Science.gov

Sample records for carbon isotope ratios

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

    NASA Astrophysics Data System (ADS)

    Price, Gregory; Grimes, Stephen

    2015-04-01

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

  2. Stable carbon isotope ratios of ambient aromatic volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Kornilova, Anna; Huang, Lin; Saccon, Marina; Rudolph, Jochen

    2016-09-01

    Measurements of mixing ratios and stable carbon isotope ratios of aromatic volatile organic compounds (VOC) in the atmosphere were made in Toronto (Canada) in 2009 and 2010. Consistent with the kinetic isotope effect for reactions of aromatic VOC with the OH radical the observed stable carbon isotope ratios are on average significantly heavier than the isotope ratios of their emissions. The change of carbon isotope ratio between emission and observation is used to determine the extent of photochemical processing (photochemical age, [OH]dt) of the different VOC. It is found that [OH]dt of different VOC depends strongly on the VOC reactivity. This demonstrates that for this set of observations the assumption of a uniform [OH]dt for VOC with different reactivity is not justified and that the observed values for [OH]dt are the result of mixing of VOC from air masses with different values for [OH]dt. Based on comparison between carbon isotope ratios and VOC concentration ratios it is also found that the varying influence of sources with different VOC emission ratios has a larger impact on VOC concentration ratios than photochemical processing. It is concluded that for this data set the use of VOC concentration ratios to determine [OH]dt would result in values for [OH]dt inconsistent with carbon isotope ratios and that the concept of a uniform [OH]dt for an air mass has to be replaced by the concept of individual values of an average [OH]dt for VOC with different reactivity.

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

    NASA Astrophysics Data System (ADS)

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

    2004-07-01

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

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

    SciTech Connect

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

    2013-11-13

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

    Isotopic Ratio Mass Spectrometry (IRMS) is an effective toll to be used for drug product authentication. The isotopic composition could be used to assist in the differentiation between batches of drugs and assist in the identification of counterfeit materials on the market. Only two factors affect the isotopic ratios in pharmaceutical components: the isotopic composition of the raw materials and the synthetic processes performed upon them. Counterfeiting of pharmaceutical drugs threatens consumer confidence in drug products companies' economical well-being. In this preliminary study, the analyzed samples consist in two types of commercially available analgesics, which were purchases from Romanian pharmacies. Differences in δ13C between batches from -29.7 to -31.6% were observed, demonstrating that this method can be used to differentiate among individual drug batches and subsequently identify counterfeits on the market. On the other hand, carbon isotopic ratios differences among producers were recorded, the variations being between -31.3 to -34.9% for the same type of analgesic, but from different manufactures.

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

    We are investigating the sources of diamonds from southern Africa by studying both their carbon isotopic composition and chemical impurities. Our samples include macro-sized diamonds from River Ranch kimberlite in Zimbabwe and the Helam and Klipspringer kimberlitic deposits from South Africa, as well as micro-sized diamonds from Klipspringer and Premier kimberlites in South Africa. We have characterized the samples for their structurally bounded nitrogen, hydrogen and platelets defect using a Fourier Transmission Infrared Spectroscopy (FTIR). Using the DiaMap routine, open source software (Howell et al., 2012), IR spectra were deconvulated and quantified for their nitrogen (A, B and D components) and hydrogen contents. High to moderate nitrogen concentrations (1810 to 400 µg/g; 400 to 50 µg/g respectively) were found in diamonds from Klipspringer and Helam. Moderate to low (<50 µg/g) nitrogen concentrations were observed in diamonds from Premier and River Ranch. Type II diamonds, i.e. diamonds with no N impurities, which are presumed to have been derived from ultramafic sources, are found in the River Ranch deposit. The macro- and micro-size diamonds from the Klipspringer deposit display similar nitrogen defects, with higher nitrogen concentration and more frequent D components found in the macro-size diamonds. One of the first steps towards reliable carbon isotope studies is the development of calibration materials for SIMS carbon isotopic analyses. We have investigated candidate materials both from a polycrystalline synthetic diamond sheet and two natural gem quality diamonds from Juina (Brazil). Electron-based images of the synthetic diamond sheet, obtained using GFZ Potsdam's dual beam FIB instrument, show many diamond grains with diameters greater than 35 µm. SIMS testing of the isotopic homogeneity of the back and front sides of the synthetic sheets reveal similar 13C/12C ratio within a RSD of <1 ‰ . SIMS isotopic analyses of the two natural diamond RMs

  7. Carbon and nitrogen isotope ratios of juvenile winter flounder ...

    EPA Pesticide Factsheets

    Stable carbon and nitrogen isotope ratios were measured in the muscle tissues of young-of-the-year (YOY) winter flounder, Pseudopleuronectes americanus, collected from several estuarine systems along the coast of Rhode Island, USA. These systems included three coastal lagoons (Ninigret Pond, Green Hill Pond and Point Judith Pond), an estuarine river (Narrow River) and Narragansett Bay. Results from sampling over a three-year period showed some year-to-year variability for 13C within waterbodies; however, 15N values were not significantly different (P > 0.05) within systems among the three years studied. he 13C trends observed along transects in Narrow River and Narragansett Bay showed isotopically depleted terrestrial signals in the upper reaches of the estuaries and more positive values indicative of marine organic material in the lower regions of these systems. Significant differences (P < 0.05) in 15N were observed among estuarine systems. Fish from the coastal lagoons had the lowest 15N values followed by those from Narrow River and then Narragansett Bay. Some unexpected trends in 15N were observed within Narragansett Bay. The Bay has a strong north-south gradient in nutrient concentrations due to large sewage inputs in the upper Bay which was not reflected in flounder 15N values. As expected, YOY flounder from stations in the lower-Bay had depleted 15N values compared to those from the other locations. However, the 15N ratios o

  8. Mathematical modeling of stable carbon isotope ratios in natural gases^@?

    NASA Astrophysics Data System (ADS)

    Tang, Y.; Perry, J. K.; Jenden, P. D.; Schoell, M.

    2000-08-01

    A new approach is presented for mathematical modeling of stable carbon isotope ratios in hydrocarbon gases based on both theoretical and experimental data. The kinetic model uses a set of parallel first-order gas generation reactions in which the relative cracking rates of isotopically substituted (k∗) and unsubstituted (k) bonds are represented by the equation k∗/k=(Af∗/Af) exp(-ΔEa/RT), where R is the gas constant and T is temperature. Quantum chemistry calculations have been used to estimate the entropic (A f∗/A f) and enthalpic (ΔEa) terms for homolytic bond cleavage in a variety of simple molecules. For loss of a methyl group from a short-chain n-alkane (≤ C 6), for example, we obtain an average ΔEa of 42.0 cal/mol and an average A f∗/A f of 1.021. Expressed differently, 13C-methane generation is predicted to be 2.4% (24‰) slower than 12C-methane generation (from a short-chain n-alkane) in a sedimentary basin at 200°C but only 0.7% (7‰) slower in a laboratory heating experiment at 500°C. Similar calculations carried out for homolytic bond cleavage in other molecules show that with few exceptions, ΔEa varies between 0 and 60 cal/mol and A f∗/A f between 1.00 and 1.04. Examination of this larger data set reveals: (1) a weak sigmoid relationship between ΔEa and bond dissociation energy; and (2) a strong positive correlation between ΔEa and A f∗/A f. The significance of these findings is illustrated by fitting a kinetic model to chemical and isotopic data for the generation of methane from n-octadecane under isothermal closed-system conditions. For a specific temperature history, the fitted model provides quantitative relationships among methane carbon isotope composition, total methane yield and methane generation rate which may have relevance to the cracking of oil-prone kerogens and crude oil. The observed variability of the kinetic reactivity of various methane source rocks highlights the need to apply and adequately calibrate such

  9. USE OF FATTY ACID STABLE CARBON ISOTOPE RATIO TO INDICATE MICROBIAL CARBON SOURCE IN TROPICAL SOILS

    EPA Science Inventory


    We use measurements of the concentration and stable carbon isotope ratio of individual microbial phospholipid fatty acids (PLFAs) in soils as indicators of live microbial biomass levels, broad microbial community structure, and microbial carbon source. For studies of soil o...

  10. USE OF FATTY ACID STABLE CARBON ISOTOPE RATIO TO INDICATE MICROBIAL CARBON SOURCE IN TROPICAL SOILS

    EPA Science Inventory


    We use measurements of the concentration and stable carbon isotope ratio of individual microbial phospholipid fatty acids (PLFAs) in soils as indicators of live microbial biomass levels, broad microbial community structure, and microbial carbon source. For studies of soil o...

  11. Carbon and Oxygen Isotopic Ratios for Nearby Miras

    NASA Astrophysics Data System (ADS)

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

    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 μm spectra were measured to derive isotopic ratios for 12C/13C, 16O/17O, and 16O/18O. 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 ⊙ 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 16O/17O ratios, similar to that of group 1 presolar grains and in agreement with theoretical expectations for the composition of mass 1.2-2 M ⊙ stars after the first dredge-up. In contrast, the 16O/18O 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 16O/18O 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-rich grains, no star in our sample shows evidence of hot bottom burning, which is expected for

  12. BOREAS TE-5 Tree Ring and Carbon Isotope Ratio Data

    NASA Technical Reports Server (NTRS)

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

    2000-01-01

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

  13. Carbon, Hydrogen, and Oxygen Isotope Ratios of Cellulose from Plants Having Intermediary Photosynthetic Modes 1

    PubMed Central

    Sternberg, Leonel O'Reilly; Deniro, Michael J.; Ting, Irwin P.

    1984-01-01

    Carbon and hydrogen isotope ratios of cellulose nitrate and oxygen isotope ratios of cellulose from species of greenhouse plants having different photosynthetic modes were determined. When hydrogen isotope ratios are plotted against carbon isotope ratios, four clusters of points are discernible, each representing different photosynthetic modes: C3 plants, C4 plants, CAM plants, and C3 plants that can shift to CAM or show the phenomenon referred to as CAM-cycling. The combination of oxygen and carbon isotope ratios does not distinguish among the different photosynthetic modes. Analysis of the carbon and hydrogen isotope ratios of cellulose nitrate should prove useful for screening different photosynthetic modes in field specimens that grew near one another. This method will be particularly useful for detection of plants which show CAM-cycling. PMID:16663360

  14. Effects of carbonate leaching on foraminifer stable isotopes ratios

    NASA Astrophysics Data System (ADS)

    Obrochta, S.; Yokoyama, Y.; Sakai, S.; Ishimura, T.

    2011-12-01

    Stable carbon and oxygen isotope ratios were measured on 125 individual epifaunal and infaunal benthic foraminifers from two discrete Holocene intervals in a shallow-water sediment core (~ 450 m) from the Timor Sea. Methane seeps are common in the area, resulting in significant precipitation of secondary calcite that is confirmed by SEM photomicrographs and has likely resulted in inconsistent downcore results. To assess the degree of removal of contaminants, individual Uvigerina peregrina were subjected to varying degrees of pretreatment prior to analysis. All foraminifers received standard cleaning with ethanol and brief sonication. A subset were further cleaned and sonicated in a dilute HCl solution (~ 0.003 M). Foraminifer tests were photographed using both reflected light and scanning electron microscopes during the course of treatment to monitor the changing degree of contaminant removal as increasingly aggressive cleaning methods were employed. Visible contamination remained on individuals not subjected to HCl treatment. The leached individuals exhibit a lower overall relative standard deviation and consistent results within morphotype groups. Based on these results, a 2% value is expected to be typical of the Holocene, though further downcore analyses are pending restoration of equipment adversely effected by the Eastern Japan 3/11 earthquake.

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

    PubMed

    Rizal, Govinda; Karki, Shanta; Thakur, Vivek; Wanchana, Samart; Alonso-Cantabrana, Hugo; Dionora, Jacque; Sheehy, John E; Furbank, Robert; von Caemmerer, Susanne; Quick, William Paul

    2017-01-01

    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 in the

  16. Investigating controls on boron isotope ratios in shallow marine carbonates

    NASA Astrophysics Data System (ADS)

    Zhang, Shuang; Henehan, Michael J.; Hull, Pincelli M.; Reid, R. Pamela; Hardisty, Dalton S.; Hood, Ashleigh v. S.; Planavsky, Noah J.

    2017-01-01

    The boron isotope-pH proxy has been widely used to reconstruct past ocean pH values. In both planktic foraminifera and corals, species-specific calibrations are required in order to reconstruct absolute values of pH, due to the prevalence of so-called vital effects - physiological modification of the primary environmental signals by the calcifying organisms. Shallow marine abiotic carbonate (e.g. ooids and cements) could conceivably avoid any such calibration requirement, and therefore provide a potentially useful archive for reconstructions in deep (pre-Cenozoic) time. However, shallow marine abiotic carbonates could also be affected by local shifts in pH caused by microbial photosynthesis and respiration, something that has up to now not been fully tested. In this study, we present boron isotope measurements from shallow modern marine carbonates, from the Bahama Bank and Belize to investigate the potential of using shallow water carbonates as pH archives, and to explore the role of microbial processes in driving nominally 'abiogenic' carbonate deposition. For Bahama bank samples, our boron-based pH estimates derived from a range of carbonate types (i.e. ooids, peloids, hardground cements, carbonate mud, stromatolitic micrite and calcified filament micrite) are higher than the estimated modern mean-annual seawater pH values for this region. Furthermore, the majority (73%) of our marine carbonate-based pH estimates fall out of the range of the estimated pre-industrial seawater pH values for this region. In shallow sediment cores, we did not observe a correlation between measured pore water pH and boron-derived pH estimates, suggesting boron isotope variability is a depositional rather than early diagenetic signal. For Belize reef cements, conversely, the pH estimates are lower than likely in situ seawater pH at the time of cement formation. This study indicates the potential for complications when using shallow marine non-skeletal carbonates as marine pH archives

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

    PubMed Central

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

    2014-01-01

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

  18. Determination of Forest Canopy Carbon Respiration From FTIR Measurements of Carbon Dioxide Isotopic Ratios

    NASA Astrophysics Data System (ADS)

    Cambaliza, M. O.; Mount, G.; Lamb, B.; Westberg, H.

    2004-12-01

    Isotopic analysis of atmospheric carbon dioxide provides a means to understand the complex carbon exchange between the biosphere and the atmosphere. Measurements of isotopic concentrations have traditionally been done by laboratory mass spectrometry analysis of grab samples taken from distant field sites with consequent limits on the number and frequency of measurements. In this work, we describe the development of an insitu carbon dioxide isotope analysis method based on Fourier transform infrared (FTIR) spectroscopy. Using molecular absorption in a 4-pass 1-meter length cell in the 2100 to 2600 cm-1 region of the 12CO2 and 13CO2 isotopic vibration-rotation bands, concentrations of both isotopes are measured, and from their ratio, \\delta13CO2 is determined. Coupled with the disjunct eddy covariance technique, CO2 fluxes can also be measured. We demonstrate the capabilities of this technique using measurements in a poplar forest plantation near Boardman, Oregon. Beer's law and a nonlinear least squares analysis algorithm were used to analyze the data. Careful attention was paid to avoid analysis in spectral regions of nonlinear absorption. Sequential measurements were made at seven levels on a 25-meter tower erected in an 11-m canopy. Carbon dioxide concentrations are calculated to a precision of about 0.5 ppmv, and \\delta13CO2 to about 0.2‰ precision. In this work, we present initial results of temporal and vertical variations of CO2 concentrations and \\delta13CO2 in this forest.

  19. Spatial and Temporal Trends in Stable Carbon and Oxygen Isotope Ratios of Juvenile Winter Flounder

    EPA Science Inventory

    Isotopic ratios of fish otoliths have been used in numerous studies as natural tags or markers to aid the study of connectivity among fish populations. We investigated the use of spatial and temporal changes in the stable carbon and oxygen isotope ratios of otoliths to different...

  20. Spatial and Temporal Trends in Stable Carbon and Oxygen Isotope Ratios of Juvenile Winter Flounder

    EPA Science Inventory

    Isotopic ratios of fish otoliths have been used in numerous studies as natural tags or markers to aid the study of connectivity among fish populations. We investigated the use of spatial and temporal changes in the stable carbon and oxygen isotope ratios of otoliths to different...

  1. Precise carbon isotopic ratio analyses of micro amounts of carbonate and non-carbonate in basalt using continuous-flow isotope ratio mass spectrometry (CF-IRMS).

    PubMed

    Zha, Xiang-Ping; Gong, Bing; Zheng, Yong-Fei; Chen, Yi-Xiang

    2017-10-07

    Continuous-flow isotope ratio mass spectrometry (CF-IRMS) is a specialized technique used to quickly analyze very small amounts of sample. We have used CF-IRMS to assess the influences of sample weight and relative carbon content on the accuracy and precision of the δ(13) C values of micro amounts of carbonate and non-carbonate in silicate rocks. The analytical work was performed on a Gasbench II (GB) sample preparation device and on an Element Analyzer (EA), which were both interfaced to CF-IRMS instruments. Potential silicate matrix effects on the carbon isotopic analyses were investigated by measuring mixtures of calibrated carbon reference materials and quartz powder. The calibration lines, established by the measured raw values and the known values of three reference materials mixing with quartz powder, were used to calibrate the δ(13) C values of basalt samples from eastern China. The δ(13) C values measured by GB-CF-IRMS of one national carbonate reference material, GBW04416, deviate slightly from the known value for approximately 20~70 μg of carbonate contained in 4.5-mL vials; the smaller the sample size, the lower the measured δ(13) C values. External precision better than 0.1‰ (1σ, n=26) is achieved at a signal intensity for mass 44 of between 868 and 1614 mV, corresponding to a sample weight of 30.8~50.2 μg, whereas it is reduced to 0.27‰ (1σ, n=34) at a signal intensity between 519 and 1614 mV, corresponding to a sample weight of 21.1~50.2 μg. In the EA-CF-IRMS experiments non-carbonate carbon, at high carbon concentration (greater than 800 ppm) and at optimum sample weights, the accuracy and precision are both better than 0.2‰. For carbon concentrations less than 500 ppm, the measured δ(13) C values deviate from the average by up to -1.2‰ and the precision is 0.74‰. The measured δ(13) C values decrease substantially at lower carbon concentration and higher sample weights, and poorer precision is obtained. Suggestions are made to

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

    EPA Science Inventory

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

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

    EPA Science Inventory

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

  4. Oxygen-18 Carbon Dioxide Isotope Ratio in Mars Atmosphere

    NASA Astrophysics Data System (ADS)

    Kostiuk, T.; Livengood, T. A.; Hewagama, T.; Smith, R.; Fast, K. E.; Annen, J.; Sonnabend, G.; Sornig, M.

    2012-09-01

    The determination of isotopic ratios on Mars is important to the study of atmospheric evolution [1]. The relative abundance of isotopes of CO2 provides insight into the loss of Mars' primordial atmosphere. Isotopic ratios also provide markers in the study of geochemistry of Mars meteorites and future returned samples formed in equilibrium with ambient atmosphere, and are probes of biogenic and abiotic chemistry, which differ in isotope fractionation. Due to its lesser gravity and relatively thin residual atmosphere, Mars' atmosphere should be enriched in heavy isotopes [1]. However Viking [2] results indicated an Earth-like singly substituted oxygen-18 CO2 isotopic ratio, 18OCO/OCO, with δ18O = 0±50‰ relative to Vienna Standard Mean Ocean Water (VSMOW). By comparison, isotopic ratios in Earth atmospheric CO2 are not uniquely defined due to seasonal and biotic variability, but have a range 0-41‰ relative to VSMOW [3, 4]. Phoenix lander TEGA [3] measurements found a modest enrichment of δ18O = 31.0±5.7‰. Only the Viking and Phoenix landers have carried a mass spectrometer to Mars, so far, until the arrival of Mars Science Laboratory in August 2012. Using ground-based spectroscopic techniques Krasnopolsky et al. [5] also found modest enrichment δ18O = 18±18‰. We present results from fully resolved spectroscopic measurements near 10.6 μm of both the normal and singly substituted oxygen- 18 CO2 lines, taken with the Goddard Space Flight Center Heterodyne Instrument for Planetary Winds And Composition (HIPWAC) at the NASA Infrared Telescope Facility on Mauna Kea, Hawaii. Measurements with spectral resolving power λ/Δλ=107 were obtained in October 2007 with an instantaneous field-of-view on the planet of ~1 arcsec, at the locations shown in Fig. 1 as open squares. The solid and broken line tracks show Mars SPICAM measurements of ozone corresponding to ozone measurements also obtained with HIPWAC and shown as hatched and solid regions [6]. Figure 1

  5. On-site isotopic analysis of dissolved inorganic carbon using an isotope ratio infrared spectrometer

    NASA Astrophysics Data System (ADS)

    Stoltmann, Tim; Mandic, Magda; Stöbener, Nils; Wapelhorst, Eric; Aepfler, Rebecca; Hinrichs, Kai-Uwe; Taubner, Heidi; Jost, Hj; Elvert, Marcus

    2016-04-01

    An Isotope Ratio Infrared Spectrometer (IRIS) has been adapted to perform measurements of δ13C of dissolved inorganic carbon (DIC) in marine pore waters. The resulting prototype allowed highly automated analysis of δ13C isotopic ratios and CO2 concentration. We achieved a throughput of up to 70 samples per day with DIC contents as low as 1.7 μmol C. We achieved an internal precision of 0.066 ‰ and an external precision of 0.16 ‰, which is comparable to values given for Isotope Ratio Mass Spectrometers (IRMS). The prototype instrument is field deployable, suitable for shipboard analysis of deep sea core pore waters. However, the validation of the prototype was centered around a field campaign in Eckernförde Bay, NW- Baltic Sea. As a proof of concept, a shallow site within an area of submarine groundwater discharge (SGD) and a site outside this area was investigated. We present profiles of δ13C of DIC over 50 cm exhibiting well understood methane turnover processes (anaerobic oxidation of methane). At the lowest point below the seafloor, microbial reduction of CO2 to CH4 dominates. 12CO2 is reduced preferentially over 13CO2, leading to more positive δ13C values in the remaining DIC pool; in layers closer to the surface, the oxidation of CH4 to CO2 becomes more prominent. Since the CH4 pool is enriched in 12C a shift to more negative δ13C can be observed in the DIC pool. In the upper 15 cm, the pore water DIC mixes with the sea water DIC, increasing δ13C again. Finally, we will present recent developments to further improve performance and future plans for deployments on research cruises.

  6. On-site isotopic analysis of dissolved inorganic carbon using an isotope ratio infrared spectrometer

    NASA Astrophysics Data System (ADS)

    Jost, H. J. H.; Stoltmann, T.; Stöbener, N.; Wapelhorst, E.; Mandic, M.; Aepfler, R.; Hinrichs, K. U.; Taubner, H.; Elvert, M.

    2015-12-01

    An Isotope Ratio Infrared Spectrometer (IRIS) has been adapted to perform measurements of δ13C of dissolved inorganic carbon (DIC) in marine pore waters. The resulting prototype allowed highly automated analysis of δ13C isotopic ratios and CO2 concentration. We achieved a throughput of up to 70 samples per day with DIC contents as low as 1.7 μmol C. We achieved an internal precision of 0.066 ‰ and an external precision of 0.16 ‰, which is comparable to values given for Isotope Ratio Mass Spectrometers (IRMS). The prototype instrument is field deployable, suitable for shipboard analysis of deep sea core pore waters. However, the validation of the prototype was centered around a field campaign in Eckernförde Bay, NW- Baltic Sea. As a proof of concept, a shallow site within an area of submarine groundwater discharge (SGD) and a site outside this area was investigated. We present profiles of δ13C of DIC over 50 cm exhibiting well understood methane turnover processes (anaerobic oxidation of methane). At the lowest point below the seafloor, microbial reduction of CO2 to CH4 dominates. 12CO2 is reduced preferentially over 13CO2, leading to more positive δ13C values in the remaining DIC pool; in layers closer to the surface, the oxidation of CH4 to CO2 becomes more prominent. Since the CH4 pool is enriched in 12C a shift to more negative δ13C can be observed in the DIC pool. In the upper 15 cm, the pore water DIC mixes with the sea water DIC, increasing δ13C again. Finally, we will present recent developments to further improve performance and future plans for deployments on research cruises.

  7. Determination of the (13)C/(12)C Carbon Isotope Ratio in Carbonates and Bicarbonates by (13)C NMR Spectroscopy.

    PubMed

    Pironti, Concetta; Cucciniello, Raffaele; Camin, Federica; Tonon, Agostino; Motta, Oriana; Proto, Antonio

    2017-10-09

    This paper is the first study focused on the innovative application of (13)C NMR (nuclear magnetic resonance) spectroscopy to determine the bulk (13)C/(12)C carbon isotope ratio, at natural abundance, in inorganic carbonates and bicarbonates. In the past, (13)C NMR spectroscopy (irm-(13)C NMR) was mainly used to measure isotope ratio monitoring with the potential of conducting (13)C position-specific isotope analysis of organic molecules with high precision. The reliability of the newly developed methodology for the determination of stable carbon isotope ratio was evaluated in comparison with the method chosen in the past for these measurements, i.e., isotope ratio mass spectrometry (IRMS), with very encouraging results. We determined the (13)C/(12)C ratio of carbonates and bicarbonates (∼50-100 mg) with a precision on the order of 1‰ in the presence of a relaxation agent, such as Cr(acac)3, and CH3(13)COONa as an internal standard. The method was first applied to soluble inorganic carbonates and bicarbonates and then extended to insoluble carbonates by converting them to Na2CO3, following a simple procedure and without observing isotopic fractionation. Here, we demonstrate that (13)C NMR spectroscopy can also be successfully adopted to characterize the (13)C/(12)C isotope ratio in inorganic carbonates and bicarbonates with applications in different fields, such as cultural heritage and geological studies.

  8. Microbial influences on local carbon isotopic ratios and their preservation in carbonate.

    PubMed

    Sumner, D Y

    2001-01-01

    Analysis of the carbon isotopic composition of carbonates is a valuable tool for studying microbial processes and looking for evidence of life. Microbial fixation of CO2 and conversion of organic carbon to CO2 can produce measurable delta 13C shifts in a microbial mat environment. Diffusion modeling demonstrates that substantial isotopic shifts can develop within the mat and in the diffusion boundary layer in the fluid when CO2 fixation is rapid and prolonged for several hours. Carbonates that precipitate during rapid CO2 fixation can preserve these microbially produced isotopic shifts. However, continued precipitation during intervals when respiration dominates or after the cessation of active microbial growth commonly dilutes autotrophic isotopic signatures. Thus, preserved isotopic signatures rarely reflect the magnitude of isotopic shifts within the mat. Interpretation of observed isotopic shifts in microbial mat carbonate depends on fully characterizing ambient delta 13C and eliminating other origins for isotopic shifts. The carbon isotopic composition of reservoirs can vary substantially, both on Earth and on other planets. Characterizing the reservoir composition and any changes through time is critical to evaluating microbially induced shifts. In addition, careful evaluation of non-microbial causes for shifts in isotopic composition is essential for a reliable interpretation. Complicating processes include recrystallization, calcite precipitation over extended periods of time, variable precipitation rates and water chemistry, and mixing of carbonates having different isotopic signatures.

  9. Mechanistic studies of sesquiterpene cyclases based on their carbon isotope ratios at natural abundance.

    PubMed

    Tan, Wenhua; Bartram, Stefan; Boland, Wilhelm

    2017-01-03

    During the process of terpene biosynthesis, C-C bond breaking and forming steps are subjected to kinetic carbon isotope effects, leading to distinct carbon isotopic signatures of the products. Accordingly, carbon isotopic signatures could be used to reveal the 'biosynthetic history' of the produced terpenoids. Five known sesquiterpene cyclases, regulating three different pathways, representing simple to complex biosynthetic sequences, were heterologously expressed and used for in vitro assays with farnesyl diphosphate as substrate. Compound specific isotope ratio mass spectrometry measurements of the enzyme substrate farnesyl diphosphate (FDP) and the products of all the five cyclases were performed. The calculated δ(13) C value for FDP, based on δ(13) C values and relative amounts of the products, was identical with its measured δ(13) C value, confirming the reliability of the approach and the precision of measurements. The different carbon isotope ratios of the products reflect the complexity of their structure and are correlated with the frequency of carbon-carbon bond forming and breaking steps on their individual biosynthetic pathways. Thus, the analysis of carbon isotopic signatures of terpenes at natural abundance can be used as a powerful tool in elucidation of associated biosynthetic mechanisms of terpene synthases and in future in vivo studies even without 'touching' the plant. © 2017 John Wiley & Sons Ltd.

  10. On-line measurement of intramolecular carbon isotope distribution of acetic acid by continuous-flow isotope ratio mass spectrometry.

    PubMed

    Yamada, Keita; Tanaka, Misato; Nakagawa, Fumiko; Yoshida, Naohiro

    2002-01-01

    Molecular and intramolecular carbon isotope measurements of acetic acid present in natural environments have been performed by off-line procedures. The off-line method is complicated and time-consuming and requires micromolar to millimolar amounts of sample. This limits geochemical isotopic studies, especially at the intramolecular level, on acetic acid present in natural samples. Here, we examine an on-line measurement of intramolecular carbon isotope distribution of acetic acid using continuous-flow isotope ratio mass spectrometry (CF-IRMS) coupled with an on-line pyrolysis system. This is achieved by measurement of the respective carbon isotope ratios of CH4 and CO2 produced by on-line pyrolysis of acetic acid. Results for authentic standards of pure acetic acid demonstrated the practicality of this on-line method, although the carbon isotope ratio of the methyl group could not be determined directly. The precision of the carbon isotope measurements was 0.4 per thousand (1sigma). The carbon isotope distribution determined by the on-line method was identical to that determined by the conventional off-line method within analytical error. The advantages of the on-line method compared with the conventional off-line method are that it is less laborious, requires less analytical time (less than one hour per sample) and, most importantly, uses smaller sample sizes (ca. 10 nanomole). An application of this on-line method to natural geochemical samples will provide an insight into the geochemical cycle of acetic acid. Copyright 2002 John Wiley & Sons, Ltd.

  11. Calibration strategies for the determination of stable carbon absolute isotope ratios in a glycine candidate reference material by elemental analyser-isotope ratio mass spectrometry.

    PubMed

    Dunn, Philip J H; Malinovsky, Dmitry; Goenaga-Infante, Heidi

    2015-04-01

    We report a methodology for the determination of the stable carbon absolute isotope ratio of a glycine candidate reference material with natural carbon isotopic composition using EA-IRMS. For the first time, stable carbon absolute isotope ratios have been reported using continuous flow rather than dual inlet isotope ratio mass spectrometry. Also for the first time, a calibration strategy based on the use of synthetic mixtures gravimetrically prepared from well characterised, highly (13)C-enriched and (13)C-depleted glycines was developed for EA-IRMS calibration and generation of absolute carbon isotope ratio values traceable to the SI through calibration standards of known purity. A second calibration strategy based on converting the more typically determined delta values on the Vienna PeeDee Belemnite (VPDB) scale using literature values for the absolute carbon isotope ratio of VPDB itself was used for comparison. Both calibration approaches provided results consistent with those previously reported for the same natural glycine using MC-ICP-MS; absolute carbon ratios of 10,649 × 10(-6) with an expanded uncertainty (k = 2) of 24 × 10(-6) and 10,646 × 10(-6) with an expanded uncertainty (k = 2) of 88 × 10(-6) were obtained, respectively. The absolute carbon isotope ratio of the VPDB standard was found to be 11,115 × 10(-6) with an expanded uncertainty (k = 2) of 27 × 10(-6), which is in excellent agreement with previously published values.

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

    NASA Astrophysics Data System (ADS)

    Wintel, J.; Hösen, E.; Koppmann, R.; Krebsbach, M.

    2013-04-01

    Measurements of stable carbon isotope ratios in VOC are a powerful tool to identify sources or to track both dynamical and chemical processes. During the field campaign ZEPTER-2 in autumn 2008 whole air samples were collected on board a Zeppelin NT airship in the planetary boundary layer and the lower free troposphere over south-west Germany. These samples were analysed with respect to VOC mixing ratios and stable carbon isotope ratios using a gas chromatograph combustion isotope ratio mass spectrometer. In this study we present the results for toluene, one of the major anthropogenic pollutants. In the boundary layer we observed rather fresh emissions mixing into the background and derived a toluene source isotope ratio of δ13C = -28.2 ± 0.5 ‰. Using the concept of the effective kinetic isotope effect, we were able to separate the effects of dilution processes and photochemical degradation in the free troposphere. We estimated the photochemical age of toluene in the atmosphere in two different ways (using isotope ratios and mixing ratios, respectively). The results differ strongly in the planetary boundary layer, probably due to mixing processes, but are compatible with each other in the free troposphere.

  13. Canopy photosynthesis estimated from sapflux and stable carbon isotope ratios in northern Idaho

    NASA Astrophysics Data System (ADS)

    Marshall, J. D.; Ubierna, N.; Kavanagh, K.; Pangle, R.; Powers, E.

    2008-12-01

    Canopy-scale estimates of photosynthesis have traditionally required either scaling up from a sample of leaf measurements or scaling down from eddy flux measurements contaminated by opposing carbon dioxide fluxes. We propose an alternative based on transpiration estimates using the well established Granier sapflux sensor and scaled by modifications of standard measurements of forest structure. The resulting sapflux estimates are converted to carbon uptake measurements by first estimating canopy conductance and then using stable carbon isotope ratios to estimate the ratio of carbon to water exchange. Carbon isotope ratios were measured on leaf bulk material, phloem contents, and the highly concentrated stem CO2 pool. As found elsewhere, leaves were highly depleted and did not provide adequate estimates. We used transfer conductances estimated in other work to adjust the carbon isotope ratios prior to estimating carbon-water exchange ratios. The resulting estimates were 11 Mg C ha-1 yr-1, well within the range to be expected based on net primar production (3.6 Mg C ha-1 yr-1) in these stands. We observed seasonal variation caused by both canopy conductance and changes in \\d13C. This method of estimating canopy photosynthesis provides an important test of one of the key, and hitherto poorly constrained, components of carbon budget analyses.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    Zuiderweg, A. T.

    2012-09-01

    Within the realm of volatile organic compounds, hydrocarbons and halocarbons form a sizable proportion of carbon input to the atmosphere. Within these compound categories, the light non-methane hydrocarbons (NMHC, two to seven carbon atoms) and monocarbon halocarbons have a special place as these have strong, if not exclusive, anthropogenic (human-caused) sources. With common atmospheric molar mixing ratios in the parts-per-trillion (10-12 mole/mole) to parts-per-billion (10-9 mole/mole) range, these trace gases, though decidedly minor constituants of the atmosphere, have diverse consequences due to their atmospheric presence and their removal processes. Effects range from causing ground level air pollution and resulting hazards to health, to contributing to anthropogenic climate change and the destruction of the ozone layer in the stratosphere, among many others. The existance of stable isotopes (otherwise identical atoms with varying amounts of neutrons that do not spontaneously disintegrate) in several elements relevant to atmospheric chemistry and physics is a boon to research. Their presence in molecules is detectable by mass and cause small intra- and intermolecular property changes. These changes range from the physical (e.g. boiling point variation) to the chemical (reaction rate variation) and can influence external interactions as well. The measurement of the ratio of a minor stable isotope of an element to the major one (the stable isotope ratio) can be used to establish source fingerprints, trace the interaction dynamics, and refine the understanding of the relative contribution of sources and sinks to the atmosphere as a whole. The stable minor stable isotope of carbon, 13C, has a natural abundance of approximately 1.1 %. It has a sufficient fractional mass difference from its major isotope as to cause significant effects, making it ideal for measuring the ratios and properties of hydro- and halocarbons. In order to enable a better understanding of the

  16. Stable hydrogen and carbon isotope ratios of extractable hydrocarbons in the Murchison meteorite

    NASA Technical Reports Server (NTRS)

    Krishnamurthy, R. V.; Epstein, S.; Pizzarello, S.; Cronin, J. R.; Yuen, G. U.

    1991-01-01

    A fairly fool-proof method to ensure that the compounds isolated from meteorites are truly part of the meteorites and not an artifact introduced by exposure to the terrestrial environment, storage, or handling is presented. The stable carbon and hydrogen isotope ratios in several of the chemical compounds extracted from the Murchison meteorite were measured. The results obtained by studying the amino acids in this meteorite gave very unusual hydrogen and carbon isotope ratios. The technique was extended to the different classes of hydrocarbons and the hydrocarbons were isolated using a variety of separation techniques. The results and methods used in this investigation are described in this two page paper.

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

    SciTech Connect

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

    2012-01-03

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

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

    SciTech Connect

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

    2012-01-01

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

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

    NASA Astrophysics Data System (ADS)

    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

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

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

  1. Global spatial distributions of nitrogen and carbon stable isotope ratios of modern human hair.

    PubMed

    Hülsemann, Frank; Lehn, Christine; Schneider, Sabine; Jackson, Glen; Hill, Sarah; Rossmann, Andreas; Scheid, Nicole; Dunn, Philip J H; Flenker, Ulrich; Schänzer, Wilhelm

    2015-11-30

    Natural stable carbon (δ(13)C) and nitrogen isotope ratios (δ(15)N) of humans are related to individual dietary habits and environmental and physiological factors. In forensic science the stable isotope ratios of human remains such as hair and nail are used for geographical allocation. Thus, knowledge of the global spatial distribution of human δ(13)C and δ(15)N values is an essential component in the interpretation of stable isotope analytical results. No substantial global datasets of human stable isotope ratios are currently available, although the amount of available (published) data has increased within recent years. We have herein summarised the published data on human global δ(13)C andδ(15)N values (around 3600 samples) and added experimental values of more than 400 additional worldwide human hair and nail samples. In order to summarise isotope ratios for hair and nail samples correction factors were determined. The current available dataset of human stable isotope ratios is biased towards Europe and North America with only limited data for countries in Africa, Central and South America and Southeast Asia. The global spatial distribution of carbon isotopes is related to latitude and supports the fact that human δ(13)C values are dominated by the amount of C4 plants in the diet, either due to direct ingestion as plant food, or by its use as animal feed. In contrast, the global spatial distribution of human δ(15)N values is apparently not exclusively related to the amount of fish or meat ingested, but also to environmental factors that influence agricultural production. There are still a large proportion of countries, especially in Africa, where there are no available data for human carbon and nitrogen isotope ratios. Although the interpretation of modern human carbon isotope ratios at the global scale is quite possible, and correlates with the latitude, the potential influences of extrinsic and/or intrinsic factors on human nitrogen isotope ratios

  2. Determination of the geographical origin of Chinese teas based on stable carbon and nitrogen isotope ratios*

    PubMed Central

    Zhang, Long; Pan, Jia-rong; Zhu, Cheng

    2012-01-01

    The objective of this study was to investigate the geographical origin of Chinese teas using carbon and nitrogen stable isotope ratio technology. The results showed that inter-provincial dispersion of teas in Guangdong (GD), Guangxi (GX), Hainan (HA), Fujian (FJ), Shandong (SD), Sichuan (SC), Chongqing (CQ), and Henan (HN) provinces was high, while in Zhejiang (ZJ), Hubei (HB), Yunnan (YN), and Anhui (AH) provinces, it was low. Tea samples from GD, GX, HA, and FJ provinces were clustered in one group and separated from those from AH and HB provinces. Thus, carbon and nitrogen stable isotope ratio technology could discriminate teas from among some provinces of China, but not from among others. Better separation might be obtained with a combination of isotopic ratios and other indexes, such as elemental data and organic components. PMID:23024049

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

    NASA Astrophysics Data System (ADS)

    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.

  4. Sample matrix effects on measured carbon and oxygen isotope ratios during continuous-flow isotope-ratio mass spectrometry.

    PubMed

    Levitt, Nicholas Paul

    2014-11-15

    Continuous-flow isotope-ratio mass spectrometry (CF-IRMS) is frequently used to analyze CO2 found in media such as air, breath, and soil pore space gas with the aid of a sample preparation and transfer device such as a Gasbench II. This study investigated the effect that matrices other than helium (He) have on the measured δ(13)C and δ(18)O isotope ratios of CO2. Identical CO2 was added to sample vials with matrices of pure He, pure N2, or a 21:79 mixture of O2/N2 and analyzed by a ThermoFinnigan Delta(Plus) XP isotope-ratio mass spectrometer coupled to a ThermoFinnigan Gasbench II. Variables such as CO2 concentration, sample analysis sequence, and sample matrix removal ('blanking') through manipulation of an injection and dilution open split were tested to identify systematic isotope ratio offsets between the different matrix types. The process of blanking induced a δ(13)C and δ(18)O offset of ≤0.2‰ between otherwise identical populations of CO2 samples in He. The (13)C/(12)C and (18)O/(16)O isotope ratios of CO2 sampled from pure N2 or a mixture of O2/N2 were found to be within 0.1 to 0.2‰ of those of an identical CO2 sampled from a He matrix when N2 or O2/N2 was removed prior to transport to the mass spectrometer. The measured oxygen isotope ratios of CO2 sampled from N2 and O2/N2 varied by as much as 0.6‰ and 4‰, respectively, if matrix gas was not removed prior to ionization. Sampling CO2 from matrices similar to air does not significantly affect the measured (13)C/(12)C and (18)O/(16)O isotope ratios of CO2 when a gas-handling procedure that includes the removal of matrix gas is utilized. This procedure is much preferable to introducing matrix gas and potentially isobaric interference to the ion source. Copyright © 2014 John Wiley & Sons, Ltd.

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

    NASA Astrophysics Data System (ADS)

    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. Observations and sources of carbon and nitrogen isotope ratio variation of pentaerythritol tetranitrate (PETN).

    PubMed

    Howa, John D; Lott, Michael J; Ehleringer, James R

    2014-11-01

    Isotope ratio analysis allows forensic investigators to discriminate materials that are chemically identical but differ in their isotope ratios. Here we focused on the discrimination of pentaerythritol tetranitrate (PETN), an explosive with military and civilian applications, using carbon (δ(13)C) and nitrogen (δ(15)N) isotope ratios. Our goal was to understand some of the factors influencing the isotope ratios of commercially manufactured PETN. PETN was isolated from bulk explosives using preparative HPLC, which reduced chemical and isotopic within-sample variability. We observed isotope ratio variation in a survey of 175 PETN samples from 22 manufacturing facilities, with δ(13)C values ranging from -49.7‰ to -28.0‰ and δ(15)N values ranging from -48.6‰ to +6.2‰. Both within-sample variability and variation of PETN within an explosive block were much smaller than between-sample variations. Isotopic ratios of PETN were shown to discriminate explosive blocks from the same manufacturer, whereas explosive component composition measurements by HPLC were not able to do so. Using samples collected from three industrial PETN manufacturers, we investigated the isotopic relationship between PETN and its reactants, pentaerythritol (PE) and nitric acid. Our observations showed that δ(13)C values of PETN were indistinguishable from that of the reactant pentaerythritol. Isotopic separation between nitric acid and PETN was consistent within each sampled manufacturer but differed among manufacturers, and was likely dependent upon reaction conditions. These data indicate that δ(13)C variation in PETN is dependent on δ(13)C variation of PE supplies, while δ(15)N variation in PETN is due to both nitric acid δ(15)N and reaction conditions. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

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

    USDA-ARS?s Scientific Manuscript database

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

  8. Stable Carbon and Oxygen Isotope Ratios of Otoliths Differentiate Winter Flounder (Pseudopleuonectes americanus) Habitats

    EPA Science Inventory

    Stable carbon (13C) and oxygen (18O) isotope ratios were measured in otoliths of juvenile winter flounder (Pseudopleuronectes americanus) collected from 18 nursery areas along the coast of Rhode Island, USA. Samples were obtained during June and July of 2002 from locations tha...

  9. Stable Carbon and Oxygen Isotope Ratios of Otoliths Differentiate Winter Flounder (Pseudopleuonectes americanus) Habitats

    EPA Science Inventory

    Stable carbon (13C) and oxygen (18O) isotope ratios were measured in otoliths of juvenile winter flounder (Pseudopleuronectes americanus) collected from 18 nursery areas along the coast of Rhode Island, USA. Samples were obtained during June and July of 2002 from locations tha...

  10. Stabel Carbon and Oxygen Isotope Ratios of Otoliths from Juvenile and Adult Winter Flounder

    EPA Science Inventory

    This study was designed to determine if stable carbon (13C) and oxygen (18O) isotope ratios in otoliths could be used to differentiate the locations that serve as important nursery areas for winter flounder along the Rhode Island, USA coastline. In recent years the populations ...

  11. Stabel Carbon and Oxygen Isotope Ratios of Otoliths from Juvenile and Adult Winter Flounder

    EPA Science Inventory

    This study was designed to determine if stable carbon (13C) and oxygen (18O) isotope ratios in otoliths could be used to differentiate the locations that serve as important nursery areas for winter flounder along the Rhode Island, USA coastline. In recent years the populations ...

  12. Carbon and nitrogen isotope ratios of juvenile winter flounder as indicators of inputs to estuarine systems

    EPA Science Inventory

    Stable carbon and nitrogen isotope ratios were measured in the muscle tissues of young-of-the-year (YOY) winter flounder, Pseudopleuronectes americanus, collected from several estuarine systems along the coast of Rhode Island, USA. These systems included three coastal lagoons (Ni...

  13. Carbon and nitrogen isotope ratios of juvenile winter flounder as indicators of inputs to estuarine systems

    EPA Science Inventory

    Stable carbon and nitrogen isotope ratios were measured in the muscle tissues of young-of-the-year (YOY) winter flounder, Pseudopleuronectes americanus, collected from several estuarine systems along the coast of Rhode Island, USA. These systems included three coastal lagoons (Ni...

  14. Correlation of carbon isotope ratios in the cellulose and wood extractives of Douglas-fir

    EPA Science Inventory

    Cellulose is usually isolated from the other components of plant material for analysis of carbon stable isotope ratios (δ13C). However, many studies have shown a strong correlation between whole-wood and cellulose δ13C values, prompting debate about the necessity of cellulose ext...

  15. Correlation of carbon isotope ratios in the cellulose and wood extractives of Douglas-fir

    EPA Science Inventory

    Cellulose is usually isolated from the other components of plant material for analysis of carbon stable isotope ratios (δ13C). However, many studies have shown a strong correlation between whole-wood and cellulose δ13C values, prompting debate about the necessity of cellulose ext...

  16. Tunable Diode Laser Measurements of Leaf-scale Carbon Isotope Discrimination and Ecosystem Respired Carbon and Oxygen Isotope Ratios in a Semi-arid Woodland

    NASA Astrophysics Data System (ADS)

    McDowell, N.; Chris, B.; Hanson, D.; Kern, S.; Meyer, C.; Pockman, W.; Powers, H.

    2005-12-01

    We present results and speculative interpretation of leaf-level carbon isotope discrimination and ecosystem respired carbon and oxygen isotope ratios from a semi-arid, C3/C4 woodland located in northern New Mexico, USA. Overstory leaf area index (LAI) is dominated by live juniper (Juniperus monosperma) trees with an LAI value of approximately 1.0 m2 per m2 ground area, and has a seasonally dynamic understory of mixed C3 forbs and C4 grasses and cacti, with a maximum LAI of 0.30 m2 per m2 ground area. Ecosystem respired carbon isotope ratios showed values characteristic of C3 dominated photosynthesis (Keeling plot intercepts of -35 to -22 per mil). Seasonal variation was typical of that found in wetter, C3 dominated forests, as was the dependence on climate (e.g. relationships with vapor pressure deficit, soil water content, and canopy conductance). Leaf-level carbon isotope discrimination of the junipers, measured by coupling a Li-Cor 6400 photosynthesis system to the TDL, provided discrimination-Ci and discrimination-vpd relationships consistent with measured ecosystem respired carbon isotope ratios. The oxygen isotope ratio of ecosystem respiration was dependent on rain water isotope composition, but was correlated with soil water content during rain-free periods. The cumulative effect of vapor pressure deficit after a rain event was tightly correlated with the oxygen isotope ratio of ecosystem respiration, suggesting the primary drivers are evaporative enrichment of soil water and perhaps nocturnal leaf enrichment. Instrument precision for carbon and oxygen isotope ratios of carbon dioxide is 0.06 to 0.18 per mil; however, overall precision is somewhat lower due to pressure and sampling effects.

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

    EPA Science Inventory

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

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

    EPA Science Inventory

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

  19. USE OF STABLE CARBON ISOTOPE RATIOS OF FATTY ACIDS TO EVALUATE MICROBIAL CARBON SOURCES IN TERRESTRIAL ENVIRONMENTS

    EPA Science Inventory

    We use measurements of the concentration and stable carbon isotopic ratio (D 13C) of individual microbial phospholipid fatty acids (PLFAs) in soils as indicators of live microbial biomass levels and microbial carbon source. We found that intensive sugar cane cultivation leads to ...

  20. Secular variation in carbon isotope ratios from Upper Proterozoic successions of Svalbard and East Greenland.

    PubMed

    Knoll, A H; Hayes, J M; Kaufman, A J; Swett, K; Lambert, I B

    1986-06-26

    Analyses of stratigraphically continuous suites of samples from Upper Proterozoic sedimentary successions of East Greenland, Spitsbergen and Nordaustlandet (Svalbard) provide an approximation to the secular variation in carbon isotope ratios during a geologically and biologically important period of change from around 900 million years ago to the beginning of the Cambrian period. Late Riphean carbonates and organic material show a stratigraphically useful pattern of enrichment in 13C relative to Phanerozoic or earlier Proterozoic samples. Isotopic compositions of isolated samples from other localities are consistent with a worldwide extended interval of enhanced organic burial and consequent net survival of oxidized material, probably O2, just before the initial radiation of metazoans.

  1. Towards a better understanding of magnesium-isotope ratios from marine skeletal carbonates

    NASA Astrophysics Data System (ADS)

    Hippler, Dorothee; Buhl, Dieter; Witbaard, Rob; Richter, Detlev K.; Immenhauser, Adrian

    2009-10-01

    This study presents magnesium stable-isotope compositions of various biogenic carbonates of several marine calcifying organisms and an algae species, seawater samples collected from the western Dutch Wadden Sea, and reference materials. The aim of this study is to explore the influence of mineralogy, taxonomy and environmental factors (e.g., seawater isotopic composition, temperature, salinity) on magnesium-isotopic (δ 26Mg) ratios of skeletal carbonates. Using high-precision multi-collector inductively coupled plasma mass spectrometry, we observed that the magnesium-isotopic composition of seawater from the semi-enclosed Dutch Wadden Sea is identical to that of open marine seawater. We further found that a considerable component of the observed variability in δ 26Mg values of marine skeletal carbonates can be attributed to differences in mineralogy. Furthermore, magnesium-isotope fractionation is species-dependent, with all skeletal carbonates being isotopically lighter than seawater. While δ 26Mg values of skeletal aragonite and high-magnesium calcite of coralline red algae indicate the absence or negligibility of metabolic influences, the δ 26Mg values of echinoids, brachiopods and bivalves likely result from a taxon-specific level of control on Mg-isotope incorporation during biocalcification. Moreover, no resolvable salinity and temperature effect were observed for coralline red algae and echinoids. In contrast, Mg-isotope data of bivalves yield ambiguous results, which require further validation. The data presented here, point to a limited use of Mg isotopes as temperature proxy, but highlight the method's potential as tracer of seawater chemistry through Earth's history.

  2. Site-specific carbon isotope analysis of aromatic carboxylic acids by elemental analysis/pyrolysis/isotope ratio mass spectrometry.

    PubMed

    Oba, Yasuhiro; Naraoka, Hiroshi

    2006-01-01

    Site-specific carbon isotope composition of organic compounds can provide useful information on their origin and history in natural environments. Site-specific isotope analyses of small amounts of organic compounds (sub-nanomolar level), such as short-chain carboxylic acids and amino acid analogues, have been performed using gas chromatography/pyrolysis/isotope ratio mass spectrometry (GC/pyrolysis/IRMS). These analyses were previously limited to volatile compounds. In this study, site-specific carbon isotope analysis has been developed for non-volatile aromatic carboxylic acids at sub-micromolar level by decarboxylation using a continuous flow elemental analysis (EA)/pyrolysis/IRMS technique. Benzoic acid, 2-naphthylacetic acid and 1-pyrenecarboxylic acid were pyrolyzed at 500-1000 degrees C by EA/pyrolysis/IRMS to produce CO2 for delta13C measurement of the carboxyl group. These three aromatic acids were most efficiently pyrolyzed at 750 degrees C. Conventional sealed-tube pyrolysis was also conducted for comparison. The delta13C values of CO2 generated by the continuous flow technique were within 1.0 per thousand of those performed by the conventional technique, indicating that the new continuous flow technique can accurately analyze the carbon isotopic composition of the carboxyl group in aromatic carboxylic acids. The new continuous flow technique is simple, rapid and uses small sample sizes, so this technique will be useful for characterizing the isotopic signature of carboxyl groups in organic compounds. Copyright 2006 John Wiley & Sons, Ltd.

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

    NASA Technical Reports Server (NTRS)

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

    2009-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    2009-01-01

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

  5. Determination of carbon isotopic measurement conditions for ceramide in skin using gas chromatography-combustion-isotope ratio mass spectrometry.

    PubMed

    Haraguchi, Hiroyuki; Yamada, Keita; Miyashita, Rumiko; Aida, Kazuhiko; Ohnishi, Masao; Gilbert, Alexis; Yoshida, Naohiro

    2014-01-01

    The ceramide (Cer) content of skin and glucosylceramide (GlcCer) intake affect skin moisture conditions, but their mutual relation in skin remains unclear. For clarification of that mutual relation, carbon stable isotopes ((12)C and (13)C) are useful as a tracer. However, carbon isotopic measurement has not been applied to the study of clarifying their skin moisturizing effects. Therefore, we used gas chromatography / combustion / isotope ratio mass spectrometry (GC-C-IRMS) to ascertain the appropriate conditions for carbon isotopic measurements using synthesized Cer (SCer) in substitution for very low concentrations of Cer in skin. SCer was derivatized to trimethylsilylated SCer (TMS-SCer) quantitatively using N-trimethylsilylimidazole (TMSI) depending on the amount of SCer. The derivatization rates were 75-85%. Excess TMSI was removed using three cycles of hexane-water distribution. Under these conditions, carbon isotopic measurements of TMS-SCer conducted using GC-C-IRMS showed high repeatability and good inter-day variation (S.D. < 0.3‰). The carbon stable isotope ratio value (δ(13)C) of SCer calculated using a mass balance equation was compared with δ(13)C of underivatized SCer, which was regarded as the actual δ(13)C of SCer obtained using sealed tube combustion method. The difference between the calculated δ(13)C of SCer and δ(13)C of the underivatized SCer depended on the TMSI reagent supplier and on the number of hydroxyl groups to be derivatized in SCer. For accurate δ(13)C of Cer in skin using GC-C-IRMS, the measured δ(13)C of a target TMS-Cer must be calculated using a correction factor representing the difference in δ(13)C of underivatized standard SCer from that of TMS-standard SCer having a structure resembling that of the target Cer in skin. In addition, we show that the same lot of TMSI reagent from a specific supplier must be used throughout the experiments.

