution. The strong absorption line constrains the temperature simultaneously at the position of the measurement. The narrow mesospheric non- LTE line emission is also seen at the core of the absorption. The standard Mars Global Surveyor temperature profile was used to obtain the modeled emergent spectrum in blue. It clearly does not fit as well as the thermal profile retrieved from the CO2 absorption line profile (red fit). EPSC Abstracts Vol. 7 EPSC2012-432 2012 European Planetary Science Congress 2012 c Author(s) 2012 EPSC European Planetary Science Congress Figure 2: HIPWAC measurements of CO2 spectrum on Mars near 10.5 μm. The broad absorption retrieves the temperature. The fitted model spectra correspond to using the standard MGS thermal profile (blue), and our retrieved profile (red). The fit to the isotopic line is excellent and yields δ18O = +9±14‰. Radiative-transfer software developed in-house at GSFC to be compatible with very high spectral resolving power [7] was used to obtain the temperature profile and spectral fit. The fit on the 952.8629 cm-1 18OC16O line retrieves δ18O = +9±14‰. There appears to be no significant enhancement in the average over the extended region measured. Additional, more global, measurements were acquired in May 2012 and these data are being analyzed. These and additional high spectral resolution ground-based global measurements of δ18O can investigate Mars' atmospheric history; help define Mars Science Laboratory (MSL) protocols to sample isotopic ratios diurnally and seasonally, throughout its prime mission; and investigate possible meridional variability due to mass-fractionation in the polar freeze-sublimate cycle, similar to effects in terrestrial polar ice formation [8]. Such measurements would also complement results from future landers drilling into polar caps for isotopic insight into climatic history on Mars.

  16. Simulation of carbon isotope discrimination of the terrestrial biosphere

    NASA Astrophysics Data System (ADS)

    Suits, N. S.; Denning, A. S.; Berry, J. A.; Still, C. J.; Kaduk, J.; Miller, J. B.; Baker, I. T.

    2005-03-01

    We introduce a multistage model of carbon isotope discrimination during C3 photosynthesis and global maps of C3/C4 plant ratios to an ecophysiological model of the terrestrial biosphere (SiB2) in order to predict the carbon isotope ratios of terrestrial plant carbon globally at a 1 resolution. The model is driven by observed meteorology from the European Centre for Medium-Range Weather Forecasts (ECMWF), constrained by satellite-derived Normalized Difference Vegetation Index (NDVI) and run for the years 1983-1993. Modeled mean annual C3 discrimination during this period is 19.2; total mean annual discrimination by the terrestrial biosphere (C3 and C4 plants) is 15.9. We test simulation results in three ways. First, we compare the modeled response of C3 discrimination to changes in physiological stress, including daily variations in vapor pressure deficit (vpd) and monthly variations in precipitation, to observed changes in discrimination inferred from Keeling plot intercepts. Second, we compare mean ?13C ratios from selected biomes (Broadleaf, Temperate Broadleaf, Temperate Conifer, and Boreal) to the observed values from Keeling plots at these biomes. Third, we compare simulated zonal ?13C ratios in the Northern Hemisphere (20N to 60N) to values predicted from high-frequency variations in measured atmospheric CO2 and ?13C from terrestrially dominated sites within the NOAA-Globalview flask network. The modeled response to changes in vapor pressure deficit compares favorably to observations. Simulated discrimination in tropical forests of the Amazon basin is less sensitive to changes in monthly precipitation than is suggested by some observations. Mean model ?13C ratios for Broadleaf, Temperate Broadleaf, Temperate Conifer, and Boreal biomes compare well with the few measurements available; however, there is more variability in observations than in the simulation, and modeled ?13C values for tropical forests are heavy relative to observations. Simulated zonal ?13C ratios in the Northern Hemisphere capture patterns of zonal ?13C inferred from atmospheric measurements better than previous investigations. Finally, there is still a need for additional constraints to verify that carbon isotope models behave as expected.

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

    NASA Astrophysics Data System (ADS)

