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Sample records for carbon isotope ratios

  1. 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.

  2. 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.

  3. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

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

  5. Combination of carbon isotope ratio with hydrogen isotope ratio determinations in sports drug testing.

    PubMed

    Piper, Thomas; Emery, Caroline; Thomas, Andreas; Saugy, Martial; Thevis, Mario

    2013-06-01

    Carbon isotope ratio (CIR) analysis has been routinely and successfully applied to doping control analysis for many years to uncover the misuse of endogenous steroids such as testosterone. Over the years, several challenges and limitations of this approach became apparent, e.g., the influence of inadequate chromatographic separation on CIR values or the emergence of steroid preparations comprising identical CIRs as endogenous steroids. While the latter has been addressed recently by the implementation of hydrogen isotope ratios (HIR), an improved sample preparation for CIR avoiding co-eluting compounds is presented herein together with newly established reference values of those endogenous steroids being relevant for doping controls. From the fraction of glucuronidated steroids 5β-pregnane-3α,20α-diol, 5α-androst-16-en-3α-ol, 3α-Hydroxy-5β-androstane-11,17-dione, 3α-hydroxy-5α-androstan-17-one (ANDRO), 3α-hydroxy-5β-androstan-17-one (ETIO), 3β-hydroxy-androst-5-en-17-one (DHEA), 5α- and 5β-androstane-3α,17β-diol (5aDIOL and 5bDIOL), 17β-hydroxy-androst-4-en-3-one and 17α-hydroxy-androst-4-en-3-one were included. In addition, sulfate conjugates of ANDRO, ETIO, DHEA, 3β-hydroxy-5α-androstan-17-one plus 17α- and androst-5-ene-3β,17β-diol were considered and analyzed after acidic solvolysis. The results obtained for the reference population encompassing n = 67 males and females confirmed earlier findings regarding factors influencing endogenous CIR. Variations in sample preparation influenced CIR measurements especially for 5aDIOL and 5bDIOL, the most valuable steroidal analytes for the detection of testosterone misuse. Earlier investigations on the HIR of the same reference population enabled the evaluation of combined measurements of CIR and HIR and its usefulness regarding both steroid metabolism studies and doping control analysis. The combination of both stable isotopes would allow for lower reference limits providing the same statistical

  6. Measurement of Absolute Carbon Isotope Ratios: Mechanisms and Implications

    NASA Astrophysics Data System (ADS)

    Vogel, J. S.; Giacomo, J. A.; Dueker, S. R.

    2012-12-01

    An accelerator mass spectrometer (AMS) produced absolute isotope ratio measurements for 14C/13C as tested against >500 samples of NIST SRM-4990-C (OxII 14C standard) to an accuracy of 2.2±0.6‰ over a period of one year with measurements made to 1% counting statistics. The spectrometer is not maximized for 13C/12C, but measured ∂13C to 0.4±0.1‰ accuracy, with known methods for improvement. An AMS produces elemental anions from a sputter ion source and includes a charge-changing collision in a gas cell to isolate the rare 14C from the common isotopes and molecular isobars. Both these physical processes have been modeled to determine the parameters providing such absolute measures. Neutral resonant ionization in a cesium plasma produces mass-independent ionization, while velocity dependent charge-state distributions in gas collisions produce relative ion beam intensities that are linear in mass at specific collision energies. The mechanisms are not specific to carbon isotopes, but stand alone absolute IRMS (AIR-MS) instruments have not yet been made. Aside from the obvious applications in metrology, AIR-MS is particularly valuable in coupled separatory MS because no internal or external standards are required. Sample definition processes can be compared, even if no exact standard reference sample exists. Isotope dilution measurements do not require standards matching the dilution end-points and can be made over an extended, even extrapolated, range.

  7. 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

  8. 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...

  9. 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

  10. 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

  11. 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).

  12. 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

  13. 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.

  14. Equations for lipid normalization of carbon stable isotope ratios in aquatic bird eggs.

    PubMed

    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 (13)C is depleted in lipids. Variation in (13)C 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.

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

    PubMed Central

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

    2014-01-01

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

  16. 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...

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

    PubMed

    Dorn, R I; Deniro, M J

    1985-03-22

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

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

    PubMed

    Dorn, R I; Deniro, M J

    1985-03-22

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

  19. 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

  20. 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...

  1. 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

  2. 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.

  3. 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.

  4. A Test of Carbon and Oxygen Stable Isotope Ratio Process Models in Tree Rings.

    NASA Astrophysics Data System (ADS)

    Roden, J. S.; Farquhar, G. D.

    2008-12-01

    Stable isotopes ratios of carbon and oxygen in tree ring cellulose have been used to infer environmental change. Process-based models have been developed to clarify the potential of historic tree ring records for meaningful paleoclimatic reconstructions. However, isotopic variation can be influenced by multiple environmental factors making simplistic interpretations problematic. Recently, the dual isotope approach, where the variation in one stable isotope ratio (e.g. oxygen) is used to constrain the interpretation of variation in another (e.g. carbon), has been shown to have the potential to de-convolute isotopic analysis. However, this approach requires further testing to determine its applicability for paleo-reconstructions using tree-ring time series. We present a study where the information needed to parameterize mechanistic models for both carbon and oxygen stable isotope ratios were collected in controlled environment chambers for two species (Pinus radiata and Eucalyptus globulus). The seedlings were exposed to treatments designed to modify leaf temperature, transpiration rates, stomatal conductance and photosynthetic capacity. Both species were grown for over 100 days under two humidity regimes that differed by 20%. Stomatal conductance was significantly different between species and for seedlings under drought conditions but not between other treatments or humidity regimes. The treatments produced large differences in transpiration rate and photosynthesis. Treatments that effected photosynthetic rates but not stomatal conductance influenced carbon isotope discrimination more than those that influenced primarily conductance. The various treatments produced a range in oxygen isotope ratios of 7 ‰. Process models predicted greater oxygen isotope enrichment in tree ring cellulose than observed. The oxygen isotope ratios of bulk leaf water were reasonably well predicted by current steady-state models. However, the fractional difference between models that

  5. Stable carbon isotope ratios of ambient secondary organic aerosols in Toronto

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

    A method to quantify concentrations and stable carbon isotope ratios of secondary organic aerosols has been applied to study atmospheric nitrophenols in Toronto, Canada. The sampling of five nitrophenols, all with substantial secondary formation from the photooxidation of aromatic volatile organic compounds (VOCs), was conducted in the gas phase and particulate matter (PM) together and in PM alone. Their concentrations in the atmosphere are in the low ng m-3 range and, consequently, a large volume of air (> 1000 m3) is needed to analyze samples for stable carbon isotope ratios, resulting in sampling periods of typically 24 h. While this extended sampling period increases the representativeness of average values, it at the same time reduces possibilities to identify meteorological conditions or atmospheric pollution levels determining nitrophenol concentrations and isotope ratios. Average measured carbon isotope ratios of the different nitrophenols are between -34 and -33 ‰, which is well within the range predicted by mass balance. However, the observed carbon isotope ratios cover a range of nearly 9 ‰ and approximately 20 % of the isotope ratios of the products have isotope ratios lower than predicted from the kinetic isotope effect of the first step of the reaction mechanism and the isotope ratio of the precursor. This can be explained by isotope fractionation during reaction steps following the initial reaction of the precursor VOCs with the OH radical. Limited evidence for local production of nitrophenols is observed since sampling was done in the Toronto area, an urban center with significant anthropogenic emission sources. Strong evidence for significant local formation of nitrophenols is only found for samples collected in summer. On average, the difference in carbon isotope ratios between nitrophenols in the particle phase and in the gas phase is insignificant, but for a limited number of observations in summer, a substantial difference is observed. This

  6. Stable carbon isotope ratios of ambient secondary organic aerosols in Toronto

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

    A method to quantify concentrations and stable carbon isotope ratios of secondary organic aerosols (SOA) has been applied to study atmospheric nitrophenols in Toronto, Canada. The sampling of five nitrophenols, all primarily formed from the photo-oxidation of aromatic volatile organic compounds (VOC), in the gas phase and particulate matter (PM) together and PM alone was conducted. Since all of the target compounds are secondary products, their concentrations in the atmosphere are in the low ng m-3 range and consequently a large volume of air (> 1000 m3) is needed to analyze samples for stable carbon isotope ratios, resulting in sampling periods of typically 24 h. While this extended sampling period increases the representativeness of average values, it at the same time reduces possibilities to identify meteorological conditions or atmospheric pollution levels determining nitrophenol concentrations and isotope ratios. Average measured carbon isotope ratios of the different nitrophenols are between -34 and -33‰, which is well within the range predicted by mass balance calculations. However, the observed carbon isotope ratios cover a range of nearly 9‰, and approximately 20% of the isotope ratios of the products have isotope ratios lower than predicted from the kinetic isotope effect of the first step of the reaction mechanism and the isotope ratio of the precursor. This can be explained by isotope fractionation during reaction steps following the initial reaction of the precursor VOCs with the OH radical. Limited evidence for local production of nitrophenols is observed since sampling was done in the Toronto area, an urban centre with significant anthropogenic emission sources. Strong evidence for significant local formation of nitrophenols is only found for samples collected in summer. On average, the difference in carbon isotope ratios between nitrophenols in the particle phase and in the gas phase is insignificant, but for a limited number of observations in

  7. 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.

  8. 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.

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

    NASA Astrophysics Data System (ADS)

    Zuiderweg, A. T.

    2012-09-01

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

  10. 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.

  11. 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.

  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.; 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.

  13. Anomalous carbon-isotope ratios in nonvolatile organic material.

    PubMed

    Kaplan, I R; Nissenbaum, A

    1966-08-12

    Organic mats are associated with sulfur deposits in Upper Pleistocene sand ridges of the coastal plain of southern Israel; black, brittle, and non-volatile, they show parallel layering but no other apparent cellular structure. Two independent carbon-14 determinations yielded ages of 27,750+/-500 and 31,370+/-1400 years. Four carbon-13:carbon-12 determinations fell within the range deltaC(13) =-82.5 to -89.3 per mille relative to the PDB standard; these appear to be the lowest values yet reported for naturally occurring high-molecular-weight organic material. The origin of the carbon is probably complex; it must have passed through at least one biologic cycle before final deposition.

  14. 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.

  15. 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

  16. 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. PMID:25244291

  17. 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...

  18. 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 ...

  19. 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...

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  1. 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...

  2. 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...

  3. 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 ...

  4. 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.

  5. 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).

  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. 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.

  8. Carbon isotopic ratios in some low-delta N-15 lunar breccias

    NASA Technical Reports Server (NTRS)

    Becker, R. H.; Epstein, S.

    1982-01-01

    Lunar soil breccias 10018, 79035 and 79135 were analyzed for carbon and nitrogen contents and isotopic compositions by vacuum pyrolysis, with a 500 C pre-combustion step in some cases. The combustion was used to remove carbon of terrestrial origin. Nitrogen isotopic ratios for the breccias are very low and are in agreement with results in the literature. Nitrogen yields in two cases were lower than literature values, a result attributable to heterogeneous mixing of implanted and implantation-free components in the breccias. Carbon isotopic ratios were found to be low in these breccias, even when reasonable account is taken of terrestrial carbon contamination. The results are consistent with the idea that low-delta N-15 values in lunar soils and breccias are accompanied by low-delta C-13 values, and imply that any secular variation which occurred in the delta N-15 of nitrogen implanted in lunar soils was accompanied by a similar but smaller variation in the delta C-13 of implanted carbon.

  9. 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.

  10. Carbon isotope ratios of Phanerozoic marine cements: Re-evaluating the global carbon and sulfur systems

    NASA Astrophysics Data System (ADS)

    Carpenter, Scott J.; Lohmann, Kyger C.

    1997-11-01

    Original δ 13C values of abiotically precipitated marine cements from a variety of stratigraphic intervals have been used to document secular variations in the δ 13C values of Phanerozoic oceans. These, together with the ° 34S values of coeval marine sulfates, are used to examine the global cycling of carbon and sulfur. It is generally accepted that secular variation in δ 13C and δ 34S values of marine carbonates and sulfates is controlled by balanced oxidation-reduction reactions and that their long-term, steady-state variation can be predicted from the present-day isotopic fractionation ratio (Δ c/Δ s) the ratio of the riverine flux of sulfur and carbon ( Fs/ Fc). The predicted slope of the linear relation between δ 13C carb and δ 34S sulfate values is approximately -0.10 to -0.14. However, temporal variation observed in marine cement δ 13C values and the 6345 values of coeval marine sulfates produces a highly significant linear relation ( r2 = 0.80; α > 95%) with a slope of -0.24; approximately twice the predicted value. This discordance suggests that either the Phanerozoic average riverine Fs/ Fc was 1.6-3.3 times greater than today's estimates or that an additional source of 34S-depleted sulfur or 13C-enriched carbon, other than continental reservoirs, was active during the Phanerozoic. This new relation between marine δ 13C and δ 34S values suggests that the flux of reduced sulfur, iron, and manganese from seafloor hydrothermal systems affects oceanic O2 levels which, in turn, control the oxidation or burial of organic matter, and thus the δ 13C value of marine DIC. Therefore, the sulfur system (driven by seafloor hydrothermal systems) controls the carbon system rather than organic carbon burial controlling the response of δ 34S values (via formation of sedimentary pyrite). Secular variation of marine 87Sr/86Sr ratios and δ 13C values argues for a coupling of δ 34S and δ 34S values to variation in the relative contribution of seafloor

  11. 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...

  12. 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.

  13. 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.

  14. 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.

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

    EPA Science Inventory

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

  16. 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.

  17. 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

  18. 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

  19. 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. PMID:23870934

  20. 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.

  1. 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.

  2. 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.

  3. Carbon Stable Isotope Analysis of Methylmercury Toxin in Biological Materials by Gas Chromatography Isotope Ratio Mass Spectrometry.

    PubMed

    Masbou, Jeremy; Point, David; Guillou, Gaël; Sonke, Jeroen E; Lebreton, Benoit; Richard, Pierre

    2015-12-01

    A critical component of the biogeochemical cycle of mercury (Hg) is the transformation of inorganic Hg to neurotoxic monomethylmercury (CH3Hg). Humans are exposed to CH3Hg by consuming marine fish, yet the origin of CH3Hg in fish is a topic of debate. The carbon stable isotopic composition (δ(13)C) embedded in the methyl group of CH3Hg remains unexplored. This new isotopic information at the molecular level is thought to represent a new proxy to trace the carbon source at the origin of CH3Hg. Here, we present a compound-specific stable isotope analysis (CSIA) technique for the determination of the δ(13)C value of CH3Hg in biological samples by gas chromatography combustion isotope ratio mass spectrometry analysis (GC-C-IRMS). The method consists first of calibrating a CH3Hg standard solution for δ(13)C CSIA. This was achieved by comparing three independent approaches consisting of the derivatization and halogenation of the CH3Hg standard solution. The determination of δ(13)C(CH3Hg) values on natural biological samples was performed by combining a CH3Hg selective extraction, purification, and halogenation followed by GC-C-IRMS analysis. Reference δ(13)C values were established for a tuna fish certified material (ERM-CE464) originating from the Adriatic Sea (δ(13)C(CH3Hg) = -22.1 ± 1.5‰, ± 2 SD). This value is similar to the δ(13)C value of marine algal-derived particulate organic carbon (δ(13)CPOC = -21‰).

  4. Carbon Stable Isotope Analysis of Methylmercury Toxin in Biological Materials by Gas Chromatography Isotope Ratio Mass Spectrometry.

    PubMed

    Masbou, Jeremy; Point, David; Guillou, Gaël; Sonke, Jeroen E; Lebreton, Benoit; Richard, Pierre

    2015-12-01

    A critical component of the biogeochemical cycle of mercury (Hg) is the transformation of inorganic Hg to neurotoxic monomethylmercury (CH3Hg). Humans are exposed to CH3Hg by consuming marine fish, yet the origin of CH3Hg in fish is a topic of debate. The carbon stable isotopic composition (δ(13)C) embedded in the methyl group of CH3Hg remains unexplored. This new isotopic information at the molecular level is thought to represent a new proxy to trace the carbon source at the origin of CH3Hg. Here, we present a compound-specific stable isotope analysis (CSIA) technique for the determination of the δ(13)C value of CH3Hg in biological samples by gas chromatography combustion isotope ratio mass spectrometry analysis (GC-C-IRMS). The method consists first of calibrating a CH3Hg standard solution for δ(13)C CSIA. This was achieved by comparing three independent approaches consisting of the derivatization and halogenation of the CH3Hg standard solution. The determination of δ(13)C(CH3Hg) values on natural biological samples was performed by combining a CH3Hg selective extraction, purification, and halogenation followed by GC-C-IRMS analysis. Reference δ(13)C values were established for a tuna fish certified material (ERM-CE464) originating from the Adriatic Sea (δ(13)C(CH3Hg) = -22.1 ± 1.5‰, ± 2 SD). This value is similar to the δ(13)C value of marine algal-derived particulate organic carbon (δ(13)CPOC = -21‰). PMID:26511394

  5. 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

  6. 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. PMID:19856915

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

    PubMed

    Pruell, Richard J; Taplin, Bryan K

    2015-12-30

    Stable carbon and nitrogen isotope ratios were measured in young-of-the-year (YOY) winter flounder, Pseudopleuronectes americanus, collected from several Rhode Island, USA estuarine systems. These included three coastal lagoons, an estuarine river and Narragansett Bay. The δ(13)C trends observed along transects in several systems showed isotopically depleted terrestrial signals in the upper reaches of the estuaries. Significant differences (P<0.05) in δ(15)N were observed among all estuarine systems and these differences correlated (P<0.01) with human population densities in the watersheds. Although Narragansett Bay has a strong north-south gradient in nutrient concentrations this trend was not reflected in flounder δ(15)N. The northernmost station with the highest nutrient concentrations unexpectedly had significantly lower δ(15)N values. Depleted δ(15)N values at this nutrient-rich station may indicate that concentration-dependent fractionation needs to be considered when using nitrogen isotope ratios in biota to monitor anthropogenic nitrogen inputs in systems with high nitrogen loadings. PMID:26541984

  8. 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). PMID:24679745

  9. 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).

  10. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  12. Detecting isotopic ratio outliers

    SciTech Connect

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

    1985-01-01

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

  13. Carbon isotope ratios in crassulacean Acid metabolism plants: seasonal patterns from plants in natural stands.

    PubMed

    Szarek, S R

    1976-09-01

    A year round study of photosynthesis and carbon isotope fractionation was conducted with plants of Opuntia phaeacantha Engelm. and Yucca baccata Torr. occurring in natural stands at elevations of 525, 970, 1450 and 1900 m. Plant water potentials and the daytime pattern of (14)CO(2) photosynthesis were similar for all cacti along the elevational gradient, despite significant differences in temperature regime and soil water status. Carbon isotope ratios of total tissue and soluble extract fractions were relatively constant throughtout the entire year. Additionally, the sigma(13)C values were similar in all plants of the same species along the elevational gradient, i.e. -12.5 +/- 0.86 per thousand for O. phaeacantha and -15.7 +/- 0.95 per thousand for Y. baccata. The results of this study indicate Crassulacean acid metabolism predominates as the major carbon pathway of these plants, which do not facultatively utilize the reductive pentose phosphate cycle of photosynthesis as the primary carboxylation reaction. PMID:16659680

  14. 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

  15. 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.

  16. Carbon isotope evidence implying high O2/CO2 ratios in the Permo-Carboniferous atmosphere

    NASA Astrophysics Data System (ADS)

    Beerling, D. J.; Lake, J. A.; Berner, R. A.; Hickey, L. J.; Taylor, D. W.; Royer, D. L.

    2002-11-01

    Theoretical models predict a marked increase in atmospheric O2 to ∼35% during the Permo-Carboniferous (∼300 Ma) occurring against a low (∼0.03%) CO2 level. An upper O2 value of 35%, however, remains disputed because ignition data indicate that excessive global forest fires would have ensued. This uncertainty limits interpretation of the role played by atmospheric oxygen in Late Paleozoic biotic evolution. Here, we describe new results from laboratory experiments with vascular land plants that establish that a rise in O2 to 35% increases isotopic fractionation (Δ13C) during growth relative to control plants grown at 21% O2. Despite some effect of the background atmospheric CO2 level on the magnitude of the increase, we hypothesize that a substantial Permo-Carboniferous rise in O2 could have imprinted a detectable geochemical signature in the plant fossil record. Over 50 carbon isotope measurements on intact carbon from four fossil plant clades with differing physiological ecologies and ranging in age from Devonian to Cretaceous reveal a substantial Δ13C anomaly (5‰) occurring between 300 and 250 Ma. The timing and direction of the Δ13C excursion is consistent with the effects of a high O2 atmosphere on plants, as predicted from photosynthetic theory and observed in our experiments. Preliminary calibration of the fossil Δ13C record against experimental data yields a predicted O2/CO2 mixing ratio of the ancient atmosphere consistent with that calculated from long-term models of the global carbon and oxygen cycles. We conclude that further work on the effects of O2 in the combustion of plant materials and the spread of wildfire is necessary before existing data can be used to reliably set the upper limit for paleo-O2 levels.

  17. Carbon and chlorine isotope ratios of chlorinated ethenes migrating through a thick unsaturated zone of a sandy aquifer.

    PubMed

    Hunkeler, Daniel; Aravena, Ramon; Shouakar-Stash, Orfan; Weisbrod, Noam; Nasser, Ahmed; Netzer, Lior; Ronen, Daniel

    2011-10-01

    Compound-specific isotope analysis (CSIA) can potentially be used to relate vapor phase contamination by volatile organic compounds (VOCs) to their subsurface sources. This field and modeling study investigated how isotope ratios evolve during migration of gaseous chlorinated ethenes across a 18 m thick unsaturated zone of a sandy coastal plain aquifer. At the site, high concentrations of tetrachloroethene (PCE up to 380 μg/L), trichloroethene (TCE up to 31,600 μg/L), and cis-1,2-dichloroethene (cDCE up to 680 μg/L) were detected in groundwater. Chlorinated ethene concentrations were highest at the water table and steadily decreased upward toward the land surface and downward below the water table. Although isotopologues have different diffusion coefficients, constant carbon and chlorine isotope ratios were observed throughout the unsaturated zone, which corresponded to the isotope ratios measured at the water table. In the saturated zone, TCE became increasingly depleted along a concentration gradient, possibly due to isotope fractionation associated with aqueous phase diffusion. These results indicate that carbon and chlorine isotopes can be used to link vapor phase contamination to their source even if extensive migration of the vapors occurs. However, the numerical model revealed that constant isotope ratios are only expected for systems close to steady state.

  18. 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.

  19. Reconstructing grassland vegetation and paleotemperatures using carbon isotope ratios of bison tooth enamel

    NASA Astrophysics Data System (ADS)

    Hoppe, Kathryn A.; Paytan, Adina; Chamberlain, Page

    2006-08-01

    Carbon isotope ratios (δ13C values) of herbivores reflect the δ13C values of dietary plants, and the δ13C values of grazers (animals that consume >90% grass) reflect the local abundance of C3 versus C4 grasses. Because grassland C3/C4 ratios correlate with climate, the δ13C of fossil grazers may serve as a proxy for reconstructing paleoclimates and paleovegetation patterns. However, the accuracy of environmental reconstructions based on herbivore δ13C values is often uncertain, because the relationship between the δ13C of many animals and the abundance of C4 and C3 grasses has not been precisely quantified. We analyzed the δ13C of tooth enamel carbonate from modern bison (Bison bison bison) from nine localities in the United States. The C4 grass biomass at these sites ranged from <1% to ˜95% of the total grass biomass. The mean δ13C of enamel for each population correlated well with the local abundance of C4 grasses and with variations in mean annual temperatures. The variability of enamel δ13C values did not differ among habitats and was not correlated with the abundance of C4 grasses. These results demonstrate that analyses of the δ13C values of fossil bison can be used as a quantitative proxy for reconstructing grassland C3/C4 ratios and paleotemperatures, and they will serve as a baseline for interpreting the δ13C of fossil bison and other large herbivores in North America.

  20. 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.

  1. Climate and habitat reconstruction using stable carbon and nitrogen isotope ratios of collagen in prehistoric herbivore teeth from Kenya

    NASA Astrophysics Data System (ADS)

    Ambrose, Stanley H.; DeNiro, Michael J.

    1989-05-01

    Stable carbon and nitrogen isotope ratios have been determined for tooth collagen of 27 prehistoric herbivores from a rock shelter in the central Rift Valley of Kenya. Collagen samples whose isotope ratios were not altered by diagenesis were identified using several analytical methods. During the later Holocene, when the climate was as dry or drier than at present, the isotopic compositions of individual animals are similar to those of modern individuals of the same species. During the earlier Holocene, when the climate was wetter than at present, the δ 15N and δ 13C values are lower than those for their modern counterparts. When diagenetic factors can be discounted and adequate modern comparative data are available, stable isotope analysis of herbivore teeth and bones can be used to evaluate prehistoric climate and habitat conditions.

  2. Stable Carbon Isotope Ratios of Specific Products in Secondary Particulate Organic Matter Formed by Photo-Oxidation of Toluene

    NASA Astrophysics Data System (ADS)

    Irei, S.; Rudolph, J.; Huang, L.; Auld, J.; Hastie, D.

    2009-04-01

    Laboratory experiments for stable carbon isotope studies of secondary particulate organic matter (POM) in the gas-phase were conducted. Secondary POM was generated using a 2.5 L flow reactor or an 8 m3 smog chamber. The initial mixing ratio of toluene and the initial toluene/NO ratio were 20 ppmV - 40 ppmV and 4 - 8 for the flow reactor experiments and ~0.5 ppmV and 0.3 - 2 for the smog chamber experiments, respectively. The flow reactor experiments were made without seed particles, while the smog chamber experiments were done with ammonium sulfate seed particles. Using these different experimental set-ups/conditions, POM generated under different extent of toluene consumption was collected on filters for compound-specific stable carbon isotope analysis as well as for the stable carbon isotope analysis of total POM carbon. For the compound specific analysis, the collected filter samples were extracted with acetonitrile, and the extracts were then concentrated under a gentle flow of pure nitrogen gas. The concentrated extracts were derivatized using N, O-bis(trimethylsilyl)trifluoroacetoamide (BSTFA). The derivatives were qualitatively and quantitatively/isotopically analyzed by GC-MS and GC-C-IRMS, respectively. The qualitative analysis by the GC-MS identified 7 nitromonohydroxy/nitrodihydroxy aromatic compounds in the POM extracts. The results from the compound-specific stable carbon analysis show that, for 6 out of the 7 identified products, the isotope ratios were the similar to that of the total POM carbon, which is predictable using the kinetic isotope effect of the initial toluene+OH reaction, the initial isotope ratio of toluene, and fraction of toluene consumed (Irei et al., 2006). In this presentation, comparison of these observations with the reaction mechanisms postulated by others will be discussed. Reference Flow reactor studies for stable carbon isotopic composition of secondary particulate organic matter generated by toluene/OH radical

  3. Stable hydrogen and carbon isotope ratios of methoxyl groups during plant litter degradation.

    PubMed

    Anhäuser, Tobias; Greule, Markus; Zech, Michael; Kalbitz, Karsten; McRoberts, Colin; Keppler, Frank

    2015-01-01

    Stable hydrogen and carbon isotope ratios of methoxyl groups (δ(2)Hmethoxyl and δ(13)Cmethoxyl values, respectively) in plant material have been shown to possess characteristic signatures. These isotopic signatures can be used for a variety of applications such as constraining the geographical origin and authenticity of biomaterials. Recently, it has also been suggested that δ(2)Hmethoxyl values of sedimentary organic matter of geological archives might serve as a palaeoclimate/-hydrology proxy. However, deposited organic matter is subject to both biotic and abiotic degradation processes, and therefore an evaluation of their potential impact on the δ(2)Hmethoxyl and δ(13)Cmethoxyl values would allow more reliable interpretations of both isotopic signatures. Here, we investigated this potential influence by exposing foliar litter of five different tree species (Sycamore maple, Mountain ash, European beech, Norway spruce and Scots pine) to natural degradation. The foliar litter was sampled at nine intervals over a 27-month period, and the bulk methoxyl content as well as the δ(2)Hmethoxyl and δ(13)Cmethoxyl values were measured. At the end of the experiment, a loss of the bulk methoxyl in the range of ∼40-70% was measured. Linear regression analysis showed no dependence of δ(2)Hmethoxyl values with methoxyl content for four out of five foliar litter samples studied (R(2) in the range of 0.03 and 0.36, p > .05). On the contrary, the δ(13)Cmethoxyl values showed significant linear correlations for the great majority of the foliar litter samples (R(2) in the range of 0.51 and 0.73, p < .05). The litter species with the greatest methoxyl loss (Mountain ash, Scots pine and Norway spruce) showed the strongest (13)C enrichment, by up to ∼5‰. Since δ(2)Hmethoxyl shows no systematic overall change during the course of degradation, we propose that there is considerable potential for its use as a palaeoclimate proxy for a wide range of geological

  4. 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.

  5. Iodine-to-calcium ratios in carbonates suggest a primary origin for the Precambrian Lomagundi and Shuram carbon isotope excursions

    NASA Astrophysics Data System (ADS)

    Hardisty, D. S.; Lu, Z.; Planavsky, N. J.; Osburn, M. R.; Bekker, A.; Lyons, T. W.

    2013-12-01

    Systematic increases in iodine-to-calcium ratios (I/Ca) in carbonates from both the Precambrian Lomagundi and Shuram carbonate carbon isotope (δ13Ccarb) excursion intervals suggest primary origins for these events. Iodate (IO3-), the oxidized iodine species, is the exclusive species incorporated into carbonates. The high redox sensitivity of IO3- to deoxygenation requires highly oxidizing fluids for IO3- production, making I/Ca in platform carbonates a simple indicator of the presence of oxidizing fluids in the surface ocean. Similarly, redox sensitivity makes the proxy host susceptible to diagenetic iodine loss during carbonate recrystallization in reducing pore fluids. Recent work has shown carbonates to experience near-complete iodine loss during dolomitization in the Permian, and work from our group evaluating modern and recent carbonates demonstrate the potential for diagenetic iodine loss during carbonate recrystallization. In some cases, however, such as meteoric aragonite-to-calcite transitions, oxidizing pore fluids have the potential to buffer IO3- concentrations, causing negligible alteration to primary I/Ca despite negative shifts in δ13Ccarb. These results highlight that diagenetic alterations to I/Ca and δ13Ccarb need not always be coupled, but importantly, no observed scenario promotes post-depositional addition of iodine to carbonates. This means that, independent of δ13Ccarb, systematic, stratigraphic increases in I/Ca ratios observed in the carbonate record are most easily interpreted as resulting from depositional controls such as surface ocean redox or shifts in the total marine iodine reservoir. From this, increasing I/Ca ratios coincident with rising and falling δ13Ccarb trends for the Paleoproterozic Lomagundi and Neoproterozoic Shuram events, respectively, support suggestions of a primary origin for the δ13Ccarb excursions. Significant increase in I/Ca in dolomites deposited during the Lomagundi excursion, rising from blank values in

  6. 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%.

  7. 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

  8. 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.

  9. 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).

  10. Determination of the geographical origin of green coffee by principal component analysis of carbon, nitrogen and boron stable isotope ratios.

    PubMed

    Serra, Francesca; Guillou, Claude G; Reniero, Fabiano; Ballarin, Luciano; Cantagallo, Maria I; Wieser, Michael; Iyer, Sundaram S; Héberger, Károly; Vanhaecke, Frank

    2005-01-01

    In this study we show that the continental origin of coffee can be inferred on the basis of coupling the isotope ratios of several elements determined in green beans. The combination of the isotopic fingerprints of carbon, nitrogen and boron, used as integrated proxies for environmental conditions and agricultural practices, allows discrimination among the three continental areas producing coffee (Africa, Asia and America). In these continents there are countries producing 'specialty coffees', highly rated on the market that are sometimes mislabeled further on along the export-sale chain or mixed with cheaper coffees produced in other regions. By means of principal component analysis we were successful in identifying the continental origin of 88% of the samples analyzed. An intra-continent discrimination has not been possible at this stage of the study, but is planned in future work. Nonetheless, the approach using stable isotope ratios seems quite promising, and future development of this research is also discussed. PMID:15988730

  11. 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.

  12. Carbon and nitrogen stable isotope ratios in body tissue and mucus of feeding and fasting earthworms (Lumbricus festivus).

    PubMed

    Schmidt, O; Scrimgeour, C M; Curry, J P

    1999-01-01

    We used natural abundance stable isotope techniques to estimate carbon and nitrogen turnover rates in body tissue and mucus of earthworms. Isotope ratios of carbon (delta(13)C) and nitrogen (delta(15)N) were monitored simultaneously in body tissue and mucus for up to 101 days in feeding or fasting Lumbricus festivus kept in an artificial substrate. When the diet of the earthworms was switched from clover (C(3) plant, legume) to maize (C(4), non-legume), the new dietary delta(13)C signature manifested itself much more rapidly in the mucus than in the body tissue of the animals, causing a delta(13)C shift of about 4 per thousand in mucus and 1 per thousand in tissue after 13.5 days. Turnover of earthworm body tissue carbon, unlike that of mucus carbon, was described adequately by an exponential, single-pool model. Nitrogen turnover could not be assessed because the delta(15)N difference between sources was too small. Fasting for 56 days did not result in the expected whole-body (15)N or (13)C enrichment, but it caused a significant decrease in mucus and tissue C:N ratios and in the ratio (mucus C:N ratio):(tissue C:N ratio). We conclude that the separate analysis of body tissue and mucus has great potential for studying the ecophysiology, feeding ecology and role in elemental cycling of earthworms and other invertebrates. PMID:20135155

  13. 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.