  6. Evaluating the deep-ocean circulation of a global ocean model using carbon isotopic ratios

    NASA Astrophysics Data System (ADS)

    Paul, André; Dutkiewicz, Stephanie; Gebbie, Jake; Losch, Martin; Marchal, Olivier

    2016-04-01

    We study the sensitivity of a global three-dimensional biotic ocean carbon-cycle model to the parameterizations of gas exchange and biological productivity as well as to deep-ocean circulation strength, and we employ the carbon isotopic ratios δ13C and Δ14C of dissolved inorganic carbon for a systematic evaluation against observations. Radiocarbon (Δ14C) in particular offers the means to assess the model skill on a time scale of 100 to 1000 years relevant to the deep-ocean circulation. The carbon isotope ratios are included as tracers in the MIT general circulation model (MITgcm). The implementation involves the fractionation processes during photosynthesis and air-sea gas exchange. We present the results of sixteen simulations combining two different parameterizations of the piston velocity, two different parameterizations of biological productivity (including the effect of iron fertilization) and four different overturning rates. These simulations were first spun up to equilibrium (more than 10,000 years of model simulation) and then continued from AD 1765 to AD 2002. For the model evaluation, we followed the OCMIP-2 (Ocean Carbon-Cycle Model Intercomparision Project phase two) protocol, comparing the results to GEOSECS (Geochemical Ocean Sections Survey) and WOCE (World Ocean Circulation Experiment) δ13C and natural Δ14C data in the world ocean. The range of deep natural Δ14C (below 1000 m) for our single model (MITgcm) was smaller than for the group of different OCMIP-2 models. Furthermore, differences between different model parameterizations were smaller than for different overturning rates. We conclude that carbon isotope ratios are a useful tool to evaluate the deep-ocean circulation. Since they are also available from deep-sea sediment records, we postulate that the simulation of carbon isotope ratios in a global ocean model will aid in estimating the deep-ocean circulation and climate during present and past.

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

    PubMed

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

    2012-03-01

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

  8. CCQM-K140: carbon stable isotope ratio delta values in honey

    NASA Astrophysics Data System (ADS)

    Dunn, P. J. H.; Goenaga-Infante, H.; Goren, A. C.; Şimşek, A.; Bilsel, M.; Ogrinc, N.; Armishaw, P.; Hai, L.

    2017-01-01

    As there can be small but measureable differences in isotope ratios between different sources of the same element/compound/material, isotope ratio measurements are applied in a number of different fields including archaeology, environmental science, geochemistry, forensic science and ecology. Isotope ratios for the light elements (H, C, N, O and S) are typically reported as δ-values which are isotope ratios expressed relative to an internationally agreed standard (this standard is the zero-point on the scale), although absolute isotope ratios which are traceable to the SI have also been reported. The IAWG has been granted a traceability exception for the use of arbitrary delta scales until SI traceability can be established at the required level of uncertainty but this goal is some years away. While the CCQM IAWG has previously organised several pilot studies on isotope ratio determination (CCQM-P75: Stable isotope delta values in methionine, 2006; CCQM-P105: Sr isotope ratios in wine, 2008; CCQM-K98: Pb isotope ratios in bronze with additional delta values in CCQM-P134, 2011), it has been a number of years since delta values of light elements have been considered and there has been no key comparison (KC). Therefore, the IAWG has included the need for a KC (CCQM-K140) based on an arbitrary delta scale in its program to support ongoing requirements to demonstrate core capabilities as well as specific claims of measurement capability (CMCs) in this area. The performance of all five of the CCQM-K140 participants was very good, illustrating their ability to obtain accurate results for carbon isotope ratios, within the calibration range afforded by internationally agreed reference materials (δ13CVPDB-LSVEC between -47.32 % and +535.3 %) with measurement uncertainties of between 0.08 and 0.28 %. This was despite the fact that no two participants used exactly the same approach in terms of instrumentation or data treatment. Main text To reach the main text of this paper

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Classification of nine malathion emulsion samples by using carbon isotope ratios and the ratio of organic solvents.

    PubMed

    Suto, Nana; Kawashima, Hiroto

    2017-01-01

    The compound specific isotope analysis is nowadays an important and powerful tool in geochemical, environmental and forensics field. On November 2013, Aqli Foods Corporation in Japan dealt with complaints about stench from frozen foods produced. Subsequently, very high concentrations of organophosphorus pesticide as malathion, ethylbenzene and xylene were detected in recovered frozen foods. In particular case, we present the method to measure the stable carbon isotope ratio (δ(13)C) of nine malathion emulsion pesticides using gas chromatography/isotope ratio mass spectrometry (GC/IRMS) to identify the source. The δ(13)C values of malathion ranged from -30.6‰ to -29.5‰. Because malathion used in all malathion emulsions sold in Japan is imported from the same overseas company, Cheminova, Denmark. The δ(13)C values of ethylbenzene ranged from -28.2‰ to -20.8‰ and those of m,p-xylene from -28.7‰ to -25.2‰. The differences in the δ(13)C values may be because of the material itself and chemical processing. We also determined the ratio of ethylbenzene to m,p-xylene and finally categorized the nine malathion samples into five groups on the basis of this ratio and the δ(13)C values of ethylbenzene and m,p-xylene. The results of isotopic fractionation during volatilization (refrigerate, room temperature and incubator) was negligible small. Copyright © 2016 The Chartered Society of Forensic Sciences. Published by Elsevier Ireland Ltd. All rights reserved.

  11. Can amino acid carbon isotope ratios distinguish primary producers in a mangrove ecosystem?

    PubMed

    Larsen, Thomas; Wooller, Matthew J; Fogel, Marilyn L; O'Brien, Diane M

    2012-07-15

    The relative contribution of carbon from terrestrial vs. marine primary producers to mangrove-based food webs can be challenging to resolve with bulk carbon isotope ratios (δ(13)C). In this study we explore whether patterns of δ(13)C values among amino acids (AAs) can provide an additional tool for resolving terrestrial and marine origins of carbon. Amino acid carbon isotope ratios (δ(13)C(AA)) were measured for several terrestrial and marine primary producers in a mangrove ecosystem at Spanish Lookout Caye (SLC), Belize, using gas chromatography-combustion-isotope ratio mass spectrometry. The δ(13)C values of essential amino acids (δ(13)C(EAA)) were measured to determine whether they could be used to differentiate terrestrial and marine producers using linear discriminant analysis. Marine and terrestrial producers had distinct patterns of δ(13)C(EAA) values in addition to their differences in bulk δ(13)C values. Microbial mat samples and consumers (Crassostrea rhizophorae, Aratus pisonii, Littoraria sp., Lutjanus griseus) were most similar to marine producers. Patterns of δ(13)C(EAA) values for terrestrial producers were very similar to those described for other terrestrial plants. The findings suggest that δ(13)C(EAA) values may provide another tool for estimating the contribution of terrestrial and marine sources to detrital foodwebs. Preliminary analyses of consumers indicate significant use of aquatic resources, consistent with other studies of mangrove foodwebs. Copyright © 2012 John Wiley & Sons, Ltd.

  12. Stable carbon and oxygen isotopic analysis of atmospheric carbon monoxide using continuous-flow isotope ratio MS by isotope ratio monitoring of CO.

    PubMed

    Tsunogai, Urumu; Nakagawa, Fumiko; Komatsu, Daisuke D; Gamo, Toshitaka

    2002-11-15

    We have developed a rapid and simple measurement system for both content and stable isotopic compositions (13C and 18O) of atmospheric CO, using continuous-flow isotope ratio mass spectrometry by simultaneously monitoring the CO+ ion currents at masses 28, 29, and 30. The analytical system consisted sequentially of a sample trapping port (liquid nitrogen temperature silica gel and molecular sieve 5A), a gas dryer, a CO purification column (molecular sieve 5A), a cryofocusing unit, and a final purification column using a GC capillary. Analytical precision of 0.2 per thousand for 13C and 0.4 per thousand for 18O can be realized for samples that contain as little as 300 pmol of CO within 40 min for one sample analysis. Analytical blanks associated with the method are less than 1 pmol. The extent of analytical error in delta13C due to mass-independent fractionation of oxygen in natural CO is estimated to be less than 0.3 per thousand. Based on this system, we report herein a kinetic isotopic effect during CO consumption in soil.

  13. Concentrations and isotope ratios of carbon, nitrogen and sulfur in ocean-floor basalts

    USGS Publications Warehouse

    Sakai, H.; Marais, D.J.D.; Ueda, A.; Moore, J.G.

    1984-01-01

    Fresh submarine basalt glasses from Galapagos Ridge, FAMOUS area, Cayman Trough and Kilauea east rift contain 22 to 160 ppm carbon and 0.3 to 2.8 ppm nitrogen, respectively, as the sums of dissolved species and vesicle-filling gases (CO2 and N2). The large range of variation in carbon content is due to combined effect of depth-dependency of the solubility of carbon in basalt melt and varying extents of vapour loss during magma emplacement as well as in sample crushing. The isotopic ratios of indigenous carbon and nitrogen are in very narrow ranges,-6.2 ?? 0.2% relative to PDB and +0.2 ?? 0.6 %. relative to atmospheric nitrogen, respectively. In basalt samples from Juan de Fuca Ridge, however, isotopically light carbon (??13C = around -24%.) predominates over the indigenous carbon; no indigenous heavy carbon was found. Except for Galapagos Ridge samples, these ocean-floor basalts contain 670 to 1100 ppm sulfur, averaging 810 ppm, in the form of both sulfide and sulfate, whereas basalts from Galapagos Ridge are higher in both sulfur (1490 and 1570 ppm) and iron (11.08% total iron as FeO). The ??34S values average +0.3 ?? 0.5%. with average fractionation factor between sulfate and sulfide of +7.4 ?? 1.6%.. The sulfate/sulfide ratios tend to increase with increasing water content of basalt, probably because the oxygen fugacity increases with increasing water content in basalt melt. ?? 1984.

  14. Concentrations and isotope ratios of carbon, nitrogen and sulfur in ocean-floor basalts.

    PubMed

    Sakai, H; Des Marais, D J; Ueda, A; Moore, J G

    1984-01-01

    Fresh submarine basalt glasses from Galapagos Ridge, FAMOUS area, Cayman Trough and Kilauea east rift contain 22 to 160 ppm carbon and 0.3 to 2.8 ppm nitrogen, respectively, as the sums of dissolved species and vesicle-filling gases (CO2 and N2). The large range of variation in carbon content is due to combined effect of depth-dependency of the solubility of carbon in basalt melt and varying extents of vapour loss during magma emplacement as well as in sample crushing. The isotopic ratios of indigenous carbon and nitrogen are in very narrow ranges, -6.2 +/- 0.2% relative to PDB and +0.2 +/- 0.6% relative to atmospheric nitrogen, respectively. In basalt samples from Juan de Fuca Ridge, however, isotopically light carbon (delta 13 C = around -24%) predominates over the indigenous carbon; no indigenous heavy carbon was found. Except for Galapagos Ridge samples, these ocean-floor basalts contain 670 to 1100 ppm sulfur, averaging 810 ppm in the form of both sulfide and sulfate, whereas basalts from Galapagos Ridge are higher in both sulfur (1490 and 1570 ppm) and iron (11.08% total iron as FeO). the delta 34S values average +0.3 +/- 0.5% with average fractionation factor between sulfate and sulfide of +7.4 +/- 1.6%. The sulfate/sulfide ratios tend to increase with increasing water content of basalt, probably because the oxygen fugacity increases with increasing water content in basalt melt.

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

    EPA Science Inventory

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

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

    EPA Science Inventory

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

  17. Intercolony variability of skeletal oxygen and carbon isotope ratios of corals: temperature-controlled tank experiment and field observation

    NASA Astrophysics Data System (ADS)

    Suzuki, A.; Omata, T.; Kawahata, H.

    2005-12-01

    We conducted tank experiments in which we grew Porites spp. colonies in thermostated seawater at five temperature settings under moderate light intensity. A skeletal isotope microprofiling technique applied along the major growth axis of each colony revealed that the oxygen isotope ratios of newly deposited skeleton in most colonies remained almost constant during tank incubation. However, the oxygen isotope ratios displayed a surprisingly large intercolony variability (~1‰ at each temperature setting) although the mean slope obtained for the temperature - skeletal oxygen isotope ratio relationship was close to previous results. The variations in the oxygen isotope ratios were apparently caused by kinetic isotope effects related to variations in the skeletal growth rate rather than by species-specific variability or genetic differences within species. Carbon isotope ratios showed significantly inverse correlation with linear growth rates, suggesting a kinetic isotope control at low growth rates. We also examined oxygen and carbon isotope ratios of Porites corals collected from coral reefs of southern Ryukyu Islands, Japan. In shallow faster-growing corals, oxygen and carbon isotope ratios showed out-of-phase annual fluctuations. In contrast, in deep slower growing corals (mean annual linear extension < 4.8 mm yr1), oxygen and carbon isotope fluctuations were in phase, which has been identified as a pattern influenced by kinetic isotope effects. The slower growing corals were strongly influenced, and the faster growing corals weakly influenced, by kinetic isotope effects over metabolic isotope effects. Growth-rate-related kinetic isotope effects found in both the cultured corals and the deep slower-growing corals may be, at least partly, attributed to low light condition.

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

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

    NASA Technical Reports Server (NTRS)

    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.

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

    NASA Technical Reports Server (NTRS)

    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.

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

    NASA Astrophysics Data System (ADS)

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

    1995-01-01

    Less than 15 min are required for the determination of δ13CPDB with a precision of 0.2‰ (1σ, 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 δ 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 sample 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 <1‰.

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

    PubMed

    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

  3. When other separation techniques fail: compound-specific carbon isotope ratio analysis of sulfonamide containing pharmaceuticals by high-temperature-liquid chromatography-isotope ratio mass spectrometry.

    PubMed

    Kujawinski, Dorothea M; Zhang, Lijun; Schmidt, Torsten C; Jochmann, Maik A

    2012-09-18

    Compound-specific isotope analysis (CISA) of nonvolatile analytes has been enabled by the introduction of the first commercial interface to hyphenate liquid chromatography with an isotope ratio mass spectrometer (LC-IRMS) in 2004, yet carbon isotope analysis of unpolar and moderately polar compounds is still a challenging task since only water as the eluent and no organic modifiers can be used to drive the separation in LC. The only way to increase the elution strength of aqueous eluents in reversed phase LC is the application of high temperatures to the mobile and stationary phases (HT-LC-IRMS). In this context we present the first method to determine carbon isotope ratios of pharmaceuticals that cannot be separated by already existing separation techniques for LC-IRMS, such as reversed phase chromatography at normal temperatures, ion-chromatography, and mixed mode chomatography. The pharmaceutical group of sulfonamides, which is generally mixed with trimethoprim in pharmaceutical products, has been chosen as probe compounds. Substance amounts as low as 0.3 μg are sufficient to perform a precise analysis. The successful applicability and reproducibility of this method is shown by the analysis of real pharmaceutical samples. The method provides the first tool to study the pharmaceutical authenticity as well as degradation and mobility of such substances in the environment by using the stable isotopic signature of these compounds.

  4. Simulating stable carbon and chlorine isotope ratios in dissolved chlorinated groundwater pollutants with BIOCHLOR-ISO

    NASA Astrophysics Data System (ADS)

    Höhener, Patrick

    2016-12-01

    BIOCHLOR is a well-known simple tool for evaluating the transport of dissolved chlorinated solvents in groundwater, ideal for rapid screening and teaching. This work extends the BIOCHLOR model for the calculation of stable isotope ratios of carbon and chlorine isotopes in chloroethenes. An exact solution for the three-dimensional reactive transport of a chain of degrading compounds including sorption is provided in a spreadsheet and applied for modeling the transport of individual isotopes 12C, 13C, 35Cl, 37Cl from a constant source. The model can consider secondary isotope effects that can occur in the breaking of Csbnd Cl bonds. The model is correctly reproducing results for δ13C and δ37Cl modeled by a previously published 1-D numerical model without secondary isotope effects, and is also reproducing results from a microcosm experiment with secondary chlorine isotope effects. Two applications of the model using field data from literature are further given and discussed. The new BIOCHLOR-ISO model is distributed as a spreadsheet (MS EXCEL) along with this publication.

  5. Simulating stable carbon and chlorine isotope ratios in dissolved chlorinated groundwater pollutants with BIOCHLOR-ISO.

    PubMed

    Höhener, Patrick

    2016-12-01

    BIOCHLOR is a well-known simple tool for evaluating the transport of dissolved chlorinated solvents in groundwater, ideal for rapid screening and teaching. This work extends the BIOCHLOR model for the calculation of stable isotope ratios of carbon and chlorine isotopes in chloroethenes. An exact solution for the three-dimensional reactive transport of a chain of degrading compounds including sorption is provided in a spreadsheet and applied for modeling the transport of individual isotopes (12)C, (13)C, (35)Cl, (37)Cl from a constant source. The model can consider secondary isotope effects that can occur in the breaking of CCl bonds. The model is correctly reproducing results for δ(13)C and δ(37)Cl modeled by a previously published 1-D numerical model without secondary isotope effects, and is also reproducing results from a microcosm experiment with secondary chlorine isotope effects. Two applications of the model using field data from literature are further given and discussed. The new BIOCHLOR-ISO model is distributed as a spreadsheet (MS EXCEL) along with this publication.

  6. Effects of caloric restriction on nitrogen and carbon stable isotope ratios in adult rat bone.

    PubMed

    Robertson, Kimberly L; Rowland, Neil E; Krigbaum, John

    2014-10-15

    Stable isotope analysis is a valuable technique for dietary estimation in ecological and archaeological research, yet many variables can potentially affect tissue stable isotope signatures. Controlled feeding studies across a range of species have consistently demonstrated impacts of caloric restriction on tissue stable isotope ratios, but most have focused on juvenile, fasting, and/or starving individuals, and most have utilized soft tissues despite the importance of bone for paleodietary analyses. The goal of this study was to determine whether temporally defined, moderate food restriction could affect stable carbon and/or nitrogen isotope ratios in adult mammalian bone - a tissue that arguably reflects long-term dietary signals. Adult rats fed a standard laboratory diet were restricted to 45% of ad libitum intakes for 3 or 6 months. Relevant anatomical and physiological parameters were measured to confirm that the restriction protocol resulted in significant nutritional stress and to provide independent data to facilitate interpretation of stable isotope ratios. Femoral bone δ(13)Ccollagen, δ(15)Ncollagen, and δ(13)Capatite values were determined by isotope ratio mass spectrometry. Calorie-restricted animals exhibited a small, yet significant enrichment in (15)Ncollagen compared with control animals, reflecting protein-calorie stress. While the δ(13)Ccollagen values did not differ, the δ(13)Capatite values revealed less enrichment in (13)C than in controls, reflecting catabolism of body fat. Independent anatomical and physiological data from these same individuals support these interpretations. Results indicate that moderate caloric restriction does not appreciably undermine broad interpretations of dietary signals in adult mammalian bone. Significant variability among individuals or groups, however, is best explained by marked differences in energy intake over variable timescales. An inverse relationship between the δ(13)Capatite and δ(15)Ncollagen

  7. Carbon isotopic ratio analysis by gas chromatography/combustion/isotope ratio mass spectrometry for the detection of gamma-hydroxybutyric acid (GHB) administration to humans.

    PubMed

    Saudan, Christophe; Augsburger, Marc; Mangin, Patrice; Saugy, Martial

    2007-01-01

    Since GHB (gamma-hydroxybutyric acid) is naturally produced in the human body, clinical and forensic toxicologists must be able to discriminate between endogenous levels and a concentration resulting from exposure. To suggest an alternative to the use of interpretative concentration cut-offs, the detection of exogenous GHB in urine specimens was investigated by means of gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). GHB was isolated from urinary matrix by successive purification on Oasis MCX and Bond Elute SAX solid-phase extraction (SPE) cartridges prior to high-performance liquid chromatography (HPLC) fractioning using an Atlantis dC18 column eluted with a mixture of formic acid and methanol. Subsequent intramolecular esterification of GHB leading to the formation of gamma-butyrolactone (GBL) was carried out to avoid introduction of additional carbon atoms for carbon isotopic ratio analysis. A precision of 0.3 per thousand was determined using this IRMS method for samples at GHB concentrations of 10 mg/L. The (13)C/(12)C ratios of GHB in samples of subjects exposed to the drug ranged from -32.1 to -42.1 per thousand, whereas the results obtained for samples containing GHB of endogenous origin at concentration levels less than 10 mg/L were in the range -23.5 to -27.0 per thousand. Therefore, these preliminary results show that a possible discrimination between endogenous and exogenous GHB can be made using carbon isotopic ratio analyses.

  8. Stable carbon isotope ratios of intact GDGTs indicate heterogeneous sources to marine sediments

    NASA Astrophysics Data System (ADS)

    Pearson, Ann; Hurley, Sarah J.; Walter, Sunita R. Shah; Kusch, Stephanie; Lichtin, Samantha; Zhang, Yi Ge

    2016-05-01

    Thaumarchaeota, the major sources of marine glycerol dibiphytanyl glycerol tetraether lipids (GDGTs), are believed to fix the majority of their carbon directly from dissolved inorganic carbon (DIC). The δ13C values of GDGTs (δ13CGDGT) may be powerful tools for reconstructing variations in the ocean carbon cycle, including paleoproductivity and water mass circulation, if they can be related to values of δ13CDIC. To date, isotope measurements primarily are made on the C40 biphytane skeletons of GDGTs, rather than on complete tetraether structures. This approach erases information revealed by the isotopic heterogeneity of GDGTs within a sample and may impart an isotopic fractionation associated with the ether cleavage. To circumvent these issues, we present δ13C values for GDGTs from twelve recent sediments representing ten continental margin locations. Samples are purified by orthogonal dimensions of HPLC, followed by measurement of δ13C values by Spooling Wire Microcombustion (SWiM)-isotope ratio mass spectrometry (IRMS) with 1σ precision and accuracy of ±0.25‰. Using this approach, we confirm that GDGTs, generally around -19‰, are isotopically ;heavy; compared to other marine lipids. However, measured δ13CGDGT values are inconsistent with predicted values based on the 13C content of DIC in the overlying water column and the previously-published biosynthetic isotope fractionation for a pure culture of an autotrophic marine thaumarchaeon. In some sediments, the isotopic composition of individual GDGTs differs, indicating multiple source inputs. The data appear to confirm that crenarchaeol primarily is a biomarker for Thaumarchaeota, but its δ13C values still cannot be explained solely by autotrophic carbon fixation. Overall the complexity of the results suggests that both organic carbon assimilation (ca. 25% of total carbon) and multiple source(s) of exogenous GDGTs (contributing generally <30% of input to sediments) are necessary to explain the observed

  9. Detection of adulteration in Australian orange juices by stable carbon isotope ratio analysis (SCIRA).

    PubMed

    Antolovich, M; Li, X; Robards, K

    2001-05-01

    Stable carbon isotope ratio analysis (SCIRA) was used to determine the authenticity of commercial Australian orange juices. Thirty-five samples of Valencia (delta(13)C values from -23.8 to -24.7 ppt) and eight samples of Navel juices (delta(13)C values from -24.1 to -24.5 ppt) of known origin were used to establish a decision level before analysis. No significant seasonal variations in (13)C/(12)C ratio were observed. Variations in combustion temperature in the method were also found to be insignificant.

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

    PubMed

    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.

  11. Environmental and biosynthetic influences on carbon and hydrogen isotope ratios of leaf wax n-alkanes

    NASA Astrophysics Data System (ADS)

    McInerney, F. A.; Freeman, K. H.; Polissar, P. J.; Feakins, S. J.

    2013-12-01

    Both carbon and hydrogen isotope ratios of leaf-wax n-alkanes are influenced by the availability of water in a plant's growth environment. Carbon isotope ratios of bulk tissues in C3 plants demonstrate a strong inverse relationship with measures of available moisture (e.g. mean annual precipitation and precipitation/evaporation). Similarly, hydrogen isotope ratios of leaf wax n-alkanes (δDl) can be enriched relative to precipitation (δDw) by transpiration, which is related to relative humidity and the leaf-to-air vapor pressure deficit. Thus, D-enrichment of leaf-wax n-alkanes relative to precipitation, termed the apparent fractionation (2ɛl/w), becomes more positive with increasing aridity. In theory, more positive values of leaf-wax δ13C (δ13Cl) and 2ɛl/w of leaf-wax n-alkanes should both correspond to more arid conditions in C3 plants. Here we review published and unpublished data on over 100 plants to examine this relationship. Contrary to expectations, C3 dicots show no clear relationship between δ13Cl and 2ɛl/w. This global lack of correlation is surprising given our understanding of aridity related isotopic effects in C3 plants. One possibility is that the implicit assumption of constant fractionation between lipid and bulk tissue is flawed due to the effects of different biosynthetic carriers and reaction pathways. We explore this possibility by examining the offset of leaf-wax carbon isotopes from the bulk leaf tissue (13ɛl/bulk). Different offsets would indicate additional biosynthetic processes are affecting δ13Cl in addition to any direct effects from aridity. We find that 13ɛl/bulk is highly variable, ranging from -1 to -16‰, which could explain the lack of correlation between δ13Cl and 2ɛl/w. In addition, 13ɛl/bulk values for C3 and C4 monocots (averages of -10.6 and -11.4‰ respectively) represent significantly greater offset between leaf wax and bulk tissue than in C3 dicots (average of -4.3‰), which is consistent with previous

  12. Authenticity of carbon dioxide bubbles in French ciders through multiflow-isotope ratio mass spectrometry measurements.

    PubMed

    Gaillard, Laetitia; Guyon, Francois; Salagoïty, Marie-Hélène; Médina, Bernard

    2013-12-01

    A procedure to detect whether carbon dioxide was added to French ciders has been developed. For this purpose, an optimised and simplified method is proposed to determine (13)C/(12)C isotope ratio of carbon dioxide (δ(13)C) in ciders. Three critical steps were checked: (1) influence of atmospheric CO2 remaining in the loaded vial, (2) impact of helium flush, (3) sampling speed. This study showed that atmospheric CO2 does not impact the measurement, that helium flush can lead to isotopic fractionation and finally, that a fractionation occurs only 5h after bottle opening. The method, without any other preparation, consists in sampling 0.2 mL of cold (4 °C) cider in a vial that is passed in an ultrasonic bath for 10 min at room temperature to enhance cider de-carbonation. The headspace CO2 is then analysed using the link Multiflow®-isotope ratio mass spectrometer. Each year, a data bank is developed by fermenting authentic apples juices in order to control cider authenticity. Over a four year span (2008-2011), the CO2 produced during the fermentation step was studied. This set of 61 authentic ciders, from various French production areas, was used to determine a δ(13)C value range of -22.59±0.92‰ for authentic ciders CO2 bubbles. 75 commercial ciders were analysed with this method. Most of the samples analysed present a gas δ(13)C value in the expected range. Nevertheless, some ciders have δ(13)C values outside the 3σ limit, revealing carbonation by technical CO2. This practice is not allowed for organic, "Controlled Appellation of Origin" ciders and ciders specifying natural carbonation on the label.

  13. Relationship between carbon and nitrogen isotope ratios for lower trophic ecosystem in marine environments

    NASA Astrophysics Data System (ADS)

    Aita, M. N.; Ishii, R.; Tadokoro, K.; Smith, S. L.; Wada, E.

    2012-12-01

    To examine the relationship between carbon and nitrogen stable isotope ratios (δ13C and δ15N) along food chains, we analyzed using the data from the Oyashio waters at the western North Pacific (samples collected from March to October 2009), the warm-core ring 86-B derived from the Kuroshio extension region (preserved samples), and previously published data from the Gulf of Alaska and Antarctic Ocean. The statistical analysis suggested a common slope of δ15N versus δ13C (Δδ15N/Δδ13C) among regions. We attribute this similarity to common physiological aspects of feeding processes (e.g., kinetic isotope effects inherent in the processes of amino acid synthesis). We also compared seasonal differences seasonal in Δδ15N/Δδ13C for the euphotic layers of the Oyashio waters. The Δδ15N/Δδ13C slope of the food chain during the spring bloom differs from its common value in other seasons. If we could better understand both carbon and nitrogen trophic fractionation within ecosystems, the stable isotope ratios may help to elucidate migratory behavior of higher trophic levels such as fishes in marine ecosystems as well as frame work of biogeochemical cycles in question.

  14. Effects of volatilization on carbon and hydrogen isotope ratios of MTBE.

    PubMed

    Kuder, Tomasz; Philp, Paul; Allen, Jon

    2009-03-15

    Contaminant attenuation studies utilizing CSIA (compound-specific isotope analysis) routinely assume that isotope effects (IEs) result only from degradation. Experimental results on MTBE behavior in diffusive volatilization and dynamic vapor extraction show measurable changes in the isotope ratios of the MTBE remaining in the aqueous or nonaqueous phase liquid (NAPL) matrix. A conceptual model for interpretation of those IEs is proposed, based on the physics of liquid-air partitioning. Normal or inverse IEs were observed for different volatilization scenarios. The range of carbon enrichment factors (epsilon) was from +0.7 per thousand (gasoline vapor extraction) to -1 per thousand (diffusive volatilization of MTBE from gasoline), the range of hydrogen epsilon was from +7 per thousand (gasoline vapor extraction) to -12 per thousand (air sparging of aqueous MTBE). The observed IEs are lower than those associated with MTBE degradation. However, under a realistic scenario for MTBE vapor removal, their magnitude is within the detection limits of CSIA. The potential for interference of those IEs is primarily in confusing the interpretation of samples with a small extent of fractionation and where only carbon CSIA data are available. The IEs resulting from volatilization and biodegradation, respectively, can be separated by combined carbon and hydrogen 2D-CSIA.

  15. Stable carbon isotope ratios in atmospheric methane and some of its sources

    NASA Technical Reports Server (NTRS)

    Tyler, Stanley C.

    1986-01-01

    Ratios of C-13/C-12 have been measured in atmospheric methane and in methane collected from sites and biota that represent potentially large sources of atmospheric methane. These include temperate marshes (about -48 percent to about -54 percent), landfills (about -51 percent to about -55 percent), and the first reported values for any species of termite (-72.8 + or - 3.1 percent for Reticulitermes tibialis and -57.3 + or - 1.6 percent for Zootermopsis angusticollis). Numbers in parentheses are delta C-13 values with respect to PDB (Peedee belemnite) carbonate. Most methane sources reported thus far are depleted in C-13 with respect to atmospheric methane (-47.0 + or - 0.3 percent). Individual sources of methane should have C-13/C-12 ratios characteristic of mechanisms of CH4 formation and consumption prior to release to the atmosphere. The mass-weighted average isotopic composition of all sources should equal the mean C-13 of atmospheric methane, corrected for a kinetic isotope effect in the OH attack of CH4. Assuming the kinetic isotope effect to be small (about -3.0 percent correction to -47.0), as in the literature, the new values given here for termite methane do not help to explain the apparent discrepancy between C-13/C-12 ratios of the known CH4 sources and that of atmospheric CH4.

  16. The fractionation factors of stable carbon and hydrogen isotope ratios for VOCs

    NASA Astrophysics Data System (ADS)

    Kawashima, H.

    2014-12-01

    Volatile organic compounds (VOCs) are important precursors of ozone and secondary organic aerosols in the atmosphere, some of which are carcinogenic, teratogenic, or mutagenic. VOCs in ambient air originate from many sources, including vehicle exhausts, gasoline evaporation, solvent use, natural gas emissions, and industrial processes, and undergo intricate chemical reactions in the atmosphere. To develop efficient air pollution remediation strategies, it is important to clearly identify the emission sources and elucidate the reaction mechanisms in the atmosphere. Recently, stable carbon isotope ratios (δ13C) of VOCs in some sources and ambient air have been measured by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). In this study, we measured δ13C and stable hydrogen isotope ratios (δD) of atmospheric VOCs by using the gas chromatography/thermal conversion/isotope ratio mass spectrometry coupled with a thermal desorption instrument (TD-GC/TC/IRMS). The wider δD differences between sources were found in comparison with the δ13C studies. Therefore, determining δD values of VOCs in ambient air is potentially useful in identifying VOC sources and their reactive behavior in the atmosphere. However, to elucidate the sources and behavior of atmospheric VOCs more accurately, isotopic fractionation during atmospheric reaction must be considered. In this study, we determined isotopic fractionation of the δ13C and δD values for the atmospheric some VOCs under irradiation conditions. As the results, δ13C for target all VOCs and δD for most VOCs were increasing after irradiation. But, the δD values for both benzene and toluene tended to decrease as irradiation time increased. We also estimated the fractionation factors for benzene and toluene, 1.27 and 1.05, respectively, which differed from values determined in previous studies. In summary, we were able to identify an inverse isotope effect for the δD values of benzene and toluene

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

    NASA Astrophysics Data System (ADS)

    Pang, J.; Wen, X.; Sun, X.

    2016-12-01

    The stable isotope composition of atmospheric CO2 can be used as a tracer in the study of urban carbon cycles, which are affected by anthropogenic and biogenic CO2 components. Continuous measurements of the mixing ratio and δ13C of atmospheric CO2 were conducted in Beijing from Nov. 15, 2012 to Mar. 8, 2014 including two heating seasons and a vegetative season. Both δ13C and the isotopic composition of source CO2 (δ13CS) were depleted in the heating seasons and enriched in the vegetative season. The diurnal variations in the CO2 mixing ratio and δ13C contained two peaks in the heating season, which are due to the effects of morning rush hour traffic. Seasonal and diurnal patterns of the CO2 mixing ratio and δ13C were affected by anthropogenic emissions and biogenic activity. Assuming that the primary CO2 sources at night (22:00-04:00) were coal and natural gas combustion during heating seasons I and II, an isotopic mass balance analysis indicated that coal combustion had average contributions of 83.83 ± 14.11% and 86.84 ± 12.27% and that natural gas had average contributions of 16.17 ± 14.11% and 13.16 ± 12.27%, respectively. The δ13C of background CO2 in air was the main error source in the isotopic mass balance model. Both the mixing ratio and δ13C of atmospheric CO2 had significant linear relationships with the air quality index (AQI) and can be used to indicate local air pollution conditions. Energy structure optimization, for example, reducing coal consumption, will improve the local air conditions in Beijing.

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

    PubMed

    Pang, Jiaping; Wen, Xuefa; Sun, Xiaomin

    2016-01-01

    The stable isotope composition of atmospheric CO2 can be used as a tracer in the study of urban carbon cycles, which are affected by anthropogenic and biogenic CO2 components. Continuous measurements of the mixing ratio and δ(13)C of atmospheric CO2 were conducted in Beijing from Nov. 15, 2012 to Mar. 8, 2014 including two heating seasons and a vegetative season. Both δ(13)C and the isotopic composition of source CO2 (δ(13)CS) were depleted in the heating seasons and enriched in the vegetative season. The diurnal variations in the CO2 mixing ratio and δ(13)C contained two peaks in the heating season, which are due to the effects of morning rush hour traffic. Seasonal and diurnal patterns of the CO2 mixing ratio and δ(13)C were affected by anthropogenic emissions and biogenic activity. Assuming that the primary CO2 sources at night (22:00-04:00) were coal and natural gas combustion during heating seasons I and II, an isotopic mass balance analysis indicated that coal combustion had average contributions of 83.83±14.11% and 86.84±12.27% and that natural gas had average contributions of 16.17±14.11% and 13.16±12.27%, respectively. The δ(13)C of background CO2 in air was the main error source in the isotopic mass balance model. Both the mixing ratio and δ(13)C of atmospheric CO2 had significant linear relationships with the air quality index (AQI) and can be used to indicate local air pollution conditions. Energy structure optimization, for example, reducing coal consumption, will improve the local air conditions in Beijing. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Flow injection analysis-isotope ratio mass spectrometry for bulk carbon stable isotope analysis of alcoholic beverages.

    PubMed

    Jochmann, Maik A; Steinmann, Dirk; Stephan, Manuel; Schmidt, Torsten C

    2009-11-25

    A new method for bulk carbon isotope ratio determination of water-soluble samples is presented that is based on flow injection analysis-isotope ratio mass spectrometry (FIA-IRMS) using an LC IsoLink interface. Advantages of the method are that (i) only very small amounts of sample are required (2-5 microL of the sample for up to 200 possible injections), (ii) it avoids complex sample preparation procedures such as needed for EA-IRMS analysis (only sample dilution and injection,) and (iii) high throughput due to short analysis times is possible (approximately 15 min for five replicates). The method was first tested and evaluated as a fast screening method with industrially produced ethanol samples, and additionally the applicability was tested by the measurement of 81 alcoholic beverages, for example, whiskey, brandy, vodka, tequila, and others. The minimal sample concentration required for precise and reproducible measurements was around 50 microL L(-1) ethanol/water (1.71 mM carbon). The limit of repeatability was determined to be r=0.49%. FIA-IRMS represents a fast screening method for beverage authenticity control. Due to this, samples can be prescreened as a decisive criterion for more detailed investigations by HPLC-IRMS or multielement GC-IRMS measurements for a verification of adulteration.

  20. Stable carbon isotope ratios in Astrangia danae : evidence for algal modification of carbon pools used in calcification

    NASA Astrophysics Data System (ADS)

    Cummings, C. E.; McCarty, H. B.

    1982-06-01

    Stable carbon isotope ratios have been measured in skeletons of the temperature shallow water scleractinian coral, Astrangia danae. δ13C values ranging from -5.42 to -7.30%. revealed the expected depletion of 13C in skeletal carbonate relative to sea water bicarbonate. Differences among the ratios could not be attributed to collection site and were not correlated to skeletal morphology. Values of δ13C were directly related to zooxanthellae density for all colonies, so that as zooxanthellae concentration increased, δ13C valued increased. Colonies maintained under high temperature conditions were offset from the normal, exhibiting ratios less enriched in 13C than similar colonies from natural conditions. These trends supported the models of Weber and Goreau in which the carbon pools used in calcification are modified by algal photosynthesis. Direct evidence of physiological differences between symbiotic and asymbiotic colonies of A. danae has also been provided.

  1. A Widely Tunable Infrared Laser Spectrometer for Measurements of Isotopic Ratios of Carbon Cycle Gases

    SciTech Connect

    Joanne H. Shorter; J. Barry McManus; David D. Nelson; Charles E. Kolb; Mark S. Zahniser; Ray Bambha; Uwe Lehmann; Tomas Kulp; Stanley C. Tyler

    2005-01-31

    The atmospheric abundances of carbon dioxide and methane have increased dramatically during the industrial era. Measurements of the isotopic composition of these gases can provide a powerful tool for quantifying their sources and sinks. This report describes the development of a portable instrument for isotopic analysis CO{sub 2} and CH{sub 4} using tunable infrared laser absorption spectroscopy. This instrument combines novel optical design and signal processing methods with a widely tunable mid-infrared laser source based on difference frequency generation (DFG) which will can access spectral regions for all the isotopes of CO{sub 2} and CH{sub 4} with a single instrument. The instrument design compensates for the large difference in concentration between major and minor isotopes by measuring them with path lengths which differ by a factor of 100 within the same multipass cell. During Phase I we demonstrated the basic optical design and signal processing by determining {sup 13}CO{sub 2} isotopic ratios with precisions as small as 0.2{per_thousand} using a conventional lead salt diode laser. During Phase II, the DFG laser source was coupled with the optical instrument and was demonstrated to detect {sup 13}CH{sub 4}/{sup 12}CH{sub 4} ratios with a precision of 0.5{per_thousand} and an averaging time of 20 s using concentrated methane in air with a mixing ratio of 2700 ppm. Methods for concentrating ambient air for isotopic analysis using this technique have been evaluated. Extensions of this instrument to other species such as {sup 13}CO{sub 2}, C{sup 18}OO, and CH{sub 3}D are possible by substituting lasers at other wavelengths in the DFG source module. The immediate commercial application of this instrument will be to compete with existing mass spectrometric isotope instruments which are expensive, large and relatively slow. The novel infrared source developed in this project can be applied to the measurement of many other gas species and will have wide

  2. Carbon isotope ratio (13C/12C) of pine honey and detection of HFCS adulteration.

    PubMed

    Çinar, Serap B; Ekşi, Aziz; Coşkun, İlknur

    2014-08-15

    Carbon isotope ratio ((13)C/(12)C=δ(13)C) of 100 pine honey samples collected from 9 different localities by Mugla region (Turkey) in years 2006, 2007 and 2008 were investigated. The δ(13)Cprotein value of honey samples ranged between -23.7 and -26.6‰, while the δ(13)Choney value varied between -22.7 and -27‰. For 90% of the samples, the difference in the C isotope ratio of protein and honey fraction (δ(13)Cpro-δ(13)Chon) was -1.0‰ and/or higher. Therefore, it can be said that the generally anticipated minimum value of C isotope difference (-1.0‰) for honey is also valid for pine honey. On the other hand, C4 sugar value (%), which was calculated from the δ(13)Cpro-δ(13)Chon difference, was found to be linearly correlated with the amount of adulterant (HFCS) in pine honey. These results indicate that C4 sugar value is a powerful criteria for detecting HFCS adulteration in pine honey. The δ(13)Choney and δ(13)Cprotein-δ(13)Choney values of the samples did not show any significant differences in terms of both year and locality (P>0.05), while the δ(13)Cprotein values showed significant differences due to year (P<0.05) but not due to locality (P>0.05).

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

    SciTech Connect

    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

  4. Carbon and Nitrogen Stable Isotope Ratios Predict Intake of Sweeteners in a Yup’ik Study Population12

    PubMed Central

    Nash, Sarah H.; Kristal, Alan R.; Bersamin, Andrea; Hopkins, Scarlett E.; Boyer, Bert B.; O’Brien, Diane M.

    2013-01-01

    The carbon isotope ratio (δ13C) is elevated in corn- and cane sugar-based foods and has recently shown associations with sweetener intake in multiple U.S. populations. However, a high carbon isotope ratio is not specific to corn- and sugar cane-based sweeteners, as other foods, including meats and fish, also have elevated δ13C. This study examines whether the inclusion of a second marker, the nitrogen isotope ratio (δ15N), can control for confounding dietary effects on δ13C and improve the validity of isotopic markers of sweetener intake. The study participants are from the Yup’ik population of southwest Alaska and consume large and variable amounts of fish and marine mammals known to have elevated carbon and nitrogen isotope ratios. Sixty-eight participants completed 4 weekly 24-h recalls followed by a blood draw. RBC δ13C and δ15N were used to predict sweetener intake, including total sugars, added sugars, and sugar-sweetened beverages. A model including both δ13C and δ15N explained more than 3 times as much of the variation in sweetener intake than did a model using only δ13C. Because carbon and nitrogen isotope ratios are simultaneously determined in a single, high-throughput analysis, this dual isotope marker provides a simple method to improve the validity of stable isotope markers of sweetener intake with no additional cost. We anticipate that this multi-isotope approach will have utility in any population where a stable isotope biomarker is elevated in several food groups and there are appropriate “covariate” isotopes to control for intake of foods not of research interest. PMID:23256142

  5. Carbon isotope ratios of human tooth enamel record the evidence of terrestrial resource consumption during the Jomon period, Japan.

    PubMed

    Kusaka, Soichiro; Uno, Kevin T; Nakano, Takanori; Nakatsukasa, Masato; Cerling, Thure E

    2015-08-17

    Archaeological remains strongly suggest that the Holocene Japanese hunter-gatherers, the Jomon people, utilized terrestrial plants as their primary food source. However, carbon and nitrogen isotope analysis of bone collagen indicates that they primarily exploited marine resources. We hypothesize that this inconsistency stems from the route of protein synthesis and the different proportions of protein-derived carbon in tooth enamel versus bone collagen. Carbon isotope ratios from bone collagen reflect that of dietary protein and may provide a biased signal of diet, whereas isotope ratios from tooth enamel reflect the integrated diet from all macronutrients (carbohydrates, lipids, and proteins). In order to evaluate the differences in inferred diet between the archaeological evidence and bone collagen isotope data, this study investigated carbon isotopes in Jomon tooth enamel from four coastal sites of the Middle to Late-Final Jomon period (5,000-2,300 years BP). Carbon isotope ratios of human teeth are as depleted as coeval terrestrial mammals, suggesting that C3 plants and terrestrial mammals were major dietary resources for the Jomon people. Dietary dependence on marine resources calculated from enamel was significantly lower than that calculated from bone collagen. The discrepancy in isotopic ratios between enamel and collagen and the nitrogen isotope ratio in collagen shows a negative correlation on individual and population levels, suggesting diets with variable proportions of terrestrial and marine resources. This study highlights the usefulness of coupling tooth enamel and bone collagen in carbon isotopic studies to reconstruct prehistoric human diet. Am J Phys Anthropol, 2015. © 2015 Wiley Periodicals, Inc. © 2015 Wiley Periodicals, Inc.

  6. Oxygen and carbon isotope ratios of hydrothermal minerals from Yellowstone drill cores

    USGS Publications Warehouse

    Sturchio, N.C.; Keith, T.E.C.; Muehlenbachs, K.

    1990-01-01

    Oxygen and carbon isotope ratios were measured for hydrothermal minerals (silica, clay and calcite) from fractures and vugs in altered rhyolite, located between 28 and 129 m below surface (in situ temperatures ranging from 81 to 199??C) in Yellowstone drill holes. The purpose of this study was to investigate the mechanism of formation of these minerals. The ??18O values of the thirty-two analyzed silica samples (quartz, chalcedony, ??-cristobalite, and ??-cristobalite) range from -7.5 to +2.8???. About one third of the silica 7samples have ??18O values that are consistent with isotopic equilibrium with present thermal waters; most of the other silica samples appear to have precipitated from water enriched in 18O (up to 4.7???) relative to present thermal water, assuming precipitation at present in situ temperatures. Available data on fluid-inclusion homogenization temperatures in hydrothermal quartz indicate that silica precipitation occurred mostly at temperatures above those measured during drilling and imply that 15O enrichments in water during silica precipitation were generally larger than those estimated from present conditions. Similarly, clay minerals (celadonite and smectite) have ??18O values higher (by 3.5 to 7.9???) than equilibrium values under present conditions. In contrast, all eight analyzed calcite samples are close to isotopic equilibrium with present thermal waters. The frequent incidence of apparent 18O enrichment in thermal water from which the hydrothermal minerals precipitated may indicate that a higher proportion of strongly 18O-enriched deep hydrothermal fluid once circulated through shallow portions of the Yellowstone system, or that a recurring transient 18O-enrichment effect occurs at shallow depths and is caused either by sudden decompressional boiling or by isotopic exchange at low water/rock ratios in new fractures. The mineralogy and apparent 18O enrichments of hydrothermal fracture-filling minerals are consistent with deposition

  7. Isotopic Ratios of Carbon and Oxygen in Titan's CO Using Alma

    NASA Technical Reports Server (NTRS)

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

    2016-01-01

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

  8. Isotopic Ratios of Carbon and Oxygen in Titan's CO Using Alma

    NASA Technical Reports Server (NTRS)

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

    2016-01-01

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

  9. The Stable Carbon Isotope Ratio Analysis of Atmospheric Non-Methane Hydrocarbons in Los Angeles, California

    NASA Astrophysics Data System (ADS)

    Gotoh, A. A.; Tyler, S. C.; Meinardi, S.; Gervais, K.; Blake, D. R.

    2003-12-01

    Los Angeles type photochemical air pollution is caused by non-methane hydrocarbons (NMHCs) reacting with hydroxyl radicals and nitrous oxides in the presence of light. To create more effective control strategies in reducing such air pollution, it is essential to have both a better understanding of the complex photochemical processes of NMHCs and the sources of these compounds. From the past successful studies of other atmospheric trace gases such as methane and carbon monoxide, we expect that the stable carbon ratio (13C/12C, reported as a δ 13C value) of each of these hydrocarbons will also reflect the δ 13C value of the source material and/or provide formation on chemical loss processes that fractionate C isotopes. We have developed a NMHC preconcentrator system which enables us to measure δ 13C values using a continuous-flow gas chromatography combustion isotope ratio mass spectrometer (cf-GC/C/IRMS). Our system is similar to the successful design pioneered in Rudolph et al. (1997), but is custom designed by our laboratory. Stable carbon isotope measurements of any of the C2-C5 NMHCs in field and/or lab studies are scarce to date. Our system allows us to report on δ 13C measurements of ethane, ethene, ethyne, propane, propene, n-butane, i-butane, 1-butene, n-pentane, i-pentane, and methyl chloride. To see if we can learn the specific sources contributing to the emissions of a given NMHC within a region by comparing isotopic signatures of its potential sources to δ 13C measurements of it within the local air mass, urban air samples were collected in 3 different cities of Los Angeles County, California, USA, during the summer of 2003 and analyzed for the concentrations and δ 13C values of NMHCs. To our knowledge, this is the first δ 13C analysis of ambient NMHCs conducted in the United States. We report the results of the δ 13C analyses and concentration measurements for selected NMHC species from the urban air samples, and their implications for the local

  10. Measurement of the stable carbon isotope ratio of atmospheric volatile organic compounds using chromatography, combustion, and isotope ratio mass spectrometry coupled with thermal desorption

    NASA Astrophysics Data System (ADS)

    Kawashima, Hiroto; Murakami, Mai

    2014-06-01

    The isotopic analysis of atmospheric volatile organic compounds (VOCs), and in particular of their stable carbon isotope ratio (δ13C), could potentially be used as an effective tool for identifying the sources of VOCs. However, to date, there have been very few such analyses. In this work, we analyze the δ13C values of VOCs using thermal desorption coupled with chromatography, combustion, and isotope ratio mass spectrometry (TD-GC/C/IRMS). The measured peak shapes were of high quality and 36 compounds in a standard gas containing 58 VOCs (C5-C11) were detected. The measured δ13C varied widely, from -49.7‰ to -22.9‰, while the standard deviation of the δ13C values varied from 0.07‰ to 0.85‰ (n = 5). We then measured samples from two passenger cars in hot and cold modes, three gas stations, roadside air, and ambient air. In comparison with existing studies, the analytical precision for the 36 compounds in this study was reasonable. By comparing the δ13C values obtained from the cars and gas stations, we could identify some degree of the sources of VOCs in the roadside and ambient air samples.

  11. Organic carbon isotope ratios (δ13C) of Arctic Amerasian Continental shelf sediments

    NASA Astrophysics Data System (ADS)

    Naidu, A. S.; Cooper, L. W.; Finney, B. P.; Macdonald, R. W.; Alexander, C.; Semiletov, I. P.

    2000-09-01

    Organic matter origins are inferred from carbon isotope ratios (δ13C) in recent continental shelf sediments and major rivers from 465 locations from the north Bering-Chukchi-East Siberian-Beaufort Sea, Arctic Amerasia. Generally, there is a cross-shelf increase in δ13C, which is due to progressive increased contribution seaward of marine-derived organic carbon to surface sediments. This conclusion is supported by the correlations between sediment δ13C, OC/N, and δ15N. The sources of total organic carbon (TOC) to the Amerasian margin sediments are primarily from marine water-column phytoplankton and terrigenous C3 plants constituted of tundra taiga and angiosperms. In contrast to more temperate regions, the source of TOC from terrigenous C4 and CAM plants to the study area is probably insignificant because these plants do not exist in the northern high latitudes. The input of carbon to the northern Alaskan shelf sediments from nearshore kelp community (Laminaria solidungula) is generally insignificant as indicated by the absence of high sediment δ13C values (-16.5 to -13.6‰) which are typical of the macrophytes. Our study suggests that the isotopic composition of sediment TOC has potential application in reconstructing temporal changes in delivery and accumulation of organic matter resulting from glacial-interglacial changes in sea level and environments. Furthermore, recycling and advection of the extensive deposits of terrestrially derived organic matter from land, or the wide Amerasian margin, could be a mechanism for elevating total CO2 and pCO2 in the Arctic Basin halocline.

  12. High-temperature pyrolysis/gas chromatography/isotope ratio mass spectrometry: simultaneous measurement of the stable isotopes of oxygen and carbon in cellulose.

    PubMed

    Woodley, Ewan J; Loader, Neil J; McCarroll, Danny; Young, Giles H F; Robertson, Iain; Heaton, Timothy H E; Gagen, Mary H; Warham, Joseph O

    2012-01-30

    Stable isotope analysis of cellulose is an increasingly important aspect of ecological and palaeoenvironmental research. Since these techniques are very costly, any methodological development which can provide simultaneous measurement of stable carbon and oxygen isotope ratios in cellulose deserves further exploration. A large number (3074) of tree-ring α-cellulose samples are used to compare the stable carbon isotope ratios (δ(13)C) produced by high-temperature (1400°C) pyrolysis/gas chromatography (GC)/isotope ratio mass spectrometry (IRMS) with those produced by combustion GC/IRMS. Although the two data sets are very strongly correlated, the pyrolysis results display reduced variance and are strongly biased towards the mean. The low carbon isotope ratios of tree-ring cellulose during the last century, reflecting anthropogenic disturbance of atmospheric carbon dioxide, are thus overestimated. The likely explanation is that a proportion of the oxygen atoms are bonding with residual carbon in the reaction chamber to form carbon monoxide. The 'pyrolysis adjustment', proposed here, is based on combusting a stratified sub-sample of the pyrolysis results, across the full range of carbon isotope ratios, and using the paired results to define a regression equation that can be used to adjust all the pyrolysis measurements. In this study, subsamples of 30 combustion measurements produced adjusted chronologies statistically indistinguishable from those produced by combusting every sample. This methodology allows simultaneous measurement of the stable isotopes of carbon and oxygen using high-temperature pyrolysis, reducing the amount of sample required and the analytical costs of measuring them separately.

  13. Carbon isotope ratios of selected volatiles in Citrus sinensis and in orange-flavoured food.

    PubMed

    Schipilliti, Luisa; Bonaccorsi, Ivana; Cotroneo, Antonella; Dugo, Paola; Mondello, Luigi

    2015-11-01

    Twenty genuine samples of industrially cold-pressed sweet orange essential oils, were analysed by gas chromatography-combustion-isotope ratio mass spectrometry to determine the values of the carbon isotope ratios (δ(13)C(VPDB)) of selected volatiles and assess the corresponding range of authenticity. Successively, four commercial orange-flavoured products were analysed under identical conditions to evaluate the authenticity of the orange flavour. The samples were extracted by solid-phase microextraction under optimised conditions. The evaluation was performed by using an internal standard procedure to neglect the contribution due to the original environment to the isotopic abundance of (13)C. The composition of the volatile fraction of the essential oils and of the flavoured products was determined by gas chromatography coupled to mass spectrometry with linear retention indices, and by gas chromatography with a flame ionisation detector. The δ(13)C(VPDB) values of seven secondary metabolites determined here were successfully used to characterise genuine orange essential oil. These values were used to evaluate the quality of orange-flavoured products, revealing the presence of compounds of different origin, not compatible with the values of genuine orange secondary metabolites. This study provides the range of authenticity of δ(13)C(VPDB) of seven different secondary metabolites in sweet orange genuine essential oil, useful for evaluating the genuineness of orange flavour. In accord with a previous study on different essential oils, the values determined here can be successfully applied for the evaluation of a large number of flavoured food stuffs and correlated with their origins. © 2014 Society of Chemical Industry.

