WorldWideScience

Sample records for carbon isotope ratio

  1. Carbon isotope ratios of atmospheric carbon dioxide

    International Nuclear Information System (INIS)

    Sakai, Hitoshi; Kishima, Noriaki; Tsutaki, Yasuhiro.

    1982-01-01

    The delta 13 C values relative to PDB were measured for carbon dioxide in air samples collected at various parts of Japan and at Mauna Loa Observatory, Hawaii in the periods of 1977 and 1978. The delta 13 C values of the ''clean air'' are -7.6 % at Hawaii and -8.1 per mille Oki and Hachijo-jima islands. These values are definitely lighter than the carbon isotope ratios (-6.9 per mille) obtained by Keeling for clean airs collected at Southern California in 1955 to 1956. The increase in 12 C in atmospheric carbon dioxide is attributed to the input of the anthropogenic light carbon dioxides (combustion of fossil fuels etc.) Taking -7.6 per mille to be the isotope ratio of CO 2 in the present clean air, a simple three box model predicts that the biosphere has decreased rather than increased since 1955, implying that it is acting as the doner of carbon rather than the sink. (author)

  2. Measurement of stable isotope ratio of organic carbon in water samples

    International Nuclear Information System (INIS)

    Fujii, Toshihiro; Otsuki, Akira

    1977-01-01

    A new method for the measurement of stable isotope ratios was investigated and applied to organic carbon's isotope ratio measurements in water samples. A few river water samples from Tsuchiura city were tested. After the wet oxidation of organic carbons to carbon dioxide in a sealed ampoule, the isotope ratios were determined with the gas chromatograph-quadrupole mass spectrometer combined with a total organic carbon analyser, under the dynamic conditions. The GC-MS had been equipped with the multiple ion detector-digital integrator system. The ion intensities at m/e 44 and 45 were simultaneously measured at a switching rate of 1 ms. The measurements with carbon dioxide acquired from sodium carbonate (53 μg) gave the isotope ratios with the variation coefficient of 0.62%. However, the variation coefficients obtained from organic carbons in natural water samples were 2 to 3 times as high as that from sodium carbonate. This method is simple and rapid and may be applied to various fields especially in biology and medicine. (auth.)

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

    Science.gov (United States)

    Price, Gregory; Grimes, Stephen

    2015-04-01

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

  4. Carbon isotope ratios in field Population II giant stars

    International Nuclear Information System (INIS)

    Sneden, C.; Pilachowski, C.A.; Vandenberg, D.A.; Kitt Peak National Observatory, Tucson, AZ; Victoria Univ., Canada)

    1986-01-01

    Carbon isotope ratios have been derived from high-resolution spectra of the CH G-band in 15 very metal-poor Population II giant stars and two similar dwarf stars. Many of the giants possess very low C-12/C-13 ratios, some approaching the CN cycle equilibrium value. The metal-poor dwarfs do not have detectable CH-13 features; thus the low carbon isotope ratios in the giants probably are due to their internal evolutions. These results strongly support the idea that at least part of the anomalously low C/N values in Population II giants arises from very efficient mixing of their envelopes into the CN cycle burning layers. Detailed calculations of the expected CNO surface abundances in Population II giants in different evolutionary states have been performed. These computations demonstrate that the observed carbon isotope ratios cannot be produced during the first dredge-up mixing phases in low-mass, low metal abundance stars. Numerical experiments show that theoretical and observational results can be brought into agreement with artificially induced extra mixing. An agent to provoke this additional mixing has not been identified with certainty yet, although internal stellar rotation is a promising candidate. 63 references

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

    Science.gov (United States)

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

    2008-12-01

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

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

    International Nuclear Information System (INIS)

    Tagami, Keiko; Uchida, Shigeo

    2008-01-01

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

  7. The puzzle of the CNO isotope ratios in asymptotic giant branch carbon stars

    Science.gov (United States)

    Abia, C.; Hedrosa, R. P.; Domínguez, I.; Straniero, O.

    2017-03-01

    Context. The abundance ratios of the main isotopes of carbon, nitrogen and oxygen are modified by the CNO-cycle in the stellar interiors. When the different dredge-up events mix the burning material with the envelope, valuable information on the nucleosynthesis and mixing processes can be extracted by measuring these isotope ratios. Aims: Previous determinations of the oxygen isotopic ratios in asymptotic giant branch (AGB) carbon stars were at odds with the existing theoretical predictions. We aim to redetermine the oxygen ratios in these stars using new spectral analysis tools and further develop discussions on the carbon and nitrogen isotopic ratios in order to elucidate this problem. Methods: Oxygen isotopic ratios were derived from spectra in the K-band in a sample of galactic AGB carbon stars of different spectral types and near solar metallicity. Synthetic spectra calculated in local thermodynamic equillibrium (LTE) with spherical carbon-rich atmosphere models and updated molecular line lists were used. The CNO isotope ratios derived in a homogeneous way, were compared with theoretical predictions for low-mass (1.5-3 M⊙) AGB stars computed with the FUNS code assuming extra mixing both during the RGB and AGB phases. Results: For most of the stars the 16O/17O/18O ratios derived are in good agreement with theoretical predictions confirming that, for AGB stars, are established using the values reached after the first dredge-up (FDU) according to the initial stellar mass. This fact, as far as the oxygen isotopic ratios are concerned, leaves little space for the operation of any extra mixing mechanism during the AGB phase. Nevertheless, for a few stars with large 16O/17O/18O, the operation of such a mechanism might be required, although their observed 12C/13C and 14N/15N ratios would be difficult to reconcile within this scenario. Furthermore, J-type stars tend to have lower 16O/17O ratios than the normal carbon stars, as already indicated in previous studies

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

    DEFF Research Database (Denmark)

    Egsgaard, Helge; Ambus, Per; Ahrenfeldt, Jesper

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

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

    Science.gov (United States)

    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).

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-11-13

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

  11. The relationship between carbon stable isotope ratios of hatchling down and egg yolk in Black-headed Gulls

    NARCIS (Netherlands)

    Klaassen, M.R.J.; Baarspul, T.; Dekkers, T.; Van Tienen, P.

    2004-01-01

    We reconstructed the nutrient source for egg synthesis by sampling Black-headed Gull (Larus ridibundus) eggs for yolk, analyzing their carbon stable isotope ratio, and comparing that to hatchling down. Most of the variation in carbon stable isotope ratio was explained by differences between nests,

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

    NARCIS (Netherlands)

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

    2014-01-01

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

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

    Science.gov (United States)

    Jackson, Glen P; An, Yan; Konstantynova, Kateryna I; Rashaid, Ayat H B

    2015-01-01

    This study compares and contrasts the ability to classify individuals into different grouping factors through either bulk isotope ratio analysis or amino-acid-specific isotope ratio analysis of human hair. Using LC-IRMS, we measured the isotope ratios of 14 amino acids in hair proteins independently, and leucine/isoleucine as a co-eluting pair, to provide 15 variables for classification. Multivariate analysis confirmed that the essential amino acids and non-essential amino acids were mostly independent variables in the classification rules, thereby enabling the separation of dietary factors of isotope intake from intrinsic or phenotypic factors of isotope fractionation. Multivariate analysis revealed at least two potential sources of non-dietary factors influencing the carbon isotope ratio values of the amino acids in human hair: body mass index (BMI) and age. These results provide evidence that compound-specific isotope ratio analysis has the potential to go beyond region-of-origin or geospatial movements of individuals-obtainable through bulk isotope measurements-to the provision of physical and characteristic traits about the individuals, such as age and BMI. Further development and refinement, for example to genetic, metabolic, disease and hormonal factors could ultimately be of great assistance in forensic and clinical casework. Copyright © 2014 Forensic Science Society. Published by Elsevier Ireland Ltd. All rights reserved.

  14. Assessment of primary production in a eutrophic lake from carbon and nitrogen isotope ratios of a carnivorous fish

    International Nuclear Information System (INIS)

    Yoshioka, Takahito

    1991-01-01

    The carbon and nitrogen isotope ratios of Hypomesus transpacificus (a pond smelt) in a eutrophic lake, Lake Suwa, were measured from April to September in 1986 and 1987. The differences in the isotope ratios between these two years were observed. The stable isotopes were transferred from phytoplankton to zooplankton and pond smelt, associated with organic matters. Therefore, the difference in the isotope ratios in two years seemed to reflect the differences of the proceeding of primary production. It was suggested that the carbon and nitrogen isotope ratios of animal, whose trophic level is far from primary producer, can be the qualitative indicators for assessing the primary production in a lake ecosystem. (author)

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

    NARCIS (Netherlands)

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

    2013-01-01

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

  16. Determination of carbon isotope ratios in plant starch via selective enzymatic hydrolysis

    International Nuclear Information System (INIS)

    Schimmelmann, A.; DeNiro, M.J.

    1983-01-01

    A method for the determination of the carbon isotope ratios in bipolymers hydrolyzed by enzymatic action consists of separating the monomer by passage through a dialysis membrane and then combusting the monomer prior to isotopic analysis. The method is described for application to the analysis of starch, but it should find application for polymers than can be degraded quantitatively to monomers and/or oligomers using specific hydrolytic enzymes

  17. Applications of compound-specific carbon isotope ratios in organic contaminant studies

    International Nuclear Information System (INIS)

    Aravena, R.; Hunkeler, D.; Bloom, Y.; Frape, S.K.; Butler, B.; Edwards, E.; Cox, E.

    1999-01-01

    In this paper results are presented on the application of compound-specific isotope ratios measurements to assess biodegradation of chlorinated solvents, in particularly on microbial dechlorination of tetrachloroethene (PCE) and trichloroethene (TCE). Analytical aspects and isotope data from laboratory and field studies are discussed. The analytical tests showed that both headspace and SPME techniques provide accurate δ 13 C values with a similar precision for a wide range of chlorinated solvents. However, the SPME method is generally more sensitive. The microcosm experiments show that a significant isotopic fractionation occurs during dechlorination of PCE and TCE to ethene. The largest fractionation factors are observed in the steps DCE-VC and VC-Ethene. In general, the δ 13 C of each dechlorination product was always more negative than the δ 13 C of the corresponding precursor. In addition, the δ 13 C values of each compound increased with time. A similar pattern was observed for dechlorination of PCE at a field site. These results show that compound-specific carbon isotope ratios technology is a very sensitive tool for evaluation of natural attenuation of chlorinated solvents in groundwater. (author)

  18. Isotope analytics for the evaluation of the feeding influence on the isotope ratio in beef samples

    International Nuclear Information System (INIS)

    Herwig, Nadine

    2010-01-01

    Information about the origin of food and associated production systems has a high significance for food control. An extremely promising approach to obtain such information is the determination of isotope ratios of different elements. In this study the correlation of the isotope ratios C-13/C-12, N-15/N-14, Mg-25/Mg-24, and Sr-87/Sr-86 in bovine samples (milk and urine) and the corresponding isotope ratios in feed was investigated. It was shown that in the bovine samples all four isotope ratios correlate with the isotope composition of the feed. The isotope ratios of strontium and magnesium have the advantage that they directly reflect the isotope ratios of the ingested feed since there is no isotope fractionation in the bovine organism which is in contrast to the case of carbon and nitrogen isotope ratios. From the present feeding study it is evident, that a feed change leads to a significant change in the delta C-13 values in milk and urine within 10 days already. For the deltaN-15 values the feed change was only visible in the bovine urine after 49 days. Investigations of cows from two different regions (Berlin/Germany and Goestling/Austria) kept at different feeding regimes revealed no differences in the N-15/N-14 and Mg-26/Mg-24 isotope ratios. The strongest correlation between the isotope ratio of the bovine samples and the kind of ingested feed was observed for the carbon isotope ratio. With this ratio even smallest differences in the feed composition were traceable in the bovine samples. Since different regions usually coincide with different feeding regimes, carbon isotope ratios can be used to distinguish bovine samples from different regions if the delta C-13 values of the ingested feed are different. Furthermore, the determination of strontium isotope ratios revealed significant differences between bovine and feed samples of Berlin and Goestling due to the different geologic realities. Hence the carbon and strontium isotope ratios allow the best

  19. Stable carbon isotope analyses of nanogram quantities of particulate organic carbon (pollen) with laser ablation nano combustion gas chromatography/isotope ratio mass spectrometry

    Science.gov (United States)

    Sluijs, Appy; Laks, Jelmer J.; Reichart, Gert‐Jan

    2016-01-01

    Rationale Analyses of stable carbon isotope ratios (δ 13C values) of organic and inorganic matter remains have been instrumental for much of our understanding of present and past environmental and biological processes. Until recently, the analytical window of such analyses has been limited to samples containing at least several μg of carbon. Methods Here we present a setup combining laser ablation, nano combustion gas chromatography and isotope ratio mass spectrometry (LA/nC/GC/IRMS). A deep UV (193 nm) laser is used for optimal fragmentation of organic matter with minimum fractionation effects and an exceptionally small ablation chamber and combustion oven are used to reduce the minimum sample mass requirement compared with previous studies. Results Analyses of the international IAEA CH‐7 polyethylene standard show optimal accuracy, and precision better than 0.5‰, when measuring at least 42 ng C. Application to untreated modern Eucalyptus globulus (C3 plant) and Zea mays (C4 plant) pollen grains shows a ~ 16‰ offset between these species. Within each single Z. mays pollen grain, replicate analyses show almost identical δ 13C values. Conclusions Isotopic offsets between individual pollen grains exceed analytical uncertainties, therefore probably reflecting interspecimen variability of ~0.5–0.9‰. These promising results set the stage for investigating both δ 13C values and natural carbon isotopic variability between single specimens of a single population of all kinds of organic particles yielding tens of nanograms of carbon. © 2016 The Authors. Rapid Communications in Mass Spectrometry Published by John Wiley & Sons Ltd. PMID:27766694

  20. USE OF GC-MS/COMBUSTION/IRMS TO IDENTIFY AND DETERMINE THE STABLE CARBON ISOTOPIC RATIO OF INDIVIDUAL LIPIDS

    Science.gov (United States)

    A system that couples a gas chromatograph (GC) via a split to a quadrapole mass spectrometer (MS) and, through a combustion interface, to an isotope ratio mass spectrometer (IRMS) allows the simultaneous detection of electron impact mass spectra and stable carbon isotope ratio an...

  1. GasBench/isotope ratio mass spectrometry: a carbon isotope approach to detect exogenous CO(2) in sparkling drinks.

    Science.gov (United States)

    Cabañero, Ana I; San-Hipólito, Tamar; Rupérez, Mercedes

    2007-01-01

    A new procedure for the determination of carbon dioxide (CO(2)) (13)C/(12)C isotope ratios, using direct injection into a GasBench/isotope ratio mass spectrometry (GasBench/IRMS) system, has been developed to improve isotopic methods devoted to the study of the authenticity of sparkling drinks. Thirty-nine commercial sparkling drink samples from various origins were analyzed. Values of delta(13)C(cava) ranged from -20.30 per thousand to -23.63 per thousand, when C3 sugar addition was performed for a second alcoholic fermentation. Values of delta(13)C(water) ranged from -5.59 per thousand to -6.87 per thousand in the case of naturally carbonated water or water fortified with gas from the spring, and delta(13)C(water) ranged from -29.36 per thousand to -42.09 per thousand when industrial CO(2) was added. It has been demonstrated that the addition of C4 sugar to semi-sparkling wine (aguja) and industrial CO(2) addition to sparkling wine (cava) or water can be detected. The new procedure has advantages over existing methods in terms of analysis time and sample treatment. In addition, it is the first isotopic method developed that allows (13)C/(12)C determination directly from a liquid sample without previous CO(2) extraction. No significant isotopic fractionation was observed nor any influence by secondary compounds present in the liquid phase. Copyright (c) 2007 John Wiley & Sons, Ltd.

  2. Stable carbon isotope analyses of nanogram quantities of particulate organic carbon (pollen) with laser ablation nano combustion gas chromatography/isotope ratio mass spectrometry

    NARCIS (Netherlands)

    van Roij, Linda; Sluijs, Appy; Laks, Jelmer J.; Reichart, Gert-Jan

    2017-01-01

    Rationale: Analyses of stable carbon isotope ratios (δ13C values) of organic and inorganic matter remains have been instrumental for much of our understanding of present and past environmental and biological processes. Until recently, the analytical window of such analyses has been limited to

  3. A Novel Framework for Quantifying past Methane Recycling by Sphagnum-Methanotroph Symbiosis Using Carbon and Hydrogen Isotope Ratios of Leaf Wax Biomarkers

    Science.gov (United States)

    Nichols, Jonathan E.; Isles, Peter D. F.; Peteet, Dorothy M.

    2014-01-01

    The concentration of atmospheric methane is strongly linked to variations in Earth's climate. Currently, we can directly reconstruct the total atmospheric concentration of methane, but not individual terms of the methane cycle. Northern wetlands, dominated by Sphagnum, are an important contributor of atmospheric methane, and we seek to understand the methane cycle in these systems. We present a novel method for quantifying the proportion of carbon Sphagnum assimilates from its methanotrophic symbionts using stable isotope ratios of leaf-wax biomarkers. Carbon isotope ratios of Sphagnum compounds are determined by two competing influences, water content and the isotope ratio of source carbon. We disentangled these effects using a combined hydrogen and carbon isotope approach. We constrained Sphagnum water content using the contrast between the hydrogen isotope ratios of Sphagnum and vascular plant biomarkers. We then used Sphagnum water content to calculate the carbon isotope ratio of Sphagnum's carbon pool. Using a mass balance equation, we calculated the proportion of recycled methane contributed to the Sphagnum carbon pool, 'PRM.' We quantified PRM in peat monoliths from three microhabitats in the Mer Bleue peatland complex. Modern studies have shown that water table depth and vegetation have strong influences on the peatland methane cycle on instrumental time scales. With this new approach, delta C-13 of Sphagnum compounds are now a useful tool for investigating the relationships among hydrology, vegetation, and methanotrophy in Sphagnum peatlands over the time scales of entire peatland sediment records, vital to our understanding of the global carbon cycle through the Late Glacial and Holocene.

  4. Stable carbon isotope ratio profiling of illicit testosterone preparations--domestic and international seizures.

    Science.gov (United States)

    Brooker, Lance; Cawley, Adam; Drury, Jason; Edey, Claire; Hasick, Nicole; Goebel, Catrin

    2014-10-01

    Gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) is now established as a robust and mature analytical technique for the doping control of endogenous anabolic androgenic steroids in human sport. It relies on the assumption that the carbon isotope ratios of naturally produced steroids are significantly different to synthetically manufactured testosterone or testosterone prohormones used in commercial medical or dietary supplement products. Recent publications in this journal have highlighted the existence of black market testosterone preparations with carbon isotope ratios within the range reported for endogenous steroids (i.e. δ(13) C ≥ -25.8 ‰). In this study, we set out to profile domestic and international law enforcement seizures of illicit testosterone products to monitor the prevalence of 'enriched' substrates--which if administered to human subjects would be considered problematic for the use of current GC-C-IRMS methodologies for the doping control of testosterone in sport. The distribution of δ(13) C values for this illicit testosterone sample population (n = 283) ranged from -23.4 ‰ to -32.9 ‰ with mean and median of -28.6 ‰--comparable to previous work. However, only 13 out of 283 testosterone samples (4.6 %) were found to display δ(13) C values ≥ -25.8 ‰, confirming that in the vast majority of cases of illicit testosterone administration, current GC-C-IRMS doping control procedures would be capable of confirming misuse. Copyright © 2014 John Wiley & Sons, Ltd.

  5. Organic chemistry of Murchison meteorite: Carbon isotopic fractionation

    Science.gov (United States)

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

    1986-01-01

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

  6. Freezing and fractionation: effects of preservation on carbon and nitrogen stable isotope ratios of some limnetic organisms.

    Science.gov (United States)

    Wolf, J Marshall; Johnson, Brett; Silver, Douglas; Pate, William; Christianson, Kyle

    2016-03-15

    Stable isotopes of carbon and nitrogen have become important natural tracers for studying food-web structure and function. Considerable research has demonstrated that chemical preservatives and fixatives shift the isotopic ratios of aquatic organisms. Much less is known about the effects of freezing as a preservation method although this technique is commonly used. We conducted a controlled experiment to test the effects of freezing (-10 °C) and flash freezing (–79 °C) on the carbon and nitrogen isotope ratios of zooplankton (Cladocera), Mysis diluviana and Rainbow Trout (Oncorhynchus mykiss). Subsamples (~0.5 mg) of dried material were analyzed for percentage carbon, percentage nitrogen, and the relative abundance of stable carbon and nitrogen isotopes (δ13C and δ15N values) using a Carlo Erba NC2500 elemental analyzer interfaced to a ThermoFinnigan MAT Delta Plus isotope ratio mass spectrometer. The effects of freezing were taxon-dependent. Freezing had no effect on the isotopic or elemental values of Rainbow Trout muscle. Effects on the δ13C and δ15N values of zooplankton and Mysis were statistically significant but small relative to typical values of trophic fractionation. The treatment-control offsets had larger absolute values for Mysis (δ13C: ≤0.76 ± 0.41‰, δ15N: ≤0.37 ± 0.16‰) than for zooplankton (δ13C: ≤0.12 ± 0.06‰, δ15N: ≤0.30 ± 0.27‰). The effects of freezing were more variable for the δ13C values of Mysis, and more variable for the δ15N values of zooplankton. Generally, both freezing methods reduced the carbon content of zooplankton and Mysis, but freezing had a negative effect on the %N of zooplankton and a positive effect on the %N of Mysis. The species-dependencies and variability of freezing effects on aquatic organisms suggest that more research is needed to understand the mechanisms responsible for freezing-related fractionation before standardized protocols for freezing as a preservation method can be adopted.

  7. Stable carbon isotope ratios: implications for the source of sediment carbon and for phytoplankton carbon assimilation in Lake Memphremagog, Quebec

    International Nuclear Information System (INIS)

    LaZerte, B.D.

    1983-01-01

    The stable carbon isotope (SCI) ratio of the sediment of Lake Memphremagog, Quebec is compared with that ot terrestrial sources and the phytoplankton to determine the relative proportion of allochthonous carbon incorporated into the sediments. Approximately 40-50% of the organic carbon in the main basins' pelagic sediment was terrestrial in origin, whereas up to 100% was terrestrial in littoral areas. The SCI method of determining the organic carbon source of sediments appears more reliable than the C/N method. A comparison of the SCI fractionation of the phytoplankton with laboratory cultures under different degrees of carbon limitation indicates that the phytoplankton of Lake Memphremagog are not carbon limited and fix carbon primarily by the C 3 pathway

  8. Stable carbon and nitrogen isotope ratios of sodium and potassium cyanide as a forensic signature.

    Science.gov (United States)

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

    2012-01-01

    Sodium and potassium cyanide are highly toxic, produced in large amounts by the chemical industry, and linked to numerous high-profile crimes. The U.S. Centers for Disease Control and Prevention has identified cyanide as one of the most probable agents to be used in a chemical terrorism event. We investigated whether stable C and N isotopic content of sodium and potassium cyanide could serve as a forensic signature for sample matching, using a collection of 65 cyanide samples. Upon analysis, a few of the cyanide samples displayed nonhomogeneous isotopic content associated with degradation to a carbonate salt and loss of hydrogen cyanide. Most samples had highly reproducible isotope content. Of the 65 cyanide samples, >95% could be properly matched based on C and N isotope ratios, with a false match rate <3%. These results suggest that stable C and N isotope ratios are a useful forensic signature for matching cyanide samples. © 2011 American Academy of Forensic Sciences.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2002-07-01

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

  10. Comparison of gas chromatography/isotope ratio mass spectrometry and liquid chromatography/isotope ratio mass spectrometry for carbon stable-isotope analysis of carbohydrates

    NARCIS (Netherlands)

    Moerdijk-Poortvliet, Tanja C. W.; Schierbeek, Henk; Houtekamer, Marco; van Engeland, Tom; Derrien, Delphine; Stal, Lucas J.; Boschker, Henricus T. S.

    2015-01-01

    We compared gas chromatography/isotope ratio mass spectrometry (GC/IRMS) and liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) for the measurement of δ(13)C values in carbohydrates. Contrary to GC/IRMS, no derivatisation is needed for LC/IRMS analysis of carbohydrates. Hence, although

  11. Comparison of gas chromatography/isotope ratio mass spectrometry and liquid chromatography/isotope ratio mass spectrometry for carbon stable-isotope analysis of carbohydrates

    NARCIS (Netherlands)

    Moerdijk-Poortvliet, T.C.W.; Schierbeek, H.; Houtekamer, M.; van Engeland, T.; Derrien, D.; Stal, L.J.; Boschker, H.T.S.

    2015-01-01

    We compared gas chromatography/isotope ratio mass spectrometry (GC/IRMS) and liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) for the measurement of d13C values in carbohydrates. Contrary to GC/IRMS, no derivatisation is needed for LC/IRMS analysis of carbohydrates. Hence, although

  12. Comparison of gas chromatography/isotope ratio mass spectrometry and liquid chromatography/isotope ratio mass spectrometry for carbon stable-isotope analysis of carbohydrates

    NARCIS (Netherlands)

    Moerdijk-Poortvliet, T.C.W.; Schierbeek, H.; Houtekamer, M.; van Engeland, T.; Derrien, D.; Stal, L.J.; Boschker, H.T.S.

    2015-01-01

    Rationale: We compared gas chromatography/isotope ratio mass spectrometry (GC/IRMS) and liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) for the measurement of δ13C values in carbohydrates. Contrary to GC/IRMS, no derivatisation is needed for LC/IRMS analysis of carbohydrates. Hence,

  13. On-line coupling of the MAT 251 with a Carlo Erba elemental analyzer for carbon isotope ratio measurements

    International Nuclear Information System (INIS)

    Pichlmayer, F.

    1986-06-01

    For carbon isotope investigations with a moderate precision demand of about 0.2 per mil in the isotope ratio fast and reliable results are attained by on line combination of the ANA 1500 Elemental Analyzer and the MAT 251 Isotope Mass Spectrometer. The crucial point hereof is the gas splitting device. By proper design and adjustment of the analytical parameters, good sample efficiency and a sharp CO 2 bulk within the He stream is reached. The main characteristics of this combined equipment are described and some isotopic results of organic and anorganic carbon in lake sediment-samples are given as well as deltasup1 3 C-analyses of spiritous liquors. (Author)

  14. Isotope Ratio Monitoring Gas Chromatography Mass Spectrometry (IRM-GCMS)

    International Nuclear Information System (INIS)

    Freeman, K.H.; Ricci, S.A.; Studley, A.; Hayes, J.M.

    1989-01-01

    On Earth, the C-13 content of organic compounds is depleted by roughly 13 to 23 permil from atmospheric carbon dioxide. This difference is largely due to isotope effects associated with the fixation of inorganic carbon by photosynthetic organisms. If life once existed on Mars, then it is reasonable to expect to observe a similar fractionation. Although the strongly oxidizing conditions on the surface of Mars make preservation of ancient organic material unlikely, carbon-isotope evidence for the existence of life on Mars may still be preserved. Carbon depleted in C-13 could be preserved either in organic compounds within buried sediments, or in carbonate minerals produced by the oxidation of organic material. A technique is introduced for rapid and precise measurement of the C-13 contents of individual organic compounds. A gas chromatograph is coupled to an isotope-ratio mass spectrometer through a combustion interface, enabling on-line isotopic analysis of isolated compounds. The isotope ratios are determined by integration of ion currents over the course of each chromatographic peak. Software incorporates automatic peak determination, corrections for background, and deconvolution of overlapped peaks. Overall performance of the instrument was evaluated by the analysis of a mixture of high purity n-alkanes of know isotopic composition. Isotopic values measured via IRM-GCMS averaged withing 0.55 permil of their conventionally measured values

  15. Postmortem study of stable carbon isotope ratios in human cerebellar DNA: preliminary results

    International Nuclear Information System (INIS)

    Slatkin, D.N.; Irsa, A.P.; Friedman, L.

    1978-01-01

    It is observed that 13 C/ 12 C ratios in tissue specimens removed postmortem in the United States and Canada are significantly different from corresponding ratios in European specimens. On the basis of this information, measurements of carbon isotope ratios in DNA isolated from cerebella of native-born and European-born North Americans are in progress with the goal of estimating the average lifetime rate of DNA turnover in human neurons. Preliminary results from twenty postmortem examinations are consistent with the hypothesis that a significant proportion of human cerebellar DNA is renewed during the lifetime of an individual

  16. Carbon isotope ratios of organic matter in Bering Sea settling particles. Extremely high remineralization of organic carbon derived from diatoms

    International Nuclear Information System (INIS)

    Yasuda, Saki; Akagi, Tasuku; Naraoka, Hiroshi; Kitajima, Fumio; Takahashi, Kozo

    2016-01-01

    The carbon isotope ratios of organic carbon in settling particles collected in the highly-diatom-productive Bering Sea were determined. Wet decomposition was employed to oxidize relatively fresh organic matter. The amount of unoxidised organic carbon in the residue following wet decomposition was negligible. The δ 13 C of organic carbon in the settling particles showed a clear relationship against SiO 2 /CaCO 3 ratio of settling particles: approximately -26‰ and -19‰ at lower and higher SiO 2 /CaCO 3 ratios, respectively. The δ 13 C values were largely interpreted in terms of mixing of two major plankton sources. Both δ 13 C and compositional data can be explained consistently only by assuming that more than 98% of diatomaceous organic matter decays and that organic matter derived from carbonate-shelled plankton may remain much less remineralized. A greater amount of diatom-derived organic matter is discovered to be trapped with the increase of SiO 2 /CaCO 3 ratio of the settling particles. The ratio of organic carbon to inorganic carbon, known as the rain ratio, therefore, tends to increase proportionally with the SiO 2 /CaCO 3 ratio under an extremely diatom-productive condition. (author)

  17. Carbon isotopes in biological carbonates: Respiration and photosynthesis

    Science.gov (United States)

    McConnaughey, Ted A.; Burdett, Jim; Whelan, Joseph F.; Paull, Charles K.

    1997-02-01

    Respired carbon dioxide is an important constituent in the carbonates of most air breathing animals but is much less important in the carbonates of most aquatic animals. This difference is illustrated using carbon isotope data from freshwater and terrestrial snails, ahermatypic corals, and chemoautotrophic and methanotrophic pelecypods. Literature data from fish otoliths and bird and mammal shell and bone carbonates are also considered. Environmental CO 2/O 2 ratios appear to be the major controlling variable. Atmospheric CO 2/O 2 ratios are about thirty times lower than in most natural waters, hence air breathing animals absorb less environmental CO 2 in the course of obtaining 0 2. Tissue CO 2 therefore, does not isotopically equilibrate with environmental CO 2 as thoroughly in air breathers as in aquatic animals, and this is reflected in skeletal carbonates. Animals having efficient oxygen transport systems, such as vertebrates, also accumulate more respired CO 2 in their tissues. Photosynthetic corals calcify mainly during the daytime when photosynthetic CO 2 uptake is several times faster than respiratory CO 2 release. Photosynthesis, therefore, affects skeletal δ13C more strongly than does respiration. Corals also illustrate how "metabolic" effects on skeletal isotopic composition can be estimated, despite the presence of much larger "kinetic" isotope effects.

  18. Development of a Method to Isolate Glutamic Acid from Foodstuffs for a Precise Determination of Their Stable Carbon Isotope Ratio.

    Science.gov (United States)

    Kobayashi, Kazuhiro; Tanaka, Masaharu; Yatsukawa, Yoichi; Tanabe, Soichi; Tanaka, Mitsuru; Ohkouchi, Naohiko

    2018-01-01

    Recent growing health awareness is leading to increasingly conscious decisions by consumers regarding the production and traceability of food. Stable isotopic compositions provide useful information for tracing the origin of foodstuffs and processes of food production. Plants exhibit different ratios of stable carbon isotopes (δ 13 C) because they utilized different photosynthetic (carbon fixation) pathways and grow in various environments. The origins of glutamic acid in foodstuffs can be differentiated on the basis of these photosynthetic characteristics. Here, we have developed a method to isolate glutamic acid in foodstuffs for determining the δ 13 C value by elemental analyzer-isotope-ratio mass spectrometry (EA/IRMS) without unintended isotopic fractionation. Briefly, following acid-hydrolysis, samples were defatted and passed through activated carbon and a cation-exchange column. Then, glutamic acid was isolated using preparative HPLC. This method is applicable to measuring, with a low standard deviation, the δ 13 C values of glutamic acid from foodstuffs derived from C3 and C4 plants and marine algae.

  19. The stable carbon isotope ratios in benthic food webs of the gulf of Calvi, Corsica

    Science.gov (United States)

    Dauby, Patrick

    1989-02-01

    The Gulf of Calvi, Corsica, presents a wide diversity of biocoenoses, amongst which the seagrass Posidonia meadow is prevalent. More than 100 plant, animal and sediment samples from various biotopes were analysed for their stable carbon isotope ratios, to assess carbon flows within the food chains. Marine plants display a wide range of δ 13C values, from -6 to -32‰ but with three relatively well distinct peaks for Posidonia, brown algae and phytoplankton (-9, -19 and -23‰, respectively), which are the main carbon sources. The range of isotopic values of animals is narrower, from -14 to -24‰, suggesting that they feed mainly on algae and plankton. Computations based on simple equations show the proportion of each carbon source in the diet of the animals. Posidonia, notwithstanding their important biomass, appear to be a minor food source; this is possibly because of the transfer of their dead leaves, towards the shorelines, in winter.

  20. Testing Urey's carbonate-silicate cycle using the calcium isotopic composition of sedimentary carbonates

    Science.gov (United States)

    Blättler, Clara L.; Higgins, John A.

    2017-12-01

    Carbonate minerals constitute a major component of the sedimentary geological record and an archive of a fraction of the carbon and calcium cycled through the Earth's surface reservoirs for over three billion years. For calcium, carbonate minerals constitute the ultimate sink for almost all calcium liberated during continental and submarine weathering of silicate minerals. This study presents >500 stable isotope ratios of calcium in Precambrian carbonate sediments, both limestones and dolomites, in an attempt to characterize the isotope mass balance of the sedimentary carbonate reservoir through time. The mean of the dataset is indistinguishable from estimates of the calcium isotope ratio of bulk silicate Earth, consistent with the Urey cycle being the dominant mechanism exchanging calcium among surface reservoirs. The variability in bulk sediment calcium isotope ratios within each geological unit does not reflect changes in the global calcium cycle, but rather highlights the importance of local mineralogical and/or diagenetic effects in the carbonate record. This dataset demonstrates the potential for calcium isotope ratios to help assess these local effects, such as the former presence of aragonite, even in rocks with a history of neomorphism and recrystallization. Additionally, 29 calcium isotope measurements are presented from ODP (Ocean Drilling Program) Site 801 that contribute to the characterization of altered oceanic crust as an additional sink for calcium, and whose distinct isotopic signature places a limit on the importance of this subduction flux over Earth history.

  1. Carbon isotopes in mollusk shell carbonates

    Science.gov (United States)

    McConnaughey, Ted A.; Gillikin, David Paul

    2008-10-01

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

  2. CARBON AND OXYGEN ISOTOPIC RATIOS FOR NEARBY MIRAS

    Energy Technology Data Exchange (ETDEWEB)

    Hinkle, Kenneth H. [National Optical Astronomy Observatory P.O. Box 26732, Tucson, AZ 85726 (United States); Lebzelter, Thomas [Department of Astrophysics, University of Vienna Türkenschanzstrasse 17, A-1180 Vienna (Austria); Straniero, Oscar, E-mail: khinkle@noao.edu, E-mail: thomas.lebzelter@univie.ac.at, E-mail: straniero@oa-teramo.inaf.it [INAF, Osservatorio Astronomico di Collurania I-64100 Teramo (Italy)

    2016-07-01

    Carbon and oxygen isotopic ratios are reported for a sample of 46 Mira and SRa-type variable asymptotic giant branch (AGB) stars. Vibration–rotation first and second-overtone CO lines in 1.5–2.5 μ m spectra were measured to derive isotopic ratios for {sup 12}C/{sup 13}C, {sup 16}O/{sup 17}O, and {sup 16}O/{sup 18}O. Comparisons with previous measurements for individual stars and with various samples of evolved stars, as available in the extant literature, are discussed. Models for solar composition AGB stars of different initial masses are used to interpret our results. We find that the majority of M-stars have main sequence masses ≤2 M {sub ⊙} and have not experienced sizable third dredge-up (TDU) episodes. The progenitors of the four S-type stars in our sample are slightly more massive. Of the six C-stars in the sample three have clear evidence relating their origin to the occurrence of TDU. Comparisons with O-rich presolar grains from AGB stars that lived before the formation of the solar system reveal variations in the interstellar medium chemical composition. The present generation of low-mass AGB stars, as represented by our sample of long period variables (LPVs), shows a large spread of {sup 16}O/{sup 17}O ratios, similar to that of group 1 presolar grains and in agreement with theoretical expectations for the composition of mass 1.2–2 M {sub ⊙} stars after the first dredge-up. In contrast, the {sup 16}O/{sup 18}O ratios of present-day LPVs are definitely smaller than those of group 1 grains. This is most probably a consequence of the the decrease with time of the {sup 16}O/{sup 18}O ratio in the interstellar medium due to the chemical evolution of the Milky Way. One star in our sample has an O composition similar to that of group 2 presolar grains originating in an AGB star undergoing extra-mixing. This may indicate that the extra-mixing process is hampered at high metallicity, or, equivalently, favored at low metallicity. Similarly to O

  3. Differentiation of endogenous and exogenous steroids by gas chromatography-combustion-mass spectrometry isotope ratio

    International Nuclear Information System (INIS)

    Montes de Oca Porto, Rodny; Rosado Perez, Aristides; Correa Vidal, Margarita Teresa

    2007-01-01

    Urinary steroids profiles are used to control the misuse of endogenous steroids such as testosterone and dihydrotestosterone. The testosterone/epistestosterone ratio, measured by Gas Chromatography-Mass Spectrometry, is used to control testosterone administration. When T/E ratio is higher than 4, consumption of testosterone or its precursors is suspected. Recent researches have demonstrated the effectiveness of Carbon Isotope Ratio Mass Spectrometry to detect and confirm endogenous steroids administration. The ratio of the two stable carbon isotopes 1 3 C and 1 2 C allows the differentiation of natural and synthetic steroids because synthetic steroids have lower 1 3 C abundance. In fact, the carbon isotope ratios can be used to determine endogenous steroids administration even when testosterone/epistestosterone ratio is at its normal value. In the current work, some of the most important aspects related to differentiation of endogenous and exogenous steroids by means of Gas Chromatography-Combustion-Isotope Ratio Mass Spectrometry are discussed. Also, this article provides a review about the purification and sample preparation previous to the analysis, and diet effects on carbon isotope ratio of endogenous anabolics steroids is presented too

  4. An Ocean Sediment Core-Top Calibration of Foraminiferal (Cibicides) Stable Carbon Isotope Ratios

    Science.gov (United States)

    Schmittner, A.; Mix, A. C.; Lisiecki, L. E.; Peterson, C.; Mackensen, A.; Cartapanis, O. A.

    2015-12-01

    Stable carbon isotope ratios (δ13C) measured on calcium carbonate shells of benthic foraminifera (cibicides) from late Holocene sediments (δ13CCib) are compiled and compared with newly updated datasets of contemporary water-column δ13C observations of dissolved inorganic carbon (δ13CDIC) as the initial core-top calibration of the international Ocean Circulation and CarbonCycling (OC3) project. Using selection criteria based on the spatial distance between samples we find high correlation between δ13CCib and natural (pre-industrial) δ13CDIC, confirming earlier work. However, our analysis reveals systematic differences such as higher (lower) δ13CCib values in the Atlantic (Indian and Pacific) oceans. Regression analyses are impacted by anthropogenic carbon and suggest significant carbonate ion, temperature, and pressure effects, consistent with lab experiments with planktonic foraminifera and theory. The estimated standard error of core-top sediment data is generally σ ~= 0.25 ‰, whereas modern foram data from the South Atlantic indicate larger errors (σ ~= 0.4 ‰).

  5. Method for determination of stable carbon isotope ratio of methylnitrophenols in atmospheric particulate matter

    Directory of Open Access Journals (Sweden)

    S. Moukhtar

    2011-11-01

    Full Text Available A technique for the measurement of the stable isotope ratio of methylnitrophenols in atmospheric particulate matter is presented. Atmospheric samples from rural and suburban areas were collected for evaluation of the procedure. Particulate matter was collected on quartz fibre filters using dichotomous high volume air samplers. Methylnitrophenols were extracted from the filters using acetonitrile. The sample was then purified using a combination of high-performance liquid chromatography and solid phase extraction. The final solution was then divided into two aliquots. To one aliquot, a derivatising agent, Bis(trimethylsilyltrifluoroacetamide, was added for Gas Chromatography-Mass Spectrometry analysis. The second half of the sample was stored in a refrigerator. For samples with concentrations exceeding 1 ng μl−1, the second half of the sample was used for measurement of stable carbon isotope ratios by Gas Chromatography-Isotope Ratio Mass Spectrometry.

    The procedure described in this paper provides a method for the analysis of methylnitrophenols in atmospheric particulate matter at concentrations as low as 0.3 pg m−3 and for stable isotope ratios with an accuracy of better than ±0.5‰ for concentrations exceeding 100 pg m−3.

    In all atmospheric particulate matter samples analysed, 2-methyl-4-nitrophenol was found to be the most abundant methylnitrophenol, with concentrations ranging from the low pg m−3 range in rural areas to more than 200 pg m−3 in some samples from a suburban location.

  6. Comparison of gas chromatography/isotope ratio mass spectrometry and liquid chromatography/isotope ratio mass spectrometry for carbon stable-isotope analysis of carbohydrates.

    Science.gov (United States)

    Moerdijk-Poortvliet, Tanja C W; Schierbeek, Henk; Houtekamer, Marco; van Engeland, Tom; Derrien, Delphine; Stal, Lucas J; Boschker, Henricus T S

    2015-07-15

    We compared gas chromatography/isotope ratio mass spectrometry (GC/IRMS) and liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) for the measurement of δ(13)C values in carbohydrates. Contrary to GC/IRMS, no derivatisation is needed for LC/IRMS analysis of carbohydrates. Hence, although LC/IRMS is expected to be more accurate and precise, no direct comparison has been reported. GC/IRMS with the aldonitrile penta-acetate (ANPA) derivatisation method was compared with LC/IRMS without derivatisation. A large number of glucose standards and a variety of natural samples were analysed for five neutral carbohydrates at natural abundance as well as at (13)C-enriched levels. Gas chromatography/chemical ionisation mass spectrometry (GC/CIMS) was applied to check for incomplete derivatisation of the carbohydrate, which would impair the accuracy of the GC/IRMS method. The LC/IRMS technique provided excellent precision (±0.08‰ and ±3.1‰ at natural abundance and enrichment levels, respectively) for the glucose standards and this technique proved to be superior to GC/IRMS (±0.62‰ and ±19.8‰ at natural abundance and enrichment levels, respectively). For GC/IRMS measurements the derivatisation correction and the conversion of carbohydrates into CO2 had a considerable effect on the measured δ(13)C values. However, we did not find any significant differences in the accuracy of the two techniques over the full range of natural δ(13)C abundances and (13)C-labelled glucose. The difference in the performance of GC/IRMS and LC/IRMS diminished when the δ(13)C values were measured in natural samples, because the chromatographic performance and background correction became critical factors, particularly for LC/IRMS. The derivatisation of carbohydrates for the GC/IRMS method was complete. Although both LC/IRMS and GC/IRMS are reliable techniques for compound-specific stable carbon isotope analysis of carbohydrates (provided that derivatisation is complete and the

  7. Seasonal changes in stable carbon isotope ratios within annual growth rings of Pinus radiata

    International Nuclear Information System (INIS)

    Walcroft, A.; Silvester, W.; Whitehead, D.; Kelliher, F.

    1997-01-01

    The stable isotope composition of photosynthetically assimilated carbon (δ 13 C) is determined by the ratio of the leaf internal CO 2 concentration (c i ) to that of the ambient air (c a ), and so reflects the contribution of both stomatal conductance (g s ) and the rate of photosynthesis (A). Assimilated carbon which is subsequently laid down as wood in annual growth rings may therefore represent a time integrated record of physiological responses by the whole tree to seasonal changes in the environmental variables regulating growth. We analysed the stable carbon isotope composition of Pinus radiata wood collected from two plantation forest sites in New Zealand which differ markedly in temperature, rainfall and soil characteristics. For both sites, discs were cut from the stem of several trees near ground level and whole wood samples were taken from within individual annual growth rings over a number of years. At one site, diameter bands were installed over the 1994 - 1996 growing seasons in order to date precisely the formation of wood during that time. Trees at each site consistently showed a seasonal pattern in the stable isotope composition of wood within individual growth rings. The amplitude of seasonal δ 13 C variation at the wet and dry sites were 1-2 per thousand and 4 per thousand respectively. Mean δ 13 C values from the wet site were 3 per thousand more 13 C depleted than those from the dry site implying lower water-use efficiency (carbon assimilation per unit transpiration). A process-based, model of stomatal conductance and CO 2 assimilation was combined with a soil-water balance model to estimate the average daily leaf-level intercellular CO 2 concentration (c i ). Over two growing seasons at each site there was generally good agreement between mean canopy-level c i derived from the tree-ring δ 13 C data and modelled leaf-level c i levels. Further, the ratio of annual CO 2 assimilation to transpiration estimated by the model for each site

  8. MIR hollow waveguide (HWG) isotope ratio analyzer for environmental applications

    Science.gov (United States)

    Wang, Zhenyou; Zhuang, Yan; Deev, Andrei; Wu, Sheng

    2017-05-01

    An advanced commercial Mid-InfraRed Isotope Ratio (IR2) analyzer was developed in Arrow Grand Technologies based on hollow waveguide (HWG) as the sample tube. The stable carbon isotope ratio, i.e. δ13C, was obtained by measuring the selected CO2 absorption peaks in the MIR. Combined with a GC and a combustor, it has been successfully employed to measure compound specific δ13C isotope ratios in the field. By using both the 1- pass HWG and 5-path HWG, we are able to measure δ13C isotope ratio at a broad CO2 concentration of 300 ppm-37,500 ppm. Here, we demonstrate its applications in environmental studies. The δ13C isotope ratio and concentration of CO2 exhaled by soil samples was measured in real time with the isotope analyzer. The concentration was found to change with the time. We also convert the Dissolved Inorganic Carbon (DIC) into CO2, and then measure the δ13C isotope ratio with an accuracy of better than 0.3 ‰ (1 σ) with a 6 min test time and 1 ml sample usage. Tap water, NaHCO3 solvent, coca, and even beer were tested. Lastly, the 13C isotope ratio of CO2 exhaled by human beings was obtained <10 seconds after simply blowing the exhaled CO2 into a tube with an accuracy of 0.5‰ (1 σ) without sample preconditioning. In summary, a commercial HWG isotope analyzer was demonstrated to be able to perform environmental and health studies with a high accuracy ( 0.3 ‰/Hz1/2 1 σ), fast sampling rate (up to 10 Hz), low sample consumption ( 1 ml), and broad CO2 concentration range (300 ppm-37,500 ppm).

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

    Science.gov (United States)

    Wierzchnicki, Ryszard

    2013-04-01

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

  10. Comparison of stable carbon isotope ratios in the whole wood, cellulose and lignin of Oak tree-rings

    CSIR Research Space (South Africa)

    Loader, NJ

    2003-08-01

    Full Text Available The stable carbon isotope ratios (N13C) of whole wood, cellulose and acid-insoluble lignin from annual latewood increments of Quereus robur L., from modern and sub-fossil wood, were measured and their potential use as palaeo environmental indicators...

  11. A 40-year record of Northern Hemisphere atmospheric carbon monoxide concentration and isotope ratios from the firn at Greenland Summit.

    Science.gov (United States)

    Place, P., Jr.; Petrenko, V. V.; Vimont, I.; Buizert, C.; Lang, P. M.; Edwards, J.; Harth, C. M.; Hmiel, B.; Mak, J. E.; Novelli, P. C.; Brook, E.; Weiss, R. F.; Vaughn, B. H.; White, J. W. C.

    2014-12-01

    Carbon Monoxide (CO) is an important atmospheric trace gas that affects the oxidative capacity of the atmosphere and contributes indirectly to climate forcing by being a major sink of tropospheric OH. A good understanding of the past atmospheric CO budget is therefore important for climate models attempting to characterize recent changes in the atmosphere. Previous work at NEEM, Greenland provided the first reconstructions of Arctic atmospheric history of CO concentration and stable isotope ratios (δC18O and δ13CO) from firn air, dating to the 1950s. In this new study, firn air was sampled from eighteen depth levels through the firn column at Summit, Greenland (in May 2013), yielding a second, independent record of Arctic CO concentration and isotopic ratios. Carbon monoxide stable isotope ratios were analyzed on replicate samples and using a newly developed system with improved precision allowing for a more robust reconstruction. The new CO concentration and stable isotope results overall confirm the earlier findings from NEEM, with a CO concentration peak around the 1970s and higher δC18O and δ13CO values associated with peak CO. Modeling and interpretation of the data are in progress.

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

    Directory of Open Access Journals (Sweden)

    J. Schmitt

    2013-05-01

    Full Text Available Stable carbon isotope analysis of methane (δ13C of CH4 on atmospheric samples is one key method to constrain the current and past atmospheric CH4 budget. A frequently applied measurement technique is gas chromatography (GC isotope ratio mass spectrometry (IRMS coupled to a combustion-preconcentration unit. This report shows that the atmospheric trace gas krypton (Kr can severely interfere during the mass spectrometric measurement, leading to significant biases in δ13C of CH4, if krypton is not sufficiently separated during the analysis. According to our experiments, the krypton interference is likely composed of two individual effects, with the lateral tailing of the doubly charged 86Kr peak affecting the neighbouring m/z 44 and partially the m/z 45 Faraday cups. Additionally, a broad signal affecting m/z 45 and especially m/z 46 is assumed to result from scattered ions of singly charged krypton. The introduced bias in the measured isotope ratios is dependent on the chromatographic separation, the krypton-to-CH4 mixing ratio in the sample, the focusing of the mass spectrometer as well as the detector configuration and can amount to up to several per mil in δ13C. Apart from technical solutions to avoid this interference, we present correction routines to a posteriori remove the bias.

  13. New manuscript guidelines for the reporting of stable hydrogen, carbon, and oxygen isotope-ratio data

    Energy Technology Data Exchange (ETDEWEB)

    Anon.

    1995-10-01

    To eliminate possible confusion in the reporting of isotopic abundances on non-corresponding scales, the Commission on Atomic Weights and Isotopic Abundances recommended at the 37{sup th} General Assembly at Lisbon, Portugal that (i) {sup 2}H/{sup 1}H relative ratios of all substances be expressed relative to VSMOW (Vienna Standard Mean Ocean Water) on a scale such that {sup 2}H/{sup 1}H of SLAP (Standard Light Antartic Precipitation) is 0.572 times that of VSMOW, (ii) {sup 13}C/{sup 12}C relative ratios of all substances be expressed relative to VPDB (Vienna Peedee belemnite) on a scale such that {sup 13}C/{sup 12}C of NBS 19 carbonate is 1.00195 times that of VPDB, and (iii) {sup 18}O/{sup 16}O ratios of all substances be expressed relative to either VSMOW or VPDB on scales such that {sup 18}O/{sup 16}O of SLAP is 0.9445 times that of VSMOW. (Author)

  14. Latest Permian carbonate carbon isotope variability traces heterogeneous organic carbon accumulation and authigenic carbonate formation

    Science.gov (United States)

    Schobben, Martin; van de Velde, Sebastiaan; Gliwa, Jana; Leda, Lucyna; Korn, Dieter; Struck, Ulrich; Vinzenz Ullmann, Clemens; Hairapetian, Vachik; Ghaderi, Abbas; Korte, Christoph; Newton, Robert J.; Poulton, Simon W.; Wignall, Paul B.

    2017-11-01

    Bulk-carbonate carbon isotope ratios are a widely applied proxy for investigating the ancient biogeochemical carbon cycle. Temporal carbon isotope trends serve as a prime stratigraphic tool, with the inherent assumption that bulk micritic carbonate rock is a faithful geochemical recorder of the isotopic composition of seawater dissolved inorganic carbon. However, bulk-carbonate rock is also prone to incorporate diagenetic signals. The aim of the present study is to disentangle primary trends from diagenetic signals in carbon isotope records which traverse the Permian-Triassic boundary in the marine carbonate-bearing sequences of Iran and South China. By pooling newly produced and published carbon isotope data, we confirm that a global first-order trend towards depleted values exists. However, a large amount of scatter is superimposed on this geochemical record. In addition, we observe a temporal trend in the amplitude of this residual δ13C variability, which is reproducible for the two studied regions. We suggest that (sub-)sea-floor microbial communities and their control on calcite nucleation and ambient porewater dissolved inorganic carbon δ13C pose a viable mechanism to induce bulk-rock δ13C variability. Numerical model calculations highlight that early diagenetic carbonate rock stabilization and linked carbon isotope alteration can be controlled by organic matter supply and subsequent microbial remineralization. A major biotic decline among Late Permian bottom-dwelling organisms facilitated a spatial increase in heterogeneous organic carbon accumulation. Combined with low marine sulfate, this resulted in varying degrees of carbon isotope overprinting. A simulated time series suggests that a 50 % increase in the spatial scatter of organic carbon relative to the average, in addition to an imposed increase in the likelihood of sampling cements formed by microbial calcite nucleation to 1 out of 10 samples, is sufficient to induce the observed signal of carbon

  15. Latest Permian carbonate carbon isotope variability traces heterogeneous organic carbon accumulation and authigenic carbonate formation

    Directory of Open Access Journals (Sweden)

    M. Schobben

    2017-11-01

    Full Text Available Bulk-carbonate carbon isotope ratios are a widely applied proxy for investigating the ancient biogeochemical carbon cycle. Temporal carbon isotope trends serve as a prime stratigraphic tool, with the inherent assumption that bulk micritic carbonate rock is a faithful geochemical recorder of the isotopic composition of seawater dissolved inorganic carbon. However, bulk-carbonate rock is also prone to incorporate diagenetic signals. The aim of the present study is to disentangle primary trends from diagenetic signals in carbon isotope records which traverse the Permian–Triassic boundary in the marine carbonate-bearing sequences of Iran and South China. By pooling newly produced and published carbon isotope data, we confirm that a global first-order trend towards depleted values exists. However, a large amount of scatter is superimposed on this geochemical record. In addition, we observe a temporal trend in the amplitude of this residual δ13C variability, which is reproducible for the two studied regions. We suggest that (sub-sea-floor microbial communities and their control on calcite nucleation and ambient porewater dissolved inorganic carbon δ13C pose a viable mechanism to induce bulk-rock δ13C variability. Numerical model calculations highlight that early diagenetic carbonate rock stabilization and linked carbon isotope alteration can be controlled by organic matter supply and subsequent microbial remineralization. A major biotic decline among Late Permian bottom-dwelling organisms facilitated a spatial increase in heterogeneous organic carbon accumulation. Combined with low marine sulfate, this resulted in varying degrees of carbon isotope overprinting. A simulated time series suggests that a 50 % increase in the spatial scatter of organic carbon relative to the average, in addition to an imposed increase in the likelihood of sampling cements formed by microbial calcite nucleation to 1 out of 10 samples, is sufficient to induce the

  16. Variation in water-use efficiency and its relation to carbon isotope ratio in cotton

    International Nuclear Information System (INIS)

    Saranga, Y.; Flash, I.; Yakir, D.

    1998-01-01

    Cotton (Gossypium spp.) is often exposed to drought, which adversely affects both yield and quality. Improved water-use efficiency (WUE = total dry matter produced or yield harvested / water used) is expected to reduce these adverse effects. Genetic variability in WUE and its association with photosynthetic rate and carbon isotope ratio (13C/12C) in cotton are reported in this paper. WUE of six cotton cultivars--G. hirsutum L., G. barbadense L., and an interspecific F1 hybrid (G. hirsutum x G. barbadense, ISH), was examined under two irrigation regimes in two field trials. The greatest WUE was obtained by two G. hirsutum cultivars (2.55 g dry matter or 1.12 g seed-cotton L-1 H2O) the ISH obtained similar or somewhat lower values, and that G. barbadense cultivars and one G. hirsutum cultivar exhibited the lowest values (2.1 g dry matter or 0.8 to 0.85 g seed-cotton L-1 H2O). These results indicate that different cotton cultivars may have evolved different environmental adaptations that affect their WUE. Photosynthetic rate was correlated with WUE in only a few cases emphasizing the limitation of this parameter as a basis for estimating crop WUE. Under both trials WUE was positively correlated with carbon isotope ratio, indicating the potential of this technique as a selection criterion for improving cotton WUE

  17. Stable-carbon isotope variability in tree foliage and wood

    International Nuclear Information System (INIS)

    Leavitt, S.W.; Long, A.

    1986-01-01

    This study documents variation of stable-carbon isotope ratios ( 13 C/ 12 C) in trees of genera Juniperus and Pinus under field conditions. Results are from cellulose analysis on leaves, twigs, and wood from a number of localities in the southwestern US. Substantial variability, typically 1-3%, exists among leaves, within wood (radially, vertically, circumferentially), and between individuals at a site. These results may help guide sampling in tracer-type studies with stable-carbon isotope ratios and aid in the interpretation of isotopic results from such studies

  18. Carbon and oxygen isotope compositions of the carbonate facies

    Indian Academy of Sciences (India)

    The Vindhyan sedimentary succession in central India spans a wide time bracket from the Paleopro- terozoic to the Neoproterozoic period.Chronostratigraphic significance of stable carbon and oxygen isotope ratios of the carbonate phase in Vindhyan sediments has been discussed in some recent studies.However,the ...

  19. The dynamics of CO2 fixation in the Southern Ocean as indicated by carboxylase activities and organic carbon isotopic ratios

    International Nuclear Information System (INIS)

    Fontugne, M.

    1991-01-01

    Recent studies have suggested a direct relationship between the dissolved CO 2 concentration and carbon isotopic composition of phytoplankton in surface ocean. Thus, measurement of δ 13 C of planktonic organic matter in deep-sea ocean cores can potentially yield a record of the past atmospheric CO 2 variations. However, results are presented from 3 cruises in Indian and Atlantic sectors of the Southern Ocean (between 40-66degS) in which biochemical and physiological factors associated with photosynthetic processes lead to carbon isotopic fractionation by phytoplankton which cannot be directly related to variations within the mineral carbon pool. Simultaneous measurements of the carboxylase activities in the 13 C/ 12 C ratio of particulate organic carbon show that there is a large variability in phytoplankton carbon metabolism, especially on a seasonal scale, in spite of a relative uniformity of the environmental conditions. Phytoplankton carbon metabolism is clearly a main factor governing variations in the stable isotopic composition of organic matter in the euphotic layer. Interrelationships between light, Rubiso activity and δ 13 C are clearly shown by the data. Heterotrophic processes may also influence the carbon isotope mass balance, especially during the break-up of the ice pack. In addition to the influence of photosynthetic metabolism, the effect of the meridoneal temperature gradient is also verified by the data set. (author). 24 refs.; 5 figs

  20. Effects of Water Vapor on the Data Quality of the Stable Oxygen Isotopic Ratio of Atmospheric Carbon Dioxide

    Science.gov (United States)

    Evans, C. U.; White, J. W.; Vaughn, B.; Tans, P. P.; Pardo, L.

    2007-12-01

    The stable oxygen isotopic ratio of carbon dioxide can potentially track fundamental indicators of environmental change such as the balance between photosynthesis and respiration on regional to global scales. The Stable Isotope Laboratory (SIL) at the Institute of Arctic and Alpine Research (INSTAAR), University of Colorado at Boulder, has measured the stable isotopes of atmospheric carbon dioxide from more than 60 NOAA/Earth System Research Laboratory (ESRL) air flask-sampling sites since the early 1990s. If air is sampled without drying, oxygen can exchange between carbon dioxide and water in the flasks, entirely masking the desired signal. An attempt to investigate how water vapor is affecting the δ18O signal is accomplished by comparing the SIL measurements with specific humidity, calculated from the National Climatic Data Center (NCDC) global integrated surface hourly temperature and dew point database, at the time of sampling. Analysis of sites where samples have been collected initially without drying, and subsequently with a drying kit, in conjunction with the humidity data, has led to several conclusions. Samples that initially appear isotopically unaltered, in that their δ18O values are within the expected range, are being subtly influenced by the water vapor in the air. At Bermuda and other tropical to semi-tropical sites, the 'wet' sampling values have a seasonal cycle that is strongly anti-correlated to the specific humidity, while the 'dry' values have a seasonal cycle that is shifted earlier than the specific humidity cycle by 1-2 months. The latter phasing is expected given the seasonal phasing between climate over the ocean and land, while the former is consistent with a small, but measurable isotope exchange in the flasks. In addition, we note that there is a strong (r > 0.96) correlation between the average specific humidity and the percent of rejected samples for 'wet' sampling. This presents an opportunity for determining a threshold of

  1. Seawater calcium isotope ratios across the Eocene-Oligocene transition

    Science.gov (United States)

    Griffith, E.M.; Paytan, A.; Eisenhauer, A.; Bullen, T.D.; Thomas, E.

    2011-01-01

    During the Eocene-Oligocene transition (EOT, ca. 34 Ma), Earth's climate cooled significantly from a greenhouse to an icehouse climate, while the calcite (CaCO3) compensation depth (CCD) in the Pacific Ocean increased rapidly. Fluctuations in the CCD could result from various processes that create an imbalance between calcium (Ca) sources to, and sinks from, the ocean (e.g., weathering and CaCO3 deposition), with different effects on the isotopic composition of dissolved Ca in the oceans due to differences in the Ca isotopic composition of various inputs and outputs. We used Ca isotope ratios (??44/40Ca) of coeval pelagic marine barite and bulk carbonate to evaluate changes in the marine Ca cycle across the EOT. We show that the permanent deepening of the CCD was not accompanied by a pronounced change in seawater ??44/40Ca, whereas time intervals in the Neogene with smaller carbonate depositional changes are characterized by seawater ??44/40Ca shifts. This suggests that the response of seawater ??44/40Ca to changes in weathering fluxes and to imbalances in the oceanic alkalinity budget depends on the chemical composition of seawater. A minor and transient fluctuation in the Ca isotope ratio of bulk carbonate may reflect a change in isotopic fractionation associated with CaCO3 precipitation from seawater due to a combination of factors, including changes in temperature and/or in the assemblages of calcifying organisms. ?? 2011 Geological Society of America.

  2. Carbon and nitrogen stable isotope ratios analysis of food sources for Chironomus acerbiphilus larvae (Diptera Chironomidae) in strongly acidic lake Katanuma

    International Nuclear Information System (INIS)

    Doi, Hideyuki; Kikuchi, Eisuke; Shikano, Shuichi

    2001-01-01

    The food sources for Chironomus acerbiphilus larvae (Diptera Chironomidae) were analyzed using carbon and nitrogen stable isotope ratios in Lake Katanuma. Lake Katanuma is a volcanic and strongly acidic lake (average pH 2.2). In Lake Katanuma, potential sources of diets for the chironomid larvae are limited including a benthic diatom (Pinnularia braunii), a phytoplankton (Chlamydomonas acidophila), sulfate oxidizing bacteria, and vascular plants supplied from vegetation surrounding the lake. Based on the average carbon and nitrogen isotope ratios among these potential sources and sediment, benthic diatoms were considered to be most probable food source of the chironomid larvae. δ 13 C values of the chironomid were significantly different among seasons and habitat depths, suggesting that diet of C. acerbiphilus changed seasonally and with habitat depth. (author)

  3. Elucidation of C{sub 2} and CN formation mechanisms in laser-induced plasmas through correlation analysis of carbon isotopic ratio

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Meirong [School of Electric Power, South China University of Technology, Guangzhou, Guangdong 510640 (China); Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Chan, George C.-Y.; Mao, Xianglei; Gonzalez, Jhanis J. [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Lu, Jidong [School of Electric Power, South China University of Technology, Guangzhou, Guangdong 510640 (China); Russo, Richard E., E-mail: RERusso@lbl.gov [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States)

    2014-10-01

    Laser ablation molecular isotopic spectrometry (LAMIS) was recently reported for rapid isotopic analysis by measuring molecular emission from laser-induced plasmas at atmospheric pressure. With {sup 13}C-labeled benzoic acid as a model sample, this research utilized the LAMIS approach to clarify the formation mechanisms of C{sub 2} and CN molecules during laser ablation of organic materials. Because the isotopic ratios in the molecular bands could deviate from statistical distribution depending on their formation pathways, the dominant mechanism can be identified through a comparison of the experimental observed isotopic patterns in the molecular emission with the theoretical statistical pattern. For C{sub 2} formation, the experimental {sup 12}C{sup 12}C/{sup 13}C{sup 12}C ratios not only support a recombination mechanism through atomic carbon at early delay time but also indicate the presence of other operating mechanisms as the plasma evolves; it is proposed that some of the C{sub 2} molecules are released directly from the aromatic ring of the sample as molecular fragments. In contrast, the temporal profiles in the {sup 12}C/{sup 13}C ratios derived from CN emission exhibited opposite behavior with those derived from C{sub 2} emission, which unambiguously refutes mechanisms that require C{sub 2} as a precursor for CN formation; CN formation likely involves atomic carbon or species with a single carbon atom. - Highlights: • C{sub 2} and CN formation mechanisms during laser ablation of organic material studied • Some C{sub 2} molecules are directly desorbed from the organic compound. • C{sub 2} molecules are not important precursor for CN-radical formation.

  4. Isotope analytics for the evaluation of the feeding influence on the isotope ratio in beef samples; Isotopenanalytik zur Bestimmung des Einflusses der Ernaehrung auf die Isotopenzusammensetzung in Rinderproben

    Energy Technology Data Exchange (ETDEWEB)

    Herwig, Nadine

    2010-11-17

    Information about the origin of food and associated production systems has a high significance for food control. An extremely promising approach to obtain such information is the determination of isotope ratios of different elements. In this study the correlation of the isotope ratios C-13/C-12, N-15/N-14, Mg-25/Mg-24, and Sr-87/Sr-86 in bovine samples (milk and urine) and the corresponding isotope ratios in feed was investigated. It was shown that in the bovine samples all four isotope ratios correlate with the isotope composition of the feed. The isotope ratios of strontium and magnesium have the advantage that they directly reflect the isotope ratios of the ingested feed since there is no isotope fractionation in the bovine organism which is in contrast to the case of carbon and nitrogen isotope ratios. From the present feeding study it is evident, that a feed change leads to a significant change in the delta C-13 values in milk and urine within 10 days already. For the deltaN-15 values the feed change was only visible in the bovine urine after 49 days. Investigations of cows from two different regions (Berlin/Germany and Goestling/Austria) kept at different feeding regimes revealed no differences in the N-15/N-14 and Mg-26/Mg-24 isotope ratios. The strongest correlation between the isotope ratio of the bovine samples and the kind of ingested feed was observed for the carbon isotope ratio. With this ratio even smallest differences in the feed composition were traceable in the bovine samples. Since different regions usually coincide with different feeding regimes, carbon isotope ratios can be used to distinguish bovine samples from different regions if the delta C-13 values of the ingested feed are different. Furthermore, the determination of strontium isotope ratios revealed significant differences between bovine and feed samples of Berlin and Goestling due to the different geologic realities. Hence the carbon and strontium isotope ratios allow the best

  5. Cavity Ring-down Spectroscopy for Carbon Isotope Analysis with 2 μm Diode Laser

    International Nuclear Information System (INIS)

    Hiromoto, K.; Tomita, H.; Watanabe, K.; Kawarabayashi, J.; Iguchi, T.

    2009-01-01

    We have made a prototype based on CRDS with 2 μm diode laser for carbon isotope analysis of CO 2 in air. The carbon isotope ratio was obtained to be (1.085±0.012)x10 -2 which shows good agreement with the isotope ratio measured by the magnetic sector-type mass spectrometer within uncertainty. Hence, we demonstrated the carbon isotope analysis based on CRDS with 2 μm tunable diode laser.

  6. Isotopic ratios in outbursting comet C/2015 ER61

    Science.gov (United States)

    Yang, Bin; Hutsemékers, Damien; Shinnaka, Yoshiharu; Opitom, Cyrielle; Manfroid, Jean; Jehin, Emmanuël; Meech, Karen J.; Hainaut, Olivier R.; Keane, Jacqueline V.; Gillon, Michaël

    2018-02-01

    Isotopic ratios in comets are critical to understanding the origin of cometary material and the physical and chemical conditions in the early solar nebula. Comet C/2015 ER61 (PANSTARRS) underwent an outburst with a total brightness increase of 2 magnitudes on the night of 2017 April 4. The sharp increase in brightness offered a rare opportunity to measure the isotopic ratios of the light elements in the coma of this comet. We obtained two high-resolution spectra of C/2015 ER61 with UVES/VLT on the nights of 2017 April 13 and 17. At the time of our observations, the comet was fading gradually following the outburst. We measured the nitrogen and carbon isotopic ratios from the CN violet (0, 0) band and found that 12C/13C = 100 ± 15, 14N/15N = 130 ± 15. In addition, we determined the 14N/15N ratio from four pairs of NH2 isotopolog lines and measured 14N/15N = 140 ± 28. The measured isotopic ratios of C/2015 ER61 do not deviate significantly from those of other comets.

  7. Carbon and nitrogen stable isotope ratios analysis of food sources for Chironomus acerbiphilus larvae (Diptera Chironomidae) in strongly acidic lake Katanuma

    Energy Technology Data Exchange (ETDEWEB)

    Doi, Hideyuki [Tohoku Univ., Sendai (Japan). Graduate School of Science; Kikuchi, Eisuke; Shikano, Shuichi

    2001-12-01

    The food sources for Chironomus acerbiphilus larvae (Diptera Chironomidae) were analyzed using carbon and nitrogen stable isotope ratios in Lake Katanuma. Lake Katanuma is a volcanic and strongly acidic lake (average pH 2.2). In Lake Katanuma, potential sources of diets for the chironomid larvae are limited including a benthic diatom (Pinnularia braunii), a phytoplankton (Chlamydomonas acidophila), sulfate oxidizing bacteria, and vascular plants supplied from vegetation surrounding the lake. Based on the average carbon and nitrogen isotope ratios among these potential sources and sediment, benthic diatoms were considered to be most probable food source of the chironomid larvae. {delta}{sup 13}C values of the chironomid were significantly different among seasons and habitat depths, suggesting that diet of C. acerbiphilus changed seasonally and with habitat depth. (author)

  8. Carbon isotopic ratio of suspended organic matter of the Gironde estuary. Application to particulate Zn and Pb distribution

    International Nuclear Information System (INIS)

    Fontugne, Michel; Jouanneau, J.M.

    1981-01-01

    In the Gironde estuary, the isotopic ratio of particulate organic carbon (P.O.C.), and the ratio metal/P.O.C. indicate the occurrence of two zones. Up-river, the concentration decreases due to the consumption of the organo-metallic phase and by mixing in the ''mud plug'' with terrestrial particles impoverished in metal and P.O.C. Down-stream, the mixing of metal rich terrestrial P.O.C. with poorer marine particles determines the metal concentrations [fr

  9. Stable isotope ratio mass spectrometry in forensic science and food adulteration research

    International Nuclear Information System (INIS)

    Kumar, B.