  14. Pretreatment technique for siderite removal for organic carbon isotope and C:N ratio analysis in geological samples.

    PubMed

    Larson, Toti E; Heikoop, Jeffrey M; Perkins, George; Chipera, Steve J; Hess, Marcey A

    2008-01-01

    A method for the removal of siderite from geological samples to determine organic carbon isotope compositions using elemental analysis isotope ratio mass spectrometry is presented which includes calculations for % organic carbon in samples that contain diagenetic carbonate. The proposed method employs in situ acidification of geological samples with 6 N HCl and silver capsule sample holders and was tested on modern peach leaf samples (NIST 1547) and ancient lacustrine samples from Valles Caldera, New Mexico. The in situ acidification technique eliminates potential errors associated with the removal of soluble organic material using standard acid decanting techniques and allows for removal of the less soluble siderite, which is not efficiently removed using vapor acidification techniques.

  15. Reconstructing bulk isotope ratios from compound-specific isotope ratios.

    PubMed

    Morrison, Douglas J; Cooper, Karen; Preston, Tom

    2010-06-30

    Carbon isotope analysis by bulk elemental analysis coupled with isotope ratio mass spectrometry has been the mainstay of delta(13)C analyses both at natural abundance and in tracer studies. More recently, compound-specific isotope analysis (CSIA) has become established, whereby organic constituents are separated online by gas or liquid chromatography before oxidation and analysis of CO(2) for constituent delta(13)C. Theoretically, there should be concordance between bulk delta(13)C measurements and carbon-weighted delta(13)C measurements of carbon-containing constituents. To test the concordance between the bulk and CSIA, fish oil was chosen because the majority of carbon in fish oil is in the triacylglycerol form and approximately 95% of this carbon is amenable to CSIA in the form of fatty acids. Bulk isotope analysis was carried out on aliquots of oil extracted from 55 fish samples and delta(13)C values were obtained. Free fatty acids (FFAs) were produced from the oil samples by saponification and derivatised to fatty acid methyl esters (FAMEs) for CSIA by gas chromatography/combustion/isotope ratio mass spectrometry. A known amount of an internal standard (C15:0 FAME) was added to allow analyte quantitation. This internal standard was also isotopically calibrated in both its FFA (delta(13)C = -34.30 per thousand) and FAME (delta(13)C = -34.94 per thousand) form. This allowed reporting of FFA delta(13)C from measured FAME delta(13)C values. The bulk delta(13)C was reconstructed from CSIA data based on each FFA delta(13)C and the relative amount of CO(2) produced by each analyte. The measured bulk mean delta(13)C (SD) was -23.75 per thousand (1.57 per thousand) compared with the reconstructed bulk mean delta(13)C of -23.76 (1.44 per thousand) from CSIA and was not significantly different. Further analysis of the data by the Bland-Altman method did not show particular bias in the data relative to the magnitude of the measurement. Good agreement between the methods

  16. 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.

  17. Wich Parameter of the Carbonate System Influences the Boron Isotopic Composition and the Boron Calcium Ratio in Foraminiferal Tests?

    NASA Astrophysics Data System (ADS)

    Kaczmarek, K.; Nehrke, G.; Horn, I.; Langer, G.; Misra, S.; Bijma, J.

    2013-12-01

    We performed culture experiments with the benthic symbiont bearing foraminifer Amphistegina lessonii in order to determine which parameter of the marine carbonate system influences the boron isotopic composition (δ11B) and the boron calcium ratio (B/Ca) in the test. A. lessonii grew for two months in treatments of culture media with decoupled pH-carbonate chemistry. We measured δ11B and B/Ca simultaneously on single tests using a recently new developed mass spectrometric technique. Our results show a clear pH dependence on δ11B. The B/Ca in the shell show a positive correlation with aqueous B(OH)4-/HCO3-.

  18. 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.

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. 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

  4. Congener-specific carbon isotopic analysis of technical PCB and PCN mixtures using two-dimensional gas chromatography-isotope ratio mass spectrometry.

    PubMed

    Horii, Yuichi; Kannan, Kurunthachalam; Petrick, Gert; Gamo, Toshitaka; Falandysz, Jerzy; Yamashita, Nobuyoshi

    2005-06-01

    Analysis of stable carbon isotope fractionation is a useful method to study the sources and fate of anthropogenic organic contaminants such as polychlorinated biphenyls (PCBs) in the environment. To evaluate the utility of carbon isotopes, determination of isotopic ratios of 13C/12C in source materials, for example, technical PCB preparations, is needed. In this study, we determined delta13C values of 31 chlorobiphenyl (CB) congeners in 18 technical PCB preparations and 15 chloronaphthalene (CN) congeners in 6 polychlorinated naphthalene preparations using two-dimensional gas chromatography-combustion furnace-isotope ratio mass spectrometry (2DGC-C-IRMS). Development of 2DGC-IRMS enabled improved resolution and sensitivity of compound-specific carbon isotope analysis (CSIA) of CB or CN congeners. Delta13C values of PCB congeners ranged from -34.4 (Delors) to -22.0/1000 (Sovol). Analogous PCB preparations with similar chlorine content, but different geographical origin, had different delta13C values. PCB preparations from Eastern European countries--Delors, Sovol, Trichlorodiphenyl, and Chlorofen--had distinct delta13C values. PCB mixtures showed increased 13C depletion with increasing chlorine content. Delta13C values for individual CB congeners varied depending on the degree of chlorination in technical mixtures. Delta13C values of CN congeners in Halowaxes ranged from -26.3 to -21.7/1000 and these values are within the ranges observed for PCBs. This study establishes the range of delta13C values in technical PCB and PCN preparations, which may prove to be useful in the determination of sources of these compounds in the environment. This is the first study to employ 2DGC-IRMS analysis of delta13C values in technical PCB and PCN preparations.

  5. 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.

  6. 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.

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

    PubMed

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

    2008-01-25

    Molecular compositions and compound specific stable carbon isotope ratios of polycyclic aromatic hydrocarbons (PAH) isolated from sediments were used to characterize possible sources of contamination at an urban lake, a harbor, a shipping waterway, and a relatively undisturbed remote lake in the northwest United States. Total PAH concentrations in urban lake sediments ranged from 66.0 to 16,500 microg g(-1) dry wt. with an average of 2600 microg g(-1), which is approximately 50, 100, and 400 times higher on average than PAH in harbor (48 microg g(-1) on average), shipping waterway (26 microg g(-1)), and remote lake (7 microg g(-1)) sediments, respectively. The PAH distribution patterns, methyl phenanthrene/phenanthrene ratios, and a pyrogenic index at the sites suggest a pyrogenic origin for PAHs. Source characterization using principal component analysis and various molecular indices including C2-dibenzothiophenes/C2-phenanthrenes, C3-dibenzothiophenes/C3-phenanthrenes, and C2-chrysenes/C2-phenanthrenes ratios, was able to differentiate PAH deposited in sediments from the four sites. The uniqueness of the source of the sediment PAHs from urban lake was also illustrated by compound specific stable carbon isotope analysis. It was concluded that urban lake sediments are accumulating PAH from sources that are unique from contamination detected at nearby sites in the same watershed. PMID:17950432

  8. 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.

  9. 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. PMID:27045381

  10. 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.

  11. 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.

  12. Modification of a commercial gas chromatography isotope ratio mass spectrometer for on-line carbon isotope dilution: Evaluation of its analytical characteristics for the quantification of organic compounds.

    PubMed

    Alonso Sobrado, Laura; Robledo Fernández, Mario; Cueto Díaz, Sergio; Ruiz Encinar, Jorge; García Alonso, J Ignacio

    2015-11-01

    We describe the instrumental modification of a commercial gas chromatography isotope ratio mass spectrometer (GC-IRMS) and its application for on-line carbon isotope dilution. The main modification consisted in the addition of a constant flow of enriched (13)CO2 diluted in helium after the chromatographic column through the splitter holder located inside the chromatographic oven of the instrument. In addition, and in contrast to the conventional mode of operation of GC-IRMS instruments where the signal at m/z 45 is amplified 100-fold with respect to the signal at m/z 44, the same signal amplification was used in both Faraday cups at m/z 44 and 45. Under these conditions isotope ratio precision for the ratio 44/45 was around 0.05% RSD (n=50). The evaluation of the instrument was performed with mixtures of organic compounds including 11 n-alkanes, 16 PAHs, 12 PCBs and 3 benzothiophenes. It was observed that compounds of very different boiling points could be analysed without discrimination in the injector when a Programmable Temperature Vaporizer (PTV) injector was employed. Moreover, the presence of heteroatoms (Cl or S) in the structure of the organic compounds did not affect their combustion efficiency and therefore the trueness of the results. Quantitative results obtained for all the analytes assayed were excellent in terms of precision (<3% RSD) and accuracy (average relative error≤4%) and what is more important using a single and simple generic internal standard for quantification. PMID:26435309

  13. 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.

  14. Cretaceous shales from the western interior of North America: sulfur/carbon ratios and sulfur-isotope composition.

    USGS Publications Warehouse

    Gautier, D.L.

    1986-01-01

    Sulphur/carbon ratios in cores of selected Cretaceous marine shales average 0.67, a value greater than that observed in recent marine sediments and much higher than global values calculated for the Cretaceous. This may be ascribed to generally low levels of bioturbation and enhanced efficiency of sulphate reduction due to low oxygen levels in Cretaceous seaways. Isotopic compositions of pyrite sulphur vary systematically with level of oxygenation of the depositional environment and therefore with organic carbon abundance and type of organic matter. Samples with >4% organic carbon are extremely depleted in 34S (mean delta 34S -31per mille) and contain hydrogen-rich organic matter. Samples containing <1.5% organic carbon display relatively 'heavy' but wide-ranging delta 34S values (-34.6 to +16.8per mille) and contain hydrogen-poor organic matter. Samples with intermediate amounts of organic carbon have average delta 34S of -25.9per mille and contain both types of organic matter. Relations between the nature of these shales, and their sedimentation rate and depositional environment are discussed.-L.C.H.

  15. 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. PMID:27082523

  16. 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.

  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. Seasonal Variation in the Carbon Isotope Ratio of Ecosystem Respiration in Two Coniferous Forests

    NASA Astrophysics Data System (ADS)

    McDowell, N. G.; Bowling, D.; Schauer, A.; Irvine, J.; Bond, B. J.; Law, B.; Ehleringer, J. R.

    2003-12-01

    We examined weekly variation in the stable carbon isotope signature of ecosystem respiration (δ 13CR) using the Keeling plot approach at two forests in Oregon USA: a wet (>2300 mm annual precipitation) 20-year-old Pseudotsuga menziesii plantation located in the Coast Range near the Pacific Ocean, and a dry ( ˜520 mm annual precipitation) 250-year-old Pinus ponderosa forest located on the eastern slope of the Cascade Mountains. The two forests experience similar regional weather patterns with wet winters and dry summers, but the coastal site has milder temperatures and greater soil and atmospheric water content. Air was sampled on 51 and 42 separate nights at the Pinus and Pseudotsuga forests, respectively, between 2001 and 2002. Both forests exhibited greater intra-annual variation in δ 13CR than has been previously observed in C3 ecosystems (>8.0 ‰ over the year). Mean annual δ 13CR matched that expected based on annual precipitation, averaging -25.4 ‰ at the Pinus forest and -26.2 ‰ at the Pseudotsuga forest. Variability in δ 13CR at both sites was highest during seasons when rainfall was abundant (autumn, winter and spring) and lowest during summer drought. During the period of drought, soil temperature was positively correlated with δ 13CR at both forests. When all seasons were analyzed, δ 13CR was negatively correlated with soil water content at both forests. The Pseudotsuga forest was more strongly coupled to soil and atmospheric water content than the Pinus forest. This difference could be related to availability of a deep water source at the Pinus forest that buffers it from drought effects. δ 13CR at the Pinus forest was significantly but weakly related to canopy conductance suggesting that δ 13CR is coupled to canopy gas exchange. δ 13CR was significantly correlated between the two forests after removal of outliers associated with extreme, site-specific meteorological events (i.e. local freezes), demonstrating that δ 13CR is coupled

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

    NASA Astrophysics Data System (ADS)

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

    2005-12-01

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

  20. 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.

  1. 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.

  2. 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.

  3. Assessing the stable carbon isotopic composition of intercellular CO2 in a CAM plant using gas chromatography-combustion-isotope ratio mass spectrometry.

    PubMed

    Nogués, Salvador; Aranjuelo, Iker; Pardo, Antoni; Azcón-Bieto, Joaquim

    2008-04-01

    Most of the literature focused on internal CO(2) (Ci) determinations in plants has used indirect methods based on gas-exchange estimations. We have developed a new method based on the capture of internal air gas samples and their analysis by gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). This method provided a direct measure of intercellular CO(2) concentrations combined with stable carbon isotopic composition in O. ficus-indica plants. Plants were grown at both ambient and elevated CO(2) concentration. During the day period, when the stomata are closed, the Ci was high and was very (13)C-enriched in both ambient and elevated CO(2)-grown plants, reflecting Rubisco's fractionation (this plant enzyme has been shown to discriminate by 29 per thousand, in vitro, against (13)CO(2)). Other enzyme fractionations involved in C metabolism in plants, such as carbonic anhydrase, could also be playing an important role in the diurnal delta(13)C enrichment of the Ci. During the night, when stomata are open, Ci concentrations were higher in elevated (and the corresponding delta(13)C values were more (13)C-depleted) than in ambient CO(2)-grown plants.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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...

  9. 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.

  10. 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.

  11. 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.

  12. Compound-specific stable carbon isotope ratios of phenols and nitrophenols derivatized with N,O-bis(trimethylsilyl)trifluoroacetamide.

    PubMed

    Irei, Satoshi; Rudolph, Jochen; Huang, Lin

    2013-07-01

    We developed an analytical method for measuring compound-specific stable carbon isotope ratios (δ(13)C) of phenols and nitrophenols in filter samples of particulate organic matter. The method was tested on 13 phenols derivatized with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA), together with four nonphenolic compounds. The data obtained by our method required two specific corrections for the determination of valid δ(13)C values: (1) for nitro compounds, the routine correction with use of m/z 46 for the contribution of (12)C(17)O(16)O molecules) to m/z 45 was modified due to impact of NO2 on the m/z 46 trace, and (2) for the derivatized phenols, measured δ(13)C values were corrected for the shift in δ(13)C due to the addition of carbon atoms from the BSTFA moiety. Analysis of standard-spiked filters showed that overall there was a small compound-dependent bias in the δ(13)C values: the average bias±the standard error of the mean of -0.21±0.1‰ for the standard compounds tested, except 3-methylcatechol, methylhydroquinone, 4-methyl-2-nitrophenol, and 2,6-dimethyl-4-nitrophenol, whereas the average biases±the standard errors of the mean for those were +1.2±0.3‰, +1.2±0.2‰, -1.2±0.2‰, and -1.4±0.5‰, respectively, when the injected mass of a derivatized compound exceeded 15 ngC. In situations where such small biases and uncertainties are acceptable, the method described here could be used to obtain valuable information about δ(13)C values. We also analyzed a real filter sample to demonstrate the practical applicability of the method.

  13. PATTERNS OF NITROGEN AND CARBON STABLE ISOTOPE RATIOS IN MACROFUNGI, PLANTS AND SOILS IN TWO OLD-GROWTH CONIFER FORESTS

    EPA Science Inventory

    Natural abundance stable isotope ratios represent a potentially valuable tool for studying fungal ecology. We measured 15N and 13C in ectomycorrhizal and saprotrophic macrofungi from two old-growth conifer forests, and in plants, woody debris, and soils. Fungi, plants, and so...

  14. 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.

  15. A controlled test of the dual-isotope approach for the interpretation of stable carbon and oxygen isotope ratio variation in tree rings.

    PubMed

    Roden, John S; Farquhar, Graham D

    2012-04-01

    Seedlings of a conifer (Pinus radiata D. Don) and a broad leaf angiosperm (Eucalyptus globulus Labill.) were grown for 100 days in two growth cabinets at 45 or 65% relative humidity. The seedlings were exposed to treatments designed to modify carbon assimilation rates and capacities, stomatal conductance and transpiration to test conceptual models that attempt to clarify the interpretation of carbon isotope discrimination (Δ(13)C) by using oxygen isotope enrichment (Δ(18)O). Differences in relative humidity and within-cabinet treatments (including lower irradiance, lower nitrogen inputs, higher leaf temperature and lower moisture status than control seedlings) produced significant differences in assimilation rates, photosynthetic capacities, stomatal conductance, leaf transpiration rates and leaf evaporative enrichment. The dual-isotope approach accurately interpreted the cause of variation in wood cellulose Δ(13)C for some of the treatments, but not for others. We also tested whether we could use Δ(13)C variation to constrain the interpretation of δ(18)O variation. Carbon isotope discrimination appears to be influenced by transpiration (providing information on leaf evaporative enrichment), but the results did not provide a clear way to interpret such variation. The dual-isotope approach appears to be valid conceptually, but more work is needed to make it operational under different scenarios. PMID:22440882

  16. 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

  17. 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

  18. 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.

    PubMed

    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 T; 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

    2016-04-19

    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 δ(2)H(VSMOW-SLAP) values from -210.8 to +397.0 mUr or ‰, for δ(13)C(VPDB-LSVEC) from -40.81 to +0.49 mUr and for δ(15)N(Air) 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 (2)H-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 δ(2)H 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 (13)C and carbon-bound organic (2)H-enrichments at different molecular sites to provide RMs for potential site-specific isotopic analysis in future studies. PMID:26974360

  19. 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.

  20. 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.

  1. Spatial changes in carbon and nitrogen stable isotope ratios of sludge and associated organisms in a biological sewage treatment system.

    PubMed

    Onodera, Takashi; Kanaya, Gen; Syutsubo, Kazuaki; Miyaoka, Yuma; Hatamoto, Masashi; Yamaguchi, Takashi

    2015-01-01

    Carbon and nitrogen stable isotope ratios (δ¹³C and δ¹⁵N) have been utilized as powerful tools for tracing energy or material flows within food webs in a range of environmental studies. However, the techniques have rarely been applied to the study of biological wastewater treatment technologies. We report on the spatial changes in δ¹³C and δ¹⁵N in sludge and its associated biotic community in a wastewater treatment system. This system consisted of an upflow anaerobic sludge blanket (UASB) and a down-flow hanging sponge (DHS) which is a novel type of trickling filter. The results showed clear spatial changes in the δ¹³C and δ¹⁵N of suspended solids (SS), retained sludge, and macrofauna (oligochaetes and fly larvae) in the system. The δ¹³C and δ¹⁵N was used as a natural tracer to determine the SS dynamic throughout the system. The results imply that SS in the DHS effluent was mainly eluted from the retained sludge in the lower section of the DHS reactor. The δ¹⁵N of the retained sludge in the DHS reactor increased drastically from the inlet towards to the outlet, from -0.7‰ to 10.3‰. This phenomenon may be attributed to nitrogen conversion processes (i.e. nitrification and denitrification). The δ¹⁵N of oligochaetes also increased from the inlet to the outlet, which corresponded well to that of the retained sludge. Thus, the δ¹⁵N of the oligochaetes might simply mirror the δ¹⁵N of the retained sludge. On the other hand, the δ¹³C and δ¹⁵N of sympatric fly larvae differed from those of the oligochaetes sampled, indicating dietary differences between the taxa. Therefore δ¹³C and δ¹⁵N reflected both treatment and dietary characteristics. We concluded that δ¹³C and δ¹⁵N values are potentially useful as alternative indicators for investigating microbial ecosystems and treatment characteristics of biological wastewater treatment systems. PMID:25462745

  2. 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

  3. Carbon isotope techniques

    SciTech Connect

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

    1991-01-01

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

  4. 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

  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. 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.

  7. 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.

  8. 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

  9. Assessing the origins of aliphatic amines in the Murchison meteorite from their compound-specific carbon isotopic ratios and enantiomeric composition

    NASA Astrophysics Data System (ADS)

    Aponte, José C.; Dworkin, Jason P.; Elsila, Jamie E.

    2014-09-01

    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 α-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 structurally 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 δ13C values ranging from +21‰ to +129‰, showing a decrease in 13C 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 linkage

  10. Keeling plots for hummingbirds: a method to estimate carbon isotope ratios of respired CO(2) in small vertebrates.

    PubMed

    Carleton, Scott A; Wolf, Blair O; del Rio, Carlos Martinez

    2004-09-01

    The carbon isotope composition of an animal's breath reveals the composition of the nutrients that it catabolizes for energy. Here we describe the use of Keeling plots, a method widely applied in ecosystem ecology, to measure the delta(13)C of respired CO(2) of small vertebrates. We measured the delta(13)C of Rufous Hummingbirds ( Selasphorus rufus) in the laboratory and of Mourning ( Zenaida macroura) and White-winged ( Z. asiatica) Doves in the field. In the laboratory, when hummingbirds were fed a sucrose based C3 diet, the delta(13)C of respired CO(2) was not significantly different from that of their diet (delta(13)C(C3 diet)). The delta(13)C of respired CO(2) for C3 fasted birds was slightly, albeit significantly, depleted in delta(13)C relative to delta(13)C(C3 diet). Six hours after birds were shifted to a sucrose based C4 diet, the isotopic composition of their breath revealed that birds were catabolizing a mixture of nutrients derived from both the C3 and the C4 diet. In the field, the delta(13)C of respired CO(2) from Mourning and White-winged Doves reflected that of their diets: the CAM saguaro cactus ( Carnegeia gigantea) and C3 seeds, respectively. Keeling plots are an easy, effective and inexpensive method to measure delta(13)C of respired CO(2) in the lab and the field. PMID:15309607

  11. Keeling plots for hummingbirds: a method to estimate carbon isotope ratios of respired CO(2) in small vertebrates.

    PubMed

    Carleton, Scott A; Wolf, Blair O; del Rio, Carlos Martinez

    2004-09-01

    The carbon isotope composition of an animal's breath reveals the composition of the nutrients that it catabolizes for energy. Here we describe the use of Keeling plots, a method widely applied in ecosystem ecology, to measure the delta(13)C of respired CO(2) of small vertebrates. We measured the delta(13)C of Rufous Hummingbirds ( Selasphorus rufus) in the laboratory and of Mourning ( Zenaida macroura) and White-winged ( Z. asiatica) Doves in the field. In the laboratory, when hummingbirds were fed a sucrose based C3 diet, the delta(13)C of respired CO(2) was not significantly different from that of their diet (delta(13)C(C3 diet)). The delta(13)C of respired CO(2) for C3 fasted birds was slightly, albeit significantly, depleted in delta(13)C relative to delta(13)C(C3 diet). Six hours after birds were shifted to a sucrose based C4 diet, the isotopic composition of their breath revealed that birds were catabolizing a mixture of nutrients derived from both the C3 and the C4 diet. In the field, the delta(13)C of respired CO(2) from Mourning and White-winged Doves reflected that of their diets: the CAM saguaro cactus ( Carnegeia gigantea) and C3 seeds, respectively. Keeling plots are an easy, effective and inexpensive method to measure delta(13)C of respired CO(2) in the lab and the field.

  12. Characterizing the Spatial and Temporal Variations in Organic Carbon Abundance and Stable Isotope Ratios in Lake Sediments Containing Evidence of Prehistoric Agriculture

    NASA Astrophysics Data System (ADS)

    Taylor, Z. P.; Finkelstein, D. B.; Horn, S. P.

    2009-12-01

    Intra-basin spatial variability in lake sediments has the potential to limit the utility of interpretations based on the analysis of a single sediment core. We analyzed a network of five sediment cores to assess geochemical and isotopic spatial variability across a lake in southern Costa Rica. Laguna Zoncho (8.813°N, 82.963°W) provides an excellent opportunity to detect spatial variability because it is a small lake (0.75 ha) with a known history of prehistoric maize agriculture in its watershed. During the agricultural period (1770-570 cal BP) at Zoncho, stable carbon isotope values in the five cores average -23 ‰ V-PDB; these values increase to -27 ‰ V-PDB during the subsequent period of forest recovery. In prior work at the lake, this forest recovery was assumed to have been initiated by the Spanish Conquest about AD 1500, but our new findings suggest it may have occurred earlier and have been driven by a different set of circumstances. We attribute the more positive values during the agricultural period to a greater abundance of C4 vegetation in the watershed as the result of agricultural activity that removed native C3 forest vegetation and created fields and disturbed environments that favor C4 plants. Organic carbon contents during the agricultural period average 5 % and increase to an average of 16 % post-Conquest. Molar C/N ratios range from 13 during the agricultural period to 16 after the cessation of agriculture in the watershed. The cores may indicate a non-simultaneous end to agriculture in the watershed. Stable carbon isotope values and organic carbon contents in three of the four cores collected closer to shore contain evidence of an abrupt end of agriculture around 1000 cal. BP. In these cores, stable carbon isotope values indicate a dramatic shift from C4 to C3 inputs and a rapid increase in organic contents. The fourth core shows this shift around 700 cal. BP. The core recovered from the center of the lake records a gradual end to

  13. 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.

  14. The forensic analysis of office paper using carbon isotope ratio mass spectrometry--part 2: method development, validation and sample handling.

    PubMed

    Jones, Kylie; Benson, Sarah; Roux, Claude

    2013-09-10

    This paper describes the development and validation of a method for the analysis of office papers by measuring carbon isotopes using isotope ratio mass spectrometry (IRMS). The method development phase included testing protocols for storage, sample materials, set-up of the analytical run; and examining the effects of other paper examination procedures on IRMS results. A method validation was performed so that the Delta(plus) XP IRMS instrument (Thermo Finnigan, Bremen, Germany) with Flash EA™ 1112 could be used to measure document paper samples for forensic casework. A validation protocol that would meet international standards for laboratory accreditation (international standard ISO 17025) was structured so that the instruments performance characteristics could be observed. All performance characteristics measured were found to be within an acceptable range and an expanded measurement uncertainty for the measurement of carbon isotopes in paper was calculated at 0.26‰, with a coverage factor of 2. This method was utilized in a large-scale study, published as part one of this series, that showed that IRMS of document papers is useful as a chemical comparison technique for 80 gsm white office papers. PMID:23810570

  15. 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.

  16. 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.

  17. 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

  18. 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

  19. 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.

  20. 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.

  1. 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. PMID:26640663

  2. Influence of recent vegetation on labile and recalcitrant carbon soil pools in central Queensland, Australia: evidence from thermal analysis-quadrupole mass spectrometry-isotope ratio mass spectrometry.

    PubMed

    Lopez-Capel, Elisa; Krull, Evelyn S; Bol, Roland; Manning, David A C

    2008-06-01

    The effect of a recent vegetation change (<100 years) from C(4) grassland to C(3) woodland in central Queensland, Australia, on soil organic matter (SOM) composition and SOM dynamics has been investigated using a novel coupled thermogravimetry-differential scanning calorimetry-quadrupole.mass spectrometry-isotope ratio mass spectrometry (TG-DSC-QMS-IRMS) system. TG-DSC-QMS-IRMS distinguishes the C isotope composition of discrete SOM pools, showing changes in labile, recalcitrant and refractory carbon in the bulk soil and particle size fractions which track the vegetation changes. Analysis of evolved gases (by QMS) from thermal decomposition, rather than observed weight loss, proved essential in determining the temperature at which SOM decomposes, because smectite and kaolinite clays contribute to observed weight losses. The delta(13)C analyses of the CO(2) evolved at different temperatures for bulk soil and particle size-separates showed that most of the labile SOM under the more recent woody vegetation was C(3)-derived carbon whereas the delta(13)C values in the recalcitrant SOM showed greater C(4) contributions. This indicated a shift from grass (C(4))- to tree (C(3))-derived carbon in the woodland, which was also supported by the two-phase (13)C enrichment with depth, i.e. C(3) vegetation dominated the top soil (0-10 cm), but the C(4) contribution increased with depth (more gradual). This is perturbed by the inclusion of charcoal from forest fires ((14)C age incursions) and by the deep incorporation of C(3) carbon due to root penetration. PMID:18446757

  3. 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.

  4. 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.

  5. Quantitative Determination of Isotope Ratios from Experimental Isotopic Distributions

    PubMed Central

    Kaur, Parminder; O’Connor, Peter B.

    2008-01-01

    Isotope variability due to natural processes provides important information for studying a variety of complex natural phenomena from the origins of a particular sample to the traces of biochemical reaction mechanisms. These measurements require high-precision determination of isotope ratios of a particular element involved. Isotope Ratio Mass Spectrometers (IRMS) are widely employed tools for such a high-precision analysis, which have some limitations. This work aims at overcoming the limitations inherent to IRMS by estimating the elemental isotopic abundance from the experimental isotopic distribution. In particular, a computational method has been derived which allows the calculation of 13C/12C ratios from the whole isotopic distributions, given certain caveats, and these calculations are applied to several cases to demonstrate their utility. The limitations of the method in terms of the required number of ions and S/N ratio are discussed. For high-precision estimates of the isotope ratios, this method requires very precise measurement of the experimental isotopic distribution abundances, free from any artifacts introduced by noise, sample heterogeneity, or other experimental sources. PMID:17263354

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

    PubMed

    Menichetti, Lorenzo; Houot, Sabine; van Oort, Folkert; Kätterer, Thomas; Christensen, Bent T; Chenu, Claire; Barré, Pierre; Vasilyeva, Nadezda A; Ekblad, Alf

    2015-03-01

    Changes in the (12)C/(13)C ratio (expressed as δ(13)C) of soil organic C (SOC) has been observed over long time scales and with depth in soil profiles. The changes are ascribed to the different reaction kinetics of (12)C and (13)C isotopes and the different isotopic composition of various SOC pool components. However, experimental verification of the subtle isotopic shifts associated with SOC turnover under field conditions is scarce. We determined δ(13)C and SOC in soil sampled during 1929-2009 in the Ap-horizon of five European long-term bare fallow experiments kept without C inputs for 27-80 years and covering a latitudinal range of 11°. The bare fallow soils lost 33-65% of their initial SOC content and showed a mean annual δ(13)C increase of 0.008-0.024‰. The (13)C enrichment could be related empirically to SOC losses by a Rayleigh distillation equation. A more complex mechanistic relationship was also examined. The overall estimate of the fractionation coefficient (ε) was -1.2 ± 0.3‰. This coefficient represents an important input to studies of long-term SOC dynamics in agricultural soils that are based on variations in (13)C natural abundance. The variance of ε may be ascribed to site characteristics not disclosed in our study, but the very similar kinetics measured across our five experimental sites suggest that overall site-specific factors (including climate) had a marginal influence and that it may be possible to isolate a general mechanism causing the enrichment, although pre-fallow land use may have some impact on isotope abundance and fractionation.

  7. Implications of carbon isotope ratios of C27-C33 alkanes and C37 alkenes for the sources of organic matter in the southern ocean surface sediments

    NASA Astrophysics Data System (ADS)

    Ohkouchi, N.; Kawamura, K.; Takemoto, N.; Ikehara, M.; Nakatsuka, T.

    2000-01-01

    Carbon isotopic ratios (δ13C) of C27-C33 n-alkanes and C37 alkenes were measured in the surface sediments from Australian sector of Southern Ocean (47.6°-65.5°S). The δ13C of C31 n-alkane derived from higher plant wax shows little change along the latitude (-28.7±0.6 ‰), whereas δ13C of C37 alkenes derived from haptophyte algae decreases from -24.6±0.7 ‰ at 47.6°S to -32.1±1.2 ‰ at 63.9°S. Relatively heavy δ13C values of C31 n-alkane suggest significant contribution of C4 plant waxes or conifer resin whose δ13C of n-alkanes are significantly heavier than those of C3 plants. The δ13C of total organic carbon exhibits a latitudinal pattern similar to that of C37 alkenes, suggesting that organic carbon in the sediments is primarily of marine origin.

  8. Variable Carbon Isotopes in ALH84001 Carbonates

    NASA Astrophysics Data System (ADS)

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

    2002-12-01

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

  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. PMID:26874765

  10. 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.

  11. 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.

  12. 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

  13. Assessment of the mobility and time of renewal of the densimetric fractions of organic matter in chestnut soils from the ratio of stable carbon isotopes

    NASA Astrophysics Data System (ADS)

    Morgun, E. G.; Boutton, T. V.; Jessip, K. D.

    2010-05-01

    The results of experimental studying of the organic matter status in soils using methods of granulodensimetric fractionation and the geochemistry of the stable carbon and nitrogen isotopes are presented. The organic and organomineral matter in chestnut soils representing a chronoseries—stages of natural changes in the vegetation with different carbon isotope compositions—were investigated. The organomineral fractions and fractions of free organic matter were distinguished, the changes in their proportion due to the changes in the vegetation were analyzed, and the residence time of the carbon in the organic matter of the fractions was assessed.

  14. 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.

  15. 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

  16. 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

  17. Mars Atmospheric Escape Recorded by H, C and O Isotope Ratios in Carbon Dioxide and Water Measured by the Sam Tunable Laser Spectrometer on the Curiosity Rover

    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.; Jones, J. H.; Franz, H.

    2013-01-01

    Stable isotope ratios in C, H, N, O and S are powerful indicators of a wide variety of planetary geophysical processes that can identify origin, transport, temperature history, radiation exposure, atmospheric escape, environmental habitability and biological activity [2]. For Mars, measurements to date have indicated enrichment in all the heavier isotopes consistent with atmospheric escape processes, but with uncertainty too high to tie the results with the more precise isotopic ratios achieved from SNC meteoritic analyses. We will present results to date of H, C and O isotope ratios in CO2 and H2O made to high precision (few per mil) using the Tunable Laser Spectrometer (TLS) that is part of the Sample Analysis at Mars (SAM) instrument suite on MSL s Curiosity Rover.