  14. Unusually low carbon isotope ratios in plants from hanging gardens in southern Utah.

    PubMed

    Flanagan, Lawrence B; Cook, Craig S; Ehleringer, James R

    1997-08-01

    Leaf carbon isotope ratios (δ(13)C) and photosynthetic gas exchange were measured on plants growing in hanging garden communities in southern Utah, USA. Hanging gardens are unusual, mesic cliff communities occurring where water seeps from the sandstone bedrock in an otherwise extremely arid region; there is very limited overlap in species distributions inside and outside these gardens. Solar exposure in hanging gardens varied with orientation and one of the gardens (Ribbon Garden) was shaded throughout the day. The leaf δ(13)C values of plants in hanging gardens were significantly more negative than for plants from either nearby ephemeral wash or riparian communities. In Ribbon Garden, the observed δ(13)C values were as low as -34.8‰, placing them among the most negative values reported for any terrestrial plant species growing in a natural environment. Hanging garden plants were exposed to normal atmospheric CO2 with an average δ(13)C value of -7.9‰ and so the low leaf δ(13)C values could not be attributed to exposure to a CO2 source with low (13)C content. There was a seasonal change toward more negative leaf δ(13)C values at the end of the growing season. The observed leaf δ(13)C values were consistent with photosynthetic gas exchange measurements that indicated unusually high leaf intercellular CO2 concentrations associated with the relatively low light levels in hanging gardens. Thus, extremely negative leaf δ(13)C values would be expected if significant amounts of the seasonal carbon gain occur at light levels low enough to be near the light compensation point. Maximum observed photosynthetic rates varied with light levels at each of the gardens, with maximum rates averaging 20.3, 14.6, and 3.1 μmol m(-2 )s(-1) at Double Garden, Lost Garden, and Ribbon Garden, respectively. Leaf nitrogen contents averaged 18.5 mg g(-1) in species from the more shaded hanging gardens (Lost and Ribbon). When expressed on a leaf area basis, nitrogen contents

  15. Stable carbon isotope ratio in atmospheric CO2 collected by new diffusive devices.

    PubMed

    Proto, Antonio; Cucciniello, Raffaele; Rossi, Federico; Motta, Oriana

    2014-02-01

    In this paper, stable carbon isotope ratios (δ (13)C) were determined in the atmosphere by using a Ca-based sorbent, CaO/Ca12Al14O33 75:25 w/w, for passively collecting atmospheric CO2, in both field and laboratory experiments. Field measurements were conducted in three environments characterized by different carbon dioxide sources. In particular, the environments under consideration were a rather heavily trafficked road, where the source of CO2 is mostly vehicle exhaust, a rural unpolluted area, and a private kitchen where the major source of CO2 was gas combustion. Samplers were exposed to the free atmosphere for 3 days in order to allow collection of sufficient CO2 for δ(13)C analysis, then the collected CO2 was desorbed from the adsorbent with acid treatment, and directly analyzed by nondispersive infrared (NDIR) instrument. δ (13)C results confirmed that the samplers collected representative CO2 samples and no fractionation occurred during passive trapping, as also confirmed by an appositely designed experiment conducted in the laboratory. Passive sampling using CaO/Ca12Al14O33 75:25 w/w proved to be an easy and reliable method to collect atmospheric carbon dioxide for δ (13)C analysis in both indoor and outdoor places.

  16. Carbon isotopic characterization of cider CO2 by isotope ratio mass spectrometry: a tool for quality and authenticity assessment.

    PubMed

    Cabañero, Ana I; Rupérez, Mercedes

    2012-08-30

    The cider market is an important sector of the food industry in certain regions. Adulteration of cider can happen in several ways: for example, by the addition of sugar, or of exogenous CO(2) to certain types of cider. Because such practices are not allowed by either Spanish legislation or the legislation of other countries, it is essential to study possible methods to detect these unauthorized practices. For this purpose a procedure was required to study the stable carbon isotopic composition of CO(2) in cider. A liquid sample of cider was transferred to a vial and CO(2) from the headspace of the vial was analyzed using a peripheral device interfaced to an isotope ratio mass spectrometer. Separation of the CO(2) from water and ethanol was achieved using a gas chromatography column located in the peripheral device. The values for repeatability and reproducibility obtained indicated the robustness of the method, which is required for routine analysis. Ninety cider samples from various origins were analyzed, most of which showed a (13)C content consistent with the declared origin. The δ(13)C ranged from -24.80‰ to -20.89‰ for ciders with endogenous carbon dioxide (-22.74 ± 0.79‰) and -37.13‰ to -26.00‰ if industrial CO(2) was added. Several samples were also suspected of C4 sugar addition prior to the fermentation. A fast, accurate and simple method for cider adulteration detection was developed. The addition of exogenous CO(2) as well as C4 sugar addition prior to fermentation could be detected. The method showed advantages over existing methods in term of simplicity (no sample preparation and very long-term stability of the sample), speed (less than 10 min/sample) and precision ((r ≤0.32 and R ≤0.42). Copyright © 2012 John Wiley & Sons, Ltd.

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

    PubMed

    Whigham, L D; Butz, D E; Johnson, L K; Schoeller, D A; Abbott, D H; Porter, W P; Cook, M E

    2014-09-01

    Rapid detection of shifts in substrate utilization and energy balance would provide a compelling biofeedback tool for individuals attempting weight loss. As a proof of concept, we tested whether the natural abundance of exhaled carbon stable isotope ratios (breath δ(13)C) reflects shifts between negative and positive energy balance. Volunteers (n=5) consumed a 40% energy-restricted diet for 6 days followed by 50% excess on day 7. Breath was sampled immediately before and 1 h and 2 h after breakfast, lunch and dinner. Exhaled breath δ(13)C values were measured by cavity ring-down spectroscopy. Using repeated measures analysis of variance (ANOVA) followed by Dunnett's contrasts, pre-breakfast breath values on days 2-6 were compared with day 1, and postprandial day 7 time points were compared with pre-breakfast day 7. Energy restriction diminished pre-breakfast breath δ(13)C by day 3 (P<0.05). On day 7, increased energy intake was first detected immediately before dinner (-23.8±0.6 vs -21.9±0.7‰, P=0.002 (means±s.d.)), and breath δ(13)C remained elevated at least 2 h post dinner. In conclusion, when shifting between negative and positive energy balance, breath δ(13)C showed anticipated isotopic changes. Although additional research is needed to determine specificity and repeatability, this method may provide a biomarker for marked increases in caloric intake.

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

    PubMed

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

    2017-01-15

    Analyses of stable carbon isotope ratios (δ(13) C 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. 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. 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(13) C values. 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(13) C 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. © 2016 The Authors. Rapid Communications in Mass Spectrometry Published by John Wiley & Sons Ltd.

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

    PubMed Central

    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. Carbon and nitrogen isotope ratios of factory-produced RDX and HMX.

    PubMed

    Howa, John D; Lott, Michael J; Chesson, Lesley A; Ehleringer, James R

    2014-07-01

    RDX and HMX are explosive compounds commonly used by the military and also occasionally associated with acts of terrorism. The isotopic characterization of an explosive can be a powerful approach to link evidence to an event or an explosives cache. We sampled explosive products and their reactants from commercial RDX manufacturers that used the direct nitration and/or the Bachmann synthesis process, and then analyzed these materials for carbon and nitrogen isotope ratios. For manufacturers using the Bachmann process, RDX (13)C enrichment relative to the hexamine substrate was small (+0.9‰) compared to RDX produced using the direct nitration process (+8.2‰ to +12.0‰). RDX (15)N depletion relative to the nitrogen-containing substrates (-3.6‰) was smaller in the Bachmann process than in the direct nitration process (-12.6‰ to -10.6‰). The sign and scale of these differences agree with theorized mechanisms of mass-dependent fractionation. We also examined the isotopic relationship between RDX and HMX isolated from explosive samples. The δ(13)C and δ(15)N values of RDX generally matched those of the HMX with few exceptions, most notably from a manufacturer known to make RDX using two different synthesis processes. The range in δ(13)C values of RDX in a survey of 100 samples from 12 manufacturers spanned 33‰ while the range spanned by δ(15)N values was 26‰; these ranges were much greater than any previously published observations. Understanding the relationship between products and reactants further explains the observed variation in industrially manufactured RDX and can be used as a diagnostic tool to analyze explosives found at a crime scene. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

  1. Oxygen and carbon isotope ratios of hydrothermal minerals from Yellowstone drill cores

    NASA Astrophysics Data System (ADS)

    Sturchio, N. C.; Keith, T. E. C.; Muehlenbachs, K.

    1990-01-01

    Oxygen and carbon isotope ratios were measured for hydrothermal minerals (silica, clay and calcite) from fractures and vugs in altered rhyolite, located between 28 and 129 m below surface ( in situ temperatures ranging from 81 to 199°C) in Yellowstone drill holes. The purpose of this study was to investigate the mechanism of formation of these minerals. The δ 18O values of the thirty-two analyzed silica samples (quartz, chalcedony, α-cristobalite, and β-cristobalite) range from -7.5 to +2.8‰ . About one third of the silica 7samples have δ 18O values that are consistent with isotopic equilibrium with present thermal waters; most of the other silica samples appear to have precipitated from water enriched in 18O (up to 4.7‰) relative to present thermal water, assuming precipitation at present in situ temperatures. Available data on fluid-inclusion homogenization temperatures in hydrothermal quartz indicate that silica precipitation occurred mostly at temperatures above those measured during drilling and imply that 15O enrichments in water during silica precipitation were generally larger than those estimated from present conditions. Similarly, clay minerals (celadonite and smectite) have δ 18O values higher (by 3.5 to 7.9‰) than equilibrium values under present conditions. In contrast, all eight analyzed calcite samples are close to isotopic equilibrium with present thermal waters. The frequent incidence of apparent 18O enrichment in thermal water from which the hydrothermal minerals precipitated may indicate that a higher proportion of strongly 18O-enriched deep hydrothermal fluid once circulated through shallow portions of the Yellowstone system, or that a recurring transient 18O-enrichment effect occurs at shallow depths and is caused either by sudden decompressional boiling or by isotopic exchange at low water/rock ratios in new fractures. The mineralogy and apparent 18O enrichments of hydrothermal fracture-filling minerals are consistent with

  2. Stable Carbon Isotope Ratios and Biodegradation Rates of BTEX Compounds at the Tranguch Gasoline Site, Hazelton, Pennsylvania

    DTIC Science & Technology

    2005-03-03

    Absence of Stable Carbon Isotope Fractionation of Satu- rated and Polycyclic Aromatic Hydrocarbons During Aerobic Bacterial Biodegradation ,” Org... biodegradation ; measure the overall metabolic activity and state of the on-site bacterial consortia; and determine fuel hydrocarbon stable isotope ratios...Hazleton, Pennsylvania. The goal of this study was to determine the rates and efficacy of on-site bacterial fuel hydrocarbon biodegradation ; measure

  3. Stable carbon isotope ratio and its use in determination of photochemical processing of ambient volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Kornilova, A.; Saccon, M. S.; Rudolph, J.; Huang, L.

    2012-12-01

    Stable Carbon Isotopic Composition measurement technique can provide valuable information about trace gas processing in the atmosphere. It can not only be used to distinguish physical processes such as dilution and mixing from photochemical ageing, but also can be an important tool in identification of sources, calculating the photochemical age and qualitatively and quantitatively connecting precursors with their atmospheric products. Even though isotopic composition analysis is a valuable technique, its use is hindered by the low concentrations of compounds in the atmosphere, complexity of the samples and complex measuring instrumentation. We have developed and validated sampling and instrumental analysis techniques that can be used to perform isotopic composition measurements of volatile organic compounds (VOC) and to apply these methods to analysis of ambient samples. In this poster application of this newly developed sampling and analysis techniques will be presented and discussed using concentrations and stable carbon isotope ratios of ambient VOC collected during 2009-2010 at urban and remote locations of southern Ontario. Photochemical ages determined using conventional hydrocarbon clock will be compared to ones determined with photochemical ages derived from isotope hydrocarbon clock. Advantages of the use of stable carbon isotope ratios over other conventional methods will be outlined and applications of isotope hydrocarbon clock in air quality monitoring will be discussed.

  4. Pedogenic Formation of Perylene in a Terrestrial Soil Profile: Evidence From Carbon Isotopic Ratios

    NASA Astrophysics Data System (ADS)

    Gocht, T.; Jochmann, M. A.; Blessing, M.; Barth, J.; Schmidt, T. C.; Grathwohl, P.

    2005-12-01

    Polycyclic aromatic hydrocarbons (PAHs) are persistent organic pollutants (POP), which are introduced into the environment mainly due to combustion of fossil fuel. Perylene is one compound of the PAHs that consists of 5 condensed rings like the well known carcinogenic benzo(a)pyrene. Apart from the pyrogenic formation, there are strong indications that it is produced biologically and/or diagenetically under anaerobic conditions. This conclusion was derived from the presence of perylene in deeper parts of marine and lacustrine sediment profiles, where the combustion-derived PAHs are almost absent ( Lima et al., 2003). 13C/12C compound-specific stable isotopic ratios were successfully applied for the differentiation of probably biologically generated perylene in tropical termite nests and pyrolytic perylene from surface soils of temperate regions ( Wilcke et al., 2002). Our study is the first aiming on the determination of the different processes of perylene formation at one location using carbon isotopic ratios such as 13C/12C. We determined PAHs in natural soils of southern Germany. At one location in the Black Forest we found for the first time evidence for natural perylene production in the subsoil of terrestrial environments. Apart from the combustion derived PAHs that accumulate at the top of all soil profiles, the depth distribution of perylene shows the highest peak in the subsoil about 1 m below the surface. Due to its very low solubility (0.4 μg l-1 at 25 °C) vertical transport of perylene with seepage water is very unlikely. Thus, we suggest atmospheric deposition of pyrogenic perylene at the top of the profile and in-situ generation in the subsoil, probably due to microbial activities. In order to distinguish between the pyrogenic and natural generation we employed 13C/12C compound-specific stable isotope analysis of perylene in soil samples from the top of the profile as well as from the subsoil. Preliminary measurements with soil extracts show strong

  5. Influences of β-HCG administration on carbon isotope ratios of endogenous urinary steroids.

    PubMed

    Piper, Thomas; Baume, Norbert; Strahm, Emanuel; Emery, Caroline; Saugy, Martial

    2012-05-01

    Several factors influencing the carbon isotope ratios (CIR) of endogenous urinary steroids have been identified in recent years. One of these should be the metabolism of steroids inside the body involving numerous different enzymes. A detailed look at this metabolism taking into account differences found between steroids excreted as glucuronides or as sulphates and hydrogen isotope ratios of different steroids pointed out possibility of unequal CIR at the main production sites inside the male body - the testes and the adrenal glands. By administration of β-HCG it is possible to strongly stimulate the steroid production within the testes without influencing the production at the adrenal glands. Therefore, this treatment should result in changed CIR of urinary androgens in contrast to the undisturbed pre-treatment values. Four male volunteers received three injections of β-HCG over a time course of 5 days and collected their urine samples at defined intervals after the last administration. Those samples showing the largest response in contrast to the pre-administration urines were identified by steroid profile measurements and subsequent analysed by GC/C/IRMS. CIR of androsterone, etiocholanolone, testosterone, 5α- and 5β-androstanediol and pregnanediol were compared. While pregnanediol was not influenced, most of the investigated androgens showed depleted values after treatment. The majority of differences were found to be statistically significant and nearly all showed the expected trend towards more depleted δ(13)C-values. These results support the hypothesis of different CIR at different production sites inside the human body. The impact of these findings on doping control analysis will be discussed.

  6. Monitoring crude oil mineralization in salt marshes: Use of stable carbon isotope ratios

    SciTech Connect

    Jackson, A.W.; Pardue, J.H.; Araujo, R.

    1996-04-01

    In laboratory microcosms using salt marsh soils and in field trials, it was possible to monitor and quantify crude oil mineralization by measuring changes in CO{sub 2} {delta}{sup 13}C signatures and the rate of CO{sub 2} production. These values are easy to obtain and can be combined with simple isotope mass balance equations to determine the rate of mineralization from both the crude oil and indigenous carbon pool. Hydrocarbon degradation was confirmed by simultaneous decreases in alkane-, isoprenoid-, and PAH-hopane ratios. Additionally, the pseudo-first-order rate constants of alkane degradation (0.087 day{sup -1}) and CO{sub 2} production (0.082 day{sup -1}) from oil predicted by the {delta}{sup 13}C signatures were statistically indistinguishable. The addition of inorganic nitrogen and phosphate increased the rate of mineralization of crude oil in aerated microcosms but had no clear effect on in situ studies. This procedure appears to offer a means of definitively quantifying crude oil mineralization in a sensitive, inexpensive, and simple manner in environments with appropriate background {delta}{sup 13}C signatures. 23 refs., 5 figs., 1 tab.

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

    NASA Astrophysics Data System (ADS)

    Botello, Alfonso V.; Mandelli, Enrique F.; Macko, Steve; Parker, Patrick L.

    1980-03-01

    The stable carbon isotope composition sedimentary organic carbon was determined in the sediments of seven coastal lagoons of the Gulf of Mexico, Mexico. For most of the lagoons the δ13C values for sediments ranged from -20.1 to -23.9%. Anomalously low values, -26.8 to 29.3%. 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 δ13C 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.

  8. Oxygen isotope ratio measurements on carbon dioxide generated by reaction of microliter quantities of biological fluids with guanidine hydrochloride

    SciTech Connect

    Wong, W.W.; Lee, L.S.; Klein, P.D.

    1987-03-01

    Guanidine hydrochloride was used to convert water in biological fluids to carbon dioxide for oxygen isotope ratio measurements. Five 10-..mu..L aliquots each of five different saliva, urine, plasma, and human milk samples were allowed to react with 100 mg of guanidine hydrochloride at 260/sup 0/C to produce ammonia and carbon dioxide. Ammonia was removed with 100% phosphoric acid and carbon dioxide was cryogenically purified before isotope ratio measurement. At natural abundances, the delta/sup 18/O values of the biological fluids were reproducible to within 0.16% (standard deviation) and accurate to within 0.11 +/- 0.73% (x vector +/- SD) of the H/sub 2/O-CO/sub 2/ equilibration values. At a 250% enrichment level of /sup 18/O, the delta/sup 18/O values of the biological fluids were reproducible to within 0.95% and accurate to -1.27 +/- 2.25%.

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

    PubMed

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

    2010-03-01

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

  10. Interpretation and application of carbon isotope ratios in freshwater diatom silica

    PubMed Central

    Webb, Megan; Wynn, Peter M.; Heiri, Oliver; van Hardenbroek, Maarten; Pick, Frances; Russell, James M.; Stott, Andy W.; Leng, Melanie J.

    2016-01-01

    ABSTRACT Carbon incorporated into diatom frustule walls is protected from degradation enabling analysis for carbon isotope composition (δ13Cdiatom). This presents potential for tracing carbon cycles via a single photosynthetic host with well‐constrained ecophysiology. Improved understanding of environmental processes controlling carbon delivery and assimilation is essential to interpret changes in freshwater δ13Cdiatom. Here relationships between water chemistry and δ13Cdiatom from contemporary regional data sets are investigated. Modern diatom and water samples were collected from river catchments within England and lake sediments from across Europe. The data suggest dissolved, biogenically produced carbon supplied proportionately to catchment productivity was critical in the rivers and soft water lakes. However, dissolved carbon from calcareous geology overwhelmed the carbon signature in hard water catchments. Both results demonstrate carbon source characteristics were the most important control on δ13Cdiatom, with a greater impact than productivity. Application of these principles was made to a sediment record from Lake Tanganyika. δ13Cdiatom co‐varied with δ13Cbulk through the last glacial and Holocene. This suggests carbon supply was again dominant and exceeded authigenic demand. This first systematic evaluation of contemporary δ13Cdiatom controls demonstrates that diatoms have the potential to supply a record of carbon cycling through lake catchments from sediment records over millennial timescales. PMID:27656013

  11. Annual Variation of Carbon Stable Isotope Ratio in Tree Rings of Riparian Cottonwood Over the Last 225 Years.

    NASA Astrophysics Data System (ADS)

    Friedman, J. M.; Stricker, C. A.; Csank, A. Z.; Zhou, H.

    2016-12-01

    Annual ring width of riparian plains cottonwood (Populus deltoides subsp. monilifera) has recently been shown to be strongly correlated with precipitation in the northern Great Plains, allowing dendrochronological reconstruction of prehistoric climate. Because growth of trees is influenced by multiple environmental drivers, multiple proxies are desirable to improve accuracy of reconstructions. This study addresses the utility of carbon stable isotope ratios of cottonwood tree rings for supplementing climate reconstructions. We analyzed stable isotope ratios (13C/12C) of each annual ring in cores of seven cottonwood trees (two cores per tree) from the floodplain of the Little Missouri River in the North Unit of Theodore Roosevelt National Park, North Dakota, USA. To distinguish effects of age from those of climate variation we used trees established at a wide range of ages, with cores beginning in 1791, 1832, 1881, 1900, 1908, 1948, and 1972. We corrected for change over time in the 13C/12C ratio of atmospheric C02, and, because a juvenile effect was observed, removed the first 26 years from pith from each series. We measured stable isotope ratios using whole wood and, for every fourth sample, purified cellulose. We also measured the proportion of cellulose by mass as a function of years from pith. Mean adjusted stable isotope ratio was strongly negatively correlated (r = -0.60) with annual September-August precipitation for the years 1954-2010. The negative correlation follows the expected pattern of decreased discrimination against 13C under drought stress, and the strength of the correlation is consistent with the fact that growth of cottonwood in the western Great Plains is generally limited by water availability. There was no correlation with temperature after removing the effect of precipitation. Isotope ratios of purified cellulose were higher than for whole wood, reflecting the relatively low isotope ratio of lignin. The difference in isotope ratio between

  12. Utility of 5A molecular sieves to measure carbon isotope ratios in lipid biomarkers.

    PubMed

    Tolosa, Imma; Ogrinc, Nives

    2007-09-21

    A procedure using 5A zeolite sorption to separate cyclic/branched organic compounds from the linear ones was developed and carbon isotopic fractionation effects were investigated in different families of compounds, e.g. within the hydrocarbon and alcohol compounds. The 5A sieve has a pore size such that only linear components can be incorporated into the pores whereas the cyclic/branched compounds are remaining free in the organic solution. The sorbed compounds were released from the molecular sieve with HF and solvent extracted with hexane. The method enables the isolation of linear saturated classes, such as n-alkanes and n-fatty alcohols from branched/cyclic compounds without isotopic fractionation for compound-specific isotope analysis (CSIA) of delta(13)C. However, alkene hydrocarbons, sterols and some aromatics were completely or partly degraded with the molecular sieve.

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

    NASA Technical Reports Server (NTRS)

    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).

  14. Diet selection by steers using microhistological and stable carbon isotope ratio analyses.

    PubMed

    Bennett, L L; Hammond, A C; Williams, M J; Chase, C C; Kunkle, W E

    1999-08-01

    Two methods of determining diet botanical composition, microhistological (MH), and stable carbon isotope ratio (CR) analyses were used to determine botanical composition of ingesta and fecal grab samples in steers grazing rhizoma peanut-mixed tropical grass pastures. Three pastures were used over two grazing seasons, 1992 and 1993, in Brooksville, FL. A weighted-disc double-sampling technique was used to determine forage mass and botanical composition, percentage of rhizoma peanut (Arachis glabrata), grass (Paspalum notatum and Cynodon dactlyon), and forb (primarily Chenopodium ambrosioides) on offer every 28 d throughout the grazing seasons. There was an effect of sampling date (P<.001), sampling date x pasture (P<.001), and sampling date x year (P<.001) on forage mass on offer. There was a pasture x year x sampling date interaction (P<.001) for all botanical components. In 1992 and 1993, using cannulated steers sampled every 56 d, there were interactions with year for rhizoma peanut and forb (P<.05), but not for grass with MH analysis (components: rhizoma peanut, grass, and forb). Ingesta and fecal rhizoma peanut (r = .73 and .92 for 1992 and 1993, respectively) and ingesta and fecal forb (r = .86 and .98 for 1992 and 1993, respectively) were positively correlated (P<.001). Ingesta and fecal grass were positively correlated (r = .52, P<.001), but the correlation was not as high. With the CR analysis (components: Calvin cycle [C3] plants and C4-dicarboxylic acid pathway [C4] plants), ingesta and corrected fecal (corrected for in vitro organic matter digestibility [IVOMD]) C3 plants were positively correlated (r = .62; P<.001). Diet composition of fecal grab samples from noncannulated steers, collected on the same sampling schedule as for hand-clipped pasture samples, differed at times due to the complexity of the sward (both rhizoma peanut and forb constituted a single component, C3, in the CR analysis). Based on these results, if there is a substantial

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  17. Isotopic ratios in planetary atmospheres.

    PubMed

    de Bergh, C

    1995-03-01

    Recent progress on measurements of isotopic ratios in planetary or satellite atmospheres include measurements of the D/H ratio in the methane of Uranus, Neptune and Titan and in the water of Mars and Venus. Implications of these measurements on our understanding of the formation and evolution of the planets and satellite are discussed. Our current knowledge of the carbon, nitrogen and oxygen isotopic ratios in the atmospheres of these planets, as well as on Jupiter and Saturn, is also reviewed. We finally show what progress can be expected in the very near future due to some new ground-based instrumentation particularly well suited to such studies, and to forthcoming space missions.

  18. Effects of organic matter on carbonate stable isotope ratios (δ13C, δ18O values)--implications for analyses of bulk sediments.

    PubMed

    Oehlerich, Markus; Baumer, Marlene; Lücke, Andreas; Mayr, Christoph

    2013-03-30

    Stable isotope ratio (δ(13)C, δ(18)O values) analyses of carbonates can be biased by CO(2) release from organic impurities. This is most critical for carbonate isotope analyses from bulk sediments containing comparably high amounts of organic matter (OM). Several methods have been developed to remove OM prior to analyses, but none of them can be universally applied. Moreover, pretreatment methods cause isotopic bias in themselves and should probably best be avoided. Thus, it is essential to have indicators for reliable isotope values of untreated carbonate-OM mixtures. Artificial mixtures of organic compounds with a standard carbonate were analyzed to investigate the bias on carbonate isotope ratios caused by OM in the sample. The total-inorganic-carbon to total-organic-carbon ratio (TIC/TOC) was used as a measure for the " organic impurity" of the sample. The target was to evaluate TIC/TOC as a measure for sample quality and to define TIC/TOC thresholds for reliable isotope measurements of mixtures between calcium carbonate and organic compounds. The effect of organic impurities on carbonate stable isotope values depended on the specific OM compound and the respective TIC/TOC ratio. Different CO(2) release rates were determined for the pure OM compounds. A sample TIC/TOC ratio ≥0.3 was found to be a threshold for reliable measurements of the isotope composition of calcium carbonate. Bulk carbonate analyses from carbonate-OM mixtures are reliable only if the TIC/TOC values do not fall below certain thresholds. This has implications for carbonate isotope studies from bulk sediments for which the TIC/TOC ratios should be considered as an easy-to-determine measure for sample-quality assessment. Copyright © 2013 John Wiley & Sons, Ltd.

  19. Longitudinal profiling of urinary steroids by gas chromatography/combustion/isotope ratio mass spectrometry: diet change may result in carbon isotopic variations.

    PubMed

    Saudan, Christophe; Kamber, Matthias; Barbati, Giulia; Robinson, Neil; Desmarchelier, Aurélien; Mangin, Patrice; Saugy, Martial

    2006-02-02

    Longitudinal profiling of urinary steroids was investigated by using a gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) method. The carbon isotope ratio of three urinary testosterone (T) metabolites: androsterone, etiocholanolone, 5beta-androstane-3alpha,17beta-diol (5beta-androstanediol) together with 16(5alpha)-androsten-3alpha-ol (androstenol) and 5beta-pregnane-3alpha,20alpha-diol (5beta-pregnanediol) were measured in urine samples collected from three top-level athletes over 2 years. Throughout the study, the subjects were living in Switzerland and were residing every year for a month or two in an African country. (13)C-enrichment larger than 2.5 per thousand was observed for one subject after a 2-month stay in Africa. Our findings reveal that (13)C-enrichment caused by a diet change might be reduced if the stay in Africa was shorter or if the urine sample was not collected within the days after return to Switzerland. The steroids of interest in each sample did not show significant isotopic fractionation that could lead to false positive results in anti-doping testing. In contrast to the results obtained with the carbon isotopic ratio, profiling of urinary testosterone/epitestosterone (T/E) ratios was found to be unaffected by a diet change.

  20. Variation in trophic shift for stable isotope ratios of carbon, nitrogen, and sulfur

    USGS Publications Warehouse

    McCutchan, J.H.; Lewis, W.M.; Kendall, C.; McGrath, C.C.

    2003-01-01

    Use of stable isotope ratios to trace pathways of organic matter among consumers requires knowledge of the isotopic shift between diet and consumer. Variation in trophic shift among consumers can be substantial. For data from the published literature and supplementary original data (excluding fluid-feeding consumers), the mean isotopic shift for C was +0.5 ?? 0.13??? rather than 0.0???, as commonly assumed. The shift for C was higher for consumers analyzed as muscle (+1.3 ?? 0.30???) than for consumers analyzed whole (+0.3 ?? 0.14???). Among consumers analyzed whole, the trophic shift for C was lower for consumers acidified prior to analysis (-0.2 ?? 0.21???) than for unacidified samples (+0.5 ?? 0.17???). For N, trophic shift was lower for consumers raised on invertebrate diets (+1.4 ?? 0.21???) than for consumers raised on other high-protein diets (+3.3 ?? 0.26???) and was intermediate for consumers raised on plant and algal diets (+2.2 ?? 0.30???). The trophic shift for S differed between high-protein (+2.0 ?? 0.65???) and low-protein diets (-0.5 ?? 0.56???). Thus, methods of analysis and dietary differences can affect trophic shift for consumers; the utility of stable isotope methods can be improved if this information is incorporated into studies of trophic relationships. Although few studies of stable isotope ratios have considered variation in the trophic shift, such variation is important because small errors in estimates of trophic shift can result in large errors in estimates of the contribution of sources to consumers or in estimates of trophic position.

  1. The relationship between needle sugar carbon isotope ratios and tree rings of larch in Siberia.

    PubMed

    Rinne, K T; Saurer, M; Kirdyanov, A V; Loader, N J; Bryukhanova, M V; Werner, R A; Siegwolf, R T W

    2015-11-01

    Significant gaps still exist in our knowledge about post-photosynthetic leaf level and downstream metabolic processes and isotopic fractionations. This includes their impact on the isotopic climate signal stored in the carbon isotope composition (δ(13)C) of leaf assimilates and tree rings. For the first time, we compared the seasonal δ(13)C variability of leaf sucrose with intra-annual, high-resolution δ(13)C signature of tree rings from larch (Larix gmelinii Rupr.). The trees were growing at two sites in the continuous permafrost zone of Siberia with different growth conditions. Our results indicate very similar low-frequency intra-seasonal trends of the sucrose and tree ring δ(13)C records with little or no indication for the use of 'old' photosynthates formed during the previous year(s). The comparison of leaf sucrose δ(13)C values with that in other leaf sugars and in tree rings elucidates the cause for the reported (13)C-enrichment of sink organs compared with leaves. We observed that while the average δ(13)C of all needle sugars was 1.2‰ more negative than δ(13)C value of wood, the δ(13)C value of the transport sugar sucrose was on an average 1.0‰ more positive than that of wood. Our study shows a high potential of the combined use of compound-specific isotope analysis of sugars (leaf and phloem) with intra-annual tree ring δ(13)C measurements for deepening our understanding about the mechanisms controlling the isotope variability in tree rings under different environmental conditions. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  2. Comparison of cellulose extraction methods for analysis of stable-isotope ratios of carbon and oxygen in plant material.

    PubMed

    Cullen, Louise E; Macfarlane, Craig

    2005-05-01

    The Jayme-Wise and diglyme-HCl methods for extracting cellulose from plant material for stable-isotope analysis differ considerably in ease of use, with the latter requiring significantly less time and specialized equipment. However, the diglyme-HCl method leaves a small lignin residue in the crude cellulose that may affect stable-isotope values, whereas alpha-cellulose produced by the Jayme-Wise method is relatively pure. We examined whether adding a bleaching step to the diglyme-HCl method could produce cellulose of comparable purity to alpha-cellulose by comparing the yield, percent carbon, and carbon (delta13C) and oxygen (delta18O) stable isotope ratios of the two celluloses. We tested each method on the wood of five species that differ in ease of delignification, Eucalyptus maculata Hook., E. botryoides Sm., E. resinifera Sm., Pinus pinaster Ait. and Callitris glaucophylla J. Thompson & L.A.S. Johnson, as well as the foliage of C. glaucophylla. For hardwoods such as the eucalypts, the diglyme-HCl method without bleaching produced cellulose with delta13C and delta18O ratios similar to alpha-cellulose. For the softwood, C. glaucophylla, 3 h of bleaching with acidified chlorite following treatment with diglyme-HCl produced cellulose with delta13C and delta18O ratios similar to alpha-cellulose. Bleached and unbleached crude celluloses and alpha-cellulose of P. pinaster were similar in delta18O, but not delta13C. Both types of crude cellulose produced from the foliage of C. glaucophylla had significantly different isotope ratios from alpha-cellulose. Overall, the diglyme-HCl method, with or without bleaching, appears to be a simple, fast method for extracting alpha-cellulose from hardwoods for stable-isotope analyses, but its suitability for softwoods and foliage needs to be evaluated depending on the species.

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

    NASA Astrophysics Data System (ADS)

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

    2012-02-01

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

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

    NASA Technical Reports Server (NTRS)

    Sneden, C.; Lambert, D. L.

    1975-01-01

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

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

    PubMed

    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.

  6. CNO abundances and carbon isotope ratios in evolved stars of the open clusters NGC 2324, NGC 2477, and NGC 3960

    NASA Astrophysics Data System (ADS)

    Tautvaišienė, Gražina; Drazdauskas, Arnas; Bragaglia, Angela; Randich, Sofia; Ženovienė, Renata

    2016-10-01

    Aims: Our main aim is to determine carbon-to-nitrogen and carbon isotope ratios for evolved giants in the open clusters NGC 2324, NGC 2477, and NGC 3960, which have turn-off masses of about 2 M⊙, and to compare them with predictions of theoretical models. Methods: High-resolution spectra were analysed using a differential synthetic spectrum method. Abundances of carbon were derived using the C2 Swan (0, 1) band heads at 5135 and 5635.5 Å. The wavelength interval 7940-8130 Å with strong CN features was analysed to determine nitrogen abundances and carbon isotope ratios. The oxygen abundances were determined from the [O i] line at 6300 Å. Results: The mean values of the CNO abundances are [C/Fe] = -0.35 ± 0.06 (s.d.), [N/Fe] = 0.28 ± 0.05, and [O/Fe] = -0.02 ± 0.10 in seven stars of NGC 2324; [C/Fe] = -0.26 ± 0.02, [N/Fe] = 0.39 ± 0.04, and [O/Fe] = -0.11 ± 0.06 in six stars of NGC 2477; and [C/Fe] = -0.39 ± 0.04, [N/Fe] = 0.32 ± 0.05, and [O/Fe] = -0.19 ± 0.06 in six stars of NGC 3960. The mean C/N ratio is equal to 0.92 ± 0.12, 0.91 ± 0.09, and 0.80 ± 0.13, respectively. The mean 12C /13C ratio is equal to 21 ± 1, 20 ± 1, and 16 ± 4, respectively. The 12C /13C and C/N ratios of stars in the investigated open clusters were compared with the ratios predicted by stellar evolution models. Conclusions: The mean values of the 12C /13C and C/N ratios in NGC 2324 and NGC 2477 agree well with the first dredge-up and thermohaline-induced extra-mixing models, which are similar for intermediate turn-off mass stars. The 12C /13C ratios in the investigated clump stars of NGC 3960 span from 10 to 20. The mean carbon isotope and C/N ratios in NGC 3960 are close to predictions of the model in which the thermohaline- and rotation-induced (if rotation velocity at the zero-age main sequence was 30% of the critical velocity) extra-mixing act together. Based on observations collected at ESO telescopes under programmes 072.D-0550 and 074.D-0571.

  7. Reformulated 17O correction of mass spectrometric stable isotope measurements in carbon dioxide and a critical appraisal of historic 'absolute' carbon and oxygen isotope ratios

    NASA Astrophysics Data System (ADS)

    Kaiser, Jan

    2008-03-01

    Mass-spectrometric stable isotope measurements of CO 2 use molecular ion currents at mass-to-charge ratios m/ z 44, 45 and 46 to derive the elemental isotope ratios n( 13C)/ n( 12C) and n( 18O)/ n( 16O), abbreviated 13C/ 12C and 18O/ 16O, relative to a reference. The ion currents have to be corrected for the contribution of 17O-bearing isotopologues, the so-called ' 17O correction'. The magnitude of this correction depends on the calibrated isotope ratios of the reference. Isotope ratio calibrations are difficult and are therefore a matter of debate. Here, I provide a comprehensive evaluation of the existing 13C/ 12C ( 13R), 17O/ 16O ( 17R) and 18O/ 16O ( 18R) calibrations of the reference material Vienna Standard Mean Ocean Water (VSMOW) and CO 2 generated from the reference material Vienna Pee Dee Belemnite (VPDB) by reaction with 100% H 3PO 4 at 25 °C (VPDB-CO 2). I find 17R/10-6=382.7-2.1+1.7, 18RVSMOW/10 -6 = 2005.20 ± 0.45, 13R/10-6= 11124 ± 45, 17R/10-6=391.1-2.1+1.7 and 18R/10-6=2088.37±0.90. I also rephrase the calculation scheme for the 17O correction completely in terms of relative isotope ratio differences ( δ values). This reveals that only ratios of isotope ratios (namely, 17R/ 13R and 13R17R/ 18R) are required for the 17O correction. These can be, and have been, measured on conventional stable isotope mass spectrometers. I then show that the remaining error for these ratios of isotope ratios can lead to significant uncertainty in the derived relative 13C/ 12C difference, but not for 18O/ 16O. Even though inter-laboratory differences can be corrected for by a common 'ratio assumption set' and/or normalisation, the ultimate accuracy of the 17O correction is hereby limited. Errors of similar magnitude can be introduced by the assumed mass-dependent relationship between 17O/ 16O and 18O/ 16O isotope ratios. For highest accuracy in the 13C/ 12C ratio, independent triple oxygen isotope measurements are required. Finally, I propose an experiment that

  8. A novel framework for quantifying past methane recycling by Sphagnum-methanotroph symbiosis using carbon and hydrogen isotope ratios of leaf wax biomarkers

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

    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, δ13C 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.

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

    NASA Technical Reports Server (NTRS)

    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.

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

    PubMed

    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

  11. Concentrations and isotope ratios of carbon, nitrogen and sulfur in ocean-floor basalts

    NASA Technical Reports Server (NTRS)

    Sakai, H.; Ueda, A.; Des Marais, D. J.; Moore, J. G.

    1984-01-01

    Ocean floor basalts studied from the Galapagos Ridge, FAMOUS area, Cayman Trough and Kilauea east rift contain 20-200 ppm carbon and 0.3-2.8 ppn nitrogen as sums of the vesicle-filling gases CO2 and N2 and dissolved species. The wide range of carbon contents found is due partly to the different extent of outgassing of vesicle-filling gases and partly to depth dependency of dissolved CO2 in the basalts. Sulfate commonly exists with sulfide in these basalts, and the sulfate/sulfide ratio increases with increasing water content, perhaps reflecting the higher oxidation potential in basalt melt of the higher water content.

  12. Concentrations and isotope ratios of carbon, nitrogen and sulfur in ocean-floor basalts

    NASA Technical Reports Server (NTRS)

    Sakai, H.; Ueda, A.; Des Marais, D. J.; Moore, J. G.

    1984-01-01

    Ocean floor basalts studied from the Galapagos Ridge, FAMOUS area, Cayman Trough and Kilauea east rift contain 20-200 ppm carbon and 0.3-2.8 ppn nitrogen as sums of the vesicle-filling gases CO2 and N2 and dissolved species. The wide range of carbon contents found is due partly to the different extent of outgassing of vesicle-filling gases and partly to depth dependency of dissolved CO2 in the basalts. Sulfate commonly exists with sulfide in these basalts, and the sulfate/sulfide ratio increases with increasing water content, perhaps reflecting the higher oxidation potential in basalt melt of the higher water content.

  13. Use of stable carbon and nitrogen isotope ratios in size segregated aerosol particles for the O/I penetration evaluation

    NASA Astrophysics Data System (ADS)

    Garbaras, Andrius; Garbariene, Inga; Masalaite, Agne; Ceburnis, Darius; Krugly, Edvinas; Kvietkus, Kestutis; Remeikis, Vidmantas; Martuzevicius, Dainius

    2015-04-01

    Stable carbon and nitrogen isotope ratio are successfully used in the atmospheric aerosol particle source identification [1, 2], transformation, pollution [3] research. The main purpose of this study was to evaluate the penetration of atmospheric aerosol particles from outdoor to indoor using stable carbon and nitrogen isotope ratios. Six houses in Kaunas (Lithuania) were investigated during February and March 2013. Electrical low pressure impactor was used to measure in real time concentration and size distribution of outdoor aerosol particles. ELPI+ includes 15 channels covering the size range from 0.017 to 10.0 µm. The 25 mm diameter aluminium foils were used to collect aerosol particles. Gravimetric analysis of samples was made using microbalance. In parallel, indoor aerosol samples were collected with a micro-orifice uniform deposition impactor (MOUDI model 110), where the aerosol particles were separated with the nominal D50 cut-off sizes of 0.056, 0.1, 0.18,0.32,0.56, 1.0, 1.8, 3.2, 5.6, 10, 18 μm for impactor stages 1-11, respectively. The impactor was run at a flow rate of 30 L/min. Air quality meters were used to record meteorological conditions (temperature, relative humidity) during the investigated period. All aerosol samples were analyzed for total carbon (TC) and total nitrogen (TN) contents and their isotopic compositions using elemental analyzer (EA) connected to the stable isotope ratio mass spectrometer (IRMS). TC concentration in indoors ranged from 1.5 to 247.5 µg/m3. During the sampling period outdoors TN levels ranged from 0.1 to 10.9 µg/m3. The obtained outdoor δ13C(PM2.5) values varied from -24.21 to -26.3‰, while the δ15N values varied from 2.4 to 11.1 ‰ (average 7.2±2.5 ‰). Indoors carbonaceous aerosol particles were depleted in 13C compared to outdoors in all sampling sites. This depletion in δ13C varied from 0.1 to 3.2 ‰. We think that this depletion occurs due ongoing chemical reactions (oxidation) when aerosol

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

    NASA Astrophysics Data System (ADS)

    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

  15. Using Isotope Ratio Infrared Spectrometer to determine δ13C and δ18O of carbonate samples

    NASA Astrophysics Data System (ADS)

    Smajgl, Danijela; Stöbener, Nils; Mandic, Magda

    2017-04-01

    The isotopic composition of calcifying organisms is a key tool for reconstruction past seawater temperature and water chemistry. Therefore stable carbon and oxygen isotopes (δ13C and δ18O) in carbonates have been widely used for reconstruction of paleoenvironments. Precise and accurate determination of isotopic composition of carbon (13C) and oxygen (18O) from carbonate sample with proper referencing and data evaluation algorithm presents a challenge for scientists. Mass spectrometry was the only widely used technique for this kind of analysis, but recent advances make laser based spectroscopy a viable alternative. The Thermo Scientific Delta Ray Isotope Ratio Infrared Spectrometer (IRIS) analyzer with the Universal Reference Interface (URI) Connect is one of those alternatives and with TELEDYNE Cetac ASX-7100 autosampler extends the traditional offerings with a system of high precision and throughput of samples. To establish precision and accuracy of measurements and also to develop optimal sample preparation method for measurements with Delta Ray IRIS and URI Connect, IAEA reference materials were used. Preparation is similar to a Gas Bench II method. Carbonate material is added into the vials, flushed with CO2 free synthetic air and acidified with few droplets of 104% H3PO4. Sample amount used for analysis can be as low as 200 μg. Samples are measured after acidification and equilibration time of one hour at 70°C. The CO2 gas generated by reaction is flushed into the variable volume inside the URI Connect through the Nafion based built-in water trap. For this step, carrier gas (CO2 free air) is used to flush the gas from the vial into the variable volume with a maximum volume of 100 ml. A small amount of the sample is then used for automatic concentration determination present in the variable volume. The Thermo Scientific Qtegra Software automatically adjusts any additional dilution of the sample to achieve the desired concentration (usually 400 ppm) in the

  16. Complementary stable carbon isotope ratio and amount of substance measurements in sports anti-doping.

    PubMed

    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.

  17. Stable carbon isotope ratios of archaeal GDGTs in the marine water column and surface sediments

    NASA Astrophysics Data System (ADS)

    Pearson, A.; Hurley, S.; Close, H. G.; Jasper, C. E.

    2016-12-01

    Archaeal glycerol dibiphytanyl glycerol tetraether (GDGT) lipids are ubiquitous throughout the marine environment and are preserved in sediments and sedimentary rocks on million-year timescales. Variations in the number of ring-containing GDGT isomers in sediments correlate with differences in overlying sea surface temperatures, a relationship formalized in the TEX86 paleotemperature proxy. Ammonia-oxidizing Thaumarchaeota are believed to be the major sources of these GDGTs, implying that the greatest production and export of GDGTs from the water column should be associated with the maximum expression of ammonia monooxygenase (amoA) genes and maximum number of thaumarchaeal cells, both of which occur in the subsurface NO2- maximum near a depth of ca. 80-250 m. To examine the relationship between production and export of GDGTs from the water column, we measured the concentrations and δ13C values of GDGTs in suspended particulate matter (SPM) of the western South Atlantic Ocean and compared them to values from pure thaumarchaeal cultures and from available sediment core-tops from other locations. Thaumarchaeota are believed to fix the majority of their carbon directly from dissolved inorganic carbon (DIC). However, both the SPM and core-top δ13C values in some cases are moderately more 13C-depleted than would be predicted based on the 13C content of local DIC and the previously-published biosynthetic isotope fractionation (ɛ). This indicates that the average metabolism of the planktonic archaeal community either is mixotrophic (≥ 25% organic carbon assimilation) or that the published ɛ value for the model organism Nitrosopumilus maritimus may not be representative of the total autotrophic community. In addition to this offset, δ13C values of GDGTs in SPM inversely mirror DIC profiles, with lowest values in the nitrite maximum and higher values in the deeper water column, similar to the overall trends for bulk SPM. Finally, while individual GDGTs in SPM samples

  18. Carbon isotope ratio mass spectrometry for detection of endogenous steroid use: a testing strategy.

    PubMed

    Ahrens, Brian D; Butch, Anthony W

    2013-07-01

    Isotope ratio mass spectrometry (IRMS) testing is performed to determine if an atypical steroid profile is due to administration of an endogenous steroid. Androsterone (Andro) and etiocholanolone (Etio), and/or the androstanediols (5α- and 5β-androstane-3α,17β-diol) are typically analyzed by IRMS to determine the (13) C/(12) C ratio. The ratios of these target compounds are compared to the (13) C/(12) C ratio of an endogenous reference compound (ERC) such as 5β-pregnane-3α,20α-diol (Pdiol). Concentrations of Andro and Etio are high so (13) C/(12) C ratios can easily be measured in most urine samples. Despite the potentially improved sensitivity of the androstanediols for detecting the use of some testosterone formulations, additional processing steps are often required that increase labour costs and turnaround times. Since this can be problematic when performing large numbers of IRMS measurements, we established thresholds for Andro and Etio that can be used to determine the need for additional androstanediol testing. Using these criteria, 105 out of 2639 urine samples exceeded the Andro and/or Etio thresholds, with 52 of these samples being positive based on Andro and Etio IRMS testing alone. The remaining 53 urine samples had androstanediol IRMS testing performed and 3 samples were positive based on the androstanediol results. A similar strategy was used to establish a threshold for Pdiol to identify athletes with relatively (13) C-depleted values so that an alternative ERC can be used to confirm or establish a true endogenous reference value. Adoption of a similar strategy by other laboratories can significantly reduce IRMS sample processing and analysis times, thereby increasing testing capacity.

  19. Stable Carbon Isotope Ratios in Atmospheric VOC across the Asian Summer Monsoon Anticyclone obtained during the OMO-ASIA campaign

    NASA Astrophysics Data System (ADS)

    Krebsbach, Marc; Koppmann, Ralf; Meisehen, Thomas

    2017-04-01

    The automated high volume air sampling system (MIRAH) has been deployed during the atmospheric measurement campaign OMO-ASIA (Oxidation Mechanism Observations) with the German High Altitude - Long-range research aircraft (HALO) in July and August 2015. The intensive measurement period with base stations in Paphos (Cyprus) and Gan (Maldives) focussed on oxidation processes and air pollution chemistry downwind of the South Asia summer monsoon anticyclone, a pivot area critical for air quality and climate change, both regionally and worldwide. The measurement region covered the Eastern Mediterranean region, the Arabian Peninsula, Egypt, and the Arabian Sea. In total 194 air samples were collected on 17 flights in a height region from 3 km up to 15 km. The air samples were analysed for stable carbon isotope ratios in VOC with GC-C-IRMS in the laboratory afterwards. We determined stable carbon isotope ratios and mixing ratios of several aldehydes, ketones, alcohols, and aromatics. The large extent of the investigated area allowed for encountering air masses with different origin, characteristic, and atmospheric processing, e.g. Mediterranean air masses, crossing of polluted filaments and remnants of the Asian monsoon outflow, split of the Asian monsoon anticyclone. In this presentation we will show first results and interpretations supported by HYSPLIT backward trajectories.

  20. Correlation between the Carbon Isotope Discrimination in Leaf Starch and Sugars of C3 Plants and the Ratio of Intercellular and Atmospheric Partial Pressures of Carbon Dioxide

    PubMed Central

    Brugnoli, Enrico; Hubick, Kerry T.; von Caemmerer, Susanne; Wong, Suan Chin; Farquhar, Graham D.

    1988-01-01

    Carbon isotope discrimination (Δ) was analyzed in leaf starch and soluble sugars, which represent most of the recently fixed carbon. Plants of three C3 species (Populus nigra L. × P. deltoides Marsh., Gossypium hirsutum L. and Phaseolus vulgaris L.) were kept in the dark for 24 hours to decrease contents of starch and sugar in leaves. Then gas exchange measurements were made with constant conditions for 8 hours, and subsequently starch and soluble sugars were extracted for analysis of carbon isotope composition. The ratio of intercellular, pi, and atmospheric, pa, partial pressures of CO2, was calculated from gas exchange measurements, integrated over time and weighted by assimilation rate, for comparison with the carbon isotope ratios in soluble sugars and starch. Carbon isotope discrimination in soluble sugars correlated strongly (r = 0.93) with pi/pa in all species, as did Δ in leaf starch (r = 0.84). Starch was found to contain significantly more 13C than soluble sugar, and possible explanations are discussed. The strong correlation found between Δ and pi/pa suggests that carbon isotope analysis in leaf starch and soluble sugars may be used for monitoring, indirectly, the average of pi/pa weighted by CO2 assimilation rate, over a day. Because pi/pa has a negative correlation with transpiration efficiency (mol CO2/mol H2O) of isolated plants, Δ in starch and sugars may be used to predict differences in this efficiency. This new method may be useful in ecophysiological studies and in selection for improved transpiration efficiency in breeding programs for C3 species. PMID:16666476

  1. Fractionation of the stable carbon isotope ratio of essential fatty acids in zebrafish Danio rerio and mud snails Bellamya chinensis.

    PubMed

    Fujibayashi, Megumu; Ogino, Masahiro; Nishimura, Osamu

    2016-02-01

    Fractionation of stable carbon (C) isotopes in the essential fatty acids 18:2n-6, 18:3n-3, 20:4n-6, 20:5n-3, and 22:6n-3 was investigated in the zebrafish Danio rerio and the mud snail Bellamya chinensis fed the same two diets. These diets differed in essential fatty acid compositions: (1) TetraMin contained all five fatty acids, and (2) Chlorella contained only two, 18:2n-6 and 18:3n-3. On average, the isotopic fractionation was -0.5 ± 0.9 ‰ for 18:2n-6 and 18:3n-3 for all experiments, indicating that the fractionation of these essential fatty acids was negligible. However, the isotopic fractionation of 20:4n-6, 20:5n-3, and 22:6n-3 varied greatly between species and between diets. The isotopic fractionation of the Chlorella diet was -0.2 and -6.9 ‰ for zebrafish and mud snail, but 4.2 and -1.3 ‰, respectively, when these consumers were fed TetraMin. This variation could be explained by the different amount of assimilation and the biosynthesis of these fatty acids from their precursors (i.e., 18:2n-6 and 18:3n-3). These results indicate that the isotopic composition of C20 and C22 essential fatty acids was strongly influenced by the fatty acid composition in the diets. Thus the stable C isotope ratios of C18 essential fatty acids in consumers are more useful as dietary tracers in food web studies.

  2. Carbon isotope ratio monitoring-gas chromatography mass spectrometric measurements in the marine environment: biomarker sources and paleoclimate applications.

    PubMed

    Tolosa, I; Lopez, J F; Bentaleb, I; Fontugne, M; Grimalt, J O

    1999-09-30

    Some applications in the use of compound-specific isotopic analyses (CSIA) for biomarker source elucidation in the marine environment and its potential applications to paleoclimatology are evaluated in the present study. The potential use of the carbon isotope ratios of marine biomarkers as recorders of CO2 levels has been considered. A significant correlation between delta 13C cholesterol of suspended particulates and seawater CO2 concentrations from the south Indian Ocean has been found. delta 13C composition in biomarkers of different functionalities from three photosynthetic organisms has been examined. Small variations within and between biosynthetically related compound classes have been observed in cyanobacteria. In algae, e.g. diatoms and dinoflagellates, significant differences between the average delta 13C composition of fatty acids and sterols were observed (7.5/1000 and 2/1000, respectively). These differences can be attributed to diverse isotope effects associated with different biosynthetic reactions. Isotopic variations among homologues of the same lipid class have also been observed. In diatoms, variations were up to 5/1000 within each class of fatty acids and sterols and in the dinoflagellate species, these variations were lower than 3/1000. These differences, and particularly the intra-specific shifts in delta 13C lipid composition, must be considered for the correct interpretation of changes in delta 13C molecular signatures in the marine environment.

  3. Annual rainfall does not directly determine the carbon isotope ratio of leaves of Eucalyptus species.

    PubMed

    Turner, Neil C; Schulze, Ernst-Detlef; Nicolle, Dean; Schumacher, Jens; Kuhlmann, Iris

    2008-04-01

    Leaf carbon isotope discrimination (delta13C) was widely considered to directly reflect the rainfall environment in which the leaf developed, but recent observations have queried this. The relationship between delta13C and rainfall was explored in Eucalyptus species growing along a rainfall gradient in Australia. The leaves of 43 species of Eucalyptus and the closely related Corymbia species produced in 2003 were sampled in September 2004 at 50 sites and grouped into 15 locations along a rainfall gradient in southwest Western Australia. At 24 sites, the same species and same trees were sampled as in a study in September 2003 when leaves produced in 2002 were sampled. The rainfall in 2004 was on average 190 mm (range 135-270 mm) higher at all locations than in 2003. In the leaves sampled in 2004, the mean carbon isotope discrimination (delta13C) across the 15 locations decreased 2.9 per thousand per 1000 mm of rainfall, the specific leaf area (SLA) increased by 2.9 m2 kg(-1) per 1000 mm of rainfall and the nitrogen (N) content decreased by 1.56 g m(-2) per 1000 mm of rainfall. In contrast, a comparison between the leaves produced in the drier 2002 year compared with the wetter 2003 year showed that there was a strong correlation (r2= 0.85) between the SLA values between years and a trend for higher values with increasing SLA, but the values of delta(13)C were on average only 0.38 per thousand lower (more negative) at all locations in the wetter year, equivalent to a decrease of 2.0 per thousand per 1000 mm of rainfall. The results suggest that while there may be constitutive differences in leaf morphology, SLA and N content per unit area, increasing rainfall or cloudiness associated with higher rainfall increases SLA and decreases N content per unit area. We conclude that rainfall does not directly influence delta13C, but induces leaf morphological and physiological changes that affect the resultant delta13C.