    2009-01-01

    Stable Isotope Ratio Mass Spectrometry (SIRMS) is an established technique for the determination of origin of geological, biological, chemical and physio-chemical samples/materials. With the development of highly precise mass spectrometers, the stable isotope ratio determination of hydrogen, carbon, nitrogen and oxygen have gained considerable interest in the fields of forensic science and food authentication. Natural variations in the isotopic composition of lighter elements occur due to fractionation effects, resulting in the finger printing of specific isotope ratio values that are characteristic of the origin, purity, and manufacturing processes of the products and their constituents. Forensic science uses scientific and technical methods to investigate traceable evidence of criminal acts. Stable isotope ratio mass spectrometry has been applied to numerous aspects of the forensic science. The analysis of explosives such as ammonium nitrate, gun powder and tri-nitro-toluene (TNT), cases of murder, armed robbery, drug smuggling, terrorism, arson and hit and run traffic accidents are a few of them. The main types of geological evidences in such cases are mud, soil, rocks, sand, gravel, dust particles, biological materials, organic particles and anthropogenic components. Stable isotopes are used as tools to corroborate and confirm the evidential leads in the investigation of such crimes. The variation in natural abundances of carbon and nitrogen and their isotopic ratios δ 13 C and δ 15 N can identify links between items found at crime scene with those of suspect. The paper discusses the applications of SIRMS in the field of forensic science and food adulteration research

  10. A Three End-Member Mixing Model Based on Isotopic Composition and Elemental Ratio

    Directory of Open Access Journals (Sweden)

    Kon-Kee Liu Shuh-Ji Kao

    2007-01-01

    Full Text Available A three end-member mixing model based on nitrogen isotopic composition and organic carbon to nitrogen ratio of suspended particulate matter in an aquatic environment has been developed. Mathematical expressions have been derived for the calculation of the fractions of nitrogen or organic carbon originating from three different sources of distinct isotopic and elemental compositions. The model was successfully applied to determine the contributions from anthropogenic wastes, soils and bedrock-derived sediments to particulate nitrogen and particulate organic carbon in the Danshuei River during the flood caused by Typhoon Bilis in August 2000. The model solutions have been expressed in a general form that allows applications to mixtures with other types of isotopic compositions and elemental ratios or in forms other than suspended particulate matter.

  11. Simultaneous stable carbon isotopic analysis of wine glycerol and ethanol by liquid chromatography coupled to isotope ratio mass spectrometry.

    Science.gov (United States)

    Cabañero, Ana I; Recio, Jose L; Rupérez, Mercedes

    2010-01-27

    A novel procedure was established for the simultaneous characterization of wine glycerol and ethanol (13)C/(12)C isotope ratio, using liquid chromatography/isotope ratio mass spectrometry (LC-IRMS). Several parameters influencing separation of glycerol and ethanol from wine matrix were optimized. Results obtained for 35 Spanish samples exposed no significant differences and very strong correlations (r = 0.99) between the glycerol (13)C/(12)C ratios obtained by an alternative method (gas chromatography/isotope ratio mass spectrometry) and the proposed new methodology, and between the ethanol (13)C/(12)C ratios obtained by the official method (elemental analyzer/isotope ratio mass spectrometry) and the proposed new methodology. The accuracy of the proposed method varied from 0.01 to 0.19 per thousand, and the analytical precision was better than 0.25 per thousand. The new developed LC-IRMS method it is the first isotopic method that allows (13)C/(12)C determination of both analytes in the same run directly from a liquid sample with no previous glycerol or ethanol isolation, overcoming technical difficulties associated with complex sample treatment and improving in terms of simplicity and speed.

  12. Isotope ratio analysis by a combination of element analyzer and mass spectrometer

    International Nuclear Information System (INIS)

    Pichlmayer, F.

    1987-06-01

    The use of stable isotope ratios of carbon, nitrogen and sulfur as analytical tool in many fields of research is of growing interest. A method has therefore been developed, consisting in essential of coupling an Elemental Analyzer with an Isotope Mass Spectrometer, which enables the gas preparation of carbon dioxide, nitrogen and sulfur dioxide from any solid or liquid sample in a fast and easy way. Results of carbon isotope measurements in food analysis are presented, whereat it is possible to check origin and treatment of sugar, oils, fats, mineral waters, spirituous liquors etc. and to detect adulterations as well. Also applications in the field of environmental research are given. (Author)

  13. Stable isotope analysis of Dacryoconarid carbonate microfossils: a new tool for Devonian oxygen and carbon isotope stratigraphy.

    Science.gov (United States)

    Frappier, Amy Benoit; Lindemann, Richard H; Frappier, Brian R

    2015-04-30

    Dacryoconarids are extinct marine zooplankton known from abundant, globally distributed calcite microfossils in the Devonian, but their shell stable isotope composition has not been previously explored. Devonian stable isotope stratigraphy is currently limited to less common invertebrates or bulk rock analyses of uncertain provenance. As with Cenozoic planktonic foraminifera, isotopic analysis of dacryoconarid shells could facilitate higher-resolution, geographically widespread stable isotope records of paleoenvironmental change, including marine hypoxia events, climate changes, and biocrises. We explored the use of Dacryoconarid isotope stratigraphy as a viable method in interpreting paleoenvironments. We applied an established method for determining stable isotope ratios (δ(13) C, δ(18) O values) of small carbonate microfossils to very well-preserved dacryoconarid shells. We analyzed individual calcite shells representing five common genera using a Kiel carbonate device coupled to a MAT 253 isotope ratio mass spectrometer. Calcite shell δ(13) C and δ(18) O values were compared by taxonomic group, rock unit, and locality. Single dacryoconarid calcite shells are suitable for stable isotope analysis using a Kiel-IRMS setup. The dacryoconarid shell δ(13) C values (-4.7 to 2.3‰) and δ(18) O values (-10.3 to -4.8‰) were consistent across taxa, independent of shell size or part, but varied systematically through time. Lower fossil δ(18) O values were associated with warmer water temperature and more variable δ(13) C values were associated with major bioevents. Dacryoconarid δ(13) C and δ(18) O values differed from bulk rock carbonate values. Dacryoconarid individual microfossil δ(13) C and δ(18) O values are highly sensitive to paleoenvironmental changes, thus providing a promising avenue for stable isotope chemostratigraphy to better resolve regional to global paleoceanographic changes throughout the upper Silurian to the upper Devonian. Our results

  14. The application of stable carbon isotope ratios as water quality indicators in coastal areas of Karachi, Pakistan

    International Nuclear Information System (INIS)

    Qureshi, R.M.; Mashiatullah, A.; Javed, T.; Tasneem, M.A.; Sajjad, M.I.; Saleem, M.; Khan, S.H.; Rizvi, S.H.N.; Siddiqui, S.A.; Qari, R.

    1998-01-01

    Stable carbon isotope ratios (δ 13 C) of total dissolved inorganic carbon (TDIC), total inorganic and organic carbon in bottom sediments, as well as sea plants in polluted water sources, non-polluted Karachi Sea water and pollution recipients are used to elaborate pollution scenario of shallow marine environment off Karachi coast. These results are supplemented with stable isotope composition of nitrogen (δ 15 N) in seaweeds and mangroves, toxic/trace metal concentration in sea-bottom sediments, total Coliform bacterial population, electrical conductivity, temperature and turbidity. Isotopic data shows that the mangrove ecosystem and the tidal fluctuations play a key role in controlling contamination inventories in shallow sea water off Karachi coast, specifically the Manora Channel. The Karachi harbour zone is found to be the most heavily polluted marine site in Manora channel during high as well as low tide regimes. Significant concentrations of toxic metals such as Pb, Ni, Cr, Zn, V, U are observed in off-shore sediments of Karachi coast. The results show that sewage and industrial wastes are the main sources of heavy metal pollution in Karachi harbour, Manora Channel exit zone and the southeast coast. However, as compared to other coastal areas, the Karachi coast is moderately polluted. Studies suggest incorporation of quick remedial measures to combat pollution in shallow marine environments off Karachi Coast. (author)

  15. Distinguishing feral and managed honeybees (Apis mellifera) using stable carbon isotopes

    OpenAIRE

    Anderson , Lucy; Dynes , Travis; Berry , Jennifer; Delaplane , Keith; McCormick , Lydia; Brosi , Berry

    2014-01-01

    International audience; The ability to distinguish feral and managed honeybees (Apis mellifera) has applications in studies of population genetics, parasite transmission, pollination, interspecific interactions, and bee breeding. We evaluated a diagnostic test based on theoretical differences in stable carbon isotope ratios generated by supplemental feeding. We evaluated (1) if carbon isotope ratios can distinguish feral and managed honeybees and (2) the temporal persistence of the signal aft...

  16. Monitoring in situ biodegradation of hydrocarbons by using stable carbon isotopes

    International Nuclear Information System (INIS)

    Aggarwal, P.K.; Hinchee, R.E.

    1991-01-01

    Spilled or leaked nonhalogenated petroleum hydrocarbons in the soil can generally be metabolized by indigenous, aerobic bacteria. In situ biological degradation of hydrocarbons may be accelerated by supplying inorganic nutrients and/or oxygen. Approaches to monitoring and verifying enhanced in situ biodegradation have included measurements of changes over time in the (a) concentration of hydrocarbons, (b) temperature, (c) number of hydrocarbon-degrading microorganisms, (d) ratio of fast-degrading hydrocarbons (e.g., pristanes or phytanes), and (e) metabolic intermediates. Measurements of oxygen consumption over time and elevated carbon dioxide concentrations in soil gas also have been used as indicators of hydrocarbon degradation. An alternative approach that may help substantiate biodegradation is to measure stable carbon isotope ratios in soil gas CO 2 . Stable carbon isotope ratio analysis is inexpensive and commercially available at many laboratories. Carbon dioxide produced by hydrocarbon degradation may be distinguished from that produced by other processes based on the carbon isotopic compositions characteristic of the source material and/or fractionation accompanying microbial metabolism. Here the authors demonstrate the applicability of the stable isotope technique for monitoring enhanced. aerobic biodegradation of hydrocarbons using data from three locations in the United States

  17. Isotopes of carbon and oxygen in the carbonate impurities of coal have potential as palaeoenvironmental indicators

    International Nuclear Information System (INIS)

    Verhagen, B.T.; Falcon, R.M.

    1990-01-01

    The nature and systematics of impurities such as carbonates need to be established in order to understand their provenance in coal seams with reference to mining, beneficiation and ultimately their elimination or reduction. To this end, mineralogical and carbon-13 and oxygen-18 isotopic studies were undertaken on carbonate occurrences in coal from the eastern Transvaal highveld. Isotopic variations of considerable amplitude and individual values of extreme ''lightness'' are to be found in the carbonates in coal of the Witbank and adjacent basins. The observed isotopic ratios have a clear bearing on the nature and origins of the carbonates. 1 tab., 1 fig

  18. Continuous flow isotope ratio mass spectrometer (CF-IRMS) and its applications in hydrocarbon research and exploration

    International Nuclear Information System (INIS)

    Kalpana, G.; Patil, D.J.; Kumar, B.

    2004-01-01

    Stable isotope ratio mass spectrometers have been widely used to determine the isotopic ratios of light elements such as hydrogen, carbon, nitrogen, oxygen and sulphur. Continuous Flow Isotope Ratio Mass Spectrometry (CFIRMS) provides reliable data on nanomole amount of sample gas without the need for cryogenic trapping using cold fingers as in dual inlet isotope ratio mass spectrometer. High sample throughput is achieved as the system is configured with automated sample preparation devices and auto samplers. This paper presents a brief description of CFIRMS exploration

  19. Modeling whole-tree carbon assimilation rate using observed transpiration rates and needle sugar carbon isotope ratios.

    Science.gov (United States)

    Hu, Jia; Moore, David J P; Riveros-Iregui, Diego A; Burns, Sean P; Monson, Russell K

    2010-03-01

    *Understanding controls over plant-atmosphere CO(2) exchange is important for quantifying carbon budgets across a range of spatial and temporal scales. In this study, we used a simple approach to estimate whole-tree CO(2) assimilation rate (A(Tree)) in a subalpine forest ecosystem. *We analysed the carbon isotope ratio (delta(13)C) of extracted needle sugars and combined it with the daytime leaf-to-air vapor pressure deficit to estimate tree water-use efficiency (WUE). The estimated WUE was then combined with observations of tree transpiration rate (E) using sap flow techniques to estimate A(Tree). Estimates of A(Tree) for the three dominant tree species in the forest were combined with species distribution and tree size to estimate and gross primary productivity (GPP) using an ecosystem process model. *A sensitivity analysis showed that estimates of A(Tree) were more sensitive to dynamics in E than delta(13)C. At the ecosystem scale, the abundance of lodgepole pine trees influenced seasonal dynamics in GPP considerably more than Engelmann spruce and subalpine fir because of its greater sensitivity of E to seasonal climate variation. *The results provide the framework for a nondestructive method for estimating whole-tree carbon assimilation rate and ecosystem GPP over daily-to weekly time scales.

  20. Analytical Validation of Accelerator Mass Spectrometry for Pharmaceutical Development: the Measurement of Carbon-14 Isotope Ratio

    International Nuclear Information System (INIS)

    Keck, B.D.; Ognibene, T.; Vogel, J.S.

    2010-01-01

    Accelerator mass spectrometry (AMS) is an isotope based measurement technology that utilizes carbon-14 labeled compounds in the pharmaceutical development process to measure compounds at very low concentrations, empowers microdosing as an investigational tool, and extends the utility of 14 C labeled compounds to dramatically lower levels. It is a form of isotope ratio mass spectrometry that can provide either measurements of total compound equivalents or, when coupled to separation technology such as chromatography, quantitation of specific compounds. The properties of AMS as a measurement technique are investigated here, and the parameters of method validation are shown. AMS, independent of any separation technique to which it may be coupled, is shown to be accurate, linear, precise, and robust. As the sensitivity and universality of AMS is constantly being explored and expanded, this work underpins many areas of pharmaceutical development including drug metabolism as well as absorption, distribution and excretion of pharmaceutical compounds as a fundamental step in drug development. The validation parameters for pharmaceutical analyses were examined for the accelerator mass spectrometry measurement of 14 C/C ratio, independent of chemical separation procedures. The isotope ratio measurement was specific (owing to the 14 C label), stable across samples storage conditions for at least one year, linear over 4 orders of magnitude with an analytical range from one tenth Modern to at least 2000 Modern (instrument specific). Further, accuracy was excellent between 1 and 3 percent while precision expressed as coefficient of variation is between 1 and 6% determined primarily by radiocarbon content and the time spent analyzing a sample. Sensitivity, expressed as LOD and LLOQ was 1 and 10 attomoles of carbon-14 (which can be expressed as compound equivalents) and for a typical small molecule labeled at 10% incorporated with 14 C corresponds to 30 fg equivalents. AMS

  1. Analytical Validation of Accelerator Mass Spectrometry for Pharmaceutical Development: the Measurement of Carbon-14 Isotope Ratio.

    Energy Technology Data Exchange (ETDEWEB)

    Keck, B D; Ognibene, T; Vogel, J S

    2010-02-05

    Accelerator mass spectrometry (AMS) is an isotope based measurement technology that utilizes carbon-14 labeled compounds in the pharmaceutical development process to measure compounds at very low concentrations, empowers microdosing as an investigational tool, and extends the utility of {sup 14}C labeled compounds to dramatically lower levels. It is a form of isotope ratio mass spectrometry that can provide either measurements of total compound equivalents or, when coupled to separation technology such as chromatography, quantitation of specific compounds. The properties of AMS as a measurement technique are investigated here, and the parameters of method validation are shown. AMS, independent of any separation technique to which it may be coupled, is shown to be accurate, linear, precise, and robust. As the sensitivity and universality of AMS is constantly being explored and expanded, this work underpins many areas of pharmaceutical development including drug metabolism as well as absorption, distribution and excretion of pharmaceutical compounds as a fundamental step in drug development. The validation parameters for pharmaceutical analyses were examined for the accelerator mass spectrometry measurement of {sup 14}C/C ratio, independent of chemical separation procedures. The isotope ratio measurement was specific (owing to the {sup 14}C label), stable across samples storage conditions for at least one year, linear over 4 orders of magnitude with an analytical range from one tenth Modern to at least 2000 Modern (instrument specific). Further, accuracy was excellent between 1 and 3 percent while precision expressed as coefficient of variation is between 1 and 6% determined primarily by radiocarbon content and the time spent analyzing a sample. Sensitivity, expressed as LOD and LLOQ was 1 and 10 attomoles of carbon-14 (which can be expressed as compound equivalents) and for a typical small molecule labeled at 10% incorporated with {sup 14}C corresponds to 30 fg

  2. Detecting isotopic ratio outliers

    Science.gov (United States)

    Bayne, C. K.; Smith, D. H.

    An alternative method is proposed for improving isotopic ratio estimates. This method mathematically models pulse-count data and uses iterative reweighted Poisson regression to estimate model parameters to calculate the isotopic ratios. This computer-oriented approach provides theoretically better methods than conventional techniques to establish error limits and to identify outliers.

  3. Detecting isotopic ratio outliers

    International Nuclear Information System (INIS)

    Bayne, C.K.; Smith, D.H.

    1986-01-01

    An alternative method is proposed for improving isotopic ratio estimates. This method mathematically models pulse-count data and uses iterative reweighted Poisson regression to estimate model parameters to calculate the isotopic ratios. This computer-oriented approach provides theoretically better methods than conventional techniques to establish error limits and to identify outliers

  4. High precision measurements of carbon isotopic ratio of atmospheric methane using a continuous flow mass spectrometer

    Directory of Open Access Journals (Sweden)

    Shinji Morimoto

    2009-03-01

    Full Text Available A high-precision measurement system for the carbon isotope ratio of atmospheric CH4 (δ^(13CH_4 was developed using a pre-concentration device for CH4 and a gas chromatograph-combustion-isotope ratio mass spectrometer (GC-C-IRMS. The measurement system required 100 mlSTP of an atmospheric air sample, corresponding to approximately 0.18μlSTP of CH_4, to determine the δ^(13CH_4 value with a reproducibility of 0.07‰. Replicated analyses of a CH_4-in-air standard gas during the period from 2002 to 2008 indicated that the value of δ^(13CH_4 measured by this system was consistent within the measurement reproducibility. To evaluate the δ^(13CH_4 measurement system, thus developed, diurnal variations of the atmospheric CH_4 concentration and δ^(13CH_4 were observed in the northern part of the Tokyo metropolitan area. From the relationship between the CH_4 concentration and δ^(13CH_4, dominant sources of the observed CH4 fluctuations were identified.

  5. Steroid isotopic standards for gas chromatography-combustion isotope ratio mass spectrometry (GCC-IRMS).

    Science.gov (United States)

    Zhang, Ying; Tobias, Herbert J; Brenna, J Thomas

    2009-03-01

    Carbon isotope ratio (CIR) analysis of urinary steroids using gas chromatography-combustion isotope ratio mass spectrometry (GCC-IRMS) is a recognized test to detect illicit doping with synthetic testosterone. There are currently no universally used steroid isotopic standards (SIS). We adapted a protocol to prepare isotopically uniform steroids for use as a calibrant in GCC-IRMS that can be analyzed under the same conditions as used for steroids extracted from urine. Two separate SIS containing a mixture of steroids were created and coded CU/USADA 33-1 and CU/USADA 34-1, containing acetates and native steroids, respectively. CU/USADA 33-1 contains 5alpha-androstan-3beta-ol acetate (5alpha-A-AC), 5alpha-androstan-3alpha-ol-17-one acetate (androsterone acetate, A-AC), 5beta-androstan-3alpha-ol-11, 17-dione acetate (11-ketoetiocholanolone acetate, 11k-AC) and 5alpha-cholestane (Cne). CU/USADA 34-1 contains 5beta-androstan-3alpha-ol-17-one (etiocholanolone, E), 5alpha-androstan-3alpha-ol-17-one (androsterone, A), and 5beta-pregnane-3alpha, 20alpha-diol (5betaP). Each mixture was prepared and dispensed into a set of about 100 ampoules using a protocol carefully designed to minimize isotopic fractionation and contamination. A natural gas reference material, NIST RM 8559, traceable to the international standard Vienna PeeDee Belemnite (VPDB) was used to calibrate the SIS. Absolute delta(13)C(VPDB) and Deltadelta(13)C(VPDB) values from randomly selected ampoules from both SIS indicate uniformity of steroid isotopic composition within measurement reproducibility, SD(delta(13)C)<0.2 per thousand. This procedure for creation of isotopic steroid mixtures results in consistent standards with isotope ratios traceable to the relevant international reference material.

  6. Stable isotope methods: The effect of gut contents on isotopic ratios of zooplankton

    Science.gov (United States)

    Hill, J. M.; McQuaid, C. D.

    2011-05-01

    In the past decade there has been an increased awareness of the potential for methodological bias resulting from multiple pre-analytical procedures in foodweb interpretations based on stable isotope techniques. In the case of small organisms, this includes the effect of gut contents on whole body signatures. Although gut contents may not reflect actual assimilation, their carbon and nitrogen values will be isotopically lighter than after the same material has been assimilated. The potential skewing of isotopic ratios in whole organism samples is especially important for aquatic environments as many studies involve trophic relationships among small zooplankton. This is particularly important in pelagic waters, where herbivorous zooplankton comprise small taxa. Hence this study investigated the effect of gut contents on the δ13C and δ15N ratios of three size classes of zooplankton (1.0-2.0, 2.0-4.0 and >4.0 mm) collected using bongo net tows in the tropical waters of the south-west Indian Ocean. Animals were collected at night, when they were likely to be feeding, sieved into size classes and separated into genera. We focused on Euphausia spp which dominated zooplankton biomass. Three treatment types were processed: bulk animals, bulk animals without guts and tail muscle from each size class at 10 bongo stations. The δ15N ratios were influenced by zooplankton size class, presumably reflecting ontogenetic changes in diet. ANOVA post hoc results and correlations in δ15N signatures among treatments suggest that gut contents may not affect overall nitrogen signatures of Euphausia spp., but that δ13C signatures may be significantly altered by their presence. Carbon interpretations however, were complicated by potential effects of variation in chitin, lipids and metabolism among tissues and the possibility of opportunistic omnivory. Consequently we advocate gut evacuation before sacrifice in euphausiids if specific tissue dissection is impractical and recommend

  7. Detecting isotopic ratio outliers

    International Nuclear Information System (INIS)

    Bayne, C.K.; Smith, D.H.

    1985-01-01

    An alternative method is proposed for improving isotopic ratio estimates. This method mathematically models pulse-count data and uses iterative reweighted Poisson regression to estimate model parameters to calculate the isotopic ratios. This computer-oriented approach provides theoretically better methods than conventional techniques to establish error limits and to identify outliers. 6 refs., 3 figs., 3 tabs

  8. Hepatoblastoma Biology Using Isotope Ratio Mass Spectrometry: Utility of a Unique Technique for the Analysis of Oncological Specimens.

    Science.gov (United States)

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

    2016-07-07

    Hepatoblastoma is the most common primary liver tumor in children. However, it occurs rarely, with an incidence of 0.5-1.5 cases per million children. There is no clear explanation of the relationship between clinicopathologic features, therapy, and outcome in hepatoblastoma cases, so far. One of the most widely accepted prognostic factors in hepatoblastoma is histology of the tumor. The aim of the study was to determine the potential differences in biology of hepatoblastoma histological subtypes at the atomic level using the unique method of isotope ratio mass spectrometry, which is especially valuable in examination of small groups of biological samples. Twenty-four measurements of nitrogen stable isotope ratio, carbon stable isotope ratio and total carbon to nitrogen mass ratio in fetal and embryonal hepatoblastoma tissue were performed using a Sercon 20-22 Continuous Flow Isotope Ratio Mass Spectrometer (CF-IRMS) coupled with a Sercon SL elemental analyzer for simultaneous carbon-nitrogen-sulfur (NCS) analysis. A difference of about 1.781‰ in stable nitrogen isotope 15N/14N ratio was found between examined hepatoblastoma histological subtypes. The prognosis in liver tumors cases in children may be challenging particularly because of the lack of versatile methods of its evaluation. Isotope ratio mass spectrometry allows one to determine the difference between hepatoblastoma histological subtypes and clearly indicates the cases with the best outcome.

  9. Determination of carbon isotope ratios for honey samples by means of a liquid chromatography/isotope ratio mass spectrometry system coupled with a post-column pump.

    Science.gov (United States)

    Kawashima, Hiroto; Suto, Momoka; Suto, Nana

    2018-05-20

    Liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) has been used to authenticate and trace products such as honey, wine, and lemon juice, and compounds such as caffeine and pesticides. However, LC/IRMS has several disadvantages, including the high cost of the CO 2 membrane and blocking by solidified sodium persulfate. Here, we developed an improved system for determining carbon isotope ratios by LC/IRMS. The main improvement was the use of a post-column pump. Using the improved system, we determined δ 13 C values for glucose with high accuracy and precision (0.1‰ and 0.1‰, respectively; n = 3). The glucose, fructose, disaccharide, trisaccharide, and organic acid constituents of the honey samples were analyzed by LC/IRMS. The δ 13 C values for glucose, fructose, disaccharides, trisaccharides, and organic acids ranged from -27.0 to -24.2‰, -26.8 to -24.0‰, -28.8 to -24.0‰, -27.8 to -22.8‰, and -30.6 to -27.4‰, respectively. The analysis time was 1/3-1/2 the times required for analysis by previously reported methods. The column flow rate could be arbitrarily adjusted with the post-column pump. We applied the improved method to 26 commercial honey samples. Our results can be expected to be useful for other researchers who use LC/IRMS. This article is protected by copyright. All rights reserved.

  10. Discrimination factors of carbon and nitrogen stable isotopes in meerkat feces

    Directory of Open Access Journals (Sweden)

    Shaena Montanari

    2017-06-01

    Full Text Available Stable isotope analysis of feces can provide a non-invasive method for tracking the dietary habits of nearly any mammalian species. While fecal samples are often collected for macroscopic and genetic study, stable isotope analysis can also be applied to expand the knowledge of species-specific dietary ecology. It is somewhat unclear how digestion changes the isotope ratios of animals’ diets, so more controlled diet studies are needed. To date, most diet-to-feces controlled stable isotope experiments have been performed on herbivores, so in this study I analyzed the carbon and nitrogen stable isotope ratios in the diet and feces of the meerkat (Suricata suricatta, a small omnivorous mammal. The carbon trophic discrimination factor between diet and feces (Δ13Cfeces is calculated to be 0.1 ± 1.5‰, which is not significantly different from zero, and in turn, not different than the dietary input. On the other hand, the nitrogen trophic discrimination factor (Δ15Nfeces is 1.5 ± 1.1‰, which is significantly different from zero, meaning it is different than the average dietary input. Based on data generated in this experiment and a review of the published literature, carbon isotopes of feces characterize diet, while nitrogen isotope ratios of feces are consistently higher than dietary inputs, meaning a discrimination factor needs to be taken into account. The carbon and nitrogen stable isotope values of feces are an excellent snapshot of diet that can be used in concert with other analytical methods to better understand ecology, diets, and habitat use of mammals.

  11. Grasland Stable Isotope Flux Measurements: Three Isotopomers of Carbon Dioxide Measured by QCL Spectroscopy

    Science.gov (United States)

    Zeeman, M. J.; Tuzson, B.; Eugster, W.; Werner, R. A.; Buchmann, N.; Emmenegger, L.

    2007-12-01

    To improve our understanding of greenhouse gas dynamics of managed ecosystems such as grasslands, we not only need to investigate the effects of management (e.g., grass cuts) and weather events (e.g., rainy days) on carbon dioxide fluxes, but also need to increase the time resolution of our measurements. Thus, for the first time, we assessed respiration and assimilation fluxes with high time resolution (5Hz) stable isotope measurements at an intensively managed farmland in Switzerland (Chamau, 400m ASL). Two different methods were used to quantify fluxes of carbon dioxide and associated fluxes of stable carbon isotopes: (1) the flux gradient method, and (2) the eddy covariance method. During a week long intensive measurement campaign, we (1) measured mixing ratios of carbon dioxide isotopomers (12C16O2, 12C16O18O, 13C16O2) with a Quantum Cascade Laser (QCL, Aerodyne Inc.) spectroscope and (2) collected air samples for isotope analyses (13C/12C) and (18O/16O) of carbon dioxide by Isotope Ratio Mass Spectrometry (IRMS, Finnigan) every two hours, concurrently along a height profile (z = 0.05; 0.10; 0.31; 2.15m). In the following week, the QCL setup was used for closed-path eddy covariance flux measurement of the carbon dioxide isotopomers, with the air inlet located next to an open-path Infra Red Gas Analyzers (IRGA, LiCor 7500) used simultaneously for carbon dioxide measurements. During this second week, an area of grass inside the footprint was cut and harvested after several days. The first results of in-field continuous QCL measurements of carbon dioxide mixing ratios and their stable isotopic ratios show good agreement with IRGA measurements and isotope analysis of flask samples by IRMS. Thus, QCL spectroscopy is a very promising tool for stable isotope flux investigations.

  12. In Situ Carbon Isotope Analysis by Laser Ablation MC-ICP-MS.

    Science.gov (United States)

    Chen, Wei; Lu, Jue; Jiang, Shao-Yong; Zhao, Kui-Dong; Duan, Deng-Fei

    2017-12-19

    Carbon isotopes have been widely used in tracing a wide variety of geological and environmental processes. The carbon isotope composition of bulk rocks and minerals was conventionally analyzed by isotope ratio mass spectrometry (IRMS), and, more recently, secondary ionization mass spectrometry (SIMS) has been widely used to determine carbon isotope composition of carbon-bearing solid materials with good spatial resolution. Here, we present a new method that couples a RESOlution S155 193 nm laser ablation system with a Nu Plasma II MC-ICP-MS, with the aim of measuring carbon isotopes in situ in carbonate minerals (i.e., calcite and aragonite). Under routine operating conditions for δ 13 C analysis, instrumental bias generally drifts by 0.8‰-2.0‰ in a typical analytical session of 2-3 h. Using a magmatic calcite as the standard, the carbon isotopic composition was determined for a suite of calcite samples with δ 13 C values in the range of -6.94‰ to 1.48‰. The obtained δ 13 C data are comparable to IRMS values. The combined standard uncertainty for magmatic calcite is ICP-MS can serve as an appropriate method to analyze carbon isotopes of carbonate minerals in situ.

  13. Hepatoblastoma Biology Using Isotope Ratio Mass Spectrometry: Utility of a Unique Technique for the Analysis of Oncological Specimens

    Directory of Open Access Journals (Sweden)

    Katarzyna Taran

    2016-07-01

    Full Text Available Introduction: Hepatoblastoma is the most common primary liver tumor in children. However, it occurs rarely, with an incidence of 0.5-1.5 cases per million children. There is no clear explanation of the relationship between clinicopathologic features, therapy, and outcome in hepatoblastoma cases, so far. One of the most widely accepted prognostic factors in hepatoblastoma is histology of the tumor. The aim of the study was to determine the potential differences in biology of hepatoblastoma histological subtypes at the atomic level using the unique method of isotope ratio mass spectrometry, which is especially valuable in examination of small groups of biological samples.Material/Methods: Twenty-four measurements of nitrogen stable isotope ratio, carbon stable isotope ratio and total carbon to nitrogen mass ratio in fetal and embryonal hepatoblastoma tissue were performed using a Sercon 20-22 Continuous Flow Isotope Ratio Mass Spectrometer (CF-IRMS coupled with a Sercon SL elemental analyzer for simultaneous carbon-nitrogen-sulfur (NCS analysis.Results: A difference of about 1.781‰ in stable nitrogen isotope 15N/14N ratio was found between examined hepatoblastoma histological subtypes.Conclusions: The prognosis in liver tumors cases in children may be challenging particularly because of the lack of versatile methods of its evaluation. Isotope ratio mass spectrometry allows one to determine the difference between hepatoblastoma histological subtypes and clearly indicates the cases with the best outcome.

  14. Compound-Specific Carbon, Nitrogen, and Hydrogen Isotopic Ratios for Amino Acids in CM and CR Chondrites and their use in Evaluating Potential Formation Pathways

    Science.gov (United States)

    Elsila, Jamie E.; Charnley, Steven B.; Burton, Aaron S.; Glavin, Daniel P.; Dworkin, Jason P.

    2012-01-01

    Stable hydrogen, carbon, and nitrogen isotopic ratios (oD, 013C, and olSN) of organic compounds can revcal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may indicate the most likely of these pathways. We have applied gas chromatography with mass spectrometry and combustion isotope ratio mass spectrometry to measure the compound-specific C, N, and H stable isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites: CM1I2 Allan Hills (ALH) 83100, CM2 Murchison, CM2 Lewis Cliff (LEW) 90500, CM2 Lonewolf Nunataks (LON) 94101, CRZ Graves Nunataks (GRA) 95229, CRZ Elephant Moraine (EET) 92042, and CR3 Queen Alexandra Range (QUE) 99177. We compare the isotopic compositions of amino acids in these meteorites with predictions of expected isotopic enrichments from potential formation pathways. We observe trends of decreasing ODC and increasing oD with increasing carbon number in the aH, (l-NH2 amino acids that correspond to predictions made for formation via Streckercyanohydrin synthesis. We also observe light ODC signatures for -alanine, which may indicate either formation via Michael addition or via a pathway that forms primarily small, straight-chain, amine-terminal amino acids (n-ro-amino acids). Higher deuterium enrichments are observed in amethyl amino acids, indicating formation of these amino acids or their precursors in cold interstellar or nebular environments. Finally, individual amino acids are more enriched in deuterium in CR chondrites than CM chondrites, reflecting different parent-body chemistry.

  15. Dissolution of barite for the analysis of strontium isotopes and other chemical and isotopic variations using aqueous sodium carbonate

    Science.gov (United States)

    Breit, G.N.; Simmons, E.C.; Goldhaber, M.B.

    1985-01-01

    A simple procedure for preparing barite samples for chemical and isotopic analysis is described. Sulfate ion, in barite, in the presence of high concentrations of aqueous sodium carbonate, is replaced by carbonate. This replacement forms insoluble carbonates with the cations commonly in barite: Ba, Sr, Ca and Pb. Sulfate is released into the solution by the carbonate replacement and is separated by filtration. The aqueous sulfate can then be reprecipitated for analysis of the sulfur and oxygen isotopes. The cations in the carbonate phase can be dissolved by acidifying the solid residue. Sr can be separated from the solution for Sr isotope analysis by ion-exchange chromatography. The sodium carbonate used contains amounts of Sr which will affect almost all barite 87Sr 86Sr ratios by less than 0.00001 at 1.95?? of the mean. The procedure is preferred over other techniques used for preparing barite samples for the determination of 87Sr 86Sr ratios because it is simple, rapid and enables simultaneous determination of many compositional parameters on the same material. ?? 1985.

  16. Continuous-flow isotope ratio mass spectrometry method for carbon and hydrogen isotope measurements on atmospheric methane

    Directory of Open Access Journals (Sweden)

    M. Brass

    2010-12-01

    Full Text Available We describe a continuous-flow isotope ratio mass spectrometry (CF-IRMS technique for high-precision δD and δ13C measurements of atmospheric methane on 40 mL air samples. CH4 is separated from other air components by utilizing purely physical processes based on temperature, time and mechanical valve switching. Chemical agents are avoided. Trace amounts of interfering compounds can be separated by gas chromatography after pre-concentration of the CH4 sample. The purified sample is then either combusted to CO2 or pyrolyzed to H2 for stable isotope measurement. Apart from connecting samples and refilling liquid nitrogen as coolant the system is fully automated and allows an unobserved, continuous analysis of samples. The analytical system has been used for analysis of air samples with CH4 mixing ratios between ~100 and ~10 000 ppb, for higher mixing ratios samples usually have to be diluted.

  17. Stable isotope ratios in hair and teeth reflect biologic rhythms.

    Directory of Open Access Journals (Sweden)

    Otto Appenzeller

    Full Text Available Biologic rhythms give insight into normal physiology and disease. They can be used as biomarkers for neuronal degenerations. We present a diverse data set to show that hair and teeth contain an extended record of biologic rhythms, and that analysis of these tissues could yield signals of neurodegenerations. We examined hair from mummified humans from South America, extinct mammals and modern animals and people, both healthy and diseased, and teeth of hominins. We also monitored heart-rate variability, a measure of a biologic rhythm, in some living subjects and analyzed it using power spectra. The samples were examined to determine variations in stable isotope ratios along the length of the hair and across growth-lines of the enamel in teeth. We found recurring circa-annual periods of slow and fast rhythms in hydrogen isotope ratios in hair and carbon and oxygen isotope ratios in teeth. The power spectra contained slow and fast frequency power, matching, in terms of normalized frequency, the spectra of heart rate variability found in our living subjects. Analysis of the power spectra of hydrogen isotope ratios in hair from a patient with neurodegeneration revealed the same spectral features seen in the patient's heart-rate variability. Our study shows that spectral analysis of stable isotope ratios in readily available tissues such as hair could become a powerful diagnostic tool when effective treatments and neuroprotective drugs for neurodegenerative diseases become available. It also suggests that similar analyses of archaeological specimens could give insight into the physiology of ancient people and animals.

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

    Directory of Open Access Journals (Sweden)

    D. Codron

    2005-06-01

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

  19. A STUDY ON CARBON ISOTOPE OF CO2 AND CH4 IN WESTERN DIENG PLATEU BY GAS CHROMATOGRAPHY- ISOTOPE RATIO MASS SPECTROMETER (GC-IRMS

    Directory of Open Access Journals (Sweden)

    Hanik Humaida

    2010-06-01

    Full Text Available The carbon isotope can be used to evaluate volcanism phenomenon of volcano. The study of carbon isotope of CO2 and CH4 was carried out in western Dieng Plateau by mass-spectrometer. Before analysis, sampel was separated by gas chromatography using a Porapak-Q column and a FID (Flame Ionization Detector detector. The gas was oxidized by copper oxide at 850oC before being ionized in mass-spectrometer for isotope analysis. The CO2 content in Candradimuka crater (-4.10 O/OO, indicated that the gas may be as volcanic gas. The other CO2 from Sumber and western Gua Jimat, had isotope value  of -10.05 and -12.07 O/OO, respectively, indicating contamination from crustal and subduction material. The carbon isotope of CH4 gas from Pancasan village was -63.42 O/OO, that may be categorized as biogenic gas.   Keywords: isotope, CO2, CH4, Dieng.

  20. Carbon isotope fractionation of 1,1,1-trichloroethane during base-catalyzed persulfate treatment

    International Nuclear Information System (INIS)

    Marchesi, Massimo; Thomson, Neil R.; Aravena, Ramon; Sra, Kanwartej S.; Otero, Neus; Soler, Albert

    2013-01-01

    Highlights: • Treatability and C fractionation of 1,1,1-TCA by base-catalyzed S 2 O 8 2− was studied. • The rate of degradation of 1,1,1-TCA increased with a higher OH − :S 2 O 8 2− ratio. •Base-catalyzed S 2 O 8 2− can potentially treat recalcitrant compound like 1,1,1-TCA. • An enrichment factor of −7.0‰ independent of the OH − :S 2 O 8 2− ratio was obtained. • Carbon isotope can potentially be used to estimate the ISCO treatment efficacy. -- Abstract: The extent of carbon isotope fractionation during degradation of 1,1,1-trichloroethane (1,1,1-TCA) by a base-catalyzed persulfate (S 2 O 8 2− ) treatment system was investigated. Significant destruction of 1,1,1-TCA was observed at a pH of ∼12. An increase in the NaOH:S 2 O 8 2− molar ratio from 0.2:1 to 8:1 enhanced the reaction rate of 1,1,1-TCA by a factor of ∼5 to yield complete (>99.9%) destruction. An average carbon isotope enrichment fractionation factor which was independent of the NaOH:S 2 O 8 2− molar ratio of −7.0 ± 0.2‰ was obtained. This significant carbon isotope fractionation and the lack of dependence on changes in the NaOH:S 2 O 8 2− molar ratio demonstrates that carbon isotope analysis can potentially be used in situ as a performance assessment tool to estimate the degradation effectiveness of 1,1,1-TCA by a base-catalyzed persulfate system

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

    Directory of Open Access Journals (Sweden)

    Govinda Rizal

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

  2. Relationships between tree height and carbon isotope discrimination

    Science.gov (United States)

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

    2011-01-01

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

  3. Isotopic ratios in the solar system

    International Nuclear Information System (INIS)

    1985-01-01

    This colloquium is aimed at presentation of isotope ratio measurements in different objects of solar system and surrounding interstellar space and evaluation of what information on composition and structure of primitive solar nebula and on chemical evolution of interstellar space in this part of the galaxy can be deduced from it. Isotope ratio in solar system got from laboratory study of extraterrestrial materials is a subject of this colloquium. Then isotope ratio measured in solar wind, planets and comets. Measurements either are made in-situ by mass spectrometry of ions in solar wind or planetery atmosphere gases either are remote measurements of spectra emitted by giant planets and comets. At last, planetology and astrophysics implications are presented and reviewed. Consraints for solar system formation model can be deduced from isotope ratio measurement. Particularly, isotope anomalies are marks of the processes, which have influenced the primitive solar nebula contraction [fr

  4. Soil Carbon: Compositional and Isotopic Analysis

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-11-01

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

  5. Source characterization using compound composition and stable carbon isotope ratio of PAHs in sediments from lakes, harbor, and shipping waterway

    International Nuclear Information System (INIS)

    Kim, Moonkoo; Kennicutt, Mahlon C.; Qian, Yaorong

    2008-01-01

    Molecular compositions and compound specific stable carbon isotope ratios of polycyclic aromatic hydrocarbons (PAH) isolated from sediments were used to characterize possible sources of contamination at an urban lake, a harbor, a shipping waterway, and a relatively undisturbed remote lake in the northwest United States. Total PAH concentrations in urban lake sediments ranged from 66.0 to 16,500 μg g -1 dry wt. with an average of 2600 μg g -1 , which is ∼ 50, 100, and 400 times higher on average than PAH in harbor (48 μg g -1 on average), shipping waterway (26 μg g -1 ), and remote lake (7 μg g -1 ) sediments, respectively. The PAH distribution patterns, methyl phenanthrene/phenanthrene ratios, and a pyrogenic index at the sites suggest a pyrogenic origin for PAHs. Source characterization using principal component analysis and various molecular indices including C2-dibenzothiophenes/C2-phenanthrenes, C3-dibenzothiophenes/C3-phenanthrenes, and C2-chrysenes/C2-phenanthrenes ratios, was able to differentiate PAH deposited in sediments from the four sites. The uniqueness of the source of the sediment PAHs from urban lake was also illustrated by compound specific stable carbon isotope analysis. It was concluded that urban lake sediments are accumulating PAH from sources that are unique from contamination detected at nearby sites in the same watershed

  6. Recent development in isotope ratio mass spectrometry

    International Nuclear Information System (INIS)

    Platzner, I.

    1992-01-01

    Within the limited of this review the following topics will be briefly discussed: a) Accuracy, precision, internal relative standard deviation (RISD) and external relative standard deviation (RESD) of isotope ratio measurements. With advanced instrumentation and use of standard reference materials, high accuracy and RESD = 0.002% (or better) may be achieved; b) The advantages of modern automatic isotope ratio mass spectrometer are briefly described. Computer controlled operation and data acquisition, and multiple ion collection are the recent important improvement; c) The isotopic fractionation during the course of isotope ratio measurement is considered as a major source of errors in thermal ionization of metallic elements. The phenomenon in strontium, neodymium, uranium, lead and calcium and methods to correct the measured data are discussed; d) Applications of isotope ratio mass spectrometry in atomic weight determinations, the isotope dilution technique, isotope geology, and isotope effects in biological systems are described together with specific applications in various research and technology area. (author)

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

    International Nuclear Information System (INIS)

    Harney, R.C.; Bloom, S.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

  8. A measuring system for the fast simultaneous isotope ratio and elemental analysis of carbon, hydrogen, nitrogen and sulfur in food commodities and other biological material.

    Science.gov (United States)

    Sieper, Hans-Peter; Kupka, Hans-Joachim; Williams, Tony; Rossmann, Andreas; Rummel, Susanne; Tanz, Nicole; Schmidt, Hanns-Ludwig

    2006-01-01

    The isotope ratio of each of the light elements preserves individual information on the origin and history of organic natural compounds. Therefore, a multi-element isotope ratio analysis is the most efficient means for the origin and authenticity assignment of food, and also for the solution of various problems in ecology, archaeology and criminology. Due to the extraordinary relative abundances of the elements hydrogen, carbon, nitrogen and sulfur in some biological material and to the need for individual sample preparations for H and S, their isotope ratio determination currently requires at least three independent procedures and approximately 1 h of work. We present here a system for the integrated elemental and isotope ratio analysis of all four elements in one sample within 20 min. The system consists of an elemental analyser coupled to an isotope ratio mass spectrometer with an inlet system for four reference gases (N(2), CO(2), H(2) and SO(2)). The combustion gases are separated by reversible adsorption and determined by a thermoconductivity detector; H(2)O is reduced to H(2). The analyser is able to combust samples with up to 100 mg of organic material, sufficient to analyse samples with even unusual elemental ratios, in one run. A comparison of the isotope ratios of samples of water, fruit juices, cheese and ethanol from wine, analysed by the four-element analyser and by classical methods and systems, respectively, yielded excellent agreements. The sensitivity of the device for the isotope ratio measurement of C and N corresponds to that of other systems. It is less by a factor of four for H and by a factor of two for S, and the error ranges are identical to those of other systems. Copyright (c) 2006 John Wiley & Sons, Ltd.

  9. Carbon isotope fractionation of 1,1,1-trichloroethane during base-catalyzed persulfate treatment

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-09-15

    Highlights: • Treatability and C fractionation of 1,1,1-TCA by base-catalyzed S{sub 2}O{sub 8}{sup 2−} was studied. • The rate of degradation of 1,1,1-TCA increased with a higher OH{sup −}:S{sub 2}O{sub 8}{sup 2−} ratio. •Base-catalyzed S{sub 2}O{sub 8}{sup 2−} can potentially treat recalcitrant compound like 1,1,1-TCA. • An enrichment factor of −7.0‰ independent of the OH{sup −}:S{sub 2}O{sub 8}{sup 2−} ratio was obtained. • Carbon isotope can potentially be used to estimate the ISCO treatment efficacy. -- Abstract: The extent of carbon isotope fractionation during degradation of 1,1,1-trichloroethane (1,1,1-TCA) by a base-catalyzed persulfate (S{sub 2}O{sub 8}{sup 2−}) treatment system was investigated. Significant destruction of 1,1,1-TCA was observed at a pH of ∼12. An increase in the NaOH:S{sub 2}O{sub 8}{sup 2−} molar ratio from 0.2:1 to 8:1 enhanced the reaction rate of 1,1,1-TCA by a factor of ∼5 to yield complete (>99.9%) destruction. An average carbon isotope enrichment fractionation factor which was independent of the NaOH:S{sub 2}O{sub 8}{sup 2−} molar ratio of −7.0 ± 0.2‰ was obtained. This significant carbon isotope fractionation and the lack of dependence on changes in the NaOH:S{sub 2}O{sub 8}{sup 2−} molar ratio demonstrates that carbon isotope analysis can potentially be used in situ as a performance assessment tool to estimate the degradation effectiveness of 1,1,1-TCA by a base-catalyzed persulfate system.

  10. Carbon Isotope Chemistry in Molecular Clouds

    Science.gov (United States)

    Robertson, Amy N.; Willacy, Karen

    2012-01-01

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

  11. Application of carbon and oxygen stable isotopes to the study of Brazilian precambrian

    International Nuclear Information System (INIS)

    Torquato, J.R.F.

    1980-01-01

    Samples of carbonated rocks of precambrian age are studied. The stable carbon and oxygen isotopes are applied to the study of terrestrial materials considering the variations of some element isotopic composition in function of the environment of sedimentation. The isotopic analysis was done using mass spectrometers. The analytical results and the description of region geology of the site of each sample are presented. The isotopic data are interpreted aiming to the environment of sedimentation. New techniques for better improvement of carbon and oxygen ratios, are proposed, such as: to use the analysis of surface trend and the isotopic logging in mapping of surface and subsurface. A new method for approximated determination of the ages of precambrian carbonated rocks, considering the limitations of their new technique, is also presented. (M.C.K.) [pt

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

    Science.gov (United States)

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

  13. Geological factors of the isotopic distribution of carbon of organic matter in sedimentary rocks

    International Nuclear Information System (INIS)

    Maass, J.

    1981-01-01

    The isotope ratio of carbon of fossile organic matter can be regarded as a definite criterion of its genetic origin. As the biofacial character of organic matter, especially the chemical composition (H/C-ratio), decisively influences the mode and quantity of the potential hydrocarbon production, isotopic analysis is an essential method for the prognostic evaluation of sedimentary basins with regard to their oil and gas perspectives. The genetic relations to the parent substance continue in the bituminization and coalification products and make it possible to apply the isotopic analysis of carbon to prospection work for hydrocarbons. (author)

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-05-15

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

  16. Geographical variations in Sr and Nd isotopic ratios of cryoconite on Asian glaciers

    International Nuclear Information System (INIS)

    Nagatsuka, Naoko; Takeuchi, Nozomu; Nakano, Takanori; Shin, Kicheol; Kokado, Emi

    2014-01-01

    Cryoconite is a dark-coloured surface dust deposited on glaciers that consists of wind-blown mineral particles, as well as organic matter derived from microbes living on glaciers. In this paper, we analyse the Sr and Nd isotopic ratios of four mineral fractions (i.e., the saline, carbonate, phosphate, and silicate mineral fractions), as well as the organic fraction, of cryoconite samples obtained from six Asian glaciers (the Altai, Pamir, Tien Shan, Qillian Shan, and Himalayan regions), and discuss their geographical variations in terms of the geological origins of the mineral particles and the biogeochemical processes on the glaciers. The silicate mineral fraction showed lower Sr and higher Nd ratios for the glaciers located to the north (Altai, 87 Sr/ 86 Sr: 0.713 490–0.715 284, εNd(0): −6.4 to −5.6), while higher Sr and lower Nd ratios for the glaciers located to the south (Himalayas, 87 Sr/ 86 Sr: 0.740 121–0.742 088, εNd(0): −16.4 to −15.7); the ratios were similar to those of desert sand, loess, and river sediments in the respective regions of the glaciers. This result suggests that the silicate minerals within the cryoconites were derived from different sources depending on the geographical locations of the glaciers. The isotopic ratios of the saline, carbonate, and phosphate mineral fractions were distinct from those of the silicate fraction, and were similar to those of evaporites and apatite deposits from the Asian deserts, but also varied geographically, indicating that they are likely to reflect their geological origin. The Sr isotopic ratios of the organic fraction were similar to those of the saline and carbonate fractions from glaciers in the central area (Tien Shan and Qillian Shan), but were higher than those of the saline and carbonate fractions, and lower than the phosphate mineral fraction, in the northern and southern areas. The ratios of organic fraction may be determined from the mixing ratio of calcium sources

  17. Stable oxygen and hydrogen isotopes of brines - comparing isotope ratio mass spectrometry and isotope ratio infrared spectroscopy

    Science.gov (United States)

    Ahrens, Christian; Koeniger, Paul; van Geldern, Robert; Stadler, Susanne

    2013-04-01

    Today's standard analytical methods for high precision stable isotope analysis of fluids are gas-water equilibration and high temperature pyrolysis coupled to isotope ratio mass spectrometers (IRMS). In recent years, relatively new laser-based analytical instruments entered the market that are said to allow high isotope precision data on nearly every media. This optical technique is referred to as isotope ratio infrared spectroscopy (IRIS). The objective of this study is to evaluate the capability of this new instrument type for highly saline solutions and a comparison of the analytical results with traditional IRMS analysis. It has been shown for the equilibration method that the presence of salts influences the measured isotope values depending on the salt concentration (see Lécuyer et al, 2009; Martineau, 2012). This so-called 'isotope salt effect' depends on the salt type and salt concentration. These factors change the activity in the fluid and therefore shift the isotope ratios measured by the equilibration method. Consequently, correction factors have to be applied to these analytical data. Direct conversion techniques like pyrolysis or the new laser instruments allow the measurement of the water molecule from the sample directly and should therefore not suffer from the salt effect, i.e. no corrections of raw values are necessary. However, due to high salt concentrations this might cause technical problems with the analytical hardware and may require labor-intensive sample preparation (e.g. vacuum distillation). This study evaluates the salt isotope effect for the IRMS equilibration technique (Thermo Gasbench II coupled to Delta Plus XP) and the laser-based IRIS instruments with liquid injection (Picarro L2120-i). Synthetic salt solutions (NaCl, KCl, CaCl2, MgCl2, MgSO4, CaSO4) and natural brines collected from the Stassfurt Salt Anticline (Germany; Stadler et al., 2012) were analysed with both techniques. Salt concentrations ranged from seawater salinity

  18. Bicarbonate adsorption band of the chromatography for carbon isotope separation using anion exchangers

    International Nuclear Information System (INIS)

    Takeda, Kunihiko; Obanawa, Heiichiro; Hata, Masahisa; Sato, Katsuya

    1985-01-01

    The equilibria of bicarbonate ion between two phases were studied for the carbon isotope separation using anion exchangers. The condition of the formation of a bicarbonate adsorption band was quantitatively discussed. The formation of the adsorption band depends on the difference of S-potential which is the sum of the standard redection chemical potentials and L-potential which is the sum of the reduction chemical potential. The isotopic separation factor observed was about 1.012, independent of the concentrations of acid and alkali in the solutions. The isotopic separation factor was considered to be determined by the reaction of bicarbonate ion on anion exchangers and carbon dioxide dissolved in solutions. The enriched carbon isotope whose isotopic abundance ratio ( 13 C/ 12 C) was 1.258 was obtained with the column packed with anion exchangers. (author)

  19. Isotope ratio 87Sr/86Sr in limestones from Bambui group, Brazil (MG)

    International Nuclear Information System (INIS)

    Kawashita, K.; Mizusaki, A.M.P.; Kiang, C.H.

    1987-01-01

    The Sr composition of ancient seawater can be estimated from the analysis of carbonate rocks and, in some cases, used to estimate the age of the analyzed carbonate. The normalized 87Sr/86Sr ratios in calcium carbonate fractions from 14 core samples in the Bambui Group near Montalvania, MG, were found to range between .7077 and .7280. The higher values are attributable to Sr isotopic exchange between silicate and carbonate phases during diagenesis. The ratio of .7077 obtained in two pure calcium carbonate samples is here suggested as the best aproximation for the 87Sr/86Sr value for the Bambui sea. This ratio is compatible with an age of about 700 Ma., estimated from the published 87Sr/86Sr curve of Veizer and others, an age in accordance with Quadros recent (1987, in preparation) identification of marine acritarchs from the latest Precambrian (Vendian). (author) [pt

  20. Variation in stable carbon isotopes in organic matter from the Gunflint Iron Formation

    International Nuclear Information System (INIS)

    Barghoorn, E.S.; Knoll, A.H.; Dembicki, H. Jr.; Meinschein, W.G.

    1977-01-01

    In order to examine possible variations in organic carbon isotopic ratios within a single Precambrian formation, the kerogen separated from 15 samples of the approximately 2000 m.y. old Gunflint Iron Formation and the conformably overlying Rove Formation, representing a wide range of lithologies and geographic localities, was isotopically analyzed. From the resulting data, four conclusions can be drawn: (1) delta 13 C values of the shallow water algal chert facies are significantly more negative (-25 to -30 parts per thousand) than those of the deeper water chert-carbonate and taconite facies (-15 to -20 parts per thousand). Comparative data for modern marine algal mats shows a range of delta 13 C values from -8.4 to -19 parts per thousand PDB. Values obtained for fresh water mats were slightly more negative. (2) These differences in isotopic ratios can be correlated with similar differences in preserved microbiotas. (3) Anthraxolite lenses are depleted in 13 C relative to the reduced carbon in surrounding sediments. (4) The effect of Keweenawan diabase intrusions upon the carbon isotopic composition is pronounced, but limited to the immediate vicinity of the contact. (author)

  1. Preliminary Study: Application of Off-Axis ICOS to Determine Stable Carbon Isotope in Dissolved Inorganic Carbon

    Science.gov (United States)

    Kim, Y. T.; Lee, J. M.; Hwang, J. H.; Piao, J.; Woo, N. C.

    2015-12-01

    CO2 is one of the major causes for global climate change. Because stable carbon isotope ratio is used to trace carbon source, several analytical techniques likes IRMS (Isotope Ratio Mass Spectrometry) and LAS (Laser Absorption Spectrometry) were extensively used. Off-axis ICOS, a kind of LAS, has merits on long-term stability and field application, therefore it is widely being used in CCS (Carbon Capture and Storage) field. The aim of this study is to extend the application scope of OA-ICOS to determine dissolved inorganic carbon (DIC). Because OA-ICOS showed dependence of δ13C on CO2 concentration, data processing is required. We tested CO2 Carbon Isotope Analyzer (CCIA-36-EP, Los Gatos Research) with both reference gas (δ13C= -28.28‰) and aqueous solutions prepared by dissolving sodium bicarbonate standards (δ13C= -12.26‰ and +3.96‰). The differences of δ13C between reference and measurement values are plotted by CO2 concentrations, then compared. At first, we checked the similarity between our curve pattern for reference gas and Guillon's research (δ13C= -43.99‰) by other Analyzer. To analyze aqueous samples, more errors can be caused than gas analysis. The carbon isotope fractionation occurs during dissolving standard reagents and extracting DIC as CO2 gas form. This effect is mixed with CO2 concentration dependence effect, therefore the curve patterns are different with that for reference gas. Our experiments are done for various δ13C values. It could be an important point to use OA-ICOS to analyze DIC, too.

  2. Accurate isotope ratio mass spectrometry. Some problems and possibilities

    International Nuclear Information System (INIS)

    Bievre, P. de

    1978-01-01

    The review includes reference to 190 papers, mainly published during the last 10 years. It covers the following: important factors in accurate isotope ratio measurements (precision and accuracy of isotope ratio measurements -exemplified by determinations of 235 U/ 238 U and of other elements including 239 Pu/ 240 Pu; isotope fractionation -exemplified by curves for Rb, U); applications (atomic weights); the Oklo natural nuclear reactor (discovered by UF 6 mass spectrometry at Pierrelatte); nuclear and other constants; isotope ratio measurements in nuclear geology and isotope cosmology - accurate age determination; isotope ratio measurements on very small samples - archaeometry; isotope dilution; miscellaneous applications; and future prospects. (U.K.)

  3. Effect of baking and fermentation on the stable carbon and nitrogen isotope ratios of grain-based food.

    Science.gov (United States)

    Bostic, Joshua N; Palafox, Sherilyn J; Rottmueller, Marina E; Jahren, A Hope

    2015-05-30

    Isotope ratio mass spectrometry (IRMS) is used extensively to reconstruct general attributes of prehistoric and modern diets in both humans and animals. In order to apply these methods to the accurate determination of specific intakes of foods/nutrients of interest, the isotopic signature of individually consumed foods must be constrained. For example, 86% of the calories consumed in the USA are derived from processed and prepared foods, but the relationship between the stable isotope composition of raw ingredients and the resulting products has not been characterized. To examine the effect of common cooking techniques on the stable isotope composition of grain-based food items, we prepared yeast buns and sugar cookies from standardized recipes and measured bulk δ(13) C and δ(15) N values of samples collected throughout a 75 min fermentation process (buns) and before and after baking at 190°C (buns and cookies). Simple isotope mixing models were used to determine if the isotopic signatures of 13 multi-ingredient foods could be estimated from the isotopic signatures of their constituent raw ingredients. No variations in δ(13) C or δ(15) N values were detected between pre- and post-baked yeast buns (pre: -24.78‰/2.61‰, post: -24.75‰/2.74‰), beet-sugar cookies (pre: -24.48‰/3.84‰, post: -24.47‰/3.57‰), and cane-sugar cookies (pre: -19.07‰/2.97‰, post: -19.02‰/3.21‰), or throughout a 75 min fermentation process in yeast buns. Using isotopic mass balance equations, the δ(13) C/δ(15) N values of multi-ingredient foods were estimated from the isotopic composition of constituent raw ingredients to within 0.14 ± 0.13‰/0.24 ± 0.17‰ for gravimetrically measured recipes and 0.40 ± 0.38‰/0.58 ± 0.53‰ for volumetrically measured recipes. Two common food preparation techniques, baking and fermentation, do not substantially affect the carbon or nitrogen isotopic signature of grain-based foods. Mass-balance equations can be used to

  4. Stable carbon and oxygen isotope ratios of malachite from the patinas of ancient bronze objects

    International Nuclear Information System (INIS)

    Smith, A.W.

    1978-01-01

    13 C/ 12 C and 18 O/ 16 O ratios have been measured for 62 samples of the mineral malachite, taken from the patinas of ancient bronze objects (from Britain, Italy, Libya and China), in order to investigate any possible relationship which may exist between the isotope ratios and the burial conditions of the objects. The results indicate that the isotope ratios are controlled by complex factors related to the climate, vegetation and soil type at the burial site. It is suggested that the technique might be used, given favourable circumstances, in the characterization of patinas and as a possible aid in the detection of synthetic patination. (author)

  5. Isotope ratio in stellar atmospheres and nucleosynthesis

    International Nuclear Information System (INIS)

    Barbuy, B.L.S.

    1987-01-01

    The determination of isotopic ratios in stellar atmospheres is studied. The isotopic shift of atomic and molecular lines of different species of a certain element is examined. CH and MgH lines are observed in order to obtain the 12 C: 13 C and 24 Mg: 25 Mg: 26 Mg isotpic ratios. The formation of lines in stellar atmospheres is computed and the resulting synthetic spectra are employed to determine the isotopic abundances. The results obtained for the isotopic ratios are compared to predictions of nucleosynthesis theories. Finally, the concept of primary and secondary element is discussed, and these definitions are applied to the observed variations in the abundance of elements as a function of metallicity. (author) [pt

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-09-01

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

  7. The assesment of the food quality by 13 C isotope ratio mass spectrometry

    International Nuclear Information System (INIS)

    Cuna, Stela; Cuna, Cornel

    2001-01-01

    Carbon 13 analysis can be a key analytical technique used in the fight to detect undeclared addition of low cost adulterants to high value foods. The natural abundance of 13 C in food is related to how the plant fix the carbon during photosynthesis. Plants that use a C3 photosynthetic cycle discriminate against 13 C more than plants with C4 cycle. We developed a method for analysis of 13 C isotope in organic samples. Because of instrumental requirements carbon must be converted to CO 2 for stable isotope ratio measurements. Conversion of organic samples to CO 2 was accomplished by combustion in an excess oxygen atmosphere. This technique involves the combustion of individual samples in sealed, evacuated quartz tubes containing CuO as the oxygen source. Because each sample is prepared in its own container, there is no chance for memory effects. The method was tested for sensitivity (the smallest increment of the isotope ratio that must be detected with confidence), sample size (the minimum quantity of a pure molecular species available to achieve the desired accuracy) and precision. The method was utilised for the detection of a synthetic flavour from natural one, namely the natural oil bitter almond from the synthetic benzaldehyde. The method can be validated for the detection or establishment of authenticity in food products. (authors)

  8. Isotope ratios of lead as pollutant source indicators

    International Nuclear Information System (INIS)

    Chow, T.J.; Snyder, C.B.; Earal, J.L.

    1975-01-01

    Each lead ore deposit has its characteristic isotope ratios which are fixed during mineral ore genesis, and this unique property can be used to indicate the source of lead pollutants in the environment. The wolld production of primary lead is tabulated, and the geochemical significances of lead isotope ratios are discussed. The manufacture of lead alkyl additives for gasoline, which is the major source of lead pollutants, utilizes about 10% of the world annual consumption of lead. The isotope ratios of lead in gasoline, aerosols, soils and plants are correlated. Lead additives in various brands of gasoline sold in one region do not have the same isotope ratios. Regional variations in isotope ratios of lead additives were observed. This reflects the fact that petroleum refineries obtained the additives from various lead alkyl manufacturers which utilized lead from different mining districts. A definite changing trend of isotope ratios of lead pollutants in the San Diego, California (USA), area was detected. The lead shows a gradual increase in its radiogenic components during the past decade. This trend can be explained by the change of lead sources used by the additive manufacturers: Lead isotope ratios of the mid-1960's gasoline additives in the United States of America reflected those of less radiogenic leads imported from Canada, Australia, Peru and Mexico. Since then, the U.S. lead production has doubled-mainly from the Missouri district of highly radiogenic lead. Meanwhile, there has been a decrease in total lead imports. These combined effects result in changes in isotope ratios, from the less to more radiogenic, of the pooled lead. (aothor)

  9. Influence of chemical structure on carbon isotope composition of lignite

    Science.gov (United States)

    Erdenetsogt, Bat-Orshikh; Lee, Insung; Ko, Yoon-Joo; Mungunchimeg, Batsaikhan

    2017-04-01

    During the last two decades, a number of studies on carbon isotopes in terrestrial organic matter (OM) have been carried out and used to determine changes in paleoatmospheric δ13C value as well as assisting in paleoclimate analysis. Coal is abundant terrestrial OM. However, application of its δ13C value is very limited, because the understanding of changes in isotopic composition during coalification is relatively insufficient. The purpose of this study was to examine the influence of the chemical structure on the carbon isotope composition of lignite. Generally, lignite has more complex chemical structures than other higher rank coal because of the existence of various types of oxygen-containing functional groups that are eliminated at higher rank level. A total of sixteen Lower Cretaceous lignite samples from Baganuur mine (Mongolia) were studied by ultimate, stable carbon isotope and solid-state 13C CP/MAS NMR analyses. The carbon contents of the samples increase with increase in depth, whereas oxygen content decreases continuously. This is undoubtedly due to normal coalification process and also consistent with solid state NMR results. The δ13C values of the samples range from -23.54‰ to -21.34‰ and are enriched in 13C towards the lowermost samples. Based on the deconvolution of the NMR spectra, the ratios between carbons bonded to oxygen (60-90 ppm and 135-220 ppm) over carbons bonded to carbon and hydrogen (0-50 ppm and 90-135 ppm) were calculated for the samples. These correlate well with δ13C values (R2 0.88). The results indicate that the δ13C values of lignite are controlled by two mechanisms: (i) depletion in 13C as a result of loss of isotopically heavy oxygen-bounded carbons and (ii) enrichment in 13C caused by a loss of isotopically light methane from aliphatic and aromatic carbons. At the rank of lignite, coal is enriched in 13C because the amount of isotopically heavy CO2 and CO, released from coal as a result of changes in the chemical

  10. Could a secular increase in organic burial explain the rise of oxygen? Insights from a geological carbon cycle model constrained by the carbon isotope record

    Science.gov (United States)

    Krissansen-Totton, J.; Kipp, M.; Catling, D. C.

    2017-12-01

    The stable isotopes of carbon in marine sedimentary rock provide a window into the evolution of the Earth system. Conventionally, a relatively constant carbon isotope ratio in marine sedimentary rocks has been interpreted as implying constant organic carbon burial relative to total carbon burial. Because organic carbon burial corresponds to net oxygen production from photosynthesis, it follows that secular changes in the oxygen source flux cannot explain the dramatic rise of oxygen over Earth history. Instead, secular declines in oxygen sink fluxes are often invoked as causes for the rise of oxygen. However, constant fractional organic burial is difficult to reconcile with tentative evidence for low phosphate concentrations in the Archean ocean, which would imply lower marine productivity and—all else being equal—less organic carbon burial than today. The conventional interpretation of the carbon isotope record rests on the untested assumption that the isotopic ratio of carbon inputs into the ocean reflect mantle isotopic values throughout Earth history. In practice, differing rates of carbonate and organic weathering will allow for changes in isotopic inputs, as suggested by [1] and [2]. However, these inputs can not vary freely because large changes in isotopic inputs would induce secular trends in carbon reservoirs, which are not observed in the isotope record. We apply a geological carbon cycle model to all Earth history, tracking carbon isotopes in crustal, mantle, and ocean reservoirs. Our model is constrained by the carbon isotope record such that we can determine the extent to which large changes in organic burial are permitted. We find both constant organic burial and 3-5 fold increases in organic burial since 4.0 Ga can be reconciled with the carbon isotope record. Changes in the oxygen source flux thus need to be reconsidered as a possible contributor to Earth's oxygenation. [1] L. A. Derry, Organic carbon cycling and the lithosphere, in Treatise on

  11. Morphology, molecular structure, and stable carbon isotopic composition of black carbon (BC) in urban topsoils.

    Science.gov (United States)

    Zong, Yutong; Xiao, Qing; Lu, Shenggao

    2018-02-01

    Urban soils contain significant amounts of black carbon (BC) from biomass and fossil fuel combustion and regard to be a pool of BC. BC in urban soils has multiple effects on environmental processes in urban system, such as global climate change, air quality, and public health. Urban topsoil samples (0-10 cm) were collected from Anshan, Liaoning Province, northeast China, which is one of the most important old steel industrial bases in China. The BC in urban topsoils was extracted using the density method. Their chemical composition, morphology, molecular structure, and stable carbon isotopic composition were examined using elemental analysis, scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and stable carbon isotope (δ 13 C). Elemental analysis shows that carbon content in the BC of studied soils ranged from 64.5 to 78.4%, with the average more than 70%. The O/C atomic ratio of BC is on average 0.18. The BC particle displays different morphology, including porous spherical, irregular porous fragmentary, and blocky shapes. The porous spherical BC particles has atomic molar O/C ratio determined by SEM-EDS ranging from 0.04 to 0.37. XRD indicates that BC exists in mainly combining with mineral phases hematite (Fe 2 O 3 ), kaolinite (Al 2 Si 2 O 5 (OH) 4 ), quartz (SiO 2 ), and calcite (CaCO 3 ). The FTIR spectra of BC particles show major bands at approximately 3400 cm -1 (O-H), 2920 cm -1 (C = H), 1600 cm -1 (C = C), 1230 cm -1 (C = O), and 1070 cm -1 (C = O). The stable carbon isotope (δ 13 C) of BC ranges from -24.48 to -23.18‰ with the average of -23.79 ± 0.39‰. The concentration of BC in the industrial area is significantly (p fuel combustion. Results indicated that a combination of atomic O/C ratio, porous structure, and stable carbon isotopic (δ 13 C) of BC could reflect effectively the origin of BC

  12. Simulation of carbon isotope discrimination of the terrestrial biosphere

    Science.gov (United States)

    Suits, N. S.; Denning, A. S.; Berry, J. A.; Still, C. J.; Kaduk, J.; Miller, J. B.; Baker, I. T.