  18. Ca Isotopic Ratios in Igneous Rocks: Some Preliminary Results

    NASA Astrophysics Data System (ADS)

    Huang, S.; Farkas, J.; Jacobsen, S. B.

    2009-12-01

    Calcium (Ca) is the 5th most abundant element on the Earth, and it is an important geochemical and cosmochemical tracer. It has six isotopes and only H and He have a larger percentage mass difference (Δm/m) between the heaviest and the lightest isotopes. Systematic Ca isotopic studies have mostly focused on low-temperature geochemical processes, and most Ca isotopic analyses have been applied on modern and ancient marine carbonates and sulphates, documenting large and systematic isotopic variations, which were used to infer the chemical evolution of seawater. Detailed work on igneous rocks is very limited. Here we show two examples of how stable Ca isotopic ratios can be a useful geochemical tool in understanding igneous processes. Ca isotopic fractionation between coexisting clinopyroxene and orthopyroxene from mantle peridotites: We report Ca isotopic ratios on co-existing clino- and ortho-pyroxenes from Kilbourne Hole and San Carlos mantle peridotites. The 44Ca/40Ca in orthopyroxenes is ~0.5 per mil heavier than that in co-existing clinopyroxenes. Combined with published Ca isotopic data on low-temperature Ca-bearing minerals (calcite, aragonite and barite), we show that the fractionation of Ca isotopes between Ca-bearing minerals (at both low-temperature and high-temperature) is primarily controlled by the strength of Ca-O bond in the minerals. The mineral with shorter (i.e., stronger) Ca-O bond yields heavier Ca isotopic ratio. Using our measured 44Ca/40Ca in mantle pyroxenes and the relative proportions of major Ca-bearing minerals in the upper mantle, the estimated 44Ca/40Ca of the upper mantle is 1.1 per mil heavier relative to the NIST 915a, ~0.1 to 0.2 per mil higher than basalts. Ca isotopic variation in Hawaiian shield lavas: Large geochemical and isotopic variations have been observed in lavas forming the large tholeiitic shields of Hawaiian volcanoes, with lavas from the surface of the Koolau volcano (Makapuu-stage) defining one compositional and

  19. 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.

  20. Century-long source apportionment of PAHs in Athabasca oil sands region lakes using diagnostic ratios and compound-specific carbon isotope signatures.

    PubMed

    Jautzy, Josué; Ahad, Jason M E; Gobeil, Charles; Savard, Martine M

    2013-06-18

    Evaluating the impact that airborne contamination associated with Athabasca oil sands (AOS) mining operations has on the surrounding boreal forest ecosystem requires a rigorous approach to source discrimination. This study presents a century-long historical record of source apportionment of polycyclic aromatic hydrocarbons (PAHs) in dated sediments from two headwater lakes located approximately 40 and 55 km east from the main area of open pit mining activities. Concentrations of the 16 Environmental Protection Agency (EPA) priority PAHs in addition to retene, dibenzothiophene (DBT), and six alkylated groups were measured, and both PAH molecular diagnostic ratios and carbon isotopic signatures (δ(13)C) of individual PAHs were used to differentiate natural from anthropogenic inputs. Although concentrations of PAHs in these lakes were low and below the Canadian Council of Ministers of the Environment (CCME) guidelines, diagnostic ratios pointed to an increasingly larger input of petroleum-derived (i.e., petrogenic) PAHs over the past 30 years concomitant with δ(13)C values progressively shifting to the value of unprocessed AOS bitumen. This petrogenic source is attributed to the deposition of bitumen in dust particles associated with wind erosion from open pit mines.

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

    PubMed

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

    2010-01-01

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

  2. Advances in laser-based isotope ratio measurements: selected applications

    NASA Astrophysics Data System (ADS)

    Kerstel, E.; Gianfrani, L.

    2008-09-01

    Small molecules exhibit characteristic ro-vibrational transitions in the near- and mid-infrared spectral regions, which are strongly influenced by isotopic substitution. This gift of nature has made it possible to use laser spectroscopy for the accurate analysis of the isotopic composition of gaseous samples. Nowadays, laser spectroscopy is clearly recognized as a valid alternative to isotope ratio mass spectrometry. Laser-based instruments are leaving the research laboratory stage and are being used by a growing number of isotope researchers for significant advances in their own field of research. In this review article, we discuss the current status and new frontiers of research on high-sensitivity and high-precision laser spectroscopy for isotope ratio analyses. Although many of our comments will be generally applicable to laser isotope ratio analyses in molecules of environmental importance, this paper concerns itself primarily with water and carbon dioxide, two molecules that were studied extensively in our respective laboratories. A complete coverage of the field is practically not feasible in the space constraints of this issue, and in any case doomed to fail, considering the large body of work that has appeared ever since the review by Kerstel in 2004 ( Handbook of Stable Isotope Analytical Techniques, Chapt. 34, pp. 759-787).

  3. The role of synoptic, seasonal, and inter-annual climate on the carbon isotope ratio of ecosystem respiration in a semi-arid woodland

    NASA Astrophysics Data System (ADS)

    Shim, J.; Powers, H. H.; Meyer, C.; Pockman, W.; McDowell, N.

    2010-12-01

    The terrestrial carbon cycle is influenced by environmental variability at time scales ranging from synoptic to inter-annual. Here we present five-years of nightly growing season (day 100-300) observations of the carbon isotope ratio of ecosystem respiration (δ 13CR) from a semi-arid, Juniperus monosperma dominated woodland. This ecosystem experienced large environmental changes, including variable frequency and intensity of precipitation-pulses and timing and intensity of droughts and monsoon seasons. Mean δ 13CR was remarkably invariant (-23.57 + 0.4 ‰), with the only exception being particularly enriched δ 13CR in 2006 following a winter with anomalously low snowfall and during other seasonal periods of low soil water content (SWC). δ 13CR was strongly coupled to climate and physiology during the dry pre-monsoon periods (typically May-June), including fast (≤2 days) responses to changes in juniper canopy conductance (Gc) and vapor pressure deficit (VPD) following rain pulses. In contrast, δ 13CR was relatively de-coupled from Gc and environmental drivers during monsoon and post-monsoon periods (July-August and September, respectively). During these latter two seasons, δ 13CR values approached the δ 13C of soil organic matter and response times to VPD and SWC were lagged significantly longer than for pre-monsoon periods (eight days average). Rainfall events caused clear immediate depletions in δ13CR,followed by progressive hourly δ 13CR enrichment. Rates of soil respiration were elevated during wet periods and had values similar to δ 13CR. These results are consistent with the source of ecosystem respiration shifting from autotrophic dominance utilizing recently assimilated C substrates in the pre-monsoon drought to an increasing heterotrophic decomposition of older carbon during the wetter monsoon and post-monsoon periods.

  4. 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. PMID:24874160

  5. 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.

  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. anteiso-Fatty Acids in Brussels Sprouts (Brassica oleracea var. gemmifera L.): Quantities, Enantioselectivities, and Stable Carbon Isotope Ratios.

    PubMed

    Eibler, Dorothee; Seyfried, Carolin; Kaffarnik, Stefanie; Vetter, Walter

    2015-10-14

    anteiso-Fatty acids (aFAs) are a class of branched-chain fatty acids that are characterized by one methyl branch on the antepenultimate carbon of the straight acyl chain. aFAs are mainly produced by bacteria, and sources in vegetables are scarce. This study reports the concentrations of odd-numbered aFAs (a15:0-a21:0) in Brussels sprout buds. Selective enrichment followed by enantioselective gas chromatography with mass spectrometry in the selected ion monitoring mode revealed that both a15:0 and a17:0 were (S)-enantiopure in Brussels sprout samples. δ(13)C values (‰) of a17:0 in Brussels sprouts were comparable with those of palmitic acid, indicating no different source for both fatty acids. PMID:26390192

  8. Orographic and Climatic Influence on Leaf Wax Carbon and Hydrogen Isotopic Ratios: a Field Survey From Northern California

    NASA Astrophysics Data System (ADS)

    Tipple, B. J.; Pagani, M.; Smith, R.; Anders, A.

    2007-12-01

    The primary objective of this research was to empirically ground-truth environmental controls on δD and δ13C values of higher plant n-alkanes, since these higher-plant specific compounds are refractory and commonly preserved in the geologic record they hold great paleoclimatic and paleoenvironmental information. Our approach was to extensively sample leaves and stems of nine species of trees across two Northern California east-west transects twice during the growing season. One hundred and ninety trees from ninety-three sites were collected along with topsoils and surface waters from most localities. Bigleaf Maple ( Acer macrophyllum), California White Oak ( Quercus lobata) and Blue Oak ( Quercus douglasii) n--alkanes δ13C have been analyzed and range from -38.0 to -29.6‰, -35.2 to - 30.4‰ and -34.5 to -30.4‰, respectively. Currently, all tree species show little to no relationship with any physical variable, such as longitude, elevation, tree height, aspect, slope, etc. The large range in tree isotope values suggests these plants are reacting to a yet unknown climatic variable or these species operate within a range of water-use efficiencies. Similarly, soil-extracted n--alkane δ13C values range between -36.5 to -29.2‰ and do not strongly correlate with any physical parameter. Surface water δD and δ18O are highly correlated and similar to the meteoric water line, however, not as robust, soil-extracted n--alkane δD show similar trends. Notably, the apparent enrichment factor between soil lipids and surface waters is not as stable as seen in other localities, varying by over 30‰, illustrating uncertainties in paleo-applications. Interestingly, water δD and δ18O from surface waters varied little between early June and mid-September and demonstrate a roughly -90‰ depletion in deuterium across the two transects. This D-depletion is reflected in the early growing season stem waters with a consistent slope to that of surface waters.

  9. Precise and traceable (13)C/(12)C isotope amount ratios by multicollector ICPMS.

    PubMed

    Santamaria-Fernandez, Rebeca; Carter, David; Hearn, Ruth

    2008-08-01

    A new method for the measurement of SI traceable carbon isotope amount ratios using a multicollector inductively coupled mass spectrometer (MC-ICPMS) is reported for the first time. Carbon (13)C/(12)C isotope amount ratios have been measured for four reference materials with carbon isotope amount ratios ranging from 0.010659 (delta(13)C(VPDB) = -46.6 per thousand) to 0.011601 (delta(13)C(VPDB) = +37 per thousand). Internal normalization by measuring boron (11)B/(10)B isotope amount ratios has been used to correct for the effects of instrumental mass bias. Absolute (13)C/(12)C ratios have been measured and corrected for instrumental mass bias and full uncertainty budgets have been calculated using the Kragten approach. Corrected (13)C/(12)C ratios for NIST RM8545 (Lithium Carbonate LSVEC), NIST RM8573 (L-Glutamic Acid USGS40), NIST RM8542 (IAEA-CH6 Sucrose) and NIST RM8574 (L-Glutamic Acid USGS41) differed from reference values by 0.06-0.20%. Excellent linear correlation (R = 0.9997) was obtained between corrected carbon isotope amount ratios and expected carbon isotope amount ratios of the four chosen NIST RMs. The method has proved to be linear within this range (from (13)C/(12)C = 0.010659 to (13)C/(12)C =0.011601), and therefore, it is suitable for the measurement of carbon isotope amount ratios within the natural range of variation of organic carbon compounds, carbonates, elemental carbon, carbon monoxide, and carbon dioxide. In addition, a CO2 gas sample previously characterized in-house by conventional dual inlet isotope ratio mass spectrometry has been analyzed and excellent agreement has been found between the carbon isotope amount ratio value measured by MC-ICPMS and the IRMS measurements. Absolute values for carbon isotope amount ratios traceable to the SI are given for each NIST RM, and the combined uncertainty budget (including instrumental error and each parameter contributing to Russell expression for mass bias correction) has been found to be < 0

  10. 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.

  11. Investigation of diachronic dietary patterns on the islands of Ibiza and formentera, Spain: Evidence from carbon and nitrogen stable isotope ratio analysis.

    PubMed

    Fuller, Benjamin T; Márquez-Grant, Nicholas; Richards, Michael P

    2010-12-01

    To examine how dietary patterns may have changed in the western Mediterranean through time, stable carbon and nitrogen isotope ratios were measured on extracted bone collagen from fauna (n = 75) and humans (n = 135) spanning four distinct chronological periods: Chalcolithic (c.2100-1600 BC), Punic (6th-2nd/1st century BC), Late Antiquity-Early Byzantine (4th-7th century AD), and Islamic (c.10th-13th century AD) on the islands of Ibiza and Formentera, Spain. The Chalcolithic, Punic, and Late Antiquity-Byzantine societies all showed evidence of a predominately C(3) terrestrial-based diet with a possible input of a small amount of marine and/or C(4) dietary resources. In contrast, the Islamic population on Ibiza had a subsistence strategy that was reliant on a significant amount of C(4) plants and/or animals fed a C(4) diet, likely millet. These results indicate a fairly constant C(3) terrestrial-based diet on the islands of Ibiza and Formentera through time, with a shift to C(4) dietary resources during the Islamic Period. Further research is needed from other Islamic populations in and around the Mediterranean to better understand this unique dietary adaptation. Am J Phys Anthropol 143:512-522, 2010. © 2010 Wiley-Liss, Inc.

  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. 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

  14. 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.

  15. Carbon isotope geochemistry and geobiology

    NASA Technical Reports Server (NTRS)

    Desmarais, D.

    1985-01-01

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

  16. 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

  17. Uranium isotope ratio measurements in field settings

    SciTech Connect

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

    1997-06-01

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

  18. 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.

  19. Lead isotope ratios in urban road runoff.

    PubMed

    Shinya, M; Funasaka, K; Katahira, K; Ishikawa, M; Matsui, S

    2006-01-01

    Lead isotopic analyses of road runoff and airborne particulate matter have been carried out to elucidate sources of lead pollution at urban and suburban sites. While lead is often observed in road runoff in suspended form, suspended particle size had no relation to the lead isotopic distribution, as a result of comparison between runoff samples with total suspended solids and those with minute particles passed through a 75 microm sieve. Lead isotope ratios in airborne particulate matter in urban areas fell within a wider range than those in road runoff. Since there was little difference of the ratios between a heavy traffic-flow site and residential sites, airborne lead derived from vehicle exhaust was found to make little contribution to the contamination of road runoff. On the other hand, the ratios in road runoff at a suburban site showed the same range as those at an urban site. Lead in road runoff was therefore suggested to be produced on site by traffic related substances, such as tire wear, other than vehicle exhaust.

  20. 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.

  1. (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.

  2. Clumped isotopes in soil carbonate

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

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

  3. Implications of the large carbon kinetic isotope effect in the reaction CH4 + Cl for the 13C/12C ratio of stratospheric CH4

    NASA Astrophysics Data System (ADS)

    Bergamaschi, P.; Brühl, C.; Brenninkmeijer, C. A. M.; Saueressig, G.; Crowley, J. N.; Grooß, J. U.; Fischer, H.; Crutzen, P. J.

    Recent investigations of the carbon kinetic isotope effect (KIE) of the reaction CH4 + Cl yielded KIECl = 1.066±0.002 at 297 K (increasing to 1.075±0.005 at 223 K) [Saueressig et al., 1995]. In order to assess the effect of the exceptionally large KIEcl on δ13C of stratospheric CH4 we applied a two-dimensional, time dependent chemical transport model. The model results demonstrate the strong influence of the CH4 + Cl reaction on δ13CH4 in particular in the middle and upper stratosphere, where this reaction contributes several tens of percent to the total CH4 sink. The Cl sink helps to explain the relatively large overall isotope fractionation of 1.010-1.012 observed in the lower stratosphere [Brenninkmeijer et al., 1995; Brenninkmeijer et al., 1996], even though the model results predict a smaller effect than observed.

  4. [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.

  5. 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.

  6. 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.

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

    PubMed

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

    2007-01-01

    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. PMID:17653263

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. Estimating the Isotope Ratio of Ecosystem Respiration Using the Keeling Plot and the Flux Ratio Method

    NASA Astrophysics Data System (ADS)

    Zhang, J.; Griffis, T. J.; Baker, J. M.

    2004-12-01

    Stable carbon isotope analyses have been used in identifying global carbon sources and sinks and in partitioning ecosystem CO2 exchange into component fluxes. The isotope ratio of ecosystem respiration (δ 13Cr) is a critical parameter in applying stable isotope techniques to carbon cycle problems. The commonly used Keeling plot method in estimating δ 13Cr has limitations related to: 1) insufficient range of CO2 mixing ratio; 2) high sensitivity to curve-fitting techniques; and 3) extrapolation of CO2 mixing ratio beyond observations. In this study, the Keeling plot method was examined and compared with the flux ratio approach using continuous measurements of the mixing ratios of 12CO2 and 13CO2 over an extensive corn canopy during the 2003 growing season. The seasonal variation of δ 13Cr estimated from both methods harmonized with the ecosystem phenology. The δ 13Cr started to increase (became more positive) from mid June and peaked in early August, followed by a decrease into October. The Keeling plot method agreed well with the flux ratio method in the seasonal pattern of δ 13Cr, but tended to give lower values (more negative). The discrepancy between the two approaches was significant in July and August (about 5 per mil) and relatively small in June and September (about 1 to 2 per mil). We examined this discrepancy with respect to wind direction/advection and measurement footprints. In addition, our analysis of high-frequency data (every two minutes) using the flux ratio method indicates that δ 13Cr may vary significantly at short time-scales (e.g., hourly), which could have significant implications for flux partitioning studies.

  13. 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.

  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. Deciphering Carbon Isotope Excursions in Separated Biogenic and Diagenetic Carbonates

    NASA Astrophysics Data System (ADS)

    Hermoso, M.; Minoletti, F.; Hesselbo, S.; Jenkyns, H.; Rickaby, R.; Diester-Haass, L.; Delsate, D.

    2008-12-01

    The long-term evolution of the carbon-isotope ratio in the sedimentary archive is classically linked with changes in primary productivity and organic matter burial. There have been sudden and pronounced shifts, so-called Carbon Isotope Excursions (CIEs) in the long-term trends as evidenced by synchronous shifts from various basins. These geochemical perturbations may have various explanations such as changes of the efficiency of the carbon sink; sudden infusion of isotopically-light carbon into the Ocean-Atmosphere system; or advection of 12C-rich source from bottom water in a stratified water column. Beside the record of primary changes in seawater chemistry, a possible diagenetic overprint may also mime such CIEs in the sedimentary record. The aim of this contribution is to illustrate through three critical intervals (the Early Toarcian, the K-P boundary and the Mid-Miocene Montery Event) how the various micron-sized sedimentary particles specifically record these CIEs, which are respectively associated with major paleoceanographical events. New techniques for getting monotaxic calcareous nannofossil assemblages from the sediment (Minoletti et al., accepted) enable the isotopic measurement at various depths within the surface water and from bottom water by analyzing early diagenetic precipitations (rhombs and micarbs). The integration of these high-resolution isotopic signals in terms of amplitudes affords to recognize diagenetic artifacts in some sections displaying coeval decrease in the carbonate content. For both Early Toarcian and K-P events, corroborative records of CIE records in both primary calcite and bottom water carbonate indicate a global C-isotope perturbation of the water column. For the Monterey event, the evolution of calcareous nannoplankton and the foraminifera isotopic records are in overall agreement, but in detail, the coccolith-discoaster and foraminifer ratio in the sediment, related to environmental changes, is likely to produce isotopic

  16. 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

  17. 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.

  18. 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,...

  19. Modelling carbon isotopes of carbonates in cave drip water

    NASA Astrophysics Data System (ADS)

    Fohlmeister, J.; Scholz, D.; Kromer, B.; Mangini, A.

    2011-09-01

    C isotopes in cave drip water are affected by both the C isotope composition of soil air and host rock carbonate. Furthermore, the C isotope composition of cave drip water strongly depends on the calcite dissolution system, i.e., open, closed and intermediate conditions. Here, we present a calcite dissolution model, which calculates the 14C activity and δ 13C value of the dissolved inorganic carbon of the drip water. The model is based on the chemical equations describing calcite dissolution ( H2O+CaCO+CO⇔Ca+2HCO3-). The most important improvement, relative to previous models, is the combination of the open and closed system conditions in order to simulate the C isotope composition during intermediate states of calcite dissolution and the application to carbon isotope measurements on cave drip waters from Grotta di Ernesto, Italy. The major changes in the C isotope composition of the drip water occur in response to variations in the open-closed system ratio. Additionally, the 14C activity and the δ 13C value of the drip water depend on changes in the partial pressure of soil CO 2. Radiocarbon and δ 13C values of the Grotta di Ernesto drip water are well reproduced by the model.

  20. 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.

  1. 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.

  2. ICP-MS for isotope ratio measurement

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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 ...

  3. Influence of the distillation step on the ratios of stable isotopes of ethanol in cherry brandies.

    PubMed

    Baudler, Ron; Adam, Ludwig; Rossmann, Andreas; Versini, Giuseppe; Engel, Karl-Heinz

    2006-02-01

    Isotope ratio mass spectrometry and site-specific natural isotope fractionation-nuclear magnetic resonance were applied to determine the overall carbon isotope ratio (delta13C) and the hydrogen isotope ratios [(D/H)I and (D/H)II] of ethanol, respectively. Ethanol was obtained by distillation of fermented cherry mash from a pot still commonly used in fruit brandy production. Analyses of distillate fractions revealed that the distillation proceeds with a fractionation of ethanol isotopologues. The inverse vapor pressure isotope effect (VPIE) observed for the carbon isotopologues is in accordance with the data reported for distillation of ethanol in spinning band columns. In contrast, the inverse VPIE for hydrogen isotopologues of ethanol observed in spinning band columns could not be confirmed. To investigate whether the observed isotope fractionations might influence the applicability of stable isotope analysis for quality and authenticity assessment of fruit brandies, the collected distillate fractions were recombined to cuts, as is common practice in commercial fruit brandy production. Taking into consideration the limits of repeatability of the method, it could be demonstrated that the isotope fractionations observed do not impair the applicability of stable isotope analysis of the carbon and hydrogen isotopes of ethanol for the authenticity assessment of cherry brandies if the cuts are placed in accordance with common distillers' practice.

  4. Rapid exchange effects on isotope ratios in groundwater systems: 2. Flow investigation using Sr isotope ratios

    NASA Astrophysics Data System (ADS)

    Johnson, Thomas M.; Depaolo, Donald J.

    1997-01-01

    Sr isotope ratios were measured in groundwater, whole rock digestions, and cation exchange extracts from a clay-rich groundwater system at Ernest O. Lawrence Berkeley National Laboratory and were used to constrain flow velocities and search for preferential flow paths. In the Orinda formation siltstone, 87Sr/86Sr increases strongly over tens of meters along presumed flow paths, indicating slow groundwater flow. Dissolved Sr is close to isotopic equilibrium with the exchangeable Sr in the clays, and the observed 87Sr/86Sr increase is interpreted as a cation exchange front moving slowly through the unit combined with dissolution of minerals with relatively high 87Sr/86Sr ratios. The data are inverted using a one-dimensional transport-dissolution-exchange model; the results indicate long-term average flow velocities of less than 0.2 m/yr which are consistent with 14C measurements. The data suggest a lack of strong preferential flow paths through this unit.

  5. Carbon Isotope Chemistry in Molecular Clouds

    NASA Technical Reports Server (NTRS)

    Robertson, Amy N.; Willacy, Karen

    2012-01-01

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

  6. 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.

  7. Stable isotope ratios of rain and vapor in 1995 hurricanes

    NASA Astrophysics Data System (ADS)

    Lawrence, James Robert; Gedzelman, Stanley David; Zhang, Xiaoping; Arnold, Robert

    1998-05-01

    Isotope ratios of rain and vapor samples collected at the surface from four tropical cyclones during the active 1995 Atlantic hurricane season were determined. A two-dimensional bulk microphysics isotope model was applied to steady symmetric tropical cyclones to explain the observed low mean values and inward decrease of isotope ratios of the rain and vapor. The low mean value is caused by the tropical cyclone's relatively large size, longevity, and deep clouds. The inward decrease is due to diffusive isotope exchange between falling rain and converging vapor in the atmospheric boundary layer. Dean, a minimal tropical storm, produced relatively high isotope ratios because of its small size and youth. Rains from the extreme outer edge of Felix, a category 3 hurricane, exhibited high isotope ratios similar to normal summer rain. Isotope ratios of rains and vapors from Hurricane Luis in Puerto Rico decreased as the storm approached. Isotope ratios of rain exhibited an abrupt jump from low values in the eastern half of Puerto Rico to high values farther west which is linked to the storm's rainbands. Isotope ratios of Hurricane Opal's rains reflected the storm's asymmetric structure, with lowest values west of the point of landfall. Record low isotope ratios from a squall line that struck eastern Texas two days before landfall are linked to low-level outflow from Opal and demonstrate that hurricanes can vent enormous quantities of vapor to the surroundings.

  8. Linking carbon isotopes and carbon-water exchange of plants across different scales

    NASA Astrophysics Data System (ADS)

    Seibt, U.; Rajabi, A.; Griffiths, H.; Berry, J.

    2007-12-01

    The anthropogenic rise in atmospheric CO2 levels may lead to increased photosynthetic uptake while transpiration rates remain constant or are reduced. Changes in plant regulation of carbon uptake and water loss also affect the carbon isotope signatures of plant material. But environmental conditions may change in addition to CO2. The resulting combination of factors can have different effects on the carbon-water balance of plants, and their carbon isotope signatures. For example, changes in evaporative demand alter the ratio of total carbon gain to water loss of a plant, the parameter of interest from the point of view of the atmosphere. Isotope values, on the other hand, also reflect physiological properties, including C:N allocation to carboxylation and internal conductance. Here, we explore how these factors shape carbon isotope signatures as well as carbon and water fluxes from leaf to ecosystem levels, and across diurnal to decadal timescales. We present new data to illustrate that a correlation between carbon isotope signatures and carbon-water exchange at the leaf level may not be passed on to the whole plant level. We then use a simple coupled model to analyse the relationships between carbon-water fluxes and isotope values. The model calculates gas exchange and carbon isotope signatures at the leaf level (for comparison with leaf samples), and propagates both gas exchange and isotope values to long- term trends in carbon-water exchange and carbon isotope signatures at the canopy scale (for comparison with samples of annual resolution). This approach is useful for exploring the sensitivity of carbon isotope ratios and carbon-water exchange of plants to simultaneous changes in external and internal factors, for example when interpreting trends in carbon isotope signatures obtained from tree rings.

  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. Latitudinal distribution of terrestrial lipid biomarkers and n-alkane compound-specific stable carbon isotope ratios in the atmosphere over the western Pacific and Southern Ocean

    NASA Astrophysics Data System (ADS)

    Bendle, James; Kawamura, Kimitaka; Yamazaki, Koji; Niwai, Takeji

    2007-12-01

    We investigated the latitudinal changes in atmospheric transport of organic matter to the western Pacific and Southern Ocean (27.58°N-64.70°S). Molecular distributions of lipid compound classes (homologous series of C 15 to C 35n-alkanes, C 8 to C 34n-alkanoic acids, C 12 to C 30n-alkanols) and compound-specific stable isotopes (δ 13C of C 29 and C 31n-alkanes) were measured in marine aerosol filter samples collected during a cruise by the R/V Hakuho Maru. The geographical source areas for each sample were estimated from air-mass back-trajectory computations. Concentrations of TC and lipid compound classes were several orders of magnitude lower than observations from urban sites in Asia. A stronger signature of terrestrial higher plant inputs was apparent in three samples collected under conditions of strong terrestrial winds. Unresolved complex mixtures (UCM) showed increasing values in the North Pacific, highlighting the influence of the plume of polluted air exported from East Asia. n-Alkane average chain length (ACL) distribution had two clusters, with samples showing a relation to latitude between 28°N and 47°S (highest ACL values in the tropics), whilst a subset of southern samples had anomalously high ACL values. Compound-specific carbon isotopic analysis of the C 29 (-25.6‰ to -34.5‰) and C 31n-alkanes (-28.3‰ to -37‰) revealed heavier δ 13C values in the northern latitudes with a transition to lighter values in the Southern Ocean. By comparing the isotopic measurements with back-trajectory analysis it was generally possible to discriminate between different source areas. The terrestrial vegetation source for a subset of the southernmost Southern Ocean is enigmatic; the back-trajectories indicate eastern Antarctica as the only intercepted terrestrial source area. These samples may represent a southern hemisphere background of well mixed and very long range transported higher plant organic material.

  11. The forensic analysis of office paper using carbon isotope ratio mass spectrometry--part 1: understanding the background population and homogeneity of paper for the comparison and discrimination of samples.

    PubMed

    Jones, Kylie; Benson, Sarah; Roux, Claude

    2013-09-10

    Isotope Ratio Mass Spectrometry (IRMS) has been shown to be a useful tool in the comparison of materials that are chemically identical either through man-made production processes or for materials that have been naturally produced. Paper therefore, is an ideal material for this type of measurement given that it is manufactured from a naturally produced product that can be difficult to discriminate based on physical feature comparison alone. To determine whether carbon isotopes are useful for discriminating document papers, 125 samples from Australia and New Zealand were collected over a 24-month period. When measured, a range of 8‰ was observed. A homogeneity study was undertaken to examine the range of values expected from paper sources including single sheets, single reams and multiple reams from the same brand. These results can also be used to suggest how best to sample from these different sources. After characterizing the natural variation of the material, a range of 1‰ was defined for use as a benchmark for discrimination. Utilizing this threshold, 68% of the 125 collected samples (when paired against each other) could be discriminated using the carbon isotope abundances alone. Additionally, correlation was observed when measured values were plotted against their production region of origin.

  12. 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

  13. Carbonate Ion Effects on Coccolith Carbon and Oxygen Isotopes

    NASA Astrophysics Data System (ADS)

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

    2006-12-01

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

  14. 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.

  15. 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.

  16. Global simulation of the carbon isotope exchange of terrestrial ecosystems

    NASA Astrophysics Data System (ADS)

    Ito, A.; Terao, Y.; Mukai, H.

    2009-12-01

    There remain large uncertainties in our quantification of global carbon cycle, which has close interactions with the climate system and is subject to human-induced global environmental change. Information on carbon isotopes is expected to reduce the uncertainty by providing additional constraints on net atmosphere-ecosystem exchange. This study attempted to simulate the dynamics of carbon isotopes at the global scale, using a process-based terrestrial ecosystem model: Vegetation Integrative SImulator for Trace gases (VISIT). The base-model of carbon cycle (Sim-CYCLE, Ito 2003) has already considered stable carbon isotope composition (13C/12C), and here radioactive carbon isotope (14C) was included. The isotope ratios characterize various aspects of terrestrial carbon cycle, which is difficult to be constrained by sole mass balance. For example, isotopic discrimination by photosynthetic assimilation is closely related with leaf stomatal conductance and composition of C3 and C4 plant in grasslands. Isotopic disequilibrium represents mean residence time of terrestrial carbon pools. In this study, global simulations (spatial resolution 0.5-deg, time-step 1-month) were conducted during the period 1901 to 2100 on the basis of observed and projected atmospheric CO2, climate, and land-use conditions. As anthropogenic CO2 accumulates in the atmosphere, heavier stable carbon isotope (13C) was diluted, while radioactive carbon isotope (14C) is strongly affected by atomic bomb experiments mainly in the 1950s and 1960s. The model simulated the decadal change in carbon isotope compositions. Leaf carbon with shorter mean residence time responded rapidly to the atmospheric change, while plant stems and soil humus showed substantial time-lag, leading to large isotopic disequilibrium. In the future, the isotopic disequilibrium was estimated to augment, due to accelerated rate of anthropogenic CO2 accumulation. Spatial distribution of stable isotope composition (12C/13C, or d13C) was

  17. 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.

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

    SciTech Connect

    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).

  19. 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

  20. 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

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

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

  2. 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.

  3. GUM Analysis for TIMS and SIMS Isotopic Ratios in Graphite

    SciTech Connect

    Heasler, Patrick G.; Gerlach, David C.; Cliff, John B.; Petersen, Steven L.

    2007-04-01

    This report describes GUM calculations for TIMS and SIMS isotopic ratio measurements of reactor graphite samples. These isotopic ratios are used to estimate reactor burn-up, and currently consist of various ratios of U, Pu, and Boron impurities in the graphite samples. The GUM calculation is a propagation of error methodology that assigns uncertainties (in the form of standard error and confidence bound) to the final estimates.

  4. 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.

  5. 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).

  6. 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

  7. 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. PMID:26859569

  8. 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.

  9. 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.

  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. Carbon isotope effects associated with aceticlastic methanogenesis.

    PubMed

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

    1994-02-01

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

  12. 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.

  13. Oxygen isotope ratios in eclogites from kimberlites.

    PubMed

    Garlick, G D; Macgregor, I D; Vogel, D E

    1971-06-01

    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.

  14. Oxygen isotope ratios in eclogites from kimberlites.

    PubMed

    Garlick, G D; Macgregor, I D; Vogel, D E

    1971-06-01

    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. PMID:17798552

  15. Direct path integral estimators for isotope fractionation ratios

    SciTech Connect

    Cheng, Bingqing; Ceriotti, Michele

    2014-12-28

    Fractionation of isotopes among distinct molecules or phases is a quantum effect which is often exploited to obtain insights on reaction mechanisms, biochemical, geochemical, and atmospheric phenomena. Accurate evaluation of isotope ratios in atomistic simulations is challenging, because one needs to perform a thermodynamic integration with respect to the isotope mass, along with time-consuming path integral calculations. By re-formulating the problem as a particle exchange in the ring polymer partition function, we derive new estimators giving direct access to the differential partitioning of isotopes, which can simplify the calculations by avoiding thermodynamic integration. We demonstrate the efficiency of these estimators by applying them to investigate the isotope fractionation ratios in the gas-phase Zundel cation, and in a few simple hydrocarbons.

