Science.gov

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

  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. 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.

  4. 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.

  5. 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.

  6. Carbon Isotope Abundances in Lichen Deposits Might Reflect Past Moisture Trends

    NASA Astrophysics Data System (ADS)

    Russ, J.; Beazley, M. J.; Rickman, R. D.; Ingram, D. K.; Boutton, T. W.

    2002-12-01

    The stable carbon isotope composition of lichens is governed primarily by moisture conditions. Lichens lack water transport systems that are characteristic of higher plants; therefore, maximum productivity occurs during periods when an equilibrium has been established between the water content of the organism and the environment. The amount of water required to initiate and maintain photosynthesis influences the carbon isotope content due to fractionation caused by diffusion of carbon dioxide through the water filled membranes, as well as morphological changes in the lichen thallus. Thus, lichens growing in relatively wet conditions have a lower carbon 13 content than those growing in drier conditions. We suggest that the carbon isotope composition of stable lichen byproducts, such as calcium oxalate that is common on rock surfaces, can be used to predict past fluctuations in moisture conditions. We are exploring this hypothesis via studies of living, oxalate producing lichens, and calcium oxalate deposits from on rock surfaces in the Lower Pecos River region. The results of these studies demonstrate that (1) lichens growing on limestone do not incorporate carbon from carbonate substrates; thus ambient carbon dioxide is the dominant, if not sole source of metabolized carbon; and (2) calcium oxalate produced by lichens is consistently enriched in carbon 13 by 6.5 permil compared to the lichen tissues. We also present here a plot of oxalate carbon 14 ages versus the stable carbon isotope ratios from analyses of 19 calcium oxalate rock coating samples from the Lower Pecos region. This graph shows a general increase in the oxalate carbon 13 content through the middle Holocene that peaks about 3000 years ago, followed by a rapid decrease in the abundance of the heavier isotope. We suggest that the increased carbon 13 content corresponds to a decrease in the amount of moisture transported to the region during this period, a trend that rapidly reversed about 3000 years

  7. 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.

  8. 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.

  9. 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.

  10. Natural-abundance stable carbon isotopes of small-subunit ribosomal RNA (SSU rRNA) from Guaymas Basin (Mexico)

    NASA Astrophysics Data System (ADS)

    MacGregor, B. J.; Mendlovitz, H.; Albert, D.; Teske, A. P.

    2012-12-01

    Small-subunit ribosomal RNA (SSU rRNA) is a phylogenetically informative molecule found in all species. Because it is poorly preserved in most environments, it is a useful marker for active microbial populations. We are using the natural-abundance stable carbon isotopic composition of specific microbial groups to help identify the carbon substrates contributing to microbial biomass in a variety of marine environments. At Guaymas Basin, hydrothermal fluids interact with abundant sedimentary organic carbon to produce natural gas and petroleum. Where this reaches the sediment surface, it can support dense patches of seafloor life, including Beggiatoa mats. We report here on the stable carbon isotopic composition of SSU rRNA from a Beggiatoa mat transect, a cold background site, a warm site with high oil concentration, and a second Beggiatoa mat. The central part of the transect mat overlay the steepest temperature gradient, and was visually dominated by orange Beggiatoa. This was fringed by white Beggiatoa mat and bare, but still warm, sediment. Methane concentrations were saturating beneath the orange and white mats and at the oily site, lower beneath bare sediment, and below detection at the background site. Our initial hypotheses were that rRNA isotopic composition would be strongly influenced by methane supply, and that archaeal rRNA might be lighter than bacterial due to contributions from methanogens and anaerobic methane oxidizers. We used biotin-labeled oligonucleotides to capture Bacterial and Archaeal SSU rRNA for isotopic determination. Background-site rRNA was isotopically heaviest, and bacterial RNA from below 2 cm at the oily site was lightest, consistent with control by methane. Within the transect mat, however, the pattern was more complicated; at some sediment depths, rRNA from the mat periphery was isotopically lightest. Part of this may be due to the spatially and temporally variable paths followed by hydrothermal fluid, which can include horizontal

  11. 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

  12. 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

  13. Determination of site-specific carbon isotope ratios at natural abundance by carbon-13 nuclear magnetic resonance spectroscopy.

    PubMed

    Caer, V; Trierweiler, M; Martin, G J; Martin, M L

    1991-10-15

    Site-specific natural isotope fractionation of hydrogen studied by deuterium NMR (SNIF-NMR) spectroscopy is a powerful source of information on hydrogen pathways occurring in biosyntheses in natural conditions. The potential of the carbon counterpart of this method has been investigated and compared. Three typical molecular species, ethanol, acetic acid, and vanillin, have been considered. Taking into account the requirements of quantitative 13C NMR, appropriate experimental procedures have been defined and the repeatability and reproducibility of the isotope ratio determinations have been checked in different conditions. It is shown that the carbon version of the SNIF-NMR method is capable of detecting small differences in the carbon-13 content of the ethyl fragment of ethanols from different botanical or synthetic origins. These results are in agreement with mass spectrometry determinations of the overall carbon isotope ratios. Deviations with respect to a statistical distribution of 13C have been detected in the case of acetic acid and vanillin. However, since the method is very sensitive to several kinds of systematic error, only a relative significance can be attached at present to the internal parameters directly accessible. Isotope dilution experiments have also been carried out in order to check the consistency of the results. In the present state of experimental accuracy, the 13C NMR method is of more limited potential than 2H SNIF-NMR spectroscopy. However it may provide complementary information. Moreover it is particularly efficient for detecting and quantifying adulterations that aim to mimic the overall carbon-13 content of a natural compound by adding a selectivity enriched species to a less expensive substrate from a different origin. PMID:1759714

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

    PubMed

    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. PMID:11539027

  15. 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.

  16. Evaluating microbial carbon sources in Athabasca oil sands tailings ponds using natural abundance stable and radiocarbon isotopes

    NASA Astrophysics Data System (ADS)

    Ahad, J. M.; Pakdel, H.

    2013-12-01

    Natural abundance stable (δ13C) and radiocarbon (Δ14C) isotopes of phospholipid fatty acids (PLFAs) were used to evaluate the carbon sources utilized by the active microbial populations in surface sediments from Athabasca oil sands tailings ponds. The absence of algal-specific PLFAs at three of the four sites investigated, in conjunction with δ13C signatures for PLFAs that were generally within ~3‰ of that reported for oil sands bitumen (~ -30‰), indicated that the microbial communities growing on petroleum constituents were dominated by aerobic heterotrophs. The Δ14C values of PLFAs ranged from -906 to -586‰ and pointed to a significant uptake of fossil carbon (up to ~90% of microbial carbon derived from petroleum), particularly in PLFAs (e.g., cy17:0 and cy19:0) often associated with petroleum hydrocarbon degrading bacteria. The comparatively higher levels of 14C in other, less specific PLFAs (e.g., 16:0) indicated the preferential uptake of younger organic matter by the general microbial population (~50-80% of microbial carbon derived from petroleum). Since the main carbon pools in tailings sediment were essentially 'radiocarbon dead' (i.e., no detectable 14C), the principal source for this modern carbon is considered to be the Athabasca River, which provides the bulk of the water used in the bitumen extraction process. The preferential uptake of the minor amount of young and presumably more biodegradable material present in systems otherwise dominated by recalcitrant petroleum constituents has important implications for remediation strategies. On the one hand, it implies that mining-related organic contaminants could persist in the environment long after tailings pond reclamation has begun. Alternatively, it may be that the young, labile organic matter provided by the Athabasca River plays an important role in stimulating or supporting the microbial utilization of petroleum carbon in oil sands tailings ponds via co-metabolism or priming processes

  17. Changes in carbon sources fueling benthic secondary production over depth and time: coupling Chironomidae stable carbon isotopes to larval abundance.

    PubMed

    Frossard, Victor; Verneaux, Valérie; Millet, Laurent; Magny, Michel; Perga, Marie-Elodie

    2015-06-01

    Stable C isotope ratio (δ(13)C) values of chironomid remains (head capsules; HC) were used to infer changes in benthic C sources over the last 150 years for two French sub-Alpine lakes. The HCs were retrieved from a series of sediment cores from different depths. The HC δ(13)C values started to decrease with the onset of eutrophication. The HC δ(13)C temporal patterns varied among depths, which revealed spatial differences in the contribution of methanotrophic bacteria to the benthic secondary production. The estimates of the methane (CH4)-derived C contribution to chironomid biomass ranged from a few percent prior to the 1930s to up to 30 % in recent times. The chironomid fluxes increased concomitantly with changes in HC δ(13)C values before a drastic decrease due to the development of hypoxic conditions. The hypoxia reinforced the implication for CH4-derived C transfer to chironomid production. In Lake Annecy, the HC δ(13)C values were negatively correlated to total organic C (TOC) content in the sediment (Corg), whereas no relationship was found in Lake Bourget. In Lake Bourget, chironomid abundances reached their maximum with TOC contents between 1 and 1.5 % Corg, which could constitute a threshold for change in chironomid abundance and consequently for the integration of CH4-derived C into the lake food webs. Our results indicated that the CH4-derived C contribution to the benthic food webs occurred at different depths in these two large, deep lakes (deep waters and sublittoral zone), and that the trophic transfer of this C was promoted in sublittoral zones where O2 gradients were dynamic. PMID:25630956

  18. Consistency of NMR and mass spectrometry determinations of natural-abundance site-specific carbon isotope ratios. The case of glycerol.

    PubMed

    Zhang, B L; Trierweiler, M; Jouitteau, C; Martin, G J

    1999-07-01

    Quantitative determinations of natural-abundance carbon isotope ratios by nuclear magnetic resonance (SNIF-NMR) have been optimized by appropriate selection of the experimental conditions and by signal analysis based on a dedicated algorithm. To check the consistency of the isotopic values obtained by NMR and mass spectrometry (IRMS) the same glycerol samples have been investigated by both techniques. To have access to site-specific isotope ratios by IRMS, the products have been degraded and transformed into two derivatives, one of which contains carbons 1 and 3 and the other carbon 2 of glycerol. The sensitivity of the isotopic parameters determined by IRMS to fractionation effects possibly occurring in the course of the chemical transformations has been investigated, and the repeatability and reproducibility of both analytical chains have been estimated. The good agreement observed between the two series of isotopic results supports the reliability of the two different approaches. SNIF-NMR is therefore a very attractive tool for routine determination, in a single nondestructive experiment, of the carbon isotope distribution in glycerol, and the method can be applied to other compounds. Using this method, the isotopic distributions have been compared for glycerol samples, obtained from plant or animal oils, extracted from fermented media, or prepared by chemical synthesis. Typical behaviors are characterized. PMID:21662780

  19. Evolution, Abundance and Biocalcification of Calcareous Nannoplankton During the Aptian (Early Cretaceous): Causes and Consequences for C Isotopic Anomalies, Climate Changes and the Carbon Cycle.

    NASA Astrophysics Data System (ADS)

    Erba, E.

    2005-12-01

    The mid Cretaceous is marked by extreme greenhouse conditions, coeval with emplacement of large igneous provinces, C isotopic anomalies, major changes in structure and composition of the oceans, and accelerated rates in the evolutionary history of calcareous plankton. The Aptian is a crucial interval to decipher links between biotic evolution and environmental pressure: it is appealing for understanding nannofloral biocalcification and feedbacks in the carbonate system and in the global carbon cycle. Ontong Java, Manihiki and Kerguelen Plateaus formed in the Aptian affecting the ocean-atmosphere system with excess CO2, changes in Ca2+ and Mg2+ concentrations, and varying nutrient cycling. Two large C isotopic anomalies are associated with episodes of prolonged high primary productivity, changes in alkality, global warming and cooling, anoxia, speciations and extinctions in planktonic communities. Nannofossil diversity, abundance and biocalcification are quantified in continuous, complete, pelagic sections to derive biosphere-geosphere interactions at short and long time scales. The early Aptian C isotopic anomaly interrupts a speciation episode in calcareous nannoplankton paralleled by a drastic reduction in nannofossil paleofluxes culminating in the nannoconid crisis preceding the Oceanic Anoxic Event 1a and the negative C isotopic spike linked to clathrate melting presumably triggered by the thermal maximum at the onset of the mid Cretaceous greenhouse climate. No extinctions are recorded. In the early late Aptian resumption of nannoconid production and appearance of several taxa are coeval with a return to normal C isotopic values. The occurrence of calpionellids and diversified planktonic foraminifers indicate successful biocalcification and restoration of the thermocline. In the late Aptian a drop in nannofossil abundance and accelerated extinction rates are associated with another C isotopic excursion under cool conditions possibly due to a prolonged volcanic

  20. 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.