    2005-03-01

    We introduce a multistage model of carbon isotope discrimination during C3 photosynthesis and global maps of C3/C4 plant ratios to an ecophysiological model of the terrestrial biosphere (SiB2) in order to predict the carbon isotope ratios of terrestrial plant carbon globally at a 1° resolution. The model is driven by observed meteorology from the European Centre for Medium-Range Weather Forecasts (ECMWF), constrained by satellite-derived Normalized Difference Vegetation Index (NDVI) and run for the years 1983-1993. Modeled mean annual C3 discrimination during this period is 19.2‰; total mean annual discrimination by the terrestrial biosphere (C3 and C4 plants) is 15.9‰. We test simulation results in three ways. First, we compare the modeled response of C3 discrimination to changes in physiological stress, including daily variations in vapor pressure deficit (vpd) and monthly variations in precipitation, to observed changes in discrimination inferred from Keeling plot intercepts. Second, we compare mean δ13C ratios from selected biomes (Broadleaf, Temperate Broadleaf, Temperate Conifer, and Boreal) to the observed values from Keeling plots at these biomes. Third, we compare simulated zonal δ13C ratios in the Northern Hemisphere (20°N to 60°N) to values predicted from high-frequency variations in measured atmospheric CO2 and δ13C from terrestrially dominated sites within the NOAA-Globalview flask network. The modeled response to changes in vapor pressure deficit compares favorably to observations. Simulated discrimination in tropical forests of the Amazon basin is less sensitive to changes in monthly precipitation than is suggested by some observations. Mean model δ13C ratios for Broadleaf, Temperate Broadleaf, Temperate Conifer, and Boreal biomes compare well with the few measurements available; however, there is more variability in observations than in the simulation, and modeled δ13C values for tropical forests are heavy relative to observations

  13. The Strontium Isotope Record of Zavkhan Terrane Carbonates: Strontium Isotope Stability Through the Ediacaran-Cambrian Transition

    OpenAIRE

    Petach, Tanya N.

    2015-01-01

    First order trends in the strontium isotopic (87Sr/86Sr) composition of seawater are controlled by radiogenic inputs from the continent and non-radiogenic inputs from exchange at mid-ocean ridges. Carbonates precipitated in seawater preserve trace amounts of strontium that record this isotope ratio and therefore record the relative importance of mid-ocean ridge and weathering chemical inputs to sea water composition. It has been proposed that environmental changes during the Ediacaran-Cambria...

  14. Measurement of the 13C/12C ratio of soil-plant individual sugars by gas chromatography/combustion/isotope-ratio mass spectrometry of silylated derivatives.

    Science.gov (United States)

    Derrien, Delphine; Balesdent, Jérôme; Marol, Christine; Santaella, Catherine

    2003-01-01

    Carbohydrate is an important pool in the terrestrial carbon cycle. The potential offered by natural and artificial 13C-labelling techniques should therefore be applied to the investigation of the dynamics of individual sugars in soils. For this reason, we evaluated the method of 13C sugar analysis by gas chromatography/combustion/isotope-ratio mass spectrometry (GC/C/IRMS) after hydrolysis and direct trimethylsilylation. Trimethylsilylation involved the addition of several carbon atoms per sugar. These atoms have to be taken into account in the estimation of the carbon isotope ratio. The analysis of standard and natural pentoses and hexoses of known 13C enrichments revealed that the number of analysed added carbon atoms was less than expected from stoichiometry. This was attributed to incomplete derivatization and/or incomplete oxidation of methylsilyl carbon before IRMS. Using a calibration of the number of analysed added carbon atoms, the isotope excess of enriched samples could be determined with a relative error close to 5%. Concerning the determination of natural abundances by GC/C/IRMS, we could measure the delta 13C of standard C3- and C4-derived sugars with an accuracy of +/-1.5 per thousand using the previous calibration. We were able to apply this technique to plant-soil systems labelled by pulse-chase of 13CO2, revealing the nature and dynamics of sugars in the plant rhizosphere. Copyright 2003 John Wiley & Sons, Ltd.

  15. Magnesium isotope fractionation in bacterial mediated carbonate precipitation experiments

    Science.gov (United States)

    Parkinson, I. J.; Pearce, C. R.; Polacskek, T.; Cockell, C.; Hammond, S. J.

    2012-12-01

    Magnesium is an essential component of life, with pivotal roles in the generation of cellular energy as well as in plant chlorophyll [1]. The bio-geochemical cycling of Mg is associated with mass dependant fractionation (MDF) of the three stable Mg isotopes [1]. The largest MDF of Mg isotopes has been recorded in carbonates, with foraminiferal tests having δ26Mg compositions up to 5 ‰ lighter than modern seawater [2]. Magnesium isotopes may also be fractionated during bacterially mediated carbonate precipitation and such carbonates are known to have formed in both modern and ancient Earth surface environments [3, 4], with cyanobacteria having a dominant role in carbonate formation during the Archean. In this study, we aim to better constrain the extent to which Mg isotope fractionation occurs during cellular processes, and to identify when, and how, this signal is transferred to carbonates. To this end we have undertaken biologically-mediated carbonate precipitation experiments that were performed in artificial seawater, but with the molar Mg/Ca ratio set to 0.6 and with the solution spiked with 0.4% yeast extract. The bacterial strain used was marine isolate Halomonas sp. (gram-negative). Experiments were run in the dark at 21 degree C for two to three months and produced carbonate spheres of various sizes up to 300 μm in diameter, but with the majority have diameters of ~100 μm. Control experiments run in sterile controls (`empty` medium without bacteria) yielded no precipitates, indicating a bacterial control on the precipitation. The carbonate spheres are produced are amenable to SEM, EMP and Mg isotopic analysis by MC-ICP-MS. Our new data will shed light on tracing bacterial signals in carbonates from the geological record. [1] Young & Galy (2004). Rev. Min. Geochem. 55, p197-230. [2] Pogge von Strandmann (2008). Geochem. Geophys. Geosys. 9 DOI:10.1029/2008GC002209. [3] Castanier, et al. (1999). Sed. Geol. 126, 9-23. [4] Cacchio, et al. (2003

  16. Isotopic Hg in an Allende carbon-rich residue

    Science.gov (United States)

    Reed, G. W., Jr.; Jovanovic, S.

    1990-01-01

    A carbon-rich residue from Allende subjected to stepwise heating yielded two isotopically resolvable types of Hg: one with an (Hg-196)/(Hg-202) concentration ratio the same as terrestrial (monitor) Hg; the other enriched in Hg-196 relative to Hg-202 by about 60 percent. Hg with the 202 isotope enriched relative to 196, as is found in bulk Allende, was not observed. Whether the result of mass fractionation or nucleosynthesis, the distinct types of Hg entered different carrier phases and were not thermally mobilized since the accretion of the Allende parent body.

  17. Biosynthetic effects on the stable carbon isotopic compositions of agal lipids: Implications for deciphering the carbon isotopic biomarker record

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Schouten, S.; Klein Breteler, W.C.M.; Blokker, P.; Schogt, N.; Rijpstra, W.I.C.; Grice, K.; Baas, M.

    1998-01-01

    Thirteen species of algae covering an extensive range of classes were cultured and stable carbon isotopic compositions of their lipids were analysed in order to assess carbon isotopic fractionation effects during their biosynthesis. The fatty acids were found to have similar stable carbon isotopic

  18. Stable Carbon Isotope Ratio (δ13C Measurement of Graphite Using EA-IRMS System

    Directory of Open Access Journals (Sweden)

    Andrius Garbaras

    2015-06-01

    Full Text Available δ13C values in non-irradiated natural graphite were measured. The measurements were carried out using an elemental analyzer combined with stable isotope ratio mass spectrometer (EA-IRMS. The samples were prepared with ground and non-ground graphite, the part of which was mixed with Mg (ClO42. The best combustion of graphite in the oxidation furnace of the elemental analyzer was achieved when the amount of pulverized graphite ranged from 200 to 490 µg and the mass ratio C:Mg(ClO42 was approximately 1:10. The method for the graphite burning avoiding the isotope fractionation is proposed.DOI: http://dx.doi.org/10.5755/j01.ms.21.2.6873

  19. Simultaneous determination of stable carbon, oxygen, and hydrogen isotopes in cellulose.

    Science.gov (United States)

    Loader, N J; Street-Perrott, F A; Daley, T J; Hughes, P D M; Kimak, A; Levanič, T; Mallon, G; Mauquoy, D; Robertson, I; Roland, T P; van Bellen, S; Ziehmer, M M; Leuenberger, M

    2015-01-06

    A technological development is described through which the stable carbon-, oxygen-, and nonexchangeable hydrogen-isotopic ratios (δ(13)C, δ(18)O, δ(2)H) are determined on a single carbohydrate (cellulose) sample with precision equivalent to conventional techniques (δ(13)C 0.15‰, δ(18)O 0.30‰, δ(2)H 3.0‰). This triple-isotope approach offers significant new research opportunities, most notably in physiology and medicine, isotope biogeochemistry, forensic science, and palaeoclimatology, when isotopic analysis of a common sample is desirable or when sample material is limited.

  20. Carbon Isotope Chemostratigraphy, the Baby and the Bathwater

    Science.gov (United States)

    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

  1. Preliminary results of oxygen isotope ratio measurement with a particle-gamma coincidence method

    Energy Technology Data Exchange (ETDEWEB)

    Borysiuk, Maciek, E-mail: maciek.borysiuk@pixe.lth.se; Kristiansson, Per; Ros, Linus; Abdel, Nassem S.; Elfman, Mikael; Nilsson, Charlotta; Pallon, Jan

    2015-04-01

    The possibility to study variations in the oxygen isotopic ratio with photon tagged nuclear reaction analysis (pNRA) is evaluated in the current work. The experiment described in the article was performed at Lund Ion Beam Analysis Facility (LIBAF) with a 2 MeV deuteron beam. Isotopic fractionation of light elements such as carbon, oxygen and nitrogen is the basis of many analytical tools in hydrology, geology, paleobiology and paleogeology. IBA methods provide one possible tool for measurement of isotopic content. During this experimental run we focused on measurement of the oxygen isotopic ratio. The measurement of stable isotopes of oxygen has a number of applications; the particular one driving the current investigation belongs to the field of astrogeology and specifically evaluation of fossil extraterrestrial material. There are three stable isotopes of oxygen: {sup 16}O, {sup 17}O and {sup 18}O. We procured samples highly enriched with all three isotopes. Isotopes {sup 16}O and {sup 18}O were easily detected in the enriched samples, but no significant signal from {sup 17}O was detected in the same samples. The measured yield was too low to detect {sup 18}O in a sample with natural abundances of oxygen isotopes, at least in the current experimental setup, but the spectral line from the reaction with {sup 16}O was clearly visible.

  2. Measurements of stable isotope ratios in milk samples from a farm placed in the mountains of Transylvania

    Energy Technology Data Exchange (ETDEWEB)

    Magdas, D. A., E-mail: gabriela.cristea@itim-cj.ro; Cristea, G., E-mail: gabriela.cristea@itim-cj.ro; Bot, A.; Puscas, R.; Radu, S.; Mirel, V. [National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath Str., 400293 Cluj-Napoca (Romania); Cordea, D. V.; Mihaiu, M. [University of Agricultural Science and Veterinary Medicine, 3-5 Calea Manastur, 400372 Cluj-Napoca (Romania)

    2013-11-13

    Product origin is of great importance for consumers especially because its association in consumer's perception with food quality, freedom from disease or pollution. Stable isotope ratio analysis is a powerful technique in food authenticity and traceability control which has been introduced within the European wine industry to ensure authenticity of wine provenance and to detect adulteration. Isotopic ratios measurements have also been successfully to other food commodities like: fruit juices, honey and dairy foods. The δ{sup 18}O and δ{sup 2}H content in milk water reflects the isotope composition of the ground water drunk by animals. Seasonal effects are also very important: in summer, milk water contains higher δ{sup 18}O and δ{sup 2}H values due to the fresh plants that are ate by animals. Relative carbon stable isotope abundances in total milk reflect the isotopic composition of the diet fed to the dairy cows. In this study the hydrogen, oxygen and carbon isotopic composition of 15 milk samples coming from a unit placed in the mountains of Transylvania was investigated. The distribution of the obtained isotopic values was than discussed taking into account that all the animals were feed with the same type of forage and consumed water was taken from the same source.

  3. Measurements of stable isotope ratios in milk samples from a farm placed in the mountains of Transylvania

    International Nuclear Information System (INIS)

    Magdas, D. A.; Cristea, G.; Bot, A.; Puscas, R.; Radu, S.; Mirel, V.; Cordea, D. V.; Mihaiu, M.

    2013-01-01

    Product origin is of great importance for consumers especially because its association in consumer's perception with food quality, freedom from disease or pollution. Stable isotope ratio analysis is a powerful technique in food authenticity and traceability control which has been introduced within the European wine industry to ensure authenticity of wine provenance and to detect adulteration. Isotopic ratios measurements have also been successfully to other food commodities like: fruit juices, honey and dairy foods. The δ 18 O and δ 2 H content in milk water reflects the isotope composition of the ground water drunk by animals. Seasonal effects are also very important: in summer, milk water contains higher δ 18 O and δ 2 H values due to the fresh plants that are ate by animals. Relative carbon stable isotope abundances in total milk reflect the isotopic composition of the diet fed to the dairy cows. In this study the hydrogen, oxygen and carbon isotopic composition of 15 milk samples coming from a unit placed in the mountains of Transylvania was investigated. The distribution of the obtained isotopic values was than discussed taking into account that all the animals were feed with the same type of forage and consumed water was taken from the same source

  4. Diagenetic fractionation of carbon isotopes in particulate and dissolved organic matter in sediments from Skan Bay, Alaska

    International Nuclear Information System (INIS)

    Alperin, M.J.; Reeburgh, W.S.

    1991-01-01

    Isotope fractionation during organic matter diagenesis was investigated by measuring detailed depth distributions of stable carbon isotope ratios in sediment particulate organic carbon (POC) and dissolved organic carbon (DOC) reservoirs. The δ 13 C value of the POC shifted systematically from -19 per-thousand at the surface to -21 per-thousand at 10 cm. Significant trends were also apparent in the δ 13 C-DOC profile. Proceeding down-core, DOC became isotopically heavier between 0 and 5 cm and isotopically lighter at greater depths. Two mechanisms could account for the observed down-core shift in δ 13 C-POC: (a) temporal changes in the isotope ratios of deposited organic matter and (b) isotope fractionation associated with diagenesis. The δ 15 C-DOC depth distribution is sensitive to which mechanism controls the isotopic composition of the POC reservoir. A diagenetic model that couples POC and DOC reservoirs was used to discriminate between temporal changes and diagenetic alteration of the POC isotopic composition. The model indicated that observed trends in δ 13 C-POC and δ 13 C-DOC depth distributions are consistent with isotopic fractionation of POC during diagenesis

  5. Finite mixture models for the computation of isotope ratios in mixed isotopic samples

    Science.gov (United States)

    Koffler, Daniel; Laaha, Gregor; Leisch, Friedrich; Kappel, Stefanie; Prohaska, Thomas

    2013-04-01

    Finite mixture models have been used for more than 100 years, but have seen a real boost in popularity over the last two decades due to the tremendous increase in available computing power. The areas of application of mixture models range from biology and medicine to physics, economics and marketing. These models can be applied to data where observations originate from various groups and where group affiliations are not known, as is the case for multiple isotope ratios present in mixed isotopic samples. Recently, the potential of finite mixture models for the computation of 235U/238U isotope ratios from transient signals measured in individual (sub-)µm-sized particles by laser ablation - multi-collector - inductively coupled plasma mass spectrometry (LA-MC-ICPMS) was demonstrated by Kappel et al. [1]. The particles, which were deposited on the same substrate, were certified with respect to their isotopic compositions. Here, we focus on the statistical model and its application to isotope data in ecogeochemistry. Commonly applied evaluation approaches for mixed isotopic samples are time-consuming and are dependent on the judgement of the analyst. Thus, isotopic compositions may be overlooked due to the presence of more dominant constituents. Evaluation using finite mixture models can be accomplished unsupervised and automatically. The models try to fit several linear models (regression lines) to subgroups of data taking the respective slope as estimation for the isotope ratio. The finite mixture models are parameterised by: • The number of different ratios. • Number of points belonging to each ratio-group. • The ratios (i.e. slopes) of each group. Fitting of the parameters is done by maximising the log-likelihood function using an iterative expectation-maximisation (EM) algorithm. In each iteration step, groups of size smaller than a control parameter are dropped; thereby the number of different ratios is determined. The analyst only influences some control

  6. Worldwide lead-isotope ratio in bivalves and sediments

    DEFF Research Database (Denmark)

    Larsen, Martin Mørk; Jacobsen, Gitte; Strand, Jakob

    The lead-isotope ratio have been used to assess and identify impact of leaded gasoline, coal combustion and  mineral activities[ref 1] due to the difference in 206Pb (~52%), 207Pb (~24%) and 208Pb (~23%) isotope ratios. The source of these differences is the decaying of the parent isotopes of 238U...

  7. Influence of diet on the distribution of carbon isotopes in animals

    International Nuclear Information System (INIS)

    DeNiro, M.J.; Epstein, S.

    1978-01-01

    The influence of diet on the distribution of carbon isotopes in animals was investigated by analyzing animals grown in the laboratory on diets of constant carbon isotopic composition. The isotopic composition of the whole body of an animal reflects the isotopic composition of its diet, but the animal is on average enriched in delta 13 C by about 1 part per thousand relative to the diet. In three of the four cases examined the 13 C enrichment of the whole body relative to the diet is balanced by a 13 C depletion of the respired CO 2 . The isotopic relationships between the whole bodies of animals and their diets are similar for different species raised on the same diet and for the same species raised on different diets. However, the delta 13 C values of whole bodies of individuals of a species raised on the same diet may differ by up to 2 parts per thousand. The relationship between the 13 C/ 12 C ratio of a tissue and the 13 C/ 12 C ratio of the diet depends both on the type of tissue and on the nature of the diet. Many of the isotopic relationships among the major biochemical fractions, namely the lipid, carbohydrate and protein fractions, are qualitatively preserved as diet carbon is incorporated into the animal. However, the difference between the delta 13 C values of a biochemical fraction in an animal and in its diet may be as large as 3 parts per thousand. The delta 13 C values of the biochemical components collagen chitin and the insoluble organic fraction of shells, all of which are often preserved in fossil material, are related to the isotopic composition of the diet. (author)

  8. Precise and accurate isotope ratio measurements by ICP-MS.

    Science.gov (United States)

    Becker, J S; Dietze, H J

    2000-09-01

    The precise and accurate determination of isotope ratios by inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) is important for quite different application fields (e.g. for isotope ratio measurements of stable isotopes in nature, especially for the investigation of isotope variation in nature or age dating, for determining isotope ratios of radiogenic elements in the nuclear industry, quality assurance of fuel material, for reprocessing plants, nuclear material accounting and radioactive waste control, for tracer experiments using stable isotopes or long-lived radionuclides in biological or medical studies). Thermal ionization mass spectrometry (TIMS), which used to be the dominant analytical technique for precise isotope ratio measurements, is being increasingly replaced for isotope ratio measurements by ICP-MS due to its excellent sensitivity, precision and good accuracy. Instrumental progress in ICP-MS was achieved by the introduction of the collision cell interface in order to dissociate many disturbing argon-based molecular ions, thermalize the ions and neutralize the disturbing argon ions of plasma gas (Ar+). The application of the collision cell in ICP-QMS results in a higher ion transmission, improved sensitivity and better precision of isotope ratio measurements compared to quadrupole ICP-MS without the collision cell [e.g., for 235U/238U approximately 1 (10 microg x L(-1) uranium) 0.07% relative standard deviation (RSD) vs. 0.2% RSD in short-term measurements (n = 5)]. A significant instrumental improvement for ICP-MS is the multicollector device (MC-ICP-MS) in order to obtain a better precision of isotope ratio measurements (with a precision of up to 0.002%, RSD). CE- and HPLC-ICP-MS are used for the separation of isobaric interferences of long-lived radionuclides and stable isotopes by determination of spallation nuclide abundances in an irradiated tantalum target.

  9. Isotopic composition of carbon in dacitic gases from Usu volcano (Japan). Relationship between the 13C/12C ratio of volatiles and the 87Sr/86Sr ratio of silicates in arc volcanism

    International Nuclear Information System (INIS)

    Allard, Patrick

    1981-01-01

    CO 2 emitted at 568 deg C by the new dacitic intrusion in Usu volcano (Japan) has a 13 C/ 12 C ratio of -4.4 per mill vs PDB. Such a value, together with previous isotopic data from other volcanoes in Japan, Indonesia, Central America, Lesser Antilles and New Zealand, enhance that the carbon released by magmas in subduction zones is systematically 13 C-enriched with respect to the primary carbon from rift areas. Such a 13 C enrichment in volatiles is explained in terms of crustal contamination by sedimentary carbon, and can be sowewhat related to a simultaneous increase of 87 Sr in the magma [fr

  10. Water relations link carbon and oxygen isotope discrimination to phloem sap sugar concentration in eucalyptus globulus

    International Nuclear Information System (INIS)

    Cernusak, L.A.; Farquhar, G.D.; Arthur, D.J; Pate, J.S.

    2002-01-01

    Full text: The carbon isotope ratio of phloem sap sugars has been previously observed to correlate strongly with the phloem sap sugar concentration in Eucalyptus globulus. We hypothesized that the correspondence between these two parameters results from co-linearity in their responses to variation in plant water potential. Carbon isotope discrimination is expected to decrease with decreasing plant water potential due to the influence of stomatal conductance on the ratio of intercellular to ambient CO 2 , concentrations (c 1 /c a ). Conversely, we expected the phloem sap sugar concentration to increase with decreasing plant water potential, thereby maintaining positive turgor pressure within the sieve tubes. The study comprised 40 individual Eucalyptus globulus trees growing in three plantations situated on opposing ends of a rainfall gradient in southwestern Australia. A strong correlation was observed between the carbon isotope ratio in phloem sap sugars and phloem sap sugar concentration. Carbon isotope discrimination correlated positively with shoot water potential, whereas phloem sap sugar concentration correlated negatively with shoot water potential. The relationship between carbon isotope discrimination measured in phloem sap sugars collected from the stem and c 1 /c a measured instantaneously on subtending leaves was close to that theoretically predicted. Accordingly, a strong, negative relationship was observed between instantaneous c 1 /c a and the phloem sap sugar concentration. Oxygen isotope discrimination in phloem sap sugars also correlated strongly with phloem sap sugar concentration. A theoretical model suggested that the observed variation in stomatal conductance was sufficient to account for the variation observed in oxygen isotope discrimination across the study. Results strongly support the contention that water relations form a mechanistic link between phloem sap sugar concentration and both instantaneous and integrated measures of the

  11. Isotopic Hg in an Allende carbon-rich residue

    International Nuclear Information System (INIS)

    Reed, G.W. Jr.; Jovanovic, S.

    1990-01-01

    A carbon-rich residue from Allende subjected to stepwise heating yielded two isotopically resolvable types of Hg: one with an (Hg-196)/(Hg-202) concentration ratio the same as terrestrial (monitor) Hg; the other enriched in Hg-196 relative to Hg-202 by about 60 percent. Hg with the 202 isotope enriched relative to 196, as is found in bulk Allende, was not observed. Whether the result of mass fractionation or nucleosynthesis, the distinct types of Hg entered different carrier phases and were not thermally mobilized since the accretion of the Allende parent body. 9 refs

  12. Carbon isotopic composition in components of a mangrove ecosystem in the Sepetiba Bay, Rio de Janeiro, Brazil

    International Nuclear Information System (INIS)

    Lacerda, L.D. de; Rezende, C.E. de; Ovalle, A.R.C.; Aragon, G.T.; Cunha, C.T. da; Ramos e Souza, C.A.; Martinelli, L.A.; Victoria, R.L.; Mozeto, A.A.; Nogueira, F.

    1986-01-01

    The carbon isotopic ratios ( 13 C/ 12 C) for various components of a mangrove ecosystem in the Sepetiba Bay, RJ, in order to evaluate the possibility of its use a tracer for organic matter in these environments are presented. The results showed consistent differences of ( 13 C/ 12 C) isotopic ratio between the organic matter from mangrove (+-26%0, PDB) and the one from marine origin (+-20%0, PDB). These results suggest that this ratio can be used as tracer of organic carbon in the studied environment. (Author) [pt

  13. Combined Stable Carbon Isotope and C/N Ratios as Indicators of Source and Fate of Organic Matter in the Bang Pa kong River Estuary, Thailand

    International Nuclear Information System (INIS)

    Boonphakdee, Thanomsak; Kasai, Akihide; Fujiwara, Tateki; Sawangwong, Pichan; Cheevaporn, Voravit

    2007-08-01

    Full text: Stable carbon isotopes and C/N ratios of particulate organic matter (POM) in suspended solids and surficial sediment were used to define the spatial and temporal variability in an anthropogenic tropical river estuary, the Bang Pa kong River Estuary. Samples were taken along salinity gradients during the four different river discharges in the beginning, high river discharge and at the end of the wet season, and low river discharge during the dry season. The values of [C/N]a ratio and d13C in the river estuary revealed significant differences from those of the offshore station. Conservative behaviors of [C/N]a and d13C in the estuary during the wet season indicated major contribution of terrigenous C3 plants derived OM. By contrast, during the dry season, marine input mainly dominated OM contribution with an evidence of anthropogenic input to the estuary. These compositions of the bulk sedimentary OM were dominated by paddy rice soils and marine derived OM during the wet and dry seasons, respectively. These results show that the combined stable carbon isotopes and C/N ratios can be used to identify the source and fate of OM even in a river estuary. This tool will be useful to achieve sustainable management in coastal zone

  14. Variations in the stable isotope ratios of specific aromatic and aliphatic hydrocarbons from coal conversion processes

    Energy Technology Data Exchange (ETDEWEB)

    McRae, C.; Snape, C.E.; Fallick, A.E. [University of Strathclyde, Glasgow (United Kingdom). Dept. of Pure and Applied Chemistry

    1998-07-01

    To establish the scope for applying gas chromatography-isotope ratio mass spectrometry ({sup {delta}-13}C GC-IRMS) to molecular recognition problems in coal utilisation, {sup 13}C/{sup 12}C isotope ratios were determined for n-alkanes and polycyclic aromatic hydrocarbons (PAHs) as a function of coal rank and process conditions. Six coals ranging from a lignite to a low volatile bituminous coal were subjected to chloroform extraction, fixed-bed pyrolysis under hydrogen pressure (hydropyrolysis) and fluidised-bed (flash) pyrolysis. No significant variations in the stable isotope ratios of n-alkanes were evident as a function of either rank or conversion regime. In contrast, the isotope ratios of PAHs show large variations with those for hydropyrolysis (-23 to -25 parts per thousand) being similar to the bulk values of the initial coals and being isotopically heavier (less negative) than their fluidised-bed pyrolysis counterparts by 2-3 parts per thousand. However, the PAHs from fluidised-bed pyrolysis, which resemble closely those obtained from high temperature coal carbonization, are still heavier (by 2-3 parts per thousand) than those from diesel particulates and coal gasification and combustion residues. This provides a firm basis for the source apportionment of airborne PAHs in the proximity of coking plants, particularly with no major variations in the PAH isotope ratios being found as a function of rank.

  15. Carbon Isotope Measurements of Experimentally-Derived Hydrothermal Mineral-Catalyzed Organic Products by Pyrolysis-Isotope Ratio Mass Spectrometry

    Science.gov (United States)

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

    2011-01-01

    We report results of experiments to measure the C isotope composition of mineral catalyzed organic compounds derived from high temperature and high pressure synthesis. These experiments make use of an innovative pyrolysis technique designed to extract and measure C isotopes. To date, our experiments have focused on the pyrolysis and C isotope ratio measurements of low-molecular weight intermediary hydrocarbons (organic acids and alcohols) and serve as a proof of concept for making C and H isotope measurements on more complicated mixtures of solid-phase hydrocarbons and intermediary products produced during high temperature and high pressure synthesis on mineral-catalyzed surfaces. The impetus for this work stems from recently reported observations of methane detected within the Martian atmosphere [1-4], coupled with evidence showing extensive water-rock interaction during Martian history [5-7]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization reactions [8,9]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [10-12]. Further, recent experiments by Fu et al. [13] focus on examining detailed C isotope measurements of hydrocarbons produced by surface-catalyzed mineral reactions. Work described in this paper details the experimental techniques used to measure intermediary organic reaction products (alcohols and organic acids).

  16. Chlorine isotope effects from isotope ratio mass spectrometry suggest intramolecular C-Cl bond competition in trichloroethene (TCE) reductive dehalogenation.

    Science.gov (United States)

    Cretnik, Stefan; Bernstein, Anat; Shouakar-Stash, Orfan; Löffler, Frank; Elsner, Martin

    2014-05-20

    Chlorinated ethenes are prevalent groundwater contaminants. To better constrain (bio)chemical reaction mechanisms of reductive dechlorination, the position-specificity of reductive trichloroethene (TCE) dehalogenation was investigated. Selective biotransformation reactions (i) of tetrachloroethene (PCE) to TCE in cultures of Desulfitobacterium sp. strain Viet1; and (ii) of TCE to cis-1,2-dichloroethene (cis-DCE) in cultures of Geobacter lovleyi strain SZ were investigated. Compound-average carbon isotope effects were -19.0‰ ± 0.9‰ (PCE) and -12.2‰ ± 1.0‰ (TCE) (95% confidence intervals). Using instrumental advances in chlorine isotope analysis by continuous flow isotope ratio mass spectrometry, compound-average chorine isotope effects were measured for PCE (-5.0‰ ± 0.1‰) and TCE (-3.6‰ ± 0.2‰). In addition, position-specific kinetic chlorine isotope effects were determined from fits of reactant and product isotope ratios. In PCE biodegradation, primary chlorine isotope effects were substantially larger (by -16.3‰ ± 1.4‰ (standard error)) than secondary. In TCE biodegradation, in contrast, the product cis-DCE reflected an average isotope effect of -2.4‰ ± 0.3‰ and the product chloride an isotope effect of -6.5‰ ± 2.5‰, in the original positions of TCE from which the products were formed (95% confidence intervals). A greater difference would be expected for a position-specific reaction (chloride would exclusively reflect a primary isotope effect). These results therefore suggest that both vicinal chlorine substituents of TCE were reactive (intramolecular competition). This finding puts new constraints on mechanistic scenarios and favours either nucleophilic addition by Co(I) or single electron transfer as reductive dehalogenation mechanisms.

  17. Applications of Isotope Ratio Mass Spectrometry in Sports Drug Testing Accounting for Isotope Fractionation in Analysis of Biological Samples.

    Science.gov (United States)

    Piper, Thomas; Thevis, Mario

    2017-01-01

    The misuse of anabolic-androgenic steroids (AAS) in sports aiming at enhancing athletic performance has been a challenging matter for doping control laboratories for decades. While the presence of a xenobiotic AAS or its metabolite(s) in human urine immediately represents an antidoping rule violation, the detection of the misuse of endogenous steroids such as testosterone necessitates comparably complex procedures. Concentration thresholds and diagnostic analyte ratios computed from urinary steroid concentrations of, e.g., testosterone and epitestosterone have aided identifying suspicious doping control samples in the past. These ratios can however also be affected by confounding factors and are therefore not sufficient to prove illicit steroid administrations. Here, carbon and, in rare cases, hydrogen isotope ratio mass spectrometry (IRMS) has become an indispensable tool. Importantly, the isotopic signatures of pharmaceutical steroid preparations commonly differ slightly but significantly from those found with endogenously produced steroids. By comparing the isotope ratios of endogenous reference compounds like pregnanediol to that of testosterone and its metabolites, the unambiguous identification of the urinary steroids' origin is accomplished. Due to the complex urinary matrix, several steps in sample preparation are inevitable as pure analyte peaks are a prerequisite for valid IRMS determinations. The sample cleanup encompasses steps such as solid phase or liquid-liquid extraction that are presumably not accompanied by isotopic fractionation processes, as well as more critical steps like enzymatic hydrolysis, high-performance liquid chromatography fractionation, and derivatization of analytes. In order to exclude any bias of the analytical results, each step of the analytical procedure is optimized and validated to exclude, or at least result in constant, isotopic fractionation. These efforts are explained in detail. © 2017 Elsevier Inc. All rights reserved.

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

    Science.gov (United States)

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

    2016-08-04

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

  19. Boron isotope fractionation in magma via crustal carbonate dissolution

    Science.gov (United States)

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

    2016-08-01

    Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ11B values down to -41.5‰, reflecting preferential partitioning of 10B into the assimilating melt. Loss of 11B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports 11B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ11B melt values in arc magmas could flag shallow-level additions to the subduction cycle.

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

    Science.gov (United States)

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

    2016-01-01

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

  1. Forensic analysis of explosives using isotope ratio mass spectrometry (IRMS)--preliminary study on TATP and PETN.

    Science.gov (United States)

    Benson, Sarah J; Lennard, Christopher J; Maynard, Philip; Hill, David M; Andrew, Anita S; Roux, Claude

    2009-06-01

    The application of isotopic techniques to investigations requiring the provision of evidence to a Court is limited. The objective of this research was to investigate the application of light stable isotopes and isotope ratio mass spectrometry (IRMS) to solve complex forensic cases by providing a level of discrimination not achievable utilising traditional forensic techniques. Due to the current threat of organic peroxide explosives, such as triacetone triperoxide (TATP), research was undertaken to determine the potential of IRMS to differentiate samples of TATP that had been manufactured utilising different starting materials and/or manufacturing processes. In addition, due to the prevalence of pentaerythritoltetranitrate (PETN) in detonators, detonating cord, and boosters, the potential of the IRMS technique to differentiate PETN samples from different sources was also investigated. Carbon isotope values were measured in fourteen TATP samples, with three definite groups appearing in the initial sample set based on the carbon data alone. Four additional TATP samples (in a second set of samples) were distinguishable utilising the carbon and hydrogen isotopic compositions individually, and also in combination with the oxygen isotope values. The 3D plot of the carbon, oxygen and hydrogen data demonstrated the clear discrimination of the four samples of TATP. The carbon and nitrogen isotope values measured from fifteen PETN samples, allowed samples from different sources to be readily discriminated. This paper demonstrates the successful application of IRMS to the analysis of explosives of forensic interest to assist in discriminating samples from different sources. This research represents a preliminary evaluation of the IRMS technique for the measurement of stable isotope values in TATP and PETN samples, and supports the dedication of resources for a full evaluation of this application in order to achieve Court reportable IRMS results.

  2. Stable carbon isotope composition of organic material and carbonate in sediment of a swamp and lakes in Honshu island, Japan

    International Nuclear Information System (INIS)

    Ishizuka, Toshio

    1978-01-01

    Recent sediments from a swamp and lakes in Honshu were analyzed for organic carbon and carbonate contents, and stable isotope ratios of carbon in the organic materials and carbonate. delta C 13 values of the carbonate tend to be distinctly larger than those of organic carbon in reducing condition as natural gas field, whereas in oxidizing SO 4 -reducing conditions, they are slightly larger than those of organic carbon within the limited range of a few per mil. Carbon isotopic compositions of organic carbon in sediment of the swamp, Obuchi-numa, were analyzed and compared with habitat analysis of associated fossil diatoms. deltaC 13 values of organic carbon in the sediment vary in correlation with the species abundance in habitat of the associated fossil diatoms, ranging from fresh-water (-0.0282) to coastal marine (-0.0236) via brackish. (auth.)

  3. Carbon and oxygen isotopic ratio bi-variate distribution for marble artifacts quarry assignment

    International Nuclear Information System (INIS)

    Pentia, M.

    1995-01-01

    Statistical description, by a Gaussian bi-variate probability distribution of 13 C/ 12 C and 18 O/ 16 O isotopic ratios in the ancient marble quarries has been done and the new method for obtaining the confidence level quarry assignment for marble artifacts has been presented. (author) 8 figs., 3 tabs., 4 refs

  4. Effects of soil strength on the relation of water-use efficiency and growth to carbon isotope discrimination in wheat seedlings

    International Nuclear Information System (INIS)

    Masle, J.; Farquhar, G.D.

    1988-01-01

    The ratio of carbon accumulation to transpiration, W, of wheat (Triticum aestivum L.) seedlings increased with increasing soil strength, measured as soil penetrometer resistance, and this was already apparent at the two leaf stage. The ratio was negatively correlated with carbon isotope discrimination, in accord with theory. This means that decrease in intercellular partial pressure of CO 2 accounted for an important part of the increase in W with increasing soil strength. Despite a lower CO 2 concentration in the leaves at high soil strength, assimilation rate per unit leaf area was enhanced. Greater ribulose 1,5-bisphosphate carboxylase activity confirmed that photosynthetic capacity was actually increased. This pattern of opposite variation of assimilation rate and of stomatal conductance is unusual. The ratio of plant carbon mass to leaf area increased markedly with increasing soil strength, mainly because of a greater investment of carbon into roots than into shoots. A strong negative correlation was found between this ratio and carbon isotope discrimination. For a given increase in discrimination, decrease in carbon mass per leaf area was proportionally larger than decrease in assimilation rate, so that relative growth rate was positively correlated to carbon isotope discrimination

  5. Carbon isotope ratios of great plains soils and in wheat-fallow systems

    International Nuclear Information System (INIS)

    Follett, R.F.; Paul, E.A.; Leavitt, S.W.; Halvorson, A.D.; Lyon, D.; Peterson, G.A.

    1997-01-01

    The purposes of this study were to improve knowledge of regional vegetation patterns of C3 and C4 plants in the North American Great Plains and to use delta 13C methodology and long-term research sites to determine contributions of small-grain crops to total soil organic carbon (SOC) now present. Archived and recent soil samples were used. Detailed soil sampling was in 1993 at long-term sites near Akron, CO, and Sidney, NE. After soil sieving, drying, and deliming, SOC and delta 13C were determined using an automated C/N analyzer interfaced to an isotope-ratio mass spectrometer. Yield records from long-term experimental sites were used to estimate the amount of C3 plant residue C returned to the soil. Results from delta 13C analyses of soils from near Waldheim, Saskatchewan, to Big Springs, TX, showed a strong north to south decrease in SOC derived from C3 plants and a corresponding increase from C4 plants. The delta 13C analyses gave evidence that C3 plant residue C (possibly from shrubs) is increasing at the Big Springs, TX, and Lawton, OK, sites. Also, delta 13C analyses of subsoil and topsoil layers shows evidence of a regional shift to more C3 species, possibly because of a cooler climate during the past few hundreds to thousands of years. Data from long-term research sites indicate that the efficiency of incorporation of small-grain crop residue C was about 5.4% during 84 yr at Akron, CO, and about 10.5% during 20 yr at Sidney, NE. The 14C age of the SOC at 0- to 10-cm depth was 193 yr and at 30 to 45 cm was 4000 yr; 14C age of nonhydrolyzable C was 2000 and 7000 yr for these same two respective depths. Natural partitioning of the 13C isotope by the photosynthetic pathways of C3 and C4 plants provides a potentially powerful tool to study SOC dynamics at both regional and local scales

  6. Liquid and gas chromatography coupled to isotope ratio mass spectrometry for the determination of 13C-valine isotopic ratios in complex biological samples

    NARCIS (Netherlands)

    Godin, Jean-Philippe; Breuillé, Denis; Obled, Christiane; Papet, Isabelle; Schierbeek, Henk; Hopfgartner, Gérard; Fay, Laurent-Bernard

    2008-01-01

    On-line gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) is commonly used to measure isotopic ratios at natural abundance as well as for tracer studies in nutritional and medical research. However, high-precision (13)C isotopic enrichment can also be measured by liquid

  7. Calculation of Site-specific Carbon-isotope Fractionation in Pedogenic Oxide Minerals

    Energy Technology Data Exchange (ETDEWEB)

    Rustad, James R.; Zarzycki, Piotr

    2008-07-29

    Ab initio molecular dynamics and quantum chemistry techniques are used to calculate the structure, vibrational frequencies, and carbon-isotope fractionation factors of the carbon dioxide component [CO2(m)] of soil (oxy)hydroxide minerals goethite, diaspore, and gibbsite. We have identified two possible pathways of incorporation of CO2(m) into (oxy)hydroxide crystal structures: one in which the C4+ substitutes for four H+ [CO2(m)A] and another in which C4+ substitutes for (Al3+,Fe3+) + H+ [CO2(m)B]. Calculations of isotope fractionation factors give large differences between the two structures, with the CO2(m)A being isotopically lighter than CO2(m)B by ≈10 per mil in the case of gibbsite and nearly 20 per mil in the case of goethite. The reduced partition function ratio of CO2(m)B structure in goethite differs from CO2(g) by <1 per mil. The predicted fractionation for gibbsite is >10 per mil higher, close to those measured for calcite and aragonite. The surprisingly large difference in the carbon-isotope fractionation factor between the CO2(m)A and CO2(m)B structures within a given mineral suggests that the isotopic signatures of soil (oxy)hydroxide could be heterogeneous.

  8. Biomedical and Forensic Applications of Combined Catalytic Hydrogenation-Stable Isotope Ratio Analysis

    Science.gov (United States)

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

    2007-01-01

    Studies of biological molecules such as fatty acids and the steroid hormones have the potential to benefit enormously from stable carbon isotope ratio measurements of individual molecules. In their natural form, however, the body’s molecules interact too readily with laboratory equipment designed to separate them for accurate measurements to be made. Some methods overcome this problem by adding carbon to the target molecule, but this can irreversibly overprint the carbon source ‘signal’. Hydropyrolysis is a newly-applied catalytic technique that delicately strips molecules of their functional groups but retains their carbon skeletons and stereochemistries intact, allowing precise determination of the carbon source. By solving analytical problems, the new technique is increasing the ability of scientists to pinpoint molecular indicators of disease, elucidate metabolic pathways and recognise administered substances in forensic investigations. PMID:19662175

  9. Development and application of liquid chromatography coupled to isotope ratio mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Lijun

    2014-02-19

    Stable isotope analysis has found widespread applications in various disciplines such as archaeology, geochemistry, biology, food authenticity, and forensic science. Coupling chromatography to isotope ratio mass spectrometry for compound-specific isotope analysis (CSIA) is a trend, as it provides several advantages over bulk isotope analysis, e.g., relatively simple sample preparation, the ability to measure individual compounds in a complex mixture in one run, and the reduced sample size required for precise isotope analysis. Gas chromatography coupled to isotope ratio mass spectrometry (GC/IRMS) has been well-established for compound-specific isotope analysis of volatile organic compounds within the last two decades. However, an interface combining liquid chromatography with isotope ratio mass spectrometry (LC/IRMS) was not commercially available until 2004. The current design of the interface requires using a carbon-free eluent in chromatographic separation. This requirement limits the application of the most frequently used reversed-phase liquid chromatography in CSIA, because the elution strength of water at room temperature is too low to serve as mobile phase in reversed-phase separations. In order to increase the elution strength of water, we propose using high temperature water for chromatographic elution. The polarity of water decreases with an increase of temperature, yielding increased elution strength in reversed-phase columns. Therefore, high temperature water can be used as eluent instead of organic solvent for combining reversed-phase liquid chromatography with isotope ratio mass spectrometry (RPLC/IRMS). Additionally, temperature gradients can replace organic solvent gradients to increase chromatographic resolution. This is very important for LC/IRMS analysis, as precise isotope analysis requires baseline separation of analytes. In this thesis, high-temperature reversed-phase liquid chromatography was coupled to, and for the first time carefully

  10. Development and application of liquid chromatography coupled to isotope ratio mass spectrometry

    International Nuclear Information System (INIS)

    Zhang, Lijun

    2014-01-01

    Stable isotope analysis has found widespread applications in various disciplines such as archaeology, geochemistry, biology, food authenticity, and forensic science. Coupling chromatography to isotope ratio mass spectrometry for compound-specific isotope analysis (CSIA) is a trend, as it provides several advantages over bulk isotope analysis, e.g., relatively simple sample preparation, the ability to measure individual compounds in a complex mixture in one run, and the reduced sample size required for precise isotope analysis. Gas chromatography coupled to isotope ratio mass spectrometry (GC/IRMS) has been well-established for compound-specific isotope analysis of volatile organic compounds within the last two decades. However, an interface combining liquid chromatography with isotope ratio mass spectrometry (LC/IRMS) was not commercially available until 2004. The current design of the interface requires using a carbon-free eluent in chromatographic separation. This requirement limits the application of the most frequently used reversed-phase liquid chromatography in CSIA, because the elution strength of water at room temperature is too low to serve as mobile phase in reversed-phase separations. In order to increase the elution strength of water, we propose using high temperature water for chromatographic elution. The polarity of water decreases with an increase of temperature, yielding increased elution strength in reversed-phase columns. Therefore, high temperature water can be used as eluent instead of organic solvent for combining reversed-phase liquid chromatography with isotope ratio mass spectrometry (RPLC/IRMS). Additionally, temperature gradients can replace organic solvent gradients to increase chromatographic resolution. This is very important for LC/IRMS analysis, as precise isotope analysis requires baseline separation of analytes. In this thesis, high-temperature reversed-phase liquid chromatography was coupled to, and for the first time carefully

  11. Carbon isotopic analysis of atmospheric methane by isotope-ratio-monitoring gas chromatography-mass spectrometry

    Science.gov (United States)

    Merritt, Dawn A.; Hayes, J. M.; Des Marais, David J.

    1995-01-01

    Less than 15 min are required for the determination of delta C(sub PDB)-13 with a precision of 0.2 ppt(1 sigma, single measurement) in 5-mL samples of air containing CH4 at natural levels (1.7 ppm). An analytical system including a sample-introduction unit incorporating a preparative gas chromatograph (GC) column for separation of CH4 from N2, O2, and Ar is described. The 15-min procedure includes time for operation of that system, high-resolution chromatographic separation of the CH4, on-line combustion and purification of the products, and isotopic calibration. Analyses of standards demonstrate that systematic errors are absent and that there is no dependence of observed values of delta on sample size. For samples containing 100 ppm or more CH4, preconcentration is not required and the analysis time is less than 5 min. The system utilizes a commercially available, high-sensitivity isotope-ratio mass spectrometer. For optimal conditions of smaple handling and combustion, performance of the system is within a factor of 2 of the shot-noise limit. The potential exists therefore for analysis of samples as small as 15 pmol CH4 with a standard deviation of less than 1 ppt.

  12. New Carbonate Standard Reference Materials for Boron Isotope Geochemistry

    Science.gov (United States)

    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

  13. Chlorine Isotope Effects from Isotope Ratio Mass Spectrometry Suggest Intramolecular C-Cl Bond Competition in Trichloroethene (TCE Reductive Dehalogenation

    Directory of Open Access Journals (Sweden)

    Stefan Cretnik

    2014-05-01

    Full Text Available Chlorinated ethenes are prevalent groundwater contaminants. To better constrain (biochemical reaction mechanisms of reductive dechlorination, the position-specificity of reductive trichloroethene (TCE dehalogenation was investigated. Selective biotransformation reactions (i of tetrachloroethene (PCE to TCE in cultures of Desulfitobacterium sp. strain Viet1; and (ii of TCE to cis-1,2-dichloroethene (cis-DCE in cultures of Geobacter lovleyi strain SZ were investigated. Compound-average carbon isotope effects were −19.0‰ ± 0.9‰ (PCE and −12.2‰ ± 1.0‰ (TCE (95% confidence intervals. Using instrumental advances in chlorine isotope analysis by continuous flow isotope ratio mass spectrometry, compound-average chorine isotope effects were measured for PCE (−5.0‰ ± 0.1‰ and TCE (−3.6‰ ± 0.2‰. In addition, position-specific kinetic chlorine isotope effects were determined from fits of reactant and product isotope ratios. In PCE biodegradation, primary chlorine isotope effects were substantially larger (by −16.3‰ ± 1.4‰ (standard error than secondary. In TCE biodegradation, in contrast, the product cis-DCE reflected an average isotope effect of −2.4‰ ± 0.3‰ and the product chloride an isotope effect of −6.5‰ ± 2.5‰, in the original positions of TCE from which the products were formed (95% confidence intervals. A greater difference would be expected for a position-specific reaction (chloride would exclusively reflect a primary isotope effect. These results therefore suggest that both vicinal chlorine substituents of TCE were reactive (intramolecular competition. This finding puts new constraints on mechanistic scenarios and favours either nucleophilic addition by Co(I or single electron transfer as reductive dehalogenation mechanisms.

  14. Si and C isotopic ratios in AGB stars: SiC grain data, models, and the galactic evolution of the Si Isotopes

    NARCIS (Netherlands)

    Zinner, E.; Nittler, L.R.; Gallino, R.; Karakas, A.I.; Lugaro, M.A.; Straniero, O.; Lattanzio, J.C.

    2006-01-01

    Presolar grains of the mainstream, Y and Z type are believed to have an origin in carbon stars. We compared the C and Si isotopic ratios of these grains [1] with the results of theoretical models for the envelope compositions of AGB stars. Two sets of models (FRANEC, Monash) use a range of stellar

  15. Study and validity of 13C stable carbon isotopic ratio analysis by mass spectrometry and 2H site-specific natural isotopic fractionation by nuclear magnetic resonance isotopic measurements to characterize and control the authenticity of honey

    International Nuclear Information System (INIS)

    Cotte, J.F.; Casabianca, H.; Lheritier, J.; Perrucchietti, C.; Sanglar, C.; Waton, H.; Grenier-Loustalot, M.F.

    2007-01-01

    Honey samples were analyzed by stable carbon isotopic ratio analysis by mass spectrometry (SCIRA-MS) and site-specific natural isotopic fractionation measured by nuclear magnetic resonance (SNIF-NMR) to first determine their potentials for characterizing the substance and then to combat adulteration. Honey samples from several geographic and botanical origins were analyzed. The δ 13 C parameter was not significant for characterizing an origin, while the (D/H) I ratio could be used to differentiate certain single-flower varieties. Application of the official control method of adding a C 4 syrup (AOAC official method 998.12) to our authentic samples revealed anomalies resulting from SCIRA indices that were more negative than -1 per mille (permil). A filtration step was added to the experimental procedure and provided results that were compliant with Natural origin of our honey samples. In addition, spiking with a C 4 syrup could be detected starting at 9-10%. The use of SNIF-NMR is limited by the detection of a syrup spike starting only at 20%, which is far from satisfying

  16. Maintaining high precision of isotope ratio analysis over extended periods of time.

    Science.gov (United States)

    Brand, Willi A

    2009-06-01

    Stable isotope ratios are reliable and long lasting process tracers. In order to compare data from different locations or different sampling times at a high level of precision, a measurement strategy must include reliable traceability to an international stable isotope scale via a reference material (RM). Since these international RMs are available in low quantities only, we have developed our own analysis schemes involving laboratory working RM. In addition, quality assurance RMs are used to control the long-term performance of the delta-value assignments. The analysis schemes allow the construction of quality assurance performance charts over years of operation. In this contribution, the performance of three typical techniques established in IsoLab at the MPI-BGC in Jena is discussed. The techniques are (1) isotope ratio mass spectrometry with an elemental analyser for delta(15)N and delta(13)C analysis of bulk (organic) material, (2) high precision delta(13)C and delta(18)O analysis of CO(2) in clean-air samples, and (3) stable isotope analysis of water samples using a high-temperature reaction with carbon. In addition, reference strategies on a laser ablation system for high spatial resolution delta(13)C analysis in tree rings is exemplified briefly.

  17. Reconstruction of limnology and microbialite formation conditions from carbonate clumped isotope thermometry.

    Science.gov (United States)

    Petryshyn, V A; Lim, D; Laval, B L; Brady, A; Slater, G; Tripati, A K

    2015-01-01

    Quantitative tools for deciphering the environment of microbialite formation are relatively limited. For example, the oxygen isotope carbonate-water geothermometer requires assumptions about the isotopic composition of the water of formation. We explored the utility of using 'clumped' isotope thermometry as a tool to study the temperatures of microbialite formation. We studied microbialites recovered from water depths of 10-55 m in Pavilion Lake, and 10-25 m in Kelly Lake, spanning the thermocline in both lakes. We determined the temperature of carbonate growth and the (18)O/(16)O ratio of the waters that microbialites grew in. Results were then compared to current limnological data from the lakes to reconstruct the history of microbialite formation. Modern microbialites collected at shallow depths (11.7 m) in both lakes yield clumped isotope-based temperatures of formation that are within error of summer water temperatures, suggesting that clumped isotope analyses may be used to reconstruct past climates and to probe the environments in which microbialites formed. The deepest microbialites (21.7-55 m) were recovered from below the present-day thermoclines in both lakes and yield radioisotope ages indicating they primarily formed earlier in the Holocene. During this time, pollen data and our reconstructed water (18)O/(16)O ratios indicate a period of aridity, with lower lake levels. At present, there is a close association between both photosynthetic and heterotrophic communities, and carbonate precipitation/microbialite formation, with biosignatures of photosynthetic influences on carbonate detected in microbialites from the photic zone and above the thermocline (i.e., depths of generally <20 m). Given the deeper microbialites are receiving <1% of photosynthetically active radiation (PAR), it is likely these microbialites primarily formed when lower lake levels resulted in microbialites being located higher in the photic zone, in warm surface waters. © 2014 John

  18. Novel proxies for reconstructing paleohydrology from ombrotrophic peatlands: biomarker and compound-specific H and C stable isotope ratios

    Science.gov (United States)

    Wang, J.; Nichols, J. E.; Huang, Y.

    2008-12-01

    Ombrotrophic peatlands are excellent archives for paleohydrologic information because they are hydrologically isolated from their surroundings. However, quantitative proxies for deciphering peatland archives are lacking. Here, we present development and application of novel organic geochemical methods for quantitative reconstruction of paleohydrology from the ombrotrophic sediments, and comparison of organic geochemical data with conventional paleoecological proxies. Application of these methods to the sediments of several North American and European peatlands has revealed significant changes in the hydroclimate throughout the Holocene. The plant assemblage living at the surface of the peatland is tightly controlled by surface moisture. Under wet conditions, Sphagnum mosses, with no active mechanism for drawing water from below the surface of the peatland, are dominant. During dry conditions, vascular plants are more productive relative to Sphagnum. A ratio of the abundance of two biomarkers representing Sphagnum and vascular plants sensitively records changes in hydrologic balance (Nichols et al., 2006, Org. Geochem. 37, 1505-1513). We have further developed stable isotope models to compute climate parameters from compound-specific H and C isotope ratios of biomarkers to create a more comprehensive climate reconstruction. Vascular plant leaf waxes carry the D/H ratio signature of precipitation that is little affected by evaporation, whereas the Sphagnum biomarker records isotopic ratios of the water at the peatland surface, which is strongly enriched by evaporation. Evaporation amount can be calculated using the differences between D/H ratios of the two types of biomarkers. C isotope ratios of Sphagnum biomarkers can also be used to quantify surface wetness. Methanotrophic bacteria live symbiotically with Sphagnum, providing isotopically light carbon for photosynthesis. These bacteria are more active when the Sphagnum is wet, thus providing more 13C-depleted CO2

  19. Following Carbon Isotopes from Methane to Molecules

    Science.gov (United States)

    Freeman, K. H.

    2017-12-01

    Continuous-flow methods introduced by Hayes (Matthews and Hayes, 1978; Freeman et al., 1990; Hayes et al., 1990) for compound-specific isotope analyses (CSIA) transformed how we study the origins and fates of organic compounds. This analytical revolution launched several decades of research in which researchers connect individual molecular structures to diverse environmental and climate processes affecting their isotopic profiles. Among the first applications, and one of the more dramatic isotopically, was tracing the flow of natural methane into cellular carbon and cellular biochemical constituents. Microbial oxidation of methane can be tracked by strongly 13C-depleted organic carbon in early Earth sedimentary environments, in marine and lake-derived biomarkers in oils, and in modern organisms and their environments. These signatures constrain microbial carbon cycling and inform our understanding of ocean redox. The measurement of molecular isotopes has jumped forward once again, and it is now possible to determine isotope abundances at specific positions within increasingly complex organic structures. In addition, recent analytical developments have lowered sample sensitivity limits of CSIA to picomole levels. These new tools have opened new ways to measure methane carbon in the natural environment and within biochemical pathways. This talk will highlight how molecular isotope methods enable us to follow the fate of methane carbon in complex environments and along diverse metabolic pathways, from trace fluids to specific carbon positions within microbial biomarkers.

  20. Stable-carbon isotope ratios for sourcing the nerve-agent precursor methylphosphonic dichloride and its products.

    Science.gov (United States)

    Moran, James J; Fraga, Carlos G; Nims, Megan K

    2018-08-15

    The ability to connect a chemical threat agent to a specific batch of a synthetic precursor can provide a fingerprint to contribute to effective forensic investigations. Stable isotope analysis can leverage intrinsic, natural isotopic variability within the molecules of a threat agent to unlock embedded chemical fingerprints in the material. Methylphosphonic dichloride (DC) is a chemical precursor to the nerve agent sarin. DC is converted to methylphosphonic difluoride (DF) as part of the sarin synthesis process. We used a suite of commercially available DC stocks to both evaluate the potential for δ 13 C analysis to be used as a fingerprinting tool in sarin-related investigations and to develop sample preparation techniques (using chemical hydrolysis) that can simplify isotopic analysis of DC and its synthetic products. We demonstrate that natural isotopic variability in DC results in at least three distinct, isotope-resolved clusters within the thirteen stocks we analyzed. Isotopic variability in the carbon feedstock (i.e., methanol) used for DC synthesis is likely inherited by the DC samples we measured. We demonstrate that the hydrolysis of DC and DF to methylphosphonic acid (MPA) can be used as a preparative step for isotopic analysis because the reaction does not impart a significant isotopic fractionation. MPA is more chemically stable, less toxic, and easier to handle than DC or DF. Further, the hydrolysis method we demonstrated can be applied to a suite of other precursors or to sarin itself, thereby providing a potentially valuable forensic tool. Copyright © 2018. Published by Elsevier B.V.

  1. LBA-ECO CD-02 Carbon, Nitrogen, Oxygen Stable Isotopes in Organic Material, Brazil

    Data.gov (United States)

    National Aeronautics and Space Administration — This data set reports the measurement of stable carbon, nitrogen, and oxygen isotope ratios in organic material (plant, litter and soil samples) in forest canopy...

  2. LBA-ECO CD-02 Carbon, Nitrogen, Oxygen Stable Isotopes in Organic Material, Brazil

    Data.gov (United States)

    National Aeronautics and Space Administration — ABSTRACT: This data set reports the measurement of stable carbon, nitrogen, and oxygen isotope ratios in organic material (plant, litter and soil samples) in forest...

  3. Novel Apparatus for the Real-Time Quantification of Dissolved Gas Concentrations and Isotope Ratios

    Science.gov (United States)

    Gupta, M.; Leen, J.; Baer, D. S.; Owano, T. G.; Liem, J.

    2013-12-01

    Measurements of dissolved gases and their isotopic composition are critical in studying a variety of phenomena, including underwater greenhouse gas generation, air-surface exchange, and pollution migration. These studies typically involve obtaining water samples from streams, lakes, or ocean water and transporting them to a laboratory, where they are degased. The gases obtained are then generally measured using gas chromatography and isotope ratio mass spectrometry for concentrations and isotope ratios, respectively. This conventional, off-line methodology is time consuming, significantly limits the number of the samples that can be measured and thus severely inhibits detailed spatial and temporal mapping of gas concentrations and isotope ratios. In this work, we describe the development of a new membrane-based degassing device that interfaces directly to Los Gatos Research (cavity enhanced laser absorption or Off-Axis ICOS) gas analyzers (cavity enhanced laser absorption or Off-Axis ICOS analyzers) to create an autonomous system that can continuously and quickly measure concentrations and isotope ratios of dissolved gases in real time in the field. By accurately controlling the water flow rate through the membrane degasser, gas pressure on the outside of the membrane, and water pressure on the inside of the membrane, the system is able to generate precise and highly reproducible results. Moreover, by accurately measuring the gas flow rates in and out of the degasser, the gas-phase concentrations (ppm) could be converted into dissolved gas concentrations (nM). We will present detailed laboratory test data that quantifies the linearity, precision, and dynamic range of the system for the concentrations and isotope ratios of dissolved methane, carbon dioxide, and nitrous oxide. By interfacing the degassing device to a novel cavity-enhanced spectrometer (developed by LGR), preliminary data will also be presented for dissolved volatile organics (VOC) and other

  4. Calibration and Data Processing in Gas Chromatography Combustion Isotope Ratio Mass Spectrometry

    Science.gov (United States)

    Zhang, Ying; Tobias, Herbert J.; Sacks, Gavin L.; Brenna, J. Thomas

    2013-01-01

    Compound-specific isotope analysis (CSIA) by gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS) is a powerful technique for the sourcing of substances, such as determination of the geographic or chemical origin of drugs and food adulteration, and it is especially invaluable as a confirmatory tool for detection of the use of synthetic steroids in competitive sport. We review here principles and practices for data processing and calibration of GCC-IRMS data with consideration to anti-doping analyses, with a focus on carbon isotopic analysis (13C/12C). After a brief review of peak definition, the isotopologue signal reduction methods of summation, curve-fitting, and linear regression are described and reviewed. Principles for isotopic calibration are considered in the context of the Δ13C = δ13CM – δ13CE difference measurements required for establishing adverse analytical findings for metabolites relative to endogenous reference compounds. Considerations for the anti-doping analyst are reviewed. PMID:22362612

  5. Measurement of the isotope ratio of acetic acid in vinegar by HS-SPME-GC-TC/C-IRMS.

    Science.gov (United States)

    Hattori, Ryota; Yamada, Keita; Shibata, Hiroki; Hirano, Satoshi; Tajima, Osamu; Yoshida, Naohiro

    2010-06-23

    Acetic acid is the main ingredient of vinegar, and the worth of vinegar often depends on the fermentation of raw materials. In this study, we have developed a simple and rapid method for discriminating the fermentation of the raw materials of vinegar by measuring the hydrogen and carbon isotope ratio of acetic acid using head space solid-phase microextraction (HS-SPME) combined with gas chromatography-high temperature conversion or combustion-isotope ratio mass spectrometry (GC-TC/C-IRMS). The measurement of acetic acid in vinegar by this method was possible with repeatabilities (1sigma) of +/-5.0 per thousand for hydrogen and +/-0.4 per thousand for carbon, which are sufficient to discriminate the origin of acetic acid. The fermentation of raw materials of several vinegars was evaluated by this method.

  6. Correction of mass spectrometric isotope ratio measurements for isobaric isotopologues of O2, CO, CO2, N2O and SO2.

    Science.gov (United States)

    Kaiser, Jan; Röckmann, Thomas

    2008-12-01

    Gas isotope ratio mass spectrometers usually measure ion current ratios of molecules, not atoms. Often several isotopologues contribute to an ion current at a particular mass-to-charge ratio (m/z). Therefore, corrections have to be applied to derive the desired isotope ratios. These corrections are usually formulated in terms of isotope ratios (R), but this does not reflect the practice of measuring the ion current ratios of the sample relative to those of a reference material. Correspondingly, the relative ion current ratio differences (expressed as delta values) are first converted into isotopologue ratios, then into isotope ratios and finally back into elemental delta values. Here, we present a reformulation of this data reduction procedure entirely in terms of delta values and the 'absolute' isotope ratios of the reference material. This also shows that not the absolute isotope ratios of the reference material themselves, but only product and ratio combinations of them, are required for the data reduction. These combinations can be and, for carbon and oxygen have been, measured by conventional isotope ratio mass spectrometers. The frequently implied use of absolute isotope ratios measured by specially calibrated instruments is actually unnecessary. Following related work on CO2, we here derive data reduction equations for the species O2, CO, N2O and SO2. We also suggest experiments to measure the required absolute ratio combinations for N2O, SO2 and O2. As a prelude, we summarise historic and recent measurements of absolute isotope ratios in international isotope reference materials. Copyright 2008 John Wiley & Sons, Ltd.

  7. Improvements in Precise and Accurate Isotope Ratio Determination via LA-MC-ICP-MS by Application of an Alternative Data Reduction Protocol

    Science.gov (United States)

    Fietzke, J.; Liebetrau, V.; Guenther, D.; Frische, M.; Zumholz, K.; Hansteen, T. H.; Eisenhauer, A.

    2008-12-01

    An alternative approach for the evaluation of isotope ratio data using LA-MC-ICP-MS will be presented. In contrast to previously applied methods it is based on the simultaneous responses of all analyte isotopes of interest and the relevant interferences without performing a conventional background correction. Significant improvements in precision and accuracy can be achieved when applying this new method and will be discussed based on the results of two first methodical applications: a) radiogenic and stable Sr isotopes in carbonates b) stable chlorine isotopes of pyrohydrolytic extracts. In carbonates an external reproducibility of the 87Sr/86Sr ratios of about 19 ppm (RSD) was achieved, an improvement of about a factor of 5. For recent and sub-recent marine carbonates a mean radiogenic strontium isotope ratio 87Sr/86Sr of 0.709170±0.000007 (2SE) was determined, which agrees well with the value of 0.7091741±0.0000024 (2SE) reported for modern sea water [1,2]. Stable chlorine isotope ratios were determined ablating pyrohydrolytic extracts with a reproducibility of about 0.05‰ (RSD). For basaltic reference material JB1a and JB2 chlorine isotope ratios were determined relative to SMOC (standard mean ocean chlorinity) δ37ClJB-1a = (-0.99±0.06) ‰ and δ37ClJB-1a = (-0.60±0.03) ‰ (SD), respectively, in accordance with published data [3]. The described strategies for data reduction are considered to be generally applicable for all isotope ratio measurements using LA-MC-ICP-MS. [1] J.M. McArthur, D. Rio, F. Massari, D. Castradori, T.R. Bailey, M. Thirlwall, S. Houghton, Palaeogeo. Palaeoclim. Palaeoeco., 2006, 242 (126), doi: 10.1016/j.palaeo.2006.06.004 [2] J. Fietzke, V. Liebetrau, D. Guenther, K. Guers, K. Hametner, K. Zumholz, T.H. Hansteen and A. Eisenhauer, J. Anal. At. Spectrom., 2008, 23, 955-961, doi:10.1039/B717706B [3] J. Fietzke, M. Frische, T.H. Hansteen and A. Eisenhauer, J. Anal. At. Spectrom., 2008, 23, 769-772, doi:10.1039/B718597A

  8. Biomarkers, carbon isotopic composition and source rock potentials of Awgu coals, middle Benue trough, Nigeria

    Science.gov (United States)

    Adedosu, Taofik A.; Sonibare, Oluwadayo O.; Tuo, Jincai; Ekundayo, Olusegun

    2012-05-01

    Coal and carbonaceous shale samples were collected from two boreholes (BH 94 and BH 120) in Awgu formation of Middle Benue Trough, Nigeria. Source rock potentials of the samples were studied using biomarkers and carbon isotopic composition. Biomarkers in the aliphatic fractions in the samples were studied using Gas Chromatography-Mass Spectrometry (GC-MS). The Carbon isotope analysis of individual n-alkanes in the aliphatic fraction was performed using Gas Chromatography-Combustion-Isotope Ratio Mass Spectrometer (GC-IRMS). The abundance of hopanes, homohopanes (C31-C35), and C29 steranes in the samples indicate terrestrial plant, phytoplankton and cyanobacteria contributions to the organic matter that formed the coal. High (Pr/Ph) ratio (3.04-11.07) and isotopic distribution of individual alkanes showed that the samples consisted of mixed terrestrial/marine organic matter deposited under oxic condition in lacustrine-fluvial/deltaic depositional environment. The maturity parameters derived from biomarker distributions showed that the samples are in the main phase of oil window.

  9. Testing of an automated online EA-IRMS method for fast and simultaneous carbon content and stable isotope measurement of aerosol samples

    Science.gov (United States)

    Major, István; Gyökös, Brigitta; Túri, Marianna; Futó, István; Filep, Ágnes; Hoffer, András; Molnár, Mihály

    2016-04-01

    Comprehensive atmospheric studies have demonstrated that carbonaceous aerosol is one of the main components of atmospheric particulate matter over Europe. Various methods, considering optical or thermal properties, have been developed for quantification of the accurate amount of both organic and elemental carbon constituents of atmospheric aerosol. The aim of our work was to develop an alternative fast and easy method for determination of the total carbon content of individual aerosol samples collected on prebaked quartz filters whereby the mass and surface concentration becomes simply computable. We applied the conventional "elemental analyzer (EA) coupled online with an isotope ratio mass spectrometer (IRMS)" technique which is ubiquitously used in mass spectrometry. Using this technique we are able to measure simultaneously the carbon stable isotope ratio of the samples, as well. During the developing process, we compared the EA-IRMS technique with an off-line catalytic combustion method worked out previously at Hertelendi Laboratory of Environmental Studies (HEKAL). We tested the combined online total carbon content and stable isotope ratio measurement both on standard materials and real aerosol samples. Regarding the test results the novel method assures, on the one hand, at least 95% of carbon recovery yield in a broad total carbon mass range (between 100 and 3000 ug) and, on the other hand, a good reproducibility of stable isotope measurements with an uncertainty of ± 0.2 per mill. Comparing the total carbon results obtained by the EA-IRMS and the off-line catalytic combustion method we found a very good correlation (R2=0.94) that proves the applicability of both preparation method. Advantages of the novel method are the fast and simplified sample preparation steps and the fully automated, simultaneous carbon stable isotope ratio measurement processes. Furthermore stable isotope ratio results can effectively be applied in the source apportionment

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

    International Nuclear Information System (INIS)

    HOLDEN, N.E.

    2005-01-01

    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

  11. Biomedical and Forensic Applications of Combined Catalytic Hydrogenation-Stable Isotope Ratio Analysis

    Directory of Open Access Journals (Sweden)

    Mark A. Sephton

    2007-01-01

    Full Text Available Studies of biological molecules such as fatty acids and the steroid hormones have the potential to benefit enormously from stable carbon isotope ratio measurements of individual molecules. In their natural form, however, the body’s molecules interact too readily with laboratory equipment designed to separate them for accurate measurements to be made.Some methods overcome this problem by adding carbon to the target molecule, but this can irreversibly overprint the carbon source ‘signal’. Hydropyrolysis is a newly-applied catalytic technique that delicately strips molecules of their functional groups but retains their carbon skeletons and stereochemistries intact, allowing precise determination of the carbon source. By solving analytical problems, the new technique is increasing the ability of scientists to pinpoint molecular indicators of disease, elucidate metabolic pathways and recognise administered substances in forensic investigations.

  12. The Roles of Sphagnum and Cyperaceae in the Methane Cycle of an Ombrotrophic Bog Revealed by the Carbon Isotope Ratios of Leaf Waxes

    Science.gov (United States)

    Isles, P. D.; Nichols, J. E.; Peteet, D. M.; Kenna, T. C.

    2011-12-01

    Methane is a strong greenhouse gas, and the role of the terrestrial carbon cycle in the concentrations of atmospheric methane is poorly understood. What is clear, is that northern peatlands are a significant source of methane to the atmosphere. A recent discovery, and a topic of much scrutiny, has been the relationship between Sphagnum in peatlands and symbiotic methanotrophic bacteria. These bacteria oxidize methane produced at depth in peatlands before it is released to the atmosphere, contributing 13C-depleted CO2 to Sphagnum photosynthate. We seek to better understand the fate of methane produced in peatlands at depth, and the relationship between methane release from peatland surfaces and parameters such as temperature, moisture, and vegetation type. We compare carbon isotope ratios of leaf wax n-alkanes from sphagnum and vascular plants and major element chemistry at three different microhabitats, hummock, hollow, and sedge tussock, in Mer Bleue an ombrotrophic peatland near Ottowa, Ontario, Canada. We use these compound-specific carbon isotope measurements to constrain the amount of methane-derived CO2 incorporated by Sphagnum. We also compare our multiannually resolved down-core measurements to data from long-term monitoring of climate parameters and methane flux from the same microhabitats to ground-truth our sedimentary signature of methane with instrumental measurements.