  16. 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.

  17. 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.

  18. 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.

  19. Recent developments in the use of isotope ratio mass spectrometry in sports drug testing.

    PubMed

    Piper, Thomas; Emery, Caroline; Saugy, Martial

    2011-08-01

    According to the annual report of the World Anti-Doping Agency, steroids are the most frequently detected class of doping agents. Detecting the misuse of endogenously occurring steroids, i.e. steroids such as testosterone that are produced naturally by humans, is one of the most challenging issues in doping control analysis. The established thresholds for urinary concentrations or concentration ratios such as the testosterone/epitestosterone quotient are sometimes inconclusive owing to the large biological variation in these parameters.For more than 15 years, doping control laboratories focused on the carbon isotope ratios of endogenous steroids to distinguish between naturally elevated steroid profile parameters and illicit administration of steroids. A variety of different methods has been developed throughout the last decade and the number of different steroids under investigation by isotope ratio mass spectrometry has recently grown considerably. Besides norandrosterone, boldenone was found to occur endogenously in rare cases and the misuse of corticosteroids or epitestosterone can now be detected with the aid of carbon isotope ratios as well. In addition, steroids excreted as sulfoconjugates were investigated, and the first results regarding hydrogen isotope ratios recently became available.All of these will be presented in detail within this review together with some considerations on validation issues and on identification of parameters influencing steroidal isotope ratios in urine.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. High Resolution Carbon and Oxygen Isotope Measurements of Laminations in Pedogenic Carbonate

    NASA Astrophysics Data System (ADS)

    Breecker, D.; Sharp, Z.

    2005-12-01

    Stable carbon and oxygen isotope ratios in pedogenic carbonate from buried soils provide a proxy for low-resolution Quaternary climate and environmental conditions. Samples of carbonate are taken from clast rinds, nodules or filaments in calcic soils. Most clast rinds exhibit micro-laminations that may preserve isotopic ratios of formation. The techniques typically utilized to sample pedogenic carbonate, however, are too coarse to sample individual laminations and likely result in time averages and therefore limit temporal resolution. We investigated the heterogeneity of both carbon and oxygen isotopes ratios in clast rinds at a 100 μm scale using a rapid CO2 laser extraction technique (Sharp and Cerling, 1996). A single 20 msec burst at low power releases CO2 from polished carbonate slabs and the CO2 is then analyzed using continuous flow GC-IRMS. Analyses take less than 5 minutes with a reproducibility of better than ±0.3‰ (δ13C) and ±0.4‰ (δ18O). We have made a two dimensional map of a thick carbonate rind on a limestone clast from a stage V soil to explore the potential for preservation of isotopic ratios in well developed soils and plan to analyze additional rinds from less well developed calcic horizons for comparison. The isotopic map reveals heterogeneities in δ13C of up to 4‰ at a sub-millimeter scale, possibly corresponding to 30% changes in the fraction of C4 plants. Also imaged are abrupt changes in δ13C of approximately 2‰ across sub-100 μm scale boundaries. One well-defined carbon isotope boundary is sub parallel to, but crosses, the lamination boundaries. Oxygen isotope compositions do not change systematically across the same boundary and generally appear more random. These observations are most easily explained by alteration of initial isotopic compositions. Alteration may preferentially affect oxygen isotope ratios leaving carbon isotope distributions relatively intact. It is also possible that both carbon and oxygen isotopes

  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. 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.

  7. 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. 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. 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

  10. 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.

  11. Carbon isotope ratios of soil respiration from soil CO2 profiles and surface chamber measurements using a tunable diode laser spectrometer

    NASA Astrophysics Data System (ADS)

    Moyes, A. B.; Schaeffer, S. M.; Schauer, A.; Bowling, D. R.

    2007-12-01

    A method was developed to measure δ13C of soil CO2 from soil gas samples injected directly into the sample air stream of a tunable diode laser (TDL) spectrometer. Measurement precision was ±0.2‰, and each measurement required two minutes. An open chamber design was also evaluated for use with the TDL. Comparison of Keeling plot intercepts from CO2 profiles generated in a laboratory soil medium and δ13C of surface fluxes showed a 4.4‰ diffusive enrichment, as predicted by theory. Surface CO2 flux rates were measured accurately by the TDL, but the precision of chamber isotope measurements with the TDL was lower than would be predicted from instrument uncertainty (RMS error >0.4‰). This may be due to small pressure fluctuations caused by flow through the chamber or variations in background air. Soil respiration δ13C signatures were calculated from soil CO2 profiles from garden plots with and without (trenched) tree (boxelder, Acer negundo) roots for a growing season. Respiration in plots containing roots was 2‰ enriched relative to trenched plots during the active leaf period of the deciduous trees. This trend was contrary to expectations and potentially caused by enriched respiration from roots, or a priming effect from root exudates, resulting in increased decomposition of enriched soil organic matter.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. Detection of adulterated honey produced by honeybee (Apis mellifera L.) colonies fed with different levels of commercial industrial sugar (C₃ and C₄ plants) syrups by the carbon isotope ratio analysis.

    PubMed

    Guler, Ahmet; Kocaokutgen, Hasan; Garipoglu, Ali V; Onder, Hasan; Ekinci, Deniz; Biyik, Selim

    2014-07-15

    In the present study, one hundred pure and adulterated honey samples obtained from feeding honeybee colonies with different levels (5, 20 and 100 L/colony) of various commercial sugar syrups including High Fructose Corn Syrup 85 (HFCS-85), High Fructose Corn Syrup 55 (HFCS-55), Bee Feeding Syrup (BFS), Glucose Monohydrate Sugar (GMS) and Sucrose Sugar (SS) were evaluated in terms of the δ(13)C value of honey and its protein, difference between the δ(13)C value of protein and honey (Δδ(13)C), and C4% sugar ratio. Sugar type, sugar level and the sugar type*sugar level interaction were found to be significant (P<0.001) regarding the evaluated characteristics. Adulterations could not be detected in the 5L/colony syrup level of all sugar types when the δ(13)C value of honey, Δδ(13)C (protein-honey), and C4% sugar ratio were used as criteria according to the AOAC standards. However, it was possible to detect the adulteration by using the same criteria in the honeys taken from the 20 and 100 L/colony of HFCS-85 and the 100L/colony of HFCS-55. Adulteration at low syrup level (20 L/colony) was more easily detected when the fructose content of HFCS syrup increased. As a result, the official methods (AOAC, 978.17, 1995; AOAC, 991.41, 1995; AOAC 998.12, 2005) and Internal Standard Carbon Isotope Ratio Analysis could not efficiently detect the indirect adulteration of honey obtained by feeding the bee colonies with the syrups produced from C3 plants such as sugar beet (Beta vulgaris) and wheat (Triticium vulgare). For this reason, it is strongly needed to develop novel methods and standards that can detect the presence and the level of indirect adulterations.

  17. Detection of adulterated honey produced by honeybee (Apis mellifera L.) colonies fed with different levels of commercial industrial sugar (C₃ and C₄ plants) syrups by the carbon isotope ratio analysis.

    PubMed

    Guler, Ahmet; Kocaokutgen, Hasan; Garipoglu, Ali V; Onder, Hasan; Ekinci, Deniz; Biyik, Selim

    2014-07-15

    In the present study, one hundred pure and adulterated honey samples obtained from feeding honeybee colonies with different levels (5, 20 and 100 L/colony) of various commercial sugar syrups including High Fructose Corn Syrup 85 (HFCS-85), High Fructose Corn Syrup 55 (HFCS-55), Bee Feeding Syrup (BFS), Glucose Monohydrate Sugar (GMS) and Sucrose Sugar (SS) were evaluated in terms of the δ(13)C value of honey and its protein, difference between the δ(13)C value of protein and honey (Δδ(13)C), and C4% sugar ratio. Sugar type, sugar level and the sugar type*sugar level interaction were found to be significant (P<0.001) regarding the evaluated characteristics. Adulterations could not be detected in the 5L/colony syrup level of all sugar types when the δ(13)C value of honey, Δδ(13)C (protein-honey), and C4% sugar ratio were used as criteria according to the AOAC standards. However, it was possible to detect the adulteration by using the same criteria in the honeys taken from the 20 and 100 L/colony of HFCS-85 and the 100L/colony of HFCS-55. Adulteration at low syrup level (20 L/colony) was more easily detected when the fructose content of HFCS syrup increased. As a result, the official methods (AOAC, 978.17, 1995; AOAC, 991.41, 1995; AOAC 998.12, 2005) and Internal Standard Carbon Isotope Ratio Analysis could not efficiently detect the indirect adulteration of honey obtained by feeding the bee colonies with the syrups produced from C3 plants such as sugar beet (Beta vulgaris) and wheat (Triticium vulgare). For this reason, it is strongly needed to develop novel methods and standards that can detect the presence and the level of indirect adulterations. PMID:24594168

  18. Homogeneous diet of contemporary Japanese inferred from stable isotope ratios of hair

    NASA Astrophysics Data System (ADS)

    Kusaka, Soichiro; Ishimaru, Eriko; Hyodo, Fujio; Gakuhari, Takashi; Yoneda, Minoru; Yumoto, Takakazu; Tayasu, Ichiro

    2016-09-01

    The globalization of food production and distribution has homogenized human dietary patterns irrespective of geography, but it is uncertain how far this homogenization has progressed. This study investigated the carbon and nitrogen isotope ratios in the scalp hair of 1305 contemporary Japanese and found values of ‑19.4 ± 0.6‰ and 9.4 ± 0.6‰ (mean ± SD), respectively. Within Japan, the inter-regional differences for both isotope ratios was less than 1‰, which indicates low dietary heterogeneity among prefectural divisions. The carbon and nitrogen isotope ratios of the hair showed a significant correlation with the results of questionnaires on self-reported dietary habits. The carbon isotope ratios from Japan were lower than those in samples from the USA but higher than those in samples from Europe. These differences stem from the varying dietary proportions of food products originally derived from C3 and C4 plants. The dietary variation of Japan is as small as those of Europe and USA and smaller than those of some Asian countries. These results indicate that dietary homogeneity has progressed in Japan, which may indicate the influence from the spread of the Western-style diet and food globalization, although dietary heterogeneity among countries is still preserved.

  19. Homogeneous diet of contemporary Japanese inferred from stable isotope ratios of hair

    PubMed Central

    Kusaka, Soichiro; Ishimaru, Eriko; Hyodo, Fujio; Gakuhari, Takashi; Yoneda, Minoru; Yumoto, Takakazu; Tayasu, Ichiro

    2016-01-01

    The globalization of food production and distribution has homogenized human dietary patterns irrespective of geography, but it is uncertain how far this homogenization has progressed. This study investigated the carbon and nitrogen isotope ratios in the scalp hair of 1305 contemporary Japanese and found values of −19.4 ± 0.6‰ and 9.4 ± 0.6‰ (mean ± SD), respectively. Within Japan, the inter-regional differences for both isotope ratios was less than 1‰, which indicates low dietary heterogeneity among prefectural divisions. The carbon and nitrogen isotope ratios of the hair showed a significant correlation with the results of questionnaires on self-reported dietary habits. The carbon isotope ratios from Japan were lower than those in samples from the USA but higher than those in samples from Europe. These differences stem from the varying dietary proportions of food products originally derived from C3 and C4 plants. The dietary variation of Japan is as small as those of Europe and USA and smaller than those of some Asian countries. These results indicate that dietary homogeneity has progressed in Japan, which may indicate the influence from the spread of the Western-style diet and food globalization, although dietary heterogeneity among countries is still preserved. PMID:27616586

  20. Homogeneous diet of contemporary Japanese inferred from stable isotope ratios of hair.

    PubMed

    Kusaka, Soichiro; Ishimaru, Eriko; Hyodo, Fujio; Gakuhari, Takashi; Yoneda, Minoru; Yumoto, Takakazu; Tayasu, Ichiro

    2016-01-01

    The globalization of food production and distribution has homogenized human dietary patterns irrespective of geography, but it is uncertain how far this homogenization has progressed. This study investigated the carbon and nitrogen isotope ratios in the scalp hair of 1305 contemporary Japanese and found values of -19.4 ± 0.6‰ and 9.4 ± 0.6‰ (mean ± SD), respectively. Within Japan, the inter-regional differences for both isotope ratios was less than 1‰, which indicates low dietary heterogeneity among prefectural divisions. The carbon and nitrogen isotope ratios of the hair showed a significant correlation with the results of questionnaires on self-reported dietary habits. The carbon isotope ratios from Japan were lower than those in samples from the USA but higher than those in samples from Europe. These differences stem from the varying dietary proportions of food products originally derived from C3 and C4 plants. The dietary variation of Japan is as small as those of Europe and USA and smaller than those of some Asian countries. These results indicate that dietary homogeneity has progressed in Japan, which may indicate the influence from the spread of the Western-style diet and food globalization, although dietary heterogeneity among countries is still preserved. PMID:27616586

  1. Heavy element stable isotope ratios: analytical approaches and applications.

    PubMed

    Tanimizu, Masaharu; Sohrin, Yoshiki; Hirata, Takafumi

    2013-03-01

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

  2. Heavy element stable isotope ratios: analytical approaches and applications.

    PubMed

    Tanimizu, Masaharu; Sohrin, Yoshiki; Hirata, Takafumi

    2013-03-01

    Continuous developments in inorganic mass spectrometry techniques, including a combination of an inductively coupled plasma ion source and a magnetic sector-based mass spectrometer equipped with a multiple-collector array, have revolutionized the precision of isotope ratio measurements, and applications of inorganic mass spectrometry for biochemistry, geochemistry, and marine chemistry are beginning to appear on the horizon. Series of pioneering studies have revealed that natural stable isotope fractionations of many elements heavier than S (e.g., Fe, Cu, Zn, Sr, Ce, Nd, Mo, Cd, W, Tl, and U) are common on Earth, and it had been widely recognized that most physicochemical reactions or biochemical processes induce mass-dependent isotope fractionation. The variations in isotope ratios of the heavy elements can provide new insights into past and present biochemical and geochemical processes. To achieve this, the analytical community is actively solving problems such as spectral interference, mass discrimination drift, chemical separation and purification, and reduction of the contamination of analytes. This article describes data calibration and standardization protocols to allow interlaboratory comparisons or to maintain traceability of data, and basic principles of isotope fractionation in nature, together with high-selectivity and high-yield chemical separation and purification techniques for stable isotope studies. PMID:23397089

  3. 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.

  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. Toward a Unique Nitrogen Isotopic Ratio in Cometary Ices

    NASA Astrophysics Data System (ADS)

    Rousselot, Philippe; Pirali, Olivier; Jehin, Emmanuël; Vervloet, Michel; Hutsemékers, Damien; Manfroid, Jean; Cordier, Daniel; Martin-Drumel, Marie-Aline; Gruet, Sébastien; Arpigny, Claude; Decock, Alice; Mousis, Olivier

    2014-01-01

    Determination of the nitrogen isotopic ratios in different bodies of the solar system provides important information regarding the solar system's origin. We unambiguously identified emission lines in comets due to the 15NH2 radical produced by the photodissociation of 15NH3. Analysis of our data has permitted us to measure the 14N/15N isotopic ratio in comets for a molecule carrying the amine (-NH) functional group. This ratio, within the error, appears similar to that measured in comets in the HCN molecule and the CN radical, and lower than the protosolar value, suggesting that N2 and NH3 result from the separation of nitrogen into two distinct reservoirs in the solar nebula. This ratio also appears similar to that measured in Titan's atmospheric N2, supporting the hypothesis that, if the latter is representative of its primordial value in NH3, these bodies were assembled from building blocks sharing a common formation location.

  6. Stable isotope ratio (13C/12C) mass spectrometry to evaluate carbon sources and sinks: changes and trends during the decomposition of vegetal debris from eucalyptus clone plantations (NW Spain)

    NASA Astrophysics Data System (ADS)

    Fernandez, I.; Cabaneiro, A.

    2014-02-01

    Vegetal debris is known to participate in key soil processes such as the formation of soil organic matter (OM), also being a potential source of greenhouse gases to the atmosphere. However, its contribution to the isotopic composition of both the soil OM and the atmospheric carbon dioxide is not clear yet. Hence, the main objective of the present research is to understand the isotopic 13C changes and trends that take place during the successive biodegradative stages of decomposing soil organic inputs. By incubating bulk plant tissues for several months under laboratory controlled conditions, the kinetics of the CO2 releases and shifts in the 13C natural abundance of the solid residues were investigated using litter samples coming from forest plantations with a different clone (Anselmo: 1st clonal generation attained by morphological selection and Odiel: 2nd clonal generation genetically obtained) of Eucalyptus globulus Labill. developed over granitic or schistic bedrocks and located in northwestern Spain. Significant isotopic variations with time were observed, probably due to the isotopically heterogeneous composition of these complex substrates in conjunction with the initial selective consumption of more easily degradable 13C-differentiated compounds during the first stages of the biodegradation, while less available or recalcitrant litter components were decomposed at later stages of biodegradation, generating products that have their own specific isotopic signatures. These results, which significantly differ depending on the type of clone, suggest that caution must be exercised when interpreting carbon isotope studies (at natural abundance levels) since perturbations associated with the quality or chemical composition of the organic debris from different terrestrial ecosystems can have an important effect on the carbon stable isotope dynamics.

  7. Advances in Isotope Ratio Mass Spectrometry and Required Isotope Reference Materials

    PubMed Central

    Vogl, Jochen

    2013-01-01

    The article gives a condensed version of the keynote lecture held at the International Mass Spectrometry Conference 2012 in Kyoto. Starting with some examples for isotope research the key requirements for metrologically valid procedures enabling traceable and comparable isotope data are discussed. Of course multi-collector mass spectrometers are required which offer sufficiently high isotope ratio precision for the intended research work. Following this, corrections for mass fractionation/discrimination, validation of the analytical procedure including chemical sample preparation and complete uncertainty budgets are the most important issues for obtaining a metrologically valid procedure for isotope ratio determination. Only the application of such metrologically valid procedures enables the generation of traceable and comparable isotope data. To realize this suitable isotope and/or δ-reference materials are required, which currently are not sufficiently available for most isotope systems. Boron is given as an example, for which the situation regarding isotope and δ-reference materials is excellent. Boron may therefore serve as prototype for other isotope systems. PMID:24349939

  8. Isotope Ratios Reveal Trickery in the Produce Aisle

    ERIC Educational Resources Information Center

    Journal of Chemical Education, 2007

    2007-01-01

    A new technique for the proper checking and banning of organic food items is proposed. The analysis of the nitrogen isotope ratio present in the food is found to be a perfect standard for the organic checking of the food products.

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

    SciTech Connect

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

    2011-04-10

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

  10. Intramolecular oxygen isotope ratios of a global stem cellulose sample set: insight into a climate proxy.

    NASA Astrophysics Data System (ADS)

    Sternberg, L.; Pinzon, M. C.; Vendramini, P.; Anderson, W.; Jahren, H.; Beuning, K.

    2006-12-01

    Oxygen isotope ratios of cellulose have been used to interpret current and paleo-climate. However, our knowledge of biochemical processes leading to cellulose oxygen isotope ratios is limited. We have previously developed a technique to determine the oxygen isotope ratio of the oxygen attached to the second carbon separate from the average oxygen isotope ratio of the oxygen attached to carbon 3, 4, 5 and 6 of the cellulose glucose moieties. Cellulose, representing the average δ18O value of oxygen attached to carbon 2, 3, 4, 5 and 6, is hydrolyzed to glucose, followed by the synthesis of phenylglucosazone, which represents the average δ18O value of oxygen attached to carbon 3, 4, 5 and 6. With the δ18O values of cellulose and phenyglucosazone it is possible to calculate the δ18O value of oxygen attached to the second carbon of the cellulose glucose moieties. We use this technique to elucidate biochemical processes causing oxygen isotopic fractionation during cellulose synthesis. We show here with stem samples from several areas of the world that the changes in the δ18O value of cellulose is non linear relative to those of stem water and this lack of linearity is in part caused by changes in the biochemical fractionation during cellulose synthesis. The biochemical cause of this non-linearity is confirmed by a compilation of previously published oxygen isotope ratios of aquatic plant cellulose in relation to that of lake water showing a curvilinear relationship parallel to the δ18O value of stem cellulose vs stem water in terrestrial plants. This non linearity is, in part, caused by the large variation in the δ18O value of the oxygen attached to the second carbon which super-imposes isotopic noise on the stem cellulose isotopic signals. This conclusion is supported by examining the three best fit multiple linear regression equations between oxygen isotope ratios of stem water and relative humidity as independent factors with either δ18O values of (1) cellulose

  11. 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.

  12. 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.

  13. Systematic Relationships between Carbon and Oxygen Isotopes in Carbonates Deposited by Modern Corals and Algae.

    PubMed

    Keith, M L; Weber, J N

    1965-10-22

    Analyses of organic carbonates from Jamaican coral reefs show a positive correlation between the O(18): O(16) ratio and the C(13) C(12) ratio in some taxonomic groups of corals and algae, but essentially no correlation (nearly constant O(18)) in one suborder of reef-building corals. The strontium and magnesium contents apparently are controlled mainly by skeletal mineralogy and show no correlation with carbon or oxygen isotopic composition. The observed positive correlations between C(13) and O(18) content may be due to calcification processes utilizing carbon-oxygen compounds from two isotopically different sources or utilizing selected portions of a wide spectrum of carbon-oxygen compounds in which there is a positive correlation between C(13) C(12) and O(18);O(16) ratios. Coral and algal carbonates from Jamaican waters, with an annual temperature range of only about 4 degrees C, exhibit a total deltaC(13) range of more than 13 per mil and a sigmaO(18) range of more than 4 per mil. The wide isotopic variability resulting from vital effects of calcifying organisms must be taken into account in applying isotopic analysis to the study of sedimentary carbonate rocks which may include reef-derived carbonates.

  14. Gluconeogenesis from labeled carbon: estimating isotope dilution

    SciTech Connect

    Kelleher, J.K.

    1986-03-01

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

  15. 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

  16. 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

  17. A 400 year reconstruction of July relative air humidity for the region Vienna (eastern Austria) based on carbon and oxygen stable isotope ratios in tree-ring latewood cellulose of oaks

    NASA Astrophysics Data System (ADS)

    Haupt, M.; Boettger, T.; Weigl, M.; Grabner, M.

    2009-04-01

    Stable isotope chronologies and correlation to climate. We present the stable isotope chronologies of carbon (^13Clw) and oxygen (^18Olw) for the period from 1600 to 2003 respectively of non-exchangeable hydrogen (^2Hlw) for the last century constructed base upon tree-ring latewood cellulose from oaks (Quercus petraea Matt. Liebl.) grown in the region Vienna (Austria). The stable isotope ratios correspond mainly to the summer climate conditions. For the calibration period (1900-2003) we found high significant correlations (p < 0.001) between ^13Clw and relative air humidity (RH) of July (-0.66), between ^18Olw and RHV I-V II (-0.61) and between ^2Hlw and RHV I-V III(-0.56). In the case of temperatures high significant correlations between the growing season temperature and ^13Clw (0.55), between the annual mean temperatures and ^18Olw ratios (0.45) and between summer mean temperatures (June to August) and ^2Hlw values (0.49) were estimated. Modeling. Various univariate and multivariate linear regressions models were proved for the reconstruction of summer relative air humidity and temperature. We found that establishing of robust models had several uncertainties: - using common linear transfer functions which oversimplify the complexity of relations; - using of pooled material and neglecting of different reactions from individual trees to climate; - high-order autocorrelations in the isotope time series; - climatic trends in the investigated region which are different in the first and in the second half of 20th century; - temporal instability of climate signals in the isotope ratios of tree ring cellulose. In the case of temperature no valid model could be estimated caused by temporal instabilities of signal strength. For relative air humidity two bivariate models RHV II = (-4.3 ± 0.7) * ^13Clw + (-2.8 ± 0.5) * ^18Olw + 44 [1] and RHV II = (-4.7 ± 0.7) * ^13Clw + (-0.35 ± 0.07) * ^2Hlw - 68 [2] were found as verifiable and applicable to reconstruct RHV II

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

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

  19. Constraining paleotemperature and water isotope signals at Lake Bonneville using carbonate clumped isotopes

    NASA Astrophysics Data System (ADS)

    Mering, J. A.; Oviatt, C. G.; Petryshyn, V. A.; Canet, J.; Tripati, A.

    2013-12-01

    Lake Bonneville was the largest pluvial system in the Great Basin during the Last Glacial Maximum (23-19 ka BP), reaching nearly 50,000 square kilometers at its high stand. Carbonate clumped isotope paleothermometry provides a new avenue to evaluate lake and atmospheric conditions by constraining the temperature and oxygen isotope ratios of lake water. Here, we present estimates of lake temperature, the oxygen isotope composition of paleowater, and Mean Annual Air Temperature (MAAT) from LGM paleoshoreline sites in Utah and Eastern Nevada. Multiple phases of ancient carbonate were evaluated, including endogenic carbonate from the ubiquitous Bonneville marl stratigraphic unit, and aragonitic shells of two species of aquatic gastropods (genera Pyrgulopsis and Stagnicola) collected from littoral deposits adjacent to the marl. These phases should record surface water conditions. Preliminary results indicate that paleotemperature estimates from gastropods and marl are similar at any given site. However, the latitudinal water isotope gradient reconstructed using marls is steeper than that reconstructed from gastropods, indicating that perhaps carbonate precipitation in marl is more evaporation-driven than shell growth of aquatic snails. Comparison with recent climate data, and clumped isotope measurements of modern samples from the Great Salt Lake, supports moderate temperature change in the Great Basin from the Last Glacial Maximum to present.

  20. NUSIMEP-7: uranium isotope amount ratios in uranium particles.

    PubMed

    Truyens, J; Stefaniak, E A; Aregbe, Y

    2013-11-01

    The Institute for Reference Materials and Measurements (IRMM) has extensive experience in the development of isotopic reference materials and the organization of interlaboratory comparisons (ILC) for nuclear measurements in compliance with the respective international guidelines (ISO Guide 34:2009 and ISO/IEC 17043:2010). The IRMM Nuclear Signatures Interlaboratory Measurement Evaluation Program (NUSIMEP) is an external quality control program with the objective of providing materials for measurements of trace amounts of nuclear materials in environmental matrices. Measurements of the isotopic ratios of the elements uranium and plutonium in small amounts, typical of those found in environmental samples, are required for nuclear safeguards and security, for the control of environmental contamination and for the detection of nuclear proliferation. The measurement results of participants in NUSIMEP are evaluated according to international guidelines in comparison to independent external certified reference values with demonstrated metrological traceability and uncertainty. NUSIMEP-7 focused on measurements of uranium isotope amount ratios in uranium particles aiming to support European Safeguards Directorate General for Energy (DG ENER), the International Atomic Energy Agency's (IAEA) network of analytical laboratories for environmental sampling (NWAL) and laboratories in the field of particle analysis. Each participant was provided two certified test samples: one with single and one with double isotopic enrichment. These NUSIMEP test samples were prepared by controlled hydrolysis of certified uranium hexafluoride in a specially designed aerosol deposition chamber at IRMM. Laboratories participating in NUSIMEP-7 received the test samples of uranium particles on two graphite disks with undisclosed isotopic ratio values n((234)U)/n((238)U), n((235)U)/n((238)U) and n((236)U)/n((238)U). The uranium isotope ratios had to be measured using their routine analytical

  1. NUSIMEP-7: uranium isotope amount ratios in uranium particles.

    PubMed

    Truyens, J; Stefaniak, E A; Aregbe, Y

    2013-11-01

    The Institute for Reference Materials and Measurements (IRMM) has extensive experience in the development of isotopic reference materials and the organization of interlaboratory comparisons (ILC) for nuclear measurements in compliance with the respective international guidelines (ISO Guide 34:2009 and ISO/IEC 17043:2010). The IRMM Nuclear Signatures Interlaboratory Measurement Evaluation Program (NUSIMEP) is an external quality control program with the objective of providing materials for measurements of trace amounts of nuclear materials in environmental matrices. Measurements of the isotopic ratios of the elements uranium and plutonium in small amounts, typical of those found in environmental samples, are required for nuclear safeguards and security, for the control of environmental contamination and for the detection of nuclear proliferation. The measurement results of participants in NUSIMEP are evaluated according to international guidelines in comparison to independent external certified reference values with demonstrated metrological traceability and uncertainty. NUSIMEP-7 focused on measurements of uranium isotope amount ratios in uranium particles aiming to support European Safeguards Directorate General for Energy (DG ENER), the International Atomic Energy Agency's (IAEA) network of analytical laboratories for environmental sampling (NWAL) and laboratories in the field of particle analysis. Each participant was provided two certified test samples: one with single and one with double isotopic enrichment. These NUSIMEP test samples were prepared by controlled hydrolysis of certified uranium hexafluoride in a specially designed aerosol deposition chamber at IRMM. Laboratories participating in NUSIMEP-7 received the test samples of uranium particles on two graphite disks with undisclosed isotopic ratio values n((234)U)/n((238)U), n((235)U)/n((238)U) and n((236)U)/n((238)U). The uranium isotope ratios had to be measured using their routine analytical

  2. Site-Specific Carbon Isotopes in Organics

    NASA Astrophysics Data System (ADS)

    Piasecki, A.; Eiler, J. M.

    2012-12-01

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

  3. MAGNESIUM ISOTOPE RATIOS IN {omega} CENTAURI RED GIANTS

    SciTech Connect

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

    2013-05-20

    We have used the high-resolution observations obtained at the Anglo-Australian Telescope with Ultra-High Resolution Facility (R {approx} 100,000) and at Gemini-S with b-HROS (R {approx} 150,000) to determine magnesium isotope ratios for seven {omega} Cen red giants that cover a range in iron abundance from [Fe/H] = -1.78 to -0.78 dex, and for two red giants in M4 (NGC 6121). The {omega} Cen stars sample both the ''primordial'' (i.e., O-rich, Na- and Al-poor) and the ''extreme'' (O-depleted, Na- and Al-rich) populations in the cluster. The primordial population stars in both {omega} Cen and M4 show ({sup 25}Mg, {sup 26}Mg)/{sup 24}Mg isotopic ratios that are consistent with those found for the primordial population in other globular clusters with similar [Fe/H] values. The isotopic ratios for the {omega} Cen extreme stars are also consistent with those for extreme population stars in other clusters. The results for the extreme population stars studied indicate that the {sup 26}Mg/{sup 24}Mg ratio is highest at intermediate metallicities ([Fe/H] < -1.4 dex), and for the highest [Al/Fe] values. Further, the relative abundance of {sup 26}Mg in the extreme population stars is notably higher than that of {sup 25}Mg, in contrast to model predictions. The {sup 25}Mg/{sup 24}Mg isotopic ratio in fact does not show any obvious dependence on either [Fe/H] or [Al/Fe] nor, intriguingly, any obvious difference between the primordial and extreme population stars.

  4. Lignin methoxyl hydrogen isotope ratios in a coastal ecosystem

    NASA Astrophysics Data System (ADS)

    Feakins, Sarah J.; Ellsworth, Patricia V.; Sternberg, Leonel da Silveira Lobo

    2013-11-01

    Stable hydrogen isotope ratios of plant lignin methoxyl groups have recently been shown to record the hydrogen isotopic composition of meteoric water. Here we extend this technique towards tracing water source variations across a saltwater to freshwater gradient in a coastal, subtropical forest ecosystem. We measure the hydrogen isotopic composition of xylem water (δDxw) and methoxyl hydrogen (δDmethoxyl) to calculate fractionations for coastal mangrove, buttonwood and hammock tree species in Sugarloaf Key, as well as buttonwoods from Miami, both in Florida, USA. Prior studies of the isotopic composition of cellulose and plant leaf waxes in coastal ecosystems have yielded only a weak correlation to source waters, attributed to leaf water effects. Here we find δDmethoxyl values range from -230‰ to -130‰, across a 40‰ range in δDxw with a regression equation of δDmethoxyl ‰ = 1.8 * δDxw - 178‰ (R2 = 0.48, p < 0.0001, n = 74). This is comparable within error to the earlier published relationship for terrestrial trees which was defined across a much larger 125‰ isotopic range in precipitation. Analytical precision for measurements of δD values of pure CH3I by gas chromatography-pyrolysis-isotope ratio mass spectrometry (GC-P-IRMS) is σ = 6‰ (n = 31), which is considerably better than for CH3I liberated through cleavage with HI from lignin with σ = 18‰ (n = 26). Our results establish that δDmethoxyl can record water sources and salinity incursion in coastal ecosystems, where variations sufficiently exceed method uncertainties (i.e., applications with δD excursions >50‰). For the first time, we also report yields of propyl iodide, which may indicate lignin synthesis of propoxyl groups under salt-stress.