  1. Carbon isotope geochemistry and geobiology

    NASA Technical Reports Server (NTRS)

    Desmarais, D.

    1985-01-01

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

  2. Absolute isotopic abundances of TI in meteorites

    NASA Astrophysics Data System (ADS)

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

    1985-03-01

    The absolute isotope abundance of Ti has been determined in Ca-Al-rich inclusions from the Allende and Leoville meteorites and in samples of whole meteorites. The absolute Ti isotope abundances differ by a significant mass dependent isotope fractionation transformation from the previously reported abundances, which were normalized for fractionation using 46Ti/48Ti. Therefore, the absolute compositions define distinct nucleosynthetic components from those previously identified or reflect the existence of significant mass dependent isotope fractionation in nature. The authors provide a general formalism for determining the possible isotope compositions of the exotic Ti from the measured composition, for different values of isotope fractionation in nature and for different mixing ratios of the exotic and normal components.

  3. The carbon abundance and 12C/13C isotopic ratio in the atmosphere of Arcturus from 2.3 µm CO bands

    NASA Astrophysics Data System (ADS)

    Pavlenko, Ya. V.

    2008-09-01

    We have modeled absorption lines of the 12CO and 13CO (Δ υ = 2) molecular bands at λλ 2.29 2.45 µm in the spectrum of Arcturus (K2III). A grid of model atmospheres and synthetic spectra were computed for the red giant using T eff = 4300, log g = 1.5, and the elemental abundances of Peterson et al. (1993), with the exception of the abundances of carbon, log N(C), and oxygen, log N(O) and the carbon isotopic ratio, 12C/13C, which were varied in our computations. The computed spectra were compared to the observed spectrum of Arcturus from the atlas of Hinkle et al. (1976). The best fit between the synthetic and observed spectra is achieved for log N(C) = -3.78, 12C/13C = 8 ± 0.5. We discuss the dependence of 12C/13C on log N(C) and log N(O) in the atmosphere of the red giant.

  4. Micron-scale coupled carbon isotope and nitrogen abundance variations in diamonds: Evidence for episodic diamond formation beneath the Siberian Craton

    NASA Astrophysics Data System (ADS)

    Wiggers de Vries, D. F.; Bulanova, G. P.; De Corte, K.; Pearson, D. G.; Craven, J. A.; Davies, G. R.

    2013-01-01

    The internal structure and growth history of six macro-diamonds from kimberlite pipes in Yakutia (Russia) were investigated with cathodoluminescence imaging and coupled carbon isotope and nitrogen abundance analyses along detailed core to rim traverses. The diamonds are characterised by octahedral zonation with layer-by-layer growth. High spatial resolution SIMS profiles establish that there is no exchange of the carbon isotope composition across growth boundaries at the μm scale and that isotopic variations observed between (sub)zones within the diamonds are primary. The macro-diamonds have δ13C values that vary within 2‰ of -5.3‰ and their nitrogen contents range between 0-1334 at. ppm. There are markedly different nitrogen aggregation states between major growth zones within individual diamonds that demonstrate Yakutian diamonds grew in multiple growth events. Growth intervals were punctuated by stages of dissolution now associated with <10 μm wide zones of nitrogen absent type II diamond. Across these resorption interfaces carbon isotope ratios and nitrogen contents record shifts between 0.5-2.3‰ and up to 407 at. ppm, respectively. Co-variation in δ13C value-nitrogen content suggests that parts of individual diamonds precipitated in a Rayleigh process from either oxidised or reduced fluids/melts, with two single diamonds showing evidence of both fluid types. Modelling the co-variation establishes that nitrogen is a compatible element in diamond relative to its growth medium and that the nitrogen partition coefficient is different between oxidised (3-4.1) and reduced (3) sources. The reduced sources have δ13C values between -7.3‰ and -4.6‰, while the oxidised sources have higher δ13C values between -5.8‰ and -1.8‰ (if grown from carbonatitic media) or between -3.8‰ and +0.2‰ (if grown from CO2-rich media). It is therefore concluded that individual Yakutian diamonds originate from distinct fluids/melts of variable compositions. The

  5. 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

  6. Carbon isotope techniques

    SciTech Connect

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

    1991-01-01

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

  7. NITROGEN AND CARBON STABLE ISOTOPE ABUNDANCES SUPPORT THE MYCO-HETEROTROPHIC NATURE AND HOST-SPECIFICITY OF CERTAIN ACHLOROPHYLLOUS PLANTS

    EPA Science Inventory


    ? Over 400 species of achlorophyllous vascular plants are thought to obtain all carbon from symbiotic fungi. Consequently, they are termed ?myco-heterotrophic.' However, direct evidence of myco-heterotrophy in these plants is limited.
    ? During an investigation of the pat...

  8. 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.

  9. 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.

  10. Carbon Isotope Ratiometer

    SciTech Connect

    Dr. Anthony O'Keefe

    2001-05-07

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

  11. 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.

  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. 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.

  14. Hydrogen and carbon abundances and isotopic ratios in apatite from alkaline intrusive complexes, with a focus on carbonatites

    NASA Astrophysics Data System (ADS)

    Nadeau, Serge L.; Epstein, Samuel; Stolper, Edward

    1999-06-01

    We report H and C contents and δD and δ 13C values of apatites from 15 alkaline intrusive complexes ranging in age from 110 Ma to 2.6 Ga. Sampling focused on carbonatites, but included silicate rocks as well. Heating at temperatures up to 1500°C is needed to extract fully H 2O and CO 2 from these apatites. Apatites from carbonatite-rich intrusive complexes contain 0.2-1.1 wt% H 2O and 0.05-0.70 wt% CO 2; apatites from two silicate-rich alkaline complexes with little or no carbonatite are generally poorer in both volatile components (0.1-0.2% H 2O and 0.01-0.11% CO 2). D/H ratios in apatites from these rocks are bimodally distributed: group I (δD = -51 to -74‰) and group II (δD = -88 to -104‰). We suggest that the δD values of group I apatites represent primitive, mantle-derived values and that the group II apatites crystallized from degassed magmas, resulting in lower H 2O contents and δD values. Although many factors influence the extent of degassing, the depth of emplacement could represent a major control. In contrast to H 2O contents and δD values, CO 2 contents and δ 13C values of gas released at high temperatures from multiple aliquots of these apatite samples are variable. This suggests the presence of more than one C-bearing component in these apatites, one of which is proposed to be dissolved carbonate; the other, with δ 13C ˜<-25‰, could be associated with hydrocarbons. Group I apatites have δD values similar to those of primitive, mantle-derived basaltic magmas and overlap with (but cover a narrower range than) mantle-derived mica, amphibole, and whole rocks. δ 13C values also overlap typical upper mantle. These results suggest that igneous apatites can retain their primary δD and δ 13C values.

  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

  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.

    PubMed Central

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

    1985-01-01

    Differences in the natural-abundance carbon stable isotopic compositions between products from aerobic cultures of Escherichia coli K-12 were measured. Respired CO2 was 3.4% depleted in 13C relative to the glucose used as the carbon source, whereas the acetate was 12.3% enriched in 13C. The acetate 13C enrichment was solely in the carboxyl group. Even though the total cellular carbon was only 0.6% depleted in 13C, intracellular components exhibited a significant isotopic heterogeneity. The protein and lipid fractions were -1.1 and -2.7%, respectively. Aspartic and glutamic acids were -1.6 and +2.7%, respectively, yet citrate was isotopically identical to the glucose. Probable sites of carbon isotopic fractionation include the enzyme, phosphotransacetylase, and the Krebs cycle. PMID:2867741

  19. 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.

  20. Variable Carbon Isotopes in ALH84001 Carbonates

    NASA Astrophysics Data System (ADS)

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

    2002-12-01

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

  1. 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).

  2. Assessment of marine-derived nutrients in the Copper River Delta, Alaska, using natural abundance of the stable isotopes of nitrogen, sulfur, and carbon

    USGS Publications Warehouse

    Kline, Thomas C.; Woody, Carol Ann; Bishop, Mary Anne; Powers, Sean P.; Knudsen, E. Eric

    2007-01-01

    We performed nitrogen, sulfur, and carbon stable isotope analysis (SIA) on maturing and juvenile anadromous sockeye and coho salmon, and periphyton in two Copper River delta watersheds of Alaska to trace salmonderived nutrients during 2003–2004. Maturing salmon were isotopically enriched relative to alternate freshwater N, S, and C sources as expected, with differences consistent with species trophic level differences, and minor system, sex, and year-to-year differences, enabling use of SIA to trace these salmon-derived nutrients. Periphyton naturally colonized, incubated, and collected using Wildco Periphtyon Samplers in and near spawning sites was 34S- and 15N-enriched, as expected, and at all freshwater sites was 13C-depleted. At nonspawning and coho-only sites, periphyton 34S and 15N was generally low. However, 34S was low enough at some sites to be suggestive of sulfate reduction, complicating the use of S isotopes. Juvenile salmon SIA ranged in values consistent with using production derived from re-mineralization as well as direct utilization, but only by a minority fraction of coho salmon. Dependency on salmon-derived nutrients ranged from relatively high to relatively low, suggesting a space-limited system. No one particular isotope was found to be superior for determining the relative importance of salmon-derived nutrients.

  3. Carbon isotopes in bulk carbonaceous chondrites

    NASA Technical Reports Server (NTRS)

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

    1985-01-01

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

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2004-07-01

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

  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. 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.

  12. 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

  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. 13 ENDOR studies of organic radicals in natural isotopic abundance

    NASA Astrophysics Data System (ADS)

    Kirste, Burkhard

    13C ENDOR studies of phenoxyls, galvinoxyls, triphenylmethyl radicals, nitroxides, and cyclosilane and semiquinone radical anions with natural isotopic distribution are reported. The method is described, and it is shown that 13C coupling constants can be measured precisely; in favorable cases even the determination of signs is possible by general TRIPLE resonance. Studies of the relaxation behavior of 13C ENDOR signals or measurements of hyperfine shifts in liquid-crystalline solutions yield information about dipolar hyperfine interactions and hence π spin populations which is of aid in assignments to molecular positions. Complete sets of 13C coupling constants have been determined for 2,4,6-tri- tert-butylphenoxyl and Coppinger's radical. For the central carbon atoms of tert-butyl groups, a Q parameter of Qτ-Bu C = -34 MHz is proposed, and for a 29Si atom in trimethylsilyl groups, QTMSSi = +49 MHz. Favorable conditions for natural-abundance 13C ENDOR experiments, e.g., small hyperfine anisotropies and use of deuterated compounds, and limitations of the method are discussed.

  16. 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.

  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.

    2016-06-01

    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. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. Carbon and oxygen isotope microanalysis of carbonate.

    PubMed

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

    2009-08-30

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

  4. 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.

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

    SciTech Connect

    Gloeckler, G. ); Geiss, J. )

    1989-03-01

    Solar wind abundances have now been measured for eleven elements and the isotopes of the noble gases. The composition of all elements up to and including Ni, as well as most of their isotopes, should become known when new high-mass-resolution solar wind spectrometers are launched in the next decade. Aside from solar wind protons and alpha particles, which have been studied extensively since the 1960's, our information for heavier elements is limited. Nevertheless, two effects stand out. First is the enrichment of abundances of elements with low first ionizaiton potential (FIP), most likely the combined result of (a) an atom-ion separation process in the upper chromosphere, and (b) 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. Studies by the ULYSSES spacecraft of the characteristics and composition of the least complicated solar wind, i.e., the flow emanating from the polar coronal holes, should significantly increase our understanding of coronal processes and solar wind acceleration. By combining these studies with measurements of the complete elemental and isotopic composition of the solar wind, we will be able to derive solar abundances for elements and isotopes that otherwise are poorly known.