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

    Science.gov (United States)

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

    2008-12-01

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

  14. Calcium isotope ratios in animal and human bone

    Science.gov (United States)

    Reynard, L. M.; Henderson, G. M.; Hedges, R. E. M.

    2010-07-01

    Calcium isotopes in tissues are thought to be influenced by an individual's diet, reflecting parameters such as trophic level and dairy consumption, but this has not been carefully assessed. We report the calcium isotope ratios (δ 44/42Ca) of modern and archaeological animal and human bone ( n = 216). Modern sheep raised at the same location show 0.14 ± 0.08‰ higher δ 44/42Ca in females than in males, which we attribute to lactation by the ewes. In the archaeological bone samples the calcium isotope ratios of the herbivorous fauna vary by location. At a single site, the archaeological fauna do not show a trophic level effect. Humans have lower δ 44/42Ca than the mean site fauna by 0.22 ± 0.22‰, and the humans have a greater δ 44/42Ca range than the animals. No effect of sex or age on the calcium isotope ratios was found, and intra-individual skeletal δ 44/42Ca variability is negligible. We rule out dairy consumption as the main cause of the lower human δ 44/42Ca, based on results from sites pre-dating animal domestication and dairy availability, and suggest instead that individual physiology and calcium intake may be important in determining bone calcium isotope ratios.

  15. Online Stable Isotope Analysis of Dissolved Organic Carbon Size Classes Using Size Exclusion Chromatography Coupled to an Isotope Ratio Mass Spectrometer

    Digital Repository Service at National Institute of Oceanography (India)

    Malik, A.; Scheibe, A.; LokaBharathi, P.A.; Gleixner, G.

    size classes by coupling high-performance liquid chromatography (HPLC) - size exclusion chromatography (SEC) to online isotope ratio mass spectrometry (IRMS). This represents a significant methodological contribution to DOC research. The interface...

  16. The measurement of the isotope ratios and concentrations of zinc by thermal ionization mass spectrometry using double isotope dilution

    International Nuclear Information System (INIS)

    Deng Zhongguo

    1994-01-01

    The isotope ratios and concentrations of zinc are measured by silicagel-thermal ionization mass spectrometry using the double isotope spikers. The double isotope spikers ( 70 Zn and 67 Zn-enriched isotopes) are used to correct the isotope mass fractionation for the zinc isotope ratios, and to certify the zinc concentrations in the unknown samples. The zinc concentrations of these double isotope spikers are surveyed by a spiker made of pure (99.99%) natural zinc metal powder. The correcting factors (f a , f t and f n ) of the zinc isotope ratios in the spiked mixture, spike and unspiked samples for the isotope mass fractionation, and the spike-to-unspiked ratios (X r ) of the zinc isotope r in the spiked mixture samples can be obtained to solve the matrix equations by numerical approximation. The natural zinc isotope ratios are: 64 Zn/ 67 Zn = 11.8498, 66 Zn/ 67 Zn = 6.7977, 68 Zn/ 67 Zn = 4.5730 and 70 Zn/ 67 Zn = 0.1520. The uncertainties determined of the isotope ratios and concentrations of zinc are +- 0.16% and +-0.31%, respectively

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

    DEFF Research Database (Denmark)

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

    2015-01-01

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

  18. Intraspecific carbon and nitrogen isotopic variability in foxtail millet (Setaria italica).

    Science.gov (United States)

    Lightfoot, Emma; Przelomska, Natalia; Craven, Martha; O Connell, Tamsin C; He, Lu; Hunt, Harriet V; Jones, Martin K

    2016-07-15

    Isotopic palaeodietary studies generally focus on bone collagen from human and/or animal remains. While plant remains are rarely analysed, it is known that plant isotope values can vary as a result of numerous factors, including soil conditions, the environment and type of plant. The millets were important food crops in prehistoric Eurasia, yet little is known about the isotopic differences within millet species. Here we compare the stable isotope ratios within and between Setaria italica plants grown in a controlled environment chamber. Using homogenised samples, we compare carbon isotope ratios of leaves and grains, and nitrogen isotope ratios of grains, from 29 accessions of Setaria italica. We find significant isotopic variability within single leaves and panicles, and between leaves and panicles within the same plant, which must be considered when undertaking plant isotope studies. We find that the leaves and grains from the different accessions have a ca 2‰ range in δ(13) C values, while the nitrogen isotope values in the grains have a ca 6‰ range. We also find an average offset of 0.9‰ between leaves and grains in their δ(13) C values. The variation found is large enough to have archaeological implications and within- and between-plant isotope variability should be considered in isotope studies. The range in δ(15) N values is particularly significant as it is larger than the typical values quoted for a trophic level enrichment, and as such may lead to erroneous interpretations of the amount of animal protein in human or animal diets. It is therefore necessary to account for the variability in plant stable isotope values during palaeodietary reconstructions. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  19. Stable-carbon isotopic composition of maple sap and foliage

    International Nuclear Information System (INIS)

    Leavitt, S.W.; Long, A.

    1985-01-01

    The 13 C/ 12 C ratios of Acer grandidentatum sap sugar collected during the dormant period are compared to those of buds, leaves, and wood developed over the following growing season. As the primary carbon source for cellulose manufacture at initiation of annual growth in deciduous trees, sap sucrose would be expected to have an isotopic composition similar to first-formed cellulose. Although constancy in concentration and 13 C/ 12 C ratios of the maple sap sugar suggests any gains or losses (e.g. to maintenance metabolism) do not appreciably alter composition, the 13 C/ 12 C ratios of cellulose of the enlarging buds in the spring are quite distinct from those of the sap sugar, seemingly precluding a simple direct biochemical pathway of sap sucrose→glucose→cellulose in favor of a more complex pathway with greater likelihood of isotopic fractionation. The 13 C/ 12 C ratios of the leaves and in the growth ring were initially similar to the sap sugar but decreased steadily over the growing season. (author)

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

    Science.gov (United States)

    Révész, Kinga M.; Doctor, Daniel H.

    2014-01-01

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

  1. Preliminary assessment of the grading of Eucalyptus clones using carbon isotope discrimination

    International Nuclear Information System (INIS)

    Bond, W.J.; Stock, W.D.

    1990-01-01

    Stable carbon isotopes were analysed in leaf material of nine Eucalyptus clones grown in field trials in the eastern Transvaal. Carbon isotope ratios, measured as d 13 C, differed within tree canopies, between replicate trees and between clones. Values from both north and south canopy positions were correlated with tree height after 13 months. Unexplained variation in the correlation may be interpreted, theoretically, as an indication that some clones use less water for the same level of productivity. With further testing, the method may have promise for early screening of clones in genotype/environment interaction trials and in selecting water-efficient trees. 3 figs., 3 tabs., 7 refs

  2. Isotope ratio monitoring LC/MS (IRM-LC/MS): new applications

    International Nuclear Information System (INIS)

    Juchelka, D; Hilkert, A.; Krummen, M.

    2005-01-01

    With the introduction of compound specific isotope analysis by isotope ratio monitoring GC/ MS (IRM-GC/MS) the immediate demand for similar applications using HPLC was created. Many compounds of biological, medical, pharmaceutical and environmental interest are not volatile or too polar. Consequently, they cannot be directly analyzed by gas chromatography. In IRM-GC/MS the carrier is helium, which does not interfere with the essential combust ion step prior to isotope ratio mass spectrometry (IRMS). In opposite the LC mobile phase has inhibited a similar direct conversion up to now. All earlier IRM-LC/MS approaches were based on the removal of the liquid phase prior to combustion risking fractionation of the isotope ratios of the eluted compounds. To avoid such restrictions we developed a new continuous flow concept for the coupling of an HPLC system to the isotope ratio MS for 13 C/ 12C isotope ratio analysis. In the Finnigan LC IsoLink, the liquid phase is not removed from the sample prior to oxidation. The sample is oxidized still in the mobile phase followed by on-line separation of the CO 2 from the liquid phase and transfer into the isotope ratio MS. Therefore, this strategy is based on water and inorganic buffers as mobile phase. The new approach opens up a whole new world in the application of gas isotope ratio mass spectrometry. The 13 C/ 12 C ratio s of organic acids, amino acids, carbohydrates and nucleotides can now be measured. These components typically within a complex matrix are separated by liquid chromatography followed by on-line determination of the isotope ratios. The draw backs of using derivatization and off-line preparation procedures can now be over come. This new technique allow s studying biochemical cycles, running tracer experiments and determining the origin of components. Applications from different scientific areas such as biogeochemistry, molecular biology, and pharmacy as well as authenticity control o f foods will be presented

  3. Emission ratio and isotopic signatures of molecular hydrogen emissions from tropical biomass burning

    Science.gov (United States)

    Haumann, F. A.; Batenburg, A. M.; Pieterse, G.; Gerbig, C.; Krol, M. C.; Röckmann, T.

    2013-09-01

    In this study, we identify a biomass-burning signal in molecular hydrogen (H2) over the Amazonian tropical rainforest. To quantify this signal, we measure the mixing ratios of H2 and several other species as well as the H2 isotopic composition in air samples that were collected in the BARCA (Balanço Atmosférico Regional de Carbono na Amazônia) aircraft campaign during the dry season. We derive a relative H2 emission ratio with respect to carbon monoxide (CO) of 0.31 ± 0.04 ppb ppb-1 and an isotopic source signature of -280 ± 41‰ in the air masses influenced by tropical biomass burning. In order to retrieve a clear source signal that is not influenced by the soil uptake of H2, we exclude samples from the atmospheric boundary layer. This procedure is supported by data from a global chemistry transport model. The ΔH2 / ΔCO emission ratio is significantly lower than some earlier estimates for the tropical rainforest. In addition, our results confirm the lower values of the previously conflicting estimates of the H2 isotopic source signature from biomass burning. These values for the emission ratio and isotopic source signatures of H2 from tropical biomass burning can be used in future bottom-up and top-down approaches aiming to constrain the strength of the biomass-burning source for H2. Hitherto, these two quantities relied only on combustion experiments or on statistical relations, since no direct signal had been obtained from in-situ observations.

  4. Development of an enantiomer-specific stable carbon isotope analysis (ESIA) method for assessing the fate of α-hexachlorocyclo-hexane in the environment.

    Science.gov (United States)

    Badea, Silviu-Laurentiu; Vogt, Carsten; Gehre, Matthias; Fischer, Anko; Danet, Andrei-Florin; Richnow, Hans-Hermann

    2011-05-30

    α-Hexachlorocyclohexane (α-HCH) is the only chiral isomer of the eight 1,2,3,4,5,6-HCHs and we have developed an enantiomer-specific stable carbon isotope analysis (ESIA) method for the evaluation of its fate in the environment. The carbon isotope ratios of the α-HCH enantiomers were determined for a commercially available α-HCH sample using a gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) system equipped with a chiral column. The GC-C-IRMS measurements revealed δ-values of -32.5 ± 0.8‰ and -32.3 ± 0.5‰ for (-) α-HCH and (+) α-HCH, respectively. The isotope ratio of bulk α-HCH was estimated to be -32.4 ± 0.6‰ which was in accordance with the δ-values obtained by GC-C-IRMS (-32.7 ± 0.2‰) and elemental analyzer-isotope ratio mass spectrometry (EA-IRMS) of the bulk α-HCH (-32.1 ± 0.1‰). The similarity of the isotope ratio measurements of bulk α-HCH by EA-IRMS and GC-C-IRMS indicates the accuracy of the chiral GC-C-IRMS method. The linearity of the α-HCH ESIA method shows that carbon isotope ratios can be obtained for a signal size above 100 mV. The ESIA measurements exhibited standard deviations (2σ) that were mostly IRMS method, the isotope compositions of individual enantiomers in biodegradation experiments of α-HCH with Clostridium pasteurianum and samples from a contaminated field site were determined. The isotopic compositions of the α-HCH enantiomers show a range of enantiomeric and isotope patterns, suggesting that enantiomeric and isotope fractionation can serve as an indicator for biodegradation and source characterization of α-HCH in the environment. Copyright © 2011 John Wiley & Sons, Ltd.

  5. Determination of uranium, thorium and radium isotope ratio

    International Nuclear Information System (INIS)

    Sokolova, Z.A.

    1983-01-01

    The problems connected with the study of isotope composition of natural radioactive elements in natural objects are considered. It is pointed out that for minerals, ores and rocks the following ratios are usually determined: 234 U/ 238 U, 230 Th/ 238 U, 226 Ra/ 238 U, 228 Th/ 230 Th, 228 Th/ 232 Th and lead isotopes; for natural waters, besides the enumerated - 226 Ra/ 228 Ra. General content of uranium and thorium in the course of isotope investigations is determined from separate samples, most frequently by the X-ray spectral method, radium content - by usual radiochemical method, uranium and radium content in waters -respectively by calorimetric and emanation methods. Radiochemical preparation of geologic powder and aqueous samples for isotope analysis is described in detail. The technique of measuring and calculating isotope ratios (α-spectrometry for determining isotope composition of uranium and thorium and emanation method for determining 226 Ra/ 228 Ra) is presented

  6. Titan's Carbon Isotopic Ratio: A Clue To Atmospheric Evolution?

    Science.gov (United States)

    Nixon, C. A.; Jennings, D. E.; Romani, P. N.; Jolly, A.; Teanby, N. A.; Irwin, P. G.; Bézard, B.; Vinatier, S.; Coustenis, A.; Flasar, F. M.

    2009-12-01

    In this presentation we describe the latest results to come from Cassini CIRS and ground-based telescopic measurements of Titan's 12C/13C ratio in atmospheric molecules, focusing on hydrocarbons. Previously, the Huygens GCMS instrument measured 12CH4/13CH4 to be 82±1 (Niemann et al., Nature, 438, 779-784, 2005), substantially and significantly lower than the VPDB inorganic Earth standard of 89.4. It is also at odds with measurements for the giant planets. Cassini CIRS infrared spectra have confirmed this enhancement in 13CH4, but also revealed that the ratio in ethane, the major photochemical product of methane photolysis, does not appear enhanced (90±7) (Nixon et al.. Icarus, 195, 778-791, 2008) and is compatible with the terrestrial and combined giant planet value (88±7, Sada et al., Ap. J., 472, p. 903-907, 1996). Recently-published results from spectroscopy using the McMath-Pierce telescope at Kitt Pitt (Jennings et al., JCP, 2009, in press) have confirmed this deviation between methane and ethane, and an explanation has been proposed. This invokes a kinetic isotope effect (KIE) in the abstraction of methane by ethynyl, a major ethane formation pathway, to preferentially partition 12C into ethane and leave an enhancement in atmospheric 13CH4 relative to the incoming flux from the reservoir. Modeling shows that a steady-state solution exists where the 12C/13C methane is decreased from the reservoir value by exactly the KIE factor (the ratio of 12CH4 to 13CH4 abstraction reaction rates): which is plausibly around 1.08, very close to the observed amount. However, a second solution exists in which we are observing Titan about ~1 methane lifetime after a major injection of methane into the atmosphere which is rapidly being eliminated. Updated measurements by Cassini CIRS of both the methane and ethane 12C/13C ratios will be presented, along with progress in interpreting this ratio. In addition, we summarize the 12C/13C measurements by CIRS in multiple other Titan

  7. Carbon and Oxygen isotopic composition in paleoenvironmental determination

    International Nuclear Information System (INIS)

    Silva, J.R.M. da.

    1978-01-01

    This work reports that the carbon and oxygen isotopic composition separate the mollusks from marine environment of the mollusks from continental environment in two groups isotopically different, making the biological control outdone by environment control, in the isotopic fragmentation mechanisms. The patterns from the continental environment are more rich in O 16 than the patterns from marine environments. The C 12 is also more frequent in the mollusks from continental environments. The carbon isotopic composition in paterns from continental environments is situated betwen - 10.31 and - 4,05% and the oxygen isotopic composition is situated between - 6,95 and - 2,41%. To the marine environment patterns the carbon isotopic composition is between - 2,08 and + 2,65% and the oxigen isotopic composition is between - 2,08 and + 0,45%. Was also analysed fossil marine mollusks shells and their isotopic composition permit the formulation of hypothesis about the environment which they lived. (C.D.G.) [pt

  8. Stable carbon isotope response to oceanic anoxic events

    International Nuclear Information System (INIS)

    Hu Xiumian; Wang Chengshan; Li Xianghui

    2001-01-01

    Based on discussion of isotope compositions and fractionation of marine carbonate and organic carbon, the author studies the relationship between oceanic anoxic events and changes in the carbon isotope fractionation of both carbonate and organic matter. During the oceanic anoxic events, a great number of organisms were rapidly buried, which caused a kind of anoxic conditions by their decomposition consuming dissolved oxygen. Since 12 C-rich organism preserved, atmosphere-ocean system will enrich relatively of 13 C. As a result, simultaneous marine carbonate will record the positive excursion of carbon isotope. There is a distinctive δ 13 C excursion during oceanic anoxic events in the world throughout the geological time. In the Cenomanian-Turonian anoxic event. this positive excursion arrived at ∼0.2% of marine carbonate and at ∼0.4% of organic matter, respectively. Variations in the carbon isotopic compositions of marine carbonate and organic carbon record the changes in the fraction of organic carbon buried throughout the geological time and may provide clues to the changes in rates of weathering and burial of organic carbon. This will provide a possibility of interpreting not only the changes in the global carbon cycle throughout the geological time, but also that in atmospheric p CO 2

  9. Stable isotope ratio measurements in hydrogen, nitrogen, and oxygen using Raman scattering

    International Nuclear Information System (INIS)

    Harney, R.C.; Bloom, S.D.; Milanovich, F.P.

    1975-01-01

    A method for measuring stable isotope ratios using laser Raman scattering was developed which may prove of significant utility and benefit in stable isotope tracer studies. Crude isotope ratio measurements obtained with a low-power laser indicate that with current technology it should be possible to construct an isotope ratio measurement system using laser Raman scattering that is capable of performing 0.1 percent accuracy isotope ratio measurements of 16 O/ 18 O in natural abundance oxygen gas or 14 N/ 15 N in natural abundance nitrogen gas in times less than two minutes per sample. Theory pertinent to the technique, designs of specific isotope ratio spectrometer systems, and data relating to isotope ratio measurements in hydrogen, nitrogen, and oxygen are presented. In addition, the current status of several studies utilizing this technique is discussed. (auth)

  10. Changes of stable isotopes carbon-13 and nitrogen-15 in different tissues of cattle

    International Nuclear Information System (INIS)

    Sun Fengmei; Yu Hongxia; Wu Wei; Yang Shuming

    2009-01-01

    Stable isotope analysis is a potential tool for tracing food origin. The stable carbon and nitrogen isotope composition in different tissues of two varieties of cattle under the same culture condition were investigated. δ 13 C and δ 15 N values of different defatted muscle and crude fat, cattle tail hair, blood, liver and feed were determined by isotope ratio mass spectrometry, and statistical analysis was carried out. The results showed that stable isotopes of carbon and nitrogen composition was not affected by cattle variety; the δ 13 C values between different defatted muscle, blood, liver and cattle hair were not significantly different, but δ 15 N value in the liver was much higher than other muscle and the δ 13 C values didn't show difference among all the crude fat samples. So these results indicated that isotope fractionation in the various tissue was discrepant. (authors)

  11. Measurement of organic carbon stable isotope composition of different soil types by EA-IRMS system

    International Nuclear Information System (INIS)

    Qi Biao; Ding Lingling; Cui Jiehua; Wang Yanhong

    2009-01-01

    Element analyzer-isotope ratio mass spectrometers (EA-IRMS) is a rapid and precise method for measuring stable carbon isotope. Pure CO 2 reference gas was calibrated via international standard-Urea, and the δ 13 C us PDB value of pure CO 2 is (-29.523 ± 0.0181)%. Stability and linearity of the EA-IRMS system, precision of δ 13 C measurement for samples were tested through experimental comparison. Moreover, determination method of organic carbon stable isotope in soil was based on the system. The EA-IRMS system had well linearity when ion intensity ranged from 1.0 to 7.0V, and it excelled the total linearity when the ion intensity was from 1.5 to 5.0V, and the accurate result of δ 13 C for sample analysis could be obtained with precision of 0.015%. If carbon content in sample is more than 5μg, the requirement for analyzing accurate result of δ 13 C could be achieved. The organic carbon stable isotope was measured in 18 different types soil samples, the average natural abundance of 13 C was 1.082%, and the organic carbon stable isotope composition was significantly different among different type soils. (authors)

  12. FATTY ACID STABLE ISOTOPE INDICATORS OF MICROBIAL CARBON SOURCE IN TROPICAL SOILS

    Science.gov (United States)

    The soil microbial community plays an important role in tropical ecosystem functioning because of its importance in the soil organic matter (SOM) cycle. We have measured the stable carbon isotopic ratio (delta13C) of individual phospholipid fatty acids (PLFAs) in a variety of tr...

  13. BIOGENIC VS. ABIOGENIC ISOTOPE SIGNATURES OF REDUCED CARBON COMPOUNDS: A LESSON FROM HYDROTHERMAL SYNTHESIS EXPERIMENTS

    International Nuclear Information System (INIS)

    Horita, J.

    2001-01-01

    With growing interest in and demonstrated cases of inorganic hydrothermal synthesis of reduced or organic carbon compounds from CO and CO(sub 2), it becomes crucial to establish geochemical criteria to distinguish reduced/organic carbon compounds of abiogenic origin from those of biogenic origin with overwhelming abundances on the surface and in subsurface of the Earth. Chemical and isotopic compositions, particularly(sup 13)C/(sup 12)C ratios, of reduced/organic carbon compounds have been widely utilized for deducing the origins and formation pathways of these compounds. An example is isotopic and C(sub 1)/(C(sub 2)+C(sub 3)) ratios of natural gases, which have been used to distinguish bacterial, thermogenic, and possible abiogenic origins. Another example is that ancient graphitic carbon with(delta)(sup 13)C values c-25per thousand has been considered of biogenic origin. Although these criteria could be largely valid, growing data including those from our hydrothermal experiments suggest that a great caution must be exercised

  14. Strontium isotopes in carbonate deposits at Crater Flat, Nevada

    International Nuclear Information System (INIS)

    Marshall, B.D.; Futa, K.; Peterman, Z.E.; Stuckless, J.S.

    1991-01-01

    Strontium isotope studies of carbonates from soils, veins, eolian dust and Paleozoic basement sampled near Crater Flat, southwest of Yucca Mountain, provide evidence for the origins of these materials. Vein and soil carbonates have nearly identical ranges of 87 Sr/ 86 Sr, and eolian material has 87 Sr/ 86 Sr ratios at the lower end of the pedogenic range. The average 87 Sr/ 86 Sr of Paleozoic basement from Black Marble Hill is similar to the 87 Sr/ 86 Sr in the eolian dust, perhaps indicating a local source for this material. Possible spring deposits have generally higher 87 Sr/ 86 Sr than the other carbonates. These data are compared with similar data from areas east of Yucca Mountain

  15. Strontium isotopes in carbonate deposits at Crater Flat, Nevada

    International Nuclear Information System (INIS)

    Marshall, B.D.; Futa, K.; Peterman, Z.E.; Stuckless, J.S.

    1991-01-01

    Strontium isotope studies of carbonates from soils, veins, eolian dust and Paleozoic basement samples near Crater Flat, southwest of Yucca Mountain, provide evidence for the origins of these materials. Vein and soil carbonates have nearly identical ranges of 87 Sr/ 86 Sr ratios at the lower end of the pedogenic range. The average 87 Sr/ 86 Sr of Paleozoic basement from Black Marble Hill is similar to the 87 Sr/ 86 Sr in the eolian dust, perhaps indicating a local source for this material. Possible spring deposits have generally higher 87 Sr/ 86 Sr than the other carbonates. These data are compared with similar data from areas east of Yucca Mountain. 7 refs., 5 figs

  16. Seasonal dynamics of stable isotopes and element ratios in authigenic calcites during their precipitation and dissolution, Sacrower See (northeastern Germany

    Directory of Open Access Journals (Sweden)

    Bernd ZOLITSCHKA

    2009-08-01

    Full Text Available The seasonal evolution of chemical and physical water properties as well as particle fluxes was monitored in Sacrower See (northeastern Germany during two consecutive years (Oct 2003 - Oct 2005. Additonally, we measured δ18O and δ13C as well as Sr:Ca and Mg:Ca ratios of authigenic calcites that were collected in sequencing sediment traps in order to disentangle environmental and climatic factors controlling these parameters. In particular, our aim was to find out if element ratios and the isotopic composition of calcites reflect changes in water and air temperatures. Lake water is highly enriched in 18O (-1.3 to -2.5‰ VSMOW with an evaporative increase of 0.6‰ during summer. Values are 5-6‰ more positive than groundwater values and 4-5‰ more positive than long-term weighted annual means of precipitation. During spring and summer, high amounts of dissolved phosphate cause eutrophic conditions and calcite precipitation in isotopic disequilibrium. Measured values are depleted in 18O by 2 to 10‰ compared to calculated equilibrium values. Resuspension and partial dissolution of calcite in the water column contribute to this isotopic divergence in summer and autumn as δ18Oca and δ13C values increased in the hypolimnion during this time. Mg:Ca and Sr:Ca ratios are altered by dissolution as well. In the hypolimnion these ratios were higher than in the epilimnion. Another reason for the huge deviation between measured and theoretical δ18Oca values during summer is the occurrence of large amounts of Phacotus lenticularis in the carbonate fraction. High amounts of Phacotus lead to more negative δ18Oca and more positive δ13C values. Several characteristics of δ18Oca and δ13C are also reflected by Mg:Ca and Sr:Ca ratios and isotopic composition of oxygen and carbon were influenced by the onset and stability of stratification. Especially the earlier onset of stratification in 2005 caused higher sediment fluxes and more positive carbon and

  17. Carbon fixation and isotope discrimination by a crassulacean plant: dependence on the photoperiod.

    Science.gov (United States)

    Lerman, J C; Queiroz, O

    1974-03-22

    Variations of more than 1 percent are observed in the carbon-13 to carbon-12 ratio of extracts of leaves of the succulent Kalanchoe blossfeldiana when the photoperiod is changed from long to short days. This indicates that the mechanism of carbon fixation switches from the Calvin (C(3)) pathway to the Hatch-Slack (C(4)) pathway of primary enzymic operation. The variations observed in the isotope compositions are tentatively explained by a model.

  18. Carbon and hydrogen isotope ratios of bacterial methane and its formation mechanism

    International Nuclear Information System (INIS)

    Sugimoto, A.; Wada, E.

    1993-01-01

    Anaerobic incubations of paddy soil collected from Konosu, Japan, were carried out for 10 weeks to clarify the general principles that govern the variation of carbon isotopic composition of bacterial methane from freshwater areas. The δ 13 C value of produced CH 4 was highly variable ranging from -60 to -33%, corresponding to change in its formation pathways: acetate fermentation and CO 2 /H 2 reduction. The δ 13 C value of CH 4 from CO 2 /H 2 was estimated as -77 to -60%, adopting 45% of δ 13 C difference between the CH 4 and its source CO 2 . The δ 13 C value of methyl carbon of acetate accumulated with addition of inhibitor for methanogenesis ranged from -43 to -30%, which was considered with the δ 13 C value of CH 4 from acetate. Variability of CH 4 δ 13 C resulted from the difference in contribution of each biological process. It was demonstrated that δ 13 C value of methane was a useful indicator for assessing the contribution of each process in wetlands and paddy fields. (author)

  19. Using a laser-based CO2 carbon isotope analyser to investigate gas transfer in geological media

    International Nuclear Information System (INIS)

    Guillon, S.; Pili, E.; Agrinier, P.

    2012-01-01

    CO 2 stable carbon isotopes are very attractive in environmental research to investigate both natural and anthropogenic carbon sources. Laser-based CO 2 carbon isotope analysis provides continuous measurement at high temporal resolution and is a promising alternative to isotope ratio mass spectrometry (IRMS). We performed a thorough assessment of a commercially available CO 2 Carbon Isotope Analyser (CCIA DLT-100, Los Gatos Research) that allows in situ measurement of C-13 in CO 2 . Using a set of reference gases of known CO 2 concentration and carbon isotopic composition, we evaluated the precision, long-term stability, temperature sensitivity and concentration dependence of the analyser. Despite good precision calculated from Allan variance (5.0 ppm for CO 2 concentration, and 0.05 per thousand for δC-13 at 60 s averaging), real performances are altered by two main sources of error: temperature sensitivity and dependence of C-13 on CO 2 concentration. Data processing is required to correct for these errors. Following application of these corrections, we achieve an accuracy of 8.7 ppm for CO 2 concentration and 1.3 per thousand for δC-13, which is worse compared to mass spectrometry performance, but still allowing field applications. With this portable analyser we measured CO 2 flux degassed from rock in an underground tunnel. The obtained carbon isotopic composition agrees with IRMS measurement, and can be used to identify the carbon source. (authors)

  20. Effectiveness of different pre-treatments in recovering pre-burial isotopic ratios of charred plants.

    Science.gov (United States)

    Brinkkemper, O; Braadbaart, F; van Os, B; van Hoesel, A; van Brussel, A A N; Fernandes, R

    2018-02-15

    Isotopic analysis of archaeological charred plant remains offers useful archaeological information. However, adequate sample pre-treatment protocols may be necessary to provide a contamination-free isotopic signal while limiting sample loss and achieving a high throughput. Under these constraints, research was undertaken to compare the performance of different pre-treatment protocols. Charred archaeological plant material was selected for isotopic analysis (δ 13 C and δ 15 N values) by isotope ratio mass spectrometry from a variety of plant species, time periods and soil conditions. Preservation conditions and the effectiveness of cleaning protocols were assessed through Fourier transform infrared spectroscopy and X-ray fluorescence (XRF) spectrometry. An acid-base-acid protocol, successfully employed in radiocarbon dating, was used to define a contamination-free isotopic reference. Acid-base-acid isotopic measurements were compared with those obtained from untreated material and an acid-only protocol. The isotopic signals of untreated material and the acid-only protocol typically did not differ more than 1‰ from those of the acid-base-acid reference. There were no significant isotopic offsets between acid-base-acid and acid-only or untreated samples. Sample losses in the acid-base-acid protocol were on average 50 ± 17% (maximum = 98.4%). Elemental XRF measurements showed promising results in the detection of more contaminated samples albeit with a high rate of false positives. For the large range of preservation conditions described in the study, untreated charred plant samples, water cleaned of sediments, provide reliable stable isotope ratios of carbon and nitrogen. The use of pre-treatments may be necessary under different preservation conditions or more conservative measurement uncertainties should be reported. Copyright © 2017 John Wiley & Sons, Ltd.

  1. A carbon isotope survey of South African honey

    International Nuclear Information System (INIS)

    Thorp, J.A.L.; Lanham, J.L.; Wenner, D.B.; Van der Merwe, N.J.

    1987-01-01

    Stable carbon isotope analysis has been successfully employed in various fields, including botany, geochemistry, archaeology and, more recently, as an analytical tool in the food industry. In the analysis of food, it has been primarily directed at quality control and the detection of cheap adulterants to 'natural' foods. The method is based on the known characteristic of differences in the 13 C to 12 C ratios produced by two groups of plants with different photosynthetic mechanisms, known as C 3 and C 4 . This patterning is useful because the cheapest sources of alcohol, sweeteners and flavourings are derived from C 4 plants, maize and sugar cane, whereas traditional Old World sources such as grapes, nectar and fruit are derived from C 3 plants. The results of an informal isotopic survey of South African honeys are reported. This isotopic method is particularly useful in that it is not possible to circumvent it by manipulation of the sugars or any of the other constituents

  2. Gluconeogenesis from labeled carbon: estimating isotope dilution

    International Nuclear Information System (INIS)

    Kelleher, J.K.

    1986-01-01

    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

  3. Do Strontium Isotope Ratios of Animal Bone and Teeth Really Reflect the Isotope Ratios of its birth- and growth-places?

    Science.gov (United States)

    Minami, M.; Goto, A.; Suzuki, K.; Kato, T.; Watanabe, K.; Hasegawa, T.

    2007-12-01

    Strontium enters the human body through the food chain as nutrients pass from bedrock through soil and water to plants and animals. Strontium substitutes for calcium in the hydroxyapatite mineral of skeletal tissue, and is stored there. 87Sr/86Sr ratios in an individual's bone and teeth could directly reflect the isotopic ratios found in the plants and animals that she or he consumed, which reflect the isotope ratios found in the soil and bedrock of that geologic region. Therefore, 87Sr/86Sr ratios of human skeletons could be useful tools for assessing human residential mobility in prehistory, and many studies on them have been often made. In this study, to evaluate whether the 87Sr/86Sr ratio of a bone or teeth really reflects the isotopic ratios of its birth and growth places, several bone and teeth samples were measured for 87Sr/86Sr ratios, compared with 87Sr/86Sr ratios of geological samples in their growth-places. Bone and teeth samples were leached with 5% acetic acid. After drying, samples were ashed in a muffle furnace at 825°C for 8h, and then digested in nitric acid, followed by cation exchange chromatography with 2.4M hydrochloric acid. 87Sr/86Sr ratios were measured using a thermal ionization mass Spectrometer (VG Sector 54) or an inductively coupled plasma mass spectrometer (Finnigan ELEMENT2). A modern boar bone collected at Asuke, Toyota City, Aichi prefecture, Japan showed a 87Sr/86Sr of 0.71001±0.00002 (2 σ), while stream sediments in the Asuke area showed around 0.710 (Asahara et al., 2006). The 87Sr/86Sr ratio of a modern black bass bone collected from Lake Biwa, Shiga prefecture, Japan was 0.71215±0.00002, while those of surface water in Lake Biwa was 0.71233±0.00002. The similar 87Sr/86Sr ratios between bone and its provenance geology could indicate that the 87Sr/86Sr ratios of bones reflect the isotopic ratios of the birth- and growth-places. The more results of modern and fossil skeletons will be shown in our presentation.

  4. Source Attribution of Cyanides using Anionic Impurity Profiling, Stable Isotope Ratios, Trace Elemental Analysis and Chemometrics

    Energy Technology Data Exchange (ETDEWEB)

    Mirjankar, Nikhil S.; Fraga, Carlos G.; Carman, April J.; Moran, James J.

    2016-01-08

    Chemical attribution signatures (CAS) for chemical threat agents (CTAs) are being investigated to provide an evidentiary link between CTAs and specific sources to support criminal investigations and prosecutions. In a previous study, anionic impurity profiles developed using high performance ion chromatography (HPIC) were demonstrated as CAS for matching samples from eight potassium cyanide (KCN) stocks to their reported countries of origin. Herein, a larger number of solid KCN stocks (n = 13) and, for the first time, solid sodium cyanide (NaCN) stocks (n = 15) were examined to determine what additional sourcing information can be obtained through anion, carbon stable isotope, and elemental analyses of cyanide stocks by HPIC, isotope ratio mass spectrometry (IRMS), and inductively coupled plasma optical emission spectroscopy (ICP-OES), respectively. The HPIC anion data was evaluated using the variable selection methods of Fisher-ratio (F-ratio), interval partial least squares (iPLS), and genetic algorithm-based partial least squares (GAPLS) and the classification methods of partial least squares discriminate analysis (PLSDA), K nearest neighbors (KNN), and support vector machines discriminate analysis (SVMDA). In summary, hierarchical cluster analysis (HCA) of anion impurity profiles from multiple cyanide stocks from six reported country of origins resulted in cyanide samples clustering into three groups: Czech Republic, Germany, and United States, independent of the associated alkali metal (K or Na). The three country groups were independently corroborated by HCA of cyanide elemental profiles and corresponded to countries with known solid cyanide factories. Both the anion and elemental CAS are believed to originate from the aqueous alkali hydroxides used in cyanide manufacture. Carbon stable isotope measurements resulted in two clusters: Germany and United States (the single Czech stock grouped with United States stocks). The carbon isotope CAS is believed to

  5. Organic carbon isotope ratios of recent sediments from coastal lagoons of the Gulf of Mexico, Mexico

    International Nuclear Information System (INIS)

    Botello, A.V.; Mandelli, E.F.; Macko, S.; Parker, P.L.

    1980-01-01

    The stable carbon isotope composition of sedimentary organic carbon was determined in the sediments of seven coastal lagoons of the Gulf of Mexico, Mexico. For most of the lagoons the delta 13 C values for sediments ranged from -20.1 to -23.9 parts per thousand. Anomalously low values, -26.8 to 29.3 parts per thousand were determined in sediments of two of the studied lagoons, probably due to the presence of organic carbon from anthropogenic sources, naturally absent in these environments. The delta 13 C values determined in the tissues of oysters collected at the same time in the different lagoons were very similar to those recorded in the sediments. (author)

  6. Carbon and nitrogen stable isotope ratios of pelagic zooplankton elucidate ecohydrographic features in the oligotrophic Red Sea

    KAUST Repository

    Kü rten, Benjamin; Al-Aidaroos, Ali M.; Kurten, Saskia; El-Sherbiny, Mohsen M.; Devassy, Reny P.; Struck, Ulrich; Zarokanellos, Nikolaos; Jones, Burton; Hansen, Thomas; Bruss, Gerd; Sommer, Ulrich

    2015-01-01

    Although zooplankton occupy key roles in aquatic biogeochemical cycles, little is known about the pelagic food web and trophodynamics of zooplankton in the Red Sea. Natural abundance stable isotope analysis (SIA) of carbon (δ13C) and N (δ15N) is one

  7. CARBON ISOTOPE FRACTIONATION IN PROTOPLANETARY DISKS

    International Nuclear Information System (INIS)

    Woods, Paul M.; Willacy, Karen

    2009-01-01

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

  8. Carbon isotope fractionation in the mangrove Avicennia marina has implications for food web and blue carbon research

    Science.gov (United States)

    Kelleway, Jeffrey J.; Mazumder, Debashish; Baldock, Jeffrey A.; Saintilan, Neil

    2018-05-01

    The ratio of stable isotopes of carbon (δ13C) is commonly used to track the flow of energy among individuals and ecosystems, including in mangrove forests. Effective use of this technique requires understanding of the spatial variability in δ13C among primary producer(s) as well as quantification of the isotopic fractionations that occur as C moves within and among ecosystem components. In this experiment, we assessed δ13C variation in the cosmopolitan mangrove Avicennia marina across four sites of varying physico-chemical conditions across two estuaries. We also compared the isotopic values of five distinct tissue types (leaves, woody stems, cable roots, pneumatophores and fine roots) in individual plants. We found a significant site effect (F3, 36 = 15.78; P 3.0‰) means that it may now be possible to partition the individual contributions of various mangrove tissues to estuarine food webs. Similarly, the contributions of mangrove leaves, woody debris and belowground sources to blue carbon stocks might also be quantified. Above all, however, our results emphasize the importance of considering appropriate mangrove tissue types when using δ13C to trace carbon cycling in estuarine systems.

  9. MAGNESIUM ISOTOPE RATIOS IN ω CENTAURI RED GIANTS

    International Nuclear Information System (INIS)

    Da Costa, G. S.; Norris, John E.; Yong, David

    2013-01-01

    We have used the high-resolution observations obtained at the Anglo-Australian Telescope with Ultra-High Resolution Facility (R ∼ 100,000) and at Gemini-S with b-HROS (R ∼ 150,000) to determine magnesium isotope ratios for seven ω Cen red giants that cover a range in iron abundance from [Fe/H] = –1.78 to –0.78 dex, and for two red giants in M4 (NGC 6121). The ω Cen stars sample both the ''primordial'' (i.e., O-rich, Na- and Al-poor) and the ''extreme'' (O-depleted, Na- and Al-rich) populations in the cluster. The primordial population stars in both ω Cen and M4 show ( 25 Mg, 26 Mg)/ 24 Mg isotopic ratios that are consistent with those found for the primordial population in other globular clusters with similar [Fe/H] values. The isotopic ratios for the ω Cen extreme stars are also consistent with those for extreme population stars in other clusters. The results for the extreme population stars studied indicate that the 26 Mg/ 24 Mg ratio is highest at intermediate metallicities ([Fe/H] 26 Mg in the extreme population stars is notably higher than that of 25 Mg, in contrast to model predictions. The 25 Mg/ 24 Mg isotopic ratio in fact does not show any obvious dependence on either [Fe/H] or [Al/Fe] nor, intriguingly, any obvious difference between the primordial and extreme population stars.

  10. Determination of fission gas yields from isotope ratios

    DEFF Research Database (Denmark)

    Mogensen, Mogens Bjerg

    1983-01-01

    This paper describes a method of calculating the actual fission yield of Kr and Xe in nuclear fuel including the effect of neutron capture reactions and decay. The bases for this calculation are the cumulative yields (ref. 1) of Kr and Xe isotopes (or pairs of isotopes) which are unaffected...... by neutron capture reactions, and measured Kr and Xe isotope ratios. Also the burnup contribution from the different fissile heavy isotopes must be known in order to get accurate fission gas yields....

  11. An improved data acquisition system for isotopic ratio mass spectrometers

    International Nuclear Information System (INIS)

    Saha, T.K.; Reddy, B.; Nazare, C.K.; Handu, V.K.

    1999-01-01

    Isotopic ratio mass spectrometers designed and fabricated to measure the isotopic ratios with a precision of better than 0.05%. In order to achieve this precision, the measurement system consisting of ion signal to voltage converters, analog to digital converters, and data acquisition electronics should be at least one order better than the overall precision of measurement. Using state of the art components and techniques, a data acquisition system, which is an improved version of the earlier system, has been designed and developed for use with multi-collector isotopic ratio mass spectrometers

  12. Liquid and gas chromatography coupled to isotope ratio mass spectrometry for the determination of 13C-valine isotopic ratios in complex biological samples.

    Science.gov (United States)

    Godin, Jean-Philippe; Breuillé, Denis; Obled, Christiane; Papet, Isabelle; Schierbeek, Henk; Hopfgartner, Gérard; Fay, Laurent-Bernard

    2008-10-01

    On-line gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) is commonly used to measure isotopic ratios at natural abundance as well as for tracer studies in nutritional and medical research. However, high-precision (13)C isotopic enrichment can also be measured by liquid chromatography-isotope ratio mass spectrometry (LC-IRMS). Indeed, LC-IRMS can be used, as shown by the new method reported here, to obtain a baseline separation and to measure (13)C isotopic enrichment of underivatised amino acids (Asp, Thr-Ser, Glu, Pro, Gly, Ala, Cys and Val). In case of Val, at natural abundance, the SD(delta(13)C) reported with this method was found to be below 1 per thousand . Another key feature of the new LC-IRMS method reported in this paper is the comparison of the LC-IRMS approach with the conventional GC-C-IRMS determination. To perform this comparative study, isotopic enrichments were measured from underivatised Val and its N(O, S)-ethoxycarbonyl ethyl ester derivative. Between 0.0 and 1.0 molar percent excess (MPE) (delta(13)C= -12.3 to 150.8 per thousand), the calculated root-mean-square (rms) of SD was 0.38 and 0.46 per thousand and the calculated rms of accuracy was 0.023 and 0.005 MPE, respectively, for GC-C-IRMS and LC-IRMS. Both systems measured accurately low isotopic enrichments (0.002 atom percent excess (APE)) with an SD (APE) of 0.0004. To correlate the relative (delta(13)C) and absolute (atom%, APE and MPE) isotopic enrichment of Val measured by the GC-C-IRMS and LC-IRMS devices, mathematical equations showing the slope and intercept of the curves were established and validated with experimental data between 0.0 to 2.3 MPE. Finally, both GC-C-IRMS and LC-IRMS instruments were also used to assess isotopic enrichment of protein-bound (13)C-Val in tibial epiphysis in a tracer study performed in rats. Isotopic enrichments measured by LC-IRMS and GC-C-IRMS were not statistically different (p>0.05). The results of this work indicate that

  13. Increase in soil stable carbon isotope ratio relates to loss of organic carbon: results from five long-term bare fallow experiments

    DEFF Research Database (Denmark)

    Menichetti, Lorenzo; Houot, Sabine; van Oort, Folkert

    2015-01-01

    Changes in the 12C/13C ratio (expressed as δ13C) of soil organic C (SOC) has been observed over long time scales and with depth in soil profiles. The changes are ascribed to the different reaction kinetics of 12C and 13C isotopes and the different isotopic composition of various SOC pool components...... examined. The overall estimate of the fractionation coefficient (ε) was −1.2 ± 0.3 ‰. This coefficient represents an important input to studies of long-term SOC dynamics in agricultural soils that are based on variations in 13C natural abundance. The variance of ε may be ascribed to site characteristics...... some impact on isotope abundance and fractionation....

  14. Unravelling spatiotemporal tree-ring signals in Mediterranean oaks: a variance-covariance modelling approach of carbon and oxygen isotope ratios.

    Science.gov (United States)

    Shestakova, Tatiana A; Aguilera, Mònica; Ferrio, Juan Pedro; Gutiérrez, Emilia; Voltas, Jordi

    2014-08-01

    Identifying how physiological responses are structured across environmental gradients is critical to understanding in what manner ecological factors determine tree performance. Here, we investigated the spatiotemporal patterns of signal strength of carbon isotope discrimination (Δ(13)C) and oxygen isotope composition (δ(18)O) for three deciduous oaks (Quercus faginea (Lam.), Q. humilis Mill. and Q. petraea (Matt.) Liebl.) and one evergreen oak (Q. ilex L.) co-occurring in Mediterranean forests along an aridity gradient. We hypothesized that contrasting strategies in response to drought would lead to differential climate sensitivities between functional groups. Such differential sensitivities could result in a contrasting imprint on stable isotopes, depending on whether the spatial or temporal organization of tree-ring signals was analysed. To test these hypotheses, we proposed a mixed modelling framework to group isotopic records into potentially homogeneous subsets according to taxonomic or geographical criteria. To this end, carbon and oxygen isotopes were modelled through different variance-covariance structures for the variability among years (at the temporal level) or sites (at the spatial level). Signal-strength parameters were estimated from the outcome of selected models. We found striking differences between deciduous and evergreen oaks in the organization of their temporal and spatial signals. Therefore, the relationships with climate were examined independently for each functional group. While Q. ilex exhibited a large spatial dependence of isotopic signals on the temperature regime, deciduous oaks showed a greater dependence on precipitation, confirming their higher susceptibility to drought. Such contrasting responses to drought among oak types were also observed at the temporal level (interannual variability), with stronger associations with growing-season water availability in deciduous oaks. Thus, our results indicate that Mediterranean deciduous

  15. A universal carbonate ion effect on stable oxygen isotope ratios in unicellular planktonic calcifying organisms

    OpenAIRE

    Ziveri, P.; Thoms, S.; Probert, I.; Geisen, M.; Langer, H.

    2012-01-01

    The oxygen isotopic composition (δ18O) of calcium carbonate of planktonic calcifying organisms is a key tool for reconstructing both past seawater temperature and salinity. The calibration of paloeceanographic proxies relies in general on empirical relationships derived from field experiments on extant species. Laboratory experiments have more often than not revealed that variables other than the target parameter influence the proxy signal, which makes proxy c...

  16. Application of sulphur isotope ratios to examine weaning patterns and freshwater fish consumption in Roman Oxfordshire, UK

    Science.gov (United States)

    Nehlich, Olaf; Fuller, Benjamin T.; Jay, Mandy; Mora, Alice; Nicholson, Rebecca A.; Smith, Colin I.; Richards, Michael P.

    2011-09-01

    This study investigates the application of sulphur isotope ratios (δ 34S) in combination with carbon (δ 13C) and nitrogen (δ 15N) ratios to understand the influence of environmental sulphur on the isotopic composition of archaeological human and faunal remains from Roman era sites in Oxfordshire, UK. Humans ( n = 83), terrestrial animals ( n = 11), and freshwater fish ( n = 5) were analysed for their isotope values from four locations in the Thames River Valley, and a broad range of δ 34S values were found. The δ 34S values from the terrestrial animals were highly variable (-13.6‰ to +0.5‰), but the δ 34S values of the fish were clustered and 34S-depleted (-20.9‰ to -17.3‰). The results of the faunal remains suggest that riverine sulphur influenced the terrestrial sulphur isotopic signatures. Terrestrial animals were possibly raised on the floodplains of the River Thames, where highly 34S-depleted sulphur influenced the soil. The humans show the largest range of δ 34S values (-18.8‰ to +9.6‰) from any archaeological context to date. No differences in δ 34S values were found between the males (-7.8 ± 6.0‰) and females (-5.3 ± 6.8‰), but the females had a linear correlation ( R2 = 0.71; p eating solely terrestrial protein resources and others showing a diet almost exclusively based on freshwater protein such as fish. Such large dietary variability was not visible by analysing only the carbon and nitrogen isotope ratios, and this research represents the largest and most detailed application of δ 34S analysis to examine dietary practices (including breastfeeding and weaning patterns) during the Romano-British Period.

  17. Continuous measurements of stable isotopes of carbon dioxide and water vapour in an urban atmosphere: isotopic variations associated with meteorological conditions.

    Science.gov (United States)

    Wada, Ryuichi; Matsumi, Yutaka; Nakayama, Tomoki; Hiyama, Tetsuya; Fujiyoshi, Yasushi; Kurita, Naoyuki; Muramoto, Kenichiro; Takanashi, Satoru; Kodama, Naomi; Takahashi, Yoshiyuki

    2017-12-01

    Isotope ratios of carbon dioxide and water vapour in the near-surface air were continuously measured for one month in an urban area of the city of Nagoya in central Japan in September 2010 using laser spectroscopic techniques. During the passages of a typhoon and a stationary front in the observation period, remarkable changes in the isotope ratios of CO 2 and water vapour were observed. The isotope ratios of both CO 2 and water vapour decreased during the typhoon passage. The decreases can be attributed to the air coming from an industrial area and the rainout effects of the typhoon, respectively. During the passage of the stationary front, δ 13 C-CO 2 and δ 18 O-CO 2 increased, while δ 2 H-H 2 Ov and δ 18 O-H 2 Ov decreased. These changes can be attributed to the air coming from rural areas and the air surrounding the observational site changing from a subtropical air mass to a subpolar air mass during the passage of the stationary front. A clear relationship was observed between the isotopic CO 2 and water vapour and the meteorological phenomena. Therefore, isotopic information of CO 2 and H 2 Ov could be used as a tracer of meteorological information.

  18. Carbon isotope geochemistry of the Cretaceous-Tertiary section of the Wasserfallgraben, Lattengebirge, southeast Germany

    International Nuclear Information System (INIS)

    Arneth, J.D.; Matzigkeit, U.; Boos, A.

    1985-01-01

    Carbonates and organic matter in sediments of the Cretaceous-Tertiary (C/T) section of the Wasserfallgraben, Lattengebirge (Bavaria) have been investigated. All parameters - the carbonate content (Csub(carb)), its isotopic composition (delta 13 Csub(carb),delta 18 Osub(carb)) as well as the organic carbon content (Csub(org)), its isotopic composition (delta 13 Csub(org)) and the H/C ratio of the sedimentary organic matter - display systematic variations across the C/T boundary which cannot be attributed to a single cause. The boundary zone as a whole is tectonically disturbed and shows significant features of detrital contaminations. Unidirectional shift in delta 13 Csub(carb) and delta 13 Csub(org) are observed when directly comparing Maastrichtian (latest Cretaceous) and Danian (earliest Tertiary) sediments. These synchronous isotope displacements towards more negative readings are interpreted to reflect the reduced photosynthetic activity as consequence of the mass extinction at the C/T boundary. The results may have some bearings on other C/T profiles investigated where measurements on the reduced carbon species are still lacking. (orig.)

  19. Platinum stable isotope ratio measurements by double-spike multiple collector ICPMS

    DEFF Research Database (Denmark)

    Creech, John; Baker, Joel; Handler, Monica

    2013-01-01

    We present a new technique for the precise determination of platinum (Pt) stable isotope ratios by multiple-collector inductively coupled plasma mass spectrometry (MC-ICPMS) using two different Pt double-spikes ( Pt-Pt and Pt-Pt). Results are expressed relative to the IRMM-010 Pt isotope standard......) can be obtained on Pt stable isotope ratios with either double-spike. Elemental doping tests reveal that double-spike corrected Pt stable isotope ratios are insensitive to the presence of relatively high (up to 10%) levels of matrix elements, although the Pt-Pt double-spike is affected by an isobaric...... = 7.308%) results in a redefined Pt atomic weight of 195.08395 ± 0.00068. Using our technique we have measured small, reproducible and statistically significant offsets in Pt stable isotope ratios between different Pt element standards and the IRMM-010 standard, which potentially indicates...

  20. Lateglacial and Holocene climatic changes in south-eastern Patagonia inferred from carbonate isotope records of Laguna Potrok Aike (Argentina)

    Science.gov (United States)

    Oehlerich, M.; Mayr, C.; Gussone, N.; Hahn, A.; Hölzl, S.; Lücke, A.; Ohlendorf, C.; Rummel, S.; Teichert, B. M. A.; Zolitschka, B.

    2015-04-01

    First results of strontium, calcium, carbon and oxygen isotope analyses of bulk carbonates from a 106 m long sediment record of Laguna Potrok Aike, located in southern Patagonia are presented. Morphological and isotopic investigations of μm-sized carbonate crystals in the sediment reveal an endogenic origin for the entire Holocene. During this time period the calcium carbonate record of Laguna Potrok Aike turned out to be most likely ikaite-derived. As ikaite precipitation in nature has only been observed in a narrow temperature window between 0 and 7 °C, the respective carbonate oxygen isotope ratios serve as a proxy of hydrological variations rather than of palaeotemperatures. We suggest that oxygen isotope ratios are sensitive to changes of the lake water balance induced by intensity variations of the Southern Hemisphere Westerlies and discuss the role of this wind belt as a driver for climate change in southern South America. In combination with other proxy records the evolution of westerly wind intensities is reconstructed. Our data suggest that weak SHW prevailed during the Lateglacial and the early Holocene, interrupted by an interval with strengthened Westerlies between 13.4 and 11.3 ka cal BP. Wind strength increased at 9.2 ka cal BP and significantly intensified until 7.0 ka cal BP. Subsequently, the wind intensity diminished and stabilised to conditions similar to present day after a period of reduced evaporation during the "Little Ice Age". Strontium isotopes (87Sr/86Sr ratio) were identified as a potential lake-level indicator and point to a lowering from overflow conditions during the Glacial (∼17 ka cal BP) to lowest lake levels around 8 ka cal BP. Thereafter the strontium isotope curve resembles the lake-level curve which is stepwise rising until the "Little Ice Age". The variability of the Ca isotope composition of the sediment reflects changes in the Ca budget of the lake, indicating higher degrees of Ca utilisation during the period with

  1. Uranium isotope ratio measurements in field settings

    International Nuclear Information System (INIS)

    Shaw, R.W.; Barshick, C.M.; Young, J.P.; Ramsey, J.M.

    1997-01-01

    The authors have developed a technique for uranium isotope ratio measurements of powder samples in field settings. Such a method will be invaluable for environmental studies, radioactive waste operations, and decommissioning and decontamination operations. Immediate field data can help guide an ongoing sampling campaign. The measurement encompasses glow discharge sputtering from pressed sample hollow cathodes, high resolution laser spectroscopy using conveniently tunable diode lasers, and optogalvanic detection. At 10% 235 U enrichment and above, the measurement precision for 235 U/( 235 U+ 238 U) isotope ratios was ±3%; it declined to ±15% for 0.3% (i.e., depleted) samples. A prototype instrument was constructed and is described

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

    Science.gov (United States)

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

    2014-01-01

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

  3. System and method for high precision isotope ratio destructive analysis

    Science.gov (United States)

    Bushaw, Bruce A; Anheier, Norman C; Phillips, Jon R

    2013-07-02

    A system and process are disclosed that provide high accuracy and high precision destructive analysis measurements for isotope ratio determination of relative isotope abundance distributions in liquids, solids, and particulate samples. The invention utilizes a collinear probe beam to interrogate a laser ablated plume. This invention provides enhanced single-shot detection sensitivity approaching the femtogram range, and isotope ratios that can be determined at approximately 1% or better precision and accuracy (relative standard deviation).

  4. A novel high-temperature combustion based system for stable isotope analysis of dissolved organic carbon in aqueous samples. : I development and validation

    NARCIS (Netherlands)

    Federherr, E.; Cerli, C.; Kirkels, F. M. S. A.; Kalbitz, K.; Kupka, H. J.; Dunsbach, R.; Lange, L.; Schmidt, T. C.

    2014-01-01

    RATIONALE: Traditionally, dissolved organic carbon (DOC) stable isotope analysis (SIA) is performed using either offline sample preparation followed by elemental analyzer/isotope ratiomass spectrometry (EA/IRMS) or a wet chemical oxidation (WCO)-based device coupled to an isotope ratio mass

  5. A carbon isotope budget for an anoxic marine sediment

    International Nuclear Information System (INIS)

    Boehme, S.E.; Blair, N.E.

    1991-01-01

    A carbon isotope budget has been determined for the coastal marine site, Cape Lookout Bight, NC. Isotope measurements of methane and σCO 2 fluxing out and buried in these sediments were applied to previously measured flux data (Martens et al., in press) to predict the isotopic composition of the incoming metabolizable organic matter. Methane leaves the sediment predominantly via ebullition with an isotopic composition of -60 per mil. Less than 2% of the methane produced is buried with an average diffusional flux value of -17 per mil and a burial value of +11 per mil. The isotope budget predicts a metabolizable organic carbon isotope signature of -19.3 per mil which is in excellent agreement with the measured total organic carbon value of -19.2 ± 0.3 per mil implying that the dominant remineralization processes have been identified

  6. Analysis of carbon stable isotope to determine the origin and migration of gaseous hydrocarbon in the Brazilian sedimentary basins

    International Nuclear Information System (INIS)

    Takaki, T.; Rodrigues, R.

    1986-01-01

    The carbon isotopic composition of natural gases to determine the origin and gaseous hydrocarbon migration of Brazilian sedimentar basins is analysed. The carbon isotopic ratio of methane from natural gases depends on the process of gas formation and stage of organic matter maturation. In the geochemical surface exploration the biogenic gases are differentiated from thermogenic gases, because the last one is isotopically heavier. As the isotopic composition of methane has not changed during migration, the migrated gases from deeper and more mature source rocks are identified by its relative 13 C enrichment. The methane was separated from chromatography and and the isotopic analysis was done with mass spectrometer. (M.C.K.) [pt

  7. Detection of counterfeit antiviral drug Heptodin and classification of counterfeits using isotope amount ratio measurements by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) and isotope ratio mass spectrometry (IRMS).

    Science.gov (United States)

    Santamaria-Fernandez, Rebeca; Hearn, Ruth; Wolff, Jean-Claude

    2009-06-01

    Isotope ratio mass spectrometry (IRMS) and multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) are highly important techniques that can provide forensic evidence that otherwise would not be available. MC-ICP-MS has proved to be a very powerful tool for measuring high precision and accuracy isotope amount ratios. In this work, the potential of combining isotope amount ratio measurements performed by MC-ICP-MS and IRMS for the detection of counterfeit pharmaceutical tablets has been investigated. An extensive study for the antiviral drug Heptodin has been performed for several isotopic ratios combining MC-ICP-MS and an elemental analyser EA-IRMS for stable isotope amount ratio measurements. The study has been carried out for 139 batches of the antiviral drug and analyses have been performed for C, S, N and Mg isotope ratios. Authenticity ranges have been obtained for each isotopic system and combined to generate a unique multi-isotopic pattern only present in the genuine tablets. Counterfeit tablets have then been identified as those tablets with an isotopic fingerprint outside the genuine isotopic range. The combination of those two techniques has therefore great potential for pharmaceutical counterfeit detection. A much greater power of discrimination is obtained when at least three isotopic systems are combined. The data from these studies could be presented as evidence in court and therefore methods need to be validated to support their credibility. It is also crucial to be able to produce uncertainty values associated to the isotope amount ratio measurements so that significant differences can be identified and the genuineness of a sample can be assessed.

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

    International Nuclear Information System (INIS)

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

    1994-01-01

    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 13 C content of soil CO 2 , CaCO 3 , precipitation mechanisms, and isotopic fractionations between parent fluids and precipitating carbonates. The 13 C content of soil carbon dioxide from Yucca Mountain and vicinity shows most of the usual patterns expected in such contexts: Decreasing 13 C content with depth decreasing 13 C with altitude and reduced 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 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

  9. Isotopic ratios D/H and 15N/14N in giant planets

    Science.gov (United States)

    Marboeuf, Ulysse; Thiabaud, Amaury; Alibert, Yann; Benz, Willy

    2018-04-01

    The determination of isotopic ratios in planets is important since it allows us to investigate the origins and initial composition of materials. The present work aims to determine the possible range of values for isotopic ratios D/H and 15N/14N in giant planets. The main objective is to provide valuable theoretical assumptions on the isotopic composition of giant planets, their internal structure, and the main reservoirs of species. We use models of ice formation and planet formation that compute the composition of ices and gas accreted in the core and the envelope of planets. Assuming a single initial value for isotopic ratios in volatile species, and disruption of planetesimals in the envelope of gaseous planets, we obtain a wide variety of D/H and 15N/14N ratios in low-mass planets (≤100 Mearth) due to the migration pathway of planets, the accretion time of gas species whose relative abundance evolves with time, and isotope exchanges among species. If giant planets with mass greater than 100 Mearth have solar isotopic ratios such as Jupiter and Saturn due to their higher envelope mass, Neptune-type planets present values ranging between one and three times the solar value. It seems therefore difficult to use isotopic ratios in the envelope of these planets to get information about their formation in the disc. For giant planets, the ratios allow us to constrain the mass fraction of volatile species in the envelope needed to reproduce the observational data by assuming initial values for isotopic ratios in volatile species.

  10. Isotopic abundance analysis of carbon, nitrogen and sulfur with a combined elemental analyzer-mass spectrometer system

    International Nuclear Information System (INIS)

    Pichlmayer, F.; Blochberger, K.

    1988-01-01

    Stable isotope ratio measurements of carbon, nitrogen and sulfur are of growing interest as analytical tool in many fields of research, but applications were somewhat hindered in the past by the fact that cumbersome sample preparation was necessary. A method has therefore been developed, consisting in essential of coupling an elemental analyzer with an isotope mass spectrometer, enabling fast and reliable conversion of C-, N- and S-compounds in any solid or liquid sample into the measuring gases carbon dioxide, nitrogen and sulfur dioxide for on-line isotopic analysis. The experimental set-up and the main characteristics are described in short and examples of application in environmental research, food analysis and clinical diagnosis are given. (orig.)

  11. Results of Am isotopic ratio analysis in irradiated MOX fuels

    Energy Technology Data Exchange (ETDEWEB)

    Koyama, Shin-ichi; Osaka, Masahiko; Mitsugashira, Toshiaki; Konno, Koichi [Power Reactor and Nuclear Fuel Development Corp., Oarai, Ibaraki (Japan). Oarai Engineering Center; Kajitani, Mikio

    1997-04-01

    For analysis of a small quantity of americium, it is necessary to separate from curium which has similar chemical property. As a chemical separation method for americium and curium, the oxidation of americium with pentavalent bismuth and subsequent co-precipitation of trivalent curium with BIP O{sub 4} were applied to analyze americium in irradiated MOX fuels which contained about 30wt% plutonium and 0.9wt% {sup 241}Am before irradiation and were irradiated up to 26.2GWd/t in the experimental fast reactor Joyo. The purpose of this study is to measure isotopic ratio of americium and to evaluate the change of isotopic ratio with irradiation. Following results are obtained in this study. (1) The isotopic ratio of americium ({sup 241}Am, {sup 242m}Am and {sup 243}Am) can be analyzed in the MOX fuels by isolating americium. The isotopic ratio of {sup 242m}Am and {sup 243}Am increases up to 0.62at% and 0.82at% at maximum burnup, respectively, (2) The results of isotopic analysis indicates that the contents of {sup 241}Am decreases, whereas {sup 242m}Am, {sup 243}Am increase linearly with increasing burnup. (author)

  12. Traceability of different apple varieties by multivariate analysis of isotope ratio mass spectrometry data.

    Science.gov (United States)

    Mimmo, Tanja; Camin, Federica; Bontempo, Luana; Capici, Calogero; Tagliavini, Massimo; Cesco, Stefano; Scampicchio, Matteo

    2015-11-15

    The awareness of customers of the origin of foods has become an important issue. The growing demand for foods that are healthy, safe and of high quality has increased the need for traceability and clear labelling. Thus, this study investigates the capability of C and N stable isotope ratios to determine the geographical origin of several apple varieties grown in northern Italy. Four apple varieties (Cripps Pink, Gala, Golden Delicious, Granny Smith) have been sampled in orchards located in the Districts of Bolzano, Ferrara, Verona and Udine (northern Italy). Carbon (δ(13) C) and nitrogen (δ(15) N) isotope values of the whole apple fruits and three sub-fractions (peel, pulp and seed) have been determined simultaneously by isotope ratio mass spectrometry. The δ(13) C and δ(15) N values of apples and apple sub-fractions, such as peel, seed and pulp, were significantly affected by the geographical origin and the fruit variety. The four varieties could be distinguished to a certain extent only within each district. A 99% correct identification of the samples according to their origin was, however, achieved by cross validation with the 'leave-one-out' method. This study proves the potential of stable isotopes to discriminate the geographical origin of apples grown in orchards located only a few hundreds of kilometres apart. Stable isotopes were also able to discriminate different apple varieties, although only within small geographical areas. Copyright © 2015 John Wiley & Sons, Ltd.

  13. A Time-Measurement System Based on Isotopic Ratios

    International Nuclear Information System (INIS)

    Vo, Duc T.; Karpius, P.J.; MacArthur, D.W.; Thron, J.L.

    2007-01-01

    A time-measurement system can be built based on the ratio of gamma-ray peak intensities from two radioactive isotopes. The ideal system would use a parent isotope with a short half-life decaying to a long half-life daughter. The activities of the parent-daughter isotopes would be measured using a gamma-ray detector system. The time can then be determined from the ratio of the activities. The best-known candidate for such a system is the 241 Pu- 241 Am parent-daughter pair. However, this 241 Pu- 241 Am system would require a high-purity germanium detector system and sophisticated software to separate and distinguish between the many gamma-ray peaks produced by the decays of the two isotopes. An alternate system would use two different isotopes, again one with a short half-life and one with a half-life that is long relative to the other. The pair of isotopes 210 Pb and 241 Am (with half-lives of 22 and 432 years, respectively) appears suitable for such a system. This time-measurement system operates by measuring the change in the ratio of the 47-keV peak of 210 Pb to the 60-keV peak of 241 Am. For the system to work reasonably well, the resolution of the detector would need to be such that the two gamma-ray peaks are well separated so that their peak areas can be accurately determined using a simple region-of-interest (ROI) method. A variety of detectors were tested to find a suitable system for this application. The results of these tests are presented here.

  14. Direct uranium isotope ratio analysis of single micrometer-sized glass particles

    International Nuclear Information System (INIS)

    Kappel, Stefanie; Boulyga, Sergei F.; Prohaska, Thomas

    2012-01-01

    We present the application of nanosecond laser ablation (LA) coupled to a ‘Nu Plasma HR’ multi collector inductively coupled plasma mass spectrometer (MC-ICP-MS) for the direct analysis of U isotope ratios in single, 10–20 μm-sized, U-doped glass particles. Method development included studies with respect to (1) external correction of the measured U isotope ratios in glass particles, (2) the applied laser ablation carrier gas (i.e. Ar versus He) and (3) the accurate determination of lower abundant 236 U/ 238 U isotope ratios (i.e. 10 −5 ). In addition, a data processing procedure was developed for evaluation of transient signals, which is of potential use for routine application of the developed method. We demonstrate that the developed method is reliable and well suited for determining U isotope ratios of individual particles. Analyses of twenty-eight S1 glass particles, measured under optimized conditions, yielded average biases of less than 0.6% from the certified values for 234 U/ 238 U and 235 U/ 238 U ratios. Experimental results obtained for 236 U/ 238 U isotope ratios deviated by less than −2.5% from the certified values. Expanded relative total combined standard uncertainties U c (k = 2) of 2.6%, 1.4% and 5.8% were calculated for 234 U/ 238 U, 235 U/ 238 U and 236 U/ 238 U, respectively. - Highlights: ► LA-MC-ICP-MS was fully validated for the direct analysis of individual particles. ► Traceability was established by using an IRMM glass particle reference material. ► Measured U isotope ratios were in agreement with the certified range. ► A comprehensive total combined uncertainty evaluation was performed. ► The analysis of 236 U/ 238 U isotope ratios was improved by using a deceleration filter.

  15. Simultaneous determination of wine sugars, glycerol and organic acids 13C/12C isotopic ratio by ion chromatography-co-IRMS

    Directory of Open Access Journals (Sweden)

    Guyon Francois

    2014-01-01

    Full Text Available Ion chromatography (IC isotope ratio mass spectrometry (IRMS coupling is possible using a liquid interface allowing chemical oxidation (co of organic compounds. Synthetic solutions containing a mixture of glycerol, sugars (sucrose, glucose and fructose and organic acids (gluconic, lactic, malic, tartaric, oxalic, fumaric, citric and isocitric were elaborated to estimate analytical applications of two different IC systems. It appears that the use of carbonated solution in the eluting phase is a perturbation for 13C isotope measurements as it creates a δ13C deviation from the expected values. A sample of authentic sweet wine was analyzed by IC-co-IRMS using KOH gradient. Ratios of isotopic, ratios of organic acids and glycerol was found to be, in average, equal 1.01 ± 0.04 that is in accordance with our previous results.

  16. Isotope ratios of H, C, and O in CO2 and H2O of the martian atmosphere.

    Science.gov (United States)

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

    2013-07-19

    Stable isotope ratios of H, C, and O are powerful indicators of a wide variety of planetary geophysical processes, and for Mars they reveal the record of loss of its atmosphere and subsequent interactions with its surface such as carbonate formation. We report in situ measurements of the isotopic ratios of D/H and (18)O/(16)O in water and (13)C/(12)C, (18)O/(16)O, (17)O/(16)O, and (13)C(18)O/(12)C(16)O in carbon dioxide, made in the martian atmosphere at Gale Crater from the Curiosity rover using the Sample Analysis at Mars (SAM)'s tunable laser spectrometer (TLS). Comparison between our measurements in the modern atmosphere and those of martian meteorites such as ALH 84001 implies that the martian reservoirs of CO2 and H2O were largely established ~4 billion years ago, but that atmospheric loss or surface interaction may be still ongoing.