  4. The influences of cultivation setting on inflorescence lipid distributions, concentrations, and carbon isotope ratios of Cannabis sp.

    PubMed

    Tipple, Brett J; Hambach, Bastian; Barnette, Janet E; Chesson, Lesley A; Ehleringer, James R

    2016-05-01

    While much is known about how the growth environment influences many aspects of floral morphology and physiology, little is known about how the growth setting influences floral lipid composition. We explored variations in paraffin wax composition in Cannabis sp., a cash crop grown both indoors and outdoors across the United States today. Given an increased focus on regulation of this crop, there are additional incentives to certify the setting of Cannabis cultivation. To understand the impacts of the growth environment, we studied distributions, concentrations, and carbon isotope ratios of n-alkanes isolated from Cannabis sp. inflorescences to assess if variations within these lipid parameters were related to known growth settings of specimens seized by federal agents. We found that Cannabis plants cultivated under open-field settings had increased inflorescence paraffin wax abundances and greater production of lower molecular weight n-alkanes relative to plants grown in enclosed environments. Further, the carbon isotope ratios of n-C29 from Cannabis plants grown in enclosed environments had relatively lower carbon isotope (δ(13)C) values compared to plants from open-field environments. While this set of observations on seized plant specimens cannot address the particular driver behind these observations, we posit that (a) variations in irradiance and/or photoperiod may influence the distribution and concentration of inflorescence lipids, and (b) the δ(13)C value of source CO2 and lipid concentration regulates the δ(13)C values of inflorescence n-C29 and bulk Cannabis plant materials. Nonetheless, by using a cultivation model based on δ(13)C values of n-C29, the model correctly identified the growth environment 90% of time. We suggest that these lipid markers may be used to trace cultivation methods of Cannabis sp. now and become a more powerful marker in the future, once the mechanism(s) behind these patterns is uncovered.

  5. Carbon Isotope Ratios Of Carbon Dioxide In The Urban Salt Lake Valley, Utah USA: Source And Long-Term Monitoring Observations

    NASA Astrophysics Data System (ADS)

    Ehleringer, J.; Lai, C.; Strong, C.; Pataki, D. E.; Bowling, D. R.; Schauer, A. J.; Bush, S.

    2011-12-01

    A high-precision, decadal record of carbon isotope ratios in atmospheric carbon dioxide has been produced for the urbanized Salt Lake Valley, Utah USA. These data complement a similar time series of atmospheric carbon dioxide concentrations for different locations in the same urban region. This isotopic record includes diurnal and nocturnal observations based on flask (IRMS-based) and continuous (TDL-based) measurement systems. These data reveal repeatable diurnal and seasonal variations in the anthropogenic and biogenic carbon sources that can be used to reconstruct different source inputs. As the Salt Lake Valley is an isolated urban region, the impacts of local anthropogenic inputs can be distinguished from regional patterns as measured by NOAA at the rural Wendover monitoring station 200 km to the west of the Salt Lake Valley. Complementary data, such as vehicle exhaust, emission from power plants and household furnaces, plant and soil organic matter, are also provided to quantify the carbon isotope ratios of the predominant anthropogenic and biogenic sources within the Salt Lake Valley. The combined source and long-term observational values will be made freely available and their utility is discussed for modeling efforts including urban metabolism modeling and atmospheric trace gas modeling.

  6. Stable isotope ratios of carbon and hydrogen to distinguish olive oil from shark squalene-squalane.

    PubMed

    Camin, Federica; Bontempo, Luana; Ziller, Luca; Piangiolino, Cristiana; Morchio, Gianni

    2010-06-30

    Squalene and its hydrogenated derivate squalane are widely used in the pharmaceutical and cosmetic fields. The two compounds are mainly produced from the liver oil of deep sea sharks and from olive oil distillates. Squalene and squalane from shark cost less than the same compounds derived from olive oil, and the use of these shark-derived compounds is unethical in cosmetic formulations. In this work we investigate whether (13)C/(12)C and (2)H/(1)H ratios can distinguish olive oil from shark squalene/squalane and can detect the presence of shark derivates in olive oil based products. The (13)C/(12)C ratios (expressed as delta(13)C values) of bulk samples and of pure compounds measured using isotope ratio mass spectrometry (IRMS) were significantly lower in authentic olive oil squalene/squalane (N: 13; -28.4 +/- 0.5 per thousand; -28.3 +/- 0.8 per thousand) than in shark squalene/squalane samples (N: 15; -20.5 +/- 0.7 per thousand; -20.4 +/- 0.6 per thousand). By defining delta(13)C threshold values of -27.4 per thousand and -26.6 per thousand for olive oil bulk and pure squalene/squalane, respectively, illegal addition of shark products can be identified starting from a minimum of 10%. (2)H/(1)H analysis is not useful for distinguishing the two different origins. Delta(13)C analysis is proposed as a suitable tool for detecting the authenticity of commercial olive oil squalene and squalane samples, using IRMS interfaced to an elemental analyser if the purity is higher than 80% and IRMS interfaced to a gas chromatography/combustion system for samples with lower purity, including solutions of squalane extracted from cosmetic products. Copyright 2010 John Wiley & Sons, Ltd.

  7. Isotope Ratios of Cellulose from Plants Having Different Photosynthetic Pathways

    PubMed Central

    Sternberg, Leonel O.; Deniro, Michael J.; Johnson, Hyrum B.

    1984-01-01

    Hydrogen and carbon isotope ratios of cellulose nitrate and oxygen isotope ratios of cellulose from C3, C4, and Crassulacean acid metabolism (CAM) plants were determined for plants growing within a small area in Val Verde County, Texas. Plants having CAM had distinctly higher deuterium/hydrogen (D/H) ratios than plants having C3 and C4 metabolism. When hydrogen isotope ratios are plotted against carbon isotope ratios, each photosynthetic mode separates into a distinct cluster of points. C4 plants had many D/H ratios similar to those of C3 plants, so that hydrogen isotope ratios cannot be used to distinguish between these two photosynthetic modes. Portulaca mundula, which may have a modified photosynthetic mode between C4 and CAM, had a hydrogen isotope ratio between those of the C4 and CAM plants. When oxygen isotope ratios are plotted against carbon isotope ratios, no distinct clustering of the C4 and CAM plants occurs. Thus, oxygen isotope ratios are not useful in distinguishing between these metabolic modes. A plot of hydrogen isotope ratios versus oxygen isotope ratios for this sample set shows considerable overlap between oxygen isotope ratios of the different photosynthetic modes without a concomitant overlap in the hydrogen isotope ratios of CAM and the other two photosynthetic modes. This observation is consistent with the hypothesis that higher D/H ratios in CAM plants relative to C3 and C4 plants are due to isotopic fractionations occurring during biochemical reactions. PMID:16663460

  8. Stable nitrogen and carbon isotope ratios indicate traditional and market food intake in an indigenous circumpolar population.

    PubMed

    Nash, Sarah H; Bersamin, Andrea; Kristal, Alan R; Hopkins, Scarlett E; Church, Rebecca S; Pasker, Renee L; Luick, Bret R; Mohatt, Gerald V; Boyer, Bert B; O'Brien, Diane M

    2012-01-01

    The transition of a society from traditional to market-based diets (termed the nutrition transition) has been associated with profound changes in culture and health. We are developing biomarkers to track the nutrition transition in the Yup'ik Eskimo population of Southwest Alaska based on naturally occurring variations in the relative abundances of carbon and nitrogen stable isotopes (δ(15)N and δ(13)C values). Here, we provide three pieces of evidence toward the validation of these biomarkers. First, we analyzed the δ(15)N and δ(13)C values of a comprehensive sample of Yup'ik foods. We found that δ(15)N values were elevated in fish and marine mammals and that δ(13)C values were elevated in market foods containing corn or sugar cane carbon. Second, we evaluated the associations between RBC δ(15)N and δ(13)C values and self-reported measures of traditional and market food intake (n = 230). RBC δ(15)N values were correlated with intake of fish and marine mammals (r = 0.52; P < 0.0001). RBC δ(13)C values were correlated with intake of market foods made from corn and sugar cane (r = 0.46; P < 0.0001) and total market food intake (r = 0.46; P < 0.0001). Finally, we assessed whether stable isotope ratios captured population-level patterns of traditional and market intake (n = 1003). Isotopic biomarkers of traditional and market intake were associated with age, community location, sex, and cultural identity. Self-report methods showed variations by age and cultural identity only. Thus, stable isotopes show potential as biomarkers for monitoring dietary change in indigenous circumpolar populations.

  9. Stable Nitrogen and Carbon Isotope Ratios Indicate Traditional and Market Food Intake in an Indigenous Circumpolar Population123

    PubMed Central

    Nash, Sarah H.; Bersamin, Andrea; Kristal, Alan R.; Hopkins, Scarlett E.; Church, Rebecca S.; Pasker, Renee L.; Luick, Bret R.; Mohatt, Gerald V.; Boyer, Bert B.; O’Brien, Diane M.

    2012-01-01

    The transition of a society from traditional to market-based diets (termed the nutrition transition) has been associated with profound changes in culture and health. We are developing biomarkers to track the nutrition transition in the Yup’ik Eskimo population of Southwest Alaska based on naturally occurring variations in the relative abundances of carbon and nitrogen stable isotopes (δ15N and δ13C values). Here, we provide three pieces of evidence toward the validation of these biomarkers. First, we analyzed the δ15N and δ13C values of a comprehensive sample of Yup’ik foods. We found that δ15N values were elevated in fish and marine mammals and that δ13C values were elevated in market foods containing corn or sugar cane carbon. Second, we evaluated the associations between RBC δ15N and δ13C values and self-reported measures of traditional and market food intake (n = 230). RBC δ15N values were correlated with intake of fish and marine mammals (r = 0.52; P < 0.0001). RBC δ13C values were correlated with intake of market foods made from corn and sugar cane (r = 0.46; P < 0.0001) and total market food intake (r = 0.46; P < 0.0001). Finally, we assessed whether stable isotope ratios captured population-level patterns of traditional and market intake (n = 1003). Isotopic biomarkers of traditional and market intake were associated with age, community location, sex, and cultural identity. Self-report methods showed variations by age and cultural identity only. Thus, stable isotopes show potential as biomarkers for monitoring dietary change in indigenous circumpolar populations. PMID:22157543

  10. High-precision, automated stable isotope analysis of atmospheric methane and carbon dioxide using continuous-flow isotope-ratio mass spectrometry.

    PubMed

    Fisher, Rebecca; Lowry, David; Wilkin, Owen; Sriskantharajah, Srimathy; Nisbet, Euan G

    2006-01-01

    Small-scale developments have been made to an off-the-shelf continuous-flow gas chromatography/isotope-ratio mass spectrometry (CF-GC/IRMS) system to allow high-precision isotopic analysis of methane (CH(4)) and carbon dioxide (CO(2)) at ambient concentrations. The repeatability (1sigma) obtainable with this system is 0.05 per thousand for delta(13)C of CH(4), 0.03 per thousand for delta(13)C of CO(2), and 0.05 per thousand for delta(18)O of CO(2) for ten consecutive analyses of a standard tank. An automated inlet system, which allows diurnal studies of CO(2) and CH(4) isotopes, is also described. The improved precision for CH(4) analysis was achieved with the use of a palladium powder on quartz wool catalyst in the combustion furnace, which increased the efficiency of oxidation of CH(4) to CO(2). The automated inlet further improved the precision for both CH(4) and CO(2) analysis by keeping the routine constant. The method described provides a fast turn-around in samples, with accurate, reproducible results, and would allow a long-term continuous record of CH(4) or CO(2) isotopes at a site to be made, providing information about changing sources of the gases both seasonally and interannually.

  11. Influence of Reproduction on Stable-Isotope Ratios: Nitrogen and Carbon Isotope Discrimination between Mothers, Fetuses, and Milk in the Fin Whale, a Capital Breeder.

    PubMed

    Borrell, A; Gómez-Campos, E; Aguilar, A

    2016-01-01

    In mammals, the influence of gestation and lactation on the tissue stable-isotope ratios of females, fetuses, and milk remains poorly understood. Here we investigate the incidence of these events on δ(13)C and δ(15)N values in fin whales sampled off northwestern Spain between 1983 and 1985. The effect of gestation on tissue stable-isotope ratios was examined in the muscle of pregnant females (n = 13) and their fetuses (n = 10) and that of lactation in the muscle of nursing females (n = 21) and their milk (n = 25). Results suggest that fetuses are enriched compared to their mothers in both (15)N (Δ(15)N = 1.5‰) and (13)C (Δ(13)C =1.1‰), while, compared to muscle, milk is enriched in (15)N (Δ(15)N = 0.3‰) but depleted in (13)C (Δ(13)C = -0.62‰). This pattern is consistent with that previously observed for other species that, like the fin whale, rely on endogenous energy during reproduction, and it substantiates a general difference in the physiological processing of nitrogen and carbon balances between income and capital breeders. These findings are relevant to the understanding of the energetic balance of mammals during gestation and lactation and are central when inferences on trophic ecology are drawn from isotopic values of reproductive females.

  12. Measurement of compound-specific carbon isotope ratios (δ(13) C values) via direct injection of whole crude oil samples.

    PubMed

    Barrie, Craig D; Taylor, Kyle W R; Zumberge, John

    2016-04-15

    Stable isotope analysis is a powerful tool in understanding the generation, history and correlation of hydrocarbons. Compound-specific δ(13) C measurements of oils allow detailed comparison of individual compound groupings; however, most studies of these sample materials separate and isolate individual fractions based on the chemistries of particular compound groups, potentially losing considerable valuable isotopic data. Even if all fractions are analyzed, this represents a large increase in the data-processing burden, effectively multiplying data evaluation time and effort by the number of fractions produced. Gas chromatography/isotope ratio mass spectrometry (GC/IRMS) of untreated, whole crude oils allows the immediate collection of a larger suite of valuable isotopic data for these studies. Untreated ('neat', undiluted), whole crude oils were directly injected and measured on a GC/IRMS system, using split (40:1) injections and a 50 m HP-PONA column. The GC method, 97 min in duration, was designed to maximize baseline separation of target analyte peaks, while an additional oxygen flow was admitted into the combustion reactor to maximize the lifetime of the combustion chemicals. The method and setup utilized allow the measurement of a much greater range of the n-alkanes (n-C4 to n-C25+ ) than traditional methods, while also retaining important cycloalkane, aromatic and isoprenoid peaks within the same analysis. Carbon isotope (δ(13) C) evaluation of these additional compound classes reveals trends in maturity and origins which are not identifiable when exclusively assessing the traditional n-alkane package (>n-C12 ). The described setup and method open up new possibilities for assessing the origins and histories of crude oil samples. The data generated for the whole oil n-alkanes by this method is equivalent to that reported for isolated n-alkane studies, while also providing valuable additional data on many other important compounds. The end result of this

  13. Characterisation of crude oils by carbon and sulphur isotope ratio measurements as a tool for pollution control.

    PubMed

    Becker, S; Hirner, A V

    1998-01-01

    The potential of carbon and sulphur isotope ratios to group crude oils with respect to their origin was investigated. Sample selection was based on the actual crude oil imports to Germany. Analysed crude oils from Algeria, the Community of Independent States (CIS), Middle East, Nigeria, the North Sea and Venezuela make up over 86% of the German crude oil imports. The oil as received was deasphalted and the maltene fraction was separated by MPLC into saturated, aromatic and polar fractions. Due to overlapping areas, it is not possible to group the crude oils by their delta 13C values alone. A complete grouping of the crude oils with respect to their origin can only be achieved by the combined use of delta 13C and delta 34S of crude oils, and isotope type-curves. In some cases isotope type-curves enable differentiation between different oil fields of the same geographical origin. In order to determine the post-spill changes of delta 13C values, an experimental spill of crude oil was studied over a period of seven weeks in an outdoor aquarium containing pond water. The delta 13C measurements of crude oil fractions showed changes up to 1.1/1000 during the oil spill simulation. The delta 13C values of the polar fraction exhibited the smallest change, with a variation of 0.3/1000, and are therefore especially useful for the characterisation of crude oil spills.

  14. Modelling the Phanerozoic carbon cycle and climate: constraints from the 87Sr/86Sr isotopic ratio of seawater

    NASA Technical Reports Server (NTRS)

    Francois, L. M.; Walker, J. C.

    1992-01-01

    A numerical model describing the coupled evolution of the biogeochemical cycles of carbon, sulfur, calcium, magnesium, phosphorus, and strontium has been developed to describe the long-term changes of atmospheric carbon dioxide and climate during the Phanerozoic. The emphasis is on the effects of coupling the cycles of carbon and strontium. Various interpretations of the observed Phanerozoic history of the seawater 87Sr/86Sr ratio are investigated with the model. More specifically, the abilities of continental weathering, volcanism, and surface lithology in generating that signal are tested and compared. It is suggested that the observed fluctuations are mostly due to a changing weatherability over time. It is shown that such a conclusion is very important for the modelling of the carbon cycle. Indeed, it implies that the conventional belief that the evolution of atmospheric carbon dioxide and climate on a long time scale is governed by the balance between the volcanic input of CO2 and the rate of silicate weathering is not true. Rather carbon exchanges between the mantle and the exogenic system are likely to have played a key role too. Further, the increase of the global weathering rates with increasing surface temperature and/or atmospheric CO2 pressure usually postulated in long-term carbon cycle and climate modelling is also inconsistent with the new model. Other factors appear to have modulated the weatherability of the continents through time, such as mountain building and the existence of glaciers and ice sheets. Based on these observations, a history of atmospheric carbon dioxide and climate during Phanerozoic time, consistent with the strontium isotopic data, is reconstructed with the model and is shown to be compatible with paleoclimatic indicators, such as the timing of glaciation and the estimates of Cretaceous paleotemperatures.

  15. Modelling the Phanerozoic carbon cycle and climate: constraints from the 87Sr/86Sr isotopic ratio of seawater.

    PubMed

    François, L M; Walker, J C

    1992-02-01

    A numerical model describing the coupled evolution of the biogeochemical cycles of carbon, sulfur, calcium, magnesium, phosphorus, and strontium has been developed to describe the long-term changes of atmospheric carbon dioxide and climate during the Phanerozoic. The emphasis is on the effects of coupling the cycles of carbon and strontium. Various interpretations of the observed Phanerozoic history of the seawater 87Sr/86Sr ratio are investigated with the model. More specifically, the abilities of continental weathering, volcanism, and surface lithology in generating that signal are tested and compared. It is suggested that the observed fluctuations are mostly due to a changing weatherability over time. It is shown that such a conclusion is very important for the modelling of the carbon cycle. Indeed, it implies that the conventional belief that the evolution of atmospheric carbon dioxide and climate on a long time scale is governed by the balance between the volcanic input of CO2 and the rate of silicate weathering is not true. Rather carbon exchanges between the mantle and the exogenic system are likely to have played a key role too. Further, the increase of the global weathering rates with increasing surface temperature and/or atmospheric CO2 pressure usually postulated in long-term carbon cycle and climate modelling is also inconsistent with the new model. Other factors appear to have modulated the weatherability of the continents through time, such as mountain building and the existence of glaciers and ice sheets. Based on these observations, a history of atmospheric carbon dioxide and climate during Phanerozoic time, consistent with the strontium isotopic data, is reconstructed with the model and is shown to be compatible with paleoclimatic indicators, such as the timing of glaciation and the estimates of Cretaceous paleotemperatures.

  16. Performance Evaluation of a New, Tunable-Diode Laser Trace-Gas Analyzer for Isotope Ratios of Carbon Dioxide

    NASA Astrophysics Data System (ADS)

    Sargent, S.

    2015-12-01

    Newly available interband cascade lasers (ICLs) have enabled the development of a family of tunable-diode laser trace-gas analyzers that do not require liquid nitrogen to cool the laser. The lasers are available in the 3000 to 6000 nm range, providing access to the strong mid-infrared absorption lines for important gases such as methane, nitrous oxide, and carbon dioxide. These ICLs are fabricated with distributed feedback to improve their stability and spectroscopic quality. A recently released trace-gas analyzer for carbon dioxide isotopes (TGA200A, Campbell Scientific, Inc.) was evaluated for short- and long-term precision using Allan variance. Accuracy and linearity of CO2 mole fraction was assessed with a set of seven NOAA standard reference gases ranging from 298.35 to 971.48 ppm. Dilution of high-concentration CO2 with CO2-free air demonstrated the linearity of isotope ratio measurements beyond 1000 ppm CO2. Two analyzer variants were tested: one for CO2, δ13C and δ18O; and the other for CO2 and δ13C at enhanced precision.

  17. The ratios of carbon and non-radiogenic helium and argon isotopes in the mantle and crustal rocks

    NASA Technical Reports Server (NTRS)

    Lokhov, K.; Levsky, L.

    1994-01-01

    The studies of the relations of carbon and primary isotopes of noble gases were carried out on the natural gases and on the mantle rocks from the mantle M-type sources, which represent the degassed mantle reservoir (MORB's). These works has the aim of estimation of the values of the C/3He ratios in the deep mantle fluids to determine the flux of the mantle CO2 on the basis of known flux of primary mantle 3He. It was found, that in the natural gases the values of the C/3He ratios fall into the range from 1 times E plus 6 to 1 times E plus 15, and in the fluids of MORB's are constant near 2 times E plus 9. We have studied the mantle rocks from the relatively undergassed mantle P minus type sources: continental; Baikal Rift (Siberia), Mongolia, Catalonia (Spain), Pannonia Depression (central Europe) and ocean; Spietzbergen isl., Hawaii isl., Canarian isl. It ws found, that in mantle xenolites and the host alkaline basalts from the continental rifts and ocean islands, the values of the C/3He ratios fall into the range from E plus 11 to E plus 15 (and this result needed to be explained; the higher carbon to helium ratios is relatively undergassed mantle reservoir compared with the degassed one, requires whether hilly compatibility of helium compared with carbon, whether additional flux of 3He to the degassed mantle reservoir). From the other hand it was found that in the mantle rocks from the sources of P minus and M minus types, continental carbonatites, the values of the C/36Ar ratios are constant in the range from E plus 9 to E plus 10, the close values have the MORB's also.

  18. The ratios of carbon and non-radiogenic helium and argon isotopes in the mantle and crustal rocks

    NASA Technical Reports Server (NTRS)

    Lokhov, K.; Levsky, L.

    1994-01-01

    The studies of the relations of carbon and primary isotopes of noble gases were carried out on the natural gases and on the mantle rocks from the mantle M-type sources, which represent the degassed mantle reservoir (MORB's). These works has the aim of estimation of the values of the C/3He ratios in the deep mantle fluids to determine the flux of the mantle CO2 on the basis of known flux of primary mantle 3He. It was found, that in the natural gases the values of the C/3He ratios fall into the range from 1 times E plus 6 to 1 times E plus 15, and in the fluids of MORB's are constant near 2 times E plus 9. We have studied the mantle rocks from the relatively undergassed mantle P minus type sources: continental; Baikal Rift (Siberia), Mongolia, Catalonia (Spain), Pannonia Depression (central Europe) and ocean; Spietzbergen isl., Hawaii isl., Canarian isl. It ws found, that in mantle xenolites and the host alkaline basalts from the continental rifts and ocean islands, the values of the C/3He ratios fall into the range from E plus 11 to E plus 15 (and this result needed to be explained; the higher carbon to helium ratios is relatively undergassed mantle reservoir compared with the degassed one, requires whether hilly compatibility of helium compared with carbon, whether additional flux of 3He to the degassed mantle reservoir). From the other hand it was found that in the mantle rocks from the sources of P minus and M minus types, continental carbonatites, the values of the C/36Ar ratios are constant in the range from E plus 9 to E plus 10, the close values have the MORB's also.

  19. Investigating trophic relationships of pinnipeds in Alaska and Washington using stable isotope ratios of nitrogen and carbon

    USGS Publications Warehouse

    Hobson, Keith A.; Sease, John L.; Merrick, Richard L.; Piatt, John F.

    1997-01-01

    We measured stable-nitrogen (δ15N) and stable-carbon (δ13C) isotope ratios in muscle and hair from 7 northern fur seals (Callorhinus ursinus) from the Pribilof Islands, Alaska, and 27 Steller sea lions (Eumetopias jubatus), and 14 harbor seals (Phoca vitulina) from the Gulf of Alaska and coast of Washington State, in order to contrast dietary information derived from isotopic vs. available conventional dietary studies. Stable-nitrogen-isotope analysis of muscle revealed that harbor seals were enriched over sea lions (mean δ15N = 18.6‰vs. 17.5‰) which were in turn enriched over northern fur seals (mean δ15N = 16.6‰). Trophic segregation among these species likely results primarily from differential reliance on herring (Clupea harengus), Atka mackerel (Pleurogrammus monopterygius), and large vs. small walleye pollock (Theregra chalcogramma). According to their δ15N values, adult male Steller sea lions showed a higher trophic position than adult females (mean δ15N: 18.0‰ vs. 17.2‰), whereas adult female northern fur seals were trophically higher than juvenile male fur seals (mean δ15N: 16.5‰vs. 15.0‰). Each of these observed differences likely resulted from differential reliance on squid or differences in the size range of pollock consumed. Three northern fur seal pups showed higher δ15N enrichment over adults (mean 17.7‰vs. 15.8‰) due to their reliance on their mother's milk. Stable-carbon isotope measurements of hair revealed a cline toward more negative values with latitude. Segregation in hair δ13C between Steller sea lions and harbor seals off the coast of Washington (mean δ13C: -13.6‰ vs. -15.0‰) reflected the greater association of harbor seals with freshwater input from the Columbia River. Our study demonstrates the utility of the stable isotope approach to augment conventional dietary analyses of pinnipeds and other marine mammals.

  20. Carbon isotope ratio analysis of endogenous glucocorticoid urinary metabolites after cortisone acetate and adrenosterone administration for doping control.

    PubMed

    Brooker, Lance; Cawley, Adam; Kazlauskas, Ray; Goebel, Catrin; George, Adrian

    2012-12-01

    Glucocorticoids are listed on the World Anti-Doping Agency (WADA) Prohibited List of substances. The detection of the administration of hydrocortisone and cortisone is complicated by the fact that the human body also produces these steroids naturally. Gas chromatography-combustion-isotope ratio mass spectrometry can be utilized to determine the use of endogenous glucocorticoids by measuring the carbon isotope ratio (CIR) of their resulting metabolites in human urine samples. A comprehensive sample preparation protocol for the analysis of endogenous glucocorticoid urinary metabolites was developed and validated, incorporating the use of high performance liquid chromatography (HPLC) for purification and chemical oxidation for derivatisation. Target compounds were tetrahydrocortisol and tetrahydrocortisone, and 11β-hydroxyetiocholanolone, 11-oxoetiocholanolone and 11β-hydroxyandrosterone, while pregnanediol functioned as the endogenous reference compound. Urine samples from a population of 50 volunteers were analyzed to determine CIR reference limits. Excretion studies of the endogenous glucocorticoid preparation cortisone acetate (25 mg oral) and the dietary supplement adrenosterone (75 mg oral) were conducted with six male individuals. Variable changes in steroid metabolite isotopic composition were found across subjects after administration. The study also revealed that CIR analysis of the major glucocorticoid metabolites tetrahydrocortisol and tetrahydrocortisone is necessary to unambiguously distinguish administration of cortisone and adrenosterone, the former officially restricted to out-of-competition use by athletes, the latter not being restricted at the current time. Moreover, this study reaffirms that CIR methods for the doping control of endogenous steroids should not rely upon a single ERC, as the administration of an appropriate precursor to that ERC could cause complications during analysis. Copyright © 2012 John Wiley & Sons, Ltd.

  1. Modelling the Phanerozoic carbon cycle and climate - Constraints from the Sr-87/Sr-86 isotopic ratio of seawater

    NASA Technical Reports Server (NTRS)

    Francois, Louis M.; Walker, James C. G.

    1992-01-01

    A numerical model is developed for simulating the long-term changes of atmospheric CO2 and climate during the Phanerozoic. The model describes the coupled evolution of the biogeochemical cycles of C, S, Ca, Mg, P, and Sr, with the emphasis on the effect of coupling the cycles of carbon and strontium and on interpreting the observed seawater Sr-87/Sr-86 ratios. The abilities of continental weathering, volcanism, and surface lithology in generating that signal are tested and compared. The results obtained are used to reconstruct a history of atmospheric CO2 and climate during Phanerozoic time, consistent with the strontium isotopic data. It is shown that the predicted history is compatible with paleoclimatic indicators, such as the timing of glaciation and the estimates of Cretaceous paleotemperatures.

  2. Diel changes in stable carbon isotope ratios and trace element concentrations in the Clark Fork River, MT.

    NASA Astrophysics Data System (ADS)

    Parker, S.; Gammons, C.; Degrandpre, M.

    2004-12-01

    down river from a site above the sampling area. One component of this project was to demonstrate the presence of a diel stable carbon isotope (δ 13C) cycle mediated by the use and production of dissolved carbon dioxide. Aquatic plants use carbon dioxide during photosynthesis and there is a carbon isotope fractionation associated with the removal of CO2 from the water column. This work demonstrates the presence of a diel cycle in the stable carbon isotope ratio δ 13C at both sites. The magnitude of the carbon isotope cycle is significantly different at the two sites and this is correlated with the rates of photosynthesis and respiration. The difference in productivity at the two sites is associated with the difference in nutrient levels and the nitrate to phosphate ratio.

  3. Stable carbon and oxygen isotope ratios of winter flounder otoliths assess connectivity between juvenile and adult habitats

    NASA Astrophysics Data System (ADS)

    Pruell, Richard; Taplin, Bryan

    2017-04-01

    Winter flounder populations (Pseudopleuronectes americanus) have significantly declined in recent years along the Rhode Island, USA coastline. The reasons for this decline are not completely clear; however, habitat loss may be a factor. Therefore, knowledge of connectivity between juvenile nearshore habitats and the adult offshore populations may be important for improved management of this fishery. This study was undertaken to determine if stable carbon (δ13C) and oxygen (δ18O) isotope ratios in otoliths could be used to differentiate the locations that serve as important juvenile habitats for winter flounder. It is generally believed that winter flounder spawn during late winter in nearshore areas, and juvenile fish reside in shallow-water habitats along the coastline during their first summer. Once young-of-the-year flounder undergo metamorphosis and settle, they remain in close proximity to that site until fall. Adult fish move offshore during the late winter and spring, and then return to their natal estuaries during the fall and winter to spawn. Juvenile flounder were collected yearly over a three-year period from 18 juvenile habitats with a wide range of salinities. Several years later adult flounder of the same cohorts were obtained from similar inshore locations and also from the offshore fishery. Sagital otoliths were removed from the adult flounder and the core of the otolith representing the juvenile period was obtained using a Micromill drilling system. These juvenile otolith cores from adult fish and whole sagittal otoliths from juvenile flounder were analyzed for δ13C and δ18O using continuous-flow isotope ratio mass spectrometry. Results from these analyses show significant differences in δ13C and δ18O signatures among water bodies (bay, coastal ponds and an estuarine river). Preliminary analysis indicates that the isotope ratios of the juvenile cores from adult flounder and whole otoliths from juvenile fish collected at the same locations

  4. Stable Carbon Isotope Ratio of OC and TC in Aerosol Particles at Urban, Marine and Forest Sites

    NASA Astrophysics Data System (ADS)

    Masalaite, Agne; Dusek, Ulrike; Holzinger, Rupert; Röckmann, Thomas; Remeikis, Vidmantas

    2014-05-01

    Atmospheric aerosols contain up to 50 % (of) organic substances, thus substantially contributing to aerosol climate forcing and affecting human health. In addition to health and climate impacts, aerosol particulate matter is increasingly recognized for its role in biogeochemical cycles. δ13C value of carbonaceous aerosols is a useful tracer for distinguishing the origin of carbonaceous materials. Stable carbon isotope ratios were determined for organic carbon (OC) fraction and total carbon (TC) of PM1 collected on quartz fiber filters in Lithuania in March 2013 at three sites: the urban location of Vilnius, the coastal location of Preila and forest location of Rugsteliskis. The isotope values varied from -27.5 o to -25.5 o for OC and -27.9 o to -25.4 o for TC. δ13C values of TC of the marine site were depleted with some exceptions, at the forest site they were most enriched and the values of the city were in between. The city had the narrowest variation in TC indicating one main source of aerosol particles. The situation was different for OC values. δ13C values of the marine and the forest sites were relatively depleted, meanwhile the city site values were enriched and OC had a highest variability (1.6 o). The city samples had the best correlation (TC via OC). The marine values varied over a wide range (1.5 o) compared to the forest ones. The difference between TC and OC was not as high at the marine and city sites as at the forest site (the variation was about 5 times larger - the average OC was 1 o depleted). This indicates that VOC had a different origin than TC in the forest and in the city. Meanwhile marine aerosol particles had more or less the same source of OC and TC.

  5. Carbon isotope ratios in logged and unlogged boreal forests: Examination of the potential for determining wildlife habitat use

    NASA Astrophysics Data System (ADS)

    France, Robert

    1996-03-01

    Due to assimilation of recycled CO2 from litter decomposition and photosynthetic changes in carbon fractionation at low light levels, the foliage at the base of a forest is often more depleted in13C compared to that exposed to the atmosphere in either the canopy or in open clearings. This is referred to as the canopy effect. African research has indicated that these habitat differences in foliar δ13C can be substantial enough to affect the carbon isotope ratios of resident fauna. Previous work documenting a 30-year chronology on moose teeth from Isle Royale National Park indicated a progressive depletion in13C and suggested that this could be due to forest regrowth following extensive burning. The present study examined the assumption implicit in this hypothesis that foliar δ13C varies between open and closed boreal forest sites. I found a marginal canopy effect of 2‰ δ13C difference between upper canopy and ground flora for a forest in northwestern Ontario and an average difference of 1.2‰ in under- and mid-story vegetation between closed forests and open clear-cuts. Because of these small differences, the utility of carbon isotope analysis in quantifying temporally integrated exploitation of deforested habitats will be low for northern boreal locations. In denser forests, such as those in the tropics or western North American where the canopy effect can be expected to be much greater, δ13C analysis may still offer some promise for determining selection by wildlife of disturbed habitats.

  6. Detection of testosterone administration based on the carbon isotope ratio profiling of endogenous steroids: international reference populations of professional soccer players.

    PubMed

    Strahm, E; Emery, C; Saugy, M; Dvorak, J; Saudan, C

    2009-12-01

    The determination of the carbon isotope ratio in androgen metabolites has been previously shown to be a reliable, direct method to detect testosterone misuse in the context of antidoping testing. Here, the variability in the 13C/12C ratios in urinary steroids in a widely heterogeneous cohort of professional soccer players residing in different countries (Argentina, Italy, Japan, South Africa, Switzerland and Uganda) is examined. Carbon isotope ratios of selected androgens in urine specimens were determined using gas chromatography/combustion/isotope ratio mass spectrometry (GC-C-IRMS). Urinary steroids in Italian and Swiss populations were found to be enriched in 13C relative to other groups, reflecting higher consumption of C3 plants in these two countries. Importantly, detection criteria based on the difference in the carbon isotope ratio of androsterone and pregnanediol for each population were found to be well below the established threshold value for positive cases. The results obtained with the tested diet groups highlight the importance of adapting the criteria if one wishes to increase the sensitivity of exogenous testosterone detection. In addition, confirmatory tests might be rendered more efficient by combining isotope ratio mass spectrometry with refined interpretation criteria for positivity and subject-based profiling of steroids.

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

    PubMed

    Moerdijk-Poortvliet, Tanja C W; Brasser, Jurian; de Ruiter, Gerjan; Houtekamer, Marco; Bolhuis, Henk; Stal, Lucas J; Boschker, Henricus T S

    2014-06-30

    Liquid 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 ((13)C/(12)C) in biological metabolites, at their natural abundance. However, until now this technique could not be applied for the analysis of nucleic acids, the building blocks of the carriers of genetic information in living cells and viruses, DNA and RNA. Mixed-mode chromatography (MMC) was applied to obtain the complete separation of nine nucleotides (eight originating from DNA/RNA and one nucleotide (inosine monophosphate) that may serve as an internal standard) in a single run using LC/IRMS. We also developed and validated a method for DNA and RNA extraction and an enzymatic hydrolysis protocol for natural samples, which is compatible with LC/IRMS analysis as it minimizes the carbon blank. The method was used to measure the concentration and stable carbon isotope ratio of DNA and RNA nucleotides in marine sediment and in the common marine macro alga (Ulva sp.) at natural abundance levels as well as for (13)C-enriched samples. The detection limit of the LC/IRMS method varied between 1.0 nmol for most nucleotides and 2.0 nmol for late-eluting compounds. The intraday and interday reproducibility of nucleotide concentration measurements was better than, respectively, 4.1% and 8.9% and for δ(13)C measurements better than, respectively, 0.3‰ and 0.5‰. The obtained nucleic acid concentrations and nucleic acid synthesis rates were in good agreement with values reported in the literature. This new method gives reproducible results for the concentration and δ(13)C values of nine nucleotides. This solvent-free chromatographic method may also be used for other purposes, such as for instance to determine nucleotide concentrations using spectrophotometric detection. This sensitive method offers a new avenue for the study of DNA and RNA biosynthesis that can be applied in various

  8. Variability in Carbon Stable Isotope Ratio of Heterotrophic Soil Respiration in a Deciduous Needle-leaf Forest

    NASA Astrophysics Data System (ADS)

    Takahashi, Y.; Liang, N.; Machida, T.; Fujinuma, Y.; Inoue, G.

    2005-12-01

    We investigated spatial and temporal variability in the carbon stable isotope ratio (δ13C) of heterotrophic soil respiration in a deciduous Japanese needle-leaf forest for 3 years. We used high-precision isotope measurement coupled with a sampling system optimized for soil respiration to capture this variability under natural conditions. The limitations of chamber-based measurements combined with spatial variation created a representation error that prevented precise estimates of flux-weighted mean δ13C, but we could nonetheless characterize the δ13C variations intrinsic to heterotrophic respiration. In the absence of root respiration, δ13C exhibited significant seasonal variation, with a greater range than in previous models. In a root-exclusion plot, δ13C was lowest at high temperatures but showed a different seasonal course from that of CO2 efflux. A simple model explained the seasonal variation in δ13C using interpool differences in δ13C of decomposed organic matter, in the temperature dependence of decomposition rates, and in the seasonal changes in pool size. The characteristic seasonality of δ13C appears to be associated with the properties of the forest, including litterfall patterns.

  9. Comparison and unification of carbon stable isotope ratios in specific aquatic biota

    NASA Astrophysics Data System (ADS)

    Wang, N.; Wu, Y.; Zhang, J.

    2009-05-01

    Stable isotope analysis has become a convenient tool for aquatic food web research in recent years. However, one controversial point on using stable isotope analysis for food web is whether to extract lipids or not before stable isotope analysis due to strong discrimination against 13C and more negative 13C in lipid-rich tissues independent of diet that can be induced by the key step of endogenous lipid synthesis. Lipid extraction may result in the loss of non-lipid compounds that alters δ15N, which urged the development of arithmetic correction techniques for δ13C, although the techniques as well as their underlying assumptions were seldom systematically verified. A novel lipid normalizing model for different aquatic biota was therefore established and applied to the East China Sea (ECS). According to the experimentally measured δ13C values of dorsal muscle of 11 common fish species, organs and whole-body of Japanese Anchovy (Engraulis japonicas), the proposed model is verified to be appropriate to the food web research on the East China Sea.

  10. Black Carbon, Metal Concentrations and Lead Isotopes Ratios in Aerosols as Tracers of Human and Natural Activities in Northern Vietnam

    NASA Astrophysics Data System (ADS)

    Guinot, B. P.

    2015-12-01

    Atmospheric brown clouds (ABC) observed as widespread layers of brownish haze are regional scale plumes of air pollutants with a hot spot of emission located in East Asia. ABC are mainly composed of aerosol particles such as Black Carbon (BC) emitted to the atmosphere during biomass burning and fossil fuels combustion. The atmospheric lifetime of BC ranges from a few days in wet season up to one month in dry season. The use of stable lead isotopes and 21 elements as tracers of air pollution was applied to identify and characterized the main sources of anthropogenic activities in Asian region. Aerosol samples from Haiphong (North Vietnam) were collected by a high volume sampler for a period of one year from October 2012 to October 2013. Vietnam's 207Pb/206Pb ratios were almost identical to those found for China. Ratios of 207Pb/206Pb ranged from 0.837 to 0.871 which agrees with values previously reported for the last 10 years in China (0.841 - 0.879). No significant variation in isotope ratio was observed during the sampling period, which suggests that there was no large seasonal variation in the isotope ratios of airborne lead. Trajectory analysis showed that almost two third of the air masses originated from East Northeast which implies that China was a major source of lead in atmosphere. Enrichment factor calculations indicated a large influence of coal activity (EF(Al) As = 1982 ± 796, EF(Al) Cd = 972 ± 659, EF(Al) Sb = 1358 ± 930) but the difference between combustion and mining exploitation could not be evidenced. Significant correlations were found between two others groups of elements: As, Cu, Ni, Zn, and Al, Fe K, Co. Wind dilution was effective on metals concentration variation. During the cold and dry season (winter) ambient concentrations were high and variable, during the warm and wet season (summer) concentrations were stable and low. Taken together, these factors also identified industrial and lithogenic activities in the region.

  11. Carbon isotope ratios suggest no additional methane from boreal wetlands during the rapid Greenland Interstadial 21.2

    NASA Astrophysics Data System (ADS)

    Sperlich, Peter; Schaefer, Hinrich; Mikaloff Fletcher, Sara; Guillevic, Myriam; Lassey, Keith; Sapart, Célia; Röckmann, Thomas; Blunier, Thomas

    2017-04-01

    Samples from two Greenland ice cores (NEEM and NGRIP) have been measured for methane carbon isotope ratios (delta 13C-CH4) to investigate the CH4 mixing ratio anomaly during Greenland Interstadial (GI) 21.2 (85,000 years before present). This extraordinarily rapid event occurred within 150 years, comprising a CH4 mixing ratio pulse of 150 ppb (˜25%). Our new measurements disclose a concomitant shift in delta 13C-CH4 of 1‰ . Keeling plot analyses reveal the delta 13C of the additional CH4 source constituting the CH4 anomaly as -56.8 ± 2.8‰ , which we confirm by means of a previously published box model. We propose tropical wetlands as the most probable additional CH4 source during GI-21.2 and present independent evidence that suggests that tropical wetlands in South America and Asia have played a key role. We find no evidence that boreal CH4 sources, such as permafrost degradation, contributed significantly to the atmospheric CH4 increase, despite the pronounced warming in the Northern Hemisphere during GI-21.2.

  12. Carbon isotope ratios suggest no additional methane from boreal wetlands during the rapid Greenland Interstadial 21.2

    NASA Astrophysics Data System (ADS)

    Sperlich, Peter; Schaefer, Hinrich; Mikaloff Fletcher, Sara E.; Guillevic, Myriam; Lassey, Keith; Sapart, Célia J.; Röckmann, Thomas; Blunier, Thomas

    2015-11-01

    Samples from two Greenland ice cores (NEEM and NGRIP) have been measured for methane carbon isotope ratios (δ13C-CH4) to investigate the CH4 mixing ratio anomaly during Greenland Interstadial (GI) 21.2 (85,000 years before present). This extraordinarily rapid event occurred within 150 years, comprising a CH4 mixing ratio pulse of 150 ppb (˜25%). Our new measurements disclose a concomitant shift in δ13C-CH4 of 1‰. Keeling plot analyses reveal the δ13C of the additional CH4 source constituting the CH4 anomaly as -56.8 ± 2.8‰, which we confirm by means of a previously published box model. We propose tropical wetlands as the most probable additional CH4 source during GI-21.2 and present independent evidence that suggests that tropical wetlands in South America and Asia have played a key role. We find no evidence that boreal CH4 sources, such as permafrost degradation, contributed significantly to the atmospheric CH4 increase, despite the pronounced warming in the Northern Hemisphere during GI-21.2.

  13. Separating Autotrophic and Heterotrophic Contributions to Soil Respiration in Maize-Based Agroecosystems Using Stable Carbon Isotope Ratio Mass Spectrometry.

    NASA Astrophysics Data System (ADS)

    Amos, B.; Walters, D. T.; Madhavan, S.; Arkebauer, T. J.; Scoby, D. L.

    2005-12-01

    Any effort to establish a carbon budget for a growing crop by means of a thorough accounting of all C sources and sinks will require the ability to discriminate between autotrophic and heterotrophic contributions to soil surface CO2 flux. Autotrophic soil respiration (Ra) is defined as combined root respiration and the respiration of soil microorganisms residing in the rhizosphere and using root-derived carbohydrates as an energy source, while heterotrophic respiration (Rh) is defined as the respiration of soil microorganisms and macroorganisms not directly under the influence of the live root system and using SOM as an energy source. We partition soil surface CO2 flux into its autotrophic and heterotrophic components by combining root exclusion with stable carbon isotope techniques in production scale (~65 ha) maize-based agroecosystems. After flux measurements, small chambers are placed on collars in both root excluded shields and in non-root excluded soil, ambient headspace CO2 is removed using a soda lime trap, and soil-respired C is allowed to collect in the chambers. Soil respiration samples are then collected in 12mL evacuated exetainers and analyzed for δ13C by means of a Finnigan Delta-S isotope ratio mass spectrometer interfaced with a Thermo Finnigan GasBench II and a cryogenic trap to increase CO2 concentration. These δ13C measurements were made throughout the 2005 growing season in maize fields representing three agroecosystems: irrigated continuous maize, irrigated maize-soybean rotation, and rainfed maize soybean rotation. Estimates of autotrophic and heterotrophic soil respiration along with other results of this study will be presented.

  14. Congener-specific concentrations and carbon stable isotope ratios (delta13C) of two technical toxaphene products (Toxaphene and Melipax).

    PubMed

    Vetter, Walter; Gleixner, Gerd; Armbruster, Wolfgang; Ruppe, Steffen; Stern, Gary A; Braekevelt, Eric

    2005-01-01

    In this study we compared the contribution of individual congeners and the ratios of stable carbon isotopes of two technical toxaphene products. The former US-American product Toxaphene was from 1978 and the East-German product Melipax from 1979. Both technical products showed the known complexity in GC/ECD measurements. Contributions of 24 peaks to each of the technical products were determined by gas chromatography in combination high resolution electron capture negative ion mass spectrometry (GC/ECNI-HRMS). The percentages of the compounds studied in the technical mixtures ranged from approximately 0.05% to approximately 2.5% but showed some individual differences. 2,2,5,5,8,9,9,10,10-nonachlorobornane (B9-1025 or P-62) was identified as a major congener in both mixtures. 2-Endo,3-exo,5-endo,6-exo,8,8,10,10-octachlorobornane (B8-1413 or P26) and 2-endo,3-exo,5-endo,6-exo,8,8,9,10,10-nonachlorobornane (B9-1679 or P-50) were found at similar concentration in both technical products. Identical amounts of Melipax or Toxaphene were combusted to CO2 in an element analyzer and their delta13C values were determined relative to the international standard Vienna PeeDee belemnite (VPDB). The mean delta13C values of both products varied by 2.8% (determined at two different locations) which is roughly one order of magnitude more than the precision obtained in repetitive analyses of the individual products. Thus, both investigated products could be unequivocally distinguished by stable isotope ratio mass spectrometry (IRMS). IRMS analyses may thus be a suitable tool for tracing back toxaphene residues in environmental and food samples to the one or both of the products.

  15. Analysis of exogenous nandrolone metabolite in horse urine by gas chromatography/combustion/carbon isotope ratio mass spectrometry.

    PubMed

    Yamada, Masayuki; Kinoshita, Kenji; Kurosawa, Masahiko; Saito, Koichi; Nakazawa, Hiroyuki

    2007-11-30

    Nandrolone (17beta-hydroxy-4-estren-3-one, NAD) is an endogenous steroid hormone; thus, the detection of its metabolites is not conclusive of NAD doping in racehorses. NAD doping control in male horses is based on the threshold, namely, the concentration ratio of 5alpha-estran-3beta,17alpha-diol (ETA) to 5(10)-estren-3beta,17alpha-diol (ETE). The ETA/ETE ratio of 1/1 was determined based on statistical data of authentic horses in International Federation of Horseracing Authorities. To individuals with complex metabolic disorders, however, such a threshold might not be applicable. The aim of this study was to establish an analytical method that discriminates endogenous steroids from exogenous ones in horse urine after NAD administration using gas chromatography/combustion/carbon isotope ratio mass spectrometry (GC/C/IRMS). Urine was sampled from NAD-administered and authentic horses. Ten millilitres of urine was hydrolyzed and subjected to liquid-liquid extraction and solid phase extraction. The residue of the extracts purified by HPLC was derivatized by acetylation. As a result of measurement of the (13)C/(12)C ratio (delta(13)C) by GC/C/IRMS, the delta(13)C values of ETA for NAD-administered and authentic horses were -32.20+/-0.35 per thousand and -27.85+/-0.75 per thousand (n=60), respectively. The detection limit of ETA in this GC/C/IRMS analysis was approximately 25 ng/ml. This study indicates that the measurement of delta(13)C by GC/C/IRMS enables us to discriminate exogenous ETA derived from NAD administration from endogenous ETA, proving that GC/C/IRMS is a useful technique to complement the ETA/ETE ratio.

  16. Carbon, hydrogen and oxygen stable isotope ratios of whole wood, cellulose and lignin methoxyl groups of Picea abies as climate proxies.

    PubMed

    Gori, Y; Wehrens, R; Greule, M; Keppler, F; Ziller, L; La Porta, N; Camin, F

    2013-01-15

    Carbon, hydrogen and oxygen (C, H and O) stable isotope ratios of whole wood and components are commonly used as paleoclimate proxies. In this work we consider eight different proxies in order to discover the most suitable wood component and stable isotope ratio to provide the strongest climate signal in Picea abies in a southeastern Alpine region (Trentino, Italy). δ(13)C, δ(18)O and δ(2)H values in whole wood and cellulose, and δ(13)C and δ(2)H values in lignin methoxyl groups were measured. Analysis was performed using an Isotopic Ratio Mass Spectrometer coupled with an Elemental Analyser for measuring (13)C/(12)C and a Pyrolyser for measuring (2)H/(1)H and (18)O/(16)O. The data were evaluated by Principal Component Analysis, and a simple Pearson's correlation between isotope chronologies and climatic features, and multiple linear regression were performed to evaluate the data. Each stable isotope ratio in cellulose and lignin methoxyl differs significantly from the same stable isotope ratio in whole wood, the values begin higher in cellulose and lignin except for the lignin δ(2)H values. Significant correlations were found between the whole wood and the cellulose fractions for each isotope ratio. Overall, the highest correlations with temperature were found with the δ(18)O and δ(2)H values in whole wood, whereas no significant correlations were found between isotope proxies and precipitation. δ(18)O and δ(2)H values in whole wood provide the best temperature signals in Picea abies in the northern Italian study area. Extraction of cellulose and lignin and analysis of other isotopic ratios do not seem to be necessary. Copyright © 2012 John Wiley & Sons, Ltd.

  17. Application of Stable Carbon Isotope Ratios to Recognize Natural Biodegradation of MTBE

    EPA Science Inventory

    The organisms that degrade MTBE under anaerobic conditions are evolved to acquire energy for growth by using molecular hydrogen and carbonate ion to cleave methyl ether bonds. Methyl ether bonds are common in nature and the bond also occurs in MTBE. MTBE in contaminated ground...

  18. Application of Stable Carbon Isotope Ratios to Recognize Natural Biodegradation of MTBE

    EPA Science Inventory

    The organisms that degrade MTBE under anaerobic conditions are evolved to acquire energy for growth by using molecular hydrogen and carbonate ion to cleave methyl ether bonds. Methyl ether bonds are common in nature and the bond also occurs in MTBE. MTBE in contaminated ground...

  19. Apportionment of carbon dioxide over central Europe: insights from combined measurements of atmospheric CO2 mixing ratios and carbon isotope composition

    NASA Astrophysics Data System (ADS)

    Zimnoch, M.; Jelen, D.; Galkowski, M.; Kuc, T.; Necki, J.; Chmura, L.; Gorczyca, Z.; Jasek, A.; Rozanski, K.

    2012-04-01

    The European continent, due to high population density and numerous sources of anthropogenic CO2 emissions, plays an important role in the global carbon budget. Nowadays, precise measurements of CO2 mixing ratios performed by both global and regional monitoring networks, combined with appropriate models of carbon cycle, allow quantification of the European input to the global atmospheric CO2 load. However, measurements of CO2 mixing ratios alone cannot provide the information necessary for the apportionment of fossil-fuel related and biogenic contributions to the total CO2 burden of the regional atmosphere. Additional information is required, for instance obtained through measurements of radiocarbon content in atmospheric carbon dioxide. Radiocarbon is a particularly useful tracer for detecting fossil carbon in the atmosphere on different spatial and temporal scales. Regular observations of atmospheric CO2mixing ratios and their isotope compositions have been performed during the period of 2005-2009 at two sites located in central Europe (southern Poland). The sites, only ca. 100 km apart, represent two extreme environments with respect to the extent of anthropogenic pressure: (i) the city of Krakow, representing typical urban environment with numerous sources of anthropogenic CO2, and (ii) remote mountain site Kasprowy Wierch, relatively free of local influences. Regular, quasi-continuous measurements of CO2 mixing ratios have been performed at both sites. In addition, cumulative samples of atmospheric CO2 have been collected (weekly sampling regime for Krakow and monthly for Kasprowy Wierch) to obtain mean carbon isotope signature (14C/12C and 13C/12C ratios) of atmospheric CO2 at both sampling locations. Partitioning of the local atmospheric CO2 load at both locations has been performed using isotope- and mass balance approach. In Krakow, the average fossil-fuel related contribution to the local atmospheric CO2 load was equal to approximately 3.4%. The biogenic

  20. Advances in coupling a commercial total organic carbon analyser with an isotope ratio mass spectrometer to determine the isotopic signal of the total dissolved nitrogen pool.

    PubMed

    Huygens, D; Boeckx, P; Vermeulen, J; Paepe, X De; Park, A; Barker, S; Pullan, C; Van Cleemput, O

    2005-01-01

    A new method has been developed to analyse 15N of the total dissolved nitrogen (TDN) pool. The method operates on a commercial total organic carbon (TOC) analyser coupled to an elemental analyser/isotope ratio mass spectrometer (EA-IRMS). Nitrogen compounds are combusted to nitric oxide (NO) and nitrogen dioxide (NO2) by high-temperature catalytic oxidation (HTCO), after which the NOx gas is transferred to an EA-IRMS for isotopic nitrogen analysis. The system is described, including five modifications of the system in order to overcome analytical problems. First, flow paths were modified to run both systems on helium as carrier gas, while complete sample oxidation was maintained. Secondly, the catalyst structure was adapted to allow high injection volumes at the given backpressures delivered by the EA system. Thirdly, we installed a Permapure dehumidification system as the standard Peltier element did not satisfy dehumidification requirements. Finally, we prevented the inflow of atmospheric nitrogen into the system. In a final stage, we are planning to automate the coupled system in order to run a continuous batch of up to 60 samples. We have obtained satisfactory results on the accuracy and precision of 180+/-1 per thousand potassium nitrate samples (IAEA, USGS-32). Running a batch of five samples resulted in a mean isotopic value of 178.8 per thousand with a standard deviation of 2.8 per thousand. Some important issues could not yet be addressed here, and will have to be evaluated once the system is running on a continuous base. However, the results appear promising and this system has the potential to become a method for TD15N analysis. An appropriate TD15N analysis method might open new challenges in aquatic and terrestrial ecosystem nitrogen studies, including a more comprehensive study of the dissolved organic nitrogen pool. Copyright (c) 2005 John Wiley & Sons, Ltd.