  6. Resonance ionization mass spectrometry for isotopic abundance measurements

    NASA Technical Reports Server (NTRS)

    Miller, C. M.

    1986-01-01

    Resonance ionization mass spectrometry (RIMS) is a relatively new laser-based technique for the determination of isotopic abundances. The resonance ionization process depends upon the stepwise absorption of photons from the laser, promoting atoms of the element of interest through progressively higher electronic states until an ion is formed. Sensitivity arises from the efficiency of the resonant absorption process when coupled with the power available from commercial laser sources. Selectivity derives naturally from the distinct electronic structure of different elements. This isobaric discrimination has provided the major impetus for development of the technique. Resonance ionization mass spectrometry was used for analysis of the isotopic abundances of the rare earth lutetium. Isobaric interferences from ytterbium severely effect the ability to measure small amounts of the neutron-deficient Lu isotopes by conventional mass spectrometric techniques. Resonance ionization for lutetium is performed using a continuous-wave laser operating at 452 nm, through a sequential two-photon process, with one photon exciting the intermediate resonance and the second photon causing ionization. Ion yields for microgram-sized quantities of lutetium lie between 10(6) and 10(7) ions per second, at overall ionization efficiencies approaching 10(-4). Discrimination factors against ytterbium greater than 10(6) have been measured. Resonance ionization for technetium is also being explored, again in response to an isobaric interference, molybdenum. Because of the relatively high ionization potential for Tc, three-photon, two-color RIMS processes are being developed.

  7. 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.

  8. Carbon and oxygen abundances in stellar populations

    NASA Astrophysics Data System (ADS)

    Nissen, P. E.; Chen, Y. Q.; Carigi, L.; Schuster, W. J.; Zhao, G.

    2014-08-01

    Context. Carbon and oxygen abundances in stars are important in many fields of astrophysics including nucleosynthesis, stellar structure, evolution of galaxies, and formation of planetary systems. Still, our knowledge of the abundances of these elements in different stellar populations is uncertain because of difficulties in observing and analyzing atomic and molecular lines of C and O. Aims: Abundances of C, O, and Fe are determined for F and G main-sequence stars in the solar neighborhood with metallicities in the range -1.6 < [Fe/H] < +0.4 in order to study trends and possible systematic differences in the C/Fe, O/Fe, and C/O ratios for thin- and thick-disk stars as well as high- and low-alpha halo stars. In addition, we investigate if there is any connection between C and O abundances in stellar atmospheres and the occurrence of planets. Methods: Carbon abundances are determined from the λλ 5052,5380 C i lines and oxygen abundances from the λ7774 O i triplet and the forbidden [O i] line at 6300 Å. MARCS model atmospheres are applied and non-LTE corrections for the O i triplet are included. Results: Systematic differences between high- and low-alpha halo stars and between thin- and thick-disk stars are seen in the trends of [C/Fe] and [O/Fe]. The two halo populations and thick-disk stars show the same trend of [C/O] versus [O/H], whereas the thin-disk stars are shifted to higher [C/O] values. Furthermore, we find some evidence of higher C/O and C/Fe ratios in stars hosting planets than in stars for which no planets have been detected. Conclusions: The results suggest that C and O in both high- and low-alpha halo stars and in thick-disk stars are made mainly in massive (M> 8 M⊙) stars, whereas thin-disk stars have an additional carbon contribution from low-mass AGB and massive stars of high metallicity causing a rising trend of the C/O ratio with increasing metallicity. However, at the highest metallicities investigated ([Fe/H] ≃ + 0.4), C/O does not

  9. Carbon isotopic composition of Amazon shelf sediments

    SciTech Connect

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

    1985-02-01

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

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

    NASA Astrophysics Data System (ADS)

    West, Christopher

    2013-03-01

    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.

  11. 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

  12. 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.

  13. 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.

  14. 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

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  16. 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.

  17. 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.

  18. Carbon isotope effects associated with aceticlastic methanogenesis.

    PubMed

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

    1994-02-01

    The carbon isotope effects associated with synthesis of methane from acetate have been determined for Methanosarcina barkeri 227 and for methanogenic archaea in sediments of Wintergreen Lake, Michigan. At 37 degrees C, the 13C isotope effect for the reaction acetate (methyl carbon) --> methane, as measured in replicate experiments with M. barkeri, was - 21.3% +/- 0.3%. The isotope effect at the carboxyl portion of acetate was essentially equal, indicating participation of both positions in the rate-determining step, as expected for reactions catalyzed by carbon monoxide dehydrogenase. A similar isotope effect, - 19.2% +/- 0.3% was found for this reaction in the natural community (temperature = 20 degrees C). Given these observations, it has been possible to model the flow of carbon to methane within lake sediment communities and to account for carbon isotope compositions of evolving methane. Extension of the model allows interpretation of seasonal fluctuations in 13C contents of methane in other systems. PMID:11536629

  19. 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

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

    NASA Astrophysics Data System (ADS)

    Freeman, K. H.

    2012-12-01

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

  1. 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.).

  2. The abundance of carbon in HU 2-1

    NASA Technical Reports Server (NTRS)

    Lutz, J. H.

    1981-01-01

    A logarithmic carbon abundance of 8.61 + or - 0.3 is derived for the planetary nebula Hu 2-1 using data taken with the International Ultraviolet Explorer satellite. This value is close to the logarithmic carbon abundance of 8.67 + or - 0.1, found for the sun by other investigators. The carbon abundance of Hu 2-1 is compared to those of other planetary nebulae and to the predictions of stellar evolution calculations.

  3. Carbon isotope effects associated with autotrophic acetogenesis.

    PubMed

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

    1989-01-01

    The carbon kinetic isotope effects associated with synthesis of acetate from CO2 and H2 during autotrophic growth of Acetobacterium woodii at 30 degrees C have been measured by isotopic analyses of CO2, methyl-carbon, and total acetate. Closed systems allowing construction of complete mass balances at varying stages of growth were utilized, and the effects of the partitioning of carbon between CO2 and HCO3- were taken account. For the overall reaction, total carbonate --> total acetate, isotope effects measured in replicate experiments ranged from -59.0 +/- 0.9% to -57.2 +/- 2.3%. Taking into account all measurements, the weighted mean and standard deviation are -58.6 +/- 0.7%. There is no evidence for intramolecular ordering in the acetate. The carbon isotopic composition of sedimentary acetate, otherwise expected to be near that of sedimentary organic carbon, is likely to be depleted in environments in which autotrophic acetogenesis is occurring. PMID:11542159

  4. Carbon isotope effects associated with autotrophic acetogenesis

    NASA Technical Reports Server (NTRS)

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

    1989-01-01

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

  5. 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.

  6. 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.

  7. 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.

  8. Potassium isotope abundances in Australasian tektites and microtektites.

    NASA Astrophysics Data System (ADS)

    Herzog, G. F.; O'D. Alexander, C. M.; Berger, E. L.; Delaney, J. S.; Glass, B. P.

    2008-10-01

    We report electron microprobe determinations of the elemental compositions of 11 Australasian layered tektites and 28 Australasian microtektites; and ion microprobe determinations of the 41K/39K ratios of all 11 tektites and 13 of the microtektites. The elemental compositions agree well with literature values, although the average potassium concentrations measured here for microtektites, 1.1 1.6 wt%, are lower than published average values, 1.9 2.9 wt%. The potassium isotope abundances of the Australasian layered tektites vary little. The average value of δ41K, 0.02 ± 0.12‰ (1σ mean), is indistinguishable from the terrestrial value (= 0 by definition) as represented by our standard, thereby confirming four earlier tektite analyses of Humayun and Koeberl (2004). In agreement with those authors, we conclude that evaporation has significantly altered neither the isotopic nor the elemental composition of Australasian layered tektites for elements less volatile than potassium. Although the average 41K/39K ratio of the microtektites, 1.1 ± 1.7‰ (1σ mean), is also statistically indistinguishable from the value for the standard, the individual ratios vary over a very large range, from -10.6 ± 1.4‰ to +13.8 ± 1.5‰ and at least three of them are significantly different from zero. We interpret these larger variations in terms of the evaporation of isotopically light potassium; condensation of potassium in the vapor plume; partial or complete stirring and quenching of the melts; and the possible uptake of potassium from seawater. That the average 41K/39K ratio of the microtektites equals the terrestrial value suggests that the microtektite-forming system was compositionally closed with respect to potassium and less volatile elements. The possibility remains open that 41K/39K ratios of microtektites vary systematically with location in the strewn field.

  9. 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.

  10. Stable carbon isotope ratios of rock varnish organic matter: a new paleoenvironmental indicator.

    PubMed

    Dorn, R I; Deniro, M J

    1985-03-22

    Stable carbon isotope ratios of organic matter in rock varnishes of Holocene age from western North America and the Middle East show a strong association with the environment. This isotopic variability reflects the abundance of plants with different photosynthetic pathways in adjacent vegetation. Analyses of different layers of varnish on late Pleistocene desert landforms indicate that the carbon isotopic composition of varnish organic matter is a paleoenvironmental indicator. PMID:17777781

  11. 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.

  12. 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.

  13. Carbon Isotope and Isotopomer Fractionation in Dense Molecular Cloud Cores

    NASA Astrophysics Data System (ADS)

    Furuya, K.; Aikawa, Y.; Sakai, N.; Yamamoto, S.

    2011-05-01

    Observations of 13C species would be useful to investigate chemistry of carbon-bearing species. Recent observations in TMC-1 indicate that the abundances are different among carbon isotopomers of the same species. For instance, Takano et al. (1998) found that HCC13CN is more abundant than HC13CCN and H13CCCN, which indicates the three carbon atoms are not equivalent in HC_3N. Sakai et al. (2007; 2010) reported the abundance ratios of C13CS/13CCS and CCH/13CCH to be 4.2 and 1.6, respectively. Again, two carbon atoms are not equivalent in CCS and CCH. Sakai et al. (2007; 2010) discussed an origin of these anomalies and pointed out two possibilities: (i) fractionation during the formation of the species and (ii) rearrangements of the 13C position after the formation of molecules by isotopomer-exchange reactions. We construct a gas-grain chemical network model which includes carbon isotopes (12C and 13C) and isotopomers in order to investigate the evolution of molecular abundances, the carbon isotope ratios (12CX/13CX) and the isotopomer ratios (12C13CX/13C12CX) of CCH and CCS in dense molecular cores. We confirm that the isotope ratios of molecules, both in the gas phase and on grain surfaces, mostly depend on whether the species is formed from the carbon atom (ion) or the CO molecule; the isotope ratio is larger than the elemental abundance ratio of 12C/13C if the species is formed from the carbon atom, while the ratio is smaller if the species is formed from the CO molecule (cf. Langer et al. 1984). We successfully reproduce the observed C13CH/13CCH ratio in TMC-1 by considering the isotopomer-exchange reaction, 13CCH + H rightleftharpoons C13CH + H + 8.1 K. However, the C13CS/13CCS ratio remains lower than observed in TMC-1. We then assume the isotopomer-exchange reaction catalyzed by the H atom, 13CCS + H rightleftharpoons C13CS + H + 17.4 K. In the model with this reaction, the observed C13CS/13CCS, CCS/C13CS and CCS/13CCS ratios can be reproduced simultaneously.

  14. 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.

  15. 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

  16. Abundance and Isotopic Composition of Solar-Wind-Implanted Methane in Lunar Soil and Breccias

    NASA Astrophysics Data System (ADS)

    Lecluse, C.; Morse, A. D.; Butterworth, A. L.; Brilliant, D. R.; Pillinger, C. T.