  17. Theoretical isotopic fractionation between structural boron in carbonates and aqueous boric acid and borate ion

    Science.gov (United States)

    Balan, Etienne; Noireaux, Johanna; Mavromatis, Vasileios; Saldi, Giuseppe D.; Montouillout, Valérie; Blanchard, Marc; Pietrucci, Fabio; Gervais, Christel; Rustad, James R.; Schott, Jacques; Gaillardet, Jérôme

    2018-02-01

    The 11B/10B ratio in calcite and aragonite is an important proxy of oceanic water pH. However, the physico-chemical mechanisms underpinning this approach are still poorly known. In the present study, we theoretically determine the equilibrium isotopic fractionation properties of structural boron species in calcium carbonates, BO33-, BO2(OH)2- and B(OH)4- anions substituted for carbonate groups, as well as those of B(OH)4- and B(OH)3 species in vacuum. Significant variability of equilibrium isotopic fractionation properties is observed among these structural species which is related to their contrasted coordination state, Bsbnd O bond lengths and atomic-scale environment. The isotopic composition of structural boron does not only depend on its coordination number but also on its medium range environment, i.e. farther than its first coordination shell. The isotopic fractionation between aqueous species and their counterparts in vacuum are assessed using previous investigations based on similar quantum-mechanical modeling approaches. At 300 K, the equilibrium isotope composition of structural trigonal species is 7-15‰ lighter than that of aqueous boric acid molecules, whereas substituted tetrahedral borate ions are heavier than their aqueous counterparts by 10-13‰. Although significant uncertainties are known to affect the theoretical prediction of fractionation factors between solids and solutions, the usually assumed lack of isotopic fractionation during borate incorporation in carbonates is challenged by these theoretical results. The present theoretical equilibrium fractionation factors between structural boron and aqueous species differ from those inferred from experiments which may indicate that isotopic equilibrium, unlike chemical equilibrium, was not reached in most experiments. Further research into the isotopic fractionation processes at the interface between calcium carbonates and aqueous solution as well as long duration experiments aimed at

  18. Plutonium isotope ratios in polychaete worms

    International Nuclear Information System (INIS)

    Beasley, T.M.; Fowler, S.W.

    1976-01-01

    Reference is made to recent reports that suggest that terrestrial and aquatic organisms may preferentially take up 238 Pu compared with sup(239+240)Pu. It is stated that although kinetic isotope effects are known to occur in biological systems for low mass number elements, such as H, C and N, such effects are generally discounted with higher mass numbers, and differences in the biological 'uptake' of isotopes of high mass number elements, such as those of Pu, are normally attributable to differences in the chemical or physical forms of the isotopes or to different quantities of isotopes available to organisms. This has been applied to explain differential Pu isotope behaviour in animals under controlled laboratory conditions, but it is not certain that it can be applied to explain anomalies of Pu isotope behaviour in organisms contaminated by nuclear test debris or by wastes from nuclear fuel reprocessing plants. Geochemical weathering may also have an effect. Described here are experiments in which it was found that deposit feeding marine worms living in sediments contaminated in different ways with Pu isotopes did not show preferential accumulation of 238 Pu. The worms had been exposed to different chemical and physical forms of the isotopes, including exposure to laboratory-labelled sediment, sediment collected from a former weapons test site, and sediment contaminated by wastes from a nuclear fuel reprocessing plant. The worms were allowed to accumulate Pu for times of 5 to 40 days. Isotope ratios were determined by α-spectrometric techniques. It is considered that the results are important for environmental samples where Pu activity levels are low. (U.K.)

  19. Development of a system for determination of the 13C/12C isotopic ratio with high spatial resolution

    International Nuclear Information System (INIS)

    Kristiansson, Per.; Hode, Tomas; Auzelyte, Vaida; Elfman, Mikael; Malmqvist, Klas; Nilsson, Christer; Pallon, Jan; Shariff, Asad; Wegden, Marie

    2004-01-01

    Stable carbon isotopes play an important role in the interpretation of biological activity, particularly when the fossil record is studied. In combination with morphological and chemical data, isotopic information can be useful in paleontology and astrobiology. In this paper the development of a microanalytical ion beam system for the measurement of the carbon isotope ratio with high spatial resolution and good statistics is presented. The technique used is elastic scattering of alpha particles with an energy of 2.75 MeV. At this energy the 13 C cross-section is enhanced relative to the Rutherford cross-section and while the 12 C cross-section is reduced. The optimisation of the system is described, including sample preparation and the design of the particle detection system for high efficiency combined with good energy resolution. Finally, some results from the initial test run of the system are shown and discussed

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

    Science.gov (United States)

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

    2004-01-01

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

  1. Stable carbon isotope ratios and intrinsic water-use efficiency of Miocene fossil leaves compared to modern congeners

    Energy Technology Data Exchange (ETDEWEB)

    Marshall, J.D.; Zhang, J.; Rember, W.C.; Jennings, D.; Larson, P. (Univ. of Idaho, Moscow, ID (United States))

    1994-06-01

    Miocene fossil leaves of forest trees were extracted from the Clarkia, Idaho fossil beds and their stable carbon isotope ratios were analyzed. Fossils had higher lignin concentrations and lower cellulose concentrations that modern leaves due to diagenesis and the HF used to extract the fossils. Therefore, [delta][sup 13]C of extracted fossil lignin was compared to that of modern lignin. Fossil lignin [delta][sup 13]C was significantly different from that of congeneric modern leaves (paired t-test, P<0.0001), but was 1.9% less negative. Gymnosperms (Metasequoia, Taxodium) were less negative than angiosperms (e.g., Magnolia, Quercus, Acer, Persea), but no difference between evergreen and deciduous species was detected. Using published estimates of the concentration and [delta][sup 13]C of atmospheric CO[sub 2] during the Miocene was estimated the CO[sub 2] partial pressure gradient across the stomata (intrinsic water-use efficiency). Intrinsic water-use efficiency was at least 70% higher during this past [open quotes]greenhouse[close quotes] period than at present.

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

    Science.gov (United States)

    Romanek, C.

    2010-12-01

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

  3. Inheritance of carbon isotope discrimination and water-use efficiency in cowpea

    International Nuclear Information System (INIS)

    Ismail, A.M.; Hall, A.E.

    1993-01-01

    Theory has been developed predicting an association between water-use efficiency (WUE = total biomass/transpiration) and leaf discrimination against 13C carbon isotope discrimination which could be used to indirectly select for WUE in C3 plants. Previous studies indicated variation in WUE and carbon isotope discrimination among genotypes of cowpea [Vigna unguiculata (L.) Walp.] and due to drought. Moreover, a highly significant negative correlation between WUE and carbon isotope discrimination was observed for both genotypic and drought effects, as expected based on theory. Present studies were conducted to investigate whether the inheritance of WUE and carbon isotope discrimination is nuclear or maternal, and whether any dominance is present. Contrasting cowpea accessions and hybrids were grown over 2 yr in two outdoor pot experiments, subjected to wet or dry treatments, and under full irrigation in natural soil conditions in 1 yr. Highly significant differences in WUE were observed among cowpea parents and hybrids, and due to drought, which were strongly and negatively correlated with carbon isotope discrimination as expected based on theory. Data from reciprocal crosses indicated that both WUE and carbon isotope discrimination are controlled by nuclear genes. High WUE and low carbon isotope discrimination exhibited partial dominance under pot conditions. In contrast, high carbon isotope discrimination was partially dominant for plants grown under natural soil conditions but in a similar aerial environment as in the pot studies. We speculate that differences in rooting conditions were responsible for the differences in extent of dominance for carbon isotope discrimination of plants growing under pot conditions compared with natural soil conditions in a similar field aerial environment

  4. Dietary heterogeneity among Western industrialized countries reflected in the stable isotope ratios of human hair.

    Science.gov (United States)

    Valenzuela, Luciano O; Chesson, Lesley A; Bowen, Gabriel J; Cerling, Thure E; Ehleringer, James R

    2012-01-01

    Although the globalization of food production is often assumed to result in a homogenization of consumption patterns with a convergence towards a Western style diet, the resources used to make global food products may still be locally produced (glocalization). Stable isotope ratios of human hair can quantify the extent to which residents of industrialized nations have converged on a standardized diet or whether there is persistent heterogeneity and glocalization among countries as a result of different dietary patterns and the use of local food products. Here we report isotopic differences among carbon, nitrogen and sulfur isotope ratios of human hair collected in thirteen Western European countries and in the USA. European hair samples had significantly lower δ(13)C values (-22.7 to -18.3‰), and significantly higher δ(15)N (7.8 to 10.3‰) and δ(34)S (4.8 to 8.3‰) values than samples from the USA (δ(13)C: -21.9 to -15.0‰, δ(15)N: 6.7 to 9.9‰, δ(34)S: -1.2 to 9.9‰). Within Europe, we detected differences in hair δ(13)C and δ(34)S values among countries and covariation of isotope ratios with latitude and longitude. This geographic structuring of isotopic data suggests heterogeneity in the food resources used by citizens of industrialized nations and supports the presence of different dietary patterns within Western Europe despite globalization trends. Here we showed the potential of stable isotope analysis as a population-wide tool for dietary screening, particularly as a complement of dietary surveys, that can provide additional information on assimilated macronutrients and independent verification of data obtained by those self-reporting instruments.

  5. Dietary heterogeneity among Western industrialized countries reflected in the stable isotope ratios of human hair.

    Directory of Open Access Journals (Sweden)

    Luciano O Valenzuela

    Full Text Available Although the globalization of food production is often assumed to result in a homogenization of consumption patterns with a convergence towards a Western style diet, the resources used to make global food products may still be locally produced (glocalization. Stable isotope ratios of human hair can quantify the extent to which residents of industrialized nations have converged on a standardized diet or whether there is persistent heterogeneity and glocalization among countries as a result of different dietary patterns and the use of local food products. Here we report isotopic differences among carbon, nitrogen and sulfur isotope ratios of human hair collected in thirteen Western European countries and in the USA. European hair samples had significantly lower δ(13C values (-22.7 to -18.3‰, and significantly higher δ(15N (7.8 to 10.3‰ and δ(34S (4.8 to 8.3‰ values than samples from the USA (δ(13C: -21.9 to -15.0‰, δ(15N: 6.7 to 9.9‰, δ(34S: -1.2 to 9.9‰. Within Europe, we detected differences in hair δ(13C and δ(34S values among countries and covariation of isotope ratios with latitude and longitude. This geographic structuring of isotopic data suggests heterogeneity in the food resources used by citizens of industrialized nations and supports the presence of different dietary patterns within Western Europe despite globalization trends. Here we showed the potential of stable isotope analysis as a population-wide tool for dietary screening, particularly as a complement of dietary surveys, that can provide additional information on assimilated macronutrients and independent verification of data obtained by those self-reporting instruments.

  6. Biomineralization and the carbon isotope record

    International Nuclear Information System (INIS)

    Degens, E.T.; Ittekkot, V.; Kazmierczak, J.

    1986-01-01

    The advent of biomineralization at the turn of the Precambrian/Cambrian boundary has been a major event in the Earth's evolutionary history. With this there has been a major shift from abiotic to biotic formation of minerals such as phosphates and carbonates and, subsequently, silica. The dominant factor which effected this shift is a change in ocean's chemistry with respect to its Ca 2+ and mineral nutrient contents. Mechanism controlling the biotic mineral formation is different from that controlling the abiotic one in that the former is enzymically controlled. It is suggested that this difference is also manifested in the stable carbon isotope fractionation between the two processes and has implication for the interpretation of stable carbon isotope record. (Author)

  7. Isotopic measurements of carbon and oxygen in carbonates from Bambui Group in the center-north region of Bahia State

    International Nuclear Information System (INIS)

    Torquato, J.R.; Misi, A.

    1978-01-01

    Analyses of 85 carbonate samples of the Bambui Group from the Chapada de Irece, Bahia, exhibit four distinct 13 C and 18 O isotopic ratio groupings. Based on these results the following sedimentation model for the Bambui Group is proposed: 1. A continental environment originating the basal dolomitic limestones and argillacceous dolomites. Isotopic ratios from these rocks fall within ranges considered typical of continental sedimentation: delta 18 C between -2.9 and -6.4%o, and delta 18 O from -5.3 to -10.7%o (PDB). 2. An alternating continental and restricted marine environment resulting in the deposition of laminated dolomitic limestones with thin interbeds of muddy sediments. Delta 13 C ratios of +0.1 to -4.9%o and a mean value of -8.2+-0.3%o delta 18 O are compatible with such an environment. 3. A restricted marine environment dominated by sedimentation of the black, fetid limestones of the upper portion of the sequence. Isotopic ratios for 13 C are all over -1.8%o, up to about +7.5%o, and 18 O ratios vary from-4.9 to -10.0%o. A number of light-grey sileceous dolomites is interbered with the lowermost black limestones of this sequence. Isotopic data for these rocks show a narrow range for delta 18 C values (-0.5 to 1.0%o) and a broader variation for delta 18 O ratios (0.0 to -8.3%o). This latter may be interpreted as indicative of intense evaporation during deposition of the dolomitic facies [pt

  8. Organic carbon and nitrogen stable isotopes in the intertidal sediments from the Yangtze Estuary, China

    International Nuclear Information System (INIS)

    Liu, M. . E-mail mliu@geo.ecnu.edu.cn; Hou, L.J.; Xu, S.Y.; Ou, D.N.; Yang, Y.; Yu, J.; Wang, Q.

    2006-01-01

    The natural isotopic compositions and C/N elemental ratios of sedimentary organic matter were determined in the intertidal flat of the Yangtze Estuary. The results showed that the ratios of carbon and nitrogen stable isotopes were respectively -29.8 per mille to - 26.0 per mille and 1.6 per mille -5.5 per mille in the flood season (July), while they were -27.3 per mille to - 25.6 per mille and 1.7 per mille -7.8 per mille in the dry season (February), respectively. The δ 13 C signatures were remarkably higher in July than in February, and gradually increased from the freshwater areas to the brackish areas. In contrast, there were relatively complex seasonal and spatial changes in stable nitrogen isotopes. It was also reflected that δ 15 N and C/N compositions had been obviously modified by organic matter diagenesis and biological processing, and could not be used to trace the sources of organic matter at the study area. In addition, it was considered that the mixing inputs of terrigenous and marine materials generally dominated sedimentary organic matter in the intertidal flat. The contribution of terrigenous inputs to sedimentary organic matter was roughly estimated according to the mixing balance model of stable carbon isotopes

  9. The relationship of uranium isotopes to oxidation/reduction in the Edwards carbonate aquifer of Texas

    International Nuclear Information System (INIS)

    Cowart, J.B.

    1980-01-01

    The concentration of dissolved uranium and 234 U/ 238 U alpha activity ratio ( A.R. ) were determined in water samples from 23 locations in the Edwards carbonate aquifer of south central Texas by isotope dilution methods and alpha spectrometry. (orig./ME)

  10. Tracing lead pollution sources in abandoned mine areas using stable Pb isotope ratios.

    Science.gov (United States)

    Yoo, Eun-Jin; Lee, Jung-A; Park, Jae-Seon; Lee, Khanghyun; Lee, Won-Seok; Han, Jin-Seok; Choi, Jong-Woo

    2014-02-01

    This study focused on Pb isotope ratios of sediments in areas around an abandoned mine to determine if the ratios can be used as a source tracer. For pretreatment, sediment samples were dissolved with mixed acids, and a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS, Nu plasma II) was used to investigate the Pb isotopic composition of the samples. The measured isotope ratios were then corrected for instrumental mass fractionation by measuring the (203)Tl/(205)Tl ratio. Repeated measurements with the NIST SRM 981 reference material showed that the precision of all ratios was below 104 ppm (±2σ) for 50 ng/g. The isotope ratios ((207)Pb/(206)Pb) found were 0.85073 ± 0.0004~0.85373 ± 0.0003 for the main stream, while they were 0.83736 ± 0.0010 for the tributary and 0.84393 ± 0.0002 for the confluence. A binary mixing equation for isotope ratios showed that the contributions of mine lead to neighboring areas were up to 60%. Therefore, Pb isotope ratios can be a good source tracer for areas around abandoned mines.

  11. About the variation mechanism of the isotopic composition of oxygen and carbon through the geological ages

    International Nuclear Information System (INIS)

    Torquato, J.R.F.; Frischkorn, H.

    1982-01-01

    The variations of the Δ 180 ratio found in the carbonates are shown as being of the primary origin. In addition it is shown that these values can be preserved, through the geological ages, even it one considers the carbonates to be worked over again. Are given some subsidies about the study of the paleoenvironments through the analysis of the isotopic composition of the carbon. (A.B.) [pt

  12. The problems of geological interpretation of mass spectroscopic isotope ratio data through the example of carbon dioxide genetic investigations

    International Nuclear Information System (INIS)

    Kecskes, A.; Izsof, K.; Cornides, I.

    1981-01-01

    The problem of the origin of carbon dioxide occurences in Slovakia is presented to point out the difficulties encountered when the results of mass spectrometric isotope geochemical investigations are to be interpreted. It is shown that two mechanisms may be responsible for the occurence of deep-seated carbon dioxide. The data and their frequency distribution curves indicate the importance of the juvenile CO 2 in this area. (author)

  13. Carbon, cesium and iodine isotopes in Japanese cedar leaves from Iwaki, Fukushima

    DEFF Research Database (Denmark)

    Xu, Sheng; Cook, Gordon T.; Cresswell, Alan J.

    2016-01-01

    Japanese cedar leaves from Iwaki, Fukushima were analyzed for carbon, cesium and iodine isotopic compositions before and after the 2011 nuclear accident. The Δ14C values reflect ambient atmospheric 14C concentrations during the year the leaves were sampled/defoliated, and also previous year......(s). The elevated 129I and 134,137Cs concentrations are attributed to direct exposure to the radioactive fallout for the pre-fallout-expended leaves and to internal translocation from older parts of the tree for post-fallout-expended leaves. 134Cs/137Cs and 129I/137Cs activity ratios suggest insignificant isotopic...

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

    Science.gov (United States)

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

    2014-09-01

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

  15. Effects of diagenesis on strontium, carbon, nitrogen and oxygen concentration and isotopic composition of bone

    Science.gov (United States)

    Nelson, Bruce K.; Deniro, Michael J.; Schoeninger, Margaret J.; De Paolo, Donald J.; Hare, P. E.

    1986-09-01

    Paleodietary analysis based on variations in the trace element and stable isotopic composition of inorganic and organic phases in fossil bone depends on the assumption that measured values reflect in vivo values. To test for postmortem alteration, we measured 87Sr /86Sr , 13C /12C , 18O /16O and 15N /14N ratios and Sr concentrations in modern and prehistoric (610 to 5470 yr old) bones of animals with marine or terrestrial diets from Greenland. Bones from modern terrestrial feeders have substantially lower Sr concentrations and more radiogenic 87Sr /86Sr ratios than those from modern marine feeders. This contrast was not preserved in the prehistoric samples, which showed almost complete overlap for both Sr concentration and isotopic composition in bones from the two types of animals. Leaching experiments, X-ray diffraction analysis and infrared spectroscopy indicate that alteration of the Sr concentration and isotopic composition in prehistoric bone probably results from nearly complete exchange with groundwater. Oxygen isotope ratios in fossil apatite carbonate also failed to preserve the original discrimination between modern terrestrial and marine feeders. The C isotope ratio of apatite carbonate did not discriminate between animals with marine or terrestrial diets in the modern samples. Even so, the ranges of apatite δ 13C values in prehistoric bone are more scattered than in modern samples for both groups, suggesting alteration had occurred. δ 13C and δ 15N values of collagen in modern bone are distinctly different for the two feeding types, and this distinction is preserved in most of the prehistoric samples. Our results suggest that postmortem alteration of dietary tracers in the inorganic phases of bone may be a problem at all archaeological sites and must be evaluated in each case. While collagen analyzed in this study was resistant to alteration, evaluation of the possibility of diagenetic alteration of its isotopic composition in bones from other

  16. The Potential of Isotope Ratio Mass Spectrometry (IRMS) and Gas Chromatography-IRMS Analysis of Triacetone Triperoxide in Forensic Explosives Investigations.

    Science.gov (United States)

    Bezemer, Karlijn D B; Koeberg, Mattijs; van der Heijden, Antoine E D M; van Driel, Chris A; Blaga, Cornelia; Bruinsma, Jildert; van Asten, Arian C

    2016-09-01

    Studying links between triacetone triperoxide (TATP) samples from crime scenes and suspects can assist in criminal investigations. Isotope ratio mass spectrometry (IRMS) and gas chromatography (GC)-IRMS were used to measure the isotopic compositions of TATP and its precursors acetone and hydrogen peroxide. In total, 31 TATP samples were synthesized with different raw material combinations and reaction conditions. For carbon, a good differentiation and a linear relationship were observed for acetone-TATP combinations. The extent of negative (δ(13) C) fractionation depended on the reaction yield. Limited enrichment was observed for the hydrogen isotope (δ(2) H) values of the TATP samples probably due to a constant exchange of hydrogen atoms in aqueous solution. For oxygen (δ(18) O), the small isotopic range and excess of water in hydrogen peroxide resulted in poor differentiation. GC-IRMS and IRMS data were comparable except for one TATP sample prepared with high acid concentration demonstrating the potential of compound-specific isotope analysis. Carbon IRMS has practical use in forensic TATP investigations. © 2016 American Academy of Forensic Sciences.

  17. Development, optimisation, and application of ICP-SFMS methods for the measurement of isotope ratios

    International Nuclear Information System (INIS)

    Stuerup, S.

    2000-07-01

    The measurement of isotopic composition and isotope ratios in biological and environmental samples requires sensitive, precise, and accurate analytical techniques. The analytical techniques used are traditionally based on mass spectrometry, among these techniques is the ICP-SFMS technique, which became commercially available in the mid 1990s. This technique is characterised by high sensitivity, low background, and the ability to separate analyte signals from spectral interferences. These features are beneficial for the measurement of isotope ratios and enable the measurement of isotope ratios of elements, which it has not previously been possible to measure due to either spectral interferences or poor sensitivity. The overall purpose of the project was to investigate the potential of the single detector ICP-SFMS technique for the measurement of isotope ratios in biological and environmental samples. One part of the work has focused on the fundamental aspects of the ICP-SFMS technique with special emphasize on the features important to the measurement of isotope ratios, while another part has focused on the development, optimisation and application of specific methods for the measurement of isotope ratios of elements of nutritional interest and radionuclides. The fundamental aspects of the ICP-SFMS technique were investigated theoretically and experimentally by the measurement of isotope ratios applying different experimental conditions. It was demonstrated that isotope ratios could be measured reliably using ICP-SFMS by educated choice of acquisition parameters, scanning mode, mass discrimination correction, and by eliminating the influence of detector dead time. Applying the knowledge gained through the fundamental study, ICP-SFMS methods for the measurement of isotope ratios of calcium, zinc, molybdenum and iron in human samples and a method for the measurement of plutonium isotope ratios and ultratrace levels of plutonium and neptunium in environmental samples

  18. Carbon-13 isotope fractionation in the decarboxylation of phenylpropiolic (PPA) below and above its melting point and in the decarboxylation of PPA in phenylacetylene medium

    International Nuclear Information System (INIS)

    Zielinski, M.; Zielinska, A.; Papiernik-Zielinska, H.

    2000-01-01

    C-13 isotope fractionation in the decarboxylation of pure phenylpropiolic acid (PPA) below and above its melting point and the decarboxylation of PPA in phenylacetylene solutions has been investigated in sealed under vacuum reaction vessels. The reactive PPA undergoing decarboxylation polymerizes with the liquid product, phenylacetylene in reaction cage producing a condensation compound, which does not decarboxylate measurably in the 120-190 o C. Especially low final carbon dioxide yields (about 11%) have been obtained in the decarboxylation of PPA in phenylacetylene solution at 132 o C and below this temperature. The carbon dioxide is depleted in carbon-13. The ratio of the carbon isotope ratios of carboxylic carbon of PPA before decarboxylation, R( 13 C/ 12 C so ), and of the first portions of carbon dioxide obtained at partial decarboxylation R( 13 C/ 12 C) pf , located in the range 1.007-1.010, indicates that the pure kinetic fractionation of 13 C in the elementary decarboxylation step is negligible and the C-13 fractionation in the condensed phase dimer/monomer equilibria contributes mainly to the resultant experimental carbon isotope fractionation. A preliminary discussion of the experimental isotope findings is presented. (author)

  19. Expanding the isotopic toolbox: Applications of hydrogen and oxygen stable isotope ratios to food web studies

    OpenAIRE

    Hannah B Vander Zanden; David X Soto; Gabriel J Bowen; Keith A Hobson; Keith A Hobson

    2016-01-01

    The measurement of stable carbon (δ13C) and nitrogen (δ15N) isotopes in tissues of organisms has formed the foundation of isotopic food web reconstructions, as these values directly reflect assimilated diet. In contrast, stable hydrogen (δ2H) and oxygen (δ18O) isotope measurements have typically been reserved for studies of migratory origin and paleoclimate reconstruction based on systematic relationships between organismal tissue and local environmental water. Recently, innovative applicat...

  20. Expanding the Isotopic Toolbox: Applications of Hydrogen and Oxygen Stable Isotope Ratios to Food Web Studies

    OpenAIRE

    Vander Zanden, Hannah B.; Soto, David X.; Bowen, Gabriel J.; Hobson, Keith A.

    2016-01-01

    The measurement of stable carbon (δ13C) and nitrogen (δ15N) isotopes in tissues of organisms has formed the foundation of isotopic food web reconstructions, as these values directly reflect assimilated diet. In contrast, stable hydrogen (δ2H) and oxygen (δ18O) isotope measurements have typically been reserved for studies of migratory origin and paleoclimate reconstruction based on systematic relationships between organismal tissue and local environmental water. Recently, innovative applicatio...

  1. Determination of the Geographical Origin of All Commercial Hake Species by Stable Isotope Ratio (SIR) Analysis.

    Science.gov (United States)

    Carrera, Mónica; Gallardo, José M

    2017-02-08

    The determination of the geographical origin of food products is relevant to comply with the legal regulations of traceability, to avoid food fraud, and to guarantee food quality and safety to the consumers. For these reasons, stable isotope ratio (SIR) analysis using an isotope ratio mass spectrometry (IRMS) instrument is one of the most useful techniques for evaluating food traceability and authenticity. The present study was aimed to determine, for the first time, the geographical origin for all commercial fish species belonging to the Merlucciidae family using SIR analysis of carbon (δ 13 C) and nitrogen (δ 15 N). The specific results enabled their clear classification according to the FAO (Food and Agriculture Organization of the United Nations) fishing areas, latitude, and geographical origin in the following six different clusters: European, North African, South African, North American, South American, and Australian hake species.

  2. The CN/C15N isotopic ratio towards dark clouds

    Science.gov (United States)

    Hily-Blant, P.; Pineau des Forêts, G.; Faure, A.; Le Gal, R.; Padovani, M.

    2013-09-01

    Understanding the origin of the composition of solar system cosmomaterials is a central question, not only in the cosmochemistry and astrochemistry fields, and requires various approaches to be combined. Measurements of isotopic ratios in cometary materials provide strong constraints on the content of the protosolar nebula. Their relation with the composition of the parental dark clouds is, however, still very elusive. In this paper, we bring new constraints based on the isotopic composition of nitrogen in dark clouds, with the aim of understanding the chemical processes that are responsible for the observed isotopic ratios. We have observed and detected the fundamental rotational transition of C15N towards two starless dark clouds, L1544 and L1498. We were able to derive the column density ratio of C15N over 13CN towards the same clouds and obtain the CN/C15N isotopic ratios, which were found to be 500 ± 75 for both L1544 and L1498. These values are therefore marginally consistent with the protosolar value of 441. Moreover, this ratio is larger than the isotopic ratio of nitrogen measured in HCN. In addition, we present model calculations of the chemical fractionation of nitrogen in dark clouds, which make it possible to understand how CN can be deprived of 15N and HCN can simultaneously be enriched in heavy nitrogen. The non-fractionation of N2H+, however, remains an open issue, and we propose some chemical way of alleviating the discrepancy between model predictions and the observed ratios. Appendices are available in electronic form at http://www.aanda.orgThe reduced spectra (in FITS format) are available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/557/A65

  3. Structure and isotopic ratios of aliphatic side chains in the insoluble organic matter of the Murchison carbonaceous chondrite

    Science.gov (United States)

    Huang, Yongsong; Alexandre, Marcelo R.; Wang, Yi

    2007-07-01

    We report in this paper the first molecular and isotopic characterization of individual aliphatic side chains from the insoluble organic matter (IOM) in the Murchison carbonaceous chondrite using a novel combined approach of RuO 4 oxidation and solid phase microextraction (SPME). The aliphatic side chains in the IOM of Murchison were first released by oxidizing aromatic structures using RuO 4. Because the IOM of carbonaceous chondrites contains predominantly short (C 1 to C 9) aliphatic substitutions, the resulting low molecular weight monocarboxylic acids (MCAs) are highly volatile and water-soluble. The conventional aqueous extraction and derivatization procedures following RuO 4 oxidation are unable to recover MCAs for subsequent analyses. We overcame this problem by employing SPME to directly capture the MCAs from the aqueous solution. We selected a SPME fiber with greater affinity for longer chain monoacids to compensate for the exponential decline of monoacid concentrations with increasing carbon numbers in meteorite IOM, allowing more accurate identification and quantification for the less abundant monoacids. We also determined the carbon and hydrogen isotopic ratios of individual MCAs derived from Murchinson IOM. Our results reveal significant similarity in both molecular structures and hydrogen isotopic ratios between the IOM aliphatic side chains and water-soluble MCAs in Murchison, suggesting that these compounds had common precursors. Our combined new approach of RuO 4 oxidation-SPME provides a new way to probe the molecular and isotopic characteristics of aliphatic side chains in carbonaceous chondrites.

  4. Investigation of the anomalous isotope ratios of the Central-Transdanubian bauxites

    International Nuclear Information System (INIS)

    Viczian, M.

    1977-01-01

    In the case of the Central Transdanubian bauxite deposits significant anomaly of the lead isotope ratios has been found. The 206 Pb/ 204 Pb isotope ratio in approximately 40 samples was investigated and the results have shown an average deviation from the literary value by about 80%. These results have been cont confirmed by thermal ionisation measurings, too. Some possibilities for the explanation of this isotope anomaly are also dealt with in the paper. (author)

  5. Quantitative measurement of carbon isotopic composition in CO2 gas reservoir by Micro-Laser Raman spectroscopy

    Science.gov (United States)

    Li, Jiajia; Li, Rongxi; Zhao, Bangsheng; Guo, Hui; Zhang, Shuan; Cheng, Jinghua; Wu, Xiaoli

    2018-04-01

    The use of Micro-Laser Raman spectroscopy technology for quantitatively determining gas carbon isotope composition is presented. In this study, 12CO2 and 13CO2 were mixed with N2 at various molar fraction ratios to obtain Raman quantification factors (F12CO2 and F13CO2), which provide a theoretical basis for calculating the δ13C value. And the corresponding values were 0.523 (0 Laser Raman analysis were carried out on natural CO2 gas from Shengli Oil-field at room temperature under different pressures. The δ13C values obtained by Micro-Laser Raman spectroscopy technology and Isotope Ratio Mass Spectrometry (IRMS) technology are in good agreement with each other, and the relative errors range of δ13C values is 1.232%-6.964%. This research provides a fundamental analysis tool for determining gas carbon isotope composition (δ13C values) quantitatively by using Micro-Laser Raman spectroscopy. Experiment of results demonstrates that this method has the potential for obtaining δ13C values in natural CO2 gas reservoirs.

  6. Investigation of the feeding effect on the 13C/12C isotope ratio of the hormones in bovine urine using gas chromatography/combustion isotope ratio mass spectrometry

    NARCIS (Netherlands)

    Balizs, Gabor; Jainz, Annett; Horvatovich, Peter

    2005-01-01

    The effect of the feeding on the 13C/12C isotope ratio of four endogenous steroid hormones testosterone (T), epi-testosterone (epi-T), dehydroepiandrosterone (DHEA) and etiocholanolone (ETIO) in bovine urine was investigated. An analytical method to determine the accurate isotope ratio was developed

  7. Stable carbon and hydrogen isotope analysis of methyl tert-butyl ether and tert-amyl methyl ether by purge and trap-gas chromatography-isotope ratio mass spectrometry: method evaluation and application.

    Science.gov (United States)

    Kujawinski, Dorothea M; Stephan, Manuel; Jochmann, Maik A; Krajenke, Karen; Haas, Joe; Schmidt, Torsten C

    2010-01-01

    In order to monitor the behaviour of contaminants in the aqueous environment effective enrichment techniques often have to be employed due to their low concentrations. In this work a robust and sensitive purge and trap-gas chromatography-isotope ratio mass spectrometry method for carbon and hydrogen isotope analysis of fuel oxygenates in water is presented. The method evaluation included the determination of method detection limits, accuracy and reproducibility of deltaD and delta(13)C values. Lowest concentrations at which reliable delta(13)C values could be determined were 5 microg L(-1) and 28 microg L(-1) for TAME and MTBE, respectively. Stable deltaD values for MTBE and TAME could be achieved for concentrations as low as 25 and 50 microg L(-1). Good long-term reproducibility of delta(13)C and deltaD values was obtained for all target compounds. But deltaD values varying more than 5 per thousand were observed using different thermal conversion tubes. Thus, a correction of deltaD values in the analysis of groundwater samples was necessary to guarantee comparability of the results. The applicability of this method was shown by the analysis of groundwater samples from a gasoline contaminated site. By two dimensional isotope analysis two locations within this site were identified at which anaerobic and aerobic degradation of methyl tert-butyl ether occurred.

  8. Measurement of boron isotope ratios in groundwater studies

    International Nuclear Information System (INIS)

    Porteous, N.C.; Walsh, J.N.; Jarvis, K.E.

    1995-01-01

    Boron is present at low levels in groundwater and rainfall in the UK, ranging between 2 and 200 ng ml -1 . A sensitive technique has been developed using inductively coupled plasma mass spectrometry (ICP-MS) to measure boron isotope ratios at low concentrations with a precision (s r ) of between 0.1 and 0.2%. Samples were evaporated to increase elemental boron concentrations to 200 ng ml -1 and interfering matrix elements were removed by an adapted cation-exchange separation procedure. The validity of measuring boron isotopic ratios by ICP-MS at this concentration level is discussed in relation to the theoretical instrument precision attainable based on counting statistics. (author)

  9. Stable carbon isotope ratios of lipid biomarkers and their applications in the marine environment

    International Nuclear Information System (INIS)

    Tolosa, I.; Mora, S. de

    2001-01-01

    Studies on the distribution of lipid biomarkers in the environment help elucidate biogeochemical processes, but recent findings have significantly reduced the specificity of some biomarkers. The analytical development of Gas Chromatography-Combustion-IRMS (GC-C-IRMS) allows the determination of the δ 13 C of specific biomarkers, thereby improving the veracity of source apportionment. In this report, we present a brief description of the analytical approach for sample preparation and carbon isotope measurements of individual biomarkers. Selected examples of the applications in the use of GC-C-IRMS for biomarker source elucidation in the marine environment and potential applications to paleoclimatological studies are reviewed. (author)

  10. Isotope yield ratios as a probe of the reaction dynamics

    International Nuclear Information System (INIS)

    Trautmann, W.; Hildenbrand, K.D.; Lynen, U.; Mueller, W.F.J.; Rabe, H.J.; Sann, H.; Stelzer, H.; Trockel, R.; Wada, R.; Brummund, N.; Glasow, R.; Kampert, K.H.; Santo, R.; Eckert, E.M.; Pochodzalla, J.; Bock, I.; Pelte, D.

    1987-04-01

    Isotopically resolved yields of particles and complex fragments from 12 C and 18 O induced reactions on 53 Ni, 54 Ni, Ag, and 197 Au in the intermediate range of bombarding energies 30 MeV ≤ E/A ≤ 84 MeV were measured. The systematic variation of the deduced isotope yield ratios with projectile and target is used to determine the degree of N/Z equilibration achieved and to establish time scales for the reaction process. A quantum statistical model is employed in order to derive entropies of the emitting systems from the measured isotope yield ratios. (orig.)

  11. Authenticity and traceability of vanilla flavors by analysis of stable isotopes of carbon and hydrogen.

    Science.gov (United States)

    Hansen, Anne-Mette Sølvbjerg; Fromberg, Arvid; Frandsen, Henrik Lauritz

    2014-10-22

    Authenticity and traceability of vanilla flavors were investigated using gas chromatography-isotope ratio mass spectrometry (GC-IRMS). Vanilla flavors produced by chemical synthesis (n = 2), fermentation (n = 1), and extracted from two different species of the vanilla orchid (n = 79) were analyzed. The authenticity of the flavor compound vanillin was evaluated on the basis of measurements of ratios of carbon stable isotopes (δ(13)C). It was found that results of δ(13)C for vanillin extracted from Vanilla planifolia and Vanilla tahitensis were significantly different (t test) and that it was possible to differentiate these two groups of natural vanillin from vanillin produced otherwise. Vanilla flavors were also analyzed for ratios of hydrogen stable isotopes (δ(2)H). A graphic representation of δ(13)C versus δ(2)H revealed that vanillin extracted from pods grown in adjacent geographic origins grouped together. Accordingly, values of δ(13)C and δ(2)H can be used for studies of authenticity and traceability of vanilla flavors.

  12. Heavy element stable isotope ratios. Analytical approaches and applications

    International Nuclear Information System (INIS)

    Tanimizu, Masaharu; Sohrin, Yoshiki; Hirata, Takafumi

    2013-01-01

    Continuous developments in inorganic mass spectrometry techniques, including a combination of an inductively coupled plasma ion source and a magnetic sector-based mass spectrometer equipped with a multiple-collector array, have revolutionized the precision of isotope ratio measurements, and applications of inorganic mass spectrometry for biochemistry, geochemistry, and marine chemistry are beginning to appear on the horizon. Series of pioneering studies have revealed that natural stable isotope fractionations of many elements heavier than S (e.g., Fe, Cu, Zn, Sr, Ce, Nd, Mo, Cd, W, Tl, and U) are common on Earth, and it had been widely recognized that most physicochemical reactions or biochemical processes induce mass-dependent isotope fractionation. The variations in isotope ratios of the heavy elements can provide new insights into past and present biochemical and geochemical processes. To achieve this, the analytical community is actively solving problems such as spectral interference, mass discrimination drift, chemical separation and purification, and reduction of the contamination of analytes. This article describes data calibration and standardization protocols to allow interlaboratory comparisons or to maintain traceability of data, and basic principles of isotope fractionation in nature, together with high-selectivity and high-yield chemical separation and purification techniques for stable isotope studies.

  13. Short-term measurement of carbon isotope fractionation in plants

    International Nuclear Information System (INIS)

    O'Leary, M.H.; Treichel, I.; Rooney, M.

    1986-01-01

    Combustion-based studies of the carbon-13 content of plants give only an integrated, long-term value for the isotope fractionation associated with photosynthesis. A method is described here which permits determination of this isotope fractionation in 2 to 3 hours. To accomplish this, the plant is enclosed in a glass chamber, and the quantity and isotopic content of the CO 2 remaining in the atmosphere are monitored during photosynthesis. Isotope fractionation studies by this method give results consistent with what is expected from combustion studies of C 3 , C 4 , and Crassulacean acid metabolism plants. This method will make possible a variety of new studies of environmental and species effects in carbon isotope fractionation

  14. Springtime carbon emission episodes at the Gosan background site revealed by total carbon, stable carbon isotopic composition, and thermal characteristics of carbonaceous particles

    Directory of Open Access Journals (Sweden)

    J. Jung

    2011-11-01

    Full Text Available In order to investigate the emission of carbonaceous aerosols at the Gosan background super-site (33.17° N, 126.10° E in East Asia, total suspended particles (TSP were collected during spring of 2007 and 2008 and analyzed for particulate organic carbon, elemental carbon, total carbon (TC, total nitrogen (TN, and stable carbon isotopic composition (δ13C of TC. The stable carbon isotopic composition of TC (δ13CTC was found to be lowest during pollen emission episodes (range: −26.2‰ to −23.5‰, avg. −25.2 ± 0.9‰, approaching those of the airborne pollen (−28.0‰ collected at the Gosan site. Based on a carbon isotope mass balance equation, we found that ~42% of TC in the TSP samples during the pollen episodes was attributed to airborne pollen from Japanese cedar trees planted around tangerine farms in Jeju Island. A negative correlation between the citric acid-carbon/TC ratios and δ13CTC was obtained during the pollen episodes. These results suggest that citric acid emitted from tangerine fruit may be adsorbed on the airborne pollen and then transported to the Gosan site. Thermal evolution patterns of organic carbon during the pollen episodes were characterized by high OC evolution in the OC2 temperature step (450 °C. Since thermal evolution patterns of organic aerosols are highly influenced by their molecular weight, they can be used as additional information on the formation of secondary organic aerosols and the effect of aging of organic aerosols during the long-range atmospheric transport and sources of organic aerosols.

  15. Broadband non-selective excitation of plutonium isotopes for isotope ratio measurements in resonance ionization mass spectrometry: a theoretical study.

    Science.gov (United States)

    Sankari, M

    2012-10-15

    Making isotope ratio measurements with minimum isotope bias has always been a challenging task to mass spectrometrists, especially for the specific case of plutonium, owing to the strategic importance of the element. In order to use resonance ionization mass spectrometry (RIMS) as a tool for isotope ratio measurements, optimization of the various laser parameters and other atomic and system parameters is critical to minimize isotopic biases. Broadband simultaneous non-selective excitation of the isotopes of plutonium in the triple resonance excitation scheme with λ(1) = 420.77 nm, λ(2) = 847.28 nm, and λ(3) = 767.53 nm based on density matrix formalism has been theoretically computed for the determination of isotope ratios. The effects of the various laser parameters and other factors such as the atomization temperature and the dimensions of the atomic beam on the estimation of isotope ratios were studied. The effects of Doppler broadening, and time-dependent excitation parameters such as Rabi frequencies, ionization rate and the effect of non-Lorenztian lineshape have all been incorporated. The average laser powers and bandwidths for the three-excitation steps were evaluated for non-selective excitation. The laser intensity required to saturate the three-excitation steps were studied. The two-dimensional lineshape contour and its features were investigated, while the reversal of peak asymmetry of two-step and two-photon excitation peaks under these conditions is discussed. Optimized powers for the non-selective ionization of the three transitions were calculated as 545 mW, 150 mW and 545 mW and the laser bandwidth for all the three steps was ~20 GHz. The isotopic bias between the resonant and off-resonant isotope under the optimized conditions was no more than 9%, which is better than an earlier reported value. These optimized laser power and bandwidth conditions are better than in the earlier experimental work since these comprehensive calculations yield

  16. Direct uranium isotope ratio analysis of single micrometer-sized glass particles.

    Science.gov (United States)

    Kappel, Stefanie; Boulyga, Sergei F; Prohaska, Thomas

    2012-11-01

    We present the application of nanosecond laser ablation (LA) coupled to a 'Nu Plasma HR' multi collector inductively coupled plasma mass spectrometer (MC-ICP-MS) for the direct analysis of U isotope ratios in single, 10-20 μm-sized, U-doped glass particles. Method development included studies with respect to (1) external correction of the measured U isotope ratios in glass particles, (2) the applied laser ablation carrier gas (i.e. Ar versus He) and (3) the accurate determination of lower abundant (236)U/(238)U isotope ratios (i.e. 10(-5)). In addition, a data processing procedure was developed for evaluation of transient signals, which is of potential use for routine application of the developed method. We demonstrate that the developed method is reliable and well suited for determining U isotope ratios of individual particles. Analyses of twenty-eight S1 glass particles, measured under optimized conditions, yielded average biases of less than 0.6% from the certified values for (234)U/(238)U and (235)U/(238)U ratios. Experimental results obtained for (236)U/(238)U isotope ratios deviated by less than -2.5% from the certified values. Expanded relative total combined standard uncertainties U(c) (k = 2) of 2.6%, 1.4% and 5.8% were calculated for (234)U/(238)U, (235)U/(238)U and (236)U/(238)U, respectively. Copyright © 2012 Elsevier Ltd. All rights reserved.

  17. Isotopic ratios of 129I/127I in mammalian thyroid glands in Japan

    International Nuclear Information System (INIS)

    Seki, R.; Hatano, T.

    1994-01-01

    The isotopic ratios of 129 I/ 127 I in cattle thyroid glands collected from various areas of Japan were measured by neutron activation analysis with combustion pre-treatment. Pig and human thyroid glands were also analyzed by the same method. The iodine isotopic ratio in cattle thyroid glands in Japan is comparable with that observed in Europe. The isotopic ratio in human thyroid glands in Japan is remarkably lower than that in Europe, which has been reported to be comparable to that of cattle. The isotopic ratio in pig thyroid glands is also lower than that in cattle. (author) 7 refs.; 3 figs.; 5 tabs

  18. Temperature dependence of carbon kinetic isotope effect for the oxidation reaction of ethane by OH radicals under atmospherically relevant conditions

    Science.gov (United States)

    Piansawan, Tammarat; Saccon, Marina; Laumer, Werner; Gensch, Iulia; Kiendler-Scharr, Astrid

    2015-04-01

    Modeling of the global distribution of atmospheric ethane sources and sinks by using the 13C isotopic composition requires accurate knowledge of the carbon kinetic isotope effect (KIE) of its atmospheric removal reactions. The quantum mechanical prediction implies the necessity to elucidate the temperature dependence of KIE within atmospherically relevant temperature range by experiment. In this study, the KIE and its temperature dependence for ethane oxidation by OH radicals was investigated at ambient pressure in a temperature range of 243 K to 303 K. The chemical reactions were carried out in a 15 L PFE reaction chamber, suspended in a thermally controlled oven. The isotope ratios of the gas phase components during the course of the reactions were measured by Thermal Desorption -- Gas Chromatography -- Isotope Ratio Mass Spectrometry (TD-GC-IRMS). For each temperature, the KIE was derived from the temporal evolution of the concentration and stable carbon isotope ratio (δ13C) of ethane using a method adapted from the relative reaction rate concept. The room temperature KIE of the ethane reaction with OH radicals was found to be 6.85 ± 0.32 ‰. This value is in agreement with the previously reported value of 8.57 ± 1.95 ‰ [Anderson et al. 2004] but has a substantially lower uncertainty. The experimental results will be discussed with the KIE temperature dependence predicted by quantum mechanical calculations. Reference: Rebecca S. Anderson, Lin Huang, Richard Iannone, Alexandra E. Thompson, and Jochen Rudolph (2004), Carbon Kinetic Isotope Effects in the Gas Phase Reactions of Light Alkanes and Ethene with the OH Radical at 296 ± 4 K, J. Phys. Chem. A, 108, 11537--11544

  19. Sulfur isotope ratios and the origins of the aerosols and cloud droplets in California stratus

    International Nuclear Information System (INIS)

    Ludwig, F.L.

    1976-01-01

    Marine aerosols often have sulfur-to-chloride ratios greater than that found in seawater. Sulfur isotope ratios ( 34 S/ 32 S) were measured in aerosol and cloud droplet samples collected in the San Francisco Bay Area in an attempt to understand the processes that produce the observed sulfur-to-chloride ratios. Seawater sulfur usually has very high sulfur isotope ratios: fossil fuel sulfur tends to have smaller isotope ratios and sulfur of bacteriogenic origin still smaller. Samples collected in unpolluted marine air over the hills south of San Francisco had sulfur ratios that were significantly lower than the values for samples collected in nearby areas that were subject to urban pollution. The highest sulfur isotope ratios were found in the offshore seawater. The results suggest bacteriogenic origins, of the marine air sulfur aerosol material. The low isotope ratios in the marine air cannot be explained as a mixture of seawater sulfur and pollutant sulfur, because both tend to have higher isotope ratios. (Auth.)

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

    Science.gov (United States)

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

    2013-04-01

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

  1. A Plant-Based Proxy for the Oxygen Isotope Ratio of Atmospheric Water Vapor

    Science.gov (United States)

    Helliker, B.

    2007-12-01

    Atmospheric water vapor is a major component of the global hydrological cycle, but the isotopic balance of vapor is largely unknown. It is shown here that the oxygen isotope ratio of leaf water in the epiphytic Crassulacean acid metabolism (CAM) plant Tillandsia usneoides (Spanish Moss) is controlled by the oxygen isotope ratio of atmospheric water vapor in both field and lab studies. Assuming that the leaf-water isotopic signature (and hence the atmospheric water vapor signature) is recorded in plant organic material, the atmospheric water vapor oxygen isotope ratios for Miami, Florida (USA) were reconstructed for several years from 1878 to 2005 using contemporary and herbarium specimens. T. usneoides ranges from Virginia, USA southwards through the tropics to Argentina, and the CAM epiphytic lifeform is widespread in other species. Therefore, epiphytes may be used to reconstruct the isotope ratio of atmospheric water for spatial scales that span over 60° of latitude and temporal scales that cover the last century of global temperature increase.

  2. Laser assisted ratio analysis - An alternative to GC/IRMS for CO2

    International Nuclear Information System (INIS)

    Murnick, D.E.

    2001-01-01

    A new technique for laser based analysis of carbon isotope ratios, with the acronym LARA, based on large isotope shifts in molecular spectra, the use of fixed frequency isotopic lasers, and sensitive detection via the laser optogalvanic effect is reviewed and compared with GC/IRMS for carbon dioxide in specific applications. The possibility for development of new classes of isotope ratio measurement systems with LARA is explored. (author)

  3. Carbon isotope effects in carbohydrates and amino acids of photosynthesizing organisms

    International Nuclear Information System (INIS)

    Ivlev, A.A.; Kaloshin, A.G.; Koroleva, M.Ya.

    1982-01-01

    The analysis of the carbon isotope distribution in carbohydrates and amino acids of some photosynthesizing organisms revealed the close relationship between distribution and the pathways of biosynthesis of the molecules. This relationship is explained on the basis of the previously proposed mechanism of carbon isotope fractionation in a cell, in which the chief part is played by kinetic isotope effects in the pyruvate decarboxylation reaction progressively increased in the conjugated processes of gluconeogenesis. Isotope differences of C 2 and C 3 fragments arising in decarboxylation of pyruvate, as well as isotope differences of biogenic acceptor and environmental CO 2 appearing in assimilation are the main reasons of the observed intramolecular isotopic heterogeneity of biomolecules. The heterogeneity is preserved in metabolites owing to an incomplete mixing of carbon atoms in biochemical reactions. The probable existence of two pools of carbohydrates in photosynthesizing organisms different in isotopic composition is predicted. Two types of intramolecular isotope distribution in amino acids are shown. (author)

  4. Carbon isotope effects in carbohydrates and amino acids of photosynthesizing organisms

    Energy Technology Data Exchange (ETDEWEB)

    Ivlev, A.A.; Kaloshin, A.G.; Koroleva, M.Ya. (Ministerstvo Geologii SSR, Moscow)

    1982-02-10

    The analysis of the carbon isotope distribution in carbohydrates and amino acids of some photosynthesizing organisms revealed the close relationship between distribution and the pathways of biosynthesis of the molecules. This relationship is explained on the basis of the previously proposed mechanism of carbon isotope fractionation in a cell, in which the chief part is played by kinetic isotope effects in the pyruvate decarboxylation reaction progressively increased in the conjugated processes of gluconeogenesis. Isotope differences of C/sub 2/ and C/sub 3/ fragments arising in decarboxylation of pyruvate, as well as isotope differences of biogenic acceptor and environmental CO/sub 2/ appearing in assimilation are the main reasons of the observed intramolecular isotopic heterogeneity of biomolecules. The heterogeneity is preserved in metabolites owing to an incomplete mixing of carbon atoms in biochemical reactions. The probable existence of two pools of carbohydrates in photosynthesizing organisms different in isotopic composition is predicted. Two types of intramolecular isotope distribution in amino acids are shown.

  5. Characterization of diesel fuel by chemical separation combined with capillary gas chromatography (GC) isotope ratio mass spectrometry (IRMS).

    Science.gov (United States)

    Harvey, Scott D; Jarman, Kristin H; Moran, James J; Sorensen, Christina M; Wright, Bob W

    2012-09-15

    The purpose of this study was to perform a preliminary investigation of compound-specific isotope analysis (CSIA) of diesel fuels to evaluate whether the technique could distinguish diesel samples from different sources/locations. The ability to differentiate or correlate diesel samples could be valuable for discovering fuel tax evasion schemes or for environmental forensic studies. Two urea adduction-based techniques were used to isolate the n-alkanes from the fuel. Both carbon isotope ratio (δ(13)C) and hydrogen isotope ratio (δD) values for the n-alkanes were then determined by CSIA in each sample. The samples investigated had δ(13)C values that ranged from -30.1‰ to -26.8‰, whereas δD values ranged from -83‰ to -156‰. Plots of δD versus δ(13)C with sample n-alkane points connected in order of increasing carbon number gave well-separated clusters with characteristic shapes for each sample. Principal components analysis (PCA) with δ(13)C, δD, or combined δ(13)C and δD data was applied to extract the maximum information content. PCA scores plots could clearly differentiate the samples, thereby demonstrating the potential of this approach for distinguishing (e.g., fingerprinting) fuel samples using δ(13)C and δD values. Copyright © 2012 Elsevier B.V. All rights reserved.

  6. Application of carbon isotope analyses in food technology

    International Nuclear Information System (INIS)

    Szanto, Zsuzsa; Svingor, E.; Futo, I.; Palcsu, L.; Molnar, M.

    2001-01-01

    The vast economic size of the food market offers great temptations for the production and sale of fraudulent products, adulterated products and synthetic products that are labeled as natural ones. Conventional techniques of chemical analyses have served the food industry well for many years but are limited in their ability to detect certain types of fraudulent or mislabelled products. The aversion to added sugar and the demand for 'all natural' food products among consumers has led to a great deal of mislabelling on the part of food processors in order to achieve greater economic gain. The nature of deceptions detectable by carbon Stable Isotope Ratio Analysis (SIRA) in food technology falls into three broad categories. The most common is the adulteration of an expensive natural product, such as apple juice, with a much cheaper natural product such as cane sugar or high fructose corn syrup (HFCS). The second is outright falsification of a food. An example is maple syrup produced by simple addition of maple flavoring to a sugar syrup or HFCS. The third general category is the sale of synthetic materials as natural ones or the addition of synthetic materials to natural ones in order to increase the volume of the product. The procedure for using carbon SIRA in monitoring food products involves two stages. It must first be established that the product to be analyzed, or some specific component of it, has a particular isotopic composition that can be distinguished from that of the materials that might be used to adulterate it. Potential adulterating components are then analyzed to establish their isotopic identity. The carbon SIRA method cannot, in general, be used to establish purity unequivocally but it can be used to establish impurity or adulteration with a high degree of success. The overall process of carbon SIRA consists of three stages: selection of the sample or the isolation of the particular compound to be analyzed, conversion of this compound into CO 2 gas

  7. Role of stable isotope mass spectroscopy in hydrological sciences

    International Nuclear Information System (INIS)

    Keesari, Tirumalesh

    2017-01-01

    Isotope Ratio Mass Spectrometry (IRMS) is a specialized technique used to provide information about a given sample about its geographic, chemical, physical and biological origin. The ability to determine the source of water molecule stems from the relative isotopic abundances of its constituent elements, viz., hydrogen and oxygen or sometimes through its dissolved elements such as carbon, nitrogen and sulphur etc. Since the isotope ratios of carbon, hydrogen, oxygen, sulfur, and nitrogen can become locally enriched or depleted through a variety of kinetic and thermodynamic factors, measurement of the isotope ratios can be used to unravel the processes and differentiate water samples which otherwise exhibit similar chemical signatures. For brevity, this article focuses mainly on measurement of water isotopes, common notation for expressing isotope data and standards, theory of isotope hydrology, field applications and advances

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-06-15

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

  9. Chromium isotope fractionation during coprecipitation with calcium carbonate

    DEFF Research Database (Denmark)

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

    The chromium (Cr) isotopic composition of carbonates can potentially be used as a paleoclimate proxy to elucidate past fluctuations of oxygen contents in atmosphere and hydrosphere. The use of Cr isotopes to track paleoenvironmental changes, for example related to the rise of oxygen during the Ar...... et al., 2007, Water Air Soil Poll. 179, 381-390. [2] Sánchez-Pastor et al., 2011, Cryst. Growth Des. 11, 3081-3089.......The chromium (Cr) isotopic composition of carbonates can potentially be used as a paleoclimate proxy to elucidate past fluctuations of oxygen contents in atmosphere and hydrosphere. The use of Cr isotopes to track paleoenvironmental changes, for example related to the rise of oxygen during...... the Archaean and Protoerozoic, needs careful assessment of the signal robustness and necessitates a thorough understanding of the Cr cycle in Earth system processes. We conducted experiments testing the incorporation and isotopic fractionation of chromate into the calcite lattice. Our experiments indicate...

  10. Dual element ((15)N/(14)N, (13)C/(12)C) isotope analysis of glyphosate and AMPA by derivatization-gas chromatography isotope ratio mass spectrometry (GC/IRMS) combined with LC/IRMS.

    Science.gov (United States)

    Mogusu, Emmanuel O; Wolbert, J Benjamin; Kujawinski, Dorothea M; Jochmann, Maik A; Elsner, Martin

    2015-07-01

    To assess sources and degradation of the herbicide glyphosate [N-(phosphonomethyl) glycine] and its metabolite AMPA (aminomethylphosphonic acid), concentration measurements are often inconclusive and even (13)C/(12)C analysis alone may give limited information. To advance isotope ratio analysis of an additional element, we present compound-specific (15)N/(14)N analysis of glyphosate and AMPA by a two step derivatization in combination with gas chromatography/isotope ratio mass spectrometry (GC/IRMS). The N-H group was derivatized with isopropyl chloroformate (iso-PCF), and remaining acidic groups were subsequently methylated with trimethylsilyldiazomethane (TMSD). Iso-PCF treatment at pH 10 indicated decomposition of the derivative. At pH 10, and with an excess of iso-PCF by 10-24, greatest yields and accurate (15)N/(14)N ratios were obtained (deviation from elemental analyzer-IRMS: -0.2 ± 0.9% for glyphosate; -0.4 ± 0.7% for AMPA). Limits for accurate δ(15)N analysis of glyphosate and AMPA were 150 and 250 ng injected, respectively. A combination of δ(15)N and δ(13)C analysis by liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) (1) enabled an improved distinction of commercial glyphosate products and (2) showed that glyphosate isotope values during degradation by MnO2 clearly fell outside the commercial product range. This highlights the potential of combined carbon and nitrogen isotopes analysis to trace sources and degradation of glyphosate.

  11. Optimal sample to tracer ratio for isotope dilution mass spectrometry: the polyisotopic case

    International Nuclear Information System (INIS)

    Laszlo, G.; Ridder, P. de; Goldman, A.; Cappis, J.; Bievre, P. de

    1991-01-01

    The Isotope Dilution Mass Spectrometry (IDMS) measurement technique provides a means for determining the unknown amount of various isotopes of an element in a sample solution of known mass. The sample solution is mixed with an auxiliary solution, or tracer, containing a known amount of the same element having the same isotopes but of different relative abundances or isotopic composition and the induced change in the isotopic composition measured by isotope mass spectrometry. The technique involves the measurement of the abundance ratio of each isotope to a (same) reference isotope in the sample solution, in the tracer solution and in the blend of the sample and tracer solution. These isotope ratio measurements, the known element amount in the tracer and the known mass of sample solution are used to calculate the unknown amount of one isotope in the sample solution. Subsequently the unknown amount of element is determined. The purpose of this paper is to examine the optimization of the ratio of the estimated unknown amount of element in the sample solution to the known amount of element in the tracer solution in order to minimize the relative uncertainty in the determination of the unknown amount of element

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

    International Nuclear Information System (INIS)

    Gromov, Sergey S.

    2014-01-01

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

  13. Carbon-13 isotopic composition of distillation fractions of some Egyptian crude oils

    International Nuclear Information System (INIS)

    Aly, A.I.M.; Hamza, M.S.; Abd Elsamie, S.G.

    1991-01-01

    13 C/ 13 C ratios were determined for some crude oil fields in the Gulf of Suez and Western Desert provinces. The crude oil was subjected to distillation at atmospheric pressure and subsequently under vacuum. Distillation fractions were collected at 25 degree C intervals. Carbon-13 content of these distillation fractions showed some differences in the degree of isotopic fractionation. The results were interpreted in view of the age of the source rocks and the degree of maturation process. The carbon-13 content of distillation fractions may be helpful in revealing petroleum mechanisms which can be exploited in exploration.4 fig

  14. Genuineness assessment of mandarin essential oils employing gas chromatography-combustion-isotope ratio MS (GC-C-IRMS).

    Science.gov (United States)

    Schipilliti, Luisa; Tranchida, Peter Quinto; Sciarrone, Danilo; Russo, Marina; Dugo, Paola; Dugo, Giovanni; Mondello, Luigi

    2010-03-01

    Cold-pressed mandarin essential oils are products of great economic importance in many parts of the world and are used in perfumery, as well as in food products. Reconstituted mandarin oils are easy to find on the market; useful information on essential oil authenticity, quality, extraction technique, geographic origin and biogenesis can be attained through high-resolution GC of the volatile fraction, or enantioselective GC, using different chiral stationary phases. Stable isotope ratio analysis has gained considerable interest for the unveiling of citrus oil adulteration, detecting small differences in the isotopic carbon composition and providing plenty of information concerning the discrimination among products of different geographical origin and the adulteration of natural essential oils with synthetic or natural compounds. In the present research, the authenticity of several mandarin essential oils was assessed through the employment of GC hyphenated to isotope ratio MS, conventional GC flame ionization detector, enantioselective GC and HPLC. Commercial mandarin oils and industrial natural (declared as such) mandarin essential oils, characterized by different harvest periods and geographic origins, were subjected to analysis. The results attained were compared with those of genuine cold-pressed Italian mandarin oils, obtained during the 2008-2009 harvest season.

  15. Stable isotope ratios in freshwater mussel shells as high resolution recorders of riverine environmental variation

    Science.gov (United States)

    Kukolich, S.; Kendall, C.; Dettman, D. L.

    2017-12-01

    The geochemical record stored in growth increments of freshwater mussel shells reveals annual to sub-annual changes in environmental conditions during the lifetime of the organism. The carbon, nitrogen, and oxygen stable isotope composition of aragonite shells responds to changes in water chemistry, temperature, streamflow, turbidity, growth rate, size, age, and reproduction. The goals of this study are to determine how stable isotopes can be used to reconstruct the conditions in which the mussels lived and to illuminate any vital effects that might obscure the isotopic record of those conditions. Previous research has suggested that annual δ13C values decrease in older freshwater mussel shells due to lower growth rates and greater incorporation of dietary carbon into the shell with increasing age. However, a high-resolution, seasonal investigation of δ13C, δ15N, and δ18O as they relate to organism age has not yet been attempted in freshwater mussels. A total of 28 Unionid mussels of three different species were collected live in 2011 in the Tennessee River near Paducah, Kentucky, USA. In this study, we analyzed the shell nacre and external organic layers for stable carbon, nitrogen, and oxygen isotope ratios, focusing on growth bands formed between 2006 and 2011. We present a time series of shell δ13C, δ18O, and δ15N values with monthly resolution. We also compare the shell-derived geochemical time series to a time series of the δ13C and δ15N of particulate organic matter, δ13C of DIC, δ18OWater, and water temperature in which the mussels lived. Results show that environmental factors such as water temperature and primary productivity dominate shell chemistry while animal age has little or no effect.

  16. Isotope ratios as pollutant source and behaviour indicators

    International Nuclear Information System (INIS)

    1975-01-01

    Recent years have witnessed significant advances in isotope techniques for identifying origins and for studying the behaviour of trace contaminants and pollutants of the environment under actual existing environmental conditions. Improvements in the supply of stable isotopes and their labelled compounds, instrumental analysis and information on stable or radioactive isotopic ratios of existing environmental contaminants as a function of origin or behaviour have provided relatively new tools for the environmental scientist. While variations in natural or existing environmental stable and radioactive nuclides could be regarded as 'background noise' in conventional tracer experiments they promised unique information about sources and behaviour to those who listened carefully. (author)

  17. Poster 9: Isotopic Ratios of Carbon and Oxygen in Titan's CO using ALMA

    Science.gov (United States)

    Serigano, Joseph; Nixion, Conor A.; Cordiner, Martin A.; Irwin, Patrick G. J.; Teanby, Nick A.; Charnley, Steven B.; Lindberg, Johan E.

    2016-06-01

    The advent of the Atacama Large Millimeter/Submillimeter Array (ALMA) has provided a new and powerful facility for probing the atmospheres of solar system targets at long wavelengths (84-720 GHz) where the rotational lines of small, polar molecules are prominent. In the complex atmosphere of Titan, photochemical processes dissociate and ionize molecular nitrogen and methane in the upper atmosphere, creating a complex inventory of trace hydrocarbons and nitriles. Additionally, the existence of oxygen on Titan facilitates the synthesis of molecules of potential astrobiological importance. Utilization of ground-based submillimeter observations of Titan has proven to be a powerful tool to complement results from spacecraft observations. ALMA provides the ability to probe this region in greater detail with unprecedented spectral and spatial resolution at high sensitivity, allowing for the derivation of vertical mixing profiles, molecular detections, and observations of latitudinal and seasonal variations. Recent ALMA studies of Titan have presented spectrally and spatially-resolved maps of HNC and HC3N emission (Cordiner et al. 2014), as well as the first spectroscopic detection of ethyl cyanide (C2H5CN) in Titan's atmosphere (Cordiner et al. 2015). This poster will focus on ALMA observations of carbon monoxide (CO) and its isotopologues 13CO, C18O, and C 17O in Titan's atmosphere. Molecular abundances and the vertical atmospheric temperature profile were derived by modeling the observed emission line profiles using NEMESIS, a line-by-line radiative transfer code (Irwin et al. 2008). This study reports the first spectroscopic detection of 17O in the outer solar system with C17O detected at >8σ confidence. The abundances of these molecules and isotopic ratios of 12C/13C, 16O/18O, and 16O/17O will be presented. General implications for the history of Titan from these measurements will be discussed.

  18. Analytical Method for Carbon and Oxygen Isotope of Small Carbonate Samples with the GasBench Ⅱ-IRMS Device

    Directory of Open Access Journals (Sweden)

    LIANG Cui-cui

    2015-01-01

    Full Text Available An analytical method for measuring carbon and oxygen isotopic compositions of trace amount carbonate (>15 μg was established by Delta V Advantage isotope Ratio MS coupled with GasBench Ⅱ. Different trace amount (5-50 μg carbonate standard samples (IAEA-CO-1 were measured by GasBench Ⅱ with 12 mL and 3.7 mL vials. When the weight of samples was less than 40 μg and it was acidified in 12 mL vials, most standard deviations of the δ13C and δ18O were more than 0.1‰, which couldn’t satisfied high-precision measurements. When the weight of samples was greater than 15 μg and it was acidified in 3.7 mL vials, standard deviations for the δ13C and δ18O were 0.01‰-0.07‰ and 0.01‰-0.08‰ respectively, which satisfied high-precision measurements. Therefore, small 3.7 mL vials were used to increase the concentration of carbon dioxide in headspace, carbonate samples even less as 15 μg can be analyzed routinely by a GasBench Ⅱ continuous-flow IRMS. Meanwhile, the linear relationship between sample’s weight and peak’s area was strong (R2>0.993 2 and it can be used to determine the carbon content of carbonate samples.

  19. Lead isotope ratios in artists' lead white: a progress report

    Energy Technology Data Exchange (ETDEWEB)

    Keisch, B; Callahan, R C [Carnegie-Mellon Univ., Pittsburgh, Pa. (USA)

    1976-07-01

    The lead isotope ratios in over four hundred samples of lead white have been determined. The samples represent various geographical sources and dates from the thirteenth century to the present. A new method for organizing this large volume of data is described which helps with the visualization of temporal and geographic patterns. A number of interesting relationships between lead isotope ratio and date or source are shown to exist. Some examples of successful applications of this methodology are described.

  20. Geospatial modeling of plant stable isotope ratios - the development of isoscapes

    Science.gov (United States)

    West, J. B.; Ehleringer, J. R.; Hurley, J. M.; Cerling, T. E.

    2007-12-01

    Large-scale spatial variation in stable isotope ratios can yield critical insights into the spatio-temporal dynamics of biogeochemical cycles, animal movements, and shifts in climate, as well as anthropogenic activities such as commerce, resource utilization, and forensic investigation. Interpreting these signals requires that we understand and model the variation. We report progress in our development of plant stable isotope ratio landscapes (isoscapes). Our approach utilizes a GIS, gridded datasets, a range of modeling approaches, and spatially distributed observations. We synthesize findings from four studies to illustrate the general utility of the approach, its ability to represent observed spatio-temporal variability in plant stable isotope ratios, and also outline some specific areas of uncertainty. We also address two basic, but critical questions central to our ability to model plant stable isotope ratios using this approach: 1. Do the continuous precipitation isotope ratio grids represent reasonable proxies for plant source water?, and 2. Do continuous climate grids (as is or modified) represent a reasonable proxy for the climate experienced by plants? Plant components modeled include leaf water, grape water (extracted from wine), bulk leaf material ( Cannabis sativa; marijuana), and seed oil ( Ricinus communis; castor bean). Our approaches to modeling the isotope ratios of these components varied from highly sophisticated process models to simple one-step fractionation models to regression approaches. The leaf water isosocapes were produced using steady-state models of enrichment and continuous grids of annual average precipitation isotope ratios and climate. These were compared to other modeling efforts, as well as a relatively sparse, but geographically distributed dataset from the literature. The latitudinal distributions and global averages compared favorably to other modeling efforts and the observational data compared well to model predictions

  1. Lead isotope ratios of ancient Chinese and Japanese glasses

    International Nuclear Information System (INIS)

    Yamasaki, Kazuo; Murozumi, Masayo; Nakamura, Seiji; Yuasa, Mitsuaki; Watarai, Motohiko.

    1980-01-01

    Lead isotope ratios of 29 archaeological glass samples (5 samples excavated in China, 10 samples excavated in Japan, and 14 samples made in Japan) were determined by surface ionization mass spectrometry with a HITACHI RMU-6 spectrometer. Of these glass samples, 28 were made of high lead glass, and one, of alkali-lime glass. Glass samples were decomposed in a mixture of hydrofluoric and nitric acids, and lead was separated from other elements by extraction with dithizone-chloroform. The lead nitrate solution thus prepared (corresponding to 0.5 μg Pb) was loaded on the rhenium single filament. The coefficients of variation of the determined ratios, 207 Pb/ 206 Pb and 208 Pb/ 206 Pb, were 0.1 -- 0.3%. Among the glasses excavated in Japan, some samples of the Yayoi period (ca. 3 rd C. B.C. -- ca. 3 rd C. A.D.) contained a large amount of barium in addition to lead, and resembled closely Chinese pre-Han glasses not only in chemical compositions, but also in lead isotope ratios. This means that pre-Han glasses were brought to Japan and then re-cast into glass beads characteristic of Japan. The lead isotope ratios of the glasses were compared with those of Chinese (2 samples), Korean (2) and Japanese (17) galena orea, and it was found that 12 glass beads made in the 8th century at Nara and 2 fine glass tubes made at Saga in the 18 th -- 19 th centuries showed similar lead isotope ratios with those of the Japanese galena ores. Consequently it is considered that the Japanese galena ores were already used as one of raw materials at manufacturing of these glass beads in ancient centuries. (author)

  2. Carbon isotope geothermometry of graphite-bearing marbles from Central Dronning Maud Land, East Antarctica

    International Nuclear Information System (INIS)

    Wand, U.; Muehle, K.