  1. The variations of stable-carbon isotope ratios in Qilian juniper in northwestern China

    NASA Astrophysics Data System (ADS)

    Zhang, Youfu; Chen, Tuo; An, Lizhe; Li, Youbin

    2007-03-01

    This is the first study of δ13C values that considers elevational influences of the Qilian mountains of China. The δ13C values of different parts of the Qilian juniper ( Sabina przewalskii Kom.) at different elevations of the Qilian mountains, China, were measured. Relatively constant differences in δ13C values existed between the tree leaves and the trunk wood. No strong dependency of δ13C values on elevation was found. The temporal changes of wood δ13C values with directions, elevations and height in the tree showed general similarity. These results suggest that the isotopic effects of environmental factors expressed initially at the site of photosynthesis, i.e., the leaves could be contained in the trunks of a tree. Regardless of elevation, direction or height in the tree, wood δ13C values have been decreasing during the past 60 years. A composite 600-year δ13C chronology developed from four trees showed that δ13C values remain relatively constant before 1800. After 1800 AD, however, δ13C values became significantly more negative. The trend in wood δ13C values was consistent with that obtained for δ13C values in atmospheric CO2. The results showed that for Qilian juniper, tree-ring δ13C chronology could be established to ascertain fluctuations of the atmospheric δ13C.

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

    PubMed

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

    2012-09-01

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

  3. Hydrogen and carbon isotopic ratios of polycyclic aromatic compounds in two CM2 carbonaceous chondrites and implications for prebiotic organic synthesis

    NASA Astrophysics Data System (ADS)

    Huang, Yongsong; Aponte, José C.; Zhao, Jiaju; Tarozo, Rafael; Hallmann, Christian

    2015-09-01

    Study of meteoritic organic compounds offers a unique opportunity to understand the origins of the organic matter in the early Solar System. Meteoritic polycyclic aromatic hydrocarbons (PAHs) and heteropolycyclic aromatic compounds (HACs) have been studied for over fifty years, however; their hydrogen stable isotopic ratios (δD) have never been reported. Compound-specific δD measurements of PAHs and HACs are important, in part because the carbon isotopic ratios (δ13C) of various meteoritic PAHs cannot be readily distinguished from their terrestrial counterparts and it is difficult to rule out terrestrial contamination based on carbon isotopic ratios alone. In this study, we have extracted and identified more than sixty PAHs and HACs present in two CM2 carbonaceous chondrites Murchison and LON 94101. Their carbon and hydrogen stable isotopic ratios (δ13C and δD) were measured and used to discuss about their synthetic environments and formation mechanisms. The concentration of aromatic compounds is ∼30% higher in Murchison than in the Antarctic meteorite LON 94101, but both samples contained similar suites of PAHs and HACs. All PAHs and HACs found exhibited positive δD values (up to 1100‰) consistent with an extraterrestrial origin, indicating the relatively low δ13C values are indeed an inherent feature of the meteoritic aromatic compounds. The hydrogen isotopic data suggest aromatic compounds in carbonaceous chondrites were mainly formed in the cold interstellar environments. Molecular level variations in hydrogen and carbon isotopic values offer new insights to the formation pathways for the aromatic compounds in carbonaceous chondrites.

  4. Stable carbon isotope ratio of methyl chloride emitted from glasshouse-grown tropical plants and its implication for the global methyl chloride budget

    NASA Astrophysics Data System (ADS)

    Saito, Takuya; Yokouchi, Yoko

    2008-04-01

    Stable carbon isotope ratios of methyl chloride (CH3Cl) were measured in foliar emissions from 14 species of tropical plants growing in a glasshouse. The isotopic ratio of CH3Cl (arithmetic mean: -83.2 +/- 15.2‰) ranged from -56‰ to -114‰ that from dipterocarp trees (-87.4 +/- 12.3‰) was on average more depleted in 13C than that from tree ferns (-61.9 +/- 9.7‰). The isotopic ratio was lower than that of CH3Cl produced by other known sources (e.g., biomass burning and salt marshes), with the exception of that by dead leaves. Using the distinctive isotope ratio of CH3Cl emitted from tropical plants together with previously reported isotopic data of CH3Cl sources and sinks to an isotopic mass balance calculation, global CH3Cl emission by tropical plants was estimated to be approximately 1500-3000 Gg yr-1 with uncertainties of 30-60%, which could account for 30-50% of the global emission.

  5. Near-infrared spectroscopy of M dwarfs. IV. A preliminary survey on the carbon isotopic ratio in M dwarfs*

    NASA Astrophysics Data System (ADS)

    Tsuji, Takashi

    2016-10-01

    Carbon isotopic ratios are estimated in 48 M dwarfs based on the medium resolution near infrared spectra (λ/Δ λ ≈ 20000) of the 13CO (3,1) band. We find clear evidence for the presence of a 13CO feature for the first time in the spectra of M dwarfs. Spectral resolution of our observed data, however, is not high enough to analyze the 13CO feature directly. Instead, we compare the observed spectrum with synthetic spectra assuming 12C/13C = 10, 25, 50, 100, and 200 for each of 48 M dwarfs and estimate the best possible 12C/13C ratio by chi-square analysis. The resulting 12C/13C ratios in M dwarfs distribute from 39 to a lower limit of 200. The mean value of 31 M dwarfs for which 12C/13C ratios are determined (i.e., excluding those with the lower limit only) is (12C/13C)dM = 87 ± 21 (p.e.), and that of 48 M dwarfs including those with the lower limit of 200 is (12C/13C)dM > 127 ± 41 (p.e.). These results are somewhat larger than the 12C/13C ratio of the present interstellar matter (ISM) determined from the molecular lines observed in the millimeter and optical wavelength regions. Since the amount of 13C in the ISM has increased with time due to mass loss from evolved stars, the 12C/13C ratios in M dwarfs, reflecting those of the past ISM, should be larger than those of the present ISM. In M dwarfs, log 13C/12C plotted against log AC shows a large scatter without clear dependence on the metallicity. This result shows a marked contrast to log 16O/12C (= log AO/AC) plotted against log AC, which shows a rather tight correlation with a larger value at the lower metallicity. Such a contrast can be a natural consequence of 16O and 12C being primary products in stellar nuclear synthesis while 13C is a secondary product, at least partly.

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

    SciTech Connect

    Marshall, J.D.; Zhang, J.; Rember, W.C.; Jennings, D.; Larson, P. )

    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.

  7. Measurements of concentrations of chlorofluoromethanes (CFMs) carbon dioxide and carbon isotope ratio in stratospheric and tropospheric air by grab-sampling systems

    NASA Technical Reports Server (NTRS)

    Itoh, T.; Kubo, H.; Honda, H.; Tominaga, T.; Makide, Y.; Yakohata, A.; Sakai, H.

    1985-01-01

    Measurements of concentrations of chlorofluoromethanes (CFMs), carbon dioxide and carbon isotope ratio in stratospheric and tropospheric air by grab-sampling systems are reported. The balloon-borne grab-sampling system has been launched from Sanriku Balloon Center three times since 1981. It consists of: (1) six sampling cylinders, (2) eight motor driven values, (3) control and monitor circuits, and (4) pressurized housing. Particular consideration is paid to the problem of contamination. Strict requirements are placed on the choice of materials and components, construction methods, cleaning techniques, vacuum integrity, and sampling procedures. An aluminum pressurized housing and a 4-m long inlet line are employed to prevent the sampling air from contamination by outgassing of sampling and control devices. The sampling is performed during the descent of the system. Vertical profiles of mixing ratios of CF2Cl2, CFCl3 and CH4 are given. Mixing ratios of CF2Cl2 and CFCl3 in the stratosphere do not show the discernible effect of the increase of those in the ground level background, and decrease with altitude. Decreasing rate of CFCl3 is larger than that of CF2Cl2. CH4 mixing ratio, on the other hand, shows diffusive equilibrium, as the photodissociation cross section of CH4 is small and concentrations of OH radical and 0(sup I D) are low.

  8. Measurements of concentrations of chlorofluoromethanes (CFMs) carbon dioxide and carbon isotope ratio in stratospheric and tropospheric air by grab-sampling systems

    NASA Technical Reports Server (NTRS)

    Itoh, T.; Kubo, H.; Honda, H.; Tominaga, T.; Makide, Y.; Yakohata, A.; Sakai, H.

    1985-01-01

    Measurements of concentrations of chlorofluoromethanes (CFMs), carbon dioxide and carbon isotope ratio in stratospheric and tropospheric air by grab-sampling systems are reported. The balloon-borne grab-sampling system has been launched from Sanriku Balloon Center three times since 1981. It consists of: (1) six sampling cylinders, (2) eight motor driven values, (3) control and monitor circuits, and (4) pressurized housing. Particular consideration is paid to the problem of contamination. Strict requirements are placed on the choice of materials and components, construction methods, cleaning techniques, vacuum integrity, and sampling procedures. An aluminum pressurized housing and a 4-m long inlet line are employed to prevent the sampling air from contamination by outgassing of sampling and control devices. The sampling is performed during the descent of the system. Vertical profiles of mixing ratios of CF2Cl2, CFCl3 and CH4 are given. Mixing ratios of CF2Cl2 and CFCl3 in the stratosphere do not show the discernible effect of the increase of those in the ground level background, and decrease with altitude. Decreasing rate of CFCl3 is larger than that of CF2Cl2. CH4 mixing ratio, on the other hand, shows diffusive equilibrium, as the photodissociation cross section of CH4 is small and concentrations of OH radical and 0(sup I D) are low.

  9. Stable Carbon Isotope Ratios of Lipid Biomarkers and Biomass for Sulfate-reducing Bacteria Grown with Different Substrates

    NASA Technical Reports Server (NTRS)

    Londry, K. L.; Jahnke, L. L.; Des Marais, D. J.

    2001-01-01

    We have determined isotope ratios of biomass and Fatty Acids Methyl Esters (FAME) for four Sulfate-Reducing Bacteria (SRB) grown lithotrophically and heterotrophically, and are investigating whether these biomarker signatures can reveal the ecological role and distribution of SRB within microbial mats. Additional information is contained in the original extended abstract.

  10. Stable Carbon Isotope Ratios of Lipid Biomarkers and Biomass for Sulfate-reducing Bacteria Grown with Different Substrates

    NASA Technical Reports Server (NTRS)

    Londry, K. L.; Jahnke, L. L.; Des Marais, D. J.

    2001-01-01

    We have determined isotope ratios of biomass and Fatty Acids Methyl Esters (FAME) for four Sulfate-Reducing Bacteria (SRB) grown lithotrophically and heterotrophically, and are investigating whether these biomarker signatures can reveal the ecological role and distribution of SRB within microbial mats. Additional information is contained in the original extended abstract.

  11. Carbon isotopes in comets

    NASA Technical Reports Server (NTRS)

    Wehinger, Peter A.

    1990-01-01

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

  12. Source identification of particulate organic matter in view of land uses in Shingil Creek using carbon, nitrogen and oxygen isotope ratios.

    NASA Astrophysics Data System (ADS)

    Kim, Dahae; Lee, Yeonjung; Ock, Giyoung; Kang, Sujin; Kim, Minseob; Choi, Jongwoo; Shin, Kyung-Hoon

    2016-04-01

    Anthropogenic inputs influence the quality and quantity of organic matter, which is important for recycling of nutrients and chemical elements. Stable isotope techniques are useful for distinguishing the origin of organic matter by using the characteristics that are distinctive between sources. Artificial Lake Shihwa, especially the Shingil creek is typically under the strong anthropogenic pressure with continuous continental inputs from various sources. Hence in this study, the characteristics and sources of organic matter in water and surface sediment of the Shingil creeks in the rural, urban, and industrial areas were evaluated by using carbon, nitrogen and oxygen isotope ratios, by analyzing samples collected during the rainy season and dry season. Among the input sources, the organic matter derived from industrial regions showed distinct nitrogen isotope values compared to other sites. Further studies including other techniques such as hydrogen isotope will provide an insight into the development of a strategy for effective water quality management in Lake Shihwa

  13. Method for determining stable isotope ratios of dissolved organic carbon in interstitial and other natural marine waters

    NASA Technical Reports Server (NTRS)

    Bauer, J. E.; Haddad, R. I.; Des Marais, D. J.

    1991-01-01

    A procedure is described for the analysis of the stable carbon isotopic composition of dissolved organic carbon (DOC) in natural waters from marine and higher-salinity environments. Rapid (less than 5 min) and complete oxidation of DOC is achieved using a modification of previous photochemical oxidation techniques. The CO2 evolved from DOC oxidation can be collected in less than 10 min for isotopic analysis. The procedure is at present suitable for oxidation and collection of 1-5 micromoles of carbon and has an associated blank of 0.1-0.2 micromole of carbon. Complete photochemical oxidation of DOC standards was demonstrated by quantitative recovery of CO2 as measured manometrically. Isotopic analyses of standards by photochemical and high-temperature sealed-tube combustion methods agreed to within 0.3%. Photochemical oxidation of DOC in a representative sediment pore-water sample was also quantitative, as shown by the excellent agreement between the photochemical and sealed-tube methods. The delta 13C values obtained for pore-water DOC using the two methods of oxidation were identical, suggesting that the modified photochemical method is adequate for the isotopically non-fractionated oxidation of pore-water DOC. The procedure was evaluated through an analysis of DOC in pond and pore waters from a hypersaline microbial mat environment. Concentrations of DOC in the water column over the mat displayed a diel pattern, but the isotopic composition of this DOC remained relatively constant (average delta 13C = -12.4%). Pore-water DOC exhibited a distinct concentration maximum in the mat surface layer, and delta 13C of pore-water DOC was nearly 8% lighter at 1.5-2.0-cm depth than in the mat surface layer (0-0.5-cm depth). These results demonstrate the effectiveness of the method in elucidating differences in DOC concentration and delta 13C over biogeochemically relevant spatial and temporal scales. Carbon isotopic analysis of DOC in natural waters, especially pore waters

  14. Carbon isotopes in mollusk shell carbonates

    NASA Astrophysics Data System (ADS)

    McConnaughey, Ted A.; Gillikin, David Paul

    2008-10-01

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

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

    NASA Technical Reports Server (NTRS)

    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.

  16. Compound-specific carbon, nitrogen, and hydrogen isotopic ratios for amino acids in CM and CR chondrites and their use in evaluating potential formation pathways

    NASA Astrophysics Data System (ADS)

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

    2012-09-01

    Stable hydrogen, carbon, and nitrogen isotopic ratios (δD, δ13C, and δ15N) of organic compounds can reveal 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: CM1/2 Allan Hills (ALH) 83100, CM2 Murchison, CM2 Lewis Cliff (LEW) 90500, CM2 Lonewolf Nunataks (LON) 94101, CR2 Graves Nunataks (GRA) 95229, CR2 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 δ13C and increasing δD with increasing carbon number in the α-H, α-NH2 amino acids that correspond to predictions made for formation via Strecker-cyanohydrin synthesis. We also observe light δ13C signatures for β-alanine, which may indicate either formation via Michael addition or via a pathway that forms primarily small, straight-chain, amine-terminal amino acids (n-ω-amino acids). Higher deuterium enrichments are observed in α-methyl 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 in CM chondrites, reflecting different parent-body chemistry.

  17. Uniform Silicon Isotope Ratios Across the Milky Way Galaxy

    NASA Astrophysics Data System (ADS)

    Monson, Nathaniel N.; Morris, Mark R.; Young, Edward D.

    2017-04-01

    We report the relative abundances of the three stable isotopes of silicon, 28Si, 29Si, and 30Si, across the Galaxy using the v=0,J=1\\to 0 transition of silicon monoxide. The chosen sources represent a range in Galactocentric radii ({R}{GC}) from 0 to 9.8 kpc. The high spectral resolution and sensitivity afforded by the Green Bank Telescope permit isotope ratios to be corrected for optical depths. The optical-depth-corrected data indicate that the secondary-to-primary silicon isotope ratios {}29{Si}{/}28{Si} and {}30{Si}{/}28{Si} vary much less than predicted on the basis of other stable isotope ratio gradients across the Galaxy. Indeed, there is no detectable variation in Si isotope ratios with {R}{GC}. This lack of an isotope ratio gradient stands in stark contrast to the monotonically decreasing trend with {R}{GC} exhibited by published secondary-to-primary oxygen isotope ratios. These results, when considered in the context of the expectations for chemical evolution, suggest that the reported oxygen isotope ratio trends, and perhaps those for carbon as well, require further investigation. The methods developed in this study for SiO isotopologue ratio measurements are equally applicable to Galactic oxygen, carbon, and nitrogen isotope ratio measurements, and should prove useful for future observations of these isotope systems.

  18. Tracing the source of sedimentary organic carbon in the Loess Plateau of China: An integrated elemental ratio, stable carbon signatures, and radioactive isotopes approach.

    PubMed

    Liu, Chun; Dong, Yuting; Li, Zhongwu; Chang, Xiaofeng; Nie, Xiaodong; Liu, Lin; Xiao, Haibing; Bashir, Hassan

    2017-02-01

    Soil erosion, which will induce the redistribution of soil and associated soil organic carbon (SOC) on the Earth's surface, is of critically importance for biogeochemical cycling of essential elements and terrestrial carbon sequestration. Despite the importance of soil erosion, surprisingly few studies have evaluated the sources of eroded carbon (C). This study used natural abundance levels of the stable isotope signature ((13)C) and radioactive isotopes ((137)Cs and (210)Pbex), along with elements ratio (C/N) based on a two end member mixing model to qualitatively and quantitatively identify the sources of sedimentary OC retained by check dam in the Qiaozigou small watershed in the Loess Plateau, China. Sediment profiles (0-200 cm) captured at natural depositional area of the basin was compared to possible source materials, which included: superficial Loess mineral soils (0-20 cm) from three land use types [i.e., grassland (Medicago sativa), forestland (Robinia pseudoacacia.), shrubland (Prunus sibirica), and gully land (Loess parent material.)]. The results demonstrated that SOC in sediments showed significantly negative correlation with pH (P < 0.01), and positive correlation with soil water content (SWC) (P < 0.05). The sedimentary OC was not derived from grasslands or gullies. Forestland and shrubland were two main sources of eroded organic carbon within the surface sediment (0-60 cm deep), except for that in the 20-40 cm soil layer. Radionuclides analyses also implied that the surface sediments retained by check-dams mainly originated from soils of forestland and shrubland. Results of the two end-member mixing model demonstrated that more than 50% SOC (mean probability estimate (MPE) 50.13% via (13)C and 60.53% via C/N) in surface sediment (0-20 cm deep) derived from forestland, whereas subsurface sedimentary SOC (20-200 cm) mainly resulted from shrubland (MPE > 50%). Although uncertainties on the sources of SOC in deep soils exist, the soil

  19. A capillary absorption spectrometer for stable carbon isotope ratio (13C/12C) analysis in very small samples

    NASA Astrophysics Data System (ADS)

    Kelly, J. F.; Sams, R. L.; Blake, T. A.; Newburn, M.; Moran, J.; Alexander, M. L.; Kreuzer, H.

    2012-02-01

    A capillary absorption spectrometer (CAS) suitable for IR laser isotope analysis of small CO2 samples is presented. The system employs a continuous-wave (cw) quantum cascade laser to study nearly adjacent rovibrational transitions of different isotopologues of CO2 near 2307 cm-1 (4.34 μm). This initial CAS system can achieve relative isotopic precision of about 10 ppm 13C, or ˜1‰ (per mil in delta notation relative to Vienna Pee Dee Belemnite) with 20-100 picomoles of entrained sample within the hollow waveguide for CO2 concentrations ˜400-750 ppm. Isotopic analyses of such gas fills in a 1-mm ID hollow waveguide of 0.8 m overall physical path length can be carried out down to ˜2 Torr. Overall 13C/12C ratios can be calibrated to ˜2‰ accuracy with diluted CO2 standards. A novel, low-cost method to reduce cw-fringing noise resulting from multipath distortions in the hollow waveguide is presented, which allows weak absorbance features to be studied at the few ppm level (peak-to-rms) after 1000 scans are co-added in ˜10 s. The CAS is meant to work directly with converted CO2 samples from a laser ablation-catalytic combustion micro-sampler to provide 13C/12C ratios of small biological isolates currently operating with spatial resolutions ˜50 μm.

  20. Stable carbon isotopic ratio measurement of polycyclic aromatic hydrocarbons as a tool for source identification and apportionment--a review of analytical methodologies.

    PubMed

    Buczyńska, A J; Geypens, B; Van Grieken, R; De Wael, K

    2013-02-15

    The measurement of the ratio of stable isotopes of carbon ((13)C/(12)C expressed as a δ(13)C) in the individual components of a sample may be used as a means to identify the origin of these components. This article reviews the approaches and reports on the successes and failures of source identification and apportionment of Polycyclic Aromatic Hydrocarbons (PAHs) with the use of compound-specific isotope analysis (CSIA). One of the conditions for a precise and accurate analysis of isotope ratios with the use of GC-C-IRMS is the need for well separated peaks, with no co-elutions, and reduced unresolved complex mixture (UCM). Additionally, special care needs to be taken for an investigation of possible isotope fractionation effects introduced during the analytical treatment of samples. With the above-mentioned problems in mind, this review discusses in detail and compares current laboratory methodologies, mainly in the extraction and subsequent clean-up techniques used for environmental samples (air particulate matter, soil and sediments). Sampling strategies, the use of isotopic internal standards and the ranges for precision and accuracy are also reported and discussed.

  1. An assessment of geochemical preparation methods prior to organic carbon concentration and carbon isotope ratio analyses of fine-grained sedimentary rocks

    NASA Astrophysics Data System (ADS)

    KöNitzer, Sven F.; Leng, Melanie J.; Davies, Sarah J.; Stephenson, Michael H.

    2012-09-01

    This study summarizes organic carbon isotope (δ13C) and total organic carbon (TOC) data from a series of tests undertaken to provide an appropriate methodology for pre-analysis treatment of mudstones from an Upper Carboniferous sedimentary succession, in order to develop a consistent preparation procedure. The main treatments involved removing both inorganic carbonate and hydrocarbons (which might be extraneous) before δ13C and TOC analysis. The results show that decarbonating using hydrochloric acid causes significant reduction in δ13C and total carbon (TC) of the bulk material due to the removal of inorganic carbonate. These changes are most pronounced where soluble calcium carbonate (rather than Ca-Mg-Fe carbonate) is present. Deoiled samples show only slightly higher mean δ13C where visible bitumen was extracted from the bulk sample. Moreover, the isotopic signatures of the extracts are closely correlated to those of their respective bulk samples, suggesting that small yields of hydrocarbons were generated in situ with no isotopic fractionation. In addition, further δ13C and TC analyses were performed on samples where mixing of oil-based drilling mud with brecciated core material had been undertaken. Brecciated mudstone material did not display distinct isotopic signals compared to the surrounding fine-grained material. Overall we show that the most accurate assessment of bulk organic carbon isotopes and concentration in these samples can be achieved through decarbonating the material prior to measurement via the `rinse method'. However, our results support recent findings that pre-analysis acid treatments can cause variable and unpredictable errors in δ13C and TOC values. We believe that, despite these uncertainties, the findings presented here can be applied to paleoenvironmental studies on organic matter contained within sedimentary rocks over a range of geological ages and compositions.

  2. The effect of lipid extraction on carbon and nitrogen stable isotope ratios in oyster tissues: Implications for glycogen-rich species.

    PubMed

    Patterson, H K; Carmichael, R H

    2016-12-30

    Extraction of lipids from tissues prior to carbon stable isotope analysis (SIA) has become a common practice, despite a lack of species-specific data to indicate when lipid extraction is needed. Marine invertebrates, including bivalves, are known to store carbon as glycogen and less in the form of lipids than other species, potentially reducing the need for lipid extraction even when C:N values are above 3.5, a value that previous studies suggest indicates a need for lipid extraction of animal tissues. We investigated the need for lipid extraction on individual tissues (adductor muscle, gut gland, gill) and whole tissue of a glycogen-storing species, the oyster Crassostrea virginica. Bulk and lipid-extracted samples were analyzed for their C and N stable isotope ratios by continuous flow isotope ratio mass spectrometry (IRMS). Samples were analyzed on a 20-20 isotope ratio mass spectrometer (PDZ Europa) after combustion in an elemental analyzer (PDZ Europa Automatic Analyzer-Gas Solid Liquid). Although the C:N values for most bulk (unextracted) tissue samples were greater than 3.5, the lipid-extracted δ(13) C values did not differ from the bulk values. Lipid extraction, however, affected δ(15) N values in all tissue types except adductor muscle, indicating that separate SIA may be required when tissues are lipid extracted. These data demonstrate that it is not necessary to lipid extract oyster tissues in all cases, and that C:N thresholds for lipid extraction in other species may not be reliable for organisms such as oysters that store glycogen. Our data indicate that minimizing unnecessary lipid extraction through preliminary testing will save researchers time and expense by avoiding superfluous sample handling, reducing concern over secondary effects on data quality, and reducing the costs of reagents and additional separate stable isotope analysis to ensure analytical accuracy. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  3. Intra-shell oxygen isotope ratios in the benthic foraminifera genus Amphistegina and the influence of seawater carbonate chemistry and temperature on this ratio

    NASA Astrophysics Data System (ADS)

    Rollion-Bard, C.; Erez, J.; Zilberman, T.

    2008-12-01

    Using secondary ion mass spectrometry (SIMS) we looked at the natural variability in the oxygen isotope ratio of the shallow water, symbionts-bearing foraminiferan Amphistegina lobifera. Live foraminifera were collected in February 2005 in the Gulf of Eilat, Israel. Vertical section exposing the knob area of this species represents the growth history of this species from August 2004 to February 2005. SIMS profile at a resolution of ˜15 μm (representing about 2 weeks considering the size of the knob area and the life span of ≈6 months of this foraminifera species) yielded δ 18O changes of ˜1.5‰ that are compatible with the known temperature changes for the Gulf of Eilat for this period (21-27 °C). Natural variability between primary and secondary calcite at the knob area were obtained on horizontal section of the upper knob area. This section is semi-tangential to the growth lines and exposes relatively wide belts of the primary calcite which could be analysed using the SIMS (beam size of 10 × 20 μm). The primary calcite δ 18O value is on average more than 3‰ lower than the secondary calcite that represents the bulk of the skeleton (more than 95% by weight). A vertical profile at the knob was obtained by rastering an area of 50 × 50 μm at vertical steps of roughly 1 μm. The profile revealed a narrow zone of lower δ 18O compared to the higher values above and below it. The difference between the lowest δ 18O and the highest one was also close to 2‰. The δ 18O in the margin - keel area of A. lobifera is also lower compared to the bulk secondary calcite. Specimens that were cultured in the laboratory at a constant temperature and inorganic carbon but at different pH have increased their CaCO 3 weight by roughly a factor of 8. Single specimen from each pH (ranging between 7.90 and 8.45) were investigated with the SIMS at the knob area. While there is some variability within each specimen (perhaps related to the primary calcite), the general trend

  4. Carbon and nitrogen isotopic ratios of urine and faeces as novel nutritional biomarkers of meat and fish intake.

    PubMed

    Kuhnle, Gunter G C; Joosen, Annemiek M C P; Kneale, Catherine J; O'Connell, Tamsin C

    2013-02-01

    Meat and fish consumption are associated with changes in the risk of chronic diseases. Intake is mainly assessed using self-reporting, as no true quantitative nutritional biomarker is available. The measurement of plasma fatty acids, often used as an alternative, is expensive and time-consuming. As meat and fish differ in their stable isotope ratios, δ(13)C and δ(15)N have been proposed as biomarkers. However, they have never been investigated in controlled human dietary intervention studies. In a short-term feeding study, we investigated the suitability of δ(13)C and δ(15)N in blood, urine and faeces as biomarkers of meat and fish intake. The dietary intervention study (n = 14) followed a randomised cross-over design with three eight-day dietary periods (meat, fish and half-meat-half-fish). In addition, 4 participants completed a vegetarian control period. At the end of each period, 24-h urine, fasting venous blood and faeces were collected and their δ(13)C and δ(15)N analysed. There was a significant difference between diets in isotope ratios in faeces and urine samples, but not in blood samples (Kruskal-Wallis test, p < 0.0001). In pairwise comparisons, δ(13)C and δ(15)N were significantly higher in urine and faecal samples following a fish diet when compared with all other diets, and significantly lower following a vegetarian diet. There was no significant difference in isotope ratio between meat and half-meat-half-fish diets for blood, urine or faecal samples. The results of this study show that urinary and faecal δ(13)C and δ(15)N are suitable candidate biomarkers for short-term meat and fish intake.

  5. Inferences on Late Holocene climate from stable carbon and oxygen isotope ratio variability in soil and land snail shells from archaeological site 41KM69 in Texas, USA

    NASA Astrophysics Data System (ADS)

    Paul, D.; Mauldin, R.; Munoz, C. M.

    2011-12-01

    Well-preserved land snail shell excavate from archaeological site 41KM69 in Texas, USA, span the past 2200 years and provide an opportunity to explore the paleoclimate implications of isotopic variability in archaeological shell carbonates, bulk soil carbonates and soil organic matter. Terrestrial snail shells belonging to three genera (Polygyra, Rabdotus, and Helicina) were hand-picked from the 120 cm thick soil profile, for stable isotopic analyses. A wood charcoal radiocarbon date constrains samples below 100 cm depth in our soil profile to be ~2200 14C yr BP. Isotopic composition of modern adult snail specimens (n=24) and plants (n=18), collected from the study area, were determined for comparison with the archaeological data sets. All isotopic analyses were performed at the University of Texas at San Antonio using a Thermo Finnigan Gasbench II and a Costech Elemental Analyzer (EA) attached online to a DeltaPlus XP Stable Isotope Ratio Mass Spectrometer in continuous flow mode. Carbon isotopic compositions of both modern (-12.72 to -5.49%) and archaeological (-5.34 to -8.99%) adult snail shell carbonates suggest significant (> 60%) input of C3 plants into the diet of the snails over the past 2200 yrs. Oxygen isotopic compositions of archaeological and modern shells vary from -2.21% to -0.71% and -2.88 to +0.99%), respectively. This suggests that isotopic composition of environmental water (mainly rainwater) available at the time of shell growth was similar to that of the present day. A linearly decreasing trend in δ13C of soil organic matter from -22.83% at 2200 14C yr BP to -25.61% for modern samples imply progressively increasing abundance of C3 plants up to the present day. This implies a progressively wetter climate, or decreasing summer rainfall and less severe water stress conditions, in agreement with other studies on Holocene climate change in the southern Great Plains of USA. The studies, in general, document warm/arid conditions at ~ 2000 BP and

  6. Measuring Isotope Ratios Across the Solar System

    NASA Technical Reports Server (NTRS)

    Webster, Chris R.; Mahaffy, Paul R.

    2012-01-01

    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 biology [1]. For the Allan Hills 84001 meteorite, for example, the (sup 1)(sup 3)C/(sup 1)(sup 2)C ratio identifies it as a Mars (SNC) meteorite; the ??K/??Ar ratio tells us the last time the rock cooled to solid, namely 4 Gya; isotope ratios in (sup 3)He, (sup 2)(sup 1)Ne and (sup 3)?Ar show it was in space (cosmic ray exposure) for 10-20 million years; (sup 1)?C dating that it sat in Antarctica for 13,000 years before discovery; and clumped isotope analysis of (sup 1)?O(sup 1)(sup 3)C(sup 1)?O in its carbonate that it was formed at 18+/-4 ?C in a near-surface aqueous environment [2]. Solar System Formation

  7. Measuring Isotope Ratios Across the Solar System

    NASA Technical Reports Server (NTRS)

    Webster, Chris R.; Mahaffy, Paul R.

    2012-01-01

    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 biology [1]. For the Allan Hills 84001 meteorite, for example, the (sup 1)(sup 3)C/(sup 1)(sup 2)C ratio identifies it as a Mars (SNC) meteorite; the ??K/??Ar ratio tells us the last time the rock cooled to solid, namely 4 Gya; isotope ratios in (sup 3)He, (sup 2)(sup 1)Ne and (sup 3)?Ar show it was in space (cosmic ray exposure) for 10-20 million years; (sup 1)?C dating that it sat in Antarctica for 13,000 years before discovery; and clumped isotope analysis of (sup 1)?O(sup 1)(sup 3)C(sup 1)?O in its carbonate that it was formed at 18+/-4 ?C in a near-surface aqueous environment [2]. Solar System Formation

  8. Study Biosphere-Atmosphere Exchange With a Field Deployable Isotope Ratio Infrared Spectrometer For Simultaneous Measurements of Carbon And Oxygen Isotopologues of CO2

    NASA Astrophysics Data System (ADS)

    Jost, Hj; Wapelhorst, Eric; Schlueter, Hans-Juergen; Kracht, Oliver; Radke, Jens; Mandic, Magda; Gangi, Laura; Bol, Roland; Brueggemann, Nicolas; van Leeuwen, Charlotte; Chen, Huilin; Meijer, Harro

    2015-04-01

    Laser-based Isotope Ratio Infrared Spectrometers (IRIS) offer the potential to perform precise, continuous, in-situ monitoring of isotopologues of trace gases at ambient concentration. We are presenting a middle-infrared laser-based sensor platform that is capable of simultaneously determining both δ 18O and δ 13C isotope ratios of carbon dioxide. Specifically, we access the fundamental bands of CO2 at 4.2 microns using a difference frequency generation (DFG) laser combined with a simple, direct absorption approach that makes use of a robust multi pass cell and a cryogen free setup. We will present data from simulations of ambient measurements as well as real world data collected in plant chambers and greenhouse gas monitoring stations. A simulation of ambient measurement conditions with a 75 ppm/hour change in CO2 concentration from 350-650 ppm showed a precision of

  9. Temporal Variations of the Atmospheric CO2 Concentration and Its Carbon Isotope Ratio at Ny-Ålesund, Svalbard and Estimation of Global Carbon Budget

    NASA Astrophysics Data System (ADS)

    Goto, D.; Morimoto, S.; Ishidoya, S.; Aoki, S.; Nakazawa, T.

    2016-12-01

    Long-term measurements of the atmospheric CO2 concentration and its carbon isotope ratio (δ13C) are useful for partitioning anthropogenic CO2 into the terrestrial biosphere and the ocean, if the carbon isotopic disequilibrium flux (so-called isoflux), combining terrestrial and oceanic contributions, is quantified. For a better understanding of the global carbon cycle, we have carried out the systematic observation of the atmospheric CO2 concentration and δ13C at Ny-Ålesund, Svalbard (78.93°N, 11.83°E) since 1991. Air samples were collected into stainless-steel flasks at the Japanese observatory in Ny-Ålesund, once a week and sent to NIPR every two months. CO2 concentrations of the air samples were determined by using a NDIR analyzer, and CO2 samples extracted cryogenically from the remaining air in the flasks were analyzed for δ13C using a mass spectrometer. Analytical precisions for CO2 and δ13C were 0.01 ppm and 0.02 ‰, respectively. The CO2 concentration shows a clear seasonal cycle with peak-to-peak amplitude of about 17 ppm, which reaches a maximum in late April to early May and a minimum in late August, superimposed on a secular increase with an average rate of 2.0 ppm/yr for the period of 1996-2013. On the other hand, the δ13C decreases secularly at an average rate of -0.018 ‰/yr, and varies seasonally in opposite phase with the CO2 concentration. By analyzing the CO2 concentration and δ13C using the isoflux calculated with a box-diffusion model, the terrestrial biospheric and oceanic CO2 sinks are estimated to be 1.5 ± 0.3 and 2.4 ± 0.4 GtC/yr, respectively, for the 13-year period (2001-2013). On the other hand, the secular trends of the atmospheric δ(O2/N2) and CO2 concentration at Ny-Ålesund (Ishidoya et al., 2012) yield the respective sink values of 1.7 ± 0.8 and 2.2 ± 0.7 GtC/yr for the same period. The estimates from the two methods are in good agreement with each other.

  10. 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.

    PubMed

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

    2007-01-16

    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 delta(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 thousand (permil). A filtration step was added to the experimental procedure and provided results that were compliant with the 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.

  11. A Capillary Absorption Spectrometer for Stable Carbon Isotope Ratio (13C/12C) Analysis in Very Small Samples

    SciTech Connect

    Kelly, James F.; Sams, Robert L.; Blake, Thomas A.; Newburn, Matthew K.; Moran, James J.; Alexander, M. L.; Kreuzer, Helen W.

    2012-02-06

    A capillary absorption spectrometer (CAS) suitable for IR laser isotope analysis of small CO{sub 2} samples is presented. The system employs a continuous-wave (cw) quantum cascade laser to study nearly adjacent rovibrational transitions of different isotopologues of CO{sub 2} near 2307 cm{sup -1} (4.34 {mu}m). This initial CAS system can achieve relative isotopic precision of about 10 ppm {sup 13}C, or {approx}1{per_thousand} (per mil in delta notation relative to Vienna Pee Dee Belemnite) with 20-100 picomoles of entrained sample within the hollow waveguide for CO{sub 2} concentrations {approx}400 to 750 ppm. Isotopic analyses of such gas fills in a 1-mm ID hollow waveguide of 0.8 m overall physical path length can be carried out down to {approx}2 Torr. Overall {sup 13}C/{sup 12}C ratios can be calibrated to {approx}2{per_thousand} accuracy with diluted CO{sub 2} standards. A novel, low-cost method to reduce cw-fringing noise resulting from multipath distortions in the hollow waveguide is presented, which allows weak absorbance features to be studied at the few ppm level (peak-to-rms) after 1,000 scans are co-added in {approx}10 sec. The CAS is meant to work directly with converted CO{sub 2} samples from a Laser Ablation-Catalytic-Combustion (LA CC) micro-sampler to provide {sup 13}C/{sup 12}C ratios of small biological isolates with spatial resolutions {approx}50 {mu}m.

  12. Simultaneous characterization of methane and carbon dioxide produced by cultured methanogens using gas chromatography/isotope ratio mass spectrometry and gas chromatography/mass spectrometry.

    PubMed

    Ai, Guomin; Zhu, Jinxing; Dong, Xiuzhu; Sun, Tong

    2013-09-15

    The stable carbon isotope ratios of methanogen-produced CH4 and CO2 are useful information for identifying and quantifying methanogenic pathways. Isotope ratio mass spectrometry combined with gas chromatography (GC/IRMS) is a very attractive tool for performing high-precision compound-specific isotope analysis. However, no GC/IRMS techniques have yet been available or been validated that give baseline separation of methanogen-produced CH4 and CO2 from N2/N-oxides and H2O vapor at ambient temperature and compatibility with analysis by mass spectrometry. Microbe-produced CH4 and CO2 in headspace gases were separated from N2/N-oxides and H2O vapor in a single run on a GS-CarbonPLOT column at 35°C and with a maximum operating temperature of 120-140°C. The simultaneous characterization of CH4 and CO2 was then performed by GC/IRMS using an optimized backflush time to eliminate the interference from N2/N-oxides and H2O vapor, and by GC/MS due to there being no interference from O2 gas in the culture. GC/MS and GC/IRMS were used to calculate the ionization efficiency of CO2 as 8.22-8.84 times that of CH4 in GC/MS analysis, and it was deduced that the N-oxides, which can potentially interfere with δ(13)C analysis, were probably produced mainly in the source of the isotope ratio mass spectrometer. We also determined the aceticlastic methanogenic pathway. The established GC/MS and GC/IRMS techniques are suitable for characterizing the gaseous carbon-containing compounds produced by microbial cultures. Through high-precision carbon isotope analysis by GC/IRMS combined with low concentrations of (13)C-labelled substrates, the technique has great potential for identifying and quantifying methanogen-mediated carbon metabolic processes and pathways. Copyright © 2013 John Wiley & Sons, Ltd.

  13. 87Sr/86Sr isotope ratio measurements by laser ablation multicollector inductively coupled plasma mass spectrometry: Reconsidering matrix interferences in bioapatites and biogenic carbonates

    NASA Astrophysics Data System (ADS)

    Irrgeher, Johanna; Galler, Patrick; Prohaska, Thomas

    2016-11-01

    This study is dedicated to the systematic investigation of the effect of interferences on Sr isotopic analyses in biological apatite and carbonate matrices using laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC ICP-MS). Trends towards higher 87Sr/86Sr ratios for LA-MC ICP-MS compared to solution-nebulization based MC ICP-MS when analysing bioapatite matrices (e.g. human teeth) and lower ratios in case of calcium carbonates (e.g. fish ear stones) were observed. This effect can be related to the presence of significant matrix-related interferences such as molecular ions (e.g. (40Ca-31P-16O)+, (40Ar-31P-16O)+, (42Ca-44Ca)+, (46Ca40Ar)+) as well as in many cases concomitant atomic ions (e.g. 87Rb+, 174Hf2 +). Direct 87Sr/86Sr ratio measurements in Ca-rich samples are conducted without the possibility of prior sample separation, which can be accomplished routinely for solution-based analysis. The presence of Ca-Ar and Ca-Ca molecular ion interferences in the mass range of Sr isotopes is shown using the mass resolving capabilities of a single collector inductively coupled plasma sector field mass spectrometer operated in medium mass resolution when analysing bioapatites and calcium carbonate samples. The major focus was set on analysing human tooth samples, fish hard parts and geological carbonates. Potential sources of interferences were identified and corrected for. The combined corrections of interferences and adequate instrumental isotopic fractionation correction procedures lead to accurate data even though increased uncertainties have to be taken into account. The results are discussed along with approaches presented in literature for data correction in laser ablation analysis.

  14. Variation of hydrogen, carbon, nitrogen, and oxygen stable isotope ratios in an American diet: fast food meals.

    PubMed

    Chesson, Lesley A; Podlesak, David W; Thompson, Alexandra H; Cerling, Thure E; Ehleringer, James R

    2008-06-11

    The stable isotopes of hydrogen, carbon, nitrogen, and oxygen provide insights into a heterotrophic organism's diet and geographic origin. Although the contribution of food delta (2)H and delta (18)O to the final tissue signal will not vary for constrained diets, it will for animals eating varied diets, that is, humans. This study surveyed the isotopic range in one portion of the American diet, fast food meals. Hamburger patties, buns, and French fries from national chain restaurants across the United States and from local restaurants (Salt Lake City, UT, and Charleston, SC) were analyzed for delta (2)H, delta (13)C, delta (15)N (patties only) and delta (18)O values. Patties and buns from local Utah restaurants were more depleted for delta (2)H, delta (13)C, and delta (18)O values than samples from other restaurants. There were no significant differences in delta values among French fries. All three components of the fast food meal displayed significant linear delta (2)H versus delta (18)O relationships (delta (2)H = 7.8delta (18)O - 237 per thousand, delta (2)H = 5.9delta (18)O - 258 per thousand, and delta (2)H = 3.3delta (18)O - 231 per thousand for patties, buns, and fries, respectively). The findings show that significant predictable variation exists in the stable isotopic composition of fast food meals. It is proposed that the variation in delta (13)C values of hamburger (beef) patties is indicative of differences in cattle-rearing practices, whereas delta (2)H and delta (18)O values are evidence of geographic variation in food sources. Although the patterns support the concept of a "continental" supermarket diet, there appears to be a strong regional component within the diet.

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

    NASA Technical Reports Server (NTRS)

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

    2014-01-01

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

  16. Carbon and oxygen isotope ratios in wood constituents of Pinus halepensis as indicators of precipitation, temperature and vapour pressure deficit

    NASA Astrophysics Data System (ADS)

    Ferrio, J. P.; Voltas, J.

    2005-04-01

    Carbon and oxygen isotope compositions (δ13C, δ18O) in tree rings have been shown to bear relevant climatic signals. However, little is known about the interrelationship between both isotopes in wood constituents for species from other than relatively wet climates. We hypothesized that in a species adapted to temporary droughts (e.g. Pinus halepensis Mill.) the signal derived from δ18O in precipitation would be hidden by the strong variability in leaf transpirative enrichment. To test this assumption, we compared the effect of precipitation, temperature and vapour pressure deficit (VPD) on δ18O and δ13C along 23 sites covering the ecological range for this species. We extracted the cores from the south side of four to six adult dominant trees per aspect (north/south) within each site. For each aspect and site, fragments of the period 1975 1999 were pooled and milled to a fine powder. To further test the postulated need for cellulose purification in the assessment of climatic information, we studied these relationships in whole and extracted wood, holocellulose and lignin. In all wood fractions, δ13C was related to annual precipitation [r=-0.58 (P< 0.01) to -0.78 (P< 0.001)] and VPD [r= 0.53 (P< 0.01) to 0.57 (P< 0.01)]. In contrast, for δ18O only holocellulose showed consistent relationships with climatic data, being strongly significant for VPD [r= 0.66 (P< 0.001)]. However, it was unrelated to modelled δ18O in precipitation, confirming that transpirative enrichment (driven by VPD) dampened the source signal in P. halepensis. The relationships between δ13C and δ18O were generally poor, regardless of the wood constituent, suggesting that although both variables were somewhat related to transpirative demand, they were relatively independent. This was further confirmed by building stepwise models using both isotopes to predict annual and seasonal precipitation [r2= 0.34 (P< 0.01) to 0.68 (P< 0.001)], temperature [r2= 0.15 (P< 0.05) to 0.37 (P< 0.01)] and

  17. Determination of origin of ephedrine used as precursor for illicit methamphetamine by carbon and nitrogen stable isotope ratio analysis.

    PubMed

    Kurashima, Naoki; Makino, Yukiko; Sekita, Setsuko; Urano, Yasuteru; Nagano, Tetsuo

    2004-07-15

    The sale of ephedrine, one of the precursors of methamphetamine, is strictly controlled and monitored in various countries to prevent the production of illicit methamphetamine. There are three kinds of production scheme for ephedrine manufacture, and it is very useful for precursor control to investigate the origin of ephedrine used for the synthesis of illicit methamphetamine. By means of stable isotope ratio mass spectrometry (IR-MS), we investigated the origin of ephedrine based on the delta(13)C and delta(15)N values. The various origins of ephedrine (biosynthetic, semisynthetic, or synthetic) could be discriminated clearly by using these values. The delta(15)N values of synthetic ephedrine were more negative than those of ephedrine from other sources. By the repeated distillation of methylamine in our laboratory, we confirmed that this could be due to isotope separation during distillation for the purification of methylamine used for ephedrine synthesis. The values for ephedrine used as the precursor were well-correlated with those for methamphetamine synthesized from it. This drug characterization analysis should be useful to illuminate the origin of the precursors used for clandestine methamphetamine and to trace the diversion of medicinal ephedrine for illicit manufacture of methamphetamine.

  18. Source inference of exogenous gamma-hydroxybutyric acid (GHB) administered to humans by means of carbon isotopic ratio analysis: novel perspectives regarding forensic investigation and intelligence issues.

    PubMed

    Marclay, François; Saudan, Christophe; Vienne, Julie; Tafti, Mehdi; Saugy, Martial

    2011-05-01

    γ-Hydroxybutyric acid (GHB) is an endogenous short-chain fatty acid popular as a recreational drug due to sedative and euphoric effects, but also often implicated in drug-facilitated sexual assaults owing to disinhibition and amnesic properties. Whilst discrimination between endogenous and exogenous GHB as required in intoxication cases may be achieved by the determination of the carbon isotope content, such information has not yet been exploited to answer source inference questions of forensic investigation and intelligence interests. However, potential isotopic fractionation effects occurring through the whole metabolism of GHB may be a major concern in this regard. Thus, urine specimens from six healthy male volunteers who ingested prescription GHB sodium salt, marketed as Xyrem(®), were analysed by means of gas chromatography/combustion/isotope ratio mass spectrometry to assess this particular topic. A very narrow range of δ(13)C values, spreading from -24.81‰ to -25.06‰, was observed, whilst mean δ(13)C value of Xyrem(®) corresponded to -24.99‰. Since urine samples and prescription drug could not be distinguished by means of statistical analysis, carbon isotopic effects and subsequent influence on δ(13)C values through GHB metabolism as a whole could be ruled out. Thus, a link between GHB as a raw matrix and found in a biological fluid may be established, bringing relevant information regarding source inference evaluation. Therefore, this study supports a diversified scope of exploitation for stable isotopes characterized in biological matrices from investigations on intoxication cases to drug intelligence programmes.

  19. Temperature exerts no influence on carbon isotope ratios in soil along the 400 mm isopleth of mean annual precipitation in China

    NASA Astrophysics Data System (ADS)

    Wang, Guoan

    2017-04-01

    Soil organic carbon is the largest pool of carbon in the terrestrial ecosystem, and its isotopic composition is affected by a number of factors. However, the influence of environmental factors, especially temperature, on soil organic carbon isotope values is poorly constrained. This impedes the application of the variability of organic carbon isotopes to reconstructions of paleoclimate, paleoecology, and global carbon cycling. Given the considerable temperature gradient along the 400 mm isohyet (isopleth of mean annual precipitation - MAP) in China, this isohyet provides ideal experimental sites for studying the influence of temperature on soil organic carbon isotopes. In this study, the effect of temperature on surface soil carbon isotope composition was assessed by a comprehensive investigation of 27 sites across a temperature gradient along the isohyet. Results demonstrate that temperature does not play a role in soil carbon isotope. This suggests that organic carbon isotopes in sediments cannot be used for paleotemperature reconstruction and that the effect of temperature on organic carbon isotopes can be neglected in the reconstruction of paleoclimate and paleovegetation. Multiple regressions with MAT (mean annual temperature), MAP, altitude, latitude, and longitude as independent variables and soil carbon isotope as the dependent variable show that these five environmental factors together account for only 9% of soil carbon isotope variance. However, one-way ANOVA analyses suggest that soil type and vegetation type are significant factors influencing soil carbon isotope. Multiple regressions, in which the five aforementioned environmental factors were taken as quantitative variables, and vegetation type, soil type based on the Chinese Soil Taxonomy, and World Reference Base (WRB) soil type were separately used as dummy variables, show that 36.2, 37.4, and 29.7%, respectively, of the variability in soil carbon isotope are explained. Compared to the multiple

  20. Effects of elevated carbon dioxide on stomatal characteristics and carbon isotope ratio of Arabidopsis thaliana ecotypes originating from an altitudinal gradient.

    PubMed

    Caldera, H Iroja U; De Costa, W A Janendra M; Woodward, F Ian; Lake, Janice A; Ranwala, Sudheera M W

    2017-01-01

    Stomatal functioning regulates the fluxes of CO2 and water vapor between vegetation and atmosphere and thereby influences plant adaptation to their habitats. Stomatal traits are controlled by external environmental and internal cellular signaling. The objective of this study was to quantify the effects of CO2 enrichment (CE) on stomatal density (SD)-related properties, guard cell length (GCL) and carbon isotope ratio (δ(13) C) of a range of Arabidopsis thaliana ecotypes originating from a wide altitudinal range [50-1260 m above sea level (asl)], and grown at 400 and 800 ppm [CO2 ], and thereby elucidate the possible adaptation and acclimation responses controlling stomatal traits and water use efficiency (WUE). There was a highly significant variation among ecotypes in the magnitude and direction of response of stomatal traits namely, SD and stomatal index (SI) and GCL, and δ(13) C to CE, which represented a short-term acclimation response. A majority of ecotypes showed increased SD and SI with CE with the response not depending on the altitude of origin. Significant ecotypic variation was shown in all stomatal traits and δ(13) C at each [CO2 ]. At 400 ppm, means of SD, SI and GCL for broad altitudinal ranges, i.e. low (<100 m), mid (100-400 m) and high (>400 m), increased with increasing altitude, which represented an adaptation response to decreased availability of CO2 with altitude. δ(13) C was negatively correlated to SD and SI at 800 ppm but not at 400 ppm. Our results highlight the diversity in the response of key stomatal characters to CE and altitude within the germplasm of A. thaliana and the need to consider this diversity when using A. thaliana as a model plant.

  1. Changes of leaf morphological, anatomical structure and carbon isotope ratio with the height of the Wangtian tree (Parashorea chinensis) in Xishuangbanna, China.

    PubMed

    He, Chun-Xia; Li, Ji-Yue; Zhou, Ping; Guo, Ming; Zheng, Quan-Shui

    2008-02-01

    Leaf morphological and anatomical structure and carbon isotope ratio (delta13C) change with increasing tree height. To determine how tree height affects leaf characteristics, we measured the leaf area, specific leaf mass (ratio of leaf mass to leaf area [LMA]), thickness of the total leaf, cuticle, epidermis, palisade and sponge mesophyll, stomata traits and delta13C at different heights of Parashorea chinensis with methods of light and scanning electron microscopy (SEM) and isotope-ratio mass spectrometry. The correlation and stepwise regression between tree height and leaf structure traits were carried out with SPSS software. The results showed that leaf structures and delta13C differed significantly along the tree height gradient. The leaf area, thickness of sponge mesophyll and size of stomata decreased with increasing height, whereas the thickness of lamina, palisade mesophyll, epidermis, and cuticle, ratios of palisade to spongy thickness, density of stomata and vascular bundles, LMA and delta13C increased with tree height. Tree height showed a significant relationship with all leaf indices and the most significant relationship was with epidermis thickness, leaf area, cuticle thickness, delta13C. The delta13C value showed a significantly positive relationship with LMA (R = 0.934). Our results supported the hypothesis that the leaf structures exhibited more xeromorphic characteristics with the increasing gradient of tree height.

  2. Diuranl variations and characteristics of organic molecular composition and stable carbon isotope ratios of PM2.5 in Beijing during the "APEC Blue"

    NASA Astrophysics Data System (ADS)

    Ren, H.; Fan, S.; Fu, P.

    2016-12-01

    Fine particulate matters (PM2.5) were collected before and during the 2014 Asian-Pacific Economic Cooperation (2014 APEC) (15 October-12 November) in Beijing to study their sources, diurnal variations, and the effects of region controls on the improving of the air quality. Organic molecular compositions of lipids, saccharides, polyacids, ligin & resin products, aromatic acids, phthalate esters, hopanes, PAHs and sterols were analyzed by GC-MS), while stable carbon isotope ratio (δ13C) of total carbon (TC) were determination using Gas Isotope Ratio MS (IRMS, MAT 253). Results indicated that five aerosol episodes were founded before and during the APEC event. Concentrations of most organic compounds showed maxima at nighttime and were obviously decreased during the APEC. These features were associated with meteorological conditions (especially high relative humidity and low wind speed), reginal emission controls (carried out during APEC), urban boundary layer movement and mountain/valley breezes in Beijing. Before the APEC, the main sources of organic aerosols in Beijing were long-range transport from surrounding cities together with local emission sources, while local emissions became the dominant source during the APEC. Biomass burning, motor emissions, fossil fuel combustion such as coal and petroleum, open-burning of municipal wastes during night significantly contributed to organic aerosols in Beijing. Our results suggest that anthropogenic emissions are important sources of aerosols in Beijing, and the regional controls is an efficient way to improve the air quality.

  3. Coupling a high-temperature catalytic oxidation total organic carbon analyzer to an isotope ratio mass spectrometer to measure natural-abundance delta13C-dissolved organic carbon in marine and freshwater samples.