    1995-09-01

    Early analyses of lunar soils have revealed the presence of ppm amounts of indigenous methane and ethane thought to originate from the interaction of carbon and hydrogen in the solar wind [1]. The carbon abundance of lunar soils are typically between 50 to 300 ppm with isotopic compositions ranging from 0 to +20 per mil [2]. Solar wind hydrogen is generally accepted to contain delta D = -1000 per mil i.e. O ppm deuterium content; as indicated from D/H measurements of lunar hydrogen, after correction for contamination effects of terrestrial water from the sample [3]. In addition, recent solar spectroscopic measurements have detected hydrogen bearing molecules e.g. water [4]. Hence, isotopic analyses of methane in lunar samples can provide valuable information about isotopic composition of solar wind implanted species. For this study, we have analyzed methane from lunar soil A12023 and a breccia fragment taken from soil A10086. The methane from these samples was released by stepped pyrolysis and introduced into a new static vacuum mass spectrometer, MIRANDA (capable of measuring the delta l3C of ng amounts of methane to a precision of +/- 0.2 per mil. Isotopic compositions and abundances are calculated from 17M/l6M ratios in methane from which the delta 13C values can be determined assuming that solar wind hydrogen is delta D = -1000 per mil. Results from A12023 are presented in Figure 1, results from A10086 are discussed elsewhere [5]. Both samples displayed a broad release of methane between 400 degrees C and 800 degrees C with yields of 1.3 ppm and 1.9 ppm for the soil and the breccia respectively, consistent with previous measurements of ppm amounts of methane [1]. Figure 1 illustrates that methane in A12023 is isotopically heavy with a plateau of delta 13C = +55 per mil at a temperature between 500 degrees C and 600 degrees C. This is consistent with the previous measurement of A10086 [5] which also revealed isotopically heavy carbon with delta 13C approximately

  17. 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.

  18. 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.

  19. 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

  20. Quantitative and In-Depth Survey of the Isotopic Abundance Distribution Errors in Shotgun Proteomics.

    PubMed

    Chang, Cheng; Zhang, Jiyang; Xu, Changming; Zhao, Yan; Ma, Jie; Chen, Tao; He, Fuchu; Xie, Hongwei; Zhu, Yunping

    2016-07-01

    Accuracy is an important metric when mass spectrometry (MS) is used in large-scale quantitative proteomics research. For MS-based quantification by extracting ion chromatogram (XIC), both the mass and intensity dimensions must be accurate. Although much research has focused on mass accuracy in recent years, less attention has been paid to intensity errors. Here, we investigated signal intensity measurement errors systematically and quantitatively using the natural properties of isotopic distributions. First, we defined a normalized isotopic abundance error model and presented its merits and demerits. Second, a comprehensive survey of the isotopic abundance errors using data sets with increasing sample complexities and concentrations was performed. We examined parameters such as error distribution, relationships between signal intensities within one isotopic cluster, and correlations between different peak errors in isotopic profiles. Our data demonstrated that the high resolution MS platforms might also generate large isotopic intensity measurement errors (approximately 20%). Meanwhile, this error can be reduced to less than 5% using a novel correction algorithm, which is based on the theoretical isotopic abundance distribution. Finally, a nonlinear relationship was observed as the abundance error decreased in isotopic profiles with higher intensity. Our findings are expected to provide insight into isotopic abundance recalibration in quantitative proteomics. PMID:27266261

  1. Carbon and nitrogen abundances determined from transition layer lines

    NASA Technical Reports Server (NTRS)

    Boehm-Vitense, Erika; Mena-Werth, Jose

    1992-01-01

    The possibility of determining relative carbon, nitrogen, and silicon abundances from the emission-line fluxes in the lower transition layers between stellar chromospheres and coronae is explored. Observations for main-sequence and luminosity class IV stars with presumably solar element abundances show that for the lower transition layers Em = BT sup -gamma. For a given carbon abundance the constants gamma and B in this relation can be determined from the C II and C IV emission-line fluxes. From the N V and S IV lines, the abundances of these elements relative to carbon can be determined from their surface emission-line fluxes. Ratios of N/C abundances determined in this way for some giants and supergiants agree within the limits of errors with those determined from molecular bands. For giants, an increase in the ratio of N/C at B-V of about 0.8 is found, as expected theoretically.

  2. New Carbonate Standard Reference Materials for Boron Isotope Geochemistry

    NASA Astrophysics Data System (ADS)

    Stewart, J.; Christopher, S. J.; Day, R. D.

    2015-12-01

    The isotopic composition of boron (δ11B) in marine carbonates is well established as a proxy for past ocean pH. Yet, before palaeoceanographic interpretation can be made, rigorous assessment of analytical uncertainty of δ11B data is required; particularly in light of recent interlaboratory comparison studies that reported significant measurement disagreement between laboratories [1]. Well characterised boron standard reference materials (SRMs) in a carbonate matrix are needed to assess the accuracy and precision of carbonate δ11B measurements throughout the entire procedural chemistry; from sample cleaning, to ionic separation of boron from the carbonate matrix, and final δ11B measurement by multi-collector inductively coupled plasma mass spectrometry. To date only two carbonate reference materials exist that have been value-assigned by the boron isotope measurement community [2]; JCp-1 (porites coral) and JCt-1 (Giant Clam) [3]. The National Institute of Standards and Technology (NIST) will supplement these existing standards with new solution based inorganic carbonate boron SRMs that replicate typical foraminiferal and coral B/Ca ratios and δ11B values. These new SRMs will not only ensure quality control of full procedural chemistry between laboratories, but have the added benefits of being both in abundant supply and free from any restrictions associated with shipment of biogenic samples derived from protected species. Here we present in-house δ11B measurements of these new boron carbonate SRM solutions. These preliminary data will feed into an interlaboratory comparison study to establish certified values for these new NIST SRMs. 1. Foster, G.L., et al., Chemical Geology, 2013. 358(0): p. 1-14. 2. Gutjahr, M., et al., Boron Isotope Intercomparison Project (BIIP): Development of a new carbonate standard for stable isotopic analyses. Geophysical Research Abstracts, EGU General Assembly 2014, 2014. 16(EGU2014-5028-1). 3. Inoue, M., et al., Geostandards and

  3. Shear heating and clumped isotope reordering in carbonate faults

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  4. Carbon abundance and silicate mineralogy of anhydrous interplanetary dust particles

    NASA Astrophysics Data System (ADS)

    Thomas, K. L.; Blanford, G. E.; Keller, L. P.; Klock, W.; McKay, D. S.

    1993-04-01

    We have studied nineteen anhydrous chondritic interplanetary dust particles (IDPs) using analytical electron microscopy. We have determined a method for quantitative light element EDX analysis of small particles and have applied these techniques to a group of IDPs. Our results show that some IDPs have significantly higher bulk carbon abundances than do carbonaceous chondrites. We have also identified a relationship between carbon abundance and silicate mineralogy in our set of anhydrous IDPs. In general, these particles are dominated by pyroxene, olivine, or a subequal mixture of olivine and pyroxene. The pyroxene-dominated IDPs have a higher carbon abundance than those dominated by olivines. Members of the mixed mineralogy IDPs can be grouped with either the pyroxene- or olivine-dominated particles based on their carbon abundance. The high carbon, pyroxene-dominated particles have primitive mineralogies and bulk compositions which show strong similarities to cometary dust particles. We believe that the lower carbon, olivine-dominated IDPs are probably derived from asteroids. Based on carbon abundances, the mixed-mineralogy group represents particles derived from either comets or asteroids. We believe that the high carbon, pyroxene-rich anhydrous IDPs are the best candidates for cometary dust.

  5. 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

  6. Site-Specific Carbon Isotopes in Organics

    NASA Astrophysics Data System (ADS)

    Piasecki, A.; Eiler, J. M.

    2012-12-01

    Natural organic molecules exhibit a wide range of internal site-specific isotope variation (i.e., molecules with same isotopic substitution type but different site). Such variations are generally unconstrained by bulk isotopic measurements. If known, site-specific variations might constrain temperatures of equilibrium, mechanisms of formation or consumption reactions, and possibly other details. For example, lipids can exhibit carbon isotope differences of up to 30‰ between adjacent carbon sites as a result of fractionations arising during decarboxylation of pyruvate and other steps in lipid biosynthesis(1). We present a method for site-specific carbon isotope analysis of propane, based on high-resolution, multi-collector gas source mass spectrometry, using a novel prototype instrument - the Thermo MAT 253 Ultra. This machine has an inlet system and electron bombardment ion source resembling those in conventional stable isotope gas source mass spectrometers, and the energy filter, magnet, and detector array resembling those in multi-collector ICPMS and TIMS. The detector array has 7 detector positions, 6 of which are movable, and each of which can collect ions with either a faraday cup (read through amplifiers ranging from 107-1012 ohms) or an SEM. High mass resolving power (up to 27,000, MRP = M/dM definition) is achieved through a narrow entrance slit, adjustable from 250 to 5 μm. Such resolution can cleanly separate isobaric interferences between isotopologues of organic molecules having the same cardinal mass (e.g., 13CH3 and 12CH2D). We use this technology to analyze the isotopologues and fragments of propane, and use such data to solve for the site-specific carbon isotope fractionation. By measuring isotopologues of both the one-carbon (13CH3) and the two-carbon (13C12CH4) fragment ion, we can solve for both bulk δ13C and the difference in δ13C between the terminal and central carbon position. We tested this method by analyzing mixtures between natural

  7. 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.

  8. 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

  9. Carbon and Carbon Isotope Cycling in the Western Canadian Arctic

    NASA Astrophysics Data System (ADS)

    Mol, Jacoba; Thomas, Helmuth

    2016-04-01

    Increasing carbon dioxide levels in the atmosphere are having drastic effects on the global oceans. The Arctic Ocean is particularly susceptible to change as warming, sea-ice loss and a weak buffering capacity all influence this complicated semi-enclosed sea. In order to investigate the inorganic carbon system in the Canadian Arctic, water samples were collected in the Beaufort Sea, on the Alaskan shelf, at the Mackenzie river delta, and in Amundsen Gulf during the summer of 2014 and were analyzed for dissolved inorganic carbon (DIC), total alkalinity (TA), DI13C and 18O isotopes. Carbon isotopes are used to investigate the role of biological production on the uptake and transfer of inorganic carbon to depth. A preferential uptake of the lighter 12C relative to the heavier 13C isotope during biological production leads to a fractionation of the 13C/12C isotopes in both the organic matter and the water column. This results in an enrichment of DI13C in the high productivity surface waters and a depletion of DI13C at depth. Physical processes including freshwater input, brine rejection, and water mass mixing are investigated through the measurement of oxygen isotopes. Differences in the carbon system across the study area due to both biological and physical processes are assessed using depth profiles of DI13C and related carbon system parameters.

  10. 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

  11. 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

  12. 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.

  13. 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...

  14. Abundances of Linear Carbon-Chain Molecules in Supernovae

    NASA Technical Reports Server (NTRS)

    Clayton, D. D.; Deneault, E.; Meyer, B. S.; The, L.-S.

    2001-01-01

    This paper evaluates the condensation of carbon solids in a gas of pure C and O atoms when these exist within the interior of an expanding young supernova. We calculate the abundances of large carbon molecules, which serve as nucleations for condensation of graphites. Additional information is contained in the original extended abstract.

  15. 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.

  16. 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.

  17. Carbon and nitrogen abundance variations in globular cluster red giants

    NASA Astrophysics Data System (ADS)

    Martell, Sarah L.