  5. Position-specific measurement of oxygen isotope ratios in cellulose: Isotopic exchange during heterotrophic cellulose synthesis

    NASA Astrophysics Data System (ADS)

    Waterhouse, John S.; Cheng, Shuying; Juchelka, Dieter; Loader, Neil J.; McCarroll, Danny; Switsur, V. Roy; Gautam, Lata

    2013-07-01

    We describe the first reported method for the measurement of oxygen isotope ratios at each position in the glucose units of the cellulose molecule. The overall process comprises a series of synthetic organic sequences, by which α-cellulose is hydrolysed to glucose, and oxygen atoms at specific positions in the glucose molecule are removed in samples of benzoic acid for measurement of δ18O. Values of δ18O at specific positions in cellulose are calculated from these δ18O values and the overall δ18O value of the cellulose. We apply the method to determine the degree to which oxygen atoms at each position undergo isotopic exchange with water during heterotrophic cellulose synthesis, such as occurs in the cambium of trees. To do this we extract α-cellulose from wheat seedlings germinated in the dark in aqueous media of differing oxygen isotope ratios. Results indicate that oxygen atoms at positions 5 and 6 (O-5 and O-6 respectively) undergo around 80% exchange with medium water, O-3 undergoes around 50% exchange, and O-2 and O-4 do not undergo isotopic exchange. The results have important implications for extracting palaeoclimatic records from oxygen isotope time series obtained from tree ring cellulose. As O-5 and O-6 undergo significant exchange with medium water during heterotrophic cellulose synthesis, oxygen isotopes at these positions in tree ring cellulose should carry a predominantly trunk (source) water signal. On the other hand, O-2 and O-4 should retain the isotopic signature of leaf water in tree ring cellulose. Our method therefore potentially enables the separate reconstruction of past temperature and humidity data from oxygen isotope ratios of tree ring cellulose - something that has hitherto not been possible. The measured degrees of isotopic exchange are to some extent unexpected and cannot be fully explained using current biochemical mechanisms, suggesting that knowledge of these processes is incomplete.

  6. 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. PMID:27010907

  7. Zinc Isotope Ratios as Indicators of Diet and Trophic Level in Arctic Marine Mammals

    PubMed Central

    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. PMID:27010907

  8. Stable isotope ratios as indicators of trophic status: Uncertainties imposed by geographic effects

    SciTech Connect

    Schell, D.M.

    1995-12-31

    Isotope ratios of carbon and nitrogen are often suggested as indicators to determine trophic status and carbon sources of marine organisms in explaining relative concentrations of pollutants. Whereas this technique is effective with organisms resident in ecosystems having homogeneous primary productivity regimes and uniform isotope ratios in the productivity base, it often is confounded by migratory movements by larger organisms across isotopic gradients. Tissues containing a temporal record such as baleen plates or whiskers show these effects clearly. Bowhead whales in Alaskan waters seasonally move across carbon isotope gradients of 5{per_thousand} in zooplankton and reflect these differences in the keratin of baleen plates and in overall body composition. However, no significant differences in {delta}{sup 15}N are evident regionally in northern Alaskan zooplankton. In contrast, the Southern Ocean is characterized by extreme latitudinal gradients in both {delta}{sup 13}C and {delta}{sup 15}N with the most pronounced effects occurring at the subtropical convergence. Prey taken by marine mammals south of this zone are depleted in both {sup 15}N and {sup 13}C by up to 8{per_thousand}. Data on southern right whales (Eubalaena glacialis), Bryde`s whale (Balaenoptera edenl), pygmy right whales (Caperea marginate) and antarctic fur seal (Arctocephalos gazella) show the effects of migratory movements across the gradient in both carbon and nitrogen isotope ratios. Similar patterns in marine mammal tissues from Australia, South Africa and South America indicate that the observed patterns are circumpolar. Within a given region, trophic effects shift {delta}{sup 15}N values consistent with observed feeding habits.

  9. Utilizing Isotopic Uranium Ratios in Groundwater Evaluations at FUSRAP Sites

    SciTech Connect

    Frederick, W.T.; Keil, K.G.; Rhodes, M.C.; Peterson, J.M.; MacDonell, M.M.

    2007-07-01

    The U.S. Army Corps of Engineers Buffalo District is evaluating environmental radioactive contamination at several Formerly Utilized Sites Remedial Action Program (FUSRAP) sites throughout New York, Pennsylvania, Ohio, and Indiana. The investigations follow the process defined in the Comprehensive Environmental Response, Compensation and Liability Act (CERCLA). Groundwater data from the Niagara Falls Storage Site (NFSS) in Lewiston, New York were evaluated for isotopic uranium ratios, specifically uranium-234 versus uranium-238 (U- 234 and U-238, respectively), and the results were presented at Waste Management 2006. Since uranium naturally occurs in all groundwater, it can be difficult to distinguish where low-concentration impacts from past releases differ from the high end of a site-specific natural background range. In natural groundwater, the ratio of U-234 to U-238 exceeds 1 (unity) due to the alpha particle recoil effect, in which U-234 is preferentially mobilized to groundwater from adjacent rock or soil. This process is very slow and may take hundreds to thousands of years before a measurable increase is seen in the natural isotopic ratio. If site releases are the source of uranium being measured in groundwater, the U-234 to U-238 ratio is commonly closer to 1, which normally reflects FUSRAP-related, uranium-contaminated wastes and soils. This lower ratio occurs because not enough residence time has elapsed since the 1940's and 1950's for the alpha particle recoil effect to have significantly altered the contamination-derived ratio. An evaluation of NFSS-specific and regional groundwater data indicate that an isotopic ratio of 1.2 has been identified as a signature value to help distinguish natural groundwater, which may have a broad background range, from zones impacted by past releases. (authors)

  10. Chromium Isotopes in Marine Carbonates - an Indicator for Climatic Change?

    NASA Astrophysics Data System (ADS)

    Frei, R.; Gaucher, C.

    2010-12-01

    Chromium (Cr) stable isotopes experience an increased interest as a tracer of Cr (VI) reduction in groundwater and thus showed their potential as a monitor of remediation of anthropogenic and natural contamination in water (Berna et al., 2009; Izbicki et al., 2008). Chromium stable isotopes in Fe-rich chemical sediments (BIFs and Fe-cherts) have recently also been used as a tracer for Earth's atmospheric oxygenation through time (Frei et al., 2009). We have applied the Cr isotope system to organic-rich carbonates from a late Ediacaran succession in Uruguay (Polanco Formation), from which we have previously analyzed BIFs with extremely fractionated (δ53Cr up to 5.0 ‰) Cr isotope signatures that are part of an underlying deep water clastic sediment (shale-dominated) sequence (Yerbal Formation) deposited in a glacio-marine environment (Gaucher et al.,2004). δ53Cr values of organic rich carbonates correlate with positive and negative carbon isotope excursions (δ13C PDB between -3 and +3 ‰) and with systematic changes in strontium isotope compositions, commonly interpreted as to reflect fluctuations in organic (photosynthetic algae) production related to fluctuations in atmospheric oxygen and weathering intensities, respectively. Slightly positively fractioned δ53Cr values (up to +0.25‰), paralleling positive (δ13C PDB and 87Sr/86Sr ratio excursions would thereby trace elevated atmospheric oxygen levels/pulses possibly related to glacier retreat/melting stages that caused bioproductivity to increase. While the causal link between these multiple isotopic tracers and the mechanisms of Cr stripping into carbonates has to be further investigated in detail, the first indications from this study point to a potentially promising use of stable Cr isotopes in organic-rich carbonates to monitor fluctuations of atmospheric oxygen, particularly over the Neoproterozoic and Phanerozoic ice age periods. E.C. Berna et al. (2010) Cr stable isotopes as indicators of Cr

  11. Influence of nutrients on carbon isotope fractionation by natural populations of Prymnesiophyte algae in NE Pacific

    NASA Astrophysics Data System (ADS)

    Eek, Magnus K.; Whiticar, Michael J.; Bishop, J. K. B.; Wong, C. S.

    1999-11-01

    Isotope effects by Prymnesiophyte algae were determined on samples of marine particulate organic material collected by MULVFS pumps during three C-JGOFS cruises along Line P in the northeast Pacific. Carbon isotope fractionation associated with photosynthetic carbon uptake was calculated from 13C/ 12C ratios of dissolved carbon dioxide and the C 37:2 alkenone, a biomarker originating from Prymnesiophyte algae. In the presence of nitrate (N) the magnitude of the carbon isotope fractionation ( ɛp) is dependent on dissolved phosphate concentration (PO 4) normalized to the concentration of dissolved carbon dioxide (C e), i.e. ɛp∝PO 4/C e for N≠0. In nitrate-depleted waters, the magnitude of carbon isotope fractionation is lower than expected from the ɛp vs PO 4/C e relationship. These results suggest that growth conditions approaching nitrogen starvation can severely affect carbon isotope fractionation in these paleo-climatically important algae.

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

    NASA Astrophysics Data System (ADS)

    Mol, Jacoba; Thomas, Helmuth

    2016-04-01

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

  13. Reduced climate sensitivity of carbon, oxygen and hydrogen stable isotope ratios in tree-ring cellulose of silver fir (Abies alba Mill.) influenced by background SO2 in Franconia (Germany, Central Europe).

    PubMed

    Boettger, Tatjana; Haupt, Marika; Friedrich, Michael; Waterhouse, John S

    2014-02-01

    The climate sensitivity of carbon (δ(13)C), oxygen (δ(18)O) and hydrogen (δ(2)H) isotope signatures in tree-ring cellulose of Abies alba Mill. from a marginally industrialized area of Franconia (Germany) was analysed for the last 130 years. All isotopes preserve climatic signals up to c. 1950 AD. After 1950 we observe a clear reduction in climate sensitivity of δ(13)C and δ(2)H while δ(18)O - climate relations remain well pronounced. Nevertheless statistical tests implied that SO2 background emissions of West Germany had influenced isotope signatures long before 1950. The relationships between isotope values and concentrations of SO2, dust, O3 and NO2 at the regional level during the period 1979-2006 indicate that δ(13)C and δ(18)O were influenced primarily by SO2. The impact of SO2 on δ(2)H was negligible, but the observed reduction of climate sensitivity may be caused by synergic influences. The results have significant implications if isotope signatures from tree-rings from anthropogenic influenced regions are used to reconstruct past climate.

  14. Stable isotope ratio measurements of royal jelly samples for controlling production procedures: impact of sugar feeding.

    PubMed

    Daniele, Gaëlle; Wytrychowski, Marine; Batteau, Magali; Guibert, Sylvie; Casabianca, Hervé

    2011-07-30

    The carbon and nitrogen stable ratios of royal jelly (RJ) samples from various origins are determined using an elemental analyser linked online to an isotope ratio mass spectrometer to evaluate authenticity and adulteration. The (13)C/(12)C and (15)N/(14)N stable isotope ratios are measured in more than 500 RJs (domestic, imported and derived from feeding experiments) in order to obtain isotopic measurements that take into account seasonal, botanical and geographical effects. Authenticity intervals are established for traditional beekeeping practices, without feeding, in the range -22.48 to -27.90‰ for δ(13)C. For these samples, the δ(15)N values range from -1.58 to 7.98‰, depending on the plant sources of pollen and nectar. The δ(13)C values of the commercial samples vary from -18.54 to -26.58‰. High δ(13)C values are typical of sugar cane or corn syrups which have distinctive isotopic (13)C signatures because both plants use the C4 photosynthetic cycle, in contrast to most RJs which are derived from C3 plants. These differences in the (13)C-isotopic composition allow the detection of the addition of such sugars. RJs from traditional sources and from industrial production by sugar feeding are thus successfully distinguished. PMID:21698675

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  16. Stable isotope ratios and uric acid preservation in termites belonging to three feeding habits in Thailand.

    PubMed

    Tayasu, I; Hyodo, F; Takematsu, Y; Sugimoto, A; Inoue, T; Kirtibutr, N; Abe, T

    2000-01-01

    Nitrogen and carbon stable isotope ratios and uric acid concentrations in termites sampled from a dry evergreen forest in Thailand, were determined across three kinds of feeding habits. Feeding habits of Microcerotermes crassus, which is an abundant wood-feeder, and Dicuspiditermes makhamensis, a common soil-feeding termite, were confirmed by isotopic signatures. Lichen feeding termites (Hospitalitermes birmanicus, H. bicolor and H. ataramensis) were characterized by low delta15N values, suggesting that they assimilated nitrogen deposited from the atmosphere. There was also a significant difference in uric acid concentrations between termites representing different feeding habits. No significant relationships were found between uric acid concentrations and delta15N or delta13C in Hospitalitermes. However, delta15N values were correlated with C/N ratios in H. birmanicus, except in one colony of H. ataramensis. delta13C values in both species were negatively correlated with C/N ratios.

  17. Exploring antimony isotope ratio variations for provenancing purposes

    NASA Astrophysics Data System (ADS)

    Lobo, L.; Degryse, P.; Vanhaecke, F.

    2012-04-01

    Production sites and trade routes of Roman glass have received much attention over the past decade. It is assumed that raw glass was produced in primary workshops near the raw material sources used, to be transported to secondary glass houses. Colourless glass was a particularly prestigious material in this process, difficult to make. It has been looked at from the perspective of the provenance of its sand and flux, but rarely from the perspective of the origin of the decolourizing material. In effect, for the production of early Roman colourless glass, antimony was used, deliberately added under the form of Sb-bearing minerals. Isotopic analysis of Sb ores could help identify the origin of the decolorizing agent present in Roman glasses and, consequently, to reconstruct how such material was traded and transported, and how this can be integrated in the network of primary and secondary glass producers. In this work, variations in the isotopic composition of Sb in different ore sources (stibnites) are explored using multi-collector ICP - mass spectrometry. A new method is proposed, where Sb is directly analysed for its isotopic composition using MC-ICP-MS after chromatographic isolation of the target element from a sample digest. The isotopic composition of the selected materials shows variations up to 6 ?-units relative to an antimony standard solution. Indium was used as internal standard for correction for instrumental mass discrimination and an external precision for the 123Sb/121Sb ratio of 0.01% RSD was obtained

  18. New Carbonate Standard Reference Materials for Boron Isotope Geochemistry

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  19. TOWARD A UNIQUE NITROGEN ISOTOPIC RATIO IN COMETARY ICES

    SciTech Connect

    Rousselot, Philippe; Cordier, Daniel; Mousis, Olivier; Pirali, Olivier; Vervloet, Michel; Martin-Drumel, Marie-Aline; Gruet, Sébastien; Jehin, Emmanuël; Hutsemékers, Damien; Manfroid, Jean; Arpigny, Claude; Decock, Alice

    2014-01-10

    Determination of the nitrogen isotopic ratios in different bodies of the solar system provides important information regarding the solar system's origin. We unambiguously identified emission lines in comets due to the {sup 15}NH{sub 2} radical produced by the photodissociation of {sup 15}NH{sub 3}. Analysis of our data has permitted us to measure the {sup 14}N/{sup 15}N isotopic ratio in comets for a molecule carrying the amine (-NH) functional group. This ratio, within the error, appears similar to that measured in comets in the HCN molecule and the CN radical, and lower than the protosolar value, suggesting that N{sub 2} and NH{sub 3} result from the separation of nitrogen into two distinct reservoirs in the solar nebula. This ratio also appears similar to that measured in Titan's atmospheric N{sub 2}, supporting the hypothesis that, if the latter is representative of its primordial value in NH{sub 3}, these bodies were assembled from building blocks sharing a common formation location.

  20. Carbon isotopes as indicators of peatland growth?

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  1. Detailed Distribution of the Helium Isotope Ratios in Northeastern Japan

    NASA Astrophysics Data System (ADS)

    Horiguchi, K.; Ueki, S.; Sano, Y.; Takahata, N.; Hasegawa, A.

    2007-12-01

    The geographical distribution of helium isotope ratios (3He/4He ratios) is characterized by high values of 4 to 8RA (where RA is the atmospheric 3He/4He ratio of 1.39×10-6) along the volcanic front and in the back-arc region at Tohoku district, northeastern Japan. In contrast forearc region shows low values less than 1RA. On the other hand, there is no clear contrast of the 3He/4He ratios except at the central region (e.g., Sano and Wakita, 1985). We perform the helium isotope ratio analysis in northeastern Japan, and around the source region of the Niigataken Chuetsu-oki Earthquake in 2007 (M6.8) where 3He/4He ratios data were reported. We have collected 41 samples of gases from hot springs, mineral springs, and deep wells, distributing mainly in the forearc region at Tohoku district. In addition, we also collected 19 samples of gases from hot springs, volcanoes and natural gas fields around the source region of the Niigataken Chuetsu-oki Earthquake in 2007. We measured 3He/4He ratios by noble gas mass spectrometers (Helix and VG5400) of Ocean Research Institute (ORI), the University of Tokyo. The 4He/20Ne were measured by a quadruple mass spectrometer to evaluate air contamination in the samples. δ13C (CO2) values were measured by using a mass spectrometer (DELTA plus XP) of ORI. Main features of our results for Tohoku region are as follows: 1) The 3He/4He ratios in the forearc region are less than 1RA. 2) The 3He/4He ratios vary along the volcanic front. In Miyagi prefecture [38-39N], the ratios range from 2 to 5 RA. On the other hand, the ratios are less than 1RA in and around the southern boundary of Iwate and Akita prefectures [39-39.5N]. The distribution of 3He/4He ratios in Niigata plans to be discussed by comparing with the well-studied seismotectonics and the structure of the crust and upper mantle.

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

    PubMed Central

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

    2007-01-01

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

  3. Local and regional oscillations of carbon and oxygen isotopes in terestrial carbonates

    NASA Astrophysics Data System (ADS)

    Skipitytė, Raminta; Stančikaitė, Miglė

    2014-05-01

    Stable isotope ratios of carbon and oxygen in sediment carbonates are used as a tool to identify climatic changes in the past [1], [2]. Carbon is more related to humidity whereas oxygen is thought to respond the temperature [2]. Nevertheless number of questions about local, regional and global scale impacts to these records is left. In this research work carbon and oxygen isotope ratios in lacustrine carbonates are used to identify palaeoenvironmental dynamics of different locations. Samples of lacutrine carbonates were obtained from 8 sequences of different sites in Lithuania (4), Poland (1), Belarus (1) and Kaliningrad (1). Every sequence was divided into 2 cm intervals. The study showed differences in average carbon and oxygen isotope ratios between Lithuania and other countries (Poland, Belarus and Kaliningrad). Carbon and oxygen isotope ratios in 4 sites in Lithuania are: ¯U la δ13C -4.72± 2.11, o and δ18O -9.46± 1.9, o ; Zervynos δ13C -4.79± 1.82, o and δ18O -9.57± 1.69, o ; Rudnia δ13C -4.94± 7.53, o and δ18O -9.3± 3.92, o ; Pauliai δ13C -4.15± 0.67, o and δ18O -9.94± 1.07, o : In other countries: Poland δ13C -1.07± 1.94, o and δ18O -7.69± 0.95, o ; Belarus δ13C 0.97± 1.94, o and δ18O -7.61± 1.42, o ; Kaliningrad δ13C -1.14± 1.43, o and δ18O -6.51± 1.00, o : Average stable carbon and oxygen isotope values from four sites in Lithuania were -4.65 o for carbon and -9.51 o for oxygen. Despite homogeneity of average isotope signals in these four sites there are relatively large oscillations of isotopic values in Rudnia and relatively small in Pauliai. These oscillations could be related to local characteristics of particular place such as environmental conditions, water balance, input of terrigenous materials into basin, etc. Total amount of CaCO3 could also play a significant role in reconstructing palaeoenvironment from stable isotopes and creating isomaps. The comparison of isotope records from different locations could enable to

  4. USE OF THE COMPOSITION AND STABLE CARBONIISOTOPE RATIO OF MICROBIAL FATTY ACIDS TO STUDY CARBON CYCLING

    EPA Science Inventory

    We use measurements of the concentration and stable carbon isotopic ratio (*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 (SOM) cy...

  5. Utilizing Isotopic Uranium Ratios in Groundwater Evaluations at NFSS

    SciTech Connect

    Rhodes, M.C.; Keil, K.G.; Frederick, W.T.; Papura, T.R.; Leithner, J.S.; Peterson, J.M.; MacDonell, M.M.

    2006-07-01

    The U.S. Army Corps of Engineers (USACE) Buffalo District is currently evaluating environmental contamination at the Niagara Falls Storage Site (NFSS) under the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) as part of its Formerly Utilized Sites Remedial Action Program (FUSRAP). The NFSS is located in the Town of Lewiston in western New York and has been used to store uranium-contaminated materials since 1944. Most of the radioactive materials are currently contained in an on-site structure, but past contamination remains in soil and groundwater. As a naturally occurring radionuclide, uranium is present in all groundwater. Because contamination levels at the site are quite low, it can be difficult to distinguish zones that have been impacted by the past releases from those at the high end of the natural background range. The differences in the isotopic ratio of uranium-234 (U-234) to uranium-238 (U-238) between natural groundwater systems and affected areas are being used in an innovative way to better define the nature and extent of groundwater contamination at NFSS. In natural groundwater, the ratio of U-234 to U-238 exceeds 1 due to the alpha particle recoil effect, in which U-234 is preferentially mobilized to groundwater from adjacent rock or soil. This process is very slow, and it can be hundreds to thousands of years before a measurable impact is seen in the isotopic ratio. Thus, as a result of the recoil effect, the ratio of U-234 to U-238 will be higher in natural groundwater than in contaminated groundwater. This means that if site releases were the source of the uranium being measured in groundwater at NFSS, the ratio of U-234 to U-238 would be expected to be very close to 1 (the same ratio that exists in wastes and soil at the site), because not enough time has elapsed for the alpha particle recoil effect to have significantly altered that ratio. From an evaluation of site and regional groundwater data, an isotopic ratio

  6. Precise determination of stable chlorine isotopic ratios in low-concentration natural samples

    NASA Astrophysics Data System (ADS)

    Magenheim, A. J.; Spivack, A. J.; Volpe, C.; Ransom, B.

    1994-07-01

    Investigation of stable chlorine isotopes in geological materials has been hindered by large sample requirements and/or lack of analytical precision. Here we describe precise methods for the extraction, isolation, and isotopic analysis of low levels of chlorine in both silicate and aerosol samples. Our standard procedure uses 2 μg of Cl for each isotopic analysis. External reproducibility (1 σ) is 0.25%. for the 37Cl /35Cl measurements. Chlorine is extracted from silicate samples (typically containing at least 20 μg of Cl) via pyrohydrolysis using induction heating and water vapor as the carrier, and the volatilized chlorine is condensed in aqueous solution. Atmospheric aerosols collected on filters are simply dissolved in water. Prior to isotopic measurement, removal of high levels of SO 42-, F -, and organic compounds is necessary for the production of stable ion beams. Sulfate is removed by BaSCO 4 precipitation, F - by CaF 2 precipitation, and organic compounds are extracted with activated carbon. Chlorine is converted to stoichiometric CsCl by cation exchange, and isotopic ratios are determined by thermal ionization mass spectrometry of Cs 2Cl +. We demonstrate that the sensitivity and precision of this method allow resolution of natural variations in chlorine isotopic composition, and thereby provide insight to some fundamental aspects of chlorine geochemistry.

  7. Extreme hydrogen, oxygen and carbon isotope anomalies in the pore waters and carbonates of the sediments and basalts from the Norwegian Sea: Methane and hydrogen from the mantle?

    NASA Astrophysics Data System (ADS)

    Lawrence, J. R.; Taviani, M.

    1988-08-01

    D/H ratios in the pore waters of the sediments from the Norwegian Sea decrease as a function of depth to values as low as -14%. Oxygen isotope ratios in the pore waters and carbon and oxygen isotope ratios in carbonates both in the sediments and basalts are low. Extensive alteration of basalt has been given as the explanation for the low oxygen isotope ratios. Material balance calculations suggest that alteration of volcanic material and oxidation of organic matter cannot explain the hydrogen and carbon isotope anomalies. Arguments are presented suggesting that methane and hydrogen from the mantle are oxidized to carbon dioxide and water by sulfate and ferric iron in the basaltic crust to yield the low hydrogen and carbon isotope ratios.

  8. Isotopic Ratios in Nitrile Species on Titan using ALMA

    NASA Astrophysics Data System (ADS)

    Molter, Edward; Nixon, Conor; Cordiner, Martin; Serigano, Joseph; Irwin, Patrick; Teanby, Nicholas; Charnley, Steven; Lindeberg, Johan

    2016-06-01

    The atmosphere of Titan is primarily composed of molecular nitrogen (N2, ˜98%) and methane (CH4, ˜2%), but also hosts a myriad of trace organic species. Two of the simplest and most abundant of these are hydrogen cyanide (HCN) and cyanoacetylene (HC3N). The advent of ALMA provides the opportunity to observe rotational transitions in these molecules and their isotopologues with unprecendented sensitivity and spatial resolution. We searched through the ALMA archive for publicly available high-resolution observations of Titan as a flux calibrator source taken between April and July 2014; each integration lasted around 160 seconds. Using spectra of HCN and HC3N isotopologues found in these data, we derive vertical abundance profiles and determine the isotopic ratios 14N/15N and 12C/13C in these molecules. We also report the detection of a new HCN isotopologue on Titan, H13C6 15N, and use a high signal-to-noise spectrum of DCN to determine the D/H ratio in HCN on Titan for the first time. These isotopic ratios are leveraged to constrain the physical and chemical processes occurring in Titan's atmosphere.

  9. The Effect of Aerosol Formation on Stable Isotopes Ratio in Titan's Atmosphere

    NASA Astrophysics Data System (ADS)

    Gautier, Thomas; Trainer, Melissa G.; Sebree, Joshua; Wold, Allison; Stern, Jennifer

    2016-10-01

    The formation of large amounts of aerosol in Titan atmosphere induces a significant sink for carbon and nitrogen in the atmosphere. Due to the high complexity of the chemistry leading to aerosol formation, there may be isotopic fractionation along the formation pathways of the aerosol. So far several stable isotopes have been measured in Titan atmosphere including the 13C/12C, 15N/14N and D/H ratios for different gaseous species. However, the fractionation effect of the aerosol formation and its impact on atmospheric stable isotope ratios has yet to be fully understood. Two experimental studies were recently published on the stable carbon [1] and nitrogen [1,2] isotope fractionation during aerosol formation in N2-CH4 reactant mixture. To better constrain the fractionation effect of aerosol formation on the Titan atmosphere we have measured the isotopic fractionation induced in laboratory aerosol analogues produced exploring the space of parameters that are expected to have an effect on fractionation processes. Parameters studied include pressure and temperature of aerosol formation and the reactant gas phase composition, including the standard "Titan" mixture of CH4/N2 as well as other trace species such as benzene (C6H6).[1] Sebree, J.A., Stern, J.C., Mandt, K.E., Domagal-Goldman, S.D., and Trainer, M.G.: C and N Fractionation of CH /N Mixtures during Photochemical Aerosol Formation: Relevance to Titan, (2016) Icarus 270:421-428[2] Kuga, M., Carrasco, N., Marty, B., Marrochi, Y., Bernard, S., Rigaudier, T., Fleury, B., Tissandier, L.: Nitrogen isotopic fractionation during abiotic synthesis of organic solid particles, (2014) EPSL 393:2-13

  10. Simultaneous measurement of CO2 concentration and isotopic ratios in gas samples using IRMS

    NASA Astrophysics Data System (ADS)

    Yu, Eun-Ji; Lee, Dongho; Bong, Yeon-Sik; Lee, Kwang-Sik

    2014-05-01

    Isotopic methods are indispensable tools for studies on atmosphere-biosphere exchanges of CO2 and environmental monitoring such as CO2 leakage detection from subsurface carbon storages. CO2 concentration is an important variable in interpreting isotopic composition of CO2 especially in atmospheric applications (e.g., 'Keeling plot'). Optical methods such as CRDS (Cavity Ring Down Spectroscopy) are gaining attention recently because of its capability to simultaneously measure CO2 concentration and isotopic ratios with a short measurement interval (up to 1 sec.). On the other hand, IRMS (Isotope Ratio Mass Spectrometer) has been used only for isotopic measurements. In this study, we propose a method to measure CO2 concentration from gas samples along with isotopic ratios using conventional IRMS system. The system consists of Delta V Plus IRMS interfaced with GasBench II (Thermo Scientific, Germany). 12-mL vials with open top screw cap and rubber septum were used for both gas sampling and analysis. For isotopic analysis, gases in the vials were transferred into GasBench II by He carrier flow and CO2 was trapped by a single cryotrap (-180 ºC) after passing a water trap (Mg(ClO4)2). Upon release of the cryotrap, liberated CO2 was separated from N2O using gas chromatography column inside the GasBench II and introduced online into the IRMS. Isotopic ratios were measured for the masses of 44, 45 and 46, and the peak intensity (mV of mass 44 and peak area) was recorded for the concentration calculation. For the determination of CO2 concentration, a calibration curve relating the peak intensity with molar concentration of CO2 was constructed. By dissolving NaHCO3 in de-ionized water, solutions containing 0.05, 0.1, 0.25 and 0.5 µmol of inorganic carbon were prepared in 12 mL vials. Phosphoric acid was injected through rubber septum of the vials to acidify the solution and released CO2 was analyzed for the isotopic ratios and the corresponding peak intensity was recorded

  11. Cesium Isotope Ratios as Indicators of Nuclear Power Plant Operations

    SciTech Connect

    Darin Snyder; James Delmore; Troy Tranter; Nick Mann; Michael Abbott; John Olson

    2011-11-01

    There are multiple paths by which radioactive cesium can reach the effluent from reactor operations. The radioactive 135Cs/137Cs ratios are controlled by these paths. In an effort to better understand the origin of this radiation, these 135Cs/137Cs ratios in effluents from three power reactor sites have been measured in offsite samples. These ratios are different from global fallout by up to six fold and as such cannot have a significant component from this source. A cesium ratio for a sample collected outside of the plant boundary provides integration over the operating life of the reactor. A sample collected inside the plant at any given time can be much different from this lifetime ratio. The measured cesium ratios vary significantly for the three reactors and indicate that the multiple paths have widely varying levels of contributions. There are too many ways these isotopes can fractionate to be useful for quantitative evaluations of operating parameters in an offsite sample, although it may be possible to obtain limited qualitative information for an onsite sample.

  12. Cesium isotope ratios as indicators of nuclear power plant operations.

    PubMed

    Delmore, James E; Snyder, Darin C; Tranter, Troy; Mann, Nick R

    2011-11-01

    There are multiple paths by which radioactive cesium can reach the effluent from reactor operations. The radioactive (135)Cs/(137)Cs ratios are controlled by these paths. In an effort to better understand the origin of this radiation, these (135)Cs/(137)Cs ratios in effluents from three power reactor sites have been measured in offsite samples. These ratios are different from global fallout by up to six fold and as such cannot have a significant component from this source. A cesium ratio for a sample collected outside of the plant boundary provides integration over the operating life of the reactor. A sample collected inside the plant at any given time can be much different from this lifetime ratio. The measured cesium ratios vary significantly for the three reactors and indicate that the multiple paths have widely varying levels of contributions. There are too many ways these isotopes can fractionate to be useful for quantitative evaluations of operating parameters in an offsite sample, although it may be possible to obtain limited qualitative information for an onsite sample.

  13. Potential uses of lead isotope ratios in gunshot cases.

    PubMed

    Keisch, B; Callahan, R C

    1978-05-01

    The determination of lead isotope ratios in 14 bullets, and in material taken from 9 hand swabs and 5 primers shows that there are potentially valuable forensic uses for such a method. While a more complete study is required, this method could possibly be used to prove (or disprove) relatiohships between bullets and manufacturers, weapons, or persons firing the weapons. Sample size requirements (1 microgram or less) are such that damaged or fragmented bullets, or minute particles therefrom, may be used for the required analyses. An experiment showed that gunshot residue from a test-fired weapon was detectable even after washing the hands.

  14. Oxygen isotope partitioning between phosphate and carbonate in mammalian apatite

    NASA Astrophysics Data System (ADS)

    Daniel Bryant, J.; Koch, Paul L.; Froelich, Philip N.; Showers, William J.; Genna, Bernard J.

    1996-12-01

    The oxygen isotope compositions of phosphate and structural carbonate in mammalian enamel and bone apatite are linked to that of body water at constant body temperature near 37°C, but the isotope systematics of oxygen in structural carbonate are not well understood. Using coupled measurements of the oxygen isotope composition of structural carbonate and phosphate from horse tooth enamel, the apparent oxygen isotope fractionation factor between structural carbonate and body water is estimated to be 1.0263 ± 0.0014. These estimates provide a quantitative basis for using the oxygen isotope composition of structural carbonate in mammalian biogenic apatite for ecological, climatological, and physiological reconstruction.

  15. Isotope ratio monitoring of small molecules and macromolecules by liquid chromatography coupled to isotope ratio mass spectrometry.

    PubMed

    Godin, Jean-Philippe; Hau, Jörg; Fay, Laurent-Bernard; Hopfgartner, Gérard

    2005-01-01

    In the field of isotope ratio mass spectrometry, the introduction of an interface allowing the connection of liquid chromatography (LC) and isotope ratio mass spectrometry (IRMS) has opened a range of new perspectives. The LC interface is based on a chemical oxidation, producing CO2 from organic molecules. While first results were obtained from the analysis of low molecular weight compounds, the application of compound-specific isotope analysis by irm-LC/MS to other molecules, in particular biomolecules, is presented here. The influence of the LC flow rate on the CO2 signal and on the observed delta13C values is demonstrated. The limits of quantification for angiotensin III and for leucine were 100 and 38 pmol, respectively, with a standard deviation of the delta13C values better than 0.4 per thousand. Also, accuracy and precision of delta13C values for elemental analyser-IRMS and flow injection analysis-IRMS (FIA-LC/MS) were compared. For compounds with molecular weights ranging from 131 to 66,390 Da, precision was better than 0.3 per thousand, and accuracy varied from 0.1 to 0.7 per thousand. In a second part of the work, a two-dimensional (2D)-LC method for the separation of 15 underivatised amino acids is demonstrated; the precision of delta13C values for several amino acids by irm-LC/MS was better than 0.3 per thousand at natural abundance. For labelled mixtures, the coefficient of variation was between 1% at 0.07 atom % excess (APE) for threonine and alanine, and around 10% at 0.03 APE for valine and phenylalanine. The application of irm-LC/MS to the determination of the isotopic enrichment of 13C-threonine in an extract of rat colon mucosa demonstrated a precision of 0.5 per thousand, or 0.001 atom %.