    1988-01-01

    In order to estimate the peak metamorphic temperatures in high-grade regional metamorphic marbles from central Dronning Maud Land (East Antarctica), 13 C/ 12 C isotope ratios have been measured for coexisting carbonate and graphite pairs. The δ 13 C values of carbonates (calcite ± dolomite) and graphite vary from -0.1 to +4.6 permill (PDB) and from -3.3 to +1.7 permill, respectively. The isotopic fractionation between carbonate and graphite ranges from 2.9 to 4.0 permill and is similar to the Δ 13 C (carb-gr) values observed in other East Antarctic and non-Antarctic granulite-facies marbles. The metamorphic temperatures calculated using the equation of VALLEY and O'NEIL (1981) for calcite-graphite pairs are predominantly in the range 700 0 - 800 0 C (x n=5 ± s = 730 0 ± 30 0 C) and agree well with metamorphic temperatures derived from mineral chemical studies in this East Antarctic region. (author)

  3. Molecular sieve isolation technique for use in stable carbon isotope analysis of individual long-chain n-alkanes in crude oil

    International Nuclear Information System (INIS)

    Yamada, Keita; Kon, Makoto; Naraoka, Hiroshi; Ishiwatari, Ryoshi; Uzaki, Minoru.

    1994-01-01

    An isolation procedure of microgram amounts of long-chain n-alkanes from crude oil using molecular sieve was examined for its applicability to stable carbon isotope analysis by gas chromatography/isotope ratio mass spectrometry (GC/IRMS). The procedure examined is as follows: molecular sieve (type 5A, 200 mg) in 1 ml of isooctane solvent are mixed with a saturated hydrocarbon fraction extracted from an appropriate amount (approx. 20 mg) of crude oil and stayed at room temperatures for more than 3 hours. Long-chain n-alkanes are isolated by extraction with n-hexane after dissolution of the resulting molecular sieve with 47% hydrofluoric acid solution. The recoveries were 90±6% for C 15 -C 34 n-alkanes when their total amounts applied do not exceed 1.4 mg. No effect of the isolation procedure on carbon isotope ratios of n-alkanes was observed. (author)

  4. Uranium Isotopes in Calcium Carbonate: A Possible Proxy for Paleo-pH and Carbonate Ion Concentration?

    Science.gov (United States)

    Chen, X.; Romaniello, S. J.; Herrmann, A. D.; Wasylenki, L. E.; Anbar, A. D.

    2015-12-01

    Natural variations of 238U/235U in marine carbonates are being explored as a paleoredox proxy. However, in order for this proxy to be robust, it is important to understand how pH and alkalinity affect the fractionation of 238U/235U during coprecipitation with calcite and aragonite. Recent work suggests that the U/Ca ratio of foraminiferal calcite may vary with seawater [CO32-] concentration due to changes in U speciation[1]. Here we explore analogous isotopic consequences in inorganic laboratory co-precipitation experiments. Uranium coprecipitation experiments with calcite and aragonite were performed at pH 8.5 ± 0.1 and 7.5 ± 0.1 using a constant addition method [2]. Dissolved U in the remaining solution was periodically collected throughout the experiments. Samples were purified with UTEVA resin and 238U/235U was determined using a 233U-236U double-spike and MC-ICP-MS, attaining a precision of ± 0.10 ‰ [3]. Small but resolvable U isotope fractionation was observed in aragonite experiments at pH ~8.5, preferentially enriching heavier U isotopes in the solid phase. 238U/235U of the dissolved U in these experiments can be fit by Rayleigh fractionation curves with fractionation factors of 1.00002 - 1.00009. In contrast, no resolvable U isotope fractionation was detected in an aragonite experiment at pH ~7.5 or in calcite experiments at either pH. Equilibrium isotope fractionation among dissolved U species is the most likely mechanism driving these isotope effects. Our quantitative model of this process assumes that charged U species are preferentially incorporated into CaCO3 relative to the neutral U species Ca2UO2(CO3)3(aq), which we hypothesize to have a lighter equilibrium U isotope composition than the charged U species. According to this model, the magnitude of U isotope fractionation should scale with the fraction of the neutral U species in the solution, in agreement with our experimental results. These findings suggest that U isotope variations in

  5. Dual temperature effects on oxygen isotopic ratio of shallow-water coral skeleton: Consequences on seasonal and interannual records

    Science.gov (United States)

    Juillet-Leclerc, A.; Reynaud, S.

    2009-04-01

    Oxygen isotopic ratio from coral skeleton is regarded for a long time as promising climate archives at seasonal scale. Although in isotopic disequilibrium relative to seawater, it is supposed to obey to the isotope thermometer. Indeed, coral oxygen isotopic records are strongly temperature dependent, but d18O-temperature calibrations derived from different corals are highly variable. The isotope thermometer assumption does not take into account vital effects due to biogenic origin of the mineral. Corals are animals living in symbiosis with algae (zooxanthellae). Interactions between symbiont photosynthesis and coral skeleton carbonation have been abundantly observed but they remain poorly understood and the effects of photosynthesis on coral growth and skeleton oxygen ratio are ignored. Coral cultured under two light conditions enabled to relate metabolic parameters and oxygen isotopic variability with photosynthetic activity. By examining responses provided by each colony they revealed that photosynthesis significantly affected d18O, by an opposite sense compared with the sole temperature influence. Since temperature and light changes are associated during seasonal variations, this complicates the interpretation of seasonal record. Additionally, this complexity is amplified because photosynthetic activity is also directly impacted by temperature variability. Thus, the annual isotopic amplitude due to the "physical" temperature influence is partly compensated through photosynthesis. Similar opposite effect is also shown by extension rate of the cultured colonies. First, we will examine and quantify consequences of photosynthesis on growth rate and oxygen isotopic signature, from cultured corals. Second, we will consider the consequences of this vital effect on data series, at seasonal and interannual time scales.

  6. Fractionation of carbon isotopes by thermophilic methanogenic bacteria

    International Nuclear Information System (INIS)

    Ivanov, M.V.; Belyaev, S.S.; Zyakun, A.M.; Bondar, V.A.; Shipin, O.P.; Laurinavichus, K.S.

    1985-01-01

    The authors investigated the pattern of fractionation of stable carbon isotopes by the thermophilic methane-forming bacteria under different growth conditions and at various rates of formation of methane. A pure culture of Methanobacterium thermoautotrophicum was used in the experiments under the following growth conditions: temperature 65-70 0 C; pH 7.2-7.6; NaCl content 0-0.9 g/liter. The methanogenic bacteria were cultivated in 0.15 liter flasks in mineral medium. A mixture of CO 2 and H 2 in a 1:4 ratio by volume served as the sole carbon and energy source. In all experiments, not more than 5% of the initial CO 2 level was utilized. The rate of methane generation was altered by adjusting the physicochemical growth parameters (temperature from 45-70 0 C, salinity from 0.9 to 40 g/liter NaCl, pH from 6.3 to 7.2). Methane in the samples was quantitatively determined in a chromatograph which had a flame-ionization detector and a column containing Porapak Q sorbent at T = 120 0 C. The carrier gas was CO 2 . The average specific rate of methane formation was calculated as ml CH 4 per mg dry biomass of bacteria per h. Soluble mineral carbon was isolated form the acidified culture liquid in the form of CO 2 and was quantitatively determined in a Chrom-4 chromatography provided with a katharometer and a column containing activated charcoal at T = 150 0 . The gas carrier was helium. The isotopic composition of carbon was determined in a CH-7 mass-spectrometer and was expressed in 13 C values (per thousand) with respect to the international PDB standard

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

    Science.gov (United States)

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

    2011-12-01

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

  8. Robust optical carbon dioxide isotope analyzer, Phase I

    Data.gov (United States)

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

  9. Characteristics of stable carbon isotopic composition of shale gas

    Directory of Open Access Journals (Sweden)

    Zhenya Qu

    2016-04-01

    Full Text Available A type Ⅱ kerogen with low thermal maturity was adopted to perform hydrocarbon generation pyrolysis experiments in a vacuum (Micro-Scale Sealed Vessel system at the heating rates of 2 °C/h and 20 °C/h. The stable carbon isotopic compositions of gas hydrocarbons were measured to investigate their evolving characteristics and the possible reasons for isotope reversal. The δ13C values of methane became more negative with the increasing pyrolysis temperatures until it reached the lightest point, after which they became more positive. Meanwhile, the δ13C values of ethane and propane showed a positive trend with elevating pyrolysis temperatures. The carbon isotopic compositions of shale gasses were mainly determined by the type of parent organic matter, thermal evolutionary extent, and gas migration in shale systems. Our experiments and study proved that the isotope reversal shouldn't occur in a pure thermogenic gas reservoir, it must be involved with some other geochemical process/es; although mechanisms responsible for the reversal are still vague. Carbon isotopic composition of the Fayetteville and Barnett shale gas demonstrated that the isotope reversal was likely involved with water–gas reaction and Fischer-Tropsch synthesis during its generation.

  10. High precision measurement by mass spectrometry of isotopic ratios δ13C and δ18O of carbon dioxide

    International Nuclear Information System (INIS)

    Bourg, Chr.; Ciais, Ph.

    1998-02-01

    Carbon dioxide (CO 2 ) is the second natural greenhouse gas in the Earth's atmosphere, after vapor water. Its concentration levels have been increasing by 25% due to human activities over the past 200 years, thus increasing the radiative forcing at the surface and potentially including major climate change for the next centuries. It is of primary importance to better quantify the role of carbon contained into the oceans and the land biota in moderating the anthropic perturbation. To do so, 13 C and 18 O isotopes are unique tools which allow to estimate indirectly the terrestrial CO 2 fluxes based on atmospheric measurements. The present reports describes the experimental set-up used at the CFR-LMCE laboratory to measure the 13 C and 18 O natural abundance in atmospheric carbon dioxide. This technique requires high levels of both precision and accuracy because the geochemical signal nevertheless consists of very small changes in isotopic composition (on the order of 0.01 permits). Also, given the large number of samples to analyses routinely, it must be run in an automatic mode. Our experiment design consists of 'extraction line' where CO 2 is separated cryogenically from the air, which is coupled to a (Finnigan MAT 252) mass spectrometer. (authors)

  11. NITROGEN ISOTOPES IN ASYMPTOTIC GIANT BRANCH CARBON STARS AND PRESOLAR SiC GRAINS: A CHALLENGE FOR STELLAR NUCLEOSYNTHESIS

    International Nuclear Information System (INIS)

    Hedrosa, R. P.; Abia, C.; Domínguez, I.; Palmerini, S.; Busso, M.; Cristallo, S.; Straniero, O.; Plez, B.

    2013-01-01

    Isotopic ratios of C, N, Si, and trace heavy elements in presolar SiC grains from meteorites provide crucial constraints to nucleosynthesis. A long-debated issue is the origin of the so-called A+B grains, as of yet no stellar progenitor thus far has been clearly identified on observational grounds. We report the first spectroscopic measurements of 14 N/ 15 N ratios in Galactic carbon stars of different spectral types and show that J- and some SC-type stars might produce A+B grains, even for 15 N enrichments previously attributed to novae. We also show that most mainstream grains are compatible with the composition of N-type stars, but in some cases might also descend from SC stars. From a theoretical point of view, no astrophysical scenario can explain the C and N isotopic ratios of SC-, J-, and N-type carbon stars together, as well as those of many grains produced by them. This poses urgent questions to stellar physics.

  12. Empirical High-Temperature Calibration for the Carbonate Clumped Isotopes Paleothermometer

    Science.gov (United States)

    Kluge, T.; John, C. M.; Jourdan, A.; Davis, S.; Crawshaw, J.

    2013-12-01

    The clumped isotope paleothermometer is being used in a wide range of applications related to carbonate mineral formation, focusing on temperature and fluid δ18O reconstruction. Whereas the range of typical Earth surface temperatures has been the focus of several studies based on laboratory experiments and biogenic carbonates of known growth temperatures, the clumped isotope-temperature relationship above 70 °C has not been assessed by direct precipitation of carbonates. We investigated the clumped isotope-temperature relationship by precipitating carbonates between 20 and 200°C in the laboratory. The setup consists of a pressurized vessel in which carbonate minerals are precipitated from the mixture of two solutions (CaCl2, NaHCO3). Both solutions are thermally and isotopically equilibrated before injection in the pressure vessel. Minerals precipitated in this setup generally consist of calcite. Samples were reacted with 105% orthophosphoric acid for 10 min at 90°C. The evolved CO2 was continuously collected and subsequently purified with a Porapak trap held at -35°C. Measurements were performed on a MAT 253 using the protocol of Huntington et al. (2009) and Dennis et al. (2011). Clumped isotope values from 20-90°C are consistent with carbonates that were precipitated from a CaCO3 super-saturated solution using the method of McCrea (1950). This demonstrates that the experimental setup does not induce any kinetic fractionation, and can be used for high-temperature carbonate precipitation. The new clumped isotope calibration at high temperature follows the theoretical calculations of Schauble et al. (2006) adjusted for phosphoric acid digestion at 90°C. We gratefully acknowledge funding from Qatar Petroleum, Shell and the Qatar Science and Technology Park.

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

    International Nuclear Information System (INIS)

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

    2007-01-01

    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, f ow 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

  14. Stable and strontium isotopic records of molluscan shells, lower jurassic, Cuenca Neuquina, southwestern Mendoza, Argentina

    International Nuclear Information System (INIS)

    Cagnoni, M.C.; Valencio, S.A.; Ramos, A.M; Riccardi, A.C; Panarello, H.O

    2001-01-01

    The strontium, carbon and oxygen isotopic signal of the past oceans is accurately recorded by authigenic marine minerals such as carbonates, sulfates and phosphates. The variation of these isotope ratios through the geological time is used as a tool in correlating and dating marine sedimentary rocks. Many works have been done concerning to the changes in carbon, oxygen and strontium isotope ratios of different marine successions in the world. These allow the construction of curves of secular variations of the isotope signals with geological time (Jones et al., 1994a, 1994b; Veizer et al., 1999; Jacobsen and Kaufman, 1999). This work presents strontium, carbon and oxygen isotope ratios of Early Jurassic biogenic marine carbonates of Cuenca Neuquina in southwestern Mendoza (au)

  15. Determination of stable isotope ratio of lead in airborne particulate matter by ICP-MS

    International Nuclear Information System (INIS)

    Mukai, Hitoshi; Ambe, Yoshinari

    1990-01-01

    ICP-MS was applied to the measurement of stable isotope ratios of lead, which are used as an indicator of the source of lead in airborne particulate matter. For the measurement of lead isotopes ratios, the influences of machine conditions, lead concentration and matrix elements to the precision and accuracy of the measurements were studied. At a scanning mode, dwell time of 40∼160 μs gave the best precision to the isotope ratio measurements; about 0.3 % of R.S.D. for 206 Pb/ 207 Pb and 206 Pb/ 208 Pb, 0.6 % for 206 Pb/ 204 Pb. Precision of the measurement was better at a high concentration of lead in sample solution. The observed value of 206 Pb/ 207 Pb ratio was not affected by the lead concentration, but in the cases of 206 Pb/ 204 Pb and 206 Pb/ 208 Pb, about 1 % of the value changed in the observed ratios with the lead concentration of 100∼500 μg/l. Six matrix elements (Na, K, Ca, Mg, Al, Fe) did not affect the observed isotope ratios up to 200 mg/l. The lead isotope ratios of reference materials {Urban Particulates (NIST) and Vehicle Exhausted Particulates (NIES)} were measured by using two kinds of sample; crude sample and lead-isolated sample from matrix elements by anodic deposition. Both cases gave the same isotope ratio values, therefore, lead isotope ratios in airborne particulate samples can be measured by ICP-MS without any separation of lead from matrix elements. (author)

  16. Isotopic Ratios of Samarium by TIMS for Nuclear Forensic Application

    Energy Technology Data Exchange (ETDEWEB)

    Louis Jean, James [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Inglis, Jeremy David [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-08-08

    The isotopic ratio of Nd, Sm, and Gd can provide important information regarding fissile material (nuclear devices, reactors), neutron environment, and device yield. These studies require precise measurement of Sm isotope ratios, by either TIMS or MC-ICP-MS. There has been an increasing trend to measure smaller and smaller quantities of Sm bearing samples. In nuclear forensics 10-100 ng of Sm are needed for precise measurement. To measure sub-ng Sm samples using TIMS for nuclear forensic analysis.

  17. Lead isotope ratios in artists' lead white: a progress report

    International Nuclear Information System (INIS)

    Keisch, B.; Callahan, R.C.

    1976-01-01

    The lead isotope ratios in over four hundred samples of lead white have been determined. The samples represent various geographical sources and dates from the thirteenth century to the present. A new method for organizing this large volume of data is described which helps with the visualization of temporal and geographic patterns. A number of interesting relationships between lead isotope ratio and date or source are shown to exist. Some examples of successful applications of this methodology are described. (author)

  18. Carbon, cesium and iodine isotopes in Japanese cedar leaves from Iwaki, Fukushima.

    Science.gov (United States)

    Xu, Sheng; Cook, Gordon T; Cresswell, Alan J; Dunbar, Elaine; Freeman, Stewart P H T; Hou, Xiaolin; Kinch, Helen; Naysmith, Philip; Sanderson, David W C; Zhang, Luyuan

    2016-01-01

    Japanese cedar leaves from Iwaki, Fukushima were analyzed for carbon, cesium and iodine isotopic compositions before and after the 2011 nuclear accident. The Δ 14 C values reflect ambient atmospheric 14 C concentrations during the year the leaves were sampled/defoliated, and also previous year(s). The elevated 129 I and 134,137 Cs concentrations are attributed to direct exposure to the radioactive fallout for the pre-fallout-expended leaves and to internal translocation from older parts of the tree for post-fallout-expended leaves. 134 Cs/ 137 Cs and 129 I/ 137 Cs activity ratios suggest insignificant isotopic and elemental fractionation during translocation. However, fractionation between radioiodine and radiocesium is significant during transportation from the source.

  19. Carbon, cesium and iodine isotopes in Japanese cedar leaves from Iwaki, Fukushima

    International Nuclear Information System (INIS)

    Sheng Xu; Cresswell, A.J.; Cook, G.T.; Dunbar, Elaine; Freeman, S.P.H.T.; Kinch, Helen; Naysmith, Philip; Sanderson, D.W.C.; Xiaolin Hou; Luyuan Zhang; Xi'an AMS Center, SKLLQG, CAS, Xi'an

    2016-01-01

    Japanese cedar leaves from Iwaki, Fukushima were analyzed for carbon, cesium and iodine isotopic compositions before and after the 2011 nuclear accident. The Δ 14 C values reflect ambient atmospheric 14 C concentrations during the year the leaves were sampled/defoliated, and also previous year(s). The elevated 129 I and 134,137 Cs concentrations are attributed to direct exposure to the radioactive fallout for the pre-fallout-expended leaves and to internal translocation from older parts of the tree for post-fallout-expended leaves. 134 Cs/ 137 Cs and 129 I/ 137 Cs activity ratios suggest insignificant isotopic and elemental fractionation during translocation. However, fractionation between radioiodine and radiocesium is significant during transportation from the source. (author)

  20. Combined simulation of carbon and water isotopes in a global ocean model

    Science.gov (United States)

    Paul, André; Krandick, Annegret; Gebbie, Jake; Marchal, Olivier; Dutkiewicz, Stephanie; Losch, Martin; Kurahashi-Nakamura, Takasumi; Tharammal, Thejna

    2013-04-01

    Carbon and water isotopes are included as passive tracers in the MIT general circulation model (MITgcm). The implementation of the carbon isotopes is based on the existing MITgcm carbon cycle component and involves the fractionation processes during photosynthesis and air-sea gas exchange. Special care is given to the use of a real freshwater flux boundary condition in conjunction with the nonlinear free surface of the ocean model. The isotopic content of precipitation and water vapor is obtained from an atmospheric GCM (the NCAR CAM3) and mapped onto the MITgcm grid system, but the kinetic fractionation during evaporation is treated explicitly in the ocean model. In a number of simulations, we test the sensitivity of the carbon isotope distributions to the formulation of fractionation during photosynthesis and compare the results to modern observations of δ13C and Δ14C from GEOSECS, WOCE and CLIVAR. Similarly, we compare the resulting distribution of oxygen isotopes to modern δ18O data from the NASA GISS Global Seawater Oxygen-18 Database. The overall agreement is good, but there are discrepancies in the carbon isotope composition of the surface water and the oxygen isotope composition of the intermediate and deep waters. The combined simulation of carbon and water isotopes in a global ocean model will provide a framework for studying present and past states of ocean circulation such as postulated from deep-sea sediment records.

  1. The Effect of Early Diagenesis on the 238U/235U Ratio of Platform Carbonates.

    Science.gov (United States)

    Tissot, F.; Chen, C.; Go, B. M.; Naziemiec, M.; Healy, G.; Swart, P. K.; Dauphas, N.

    2017-12-01

    In the past 15 years, the so-called non-traditional stable isotopes systems (e.g., Mg, Fe, Mo, U) have emerged as powerful tracers of both high-T and low-T geochemical processes (e.g., [1]). Of particular interest for paleoredox studies is the ratio of "stable" isotopes of U (238U/235U), which has the potential to track the global extent of oceanic anoxia (e.g., [2, 3]). Indeed, in the modern ocean, U exists in two main oxidation states, soluble U6+ and insoluble U4+, and has a mean residence time of 400 kyr ([4]), much longer than the global ocean mixing time (1-2 kyr). As such the salinity-normalized ocean is homogeneous with regards to both U concentrations and isotopes (δ238USW = -0.392±0.005 ‰, [2]). The value of δ238USW at any given time is therefore the balance between U input to the ocean, mainly from rivers, and U removal, mostly into biogenic carbonates, anoxic/euxinic sediments and suboxic/hypoxic sediments (e.g., [2, 5]). Because the 238U/235U ratio of the past ocean cannot be measured directly, it has to be estimated from the measurement of the 238U/235U ratio of a sedimentary rock and assuming a constant fractionation factor. Carbonates appear as a promising record since they span most of Earth's history, and the δ238U values of modern primary carbonate precipitates and well-preserved fossil aragonitic coral up to 600 ka are indistinguishable from that of seawater (e.g., [2, 6, 7]). Yet, the effect of secondary processes on the δ238U values of non-coral carbonates, which represent the bulk of the rock record, has only been studied in a handful of shallow samples (down to 40cm, [6]) and remains poorly understood. To investigate the effect of early diagenesis on the 238U/235U ratio of carbonates on the 30kyr to 1Myr timescale, we measured δ13C, δ18O, and δ238U in samples from a 220m long drill core from the Bahamas carbonate platform. In order to separate lattice bound U from secondary U we developed a leaching protocol applicable to carbonate

  2. Covalently bound molecular states in beryllium and carbon isotopes

    International Nuclear Information System (INIS)

    Wolfram von, Oertzen; Hans-Gerhard, Bohlen; Wolfram von, Oertzen

    2003-01-01

    Nuclear clustering in N=Z nuclei has been studied since many decades. States close to the decay thresholds, as described by the Ikeda diagram, are of particular interest. Recent studies in loosely bound systems, as observed with neutron-rich nuclei has revived the interest in cluster structures in nuclei, with additional valence neutrons, which give rise to pronounced covalent molecular structures. The Beryllium isotopes represent the first example of such unique states in nuclear physics with extreme deformations. In the deformed shell model these are referred to as super- and hyper-deformation. These states can be described explicitly by molecular concepts, with neutrons in covalent binding orbits. Examples of recent experiments performed at the HMI-Berlin demonstrating the molecular structure of the rotational bands in Beryllium isotopes are presented. Further work on chain states (nuclear polymers) in the carbon isotopes is in progress, these are the first examples of deformed structures in nuclei with an axis ratio of 3:1. A threshold diagram with clusters bound via neutrons in covalent molecular configurations can be established, which can serve as a guideline for future work. (authors)

  3. Temperature dependence of carbon isotope fractionation in CAM plants

    International Nuclear Information System (INIS)

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

    1985-01-01

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

  4. Temperature dependence of carbon isotope fractionation in CAM plants

    Energy Technology Data Exchange (ETDEWEB)

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

    1985-09-01

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

  5. On the cross-sensitivity between water vapor mixing ratio and stable isotope measurements of in-situ analyzers

    KAUST Repository

    Parkes, Stephen

    2015-04-01

    In recent years there has been an increasing amount of water vapor stable isotope data collected using in-situ instrumentation. A number of papers have characterized the performance of these in-situ analyzers and suggested methods for calibrating raw measurements. The cross-sensitivity of the isotopic measurements on the mixing ratio has been shown to be a major uncertainty and a variety of techniques have been suggested to characterize this inaccuracy. However, most of these are based on relating isotopic ratios to water vapor mixing ratios from in-situ analyzers when the mixing ratio is varied and the isotopic composition kept constant. An additional correction for the span of the isotopic ratio scale is then applied by measuring different isotopic standards. Here we argue that the water vapor cross-sensitivity arises from different instrument responses (span and offset) of the parent H2O isotope and the heavier isotopes, rather than spectral overlap that could cause a true variation in the isotopic ratio with mixing ratio. This is especially relevant for commercial laser optical instruments where absorption lines are well resolved. Thus, the cross-sensitivity determined using more conventional techniques is dependent on the isotopic ratio of the standard used for the characterization, although errors are expected to be small. Consequently, the cross-sensitivity should be determined by characterizing the span and zero offset of each isotope mixing ratio. In fact, this technique makes the span correction for the isotopic ratio redundant. In this work we model the impact of changes in the span and offset of the heavy and light isotopes and illustrate the impact on the cross-sensitivity of the isotopic ratios on water vapor. This clearly shows the importance of determining the zero offset for the two isotopes. The cross-sensitivity of the isotopic ratios on water vapor is then characterized by determining the instrument response for the individual isotopes for a

  6. On the cross-sensitivity between water vapor mixing ratio and stable isotope measurements of in-situ analyzers

    KAUST Repository

    Parkes, Stephen; Wang,  Lixin; McCabe, Matthew

    2015-01-01

    In recent years there has been an increasing amount of water vapor stable isotope data collected using in-situ instrumentation. A number of papers have characterized the performance of these in-situ analyzers and suggested methods for calibrating raw measurements. The cross-sensitivity of the isotopic measurements on the mixing ratio has been shown to be a major uncertainty and a variety of techniques have been suggested to characterize this inaccuracy. However, most of these are based on relating isotopic ratios to water vapor mixing ratios from in-situ analyzers when the mixing ratio is varied and the isotopic composition kept constant. An additional correction for the span of the isotopic ratio scale is then applied by measuring different isotopic standards. Here we argue that the water vapor cross-sensitivity arises from different instrument responses (span and offset) of the parent H2O isotope and the heavier isotopes, rather than spectral overlap that could cause a true variation in the isotopic ratio with mixing ratio. This is especially relevant for commercial laser optical instruments where absorption lines are well resolved. Thus, the cross-sensitivity determined using more conventional techniques is dependent on the isotopic ratio of the standard used for the characterization, although errors are expected to be small. Consequently, the cross-sensitivity should be determined by characterizing the span and zero offset of each isotope mixing ratio. In fact, this technique makes the span correction for the isotopic ratio redundant. In this work we model the impact of changes in the span and offset of the heavy and light isotopes and illustrate the impact on the cross-sensitivity of the isotopic ratios on water vapor. This clearly shows the importance of determining the zero offset for the two isotopes. The cross-sensitivity of the isotopic ratios on water vapor is then characterized by determining the instrument response for the individual isotopes for a

  7. Absorption of carbon dioxide and isotope exchange rate of carbon in a reaction system between carbon dioxide and carbamic acid

    International Nuclear Information System (INIS)

    Takeshita, Kenji; Kitamoto, Asashi

    1985-01-01

    The performance of isotope separation of carbon-13 by chemical exchange between carbon dioxide and carbamic acid was studied. The working fluid used in the study was a solution of DNBA, (C 4 H 9 ) 2 NH and n-octane mixture. Factors related to the isotope exchange rate were measured, such as the absorption rate of carbon dioxide into the solution of DNBA and n-octane, the isotope exchange rate and the separation factor in the reaction between CO 2 and carbamic acid. The absorption of CO 2 into the working fluid was the sum of chemical absorption by DNBA and physical absorption by n-octane. The absorption of carbon dioxide into the working fluid was negligible at temperatures over 90 0 C, but increased gradually at lower temperatures. Carbon dioxide was absorbed into DNBA by chemical absorption, and DNBA was converted to carbamic acid by the reaction. The reaction for synthesis and decomposition of carbamic acid was reversible. The separation factor in equilibrium reached a large value at lower temperatures. The isotope exchange rate between gas and liquid was proportional to the product of the concentration of carbamic acid and the concentration of CO 2 by physical absorption. The isotope separation of carbon by chemical exchange reaction is better operated under the conditions of lower temperature and higher pressure. (author)

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

    Science.gov (United States)

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

    2008-07-01

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

  9. Stable carbon and nitrogen isotope signatures indicate recovery of marine biota from sewage pollution at Moa Point, New Zealand

    International Nuclear Information System (INIS)

    Rogers, Karyne M.

    2003-01-01

    Stable carbon and nitrogen isotopes have been used to assess sewage contamination of a sewage outfall, discharging milli-screened effluent into Moa Point Bay, New Zealand, and monitor the recovery of flora and fauna after the outfall's closure. An initial study characterising the extent of the discharge and the effects on seaweed (Ulva lactuca L.), blue mussels (Mytilus galloprovincialis) and limpets (Cellana denticulata) from the area, showed effects of the sewage discharge on flora and fauna were localised within in the bay. The immediate area surrounding the discharge area was found to contain limited biodiversity, with an abundance of Ulva lactuca, a bright green lettuce-like seaweed, typically found in areas with high nutrient input, limpets and small blue mussels. The nitrogen isotopic signature (δ 15 N) is shown to be a good tracer of sewage pollution in seaweed and associated grazers (i.e. limpets) as a result of the increased contribution of urea and ammonia to seawater nitrogen derived from the effluent. The carbon isotopic signature (δ 13 C) is suggested as a more appropriate sewage tracer for mussels, which filter feed the effluent's particulate organic matter from the water. Lower carbon:nitrogen ratios were found in Ulva lactuca sampled from around the outfall region compared to uncontaminated control sites. However carbon:nitrogen ratios do not vary significantly amongst shellfish species. After closure, monitoring continued for 9 months and showed that the carbon and nitrogen isotopic signatures of algae (Ulva lactuca L.) returned to similar control site levels within 3 months. Limpet and blue mussels (Cellana denticulata and Mytilus galloprovincialis) showed slower recovery times than the Ulva lactuca, with detectable levels of the sewage-derived carbon and nitrogen remaining in the animal's tissue for up to 9 months

  10. Stable carbon and nitrogen isotope signatures indicate recovery of marine biota from sewage pollution at Moa Point, New Zealand

    Energy Technology Data Exchange (ETDEWEB)

    Rogers, Karyne M

    2003-07-01

    Stable carbon and nitrogen isotopes have been used to assess sewage contamination of a sewage outfall, discharging milli-screened effluent into Moa Point Bay, New Zealand, and monitor the recovery of flora and fauna after the outfall's closure. An initial study characterising the extent of the discharge and the effects on seaweed (Ulva lactuca L.), blue mussels (Mytilus galloprovincialis) and limpets (Cellana denticulata) from the area, showed effects of the sewage discharge on flora and fauna were localised within in the bay. The immediate area surrounding the discharge area was found to contain limited biodiversity, with an abundance of Ulva lactuca, a bright green lettuce-like seaweed, typically found in areas with high nutrient input, limpets and small blue mussels. The nitrogen isotopic signature ({delta}{sup 15}N) is shown to be a good tracer of sewage pollution in seaweed and associated grazers (i.e. limpets) as a result of the increased contribution of urea and ammonia to seawater nitrogen derived from the effluent. The carbon isotopic signature ({delta}{sup 13}C) is suggested as a more appropriate sewage tracer for mussels, which filter feed the effluent's particulate organic matter from the water. Lower carbon:nitrogen ratios were found in Ulva lactuca sampled from around the outfall region compared to uncontaminated control sites. However carbon:nitrogen ratios do not vary significantly amongst shellfish species. After closure, monitoring continued for 9 months and showed that the carbon and nitrogen isotopic signatures of algae (Ulva lactuca L.) returned to similar control site levels within 3 months. Limpet and blue mussels (Cellana denticulata and Mytilus galloprovincialis) showed slower recovery times than the Ulva lactuca, with detectable levels of the sewage-derived carbon and nitrogen remaining in the animal's tissue for up to 9 months.

  11. Carbon isotope discrimination by photosynthesis: implications for the bio- and geosciences

    International Nuclear Information System (INIS)

    Lerman, J.C.; Troughton, J.H.

    1975-01-01

    Land plants are depleted in the heavy isotopes of natural carbon 14 C (radioactive) and 13 C (stable) compared with the isotope composition of atmospheric CO 2 . These depletions can be assayed on milligram quantities of organic matter converted to CO 2 and analyzed in a double inlet-double collector mass spectrometer, the ratio 13 C/ 12 C usually being expressed as delta 13 C vs. PDB, in per mil ( 0 / 00 ). The delta value in higher plants ranges between -39 and -9 0 / 00 . The variations of this delta value are mainly determined by the type of carbon fixation reaction, e.g., the delta value allows us to distinguish between C 3 (Calvin-Benson) plants typically -28 0 / 00 , and C 4 (Hatch-Slack) plants typically -13 0 / 00 . These corrections are important for archaeologic and groundwater dating. Since the carbon delta values persist in dead and ancient plant remains such as wood, pollen, peat, soil, coal and oil, it is possible to investigate previous environmental conditions, past climate, paleoecology, plant interaction with the environment and evolution of photosynthetic mechanisms. The delta value also tags the commercial products derived from plants and animals allowing their origin to be traced in investigations of fraud. Some of these naturally labeled products have medical applications

  12. Non-chondritic iron isotope ratios in planetary mantles as a result of core formation

    Science.gov (United States)

    Elardo, Stephen M.; Shahar, Anat

    2017-02-01

    Information about the materials and conditions involved in planetary formation and differentiation in the early Solar System is recorded in iron isotope ratios. Samples from Earth, the Moon, Mars and the asteroid Vesta reveal significant variations in iron isotope ratios, but the sources of these variations remain uncertain. Here we present experiments that demonstrate that under the conditions of planetary core formation expected for the Moon, Mars and Vesta, iron isotopes fractionate between metal and silicate due to the presence of nickel, and enrich the bodies' mantles in isotopically light iron. However, the effect of nickel diminishes at higher temperatures: under conditions expected for Earth's core formation, we infer little fractionation of iron isotopes. From our experimental results and existing conceptual models of magma ocean crystallization and mantle partial melting, we find that nickel-induced fractionation can explain iron isotope variability found in planetary samples without invoking nebular or accretionary processes. We suggest that near-chondritic iron isotope ratios of basalts from Mars and Vesta, as well as the most primitive lunar basalts, were achieved by melting of isotopically light mantles, whereas the heavy iron isotope ratios of terrestrial ocean floor basalts are the result of melting of near-chondritic Earth mantle.

  13. Expanding the isotopic toolbox: Applications of hydrogen and oxygen stable isotope ratios to food web studies

    Directory of Open Access Journals (Sweden)

    Hannah B Vander Zanden

    2016-03-01

    Full Text Available The measurement of stable carbon (δ13C and nitrogen (δ15N isotopes in tissues of organisms has formed the foundation of isotopic food web reconstructions, as these values directly reflect assimilated diet. In contrast, stable hydrogen (δ2H and oxygen (δ18O isotope measurements have typically been reserved for studies of migratory origin and paleoclimate reconstruction based on systematic relationships between organismal tissue and local environmental water. Recently, innovative applications using δ2H and, to a lesser extent, δ18O values have demonstrated potential for these elements to provide novel insights in modern food web studies. We explore the advantages and challenges associated with three applications of δ2H and δ18O values in food web studies. First, large δ2H differences between aquatic and terrestrial ecosystem end members can permit the quantification of energy inputs and nutrient fluxes between these two sources, with potential applications for determining allochthonous vs. autochthonous nutrient sources in freshwater systems and relative aquatic habitat utilization by terrestrial organisms. Next, some studies have identified a relationship between δ2H values and trophic position, which suggests that this marker may serve as a trophic indicator, in addition to the more commonly used δ15N values. Finally, coupled measurements of δ2H and δ18O values are increasing as a result of reduced analytical challenges to measure both simultaneously and may provide additional ecological information over single element measurements. In some organisms, the isotopic ratios of these two elements are tightly coupled, whereas the isotopic disequilibrium in other organisms may offer insight into the diet and physiology of individuals. Although a coherent framework for interpreting δ2H and δ18O data in the context of food web studies is emerging, many fundamental uncertainties remain. We highlight directions for targeted research that

  14. Plutonium speciation and isotope ratios in Yenisey and Ob river and Yenisey estuary

    International Nuclear Information System (INIS)

    Skipperud, L.; Oughton, DH.; Fifield, K.; Lind, O.C.; Salbu, B.; Brown, J.

    2004-01-01

    Plutonium isotope ratios are known to vary with reactor type, nuclear fuel-burn up time, neutron flux, and energy, and for fallout from nuclear detonations, weapon type and yield. Weapons-grade plutonium is characterized by a low content of the 240 Pu isotope, with 240 Pu/ 239 Pu isotope ratio less than 0.05. In contrast, both global weapons fallout and spent nuclear fuel from civil reactors have higher 240 Pu/ 239 Pu isotope ratios (civil nuclear power reactors have 240 Pu/ 239 Pu atom ratios of between about 0.2-1). Thus, different sources often exhibit characteristic plutonium isotope ratios and these ratios can be used to identify the origin of contamination, calculate inventories, or follow the migration of contaminated sediments and waters. Together with activity measurements and isotope ratios, knowledge of plutonium speciation in the Ob and Yenisey rivers and processes controlling its behaviour in estuarine systems is a prerequisite for predicting the transfer and subsequent environmental impact to Arctic Seas. With this in mind, the study had two objectives: first to determine whether discharges from nuclear installations in the river catchment areas are having any influence on Pu levels in the estuaries; and, second, to investigate the transfer and mobility of plutonium in the Yenisey river and estuary. Plutonium 240/239 ratios were determined using accelerator mass spectrometry (AMS). The data indicated a clear influence from a low 240 Pu: 239 Pu source in surface sediments collected from the Yenisey Estuary, whereas plutonium in the Ob Estuary sediments are dominated by global fallout. The results also show an increase in plutonium concentration and a decrease in isotope ratio going upstream from the estuary. Sequential extractions of sediments indicate that up 70% of the Pu in the Yenisey river is easily mobilized with weak oxidizing agents, which indicates that the Pu is organically bound, while the Pu is more strongly irreversible bound further out

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

    Science.gov (United States)

    Bowen, G. J.; Abels, H.

    2015-12-01

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

  16. Triple oxygen isotopes in biogenic and sedimentary carbonates

    Science.gov (United States)

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

    2014-09-01

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

  17. Modeling of the global carbon cycle - isotopic data requirements

    International Nuclear Information System (INIS)

    Ciais, P.

    1994-01-01

    Isotopes are powerful tools to constrain carbon cycle models. For example, the combinations of the CO 2 and the 13 C budget allows to calculate the net-carbon fluxes between atmosphere, ocean, and biosphere. Observations of natural and bomb-produced radiocarbon allow to estimate gross carbon exchange fluxes between different reservoirs and to deduce time scales of carbon overturning in important reservoirs. 18 O in CO 2 is potentially a tool to make the deconvolution of C fluxes within the land biosphere (assimilation vs respirations). The scope of this article is to identify gaps in our present knowledge about isotopes in the light of their use as constraint for the global carbon cycle. In the following we will present a list of some future data requirements for carbon cycle models. (authors)

  18. Stable strontium isotopic ratios from archaeological organic remains from the Thorsberg peat bog

    DEFF Research Database (Denmark)

    Nosch, Marie-Louise Bech; von Carnap-Bornheim, Claus; Grupe, Gisela

    2007-01-01

    Pilot study analysing stable strontium isotopic ratios from Iron Age textile and leather finds from the Thorsberg peat bog.......Pilot study analysing stable strontium isotopic ratios from Iron Age textile and leather finds from the Thorsberg peat bog....

  19. Lead isotope ratios in Japanese galena ores and archaeological objects

    International Nuclear Information System (INIS)

    Yamasaki, Kazuo; Murozumi, Masayo; Nakamura, Seiji; Hinata, Makoto; Yuasa, Mitsuaki.

    1978-01-01

    Lead isotope ratios 206 Pb/ 204 Pb, 207 Pb/ 204 Pb, 208 Pb/ 204 Pb, 207 Pb/ 206 Pb and 208 Pb/ 206 Pb in Japanese galena ores and archaeological bronze objects were determined by a Hitachi RMU-6 mass spectrometer using a rhenium single filament as a surface ionization device. Basic experimental conditions including detection limit, fractionation effect, memory effect, etc. were examined, and the accuracy of determination was checked using the CIT shelf standard No. 1. Archaeological bronze objects were dissolved in nitric acid and lead was extracted by the dithizone method using specially purified reagents in a so-called clean laboratory. When 0.5 μg lead was loaded on the rhenium filament with phosphoric acid and silica gel as stabilizers, an ion current of 10 -13 -- 10 -15 A due to Pb + was obtained and maintained stable for several hours. Coefficients of variation found for the isotope ratios 207 Pb/ 206 Pb and 208 Pb/ 206 Pb were 0.1 -- 0.5%. Lead isotope ratios are given for 17 Japanese galena ores and for archaeological bronze objects such as bronze bells, halberds (Yayoi period), Horyuji pagoda spire (7th century), and Northern Sung coins (11th century). A close resemblance of the isotope ratios was found between Japanese galena ores and some Japanese bronze objects of the 7th century, suggesting the use of the former as raw materials of the latter. (auth.)

  20. Stable carbon isotope fractionation in pollen of Atlas cedar: first steps towards a new palaeoecological proxy for Northwest Africa

    Science.gov (United States)

    Bell, Benjamin; Fletcher, William; Ryan, Peter; Grant, Helen; Ilmen, Rachid

    2016-04-01

    Analysis of stable carbon isotopes can provide information on climate and the environmental conditions at different growth stages of the plant, both past and present. Carbon isotope discrimination in plant tissue is already well understood, and can be used as a drought stress indicator for semi-arid regions. Stable carbon isotope ratios measured directly on pollen provides the potential for the development of long-term environmental proxies (spanning thousands of years), as pollen is well preserved in the environment. Atlas Cedar (Cedrus atlantica Endl. Manetti ex Carrière), is an ideal test case to develop a pollen stable carbon isotope proxy. The tree grows across a wide altitudinal and climatic range and is extremely sensitive to moisture availability. The pollen is abundant, and easily identifiable to the species level in pollen analysis because different cedar species are geographically confined to different regions of the world. In 2015 we sampled 76 individual cedar trees across latitudinal, altitudinal and environmental gradients, highly focused on the Middle Atlas region of Morocco, with 25 additional samples from botanical gardens across Europe and the US to extend these gradients. Here, we report new stable carbon isotope data from pollen, leaf and stem wood from these samples with a view to assessing and quantifying species-specific fractionation effects associated with pollen production. The isotopic response of individual trees at local and wider geographical scales to altitude and climatic conditions is presented. This research forms part of an ongoing PhD project working to develop and calibrate a modern carbon isotope proxy in Atlas cedar pollen, which can ultimately be applied to fossil sequences and complement existing multi-proxy records (e.g. pollen analysis in lake sediments, tree-rings).

  1. Rapid-swept CW cavity ring-down laser spectroscopy for carbon isotope analysis

    International Nuclear Information System (INIS)

    Tomita, Hideki; Watanabe, Kenichi; Takiguchi, Yu; Kawarabayashi, Jun; Iguchi, Tetsuo

    2006-01-01

    With the aim of developing a portable system for an in field isotope analysis, we investigate an isotope analysis based on rapid-swept CW cavity ring-down laser spectroscopy, in which the concentration of a chemical species is derived from its photo absorbance. Such a system can identify the isotopomer and still be constructed as a quite compact system. We have made some basic experimental measurements of the overtone absorption lines of carbon dioxide ( 12 C 16 O 2 , 13 C 16 O 2 ) by rapid-swept cavity ring-down spectroscopy with a CW infrared diode laser at 6,200 cm -1 (1.6 μm). The isotopic ratio has been obtained as (1.07±0.13)x10 -2 , in good agreement with the natural abundance within experimental uncertainty. The detection sensitivity in absorbance has been estimated to be 3x10 -8 cm -1 . (author)

  2. Carbon isotope fractionation between amorphous calcium carbonate and calcite in earthworm-produced calcium carbonate

    International Nuclear Information System (INIS)

    Versteegh, E.A.A.; Black, S.; Hodson, M.E.

    2017-01-01

    In this study we investigate carbon isotope fractionation during the crystallization of biogenic calcium carbonate. Several species of earthworm including Lumbricus terrestris secrete CaCO_3. Initially a milky fluid comprising micro-spherules of amorphous CaCO_3 (ACC) is secreted into pouches of the earthworm calciferous gland. The micro-spherules coalesce and crystalize to form millimetre scale granules, largely comprising calcite. These are secreted into the earthworm intestine and from there into the soil. L. terrestris were cultured for 28 days in two different soils, moistened with three different mineral waters at 10, 16 and 20 °C. The milky fluid in the calciferous glands, granules in the pouches of the calciferous glands and granules excreted into the soil were collected and analysed by FTIR spectroscopy to determine the form of CaCO_3 present and by IRMS to determine δ"1"3C values. The milky fluid was ACC. Granules removed from the pouches and soil were largely calcite; the granules removed from the pouches contained more residual ACC than those recovered from the soil. The δ"1"3C values of milky fluid and pouch granules became significantly more negative with increasing temperature (p ≤ 0.001). For samples from each temperature treatment, δ"1"3C values became significantly (p ≤ 0.001) more negative from the milky fluid to the pouch granules to the soil granules (−13.77, −14.69 and −15.00 respectively at 10 °C; −14.37, −15.07 and −15.18 respectively at 16 °C and −14.89, −15.41 and −15.65 respectively at 20 °C). Fractionation of C isotopes occurred as the ACC recrystallized to form calcite with the fractionation factor ε_c_a_l_c_i_t_e_-_A_C_C = −1.20 ± 0.52‰. This is consistent with the crystallization involving dissolution and reprecipitation rather than a solid state rearrangement. Although C isotopic fractionation has previously been described between different species of dissolved inorganic carbon

  3. Forensic Applications of Light-Element Stable Isotope Ratios of Ricinus communis Seeds and Ricin Preparations

    Energy Technology Data Exchange (ETDEWEB)

    Kreuzer, Helen W.; West, Jason B.; Ehleringer, James

    2013-01-01

    Seeds of the castor plant Ricinus communis, also known as castor beans, are of forensic interest because they are the source of the poison ricin. We have tested whether stable isotope ratios of castor seeds and ricin prepared by various methods can be used as a forensic signature. We collected over 300 castor seed samples from locations around the world and measured the C, N, O, and H stable isotope ratios of the whole seeds, oil, and three types of ricin preparations. Our results demonstrate that N isotope ratios can be used to correlate ricin prepared by any of these methods to source seeds. Further, stable isotope ratios distinguished >99% of crude and purified ricin protein samples in pair-wise comparison tests. Stable isotope ratios therefore constitute a valuable forensic signature for ricin preparations.

  4. Carbon and Noble Gas Isotopes in the Tengchong Volcanic Geothermal Area, Yunnan, Southwestern China

    Institute of Scientific and Technical Information of China (English)

    XU Sheng; Shun'ich NAKAI; Hiroshi WAKITA; WANG Xianbin

    2004-01-01

    Carbon and noble gas isotope analyses are reported for bubbling gas samples from the Tengchong volcanic geothermal area near the Indo-Eurasian suture zone. All samples contain a resolvable component of mantle-derived 3He.Occurrence of mantle-derived 3He coincides with surface volcanism. However, 3He occurs over a larger geographic area than do surface volcanics. δ13C values for CO2 and CH4 vary from -33.4 ‰ to 1.6 ‰ and from -52.8 ‰ to -2.8 ‰,respectively. He and C isotope systematics indicate that CO2 and CH4 in the CO2-rich gases originated predominantly from magmatic component mixed with crustal CO2 produced from carbonate. However, breakdown of organic matter and nearsurface processes accounts for the CH4 and CO2 in N2-rich gases. 3He/4He ratio distribution pattern suggests that mantlederived He and heat sources of high-temperature system in central Tengchong originate from a hidden magma reservoir at subsurface. CO2-rich gases with the highest 3He/4He ratio (5.2 Ra) may be representative of the Tengchong magmatic component. Compared with MORB, this relative low 3He/4He ratio could be fully attributed to either deep crustal contamination, or radioactive aging, or past contamination of the local mantle by U- and Th-rich subducted crustal material.However, a combination of low 3He/4He, high radiogenic 4He/40Ar ratio and identical CO2/3He and δ13Cco2 relative to MORB may suggest addition of prior subductedd crsustal material (ca 1%-2%) to the MORB reservoir around 1.3 Ga ago,which is essentially compatible with the LIL-elements, and Sr-Nd-Pb isotopes of volcanic rocks.

  5. Carbon and oxygen stable isotope and trace element studies in speleothems and across the J-K boundary, Central Italy

    International Nuclear Information System (INIS)

    Kudielka, G.

    2001-07-01

    Carbon and Oxygen stable isotope ratios of carbonates decisively depend on fractionation during physicochemical processes. Therefore, they represent a powerful tool to derive information on past conditions under which the carbonates formed. Isotope ratio mass spectrometry (IRMS) offers a large range of applications. This thesis presents two projects based upon investigation of carbon and oxygen stable isotope ratios combined with trace element abundances (determined by instrumental neutron activation analysis, INAA) in carbonates. (1) Palaeoclimatic investigation on speleothems from central Italy. Four speleothems from Grotta Grande del Vento, central Italy, were analyzed for stable isotope ratios and trace element abundances, and age dated to obtain a chronologically reliable stable isotope profile. The speleothems were sampled by means of a dental drill to gain a stable isotope profile with a 0.5 mm resolution, trace element abundances have been performed by INAA every 0.5 cm, and the samples for age dating were picked according to remarkable features in the stable isotope trends and analyzed by TIMS. The record covers the period from 93 ka until the early holocene with a hiatus lasting from 75 ka until 65.0 ka. Speleothem growth during the last glacial indicates moderate conditions in the Frasassi region back then. Comparison with speleothems from Ireland, France and northern Italy reveal a north-south slope in d18O, indicating, that the rain over central Italy mainly originates from the North Atlantic. Depletion of moisture in d18O during its continental trajectory is due to rainout, which primarily extracts the heavy isotopes. The stable isotope record is in good agreement with the high-resolution speleothem record from Soreq Cave, Israel. Distinct isotopic events coincide between 85 ka and 80 ka, between ∼ 60 ka and 50 ka and from the last glacial to the early holocene. An offset has been existing between the two records at any time. The speleothems of

  6. The isotopic composition of lead in man and the environment in Finland: isotope ratios of lead as indicators of pollutant source

    International Nuclear Information System (INIS)

    Keinonen, M.

    1989-01-01

    The isotopic composition of lead was determined in samples from the Helsinki area: in emission sources (gasoline, incinerator and lead smelter emissions, coal), in sources of intake to man (air, diet), in samples representing long-term deposition (lichen, soil, lake sediments) and in human tissue. The measurements of the isotope ratios 206 Pb/ 204 Pb and 206 Pb/ 207 Pb were done by thermal ionization mass spectrometry after chemical separation of lead by anion exchange and cathodic electrodeposition. The origin of lead in man and the environment in the Helsinki area was evaluated by using the differences in the measured isotope ratios as an indicator. The means of the ratios in gasoline ( 206 Pb/ 207 Pb 1.124+-0.026, 206 Pb/ 204 Pb 17.45+-0.42) and the ratios in other emission sources in Helsinki ( 206 Pb/ 207 Pb 1.149-1.226, 206 Pb/ 204 Pb 17.94-19.24) were significantly different. Lead in air samples from Helsinki (1.123+-0.013) could be attributed to gasoline, as lead in soil near a highway (1.136+-0.003). By contrast, isotope ratios measured in lichen (1.148+-0.006) indicated considerable amounts of lead from sources with higher 206 Pb abundances, evidently industrial sources. The isotope ratios in human liver, lung, and bone ( 206 Pb/ 207 Pb 1.142+-0.015, 1.151+-0.011, and 1.156+-0.013, respectively and 206 Pb/ 204 Pb 17.76+-0.28, 17.91+-0.20, and 17.96+-0.09, respectively) were practically the same and no significant dependence of the isotope ratios on age or concentration of lead was seen. In lake sediment cores a correlation was found between the isotope ratios, lead concentration, and depth. The non-anthropogenic lead of high isotope ratios from bedrock was the major component at depths dated older than 100 years. At the surface of the sediment atmospheric lead prevailed, with ratios similar to those of gasoline, air samples and lichen. In the post-1900 layers, anthropogenic lead made up about 40-60% of the total sedimentary lead

  7. Diode laser absorption spectrometry for (CO2)-C-13/(CO2)-C-12 isotope ratio analysis : Investigation on precision and accuracy levels

    NARCIS (Netherlands)

    Castrillo, A; Casa, G; Kerstel, E; Gianfrani, L

    2005-01-01

    Near-infrared laser spectroscopy is used to measure the C-13/C-12 isotope abundance ratio in gas phase carbon dioxide. The spectrometer, developed expressly for field applications, is based on a 2 mu m distributed feedback diode laser in combination with sensitive wavelength modulation detection. It

  8. Temperature evolution and the oxygen isotope composition of Phanerozoic oceans from carbonate clumped isotope thermometry

    Science.gov (United States)

    Henkes, Gregory A.; Passey, Benjamin H.; Grossman, Ethan L.; Shenton, Brock J.; Yancey, Thomas E.; Pérez-Huerta, Alberto

    2018-05-01

    Surface temperature is among the most important parameters describing planetary climate and habitability, and yet there remains considerable debate about the temperature evolution of the Earth's oceans during the Phanerozoic Eon (541 million years ago to present), the time during which complex metazoan life radiated on Earth. Here we critically assess the emerging record of Phanerozoic ocean temperatures based on carbonate clumped isotope thermometry of fossil brachiopod and mollusk shells, and we present new data that fill important gaps in the Late Paleozoic record. We evaluate and reject the hypothesis that solid-state reordering of 13C-18O bonds has destroyed the primary clumped isotope temperature signal of most fossils during sedimentary burial at elevated temperatures. The resulting Phanerozoic record, which shows a general coupling between tropical seawater temperatures and atmospheric carbon dioxide (CO2) levels since the Paleozoic, indicates that tropical temperatures during the icehouse climate of the Carboniferous period were broadly similar to present (∼25-30 °C), and suggests that benthic metazoans were able to thrive at temperatures of 35-40 °C during intervals of the early and possibly the latest Paleozoic when CO2 levels were likely 5-10× higher than present-day values. Equally important, there is no resolvable trend in seawater oxygen isotope ratios (δ18 O) over the past ∼500 million years, indicating that the average temperature of oxygen exchange between seawater and the oceanic crust has been high (∼270 °C) since at least the early Paleozoic, which points to mid-ocean ridges as the dominant locus of water-rock interaction over the past half-billion years.

  9. Stable carbon isotope fractionation in the search for life on early Mars

    Science.gov (United States)

    Rothschild, L. J.; Desmarais, D.

    1989-01-01

    The utility of measurements of C-13/C-12 ratios in organic vs inorganic deposits for searching for signs of life on early Mars is considered. It is suggested that three assumptions are necessary. First, if there was life on Mars, it caused the fractionation of carbon isotopes in analogy with past biological activity on earth. Second, the fractionation would be detectable. Third, if a fractionation would be observed, there exist no abiotic explanations for the observed fractionation pattern.

  10. Response of carbon isotopic compositions of Early-Middle Permian coals in North China to palaeo-climate change

    Science.gov (United States)

    Ding, Dianshi; Liu, Guijian; Sun, Xiaohui; Sun, Ruoyu

    2018-01-01

    To investigate the magnitude to which the carbon isotopic ratio (δ13C) varies in coals in response to their contemporary terrestrial environment, the Early-Middle Permian Huainan coals (including coals from the Shanxi Formation, Lower Shihezi Formation and Upper Shihezi Formation) in North China were systematically sampled. A 2.5‰ variation range of δ13C values (-25.15‰ to -22.65‰) was observed in Huainan coals, with an average value of -24.06‰. As coal diagenesis exerts little influence on carbon isotope fractionation, δ13C values in coals were mainly imparted by those of coal-forming flora assemblages which were linked to the contemporary climate. The δ13C values in coals from the Shanxi and Lower Shihezi Formations are variable, reflecting unstable climatic oscillations. Heavy carbon isotope is enriched in coals of the Capitanian Upper Shihezi Formation, implying a shift to high positive δ13C values of coeval atmospheric CO2. Notably, our study provides evidence of the Kamura event in the terrestrial environment for the first time.

  11. The carbon isotope ratios and contents of mineral elements in leaves of Chinese medicinal plants

    International Nuclear Information System (INIS)

    Lin Zhifang; Sun Guchou; Wang Wei

    1989-01-01

    Leaf carbon isotope ratios and 13 kinds of mineral elements were measured on 36 species of common Chinese medicinal plants in a subtropical monsoon forest of Ding Hu Shan in Guangdong Province. The .delta.13C value were from -26.4 to -32.6%, indicating that all of the species belonged the photosynthetic C3 types. The relative lower value of δ13C was observed in the life form of shrubs. The contents of 7 elements (N, P, K, Ca, Na Mg, Si) were dependent upon the species, life form, medicinal function and medicinal part. Herb type medicine and the used medicinal part of leaves or whole plant showed higher levels of above elements than the others. Among the nine groups with different medicinal functions, it was found that more nitrogen was in the leaves of medicinal plants for hemophthisis, hypertension and stomachic troubles, more phosphorus and potassium were in the leaves for cancer and snake bite medicines, but more calcium and magnesium were in the leaves for curing rheumatics. Ferric, aluminium and manganese were the main composition of microelements in leaves. There were higher content of ferric in leaves for hemophthisis medicine, higher zinc in leaves for cold and hypertension medicine, and higher Cup in leaves of stomachic medicine. It was suggested that the pattern of mineral elements in leaves of Chinese medicinal plants reflected the different properties of absorption and accumulation. Some additional effect due to the high content of certain element might be associated with the main function of that medicine

  12. Effects of euthanasia method on stable-carbon and stable-nitrogen isotope analysis for an ectothermic vertebrate.

    Science.gov (United States)

    Atwood, Meredith A

    2013-04-30

    Stable isotope analysis is a critical tool for understanding ecological food webs; however, results can be sensitive to sample preparation methods. To limit the possibility of sample contamination, freezing is commonly used to euthanize invertebrates and preserve non-lethal samples from vertebrates. For destructive sampling of vertebrates, more humane euthanasia methods are preferred to freezing and it is essential to evaluate how these euthanasia methods affect stable isotope results. Stable isotope ratios and elemental composition of carbon and nitrogen were used to evaluate whether the euthanasia method compromised the integrity of the sample for analysis. Specifically, the stable isotope and C:N ratios were compared for larval wood frogs (Rana sylvatica  =  Lithobates sylvaticus), an ectothermic vertebrate, that had been euthanized by freezing with four different humane euthanasia methods: CO2, benzocaine, MS-222 (tricaine methanesulfonate), and 70% ethanol. The euthanasia method was not related to the δ(13)C or δ(15)N values and the comparisons revealed no differences between freezing and any of the other treatments. However, there were slight (non-significant) differences in the isotope ratios of benzocaine and CO2 when each was compared with freezing. The elemental composition was altered by the euthanasia method employed. The percentage nitrogen was higher in CO2 treatments than in freezing, and similar (non-significant) trends were seen for ethanol treatments relative to freezing. The resulting C:N ratios were higher for benzocaine treatments than for both CO2 and ethanol. Similar (non-significant) trends suggested that the C:N ratios were also higher for animals euthanized by freezing than for both CO2 and ethanol euthanasia methods. The euthanasia method had a larger effect on elemental composition than stable isotope ratios. The percentage nitrogen and the subsequent C:N ratios were most affected by the CO2 and ethanol euthanasia methods, whereas

  13. Computer-controlled detection system for high-precision isotope ratio measurements

    International Nuclear Information System (INIS)

    McCord, B.R.; Taylor, J.W.

    1986-01-01

    In this paper the authors describe a detection system for high-precision isotope ratio measurements. In this new system, the requirement for a ratioing digital voltmeter has been eliminated, and a standard digital voltmeter interfaced to a computer is employed. Instead of measuring the ratio of the two steadily increasing output voltages simultaneously, the digital voltmeter alternately samples the outputs at a precise rate over a certain period of time. The data are sent to the computer which calculates the rate of charge of each amplifier and divides the two rates to obtain the isotopic ratio. These results simulate a coincident measurement of the output of both integrators. The charge rate is calculated by using a linear regression method, and the standard error of the slope gives a measure of the stability of the system at the time the measurement was taken

  14. On the relations between the oceanic uptake of CO2 and its carbon isotopes

    International Nuclear Information System (INIS)

    Heimann, M.; Maier-Reimer, E.

    1994-01-01

    The recent proposals to estimate the oceanic uptake of CO 2 by monitoring the oceanic change in 13 C/ 12 C isotope ratio or the air-sea 13 C/ 12 C isotopic disequilibrium is reviewed. Because the history of atmospheric CO 2 and 13 CO 2 since preindustrial times is almost the same, the oceanic penetration depth of both tracers must be the same. This dynamic constraint permits the establishment of yet a third method to estimate the global ocean uptake of CO 2 from 13 C measurements. Using available observations in conjunction with canonical values for the global carbon cycle parameters the three methods yield inconsistent oceanic CO 2 uptake rates for the time period 1970-1990, ranging from 0 to over 3 GtC year -1 . However, uncertainties in the available carbon cycle data must be taken into account. Using a non-linear estimation procedure, a consistent scenario with an oceanic CO 2 uptake rate of 2.2±0.8 GtC year -1 can be established. The method also permits an investigation of the sensitivities of the different approaches. An analysis of the results of two three-dimensional simulations with the Hamburg Model of the Oceanic Carbon Cycle shows that the 13 C isotope indeed tracks the oceanic penetration of anthropogenic CO 2 . Because of its different time history, bomb produced radiocarbon, as measured at the time of GEOSECS, correlates much less well to excess carbon. (orig.)

  15. SRS-sensor 13C/12C isotops measurements for detecting Helicobacter Pylori

    Science.gov (United States)

    Grishkanich, Aleksandr; Chubchenko, Yan; Elizarov, Valentin; Zhevlakov, Aleksandr; Konopelko, Leonid

    2018-02-01

    We developed SRS-sensor 13C/12C isotops measurements detecting Helicobacter Pylori for medical diagnostics of human health. Measuring of absolute 13C/12C isotope amount ratios allows to explore the topical problems of the modern world, alcoholic beverages and tobacco, medical diagnostics of human health. SRS method is used to measure the ratio of carbon isotopes in the exhaled carbon dioxide, which is used to diagnose the human infection of Helicobacter pylori and the influence of the Helicobacter pylori bacterium on the occurrence of gastritis, gastric and duodenal ulcers. A method for the analysis of human infection with Helicobacter pylori was developed on the basis of measurements of the ratio of 13C / 12C carbon isotopes in human exhaled air with a high level of measurement accuracy. The article reviews the work in the field of provision comparability of absolute 13C/12C isotope amount ratios in the environment and food. The analysis of the technical and metrological characteristics of traditional and perspective instruments for measuring isotope ratios is presented. The provision of comparability of absolute 13C/12C isotope amount ratios is carried by gravimetrically prepared reference standards. The key features and emerging issues are discussed.

  16. Locally Grown, Natural Ingredients? The Isotope Ratio Can Reveal a Lot!

    Science.gov (United States)

    Rossier, Joël S; Maury, Valérie; Pfammatter, Elmar

    2016-01-01

    This communication gives an overview of selected isotope analyses applied to food authenticity assessment. Different isotope ratio detection technologies such as isotope ratio mass spectrometry (IRMS) and cavity ring down spectroscopy (CRDS) are briefly described. It will be explained how δ(18)O of water contained in fruits and vegetables can be used to assess their country of production. It will be explained why asparagus grown in Valais, in the centre of the Alps carries much less heavy water than asparagus grown closer to the sea coast. On the other hand, the use of δ(13)C can reveal whether a product is natural or adulterated. Applications including honey or sparkling wine adulteration detection will be briefly presented.

  17. Direct gas injection method: A simple modification to an elemental analyzer/isotope ratio mass spectrometer for stable isotope analysis of N and C from N2O and CO2 gases in nanomolar concentrations

    Science.gov (United States)

    A simple modification to the Elemental Analyzer coupled to Isotope Ratio Mass-Spectrometer (EA-IRMS) setup is described. This modification allows the users to measure nitrous oxide (N2O) and carbon dioxide (CO2) by injecting the gases directly into an online injector placed befor...

  18. Carbon and hydrogen isotope fractionation during aerobic biodegradation of quinoline and 3-methylquinoline.

    Science.gov (United States)

    Cui, Mingchao; Zhang, Wenbing; Fang, Jun; Liang, Qianqiong; Liu, Dongxuan

    2017-08-01

    Compound-specific isotope analysis has been used extensively to investigate the biodegradation of various organic pollutants. To date, little isotope fractionation information is available for the biodegradation of quinolinic compounds. In this study, we report on the carbon and hydrogen isotope fractionation during quinoline and 3-methylquinoline aerobic microbial degradation by a Comamonas sp. strain Q10. Degradation of quinoline and 3-methylquinoline was accompanied by isotope fractionation. Large hydrogen and small carbon isotope fractionation was observed for quinoline while minor carbon and hydrogen isotope fractionation effects occurred for 3-methylquinoline. Bulk carbon and hydrogen enrichment factors (ε bulk ) for quinoline biodegradation were -1.2 ± 0.1 and -38 ± 1‰, respectively, while -0.7 ± 0.1 and -5 ± 1‰ for 3-methylquinoline, respectively. This reveals a potential advantage for employing quinoline as the model compound and hydrogen isotope analysis for assessing aerobic biodegradation of quinolinic compounds. The apparent kinetic isotope effects (AKIE C ) values of carbon were 1.008 ± 0.0005 for quinoline and 1.0048 ± 0.0005 for 3-methylquinoline while AKIE H values of hydrogen of 1.264 ± 0.011 for quinoline and 1.0356 ± 0.0103 for 3-methylquinoline were obtained. The combined evaluation of carbon and hydrogen isotope fractionation yields Λ values (Λ = Δδ 2 H/Δδ 13 C ≈ εH bulk /εC bulk ) of 29 ± 2 for quinoline and 8 ± 2 for 3-methylquinoline. The results indicate that the substrate specificity may have a significant influence on the isotope fractionation for the biodegradation of quinolinic compounds. The substrate-specific isotope enrichment factors would be important for assessing the behavior and fate of quinolinic compounds in the environment.

  19. Romanian wines characterization with CF-IRMS (Continuous Flow Isotope Ratio Mass Spectrometry) isotopic analysis

    International Nuclear Information System (INIS)

    Costinel, Diana; Ionete, Roxana Elena; Vremera, Raluca; Stanciu, Vasile

    2007-01-01

    Wine growing has been known for centuries long in Romania. The country has been favored by its geographical position in south-eastern Europe, by its proximity to the Black Sea, as well as by the specificity of the local soil and climate. Alongside France, Italy, Spain, Germany, countries in this area like Romania could also be called 'a vine homeland' in Europe. High quality wines produced in this region were object of trade ever since ancient times. Under current EU research projects, it is necessary to develop new methods of evidencing wine adulteration and safety. The use of mass spectrometry (MS) to determine the ratios of stable isotopes in bio-molecules now provides the means to prove the botanical and geographical origin of a wide variety of foodstuffs - and therefore, to authenticate and eliminate fraud. Isotope analysis has been officially adopted by the EU as a means of controlling adulteration of wine. Adulteration of wine can happen in many ways, e.g. addition of non-grape ethanol, addition of non-grape sugar, water or other unauthorized substances, undeclared mixing of wines from different wards, geographical areas or countries, mislabelling of variety and age. The present paper emphasize the isotopic analysis for D/H, 18 O/ 16 O, 13 C/ 12 C from wines, using a new generation Isotope Ratio MS, Finnigan Delta V Plus, coupling with a three flexible continuous flow preparation device (GasBench II, TC Elemental Analyser and GC-C/TC). Therefore authentication of wines is an important problem to which isotopic analysis has made a significant contribution. (authors)

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

    DEFF Research Database (Denmark)

    Hesselbo, Stephen P.; Korte, Christoph

    2010-01-01

    , to the extent that meaningful comparisons between these events can begin to be made. Here we present new carbon and oxygen isotope data from mollusks (bivalves and belemnites) and brachiopods collected through the marine Early Jurassic succession of NE England, including the Sinemurian-Plienbachian boundary...... GSSP. All materials have been screened by chemical analysis and scanning electron microscopy to check for diagenetic alteration. Analysis of carbon isotopes from marine calcite is supplemented by analysis of carbon-isotope values from fossil wood collected through the same section. It is demonstrated...... that both long-term and short-term carbon-isotope shifts from the UK Early Jurassic represent global changes in carbon cycle balances. The Sinemurian-Pliensbachian boundary event is an event of global significance and shows several similarities to the Toarcian OAE (relative sea-level change, carbon-isotope...

  1. Biological fractionation of oxygen and carbon isotopes by recent benthic foraminifera

    International Nuclear Information System (INIS)

    Woodruff, F.; Douglas, R.G.

    1980-01-01

    Recent deep-sea benthic foraminifera from five East Pacific Rise box core tops have been analyzed for oxygen and carbon isotopic composition. The five equatorial stations, with water depths of between 3200 and 4600 m, yielded fourteen specific and generic taxonomic groups. Of the taxa analyzed, Uvigerina spp. most closely approaches oxygen isotopic equilibrium with ambient sea water. Pyrgo spp. was next closest to isotopic equilibrium, being on the average 0.59 per thousand depleted in 18 O relative to Uvigerina spp. Oridorsalis umbonatus also has relatively high delta 18 O values. Most other taxa were depleted in 18 O by large amounts. In no taxa was the carbon in the CaCO 3 secreted in carbon isotopic equilibrium with the dissolved HCO 3 - of ambient sea water. (Auth.)

  2. Uncertainties achievable for uranium isotope-amount ratios. Estimates based on the precision and accuracy of recent characterization measurements

    International Nuclear Information System (INIS)

    Mathew, K.J.; Essex, R.M.; Gradle, C.; Narayanan, U.

    2015-01-01

    Certified reference materials (CRMs) recently characterized by the NBL for isotope-amount ratios are: (i) CRM 112-A, Uranium (normal) Metal Assay and Isotopic Standard, (ii) CRM 115, Uranium (depleted) Metal Assay and Isotopic Standard, and (iii) CRM 116-A, Uranium (enriched) Metal Assay and Isotopic Standard. NBL also completed re-characterization of the isotope-amount ratios in CRM 125-A, Uranium (UO 2 ) Pellet Assay, Isotopic, and Radio-chronometric Standard. Three different TIMS analytical techniques were employed for the characterization analyses. The total evaporation technique was used for the major isotope-amount ratio measurement, the modified total evaporation technique was used for both the major and minor isotope-amount ratios, and minor isotope-amount ratios were also measured using a Conventional technique. Uncertainties for the characterization studies were calculated from the combined TIMS data sets following the ISO Guide to the expression of uncertainty in measurement. The uncertainty components for the isotope-amount ratio values are discussed. (author)

  3. Late Carboniferous to Late Permian carbon isotope stratigraphy

    DEFF Research Database (Denmark)

    Buggisch, Werner; Krainer, Karl; Schaffhauser, Maria

    2015-01-01

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

  4. Relationship between climate and vegetation and the stable carbon isotope chemistry of soils in the eastern Mojave Desert, Nevada

    International Nuclear Information System (INIS)

    Amundson, R.G.; Chadwick, O.A.; Sowers, J.M.; Doner, H.E.