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

    2005-12-01

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

  18. Patterns and controls of seasonal variability of carbon stable isotopes of particulate organic matter in lakes.

    PubMed

    Gu, Binhe; Schelske, Claire L; Waters, Matthew N

    2011-04-01

    Carbon stable isotopes (δ(13)C) of particulate organic matter (POM) have been used as indicators for energy flow, primary productivity and carbon dioxide concentration in individual lakes. Here, we provide a synthesis of literature data from 32 freshwater lakes around the world to assess the variability of δ(13)C(POM) along latitudinal, morphometric and biogeochemical gradients. Seasonal mean δ(13)C(POM), a temporally integrated measure of the δ(13)C(POM), displayed weak relationships with all trophic state indices [total phosphorus (TP), total nitrogen (TN), and chlorophyll a (Chl a)], but decreased significantly with the increase in latitude, presumably in response to the corresponding decrease in water temperature and increase in CO(2) concentration. The seasonal minimum δ(13)C(POM) also correlated negatively with latitude while seasonal maximum δ(13)C(POM) correlated positively with all trophic state indices, pH, and δ(13)C of dissolved inorganic carbon (DIC). Seasonal amplitude of δ(13)C(POM) (the difference between seasonal maximum and minimum values) correlated significantly with pH, TP and Chl a concentrations and displayed small variations in oligotrophic, mesotrophic and low latitude eutrophic lakes, which is attributed to low primary productivity and abundant non-living POM in the low trophic state lakes and relatively stable environmental conditions in the subtropics. Seasonal amplitude of δ(13)C(POM) was the greatest in high latitude eutrophic lakes. Greater seasonal changes in solar energy and light regime may be responsible for the large seasonal variability in high latitude productive lakes. This synthesis provides new insights on the factors controlling variations in stable carbon isotopes of POM among lakes on the global scale. PMID:21197547

  19. Remote Detection of Carbon Stable Isotope of CO2 for Carbon Sequestration

    NASA Astrophysics Data System (ADS)

    Humphries, S. D.; Clegg, S. M.; Fessenden, J. E.; Dobeck, L.; Spangler, L.

    2009-12-01

    Carbon storage in geologic formations is one method to prevent carbon dioxide (CO2), produced by fossil fuel combustion, from entering the Earth's atmosphere. The monitoring, verification and accounting (MVA) of geologically sequestered CO2 is critical to measure the operation and functioning of a geologic storage site. Surface monitoring techniques need to identify seepage from the sequestration reservoir at or below ambient CO2 concentrations. The Zero Emissions Research & Technology (ZERT) group at Montana State University established a field test site where controlled amounts of CO2 are released to test the performance of CO2 detection instruments and measurement techniques. The field site allows a controlled flow rate of CO2 to be released into the near surface, just below the water table, through a 100 m long horizontal pipe. In July of 2009, a release was conducted, with a uniform flow rate of 0.2 tons per day, and the seepage rate was measured. The carbon stable isotope ratio of CO2 is a sensitive diagnostic signature to distinguish between anthropogenic and natural sources of CO2. However, natural concentrations of 13C16O2 are approximately 100 times smaller than 12C16O2. Frequency-modulated spectroscopy (FMS) is an ultra-sensitive technique developed to detect the CO2 stable carbon isotopes. An instrument has been developed that uses this FMS technique and an integrated volume over a long, open-air path to detect changes in the carbon isotope ratio. This paper will briefly describe the FMs technique and present results from instrument deployment to the ZERT field site to monitor the 13C16O2/12C16O2 stable isotope ratio. LA-UR 09-05648

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

    PubMed

    Yeh, H W; Wang, W M

    2001-07-01

    The stable isotope composition of the light elements (i.e., H, C, N, O and S) of organic samples varies significantly and, for C, is also unique and distinct from that of inorganic carbon. This is the result of (1) the isotope composition of reactants, (2) the nature of the reactions leading to formation and post-formational modification of the samples, (3) the environmental conditions under which the reactions took place, and (4) the relative concentration of the reactants compared to that of the products (i.e., [products]/[reactants] ratio). This article will examine the carbon isotope composition of terrestrial plant materials and its relationship with the above factors. delta13C(PDB) values of terrestrial plants range approximately from -8 to -38%, inclusive of C3-plants (-22 to -38%), C4-plants (-8 to -15%) and CAM-plants (-13 to -30%). Thus, the delta13C(PDB) values largely reflect the photosynthesis pathways of a plant as well as the genetics (i.e., species difference), delta13C(PDB) values of source CO2, relevant humidity, CO2/O2 ratios, wind and light intensity etc. Significant variations in these values also exist among different tissues, different portions of a tissue and different compounds. This is mainly a consequence of metabolic reactions. Animals mainly inherit the delta13C(PDB) values of the foods they consume; therefore, their delta13C(PDB) values are similar. The delta13C(PDB) values of plant materials, thus, contain information regarding the inner workings of the plants, the environmental conditions under which they grow, the delta13C(PDB) values of CO2 sources etc., and are unique. Furthermore, this uniqueness is passed on to their derivative matter, such as animals, humus etc. Hence, they are very powerful tools in many areas of research, including the ecological and environmental sciences. PMID:11480769

  1. Carbon, Hydrogen, and Oxygen Isotope Ratios of Cellulose from Plants Having Intermediary Photosynthetic Modes 1

    PubMed Central

    Sternberg, Leonel O'Reilly; Deniro, Michael J.; Ting, Irwin P.

    1984-01-01

    Carbon and hydrogen isotope ratios of cellulose nitrate and oxygen isotope ratios of cellulose from species of greenhouse plants having different photosynthetic modes were determined. When hydrogen isotope ratios are plotted against carbon isotope ratios, four clusters of points are discernible, each representing different photosynthetic modes: C3 plants, C4 plants, CAM plants, and C3 plants that can shift to CAM or show the phenomenon referred to as CAM-cycling. The combination of oxygen and carbon isotope ratios does not distinguish among the different photosynthetic modes. Analysis of the carbon and hydrogen isotope ratios of cellulose nitrate should prove useful for screening different photosynthetic modes in field specimens that grew near one another. This method will be particularly useful for detection of plants which show CAM-cycling. PMID:16663360

  2. Heterogeneity of Carbon Age and Carbon Quality in Soil Organic Matter: Identification of Carbon Stabilization using Radiocarbon and Stable Isotopes

    NASA Astrophysics Data System (ADS)

    Feng, X.; Xu, X.; Zhou, L.; Coplin, A.; Liu, K.