  16. The lithium isotopic ratio in very metal-poor stars

    NASA Astrophysics Data System (ADS)

    Lind, K.; Melendez, J.; Asplund, M.; Collet, R.; Magic, Z.

    2013-06-01

    Context. Un-evolved, very metal-poor stars are the most important tracers of the cosmic abundance of lithium in the early universe. Combining the standard Big Bang nucleosynthesis model with Galactic production through cosmic ray spallation, these stars at [Fe / H] < - 2 are expected to show an undetectably small 6Li / 7Li isotopic signature. Evidence to the contrary may necessitate an additional pre-galactic production source or a revision of the standard model of Big Bang nucleosynthesis. It would also cast doubts on Li depletion from stellar atmospheres as an explanation for the factor 3-5 discrepancy between the predicted primordial 7Li from the Big Bang and the observed value in metal-poor dwarf/turn-off stars. Aims: We revisit the isotopic analysis of four halo stars, two with claimed 6Li-detections in the literature, to investigate the influence of improved model atmospheres and line formation treatment. Methods: For the first time, a combined 3D, non-local thermodynamic equilibrium (NLTE) modelling technique for Li, Na, and Ca lines is utilised to constrain the intrinsic line-broadening and to determine the Li isotopic ratio. We discuss the influence of 3D NLTE effects on line profile shapes and assess the realism of our modelling using the Ca excitation and ionisation balance. Results: By accounting for NLTE line formation in realistic 3D hydrodynamical model atmospheres, we can model the Li resonance line and other neutral lines with a consistency that is superior to LTE, with no need for additional line asymmetry caused by the presence of 6Li. Contrary to the results from 1D and 3D LTE modelling, no star in our sample has a significant (2σ) detection of the lighter isotope in NLTE. Over a large parameter space, NLTE modelling systematically reduces the best-fit Li isotopic ratios by up to five percentage points. As a bi-product, we also present the first ever 3D NLTE Ca and Na abundances of halo stars, which reveal significant departures from LTE

  17. Dietary Heterogeneity among Western Industrialized Countries Reflected in the Stable Isotope Ratios of Human Hair

    PubMed Central

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

    2012-01-01

    Although the globalization of food production is often assumed to result in a homogenization of consumption patterns with a convergence towards a Western style diet, the resources used to make global food products may still be locally produced (glocalization). Stable isotope ratios of human hair can quantify the extent to which residents of industrialized nations have converged on a standardized diet or whether there is persistent heterogeneity and glocalization among countries as a result of different dietary patterns and the use of local food products. Here we report isotopic differences among carbon, nitrogen and sulfur isotope ratios of human hair collected in thirteen Western European countries and in the USA. European hair samples had significantly lower δ13C values (−22.7 to −18.3‰), and significantly higher δ15N (7.8 to 10.3‰) and δ34S (4.8 to 8.3‰) values than samples from the USA (δ13C: −21.9 to −15.0‰, δ15N: 6.7 to 9.9‰, δ34S: −1.2 to 9.9‰). Within Europe, we detected differences in hair δ13C and δ34S values among countries and covariation of isotope ratios with latitude and longitude. This geographic structuring of isotopic data suggests heterogeneity in the food resources used by citizens of industrialized nations and supports the presence of different dietary patterns within Western Europe despite globalization trends. Here we showed the potential of stable isotope analysis as a population-wide tool for dietary screening, particularly as a complement of dietary surveys, that can provide additional information on assimilated macronutrients and independent verification of data obtained by those self-reporting instruments. PMID:22479574

  18. Detection of exogenous citric acid in fruit juices by stable isotope ratio analysis.

    PubMed

    Jamin, Eric; Martin, Frédérique; Santamaria-Fernandez, Rebeca; Lees, Michèle

    2005-06-29

    A new method has been developed for measuring the D/H ratio of the nonexchangeable sites of citric acid by isotope ratio mass spectrometry (IRMS). Pure citric acid is transformed into its calcium salt and subsequently analyzed by pyrolysis-IRMS. The citric acid isolated from authentic fruit juices (citrus, pineapple, and red fruits) systematically shows higher D/H values than its nonfruit counterpart produced by fermentation of various sugar sources. The discrimination obtained with this simplified method is similar to that obtained previously by applying site specific isotopic fractionation-nuclear magnetic resonance (SNIF-NMR) to an ester derivative of citric acid. The combination of carbon 13 and deuterium measurements of extracted citric acid is proposed as a routine method for an optimum detection of exogenous citric acid in all kinds of fruit juices.

  19. The use of δ13C isotope ratio mass spectrometry for methamphetamine profiling: comparison of ephedrine and pseudoephedrine-based samples to P2P-based samples.

    PubMed

    Toske, Steven G; Morello, David R; Berger, Jennifer M; Vazquez, Etienne R

    2014-01-01

    Differentiating methamphetamine samples produced from ephedrine and pseudoephedrine from phenyl-2-propanone precursors is critical for assigning synthetic route information for methamphetamine profiling. The use of isotope ratio mass spectrometry data is now a key component for tracking precursor information. Recent carbon (δ(13)C) isotope results from the analysis of numerous methamphetamine samples show clear differentiation for ephedrine and pseudoephedrine-produced samples compared to P2P-produced samples. The carbon isotope differences were confirmed from synthetic route precursor studies.

  20. Radiohalos: some unique lead isotope ratios and unknown alpha radioactivity.

    PubMed

    Gentry, R V

    1971-08-20

    Previously unreported lead isotope ratios, that is, values for the lead-206/lead-207 ratio ranging from about 20 to 60, primarily radiogenic in origin but unsupported by uranium decay, have been determined in the inclusions of certain polonium halos by means of ion microprobe techniques. Evidence for radiogenic lead-208 unsupported by thorium decay may also be inferred from the existence of a composite polonium halo type with rings from the radioactive precursors of lead-208. Several new dwarf halo sizes, seem to indicate the existence of unknown, very low-energy alpha-emitters. Furthermore, the three-ring "X halo" also provides evidence for an unknown series of genetically related alpha-emitters with energies in the range from 3 to 7 million electron volts.

  1. Last Glacial Maximum and deglacial abyssal seawater oxygen isotopic ratios

    NASA Astrophysics Data System (ADS)

    Wunsch, Carl

    2016-06-01

    An earlier analysis of pore-water salinity (chlorinity) in two deep-sea cores, using terminal constraint methods of control theory, concluded that although a salinity amplification in the abyss was possible during the LGM, it was not required by the data. Here the same methodology is applied to δ18Ow in the upper 100 m of four deep-sea cores. An ice volume amplification to the isotopic ratio is, again, consistent with the data but not required by it. In particular, results are very sensitive, with conventional diffusion values, to the assumed initial conditions at -100 ky and a long list of noise (uncertainty) assumptions. If the calcite values of δ18O are fully reliable, then published enriched values of the ratio in seawater are necessary to preclude sub-freezing temperatures, but the seawater δ18O in pore fluids does not independently require the conclusion.

  2. Carbon kinetic isotope effect in the reaction of CH{sub 4} with Cl atoms

    SciTech Connect

    Saueressig, G.; Bergamaschi, P.; Crowley, J.N.

    1995-05-15

    The authors report laser absorption spectroscopy measurements of the carbon kinetic isotope effect involving chlorine reacting with methane under stratospheric type conditions. The authors find a slight isotope effect of 1.066 {+-} 0.002 at 297 K for the ratio of {sup 13}CH{sub 4}/{sup 12}CH{sub 4}. There was also a slight temperature dependence observed.

  3. Lipid Correction for Carbon Stable Isotope Analysis of Deep-sea Fishes

    EPA Science Inventory

    Lipid extraction is used prior to stable isotope analysis of fish tissues to remove variability in the carbon stable isotope ratio (d13C) caused by varying lipid content among samples. Our objective was to evaluate an application of a mass balance correction for the effect of lip...

  4. Correlation between the oxygen isotope ratio of North American bison teeth and local waters: Implication for paleoclimatic reconstructions

    NASA Astrophysics Data System (ADS)

    Hoppe, Kathryn A.

    2006-04-01

    The oxygen isotope ratios of tooth enamel carbonate from 64 North American bison ( Bison bison) from eleven locations were measured. The mean enamel oxygen isotope ratios for bison populations ranged from 28.3 to 15.9 ‰ SMOW and correlated well with the annual mean oxygen isotope ratios of local surface waters and precipitation. The standard deviation of oxygen isotope values among different individuals within each bison population averaged 1.0 ‰, and ranged from 0.7 to 1.4 ‰. The variability of enamel oxygen isotope ratios was not significantly different among different populations and did not correlate with changes in temperature, precipitation, or relative humidity. These results demonstrate that the average oxygen isotope values of bison tooth enamel can be used for use as a quantitative proxy for reconstructing the values of surface waters, and therefore may provide valuable paleoclimatic information. This study provides a baseline comparison for analyses of the oxygen isotope ratios of bison and other large herbivores from across North America.

  5. Improving the Sensitivity of Uranium Isotope Ratio Measurements

    NASA Astrophysics Data System (ADS)

    Friedrich, J.; Snow, J.

    2003-12-01

    Accurate and precise measurements of natural and anthropogenic 235/238 U isotope ratios are important for a range of investigations where the amount of sample is extremely restricted and/or the analyte is only present in ultra-trace quantities. Examples include biological, cosmochemical, environmental, geological, and radiological studies. We have developed and validated a novel method using our Nu Instruments Nu Plasma Multi Collector Inductively Coupled Plasma Mass Spectrometer (MC-ICPMS) and a 233U, 236U mixed double spike for the measurement of 235U/238U ratios. Our multi-dynamic technique employs the installed quadrupole zoom optics and fixed positioning of the ion counting detectors such that rather than the commonly used mass dispersion of 1 or 2, we utilize a mass dispersion of 1.5. Using this configuration, we can simultaneously monitor the 235U and 238U ion beams in the first cycle followed by a second cycle that simultaneously monitors the 233U and 236U beams. This innovative approach allows us to correct for the considerable, but consistent, instrumental mass fractionation and ion-counter amplification bias within each sequence. Since we were hesitant to use a U500 (235U, 238U equal atom) solution for spike calibration because of possible enriched U laboratory and instrumentation contamination, we used a U960 (terrestrial 235U/238U) solution for isotopic calibration of the spike. This standardization corrected for the small amounts of 235U and 238U in the spike solution by using a U960 standard solution. With a mean intraday 2-sigma precision of 1.5 permil and an overall 2-sigma precision of 2.25 permil using individual sample sizes of 350 pg (8.8 x10 E11 atoms), we are confident our technique will be useful for identifying U isotopic anomalies present in many sample types.

  6. Constraining the global bromomethane budget from carbon stable isotopes

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  7. Examining Changes in Radioxenon Isotope Activity Ratios during Subsurface Transport

    NASA Astrophysics Data System (ADS)

    Annewandter, R.

    2013-12-01

    The Non-Proliferation Experiment (NPE) has demonstrated and modelled the usefulness of barometric pumping induced soil gas sampling during On-Site inspections. Gas transport has been widely studied with different numerical codes. However, gas transport of all radioxenons in the post-detonation regime and their possible fractionation is still neglected in the open literature. Atmospheric concentrations of the radioxenons Xe-135, Xe-133m, Xe-133 and Xe-131m can be used to discriminate between civilian releases (nuclear power plants or medical isotope facilities), and nuclear explosion sources. It is based on the isotopic activity ratio method. Yet it is not clear whether subsurface migration of the radioxenons, with eventual release into the atmosphere, can affect the activity ratios due to fractionation. Fractionation can be caused by different diffusivities due to mass differences between the radioxenons. A previous study showed surface arrival time of a chemically inert gaseous tracer is affected by its diffusivity. They observed detectable amount for SF6 50 days after detonation and 375 days for He-3. They predict 50 and 80 days for Xe-133 and Ar-37 respectively. Cyclical changes in atmospheric pressure can drive subsurface gas transport. This barometric pumping phenomenon causes an oscillatoric flow in upward trending fractures which, combined with diffusion into the porous matrix, leads to a net transport of gaseous components - a ratcheting effect. We use a general purpose reservoir simulator (Complex System Modelling Platform, CSMP++) which has been applied in a range of fields such as deep geothermal systems, three-phase black oil simulations , fracture propagation in fractured, porous media, Navier-Stokes pore-scale modelling among others. It is specifically designed to account for structurally complex geologic situation of fractured, porous media. Parabolic differential equations are solved by a continuous Galerkin finite-element method, hyperbolic

  8. Understanding radioxenon isotopical ratios originating from radiopharmaceutical facilities

    NASA Astrophysics Data System (ADS)

    Saey, P. R. J.; Ringbom, A.; Bowyer, T. W.; Becker, A.; de Geer, L.-E.; Nikkinen, M.; Payne, R. F.

    2009-04-01

    It was recently shown that radiopharmaceutical facilities (RPF) are major contributors to the general background of 133Xe and other xenon isotopes both in the northern and southern hemisphere. To distinguish a nuclear explosion signal from releases from civil nuclear facilities, not only the activity concentrations but also the ratios of the four different CTBT relevant radioxenon isotopes (131mXe, 133mXe, 133Xe and 135Xe) have to be well understood. First measurements taken recently in and around two of the world's largest RPF's: NTP at Pelindaba, South Africa and IRE at Fleurus, Belgium have been presented. At both sites, also stack samples were taken in close cooperation with the facility operators. The radioxenon in Belgium could be classified in four classes: the normal European background (133Xe activity between 0 - 5 mBq/m3) on one hand and then the samples where all four isotopes were detected with 133mXe/131mXe > 1. In northern South Africa the Pelindaba RPF is in practice the sole source of radioxenon. It generated a background of 133Xe at the measurement site some 230 km to the west of the RPF of 0 - 5 mBq/m3. In the cases where the air from the Pelindaba facility reached the measurement site directly and in a short time period, the 133Xe was higher, also 135Xe was present and in some samples 133mXe as well. The ratios of the activity concentrations of 135Xe/133Xe vs. 133mXe/131mXe (Multiple Isotope Ratio Plot - MIRC) have been analysed. For both facilities, the possible theoretical ratio's for different scenarios were calculated with the information available and compared with the measurements. It was found that there is an excess of 131mXe present in the European samples compared to theoretical calculations. A similar excess has also been seen in samples measured in northern America. In South Africa, neither the environmental samples nor the stack ones contained 131mXe at measurable levels. This can probably be explained by different processes and

  9. BOREAS TE-5 Leaf Carbon Isotope Data

    NASA Technical Reports Server (NTRS)

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

    2000-01-01

    The BOREAS TE-5 team collected measurements in the NSA and SSA on gas exchange, gas composition, and tree growth. This documentation describes leaf carbon isotope data that were collected in 1993 and 1994 at the NSA and SSA OJP sites, the SSA OBS site, and the NSA UBS site. In addition, leaf carbon isotope data were collected in 1994 only at the NSA and SSA OA sites. These data was collected to provide seasonal integrated physiological information for 10 to 15 common species at these 6 BOREAS sites. The data are stored in tabular ASCII files. The data files are available on a CD-ROM (see document number 20010000884), or from the Oak Ridge National Laboratory (ORNL) Distributed Active Archive Center (DAAC).

  10. Magnesium isotope fractionation in bacterial mediated carbonate precipitation experiments

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

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

    PubMed

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

    2016-08-04

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

  12. Boron isotope fractionation in magma via crustal carbonate dissolution

    PubMed Central

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

    2016-01-01

    Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ11B values down to −41.5‰, reflecting preferential partitioning of 10B into the assimilating melt. Loss of 11B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports 11B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ11B melt values in arc magmas could flag shallow-level additions to the subduction cycle. PMID:27488228

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

    PubMed

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

    2016-01-01

    Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ(11)B values down to -41.5‰, reflecting preferential partitioning of (10)B into the assimilating melt. Loss of (11)B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports (11)B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ(11)B melt values in arc magmas could flag shallow-level additions to the subduction cycle. PMID:27488228

  14. Boron isotope fractionation in magma via crustal carbonate dissolution

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  15. Forensic applications of light-element stable isotope ratios of Ricinus communis seeds and ricin preparations.

    PubMed

    Kreuzer, Helen W; West, Jason B; Ehleringer, James R

    2013-01-01

    Seeds of the castor plant Ricinus communis are of forensic interest because they are the source of the poison ricin. We tested whether stable isotope ratios of castor seeds and ricin preparations can be used as a forensic signature. We collected over 300 castor seed samples worldwide and measured the C, N, O, and H isotope ratios of the whole seeds and oil. We prepared ricin by three different procedures, acetone extraction, salt precipitation, and affinity chromatography, and compared their isotope ratios to those of the source seeds. The N isotope ratios of the ricin samples and source seeds were virtually identical. Therefore, N isotope ratios can be used to correlate ricin prepared by any of these methods to source seeds. Further, stable isotope ratios distinguished >99% of crude and purified ricin protein samples in pairwise comparison tests. Stable isotope ratios therefore constitute a valuable forensic signature for ricin preparations.

  16. Detritus derived from eelgrass and macroalgae as potential carbon source for Mytilus edulis in Kiel Fjord, Germany: a preliminary carbon isotopic study

    NASA Astrophysics Data System (ADS)

    Wiedemeyer, W. L.; Schwamborn, R.

    1996-09-01

    Stable carbon isotope ratios were measured for the muscle tissue of blue mussel Mytilus edulis, eelgrass Zostera marina, macroalgae Fucus vesiculosus, and phytoplankton in two areas in Kiel Fjord, Germany. Carbon isotope evidence is presented to show the predominance of phytoplanktonic production as a carbon source for M. edulis tissue carbon. Via decomposition processes for both eelgrass and macroalgal primary production, each contributed 0.5 6.5% to mussel carbon.

  17. Effects of environmental and biotic factors on carbon isotopic fractionation during decomposition of soil organic matter

    PubMed Central

    Wang, Guoan; Jia, Yufu; Li, Wei

    2015-01-01

    Decomposition of soil organic matter (SOM) plays an important role in the global carbon cycle because the CO2 emitted from soil respiration is an important source of atmospheric CO2. Carbon isotopic fractionation occurs during SOM decomposition, which leads to 12C to enrich in the released CO2 while 13C to enrich in the residual SOM. Understanding the isotope fractionation has been demonstrated to be helpful for studying the global carbon cycle. Soil and litter samples were collected from soil profiles at 27 different sites located along a vertical transect from 1200 to 4500 m above sea level (a.s.l.) in the south-eastern side of the Tibetan Plateau. Their carbon isotope ratios, C and N concentrations were measured. In addition, fiber and lignin in litter samples were also analyzed. Carbon isotope fractionation factor (α) during SOM decomposition was estimated indirectly as the slope of the relationship between carbon isotope ratios of SOM and soil C concentrations. This study shows that litter quality and soil water play a significant role in isotope fractionation during SOM decomposition, and the carbon isotope fractionation factor, α, increases with litter quality and soil water content. However, we found that temperature had no significant impact on the α variance. PMID:26056012

  18. Effects of environmental and biotic factors on carbon isotopic fractionation during decomposition of soil organic matter.

    PubMed

    Wang, Guoan; Jia, Yufu; Li, Wei

    2015-06-09

    Decomposition of soil organic matter (SOM) plays an important role in the global carbon cycle because the CO2 emitted from soil respiration is an important source of atmospheric CO2. Carbon isotopic fractionation occurs during SOM decomposition, which leads to (12)C to enrich in the released CO2 while (13)C to enrich in the residual SOM. Understanding the isotope fractionation has been demonstrated to be helpful for studying the global carbon cycle. Soil and litter samples were collected from soil profiles at 27 different sites located along a vertical transect from 1200 to 4500 m above sea level (a.s.l.) in the south-eastern side of the Tibetan Plateau. Their carbon isotope ratios, C and N concentrations were measured. In addition, fiber and lignin in litter samples were also analyzed. Carbon isotope fractionation factor (α) during SOM decomposition was estimated indirectly as the slope of the relationship between carbon isotope ratios of SOM and soil C concentrations. This study shows that litter quality and soil water play a significant role in isotope fractionation during SOM decomposition, and the carbon isotope fractionation factor, α, increases with litter quality and soil water content. However, we found that temperature had no significant impact on the α variance.

  19. Effects of environmental and biotic factors on carbon isotopic fractionation during decomposition of soil organic matter.

    PubMed

    Wang, Guoan; Jia, Yufu; Li, Wei

    2015-01-01

    Decomposition of soil organic matter (SOM) plays an important role in the global carbon cycle because the CO2 emitted from soil respiration is an important source of atmospheric CO2. Carbon isotopic fractionation occurs during SOM decomposition, which leads to (12)C to enrich in the released CO2 while (13)C to enrich in the residual SOM. Understanding the isotope fractionation has been demonstrated to be helpful for studying the global carbon cycle. Soil and litter samples were collected from soil profiles at 27 different sites located along a vertical transect from 1200 to 4500 m above sea level (a.s.l.) in the south-eastern side of the Tibetan Plateau. Their carbon isotope ratios, C and N concentrations were measured. In addition, fiber and lignin in litter samples were also analyzed. Carbon isotope fractionation factor (α) during SOM decomposition was estimated indirectly as the slope of the relationship between carbon isotope ratios of SOM and soil C concentrations. This study shows that litter quality and soil water play a significant role in isotope fractionation during SOM decomposition, and the carbon isotope fractionation factor, α, increases with litter quality and soil water content. However, we found that temperature had no significant impact on the α variance. PMID:26056012

  20. CO (Carbon Monoxide Mixing Ratio System) Handbook

    SciTech Connect

    Biraud, S

    2011-02-23

    The main function of the CO instrument is to provide continuous accurate measurements of carbon monoxide mixing ratio at the ARM SGP Central Facility (CF) 60-meter tower (36.607 °N, 97.489 °W, 314 meters above sea level). The essential feature of the control and data acquisition system is to record signals from a Thermo Electron 48C and periodically calibrate out zero and span drifts in the instrument using the combination of a CO scrubber and two concentrations of span gas (100 and 300 ppb CO in air). The system was deployed on May 25, 2005.

  1. Isotopic ratio correlation for the isotopic composition analysis of plutonium in Am-Pu mixed samples having high americium content.

    PubMed

    Patra, Sabyasachi; Agarwal, Chhavi; Chaudhury, Sanhita; Newton Nathaniel, T; Gathibandhe, M; Goswami, A

    2013-08-01

    Interference of high amount of americium in the plutonium isotopic composition analysis has been studied by simulating gamma-ray spectra for Am-Pu samples over a wide composition range (5-97% (241)Am) for both power and research reactor grade plutonium. An alternate way for isotopic composition analysis has been proposed by correlating the isotopic ratios available in our old database with the experimentally obtained (241)Pu/(239)Pu isotopic ratio. The proposed method has been validated using simulated spectra of known isotopic compositions.

  2. Examining Changes in Radioxenon Isotope Activity Ratios during Subsurface Transport

    NASA Astrophysics Data System (ADS)

    Annewandter, Robert

    2014-05-01

    The Non-Proliferation Experiment (NPE) has demonstrated and modelled the usefulness of barometric pumping induced gas transport and subsequent soil gas sampling during On-Site inspections. Generally, gas transport has been widely studied with different numerical codes. However, gas transport of radioxenons and radioiodines in the post-detonation regime and their possible fractionation is still neglected in the open peer-reviewed literature. Atmospheric concentrations of the radioxenons Xe-135, Xe-133m, Xe-133 and Xe-131m can be used to discriminate between civilian releases (nuclear power plants or medical isotope facilities), and nuclear explosion sources. It is based on the multiple isotopic activity ratio method. Yet it is not clear whether subsurface migration of the radionuclides, with eventual release into the atmosphere, can affect the activity ratios due to fractionation. Fractionation can be caused by different mass diffusivities due to mass differences between the radionuclides. Cyclical changes in atmospheric pressure can drive subsurface gas transport. This barometric pumping phenomenon causes an oscillatoric flow in upward trending fractures or highly conductive faults which, combined with diffusion into the porous matrix, leads to a net transport of gaseous components - a so-called ratcheting effect. We use a general purpose reservoir simulator (Complex System Modelling Platform, CSMP++) which is recognized by the oil industry as leading in Discrete Fracture-Matrix (DFM) simulations. It has been applied in a range of fields such as deep geothermal systems, three-phase black oil simulations, fracture propagation in fractured, porous media, and Navier-Stokes pore-scale modelling among others. It is specifically designed to account for structurally complex geologic situation of fractured, porous media. Parabolic differential equations are solved by a continuous Galerkin finite-element method, hyperbolic differential equations by a complementary finite

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

    PubMed

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

    2016-02-01

    Chemical attribution signatures (CAS) for chemical threat agents (CTAs), such as cyanides, are being investigated to provide an evidentiary link between CTAs and specific sources to support criminal investigations and prosecutions. Herein, stocks of KCN and NaCN were analyzed for trace anions by high performance ion chromatography (HPIC), carbon stable isotope ratio (δ(13)C) by isotope ratio mass spectrometry (IRMS), and trace elements by inductively coupled plasma optical emission spectroscopy (ICP-OES). The collected analytical data were evaluated using hierarchical cluster analysis (HCA), Fisher-ratio (F-ratio), interval partial least-squares (iPLS), genetic algorithm-based partial least-squares (GAPLS), partial least-squares discriminant analysis (PLSDA), K nearest neighbors (KNN), and support vector machines discriminant analysis (SVMDA). HCA of anion impurity profiles from multiple cyanide stocks from six reported countries of origin resulted in cyanide samples clustering into three groups, independent of the associated alkali metal (K or Na). The three groups were independently corroborated by HCA of cyanide elemental profiles and corresponded to countries each having one known solid cyanide factory: Czech Republic, Germany, and United States. Carbon stable isotope measurements resulted in two clusters: Germany and United States (the single Czech stock grouped with United States stocks). Classification errors for two validation studies using anion impurity profiles collected over five years on different instruments were as low as zero for KNN and SVMDA, demonstrating the excellent reliability associated with using anion impurities for matching a cyanide sample to its factory using our current cyanide stocks. Variable selection methods reduced errors for those classification methods having errors greater than zero; iPLS-forward selection and F-ratio typically provided the lowest errors. Finally, using anion profiles to classify cyanides to a specific stock

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

    PubMed

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

    2016-02-01

    Chemical attribution signatures (CAS) for chemical threat agents (CTAs), such as cyanides, are being investigated to provide an evidentiary link between CTAs and specific sources to support criminal investigations and prosecutions. Herein, stocks of KCN and NaCN were analyzed for trace anions by high performance ion chromatography (HPIC), carbon stable isotope ratio (δ(13)C) by isotope ratio mass spectrometry (IRMS), and trace elements by inductively coupled plasma optical emission spectroscopy (ICP-OES). The collected analytical data were evaluated using hierarchical cluster analysis (HCA), Fisher-ratio (F-ratio), interval partial least-squares (iPLS), genetic algorithm-based partial least-squares (GAPLS), partial least-squares discriminant analysis (PLSDA), K nearest neighbors (KNN), and support vector machines discriminant analysis (SVMDA). HCA of anion impurity profiles from multiple cyanide stocks from six reported countries of origin resulted in cyanide samples clustering into three groups, independent of the associated alkali metal (K or Na). The three groups were independently corroborated by HCA of cyanide elemental profiles and corresponded to countries each having one known solid cyanide factory: Czech Republic, Germany, and United States. Carbon stable isotope measurements resulted in two clusters: Germany and United States (the single Czech stock grouped with United States stocks). Classification errors for two validation studies using anion impurity profiles collected over five years on different instruments were as low as zero for KNN and SVMDA, demonstrating the excellent reliability associated with using anion impurities for matching a cyanide sample to its factory using our current cyanide stocks. Variable selection methods reduced errors for those classification methods having errors greater than zero; iPLS-forward selection and F-ratio typically provided the lowest errors. Finally, using anion profiles to classify cyanides to a specific stock

  5. Carbonate clumped isotope bond reordering and geospeedometry

    NASA Astrophysics Data System (ADS)

    Passey, Benjamin H.; Henkes, Gregory A.

    2012-10-01

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

  6. Using isotopic ratios for discrimination of environmental anthropogenic radioactivity.

    PubMed

    Hayes, Robert B; Akbarzadeh, Mansour

    2014-10-01

    When air is pulled into the WIPP repository for ventilation purposes, this air is unfiltered and contains all the components of ubiquitous anthropogenic radionuclides from global nuclear fallout (including Cs and Pu isotopes). Although the NORM in aeolian sand and dust contribute to the gross alpha beta activity on effluent air filters, there remains a need to discriminate effluent TRU generated in the disposal process at WIPP from TRU being pulled into the repository with the unfiltered surface air. This is only evaluated using ratios of Cs and Pu activity found through radioassay of air filters taken from the mine effluent. By characterizing both the credible range of Cs/Pu ratios from the environment and those known to exist in the waste, a rigorous test criteria is attained. The use of HPGE to assay Cs in the intake dust plated out in the mine allowed a gross assay of total TRU radioactivity pulled into the mine over time from global fallout. Radiochemistry of samples from deposition in the mine's air intake shaft was also carried out. The use of net activity ratios at background levels is also shown to follow a Cauchy distribution in terms of their expected statistical distributions.

  7. A new method for carbon isotopic analysis of protein

    SciTech Connect

    Nelson, D.E. )

    1991-02-01

    The reaction of ninhydrin with amino acids can be used in carbon isotopic studies of protein. The reaction can be applied to extract as carbon dioxide only peptide-bonded carbon in proteinaceous material, thus avoiding most, if not all, contaminants. Test radiocarbon dates on ancient bone indicate that the method provides reliable ages, and stable carbon isotopic data suggest that our understanding of isotopic dietary reconstruction needs detailed examination. The technique should also be useful in biochemical tracing experiments and in global carbon budget studies, and the underlying principle may be applicable to other isotopes and molecules. 28 refs., 1 fig., 1 tab.

  8. Carbon to oxygen ratios in extrasolar planetesimals

    NASA Astrophysics Data System (ADS)

    Wilson, David J.; Gänsicke, Boris T.; Farihi, Jay; Koester, Detlev

    2016-07-01

    Observations of small extrasolar planets with a wide range of densities imply a variety of planetary compositions and structures. Currently, the only technique to measure the bulk composition of extrasolar planetary systems is the analysis of planetary debris accreting on to white dwarfs, analogous to abundance studies of meteorites. We present measurements of the carbon and oxygen abundances in the debris of planetesimals at ten white dwarfs observed with the Hubble Space Telescope, along with C/O ratios of debris in six systems with previously reported abundances. We find no evidence for carbon-rich planetesimals, with C/O < 0.8 by number in all 16 systems. Our results place an upper limit on the occurrence of carbon-rich systems at <17 per cent with a 2σ confidence level. The range of C/O of the planetesimals is consistent with that found in the Solar system, and appears to follow a bimodal distribution: a group similar to the CI chondrites, with log (< C/O >) = -0.92, and oxygen-rich objects with C/O less than or equal to that of the bulk Earth. The latter group may have a higher mass fraction of water than the Earth, increasing their relative oxygen abundance.

  9. Water isotopic ratios from a continuously melted ice core sample

    NASA Astrophysics Data System (ADS)

    Gkinis, V.; Popp, T. J.; Blunier, T.; Bigler, M.; Schüpbach, S.; Johnsen, S. J.

    2011-06-01

    A new technique for on-line high resolution isotopic analysis of liquid water, tailored for ice core studies is presented. We build an interface between an Infra Red Cavity Ring Down Spectrometer (IR-CRDS) and a Continuous Flow Analysis (CFA) system. The system offers the possibility to perform simultaneuous water isotopic analysis of δ18O and δD on a continuous stream of liquid water as generated from a continuously melted ice rod. Injection of sub μl amounts of liquid water is achieved by pumping sample through a fused silica capillary and instantaneously vaporizing it with 100 % efficiency in a home made oven at a temperature of 170 °C. A calibration procedure allows for proper reporting of the data on the VSMOW scale. We apply the necessary corrections based on the assessed performance of the system regarding instrumental drifts and dependance on humidity levels. The melt rates are monitored in order to assign a depth scale to the measured isotopic profiles. Application of spectral methods yields the combined uncertainty of the system at below 0.1 ‰ and 0.5 ‰ for δ18O and δD, respectively. This performance is comparable to that achieved with mass spectrometry. Dispersion of the sample in the transfer lines limits the resolution of the technique. In this work we investigate and assess these dispersion effects. By using an optimal filtering method we show how the measured profiles can be corrected for the smoothing effects resulting from the sample dispersion. Considering the significant advantages the technique offers, i.e. simultaneuous measurement of δ18O and δD, potentially in combination with chemical components that are traditionally measured on CFA systems, notable reduction on analysis time and power consumption, we consider it as an alternative to traditional isotope ratio mass spectrometry with the possibility to be deployed for field ice core studies. We present data acquired in the framework of the NEEM deep ice core drilling project in

  10. Water isotopic ratios from a continuously melted ice core sample

    NASA Astrophysics Data System (ADS)

    Gkinis, V.; Popp, T. J.; Blunier, T.; Bigler, M.; Schüpbach, S.; Kettner, E.; Johnsen, S. J.