    2008-06-01

    This dissertation describes investigations into two of the persistent questions of elemental abundances in Galactic globular clusters: the phenomenon of deep mixing, observed through the progressive depletion of surface carbon abundance as stars evolve along the red giant branch, and abundance bimodality, a phenomenon observed only in globular clusters, in which a subset of stars in a given globular cluster have a distinctive pattern of elemental enhancements and depletions relative to the Solar pattern. The first chapter gives an introduction to the history of globular cluster abundance studies, with particular focus on low-resolution spectroscopy. For both deep mixing and abundance bimodality, the leading theoretical models and the data which support and challenge them are laid out. Each section ends with a description of presently-unanswered questions; these are the motivation for the various projects contained in this dissertation. The second chapter describes the use of molecular handstrengths for determining elemental abundances from low-resolution spectra, and introduces a new CH bandstrength index that is designed to be sensitive to carbon abundance and insensitive to nitrogen abundance in Pop. II red giants over a wide range of metallicity. Various CH indices defined elsewhere in the literature are also discussed, and are shown to have comparable accuracy to the new index only over a limited range of stellar properties. Carbon abundances determined using the new CH index are compared to literature abundances for a few stars, and general concordance with published abundances is found. The third chapter contains a large-scale application of the new CH index: a survey of present-day carbon abundances and calculated carbon depletion rates in bright red giants belonging to eleven Galactic globular clusters spanning the full metallicity range of halo globular clusters. Targets were selected with similar evolutionary states, were observed with one instrument on

  18. 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.

  19. Carbon isotope composition of Antarctic plants

    NASA Astrophysics Data System (ADS)

    Galimov, E. M.

    2000-05-01

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

  20. Clumped isotope thermometry of cryogenic cave carbonates

    NASA Astrophysics Data System (ADS)

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

    2014-02-01

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

  1. 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.

  2. 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.

  3. Carbon isotopes as indicators of peatland growth?

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  4. 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.

  5. 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

  6. 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.

  7. 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

  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. Abundance of atomic carbon /C I/ in dense interstellar clouds

    NASA Technical Reports Server (NTRS)

    Phillips, T. G.; Huggins, P. J.

    1981-01-01

    The abundance of interstellar neutral atomic carbon is investigated by means of its ground state fine-structure line emission at 492 GHz using the 91.5 cm telescope of NASAs Kuiper Airborne Observatory. Atomic carbon is found to be very abundant in dense interstellar molecular clouds with column densities of about 10 to the 19th per sq cm. Because the observations have considerably greater column densities than current theories of carbon chemistry, it is suggested that the physical conditions of these clouds are not as simple as assumed in the models. Various situations are discussed which would lead to large C I abundances, including the possibility that the chemical lifetimes of the clouds are relatively short.

  10. 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.

  11. Daily Variation of Isotope Ratios in Mars Atmospheric Carbon Dioxide

    NASA Astrophysics Data System (ADS)

    Livengood, Timothy A.; Kostiuk, Theodor; Kolasinski, John R.; Hewagama, Tilak; Henning, Wade G.; Sornig, Manuela; Stangier, Tobias; Krause, Pia; Sonnabend, Guido; Mahaffy, Paul R.

    2014-11-01

    The atmosphere of Mars has been shown by ground based high-resolution infrared spectroscopy and in situ measurements with the Phoenix lander and Mars Science Laboratory Curiosity rover to be enriched in C and O heavy isotopes, consistent with preferential loss of light isotopes in eroding Mars’ primordial atmosphere. The relative abundance of heavy isotopes, combined with contemporary measurements of loss rates to be obtained with MAVEN, will enable estimating the primordial atmospheric inventory on Mars. IR spectroscopy of Mars collected in May 2012 as well as in March and May of 2014 from the NASA IRTF has resolved transitions of all three singly-substituted minor isotopologues of carbon dioxide in addition to the normal isotope, enabling remote measurements of all the carbon and oxygen isotope ratios as a function of latitude, longitude, and time of day. Earlier measurements obtained in October 2007 demonstrated that the relative abundance of O-18 increased linearly with increasing surface temperature over a relatively warm early-afternoon temperature range, but did not extend far enough to inspect the effect of late-afternoon cooling. These results imply that isotopically enriched gas is sequestered overnight when surface temperature is minimum and desorbs through the course of the day as temperature increases. Current spectroscopic constants indicate that the peak isotopic enrichment could be significantly greater than what has been measured in situ, apparently due to sampling the atmosphere at different time of day and surface temperature. The observing runs in 2012 and 2014 measured O-18 enrichment at several local times in both morning and afternoon sectors as well as at the subsolar, equatorial, and anti-subsolar latitudes. The two runs in 2014 have additionally observed O-17 and C-13 transitions in the morning sector, from local dawn to noon. These observations include a limited sampling of measurements over Gale Crater, which can be compared with

  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

  13. 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.

  14. Carbon isotopic composition of individual Precambrian microfossils

    NASA Astrophysics Data System (ADS)

    House, Christopher H.; Schopf, J. William; McKeegan, Kevin D.; Coath, Christopher D.; Harrison, T. Mark; Stetter, Karl O.

    2000-08-01

    Ion microprobe measurements of carbon isotope ratios were made in 30 specimens representing six fossil genera of microorganisms petrified in stromatolitic chert from the ˜850 Ma Bitter Springs Formation, Australia, and the ˜2100 Ma Gunflint Formation, Canada. The δ13CPDB values from individual microfossils of the Bitter Springs Formation ranged from -21.3 ± 1.7‰ to -31.9 ± 1.2‰, and the δ13CPDB values from microfossils of the Gunflint Formation ranged from -32.4 ± 0.7‰ to -45.4 ± 1.2‰. With the exception of two highly 13C-depleted Gunflint microfossils, the results generally yield values consistent with carbon fixation via either the Calvin cycle or the acetyl-CoA pathway. However, the isotopic results are not consistent with the degree of fractionation expected from either the 3-hydroxypropionate cycle or the reductive tricarboxylic acid cycle, suggesting that the microfossils studied did not use either of these pathways for carbon fixation. The morphologies of the microfossils suggest an affinity to the cyanobacteria, and our carbon isotopic data are consistent with this assignment.

  15. 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.

  16. 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.

  17. DETERMINING INTERSTELLAR CARBON ABUNDANCES FROM STRONG-LINE TRANSITIONS

    SciTech Connect

    Sofia, U. J.; Parvathi, V. S.; Babu, B. R. S.; Murthy, J.

    2011-01-15

    Carbon is arguably the most important element in the interstellar medium, yet its abundance in gas and dust is poorly understood due to a paucity of data. We explore the possibility of substantially increasing our knowledge of interstellar carbon by applying and assessing a new method for determining the column density of the dominant ion of interstellar carbon in diffuse neutral lines of sight. The method relies on profile fitting of the strong transition of C II at 1334 A in spectra continuum normalized with stellar models. We apply our method to six sight lines for which the carbon abundance has previously been determined with a weak intersystem absorption transition. Our strong-line method consistently shows a significantly lower gas-phase C abundance than the measurements from the weak lines. This result implies that more carbon could reside in dust than was previously thought. This has implications for dust models, which often suffer from a lack of sufficient carbon to plausibly explain extinction. There is no immediately clear explanation for the difference found between the strong- and weak-line C II determinations, but there are indications that the results from the method presented here have advantages over the weak-line column densities. If this is the case, then the reported oscillator strength for the C II transition at 2325 A may be too small. Our findings further suggest that damping wings modeled with a single absorption component may not produce accurate abundances. This problem could affect a large number of H I abundances determined through absorption line analysis that are reported in the literature.

  18. 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

  19. Evidence of 13C non-covalent isotope effects obtained by quantitative 13C nuclear magnetic resonance spectroscopy at natural abundance during normal phase liquid chromatography.

    PubMed

    Botosoa, Eliot P; Silvestre, Virginie; Robins, Richard J; Rojas, Jose Manuel Moreno; Guillou, Claude; Remaud, Gérald S

    2009-10-16

    Quantitative isotopic (13)C NMR at natural abundance has been used to determine the site-by-site (13)C/(12)C ratios in vanillin and a number of related compounds eluted from silica gel chromatography columns under similar conditions. Head-to-tail isotope fractionation is observed in all compounds at the majority of carbon positions. Furthermore, the site-specific isotope deviations show signatures characteristic of the position and functionality of the substituents present. The observed effects are more complex than would be obtained by simply summing the individual effects. Such detail is hidden when only the global (13)C content is measured by mass spectrometry. In particular, carbon positions within the aromatic ring are found to show site-specific isotope fractionation between the solute and the stationary phase. These interactions, defined as non-covalent isotope effects, can be normal or inverse and vary with the substitution pattern present. PMID:19748628

  20. 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.

  1. 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

  2. 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.

  3. 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).

  4. 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.

  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. 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.

  7. 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.

  8. On the Evolution of Stars That Form Electron-degenerate Cores Processed by Carbon Burning. II. Isotope Abundances and Thermal Pulses in a 10 Msun Model with an ONe Core and Applications to Long-Period Variables, Classical Novae, and Accretion-induced Collapse

    NASA Astrophysics Data System (ADS)

    Ritossa, Claudio; Garcia-Berro, Enrique; Iben, Icko, Jr.

    1996-03-01

    A 10 Msun model of Population I composition is evolved from the hydrogen-burning main sequence to the thermally pulsing `super' asymptotic giant branch (TPSAGB) stage, where it has an oxygen-neon (ONe) core of mass 1.196 Msun and is experiencing thermal pulses driven by helium-burning thermonuclear flashes. Interior abundance characteristics are relevant to an understanding of the core collapse of massive acereting white dwarfs in close binary star systems. At mass point 0.2 Msun., abundances by mass are X(16O) = 0.656, X(20Ne) = 0.215, X(23Na) = 0.0467, X(24Mg) = 0.0325, X(25Mg) = 0.0115, X(12 C)= 0.0112, X(22Ne) = 0.00893, X(21Ne) = 0.00689, X(26Mg) = 0.00560, and X(27Al) = 0.00528. Abundances near the surface of the core are relevant to an understanding of nova outbursts in cataclysmic variables. At mass point 1.17 Msun, abundances by mass are X(16O) = 0.511, X(20Ne) = 0.313, X(23Na) = 0.0644, X(24Mg) = 0.0548, X(25Mg) = 0.0158, X(27 Al)= 0.0108, X(12C) = 0.00916, X(26Mg) = 0.00989, X(21Ne) = 0.00598, and X(22Ne) = 0.00431. Carbon burning is quenched at the beginning of the thermally pulsing phase, and a layer of CO matter of mass 0.015 Msun separates the ONe core from overlying helium- and hydrogen-rich layers. The outer 0.01 M of the CO layer contains essentially no neon: very little new 20Ne has been made, and most of the 22Ne which has been made from the original CNO elements has been converted into 25Mg and neutrons which have been captured to form neutron-rich isotopes. If the observational counterpart of the model is in a close binary and fills its Roche lobe near the end of the carbon-burning phase, and if the binary evolves into a cataclysmic variable, one expects that the ejecta of approximately 1000 nova outbursts will exhibit an under- abundance of neon and overabundance of carbon, oxygen, and magnesium. During the TPSAGB phase, characteristics of a pulse cycle approach local limit-cycle values after ˜30 pulses. Helium-shell flashes are of about the

  9. 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).

  10. 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.

  11. 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.

  12. The Li isotope composition of modern biogenic carbonates

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  13. Isotopic abundances of silicon in four red giants

    NASA Astrophysics Data System (ADS)

    Lambert, David L.; McWilliam, Andrew; Smith, Verne V.

    1987-05-01

    High-resolution spectra of Beta Peg, Omicron1 Ori, 10 Dra, and HR 1105 are analyzed in order to estimate Si-28/Si-29 and Si-28/Si-30 abundance ratios. The elimination of the Fourier Transform Spectrometer ripple, telluric N2O absorption, and the detector noise from the observations is discussed. The various methods used to derive the Si-28 and Si-29 abundance ratios are described. The equivalent and half widths of a number of strong and weak Si-28O lines, and the microturbulent and macroturbulent velocities of the Si-28O line are measured. The nucleosynthesis of Si-29 and Si-30 is examined. It is observed that the Si-28/Si-29 ratio is within 20 to 25 percent of the terrestrial ratio of 20 in Beta Peg and HR 1105, but that Si-29 is underabundant in 10 Dra and Omicron1 Ori; and Si-30 is underabundant in all four stars with respect to the terrestrial ratio of 30.