    PubMed

    Panetta, Robert J; Ibrahim, Mina; Gélinas, Yves

    2008-07-01

    The stable isotope composition of dissolved organic carbon (delta(13)C-DOC) provides powerful information toward understanding carbon sources and cycling, but analytical limitations have precluded its routine measurement in natural samples. Recent interfacing of wet oxidation-based dissolved organic carbon analyzers and isotope ratio mass spectrometers has simplified the measurement of delta(13)C-DOC in freshwaters, but the analysis of salty estuarine/marine samples still proves difficult. Here we describe the coupling of the more widespread high-temperature catalytic oxidation-based total organic carbon analyzer to an isotope ratio mass spectrometer (HTC-IRMS) through cryogenic trapping of analyte gases exiting the HTC analyzer for routine analysis of delta(13)C-DOC in aquatic and marine samples. Targeted elimination of major sources of background CO2 originating from the HTC analyzer allows for the routine measurement of samples over the natural range of DOC concentrations (from 40 microM to over 2000 microM), and salinities (<0.1-36 g/kg). Because consensus reference natural samples for delta(13)C-DOC do not exist, method validation was carried out with water-soluble stable isotope standards as well as previously measured natural samples (IAEA sucrose, Suwannee River Fulvic Acids, Deep Sargasso Sea consensus reference material, and St. Lawrence River water) and result in excellent delta(13)C-DOC accuracy (+/-0.2 per thousand) and precision (+/-0.3 per thousand).

  4. Stable Carbon Isotope Ratios and Mixing Ratios of Several VOC Including n-Hexane, Benzene, Toluene, p-Xylene, n-Octane, and n-Decane Measured During the Border Air Quality Study Campaign (June-July, 2007)

    NASA Astrophysics Data System (ADS)

    Kornilova, A.; Moukhtar, S.; Huang, L.; Rudolph, J.

    2008-12-01

    Many important secondary pollutants are formed during the oxidation of Volatile Organic Compounds (VOC) in the atmosphere. These organic compounds can contribute significant mass to atmospheric particulate matter (PM) and therefore impact physical properties and composition of aerosols. Despite numerous studies, the formation processes for atmospheric PM are still not well understood. While there have been very extensive laboratory investigations of PM formation, nearly all of these studies have been conducted at VOC concentrations which exceed ambient atmospheric levels by several orders of magnitude. Consequently there is substantial uncertainty in the extrapolation of laboratory results to the atmosphere. Recently it has been demonstrated that stable carbon isotopic composition measurements can be very valuable in providing increased insight into the chemical and transport processes of VOC in the troposphere. Studies showed that isotope ratio measurements could aid in the determination of photochemical processing of individual VOC. It is expected that applying isotope measurements to studies of VOC oxidation products in the atmosphere will allow to establish quantitative relationship between the amount of precursor oxidized and the concentration of secondary pollutants formed during this process. Thus, the yield of secondary organic aerosols (SOA) from this reaction can be calculated. A cartridge technique was developed for field sampling of VOC and subsequent laboratory analysis by gas chromatography coupled with isotope ratio mass spectrometry. It was first implemented during the BAQS field study (June-July, 2007) parallel to PM sampling. Stable carbon isotopic composition and concentrations of several VOC were determined and compared to those of PM. The results of these measurements will be presented and discussed.

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

    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 approach to elucidating pelagic food web structures and diet assimilation. Integrating the combined effects of ecological processes and hydrography, ecohydrographic features often translate into geographic patterns in δ13C and δ15N values at the base of food webs. This is due, for example, to divergent 15N abundances in source end-members (deep water sources: high δ15N, diazotrophs: low δ15N). Such patterns in the spatial distributions of stable isotope values were coined isoscapes. Empirical data of atmospheric, oceanographic, and biological processes, which drive the ecohydrographic gradients of the oligotrophic Red Sea, are under-explored and some rather anticipated than proven. Specifically, five processes underpin Red Sea gradients: (a) monsoon-related intrusions of nutrient-rich Indian Ocean water; (b) basin scale thermohaline circulation; (c) mesoscale eddy activity that causes up-welling of deep water nutrients into the upper layer; (d) the biological fixation of atmospheric nitrogen (N2) by diazotrophs; and (e) the deposition of dust and aerosol-derived N. This study assessed relationships between environmental samples (nutrients, chlorophyll a), oceanographic data (temperature, salinity, current velocity [ADCP]), particulate organic matter (POM), and net-phytoplankton, with the δ13C and δ15N values of zooplankton collected in spring 2012 from 16°28‧ to 26°57‧N along the central axis of the Red Sea. The δ15N of bulk POM and most zooplankton taxa increased from North (Duba) to South (Farasan). The potential contribution of deep water nutrient-fueled phytoplankton, POM, and diazotrophs varied among sites. Estimates suggested higher diazotroph contributions in the North, a greater contribution of

  6. Authenticity testing of environment-friendly Korean rice (Oryza sativa L.) using carbon and nitrogen stable isotope ratio analysis.

    PubMed

    Chung, Ill-Min; Park, Sung-Kyu; Lee, Kyoung-Jin; An, Min-Jeong; Lee, Ji-Hee; Oh, Yong-Taek; Kim, Seung-Hyun

    2017-11-01

    The increasing demand for organic foods creates, in turn, a pressing need for the development of more accurate tools for the authentication of organic food in order to ensure both fair trade and food safety. This study examines the feasibility of δ(13)C and δ(15)N analyses as potential tools for authentication of environment-friendly rice sold in Korea. δ(13)C and δ(15)N examination in different rice grains showed that environment-friendly rice can be successfully distinguished from conventional rice. No multi-residue pesticides were detected in the examined rice samples, including conventional rice. This study demonstrates the complementary feasibility of δ(13)C and δ(15)N analyses for the authentication of environment-friendly rice sold in Korea in cases where pesticide residue analysis alone is insufficient for discrimination of organic and conventional rice. In future, complementary analyses including compound-specific isotope ratio analysis might be employed for improving the reliability of organic authentication. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Temperature Dependence of Isotope Ratios in Tree Rings

    PubMed Central

    Libby, L. M.; Pandolfi, L. J.

    1974-01-01

    The stable isotope ratios of carbon, oxygen, and hydrogen have been measured for a German oak in wood samples of roughly three years each, for the years 1712-1954 A.D., and correlated with the existing weather records from England, Basel, and Geneva to evaluate the empirical temperature coefficients. Isotope ratios in a second official oak, measured for the years 1530-1800 A.D., show the cold temperatures of the Little Ice Age interspersed with warm intervals. PMID:16592163

  8. Diet and habitat of the saiga antelope during the late Quaternary using stable carbon and nitrogen isotope ratios

    NASA Astrophysics Data System (ADS)

    Jürgensen, Jonathan; Drucker, Dorothée G.; Stuart, Anthony J.; Schneider, Matthias; Buuveibaatar, Bayarbaatar; Bocherens, Hervé

    2017-03-01

    Saiga antelope (Saiga tatarica) is one of the typical late Pleistocene species of the cold and arid mammoth steppe that covered a large area of northern hemisphere. The species is currently endangered and persists only in small areas of Central Asian steppe and desert ecosystems. The investigation of the ecology of the Pleistocene saiga using stable isotope ratios (δ13C, δ15N) aimed to decipher how different their diet and habitat were from those observed nowadays in relict populations. Up to 76 samples of bone collagen of ancient saiga from Western Europe, Siberia and Eastern Beringia were analysed and compared with 52 samples of hair and bone collagen of modern specimens from Kazahkstan, Russia and Mongolia. The δ13C values of the ancient saiga do not exhibit a clear trend over time. They cover the same range of values as the modern ones, from a C3-dominated to a C3-C4-dominated mixed diet (including probably Chenopodiaceae). In contrast, the δ15N values of fossil saigas are more variable and lower on average than the extant ones. The lowest δ15N values of ancient saiga are found around the Last Glacial Maximum, reflecting the influence of the cold conditions at that time. On the other hand, fossil saiga occupying the same regions as the historical and modern populations exhibit high δ15N values similar to the modern ones, confirming ecological continuity over time. Modern saiga is thus occupying just one of its potential diverse habitats they used in the past. Therefore, the extant saiga is not a refugee species confined to a suboptimal habitat. During the late Pleistocene, the saiga occupied a separate niche compared with the other ungulates of the mammoth steppe. However, this species could also adapt to a lichen-dominated diet normally seen in reindeer, leading to an isotopic overlap between the two species in south-western France and Alaska around the Last Glacial Maximum. This adaptation allowed a geographical expansion that does not correspond to a

  9. Photosynthetic Mechanisms and Paleoecology from Carbon Isotope Ratios in Ancient Specimens of C4 and CAM Plants.

    PubMed

    Troughton, J H; Wells, P V; Mooney, H A

    1974-08-16

    Carbon istotope ratios of modern, 10,000-year-old, and more than 40,000-year-old Atriplex confertifolia (C(4)) material from Nevada caves indicate that the C(4) photosynthetic pathway was operating in these plants over that period. Samples of a plant with crassulacean acid metabolism, Opuntia polyacantha, were also measured, and a shift in the 8(13)C value from -21.9 per mil (more than 40,000 years ago) to -13.9 per mil (10,000 years ago) was observed. This provides unique physiological evidence to support the hypothesis that the late Pleistocene pluvial climate in the region already had become drier about 10,000 years ago.

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

    NASA Technical Reports Server (NTRS)

    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.

  11. The carbon isotopic composition of ecosystem breath

    NASA Astrophysics Data System (ADS)

    Ehleringer, J.

    2008-05-01

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

  12. Effects of fasting and nutritional restriction on the isotopic ratios of nitrogen and carbon: a meta-analysis.

    PubMed

    Hertz, Eric; Trudel, Marc; Cox, Marlin K; Mazumder, Asit

    2015-11-01

    Many organisms experience fasting in their life time, and this physiological process has the potential to alter stable isotope values of organisms, and confound interpretation of food web studies. However, previous studies on the effects of fasting and starvation on stable isotopes show disparate results, and have never been quantitatively synthesized. We performed a laboratory experiment and meta-analysis to determine how stable isotopes of δ (15)N and δ (13)C change with fasting, and we tested whether moderators such as taxa and tissue explain residual variation. We collected literature data from a wide variety of taxa and tissues. We surveyed over 2000 papers, and of these, 26 met our selection criteria, resulting in 51 data points for δ (15)N, and 43 data points for δ (13)C. We determine that fasting causes an average increase in the isotopic value of organisms of 0.5‰ for δ (15)N and that the only significant moderator is tissue type. We find that the overall effect size for δ (13)C is not significant, but when the significant moderator of tissue is considered, significant increases in blood and whole organisms are seen with fasting. Our results show that across tissues and taxa, the nutritional status of an organism must be considered when interpreting stable isotope data, as fasting can cause large differences in stable isotope values that would be otherwise attributed to other factors.

  13. Sources and fate of organic carbon and nitrogen from land to ocean: Identified by coupling stable isotopes with C/N ratio

    NASA Astrophysics Data System (ADS)

    Li, Yuan; Zhang, Haibo; Tu, Chen; Fu, Chuancheng; Xue, Yong; Luo, Yongming

    2016-11-01

    The transport of organic matter in coastal areas plays an important role in global biogeochemical cycles. The present study used stable isotopes including carbon (δ13C) and nitrogen (δ15N) and C/N ratio to assess the sources and fate of organic carbon and nitrogen in soils and sediments of a coastal plain-river plume-bay system. Changes of the δ13C and δ15N values from natural to agricultural soils in the Yellow River coastal plain reflected the contribution of C4 carbon, decomposition of organic matter and application of nitrogen fertilizer. The organic carbon in the marine sediments adjacent to the coastal plain mainly originated from C3-dominated terrestrial systems. The spatial heterogeneity of both δ13C and δ15N values indicated that Yellow River sediment transport and anthropogenic wastewater discharge were two driving forces for the sedimentary organic carbon and nitrogen dynamics in large river plume and inner bay areas. Meanwhile, the marine primary production and denitrification process as affected by excessive nutrient input also contributed to the cycling of organic matter. Wetland soils, cropland soils, vegetable soils, coastal and deep-sea sediments were the five systems controlling the cycle of organic carbon and nitrogen in the study area. A significant positive correlation between δ13C and δ15N in the Yellow River coastal plain-plume-bay region was observed, which implied the flux of organic matter from a labile pool in source regions into a more recalcitrant pool in sink regions. These findings would provide a better understanding of carbon sequestration in the coastal soil and sediment.

  14. Use of stable carbon isotope ratios to determine the source of cypermethrin in so-called natural plant extract formulations used for organic farming.

    PubMed

    Kawashima, Hiroto; Kariya, Takuro

    2017-03-01

    Some natural plant extract formulations (NPEFs, also referred to as essential oils) used in organic farming have been shown to contain synthetic pesticides. We obtained samples of four NPEFs (Muso, Hekiro, Kensogen-Ten, and Nurse Green) that were contaminated with the synthetic pyrethroid cypermethrin, and we used gas chromatography coupled with combustion, cryofocusing, and isotope ratio mass spectrometry to determine the stable carbon isotope ratios (δ(13)C) for the cypermethrin in the four NPEF samples, as well as in ten cypermethrin reagents and two commercial pesticide formulations (Agrothrin emulsion and Agrothrin water-dispersible powder). Our goal was to identify the source of the cypermethrin in the NPEFs. Cryofocusing markedly sharpened the cypermethrin peak and thus improved the accuracy and precision of the determined δ(13)C values. The δ(13)C values (± SD) of the 16 cypermethrin samples ranged from -28.3 ± 0.2 to -24.5 ± 0.2 ‰. Surprisingly, the four NPEFs showed similar δ(13)C values (-26.8 to -27.3 ‰), suggesting that the cypermethrin in all the samples came from the same source (either the same chemical reaction or the same primary material). This possibility was supported by previously published results. In addition, the δ(13)C values of the two commercial pesticides were similar to the values for the NPEFs, suggesting that the commercial pesticides had been diluted and sold as NPEFs.

  15. Size distributions of organic nitrogen and carbon in remote marine aerosols: Evidence of marine biological origin based on their isotopic ratios

    NASA Astrophysics Data System (ADS)

    Miyazaki, Yuzo; Kawamura, Kimitaka; Sawano, Maki

    2010-03-01

    Size-segregated aerosol samples were collected over the western North Pacific in summer 2008 for the measurements of organic nitrogen (ON) and organic carbon (OC). ON and OC showed bimodal size distributions. Their concentrations showed positive correlation with those of biogenic tracers, methanesulfonic acid (MSA) and azelaic acid (C9). We found that average ON and OC concentrations were twice greater in aerosols collected in the oceanic region with higher biological productivity than in the regions with lower productivity. The average ON/OC ratios are higher (0.49 ± 0.11) in more biologically influenced aerosols than those (0.35 ± 0.10) in less influenced aerosols. Stable carbon isotopic analysis indicates that marine-derived carbon accounted for ˜46-72% of total carbon in more biologically influenced aerosols. These results provide evidence that organic aerosols in this region are enriched in ON that is linked to oceanic biological activity and the subsequent emissions to the atmosphere.

  16. Diurnal variations of carbonaceous components, major ions, and stable carbon and nitrogen isotope ratios in suburban aerosols from northern vicinity of Beijing

    NASA Astrophysics Data System (ADS)

    He, Nannan; Kawamura, Kimitaka; Kanaya, Yugo; Wang, Zifa

    2015-12-01

    We report diurnal variations of organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC) and major ions as well as stable carbon and nitrogen isotope ratios (δ13C and δ15N) in ambient aerosols at a suburban site (Mangshan), 40 km north of Beijing, China. We found that aerosol chemical compositions were largely controlled by the air mass transport from Beijing in daytime with southerly winds and by relatively fresh air mass in nighttime from the northern forest areas with northerly winds. Higher concentrations of aerosol mass and total carbon were obtained in daytime. Further, higher OC/EC ratios were recorded in daytime (4.0 ± 1.7) than nighttime (3.2 ± 0.7), suggesting that OC is formed by photochemical oxidation of gaseous precursors in daytime. Contributions of WSOC to OC were slightly higher in daytime (38%) than nighttime (34%), possibly due to secondary formation of WSOC in daytime. We also found higher concentrations of Ca2+ in daytime, which was originated from the construction dust in Beijing area and transported to the sampling site. δ13C ranged from -25.3 to -21.2‰ (ave. -23.5 ± 0.9‰) in daytime and -29.0 to -21.4‰ (-24.0 ± 1.5‰) in nighttime, suggesting that Mangshan aerosols were more influenced by fossil fuel combustion products in daytime and by terrestrial C3 plants in nighttime. This study suggests that daytime air mass delivery from megacity Beijing largely influence the air quality at the receptor site in the north together with photochemical processing of organic aerosols during the atmospheric transport, whereas the Mangshan site is covered with relatively clean air masses at night.

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

    NASA Technical Reports Server (NTRS)

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

    1983-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1983-01-01

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

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

    NASA Astrophysics Data System (ADS)

    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).

  20. Towards absolute laser spectroscopic CO2 isotope ratio measurements

    NASA Astrophysics Data System (ADS)

    Anyangwe Nwaboh, Javis; Werhahn, Olav; Ebert, Volker

    2017-04-01

    Knowledge of isotope composition of carbon dioxide (CO2) in the atmosphere is necessary to identify sources and sinks of this key greenhouse gas. In the last years, laser spectroscopic techniques such as cavity ring-down spectroscopy (CRDS) and tunable diode laser absorption spectroscopy (TDLAS) have been shown to perform accurate isotope ratio measurements for CO2 and other gases like water vapour (H2O) [1,2]. Typically, isotope ratios are reported in literature referring to reference materials provided by e.g. the International Atomic Energy Agency (IAEA). However, there could be some benefit if field deployable absolute isotope ratio measurement methods were developed to address issues such as exhausted reference material like the Pee Dee Belemnite (PDB) standard. Absolute isotope ratio measurements would be particularly important for situations where reference materials do not even exist. Here, we present CRDS and TDLAS-based absolute isotope ratios (13C/12C ) in atmospheric CO2. We demonstrate the capabilities of the used methods by measuring CO2 isotope ratios in gas standards. We compare our results to values reported for the isotope certified gas standards. Guide to the expression of uncertainty in measurement (GUM) compliant uncertainty budgets on the CRDS and TDLAS absolute isotope ratio measurements are presented, and traceability is addressed. We outline the current impediments in realizing high accuracy absolute isotope ratio measurements using laser spectroscopic methods, propose solutions and the way forward. Acknowledgement Parts of this work have been carried out within the European Metrology Research Programme (EMRP) ENV52 project-HIGHGAS. The EMRP is jointly funded by the EMRP participating countries within EURAMET and the European Union. References [1] B. Kühnreich, S. Wagner, J. C. Habig,·O. Möhler, H. Saathoff, V. Ebert, Appl. Phys. B 119:177-187 (2015). [2] E. Kerstel, L. Gianfrani, Appl. Phys. B 92, 439-449 (2008).

  1. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

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

    1991-01-01

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

  2. Irrigation and fertilization effects on foliar and soil carbon and nitrogen isotope ratios in a loblolly pine stand

    Treesearch

    Woo-Jung Choi; Scott X. Chang; H. Lee Allen; Daniel L. Kelting; Hee-Myong Ro

    2005-01-01

    We examined 813C and 815N in needle (current and 1-year-old) and soil samples collected on two occasions (July and September 1999) from a 15-year-old loblolly pine (Pinus taeda L.) stand in an irrigation and fertilization experiment to investigate whether these treatments leave specific isotope signals in...

  3. Carbon and oxygen isotopic ratios in Arcturus and Aldebaran. Constraining the parameters for non-convective mixing on the red giant branch

    NASA Astrophysics Data System (ADS)

    Abia, C.; Palmerini, S.; Busso, M.; Cristallo, S.

    2012-12-01

    Context. We re-analyzed the carbon and oxygen isotopic ratios in the atmospheres of the two bright K giants Arcturus (α Boo) and Aldebaran (α Tau). Aims: These stars are in the evolutionary stage following the first dredge-up (FDU). Previous determinations (dating back more than 20 years) of their 16O/18O ratios showed a rough agreement with FDU expectations; however, the estimated 16O/17O and 12C/13C ratios were lower than in the canonical predictions for red giants. Today these anomalies are interpreted as signs of the occurrence of non-convective mixing episodes. We therefore re-investigated this problem to verify whether the observed data can be reproduced in this scenario and if the fairly well determined properties of the two stars can help us in fixing the uncertain parameters that characterize non-convective mixing and in constraining its physical nature. Methods: We used high-resolution infrared spectra from the literature to derive the 12C/13C and 16O/17O/18O ratios from CO molecular lines near 5 μm, using the local termodynamic equilibrium (LTE) spectral synthesis method. We made use of the recently published ACE-FTS atlas of the infrared solar spectrum for constructing an updated atomic and molecular line lists in this spectral range. We also reconsidered the determination of the stellar parameters to build the proper atmospheric and evolutionary models. Results: We found that both the C and the O isotopic ratios for the two stars considered actually disagree with pure FDU predictions. This reinforces the idea that non-convective transport episodes occurred in these stars. By reproducing the observed elemental and isotopic abundances with the help of parametric models for the coupled occurrence of nucleosynthesis and mass circulation, we derived constraints on the properties of non-convective mixing, providing information on the so far elusive physics of these phenomena. We find that very slow mixing, like that associated to diffusive processes, is

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

    SciTech Connect

    Nadeau, S.L.; Epstein, S.; Stolper, E.

    1999-06-01

    The authors report H and C contents and {delta}D and {delta}{sup 13}C values of apatites from 15 alkaline intrusive complexes ranging in age from 110 Ma to 2.6 Ga. Sampling focused on carbonatites, but included silicate rocks as well. Heating temperatures up to 1,500 C is needed to extract fully H{sub 2}O and CO{sub 2} from these apatites. Apatites from carbonatite-rich intrusive complexes contain 0.2--1.1 wt% H{sub 2}O and 0.05--0.70 wt% CO{sub 2}; apatites from two silicate-rich alkaline complexes with little or no carbonatite are generally poorer in both volatile components (0.1--0.2% H{sub 2}O and 0.01--0.11% CO{sub 2}). D/H ratios in apatites from these rocks are bimodally distributed. The authors suggest that the {delta}D values of group I apatites represent primitive, mantle-derived values and that the group II apatites crystallized from degassed magmas, resulting in lower H{sub 2}O contents and {delta}D values. In contrast to H{sub 2}O contents and {delta}D values, CO{sub 2} contents and {delta}{sup 13}C values of gas released at high temperatures from multiple aliquots of these apatite samples are variable. This suggests the presence of more than one C-bearing component in these apatites, one of which is proposed to be dissolved carbonate; the other could be associated with hydrocarbons.

  5. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

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

    1990-05-01

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

  6. Silylated Derivatives Retain Carbon and Alter Expected 13C-Tracer Enrichments Using Continuous Flow-Combustion-Isotope Ratio Mass Spectrometry

    PubMed Central

    Shinebarger, Steven R.; Haisch, Michael; Matthews, Dwight E.

    2008-01-01

    Continuous-flow inlets from oxidation reactors are commonly used systems for biological sample introduction into isotope ratio mass spectrometers (IRMS) to measure 13C enrichment above natural abundance. Because the samples must be volatile enough to pass through a gas chromatograph, silylated derivatization reactions are commonly used to modify biological molecules to add the necessary volatility. Addition of a t-butyldimethylsilyl (TBDMS) group is a common derivatization approach. However, we have found that samples do not produce the expected increment in measured 13C abundance as the TBDMS derivatives. We have made measurements of 13C enrichment of leucine and glutamate standards of known 13C enrichment using derivatives without silicon (N-acetyl n-propyl ester), with silicon (TBDMS), and an intermediate case. The measurements of 13C in amino acids derivatized without silicon were as expected. The 13C enrichment measurements using the TBDMS derivative were higher than expected, but could be corrected to produce the expected 13C enrichment measurement by IRMS if one carbon was removed per silicon. We postulate that the silicon in the derivative forms silicon carbide compounds in the heated cupric oxide reactor, rather than forming silicon dioxide. Doing so reduces the amount of CO2 formed from the carbon in the sample. Silylated derivatives retain carbon with the silicon and must be used carefully and with correction factors to measure 13C enrichments by continuous-flow IRMS. PMID:12510745

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

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

  8. Shifts in bryophyte carbon isotope ratio across an elevation × soil age matrix on Mauna Loa, Hawaii: do bryophytes behave like vascular plants?

    PubMed

    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.

  9. Pan-Arctic concentrations of mercury and stable isotope ratios of carbon (δ(13)C) and nitrogen (δ(15)N) in marine zooplankton.

    PubMed

    Pomerleau, Corinne; Stern, Gary A; Pućko, Monika; Foster, Karen L; Macdonald, Robie W; Fortier, Louis

    2016-05-01

    Zooplankton play a central role in marine food webs, dictating the quantity and quality of energy available to upper trophic levels. They act as "keystone" species in transfer of mercury (Hg) up through the marine food chain. Here, we present the first Pan-Arctic overview of total and monomethylmercury concentrations (THg and MMHg) and stable isotope ratios of carbon (δ(13)C) and nitrogen (δ(15)N) in selected zooplankton species by assembling data collected between 1998 and 2012 from six arctic regions (Laptev Sea, Chukchi Sea, southeastern Beaufort Sea, Canadian Arctic Archipelago, Hudson Bay and northern Baffin Bay). MMHg concentrations in Calanus spp., Themisto spp. and Paraeuchaeta spp. were found to increase with higher δ(15)N and lower δ(13)C. The southern Beaufort Sea exhibited both the highest THg and MMHg concentrations. Biomagnification of MMHg between Calanus spp. and two of its known predators, Themisto spp. and Paraeuchaeta spp., was greatest in the southern Beaufort Sea. Our results show large geographical variations in Hg concentrations and isotopic signatures for individual species related to regional ecosystem features, such as varying water masses and freshwater inputs, and highlight the increased exposure to Hg in the marine food chain of the southern Beaufort Sea. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. A Dual-Carbon-and-Nitrogen Stable Isotope Ratio Model Is Not Superior to a Single-Carbon Stable Isotope Ratio Model for Predicting Added Sugar Intake in Southwest Virginian Adults.

    PubMed

    Hedrick, Valisa E; Zoellner, Jamie M; Jahren, A Hope; Woodford, Natalie A; Bostic, Joshua N; Davy, Brenda M

    2015-06-01

    An objective measure of added sugar (AS) and sugar-sweetened beverage (SSB) intake is needed. The δ(13)C value of finger-stick blood is a novel validated biomarker of AS/SSB intake; however, nonsweetener corn products and animal protein also carry a δ(13)C value similar to AS sources, which may affect blood δ(13)C values. The δ(15)N value of blood has been proposed as a "correction factor" for animal protein intake. The objectives were to 1) identify foods associated with δ(13)C and δ(15)N blood values, 2) determine the contribution of nonsweetener corn to the diet relative to AS intake, and 3) determine if the dual-isotope model (δ(13)C and δ(15)N) is a better predictor of AS/SSB intake than δ(13)C alone. A cross-sectional sample of southwest Virginian adults (n = 257; aged 42 ± 15 y; 74% overweight/obese) underwent dietary intake assessments and provided finger-stick blood samples, which were analyzed for δ(13)C and δ(15)N values by using natural abundance stable isotope mass spectrometry. Statistical analyses included ANOVAs, paired-samples t tests, and multiple linear regressions. The mean ± SD daily AS intake was 88 ± 59 g and nonsweetener corn intake was 13 ± 13 g. The mean δ(13)C value was -19.1 ± 0.9‰, which was significantly correlated with AS and SSB intakes (r = 0.32 and 0.39, respectively; P ≤ 0.01). The δ(13)C value and nonsweetener corn intake and the δ(15)N value and animal protein intake were not correlated. AS intake was significantly greater than nonsweetener corn intake (mean difference = 76.2 ± 57.2 g; P ≤ 0.001). The δ(13)C value was predictive of AS/SSB intake (β range: 0.28-0.35; P ≤ 0.01); however, δ(15)N was not predictive and minimal increases in R(2) values were observed when the δ(15)N value was added to the model. The data do not provide evidence that the dual-isotope method is superior for predicting AS/SSB intakes within a southwest Virginian population. Our results support the potential of the δ(13)C

  11. A Dual-Carbon-and-Nitrogen Stable Isotope Ratio Model Is Not Superior to a Single-Carbon Stable Isotope Ratio Model for Predicting Added Sugar Intake in Southwest Virginian Adults12

    PubMed Central

    Hedrick, Valisa E; Zoellner, Jamie M; Jahren, A Hope; Woodford, Natalie A; Bostic, Joshua N; Davy, Brenda M

    2015-01-01

    Background: An objective measure of added sugar (AS) and sugar-sweetened beverage (SSB) intake is needed. The δ13C value of finger-stick blood is a novel validated biomarker of AS/SSB intake; however, nonsweetener corn products and animal protein also carry a δ13C value similar to AS sources, which may affect blood δ13C values. The δ15N value of blood has been proposed as a “correction factor” for animal protein intake. Objectives: The objectives were to 1) identify foods associated with δ13C and δ15N blood values, 2) determine the contribution of nonsweetener corn to the diet relative to AS intake, and 3) determine if the dual-isotope model (δ13C and δ15N) is a better predictor of AS/SSB intake than δ13C alone. Methods: A cross-sectional sample of southwest Virginian adults (n = 257; aged 42 ± 15 y; 74% overweight/obese) underwent dietary intake assessments and provided finger-stick blood samples, which were analyzed for δ13C and δ15N values by using natural abundance stable isotope mass spectrometry. Statistical analyses included ANOVAs, paired-samples t tests, and multiple linear regressions. Results: The mean ± SD daily AS intake was 88 ± 59 g and nonsweetener corn intake was 13 ± 13 g. The mean δ13C value was −19.1 ± 0.9‰, which was significantly correlated with AS and SSB intakes (r = 0.32 and 0.39, respectively; P ≤ 0.01). The δ13C value and nonsweetener corn intake and the δ15N value and animal protein intake were not correlated. AS intake was significantly greater than nonsweetener corn intake (mean difference = 76.2 ± 57.2 g; P ≤ 0.001). The δ13C value was predictive of AS/SSB intake (β range: 0.28–0.35; P ≤ 0.01); however, δ15N was not predictive and minimal increases in R2 values were observed when the δ15N value was added to the model. Conclusions: The data do not provide evidence that the dual-isotope method is superior for predicting AS/SSB intakes within a southwest Virginian population. Our results support

  12. Lipid Biomarkers and Carbon Isotope Ratios of Lipids Isolated from Acid Mine Drainage Biofilms: Dual Biosignatures for Eukaryotic Evolution and Oxygenation of Primitive Earth

    NASA Astrophysics Data System (ADS)

    Dasgupta, S.; Fang, J.; Zhang, L.; Li, J.

    2012-12-01

    Lipid analysis and carbon isotope ratios (δ13C) of lipids in biofilms in an acid mine drainage site (AMD) site in western Indiana revealed unique biogeochemical signatures of microeukaryotes, never recorded before. Dominance of photosynthetic microeukaryote Euglena was indicated by the detection of abundant phytadiene, phytol, phytanol, polyunsaturated n-alkenes, polyunsaturated fatty acids, short-chain (C25-32) wax esters (WE), ergosterol, and tocopherols. The WE were probably synthesized in mitochondria under anoxic conditions by the reverse β-oxidation pathway, whereas the sterols (ergosterol and ergosta-7,22-dien-3β-ol) were likely synthesized in the cytosol in the presence of molecular oxygen. The dual aerobic and anaerobic biosynthetic pathways of Euglena may be a response to survive the recurring anoxic and oxic conditions in primitive Earth, whereby microeukaryotes retained this mechanism of conserved compartmentalization within their physiology to evolve and diversify in extreme conditions. Hydrocarbons, including n-alkenes, phytadienes, and wax esters showed heavy δ13C values than usual. The primary cause for the 13C-enrichment can be attributed to a CO2-limiting system that exists in the AMD, which is further regulated by the pH of the AMD. Floating biofilms BF2, 4, and 6 showed more depleted δ13C values for phytadienes and n-alkenes (average of -23.6‰) as compared to benthic biofilm BF5 (average of -20.8‰), indicating that physiology plays an important role in isotopic discrimination. 13C-enriched values of the esters could result from kinetic isotope effects at two branch points (pyruvate and/or acetyl CoA) in the biosynthetic pathway. Our understanding of biogeochemical conditions in this AMD environment would allow us to identify unique sets of biosignatures that can act as a proxy in deciphering the links between eukaryotic evolutions, oxygenation of the early atmosphere, formation of BIF, and possibly iron-rich extraterrestrial

  13. Isotope ratio determination in boron analysis.

    PubMed

    Sah, R N; Brown, P H

    1998-01-01

    Traditionally, boron (B) isotope ratios have been determined using thermal ionization mass spectrometry (TIMS) and, to some extent, secondary ion mass spectrometry (SIMS). Both TIMS and SIMS use a high-resolution mass analyzer, but differ in analyte ionization methods. TIMS uses electrons from a hot filament, whereas SIMS employs an energetic primary ion beam of Ga+, Cs+, or O- for analyte ionization. TIMS can be used in negative or positive ion modes with high sensitivity and precision of B isotope ratio determination. However, isobaric interferences may be a problem, if the sample is not well purified and/or memory of the previous sample is not removed. Time-consuming sample preparation, analyte (B) purification, and sample determination processes limit the applications of TIMS for routine analyses. SIMS can determine B and its isotope ratio in intact solid samples without destroying them, but has poorer resolution and sensitivity than TIMS, and is difficult to standardize for biological samples. Development of plasma-source mass spectrometry (MS) enabled the determination of B concentration and isotope ratio without requiring sample purification. Commonly used plasma-source MS uses an Ar inductively coupled plasma (ICP) as an ionization device interfaced to a low-resolution quadrupole mass analyzer. The quadrupole ICP-MS is less precise than TIMS and SIMS, but is a popular method for B isotope ratio determination because of its speed and convenience. B determination by ICP-MS suffers no spectroscopic interferences. However, sample matrices, memory effects, and some instrument parameters may affect the accuracy and precision of B isotope ratio determination if adequate precautions are not taken. New generations of plasma-source MS instruments using high-resolution mass analyzers provide better sensitivity and precision than the currently used quadrupole ICP-MS. Because of the convenience and high sample throughput, the high-resolution ICP-MS is expected to be the

  14. The Carbon Isotope Ratio of Alanine in Red Blood Cells Is a New Candidate Biomarker of Sugar-Sweetened Beverage Intake12

    PubMed Central

    Choy, Kyungcheol; Nash, Sarah H.; Kristal, Alan R.; Hopkins, Scarlett; Boyer, Bert B.; O’Brien, Diane M.

    2013-01-01

    An objective dietary biomarker would help clarify the contribution of sugar-sweetened beverage (SSB) intake to obesity and chronic disease risk. Previous studies have proposed the carbon isotope ratio (δ13C) as a biomarker of SSB intake but found associations that were of modest size and confounded by other components of the diet. We investigated whether the δ13C values of nonessential amino acids (δ13CNEAA) in RBCs could provide valid biomarkers that are more specific to SSBs. We assessed the associations of RBC δ13CNEAA with SSB intake in a study population of 68 Yup’ik people, using gas chromatography/combustion/isotope ratio mass spectrometry to measure δ13CNEAA and four 24-h dietary recalls to assess intake. Among RBC nonessential amino acids, alanine δ13C (δ13Calanine) was strongly correlated with intake of SSBs, added sugar, and total sugar (r = 0.70, 0.59, and 0.57, respectively; P < 0.0001) but uncorrelated with other dietary sources of elevated δ13C. We also evaluated whether sweetener intake could be noninvasively assessed using hair δ13Calanine in a subset of the study population (n = 30). Hair δ13Calanine was correlated with RBC δ13Calanine (r = 0.65; P < 0.0001) and showed similar associations with SSB intake. These results show that δ13Calanine in RBCs provides a valid and specific biomarker of SSB intake for the Yup’ik population and suggest RBCs and hair δ13Calanine as candidate biomarkers of SSB intake for validation in the general U.S. population. Ultimately, these biomarkers could clarify our understanding of whether and how SSB intake contributes to chronic disease. PMID:23616504

  15. Carbon isotope ratios of nandrolone, boldenone, and testosterone preparations seized in Norway compared to those of endogenously produced steroids in a Nordic reference population.

    PubMed

    Hullstein, Ingunn; Sagredo, Carlos; Hemmersbach, Peter

    2014-01-01

    Determining the origin of anabolic androgenic steroids (AAS) that also are produced endogenously in the human body is a major issue in doping control. In some cases, the presence of nandrolone and boldenone metabolites might result from endogenous production. The GC-C-IRMS technique (gas chromatography-combustion-isotope ratio mass spectrometry) enables the carbon isotopic ratio (CIR) to be measured to determine the origin of these metabolites. The aim of this study was to use GC-C-IRMS to determine the δ(13) CVPDB values of seized boldenone and nandrolone preparations to decide if the steroids themselves were depleted in (13) C, compared to what is normally seen in endogenously produced steroids. In addition, several testosterone preparations were analyzed. A total of 69 seized preparations were analyzed. The nandrolone preparations showed δ(13) CVPDB values in the range of -31.5 ‰ to -26.7 ‰. The boldenone preparations showed δ(13) CVPDB values in the range of -32.0 ‰ to -27.8 ‰, and for comparison the testosterone preparations showed δ(13) CVPDB values of -31.0 ‰ to -24.2 ‰. The results showed that the values measured in the nandrolone and boldenone preparations were in the same range as those measured in the testosterone preparations. The study also included measurements of CIR of endogenously produced steroids in a Norwegian/Danish reference population. The δ(13) CVPDB values measured for the endogenous steroids in this population were in the range of -21.7 to -26.8. In general, most of the preparations investigated in this study show (13) C-depleted delta values compared to endogenously produced steroids reflecting a northern European diet.

  16. Quantifying sediment source contributions in coastal catchments impacted by the Fukushima nuclear accident with carbon and nitrogen elemental concentrations and stable isotope ratios

    NASA Astrophysics Data System (ADS)

    Laceby, J. Patrick; Huon Huon, Sylvain; Onda, Yuichi; Evrard, Olivier

    2016-04-01

    The Fukushima Dai-ichi Nuclear Power Plant accidental release of radioactive contaminants resulted in the significant fallout of radiocesium over several coastal catchments in the Fukushima Prefecture. Radiocesium, considered to be the greatest risk to the short and long term health of the local community, is rapidly bound to fine soil particles and thus is mobilized and transported during soil erosion and runoff processes. As there has been a broad-scale decontamination of rice paddy fields and rural residential areas in the contaminated region, one important long term question is whether there is, or may be, a downstream transfer of radiocesium from forests that covered over 65% of the most contaminated region. Accordingly, carbon and nitrogen elemental concentrations and stable isotope ratios are used to determine the relative contributions of forests and rice paddies to transported sediment in three contaminated coastal catchments. Samples were taken from the three main identified sources: cultivated soils (rice paddies and fields, n=30), forest soils (n=45), and subsoils (channel bank and decontaminated soils, n = 25). Lag deposit sediment samples were obtained from five sampling campaigns that targeted the main hydrological events from October 2011 to October 2014. In total, 86 samples of deposited sediment were analyzed for particulate organic matter elemental concentrations and isotope ratios, 24 from the Mano catchment, 44 from the Niida catchment, and 18 from the Ota catchment. Mann-Whitney U-tests were used to examine the source discrimination potential of this tracing suite and select the appropriate tracers for modelling. The discriminant tracers were modelled with a concentration-dependent distribution mixing model. Preliminary results indicate that cultivated sources (predominantly rice paddies) contribute disproportionately more sediment per unit area than forested regions in these contaminated catchments. Future research will examine if there are

  17. Determination of Biological Carbon Uptake on the North American West Coast Using Dissolved Oxygen Isotopes and the O2/Ar Gas Ratio

    NASA Astrophysics Data System (ADS)

    Juranek, L. W.; Feely, R. A.; Sabine, C. L.; Quay, P. D.; Ianson, D.; Alin, S. R.

    2008-12-01

    Coastal margins are regularly cited to contribute to the global carbon budget disproportionately to their area because their air-sea CO2 and organic carbon sinking fluxes are often orders of magnitude higher than in the open ocean. Unfortunately, the spatially and temporally dynamic nature of these environments and a lack of extensive field observations have prevented an assessment of the source/sink status of most coastal regimes and a comprehensive evaluation of the environmental factors that influence these fluxes. We evaluate the biological modulation of inorganic carbon inventories for 13 cross-shelf transects occupied during a May/June 2007 hydrographic survey cruise along the western North American coast, from Queen Charlotte Sound, Canada, to Southern Baja California, Mexico. In situ mixed layer gross primary production (GPP) and net community production (NCP) rates were determined from measured oxygen isotopes and dissolved O2/Ar gas ratios at over 100 locations during the cruise. Our GPP and NCP observations at some locations (e.g., Queen Charlotte Sound, Canada) were only slightly elevated from adjacent open ocean values (GPP: 40-80 mmol C m-2 d-1 and NCP: 15-35 mmol C m-2 d-1) . In other locations the rates were >10 times open ocean values (N. California coast, GPP up to 1000 mmol C m- 2 d-1 and NCP up to 500 mmol C m-2 d-1). We will show how biological rates relate to local wind and circulation forcing and how they compare to changes in inventories of dissolved inorganic carbon. We will also compare our results to historical observations and concurrent satellite chlorophyll observations and remotely-sensed PP estimates.

  18. 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

    NASA Technical Reports Server (NTRS)

    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.

  19. Seawater calcium isotopic ratios across the Eocene-Oligocene Transition

    NASA Astrophysics Data System (ADS)

    Griffith, E. M.; Paytan, A.

    2009-12-01

    We reconstructed the evolution of the seawater calcium (Ca) isotopic ratio from marine (pelagic) barite and bulk calcium carbonate over the Eocene-Oligocene Transition (EOT), a period of extreme and rapid change in the global calcite compensation depth (CCD) (Lyle et al., 2008). The CCD is controlled by the balance between calcium carbonate deposition and dissolution in deep sea sediments. Large fluctuations in the CCD may cause changes in the concentration of dissolved Ca in seawater and its isotopic composition if accompanied by imbalances in marine Ca sources and sinks (De La Rocha and DePaolo, 2000). Our results show that the permanent deepening of the CCD during the EOT, which coincided with the major Cenozoic glaciation around 34 million years ago (Zachos et al., 2001), was not accompanied by a significant long-term change in the isotopic ratio of Ca in seawater or its sink (calcium carbonate). A simple isotopic mass balance model is constructed to compare predicted and observed isotopic fluctuations. References: Lyle, M. et al. Pacific Ocean and Cenozoic evolution of climate. Rev. Geophys. 46, 1-47 (2008). De La Rocha, C. L. & DePaolo, D. J. Isotopic evidence for variations in the marine calcium cycle over the Cenozoic. Science 289, 1176-1178 (2000). Zachos, J., Pagani, M., Sloan, L., Thomas, E. & Billups, K. Trends, rhythms, and aberrations in global climate 65 ma to present. Science 292, 686-693 (2001).

  20. Stable Isotope Ratios and the Forensic Analysis of Microorganisms

    SciTech Connect

    Kreuzer-Martin, Helen W.; Jarman, Kristin H.

    2007-06-01

    In the aftermath of the anthrax letters of 2001, researchers have been exploring various analytical signatures for the purpose of characterizing the production environment of microorganisms. One such signature is stable isotope ratios, which in heterotrophs are a function of nutrient and water sources. Here we discuss the use of stable isotope ratios in microbe forensics, using as a database the carbon, nitrogen, oxygen and hydrogen stable isotope ratios of 247 separate cultures of B. subtilis 6051 spores produced on a total of 32 different culture media. In the context of using stable isotope ratios as a signature for sample matching, we present an analysis of variation between individual samples, between cultures produced in tandem, and between cultures produced in the same medium but at different times. Additionally, we correlate the stable isotope ratios of carbon, nitrogen, oxygen, and hydrogen for growth medium nutrients or water with those of spores and show examples of how these relationships can be used to exclude nutrient or water samples as possible growth substrates for specific cultures.

  1. Stable Isotope Ratios and Forensic Analysis of Microorganisms▿

    PubMed Central

    Kreuzer-Martin, Helen W.; Jarman, Kristin H.

    2007-01-01

    In the aftermath of the anthrax letters of 2001, researchers have been exploring various analytical signatures for the purpose of characterizing the production environment of microorganisms. One such signature is stable isotope ratios, which in heterotrophs, are a function of nutrient and water sources. Here we discuss the use of stable isotope ratios in microbial forensics, using as a database the carbon, nitrogen, oxygen, and hydrogen stable isotope ratios of 247 separate cultures of Bacillus subtilis 6051 spores produced on a total of 32 different culture media. In the context of using stable isotope ratios as a signature for sample matching, we present an analysis of variations between individual samples, between cultures produced in tandem, and between cultures produced in the same medium but at different times. Additionally, we correlate the stable isotope ratios of carbon, nitrogen, oxygen, and hydrogen for growth medium nutrients or water with those of spores and show examples of how these relationships can be used to exclude nutrient or water samples as possible growth substrates for specific cultures. PMID:17468274

  2. Wetting and drying cycles drive variations in the stable carbon isotope ratio of respired carbon dioxide in semi-arid grassland.

    PubMed

    Shim, Jee H; Pendall, Elise; Morgan, Jack A; Ojima, Dennis S

    2009-05-01

    In semi-arid regions, where plants using both C(3) and C(4) photosynthetic pathways are common, the stable C isotope ratio (delta(13)C) of ecosystem respiration (delta(13)C(R)) is strongly variable seasonally and inter-annually. Improved understanding of physiological and environmental controls over these variations will improve C cycle models that rely on the isotopic composition of atmospheric CO(2). We hypothesized that timing of precipitation events and antecedent moisture interact with activity of C(3) and C(4) grasses to determine net ecosystem CO(2) exchange (NEE) and delta(13)C(R). Field measurements included CO(2) and delta(13)C fluxes from the whole ecosystem and from patches of different plant communities, biomass and delta(13)C of plants and soils over the 2000 and 2001 growing seasons. NEE shifted from C source to sink in response to rainfall events, but this shift occurred after a time lag of up to 2 weeks if a dry period preceded the rainfall. The seasonal average of delta(13)C(R) was higher in 2000 (-16 per thousand) than 2001 (20 per thousand), probably due to drier conditions during the 2000 growing season (79.7 mm of precipitation from April up to and including July) than in 2001 (189 mm). During moist conditions, delta(13)C averaged -22 per thousand from C(3) patches, -16 per thousand from C(4) patches, and -19 per thousand from mixed C(3) and C(4) patches. However, during dry conditions the apparent spatial differences were not obvious, suggesting reduced autotrophic activity in C(4) grasses with shallow rooting depth, soon after the onset of dry conditions. Air and soil temperatures were negatively correlated with delta(13)C(R); vapor pressure deficit was a poor predictor of delta(13)C(R), in contrast to more mesic ecosystems. Responses of respiration components to precipitation pulses were explained by differences in soil moisture thresholds between C(3) and C(4) species. Stable isotopic composition of respiration in semi-arid ecosystems is

  3. Using Isotope Ratio Infrared Spectrometer to determine δ13C of CaCO3 carbonate and DIC samples and δ18O of water

    NASA Astrophysics Data System (ADS)

    Mandic, M.; Stöbener, N.; Mandic, L.; Smajgl, D.; Jost, H. J. H.

    2016-12-01

    Precise and accurate determination of isotopic composition of carbon (13C) and oxygen (18O) from carbonate or DIC sample with proper referencing and data evaluation algorithm presents a challenge for scientists. Mass spectrometry was the only widely used technique for this kind of analysis, but recent advances make laser based isotope ratio infrared spectroscopy (IRIS) a viable alternative. To analyze discrete samples, the Universal Reference Interface (URI) Connect was developed. CO2 free syntethic air is used to flush out the contents of a sample container into a variable volume. If necessary, the sample is further diluted before entering the analysis chamber. Reference gas measurements are automatically performed at the same concentration as sample measurements to compensate for instrument drifts and non linearity. The URI Connect can handle about 100 samples per day from an autosampler, or samples can be injected one at a time through a septum on the front of the instrument. Gas samples collected in flasks, bags, syringes, or vials can be analyzed. The system only needs the equivalent of about 80µg - or 40µL - of pure CO2 gas to complete an analysis. Due to it's small weight and robustness, sample analysis can be performed in the field, e.g. aboard a research vessel. To demonstrate the performance, a test experiment with 1% CO2 in 12 ml vials was performed. We achieved an internal precision of better than 0.07‰ and 0.1‰ for δ13C and δ18O, respectively. Analyses with sample amounts as low as 200 μg of carbonate can also be performed reliably with IRIS. We present measurements of three international reference materials, and one of them treated as an unknown. Five samples each of approximately 1mg each were acidified using a few droplets of 43% H3PO4 and left for equilibration overnight at 25°C. The standard deviation was less than 0.1‰ δ13C and the accuracy <0.01‰ As another example of head space analysis in 12 ml vials, we determined δ18O of

  4. Carbon isotope geochemistry and geobiology

    NASA Technical Reports Server (NTRS)

    Desmarais, D.

    1985-01-01

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

  5. Carbon isotope ratios document that the elytra of western corn rootworm (Coleoptera: Chrysomelidae) reflects adult versus larval feeding and later instar larvae prefer Bt corn to alternate hosts.

    PubMed

    Hiltpold, Ivan; Adamczyk, John J; Higdon, Matthew L; Clark, Thomas L; Ellersieck, Mark R; Hibbard, Bruce E

    2014-06-01

    In much of the Corn Belt and parts of Europe, the western corn rootworm, Diabrotica virgifera virgifera LeConte, is the most important insect pest of maize. The need for additional basic knowledge of this pest has been highlighted while developing resistance management plans for insecticidal genetically modified crops. This study evaluated the possibility of tracking feeding habits of western corn rootworm larvae using stable carbon isotope signatures. Plants accumulate different ratios of (13)C:(12)C isotopes, usually expressed as δ(13)C, according to whether they use the C3 or C4 photosynthetic pathway. Herbivore biomass is expected to reflect the δ(13)C of the food they eat. For the current experiment, western corn rootworm larvae were grown on different species of plants exhibiting different δ(13)C values. The δ(13)C values were then measured in elytra of emerged beetles. When beetles were unfed, biomass reflected larval feeding. When beetles were fed for 31 d postemergence, δ(13)C values of elytra almost exclusively reflected adult feeding. These results suggest the use of caution in the interpretation of δ(13)C data aiming to document larval diet history when adult feeding history is unknown. The technique was also used to evaluate western corn rootworm larval choice between alternate hosts and maize with and without genetically modified (Bt) traits aimed at their control. Propensity for feeding on alternate hosts versus maize was biased toward feeding on maize regardless whether the maize had Bt or not, suggesting western corn rootworm larvae were not repelled by Bt. These data will be helpful for regulators in interpreting western corn rootworm feeding data on Bt maize.

  6. Pacific sleeper shark Somniosus pacificus trophic ecology in the eastern North Pacific Ocean inferred from nitrogen and carbon stable-isotope ratios and diet.

    PubMed

    Courtney, D L; Foy, R

    2012-04-01

    Stable-isotope ratios of nitrogen (δ¹⁵N) and lipid-normalized carbon (δ¹³C') were used to examine geographic and ontogenetic variability in the trophic ecology of a high latitude benthopelagic elasmobranch, the Pacific sleeper shark Somniosus pacificus. Mean muscle tissue δ¹³C' values of S. pacificus differed significantly among geographic regions of the eastern North Pacific Ocean. Linear models identified significant ontogenetic and geographic variability in muscle tissue δ¹⁵N values of S. pacificus. The trophic position of S. pacificus in the eastern North Pacific Ocean estimated here from previously published stomach-content data (4·3) was within the range of S. pacificus trophic position predicted from a linear model of S. pacificus muscle tissue δ¹⁵N (3·3-5·7) for fish of the same mean total length (L(T) ; 201·5 cm), but uncertainty in predicted trophic position was very high (95% prediction intervals ranged from 2·9 to 6·4). The relative trophic position of S. pacificus determined here from a literature review of δ¹⁵N by taxa in the eastern North Pacific Ocean was also lower than would be expected based on stomach-content data alone when compared to fishes, squid and filter feeding whales. Stable-isotope analysis revealed wider variability in the feeding ecology of S. pacificus in the eastern North Pacific Ocean than shown by diet data alone, and expanded previous conclusions drawn from analyses of stomach-content data to regional and temporal scales meaningful for fisheries management.

  7. Environmental variables across Pan troglodytes study sites correspond with the carbon, but not the nitrogen, stable isotope ratios of chimpanzee hair.

    PubMed

    Schoeninger, Margaret J; Most, Corinna A; Moore, Jim J; Somerville, Andrew D

    2016-10-01

    Diet influences the stable isotope ratios of carbon and nitrogen (δ(13) C and δ(15) N values) in animal tissue; but here we explore the influences of particular aspects of the local environment on those values in chimpanzees (Pan troglodytes). In this article we present new δ(13) C and δ(15) N values in Gombe chimpanzees using hairs collected from night nests in 1989. Then, we explore the influence of environmental factors by comparing our Gombe data to those from eight additional Pan study sites with previously published stable isotope data. We compare chimpanzee δ(13) Chair and δ(15) Nhar values to specific characteristics of local site ecology (biome and ecoregion) and to local Mean Annual Precipitation (MAP) to test hypotheses based on known effects of these variables on the δ(13) C and δ(15) N values in plant tissues. The comparison shows that hair from chimpanzees living in savanna sites with lower MAP have higher δ(13) Chair values than do chimpanzees living in woodland and forested sites with higher MAP. These results demonstrate the potential of using δ(13) C values in primate tissue to indicate aspects of their local ecology in cases where the ecology is uncertain, such as samples collected early in the last century and in fossil hominins. In contrast to expectations, however, chimpanzee δ(15) Nhair values from some savanna sites with lower MAP are lower, not higher, than those living in more forested areas with higher MAP. It is likely that diet selectivity by chimpanzees affects δ(15) Nhair values to a greater extent than does the influence of precipitation on plants. Am. J. Primatol. 78:1055-1069, 2016. © 2015 Wiley Periodicals, Inc. © 2015 Wiley Periodicals, Inc.

  8. Isotope ratio mass spectrometry in nutrition research

    SciTech Connect

    Luke, A.H.

    1994-12-31

    Many of the biochemical pathways and processes that form the foundation of modern nutrition research was elucidated using stable isotopes as physiological tracers. Since the discovery of stable isotopes, improvements and innovations in mass spectrometry and chromatography have led to greatly expanded applications. This research project was designed to evaluate gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) as a tool for isotopic tracer studies and to delineate the operational parameters for the analysis of {sup 13}C-labeled cholesterol, leucine and {alpha}-ketoisocaproate. The same isotope ratio mass spectrometer was then used as the base instrument for the ratio mass spectrometer was then used as the base instrument for the development of two additional inlet systems: a continuous-flow inlet for the analyses of {sup 13}C and {sup 18}O as CO{sub 2} and a filament inlet for on-line combustion and isotopic analysis of non-volatile organic compounds. Each of these three inlets was evaluated and their utility in nutrition research illustrated. GC/C/IRMS was used to analyze cholesterol, leucine and {alpha}-ketoisocaproate with good accuracy, precision and little isotopic memory. For all three compounds the detection limits achieved well surpassed currently used technologies. For compounds that can be well separated by GC, GC/C/IRMS is a valuable analytical tool. The continuous-flow inlet provided good accuracy and precision for measurements of {sup 13}CO{sub 2} from breath tests and {sup 18}O as CO{sub 2} from total energy expenditure tests. Most importantly, the continuous-flow inlet increased sample throughput by at least a factor of three over conventional analytical techniques. The filament inlet provided accurate and precise {sup 13}C ratio measurements of both natural abundance and enriched standards of non-volatile organic compounds of physiological interest.