    2011-11-01

    A new technique for on-line high resolution isotopic analysis of liquid water, tailored for ice core studies is presented. We built an interface between a Wavelength Scanned Cavity Ring Down Spectrometer (WS-CRDS) purchased from Picarro Inc. and a Continuous Flow Analysis (CFA) system. The system offers the possibility to perform simultaneuous water isotopic analysis of δ18O and δD on a continuous stream of liquid water as generated from a continuously melted ice rod. Injection of sub μl amounts of liquid water is achieved by pumping sample through a fused silica capillary and instantaneously vaporizing it with 100% efficiency in a~home made oven at a temperature of 170 °C. A calibration procedure allows for proper reporting of the data on the VSMOW-SLAP scale. We apply the necessary corrections based on the assessed performance of the system regarding instrumental drifts and dependance on the water concentration in the optical cavity. The melt rates are monitored in order to assign a depth scale to the measured isotopic profiles. Application of spectral methods yields the combined uncertainty of the system at below 0.1‰ and 0.5‰ for δ18O and δD, respectively. This performance is comparable to that achieved with mass spectrometry. Dispersion of the sample in the transfer lines limits the temporal resolution of the technique. In this work we investigate and assess these dispersion effects. By using an optimal filtering method we show how the measured profiles can be corrected for the smoothing effects resulting from the sample dispersion. Considering the significant advantages the technique offers, i.e. simultaneuous measurement of δ18O and δD, potentially in combination with chemical components that are traditionally measured on CFA systems, notable reduction on analysis time and power consumption, we consider it as an alternative to traditional isotope ratio mass spectrometry with the possibility to be deployed for field ice core studies. We present

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

    SciTech Connect

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

    2013-11-13

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

    Product origin is of great importance for consumers especially because its association in consumer's perception with food quality, freedom from disease or pollution. Stable isotope ratio analysis is a powerful technique in food authenticity and traceability control which has been introduced within the European wine industry to ensure authenticity of wine provenance and to detect adulteration. Isotopic ratios measurements have also been successfully to other food commodities like: fruit juices, honey and dairy foods. The δ18O and δ2H content in milk water reflects the isotope composition of the ground water drunk by animals. Seasonal effects are also very important: in summer, milk water contains higher δ18O and δ2H values due to the fresh plants that are ate by animals. Relative carbon stable isotope abundances in total milk reflect the isotopic composition of the diet fed to the dairy cows. In this study the hydrogen, oxygen and carbon isotopic composition of 15 milk samples coming from a unit placed in the mountains of Transylvania was investigated. The distribution of the obtained isotopic values was than discussed taking into account that all the animals were feed with the same type of forage and consumed water was taken from the same source.

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

    NASA Astrophysics Data System (ADS)

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

    2010-06-01

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

  14. Mg Isotopic Compositions of Modern Marine Carbonates

    NASA Astrophysics Data System (ADS)

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

    2003-12-01

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

  15. Unusual stable isotope ratios in amino acid and carboxylic acid extracts from the Murchison meteorite

    NASA Technical Reports Server (NTRS)

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

    1987-01-01

    The isotopic composition of hydrogen, nitrogen, and carbon in amino acid and monocarboxylic acid extracts from the Murchison meteorite has been determined. The unusually high D/H and N-15/N-14 ratios in the amino acid fraction are uniquely characteristic of known interstellar organic materials. The delta D value of the monocarboxylic acid fraction is lower but still consistent with an interstellar origin. These results confirm the extraterrestrial origin of both classes of compound and provide the first evidence suggesting a direct relationship between the massive organosynthesis occurring in interstellar clouds and the presence of prebiotic compounds in primitive planetary bodies.

  16. Reactive transport modeling of stable carbon isotope fractionation in a multi-phase multi-component system during carbon sequestration

    SciTech Connect

    Zhang, Shuo; DePaolo, Donald J.; Zheng, Liange; Mayer, Bernhard

    2014-12-31

    Carbon stable isotopes can be used in characterization and monitoring of CO2 sequestration sites to track the migration of the CO2 plume and identify leakage sources, and to evaluate the chemical reactions that take place in the CO2-water-rock system. However, there are few tools available to incorporate stable isotope information into flow and transport codes used for CO2 sequestration problems. We present a numerical tool for modeling the transport of stable carbon isotopes in multiphase reactive systems relevant to geologic carbon sequestration. The code is an extension of the reactive transport code TOUGHREACT. The transport module of TOUGHREACT was modified to include separate isotopic species of CO2 gas and dissolved inorganic carbon (CO2, CO32-, HCO3-,…). Any process of transport or reaction influencing a given carbon species also influences its isotopic ratio. Isotopic fractionation is thus fully integrated within the dynamic system. The chemical module and database have been expanded to include isotopic exchange and fractionation between the carbon species in both gas and aqueous phases. The performance of the code is verified by modeling ideal systems and comparing with theoretical results. Efforts are also made to fit field data from the Pembina CO2 injection project in Canada. We show that the exchange of carbon isotopes between dissolved and gaseous carbon species combined with fluid flow and transport, produce isotopic effects that are significantly different from simple two-component mixing. These effects are important for understanding the isotopic variations observed in field demonstrations.

  17. Reactive transport modeling of stable carbon isotope fractionation in a multi-phase multi-component system during carbon sequestration

    DOE PAGESBeta

    Zhang, Shuo; DePaolo, Donald J.; Zheng, Liange; Mayer, Bernhard

    2014-12-31

    Carbon stable isotopes can be used in characterization and monitoring of CO2 sequestration sites to track the migration of the CO2 plume and identify leakage sources, and to evaluate the chemical reactions that take place in the CO2-water-rock system. However, there are few tools available to incorporate stable isotope information into flow and transport codes used for CO2 sequestration problems. We present a numerical tool for modeling the transport of stable carbon isotopes in multiphase reactive systems relevant to geologic carbon sequestration. The code is an extension of the reactive transport code TOUGHREACT. The transport module of TOUGHREACT was modifiedmore » to include separate isotopic species of CO2 gas and dissolved inorganic carbon (CO2, CO32-, HCO3-,…). Any process of transport or reaction influencing a given carbon species also influences its isotopic ratio. Isotopic fractionation is thus fully integrated within the dynamic system. The chemical module and database have been expanded to include isotopic exchange and fractionation between the carbon species in both gas and aqueous phases. The performance of the code is verified by modeling ideal systems and comparing with theoretical results. Efforts are also made to fit field data from the Pembina CO2 injection project in Canada. We show that the exchange of carbon isotopes between dissolved and gaseous carbon species combined with fluid flow and transport, produce isotopic effects that are significantly different from simple two-component mixing. These effects are important for understanding the isotopic variations observed in field demonstrations.« less

  18. Demonstration of compound-specific isotope analysis of hydrogen isotope ratios in chlorinated ethenes.

    PubMed

    Kuder, Tomasz; Philp, Paul

    2013-02-01

    High-temperature pyrolysis conversion of organic analytes to H(2) in hydrogen isotope ratio compound-specific isotope analysis (CSIA) is unsuitable for chlorinated compounds such as trichloroethene (TCE) and cis-1,2-dichloroethene (DCE), due to competition from HCl formation. For this reason, the information potential of hydrogen isotope ratios of chlorinated ethenes remains untapped. We present a demonstration of an alternative approach where chlorinated analytes reacted with chromium metal to form H(2) and minor amounts of HCl. The values of δ(2)H were obtained at satisfactory precision (± 10 to 15 per thousand), however the raw data required daily calibration by TCE and/or DCE standards to correct for analytical bias that varies over time. The chromium reactor has been incorporated into a purge and trap-CSIA method that is suitable for CSIA of aqueous environmental samples. A sample data set was obtained for six specimens of commercial product TCE. The resulting values of δ(2)H were between -184 and +682 ‰, which significantly widened the range of manufactured TCE δ(2)H signatures identified by past work. The implications of this finding to the assessment of TCE contamination are discussed.

  19. A Modern Analogue for Proterozoic Inverse Carbon Isotope Signatures

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

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

  20. Grain size dependency in clumped isotope ratios in high temperature calcites

    NASA Astrophysics Data System (ADS)

    Banerjee, Y.; Ghosh, P.; Misra, S.

    2013-12-01

    Here we have extended the application of clumped isotope thermometry for understanding the geospeedometers using calcite produced at high temperature and pressure. Static recrystallization experiments were conducted on cylindrical discs of AR grade carbonate with three different grain sizes (40μm, 200μm and 400μm) at constant pressure (170×5 MPa) and two different temperatures (6000×10°C and 8000×10°C) for 24 hours. The rate of temperature ramps for heating and cooling were set at 20°C/min and 60°C/min, respectively, mimicking a laboratory scale metamorphic condition of sudden burial and exhumation. The carbonate rocks, with prominent calcite mineral composition were prepared in a cylindrical capsule and were investigated for grain size distribution using Mastersizer, a laser technology to measure grain size. We identified three categories of crystals with grain size varying between 40μm, 200μm and 400μm. 15mg carbonate powder drilled from the periphery of the cylindrical discs were analysed for Clumped isotope ratio (Ghosh et al., 2006). Calcite formation experiment allowed re-crystallization of original powder produced at ambient temperature by subjecting the experimental setup to the temperatures of 800 and 600°C (Pressure was maintained constant at 170×5 MPa). We found broadly three different grain size fractions measured using in-situ laser probe. The present experiments were performed in dry environment unlike the wet high pressure experiment presented in the Passey and Henkes (2012). The present experimental value for Δ 47 was translated into absolute temperature using thermometry equation proposed by Ghosh et al., (2006). We observed a strong relationship of clumped isotopic composition with grain sizes of carbonates, which was rather inconsistent with the earlier presumption (Passey and Henkes 2012). The clumped temperature value was found matching with the true temperature in cases where grain size attained 400 micron, while finer fraction

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

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

    correspond to the highest grain sizes and lowest weight percent carbon. We hypothesize that the difference between the n-alkane and DOC δ13C records is due to contamination of the DOC δ13C signal by weathering of older, refractory Jurassic-Cretaceous carbon. According to this hypothesis, before and after the CIE the difference in the isotopic composition of autochthonous (Cenozoic) and allochthonous (Jurassic-Cretaceous) organic matter would have been small because C3 plants in the Jurassic-Cretaceous and pre- and post-PETM had relatively similar values. Thus, the ratio of autochthonous: allochthonous organic matter would be uncorrelated with isotopic composition. During the CIE, the isotopic composition of autochthonous organic carbon decreased dramatically. Therefore, autochthonous and allochthonous carbon pools were isotopically distinct and a correlation between weight percent carbon and isotopic composition is expected: the lower the weight percent carbon, the higher the proportion of allochthonous carbon, the larger the anomaly.

  2. Further carbon isotope measurements of LEW 88516

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

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

  3. Boron isotope ratios in meteorites and lunar rocks

    NASA Astrophysics Data System (ADS)

    Zhai, Mingzhe; Nakamura, Eizo; Shaw, Denis M.; Nakano, Toshio

    1996-12-01

    The 11B/10B ratios of thirty-two meteorite falls and nine lunar rocks were measured as Cs2BO2+ using thermal ionization mass-spectrometry. The 11B/10B ratios of meteorites vary from 4.011 to 4.098, i.e., their δ11B values (relative to NIST SRM 951) range from -10.5 to +19.2%; however, excluding two outliers, Mokoia and Norton County, the range of most meteorites is smaller (-10.5 to +7.5). The average of two C11 meteorites, Ivuna and Orgueil, is -3.3, in the middle of the range. The δ11B values of the lunar rocks vary less than those of meteorites, from -6.0 to -3.9. The average δ11B of CI1 chondrites is -3.3, similar to that of terrestrial fresh mid-ocean ridge basalts (-6.5 to -1.2) and to the estimated mantle value of +0.2 (Ishikawa and Nakamura, 1992), which is the best representative of the whole Earth. The similarity of δ11B values in meteorites, lunar rocks, and those parts of the Earth unaffected by water implies that the boron isotopic composition of the Solar System is rather homogeneous. Recently, Chaussidon and Robert (1995) reported larger variation of δ11B values in chondrules of three chondrites, from -50 to +40. This degree of heterogeneity is absent from bulk meteorites.

  4. Tungsten isotope ratio determinations by negative thermal ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Völkening, Joachim; Köppe, Manfred; Heumann, Klaus G.

    1991-07-01

    A precise determination of the isotopic abundances of tungsten with natural isotopic composition is presented. WO-3 ions are generated by negative thermal ionization (NTI) in a double-filament ion source. La2O3 is used as a chemical substance to reduce the electron work function of the rhenium filament material. An ionization efficiency of 1% is obtained for sample loadings of 100 ng. The isotopic abundances are measured with relative standard deviations of 0.2% for the least abundant 180W isotope and 0.02-0.004% for the other tungsten isotopes. These improved isotopic data are used to recalculate the atomic weight of tungsten as 183.8417 ± 0.0001. The new NTI technique is an ideal tool for the application of isotope dilution mass spectrometry to analyse tungsten traces and for the measurement of isotopic shifts of this element in meteorites produced by the decay of 182Hf.

  5. Tracing carbonate-silicate interaction during subduction using magnesium and oxygen isotopes.

    PubMed

    Wang, Shui-Jiong; Teng, Fang-Zhen; Li, Shu-Guang

    2014-01-01

    Subduction of carbonates and carbonated eclogites into the mantle plays an important role in transporting carbon into deep Earth. However, to what degree isotopic exchanges occur between carbonate and silicate during subduction remains unclear. Here we report Mg and O isotopic compositions for ultrahigh pressure metamorphic marbles and enclosed carbonated eclogites from China. These marbles include both calcite- and dolomite-rich examples and display similar O but distinct Mg isotopic signatures to their protoliths. Their δ(26)Mg values vary from -2.508 to -0.531‰, and negatively correlate with MgO/CaO ratios, unforeseen in sedimentary carbonates. Carbonated eclogites have extremely heavy δ(18)O (up to +21.1‰) and light δ(26)Mg values (down to -1.928‰ in garnet and -0.980‰ in pyroxene) compared with their protoliths. These unique Mg-O isotopic characteristics reflect differential isotopic exchange between eclogites and carbonates during subduction, making coupled Mg and O isotopic studies potential tools for tracing deep carbon recycling. PMID:25367068

  6. [Effects of lipid extraction on stable carbon and nitrogen isotope analyses of Ommastrephes bartramii muscle].

    PubMed

    Gong, Yi; Chen, Xin-Jun; Gao, Chun-Xia; Li, Yun-Kai

    2014-11-01

    Stable isotope analysis (SIA) has become an important tool to investigate diet shift, habitat use and trophic structure of animal population. Muscle is considered to be the most common tissue for SIA, however, lipid content in muscle causes a considerable bias to the interpretation of isotopic ratios of animals. Neon flying squid (Ommastrephes bartramii) is an important economic cephalopod of Chinese distant water fishery, and plays a major role in marine ecosystems. In this study, the effects of lipid extraction on stable isotope ratios of the muscles of 53 neon flying squids were investigated and the interference mechanism of lipid in SIA was clarified with the aim of contrasting the suitability of different lipid correction models of stable carbon isotope. Results showed that the stable carbon and nitrogen isotopic values of non-lipid extracted samples significantly increased after lipid extractions by 0.71 per thousand and 0.47 per thousand, respectively, which suggested that lipid extraction in cephalopod isotope study is needed prior to stable carbon isotope analysis but not recommended for stable nitrogen isotope analysis. The results could help remove the effects of lipid contents and standardize SIA muscle samples, thereby getting better understanding of the isotopic change of neon flying squids in the future. PMID:25898636

  7. Performance and optimization of a combustion interface for isotope ratio monitoring gas chromatography/mass spectrometry

    NASA Technical Reports Server (NTRS)

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

    1995-01-01

    Conditions and systems for on-line combustion of effluents from capillary gas chromatographic columns and for removal of water vapor from product streams were tested. Organic carbon in gas chromatographic peaks 15 s wide and containing up to 30 nanomoles of carbon was quantitatively converted to CO2 by tubular combustion reactors, 200 x 0.5 mm, packed with CuO or NiO. No auxiliary source of O2 was required because oxygen was supplied by metal oxides. Spontaneous degradation of CuO limited the life of CuO reactors at T > 850 degrees C. Since NiO does not spontaneously degrade, its use might be favored, but Ni-bound carbon phases form and lead to inaccurate isotopic results at T < 1050 degrees C if gas-phase O2 is not added. For all compounds tested except CH4, equivalent isotopic results are provided by CuO at 850 degrees C, NiO + O2 (gas-phase mole fraction, 10(-3)) at 1050 degrees C and NiO at 1150 degrees C. The combustion interface did not contribute additional analytical uncertainty, thus observed standard deviations of 13C/12C ratios were within a factor of 2 of shot-noise limits. For combustion and isotopic analyses of CH4, in which quantitative combustion required T approximately 950 degrees C, NiO-based systems are preferred, and precision is approximately 2 times lower than that observed for other analytes. Water must be removed from the gas stream transmitted to the mass spectrometer or else protonation of CO2 will lead to inaccuracy in isotopic analyses. Although thresholds for this effect vary between mass spectrometers, differential permeation of H2O through Nafion tubing was effective in both cases tested, but the required length of the Nafion membrane was 4 times greater for the more sensitive mass spectrometer.

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

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

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

  9. Calibration and data processing in gas chromatography combustion isotope ratio mass spectrometry.

    PubMed

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

    2012-12-01

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

  10. Predicting the Hydrogen Isotope Ratios of Leaf Waxes Across Landscapes

    NASA Astrophysics Data System (ADS)

    Tipple, B. J.; Berke, M. A.; Hambach, B.; Ehleringer, J. R.

    2014-12-01

    Leaf wax n-alkanes 2H/1H ratios are widely used as a proxy of paleoprecipitation in climate reconstruction. While the broad nature of the relationships between n-alkane δ2H values and climate are appreciated on geologic scales, the quantitative details of what this proxy is reflecting remain ambiguous on plant and ecosystem levels. Areas of uncertainty on these smaller scales of importance to geologic interpretations are both the biosynthetic fractionation and the leaf-growth interval that is recorded by the isotope signal. To clarify these details, we designed a series of experiments in which modern plants were grown under controlled and monitored conditions. To determine the biosynthetic fractionation, we analyzed n-alkanes from plant grown hydroponically on isotopically distinct waters and under contrasting and controlled humidities. We observed δ2H values of n-alkane were linearly related to growth water δ2H values, but with slope differences associated with humidity. These findings suggested leaf water were central controls on δ2H values of n-alkane and support a relatively constant biosynthetic fractionation factor between leaf water and n-alkanes. To determine the interval that the leaf wax isotope signal reflects, we studied a species naturally growing on water with a constant δ2H value. Here we found the δ2H values of n-alkanes recorded only a two-week period during leaf flush and did not vary thereafter. These data indicated the δ2H values of n-alkanes record conditions early in the season, rather than integrating over the entire growing season. Using these data, we are beginning to develop geospatial predictions of the δ2H values of n-alkane across landscapes for given climate conditions, plant phenologies, and ecosystems. These emerging modeling tools may be used to assess modern ecosystem dynamics, to estimate weathering of leaf waxes to geologic repositories, and to define and test paleoclimate reconstructions from the δ2H values of n-alkanes.

  11. Nitrogen isotopic analyses by isotope-ratio-monitoring gas chromatography/mass spectrometry

    NASA Technical Reports Server (NTRS)

    Merritt, D. A.; Hayes, J. M.

    1994-01-01

    Amino acids containing natural-abundance levels of 15N were derivatized and analyzed isotopically using a technique in which individual compounds are separated by gas chromatography, combusted on-line, and the product stream sent directly to an isotope-ratio mass spectrometer. For samples of N2 gas, standard deviations of ratio measurement were better than 0.1% (Units for delta are parts per thousand or per million (%).) for samples larger than 400 pmol and better than 0.5% for samples larger than 25 pmol (0.1% 15N is equivalent to 0.00004 atom % 15N). Results duplicated those of conventional, batchwise analyses to within 0.05%. For combustion of organic compounds yielding CO2/N2 ratios between 14 and 28, in particular for N-acetyl n-propyl derivatives of amino acids, delta values were within 0.25% of results obtained using conventional techniques and standard deviations were better than 0.35%. Pooled data for measurements of all amino acids produced an accuracy and precision of 0.04 and 0.23%, respectively, when 2 nmol of each amino acid was injected on column and 20% of the stream of combustion products was delivered to the mass spectrometer.

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

    NASA Technical Reports Server (NTRS)

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

    1987-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  14. Isotopic composition of Murchison organic compounds: Intramolecular carbon isotope fractionation of acetic acid. Simulation studies of cosmochemical organic syntheses

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

    Recently, in our laboratories, samples of Murchison acetic acid were decarboxylated successfully and the carbon isotopic composition was measured for the methane released by this procedure. These analyses showed significant differences in C-13/C-12 ratios for the methyl and carboxyl carbons of the acetic acid molecule, strongly suggesting that more than one carbon source may be involved in the synthesis of the Murchison organic compounds. On the basis of this finding, laboratory model systems simulating cosmochemical synthesis are being studied, especially those processes capable of involving two or more starting carbon sources.

  15. Carbon-isotopic analysis of dissolved acetate

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

    Heating of dried, acetate-containing solids together with oxalic acid dihydrate conveniently releases acetic acid for purification by gas chromatography. For determination of the carbon-isotopic composition of total acetate, the acetate-containing zone of the chromatographic effluent can be routed directly to a combustion furnace coupled to a vacuum system allowing recovery, purification, and packaging of CO2 for mass-spectrometric analysis. For analysis of methyl carbon, acetic acid can be cryogenically trapped from the chromatographic effluent, then transferred to a tube containing excess NaOH. The tube is evacuated, sealed, and heated to 500 degrees C to produce methane by pyrolysis of sodium acetate. Subsequent combustion of the methane allows determination of the 13C content at the methyl position in the parent acetate. With typical blanks, the standard deviation of single analyses is less than 0.4% for acetate samples larger than 5 micromoles. A full treatment of uncertainties is outlined.

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

    NASA Technical Reports Server (NTRS)

    Blake, Geoffrey A.

    2004-01-01

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

  17. The Oxidant Budget of Dissolved Organic Carbon Driven Isotope Excursions

    NASA Astrophysics Data System (ADS)

    Bristow, T. F.; Kennedy, M. J.

    2008-12-01

    Negative carbon isotope values, falling below the mantle average of about -5 per mil, in carbonate phases of Ediacaran age sedimentary rocks are widely regarded as reflecting negative excursions in the carbon isotopic composition of seawater lasting millions of years. These isotopic signals form the basis of chemostratigraphic correlations between Ediacaran aged sections in different parts of the world, and have been used to track the oxidation of the biosphere. However, these isotopic values are difficult to accommodate within limits prescribed by the current understanding of the carbon cycle, and a hypothetical Precambrian ocean dissolved organic carbon (DOC) pool 100 to 1000 times the size of the modern provides a potential source of depleted carbon not considered in Phanerozoic carbon cycle budgets. We present box model results that show the remineralization of such a DOC pool to drive an isotope excursion of the magnitude observed in the geological record exhausts global budgets of free oxygen and sulfate in 800 k.y. These results are incompatible with the estimated duration of late Ediacaran isotope excursions of more than 10 m.y., as well as geochemical and biological indicators that oceanic sulfate and oxygen levels were maintained or even increased at the same time. Therefore the carbon isotope record is probably not a useful tool for monitoring oxygen levels in the atmosphere and ocean. Covariation between the carbon and oxygen isotope records is often observed during negative excursions and is indicative of local processes or diagenetic overprinting.

  18. Sensitivity analysis and quantification of uncertainty for isotopic mixing relationships in carbon cycle research

    NASA Astrophysics Data System (ADS)

    Zobitz, J. M.; Keener, J. P.; Bowling, D. R.

    2004-12-01

    Quantifying and understanding the uncertainty in isotopic mixing relationships is critical to isotopic applications in carbon cycle studies at all spatial and temporal scales. Studies associated with the North American Carbon Program will depend on stable isotope approaches and quantification of isotopic uncertainty. An important application of isotopic mixing relationships is determination of the isotopic content of large-scale respiration (δ 13CR) via an inverse relationship (a Keeling plot) between atmospheric CO2 concentrations ([CO2]) and carbon isotope ratios of CO2 (δ 13C). Alternatively, a linear relationship between [CO2] and the product of [CO2] and δ 13C (a Miller/Tans plot) can also be applied. We used an extensive dataset from the Niwot Ridge Ameriflux Site of [CO2] and δ 13C in forest air to examine contrasting approaches to determine δ 13CR and its uncertainty. These included Keeling plots, Miller/Tans plots, Model I, and Model II regressions Our analysis confirms previous observations that increasing the range of measurements ([CO2] range) reduces the uncertainty associated with δ 13CR. For carbon isotope studies, uncertainty in the isotopic measurements has a greater effect on the uncertainty of δ 13CR than the uncertainty in [CO2]. Reducing the uncertainty of isotopic measurements reduces the uncertainty of δ 13CR even when the [CO2] range of samples is small (< 20 ppm). As a result, improvement in isotope (rather than CO2) measuring capability is needed to substantially reduce uncertainty in δ 13CR. We also find for carbon isotope studies no inherent advantage to using either a Keeling or a Miller/Tans approach to determine δ 13CR.

  19. Carbon Isotopic Fractionation During Formation of Macromolecular Organic Grain Coatings via FTT Reactions

    NASA Technical Reports Server (NTRS)

    Nuth, J. A.; Johnson, N. M.; Elsila-Cook, J.; Kopstein, M.

    2011-01-01

    Observations of carbon isotopic fractionation of various organic compounds found in meteorites may provide useful diagnostic information concerning the environments and mechanisms that were responsible for their formation. Unfortunately, carbon has only two stable isotopes, making interpretation of such observations quite problematic. Chemical reactions can increase or decrease the C-13/C-12 ratio by various amounts, but the final ratio will depend on the total reaction pathway followed from the source carbon to the final product, a path not readily discernable after 4.5 billion years. In 1970 Libby showed that the C-13/C-12 ratios of terrestrial and meteoritic carbon were similar by comparing carbon from the Murchison meteorite to that of terrestrial sediments. More recent studies have shown that the C-13/C-12 ratio of the Earth and meteorites may be considerably enriched in C-13 compared to the ratio observed in the solar wind [2], possibly suggesting that carbon produced via ion-molecule reactions in cold dark clouds could be an important source of terrestrial and meteoritic carbon. However, meteoritic carbon has been subjected to parent body processing that could have resulted in significant changes to the C-13/C-12 ratio originally present while significant variation has been observed in the C-13/C-12 ratio of the same molecule extracted from different terrestrial sources. Again we must conclude that understanding the ratio found in meteorites may be difficult.

  20. A carbon isotope mass balance for an anoxic marine sediment: Isotopic signatures of diagenesis

    NASA Technical Reports Server (NTRS)

    Boehme, Susan E.

    1993-01-01

    A carbon isotope mass balance was determined for the sediments of Cape Lookout Bight, NC to constrain the carbon budgets published previously. The diffusive, ebullitive and burial fluxes of sigma CO2 and CH4, as well as the carbon isotope signatures of these fluxes, were measured. The flux-weighted isotopic signature of the remineralized carbon (-18.9 plus or minus 2.7 per mil) agreed with the isotopic composition of the remineralized organic carbon determined from the particulate organic carbon (POC) delta(C-13) profiles (-19.2 plus or minus 0.2), verifying the flux and isotopic signature estimates. The measured delta(C-13) values of the sigma CO2 and CH4 diffusive fluxes were significantly different from those calculated from porewater gradients. The differences appear to be influenced by methane oxidation at the sediment-water interface, although other potential processes cannot be excluded. The isotope mass balance provides important information concerning the locations of potential diagenetic isotope effects. Specifically, the absence of downcore change in the delta(C-13) value of the POC fraction and the identical isotopic composition of the POC and the products of remineralization indicate that no isotopic fractionation is expressed during the initial breakdown of the POC, despite its isotopically heterogeneous composition.

  1. Biogeochemistry of the Stable Isotopes of Hydrogen and Carbon in Salt Marsh Biota 1

    PubMed Central

    Smith, Bruce N.; Epstein, Samuel

    1970-01-01

    Deuterium to hydrogen ratios of 14 plant species from a salt marsh and lagoon were 55‰ depleted in deuterium relative to the environmental water. Carbon tetrachloride-extractable material from these plants was another 92‰ depleted in deuterium. This gave a fractionation factor from water to CCl4 extract of 1.147. This over-all fractionation was remarkably constant for all species analyzed. Plants also discriminate against 13C, particularly in the lipid fraction. Data suggest that different mechanisms for carbon fixation result in different fractionations of the carbon isotopes. Herbivore tissues reflected the isotopic ratios of plants ingested. Apparently different metabolic processes are responsible for the different degrees of fractionation observed for hydrogen and carbon isotopes. PMID:16657539

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

    NASA Astrophysics Data System (ADS)

    Nowak-Lovato, K.

    2014-12-01

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

  3. Examination of the kinetic isotopic effect to the acetylation derivatization for the gas chromatographic-combustion-isotope ratio mass spectrometric doping control analysis of endogenous steroids.

    PubMed

    Angelis, Yiannis S; Kioussi, Maroula K; Kiousi, Polyxeni; Brenna, J Thomas; Georgakopoulos, Costas G

    2012-12-01

    In gas chromatographic-combustion-isotope ratio mass spectrometry (GC-C-IRMS) doping control analysis, endogenous androgenic anabolic steroids and their metabolites are commonly acetylated using acetic anhydride reagent, thus incorporating exogenous carbon that contributes to the measured isotope ratio. Comparison of the endogenous δ(13)C of free, mono-, and di-acetylated steroids requires application of corrections, typically through straightforward use of the mass balance equation. Variability in kinetic isotope effects (KIE) due to steroid structures could cause fractionation of endogenous steroid carbon, resulting in inaccurate results. To test for possible KIE influence on δ(13)C, acetic anhydride of graded isotope ratio within the natural abundance range was used under normal derivatization conditions to test for linearity. In all cases, plots of measured steroid acetate δ(13)C versus acetic anhydride δ(13)C were linear and slopes were not significantly different. Regression analysis of the Δδ(13)C of enriched acetic anhydrides versus Δδ(13)C of derivatized steroids shows that KIE are similar in all cases. We conclude that δ(13)C calculated from the mass balance equation is independent of the δ(13)C of the acetic anhydride reagent, and that net KIE under normal derivatization conditions do not bias the final reported steroid δ(13)C.

  4. Carbon and chlorine isotope fractionation during Fenton-like degradation of trichloroethene.

    PubMed

    Liu, Yunde; Gan, Yiqun; Zhou, Aiguo; Liu, Cunfu; Li, Xiaoqian; Yu, Tingting

    2014-07-01

    Dual isotope approach has been proposed as a viable tool for characterizing and assessing in situ contaminant transformation, however, little data is currently available on its applicability to chlorinated ethenes. This study determined carbon and chlorine isotope fractionation during Fenton-like degradation of trichloroethene (TCE). Carbon and chlorine isotope enrichment factors were εC=-2.9 ± 0.3‰ and εCl=-0.9 ± 0.1‰, respectively. An observed small secondary chlorine isotope effect (AKIECl=1.001) was consistent with an initial transformation by adding hydroxyl radicals (OH) to CC bonds without cleavage of CCl bonds. The relative change in carbon and chlorine isotope ratios (Δ=Δδ(13)C/Δδ(37)Cl) was calculated to be 3.1 ± 0.2, approximately equal to the ratio of chlorine and carbon isotope enrichment factors (εC/εCl=3.2). The similarity of the Δ (or εC/εCl) values between Fenton-like degradation and microbial reductive dechlorination of TCE was observed, indicating that application of solely dual isotope approach may be limited in distinguishing the two transformation pathways.

  5. Phanerozoic and Neoproterozoic Negative Carbon Isotope Excursions, Diagenesis and Terrestrialization

    NASA Astrophysics Data System (ADS)

    Paul, K.; Kennedy, M. J.

    2008-12-01

    Comprehensive data sets of Phanerozoic and late Precambrian carbon isotope data derived from carbonate rocks show a similar positive relation when cross-plotted with oxygen isotope values. The range and slope between the time periods is identical and the processes responsible for the relation have been well documented in Quaternary sediments. These processes include the stabilization of isotope values to ambient meteoric water values during shallow burial and flushing of carbonate sediments. Both data sets show strongly depleted carbon (-9 per mil PDB) and oxygen isotope values that retain seemingly systematic stratigraphic patterns with the Quaternary and Phanerozoic examples that demonstrably record meteroric water values. Similar values and patterns in the Precambrian are interpreted as primary marine in origin with significant implications for an ocean carbon mass balance not possible in the Phanerozoic carbon cycle. A similar compilation of carbonates older than one billion years do not show a relation between carbon and oxygen isotopes, lacking the negative carbon values evident in the younger record. We hypothesize that this difference records the onset of significant organic carbon on the land surface and the alteration of meteoric waters toward Phanerozoic values. We demonstrate the meteoric affinities of Neoproterozoic carbonates containing prominent negative isotope excursions recorded in the Shuram and Wonoka Formations of Oman and South Australia commonly attributed to whole ocean isotope variation. The conspicuous absence of negative carbon isotope values with normal marine oxygenisotope values in the Phanerozoic and Neoproterozic identifies a consistent relation between these time intervals and suggests that, as well accepted in the Phanerozoic, negative carbon isotope excursions less than -3 per mil are not a record of marine processes, but rather the later terrestrial biotic influence on meteoric water values.