  14. Carbonate clumped isotope bond reordering and geospeedometry

    NASA Astrophysics Data System (ADS)

    Passey, Benjamin H.; Henkes, Gregory A.

    2012-10-01

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

  15. 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.

  16. 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...

  17. 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

  18. Mg Isotopic Compositions of Modern Marine Carbonates

    NASA Astrophysics Data System (ADS)

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

    2003-12-01

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

  19. Carbon Isotope Chemostratigraphy, the Baby and the Bathwater

    NASA Astrophysics Data System (ADS)

    Arthur, M. A.

    2008-12-01

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

  20. 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

  1. 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.

  2. Further carbon isotope measurements of LEW 88516

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

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

  3. Stable Carbon Isotope Ratios for Giant Stars in the Globular Cluster M13

    NASA Astrophysics Data System (ADS)

    Rhee, Jaehyon; Pilachowski, C. A.

    2013-01-01

    Recently, our paradigm for the formation and evolution of globular clusters has shifted. We now understand that the majority of present-day stars in globular clusters formed as second-generation stars, primarily from the ejecta of first-generation AGB stars, while the majority of first generation, less centrally concentrated stars, have been dynamically lost to the cluster (D'Ercole et al. 2011). This paradigm explains the observed star-to-star variations in the abundances of light element observed in globular clusters, and suggests that the carbon isotope ratio should be similarly differentiated between first and second generation stars. In an effort to verify this scenario, we have recently utilized the Gemini/NIFS to determine carbon isotope abundances (12C and 13C) for 18 giant stars in the globular clusters M13 through medium-resolution (R ˜ 5300) infrared spectroscopy of the first-overtone CO bands near 2.3 μm. Our program stars are distributed from the tip of the RGB to the BLF (the bump in the luminosity function) of M13, and their Na, Mg, and Al abundances are already known from homogeneous data set analysis. Therefore, adding reliable abundances of the stable carbon isotopes to this homogeneous spectroscopic sample permits systematic tests of cluster chemical evolution models. We report preliminary results of the carbon abundance analysis for our NIFS K-band spectra and present an overview of our ongoing effort with other globular clusters.

  4. Relative isotopic abundances of zirconium in R Cygni and V CANCRI

    NASA Astrophysics Data System (ADS)

    Zook, A. C.

    1985-02-01

    The relative abundances of the isotopes of Zr in the S stars R Cyg and V Cnc are calculated by determining isotopic splitting at the head of the 1Pi - 1Sigma (0, 1) band of ZrO in spectra obtained at resolution 30 pm on hypersensitized 127-O4 plates with a Varo tube on the 51-cm camera at the Coude focus of the 3-m telescope at Lick Observatory. The data reduction techniques and the fit to the model synthetic spectra of Kurucz (1970) are described, and the ratio (Zr-90):(Zr-91):(Zr-92):(Zr-93):(Zr-94):(Zr-96) is given as 47:10:17:6:20:00 percent. The presence of the long-lived unstable isotope Zr-93 is interpreted as evidence for recent nucleosynthesis, and the abundances found are shown to be consistent with s-process nucleosynthesis.

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  6. 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.

  7. 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

  8. Carbon and Oxygen Abundances in Low Metallicity Dwarf Galaxies

    NASA Astrophysics Data System (ADS)

    Berg, Danielle A.; Skillman, Evan D.; Henry, Richard B. C.; Erb, Dawn K.; Carigi, Leticia

    2016-08-01

    The study of carbon and oxygen abundances yields information on the time evolution and nucleosynthetic origins of these elements, yet they remain relatively unexplored. At low metallicities, (12+log(O/H) < 8.0), nebular carbon measurements are limited to rest-frame UV collisionally excited emission lines. Therefore, we present the UV spectrophotometry of 12 nearby low-metallicity high-ionization H ii regions in dwarf galaxies obtained using the Cosmic Origins Spectrograph on the Hubble Space Telescope. We present the first analysis of the C/O ratio in local galaxies based solely on simultaneous significant detections of the UV {{{O}}}+2 and {{{C}}}+2 collisionally excited lines in seven of our targets and five objects from the literature to create a final sample of 12 significant detections. Our sample is complemented by optical SDSS spectra, from which we measured the nebular physical conditions and oxygen abundances using the direct method. At low metallicity, (12+log(O/H) < 8.0), no clear trend is evident in C/O versus O/H for the present sample given the large dispersion observed. When combined with recombination line observations at higher values of O/H, a general trend of increasing C/O with increasing O/H is also viable but with some significant outliers. Additionally, we find the C/N ratio appears to be constant (but with significant scatter) over a large range in oxygen abundance, indicating that carbon is predominantly produced by similar nucleosynthetic mechanisms as nitrogen. If true, and our current understanding of nitrogen production is correct, this would indicate that primary production of carbon (a flat trend) dominates at low metallicity, but quasi-secondary production (an increasing trend) becomes prominent at higher metallicities. A larger sample will be needed to determine the true nature and dispersion of the relation.

  9. Carbon isotope fractionation in synthetic magnesian calcite

    NASA Astrophysics Data System (ADS)

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

    2006-03-01

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

  10. Syndepositional diagenesis of modern platform carbonates: Evidence from isotopic and minor element data

    NASA Astrophysics Data System (ADS)

    Patterson, William P.; Walter, Lynn M.

    1994-02-01

    Physical, elemental, and stable isotopic evidence documents significant syndepositional diagenesis off biogenic carbonate in modern sediment pore water. Halimeda (aragonite) and Neogoniolithon (high-Mg calcite) fragments from sediment cores and experimental substrates were compared with fresh samples to determine the magnitude of minor element (Sr, Mg), and stable isotopic (C and O) compositional shifts. Although no significant shift in bulk sediment mineralogy is apparent, experimental substrates and natural biogenic grains exhibit significant diagenetic changes. These changes include dissolution textures, net loss of mass, changes in minor element composition, and progressive evolution toward carbon and oxygen isotopic equilibrium with p ore water. Our results demonstrate that carbonate sediment can undergo rapid syndepositional dissolution and reprecipitation. Pore waters likely are buffered chemically and isotopically by most abundant carbonate grain types. In turn, compositions of less abundant carbonate grains may shift toward equilibrium with respect to pore water. Therefore, many components of shelf limestone have compositions controlled by chemically evolved pore waters rather than by seawater from which the biotic carbonate originally precipitated.

  11. 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.

  12. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  14. 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.

  15. The origin of fluorine: abundances in AGB carbon stars revisited

    NASA Astrophysics Data System (ADS)

    Abia, C.; Cunha, K.; Cristallo, S.; de Laverny, P.

    2015-09-01

    Context. Revised spectroscopic parameters for the HF molecule and a new CN line list in the 2.3 μm region have recently become available, facilitating a revision of the F content in asymptotic giant branch (AGB) stars. Aims: AGB carbon stars are the only observationally confirmed sources of fluorine. Currently, there is no consensus on the relevance of AGB stars in its Galactic chemical evolution. The aim of this article is to better constrain the contribution of these stars with a more accurate estimate of their fluorine abundances. Methods: Using new spectroscopic tools and local thermodynamical equilibrium spectral synthesis, we redetermine fluorine abundances from several HF lines in the K-band in a sample of Galactic and extragalactic AGB carbon stars of spectral types N, J, and SC, spanning a wide range of metallicities. Results: On average, the new derived fluorine abundances are systematically lower by 0.33 dex with respect to previous determinations. This may derive from a combination of the lower excitation energies of the HF lines and the larger macroturbulence parameters used here as well as from the new adopted CN line list. Yet, theoretical nucleosynthesis models in AGB stars agree with the new fluorine determinations at solar metallicities. At low metallicities, an agreement between theory and observations can be found by handling the radiative/convective interface at the base of the convective envelope in a different way. Conclusions: New fluorine spectroscopic measurements agree with theoretical models at low and at solar metallicity. Despite this, complementary sources are needed to explain its observed abundance in the solar neighbourhood.

  16. 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.

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

    SciTech Connect

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

    2004-02-27

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

  18. 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

  19. 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.

  20. 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.

  1. 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

  2. Oxygen and carbon isotopic growth record in a reef coral from the florida keys and a deep-sea coral from blake plateau

    USGS Publications Warehouse

    Emiliani, C.; Harold, Hudson J.; Shinn, E.A.; George, R.Y.

    1978-01-01

    Carbon and oxygen isotope analysis through a 30-year (1944 to 1974) growth of Montastrea annularis from Hen and Chickens Reef (Florida Keys) shows a strong yearly variation in the abundances of both carbon-13 and oxygen-18 and a broad inverse relationship between the two isotopes. Normal annual dense bands are formed during the summer and are characterized by heavy carbon and light oxygen. "Stress bands" are formed during particularly severe winters and are characterized by heavy carbon and heavy oxygen. The isotopic effect of Zooxanthellae metabolism dominates the temperature effect on the oxygen-18/oxygen-16 ratio. The isotopic results on the deep-sea solitary coral Bathypsammia tintinnabulum, where Zooxanthellae are nonexistent, indicates that the abundance of the heavy isotopes carbon-13 and oxygen-18 is inversely related to the growth rate, with both carbon and oxygen approaching equilibrium values with increasing skeletal age.

  3. Determining carbon-carbon connectivities in natural abundance organic powders using dipolar couplings.

    PubMed

    Dekhil, Myriam; Mollica, Giulia; Bonniot, Tristan Texier; Ziarelli, Fabio; Thureau, Pierre; Viel, Stéphane

    2016-06-30

    We present a solid-state NMR methodology capable of investigating the carbon skeleton of natural abundance organic powders. The methodology is based on the (13)C-(13)C dipolar coupling interaction and allows carbon-carbon connectivities to be unambiguously established for a wide range of organic solids. This methodology is particularly suitable for disordered solids, such as natural or synthetic macromolecules, which cannot be studied using conventional diffraction or NMR techniques. PMID:27319808

  4. Lead Abundance In The Martian Mantle Deduced From The Isotopic Data In Snc Meteorites

    NASA Astrophysics Data System (ADS)

    Dreibus, G.; Jagoutz, E.

    Isotopic data are a powerful tool for the study of planetary evolution. Assuming that the SNC meteorites are rocks from Mars their Sm-Nd-, Rb-Sr- and Pb-Pb-isotope systematics reveal the time scale for the chemical evolution of the Martian mantle. From the Rb -Sr isotopic systematic the existence of 3 isotopically distinct reservoirs on Mars was postulated, which remained isolated for a period of 4.3 +/- 0.2 Ga. The basaltic shergottites Shergotty, Zagami and Los Angeles have relatively high radiogenic Sr, which might come from a planetary crust. A second group, characterized by non radiogenic Sr, consists of the two mafic cumulates Nakhla and Chassigny, the olivine rich basaltic shergottites DaG 476, SaU 005, Dhofar 019and the basaltic shergottite QUE 94201, which may represent the depleted mantle. The depletion of this reservoir must have taken place during a very early process. as derived from the primitive Sr isotopes and the existence of Nd-142, the daughter product of the extinct Sm-146, found in Chassigny, the Nakhlites, SaU 005, and DaG476. A third group, with intermediate Sr isotopic composition, represented by the lherzolitic shergottites, could be derived from a primitive, unfractionated mantle. Our observed correlation of Sr-isotopes with Pb-isotopes in SNC's permits to estimate the Pb abundance for the Martian mantle. The Pb isotopes of all measured SNCs show a similar pattern as Sr isotopes. The initial Pb data of Los Angeles, Shergotty, and Zagami from the enriched crustal reservoir and of Nakhla and SaU 005 from the depleted mantle reservoir plot close to the 4.5 Ga Pb -Pb isochron.. We used this correlation to estimate the µ value (238U/204Pb) of 3.1 for the Martian mantle. This corresponds to 366 ppb Pb. Compared to the Earth with a µ = 8.8, Pb is enriched on Mars by at least a fact or of 2.5. The same enrichment was found for all other moderately volatile and volatile elements on Mars. From the high abundance of Pb in the sulfide phases of iron

  5. Isotope Dependence of Chemical Erosion of Carbon

    SciTech Connect

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

    2010-01-01

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

  6. 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

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

    NASA Astrophysics Data System (ADS)

    Tripati, A.