    2010-12-01

    It is well known that carbon concentration, stable carbon isotopes and radiocarbon contents in soil organic matter (SOM) systematically change with soil depth. There have been few attempts to integrate distributions of all carbon isotopic species in a process-oriented model. We present a steady state carbon model that simultaneously describes variations in carbon density (gC/cm), stable carbon isotopic ratio (C-13 to C-12), and radiocarbon content (expressed as the conventional radiocarbon age, CRA) as a function of soil depth. The model was originally developed by Bosatta and Ågreen (1996) for the carbon density; Poage and Feng (2004) incorporated C-13 tracer into the model, and here we add radiocarbon as a second tracer. An analytical solution can be obtained using a set of simple assumptions adopted from the earlier researchers. The solution allows independent determination of two parameters. The carbon isotopic fractionation by microbial decomposition can be determined using the predicted linear relationship between the natural logarithm of carbon density and δ13C values (Poage and Feng, 2004), and the vertical carbon transport velocity (cm/yr) can be obtained using the linear relationship between CRA and the soil depth (this work). Other ecological variables can then be constrained by fitting the model into observations. Compared to models without isotopic tracers, these features significantly increase the power for predicting ecological variables. A 100-cm soil profile is use to illustrate/verify the model. The model produces a relationship between δ13C and CRA, with δ13C increasing with the SOM age. The shape of this relationship depends upon several ecological variables, including the ecological efficiency and microbial growth rate. The δ13C-CRA relationship is also controlled by mineral stabilization of the SOM. In an extreme case, where carbon is completely protected against microbial access, the δ13C would cease to increase with time, while radiocarbon continues to decay following the physical law (CRA increase). We have conducted a study of a forest soil from Hanover, NH. We find that, at a given soil depth, small aggregate particles are associated with SOM that is relatively depleted in C-13, and older than the SOM associated with intermediate aggregates. We interpret this to indicate that small particles are more strongly protected by the mineral matter than larger particles.

  3. The reduction and oxidation of ceria: A natural abundance triple oxygen isotope perspective

    NASA Astrophysics Data System (ADS)

    Hayles, Justin; Bao, Huiming

    2015-06-01

    Ceria (CeO2) is a heavily studied material in catalytic chemistry for use as an oxygen storage medium, oxygen partial pressure regulator, fuel additive, and for the production of syngas, among other applications. Ceria powders are readily reduced and lose structural oxygen when subjected to low pO2 and/or high temperature conditions. Such dis-stoichiometric ceria can then re-oxidize under higher pO2 and/or lower temperature by incorporating new oxygen into the previously formed oxygen site vacancies. Despite extensive studies on ceria, the mechanisms for oxygen adsorption-desorption, dissociation-association, and diffusion of oxygen species on ceria surface and within the crystal structure are not well known. We predict that a large kinetic oxygen isotope effect should accompany the release and incorporation of ceria oxygen. As the first attempt to determine the existence and the degree of the isotope effect, this study focuses on a set of simple room-temperature re-oxidation experiments that are also relevant to a laboratory procedure using ceria to measure the triple oxygen isotope composition of CO2. Triple-oxygen-isotope labeled ceria powders are heated at 700 °C and cooled under vacuum prior to exposure to air. By combining results from independent experimental sets with different initial oxygen isotope labels and using a combined mass-balance and triangulation approach, we have determined the isotope fractionation factors for both high temperature reduction in vacuum (⩽10-4 mbar) and room temperature re-oxidation in air. Results indicate that there is a 1.5‰ ± 0.8‰ increase in the δ18O value of ceria after being heated in vacuum at 700 °C for 1 h. When the vacuum is broken at room temperature, the previously heated ceria incorporates 3-19% of its final structural oxygen from air, with a δ18O value of 2.1-4.1+7.7 ‰ for the incorporated oxygen. The substantial incorporation of oxygen from air supports that oxygen mobility is high in vacancy-rich ceria during re-oxidation at room temperature. The quantified oxygen isotope fractionation factors are consistent with the direct involvement of O2 in the rate limiting step for ceria reoxidation in air at room temperature. While additional parameters may reduce some of the uncertainties in our approach, this study demonstrates that isotope effects can be an encouraging tool for studying oxygen transport kinetics in ceria and other oxides. In addition, our finding warns of the special cares and limits in using ceria as an exchange medium for laboratory triple oxygen isotope analysis of CO2 or other oxygen-bearing gases.

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

    NASA Astrophysics Data System (ADS)

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

    2006-12-01

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