  6. Oxygen and hydrogen isotope ratios in tree rings: how well do models predict observed values?

    NASA Astrophysics Data System (ADS)

    Waterhouse, J. S.; Switsur, V. R.; Barker, A. C.; Carter, A. H. C.; Robertson, I.

    2002-07-01

    We have measured annual oxygen and hydrogen isotope ratios in the α-cellulose of the latewood of oak ( Quercus robur L.) growing on well-drained ground in Norfolk, UK. We compare the observed values of isotope ratios with those calculated using equations that allow for isotopic fractionation during the transfer of oxygen and hydrogen from source water taken by the tree to cellulose laid down in the cambium. The equations constitute a model in which isotopic fractionation occurs during evaporative enrichment within the leaf and during isotopic change between carbohydrates and water in the trunk during cellulose synthesis. From the relationship between isotope ratios in precipitation and α-cellulose, we deduce that the source water used by the tree comprises a constant mixture of groundwater and precipitation, chiefly from the months of May, June and July of the growth year. By selection of isotopic fractionation factors and the degree of isotope exchange within the trunk, we are able to model the observed annual values of oxygen isotope ratios of α-cellulose to a significant level ( r=0.77, P<0.01). When we apply the same model to hydrogen isotope ratios, however, we find that, although we can predict the average value over the time series, we can no longer predict the year-to-year variation. We suggest that this loss of environmental signal in the hydrogen isotopes is caused by differences in the kinetic isotope effects of the biochemical reactions involved in the fixation of hydrogen in different positions of the glucose molecule. Owing to these effects, the hydrogen isotope ratios of cellulose can vary in a way not anticipated in current models and hence may induce non-climatic 'noise' in the hydrogen isotope time series.

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

    USGS Publications Warehouse

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

    1985-01-01

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

  8. Atomic and Molecular Isotope Ratios in Circumstellar Envelopes: Fractionation vs. Nucleosynthesis

    NASA Astrophysics Data System (ADS)

    Milam, Stefanie

    The long standing question of "What are the origin, evolution, and fate of our Universe and/or Galaxy?" has puzzled humankind for centuries. One approach to answering this question is to gain further understanding of stellar evolution, since stars are fundamental in galaxy development and evolution. A compilation of stellar composition can reveal the age, dynamics, and possibly the evolutionary state of a galaxy. Stars are the factories of heavy elements, including carbon, nitrogen, and oxygen, that are key to the chemical complexity associated with planetary systems. Primitive materials, such as meteorites and IDPs, have revealed a component of "atypical" isotopic signatures of these fundamental elements denoting a possible stellar origin. Understanding the processes by which these elements derive is essential for astrophysics on cosmochemical, galactic, stellar, and planetary scales. We propose to analyze data obtained from the Herschel Space Observatory of circumstellar envelopes to definitively measure C, N, and O isotope ratios and test current models of photo-selective isotope fractionation vs. nucleosynthetically determined values. This proposal augments completed programs from the Herschel Space Observatory, namely the the HIFISTARS program (PI: Bujarrabal), which at the time of proposal submission a significant portion of data will no longer be under proprietary regulations (https://nhscsci.ipac.caltech.edu/sc/).) The broader implications for this study include fundamental data necessary for furthering our current understanding of stellar nucleosynthesis, circumstellar chemistry, Galactic chemical evolution, and the origin of presolar grains found in primitive materials. We will focus on isotopologues of species formed in thermochemical equilibrium and trace their natal, nucleosynthetic isotope ratios. We will analyze Herschel data obtained for a survey of evolved stars with varying degrees of nuclear processing, evolutionary states, and envelope chemistry

  9. Stable isotope ratio determination of the origin of vanillin in vanilla extracts and its relationship to vanillin/potassium ratios

    SciTech Connect

    Martin, G.E.; Alfonso, F.C.; Figert, D.M.; Burggraff, J.M.

    1981-09-01

    A method is described for isolating vanillin from vanilla extract, followed by stable isotope ratio analysis to determine the amount of natural vanillin contained in adulterated vanilla extracts. After the potassium content is determined, the percent Madagascar and/or Java vanilla beans incorporated into the extract may then be approximated from the vanillin/potassium ratio.

  10. Unusual stable isotope ratios in amino acid and carboxylic acid extracts from the Murchison meteorite.

    PubMed

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

    1987-04-01

    Much effort has been directed to analyses of organic compounds in carbonaceous chondrites because of their implications for organic chemical evolution and the origin of life. We have determined the isotopic composition of hydrogen, nitrogen and carbon in amino acid and monocarboxylic acid extracts from the Murchison meteorite. The unusually high D/H and 15N/14N ratios in the amino acid fraction (delta D = 1,370% after correction for isotope exchange; delta 15N = 90) are uniquely characteristic of known interstellar organic materials. The delta D value of the monocarboxylic acid fraction is lower (377%), but still consistent with an interstellar origin. These results confirm the extraterrestrial origin of both classes of compound, and provide the first evidence suggesting a direct relationship between the massive organo-synthesis occurring in interstellar clouds and the presence of pre-biotic compounds in primitive planetary bodies. The isotope data also bear on the historical problem of distinguishing indigenous material from terrestrial contaminants.

  11. Intra-Shell boron isotope ratios in benthic foraminifera: Implications for paleo-pH reconstructions

    NASA Astrophysics Data System (ADS)

    Rollion-Bard, C.; Erez, J.

    2009-12-01

    The boron isotope composition of marine carbonates is considered to be a seawater pH proxy. Nevertheless, the use of δ11B has some limitations: 1) the knowledge of fractionation factor (α4-3) between the two boron dissolved species (boric acid and borate ion), 2) the δ11B of seawater may have varied with time and 3) the amplitude of the "vital effects" of this proxy. Using secondary ion mass spectrometry (SIMS), we looked at the internal variability in the boron isotope ratio of the shallow water, symbionts bearing foraminiferan Amphistegina lobifera. Specimens were cultured at constant temperature (24±0.1 °C) in seawater with pH ranging between 7.90 and 8.45. We performed 6 to 8 measurements of δ11B in each foraminifera. Intra-shell boron isotopes show large variability with an upper threshold value of pH ~ 9. The ranges of the skeletal calculated pH values in different cultured foraminifera, show strong correlation with the culture pH values and may thus serve as proxy for pH in the past ocean.

  12. LASER BIOLOGY AND MEDICINE: Laser analysis of the 13C/12C isotope ratio in CO2 in exhaled air

    NASA Astrophysics Data System (ADS)

    Stepanov, E. V.

    2002-11-01

    Tunable diode lasers (TDLs) are applied to the diagnostics of gastroenterological diseases using respiratory tests and preparations enriched with the stable 13C isotope. This method of the analysis of the 13C/12C isotope ratio in CO2 in exhaled air is based on the selective measurement of the resonance absorption at the vibrational — rotational structure of 12CO2 and 13CO2. The CO2 transmission spectra in the region of 4.35 μm were measured with a PbEuSe double-heterostructure TDL. The accuracy of carbon isotope ratio measurements in CO2 of exhaled air performed with the TDL was ~0.5%. The data of clinical tests of the developed laser-based analyser are presented.

  13. Microbial in situ degradation of aromatic hydrocarbons in a contaminated aquifer monitored by carbon isotope fractionation.

    PubMed

    Richnow, Hans H; Annweiler, Eva; Michaelis, Walter; Meckenstock, Rainer U

    2003-08-01

    We present an approach for characterizing in situ microbial degradation using the 13C/12C isotope fractionation of contaminants as an indicator of biodegradation. The 13C/12C isotope fractionation of aromatic hydrocarbons was studied in anoxic laboratory soil percolation columns with toluene or o-xylene as the sole carbon and electron source, and sulfate as electron acceptor. After approximately 2 months' of incubation, the soil microbial community degraded 32 mg toluene l(-1) and 44 mg o-xylene l(-1) to less than 0.05 mg l(-1), generating a stable concentration gradient in the column. The 13C/12C isotope ratio in the residual non-degraded fraction of toluene and o-xylene increased significantly, corresponding to isotope fractionation factors (alphaC) of 1.0015 and 1.0011, respectively. When the extent of biodegradation in the soil column was calculated based on the measured isotope ratios (R(t)) and an isotope fractionation factor (alphaC=1.0017) obtained from a sulfate-reducing batch culture the theoretical residual substrate concentrations (C(t)) matched the measured toluene concentrations in the column. This indicated that a calculation of biodegradation based on isotope fractionation could work in systems like soil columns. In a field study, a polluted, anoxic aquifer was analyzed for BTEX and PAH contaminants. These compounds were found to exhibit a significant concentration gradient along an 800-m groundwater flow path downstream of the source of contamination. A distinct increase in the carbon isotope ratio (delta13C) was observed for the residual non-degraded toluene (7.2 per thousand ), o-xylene (8.1 per thousand ) and naphthalene fractions (1.2 per thousand ). Based on the isotope values and the laboratory-derived isotope fractionation factors for toluene and o-xylene, the extent to which the residual substrate fraction in the monitoring wells had been degraded by microorganisms was calculated. The results revealed significant biodegradation along the

  14. Oxygen isotope ratios of cellulose-derived phenylglucosazone: An improved paleoclimate indicator of environmental water and relative humidity

    NASA Astrophysics Data System (ADS)

    Sternberg, Leonel da S. L.; Pinzon, Maria C.; Vendramini, Patricia F.; Anderson, William T.; Jahren, A. Hope; Beuning, Kristina

    2007-05-01

    Oxygen atoms within fossil wood provide high-resolution records of climate change, particularly for the Quaternary. However, current analysis methods of fossil cellulose do not differentiate between different positions of the oxygen atoms. Here, we propose a refinement to tree-cellulose paleoclimatology modeling, using the cellulose-derived compound phenylglucosazone as the isotopic substrate. Stem samples from trees were collected at northern latitudes as low as 24°37'N and as high as 69°00'N. We extracted stem water and cellulose from each stem sample and analyzed them for their 18O content. In addition, we derived the cellulose to phenylglucosazone, a compound which lacks the oxygen attached to the second carbon of the cellulose-glucose moieties. Oxygen isotope analysis of phenylglucosazone allowed us to calculate the 18O content of the oxygen attached to the second carbon of the cellulose-glucose moieties. By way of these analyses, we tested two hypotheses: first, that the 18O content of the oxygen attached to second carbon will more closely reflect the 18O content of the stem water, and will not resemble the 18O content of either cellulose or its derivative phenylglucosazone. Second, tree-ring models that incorporate the variable oxygen isotope fractionation shown here and elsewhere are more accurate than those that do not. Our first hypothesis was rejected on the basis that the oxygen isotope ratios of the oxygen attached to the second carbon of the glucose moieties had a noisy isotopic signal with a large standard deviation and gave the poorest correlation with the oxygen isotope ratios of stem water. Related to this isotopic noise, we observed that the correlation between oxygen isotope ratios of phenylglucosazone with both stem water and relative humidity were higher than those observed for cellulose. Our hypothesis about tree-ring models which account for changes in the oxygen isotopic fractionation during cellulose synthesis was consistent only for the

  15. Forensic Applications of Light-Element Stable Isotope Ratios of Ricinus communis Seeds and Ricin Preparations

    SciTech Connect

    Kreuzer, Helen W.; West, Jason B.; Ehleringer, James

    2013-01-01

    Seeds of the castor plant Ricinus communis, also known as castor beans, are of forensic interest because they are the source of the poison ricin. We have tested whether stable isotope ratios of castor seeds and ricin prepared by various methods can be used as a forensic signature. We collected over 300 castor seed samples from locations around the world and measured the C, N, O, and H stable isotope ratios of the whole seeds, oil, and three types of ricin preparations. Our results demonstrate that N isotope ratios can be used to correlate ricin prepared by any of these methods to source seeds. Further, stable isotope ratios distinguished >99% of crude and purified ricin protein samples in pair-wise comparison tests. Stable isotope ratios therefore constitute a valuable forensic signature for ricin preparations.

  16. Recent measurements of 234U/238U isotope ratio in spring waters from the Hadzici area.

    PubMed

    Vidic, Alfred; Ilić, Zorana; Benedik, Ljudmila

    2013-06-01

    The Hadzici area has become interesting for investigation since depleted uranium ammunition had been employed in 1995 during the NATO air strike campaign in Bosnia and Herzegovina. The purpose of this study is to determine uranium concentration and (234)U/(238)U activity ratio in the spring waters of this area and to investigate their relationship, as well as spatial variations. The spring water samples were taken at 18 sites in total. For the determination of uranium radioisotopes, radiochemical separation procedure followed by alpha-particle spectrometry was applied. Uranium concentration in analyzed waters range from 0.15 to 1.12 μg/L. Spring waters from carbonate based sediments have a lower uranium concentration of between 0.15 and 0.43 μg/L, in comparison to waters sampled within sandstone-based sediments ranging from 0.53 to 1.12 μg/L. Dissolved uranium shows significant spatial variability and correlation with bedrock type confirmed by Principal Component Analysis and Hierarchical Cluster Analysis. The majority of the analyzed waters have a (234)U/(238)U activity ratio ranging from 1.02 to 1.90, of which half of the results range between 1.02 and 1.16. No apparent depleted uranium (DU) contamination was observed, as (234)U/(238)U activity ratio is dependent on geochemical conditions in the environment. Even though the tested spring waters demonstrate significant variability in uranium concentration, (234)U/(238)U activity ratio and (234)U excess, waters with similar uranium isotopic signatures are observable within the region. The guidelines on the spatial redistribution of dissolved uranium (corresponding to (238)U mass concentration), along with (234)U/(238)U activity ratios were provided by the Inverse Distance Weighting (IDW) method. Waters having similar isotopic signature have been delineated.

  17. Recent measurements of 234U/238U isotope ratio in spring waters from the Hadzici area.

    PubMed

    Vidic, Alfred; Ilić, Zorana; Benedik, Ljudmila

    2013-06-01

    The Hadzici area has become interesting for investigation since depleted uranium ammunition had been employed in 1995 during the NATO air strike campaign in Bosnia and Herzegovina. The purpose of this study is to determine uranium concentration and (234)U/(238)U activity ratio in the spring waters of this area and to investigate their relationship, as well as spatial variations. The spring water samples were taken at 18 sites in total. For the determination of uranium radioisotopes, radiochemical separation procedure followed by alpha-particle spectrometry was applied. Uranium concentration in analyzed waters range from 0.15 to 1.12 μg/L. Spring waters from carbonate based sediments have a lower uranium concentration of between 0.15 and 0.43 μg/L, in comparison to waters sampled within sandstone-based sediments ranging from 0.53 to 1.12 μg/L. Dissolved uranium shows significant spatial variability and correlation with bedrock type confirmed by Principal Component Analysis and Hierarchical Cluster Analysis. The majority of the analyzed waters have a (234)U/(238)U activity ratio ranging from 1.02 to 1.90, of which half of the results range between 1.02 and 1.16. No apparent depleted uranium (DU) contamination was observed, as (234)U/(238)U activity ratio is dependent on geochemical conditions in the environment. Even though the tested spring waters demonstrate significant variability in uranium concentration, (234)U/(238)U activity ratio and (234)U excess, waters with similar uranium isotopic signatures are observable within the region. The guidelines on the spatial redistribution of dissolved uranium (corresponding to (238)U mass concentration), along with (234)U/(238)U activity ratios were provided by the Inverse Distance Weighting (IDW) method. Waters having similar isotopic signature have been delineated. PMID:23410592

  18. Guidelines and recommended terms for expression of stable-isotope-ratio and gas-ratio measurement results

    USGS Publications Warehouse

    Coplen, Tyler B.

    2011-01-01

    To minimize confusion in the expression of measurement results of stable isotope and gas-ratio measurements, recommendations based on publications of the Commission on Isotopic Abundances and Atomic Weights of the International Union of Pure and Applied Chemistry (IUPAC) are presented. Whenever feasible, entries are consistent with the Système International d'Unités, the SI (known in English as the International System of Units), and the third edition of the International Vocabulary of Basic and General Terms in Metrology (VIM, 3rd edition). The recommendations presented herein are approved by the Commission on Isotopic Abundances and Atomic Weights and are designed to clarify expression of quantities related to measurement of isotope and gas ratios to ensure that quantity equations instead of numerical value equations are used for quantity definitions. Examples of column headings consistent with quantity calculus (also called the algebra of quantities) and examples of various deprecated usages connected with the terms recommended are presented.

  19. Variability in carbon and nitrogen isotope fractionation associated with bacterial hydrolysis of atrazine

    NASA Astrophysics Data System (ADS)

    Meyer, A.; Penning, H.; Elsner, M.

    2009-04-01

    Even after legislative prohibition in 1991 by the European Union, the pesticide atrazine and its metabolites are still detected in surface and ground water frequently exceeding the permitted drinking water concentration limit of 0,1 g/L. Despite much recent research on atrazine, its risk assessment in the environment is still a major challenge because of the difficulty of establishing mass balances in the subsurface. To obtain a better insight into the fate of atrazine, we developed compound-specific stable isotope analysis (CSIA) for atrazine. CSIA has proven valuable for assessing organic contaminants in subsurface environments, on the one hand for source identification and on the other hand to trace (bio)chemical degradation reactions through isotope fractionation in the compounds. Such assessment is based on the Rayleigh equation and therein on the isotope enrichment factor ɛ, which must be determined experimentally beforehand. In ongoing work, we therefore measured carbon and nitrogen isotope fractionation associated with biotic hydrolsis of atrazine. C and N isotope enrichment factors were determined in resting cell experiments for Pseudomonas sp. ADP, Chelatobacter heintzii and Arthrobacter aurescens TC1, strains that hydrolyse atrazine in the initial transformation reaction. Carbon and nitrogen isotope enrichment factors were distinctly different between the bacterial strains. However, when plotting shifts in carbon isotope ratios versus shifts in nitrogen isotope ratios the slopes of the different degradation experiments coincided well. These results give evidence that all bacterial strains were carrying out the same initial biochemical degradation reaction, but that the associated isotope fractionation, as represented by the enrichment factors, was masked to a different extent owing to different rate determining steps prior to the isotopically sensitive bond cleavage (commitment to catalysis). Our study therefore illustrates the benefit of multi

  20. Helium-carbon isotopic composition of thermal waters from Tunisia

    NASA Astrophysics Data System (ADS)

    Fourré, E.; Aiuppa, A.; di Napoli, R.; Parello, F.; Gaubi, E.; Jean-Baptiste, P.; Allard, P.; Calabrese, S.; Ben Mammou, A.

    2010-12-01

    Tunisia has numerous thermo-mineral springs. Previous studies have shown that their chemical composition and occurrence are strongly influenced by the regional geology, however little work has been conducted to date to investigate the isotopic composition of volatiles associated with these geothermal manifestations. Here, we report the results of an extensive survey of both natural hot springs and production wells across Tunisia aimed at investigating the spatial distribution of the 3He/4He ratio and associated carbon isotopic compositions. With respect to helium isotopes, not unexpectedly, the lowest 3He/4He values (0.01-0.02 Ra) are associated with the old groundwaters of the “Continental Intercalaire” aquifer of the stable Saharan Platform. The 3He/4He values are equal to the crustal production ratio, with no detectable amount of mantle-derived 3He, in agreement with previous studies of helium isotopes in sedimentary basin, which conclude that tectonically-stable regions are essentially impermeable to mantle volatiles. The low 3He/4He domain extends to the entire Atlasic domain of central Tunisia. This Atlasic domain also displays the highest helium concentrations : along the Gafsa Fault, helium concentrations of 1777 and 4723 x 10-8 cm3STP/g (the highest value of our data set) are observed in the production wells of Sidi Ahmed Zarrouk. This emphasizes the role of deep tectonic features in channelling and transporting deep crustal volatiles to shallow levels. The eastern margin of Tunisia displays higher 3He/4He values indicative of a substantial mantle volatile input. The highest value is recorded in the carbo-gaseous mineral water of Ain Garci (2.4 Ra). This northeastern part of the African plate commonly referred to as the Pelagian block extends from Tunisia to Sicily and is characterized by strong extensional tectonics (Pantelleria rift zone) and present-day magmatic activity. This lithospheric stretching and decompressional mantle melts production in

  1. Source indicators of humic substances and proto-kerogen - Stable isotope ratios, elemental compositions and electron spin resonance spectra

    NASA Technical Reports Server (NTRS)

    Stuermer, D. H.; Peters, K. E.; Kaplan, I. R.

    1978-01-01

    Stable isotope ratios of C, N and H, elemental compositions, and electron spin resonance (ESR) data of humic acids and proto-kerogens from twelve widely varying sampling locations are presented. Humic acids and proto-kerogens from algal sources are more aliphatic and higher in N than those from higher plant sources. Oxygen content appears to represent a measure of maturation, even in Recent sediments, and S content may reflect redox conditions in the environment of deposition. The ESR data indicate that the transformation of humic substances to proto-kerogens in Recent sediments is accompanied by an increase in aromatic character. A combination of stable carbon isotope ratio and H/C ratio may be a simple but reliable source indicator which allows differentiation of marine-derived from terrestrially-derived organic matter. The stable nitrogen isotope ratios are useful indicators of nitrogen nutrient source. Deuterium/hydrogen isotope ratios appear to reflect variations in meteoric waters and are not reliable source indicators.

  2. Uranium Isotope Ratios in Modern and Precambrian Soils

    NASA Astrophysics Data System (ADS)

    DeCorte, B.; Planavsky, N.; Wang, X.; Auerbach, D. J.; Knudsen, A. C.

    2015-12-01

    Uranium isotopes (δ238U values) are an emerging paleoredox proxy that can help to better understand the redox evolution of Earth's surface environment. Recently, uranium isotopes have been used to reconstruct ocean and atmospheric redox conditions (Montoya-Pino et al., 2010; Brennecka et al., 2011; Kendall et al., 2013; Dahl et al., 2014). However, to date, there have not been studies on paleosols, despite that paleosols are, arguably better suited to directly tracking the redox conditions of the atmosphere. Sedimentary δ238U variability requires the formation of the soluble, oxidized form of U, U(VI). The formation of U(VI) is generally thought to require oxygen levels orders of magnitude higher than prebiotic levels. Without significant U mobility, it would have been impossible to develop isotopically distinct pools of uranium in ancient Earth environments. Conversely, an active U redox cycle leads to significant variability in δ238U values. Here we present a temporally and geographically expansive uranium isotope record from paleosols and modern soils to better constrain atmospheric oxygen levels during the Precambrian. Preliminary U isotope measurements of paleosols are unfractionated (relative to igneous rocks), possibly because of limited fractionation during oxidation (e.g., {Wang, 2015 #478}) or insufficient atmospheric oxygen levels to oxidize U(IV)-bearing minerals in the bedrock. Further U isotope measurements of paleosols with comparison to modern soils will resolve this issue.

  3. Climate controls on forest soil C isotope ratios in the southern Appalachian Mountains

    SciTech Connect

    Garten Jr, Charles T; Cooper, Lee W; Post, Wilfred M; Hanson, Paul J

    2000-04-01

    A large portion of terrestrial carbon (C) resides in soil organic carbon (SOC). The dynamics of this large reservoir depend on many factors, including climate. Measurements of {sup 13}C:{sup 12}C ratios, C concentrations, and C:N ratios at six forest sites in the Southern Appalachian Mountains (USA) were used to explore several hypotheses concerning the relative importance of factors that control soil organic matter (SOM) decomposition and SOC turnover. Mean {delta}{sup 13}C values increased with soil depth and decreasing C concentrations along a continuum from fresh litter inputs to more decomposed soil constituents. Data from the six forest sites, in combination with data from a literature review, indicate that the extent of change in {delta}{sup 13}C values from forest litter inputs to mineral soil (20 cm deep) is significantly associated with mean annual temperature. The findings support a conceptual model of vertical changes in forest soil {delta}{sup 13}C values, C concentrations, and C:N ratios that are interrelated through climate controls on decomposition. We hypothesize that, if other environmental factors (like soil moisture) are not limiting, then temperature and litter quality indirectly control the extent of isotopic fractionation during SOM decomposition in temperate forest ecosystems.

  4. Climate controls on forest soil C isotope ratios in the Southern Appalachian Mountains

    SciTech Connect

    Garten, C.T. Jr.; Cooper, L.W.; Post, W.M. III; Hanson, P.J.

    2000-04-01

    A large portion of terrestrial carbon (C) resides in soil organic carbon (SOC). The dynamics of this large reservoir depend on many factors, including climate. Measurements of {sup 13}C:{sup 12}C ratios, C concentrations, and C:N ratios at six forest sites in the Southern Appalachian Mountains (USA) were used to explore several hypotheses concerning the relative importance of factors that control soil organic matter (SOM) decomposition and SOC turnover. Mean {delta}{sup 13}C values increased with soil depth and decreasing C concentrations along a continuum from fresh litter inputs to more decomposed soil constituents. Data from the six forest sites, in combination with data from a literature review, indicate that the extent of change in {delta}{sup 13}C values from forest litter inputs to mineral soil is significantly associated with mean annual temperature. The findings support a conceptual model of vertical changes in forest soil {delta}{sup 13}C values, C concentrations, and C:N ratios that are interrelated through climate controls on decomposition. The authors hypothesize that, if other environmental factors are not limiting, then temperature and litter quality indirectly control the extent of isotopic fractionation during SOM decomposition in temperate forest ecosystems.

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

    PubMed

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

    2013-07-19

    Stable isotope ratios of H, C, and O are powerful indicators of a wide variety of planetary geophysical processes, and for Mars they reveal the record of loss of its atmosphere and subsequent interactions with its surface such as carbonate formation. We report in situ measurements of the isotopic ratios of D/H and (18)O/(16)O in water and (13)C/(12)C, (18)O/(16)O, (17)O/(16)O, and (13)C(18)O/(12)C(16)O in carbon dioxide, made in the martian atmosphere at Gale Crater from the Curiosity rover using the Sample Analysis at Mars (SAM)'s tunable laser spectrometer (TLS). Comparison between our measurements in the modern atmosphere and those of martian meteorites such as ALH 84001 implies that the martian reservoirs of CO2 and H2O were largely established ~4 billion years ago, but that atmospheric loss or surface interaction may be still ongoing. PMID:23869013

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

    PubMed

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

    2010-06-23

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

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

    PubMed

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

    2013-07-19

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

  8. Effect of photosynthetic light dosage on carbon isotope composition in the coral skeleton: Long-term culture of Porites spp.

    NASA Astrophysics Data System (ADS)

    Omata, Tamano; Suzuki, Atsushi; Sato, Takanori; Minoshima, Kayo; Nomaru, Eriko; Murakami, Akio; Murayama, Shohei; Kawahata, Hodaka; Maruyama, Tadashi

    2008-06-01

    Whereas the oxygen isotope ratio of the coral skeleton is used for reconstruction of past information on seawater, the carbon isotope ratio is considered a proxy for physiological processes, principally photosynthesis and respiration. However, the fractionation of carbon isotopes in biogenic carbonate such as coral skeleton is still unclear. We conducted a long-term culture experiment of Porites spp. corals at different light dosages (light intensity, 100, 300, or 500 μmol m-2 s-1; daily light period, 10 or 12 h) at 25 ± 0.6°C to examine the contribution of photosynthetic activity to skeletal carbon isotope composition. Corals were grown in sand-filtered seawater and not fed; thus, they subsisted from photosynthesis of symbiotic algae. As the daily dose of photosynthetically active radiation increased, the rate of annual extension also increased. Mean isotope compositions shifted; the carbon isotope compositions (δ13C) became heavier and the oxygen isotope compositions (δ18O) became lighter at higher radiation dose. Skeletal δ18O decrease coincided with increasing skeletal growth rate, indicating the influence of so-called kinetic isotope effects. The observed δ13C increase should be subject to both kinetic and metabolic isotope effects, with the latter reflecting skeletal δ13C enrichment due to photosynthesis by symbiotic algae. Using a vector approach in the δ13C-δ18O plane, we discriminated between kinetic and metabolic isotope effects on δ13C. The calculated δ13C changes from metabolic isotope effects were light dose dependent. The δ13C fractionation curve related to metabolic isotope effects is very similar to the photosynthesis-irradiance curve, indicating the direct contribution of photosynthetic activity to metabolic isotope effects. In contrast, δ13C fractionation related to kinetic isotope effects gradually increased as the growth rate increased. Our experiment demonstrated that the kinetic and metabolic isotope effects in coral skeleton

  9. Carbon isotope composition of low molecular weight hydrocarbons and monocarboxylic acids from Murchison meteorite

    NASA Astrophysics Data System (ADS)

    Yuen, G.; Blair, N.; Des Marais, D. J.; Chang, S.

    1984-01-01

    Carbon isotopic compositions have been measured for individual hydrocarbons and monocarboxylic acids from the Murchison meteorite, a C2 carbonaceous chondrite which fell in Australia in 1969. With few exceptions, notably benzene, the volatile products are substantially isotopically heavier than their terrestrial counterparts, signifying their extraterrestrial origin. For both classes of compounds, the ratio of C-13 to C-12 decreases with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic ratio than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with the kinetically controlled synthesis of higher homologues from lower ones. The results suggest the possibility that the production mechanisms for hydrocarbons and carboxylic acids may be similar, and impose constraints on the identity of the reactant species.

  10. Carbon kinetic isotope effect in the reaction of CH4 with HO

    NASA Technical Reports Server (NTRS)

    Davidson, J. A.; Cantrell, C. A.; Tyler, S. C.; Shetter, R. E.; Cicerone, R. J.

    1987-01-01

    The carbon kinetic isotope effect in the CH4 + HO reaction is measured experimentally and the use of carbon isotope ratios to diagnose atmospheric methane is examined. The chemical, photolysis, and analytical experimental conditions and procedures are described. It is determined that the CH4 + HO reaction has a carbon kinetic isotope effect of 1.010 + or 0.007 for k(12)k(13) (rate constants ratio) at 297 + or - 3 K. This value is compared with the data of Rust and Stevens (1980). Causes for the poor correlation between the data at high methane conversions are discussed. It is supposed that the difference between the k(12) and k(13) values is due to a difference in the activation energy of the two reactions.

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

    USGS Publications Warehouse

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

    1978-01-01

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

  12. Oligocene to Miocene carbon isotope cycles and abyssal circulation changes

    NASA Astrophysics Data System (ADS)

    Miller, Kenneth G.; Fairbanks, Richard G.

    Three cycles of δ13C occurred in Oligocene to Miocene benthic and planktonic foraminifera at western North Atlantic Sites 558 and 563. Intervals of high δ13C occurred at about 35-33 Ma (early Oligocene), 25-22 Ma (across the Oligocene/Miocene boundary), and 18-14 Ma (across the early/middle Miocene boundary). Similar carbon isotopic fluctuations have been measured in benthic and planktonic foraminifera from the Atlantic, Pacific, and Indian oceans, suggesting that these cycles represent global changes in the δ13C of mean ocean water. The average duration of the carbon cycles is 50 times greater than the residence time of carbon in the oceans. Therefore, the mechanism controlling these cycles must be tied to changes in the input ratio of organic carbon to carbonate from weathering rocks or to changes in the output ratio of organic carbon to carbonate in marine sediments. Following a strategy used to study modern and Pleistocene oceans, benthic foraminiferal δ13C differences between the Atlantic and Pacific are used to infer Oligocene through Miocene abyssal circulation changes. The Atlantic was most enriched in l3C relative to the Pacific from about 36-33 Ma (early Oligocene) and 26-10 Ma (late Oligocene to late Miocene). We interpret this as indicating supply of nutrient-depleted bottom water in the North Atlantic, perhaps analogous to modern North Atlantic Deep Water. High benthic foraminiferal δ13O values at about 36-35 Ma, 31-28 Ma, 25-24 Ma, and younger than 15 Ma indicate the presence of ice sheets at these times. Covariance between benthic and planktonic foraminiferal δ18O records of 0.3-0.5°/ºº at 36 Ma, 31 Ma, and 25 Ma suggests that three periods of continental glaciation caused eustatic (global sea-level) lowerings of 30-50 m during the Oligocene epoch. The δ13C cycles do not correlate with sea-level changes deduced from oxygen isotopic data, nor do they correlate with other proxy indicators for sea level.

  13. The quality control of fruit juices by using the stable isotope ratios and trace metal elements concentrations

    NASA Astrophysics Data System (ADS)

    Magdas, D. A.; Dehelean, A.; Puscas, R.; Cristea, G.; Tusa, F.; Voica, C.

    2012-02-01

    In the last years, a growing number of research articles detailing the use of natural abundance light stable isotopes variations and trace metal elements concentration as geographic "tracers" to determine the provenance of food have been published. These investigations exploit the systematic global variations of stable hydrogen, oxygen and carbon isotope ratios in (combination) relation with trace metal element concentrations. The trace metal elements content of plants and also their light stable isotopic ratios are mainly related to the geological and pedoclimatic characteristics of the site of growth. The interpretation of such analysis requires an important number of data for authentic natural juices regarding the same seasonal and regional origin, because the isotopic analysis parameters of fruit juices show remarkable variability depending on climatologically factors. In this work was mesured H, C, O stable isotope ratios and the concentrations of 16 elements (P, K, Mg, Na, Ca, Cu, Cr, Ni, Zn, Pb, Co, As, Cd, Mn, Fe and Hg) from 12 single strength juices. The natural variations that appear due to different environmental and climatic conditions are presented and discussed.

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

    NASA Technical Reports Server (NTRS)

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

    1984-01-01

    Sample surface carbon, mantle carbon dioxide in vesicles, and mantle carbon dissolved in glasses, are the three carbon components evident in the 11 mid-oceanic basalts presently analyzed. The total carbon content may be controlled by the depth of the shallowest ridge magma chamber, and carbon isotopic fractionation accompanies magma degassing. Using He-3 and carb