    2015-12-01

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

  8. Boron abundances and isotopic ratios of olivine grains on Itokawa returned by the Hayabusa spacecraft

    NASA Astrophysics Data System (ADS)

    Fujiya, Wataru; Hoppe, Peter; Ott, Ulrich

    2016-07-01

    We report the B abundances and isotopic ratios of two olivine grains from the S-type asteroid Itokawa sampled by the Hayabusa spacecraft. Olivine grains from the Dar al Gani (DaG) 989 LL6 chondrite were used as a reference. Since we analyzed polished thin sections in both cases, we expect the contribution from the solar wind B (rich in 10B) to be minimal because the solar wind was implanted only within very thin layers of the grain surface. The Itokawa and DaG 989 olivine grains have homogeneous B abundances (~400 ppb) and 11B/10B ratios compatible with the terrestrial standard and bulk chondrites. The observed homogeneous B abundances and isotopic ratios of the Itokawa olivine grains are likely the result of thermal metamorphism which occurred in the parent asteroid of Itokawa, which had a similar composition as LL chondrites. The chondritic B isotopic ratios of the Itokawa samples suggest that they contain little cosmogenic B (from cosmic-ray spallation reactions) rich in 10B. This observation is consistent with the short cosmic-ray exposure ages of Itokawa samples inferred from the small concentrations of cosmogenic 21Ne. If other Itokawa samples have little cosmogenic B as well, the enrichment in 10B found previously on the surface of another Itokawa particle (as opposed to the bulk grain study here) may be attributed to implanted solar wind B.

  9. Boron abundances and isotopic ratios of olivine grains on Itokawa returned by the Hayabusa spacecraft

    NASA Astrophysics Data System (ADS)

    Fujiya, Wataru; Hoppe, Peter; Ott, Ulrich

    2016-09-01

    We report the B abundances and isotopic ratios of two olivine grains from the S-type asteroid Itokawa sampled by the Hayabusa spacecraft. Olivine grains from the Dar al Gani (DaG) 989 LL6 chondrite were used as a reference. Since we analyzed polished thin sections in both cases, we expect the contribution from the solar wind B (rich in 10B) to be minimal because the solar wind was implanted only within very thin layers of the grain surface. The Itokawa and DaG 989 olivine grains have homogeneous B abundances (~400 ppb) and 11B/10B ratios compatible with the terrestrial standard and bulk chondrites. The observed homogeneous B abundances and isotopic ratios of the Itokawa olivine grains are likely the result of thermal metamorphism which occurred in the parent asteroid of Itokawa, which had a similar composition as LL chondrites. The chondritic B isotopic ratios of the Itokawa samples suggest that they contain little cosmogenic B (from cosmic-ray spallation reactions) rich in 10B. This observation is consistent with the short cosmic-ray exposure ages of Itokawa samples inferred from the small concentrations of cosmogenic 21Ne. If other Itokawa samples have little cosmogenic B as well, the enrichment in 10B found previously on the surface of another Itokawa particle (as opposed to the bulk grain study here) may be attributed to implanted solar wind B.

  10. Carbon isotopic fractionation in the biosynthesis of bacterial fatty acids. Ozonolysis of unsaturated fatty acids as a means of determining the intramolecular distribution of carbon isotopes

    NASA Astrophysics Data System (ADS)

    Monson, K. David; Hayes, J. M.

    1982-02-01

    Methods for the determination of 13C abundances at individual olefinic carbon positions have been developed, tested, and shown to perform accurately. (1) The double bond is oxidized with ozone; (2) silver oxide is used to cleave the resulting ozonide quantitatively to carboxylic-acid fragments; (3) a modified Schmidt decarboxylation is used to produce CO 2 quantitatively from the carboxyl groups of the separated cleavage products; (4) the CO 2 is utilized for mass spectrometric analysis. The results of intramolecular isotopic analyses are combined with molecular-average isotopic compositions determined by total combustion in order to show that fatty acids biosynthesized by Escherichia coli grown aerobically with glucose as the sole carbon source and harvested at late log phase are depleted by approximately 3%. in 13C relative to the glucose. This fractionation arises in the formation of acetylcoenzyme A by pyruvate dehydrogenase and is localized at the carboxyl position in the acetyl-CoA product. The isotopic order in that two-carbon subunit is carried through the biosynthesis of fatty acids so that alternate positions in the fatty-acid chains are depleted in 13C by an amount equal to twice the molecular-average depletion. The kinetic isotope effect at C-2 for pyruvate dehydrogenase in vivo is shown to be approximately 2.3%. While it appears that no other fractionation mechanism has controlled the overall depletion of 13C in these fatty acids, a separate process responsible for control of isotopic abundances in the carboxyl groups has been identified and described elsewhere [Monson K.D. and Hayes J.M. (1980) J. Biol. Chem. 255, 11435-11441]. It is concluded that kinetic, rather than thermodynamic, factors have controlled isotopic distributions in these cells and that kinetic factors will be dominant in most biological reactions.

  11. 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

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

    SciTech Connect

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

    1994-12-31

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

  13. 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

  14. 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

  15. 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.

  16. Isotopic abundance in the CN coma of comets: Ten years of measurements

    NASA Astrophysics Data System (ADS)

    Schulz, R.; Jehin, E.; Manfroid, J.; Hutsemékers, D.; Arpigny, C.; Cochran, A.; Zucconi, J.-M.; Stüwe, J. A.

    2008-11-01

    Over the past 10 years the isotopic ratios of carbon ( 12C/ 13C) and nitrogen ( 14N/ 15N) have been determined for a dozen comets, bright enough to allow obtaining the required measurements from the ground. The ratios were derived from high-resolution spectra of the CN coma measured in the B 2∑ +-X 2∑ + (0, 0) emission band around 387 nm. The observed comets belong to different dynamical classes, including dynamically new as well as long- and short-period comets from the Halley- and Jupiter-family. In some cases the comets could be observed at various heliocentric distances. All values determined for the carbon and nitrogen isotopic ratios were consistent within the error margin irrespective of the type of comet or the heliocentric distance at which it was observed. Our investigations resulted in average ratios of 12C/ 13C=91±21 and nitrogen 14N/ 15N=141±29. Whilst the value for the carbon isotopic ratio is in good agreement with the solar and terrestrial value of 89, the nitrogen isotopic ratio is very different from the telluric value of 272.

  17. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

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

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. 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

  5. Linking Carbonic Anhydrase Abundance and Diversity in Soils to Ecological Function

    NASA Astrophysics Data System (ADS)

    Pang, E.; Meredith, L. K.; Welander, P. V.

    2015-12-01

    Carbonic anhydrase (CA) is an ancient enzyme widespread among bacteria, archaea, and eukarya that catalyzes the following reaction: CO2 + H2O ⇌ HCO3- + H+. Its functions are critical for key cellular processes such as concentrating CO2 for autotrophic growth, pH regulation, and pathogen survival in hosts. Currently, there are six known CA classes (α, β, γ, δ, η, ζ) arising from several distinct evolutionary lineages. CA are widespread in sequenced genomes, with many organisms containing multiple classes of CA or multiple CA of the same class. Soils host rich microbial communities with diverse and important ecological functions, but the diversity and abundance of CA in soils has not been explored. CA appears to play an important, but poorly understood, role in some biogeochemical cycles such as those of CO2 and its oxygen isotope composition and also carbonyl sulfide (COS), which are potential tracers in predictive carbon cycle models. Recognizing the prevalence and functional significance of CA in soils, we used a combined bioinformatics and molecular biology approach to address fundamental questions regarding the abundance, diversity, and function of CA in soils. To characterize the abundance and diversity of the different CA classes in soils, we analyzed existing soil metagenomic and metatranscriptomic data from the DOE Joint Genome Institute databases. Out of the six classes of CA, we only found the α, β, and γ classes to be present in soils, with the β class being the most abundant. We also looked at genomes of sequenced soil microorganisms to learn what combination of CA classes they contain, from which we can begin to predict the physiological role of CA. To characterize the functional roles of the different CA classes in soils, we collected soil samples from a variety of biomes with diverse chemical and physical properties and quantified the rate of two CA-mediated processes: soil uptake of COS and acceleration of the oxygen isotope exchange

  6. 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

  7. 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

  8. 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.

  9. 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.

  10. 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

  11. 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).

  12. 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).

  13. Cryogenian-Ediacaran Carbon Isotope Stratigraphy of the Amadeus Basin, Central Australia

    NASA Astrophysics Data System (ADS)

    Joubert, R. L.; Verdel, C.; Schultz, I.

    2014-12-01

    Deciphering the nature of extreme Neoproterozoic climatic and biogeochemical perturbations hinges on correlating sedimentary sequences within and across different basins. To improve these correlations within central Australia, we have focused on the abundant and laterally extensive glaciogenic and carbonate deposits of the Amadeus Basin. Here, we present new high-resolution carbonate C isotope profiles from Cryogenian-Ediacaran stratigraphic successions (the Areyonga, Aralka, Olympic, and Julie Formations) that are particularly well exposed in the northeastern part of the basin. The data appear to span a duration of >100 Ma, from the end of the older Cryogenian glaciation to the upper Ediacaran. In addition to major isotopic excursions resembling those described from other Neoproterozoic successions, the Amadeus Basin isotopic profiles display consistent fine-scale patterns and lateral trends that allow us to identify diachronous strata and refine the overall stratigraphic and tectonic architecture of the basin.

  14. 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.

  15. 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.

  16. 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,...

  17. 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.

  18. 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

  19. Abundance and Isotopic Composition of Gases in the Martian Atmosphere from the Curiosity Rover

    NASA Astrophysics Data System (ADS)

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

    2013-07-01

    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 (40Ar), 0.0193(±0.0001); nitrogen (N2), 0.0189(±0.0003); oxygen, 1.45(±0.09) × 10-3; carbon monoxide, < 1.0 × 10-3; and 40Ar/36Ar, 1.9(±0.3) × 103. The 40Ar/N2 ratio is 1.7 times greater and the 40Ar/36Ar 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 40Ar/36Ar ratio is consistent with martian meteoritic values, which provides additional strong support for a martian origin of these rocks. The isotopic signature δ13C 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.

  20. 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

  1. 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.

  2. High Spatial Resolution Isotopic Abundance Measurements by Secondary Ion Mass Spectrometry: Status and Prospects

    NASA Astrophysics Data System (ADS)

    McKeegan, K. D.

    2007-12-01

    Secondary Ion Mass Spectrometry, SIMS or ion microprobe analysis, has become an important tool for geochemistry because of its ability study the distributions of elemental and isotopic abundances in situ on polished samples with high (typically a few microns to sub-micron) spatial resolution. In addition, SIMS exhibits high sensitivity for a wide range of elements (H to Pu) so that isotope analyses can sometimes be performed for elements that comprise only trace quantities of some mineral phase (e.g., Pb in zircon) or on major and/or minor elements in very small samples (e.g., presolar dust grains). Offsetting these positive attributes are analytical difficulties due to the complexity of the sputtering source of analyte ions: (1) relatively efficient production of molecular ion species (especially from a complex matrix such as most natural minerals) that cause interferences at the same nominal mass as atomic ions of interest, and (2) quantitation problems caused by variations in the ionization efficiencies of different elements and/or isotopes depending upon the chemical state of the sample surface during sputtering--the so-called "matrix effects". Despite the availability of high mass resolution instruments (e.g., SHRIMP II/RG, CAMECA 1270/1280/NanoSIMS), the molecular ion interferences effectively limit the region of the mass table that can be investigated in most samples to isotope systems at Ni or lighter or at Os or heavier. The matrix effects and the sensitivity of instrumental mass discrimination to the physical state of the sample surface can hamper reproducibility and have contributed to a view that SIMS analyses, especially for so- called stable isotopes, are most appropriate for extraterrestrial samples which are often small, rare, and can exhibit large magnitude isotopic effects. Recent improvements in instrumentation and technique have extended the scope of SIMS isotopic analyses and applications now range from geochronology to paleoclimatology to

  3. 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).