  9. Helium isotope ratios in Easter microplate basalts

    NASA Astrophysics Data System (ADS)

    Poreda, R. J.; Schilling, J. G.; Craig, H.

    1993-09-01

    He-3/He-4 ratios in Easter Microplate basalt glasses show clear evidence of the effects of a mantle plume. The East Rift of the microplate between 26 and 28 deg S, identified by La/Sm, Sr and Pb isotopes and ridge crest elevation as the region of maximum plume influence, has He-3/He-4 ratios spanning the entire range from 7.5 to 11.7 R(sub A). The Easter Microplate is the only section of the entire East Pacific Rise that is associated with a known `hotspot' track (mantle plume) and has elevated He-3/He-4 ratios. Although most of the West Rift basalts contain MORB helium (8.0 - 8.7 (R sub A)), the basalt closest to the East Rift has an elevated He-3/He-4 ratio (11.3 R(sub A)), consistent with a significant plume component. The diversity in isotopic signatures also indicates that homogenization of isotopic anomalies does not occur, even in this region of `super-fast' spreading. The overall He-3/He-4-Pb-206/Pb-204 and He-3/He-4-Sr-87/Sr-86 trends have positive correlations, although the high between the He and Sr isotope distribution is modeled in the context of a plume source-migrating ridge sink. During channeling of the plume toward the ridge, helium if preferentially lost from the center of the channeled plume, resulting in lower He/Pb and He/Sr concentration ratios in the high He-3/He-4 component. Mixing trajectories in He-Sr isotopic space between a LILE depleted asthenosphere and a variably degassed plume component provide a reasonably good fit to the data and may explain the isotope systematics of plume-ridge interactions in the context of modern theories of plume dynamics.

  10. Clumped isotope thermometry of cryogenic cave carbonates

    NASA Astrophysics Data System (ADS)

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

    2014-02-01

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

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

    USGS Publications Warehouse

    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.

  12. Feasibility of Isotopic Measurements: Graphite Isotopic Ratio Method

    SciTech Connect

    Wood, Thomas W.; Gerlach, David C.; Reid, Bruce D.; Morgan, W. C.

    2001-04-30

    This report addresses the feasibility of the laboratory measurements of isotopic ratios for selected trace constituents in irradiated nuclear-grade graphite, based on the results of a proof-of-principal experiment completed at Pacific Northwest National Laboratory (PNNL) in 1994. The estimation of graphite fluence through measurement of isotopic ratio changes in the impurity elements in the nuclear-grade graphite is referred to as the Graphite Isotope Ratio Method (GIRM). Combined with reactor core and fuel information, GIRM measurements can be employed to estimate cumulative materials production in graphite moderated reactors. This report documents the laboratory procedures and results from the initial measurements of irradiated graphite samples. The irradiated graphite samples were obtained from the C Reactor (one of several production reactors at Hanford) and from the French G-2 Reactor located at Marcoule. Analysis of the irradiated graphite samples indicated that replicable measurements of isotope ratios could be obtained from the fluence sensitive elements of Ti, Ca, Sr, and Ba. While these impurity elements are present in the nuclear-grade graphite in very low concentrations, measurement precision was typically on the order of a few tenths of a percent to just over 1 percent. Replicability of the measurements was also very good with measured values differing by less than 0.5 percent. The overall results of this initial proof-of-principal experiment are sufficiently encouraging that a demonstration of GIRM on a reactor scale basis is planned for FY-95.

  13. Soil Carbon: Compositional and Isotopic Analysis

    SciTech Connect

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

    2016-11-01

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

  14. Evaluation of bioremediation systems utilizing stable carbon isotope analysis

    SciTech Connect

    Van de Velde, K.; Nowell, C.; Marley, M.C.

    1994-12-31

    Carbon, whether in an organic or inorganic form, is composed primarily of two stable isotopes, carbon-12 and carbon-13. The ratio of carbon-12 to carbon-13 is approximately 99:1. The stable carbon isotope ratios of most natural carbon materials of biological interest range from approximately 0 to {minus}110 per mil ({per_thousand}) versus the PDB standard. Utilizing stable carbon isotope analysis, it is often possible to determine the source(s) of the liberated carbon dioxide, thereby confirming successful mineralization of the targeted carbon compound(s) and, if the carbon dioxide results from multiple carbon compounds, in what ratio the carbon compounds are mineralized. Basic stable isotope `theory` recommended sampling procedures and analysis protocols are reviewed. A case study involving fuel oil presented on the application of stable carbon isotope analysis for the monitoring and evaluation of in situ bioremediation. At the site, where a field bioventing study was being conducted, multiple potential sources of carbon dioxide production existed. Additional potential applications of stable carbon isotope analysis for bioremediation evaluation and monitoring are discussed.

  15. Organic chemistry of Murchison meteorite: Carbon isotopic fractionation

    NASA Technical Reports Server (NTRS)

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

    1986-01-01

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

  16. Organic chemistry of Murchison meteorite: Carbon isotopic fractionation

    NASA Technical Reports Server (NTRS)

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

    1986-01-01

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

  17. Helium isotope ratios in Ethiopian Rift basalts

    NASA Astrophysics Data System (ADS)

    Scarsi, P.; Craig, H.

    1996-11-01

    Helium isotope ratios were measured in olivine and pyroxene phenocrysts from basalts of the Ethiopian Rift Valley and Afar Depression between 6° and 15°N and 37° and 43°E. 3He/4He ratios range from 6 to 17 times the atmospheric value (RA = 1.4 × 10-6), that is, from ratios less than typical MORB (depleted mantle) helium (R/RA= 8 ± 1) to ratios similar to high-3He hotspots and to the Yellowstone hotspot (R/RA= 16.5). The high 3He/4He ratios occur all along the Ethiopian Rift and well up into the Afar Depression, with a maximum value of 17.0 RA at 8°N in the Rift Axis and a high value of 14.2 RA in the central Tat'Ali sector of the Afar Depression. The ratios decrease to MORB-like values near the edge of the Red Sea, and to sub-MORB ratios (5-6 RA) at the northern end of the Rift (Zula Peninsula) and at the southern end, at lakes Abaya and Chamo. The Ethiopian Rift provides the only continental hotspot terrain in which helium isotope ratios can be compared in detail between volcanic lavas and associated geothermal and volcanic gases, a primary motivation for this work. Comparison with our previously measured ratios in fluids and gases (range 2-15 RA) shows excellent agreement in the areas sampled for both lavas and fluids, and indicates that high-temperature volcanic fluids can be used for establishing helium isotope signatures in such terrains. The high-3He values in both fluids and basalts show that a Primitive Mantle (PM) component is required and that a Lower Mantle High-3He plume is strongly involved as a driving force in the rifting process of the East African Rift System.

  18. (Carbon isotope fractionation inplants)

    SciTech Connect

    O'Leary, M.H.

    1990-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2007-12-01

    C3 and C4 grasses have distinct influences on major biogeochemical processes and unique responses to important environmental controls. Difficulties in distinguishing between these two functional groups of grasses have hindered paleoecological studies of grass-dominated ecosystems. We recently developed a technique to analyze the stable carbon isotope composition of individual grass-pollen grains using a spooling- wire microcombustion device interfaced with an isotope-ratio mass spectrometer (Nelson et al. 2007). This technique holds promise for improving C3 and C4 grass reconstructions. It requires ~90% fewer grains than typical methods and avoids assumptions associated with mixing models. However, our previous work was based on known C3 and C4 grasses from herbarium specimens and field collections and the technique had not been test using geological samples. To test the ability of this technique to reproduce the abundance of C3 and C4 grasses on the landscape, we measured δ13C values of >1500 individual grains of grass pollen isolated from the surface sediments of 10 North American lakes that span a large gradient of C3 and C4 grass abundance. Results indicate a strong positive correlation (r=0.94) between % C4-grass pollen (derived from classifying δ13C values from single grains as C3 and C4) and the literature-reported abundance of C4 grasses on the landscape. However, the measured % C4-grass pollen shows some deviation from the actual abundance at sites with high proportions of C4 grasses. This is likely caused by uncertainty in the magnitude, composition, and variability of the analytical blank associated with these measurements. Correcting for this deviation using regression analysis improves the estimation of the abundance of C4 grasses on the landscape. Comparison of the % C4-grass pollen with C/N and δ13C measurements of total organic matter in the same lake-sediment samples illustrates the distinct advantage of grass-pollen δ13C as a proxy for

  20. Isotopic ratio measurements with ICP-MS

    SciTech Connect

    Russ, G.P. III; Bazan, J.M.

    1986-06-03

    An inductively-coupled-plasma source mass spectrometer (ICP-MS) has been used to measure the isotopic composition of U, Pb, Os, and B standards. Particular emphasis has been placed on uranium because of its nuclear and environmental interest and because of the availability of a well-characterized set of standards with a wide range of isotopic compositions. The precision and accuracy obtainable in isotope ratio measurements by ICP-MS depend on many factors including background, interferences, dead time, mass fractionation (bias), abundance sensitivity, and counting statistics. Which, if any, of these factors controls accuracy and precision depends on the type of sample being analyzed and the characteristics of the mass spectrometer. These issues are discussed in detail.

  1. Regional differences in bone collagen carbon- and nitrogen-isotope ratios of Pleistocene mammoths: Implications for paleoecology of the mammoth steppe

    NASA Astrophysics Data System (ADS)

    Grocke, Darren R.; Szpak, Paul; Poinar, Hendrik N.

    2010-05-01

    In this study, we present bone collagen carbon- and nitrogen-isotope values from a large set of Pleistocene woolly mammoths (Mammuthus primigenius) from Siberia, Alaska and Yukon (n=58). Overall, results for mammoth specimens from eastern Beringia (Alaska and Yukon) significantly differ, for both carbon- and nitrogen-isotope values, from those from western Beringia (northeastern Siberia). In agreement with palynological, entomological, and physiographic data from the same regions, these isotopic differences strongly imply that the ‘mammoth steppe', the extensive ice-free region spanning northern Eurasia and northwestern North America, was ecologically variable along its east-west axis to a significant degree. Prior to the Last Glacial Maximum (LGM), the high-latitude portions of Siberia and the Russian Far East appear to have been colder and more arid than central Alaska and Yukon, which were ecologically more diverse. During the LGM itself, however, isotopic signatures of mammoths from eastern Beringia support the argument that this region also experienced an extremely cold and arid climate. In terms of overall temporal trend, Beringia thus went from a condition prior to the LGM of greater ecological variability in the east to one of uniformly cold and dry conditions during the LGM.

  2. Stable carbon isotope ratios in tree rings of co-occurring species from semi-arid tropics in Africa: Patterns and climatic signals

    NASA Astrophysics Data System (ADS)

    Gebrekirstos, Aster; Worbes, Martin; Teketay, Demel; Fetene, Masresha; Mitlöhner, Ralph

    2009-04-01

    Although several proxies have been proposed to trace the course of environmental and climatological fluctuations, precise paleoclimate records from the tropics, notably from Africa are still sorely lacking today. Stable carbon isotopes ( δ13C) in tree rings are an attractive record of climate. In this study, the patterns and climatic signals of δ13C ratios were determined on tree rings of deciduous ( Acacia senegal, Acacia tortilis, Acacia seyal) and an evergreen ( Balanites aegyptiaca) species, from a semi-arid Acacia Woodland in Ethiopia. δ13C inter-annual patterns are synchronous among the co-occurring species. A declining trend with time was observed in δ13C, notably for B. aegyptiaca, which could be due to anthropogenic increases in atmospheric CO 2 concentration and decrease in atmospheric δ13C. Tree ring δ13C values of all the species revealed significant negative correlation with precipitation amount but not with temperature and relative humidity. The δ13C series of the deciduous species shows a higher correlation ( r = - 0.70 to - 0.78) with precipitation than the evergreen species ( r = - 0.55). A master δ13C series, composed of the average of the three Acacia species, displayed stronger significant correlation ( r = - 0.82) than any of the individual species δ13C series. The weak relationship between temperature and δ13C in this study indicates that photosynthetic rate is not a significant factor. Moisture stress, however, may have a direct impact on the stomatal conductance and explain the strong negative relationship between δ13C and precipitation. The results demonstrate the potential of δ13C in tree rings to reflect physiological responses to environmental changes as a vehicle for paleoclimatic reconstruction, which is important to understand tree response to past and future climate change.

  3. Pacific Ocean–Wide Profile of CYP1A1 Expression, Stable Carbon and Nitrogen Isotope Ratios, and Organic Contaminant Burden in Sperm Whale Skin Biopsies

    PubMed Central

    Godard-Codding, Céline A.J.; Clark, Rebecca; Fossi, Maria Cristina; Marsili, Letizia; Maltese, Silvia; West, Adam G.; Valenzuela, Luciano; Rowntree, Victoria; Polyak, Ildiko; Cannon, John C.; Pinkerton, Kim; Rubio-Cisneros, Nadia; Mesnick, Sarah L.; Cox, Stephen B.; Kerr, Iain; Payne, Roger; Stegeman, John J.

    2011-01-01

    Background Ocean pollution affects marine organisms and ecosystems as well as humans. The International Oceanographic Commission recommends ocean health monitoring programs to investigate the presence of marine contaminants and the health of threatened species and the use of multiple and early-warning biomarker approaches. Objective We explored the hypothesis that biomarker and contaminant analyses in skin biopsies of the threatened sperm whale (Physeter macrocephalus) could reveal geographical trends in exposure on an oceanwide scale. Methods We analyzed cytochrome P450 1A1 (CYP1A1) expression (by immunohistochemistry), stable nitrogen and carbon isotope ratios (as general indicators of trophic position and latitude, respectively), and contaminant burdens in skin biopsies to explore regional trends in the Pacific Ocean. Results Biomarker analyses revealed significant regional differences within the Pacific Ocean. CYP1A1 expression was highest in whales from the Galapagos, a United Nations Educational, Scientific, and Cultural Organization World Heritage marine reserve, and was lowest in the sampling sites farthest away from continents. We examined the possible influence of the whales’ sex, diet, or range and other parameters on regional variation in CYP1A1 expression, but data were inconclusive. In general, CYP1A1 expression was not significantly correlated with contaminant burdens in blubber. However, small sample sizes precluded detailed chemical analyses, and power to detect significant associations was limited. Conclusions Our large-scale monitoring study was successful at identifying regional differences in CYP1A1 expression, providing a baseline for this known biomarker of exposure to aryl hydrocarbon receptor agonists. However, we could not identify factors that explained this variation. Future oceanwide CYP1A1 expression profiles in cetacean skin biopsies are warranted and could reveal whether globally distributed chemicals occur at biochemically

  4. Pacific Ocean-wide profile of CYP1A1 expression, stable carbon and nitrogen isotope ratios, and organic contaminant burden in sperm whale skin biopsies.

    PubMed

    Godard-Codding, Céline A J; Clark, Rebecca; Fossi, Maria Cristina; Marsili, Letizia; Maltese, Silvia; West, Adam G; Valenzuela, Luciano; Rowntree, Victoria; Polyak, Ildiko; Cannon, John C; Pinkerton, Kim; Rubio-Cisneros, Nadia; Mesnick, Sarah L; Cox, Stephen B; Kerr, Iain; Payne, Roger; Stegeman, John J

    2011-03-01

    Ocean pollution affects marine organisms and ecosystems as well as humans. The International Oceanographic Commission recommends ocean health monitoring programs to investigate the presence of marine contaminants and the health of threatened species and the use of multiple and early-warning biomarker approaches. We explored the hypothesis that biomarker and contaminant analyses in skin biopsies of the threatened sperm whale (Physeter macrocephalus) could reveal geographical trends in exposure on an oceanwide scale. We analyzed cytochrome P450 1A1 (CYP1A1) expression (by immunohistochemistry), stable nitrogen and carbon isotope ratios (as general indicators of trophic position and latitude, respectively), and contaminant burdens in skin biopsies to explore regional trends in the Pacific Ocean. Biomarker analyses revealed significant regional differences within the Pacific Ocean. CYP1A1 expression was highest in whales from the Galapagos, a United Nations Educational, Scientific, and Cultural Organization World Heritage marine reserve, and was lowest in the sampling sites farthest away from continents. We examined the possible influence of the whales' sex, diet, or range and other parameters on regional variation in CYP1A1 expression, but data were inconclusive. In general, CYP1A1 expression was not significantly correlated with contaminant burdens in blubber. However, small sample sizes precluded detailed chemical analyses, and power to detect significant associations was limited. Our large-scale monitoring study was successful at identifying regional differences in CYP1A1 expression, providing a baseline for this known biomarker of exposure to aryl hydrocarbon receptor agonists. However, we could not identify factors that explained this variation. Future oceanwide CYP1A1 expression profiles in cetacean skin biopsies are warranted and could reveal whether globally distributed chemicals occur at biochemically relevant concentrations on a global basis, which may

  5. Carbon isotopes in biological carbonates: Respiration and photosynthesis

    USGS Publications Warehouse

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

    1997-01-01

    Respired carbon dioxide is an important constituent in the carbonates of most air breathing animals but is much less important in the carbonates of most aquatic animals. This difference is illustrated using carbon isotope data from freshwater and terrestrial snails, ahermatypic corals, and chemoautotrophic and methanotrophic pelecypods. Literature data from fish otoliths and bird and mammal shell and bone carbonates are also considered. Environmental CO2/O2 ratios appear to be the major controlling variable. Atmospheric CO2/O2 ratios are about thirty times lower than in most natural waters, hence air breathing animals absorb less environmental CO2 in the course of obtaining O2. Tissue CO2 therefore, does not isotopically equilibrate with environmental CO2 as thoroughly in air breathers as in aquatic animals, and this is reflected in skeletal carbonates. Animals having efficient oxygen transport systems, such as vertebrates, also accumulate more respired CO2 in their tissues. Photosynthetic corals calcify mainly during the daytime when photosynthetic CO2 uptake is several times faster than respiratory CO2 release. Photosynthesis, therefore, affects skeletal ??13C more strongly than does respiration. Corals also illustrate how "metabolic" effects on skeletal isotopic composition can be estimated, despite the presence of much larger "kinetic" isotope effects. Copyright ?? 1997 Elsevier Science Ltd.

  6. Carbon isotopes in biological carbonates: Respiration and photosynthesis

    NASA Astrophysics Data System (ADS)

    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.

  7. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

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

    1989-06-01

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

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

    PubMed

    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

  9. Stable isotope ratios and reforestation potential in Acacia koa populations on Hawai'i

    Treesearch

    Shaneka Lawson; Carrie Pike

    2017-01-01

    Stable carbon and nitrogen isotopes can be influenced by a multitude of factors including elevation, precipitation rate, season, and temperature. This work examined variability in foliar stable carbon (δ13C) and nitrogen (δ15N) isotope ratios of koa (Acacia koa) across 17 sites on Hawai'i Island, delineated by elevation and precipitation...

  10. Carbon isotope fractionation during microbial methane oxidation

    NASA Astrophysics Data System (ADS)

    Barker, James F.; Fritz, Peter

    1981-09-01

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

  11. Carbonate abundances and isotopic compositions in chondrites

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

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

    DOEpatents

    Harney, Robert C.; Bloom, Stewart D.

    1978-01-01

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

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

    EPA Science Inventory

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

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

    EPA Science Inventory

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

  15. [On-line method for measurement of the carbon isotope ratio of atmospheric methane and its application to atmosphere of Yakela condensed gas field].

    PubMed

    Tang, Jun-Hong; Bao, Zheng-Yu; Xiang, Wu; Qiao, Sheng-Ying; Li, Bing

    2006-01-01

    An on-line method for measurement of the 13C/12C ratio of methane by a gas chromatography/high-temperature conversion/ isotope ratio mass spectrometry (GC/C/MS) technique was developed. This method is less laborious, more rapid (45 min), of high precision (+/- 0.4 x 10(-3)) and by using a small amount of sample (about 200 mL of atmosphere). Its application to isotopic characterization, and hence methane source identification, was demonstrated by examination of atmosphere sample collected in Yakela condensed gas field, China. The average 13C/12C ratio of atmospheric methane in Yakela field was -45.0 x 10(-3) heavier by 1.2 x 10(-3) -2.0 x 10(-3) than the global average. This is caused by seepage and diffusing of methane from Yakela condensed gas reservoir. The concentrations of atmospheric methane in daytimes are found to be lower than those in nighttimes, and the corresponding 13C/12C ratios in daytimes are lighter compared to those in nighttimes, a phenomena probably caused by the fact that a small part of methane from Yakela condensate reservoir is consumed in soil's surface under sunlight.

  16. Reconstructing C3 and C4 vegetation cover using n-alkane carbon isotope ratios in recent lake sediments from Cameroon, Western Central Africa

    NASA Astrophysics Data System (ADS)

    Garcin, Yannick; Schefuß, Enno; Schwab, Valérie F.; Garreta, Vincent; Gleixner, Gerd; Vincens, Annie; Todou, Gilbert; Séné, Olivier; Onana, Jean-Michel; Achoundong, Gaston; Sachse, Dirk

    2014-10-01

    Trees and shrubs in tropical Africa use the C3 cycle as a carbon fixation pathway during photosynthesis, while grasses and sedges mostly use the C4 cycle. Leaf-wax lipids from sedimentary archives such as the long-chain n-alkanes (e.g., n-C27 to n-C33) inherit carbon isotope ratios that are representative of the carbon fixation pathway. Therefore, n-alkane δ13C values are often used to reconstruct past C3/C4 composition of vegetation, assuming that the relative proportions of C3 and C4 leaf waxes reflect the relative proportions of C3 and C4 plants. We have compared the δ13C values of n-alkanes from modern C3 and C4 plants with previously published values from recent lake sediments and provide a framework for estimating the fractional contribution (areal-based) of C3 vegetation cover (fC3) represented by these sedimentary archives. Samples were collected in Cameroon, across a latitudinal transect that accommodates a wide range of climate zones and vegetation types, as reflected in the progressive northward replacement of C3-dominated rain forest by C4-dominated savanna. The C3 plants analysed were characterised by substantially higher abundances of n-C29 alkanes and by substantially lower abundances of n-C33 alkanes than the C4 plants. Furthermore, the sedimentary δ13C values of n-C29 and n-C31 alkanes from recent lake sediments in Cameroon (-37.4‰ to -26.5‰) were generally within the range of δ13C values for C3 plants, even when from sites where C4 plants dominated the catchment vegetation. In such cases simple linear mixing models fail to accurately reconstruct the relative proportions of C3 and C4 vegetation cover when using the δ13C values of sedimentary n-alkanes, overestimating the proportion of C3 vegetation, likely as a consequence of the differences in plant wax production, preservation, transport, and/or deposition between C3 and C4 plants. We therefore tested a set of non-linear binary mixing models using δ13C values from both C3 and C4

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

    PubMed

    Appenzeller, Otto; Qualls, Clifford; Barbic, Franca; Furlan, Raffaello; Porta, Alberto

    2007-07-25

    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. Final Report on Isotope Ratio Techniques for Light Water Reactors

    SciTech Connect

    Gerlach, David C.; Gesh, Christopher J.; Hurley, David E.; Mitchell, Mark R.; Meriwether, George H.; Reid, Bruce D.

    2009-07-01

    The Isotope Ratio Method (IRM) is a technique for estimating the energy or plutonium production in a fission reactor by measuring isotope ratios in non-fuel reactor components. The isotope ratios in these components can then be directly related to the cumulative energy production with standard reactor modeling methods.

  19. Stable isotopes of carbon and nitrogen in the study of avian and mammalian trophic ecology

    Treesearch

    Jeffrey F. Kelly

    2000-01-01

    Differential fractionation of stable isotopes of carbon during photosynthesis causes C4 plants and C3 plants to have distinct carbon-isotope signatures. In addition, marine C3 plants have stable-isotope ratios of carbon that are intermediate between C4 and terrestrial C3 plants. The direct incorporation of the carbon-isotope ratio (13C/12C) of plants into consumers...

  20. New organic reference materials for hydrogen, carbon, and nitrogen stable isotope-ratio measurements: caffeines, n-alkanes, fatty acid methyl esters, glycines, L-valines, polyethylenes, and oils

    USGS Publications Warehouse

    Schimmelmann, Arndt; Qi, Haiping; Coplen, Tyler B.; Brand, Willi A.; Fong, Jon; Meier-Augenstein, Wolfram; Kemp, Helen F.; Toman, Blaza; Ackermann, Annika; Assonov, Sergey; Aerts-Bijma, Anita; Brejcha, Ramona; Chikaraishi, Yoshito; Darwish, Tamim; Elsner, Martin; Gehre, Matthias; Geilmann, Heike; Gröning, Manfred; Hélie, Jean-François; Herrero-Martín, Sara; Meijer, Harro A.J.; Sauer, Peter E.; Sessions, Alex L.; Werner, Roland A.

    2016-01-01

    An international project developed, quality-tested, and determined isotope−δ values of 19 new organic reference materials (RMs) for hydrogen, carbon, and nitrogen stable isotope-ratio measurements, in addition to analyzing pre-existing RMs NBS 22 (oil), IAEA-CH-7 (polyethylene foil), and IAEA-600 (caffeine). These new RMs enable users to normalize measurements of samples to isotope−δ scales. The RMs span a range of δ2HVSMOW-SLAP values from −210.8 to +397.0 mUr or ‰, for δ13CVPDB-LSVEC from −40.81 to +0.49 mUr and for δ15NAir from −5.21 to +61.53 mUr. Many of the new RMs are amenable to gas and liquid chromatography. The RMs include triads of isotopically contrasting caffeines, C16 n-alkanes, n-C20-fatty acid methyl esters (FAMEs), glycines, and l-valines, together with polyethylene powder and string, one n-C17-FAME, a vacuum oil (NBS 22a) to replace NBS 22 oil, and a 2H-enriched vacuum oil. A total of 11 laboratories from 7 countries used multiple analytical approaches and instrumentation for 2-point isotopic normalization against international primary measurement standards. The use of reference waters in silver tubes allowed direct normalization of δ2H values of organic materials against isotopic reference waters following the principle of identical treatment. Bayesian statistical analysis yielded the mean values reported here. New RMs are numbered from USGS61 through USGS78, in addition to NBS 22a. Because of exchangeable hydrogen, amino acid RMs currently are recommended only for carbon- and nitrogen-isotope measurements. Some amino acids contain 13C and carbon-bound organic 2H-enrichments at different molecular sites to provide RMs for potential site-specific isotopic analysis in future studies.

  1. Isotopic ratio method for determining uranium contamination

    SciTech Connect

    Miles, R.E.; Sieben, A.K.

    1994-02-03

    The presence of high concentrations of uranium in the subsurface can be attributed either to contamination from uranium processing activities or to naturally occurring uranium. A mathematical method has been employed to evaluate the isotope ratios from subsurface soils at the Rocky Flats Nuclear Weapons Plant (RFP) and demonstrates conclusively that the soil contains uranium from a natural source and has not been contaminated with enriched uranium resulting from RFP releases. This paper describes the method used in this determination which has widespread application in site characterizations and can be adapted to other radioisotopes used in manufacturing industries. The determination of radioisotope source can lead to a reduction of the remediation effort.

  2. BIODEGRADATION OF FLUORANTHENE AS MONITORED USING STABLE CARBON ISOTOPES

    EPA Science Inventory

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

  3. BIODEGRADATION OF FLUORANTHENE AS MONITORED USING STABLE CARBON ISOTOPES

    EPA Science Inventory

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

  4. Depth Profiles of Stable Nitrogen and Carbon Isotopes and C:N Ratios in Surficial Sediments From the NW Insular Slope of Cuba.

    NASA Astrophysics Data System (ADS)

    Soto, L. A.; de La Lanza, G.; López-Veneroni, D.

    2007-05-01

    The deep sea floor in the studied area remained unexplored for several decades. Recent searching for fossil fuels and gas hydrates in the seabed has renewed interest in studying deep sea processes in the region. Near- surface sediments were recovered with a Reineick box-corer at 3 preselected quadrants located at the channel axis of the Florida Straits and the slope rise off NW Cuba at depths ranging from 1468 to 2094 m. A total of 12- 30 cm long- subcores were sampled for isotopic (15N/14N and 13C/12C) and C:N ratio analyses. Surficial sediment samples exhibited mostly enriched δ15N values ranging from +3.6 to +6.4‰ with an average of +5.4 ± 0.7. δ15N values in the deeper quadrants (I and II) near the channel axis were fairly homogeneous in contrast to the shallower one (III) located at the slope rise, which showed a higher variability and significantly depleted values (+3.6‰). Testing of equality of δ15N values among quadrants was rejected (Friedman's test p<0.368. From the estimated δ15N average value here recorded a significant input of organic matter from a pelagic source is inferred. The δ13C values had a narrow range in all quadrants (-18.5 to -19.13‰) with an average of - 18.71±0.17. A gradient slightly enriched is noted on the seabed from the westernmost quadrants(I and II)towards the slope rise (quadrant III). The average δ13C signal in surficial sediments from the Southern Straits approaches that known for the continental shelf of South Florida (-18.5±0.7). Vertical profiles of TOC and TN are highly heterogeneous among quadrants displaying a diminishing trend with depth (0- 18 cm). TOC values are mostly impoverished ranging from 0.16 to 0.67 mmol/g. Slope rise sites concentrated less TOC than locations near the channel axis. The opposite occurred with TN values. Sites near the slope rise attained 0.90 mmol/g whereas in the channel axis, nitrogen was reduced to 0.46mmol/g. C:N ratios ranged from 1.9 to 10.2. An increasing gradient was noted

  5. Laser ablation molecular isotopic spectrometry of carbon isotopes

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

    Quantitative determination of carbon isotopes using Laser Ablation Molecular Isotopic Spectrometry (LAMIS) is described. Optical emission of diatomic molecules CN and C2 is used in these measurements. Two quantification approaches are presented: empirical calibration of spectra using a set of reference standards and numerical fitting of a simulated spectrum to the experimental one. Formation mechanisms of C2 and CN in laser ablation plasma are briefly reviewed to provide insights for implementation of LAMIS measurements. A simulated spectrum of the 12C2 Swan system was synthesized using four constituents within 473.5-476.5 nm. Simulation included three branches of 12C2 (1-0), branches R(0-0) and R(1-1), and branch P(9-8) of 12C2. Spectral positions of the tail lines in R(0-0) and R(1-1) were experimentally measured, since they were not accurately known before. The Swan band (1-0) of the isotopologue 13C12C was also simulated. Fitting to the experimental spectrum yielded the ratio 13C/12C = 1.08% in a good agreement with measurements by isotope ratio mass spectrometry. LAMIS promises to be useful in coal, oil and shale exploration, carbon sequestration monitoring, and agronomy studies.

  6. Aerosol carbon isotope composition over Baltic Sea

    NASA Astrophysics Data System (ADS)

    Garbaras, Andrius; Pabedinskas, Algirdas; Masalaite, Agne; Petelski, Tomasz; Gorokhova, Elena; Sapolaite, Justina; Ezerinskis, Zilvinas; Remeikis, Vidmantas

    2017-04-01

    Particulate carbonaceous matter is significant contributor to ambient particulate matter originating from intervening sources which contribution is difficult to quantify due to source diversity, chemical complexity and processes during atmospheric transport. Carbon isotope analysis can be extremely useful in source apportionment of organic matter due to the unique isotopic signatures associated with anthropocentric (fossil fuel), continental (terrestrial plants) and marine sources, and is particularly effective when these sources are mixed (Ceburnis et al., 2011;Ceburnis et al., 2016). We will present the isotope ratio measurement results of aerosol collected during the cruise in the Baltic Sea. Sampling campaign of PM10 and size segregated aerosol particles was performed on the R/V "Oceania" in October 2015. Air mass back trajectories were prevailing both from the continental and marine areas during the sampling period. The total carbon concentration varied from 1 µg/m3 to 8 µg/m3. Two end members (δ13C = -25‰ and δ13C = -28 ‰ ) were established from the total stable carbon isotope analysis in PM10 fraction. δ13C analysis in size segregated aerosol particles revealed δ13C values being highest in the 1 - 2.5 µm range (δ13C = -24.9 ‰ ) during continental transport, while lowest TC δ13C values (δ13C ≈ -27 ‰ ) were detected in the size range D50 <1 µm during stormy weather when air mass trajectory prevailed from the western direction. These measurements revealed that simplified isotope mixing model can not be applied for the aerosol source apportionment (Masalaite et al., 2015) in the perturbed marine environment. Additionally, concentration of bacteria and fungi were measured in size segregated and PM10 aerosol fraction. We were able to relate aerosol source δ13C end members with the abundance of bacteria and fungi over Baltic Sea combining air mass trajectories, stable isotope data, fungi and bacteria concentrations. Ceburnis, D., Garbaras, A

  7. Anthropogenic impacts on mercury concentrations and nitrogen and carbon isotope ratios in fish muscle tissue of the Truckee River watershed, Nevada, USA.

    PubMed

    Sexauer Gustin, Mae; Saito, Laurel; Peacock, Mary

    2005-07-15

    The lower Truckee River originates at Lake Tahoe, California/Nevada (NV), USA and ends in the terminal water body, Pyramid Lake, NV. The river has minimal anthropogenic inputs of contaminants until it encounters the cities of Reno and Sparks, NV, and receives inflows from Steamboat Creek (SBC). SBC originates at Washoe Lake, NV, where there were approximately six mills that used mercury for gold and silver amalgamation in the late 1800s. Since then, mercury has been distributed down the creek to the Truckee River. In addition, SBC receives agricultural and urban nonpoint source pollution, and treated effluent from the Reno-Sparks water reclamation facility. Fish muscle tissue was collected from different species in SBC and the Truckee River and analyzed for mercury and stable isotopes. Nitrogen (delta(15)N) and carbon (delta(13)C) isotopic values in these tissues provide insight as to fish food resources and help to explain their relative Hg concentrations. Mercury concentrations, and delta(15)N and delta(13)C values in fish muscle from the Truckee River, collected below the SBC confluence, were significantly different than that found in fish collected upstream. Mercury concentrations in fish tissue collected below the confluence for all but three fish sampled were significantly greater (0.1 to 0.65 microg/g wet wt.) than that measured in the tissue collected above the confluence (0.02 to 0.1 microg/g). Delta(15)N and delta(13)C isotopic values of fish muscle collected from the river below the confluence were higher and lower, respectively, than that measured in fish collected up river, most likely reflecting wastewater inputs. The impact of SBC inputs on muscle tissue isotope values declined down river whereas the impact due to Hg inputs showed the opposite trend.

  8. Biology and air-sea gas exchange controls on the distribution of carbon isotope ratios (δ13C) in the ocean

    NASA Astrophysics Data System (ADS)

    Schmittner, A.; Gruber, N.; Mix, A. C.; Key, R. M.; Tagliabue, A.; Westberry, T. K.

    2013-09-01

    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 δ13CDIC are influenced by

  9. Effects of roasting conditions on the changes of stable carbon isotope ratios (δ13 C) in sesame oil and usefulness of δ13 c to differentiate blended sesame oil from corn oil.

    PubMed

    Seol, Nam Gyu; Jang, Eun Yeong; Kim, Mi-Ja; Lee, Jaehwan

    2012-12-01

    Differentiating blended sesame oils from authentic sesame oil (SO) is a critical step in protecting consumer rights. Stable carbon isotope ratios (δ(13) C), color, fluorescence intensity, and fatty acid profiles were analyzed in SO prepared from sesame seeds with different roasting conditions and in corn oil blended with SO. Sesame seeds were roasted at 175, 200, 225, or 250 °C for 15 or 30 min at each temperature. SO was mixed with corn oil at varying ratios. Roasting conditions ranging from175 to 250 °C at the 30 min time point did not result in significant changes in δ(13) C (P > 0.05). Values of δ(13) C in corn oil and SO from sesame seeds roasted at 250 °C for 15 min were -17.55 and -32.13 ‰, respectively. Fatty acid ratios, including (O + L)/(P × Ln) and (L × L)/O, where O, L, P, and Ln were oleic, linoleic, palmitic, and linolenic acids, respectively, showed good discriminating abilities among the SO blended with corn oil. Therefore, using different combinations of stable carbon isotope ratios and some fatty acid ratios can allow successful differentiation of authentic SO from SO blended with corn oil. © 2012 Institute of Food Technologists®

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

    SciTech Connect

    McConnaughey, T.A.

    1986-01-01

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

  11. Isotope ratio analysis by Orbitrap mass spectrometry

    NASA Astrophysics Data System (ADS)

    Eiler, J. M.; Chimiak, L. M.; Dallas, B.; Griep-Raming, J.; Juchelka, D.; Makarov, A.; Schwieters, J. B.

    2016-12-01

    Several technologies are being developed to examine the intramolecular isotopic structures of molecules (i.e., site-specific and multiple substitution), but various limitations in sample size and type or (for IRMS) resolution have so far prevented the creation of a truly general technique. We will discuss the initial findings of a technique based on Fourier transform mass spectrometry, using the Thermo Scientific Q Exactive GC — an instrument that contains an Orbitrap mass analyzer. Fourier transform mass spectrometry is marked by exceptionally high mass resolutions (the Orbitrap reaches M/∆M in the range 250,000-1M in the mass range of greatest interest, 50-200 amu). This allows for resolution of a large range of nearly isobaric interferences for isotopologues of volatile and semi-volatile compounds (i.e., involving isotopes of H, C, N, O and S). It also provides potential to solve very challenging mass resolution problems for isotopic analysis of other, heavier elements. Both internal and external experimental reproducibilities of isotope ratio analyses using the Orbitrap typically conform to shot-noise limits down to levels of 0.2 ‰ (1SE), and routinely in the range 0.5-1.0 ‰, with similar accuracy when standardized to concurrently run reference materials. Such measurements can be made without modifications to the ion optics of the Q Exactive GC, but do require specially designed sample introduction devices to permit sample/standard comparison and long integration times. The sensitivity of the Q Exactive GC permits analysis of sub-nanomolar samples and quantification of multiply-substituted species. The site-specific capability of this instrument arises from the fact that mass spectra of molecular analytes commonly contain diverse fragment ion species, each of which samples a specific sub-set of molecular sites. We will present applications of this technique to the biological and abiological chemistry of amino acids, forensic identification of

  12. The separation of stable isotopes of carbon

    NASA Astrophysics Data System (ADS)

    Oziashvili, E. D.; Egiazarov, A. S.

    1989-04-01

    The present state of work on the separation of carbon isotopes by diffusion, fractional distillation, chemical isotopic exchange, and the selective excitation and dissociation of molecules in electrical discharges or in the field of laser radiation has been examined. The characteristics of new laboratory and industrial assemblies for separating carbon isotopes have been described. Promising directions of study aimed at developing effective technological processes for separating carbon isotopes have been noted. The bibliography contains 148 references.

  13. Carbon Isotope Chemistry in Molecular Clouds

    NASA Technical Reports Server (NTRS)

    Robertson, Amy N.; Willacy, Karen

    2012-01-01

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

  14. Carbon Isotope Chemistry in Molecular Clouds

    NASA Technical Reports Server (NTRS)

    Robertson, Amy N.; Willacy, Karen

    2012-01-01

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

  15. Stable carbon isotope ratios of low molecular weight dicarboxylic acids, ketoacids and glyoxal in marine aerosols from the western North Pacific: Long-term trends in Chichijima Island

    NASA Astrophysics Data System (ADS)

    Kawamura, K.; Tachibana, E.

    2012-12-01

    Dicarboxylic acids such as oxalic, malonic and succinic acids are the most abundant water-soluble organic compound class in aerosols. To better understand the source and photochemical processes of water-soluble organic aerosols in the remote marine aerosols, we measured stable carbon isotopic composition (δ13C) of dicarboxylic acids and related compounds using a GC/IR/MS technique. The aerosol samples were collected in 2001-2011 at a remote island, Chichijima (27°04'E; 142°13'N) in the western North Pacific. Here we present decadal variations of the isotopic composition of dicarboxylic acids (C2-C9), ketoacids (C2-C8) and glyoxal in summertime aerosols (June, July and August). The molecular distributions of diacids were characterized by the predominance of oxalic (C2) acid followed by malonic (C3) and succinic (C4) acids. Oxalic acid showed higher δ13C values than other species ranging from -18‰ to -2‰ with no clear decadal trend. In contrast, C3 and C4 diacids showed δ13C values of -24 to -5‰ and -40 to -12‰ with a decadal decline. Glyoxal (-60 to -10‰) and ωC7 acid (-34 to -12‰) also showed lower values toward 2011. However, azelaic acid (C9) (-32 to -24‰) stayed relatively constant throughout the observation period. We will discuss the detailed isotopic compositions of these organic species in terms of the photochemical aging and processing in the western North Pacific and the changes in the sources and source regions.

  16. Laser spectroscopic measurement of helium isotope ratios.

    SciTech Connect

    Wang, L.-B.; Mueller, P.; Holt, R. J.; Lu, Z.-T.; O'Connor, T. P.; Sano, Y.; Sturchio, N.; Univ. of Illinois; Univ. of Tokyo; Univ. of Illinois at Chicago

    2003-06-13

    A sensitive laser spectroscopic method has been applied to the quantitative determination of the isotope ratio of helium at the level of {sup 3}He/{sup 4}He = 10{sup -7}--10{sup -5}. The resonant absorption of 1083 nm laser light by the metastable {sup 3}He atoms in a discharge cell was measured with the frequency modulation saturation spectroscopy technique while the abundance of {sup 4}He was measured by a direct absorption technique. The results on three different samples extracted from the atmosphere and commercial helium gas were in good agreement with values obtained with mass spectrometry. The achieved 3{sigma} detection limit of {sup 3}He in helium is 4 x 10{sup -9}. This demonstration required a 200 {mu}L STP sample of He. The sensitivity can be further improved, and the required sample size reduced, by several orders of magnitude with the addition of cavity enhanced spectroscopy.

  17. Carbon isotopic composition of individual Precambrian microfossils

    NASA Technical Reports Server (NTRS)

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

    2000-01-01

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

  18. Carbon isotopic composition of individual Precambrian microfossils

    NASA Technical Reports Server (NTRS)

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

    2000-01-01

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

  19. Carbon isotopic composition of individual Precambrian microfossils.

    PubMed

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

    2000-08-01

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

  20. Carbon isotopic composition of individual Precambrian microfossils

    NASA Astrophysics Data System (ADS)

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

    2000-08-01

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

  1. Cavity Ring-down Spectroscopy for Carbon Isotope Analysis with 2 {mu}m Diode Laser

    SciTech Connect

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

    2009-03-17

    We have made a prototype based on CRDS with 2 {mu}m diode laser for carbon isotope analysis of CO{sub 2} in air. The carbon isotope ratio was obtained to be (1.085{+-}0.012)x10{sup -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 {mu}m tunable diode laser.

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

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

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

  3. Global carbon isotope records and carbon cycle feedbacks following the PETM perturbation (Invited)

    NASA Astrophysics Data System (ADS)

    Bowen, G. J.

    2009-12-01

    Global warming during the Paleocene-Eocene Thermal Maximum is associated with a transient, multi-phase negative carbon isotope excursion documented throughout the global exogenic carbon cycle. The precipitous drop in carbon isotope ratios at the onset of the event is widely accepted to reflect a massive addition of 13C-depleted carbon to the ocean/atmosphere system and resultant increases in atmospheric pCO2 and ocean water acidity. But what, if anything, does the pattern of continued carbon isotope change tell us about the patterns and mechanisms of carbon cycle change during the subsequent 170 kyr? Carbon isotope ratios remain relatively stable and low for some 60 kyr following the initiation of the event, suggesting either continued perturbation of the system away from its pre-PETM state or a change in the rate or net isotopic composition of the carbon burial flux during this interval. The interval of δ13C stability ended abruptly ca. 80 kyr after the beginning of the PETM, when carbon isotope ratios rapidly increased by at least 2‰ over no more than 30 kyr. The rebound rate of δ13C values was an order of magnitude faster than expected based on the residence time of carbon in the exogenic system, and implies either a dramatic decrease in residence time or a substantial change in the isotopic composition of carbon fluxes between this system and the lithosphere. The isotopic record of the PETM carbon cycle oscillates between stability and instability, suggesting discrete changes in global carbon fluxes at points throughout the event. Understanding whether these changes were driven by variation in bulk carbon fluxes or ‘isofluxes’ will be necessary to accurately interpret the carbon isotope record to better understand lithospheric carbon burial feedbacks, CO2 drawdown, and the termination of the PETM hyperthermal climate.

  4. Intramolecular carbon isotope distribution of acetic acid in vinegar.

    PubMed

    Hattori, Ryota; Yamada, Keita; Kikuchi, Makiko; Hirano, Satoshi; Yoshida, Naohiro

    2011-09-14

    Compound-specific carbon isotope analysis of acetic acid is useful for origin discrimination and quality control of vinegar. Intramolecular carbon isotope distributions, which are each carbon isotope ratios of the methyl and carboxyl carbons in the acetic acid molecule, may be required to obtain more detailed information to discriminate such origin. In this study, improved gas chromatography-pyrolysis-gas chromatography-combustion-isotope ratio mass spectrometry (GC-Py-GC-C-IRMS) combined with headspace solid-phase microextraction (HS-SPME) was used to measure the intramolecular carbon isotope distributions of acetic acid in 14 Japanese vinegars. The results demonstrated that the methyl carbons of acetic acid molecules in vinegars produced from plants were mostly isotopically depleted in (13)C relative to the carboxyl carbon. Moreover, isotopic differences (δ(13)C(carboxyl) - δ(13)C(methyl)) had a wide range from -0.3 to 18.2‰, and these values differed among botanical origins, C3, C4, and CAM plants.

  5. ICP-MS for isotope ratio measurement

    USDA-ARS?s Scientific Manuscript database

    The use of stable isotopes in mineral nutrition research has become a fundamental aspect of conducting this research. A gradual transition has occurred, now virtually complete, from radioactive isotope studies to those using stable isotopes. Although primarily used in human research, mineral stable ...

  6. Identification and quantification of base flow using carbon isotopes.

    PubMed

    Meredith, Elizabeth L; Kuzara, Shawn L

    2012-01-01

    Six surface water samples from locations along Otter Creek in Southeastern Montana and a groundwater sample from a nearby monitoring well completed in the Knobloch coal were analyzed for stable carbon isotope ratios. Along the length of its perennial reach, between the towns of Otter and Ashland, Otter Creek crosses several coal outcrops, including the Knobloch coal zone. The carbon isotope ratio of the creek becomes progressively more similar to that of the Knobloch coal aquifer groundwater in samples collected downgradient from the town of Otter. The isotope ratio of the stream changes from -10.5 to -8.9‰ reflecting the influence of the coal-aquifer base flow contribution, as represented by Knobloch coal groundwater, which has a carbon isotope value of +3.9‰. The dissolved inorganic carbon concentrations of the groundwater and surface water are similar (~100 mg/L), which allowed the use of the simplified, first-order, two-end-member mixing equation. Using carbon isotope ratios, calculations of the fraction of water contributed by coal aquifers indicate that approximately 11% of the surface water in Otter Creek at its mouth near Ashland was supplied by groundwater from the coal aquifers that crop out between Otter and Ashland. This study was conducted in December, when Otter Creek is at low flow. At times of higher surface flow, the contribution from groundwater base flow will be correspondingly smaller. This study illustrates that carbon isotopes can be an effective, low-cost tool in base flow studies.

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

    PubMed

    Tiunov, A V

    2007-01-01

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

  8. Infant and child diet in Neolithic hunter-fisher-gatherers from Cis-Baikal, Siberia: intra-long bone stable nitrogen and carbon isotope ratios.

    PubMed

    Waters-Rist, Andrea L; Bazaliiskii, Vladimir I; Weber, Andrzej W; Katzenberg, M Anne

    2011-10-01

    Analysis of stable nitrogen and carbon isotopes (δ(15) N and δ(13) C) from subadults and adults allows for assessment of age-related dietary changes, including breastfeeding and weaning, and adoption of an adult diet. In one of the first studies of hunter-fisher-gatherer subadults from Eurasia, three Neolithic (8,800-5,200 calBP) mortuary sites from southwestern Siberia are analyzed to evaluate hypothesized differences in weaning age between Early versus Late Neolithic groups. An intra-individual sampling methodology is used to compare bone formed at different ages. Collagen samples (n = 143) from three different growth areas of long bones-the proximal metaphysis, diaphysis, and distal metaphysis-were obtained from 49 subadults aged birth to 10 years. In infants (birth to 3 years, n = 23) contrasting the δ(15) N values of the metaphysis, which contains newer bone, to the δ(15) N values of the diaphysis, which contains older bone, permits a more precise determination of breastfeeding-weaning status. In Early and Late Neolithic groups breast milk was the major protein source until the age of 2-3 years. However, there are differences in the age of weaning completion and duration: Early Neolithic groups weaned their infants at a later age and over a shorter amount of time. Differences may have affected infant morbidity and mortality, and female fecundity and inter-birth intervals. Stable isotope values in older subadults (4-10 years, n = 26) do not differ from adults suggesting the absence of age-based food allocation. Copyright © 2011 Wiley-Liss, Inc.

  9. Si Isotopic Ratios in Mainstream Presolar SIC Grains Revisited

    NASA Astrophysics Data System (ADS)

    Lugaro, Maria; Zinner, Ernst; Gallino, Roberto; Amari, Sachiko

    1999-12-01

    Although mainstream SiC grains, the major group of presolar SiC grains found in meteorites, are believed to have originated in the expanding envelope of asymptotic giant branch (AGB) stars during their late carbon-rich phases, their Si isotopic ratios show a distribution that cannot be explained by nucleosynthesis in this kind of star. Previously, this distribution has been interpreted to be the result of contributions from many AGB stars of different ages whose initial Si isotopic ratios vary owing to the Galactic chemical evolution of the Si isotopes. This paper presents a new interpretation based on local heterogeneities of the Si isotopes in the interstellar medium at the time the parent stars of the mainstream grains were born. Recently, several authors have presented inhomogeneous chemical evolution models of the Galactic disk in order to account for the well-known evidence that F and G dwarfs of similar age show an intrinsic scatter in their elemental abundances. First we report new calculations of the s-process nucleosynthesis of the Si and Ti isotopes in four AGB models (1.5, 3, and 5 Msolar with Z=0.02; 3 Msolar with Z=0.006). These calculations are based on the release of neutrons in the He intershell by the 13C source during the interpulse periods followed by a second small burst of neutrons released in the convective thermal pulse by the marginal activation of the 22Ne source. In the 1.5 and 3 Msolar models with solar metallicity the predicted shifts of the Si isotopic ratios in the stars' envelope are much smaller (<30‰ for the 29Si/28Si ratio and <40‰ for the 30Si/28Si ratio; the two ratios are normalized to solar) than the range observed in the mainstream grains (up to 180‰). Isotopic shifts are of the same order as in the SiC grains for the 5 Msolar and Z=0.006 models, but the slope of the 29Si/28Si versus 30Si/28Si correlation line is much smaller than that of the grains. We also show that none of the models can reproduce the correlations

  10. Environmental controls on stable isotope ratios in New Zealand Podocarpaceae: Implications for palaeoclimate reconstruction

    NASA Astrophysics Data System (ADS)

    Brett, Marianne J.; Baldini, James U. L.; Gröcke, Darren R.

    2014-09-01

    Stable isotope ratios of various proxies are widely used for palaeoclimate reconstruction, and it is often assumed that isotope ratios reflect vegetation abundance or type. However, very little research exists on the isotopic equilibration of extant biomes under variable environmental conditions. In this study, carbon and oxygen isotope ratios from leaves of various Podocarpaceae genera, endemic to New Zealand, are linked to environmental parameters from the Land Environments New Zealand model. The dominant influence on stable isotope ratios within the majority of Podocarpaceae studied here is vapour pressure deficit (VPD). A simple latitudinal trend does not exist, and neither temperature nor rainfall (decoupled from VPD) controls the stable isotope ratios. The results suggest that modern spatial heterogeneity in VPD affects the stable isotope values of vegetation, and that historic VPD variability would change the stable isotope ratios of Podocarpaceae without necessitating a change in vegetation type, density, or productivity. This represents an alternative model for temporal isotope change within geochemical proxies and reinforces the need for increased stable isotopic research in modern plant ecosystems to better understand modern, and eventually palaeoclimatic processes affecting the terrestrial biosphere.

  11. Biology and air-sea gas exchange controls on the distribution of carbon isotope ratios (δ13C) in the ocean

    NASA Astrophysics Data System (ADS)

    Schmittner, A.; Gruber, N.; Mix, A. C.; Key, R. M.; Tagliabue, A.; Westberry, T. K.

    2013-05-01

    Analysis of observations and sensitivity experiments with a new three-dimensional global model of stable carbon isotope cycling elucidate the processes that control the distribution of δ13C in the contemporary and preindustrial ocean. Biological fractionation dominates the distribution of δ13CDIC of dissolved inorganic carbon (DIC) due to the sinking of isotopically light δ13C organic matter from the surface into the interior ocean. This process leads to low δ13CDIC values at dephs 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 provides an important secondary influence due to 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, air-sea gas exchange is slow, so biological effect dominate spatial δ13CDIC gradients both in the interior and at the surface, in constrast to conclusions from some previous studies. Analysis of a new synthesis of δ13CDIC measurements from years 1990 to 2005 is used to quantify preformed (δ13Cpre) and remineralized (δ13Crem) contributions as well as the effects of biology (Δδ13Cbio) and air-sea gas exchange (δ13C*). The model reproduces major features of the observed large-scale distribution of δ13CDIC, δ13Cpre, δ13Crem, δ13C*, and Δδ13Cbio. Residual misfits are documented and analyzed. Simulated surface and subsurface δ13CDIC are influenced by details of the ecosystem model formulation. For example, inclusion of a simple parameterization of iron limitation of phytoplankton growth rates and temperature-dependent zooplankton grazing rates improves the agreement with δ13CDIC

  12. Stable isotope ratios of carbon and nitrogen in pollen grains in order to characterize plant functional groups and photosynthetic pathway types.

    PubMed

    Descolas-Gros, Chantal; Schölzel, Christian

    2007-01-01

    Measurements of delta(13)C, delta(15)N and C : N ratios on modern pollen grains from temperate plants, including whole grains as well as extracted sporopollenin, were analysed in order to characterize physiological plant types at the pollen level and to determine the variation of these parameters in modern pollen grains of the same climatic area. Measurements are presented for 95 batches of whole modern pollen from 58 temperate species and on the stable fraction of modern pollen grains, chemically extracted sporopollenin, for two modern species. Fourier transform infrared (FTIR) and cross-polarization and magic-angle spinning (CP/MAS) sporopollenin spectra were conducted in parallel. C(3) and C(4) plants can be separated by delta(13)C measurements based on pollen. Probabilistic assignments to plant functional groups (herbaceous, deciduous woody, evergreen woody) of C(3) plants by the means of a discriminant analysis can be made for C : N ratios and for delta(13)C. The results are related to other studies on sporopollenin in order to use this method in future work on fossil samples. Stable isotope measurements on pollen allow improved pollen diagrams, including forms that cannot be differentiated at species level, increasing the accuracy and resolution of plant physiological type distribution in quaternary and older fossil sediments.