    1988-01-01

    The relationship between the stable C-isotope composition of the soil environment and modern climate and vegetation was determined empirically along a present-day climatic transect in the eastern Mojave Desert. The δ 13 C of the soil CO 2 and carbonates decreased with increasing elevation and plant density, even though plant assemblages at all elevations were isotopically similar. Several factors, including differences in the ratios of pedogenic of limestone calcite and differences in past vegetation, were considered as explanations of this trend, However, it appears that in the sparsely vegetated Mojave Desert, the δ 13 C of pedogenic carbonate is controlled by differences in plant density and biological activity. This relationship may provide a tool for assessing past vegetational densities, as long as the vegetation is isotopically homogeneous. (author)

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

    Science.gov (United States)

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

    2010-10-01

    This study investigates patterns of mobility in Early Medieval Bavaria through a combined study of diet and associated burial practice. Carbon and nitrogen isotope ratios were analyzed in human bone samples from the Late Roman cemetery of Klettham and from the Early Medieval cemeteries of Altenerding and Straubing-Bajuwarenstrasse. For dietary comparison, samples of faunal bone from one Late Roman and three Early Medieval settlement sites were also analyzed. The results indicate that the average diet was in keeping with a landlocked environment and fairly limited availability of freshwater or marine resources. The diet appears not to have changed significantly from the Late Roman to the Early Medieval period. However, in the population of Altenerding, there were significant differences in the diet of men and women, supporting a hypothesis of greater mobility among women. Furthermore, the isotopic evidence from dietary outliers is supported by "foreign" grave goods and practices, such as artificial skull modification. These results reveal the potential of carbon and nitrogen isotope analysis for questions regarding migration and mobility. © 2010 Wiley-Liss, Inc.

  6. A Microdrop Generator for the Calibration of a Water Vapor Isotope Ratio Spectrometer

    NARCIS (Netherlands)

    Iannone, Rosario Q.; Romanini, Daniele; Kassi, Samir; Meijer, Harro A. J.; Kerstel, Erik R. Th.

    A microdrop generator is described that produces water vapor with a known isotopic composition and volume mixing ratio for the calibration of a near-infrared diode laser water isotope ratio spectrometer. The spectrometer is designed to measure in situ the water vapor deuterium and oxygen ((17)O and

  7. Tracing carbon sources through aquatic and terrestrial food webs using amino acid stable isotope fingerprinting.

    Directory of Open Access Journals (Sweden)

    Thomas Larsen

    Full Text Available Tracing the origin of nutrients is a fundamental goal of food web research but methodological issues associated with current research techniques such as using stable isotope ratios of bulk tissue can lead to confounding results. We investigated whether naturally occurring δ(13C patterns among amino acids (δ(13CAA could distinguish between multiple aquatic and terrestrial primary production sources. We found that δ(13CAA patterns in contrast to bulk δ(13C values distinguished between carbon derived from algae, seagrass, terrestrial plants, bacteria and fungi. Furthermore, we showed for two aquatic producers that their δ(13CAA patterns were largely unaffected by different environmental conditions despite substantial shifts in bulk δ(13C values. The potential of assessing the major carbon sources at the base of the food web was demonstrated for freshwater, pelagic, and estuarine consumers; consumer δ(13C patterns of essential amino acids largely matched those of the dominant primary producers in each system. Since amino acids make up about half of organismal carbon, source diagnostic isotope fingerprints can be used as a new complementary approach to overcome some of the limitations of variable source bulk isotope values commonly encountered in estuarine areas and other complex environments with mixed aquatic and terrestrial inputs.

  8. Tracing carbon sources through aquatic and terrestrial food webs using amino acid stable isotope fingerprinting.

    Science.gov (United States)

    Larsen, Thomas; Ventura, Marc; Andersen, Nils; O'Brien, Diane M; Piatkowski, Uwe; McCarthy, Matthew D

    2013-01-01

    Tracing the origin of nutrients is a fundamental goal of food web research but methodological issues associated with current research techniques such as using stable isotope ratios of bulk tissue can lead to confounding results. We investigated whether naturally occurring δ(13)C patterns among amino acids (δ(13)CAA) could distinguish between multiple aquatic and terrestrial primary production sources. We found that δ(13)CAA patterns in contrast to bulk δ(13)C values distinguished between carbon derived from algae, seagrass, terrestrial plants, bacteria and fungi. Furthermore, we showed for two aquatic producers that their δ(13)CAA patterns were largely unaffected by different environmental conditions despite substantial shifts in bulk δ(13)C values. The potential of assessing the major carbon sources at the base of the food web was demonstrated for freshwater, pelagic, and estuarine consumers; consumer δ(13)C patterns of essential amino acids largely matched those of the dominant primary producers in each system. Since amino acids make up about half of organismal carbon, source diagnostic isotope fingerprints can be used as a new complementary approach to overcome some of the limitations of variable source bulk isotope values commonly encountered in estuarine areas and other complex environments with mixed aquatic and terrestrial inputs.

  9. Tracing the origin of pollution in French Alpine snow and aerosols using lead isotopic ratios.

    Science.gov (United States)

    Veysseyre, A M; Bollhöfer, A F; Rosman, K J; Ferrari, C P; Boutron, C F

    2001-11-15

    Fresh snow samples collected at 15 remote locations and aerosols collected at one location in the French Alps between November 1998 and April 1999 have been analyzed for Pb concentration and isotopic composition by thermal ionization mass spectrometry. The snow samples contained 19-1300 pg/g of Pb with isotopic ratios 206Pb/207Pb (208Pb/207Pb) of 1.1279-1.1607 (2.3983-2.4302). Airborne Pb concentrations at one sampling site ranged from 0.42 to 6.0 ng/m3 with isotopic ratios of 1.1321-1.1427 (2.4029-2.4160). Air mass trajectory analysis combined with isotopic compositions of potential source regions did not show discernible evidence of the long-range atmospheric transport of pollutants. Isotopic ratios in the Alpine snow samples and thus the free troposphere were generally higher than airborne Pb isotopic ratios in urban France, which coupled with the relatively high Pb concentrations suggested a regional anthropogenic Pb source, probably Italy but possibly Eastern Europe.

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

    Science.gov (United States)

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

    2017-09-01

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

  11. [Carbon isotope fractionation in plants]: Annual technical progress report

    International Nuclear Information System (INIS)

    O'Leary, M.H.

    1988-01-01

    Plants fractionate carbon isotopes during photosynthesis in ways which reflect photosynthetic pathway and environment. The fractionation is product of contributions from diffusion, carboxylation and other factors which can be understood using models which have been developed in our work. The object of our work is to use this fractionation to learn about the factors which control the efficiency of photosynthesis. Unlike previous studies, we do not rely principally on combustion methods, but instead develop more specific methods with substantially higher resolving power. We have recently developed a new short-term method for studying carbon isotope fractionation which promises to provide a level of detail about temperature, species, and light intensity effects on photosynthesis which has not been available until now. We are studying the isotopic compositions of metabolites (particularly aspartic acid) in C 3 plants in order to determine the role of phosphoenolpyruvate carboxylase in C 3 photosynthesis. We are studying the relative roles of diffusion and carboxylation in nocturnal CO 2 fixation in CAM plants. We are studying the use of isotopic content as an index of water-use efficiency in C 3 plants. We are developing new methods for studying carbon metabolism in plants. 3 refs

  12. The calibration of the intramolecular nitrogen isotope distribution in nitrous oxide measured by isotope ratio mass spectrometry.

    Science.gov (United States)

    Westley, Marian B; Popp, Brian N; Rust, Terri M

    2007-01-01

    Two alternative approaches for the calibration of the intramolecular nitrogen isotope distribution in nitrous oxide using isotope ratio mass spectrometry have yielded a difference in the 15N site preference (defined as the difference between the delta15N of the central and end position nitrogen in NNO) of tropospheric N2O of almost 30 per thousand. One approach is based on adding small amounts of labeled 15N2O to the N2O reference gas and tracking the subsequent changes in m/z 30, 31, 44, 45 and 46, and this yields a 15N site preference of 46.3 +/- 1.4 per thousand for tropospheric N2O. The other involves the synthesis of N2O by thermal decomposition of isotopically characterized ammonium nitrate and yields a 15N site preference of 18.7 +/- 2.2 per thousand for tropospheric N2O. Both approaches neglect to fully account for isotope effects associated with the formation of NO+ fragment ions from the different isotopic species of N2O in the ion source of a mass spectrometer. These effects vary with conditions in the ion source and make it impossible to reproduce a calibration based on the addition of isotopically enriched N2O on mass spectrometers with different ion source configurations. These effects have a much smaller impact on the comparison of a laboratory reference gas with N2O synthesized from isotopically characterized ammonium nitrate. This second approach was successfully replicated and leads us to advocate the acceptance of the site preference value 18.7 +/- 2.2 per thousand for tropospheric N2O as the provisional community standard until further independent calibrations are developed and validated. We present a technique for evaluating the isotope effects associated with fragment ion formation and revised equations for converting ion signal ratios into isotopomer ratios. Copyright 2007 John Wiley & Sons, Ltd.

  13. Improved detection of sugar addition to maple syrup using malic acid as internal standard and in 13C isotope ratio mass spectrometry (IRMS).

    Science.gov (United States)

    Tremblay, Patrice; Paquin, Réal

    2007-01-24

    Stable carbon isotope ratio mass spectrometry (delta13C IRMS) was used to detect maple syrup adulteration by exogenous sugar addition (beet and cane sugar). Malic acid present in maple syrup is proposed as an isotopic internal standard to improve actual adulteration detection levels. A lead precipitation method has been modified to isolate quantitatively malic acid from maple syrup using preparative reversed-phase liquid chromatography. The stable carbon isotopic ratio of malic acid isolated from this procedure shows an excellent accuracy and repeatability of 0.01 and 0.1 per thousand respectively, confirming that the modified lead precipitation method is an isotopic fractionation-free process. A new approach is proposed to detect adulteration based on the correlation existing between the delta13Cmalic acid and the delta13Csugars-delta13Cmalic acid (r = 0.704). This technique has been tested on a set of 56 authentic maple syrup samples. Additionally, authentic samples were spiked with exogeneous sugars. The mean theoretical detection level was statistically lowered using this technique in comparison with the usual two-standard deviation approach, especially when maple syrup is adulterated with beet sugar : 24 +/- 12% of adulteration detection versus 48 +/- 20% (t-test, p = 7.3 x 10-15). The method was also applied to published data for pineapple juices and honey with the same improvement.

  14. What Drives Carbon Isotope Fractionation by the Terrestrial Biosphere?

    Science.gov (United States)

    Still, Christopher; Rastogi, Bharat

    2017-11-01

    During photosynthesis, terrestrial plants preferentially assimilate the lighter and much more abundant form of carbon, 12C, which accounts for roughly 99% of naturally occurring forms of this element. This photosynthetic preference for lighter carbon is driven principally by differences in molecular diffusion of carbon dioxide with differing 13C/12C across stomatal pores on leaves, followed by differences in carboxylation rates by the Rubisco enzyme that is central to the process of photosynthesis. As a result of these slight preferences, which work out to about a 2% difference in the fixation rates of 12CO2 versus 13CO2 by C3 vegetation, plant tissues are depleted in the heavier form of carbon (13C) relative to atmospheric CO2. This difference has been exploited in a wide range of scientific applications, as the photosynthetic isotope signature is passed to ecosystem carbon pools and through ecological food webs. What is less appreciated is the signature that terrestrial carbon exchanges leave on atmospheric CO2, as the net uptake of carbon by land plants during their growing season not only draws down the local CO2 concentration, it also leaves behind relatively more CO2 molecules containing 13C. The converse happens outside the growing season, when autotrophic and heterotrophic respiration predominate. During these periods, atmospheric CO2 concentration increases and its corresponding carbon isotope composition becomes relatively depleted in 13C as the products of photosynthesis are respired, along with some small isotope fractionation that happen downstream of the initial photosynthetic assimilation. Similar phenomena were first observed at shorter time scales by the eminent carbon cycle scientist, Charles (Dave) Keeling. Keeling collected samples of air in glass flasks from sites along the Big Sur coast that he later measured for CO2 concentration and carbon isotope composition (δ13C) in his lab (Keeling, 1998). From these samples, Keeling observed increasing

  15. Isotope ratio mass spectrometry coupled to liquid and gas chromatography for wine ethanol characterization.

    Science.gov (United States)

    Cabañero, Ana I; Recio, Jose L; Rupérez, Mercedes

    2008-10-01

    Two new procedures for wine ethanol 13C/12C isotope ratio determination, using high-performance liquid chromatography and gas chromatography isotope ratio mass spectrometry (HPLC/IRMS and GC/IRMS), have been developed to improve isotopic methods dedicated to the study of wine authenticity. Parameters influencing separation of ethanol from wine matrix such as column, temperature, mobile phase, flow rates and injection mode were investigated. Twenty-three wine samples from various origins were analyzed for validation of the procedures. The analytical precision was better than 0.15 per thousand, and no significant isotopic fractionation was observed employing both separative techniques coupled to IRMS. No significant differences and a very strong correlation (r = 0.99) were observed between the 13C/12C ratios obtained by the official method (elemental analyzer/isotope ratio mass spectrometry) and the proposed new methodology. The potential advantages of the developed methods over the traditional one are speed (reducing time required from hours to minutes) and simplicity. In addition, these are the first isotopic methods that allow 13C/12C determination directly from a liquid sample with no previous ethanol isolation, overcoming technical difficulties associated with sample treatment.

  16. Suitability of selected free-gas and dissolved-gas sampling containers for carbon isotopic analysis.

    Science.gov (United States)

    Eby, P; Gibson, J J; Yi, Y

    2015-07-15

    Storage trials were conducted for 2 to 3 months using a hydrocarbon and carbon dioxide gas mixture with known carbon isotopic composition to simulate typical hold times for gas samples prior to isotopic analysis. A range of containers (both pierced and unpierced) was periodically sampled to test for δ(13)C isotopic fractionation. Seventeen containers were tested for free-gas storage (20°C, 1 atm pressure) and 7 containers were tested for dissolved-gas storage, the latter prepared by bubbling free gas through tap water until saturated (20°C, 1 atm) and then preserved to avoid biological activity by acidifying to pH 2 with phosphoric acid and stored in the dark at 5°C. Samples were extracted using valves or by piercing septa, and then introduced into an isotope ratio mass spectrometer for compound-specific δ(13)C measurements. For free gas, stainless steel canisters and crimp-top glass serum bottles with butyl septa were most effective at preventing isotopic fractionation (pierced and unpierced), whereas silicone and PTFE-butyl septa allowed significant isotopic fractionation. FlexFoil and Tedlar bags were found to be effective only for storage of up to 1 month. For dissolved gas, crimp-top glass serum bottles with butyl septa were again effective, whereas silicone and PTFE-butyl were not. FlexFoil bags were reliable for up to 2 months. Our results suggest a range of preferred containers as well as several that did not perform very well for isotopic analysis. Overall, the results help establish better QA/QC procedures to avoid isotopic fractionation when storing environmental gas samples. Recommended containers for air transportation include steel canisters and glass serum bottles with butyl septa (pierced and unpierced). Copyright © 2015 John Wiley & Sons, Ltd.

  17. Mars Atmospheric Escape Recorded by H, C and O Isotope Ratios in Carbon Dioxide and Water Measured by the Sam Tunable Laser Spectrometer on the Curiosity Rover

    Science.gov (United States)

    Webster, C. R.; Mahaffy, P. R.; Leshin, L. A.; Atreya, S. K.; Flesch, G. J.; Stern, J.; Christensen, L. E.; Vasavada, A. R.; Owen, T.; Niles, P. B.; hide

    2013-01-01

    Stable isotope ratios in C, H, N, O and S are powerful indicators of a wide variety of planetary geophysical processes that can identify origin, transport, temperature history, radiation exposure, atmospheric escape, environmental habitability and biological activity [2]. For Mars, measurements to date have indicated enrichment in all the heavier isotopes consistent with atmospheric escape processes, but with uncertainty too high to tie the results with the more precise isotopic ratios achieved from SNC meteoritic analyses. We will present results to date of H, C and O isotope ratios in CO2 and H2O made to high precision (few per mil) using the Tunable Laser Spectrometer (TLS) that is part of the Sample Analysis at Mars (SAM) instrument suite on MSL s Curiosity Rover.

  18. Metrology for stable isotope reference materials: 13C/12C and 18O/16O isotope ratio value assignment of pure carbon dioxide gas samples on the Vienna PeeDee Belemnite-CO2 scale using dual-inlet mass spectrometry.

    Science.gov (United States)

    Srivastava, Abneesh; Michael Verkouteren, R

    2018-05-25

    Isotope ratio measurements have been conducted on a series of isotopically distinct pure CO 2 gas samples using the technique of dual-inlet isotope ratio mass spectrometry (DI-IRMS). The influence of instrumental parameters, data normalization schemes on the metrological traceability and uncertainty of the sample isotope composition have been characterized. Traceability to the Vienna PeeDee Belemnite(VPDB)-CO 2 scale was realized using the pure CO 2 isotope reference materials(IRMs) 8562, 8563, and 8564. The uncertainty analyses include contributions associated with the values of iRMs and the repeatability and reproducibility of our measurements. Our DI-IRMS measurement system is demonstrated to have high long-term stability, approaching a precision of 0.001 parts-per-thousand for the 45/44 and 46/44 ion signal ratios. The single- and two-point normalization bias for the iRMs were found to be within their published standard uncertainty values. The values of 13 C/ 12 C and 18 O/ 16 O isotope ratios are expressed relative to VPDB-CO 2 using the [Formula: see text] and [Formula: see text] notation, respectively, in parts-per-thousand (‰ or per mil). For the samples, value assignments between (-25 to +2) ‰ and (-33 to -1) ‰ with nominal combined standard uncertainties of (0.05, 0.3) ‰ for [Formula: see text] and [Formula: see text], respectively were obtained. These samples are used as laboratory reference to provide anchor points for value assignment of isotope ratios (with VPDB traceability) to pure CO 2 samples. Additionally, they serve as potential parent isotopic source material required for the development of gravimetric based iRMs of CO 2 in CO 2 -free dry air in high pressure gas cylinder packages at desired abundance levels and isotopic composition values. Graphical abstract CO 2 gas isotope ratio metrology.

  19. Application of ICP-MS and AMS for determination of Pu- and U-isotope ratios for source identification

    Energy Technology Data Exchange (ETDEWEB)

    Skipperud, L. (Norwegian Univ. of Life Sciences, Isotope Lab.. Dept. of Plant and Environmental Sciences, AAs (Norway))

    2010-03-15

    Full text: Anthropogenic plutonium has been introduced into the environment over the past 50 years as the result of the detonation of nuclear weapons and operational releases from the nuclear industry. In the Arctic environment, the main source of plutonium is from atmospheric weapons testing, which have resulted in a relatively uniform, underlying global distribution of plutonium. Plutonium isotope ratios are known to vary with reactor type, nuclear fuel-burn up time, neutron flux, and energy, and for fallout from nuclear detonations, weapon type and yield. Weapons-grade plutonium is characterized by a low content of the 240Pu isotope, with 240Pu/239Pu isotope ratio less than 0.05. In contrast, both global weapons fallout and spent nuclear fuel from civil reactors have higher 240Pu/239Pu isotope ratios (civil nuclear power reactors have 240Pu/239Pu atom ratios of between about 0.2-1). Thus, different sources often exhibit characteristic plutonium isotope ratios and these ratios can be used to identify the origin of contamination, calculate inventories, or follow the migration of contaminated sediments and waters. The measurement of the plutonium-isotope ratios in these studies offers both a means of identifying the origin of radionuclide contamination and the influence of the various nuclear installations on inputs to the Arctic, as well as a potential method for following the movement of water and sediment loads in the rivers. The present paper presents results from determination of plutonium concentrations and isotope ratios in sediment samples collected during various expeditions to the Kara Sea, the Ob and Yenisey estuaries and their river systems and also Pu isotope ratios in the near area of Mayak PA. Weapons-grade plutonium is characterized by a low content of the Pu-240 isotope, with Pu-240/Pu-239 isotope ratio less than 0.05. In contrast, both global weapons fallout and spent nuclear fuel from civil reactors have higher Pu-240/Pu-239 isotope ratios, and

  20. A carbon isotope challenge to the snowball Earth.

    Science.gov (United States)

    Sansjofre, P; Ader, M; Trindade, R I F; Elie, M; Lyons, J; Cartigny, P; Nogueira, A C R

    2011-10-05

    The snowball Earth hypothesis postulates that the planet was entirely covered by ice for millions of years in the Neoproterozoic era, in a self-enhanced glaciation caused by the high albedo of the ice-covered planet. In a hard-snowball picture, the subsequent rapid unfreezing resulted from an ultra-greenhouse event attributed to the buildup of volcanic carbon dioxide (CO(2)) during glaciation. High partial pressures of atmospheric CO(2) (pCO2; from 20,000 to 90,000 p.p.m.v.) in the aftermath of the Marinoan glaciation (∼635 Myr ago) have been inferred from both boron and triple oxygen isotopes. These pCO2 values are 50 to 225 times higher than present-day levels. Here, we re-evaluate these estimates using paired carbon isotopic data for carbonate layers that cap Neoproterozoic glacial deposits and are considered to record post-glacial sea level rise. The new data reported here for Brazilian cap carbonates, together with previous ones for time-equivalent units, provide estimates lower than 3,200 p.p.m.v.--and possibly as low as the current value of ∼400 p.p.m.v. Our new constraint, and our re-interpretation of the boron and triple oxygen isotope data, provide a completely different picture of the late Neoproterozoic environment, with low atmospheric concentrations of carbon dioxide and oxygen that are inconsistent with a hard-snowball Earth.

  1. Evaluation of salt tolerance in wheat genotypes using growth and carbon isotopes discrimination technique

    International Nuclear Information System (INIS)

    Shirazi, M.U.; Khan, M.A.; Mujtaba, S.M.; Shereen, A.

    2015-01-01

    Studies were conducted in green house to select suitable salt tolerant wheat genotypes on the basis of growth performance and carbon isotopes discrimination (CID) technique. Nine newly developed double haploids (DH) wheat genotypes were tested under gravel culture, along with salt tolerant (LU-26s) and high yielding (Sarsabz) checks. The crop was irrigated by non-saline (control) and saline (12dS/m) water and raised up to maturity, growth parameters (i.e. plant height, plant biomass, productive tillers, spike length, number of spiklets/spike, number of grains / spike, grain weight/ spike and grain yield/ 15 plants) were recorded after harvesting. Plant samples (straw) were collected and were analyzed for carbon isotopic ratio (C12/ C13) from IAEA laboratories Vienna Austria. The data showed that there was significant decrease in all the growth parameters due to salinity. On the basis of performance in different growth parameters it was found that wheat genotypes V3-DH, V9-DH, V10-DH, V13-DH, and LU-26s had good response at 12dSm-1, thus can be categorized as better performing genotypes. Studies on carbon isotopes discrimination (CID) showed a decreasing trend under salinity. Mean CID values were 20.86 and 17.49 under two environments (non saline and saline, respectively), showing an overall 19% decrease under salinity. Generally the wheat genotypes having higher grain yield also had high carbon isotopes discrimination (CID). The relationship between grain yield and CID was positive (R2 = 0.695). The genotypes V10-DH, V13-DH with lower decrease in CID (i.e. 1.2 and 11.0%, respectively), also had high grain yield under salinity. Therefore the studies suggest that we can include CID technique as one of the selection criteria for salt tolerance. (author)

  2. Isotopic measurements (C,N,O) of detonation soot produced from labeled and unlabeled Composition B-3 indicate source of solid carbon residues

    Science.gov (United States)

    Podlesak, David; Manner, Virginia; Amato, Ronald; Dattelbaum, Dana; Gusavsen, Richard; Huber, Rachel

    2017-06-01

    Detonation of HE is an exothermic process whereby metastable complex molecules are converted to simple stable molecules such as H2 O, N2, CO, CO2, and solid carbon. The solid carbon contains various allotropes such as detonation nanodiamonds, graphite, and amorphous carbon. It is well known that certain HE formulations such as Composition B (60% RDX, 40% TNT) produce greater amounts of solid carbon than other more oxygen-balanced formulations. To develop a greater understanding of how formulation and environment influence solid carbon formation, we synthesized TNT and RDX with 13 C and 15 N at levels slightly above natural abundance levels. Synthesized RDX and TNT were mixed at a ratio of 60:40 to form Composition B and solid carbon residues were collected from detonations of isotopically-labeled as well as un-labelled Composition B. The raw HE and detonation residues were analyzed isotopically for C, N, O isotopic compositions. We will discuss differences between treatments groups as a function of formulation and environment. LA-UR - 17-21266.

  3. Mg and Ca isotope fractionation during CaCO3 biomineralisation

    International Nuclear Information System (INIS)

    Chang, Veronica T.-C.; Williams, R.J.P.; Makishima, Akio; Belshawl, Nick S.; O'Nions, R. Keith

    2004-01-01

    The natural variation of Mg and Ca stable isotopes of carbonates has been determined in carbonate skeletons of perforate foraminifera and reef coral together with Mg/Ca ratios to assess the influence of biomineralisation processes. The results for coral aragonite suggest its formation, in terms of stable isotope behaviour, approximates to inorganic precipitation from a seawater reservoir. In contrast, results for foraminifera calcite suggest a marked biological control on Mg isotope ratios presumably related to its low Mg content compared with seawater. The bearing of these observations on the use of Mg and Ca isotopes as proxies in paleoceanography is considered

  4. Global Carbon Reservoir Oxidative Ratios

    Science.gov (United States)

    Masiello, C. A.; Gallagher, M. E.; Hockaday, W. C.

    2010-12-01

    Photosynthesis and respiration move carbon and oxygen between the atmosphere and the biosphere at a ratio that is characteristic of the biogeochemical processes involved. This ratio is called the oxidative ratio (OR) of photosynthesis and respiration, and is defined as the ratio of moles of O2 per moles of CO2. This O2/CO2 ratio is a characteristic of biosphere-atmosphere gas fluxes, much like the 13C signature of CO2 transferred between the biosphere and the atmosphere has a characteristic signature. OR values vary on a scale of 0 (CO2) to 2 (CH4), with most ecosystem values clustered between 0.9 and 1.2. Just as 13C can be measured for both carbon fluxes and carbon pools, OR can also be measured for fluxes and pools and can provide information about the processes involved in carbon and oxygen cycling. OR values also provide information about reservoir organic geochemistry because pool OR values are proportional to the oxidation state of carbon (Cox) in the reservoir. OR may prove to be a particularly valuable biogeochemical tracer because of its ability to couple information about ecosystem gas fluxes with ecosystem organic geochemistry. We have developed 3 methods to measure the OR of ecosystem carbon reservoirs and intercalibrated them to assure that they yield accurate, intercomparable data. Using these tools we have built a large enough database of biomass and soil OR values that it is now possible to consider the implications of global patterns in ecosystem OR values. Here we present a map of the natural range in ecosystem OR values and begin to consider its implications. One striking pattern is an apparent offset between soil and biospheric OR values: soil OR values are frequently higher than that of their source biomass. We discuss this trend in the context of soil organic geochemistry and gas fluxes.

  5. Lead isotope ratio analysis of bullet samples by using quadrupole ICP-MS

    International Nuclear Information System (INIS)

    Tamura, Shu-ichi; Hokura, Akiko; Nakai, Izumi; Oishi, Masahiro

    2006-01-01

    The measurement conditions for the precise analysis of the lead stable isotope ratio by using an ICP-MS equipped with a quadrupole mass spectrometer were studied in order to apply the technique to the forensic identification of bullet samples. The values of the relative standard deviation obtained for the ratio of 208 Pb/ 206 Pb, 207 Pb/ 206 Pb and 204 Pb/ 206 Pb were lower than 0.2% after optimization of the analytical conditions, including the optimum lead concentration of the sample solution to be about 70 ppb and an integration time for 1 m/s of 15 s. This method was applied to an analysis of lead in bullets for rifles and handguns; a stable isotope ratio of lead was found to be suitable for the identification of bullets. This study has demonstrated that the lead isotope ratio measured by using a quadrupole ICP-MS was useful for a practical analysis of bullet samples in forensic science. (author)

  6. Direct uranium isotope ratio analysis of single micrometer-sized glass particles

    OpenAIRE

    Kappel, Stefanie; Boulyga, Sergei F.; Prohaska, Thomas

    2012-01-01

    We present the application of nanosecond laser ablation (LA) coupled to a ‘Nu Plasma HR’ multi collector inductively coupled plasma mass spectrometer (MC-ICP-MS) for the direct analysis of U isotope ratios in single, 10–20 μm-sized, U-doped glass particles. Method development included studies with respect to (1) external correction of the measured U isotope ratios in glass particles, (2) the applied laser ablation carrier gas (i.e. Ar versus He) and (3) the accurate determination of lower abu...

  7. Assessment of Bacterial Degradation of Aromatic Hydrocarbons in the Environment by Analysis of Stable Carbon Isotope Fractionation

    International Nuclear Information System (INIS)

    Meckenstock, Rainer U.; Morasch, Barbara; Kaestner, Matthias; Vieth, Andrea; Richnow, Hans Hermann

    2002-01-01

    concentrations accompanied with an increase in the 13 C/ 12 C stable carbon isotope ratio of the residual toluene. Calculation of the extent of biodegradation based on the isotope values and laboratory derived isotope fractionation factors showed that the residual toluene was degraded to more than 99% by microbial activity. Calculation of the theoretical residual toluene concentrations based on the measured isotope values described the strongly decreasing concentrations along the plume. Other aromatic hydrocarbons like benzene and naphthalene which were analysed in the same course also showed decreasing concentrations along the groundwater flow path accompanied by increasing δ 13 C values indicating biodegradation

  8. Deciphering biodegradation effects on light hydrocarbons in crude oils using their stable carbon isotopic composition: a case study from the Gullfaks oil field, offshore Norway

    OpenAIRE

    Andrea Vieth-Hillebrand [Vieth; Heinz Wilkes

    2006-01-01

    Compound-specific isotope analysis has become an important tool in environmental studies and is an especially powerful way to evaluate biodegradation of hydrocarbons. Here, carbon isotope ratios of light hydrocarbons were used to characterise in-reservoir biodegradation in the Gullfaks oil field, offshore Norway. Increasing biodegradation, as characterised, for example, by increasing concentration ratios of Pr/n-C17 and Ph/n-C18, and decreasing concentrations of individual light hydrocarbons ...

  9. Hydrogen and oxygen isotope ratios of geothermal waters in the southern hachimantai area

    International Nuclear Information System (INIS)

    Matsubaya, Osamu; Etchu, Hiroshi; Takenaka, Teruo; Yoshida, Yutaka.

    1985-01-01

    Geothermal waters from the Matsukawa and Kakkonda Geothermal Plants, wells at Amihari-Motoyu, and Nyuto and Tazawako areas were isotopically studied. The geothermal waters from Mutsukawa, Kakkonda and Amihari-Motoyu have hydrogen isotope ratios similar to the local meteoric waters, while have higher oxygen isotope ratios than the local meteoric waters. This relationship of hydrogen and oxygen isotope ratios, that is called ''oxygen shift'', means that these geothermal waters are meteoric waters undergone the oxygen isotope exchange with rocks at high temperature of underground. The exygen shifts are 2 -- 3 per mil in Matsukawa and Kakkonda, and 7 per mil in Amihari-Motoyu. This difference may be important to understand the processe of water-rock interaction in this area. The geothermal waters at Nyuto and Tazawako areas also show 2 -- 3 per mil oxygen shift. The steam from the Tazawako-cho well and the hot spring water form the Tsurunoyu are estimated to be vapor and liquid phases separated form a single geothermal water of NaCl type, though the hot water from the Tsurunoyu is diluted with shallow meteoric water. (author)

  10. Fractionation of boron isotopes in Icelandic hydrothermal systems

    International Nuclear Information System (INIS)

    Aggarwal, J.K.

    1995-01-01

    Boron isotope ratios have been determined in a variety of different geothermal waters from hydrothermal systems across Iceland. Isotope ratios from the high temperature meteoric water recharged systems reflect the isotope ratio of the host rocks without any apparent fractionation. Seawater recharged geothermal systems exhibit more positive δ 1 1B values than the meteoric water recharged geothermal systems. Water/rock ratios can be assessed from boron isotope ratios in the saline hydrothermal systems. Low temperature hydrothermal systems also exhibit more positive δ 1 1B than the high temperature systems, indicating fractionation of boron due to absorption of the lighter isotope onto secondary minerals. Fractionation of boron in carbonate deposits may indicate the level of equilibrium attained within the systems. (author). 14 refs., 2 figs

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

    Science.gov (United States)

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

    2015-12-01

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

  12. Production of exotic, short lived carbon isotopes in ISOL-type facilities

    CERN Document Server

    Franberg, Hanna; Köster, Ulli; Ammann, Markus

    2008-01-01

    The beam intensities of short-lived carbon isotopes at Isotope Separation On-Line (ISOL) facilities have been limited in the past for technical reasons. The production of radioactive ion beams of carbon isotopes is currently of high interest for fundamental nuclear physics research. To produce radioactive ions a target station consisting of a target in a container connected to an ion source via a transfer line is commonly used. The target is heated to vaporize the product for transport. Carbon in elementary form is a very reactive element and react strongly with hot metal surfaces. Due to the strong chemisorption interaction, in the target and ion source unit, the atoms undergo significant retention on their way from the target to the ion source. Due to this the short lived isotopes decays and are lost leading to low ion yields. A first approach to tackle these limitations consists of incorporating the carbon atoms into less reactive molecules and to use materials for the target housing and the transfer line ...

  13. Effects of sewage contamination on macro-algae and shellfish at Moa Point, New Zealand, using stable carbon and nitrogen isotopes

    International Nuclear Information System (INIS)

    Rogers, K.M.

    1999-01-01

    Stable carbon and nitrogen isotopes have been used to characterise sewage discharge and effects on seaweed (Ulva lactuca L.), blue mussels (Mytilus galloprovincialis), and limpets (Cellana denticulata) from Moa Point Bay, New Zealand. The nitrogen ( 15 N / 14 N) ratio is shown to be a good tracer of sewage pollution in Ulva lactuca and associated grazers (Cellana denticulata) as a result of the increased contribution of urea and ammonia to the surrounding marine environment from the sewage outfall. The carbon ( 13 C / 12 C) ratio is suggested as a more appropriate sewer tracer for mussels (Mytilus galloprovincialis), which filter feed the particulate organic matter from the effluent. Lower carbon : nitrogen ratios were found in U. lactuca sampled from the outfall region, compared to uncontaminated control sites, however carbon : nitrogen ratios do not vary significantly amongst shellfish species. (author). 18 refs., 4 figs., 2 tabs

  14. The 12C/13C Isotopic Ratio in Planetary Nebulae as Deduced from IUE Data

    Science.gov (United States)

    Miskey, C. L.; Feibelman, W. A.; Bruhweiler, F. C.

    2000-05-01

    The relative abundances of C, N, and O and the isotopic ratio of 12C/13C represent tracers of nucleosynthesis in intermediate stars with main-sequence masses between 0.6 and 8.0 solar masses in our Galaxy. Determining these abundances and the isotopic 12C/13C ratio in planetary nebulae (PNe) represent perhaps the best means to discern exactly how the ISM is enriched by CNO stellar nucleosynthesis. Walsh et al. (1996) and Clegg et al. (1997), using the Hubble Space Telescope, have derived the isotopic 12C/13C abundance ratio in the galactic carbon-rich PN, NGC 3918, and placed marginal constraints on it for the Magellanic PNe, N2 (SMC) and N122 (LMC). This was done using the well-known 12C 3P-1S (J=1-0 and J=2-0) transitions of C+2 at 1906.68 Angstroms and 1908.77 Angstroms and a J=0-0 transition at 1909.6 Angstroms, which is strictly forbidden in 12C. The finite nuclear spin of 13C (I=1/2) permits a corresponding F=1/2-1/2 electric dipole transition not seen in 12C. Since the 1909.6 Angstroms line is well separated from the other two 12C transitions, it provides an important means of determining 12C/13C in planetary nebulae. We have just completed a search of archival International Ultraviolet Explorer (IUE) high-dispersion spectra of approximately three dozen PNe, and derived 12C/13C ratios of 39 and 23 for the galactic PNe, NGC 2440 and NGC 6302, respectively. These are values much lower than the solar value of 89. In the other objects, the limited S/N of the IUE data indicate 12C/13C ratio upper limits much higher than 50. The implications of these results and their pertinence to stellar evolution are discussed.

  15. Stable carbon isotope fractionation during the biodegradation of lambda-cyhalothrin

    Energy Technology Data Exchange (ETDEWEB)

    Shen, Xiaoli [MOE Key Laboratory of Environmental Remediation and Ecosystem Health, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Department of Environmental Engineering, Quzhou University, Quzhou 324000 (China); Xu, Zemin [MOE Key Laboratory of Environmental Remediation and Ecosystem Health, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Zhang, Xichang [Laboratory for Teaching in Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Yang, Fangxing, E-mail: fxyang@zju.edu.cn [MOE Key Laboratory of Environmental Remediation and Ecosystem Health, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Department of Effect-Directed Analysis, Helmholtz Centre for Environmental Research — UFZ, Leipzig 04318 (Germany)

    2015-11-01

    In this study, the microbial degradation of lambda-cyhalothrin in soil was investigated using compound-specific stable isotope analysis. The results revealed that lambda-cyhalothrin was biodegraded in soil under laboratory conditions. The half-lives of lambda-cyhalothrin were determined to be 49 and 161 days in non-sterile and sterile soils spiked with 2 mg/kg lambda-cyhalothrin and 84 and 154 days in non-sterile and sterile soils spiked with 10 mg/kg lambda-cyhalothrin, respectively. The biodegradation of lambda-cyhalothrin resulted in carbon isotope fractionation, which shifted from − 29.0‰ to − 26.5‰ in soil spiked with 2 mg/kg lambda-cyhalothrin, and to − 27.5‰ with 10 mg/kg lambda-cyhalothrin. A relationship was established between the stable carbon isotope fraction and the residual concentrations of lambda-cyhalothrin by the Rayleigh equation in which the carbon isotope enrichment factor ε of the microbial degradation of lambda-cyhalothrin in the soil was calculated as − 2.53‰. This study provides an approach to quantitatively evaluate the biodegradation of lambda-cyhalothrin in soil in field studies. - Highlights: • Abiotic and biotic degradation of lambda-cyhalothrin were observed in soil. • Biodegradation of lambda-cyhalothrin was evaluated by CSIA. • Biodegradation of lambda-cyhalothrin leads to carbon isotope fractionation. • An enrichment factor ε of lambda-cyhalothrin was determined as − 2.53‰.

  16. Stable carbon isotope fractionation during the biodegradation of lambda-cyhalothrin

    International Nuclear Information System (INIS)

    Shen, Xiaoli; Xu, Zemin; Zhang, Xichang; Yang, Fangxing

    2015-01-01

    In this study, the microbial degradation of lambda-cyhalothrin in soil was investigated using compound-specific stable isotope analysis. The results revealed that lambda-cyhalothrin was biodegraded in soil under laboratory conditions. The half-lives of lambda-cyhalothrin were determined to be 49 and 161 days in non-sterile and sterile soils spiked with 2 mg/kg lambda-cyhalothrin and 84 and 154 days in non-sterile and sterile soils spiked with 10 mg/kg lambda-cyhalothrin, respectively. The biodegradation of lambda-cyhalothrin resulted in carbon isotope fractionation, which shifted from − 29.0‰ to − 26.5‰ in soil spiked with 2 mg/kg lambda-cyhalothrin, and to − 27.5‰ with 10 mg/kg lambda-cyhalothrin. A relationship was established between the stable carbon isotope fraction and the residual concentrations of lambda-cyhalothrin by the Rayleigh equation in which the carbon isotope enrichment factor ε of the microbial degradation of lambda-cyhalothrin in the soil was calculated as − 2.53‰. This study provides an approach to quantitatively evaluate the biodegradation of lambda-cyhalothrin in soil in field studies. - Highlights: • Abiotic and biotic degradation of lambda-cyhalothrin were observed in soil. • Biodegradation of lambda-cyhalothrin was evaluated by CSIA. • Biodegradation of lambda-cyhalothrin leads to carbon isotope fractionation. • An enrichment factor ε of lambda-cyhalothrin was determined as − 2.53‰

  17. Amino acid δ13C analysis of hair proteins and bone collagen using liquid chromatography/isotope ratio mass spectrometry

    DEFF Research Database (Denmark)

    Raghavan, Maanasa; McCullagh, James S. O.; Lynnerup, Niels

    2010-01-01

    We report a novel method for the chromatographic separation and measurement of stable carbon isotope ratios (delta(13)C) of individual amino acids in hair proteins and bone collagen using the LC-IsoLink system, which interfaces liquid chromatography (LC) with isotope ratio mass spectrometry (IRMS......). This paper provides baseline separation of 15 and 13 of the 18 amino acids in bone collagen and hair proteins, respectively. We also describe an approach to analysing small hair samples for compound-specific analysis of segmental hair sections. The LC/IRMS method is applied in a historical context...... by the delta(13)C analysis of hair proteins and bone collagen recovered from six individuals from Uummannaq in Greenland. The analysis of hair and bone amino acids from the same individual, compared for the first time in this study, is of importance in palaeodietary reconstruction. If hair proteins can be used...

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

    Science.gov (United States)

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

    2016-04-01

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

  19. Spectral isotopic methods of determining nitrogen and carbon in plant specimens with laser volatization

    International Nuclear Information System (INIS)

    Lazeeva, G.S.

    1986-01-01

    Methods have been devised for the local determination of nitrogen and carbon isotope compositions in plant specimens, which provide separate and joint determination. Local laser evaporation has been combined with spectroscopic determination of the isotope compositions in the gas phase. A continuous-wave CO 2 laser is preferable for the local evaporation; the carbon isotope composition may be determined directly on the sum of the evaporation products, whereas nitrogen must first be separated as N 2 . Methods have also been developed for the local determination of total nitrogen and carbon in a sample with isotope dilution on the basis of laser evaporation. In order to eliminate systematic errors in determining total carbon in plant material, an evaporation method free from a rim has been devised. These methods have been used in determining isotope concentration profiles in plant specimens grown in experiments employing labeled nitrogen and carbon

  20. High precision isotopic ratio analysis of volatile metal chelates

    International Nuclear Information System (INIS)

    Hachey, D.L.; Blais, J.C.; Klein, P.D.

    1980-01-01

    High precision isotope ratio measurements have been made for a series of volatile alkaline earth and transition metal chelates using conventional GC/MS instrumentation. Electron ionization was used for alkaline earth chelates, whereas isobutane chemical ionization was used for transition metal studies. Natural isotopic abundances were determined for a series of Mg, Ca, Cr, Fe, Ni, Cu, Cd, and Zn chelates. Absolute accuracy ranged between 0.01 and 1.19 at. %. Absolute precision ranged between +-0.01-0.27 at. % (RSD +- 0.07-10.26%) for elements that contained as many as eight natural isotopes. Calibration curves were prepared using natural abundance metals and their enriched 50 Cr, 60 Ni, and 65 Cu isotopes covering the range 0.1-1010.7 at. % excess. A separate multiple isotope calibration curve was similarly prepared using enriched 60 Ni (0.02-2.15 at. % excess) and 62 Ni (0.23-18.5 at. % excess). The samples were analyzed by GC/CI/MS. Human plasma, containing enriched 26 Mg and 44 Ca, was analyzed by EI/MS. 1 figure, 5 tables

  1. Reproducibility of isotope ratio measurements

    International Nuclear Information System (INIS)

    Elmore, D.

    1981-01-01

    The use of an accelerator as part of a mass spectrometer has improved the sensitivity for measuring low levels of long-lived radionuclides by several orders of magnitude. However, the complexity of a large tandem accelerator and beam transport system has made it difficult to match the precision of low energy mass spectrometry. Although uncertainties for accelerator measured isotope ratios as low as 1% have been obtained under favorable conditions, most errors quoted in the literature for natural samples are in the 5 to 20% range. These errors are dominated by statistics and generally the reproducibility is unknown since the samples are only measured once

  2. Effects of inorganic anions on carbon isotope fractionation during Fenton-like degradation of trichloroethene

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yunde [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China); Laboratory of Basin Hydrology and Wetland Eco-restoration, China University of Geosciences, Wuhan 430074 (China); Zhou, Aiguo, E-mail: aiguozhou@cug.edu.cn [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China); Gan, Yiqun; Li, Xiaoqian [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China)

    2016-05-05

    Highlights: • The effect of inorganic anions on carbon isotope fractionation was evaluated. • The enrichment factors was independent concentration of NO{sub 3}{sup −}, or SO{sub 4}{sup 2−}. • Cl{sup −} significantly influenced the carbon isotope fractionation. - Abstract: Understanding the magnitude and variability in isotope fractionation with respect to specific processes is crucial to the application of stable isotopic analysis as a tool to infer and quantify transformation processes. The variability of carbon isotope fractionation during Fenton-like degradation of trichloroethene (TCE) in the presence of different inorganic ions (nitrate, sulfate, and chloride), was investigated to evaluate the potential effects of inorganic anions on carbon isotope enrichment factor (ε value). A comparison of ε values obtained in deionized water, nitrate solution, and sulfate solution demonstrated that the ε values were identical and not affected by the presence of nitrate and sulfate. In the presence of chloride, however, the ε values (ranging from −6.3 ± 0.8 to 10 ± 1.3‰) were variable and depended on the chloride concentration, indicating that chloride could significantly affect carbon isotope fractionation during Fenton-like degradation of TCE. Thus, caution should be exercised in selecting appropriate ε values for the field application of stable isotope analysis, as various chloride concentrations may be present due to naturally present or introduced with pH adjustment and iron salts during Fenton-like remediation. Furthermore, the effects of chloride on carbon isotope fractionation may be able to provide new insights about reaction mechanisms of Fenton-like processes.

  3. Effects of inorganic anions on carbon isotope fractionation during Fenton-like degradation of trichloroethene

    International Nuclear Information System (INIS)

    Liu, Yunde; Zhou, Aiguo; Gan, Yiqun; Li, Xiaoqian

    2016-01-01

    Highlights: • The effect of inorganic anions on carbon isotope fractionation was evaluated. • The enrichment factors was independent concentration of NO_3"−, or SO_4"2"−. • Cl"− significantly influenced the carbon isotope fractionation. - Abstract: Understanding the magnitude and variability in isotope fractionation with respect to specific processes is crucial to the application of stable isotopic analysis as a tool to infer and quantify transformation processes. The variability of carbon isotope fractionation during Fenton-like degradation of trichloroethene (TCE) in the presence of different inorganic ions (nitrate, sulfate, and chloride), was investigated to evaluate the potential effects of inorganic anions on carbon isotope enrichment factor (ε value). A comparison of ε values obtained in deionized water, nitrate solution, and sulfate solution demonstrated that the ε values were identical and not affected by the presence of nitrate and sulfate. In the presence of chloride, however, the ε values (ranging from −6.3 ± 0.8 to 10 ± 1.3‰) were variable and depended on the chloride concentration, indicating that chloride could significantly affect carbon isotope fractionation during Fenton-like degradation of TCE. Thus, caution should be exercised in selecting appropriate ε values for the field application of stable isotope analysis, as various chloride concentrations may be present due to naturally present or introduced with pH adjustment and iron salts during Fenton-like remediation. Furthermore, the effects of chloride on carbon isotope fractionation may be able to provide new insights about reaction mechanisms of Fenton-like processes.

  4. Lipid Biomarkers and Molecular Carbon Isotopes for Elucidating Carbon Cycling Pathways in Hydrothermal Vents

    Science.gov (United States)

    Zhang, C. L.; Dai, J.; Campbell, B.; Cary, C.; Sun, M.

    2003-12-01

    Increasing molecular evidence suggests that hydrothermal vents in mid-ocean ridges harbor large populations of free-living bacteria, particularly the epsilon Proteobacteria. However, pathways for carbon metabolism by these bacteria are poorly known. We are addressing this question by analyzing the lipid biomarkers and their isotope signatures in environments where the epsilon Proteobacteria are likely predominant. Solid materials were collected from hydrothermal vents in the East Pacific Rise and at the Guaymas Basin in the Gulf of California. Fatty acids extracted from these samples are dominated by 16:0 (27-41%), 18:0 (16-48%), 18:1 (11-42%), 16:1 (7-12%), and 14:0 (5-28%). In addition, 15:0 and anteiso-15:0 are significantly present (2-3%) in samples from the Guaymas Basin. The isotopic compositions of these fatty acids range from -15.0\\permil to -33.1\\permil with the most positive values occurring only in monounsaturated fatty acids (16:1 and 18:1). We are currently unable to assign these biomarkers to any of the epsilon Proteobacteria because biomarkers are poorly known for these organisms isolated from the vents. However, no polyunsaturated fatty acids were detected in these samples, which are consistent with the absence of vent animals at the sampling sites. Signature biomarkers of 20:1 and cy21:0, which are characteristic of the thermophilic chemolithoautotrophs such as Aquificales, are also absent in these samples. These results imply that the deeply branched Aquificales species do not constitute the major microbial community in these vent environments. The large range of molecular isotopic compositions suggests that these lipids are synthesized from various carbon sources with different isotopic compositions or through different biosynthetic pathways, or both. We are currently measuring the isotopic compositions of the total organic carbon in the bulk samples and will determine the fractionations between lipid biomarkers and the total organic carbon

  5. Changes in hydrogen isotope ratios in sequential plumage stages: an implication for the creation of isotope-base maps for tracking migratory birds.

    Science.gov (United States)

    Duxbury, J M; Holroyd, G L; Muehlenbachs, K

    2003-09-01

    Accurate reference maps are important in the use of stable-isotopes to track the movements of migratory birds. Reference maps created by the analysis of samples collected from young at the nest site are more accurate than simply referring to naturally occurring patterns of hydrogen isotope ratios created by precipitation cycles. Ratios of hydrogen isotopes in the nutrients incorporated early in the development of young birds can be derived from endogenous, maternal sources. Base-maps should be created with the analysis of tissue samples from hatchlings after local the isotopic signature of exogenous nutrients is dominant. Migratory species such as Peregrine Falcons are known to use endogenous sources in the creation of their eggs, therefore knowledge of what plumage stage best represents the local hydrogen ratios would assist in the planning of nest visits. We conducted diet manipulation experiments involving Japanese Quail and Peregrine Falcons to determine the plumage stage when hydrogen isotope ratios were indicative of a switch in their food source. The natal down of both the quail and falcons reflected the diet of breeding adult females. The hydrogen isotope ratios of a new food source were dominant in the juvenile down of the young falcons, although a further shift was detected in the final juvenile plumage. The juvenile plumage is grown during weeks 3-4 after hatch on Peregrine Falcons. Nest visits for the purpose of collecting feathers for isotope-base-map creation should be made around 4 weeks after the presumed hatch of the young falcons.

  6. Evaluation strategies for isotope ratio measurements of single particles by LA-MC-ICPMS.

    Science.gov (United States)

    Kappel, S; Boulyga, S F; Dorta, L; Günther, D; Hattendorf, B; Koffler, D; Laaha, G; Leisch, F; Prohaska, T

    2013-03-01

    Data evaluation is a crucial step when it comes to the determination of accurate and precise isotope ratios computed from transient signals measured by multi-collector-inductively coupled plasma mass spectrometry (MC-ICPMS) coupled to, for example, laser ablation (LA). In the present study, the applicability of different data evaluation strategies (i.e. 'point-by-point', 'integration' and 'linear regression slope' method) for the computation of (235)U/(238)U isotope ratios measured in single particles by LA-MC-ICPMS was investigated. The analyzed uranium oxide particles (i.e. 9073-01-B, CRM U010 and NUSIMEP-7 test samples), having sizes down to the sub-micrometre range, are certified with respect to their (235)U/(238)U isotopic signature, which enabled evaluation of the applied strategies with respect to precision and accuracy. The different strategies were also compared with respect to their expanded uncertainties. Even though the 'point-by-point' method proved to be superior, the other methods are advantageous, as they take weighted signal intensities into account. For the first time, the use of a 'finite mixture model' is presented for the determination of an unknown number of different U isotopic compositions of single particles present on the same planchet. The model uses an algorithm that determines the number of isotopic signatures by attributing individual data points to computed clusters. The (235)U/(238)U isotope ratios are then determined by means of the slopes of linear regressions estimated for each cluster. The model was successfully applied for the accurate determination of different (235)U/(238)U isotope ratios of particles deposited on the NUSIMEP-7 test samples.

  7. Microbial degradation of alpha-cypermethrin in soil by compound-specific stable isotope analysis

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Zemin [MOE Key Laboratory of Environmental Remediation and Ecosystem Health, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Shen, Xiaoli [MOE Key Laboratory of Environmental Remediation and Ecosystem Health, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Department of Environmental Engineering, Quzhou University, Quzhou 324000 (China); Zhang, Xi-Chang [Laboratory for Teaching in Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Liu, Weiping [MOE Key Laboratory of Environmental Remediation and Ecosystem Health, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Yang, Fangxing, E-mail: fxyang@zju.edu.cn [MOE Key Laboratory of Environmental Remediation and Ecosystem Health, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Department of Effect-Directed Analysis, Helmholtz Center for Environmental Research – UFZ, Leipzig 04318 (Germany)

    2015-09-15

    Highlights: • Alpha-cypermethrin (α-CP) can be degraded by microorganisms in soil. • Biodegradation of α-CP resulted in carbon isotope fractionation. • A relationship was found between carbon isotope ratios and concentrations of α-CP. • An enrichment factor ϵ of α-CP was determined as −1.87‰. • CSIA is applicable to assess biodegradation of α-CP. - Abstract: To assess microbial degradation of alpha-cypermethrin in soil, attenuation of alpha-cypermethrin was investigated by compound-specific stable isotope analysis. The variations of the residual concentrations and stable carbon isotope ratios of alpha-cypermethrin were detected in unsterilized and sterilized soils spiked with alpha-cypermethrin. After an 80 days’ incubation, the concentrations of alpha-cypermethrin decreased to 0.47 and 3.41 mg/kg in the unsterilized soils spiked with 2 and 10 mg/kg, while those decreased to 1.43 and 6.61 mg/kg in the sterilized soils. Meanwhile, the carbon isotope ratios shifted to −29.14 ± 0.22‰ and −29.86 ± 0.33‰ in the unsterilized soils spiked with 2 and 10 mg/kg, respectively. The results revealed that microbial degradation contributed to the attenuation of alpha-cypermethrin and induced the carbon isotope fractionation. In order to quantitatively assess microbial degradation, a relationship between carbon isotope ratios and residual concentrations of alpha-cypermethrin was established according to Rayleigh equation. An enrichment factor, ϵ = −1.87‰ was obtained, which can be employed to assess microbial degradation of alpha-cypermethrin. The significant carbon isotope fractionation during microbial degradation suggests that CSIA is a proper approach to qualitatively detect and quantitatively assess the biodegradation during attenuation process of alpha-cypermethrin in the field.

  8. Increase in soil stable carbon isotope ratio relates to loss of organic carbon: results from five long-term bare fallow experiments.

    Science.gov (United States)

    Menichetti, Lorenzo; Houot, Sabine; van Oort, Folkert; Kätterer, Thomas; Christensen, Bent T; Chenu, Claire; Barré, Pierre; Vasilyeva, Nadezda A; Ekblad, Alf

    2015-03-01

    Changes in the (12)C/(13)C ratio (expressed as δ(13)C) of soil organic C (SOC) has been observed over long time scales and with depth in soil profiles. The changes are ascribed to the different reaction kinetics of (12)C and (13)C isotopes and the different isotopic composition of various SOC pool components. However, experimental verification of the subtle isotopic shifts associated with SOC turnover under field conditions is scarce. We determined δ(13)C and SOC in soil sampled during 1929-2009 in the Ap-horizon of five European long-term bare fallow experiments kept without C inputs for 27-80 years and covering a latitudinal range of 11°. The bare fallow soils lost 33-65% of their initial SOC content and showed a mean annual δ(13)C increase of 0.008-0.024‰. The (13)C enrichment could be related empirically to SOC losses by a Rayleigh distillation equation. A more complex mechanistic relationship was also examined. The overall estimate of the fractionation coefficient (ε) was -1.2 ± 0.3‰. This coefficient represents an important input to studies of long-term SOC dynamics in agricultural soils that are based on variations in (13)C natural abundance. The variance of ε may be ascribed to site characteristics not disclosed in our study, but the very similar kinetics measured across our five experimental sites suggest that overall site-specific factors (including climate) had a marginal influence and that it may be possible to isolate a general mechanism causing the enrichment, although pre-fallow land use may have some impact on isotope abundance and fractionation.

  9. Influences of large-scale convection and moisture source on monthly precipitation isotope ratios observed in Thailand, Southeast Asia

    Science.gov (United States)

    Wei, Zhongwang; Lee, Xuhui; Liu, Zhongfang; Seeboonruang, Uma; Koike, Masahiro; Yoshimura, Kei

    2018-04-01

    Many paleoclimatic records in Southeast Asia rely on rainfall isotope ratios as proxies for past hydroclimatic variability. However, the physical processes controlling modern rainfall isotopic behaviors in the region is poorly constrained. Here, we combined isotopic measurements at six sites across Thailand with an isotope-incorporated atmospheric circulation model (IsoGSM) and the Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model to investigate the factors that govern the variability of precipitation isotope ratios in this region. Results show that rainfall isotope ratios are both correlated with local rainfall amount and regional outgoing longwave radiation, suggesting that rainfall isotope ratios in this region are controlled not only by local rain amount (amount effect) but also by large-scale convection. As a transition zone between the Indian monsoon and the western North Pacific monsoon, the spatial difference of observed precipitation isotope among different sites are associated with moisture source. These results highlight the importance of regional processes in determining rainfall isotope ratios in the tropics and provide constraints on the interpretation of paleo-precipitation isotope records in the context of regional climate dynamics.

  10. The Methane to Carbon Dioxide Ratio Produced during Peatland Decomposition and a Simple Approach for Distinguishing This Ratio

    Science.gov (United States)

    Chanton, J.; Hodgkins, S. B.; Cooper, W. T.; Glaser, P. H.; Corbett, J. E.; Crill, P. M.; Saleska, S. R.; Rich, V. I.; Holmes, B.; Hines, M. E.; Tfaily, M.; Kostka, J. E.

    2014-12-01

    Peatland organic matter is cellulose-like with an oxidation state of approximately zero. When this material decomposes by fermentation, stoichiometry dictates that CH4 and CO2 should be produced in a ratio approaching one. While this is generally the case in temperate zones, this production ratio is often departed from in boreal peatlands, where the ratio of belowground CH4/CO2 production varies between 0.1 and 1, indicating CO2 production by a mechanism in addition to fermentation. The in situ CO2/CH4 production ratio may be ascertained by analysis of the 13C isotopic composition of these products, because CO2 production unaccompanied by methane production produces CO2 with an isotopic composition similar to the parent organic matter while methanogenesis produces 13C depleted methane and 13C enriched CO2. The 13C enrichment in the subsurface CO2 pool is directly related to the amount of if formed from methane production and the isotopic composition of the methane itself. Excess CO2 production is associated with more acidic conditions, Sphagnum vegetation, high and low latitudes, methane production dominated by hydrogenotrophic methane production, 13C depleted methane, and generally, more nutrient depleted conditions. Three theories have been offered to explain these observations— 1) inhibition of acetate utilization, acetate build-up and diffusion to the surface and eventual aerobic oxidation, 2) the use of humic acids as electron acceptors, and the 3) utilization of organic oxygen to produce CO2. In support of #3, we find that 13C-NMR, Fourier transform infrared (FT IR) spectroscopy, and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) clearly show the evolution of polysaccharides and cellulose towards more decomposed humified alkyl compounds stripped of organic oxygen utilized to form CO2. Such decomposition results in more negative carbon oxidation states varying from -1 to -2. Coincident with this reduction in oxidation state, is the

  11. Nicotine, acetanilide and urea multi-level2H-,13C- and15N-abundance reference materials for continuous-flow isotope ratio mass spectrometry

    Science.gov (United States)

    Schimmelmann, A.; Albertino, A.; Sauer, P.E.; Qi, H.; Molinie, R.; Mesnard, F.

    2009-01-01

    Accurate determinations of stable isotope ratios require a calibration using at least two reference materials with different isotopic compositions to anchor the isotopic scale and compensate for differences in machine slope. Ideally, the S values of these reference materials should bracket the isotopic range of samples with unknown S values. While the practice of analyzing two isotopically distinct reference materials is common for water (VSMOW-SLAP) and carbonates (NBS 19 and L-SVEC), the lack of widely available organic reference materials with distinct isotopic composition has hindered the practice when analyzing organic materials by elemental analysis/isotope ratio mass spectrometry (EA-IRMS). At present only L-glutamic acids USGS40 and USGS41 satisfy these requirements for ??13C and ??13N, with the limitation that L-glutamic acid is not suitable for analysis by gas chromatography (GC). We describe the development and quality testing of (i) four nicotine laboratory reference materials for on-line (i.e. continuous flow) hydrogen reductive gas chromatography-isotope ratio mass-spectrometry (GC-IRMS), (ii) five nicotines for oxidative C, N gas chromatography-combustion-isotope ratio mass-spectrometry (GC-C-IRMS, or GC-IRMS), and (iii) also three acetanilide and three urea reference materials for on-line oxidative EA-IRMS for C and N. Isotopic off-line calibration against international stable isotope measurement standards at Indiana University adhered to the 'principle of identical treatment'. The new reference materials cover the following isotopic ranges: ??2Hnicotine -162 to -45%o, ??13Cnicotine -30.05 to +7.72%, ?? 15Nnicotine -6.03 to +33.62%; ??15N acetanilide +1-18 to +40.57%; ??13Curea -34.13 to +11.71%, ??15Nurea +0.26 to +40.61% (recommended ?? values refer to calibration with NBS 19, L-SVEC, IAEA-N-1, and IAEA-N-2). Nicotines fill a gap as the first organic nitrogen stable isotope reference materials for GC-IRMS that are available with different ??13N

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  13. Transpiration efficiency over an annual cycle, leaf gas exchange and wood carbon isotope ratio of three tropical tree species.

    Science.gov (United States)

    Cernusak, Lucas A; Winter, Klaus; Aranda, Jorge; Virgo, Aurelio; Garcia, Milton

    2009-09-01

    Variation in transpiration efficiency (TE) and its relationship with the stable carbon isotope ratio of wood was investigated in the saplings of three tropical tree species. Five individuals each of Platymiscium pinnatum (Jacq.) Dugand, Swietenia macrophylla King and Tectona grandis Linn. f. were grown individually in large (760 l) pots over 16 months in the Republic of Panama. Cumulative transpiration was determined by repeatedly weighing the pots with a pallet truck scale. Dry matter production was determined by destructive harvest. The TE, expressed as experiment-long dry matter production divided by cumulative water use, averaged 4.1, 4.3 and 2.9 g dry matter kg(-1) water for P. pinnatum, S. macrophylla and T. grandis, respectively. The TE of T. grandis was significantly lower than that of the other two species. Instantaneous measurements of the ratio of intercellular to ambient CO(2) partial pressures (c(i)/c(a)), taken near the end of the experiment, explained 66% of variation in TE. Stomatal conductance was lower in S. macrophylla than in T. grandis, whereas P. pinnatum had similar stomatal conductance to T. grandis, but with a higher photosynthetic rate. Thus, c(i)/c(a) and TE appeared to vary in response to both stomatal conductance and photosynthetic capacity. Stem-wood delta(13)C varied over a relatively narrow range of just 2.2 per thousand, but still explained 28% of variation in TE. The results suggest that leaf-level processes largely determined variation among the three tropical tree species in whole-plant water-use efficiency integrated over a full annual cycle.

  14. Engineered in situ bioremediation of a petroleum hydrocarbon-contaminated aquifer: assessment of mineralization based on alkalinity, inorganic carbon and stable carbon isotope balances

    Science.gov (United States)

    Hunkeler, Daniel; Höhener, Patrick; Bernasconi, Stefano; Zeyer, Josef

    1999-04-01

    A concept is proposed to assess in situ petroleum hydrocarbon mineralization by combining data on oxidant consumption, production of reduced species, CH 4, alkalinity and dissolved inorganic carbon (DIC) with measurements of stable isotope ratios. The concept was applied to a diesel fuel contaminated aquifer in Menziken, Switzerland, which was treated by engineered in situ bioremediation. In the contaminated aquifer, added oxidants (O 2 and NO 3-) were consumed, elevated concentrations of Fe(II), Mn(II), CH 4, alkalinity and DIC were detected and the DIC was generally depleted in 13C compared to the background. The DIC production was larger than expected based on the consumption of dissolved oxidants and the production of reduced species. Stable carbon isotope balances revealed that the DIC production in the aquifer originated mainly from microbial petroleum hydrocarbon mineralization, and that geochemical reactions such as carbonate dissolution produced little DIC. This suggests that petroleum hydrocarbon mineralization can be underestimated if it is determined based on concentrations of dissolved oxidants and reduced species.

  15. Lead isotope ratios as a tracer for lead contamination sources: A lake Andong case study

    Directory of Open Access Journals (Sweden)

    Kim Y. H

    2013-04-01

    Full Text Available The objective of this study was to evaluate stable Pb isotope signatures as a tracer for Pb contamination in Lake Andong. For Pb isotope analysis, we collected water and sediment from Lake Andong, particles in the air, soils, and stream water, mine tailings, sludge and wastewater from zinc smelting around lake Andong watershed. The results showed that Pb isotope ratios (206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb for zinc concentrate were 18.809 ± 0.322, 15.650 ± 0.062, and 38.728 ± 0.421, respectively. In wastewater, isotopic ratio values (206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb were 17.363 ± 0.133, 15.550 ± 0.025, and 37.217 ± 0.092, respectively. Additionally, isotopic ratio values (206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb for sludge were 17.515 ± 0.155, 15.537 ± 0.018, and 37.357 ± 0.173, respectively. These values were similar to those in zinc and lead concentrate originated from Canada and South America. In contrast, Pb isotope ratios of soil, tailings and sediment from Lake Andong were similar to those of Korean ore. Atmospheric particles showed different patterns of Pb isotope ratios from sediments, soils, and zinc smelting and this needs further investigation in order to identify atmospheric Pb sources.

  16. Studies in the determination of lead isotope ratios by inductively coupled plasma mass spectrometry

    International Nuclear Information System (INIS)

    Date, A.R.; Yuk Ying Cheung

    1987-01-01

    The application of ICP-MS to the determination of lead isotope ratios in geological materials is described. Data presented for a series of lead mineral concentrates are compared with reference values obtained by conventional solid source thermal ionisation mass spectrometry. The simultaneous determination of lead isotope ratios and trace elements is carried out in a rapid analysis mode. The application of an electrothermal vaporisation technique for small solution aliquots is described. Lead isotope ratio data for the United States Geological Survey standard reference silicate rock BCR-1, obtained without separation of lead from the matrix, are compared with previously published values obtained after separation. (author)

  17. Investigations of the ratios of stable carbon isotopes in atmospheric relevant VOC using simulation and field experiments; Untersuchungen der Verhaeltnisse stabiler Kohlenstoffisotope in atmosphaerisch relevanten VOC in Simulations- und Feldexperimenten

    Energy Technology Data Exchange (ETDEWEB)

    Spahn, Holger

    2010-07-01

    Volatile organic compounds (VOC) play an important role in the regional and global atmospheric chemistry. The author of the contribution under consideration reports on the analysis of the ratios of stable carbon isotopes ({delta}({sup 13}C) analysis) in atmospheric VOCs. At first, the state of the art of this analytical technique is described. For the first time {delta}({sup 13}C) values of different monoterpenes have been determined in the investigation of vegetable emissions at a plant chamber. By means of the oxidation of {beta}-pinene by ozone in an aerosol chamber, the kinetic isotope effect of this reaction was determined. In southern Germany, air samples for the {delta}({sup 13}C) analysis were collected using a zeppelin. This enables a height-resolved measurement of {delta}({sup 13}C) values. Based on these measurements, the average photochemical age for methanol, toluene and p-xylene at different heights was calculated.

  18. High Relative Abundance of Biofuel Sourced Ethanol in Precipitation in the US and Brazil Determined Using Compound Specific Stable Carbon Isotopes

    Science.gov (United States)

    Shimizu, M. S.; Felix, J. D. D.; Casas, M.; Avery, G. B., Jr.; Kieber, R. J.; Mead, R. N.; Willey, J. D.; Lane, C.

    2017-12-01

    Ethanol biofuel production and consumption have increased exponentially over the last two decades to help reduce greenhouse gas emissions. Currently, 85% of global ethanol production and consumption occurs in the US and Brazil. Increasing biofuel ethanol usage in these two countries enhances emissions of uncombusted ethanol to the atmosphere contributing to poor air quality. Although measurements of ethanol in the air and the precipitation reveal elevated ethanol concentrations in densely populated cities, other sources such as natural vegetation can contribute to emission to the atmosphere. Previous modeling studies indicated up to 12% of atmospheric ethanol is from anthropogenic emissions. Only one gas phase study in southern Florida attempted to constrain the two sources through direct isotopic measurements. The current study used a stable carbon isotope method to constrain sources of ethanol in rainwater from the US and Brazil. A method was developed using solid phase microextraction (SPME) with subsequent analysis by gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). Stable carbon isotope signatures (δ13C) of vehicle ethanol emission sources for both the US (-9.8‰) and Brazil (-12.7‰) represented C4 plants as feedstock (corn and sugarcane) for biofuel production. An isotope mixing model using biofuel from vehicles (C4 plants) and biogenic (C3 plants) end-members was implemented to estimate ethanol source apportionment in the rain. We found that stable carbon isotope ratio of ethanol in the rain ranged between -22.6‰ and -12.7‰. Our results suggest that the contribution of biofuel to atmospheric ethanol can be higher than previously estimated. As biofuel usage increasing globally, it is essential to determine the relative abundance of anthropogenic ethanol in other areas of the world.

  19. The magnesium isotope record of cave carbonate archives

    Science.gov (United States)

    Riechelmann, S.; Buhl, D.; Schröder-Ritzrau, A.; Riechelmann, D. F. C.; Richter, D. K.; Vonhof, H. B.; Wassenburg, J. A.; Geske, A.; Spötl, C.; Immenhauser, A.

    2012-11-01

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

  20. A new CF-IRMS system for quantifying stable isotopes of carbon monoxide from ice cores and small air samples

    Directory of Open Access Journals (Sweden)

    Z. Wang

    2010-10-01

    Full Text Available We present a new analysis technique for stable isotope ratios13C and δ18O of atmospheric carbon monoxide (CO from ice core samples. The technique is an online cryogenic vacuum extraction followed by continuous-flow isotope ratio mass spectrometry (CF-IRMS; it can also be used with small air samples. The CO extraction system includes two multi-loop cryogenic cleanup traps, a chemical oxidant for oxidation to CO2, a cryogenic collection trap, a cryofocusing unit, gas chromatography purification, and subsequent injection into a Finnigan Delta Plus IRMS. Analytical precision of 0.2‰ (±1δ for δ13C and 0.6‰ (±1δ for δ18O can be obtained for 100 mL (STP air samples with CO mixing ratios ranging from 60 ppbv to 140 ppbv (~268–625 pmol CO. Six South Pole ice core samples from depths ranging from 133 m to 177 m were processed for CO isotope analysis after wet extraction. To our knowledge, this is the first measurement of stable isotopes of CO in ice core air.