  4. 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.

  5. The Antarctic environment and its effect upon the total carbon and sulfur abundances in recovered meteorites

    NASA Technical Reports Server (NTRS)

    Gibson, E. K., Jr.; Andrawes, F. F.

    1980-01-01

    Total carbon and sulfur abundances have been measured for 25 meteorites recovered from the Allan Hills area of Antarctica. The majority (greater than 67%) of the meteorites analyzed do not contain enriched carbon abundances resulting from weathering processes. The presence of secondary carbonates in samples which give no apparent evidence of weathering was noted during pyrolysis experiments, despite the 'normal' total carbon abundances. In selected cases, the surfaces of weathered samples may contain up to a factor of two greater carbon content than the interior. Variations in carbon abundances may reflect the degree of weathering and the amount of secondary minerals present. One of the surprises of this study is that the majority of the Antarctic meteorites studied do not exhibit total carbon and sulfur abundances outside the ranges previously observed for falls.

  6. 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.

  7. 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

  8. 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.

  9. Rhenium-osmium isotope and highly-siderophile-element abundance systematics of angrite meteorites

    NASA Astrophysics Data System (ADS)

    Riches, Amy J. V.; Day, James M. D.; Walker, Richard J.; Simonetti, Antonio; Liu, Yang; Neal, Clive R.; Taylor, Lawrence A.

    2012-11-01

    Coupled 187Os/188Os compositions and highly-siderophile-element (HSE: Os, Ir, Ru, Pt, Pd, and Re) abundance data are reported for eight angrite achondrite meteorites that include quenched- and slowly-cooled textural types. These data are combined with new major- and trace-element concentrations determined for bulk-rock powder fractions and constituent mineral phases, to assess angrite petrogenesis. Angrite meteorites span a wide-range of HSE abundances from <0.005 ppb Os (e.g., Northwest Africa [NWA] 1296; Angra dos Reis) to >100 ppb Os (NWA 4931). Chondritic to supra-chondritic 187Os/188Os (0.1201-0.2127) measured for Angra dos Reis and quenched-angrites correspond to inter- and intra-sample heterogeneities in Re/Os and HSE abundances. Quenched-angrites have chondritic-relative rare-earth-element (REE) abundances at 10-15×CI-chondrite, and their Os-isotope and HSE abundance variations represent mixtures of pristine uncontaminated crustal materials that experienced addition (<0.8%) of exogenous chondritic materials during or after crystallization. Slowly-cooled angrites (NWA 4590 and NWA 4801) have fractionated REE-patterns, chondritic to sub-chondritic 187Os/188Os (0.1056-0.1195), as well as low-Re/Os (0.03-0.13), Pd/Os (0.071-0.946), and relatively low-Pt/Os (0.792-2.640). Sub-chondritic 187Os/188Os compositions in NWA 4590 and NWA 4801 are unusual amongst planetary basalts, and their HSE and REE characteristics may be linked to melting of mantle sources that witnessed prior basaltic melt depletion. Angrite HSE-Yb systematics suggest that the HSE behaved moderately-incompatibly during angrite magma crystallization, implying the presence of metal in the crystallizing assemblage. The new HSE abundance and 187Os/188Os compositions indicate that the silicate mantle of the angrite parent body(ies) (APB) had HSE abundances in chondritic-relative proportions but at variable abundances at the time of angrite crystallization. The HSE systematics of angrites are

  10. 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

  11. Code System to Determine Pu Isotope Abundances from Multichannel Analyzer Gamma Spectra.

    Energy Science and Technology Software Center (ESTSC)

    2008-09-26

    Version 00 The MGA (Multiple Group Analysis) program determines the relative abundances of plutonium and other actinide isotopes in different materials. The program analyzes spectra taken of such samples using a 4096-channel germanium (Ge) gamma-ray spectrometer. The code can be run in a one or two detector mode. The first spectrum, which is required and must be taken at a gain of 0.075 Kev/channel with a high resolution planar detector, contains the 0-300Kev energy region.more » The second spectrum, which is optional, must be taken at a gain of 0.25 Kev/channel; it becomes important when analyzing high burnup samples (concentration of Pu241 greater than one percent). Isotopic analysis precisions of one percent or better can be obtained, and no calibrations are required. The system also measures the abundances of U235, U238, Np237, and Am241. A special calibration option is available to perform a one-time peak-shape characterization when first using a new detector system.« less

  12. 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.

  13. 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

  14. 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.

  15. [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.

  16. 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

  17. 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.

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

    NASA Technical Reports Server (NTRS)

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

    1972-01-01

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

  19. Carbon isotope fractionation and the acetyl-CoA pathway

    NASA Astrophysics Data System (ADS)

    Blaser, Martin; Conrad, Ralf

    2010-05-01

    Homoacetogenic bacteria can catalyze the reductive synthesis of acetate from CO2 via the acetyl-CoA pathway. Besides this unifying property homoacetogenic bacteria constitute a metabolically and phylogenetically diverse bacteriological group. Therefore their environmental role is difficult to address. It has been recognized that in methanogenic environments homoacetogenic bacteria contribute to the degradation of organic matter. The natural abundance of 13C may be used to understand the functional impact of homoacetogenic bacteria in the soil environment. To distinguish the acetyl-CoA pathway from other dominant processes, the isotopic composition of acetate and CO2 can be determined and the fractionation factors of the individual processes may be used to discriminate between the dominant pathways. To characterize the fractionation factor associated with the acetyl-CoA pathway the phylogenetic and metabolic diversity needs to be considered. Therefore the fractionation factor of substrate utilization and product formation of different homoacetogens (Acetobacterium woodii, Sporomusa ovata, Thermoanaerobacter kivui, Morella thermoautotrophica) has been studied under pure culture conditions in two defined minimal medium with H2/CO2 as sole source of carbon and energy. It became obvious that the cultivation conditions have a major impact on the obtained fractionation factors.

  20. Absolute isotopic composition of molybdenum and the solar abundances of the p-process nuclides Mo92,94

    NASA Astrophysics Data System (ADS)

    Wieser, M. E.; de Laeter, J. R.

    2007-05-01

    The isotopic composition of molybdenum has been measured with high precision using a thermal ionization mass spectrometer, the linearity of which has been verified by measuring the isotopically-certified reference material for strontium (NIST 987). The abundance sensitivity of the mass spectrometer in the vicinity of the molybdenum ion beams has been carefully examined to ensure the absence of tailing effects. Particular care was given to ensuring that potential isobaric interferences from zirconium and ruthenium did not affect the measurement of the isotopic composition of molybdenum. Gravimetric mixtures of two isotopically enriched isotopes, Mo92 and Mo98, were analyzed mass spectrometrically to calibrate the mass spectrometer, in order to establish the isotope fractionation of the spectrometer for the molybdenum isotopes. This enabled the “absolute” isotopic composition of molybdenum to be determined. An accurate determination of the isotopic composition is required in order to calculate the atomic weight of molybdenum, which is one of the least accurately known values of all the elements. The absolute isotope abundances (in atom %) of molybdenum measured in this experiment are as follows: Mo92=14.5246±0.0015; Mo94=9.1514±0.0074; Mo95=15.8375±0.0098; Mo96=16.672±0.019; Mo97=9.5991±0.0073; Mo98=24.391±0.018; and Mo100=9.824±0.050, with uncertainties at the 1s level. These values enable an atomic weight Ar(Mo) of 95.9602±0.0023 (1s) to be calculated, which is slightly higher than the current Standard Atomic Weight Ar(Mo) =95.94±0.02 and with a much improved uncertainty interval. These “absolute” isotope abundances also enable the Solar System abundances of molybdenum to be calculated for astrophysical purposes. Of particular interest are the Solar System abundances of the two p-process nuclides—Mo92 and Mo94, which are present in far greater abundance than p-process theory suggests. The Solar System abundances for Mo92 and Mo94 of 0.364±0

  1. 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.

  2. An high resolution FDIRC for the measurement of cosmic-ray isotopic abundances

    NASA Astrophysics Data System (ADS)

    Marrocchesi, P. S.; Bagliesi, M. G.; Batkov, K.; Bigongiari, G.; Kim, M. Y.; Maestro, P.

    2011-08-01

    Measurements of the relative abundance of cosmic isotopes and of the energy dependence of their fluxes may clarify our present understanding on the confinement time of charged cosmic rays in the Galaxy. Experimental studies of these propagation clocks have been carried out by balloon and space missions at energies of a few 100 MeV/amu by means of detection techniques based on multiple d E/d x sampling, coupled with a measurement of the energy released in a thick absorber. At larger energies, the isotopic separation of light nuclei (as, for instance, 9Be/ 10Be) can be achieved by combining a precise measurement of the particle's rigidity with an high resolution determination of its velocity, via the observation of the Cherenkov effect in a radiator. In this paper, we propose the introduction - for the first time in a space experiment - of the DIRC technique (Detection of Internal Reflected Cherenkov light) for the identification of cosmic-ray isotopes. This type of detector has been successfully used in electron-positron colliders for particle identification and in particular for π-K separation. While for particles with unit charge the light yield is a limiting factor, in the case of a nucleus of charge Z the larger photostatistics (due to the Z2 dependence of Cherenkov light emission) is the key to reach an adequate angular resolution to provide a mass discrimination for isotopes of astrophysical interest. We report on the early development phase of a DIRC prototype with a focussing scheme (FDIRC) to collect the Cherenkov light onto a detector plane instrumented with a Silicon PhotoMultiplier (SiPM) array.

  3. 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

  4. 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

  5. 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.

  6. 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.

  7. Kinetic Fractionation of Carbon Isotopes During Carbonate Weathering in Glaciated Catchments: Implications for the Detection of Subglacial Microbial Activity

    NASA Astrophysics Data System (ADS)

    Skidmore, M.; Sharp, M.; Tranter, M.; Bottrell, S.

    2003-12-01

    Microbes are abundant at the water-rock-ice interface beneath valley glaciers at Haut Glacier d'Arolla, Switzerland (HGA) and at John Evans Glacier, Ellesmere Island Nunavut, Canada (JEG). However, the importance of in-situ microbial activity in driving subglacial weathering reactions remains unknown. This is a key question when considering the potential role of microbes in mediating subglacial weathering and carbon cycling on a continental scale beneath the Pleistocene mid-latitude ice sheets. This study measured the chemical composition of meltwaters, including δ {13}C-DIC at the two glaciers to quantify microbial CO2 inputs to the DIC budget using isotope mass balance techniques. However, PCO2 data indicates that most of the glacial meltwaters are far from equilibrium with respect to atmospheric CO2 and thus kinetic processes are important in determining the water chemistry. Consequently, conventional equilibrium isotope mass balance techniques were inappropriate in this case. Hence, laboratory experiments were conducted with calcium carbonate and carbonate rich glacial sediments from JEG under simulated subglacial conditions (< 63 micron size fraction, sediment concentrations 0.01 to 5 g/l, 5° C) to investigate potential kinetic isotopic effects and aid in interpretation of the field data (δ {13}C-DIC values ranging from -2.4 to -15.7 ‰ ). The laboratory experiments demonstrate previously unreported kinetic fractionation of carbon isotopes during the initial hydrolysis (closed system conditions) and early stages of carbonate dissolution driven by atmospheric CO2 (open system conditions). Preferential dissolution of Ca12CO3, results in δ {13}C-DIC values that are significantly isotopically lighter than the bulk carbonate. This kinetic isotopic effect (KIE) is more pronounced at higher sediment concentrations and can be up to -17.4 ‰ for glacial sediments under closed system conditions and sediment concentrations of 5g/l. The KIE is also significant

  8. 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

  9. 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.

  10. 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