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

    NASA Astrophysics Data System (ADS)

    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

  14. Carbon isotope fractionation in wood during carbonization

    NASA Astrophysics Data System (ADS)

    Turney, C. S. M.; Wheeler, D.; Chivas, Allan R.

    2006-02-01

    A significant uncertainty exists as to whether δ 13C values in charcoal meaningfully represent the stable isotopic content of the original material, with studies suggesting variable responses to both natural and laboratory heating. An extensive study was undertaken using fully homogenised samples of wood taken from Eucalyptus spp., Quercus robur and Pinus radiata. The results demonstrate that the duration of heating had no tangible effect on the final composition of the charred material, with the δ 13C and carbon content of wood fixed after 30 min of heating. Furthermore, all three wood types become progressively depleted in 13C with increasing temperature. The results demonstrate that even at temperatures commonly reached in natural fires (<450 °C) isotopic fractionation of up to 1.3‰ can take place indicating that the absolute values obtained from charcoal extracted for paleoenvironmental reconstruction must be interpreted with caution.

  15. Influence of isotopic re-equilibration on speleothem and fluid inclusion isotope ratios after primary calcite precipitation

    NASA Astrophysics Data System (ADS)

    Kluge, Tobias; Haderlein, Astrid; Weißbach, Therese

    2016-04-01

    Oxygen isotope ratios in speleothems (notably stalagmites) have been used since decades to successfully infer paleotemperatures and deduce paleo-environmental information. In addition, recent technical developments allow to increasingly use fluid inclusions as an archive for drip-water and together with the surrounding calcite as paleothermometer. A basic requirement for isotope data interpretation is the complete knowledge of the fractionation between calcite and fluid. Most laboratory and in-situ cave experiments focus on calcite growth and the isotope fractionation between calcite and feed solution. Potential isotope exchange and re-equilibration processes after the initial deposition have mostly been neglected. However, experiments of Oelkers et al. (2015) showed that the isotope exchange between minerals and fluid can proceed rapidly (within days), even at chemical equilibrium. In hydrous Mg carbonates a similar process of continuous isotope exchange between carbonate and fluid was observed after the carbonate precipitation was completed (Mavromatis et al., 2015). These observations suggest that the isotope ratios of speleothem calcite may be affected by this continuous exchange, likely driving the isotope composition continuously towards equilibrium at the respective cave conditions. In addition, fluid inclusions are suspected to be sensitive to an isotope exchange with the surrounding carbonate highlighting the need to precisely understand and quantify this effect. We assessed the oxygen isotope exchange between calcite and solution at chemical equilibrium conditions with theoretical estimates and laboratory experiments over an intermediate time scale (hours-weeks). A large isotope gradient (~20 ‰)) between solution and calcite was prepared in the experiment to investigate the dynamics of this re-equilibration process. We used a theoretical model based on a Rayleigh fractionation approach and the direct comparison with the experiment to determine

  16. Carbon isotopic composition of Amazon shelf sediments

    SciTech Connect

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

    1985-02-01

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

  17. Oxygen isotope fractionation in divalent metal carbonates

    USGS Publications Warehouse

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

    1969-01-01

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

  18. Relationships between tree height and carbon isotope discrimination

    Treesearch

    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...

  19. Determination of nitrogen-15 isotope fractionation in tropine: evaluation of extraction protocols for isotope ratio measurement by isotope ratio mass spectrometry.

    PubMed

    Molinié, Roland; Kwiecień, Renata A; Silvestre, Virginie; Robins, Richard J

    2009-12-01

    N-Demethylation of tropine is an important step in the degradation of this compound and related metabolites. With the purpose of understanding the reaction mechanism(s) involved, it is desirable to measure the 15N kinetic isotope effects (KIEs), which can be accessed through the 15N isotope shift (Deltadelta15N) during the reaction. To measure the isotope fractionation in 15N during tropine degradation necessitates the extraction of the residual substrate from dilute aqueous solution without introducing artefactual isotope fractionation. Three protocols have been compared for the extraction and measurement of the 15N/14N ratio of tropine from aqueous medium, involving liquid-liquid phase partitioning or silica-C18 solid-phase extraction. Quantification was by gas chromatography (GC) on the recovered organic phase and delta15N values were obtained by isotope ratio measurement mass spectrometry (irm-MS). Although all the protocols used can provide satisfactory data and both irm-EA-MS and irm-GC-MS can be used to obtain the delta15N values, the most convenient method is liquid-liquid extraction from a reduced aqueous volume combined with irm-GC-MS. The protocols are applied to the measurement of 15N isotope shifts during growth of a Pseudomonas strain that uses tropane alkaloids as sole source of carbon and nitrogen. The accuracy of the determination of the 15N/14N ratio is sufficient to be used for the determination of 15N-KIEs. Copyright 2009 John Wiley & Sons, Ltd.

  20. Isotopic ratio outlier analysis global metabolomics of Caenorhabditis elegans.

    PubMed

    Stupp, Gregory S; Clendinen, Chaevien S; Ajredini, Ramadan; Szewc, Mark A; Garrett, Timothy; Menger, Robert F; Yost, Richard A; Beecher, Chris; Edison, Arthur S

    2013-12-17

    We demonstrate the global metabolic analysis of Caenorhabditis elegans stress responses using a mass-spectrometry-based technique called isotopic ratio outlier analysis (IROA). In an IROA protocol, control and experimental samples are isotopically labeled with 95 and 5% (13)C, and the two sample populations are mixed together for uniform extraction, sample preparation, and LC-MS analysis. This labeling strategy provides several advantages over conventional approaches: (1) compounds arising from biosynthesis are easily distinguished from artifacts, (2) errors from sample extraction and preparation are minimized because the control and experiment are combined into a single sample, (3) measurement of both the molecular weight and the exact number of carbon atoms in each molecule provides extremely accurate molecular formulas, and (4) relative concentrations of all metabolites are easily determined. A heat-shock perturbation was conducted on C. elegans to demonstrate this approach. We identified many compounds that significantly changed upon heat shock, including several from the purine metabolism pathway. The metabolomic response information by IROA may be interpreted in the context of a wealth of genetic and proteomic information available for C. elegans . Furthermore, the IROA protocol can be applied to any organism that can be isotopically labeled, making it a powerful new tool in a global metabolomics pipeline.

  1. Isotopic Ratio Outlier Analysis Global Metabolomics of Caenorhabditis elegans

    PubMed Central

    Szewc, Mark A.; Garrett, Timothy; Menger, Robert F.; Yost, Richard A.; Beecher, Chris; Edison, Arthur S.

    2014-01-01

    We demonstrate the global metabolic analysis of Caenorhabditis elegans stress responses using a mass spectrometry-based technique called Isotopic Ratio Outlier Analysis (IROA). In an IROA protocol, control and experimental samples are isotopically labeled with 95% and 5% 13C, and the two sample populations are mixed together for uniform extraction, sample preparation, and LC-MS analysis. This labeling strategy provides several advantages over conventional approaches: 1) compounds arising from biosynthesis are easily distinguished from artifacts, 2) errors from sample extraction and preparation are minimized because the control and experiment are combined into a single sample, 3) measurement of both the molecular weight and the exact number of carbon atoms in each molecule provides extremely accurate molecular formulae, and 4) relative concentrations of all metabolites are easily determined. A heat shock perturbation was conducted on C. elegans to demonstrate this approach. We identified many compounds that significantly changed upon heat shock, including several from the purine metabolism pathway, which we use to demonstrate the approach. The metabolomic response information by IROA may be interpreted in the context of a wealth of genetic and proteomic information available for C. elegans. Furthermore, the IROA protocol can be applied to any organism that can be isotopically labeled, making it a powerful new tool in a global metabolomics pipeline. PMID:24274725

  2. Carbon isotope controlled molecular switches

    NASA Astrophysics Data System (ADS)

    Foster, Brian K.

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

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

    DOEpatents

    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. Developing a methodology for carbon isotope analysis of lacustrine diatoms.

    PubMed

    Hurrell, Elizabeth R; Barker, Philip A; Leng, Melanie J; Vane, Christopher H; Wynn, Peter; Kendrick, Chris P; Verschuren, Dirk; Street-Perrott, F Alayne

    2011-06-15

    Stable isotope analysis of sedimentary carbon in lakes can help reveal changes in terrestrial and aquatic carbon cycles. A method based on a single, photosynthetic organism, where host effects are minimised, should offer more precision than carbon isotope studies of bulk lake sediments. Here we report the development of a systematic method for use on fossil lacustrine diatom frustules, adapted from previous studies in marine environments. A step-wise cleaning experiment on diatomaceous lake sediments from Lake Challa, near Mount Kilimanjaro, was made to demonstrate the necessary treatment stages to remove external sedimentary carbon. Changes in soluble carbon compounds during these cleaning experiments were measured using gas chromatography/mass spectrometry (GC/MS). The mass spectrometry methods were refined to measure the small percentage of carbon in these samples and details of these methods are presented. Samples of cleaned diatoms containing <1% carbon yielded robust results. Carbon isotope analyses of diatom samples containing different species mixtures were performed and suggested that differences existed, although the effects lay within current experimental error and require further work. Unlike what was found in work on oxygen and silicon isotopes from diatom frustules, mineral contamination had no discernible impact on the diatom carbon isotope ratios from these sediments. The range of values found in the lakes investigated thus far can be interpreted with reference to the supply and nature of carbon from the catchment as well as to the demand generated from lake primary productivity. Copyright © 2011 John Wiley & Sons, Ltd.

  5. Zinc Isotope Ratios as Indicators of Diet and Trophic Level in Arctic Marine Mammals.

    PubMed

    Jaouen, Klervia; Szpak, Paul; Richards, Michael P

    2016-01-01

    Carbon and nitrogen stable isotope ratios of bone collagen are an established method for dietary reconstruction, but this method is limited by the protein preservation. Zinc (Zn) is found in bioapatite and the isotopic compositions of this element constitute a very promising dietary indicator. The extent of fractionation of Zn isotopes in marine environments, however, remains unknown. We report here on the measurement of zinc, carbon and nitrogen isotopes in 47 marine mammals from the archaeological site of Arvik in the Canadian Arctic. We undertook this study to test and demonstrate the utility of Zn isotopes in recent mammal bone minerals as a dietary indicator by comparing them to other isotopic dietary tracers. We found a correlation between δ66Zn values and trophic level for most species, with the exception of walruses, which may be caused by their large seasonal movements. δ6Zn values can therefore be used as a dietary indicator in marine ecosystems for both modern and recent mammals.

  6. Carbon isotope effects in carbonate systems

    NASA Astrophysics Data System (ADS)

    Deines, Peter

    2004-06-01

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

  7. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

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

    1991-04-01

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

  8. Experiments directed to the compound-specific determination of the stable carbon isotope ratios of the Toxaphene congener B8-1413 in two technical mixtures and Antarctic Weddell seal.

    PubMed

    Vetter, Walter; Schlatterer, Jörg; Gleixner, Gerd

    2006-03-31

    The carbon stable isotope ratio (delta(13)C value) of an environmentally-relevant Toxaphene congener in technical products and a biological sample from a remote region was in the focus of this work. For this reason, the major octachlorobornane residue of the multicomponent pesticide Toxaphene in biological samples, 2-endo,3-exo,5-endo,6-exo,8,8,10,10-octachlorobornane (B8-1413 or P26), was quantitatively enriched from two technical Toxaphene mixtures (Toxaphene and Melipax) in duplicates as well as from an Antarctic Weddell seal sample. Normal phase followed by reversed-phase high-performance liquid chromatography (HPLC) with three columns, respectively, coupled in series was used for this purpose. Four of the five fractionated samples fulfilled the requirement of an interference-free GC-elution for subsequent determination of the delta(13)C value by gas chromatography interfaced to an isotope ratio mass spectrometer (GC-IRMS). B8-1413 in Toxaphene (n=1) was more depleted in (12)C than in Melipax (n=2), which agrees with previous results obtained for the entire mixtures. The B8-1413 isolate from a Weddell seal sample from the Antarctic showed a delta(13)C value between the two technical products. Although a source appointment to the one or the other product was not possible, this example indicates that long range transport to the Antarctic and by uptake and food-chain bioaccumulation of B8-1413 in seals did not change the delta(13)C value significantly. The observed differences in one duplicate sample indicate that statistic evaluation of samples used for isotope ratio MS measurements is an important issue.

  9. Carbon isotope effects associated with aceticlastic methanogenesis

    NASA Technical Reports Server (NTRS)

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

    1994-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Dong, Feng; Baer, Douglas

    2010-05-01

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

  11. Effects of distilled water rinsing on stable isotope ratios of acid-treated marine invertebrate (Paguridae) samples.

    PubMed

    Guerin, Andrew J; Jensen, Antony C; McGill, Rona A R

    2013-09-30

    Stable isotope ratios are widely used to infer trophic relationships, although a growing number of studies show that sample pre-treatments (such as acidification to remove carbonates) can cause changes in isotope ratios. Samples are often rinsed in distilled water after acidification, and we examine the effects of this step in particular on the isotope ratios of marine invertebrate samples. Samples of whole hermit crabs (Paguridae) were subjected to one of three treatments: acidification using dilute hydrochloric acid without subsequent distilled water rinsing; acidification with rinsing; and rinsing with no acidification. Continuous-flow isotope ratio mass spectrometry was used to compare the mean carbon and nitrogen stable isotope ratios of treated and untreated material. Acidification (both with and without subsequent distilled water rinsing) resulted in reductions in mean δ(13)C values (1.939 and 3.146‰, respectively), while rinsing without prior acidification led to a smaller (but still significant) increase. Nitrogen isotope ratios were not affected by acidification, but subsequent rinsing with distilled water caused a decrease of approximately 1‰. Acidification of samples is clearly necessary in the presence of carbonates to obtain useful carbon isotope ratio data. However, post-acidification rinsing can result in further (potentially undesirable) changes to both carbon and nitrogen isotope ratios. Ideally, rinsing should be avoided, but the impacts are small enough to be of little concern in many studies. Rinsing (or not) should be considered carefully on the basis of the aims of a study. Copyright © 2013 John Wiley & Sons, Ltd.

  12. Kinetic and equilibrium Ba isotope fractionation during carbonate precipitation

    NASA Astrophysics Data System (ADS)

    van Zuilen, Kirsten; Mavromatis, Vasileios; Purgstaller, Bettina; Baldermann, Andre; Nägler, Thomas F.; Dietzel, Martin

    2017-04-01

    Variations in stable isotope ratios recorded in carbonates are widely used to reconstruct the physicochemical conditions, e.g., pH, temperature and redox conditions, prevailing at the time of carbonate mineral formation. Knowledge of isotope fractionation factors during mineral precipitation under varying environmental conditions is irremissible for the interpretation of isotope variations in natural sedimentary archives. However, experimentally derived fractionation factors, of for instance Ca isotopes, are often ambiguous and incommensurable due to differences in experimental parameters. Here, Ba isotope fractionation during carbonate mineral formation was investigated [1]. Time-resolved experiments of witherite (BaCO3) precipitation revealed an initial kinetic isotope effect with increasing Δ137/134Ba values of the ambient solution, following Rayleigh fractionation (αwitherite-fluid = 0.99993 ± 0.00004). After precipitation, the witherite crystals remained in contact with the ambient solution for about nine days. During this time, chemical steady state was achieved between solution and witherite; however, the Δ137/134Ba values of the solution decreased. At isotopic equilibrium, the ambient solution and the witherite crystals exhibited identical δ137/134Ba values, within the analytical uncertainty of ±0.04 ‰Ṫhis observation is interpreted as the result of continuous exchange of Ba2+ ions between witherite and solution after initial preferential uptake of the lighter Ba isotopes in the precipitating carbonates. Mass balance calculations indicate that the ion exchange affects several subsurface layers of the crystals. In summary, Ba isotope exchange between carbonate and ambient solution occurs at chemical equilibrium, and pristine isotopic signatures in carbonates may thus be reset at low temperatures. [1] Mavromatis et al. (2016) Geochim. Cosmochim. Acta 190, 72-84.

  13. Carbon isotope effects associated with autotrophic acetogenesis

    USGS Publications Warehouse

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

    1989-01-01

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

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

    SciTech Connect

    HOLDEN, N.E.

    2005-08-07

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

  15. Stable isotope ratio method for the characterisation of the poultry house environment.

    PubMed

    Skipitytė, Raminta; Mašalaitė, Agnė; Garbaras, Andrius; Mickienė, Rūta; Ragažinskienė, Ona; Baliukonienė, Violeta; Bakutis, Bronius; Šiugždaitė, Jūratė; Petkevičius, Saulius; Maruška, Audrius Sigitas; Remeikis, Vidmantas

    2017-06-01

    Stable isotope analysis was applied to describe the poultry house environment. The poultry house indoor environment was selected for this study due to the relevant health problems in animals and their caretakers. Air quality parameters including temperature, relative humidity, airflow rate, NH3, CO2 and total suspended particles, as well as mean levels of total airborne bacteria and fungi count, were measured. Carbon isotope ratios ((13)C/(12)C) were obtained in size-segregated aerosol particles. The carbon ((13)C/(12)C) and nitrogen ((15)N/(14)N) isotope ratios were measured in feed, litter, scrapings from the ventilation system, feathers and eggs. Additionally, the distribution of δ(13)C and δ(15)N values in different tissues of the chicken was examined. The airborne bacteria and fungi extracted from the air filters collected from poultry farms were grown in the laboratory in media with known isotope values and measured for stable isotope ratios. Analysis of isotope fractionation between microorganisms and their media indicated the applicability of stable isotope analysis in bulk samples for the identification of source material. The analysed examples imply that stable isotope analysis can be used to examine the indoor environment along with its biology and ecology, and serve as an informative bioanalytical tool.

  16. A review of various factors influencing the stable carbon isotope ratio of organic lake sediments by the change from glacial to post-glacial environmental conditions

    NASA Astrophysics Data System (ADS)

    Håkansson, Sören

    A survey is made of various factors influencing the {13C}/{12C} ratio of the organic component in lake sediments, focusing on the behaviour at the change from glacial to post-glacial environmental conditions. Increase in the 13C content of the organic sediment is caused by increase in temperature and the corresponding decrease of the supply of molecular CO 2 in the water of the lakes. An increase in the rate of organic production in the lakes may also, perhaps, cause a corresponding 13C increase. An increase of the fermentation of organic mud in the lakes may also have an effect in the same direction. Decrease in the 13C content of the organic sediment is caused by the change of the relative amounts of production of plankton and submersed macrophytes in the lakes from mainly submersed macrophytes to mainly plankton. A decrease towards almost complete absence of bicarbonate and CO 2 originating from carbonate rocks will also lead to a 13C decrease in the organic sediments. The same effect has the change of the terrestrial vegetation cover from almost complete absence to complete cover. A possible decrease of the 13C content in the atmospheric CO 2 has an effect in the same direction.

  17. Metal Concentrations in the Liver and Stable Isotope Ratios of Carbon and Nitrogen in the Muscle of Silvertip Shark (Carcharhinus albimarginatus) Culled off Ishigaki Island, Japan: Changes with Growth.

    PubMed

    Endo, Tetsuya; Kimura, Osamu; Ohta, Chiho; Koga, Nobuyuki; Kato, Yoshihisa; Fujii, Yukiko; Haraguchi, Koichi

    2016-01-01

    We analyzed Hg, Cd, Zn, Cu and Fe concentrations in liver samples as well as the Hg concentration and stable isotope ratios of carbon and nitrogen (δ13C and δ15N) in muscle samples from silvertip sharks (Carcharhinus albimarginatus) in Japan. Muscular and hepatic Hg concentrations increased with increased body length. However, these increases were more prominent in the liver than in the muscle samples, and appeared to occur after maturation. Hepatic Zn and Cu concentrations decreased during the growth stage, and then increased concomitantly thereafter with increases in Cd burden. Hepatic Fe concentration from males increased proportionally with increases in body length, whereas no increase was observed in samples from females, probably due to the mother-to-embryo transfer of Fe. The δ13C values tended to decrease with increases in body length, whereas no decrease in the δ15N values was observed.

  18. Metal Concentrations in the Liver and Stable Isotope Ratios of Carbon and Nitrogen in the Muscle of Silvertip Shark (Carcharhinus albimarginatus) Culled off Ishigaki Island, Japan: Changes with Growth

    PubMed Central

    Endo, Tetsuya; Kimura, Osamu; Ohta, Chiho; Koga, Nobuyuki; Kato, Yoshihisa; Fujii, Yukiko; Haraguchi, Koichi

    2016-01-01

    We analyzed Hg, Cd, Zn, Cu and Fe concentrations in liver samples as well as the Hg concentration and stable isotope ratios of carbon and nitrogen (δ13C and δ15N) in muscle samples from silvertip sharks (Carcharhinus albimarginatus) in Japan. Muscular and hepatic Hg concentrations increased with increased body length. However, these increases were more prominent in the liver than in the muscle samples, and appeared to occur after maturation. Hepatic Zn and Cu concentrations decreased during the growth stage, and then increased concomitantly thereafter with increases in Cd burden. Hepatic Fe concentration from males increased proportionally with increases in body length, whereas no increase was observed in samples from females, probably due to the mother-to-embryo transfer of Fe. The δ13C values tended to decrease with increases in body length, whereas no decrease in the δ15N values was observed. PMID:26859569

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

    PubMed Central

    Libby, W. F.

    1971-01-01

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

  20. Symbiodinium Clade Affects Coral Skeletal Isotopic Ratio

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

    The influence of different physiologies of Symbiodinium dinoflagellate symbiont clades on the skeletal chemistry of associated coral hosts has not previously been investigated. This is an important issue because coral skeletons are routinely used for tropical paleoclimatic reconstructions. We analyzed coral skeletal samples collected simultaneously from neighboring colonies off Belize and found that those harboring different clades of Symbiodinium displayed significantly different skeletal oxygen isotopic compositions. We also found evidence for mean shifts in skeletal oxygen isotopic composition after coral bleaching (the loss and potential exchange of symbionts) in two of four longer coral cores from the Mesoamerican Reef, though all experienced similar climatic conditions. Thus, we suggest that symbiont clade identity leaves a signature in the coral skeletal archive and that this influence must be considered for quantitative environmental reconstruction. In addition, we suggest that the skeletal isotopic signature may be used to identify changes in the dominant symbiont clade that have occurred in the past, to identify how common and widespread this phenomenon is--a potential adaptation to climate change.

  1. Isotopic fractionation of alkali earth metals during carbonate precipitation

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  2. Leaf and wood carbon isotope ratios, specific leaf areas and wood growth of Eucalyptus species across a rainfall gradient in Australia.

    PubMed

    Schulze, Ernst-Detlef; Turner, Neil C; Nicolle, Dean; Schumacher, Jens

    2006-04-01

    Leaves and samples of recent wood of Eucalyptus species were collected along a rainfall gradient parallel to the coast of Western Australia between Perth in the north and Walpole in the south and along a southwest to northeast transect from Walpole in southwestern Australia, to near Mount Olga in central Australia. The collection included 65 species of Eucalyptus sampled at 73 sites and many of the species were collected at several sites along the rainfall gradient. Specific leaf area (SLA) and isotopic ratio of 13C to 12C (delta 13C) of leaves that grew in 2002, and tree ring growth and delta 13C of individual cell layers of the wood were measured. Rainfall data were obtained from the Australian Bureau of Meteorology for 29 locations that represented one or a few closely located collection sites. Site-averaged data and species-specific values of delta 13C decreased with decreasing annual rainfall between 1200 and 300 mm at a rate of 1.63 per thousand per 1000 mm decrease in rainfall. Responses became variable in the low rainfall region (< 300 mm), with some species showing decreasing delta 13C with rainfall, whereas delta 13C increased or remained constant in other species. The range of delta 13C values in the low rainfall region was as large as the range observed at sites receiving > 300 mm of annual rainfall. Specific leaf area varied between 2 and 6 m2 kg(-1) and tended to increase with decreasing annual rainfall in some species, but not all, whereas delta 13C decreased with SLA. The relationship between delta 13C and SLA was highly species and soil-type specific. Leaf-area-based nitrogen (N) content varied between 2 and almost 6 g m(-2) and decreased with rainfall. Thus, thicker leaves were associated with higher N content and this compensated for the effect of drought on delta 13C. Nitrogen content was also related to soil type and species identity. Based on a linear mixed model, statistical analysis of the whole data set showed that 27% of the variation in

  3. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

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

    1991-01-01

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

  4. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

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

    1991-12-31

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

  5. Sediment Tracking Using Carbon and Nitrogen Stable Isotopes

    NASA Astrophysics Data System (ADS)

    Fox, J. F.; Papanicolaou, A.

    2002-12-01

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

  6. Characterization of the origin of coalbed gases in southeastern Illinois Basin by compound-specific carbon and hydrogen stable isotope ratios

    USGS Publications Warehouse

    Strapoc, D.; Mastalerz, Maria; Eble, C.; Schimmelmann, A.

    2007-01-01

    Coalbed gases and waters from exploratory and production gas wells in the southeastern Illinois Basin were sampled to assess geochemically the origin of coalbed gases, with an emphasis on the Springfield and Seelyville Coal Members that are commercially targeted for coalbed methane production in Indiana. On-line analyses of hydrocarbon gases methane to butanes (C1, C2, C3, n-C4, i-C4) and CO2 yielded gas concentrations, plus ??D and ??13C values. The low thermal maturity of Indiana coals with vitrinite reflectance R0 ??? 0.6% is in agreement with an overwhelmingly biogenic isotopic signature of coalbed gases containing ???96% methane generated via bacterial CO2-reduction. In contrast, thermogenic gas was generated in the stratigraphically equivalent coal beds in western Kentucky's Rough Creek Graben zone where higher maturities of up to R0 ??? 0.8% were reached owing to tectonic and hydrothermal activity. No secondary biogenic methane was observed in more mature western Kentucky coal beds where greater burial depth limits the recharge of meteoric water. Biogenic and thermogenic coalbed gases represent two end-members that are compositionally and isotopically distinct. Microbial biodegradation of thermogenic C2+ hydrocarbon gases in Indiana coal beds preferentially targets C3 and introduces isotope fractionation whereby remaining C3 is enriched in deuterium and 13C.

  7. Oxygen isotope ratios in eclogites from kimberlites.

    PubMed

    Garlick, G D; Macgregor, I D; Vogel, D E

    1971-06-04

    The oxygen isotope compositions (delta(18)O) of eclogitic xenoliths from the Roberts Victor kimberlite range from 2 to 8 per mil relative to SMOW (standard mean ocean water). This surprising variation appears to be due to fractional crystallization: the eclogites rich in oxygen-18 represent early crystal accumulates; the eclogites poor in oxygen-18 represent residual liquids. Crystal-melt partitioning probably exceeded 3 per mil and is interpreted to be pressure-dependent. Anomalous enrichment of oxygen-18 in cumulate eclogites relative to ultramafic xenoliths suggests that crystal-melt partitioning increased after melt-formation but prior to crystallization.

  8. Methods and limitations of 'clumped' CO2 isotope (Delta47) analysis by gas-source isotope ratio mass spectrometry.

    PubMed

    Huntington, K W; Eiler, J M; Affek, H P; Guo, W; Bonifacie, M; Yeung, L Y; Thiagarajan, N; Passey, B; Tripati, A; Daëron, M; Came, R

    2009-09-01

    The geochemistry of multiply substituted isotopologues ('clumped-isotope' geochemistry) examines the abundances in natural materials of molecules, formula units or moieties that contain more than one rare isotope (e.g. (13)C(18)O(16)O, (18)O(18)O, (15)N(2), (13)C(18)O(16)O(2) (2-)). Such species form the basis of carbonate clumped-isotope thermometry and undergo distinctive fractionations during a variety of natural processes, but initial reports have provided few details of their analysis. In this study, we present detailed data and arguments regarding the theoretical and practical limits of precision, methods of standardization, instrument linearity and related issues for clumped-isotope analysis by dual-inlet gas-source isotope ratio mass spectrometry (IRMS). We demonstrate long-term stability and subtenth per mil precision in 47/44 ratios for counting systems consisting of a Faraday cup registered through a 10(12) ohm resistor on three Thermo-Finnigan 253 IRMS systems. Based on the analyses of heated CO(2) gases, which have a stochastic distribution of isotopes among possible isotopologues, we document and correct for (1) isotopic exchange among analyte CO(2) molecules and (2) subtle nonlinearity in the relationship between actual and measured 47/44 ratios. External precisions of approximately 0.01 per thousand are routinely achieved for measurements of the mass-47 anomaly (a measure mostly of the abundance anomaly of (13)C-(18)O bonds) and follow counting statistics. The present technical limit to precision intrinsic to our methods and instrumentation is approximately 5 parts per million (ppm), whereas precisions of measurements of heterogeneous natural materials are more typically approximately 10 ppm (both 1 s.e.). These correspond to errors in carbonate clumped-isotope thermometry of +/-1.2 degrees C and +/-2.4 degrees C, respectively. 2009 John Wiley & Sons, Ltd.

  9. The carbon and oxygen isotopic composition of meteoritic carbonates

    SciTech Connect

    Grady, M.M.; Wright, I.P.; Swart, P.K.; Pillinger, C.T. )

    1988-12-01

    The {sup 13}C/{sup 12}C and {sup 18}O/{sup 16}O isotopic ratios of carbonates from carbonaceous and ordinary chondrites have been measured on CO{sub 2} released by the action of H{sub 3}PO{sub 4} on whole-rock samples. Carbonates from CI, CM and CR carbonaceous chondrites exhibit a range in {delta}{sup 18}O of ca. 15{per thousand} (+20.5{per thousand} to +35.1{per thousand} relative to SMOW). Limited data from CO{sub 2}-water equilibration experiments suggest that meteoritic carbonates do not possess grossly anomalous {sup 17}O isotopic compositions; therefore, they are truly enriched in {sup 13}C, with {delta}{sup 13}C between +23.7{per thousand} and +80.7{per thousand} relative to PDB. Large internal variations in {delta}{sup 13}C and {delta}{sup 18}O were found in individual meteorites and suggest that two or more isotopically distinct carbonates of different origin may be present. The abundance, {delta}{sup 13}C and {delta}{sup 18}O of carbonate in CM2 chondrites may be related to the extent of aqueous alteration of the meteorites. Carbonates in CI and CR chondrites have a median {delta}{sup 13}C ca. +50 to +60{per thousand}, whereas {delta}{sup 13}C of CM meteorites lie in the range +40 to +50 {per thousand}, although exceptions exist in both sets of samples. CV3 and CO3 carbonaceous chondrites and unequilibrated ordinary chondrites release small amounts of CO{sub 2} on acid treatment, which might be from carbonate dissolution, but which is not enriched in {sup 13}C, exhibiting {delta}{sup 13}C values ca. 0 {plus minus} 10{per thousand}. The exception to this is Bishunpur, with {delta}{sup 13}C ca. {minus}23.5{per thousand}. The difference in {delta}{sup 13}C of the CI, CM and CR vs. CV, CO and ordinary chondrite carbonates may be a result of the progressive enrichment in {sup 13}C of percolating fluids, brought about by increasing solubilization of exotic {sup 13}C-enriched grains.

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

    NASA Astrophysics Data System (ADS)

    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

  11. Isotope engineering of carbon nanotube systems.

    PubMed

    Simon, F; Kramberger, Ch; Pfeiffer, R; Kuzmany, H; Zólyomi, V; Kürti, J; Singer, P M; Alloul, H

    2005-07-01

    The synthesis of a unique isotope engineered system, double-wall carbon nanotubes with natural carbon outer and highly 13C enriched inner walls, is reported from isotope enriched fullerenes encapsulated in single-wall carbon nanotubes (SWCNTs). The material allows the observation of the D line of the highly defect-free inner tubes that can be related to a curvature induced enhancement of the electron-phonon coupling. Ab initio calculations explain the inhomogeneous broadening of inner tube Raman modes due to the distribution of different isotopes. Nuclear magnetic resonance shows a significant contrast of the isotope enriched inner SWCNTs compared to other carbon phases and provides a macroscopic measure of the inner tube mass content. The high curvature of the small diameter inner tubes manifests in an increased distribution of the chemical shift tensor components.

  12. Carbon isotopic fractionation in heterotrophic microbial metabolism

    NASA Technical Reports Server (NTRS)

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

    1985-01-01

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

  13. Carbon isotopic fractionation in heterotrophic microbial metabolism

    SciTech Connect

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

    1985-10-01

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

  14. Carbon isotopic fractionation in heterotrophic microbial metabolism.

    PubMed Central

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

    1985-01-01

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

  15. Carbon isotopic fractionation in heterotrophic microbial metabolism

    NASA Technical Reports Server (NTRS)

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

    1985-01-01

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

  16. Isotope Engineering of Carbon Nanotube Systems

    NASA Astrophysics Data System (ADS)

    Simon, F.; Kramberger, Ch.; Pfeiffer, R.; Kuzmany, H.; Zólyomi, V.; Kürti, J.; Singer, P. M.; Alloul, H.

    2005-06-01

    The synthesis of a unique isotope engineered system, double-wall carbon nanotubes with natural carbon outer and highly 13C enriched inner walls, is reported from isotope enriched fullerenes encapsulated in single-wall carbon nanotubes (SWCNTs). The material allows the observation of the D line of the highly defect-free inner tubes that can be related to a curvature induced enhancement of the electron-phonon coupling. Ab initio calculations explain the inhomogeneous broadening of inner tube Raman modes due to the distribution of different isotopes. Nuclear magnetic resonance shows a significant contrast of the isotope enriched inner SWCNTs compared to other carbon phases and provides a macroscopic measure of the inner tube mass content. The high curvature of the small diameter inner tubes manifests in an increased distribution of the chemical shift tensor components.

  17. Application of Organic Carbon and Nitrogen Stable Isotope and C/N Ratios as Source Indicators of Organic Matter Provenance in Estuarine Systems: Evidence from the Tay Estuary, Scotland

    NASA Astrophysics Data System (ADS)

    Thornton, S. F.; McManus, J.

    1994-03-01

    The source of particulate organic matter (POM) in lacustrine and estuarine sediments from the Tay River catchment has been evaluated using stable carbon and nitrogen isotope and elemental C/N ratios. The δ 13C, δ 15N and C/N compositions of POM from the two environments (respectively -25·4 to -28·0%, 0·2 to 4·0%, 12·17 to 19·5 and -23·2 to -26·6%, 2·6 to 10·6%, 9·03 to 15·71) were statistically distinct, enabling, by use of a simple two component mixing equation, assessment of the ability of each tracer to estimate the terrigenous flux to the estuarine organic matter pool. Estuarial mixing of terrigenous, indigenous estuarine and marine derived organics, recorded by δ 13C data, was only partly confirmed by equivalent δ 15N and C/N compositions which reflected greater control by organic matter diagenesis and biological processing. Limited data indicate sewage derived contributions are insignificant. Of the three tracers employed, only δ 13C ratios are reliable as provenance indicators. Both δ 15N and C/N ratios are limited because the original POM source signature may be lost or overprinted by biochemical alteration prior to and/or soon after deposition. The simultaneous application of these tracers provides substantially more information regarding the source, quality and turnover of sedimentary POM in these contrasting systems than could be achieved using one technique alone.

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

    NASA Astrophysics Data System (ADS)

    Borysiuk, Maciek; 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: 16O, 17O and 18O. We procured samples highly enriched with all three isotopes. Isotopes 16O and 18O were easily detected in the enriched samples, but no significant signal from 17O was detected in the same samples. The measured yield was too low to detect 18O in a sample with natural abundances of oxygen isotopes, at least in the current experimental setup, but the spectral line from the reaction with 16O was clearly visible.

  19. Stable Isotope Ratios as a Biomarker on Mars

    NASA Astrophysics Data System (ADS)

    van Zuilen, Mark

    2008-03-01

    As both Earth and Mars have had similar environmental conditions at least for some extended time early in their history (Jakosky and Phillips in Nature 412:237-244, 2001), the intriguing question arises whether life originated and evolved on Mars as it did on Earth (McKay and Stoker in Rev. Geophys. 27:189-214, 1989). Conceivably, early autotrophic life on Mars, like early life on Earth, used irreversible enzymatically enhanced metabolic processes that would have fractionated stable isotopes of the elements C, N, S, and Fe. Several important assumptions are made when such isotope fractionations are used as a biomarker. The purpose of this article is two-fold: (1) to discuss these assumptions for the case of carbon and to summarize new insights in abiologic reactions, and (2) to discuss the use of other stable isotope systems as a potential biomarker. It is concluded that isotopic biomarker studies on Mars will encounter several important obstacles. In the case of carbon isotopes, the most important obstacle is the absence of a contemporary abiologic carbon reservoir (such as carbonate deposits on Earth) to act as isotopic standard. The presence of a contemporary abiologic sulfate reservoir (evaporite deposits) suggests that sulfur isotopes can be used as a potential biomarker for sulfate-reducing bacteria. The best approach for tracing ancient life on Mars will be to combine several biomarker approaches; to search for complexity, and to combine small-scale isotopic variations with chemical, mineralogical, and morphological observations. An example of such a study can be a layer-specific correlation between δ 13C and δ 34S within an ancient Martian evaporite, which morphologically resembles the typical setting of a shallow marine microbial mat.

  20. Stable Isotope Ratios as a Biomarker on Mars

    NASA Astrophysics Data System (ADS)

    van Zuilen, Mark

    As both Earth and Mars have had similar environmental conditions at least for some extended time early in their history (Jakosky and Phillips in Nature 412:237-244, 2001), the intriguing question arises whether life originated and evolved on Mars as it did on Earth (McKay and Stoker in Rev. Geophys. 27:189-214, 1989). Conceivably, early autotrophic life on Mars, like early life on Earth, used irreversible enzymatically enhanced metabolic processes that would have fractionated stable isotopes of the elements C, N, S, and Fe. Several important assumptions are made when such isotope fractionations are used as a biomarker. The purpose of this article is two-fold: (1) to discuss these assumptions for the case of carbon and to summarize new insights in abiologic reactions, and (2) to discuss the use of other stable isotope systems as a potential biomarker. It is concluded that isotopic biomarker studies on Mars will encounter several important obstacles. In the case of carbon isotopes, the most important obstacle is the absence of a contemporary abiologic carbon reservoir (such as carbonate deposits on Earth) to act as isotopic standard. The presence of a contemporary abiologic sulfate reservoir (evaporite deposits) suggests that sulfur isotopes can be used as a potential biomarker for sulfate-reducing bacteria. The best approach for tracing ancient life on Mars will be to combine several biomarker approaches; to search for complexity, and to combine small-scale isotopic variations with chemical, mineralogical, and morphological observations. An example of such a study can be a layer-specific correlation between δ 13C and δ 34S within an ancient Martian evaporite, which morphologically resembles the typical setting of a shallow marine microbial mat.

  1. Plutonium isotope ratio variations in North America

    SciTech Connect

    Steiner, Robert E; La Mont, Stephen P; Eisele, William F; Fresquez, Philip R; Mc Naughton, Michael; Whicker, Jeffrey J

    2010-12-14

    Historically, approximately 12,000 TBq of plutonium was distributed throughout the global biosphere by thermo nuclear weapons testing. The resultant global plutonium fallout is a complex mixture whose {sup 240}Pu/{sup 239}Pu atom ratio is a function of the design and yield of the devices tested. The average {sup 240}Pu/{sup 239}Pu atom ratio in global fallout is 0.176 + 014. However, the {sup 240}Pu/{sup 239}Pu atom ratio at any location may differ significantly from 0.176. Plutonium has also been released by discharges and accidents associated with the commercial and weapons related nuclear industries. At many locations contributions from this plutonium significantly alters the {sup 240}Pu/{sup 239}Pu atom ratios from those observed in global fallout. We have measured the {sup 240}Pu/{sup 239}Pu atom ratios in environmental samples collected from many locations in North America. This presentation will summarize the analytical results from these measurements. Special emphasis will be placed on interpretation of the significance of the {sup 240}Pu/{sup 239}Pu atom ratios measured in environmental samples collected in the Arctic and in the western portions of the United States.

  2. D/H Isotope Ratio Measurements of Atmospheric Volatile Organic Compounds

    NASA Astrophysics Data System (ADS)

    Meisehen, Thomas; Bühler, Fred; Koppmann, Ralf; Krebsbach, Marc

    2015-04-01

    Analysis of isotope ratios in atmospheric volatile organic compounds (VOC) is a reliable method to allocate their sources, to estimate atmospheric residence times and investigate physical and chemical processes on various temporal and spatial scales. Most investigations yet focus on carbon isotope ratios. Certainly more detailed information can be gained by the ratio of deuterium (D) to hydrogen (H) in VOC, especially due to the high mass ratio. Combining measurements of carbon and hydrogen isotopes could lead to considerable improvement in our understanding of atmospheric processes. For this purpose we set up and thoroughly characterised a gas chromatograph pyrolysis isotope ratio mass spectrometer to measure the D/H ratio in atmospheric VOC. From a custom-made gas standard mixture VOC were adsorbed on Tenax®TA which has the advantage that CO2 is not preconcentrated when measuring ambient air samples. Our results show that the pyrolysis method has significant impact on the D/H ratios. A pyrolysis temperature of at least 1723 K and conditioning of the ceramic tube on a regular basis is essential to obtain reproducible D/H isotope ratios. For an independent comparison D/H ratios of the pure VOC used in the gas standard were determined using elemental analysis by Agroisolab (Jülich, Germany). Comparisons of 10 VOC show perfect agreement within the standard deviations of our measurements and the errors given by Agroisolab, e.g. for n-pentane, toluene, 4-methyl-2-pentanone and n-octane. A slight mean difference of 5.1 o was obtained for n-heptane while significant mean differences of 15.5 o and 20.3 o arose for 1,2,4-trimethylbenzene and isoprene, respectively. We further demonstrate the stability of our system and show that the sample preparation does not affect the isotope ratios. Moreover the applicability of our system to ambient air samples is demonstrated.

  3. Copper and zinc isotope ratios in human bone and enamel.

    PubMed

    Jaouen, Klervia; Herrscher, Estelle; Balter, Vincent

    2017-03-01

    Here, we report Cu and Zn isotope ratios of bones and teeth of French people from various historical periods with the aim to understand how Cu and Zn isotope ratios of bone, a tissue that is continuously remodeled throughout life but that is prone to post-mortem diagenesis, compare with that of tooth enamel, a tissue that forms once during childhood but that is more resistant to diagenesis. Specifically, we examine (1) the potential existence of sex-related differences in the Cu isotope ratios (represented as δ(65) Cu) in the tooth enamel of identified men and women, and (2) a decrease of Zn isotope delta ratios (represented as δ(66) Zn) related to the increase of meat and fish consumption during the 20(th) century. Four series of material were studied: the archeological population of Saint-Laurent de Grenoble (17(th) -18(th) centuries AD), an anatomical collection of skulls (19(th) century AD), a contemporary anatomical collection of bones never buried, and contemporary teeth samples. The metals were purified by liquid chromatography and their isotopic ratios measured by means of multicollector inductively coupled plasma mass spectrometry. We describe a clear offset between bone and tooth enamel for Zn isotope ratios, as previously observed in animals. There is a similar offset for Cu isotope ratios. We did not observe any difference between the δ(65) Cu values of men and women when looking at dental enamel. For the contemporary samples, the δ(66) Zn values of bioapatite decreased, which might be explained by the increase of animal product consumption among the French people during this period, notably when the access to seafood became widespread. Our study demonstrates that the Cu and Zn isotope compositions of dental enamel are promising tools for childhood diet reconstruction. Meanwhile, the Cu isotope ratio of tooth enamel is unlikely to be useful for the identification of biological sex, even in the case of populations with early menarche. Further works

  4. Oxygen isotope fractionation in double carbonates.

    PubMed

    Zheng, Yong-Fei; Böttcher, Michael E

    2016-01-01

    Oxygen isotope fractionations in double carbonates of different crystal structures were calculated by the increment method. Synthesis experiments were performed at 60 °C and 100 °C to determine oxygen and carbon isotope fractionations involving PbMg[CO3]2. The calculations suggest that the double carbonates of calcite structure are systematically enriched in (18)O relative to those of aragonite and mixture structures. Internally consistent oxygen isotope fractionation factors are obtained for these minerals with respect to quartz, calcite and water at a temperature range of 0-1200 °C. The calculated fractionation factors for double carbonate-water systems are generally consistent with the data available from laboratory experiments. The experimentally determined fractionation factors for PbMg[CO3]2, BaMg[CO3]2 and CaMg[CO3]2 against H2O not only fall between fractionation factors involving pure carbonate end-members but are also close to the calculated fractionation factors. In contrast, experimentally determined carbon isotope fractionation factors between PbMg[CO3]2 and CO2 are much closer to theoretical predictions for the cerussite-CO2 system than for the magnesite-CO2 system, similar to the fractionation behavior for BaMg[CO3]2. Therefore, the combined theoretical and experimental results provide insights into the effects of crystal structure and exchange kinetics on oxygen isotope partitioning in double carbonates.

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

    SciTech Connect

    HOLDEN, N.E.

    2005-08-13

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

  6. Chlorine and carbon isotopes fractionation during volatilization and diffusive transport of trichloroethene in the unsaturated zone.

    PubMed

    Jeannottat, Simon; Hunkeler, Daniel

    2012-03-20

    To apply compound-specific isotope methods to the evaluation of the origin and fate of organic contaminants in the unsaturated subsurface, the effect of physicochemical processes on isotope ratios needs to be known. The main objective of this study is to quantify chlorine and carbon isotope fractionation during NAPL-vapor equilibration, air-water partitioning, and diffusion of trichloroethene (TCE) and combinations of these effects during vaporization in porous media. Isotope fractionation is larger during NAPL-vapor equilibration than air-water partitioning. During NAPL-vapor equilibration, carbon, and chlorine isotope ratios evolve in opposite directions although both elements are present in the same bond, with a normal isotope effect for chlorine (ε(Cl) = -0.39 ± 0.03‰) and an inverse effect for carbon (ε(C) = +0.75 ± 0.04‰). During diffusion-controlled vaporization in a sand column, no significant carbon isotope fractionation is observed (ε(C) = +0.10 ± 0.05‰), whereas fairly strong chlorine isotope fractionation occurs (ε(Cl) = -1.39 ± 0.06‰) considering the molecular weight of TCE. In case of carbon, the inverse isotope fractionation associated with NAPL-vapor equilibration and normal diffusion isotope fractionation cancel, whereas for chlorine both processes are accompanied by normal isotope fractionation and hence they cumulate. A source of contamination that aged might thus show a shift toward heavier chlorine isotope ratios.

  7. Stable Isotope Ratios as Biomarkers of Diet for Health Research

    PubMed Central

    O’Brien, Diane M.

    2016-01-01

    Diet is a leading modifiable risk factor for chronic disease, but it remains difficult to measure accurately due to the error and bias inherent in self-reported methods of diet assessment. Consequently there is a pressing need for more objective biomarkers of diet for use in health research. The stable isotope ratios of light elements are a promising set of candidate biomarkers because they vary naturally and reproducibly among foods, and those variations are captured in molecules and tissues with high fidelity. Recent studies have identified valid isotopic measures of short and long-term sugar intake, meat intake, and fish intake in specific populations. These studies provide a strong foundation for validating stable isotopic biomarkers in the general United States population. Approaches to improve specificity for specific foods are needed, for example, by modeling intake using multiple stable isotope ratios, or by isolating and measuring specific molecules linked to foods of interest. PMID:26048703

  8. Stable Isotope Ratios as Biomarkers of Diet for Health Research.

    PubMed

    O'Brien, Diane M

    2015-01-01

    Diet is a leading modifiable risk factor for chronic disease, but it remains difficult to measure accurately due to the error and bias inherent in self-reported methods of diet assessment. Consequently, there is a pressing need for more objective biomarkers of diet for use in health research. The stable isotope ratios of light elements are a promising set of candidate biomarkers because they vary naturally and reproducibly among foods, and those variations are captured in molecules and tissues with high fidelity. Recent studies have identified valid isotopic measures of short- and long-term sugar intake, meat intake, and fish intake in specific populations. These studies provide a strong foundation for validating stable isotopic biomarkers in the general US population. Approaches to improve specificity for specific foods are needed; for example, by modeling intake using multiple stable isotope ratios or by isolating and measuring specific molecules linked to foods of interest.

  9. Exotic Structure of Carbon Isotopes

    NASA Astrophysics Data System (ADS)

    Suzuki, Toshio; Sagawa, Hiroyuki; Hagino, Kouichi

    2003-12-01

    Ground state properties of C isotopes, deformation and elecromagnetic moments, as well as electric dipole transition strength are investigated. We first study the ground state properties of C isotopes using a deformed Hartree-Fock (HF) + BCS model with Skyrme interactions. Isotope dependence of the deformation properties is investigated. Shallow deformation minima are found in several neutron-rich C isotopes. It is also shown that the deformation minima appear in both the oblate and the prolate sides in 17C and 19C having almost the same binding energies. Next, we carry out shell model calculations to study electromagnetic moments and electric dipole transitions of C isotopes. We point out the clear configuration dependence of the quadrupole and magnetic moments in the odd C isotopes, which will be useful to find out the deformation and spin-parities of the ground states of these nuclei. Electric dipole states of C isotopes are studied focusing on the interplay between low energy Pigmy strength and giant dipole resonances. Low peak energies, two-peak structure and large widths of the giant resonances show deformation effects. Calculated transition strength below dipole giant resonance in heavier C isotopes than 15C is found to exhaust 12 ~ 15% of the Thomas-Reiche-Kuhn sum rule value and 50 ~ 80% of the cluster sum rule value.

  10. Geochemistry of organic carbon and nitrogen in surface sediments of coastal Bohai Bay inferred from their ratios and stable isotopic signatures.

    PubMed

    Gao, Xuelu; Yang, Yuwei; Wang, Chuanyuan

    2012-06-01

    Total organic carbon (TOC), total nitrogen (TN) and their δ(13)C and δ(15)N values were determined for 42 surface sediments from coastal Bohai Bay in order to determine the concentration and identify the source of organic matter. The sampling sites covered both the marine region of coastal Bohai Bay and the major rivers it connects with. More abundant TOC and TN in sediments from rivers than from the marine region reflect the situation that most of the terrestrial organic matter is deposited before it meets the sea. The spatial variation in δ(13)C and δ(15)N signatures implies that the input of organic matter from anthropogenic activities has a more significant influence on its distribution than that from natural processes. Taking the area as a whole, surface sediments in the marine region of coastal Bohai Bay are dominated by marine derived organic carbon, which on average accounts for 62±11% of TOC.

  11. High Resolution Double-Focusing Isotope Ratio Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Radke, J.; Deerberg, M.; Hilkert, A.; Schlüter, H.-J.; Schwieters, J.

    2012-04-01

    In recent years isotope ratio mass spectrometry has extended to the capability of quantifying very small isotope signatures related with low abundances and simultaneously detecting molecular masses such as isotopomers and isotopologues containing clumped isotopes. Some of those applications are limited by molecular interferences like different gas molecules with the same nominal mass, e.g. Ar/O2, adducts of the same molecule or of different molecules, and very small isotope abundances. The Thermo Scientific MAT 253 ULTRA is the next generation of high precision gas isotope ratio mass spectrometry, which combines a 10 KV gas ionization source (Thermo Scientific MAT 253) with a double focusing multi-collector mass analyzer (Thermo Scientific Neptune) and reduces those limitations by measuring isotope ratios on a larger dynamic range with high precision. Small ion beam requirements and high sensitivity are achieved by signal-to-noise improvements through enhanced ion beam amplification in faraday cups and ion counters. Interfering backgrounds, e.g. interfering isotopologues or isobaric ions of contaminants, are dramatically decreased by a dynamic range increase combined with high evacuation leading to undisturbed ion transmission through the double-focusing analyser. Furthermore, automated gain calibration for mathematical baseline corrections, switchable detector arrays, ion source control, analyser focusing and full data export is controlled under Isodat data control. New reference/sample strategies are under investigation besides incorporation of the continuous-flow technique and its versatile inlet devices. We are presenting first results and applications of the MAT 253 Ultra.

  12. Stable carbon isotope ratio of tree leaves, boles and fine litter in a tropical forest in Rondônia, Brazil.

    PubMed

    Martinelli, L A; Almeida, S; Brown, I F; Moreira, M Z; Victoria, R L; Sternberg, L S L; Ferreira, C A C; Thomas, W W

    1998-04-01

    Leaves of 208 trees were collected for isotopic analysis together with wood from 36 tree boles and 18 samples of fine litter from a terra-firme forest located at Samuel Ecological Reserve, Rondônia State, in the southwestern Amazon region. The range of δ(13)C values in leaves was from -28 to -36‰, with an average (±1 SD) of -32.1 ± 1.5‰, which was more negative than the δ(13)C values of bole samples (-28.4 ± 2.0‰) and fine litter (-28.7 ± 2.0‰). These values are within the range found for tropical and subtropical forests. Pooling the δ(13)C values for leaf samples from trees of the same height gave averages which were positively correlated with plant height at a highly significant level, with a slope of 0.06 and an intercept of -33.3‰ and a correlation coefficient r (2)=0.70 (P<0.001).

  13. Carbonate clumped isotope thermometry in continental tectonics

    NASA Astrophysics Data System (ADS)

    Huntington, Katharine W.; Lechler, Alex R.

    2015-04-01

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

  14. Radioactive halos and ion microprobe measurement of Pb isotope ratios

    NASA Technical Reports Server (NTRS)

    Gentry, R. V.

    1974-01-01

    This investigation was to obtain, if possible, the Pb isotope ratios of both lunar and meteoritic troilite grains by utilizing ion microprobe techniques. Such direct in situ measurement of Pb isotope ratios would eliminate contamination problems inherent in wet chemistry separation procedures, and conceivably determine whether lunar troilite grains were of meteoritic origin. For comparison purposes two samples of meteoritic troilite were selected (one from Canyon Diablo) for analysis along with two very small lunar troilite grains (approximately 50-100 microns). It was concluded that the ion microprobe as presently operating, does not permit the in situ measurement of Pb isotope ratios in lunar or meteoritic troilite. On the basis of these experiments no conclusions could be drawn as to the origin of the lunar troilite grains.

  15. Calcium isotope ratios in animal and human bone

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-05-01

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

  19. Isotopic ratios at z = 0.68 from molecular absorption lines toward B 0218+357

    NASA Astrophysics Data System (ADS)

    Wallström, S. H. J.; Muller, S.; Guélin, M.

    2016-11-01

    Isotopic ratios of heavy elements are a key signature of the nucleosynthesis processes in stellar interiors. The contribution of successive generations of stars to the metal enrichment of the Universe is imprinted on the evolution of isotopic ratios over time. We investigate the isotopic ratios of carbon, nitrogen, oxygen, and sulfur through millimeter molecular absorption lines arising in the z = 0.68 absorber toward the blazar B 0218+357. We find that these ratios differ from those observed in the Galactic interstellar medium, but are remarkably close to those in the only other source at intermediate redshift for which isotopic ratios have been measured to date, the z = 0.89 absorber in front of PKS 1830-211. The isotopic ratios in these two absorbers should reflect enrichment mostly from massive stars, and they are indeed close to the values observed toward local starburst galaxies. Our measurements set constraints on nucleosynthesis and chemical evolution models. The reduced spectra are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/595/A96

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

    NASA Astrophysics Data System (ADS)

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

    2010-11-01

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