  1. Fractionation in position-specific isotope composition during vaporization of environmental pollutants measured with isotope ratio monitoring by 13C nuclear magnetic resonance spectrometry

    International Nuclear Information System (INIS)

    Julien, Maxime; Parinet, Julien; Nun, Pierrick; Bayle, Kevin; Höhener, Patrick; Robins, Richard J.; Remaud, Gérald S.

    2015-01-01

    Isotopic fractionation of pollutants in terrestrial or aqueous environments is a well-recognized means by which to track different processes during remediation. As a complement to the common practice of measuring the change in isotope ratio for the whole molecule using isotope ratio monitoring by mass spectrometry (irm-MS), position-specific isotope analysis (PSIA) can provide further information that can be exploited to investigate source and remediation of soil and water pollutants. Position-specific fractionation originates from either degradative or partitioning processes. We show that isotope ratio monitoring by 13 C NMR (irm- 13 C NMR) spectrometry can be effectively applied to methyl tert-butylether, toluene, ethanol and trichloroethene to obtain this position-specific data for partitioning. It is found that each compound exhibits characteristic position-specific isotope fractionation patterns, and that these are modulated by the type of evaporative process occurring. Such data should help refine models of how remediation is taking place, hence back-tracking to identify pollutant sources. - Highlights: • Position-Specific Isotope Analysis (PSIA) by 13 C NMR spectrometry. • PSIA on isotope fractionation during several vaporization processes. • PSIA for isotope profiling in environment pollutants. • Intramolecular 13 C reveal normal and inverse effects, bulk values being unchanged. - PSIA in pollutants during evaporation processes shows more detailed information for discerning the nature of the process involved than does bulk isotope measurements

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

    Science.gov (United States)

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

    2013-01-01

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

  3. Evaluation of gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) for the quality assessment of citrus liqueurs.

    Science.gov (United States)

    Schipilliti, Luisa; Bonaccorsi, Ivana; Cotroneo, Antonella; Dugo, Paola; Mondello, Luigi

    2013-02-27

    Citrus liqueurs are alcoholic beverages obtained by maceration. The European Parliament protects these alcoholic beverages, forbidding the addition of nature-identical flavoring substances. However, for economical and technological reasons, producers often add natural and/or synthetic flavors to the alcoholic syrup, obtaining artificial spirit drinks. The aim of this study is to investigate the authenticity of Italian liqueurs, of lemon, bergamot, and mandarin (locally known as "limoncello", "bargamino", and "mandarinetto"), comparing the carbon isotope ratios with values determined in genuine cold-pressed peel oils. Authenticity assessment was performed using headspace-solid phase microextraction coupled to gas chromatography-combustion-isotope ratio mass spectrometry. Additional analyses were performed by direct enantioselective gas chromatography to determine the enantiomeric distribution of selected chiral volatiles and by gas chromatography-mass spectrometry for the qualitative analyses of the samples. The method allowed confirmation of genuineness. Enantioselective gas chromatography analyses confirmed the results, demonstrating the reliability of the method.

  4. Absolute measurement of the isotopic ratio of a water sample with very low deuterium content

    International Nuclear Information System (INIS)

    Hagemann, R.; Nief, G.; Roth, E.

    1968-01-01

    The presence of H 3+ ions which are indistinguishable from HD + ions presents the principal difficulty encountered in the measurement of isotopic ratios of water samples with very low deuterium contents using a mass spectrometer. Thus, when the sample contains no deuterium, the mass spectrometer does not indicate zero. By producing, in situ, from the sample to be measured, water vapor with an isotopic ratio very close to zero using a small distilling column, this difficulty is overcome. This column, its operating parameters, as well as the way in which the measurements are made are described. An arrangement is employed in which the isotopic ratios can be measured with a sensitivity better than 0.01 x 10 -6 . The method is applied to the determination of the isotopic ratios of three low deuterium content water samples. The results obtained permit one to assign to the sample with the lowest deuterium content an absolute value equal to 1.71 ± 0.03 ppm. This water sample is a primary standard from which is determined the isotopic ratio of a natural water sample which serves as the laboratory standard. (author) [fr

  5. Stable carbon isotope fractionation during the biodegradation of lambda-cyhalothrin.

    Science.gov (United States)

    Shen, Xiaoli; Xu, Zemin; Zhang, Xichang; Yang, Fangxing

    2015-11-01

    In this study, the microbial degradation of lambda-cyhalothrin in soil was investigated using compound-specific stable isotope analysis. The results revealed that lambda-cyhalothrin was biodegraded in soil under laboratory conditions. The half-lives of lambda-cyhalothrin were determined to be 49 and 161 days in non-sterile and sterile soils spiked with 2mg/kg lambda-cyhalothrin and 84 and 154 days in non-sterile and sterile soils spiked with 10mg/kg lambda-cyhalothrin, respectively. The biodegradation of lambda-cyhalothrin resulted in carbon isotope fractionation, which shifted from -29.0‰ to -26.5‰ in soil spiked with 2mg/kg lambda-cyhalothrin, and to -27.5‰ with 10mg/kg lambda-cyhalothrin. A relationship was established between the stable carbon isotope fraction and the residual concentrations of lambda-cyhalothrin by the Rayleigh equation in which the carbon isotope enrichment factor ε of the microbial degradation of lambda-cyhalothrin in the soil was calculated as -2.53‰. This study provides an approach to quantitatively evaluate the biodegradation of lambda-cyhalothrin in soil in field studies. Copyright © 2015 Elsevier B.V. All rights reserved.

  6. Assessment of Bacterial Degradation of Aromatic Hydrocarbons in the Environment by Analysis of Stable Carbon Isotope Fractionation

    Energy Technology Data Exchange (ETDEWEB)

    Meckenstock, Rainer U. [Eberhard-Karls University of Tuebingen, Center for Applied Geoscience (Germany)], E-mail: rainer.meckenstock@uni-tuebingen.de; Morasch, Barbara [University of Konstanz, Faculty of Biology (Germany); Kaestner, Matthias; Vieth, Andrea; Richnow, Hans Hermann [Center for Environmental Research, Department of Remediation Research (Germany)

    2002-05-15

    direction of the groundwater flow and revealed decreasing concentrations accompanied with an increase in the {sup 13}C/{sup 12}C stable carbon isotope ratio of the residual toluene. Calculation of the extent of biodegradation based on the isotope values and laboratory derived isotope fractionation factors showed that the residual toluene was degraded to more than 99% by microbial activity. Calculation of the theoretical residual toluene concentrations based on the measured isotope values described the strongly decreasing concentrations along the plume. Other aromatic hydrocarbons like benzene and naphthalene which were analysed in the same course also showed decreasing concentrations along the groundwater flow path accompanied by increasing {delta}{sup 13}C values indicating biodegradation.

  7. Hafnium isotope ratios of nine GSJ reference samples

    International Nuclear Information System (INIS)

    Hanyu, Takeshi; Nakai, Shun'ichi; Tatsuta, Riichiro

    2005-01-01

    176 Hf/ 177 Hf ratios of nine geochemical reference rocks from the Geological Survey of Japan, together with BIR-1 and BCR-2, were determined using multi-collector inductively coupled plasma mass spectrometry. Our data for BIR-1, BCR-2 and JB-1 are in agreement with those previously reported, demonstrating the appropriateness of the chemical procedure and isotopic measurement employed in this study. The reference rocks have a wide range of 176 Hf/ 177 Hf covering the field defined by various volcanic rocks, such as mid-ocean ridge basalts, ocean island basalts, and subduction related volcanic rocks. They are therefore suitable as rock standards for Hf isotope measurement of geological samples. (author)

  8. Aragonite-Calcite Inversion During Biogenic Carbonate Sampling: Considerations for Interpreting Isotopic Measurements in Paleoclimate Studies

    Science.gov (United States)

    Waite, A. J.; Swart, P. K.

    2011-12-01

    , suggests that the isotopic depletion is tied to the polymorphic inversion of aragonite to calcite, and not just random chance based on natural isotopic variability in the skeleton. There appears to be no relationship between the percent inversion and carbon isotopic composition. Elemental ratios also appear to remain stable during the heating and inversion process. The findings of this and published studies present, in many cases, conflicting views of the isotopic fractionation associated with inversion of aragonite to calcite. Discrepancies such as this likely result from subtle differences in sampling protocol related to instruments, drill bits, skeletal density, and possibly even laboratory conditions like temperature and humidity, further complicating our understanding and interpretation of such observations. Preliminary investigation suggests that altering milling conditions or wet milling may reduce the extent of alteration. Unfortunately, milling/drilling remains one of the only practical methods of sampling biogenic carbonates at a high resolution for paleoclimate work and, as such, caution should be taken in the interpretation of oxygen isotopic measurements from specimens of this nature.

  9. Stable isotopes of authigenic minerals in variably-saturated fractured tuff

    International Nuclear Information System (INIS)

    Weber, D.S.; Evans, D.D.

    1988-11-01

    Identifying stable isotope variation and mineralogical changes in fractured rock may help establish the history of climatic and geomorphological processes that might affect the isolation properties of a waste repository site. This study examines the use of the stable isotope ratios of oxygen ( 18 O/ 16 O) and carbon ( 13 C/ 12 C) in authigenic minerals as hydrogeochemical tools tracing low-temperature rock-water interaction in variably-saturated fractured stuff. Isotopic compositions of fracture-filling and rock matrix minerals in the Apache Leap tuff, near Superior, Arizona were concordant with geothermal temperatures and in equilibrium with water isotopically similar to present-day meteoric water and groundwater. Oxygen and carbon isotope ratios of fracture-filling, in unsaturated fractured tuff, displayed an isotopic gradient believed to result from near-surface isotopic enrichment due to evaporation rather than the effects of rock-water interaction. Oxygen isotope ratios of rock matrix opal samples exhibited an isotopic gradient believed to result from, leaching and reprecipitation of silica at depth. Methods and results can be used to further define primary flowpaths and the movement of water in variably-saturated fractured rock. 71 refs., 23 figs., 3 tabs

  10. Stable isotopes of authigenic minerals in variably-saturated fractured tuff

    Energy Technology Data Exchange (ETDEWEB)

    Weber, D.S.; Evans, D.D.

    1988-11-01

    Identifying stable isotope variation and mineralogical changes in fractured rock may help establish the history of climatic and geomorphological processes that might affect the isolation properties of a waste repository site. This study examines the use of the stable isotope ratios of oxygen ({sup 18}O/{sup 16}O) and carbon ({sup 13}C/{sup 12}C) in authigenic minerals as hydrogeochemical tools tracing low-temperature rock-water interaction in variably-saturated fractured stuff. Isotopic compositions of fracture-filling and rock matrix minerals in the Apache Leap tuff, near Superior, Arizona were concordant with geothermal temperatures and in equilibrium with water isotopically similar to present-day meteoric water and groundwater. Oxygen and carbon isotope ratios of fracture-filling, in unsaturated fractured tuff, displayed an isotopic gradient believed to result from near-surface isotopic enrichment due to evaporation rather than the effects of rock-water interaction. Oxygen isotope ratios of rock matrix opal samples exhibited an isotopic gradient believed to result from, leaching and reprecipitation of silica at depth. Methods and results can be used to further define primary flowpaths and the movement of water in variably-saturated fractured rock. 71 refs., 23 figs., 3 tabs.

  11. Plutonium isotopes/137Cs activity ratios for soil in Montenegro

    International Nuclear Information System (INIS)

    Antovic, N. M.; Vukotic, P.; Svrkota, N.; Andrukhovich, S.K.

    2011-01-01

    Plutonium isotopes/ 137 Cs activity ratios were determined for six soil samples from Montenegro, using the results of alpha-spectrometric measurements of 239+240 Pu and 238 Pu, as well as gamma-spectrometric cesium measurements. An average 239+240 Pu/ 137 Cs activity ratio is found to be 0.02, as the 238 Pu/ 137 Cs and 238 Pu/ 239+240 Pu one - 0.0006 and 0.03, respectively. It follows from the results that the source of plutonium in Montenegro soil is nuclear weapon testing during the fifties and sixties of the twentieth century. On the other hand, there is a contribution of the accident at the Chernobyl nuclear power plant to the soil contamination with 137 Cs isotope. [sr

  12. Asymptotic giant branch stars as producers of carbon and of neutron-rich isotopes

    International Nuclear Information System (INIS)

    Iben, I. Jr.

    1984-01-01

    Carbon stars are thought to be in the asymptotic giant branch (AGB) phase of evolution, alternately burning hydrogen and helium in shells above an electron-degenerate carbon-oxygen (CO) core. The excess of carbon relative to oxygen at the surfaces of these stars is thought to be due to convective dredge-up which occurs following a thermal pulse. During a thermal pulse, carbon and neutron-rich isotopes are made in a convective helium-burning zone. In model stars of large CO core mass, the source of neutrons for producing the neutron-rich isotopes is the 22 Ne(α,n) 25 Mg reaction and the isotopes are produced in the solar system s-process distribution. In models of small core mass, the 13 C(α,n) 16 reaction is thought to be responsible for the release of neutrons, and the resultant distribution of neutron-rich isotopes is expected to vary considerably from one star to the next, with the distribution in isolated instances possibly resembling the solar system distribution of r-process isotopes

  13. Sulfur and Hydrogen Isotope Anomalies in Meteorite Sulfonic Acids

    Science.gov (United States)

    Cooper, George W.; Thiemens, Mark H.; Jackson, Teresa L.; Chang, Sherwood

    1997-01-01

    Intramolecular carbon, hydrogen, and sulfur isotope ratios were measured on a homologous series of organic sulfonic acids discovered in the Murchison meteorite. Mass-independent sulfur isotope fractionations were observed along with high deuterium/hydrogen ratios. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low-temperature environment that is consistent with that of interstellar clouds. Sulfur-33 enrichments observed in methanesulfonic acid could have resulted from gas-phase ultraviolet irradiation of a precursor, carbon disulfide. The source of the sulfonic acid precursors may have been the reactive interstellar molecule carbon monosulfide.

  14. Characterization of sources of lead in the urban air of Asia using ratios of stable lead isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Mukai, H.; Furuta, N.; Fujii, T.; Ambe, Y.; Sakamoto, K.; Hashimoto, Y. (National Institute of Environmental Studies, Tsukuba (Japan). Environmental Chemistry Division)

    1993-07-01

    Airborne particulate matter was collected at urban sites in six Asian countries (Japan, South Korea, China, Thailand, Sri Lanka, and Indonesia), and the stable lead isotope ratios were measured. Some source-related materials, such as coal and leaded gasoline, were also analyzed and compared to the ratios observed in airborne lead. Airborne lead isotope ratios differed considerably from each other, and these differences corresponded to differences in the regional source of lead. Leaded gasoline was still the primary source of lead in some cities in Asia, and the lead isotope ratios were strongly influenced by those of leaded gasoline. In Chinese and Korean cities, however, the considerable effect from coal combustion and industrial activity was also observed in their isotope ratios, despite leaded gasoline use. On the other hand, only refuse incineration was a possible single source of lead in Japanese air from the view of lead isotope ratios. 49 refs., 13 figs., 3 tabs.

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

    Directory of Open Access Journals (Sweden)

    M. E. Nowak

    2017-08-01

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

  16. Quantitative measurement of carbon isotopic composition in CO2 gas reservoir by Micro-Laser Raman spectroscopy.

    Science.gov (United States)

    Li, Jiajia; Li, Rongxi; Zhao, Bangsheng; Guo, Hui; Zhang, Shuan; Cheng, Jinghua; Wu, Xiaoli

    2018-04-15

    The use of Micro-Laser Raman spectroscopy technology for quantitatively determining gas carbon isotope composition is presented. In this study, 12 CO 2 and 13 CO 2 were mixed with N 2 at various molar fraction ratios to obtain Raman quantification factors (F 12CO2 and F 13CO2 ), which provide a theoretical basis for calculating the δ 13 C value. And the corresponding values were 0.523 (0Raman peak area can be used for the determination of δ 13 C values within the relative errors range of 0.076% to 1.154% in 13 CO 2 / 12 CO 2 binary mixtures when F 12CO2 /F 13CO2 is 0.466972625. In addition, measurement of δ 13 C values by Micro-Laser Raman analysis were carried out on natural CO 2 gas from Shengli Oil-field at room temperature under different pressures. The δ 13 C values obtained by Micro-Laser Raman spectroscopy technology and Isotope Ratio Mass Spectrometry (IRMS) technology are in good agreement with each other, and the relative errors range of δ 13 C values is 1.232%-6.964%. This research provides a fundamental analysis tool for determining gas carbon isotope composition (δ 13 C values) quantitatively by using Micro-Laser Raman spectroscopy. Experiment of results demonstrates that this method has the potential for obtaining δ 13 C values in natural CO 2 gas reservoirs. Copyright © 2018. Published by Elsevier B.V.

  17. Spatially-resolved isotopic study of carbon trapped in ∼3.43 Ga Strelley Pool Formation stromatolites

    Science.gov (United States)

    Flannery, David T.; Allwood, Abigail C.; Summons, Roger E.; Williford, Kenneth H.; Abbey, William; Matys, Emily D.; Ferralis, Nicola

    2018-02-01

    The large isotopic fractionation of carbon associated with enzymatic carbon assimilation allows evidence for life's antiquity, and potentially the early operation of several extant metabolic pathways, to be derived from the stable carbon isotope record of sedimentary rocks. Earth's organic carbon isotope record extends to the Late Eoarchean-Early Paleoarchean: the age of the oldest known sedimentary rocks. However, complementary inorganic carbon reservoirs are poorly represented in the oldest units, and commonly reported bulk organic carbon isotope measurements do not capture the micro-scale isotopic heterogeneities that are increasingly reported from younger rocks. Here, we investigated the isotopic composition of the oldest paired occurrences of sedimentary carbonate and organic matter, which are preserved as dolomite and kerogen within textural biosignatures of the ∼3.43 Ga Strelley Pool Formation. We targeted least-altered carbonate phases in situ using microsampling techniques guided by non-destructive elemental mapping. Organic carbon isotope values were measured by spatially-resolved bulk analyses, and in situ using secondary ion mass spectrometry to target microscale domains of organic material trapped within inorganic carbon matrixes. Total observed fractionation of 13C ranges from -29 to -45‰. Our data are consistent with studies of younger Archean rocks that host biogenic stromatolites and organic-inorganic carbon pairs showing greater fractionation than expected for Rubisco fixation alone. We conclude that organic matter was fixed and/or remobilized by at least one metabolism in addition to the CBB cycle, possibly by the Wood-Ljungdahl pathway or methanogenesis-methanotrophy, in a shallow-water marine environment during the Paleoarchean.

  18. Oxygen isotope ratios of the Icelandic crust

    International Nuclear Information System (INIS)

    Hattori, K.; Muehlenbachs, K.

    1982-01-01

    Oxygen isotope ratios of hydrothermally altered basalts from depth of up to approx.3 km are reported from three localities in Iceland: International Research Drilling Project (IRDP) core at Reydarfjordur, eastern Iceland (Tertiary age); drill cuttings from Reykjavik (Plio-Pleistocene age); and Halocene drill cuttings from the active Krafla central volcano. Whole rock samples from these three localities have delta 18 O values averaging +3.9 +- 1.3, +2.4 +- 1.1, and -7.7 +- 2.4%, respectively. The observed values in the deeper samples from Krafla are as low as the values for any rocks previously reported. There seems to be a slight negative gradient in delta 18 O with depth at the former two localities and a more pronounced one at Krafla. Oxygen isotope fractionations between epidote and quartz and those between calcite and fluid suggests that the basalts were altered at temperatures of 300 0 --400 0 C. Low deltaD and delta 18 O of epidote and low delta 34 S of anhydrite indicate that the altering fluids in all three areas originated as meteoric waters and have undergone varied 'oxygen shifts'. Differences in the 18 O shift of the fluids are attributed to differences in hydrothermal systems; low water/rock ratios ( 5) at Krafla. The convective hydrothermal activity, which is probably driven by silicic magma beneath the central volcanoes, has caused strong subsolidus depletion of 18 O in the rocks. The primary-magnetic delta 18 O value of the rocks in the Tertiary IRDP core was about +3.9%, which is lower than that obtained for fresh basalt from other places. Such exceptionally low delta 18 O magmas are common in Iceland and may occur as the result of oxygen isotope exchange with or assimilation of altered rocks that form a thick sequence beneath the island due to isostatic subsidence

  19. Carbon Isotope Characterization of Organic Intermediaries in Hydrothermal Hydrocarbon Synthesis by Pyrolysis-GC-MS-C-IRMS

    Science.gov (United States)

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

    2010-01-01

    We report results of experiments designed to characterize the carbon isotope composition of intermediate organic compounds produced as a result of mineral surface catalyzed reactions. The impetus for this work stems from recently reported detection of methane in the Martian atmosphere coupled with evidence showing extensive water-rock interaction during Martian history. Abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions may be one possible process responsible for methane generation on Mars, and measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible isotope measurements. Our isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-Combustion-Isotope Ratio Mass Specrometry (Py-GC-MS-C-IRMS). Others have conducted similar pyrolysis-IRMS experiments on low molecular weight organic acids (Dias, et al, Organic Geochemistry, 33 [2002]). Our technique differs in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of the organic compounds. A sample of carboxylic acid (mixture of C1 through C6) was pyrolyzed at 100 XC and passed through the GC-MS-C-IRMS (combusted at 940 XC). In order to test the reliability of our technique we compared the _13C composition of different molecular weight organic acids (from C1 through C6) extracted individually by the traditional sealed-tube cupric oxide combustion (940 XC) method with the _13C produced by our pyrolysis technique. Our data indicate that an average 4.3. +/-0.5. (V

  20. Carbon isotope analysis of carbonaceous compounds in Puget Sound and Lake Washington

    International Nuclear Information System (INIS)

    Swanson, J.R.

    1980-01-01

    A new method has been developed and tested for determining chronological profiles of organic pollutants. This method, Carbon Isotope Analysis (CIA), involves measurements of 12 C, 13 C and 14 C in carbonaceous compounds found in layers of sediment. Lipids, total aliphatic hydrocarbons (TAHs) and polycyclic aromatic hydrocarbons (PAHs) are separated from kg quantities of sediment. Large Soxhlet extractors are used to remove the extractable organics, using ultra-pure benzene-methanol solution and having an extraction efficiency of about 86% for compounds with boiling points higher than n-tetradecane (n-C 14 ). The basic steps in compound separation include freeze-drying, extraction, fractionation, column chromatography and evaporation. Isolating the TAH and PAH fractions is accomplished by eluting samples from Sephadex and alumina/silica-gel columns. The amount of each fraction recovered is determined by converting the hydrocarbons to carbon dioxide and measuring this gas manometrically. Variations in 12 C and 13 C abundances for carbonaceous compounds are primarily due to thermodynamic, photosynthetic and metabolic fractionation processes. Thus, the source of a particular organic compound can often be determined by measuring its 13 C/ 12 C ratio. Combining the information from both the 13 C analysis and 14 C analysis makes source identification more certain. In addition, this investigation reviews carbon isotopic data and carbon cycling and analyzes organic pollution in two limited ecosystems (Puget Sound and Lake Washington). Specifically, distinct carbonaceous species are analyzed for pollution in sediments of Lake Washington, Elliott Bay, Commencement Bay, central Puget Sound and northern Puget Sound near the Cherry Point oil refineries

  1. Carbon-Isotopic Analysis of Individual Pigments by HPLC-Moving Wire-IRMS

    Science.gov (United States)

    Sessions, A. L.; Keely, B. J.; Hayes, J. M.

    2003-12-01

    We have developed a method for directly analyzing the carbon isotope ratios of individual pigments, including chlorophyll (chl) and its derivatives, by coupling a high-performance liquid chromatograph (HPLC) to an isotope-ratio mass spectrometer (IRMS) via a novel `moving-wire' interface. Pigments were separated on a reversed-phase C18 column, using a binary gradient modified from Airs et al. (2001, J. Chrom. A 917, 167-177). The HPLC effluent was dried onto a continuously-spooling nickel wire, and the involatile sample residue was combusted to CO2 and transferred to the IRMS for isotopic analysis. Replicate analyses of a standard solution yield precision for delta13C of better than 0.2‰ for injections containing ~5 μ g of chl-a. A five-fold improvement in sensitivity should be attainable using capillary HPLC to further reduce solvent volumes. The biomarker potential of tetrapyrrole pigments, combined with the geochemical information recorded by isotopic compositions, makes this combination a potent tool for biogeochemical studies. As a demonstration, we analyzed chlorophyll degradation products in sediments from a lake and a salina. First, compounds derived from bacteriochlorophylls (bchl)-c and -d were extracted from sediment cores taken at Kirisjes Lake (Larsmann Hills, Antarctica). These pigments are products of green sulfur bacteria and indicate the presence of an anoxic photic zone. The δ 13C values of bchl-related compounds are near -25‰ . Using published fractionations for Chlorobium species to extrapolate, dissolved CO2 in Kirisjes Lake probably had a δ 13C value of -12 to -21‰ and was strongly influenced by the recycling of organic carbon, possibly including methane. Second, compounds derived from chl-a, bchl-c, and bchl-d were isolated from sediments taken below a living microbial mat in the hypersaline les Salines de la Trinital (South Catalonia, Spain). The sediments contain visible remnants of past microbial mats and pigment distributions

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

    Science.gov (United States)

    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 104 to 108 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 (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 D2O indicate that the number of D atoms incorporated during

  3. Determination of Light Water Reactor Fuel Burnup with the Isotope Ratio Method

    International Nuclear Information System (INIS)

    Gerlach, David C.; Mitchell, Mark R.; Reid, Bruce D.; Gesh, Christopher J.; Hurley, David E.

    2007-01-01

    For the current project to demonstrate that isotope ratio measurements can be extended to zirconium alloys used in LWR fuel assemblies we report new analyses on irradiated samples obtained from a reactor. Zirconium alloys are used for structural elements of fuel assemblies and for the fuel element cladding. This report covers new measurements done on irradiated and unirradiated zirconium alloys, Unirradiated zircaloy samples serve as reference samples and indicate starting values or natural values for the Ti isotope ratio measured. New measurements of irradiated samples include results for 3 samples provided by AREVA. New results indicate: 1. Titanium isotope ratios were measured again in unirradiated samples to obtain reference or starting values at the same time irradiated samples were analyzed. In particular, 49Ti/48Ti ratios were indistinguishably close to values determined several months earlier and to expected natural values. 2. 49Ti/48Ti ratios were measured in 3 irradiated samples thus far, and demonstrate marked departures from natural or initial ratios, well beyond analytical uncertainty, and the ratios vary with reported fluence values. The irradiated samples appear to have significant surface contamination or radiation damage which required more time for SIMS analyses. 3. Other activated impurity elements still limit the sample size for SIMS analysis of irradiated samples. The sub-samples chosen for SIMS analysis, although smaller than optimal, were still analyzed successfully without violating the conditions of the applicable Radiological Work Permit

  4. Cross sections for the production of Li and Be isotopes in carbon targets irradiated by 300 GeV protons

    International Nuclear Information System (INIS)

    Raisbeck, G.M.; Lestringuez, J.; Yiou, F.

    1975-01-01

    Cross sections for the production of Li and Be isotopes in carbon targets irradiated by 300 GeV protons were measured by mass spectrometry. The results are compared with lower energy measurements and discussed in terms of the variation of the cosmic ray L/M ratio in this energy region [fr

  5. Strontium concentrations and isotope ratios in a forest-river system in the South Qinling Mts., China.

    Science.gov (United States)

    Bu, Hongmei; Song, Xianfang; Zhang, Quanfa; Burford, Michele A

    2016-04-15

    The concentrations of dissolved strontium (Sr) and isotope ratios ((87)Sr/(86)Sr) in rainwater, river water, and water from forest soil are measured to investigate the contributions of these sources to a river during base flow conditions in the relatively pristine South Qinling Mountains, China. Dissolved Sr concentrations and (87)Sr/(86)Sr ratios vary significantly between different water types (p water samples including Ca(2+), Mg(2+), EC, and TDS (p water chemistry in the river water. Using the three-source mixing model, atmospheric inputs, carbonate, and silicate weathering contribute 74%, 20%, and 6% respectively to the dissolved Sr in the river water. This research has provided new insights into the contribution of sources of Sr to a river system in a mountainous catchment. Copyright © 2016 Elsevier Ltd. All rights reserved.

  6. Forensic analysis of explosives using isotope ratio mass spectrometry (IRMS)--part 1: instrument validation of the DELTAplusXP IRMS for bulk nitrogen isotope ratio measurements.

    Science.gov (United States)

    Benson, Sarah J; Lennard, Christopher J; Hill, David M; Maynard, Philip; Roux, Claude

    2010-01-01

    A significant amount of research has been conducted into the use of stable isotopes to assist in determining the origin of various materials. The research conducted in the forensic field shows the potential of isotope ratio mass spectrometry (IRMS) to provide a level of discrimination not achievable utilizing traditional forensic techniques. Despite the research there have been few, if any, publications addressing the validation and measurement uncertainty of the technique for forensic applications. This study, the first in a planned series, presents validation data for the measurement of bulk nitrogen isotope ratios in ammonium nitrate (AN) using the DELTA(plus)XP (Thermo Finnigan) IRMS instrument equipped with a ConFlo III interface and FlashEA 1112 elemental analyzer (EA). Appropriate laboratory standards, analytical methods and correction calculations were developed and evaluated. A validation protocol was developed in line with the guidelines provided by the National Association of Testing Authorities, Australia (NATA). Performance characteristics including: accuracy, precision/repeatability, reproducibility/ruggedness, robustness, linear range, and measurement uncertainty were evaluated for the measurement of nitrogen isotope ratios in AN. AN (99.5%) and ammonium thiocyanate (99.99+%) were determined to be the most suitable laboratory standards and were calibrated against international standards (certified reference materials). All performance characteristics were within an acceptable range when potential uncertainties, including the manufacturer's uncertainty of the technique and standards, were taken into account. The experiments described in this article could be used as a model for validation of other instruments for similar purposes. Later studies in this series will address the more general issue of demonstrating that the IRMS technique is scientifically sound and fit-for-purpose in the forensic explosives analysis field.

  7. Tracing contamination sources in soils with Cu and Zn isotopic ratios

    Energy Technology Data Exchange (ETDEWEB)

    Fekiacova, Z.; Cornu, S. [INRA, UR 1119 Géochimie des Sols et des Eaux, F-13100 Aix en Provence (France); Pichat, S. [Laboratoire de Géologie de Lyon (LGL-TPE), Ecole Normale Supérieure de Lyon, CNRS, UMR 5276, 69007 Lyon (France)

    2015-06-01

    Copper (Cu) and zinc (Zn) are naturally present and ubiquitous in soils and are important micronutrients. Human activities contribute to the input of these metals to soils in different chemical forms, which can sometimes reach a toxic level for soil organisms and plants. Isotopic signatures could be used to trace sources of anthropogenic Cu and Zn pollution. The aim of this paper is to determine whether it is possible to identify (i) Cu and Zn contamination in soils and their sources, on the basis of their isotopic signatures, and (ii) situations that are a priori favorable or not for tracing Cu and Zn pollution using the isotopic approach. Therefore, we compiled data from the literature on Cu and Zn isotopes in soils, rocks and pollutants and added to this database the results of our own research. As only a few studies have dealt with agricultural contamination, we also studied a soil toposequence from Brittany, France, that experienced spreading of pig slurry for tens of years. In the surface horizons of the natural soils, the δ{sup 65}Cu values vary from − 0.15 to 0.44‰ and the δ{sup 66}Zn from − 0.03 to 0.43‰. Furthermore, vertical variations along soil profiles range from − 0.95 to 0.44‰ for δ{sup 65}Cu and from − 0.53 to 0.64‰ for δ{sup 66}Zn values. We concluded that pedogenetic processes can produce isotopic fractionation, yet, it is not always discernible and can be overprinted by an exogenous isotopic signature. Furthermore, some contaminants are enriched in heavy Cu or in light Zn compared to the rock or soil, but no generalization can be made. The anthropogenic inputs can be identified based on stable Cu and Zn isotope ratios if the isotope ratios of the sources are different from those of the soil, which needs to be tested for each individual case. - Highlights: • Pedogenetic processes produce some Cu and Zn isotope fractionation. • Pollution with distinct isotopic signatures can be traced using Cu and Zn isotopes. • Tracing

  8. Tracing contamination sources in soils with Cu and Zn isotopic ratios

    International Nuclear Information System (INIS)

    Fekiacova, Z.; Cornu, S.; Pichat, S.

    2015-01-01

    Copper (Cu) and zinc (Zn) are naturally present and ubiquitous in soils and are important micronutrients. Human activities contribute to the input of these metals to soils in different chemical forms, which can sometimes reach a toxic level for soil organisms and plants. Isotopic signatures could be used to trace sources of anthropogenic Cu and Zn pollution. The aim of this paper is to determine whether it is possible to identify (i) Cu and Zn contamination in soils and their sources, on the basis of their isotopic signatures, and (ii) situations that are a priori favorable or not for tracing Cu and Zn pollution using the isotopic approach. Therefore, we compiled data from the literature on Cu and Zn isotopes in soils, rocks and pollutants and added to this database the results of our own research. As only a few studies have dealt with agricultural contamination, we also studied a soil toposequence from Brittany, France, that experienced spreading of pig slurry for tens of years. In the surface horizons of the natural soils, the δ 65 Cu values vary from − 0.15 to 0.44‰ and the δ 66 Zn from − 0.03 to 0.43‰. Furthermore, vertical variations along soil profiles range from − 0.95 to 0.44‰ for δ 65 Cu and from − 0.53 to 0.64‰ for δ 66 Zn values. We concluded that pedogenetic processes can produce isotopic fractionation, yet, it is not always discernible and can be overprinted by an exogenous isotopic signature. Furthermore, some contaminants are enriched in heavy Cu or in light Zn compared to the rock or soil, but no generalization can be made. The anthropogenic inputs can be identified based on stable Cu and Zn isotope ratios if the isotope ratios of the sources are different from those of the soil, which needs to be tested for each individual case. - Highlights: • Pedogenetic processes produce some Cu and Zn isotope fractionation. • Pollution with distinct isotopic signatures can be traced using Cu and Zn isotopes. • Tracing of the metal

  9. Stable isotope ratio mass spectrometry and physical comparison for the forensic examination of grip-seal plastic bags.

    Science.gov (United States)

    Taylor, Erica; Carter, James F; Hill, Jenny C; Morton, Carolyn; Daeid, Niamh Nic; Sleeman, Richard

    2008-05-20

    Plastic bags are frequently used to package drugs, explosives and other contraband. There exists, therefore, a requirement in forensic casework to compare bags found at different locations. This is currently achieved almost exclusively by the use of physical comparisons such as birefringence patterns. This paper discusses some of the advantages and shortcomings of this approach, and presents stable isotope ratio mass spectrometry (IRMS) as a supplementary tool for effecting comparisons of this nature. Carbon and hydrogen isotopic data are presented for sixteen grip-seal plastic bags from a wide range of sources, in order to demonstrate the range of values which is likely to be encountered. Both isotopic and physical comparison (specifically birefringence) techniques are then applied to the analysis of rolls of bags from different manufacturing lots from a leading manufacturer. Both approaches are able to associate bags from a common production batch. IRMS can be applied to small fragments which are not amenable to physical comparisons, and is able to discriminate bags which could be confused using birefringence patterns alone. Similarly, in certain cases birefringence patterns discriminate bags with similar isotopic compositions. The two approaches are therefore complementary. When more than one isotopically distinct region exists within a bag (e.g. the grip-seal is distinct from the body) the ability to discriminate and associate bags is greatly increased.

  10. A Graphite Isotope Ratio Method: A Primer on Estimating Plutonium Production in Graphite Moderated Reactors

    International Nuclear Information System (INIS)

    Gesh, Christopher J.

    2004-01-01

    The Graphite Isotope Ratio Method (GIRM) is a technique used to estimate the total plutonium production in a graphite-moderated reactor. The cumulative plutonium production in that reactor can be accurately determined by measuring neutron irradiation induced isotopic ratio changes in certain impurity elements within the graphite moderator. The method does not require detailed knowledge of a reactor's operating history, although that knowledge can decrease the uncertainty of the production estimate. The basic premise of the Graphite Isotope Ratio Method is that the fluence in non-fuel core components is directly related to the cumulative plutonium production in the nuclear fuel

  11. Results from an interlaboratory exercise on the determination of plutonium isotopic ratios by gamma spectrometry

    International Nuclear Information System (INIS)

    Ottmar, H.

    1981-07-01

    Results form interlaboratory comparison measurements on the determination of plutonium isotopic ratios by gamma spectrometry, organized by the ESARDA Working Group on Techniques and Standards for Nondestructive Analysis, are presented and discussed. Nine laboratories from nine countries or international organizations participated in the intercomparison exercise, which included both laboratories' own measurements on the plutonium isotopic reference materials NBS-SRM 946, 947, 948 and comparison analyses of gamma spectra from these materials distributed to the participating laboratories. Results from the intercomparison analyses have been used to reevaluate some gamma branching intensity ratios required for plutonium isotopic ratio measurements. (orig.) [de

  12. Biology and air–sea gas exchange controls on the distribution of carbon isotope ratios (δ13C in the ocean

    Directory of Open Access Journals (Sweden)

    A. Schmittner

    2013-09-01

    Full Text Available Analysis of observations and sensitivity experiments with a new three-dimensional global model of stable carbon isotope cycling elucidate processes that control the distribution of δ13C of dissolved inorganic carbon (DIC in the contemporary and preindustrial ocean. Biological fractionation and the sinking of isotopically light δ13C organic matter from the surface into the interior ocean leads to low δ13CDIC values at depths and in high latitude surface waters and high values in the upper ocean at low latitudes with maxima in the subtropics. Air–sea gas exchange has two effects. First, it acts to reduce the spatial gradients created by biology. Second, the associated temperature-dependent fractionation tends to increase (decrease δ13CDIC values of colder (warmer water, which generates gradients that oppose those arising from biology. Our model results suggest that both effects are similarly important in influencing surface and interior δ13CDIC distributions. However, since air–sea gas exchange is slow in the modern ocean, the biological effect dominates spatial δ13CDIC gradients both in the interior and at the surface, in contrast to conclusions from some previous studies. Calcium carbonate cycling, pH dependency of fractionation during air–sea gas exchange, and kinetic fractionation have minor effects on δ13CDIC. Accumulation of isotopically light carbon from anthropogenic fossil fuel burning has decreased the spatial variability of surface and deep δ13CDIC since the industrial revolution in our model simulations. Analysis of a new synthesis of δ13CDIC measurements from years 1990 to 2005 is used to quantify preformed and remineralized contributions as well as the effects of biology and air–sea gas exchange. The model reproduces major features of the observed large-scale distribution of δ13CDIC as well as the individual contributions and effects. Residual misfits are documented and analyzed. Simulated surface and subsurface

  13. Carbon isotopes in the ocean model of the Community Earth System Model (CESM1

    Directory of Open Access Journals (Sweden)

    A. Jahn

    2015-08-01

    Full Text Available Carbon isotopes in the ocean are frequently used as paleoclimate proxies and as present-day geochemical ocean tracers. In order to allow a more direct comparison of climate model results with this large and currently underutilized data set, we added a carbon isotope module to the ocean model of the Community Earth System Model (CESM, containing the cycling of the stable isotope 13C and the radioactive isotope 14C. We implemented the 14C tracer in two ways: in the "abiotic" case, the 14C tracer is only subject to air–sea gas exchange, physical transport, and radioactive decay, while in the "biotic" version, the 14C additionally follows the 13C tracer through all biogeochemical and ecological processes. Thus, the abiotic 14C tracer can be run without the ecosystem module, requiring significantly fewer computational resources. The carbon isotope module calculates the carbon isotopic fractionation during gas exchange, photosynthesis, and calcium carbonate formation, while any subsequent biological process such as remineralization as well as any external inputs are assumed to occur without fractionation. Given the uncertainty associated with the biological fractionation during photosynthesis, we implemented and tested three parameterizations of different complexity. Compared to present-day observations, the model is able to simulate the oceanic 14C bomb uptake and the 13C Suess effect reasonably well compared to observations and other model studies. At the same time, the carbon isotopes reveal biases in the physical model, for example, too sluggish ventilation of the deep Pacific Ocean.

  14. Carbon isotopes in the ocean model of the Community Earth System Model (CESM1)

    Science.gov (United States)

    Jahn, A.; Lindsay, K.; Giraud, X.; Gruber, N.; Otto-Bliesner, B. L.; Liu, Z.; Brady, E. C.

    2015-08-01

    Carbon isotopes in the ocean are frequently used as paleoclimate proxies and as present-day geochemical ocean tracers. In order to allow a more direct comparison of climate model results with this large and currently underutilized data set, we added a carbon isotope module to the ocean model of the Community Earth System Model (CESM), containing the cycling of the stable isotope 13C and the radioactive isotope 14C. We implemented the 14C tracer in two ways: in the "abiotic" case, the 14C tracer is only subject to air-sea gas exchange, physical transport, and radioactive decay, while in the "biotic" version, the 14C additionally follows the 13C tracer through all biogeochemical and ecological processes. Thus, the abiotic 14C tracer can be run without the ecosystem module, requiring significantly fewer computational resources. The carbon isotope module calculates the carbon isotopic fractionation during gas exchange, photosynthesis, and calcium carbonate formation, while any subsequent biological process such as remineralization as well as any external inputs are assumed to occur without fractionation. Given the uncertainty associated with the biological fractionation during photosynthesis, we implemented and tested three parameterizations of different complexity. Compared to present-day observations, the model is able to simulate the oceanic 14C bomb uptake and the 13C Suess effect reasonably well compared to observations and other model studies. At the same time, the carbon isotopes reveal biases in the physical model, for example, too sluggish ventilation of the deep Pacific Ocean.

  15. Tracing organic matter sources of estuarine tidal flat nematodes with stable carbon isotopes

    NARCIS (Netherlands)

    Moens, T.; Luyten, C.; Middelburg, J.J.; Herman, P.M.J.; Vincx, M.

    2002-01-01

    The present study explores the use of stable carbon isotopes to trace organic matter sources of intertidal nematodes in the Schelde estuary (SW Netherlands). Stable carbon isotope signatures of nematodes from a saltmarsh and 4 tidal flat stations were determined in spring and winter situations, and

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

    Science.gov (United States)

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

    2016-11-01

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

  17. Linking the distribution of carbon isotope ratios in soil carbonates and speleothems to climate conditions in the past: A model for the dependence of respiration rate on soil moisture

    Science.gov (United States)

    Liu, Y.; Ibarra, D. E.; Winnick, M.; Caves Rugenstein, J. K.; Oster, J. L.; Druhan, J. L.

    2017-12-01

    The carbon isotope compositions (δ13C) of atmospheric CO2, C3-origin organic carbon, and limestone epikarst differ substantially, resulting in variable δ13C signatures recorded in secondary soil carbonates and speleothems which represent a mixture of these sources. Even though this signal has been widely used in paleoclimate studies, the extent to which carbonate δ13C is influenced by the dynamic response of organic carbon respiration rates to soil moisture variations has yet to be fully evaluated [1]. Soils that are rewetted after a prolonged drought commonly display a peak in respiration rate followed by relaxation to a lower steady state in both lab incubation experiments and field observations. This transient behavior, known as the Birch effect, has been extensively observed across a broad range of locations and soil types, and may generate more than 50% of the total respired CO2 in some ecosystems [2]. Here, we seek to identify the influence of the Birch effect on carbonate δ13C records based on a moisture-dependent modeling approach. We report compiled respiration rates of soils from the literature and fit these data as a function of soil moisture, before imposing exponential dampening with depth and applying the resulting function in a production-diffusion equation [3]. We then implement a mass balance calculation for the δ13C value of carbonate precipitated from a mixture of atmospheric and respired CO2, including mass-dependent fractionation associated with diffusive transport. Our results offer a novel prediction for depth-resolved carbonate δ13C as a function of soil moisture, and suggest that Birch effect signals may be recorded in soil carbonates and influence the magnitude of carbonate δ13C variations in speleothems. Thus, we illustrate a prediction for the range of carbonate δ13C recorded in terrestrial carbonates and suggest that differences in the range of carbonate δ13C may indicate changes in soil moisture variability, providing a new

  18. Carbon and hydrogen isotope fractionation under continuous light: implications for paleoenvironmental interpretations of the High Arctic during Paleogene warming.

    Science.gov (United States)

    Yang, Hong; Pagani, Mark; Briggs, Derek E G; Equiza, M A; Jagels, Richard; Leng, Qin; Lepage, Ben A

    2009-06-01

    The effect of low intensity continuous light, e.g., in the High Arctic summer, on plant carbon and hydrogen isotope fractionations is unknown. We conducted greenhouse experiments to test the impact of light quantity and duration on both carbon and hydrogen isotope compositions of three deciduous conifers whose fossil counterparts were components of Paleogene Arctic floras: Metasequoia glyptostroboides, Taxodium distichum, and Larix laricina. We found that plant leaf bulk carbon isotopic values of the examined species were 1.75-4.63 per thousand more negative under continuous light (CL) than under diurnal light (DL). Hydrogen isotope values of leaf n-alkanes under continuous light conditions revealed a D-enriched hydrogen isotope composition of up to 40 per thousand higher than in diurnal light conditions. The isotope offsets between the two light regimes is explained by a higher ratio of intercellular to atmospheric CO(2) concentration (C (i)/C (a)) and more water loss for plants under continuous light conditions during a 24-h transpiration cycle. Apparent hydrogen isotope fractionations between source water and individual lipids (epsilon(lipid-water)) range from -62 per thousand (Metasequoia C(27) and C(29)) to -87 per thousand (Larix C(29)) in leaves under continuous light. We applied these hydrogen fractionation factors to hydrogen isotope compositions of in situ n-alkanes from well-preserved Paleogene deciduous conifer fossils from the Arctic region to estimate the deltaD value in ancient precipitation. Precipitation in the summer growing season yielded a deltaD of -186 per thousand for late Paleocene, -157 per thousand for early middle Eocene, and -182 per thousand for late middle Eocene. We propose that high-latitude summer precipitation in this region was supplemented by moisture derived from regionally recycled transpiration of the polar forests that grew during the Paleogene warming.

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

    Science.gov (United States)

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

    1993-01-01

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

  20. Nicotine, acetanilide and urea multi-level 2H-, 13C- and 15N-abundance reference materials for continuous-flow isotope ratio mass spectrometry.

    Science.gov (United States)

    Schimmelmann, Arndt; Albertino, Andrea; Sauer, Peter E; Qi, Haiping; Molinie, Roland; Mesnard, François

    2009-11-01

    Accurate determinations of stable isotope ratios require a calibration using at least two reference materials with different isotopic compositions to anchor the isotopic scale and compensate for differences in machine slope. Ideally, the delta values of these reference materials should bracket the isotopic range of samples with unknown delta values. While the practice of analyzing two isotopically distinct reference materials is common for water (VSMOW-SLAP) and carbonates (NBS 19 and L-SVEC), the lack of widely available organic reference materials with distinct isotopic composition has hindered the practice when analyzing organic materials by elemental analysis/isotope ratio mass spectrometry (EA-IRMS). At present only L-glutamic acids USGS40 and USGS41 satisfy these requirements for delta13C and delta15N, with the limitation that L-glutamic acid is not suitable for analysis by gas chromatography (GC). We describe the development and quality testing of (i) four nicotine laboratory reference materials for on-line (i.e. continuous flow) hydrogen reductive gas chromatography-isotope ratio mass-spectrometry (GC-IRMS), (ii) five nicotines for oxidative C, N gas chromatography-combustion-isotope ratio mass-spectrometry (GC-C-IRMS, or GC-IRMS), and (iii) also three acetanilide and three urea reference materials for on-line oxidative EA-IRMS for C and N. Isotopic off-line calibration against international stable isotope measurement standards at Indiana University adhered to the 'principle of identical treatment'. The new reference materials cover the following isotopic ranges: delta2H(nicotine) -162 to -45 per thousand, delta13C(nicotine) -30.05 to +7.72 per thousand, delta15N(nicotine) -6.03 to +33.62 per thousand; delta15N(acetanilide) +1.18 to +40.57 per thousand; delta13C(urea) -34.13 to +11.71 per thousand, delta15N(urea) +0.26 to +40.61 per thousand (recommended delta values refer to calibration with NBS 19, L-SVEC, IAEA-N-1, and IAEA-N-2). Nicotines fill a gap as

  1. Isotope ratio of carbon in lipids of the zooplankton from the Kuril-Kamchatka region of the Pacific Ocean

    International Nuclear Information System (INIS)

    Bordovskij, O.K.; Shirinskij, V.G.; Akhmet'eva, E.A.; AN SSSR, Novosibirsk. Inst. Geokhimii)

    1976-01-01

    Isotopic composition has been studied of carbon of lipids of zooplancton in Kuril-Kamchatka region in the depth range from the surface down to 7km. The main task of the research is the investigation of isotopic composition variations along the vertical line - in producing and consuming zones under fairly uniform thermal conditions. The study has revealed that biochemical content of plancton in Kuril-Kamchatka region is characterized by elevated content of organic matter, the quantity of which, expressed in Csup(org), comprises from 41.9 to 59.5% of the dry weigth, that is 1.5-2 times more than Csup(org) preservation in zooplancton in the tropical part of the Indian Ocean. The plancton at the depth of 100-200 m from the cold intermediate layer and from that of 1000-2000 m has proved to be the richest in organic matter and lipids. As for the lipids content and fractionation, the greatest differences are observed between the surface plancton and that located lower, including the maximal depth, that is, between the producing and consuming zones

  2. Carbon and nitrogen isotopic compositions of particulate organic matter and biogeochemical processes in the eutrophic Danshuei Estuary in northern Taiwan

    International Nuclear Information System (INIS)

    Liu, K.-K.; Kao, S.-J.; Wen, L.-S.; Chen, K.-L.

    2007-01-01

    The Danshuei Estuary is distinctive for the relatively short residence time (1-2 d) of its estuarine water and the very high concentration of ammonia, which is the dominant species of dissolved inorganic nitrogen in the estuary, except near the river mouth. These characteristics make the dynamics of nitrogen cycling distinctively different from previously studied estuaries and result in unusual isotopic compositions of particulate nitrogen (PN). The δ 15 N PN values ranging from - 16.4 per mille to 3.8 per mille lie in the lower end of nitrogen isotopic compositions (- 16.4 to + 18.7 per mille ) of suspended particulate matter observed in estuaries, while the δ 13 C values of particulate organic carbon (POC) and the C/N (organic carbon to nitrogen) ratios showed rather normal ranges from - 25.5 per mille to - 19.0 per mille and from 6.0 to 11.3, respectively. There were three major types of particulate organic matter (POM) in the estuary: natural terrigenous materials consisting mainly of soils and bedrock-derived sediments, anthropogenic wastes and autochthonous materials from the aquatic system. During the typhoon induced flood period in August 2000, the flux-weighted mean of δ 13 C POC values was - 24.4 per mille , that of δ 15 N PN values was + 2.3 per mille and that of C/N ratio was 9.3. During non-typhoon periods, the concentration-weighted mean was - 23.6 per mille for δ 13 C POC , - 2.6 per mille for δ 15 N PN and 8.0 for C/N ratio. From the distribution of δ 15 N PN values of highly polluted estuarine waters, we identified the waste-dominated samples and calculated their mean properties: δ 13 C POC value of - 23.6 ± 0.7 per mille , δ 15 N PN value of - 3.0 ± 0.1 per mille and C/N ratio of 8.0 ± 1.4. Using a three end-member mixing model based on δ 15 N PN values and C/N ratios, we calculated contributions of the three major allochthonous sources of POC, namely, wastes, soils and bedrock-derived sediments, to the estuary. Their contributions

  3. Insights into Wilson's Warbler migration from analyses of hydrogen stable-isotope ratios

    Science.gov (United States)

    Jeffrey F. Kelly; Viorel Atudorei; Zachary D. Sharp; Deborah M. Finch

    2002-01-01

    Our ability to link the breeding locations of individual passerines to migration stopover sites and wintering locations is limited. Stable isotopes of hydrogen contained in bird feathers have recently shown potential in this regard. We measured hydrogen stable-isotope ratios (deltaD) of feathers from breeding, migrating, and wintering Wilson's Warblers. Analyses...

  4. Improved constraints on in situ rates and on quantification of complete chloroethene degradation from stable carbon isotope mass balances in groundwater plumes

    Science.gov (United States)

    Höhener, Patrick; Elsner, Martin; Eisenmann, Heinrich; Atteia, Olivier

    2015-11-01

    Spills of chloroethenes (CEs) at industrial and urban sites can create groundwater plumes in which tetrachloro- and trichloroethene sequentially degrade to dichloroethenes, vinyl chloride (VC) and ethene, or ethane under reducing conditions. For detoxification, degradation must go beyond VC. Assessments based on ethene and ethane, however, are difficult because these products are volatile, may stem from alternative sources, can be further transformed and are not always monitored. To alternatively quantify degradation beyond VC, stable carbon isotope mass balances have been proposed where concentration-weighted CE isotope ratios are summed up and compared to the original source isotope ratio. Reported assessments, however, have provided not satisfactorily quantified results entailing greatly differing upper and lower estimates. This work proposes an integrative approach to better constrain the extent of total chloroethene degradation in groundwater samples. It is based on fitting of measured concentration and compound-specific stable carbon isotope data to an analytical reactive transport equation simulating steady-state plumes in two dimensions using an EXCEL spreadsheet. The fitting also yields estimates of degradation rates, of source width and of dispersivities. The approach is validated using two synthetic benchmark cases where the true extent of degradation is well known, and using data from two real field cases from literature.

  5. Cross sections for the production of Li and Be isotopes in carbon targets irradiated by 300 GeV protons

    International Nuclear Information System (INIS)

    Raisbeck, G.M.; Lestringuez, J.; Yiou, F.

    1975-01-01

    Cross sections for the production of Li and Be isotopes in carbon targets irradiated by 300 GeV protons have been measured by mass spectrometry. The results are compared with lower energy measurements and discussed in terms of the variation of the cosmic ray L/M ratio in the energy region [fr

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

    Science.gov (United States)

    Zhang, Naizhong; Yamada, Keita; Yoshida, Naohiro

    2014-05-01

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

  7. Complementary stable carbon isotope ratio and amount of substance measurements in sports anti-doping.

    Science.gov (United States)

    Cawley, Adam T; George, Adrian V

    2012-12-01

    The detection of steroids originating from synthetic precursors against a background of their chemically identical natural analogues has proven to be a significant challenge for doping control laboratories accredited by the World Anti-Doping Agency (WADA). The complementary application of gas chromatography-mass spectrometry (GC-MS) and gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) has been demonstrated to provide specific detection of endogenous steroid misuse for improved anti-doping analysis. Markers of synthetically derived steroids are reviewed on the basis of abnormal urinary excretions and low (13)C content. A combinatorial approach is presented for the interpretation of GC-MS and GC-C-IRMS data in the anti-doping context. This methodology can allow all relevant information concerning an individual's metabolism to be assessed in order to make an informed decision with respect to a doping violation. Copyright © 2012 John Wiley & Sons, Ltd.

  8. Sulfur isotope in nature. Determination of sulfur isotope ratios in coal and petroleum by mass spectrometry

    International Nuclear Information System (INIS)

    Derda, M.

    1999-01-01

    Elementary sulfur or in chemical compounds is one of the elements widespread in the earth's crust and biosphere. Its participation in earth's crust amounts to 0.26 % by weight. Measurement of isotope composition of natural samples can deliver many information about origin, creation and transformation ranges of rocks and minerals. Sulfur isotope ratio contained in minerals is variable and for this reason investigation of isotope sulfur composition can deliver useful information about the geochemistry of each component. Therefore in the investigated sample it is necessary to determine not only the content of sulfur but also the isotope composition of each component. Differentiation of contents of sulfur-34 in natural sulfur compounds can reach up to 110 per mile. So large divergences can be explained by a kinetic effect or by bacterial reduction of sulphates. In this report a wide review of the results of investigations of isotope sulfur compositions in coal and petroleum are presented as well as the methods for the preparation of samples for mass spectrometry analysis are proposed. (author)

  9. Intrinsic ratios of glucose, fructose, glycerol and ethanol 13C/12C isotopic ratio determined by HPLC-co-IRMS: toward determining constants for wine authentication.

    Science.gov (United States)

    Guyon, François; Gaillard, Laetitia; Salagoïty, Marie-Hélène; Médina, Bernard

    2011-09-01

    High-performance liquid chromatography linked to isotope ratio mass spectrometry (HPLC-co-IRMS) via a Liquiface© interface has been used to simultaneously determine (13)C isotope ratios of glucose (G), fructose (F), glycerol (Gly) and ethanol (Eth) in sweet and semi-sweet wines. The data has been used the study of wine authenticity. For this purpose, 20 authentic wines from various French production areas and various vintages have been analyzed after dilution in pure water from 20 to 200 times according to sugar content. If the (13)C isotope ratios vary according to the production area and the vintage, it appears that internal ratios of (13)C isotope ratios (R((13)C)) of the four compounds studied can be considered as a constant. Thus, ratios of isotope ratios are found to be 1.00 ± 0.04 and 1.02 ± 0.08 for R((13)C(G/F)) and R((13)C(Gly/Eth)), respectively. Moreover, R((13)C(Eth/Sugar)) is found to be 1.15 ± 0.10 and 1.16 ± 0.08 for R((13)C(Gly/Sugar)). Additions of glucose, fructose and glycerol to a reference wine show a variation of the R((13)C) value for a single product addition as low as 2.5 g/L(-1). Eighteen commercial wines and 17 concentrated musts have been analyzed. Three wine samples are suspicious as the R((13)C) values are out of range indicating a sweetening treatment. Moreover, concentrated must analysis shows that (13)C isotope ratio can be also used directly to determine the authenticity of the matrix.

  10. Distinguishing ectomycorrhizal and saprophytic fungi using carbon and nitrogen isotopic compositions

    Directory of Open Access Journals (Sweden)

    Weiguo Hou

    2012-05-01

    Full Text Available Ectomycorrhizal fungi, a group of widespread symbiotic fungi with plant, obtain carbon source from trees and improve plant mineral nutrient uptake with their widespread hyphal network. Ectomycorrhizal fungi can be used as inoculants to improve the survival rates of plantation. Saprophytic fungi use the nutrition from the debris of plant or animals, and it is difficult to distinguish the saprophytic and ectomycorrhizal fungi by morphological and anatomic methods. In this research, the differences of stable carbon and nitrogen isotopic compositions of these fungi were analyzed. The results showed that the abundances of 13C of were higher than those of ectomycorrhizal fungi and the abundances of 15N of saprophytic fungi were lower than those of ectomycorrhizal fungi. Such differences of stable carbon and nitrogen isotopic compositions between ectomycorrhizal fungi and saprophytic fungi can be ascribed to their different nutrition sources and ecological functions. These results collectively indicate that stable carbon and nitrogen isotopic compositions are an effective proxy for distinguishing between ectomycorrhizal and saprophytic fungi.

  11. The calculation of isotopic partition function ratios by a perturbation theory technique

    International Nuclear Information System (INIS)

    Singh, G.; Wolfsberg, M.

    1975-01-01

    The vibrational Hamiltonian of a molecule in the harmonic approximation, H = (1/2) Σ (g/subi/jp/subi/p/subj/ + f/subi/jq/subi/q/subj/), has been divided into a diagonal part (terms with i=j) and an off-diagonal part (inot-equalj), which is regarded as the perturbation. The vibrational partition function of the molecule is then calculated by Schwinger perturbation theory as the partition function of the unperturbed problem, corresponding to a collection of oscillators with frequencies 2πν/subi/' = (f/subi/ig/subi/i)/sup 1 / 2 /, plus perturbation correction terms which are calculated to second order. With the usual assumptions of isotope effect calculations that the molecular translations and rotations are classical and separable from the vibrations, the perturbation formulation of the vibrational partition function is easily transformed into a perturbation theory formulation of (reduced) isotopic partition function ratios. If, for example, the molecular potential function is expressed in terms of the displacements of bond stretches and bond angle bends from their respective equilibrium values, the unperturbed partition function ratio corresponds to the isotope effect expected for noninteracting bond-stretch and bond-angle-bend oscillators. Detailed comparison is made for a number of molecular systems of perturbation theory calculations of partition functions and isotopic partition function ratios with exact calculations carried out by actually obtaining the normal mode vibrational frequencies of the vibrational Hamiltonian. Good agreement is found. The utility of the perturbation theory formulation resides in the fact that it permits one to look at isotope effects in a very simple manner; some demonstrations are given

  12. Shifts in bryophyte carbon isotope ratio across an elevation × soil age matrix on Mauna Loa, Hawaii: do bryophytes behave like vascular plants?

    Science.gov (United States)

    Waite, Mashuri; Sack, Lawren

    2011-05-01

    The carbon isotope ratio (δ(13)C) of vascular plant leaf tissue is determined by isotope discrimination, primarily mediated by stomatal and mesophyll diffusion resistances and by photosynthetic rate. These effects lead to predictable trends in leaf δ(13)C across natural gradients of elevation, irradiance and nutrient supply. Less is known about shifts in δ(13)C for bryophytes at landscape scale, as bryophytes lack stomata in the dominant gametophyte phase, and thus lack active control over CO(2) diffusion. Twelve bryophyte species were sampled across a matrix of elevation and soil ages on Mauna Loa, Hawaii Island. We tested hypotheses based on previous findings for vascular plants, which tend to have less negative δ(13)C at higher elevations or irradiances, and for leaves with higher leaf mass per area (LMA). Across the matrix, bryophytes spanned the range of δ(13)C values typical of C(3) vascular plants. Bryophytes were remarkably similar to vascular plants in exhibiting less negative δ(13)C with increasing elevation, and with lower overstory cover; additionally δ(13)C was related to bryophyte canopy projected mass per area, a trait analogous to LMA in vascular plants, also correlated negatively with overstory cover. The similarity of responses of δ(13)C in bryophytes and vascular plants to environmental factors, despite differing morphologies and diffusion pathways, points to a strong direct role of photosynthetic rate in determining δ(13)C variation at the landscape scale.

  13. Hydrogen and oxygen stable isotope ratios of milk in the United States.

    Science.gov (United States)

    Chesson, Lesley A; Valenzuela, Luciano O; O'Grady, Shannon P; Cerling, Thure E; Ehleringer, James R

    2010-02-24

    Models of hydrogen and oxygen incorporation in human tissues recognize the impact of geographic location on the isotopic composition of fluid intake, but inputs can include nonlocal beverages, such as milk. Milk and cow drinking water were collected from dairies, and commercially available milk was purchased from supermarkets and fast food restaurants. It was hypothesized that milk water delta(2)H and delta(18)O values record geographic location information. Correlations between milk water isotope ratios and purchase location tap water were significant. However, the amount of variation in milk delta(2)H and delta(18)O values explained by tap water was low, suggesting a single estimation of fluid input isotope ratios may not always be adequate in studies. The delta(2)H and delta(18)O values of paired milk and cow drinking water were related, suggesting potential for geographical origin assignment using stable isotope analysis. As an application example, milk water delta(18)O values were used to predict possible regions of origin for restaurant samples.

  14. Sealing process with calcite in the Nojima active fault zone revealed from isotope analysis of calcite

    International Nuclear Information System (INIS)

    Arai, Takashi; Tsukahara, Hiroaki; Morikiyo, Toshiro

    2003-01-01

    The Nojima fault appeared on the surface in the northern part of Awaji Island, central Japan as a result of the Hyogo-ken Nanbu earthquake (1995, M=7.2). Active fault drilling was performed by the Disaster Prevention Research Institute (DPRI), Kyoto University, and core samples were retrieved from 1410 to 1710 m, which were composed of intact and fractured granodiorites. We obtained calcite samples and gas samples from the vein in marginal fracture and non-fracture zones. We analyzed the carbon and oxygen isotope ratios of calcite and carbon dioxide to investigate the characteristic isotope ratios of fluids in the active fault zone, to estimate the origins of fluids, and to determine the sealing process of fractures. The analyzed values of carbon and oxygen isotope ratios of calcite were -10.3 to -7.2 per mille, 18 to 23 per mille, respectively, and carbon isotope ratios of CO 2 were -21 to -17 per mille. If carbon isotope ratios of calcite were at equilibrium with those of CO 2 , the precipitation temperature of calcite is calculated to be 30 to 50 deg C. This temperature is consistent with the present temperature of the depth where drilling cores were retrieved. Oxygen isotope ratios of H 2 O that, precipitated calcite were calculated to be -1.8 to -5.5 per mille. These values indicate calcite were precipitated from mixed fluids of sea water and meteoric water. Therefore, the marginal fracture zone of the Nojima fault was sealed with calcite, which was generated from mixing of sea water and meteoric water in situ. (author)

  15. The magnesium isotope record of cave carbonate archives

    Directory of Open Access Journals (Sweden)

    S. Riechelmann

    2012-11-01

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

  16. Cross contamination in dual inlet isotope ratio mass spectrometers

    NARCIS (Netherlands)

    Meijer, H.A.J.; Neubert, R.E.M.; Visser, G.H.

    2000-01-01

    Since the early days of geochemical isotope ratio mass spectrometry there has always been the problem of cross contamination, i.e. the contamination of the sample gas with traces of reference gas land vice versa) in a dual inlet system and the analyzer itself. This was attributable to valve leakages

  17. Tracing contamination sources in soils with Cu and Zn isotopic ratios.

    Science.gov (United States)

    Fekiacova, Z; Cornu, S; Pichat, S

    2015-06-01

    Copper (Cu) and zinc (Zn) are naturally present and ubiquitous in soils and are important micronutrients. Human activities contribute to the input of these metals to soils in different chemical forms, which can sometimes reach a toxic level for soil organisms and plants. Isotopic signatures could be used to trace sources of anthropogenic Cu and Zn pollution. The aim of this paper is to determine whether it is possible to identify (i) Cu and Zn contamination in soils and their sources, on the basis of their isotopic signatures, and (ii) situations that are a priori favorable or not for tracing Cu and Zn pollution using the isotopic approach. Therefore, we compiled data from the literature on Cu and Zn isotopes in soils, rocks and pollutants and added to this database the results of our own research. As only a few studies have dealt with agricultural contamination, we also studied a soil toposequence from Brittany, France, that experienced spreading of pig slurry for tens of years. In the surface horizons of the natural soils, the δ(65)Cu values vary from -0.15 to 0.44‰ and the δ(66)Zn from -0.03 to 0.43‰. Furthermore, vertical variations along soil profiles range from -0.95 to 0.44‰ for δ(65)Cu and from -0.53 to 0.64‰ for δ(66)Zn values. We concluded that pedogenetic processes can produce isotopic fractionation, yet, it is not always discernible and can be overprinted by an exogenous isotopic signature. Furthermore, some contaminants are enriched in heavy Cu or in light Zn compared to the rock or soil, but no generalization can be made. The anthropogenic inputs can be identified based on stable Cu and Zn isotope ratios if the isotope ratios of the sources are different from those of the soil, which needs to be tested for each individual case. Copyright © 2015 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

    Brookman, Tom H.; Ambrose, Stanley H.

    2012-09-01

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

  19. Toward a simple, repeatable, non-destructive approach to measuring stable-isotope ratios of water within tree stems

    Science.gov (United States)

    Raulerson, S.; Volkmann, T.; Pangle, L. A.

    2017-12-01

    Traditional methodologies for measuring ratios of stable isotopes within the xylem water of trees involve destructive coring of the stem. A recent approach involves permanently installed probes within the stem, and an on-site assembly of pumps, switching valves, gas lines, and climate-controlled structure for field deployment of a laser spectrometer. The former method limits the possible temporal resolution of sampling, and sample size, while the latter may not be feasible for many research groups. We present results from initial laboratory efforts towards developing a non-destructive, temporally-resolved technique for measuring stable isotope ratios within the xylem flow of trees. Researchers have used direct liquid-vapor equilibration as a method to measure isotope ratios of the water in soil pores. Typically, this is done by placing soil samples in a fixed container, and allowing the liquid water within the soil to come into isotopic equilibrium with the headspace of the container. Water can also be removed via cryogenic distillation or azeotropic distillation, with the resulting liquid tested for isotope ratios. Alternatively, the isotope ratios of the water vapor can be directly measured using a laser-based water vapor isotope analyzer. Well-established fractionation factors and the isotope ratios in the vapor phase are then used to calculate the isotope ratios in the liquid phase. We propose a setup which would install a single, removable chamber onto a tree, where vapor samples could non-destructively and repeatedly be taken. These vapor samples will be injected into a laser-based isotope analyzer by a recirculating gas conveyance system. A major part of what is presented here is in the procedure of taking vapor samples at 100% relative humidity, appropriately diluting them with completely dry N2 calibration gas, and injecting them into the gas conveyance system without inducing fractionation in the process. This methodology will be helpful in making

  20. Calcium Isotope Fractionation during Carbonate Weathering in the Northern Guangdong, South China

    Science.gov (United States)

    Liu, F.; Mao, G.; Wei, G.; Zhang, Z.

    2017-12-01

    CO2 is consumed during the weathering of carbonates, whereas carbonates are precipitated rapidly in the oceans, which are pivotal to modulate atmospheric CO2, oceanic pH and climate. Calcium carbonate in limestone is one of the largest reservoirs of carbon at the Earth's surface, so calcium is an important element that links the lithosphere, hydrosphere, biosphere, and the atmosphere. Compared with silicate rocks, carbonate rocks have more rapid rates of physical and chemical erosions, so the carbonate weathering will respond more quickly to the climatic changes. In the southeast of China, enormous of carbonate rocks are widely distributed. Due to the influence of the subtropical monsoon climate, the rocks experienced strong chemical weathering and pedogenic process, resulting in red weathering crust of carbonate rocks. This type of weathering crust is geochemistry-sensitive and ecology-vulnerable, which can provide important insights into the recycle of supergene geochemistry in the karst areas. In this study, we report calcium isotopic compositions of saprolites from a weathering profile developed on argillaceous carbonate rocks in northern Guangdong, South China. The acid-leachable fraction, which was extracted by 1N hydrochloride acid, showed limited variation of δ44/40Ca(NIST 915a) spanning from 0.55 ± 0.06‰ (2SD) to 0.72 ± 0.05‰ (2SD) despite CaO content ranging from 0.01 wt.% to 45.7 wt.%, implying that Ca isotope didn't fractionate much which may due to the congruent dissolution of limestone minerals. In contrast, radiogenic 87Sr/86Sr ratios of the whole rocks changed with depth from 0.710086 ± 6 (2SE) at the base rock to 0.722164± 8 (2SE) at the top-soil, which are possibly attributed to the mixing effect between carbonate and silicate fractions. Sr is an analogue for Ca due to its similar ionic size and charge; however, these two systems can differ in certain respects. The coupled study of Ca and Sr will be helpful to verify sources of Ca and the