Sample records for absolute isotopic composition

  1. Towards absolute laser spectroscopic CO2 isotope ratio measurements

    NASA Astrophysics Data System (ADS)

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

    2017-04-01

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

  2. Absolute and Mass-Dependent Titanium Isotope Compositions of Solar System Materials

    NASA Astrophysics Data System (ADS)

    Williams, N. H.; Fehr, M. A.; Akram, W. M.; Parkinson, I. J.; Schönbächler, M.

    2013-09-01

    Mass dependent Ti isotope data for various solar system material will be presented. This data has been obtained via double spike technique using ^47 Ti and ^49Ti as spikes. Absolute nucleosynthetic anomalie data for Ti will be presented also.

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

    PubMed

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

    2015-04-01

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

  4. Absolute Isotopic Abundance Ratios and the Accuracy of Δ47 Measurements

    NASA Astrophysics Data System (ADS)

    Daeron, M.; Blamart, D.; Peral, M.; Affek, H. P.

    2016-12-01

    Conversion from raw IRMS data to clumped isotope anomalies in CO2 (Δ47) relies on four external parameters: the (13C/12C) ratio of VPDB, the (17O/16O) and (18O/16O) ratios of VSMOW (or VPDB-CO2), and the slope of the triple oxygen isotope line (λ). Here we investigate the influence that these isotopic parameters exert on measured Δ47 values, using real-world data corresponding to 7 months of measurements; simulations based on randomly generated data; precise comparisons between water-equilibrated CO2 samples and between carbonate standards believed to share quasi-identical Δ47 values; reprocessing of two carbonate calibration data sets with different slopes of Δ47 versus T. Using different sets of isotopic parameters generally produces systematic offsets as large as 0.04 ‰ in final Δ47 values. What's more, even using a single set of isotopic parameters can produce intra- and inter-laboratory discrepancies in final Δ47 values, if some of these parameters are inaccurate. Depending on the isotopic compositions of the standards used for conversion to "absolute" values, these errors should correlate strongly with either δ13C or δ18O, or more weakly with both. Based on measurements of samples expected to display identical Δ47 values, such as 25°C water-equilibrated CO2 with different carbon and oxygen isotope compositions, or high-temperature standards ETH-1 and ETH-2, we conclude that the isotopic parameters used so far in most clumped isotope studies produces large, systematic errors controlled by the relative bulk isotopic compositions of samples and standards, which should be one of the key factors responsible for current inter-laboratory discrepancies. By contrast, the isotopic parameters of Brand et al. [2010] appear to yield accurate Δ47 values regardless of bulk isotopic composition. References:Brand, Assonov and Coplen [2010] http://dx.doi.org/10.1351/PAC-REP-09-01-05

  5. The ruthenium isotopic composition of the oceanic mantle

    NASA Astrophysics Data System (ADS)

    Bermingham, K. R.; Walker, R. J.

    2017-09-01

    The approximately chondritic relative, and comparatively high absolute mantle abundances of the highly siderophile elements (HSE), suggest that their concentrations in the bulk silicate Earth were primarily established during a final ∼0.5 to 1% of ;late accretion; to the mantle, following the cessation of core segregation. Consequently, the isotopic composition of the HSE Ru in the mantle reflects an amalgamation of the isotopic compositions of late accretionary contributions to the silicate portion of the Earth. Among cosmochemical materials, Ru is characterized by considerable mass-independent isotopic variability, making it a powerful genetic tracer of Earth's late accretionary building blocks. To define the Ru isotopic composition of the oceanic mantle, the largest portion of the accessible mantle, we report Ru isotopic data for materials from one Archean and seven Phanerozoic oceanic mantle domains. A sample from a continental lithospheric mantle domain is also examined. All samples have identical Ru isotopic compositions, within analytical uncertainties, indicating that Ru isotopes are well mixed in the oceanic mantle, defining a μ100Ru value of 1.2 ± 7.2 (2SD). The only known meteorites with the same Ru isotopic composition are enstatite chondrites and, when corrected for the effects of cosmic ray exposure, members of the Main Group and sLL subgroup of the IAB iron meteorite complex which have a collective CRE corrected μ100Ru value of 0.9 ± 3.0. This suggests that materials from the region(s) of the solar nebula sampled by these meteorites likely contributed the dominant portion of late accreted materials to Earth's mantle.

  6. Stable isotopic compositions of carbon in vegetation and soil organic matter along the bioclimatic transect, North Caucasus

    NASA Astrophysics Data System (ADS)

    Kovda, Irina; Morgun, Evgeny; Golubeva, Natalia

    2010-05-01

    Stable isotopic composition of carbon in plant species and soil organic matter was investigated along the bioclimatic transect in the North Caucasus. The aim of this research was to find the possible shift of stable isotopic composition of carbon reflecting the gradual successive changes of landscapes connected with the changes of climatic conditions (temperature, precipitation, air humidity) at a various absolute heights above sea level i.e. along the vertical zonation. The study site was located in the North Caucasus near Arkhiz, Big Zelentchuk valley (43o33-40'N; 41o16-27'E). Soil and vegetation samples were collected along Precaucasus and Caucasus slopes at an absolute heights interval of 1280 - 2065 m. Soils are formed at eluvo-deluvium of noncarbonated silicate massive rocks under warm temperate climate with MAT 4-5oC and MAP ~ 860 mm and more. Samples of vegetation (whole grasses and tree leaves) represented several altitudinal vegetation belts including forest and subalpine belts with coniferous (pine, spruce, fir), mixed coniferous-deciduous (fir + beech), broad-leaved (beech, maple), small-leaved (birch, aspen) forests, elfin birch wood and subalpine meadows. Stable isotope composition of carbon was determined using IRMS Finnigan Delta V+. Stable isotopic composition of vegetal species ranges from -33.04 to -27.29 o/oo with the general trend of lighter δ13С with the decreasing of absolute heights. The most heavier δ13С = ~ -27o/oo were found in subalpine meadow plants, while at a smaller altitudes in the forest belt δ13С shifts to ~ 30-31, and up to ~ - 32-33o/oo. More clear regularities were found for vegetation specimens grouped into three categories such as "trees", "grasses" and "litter". δ13С of each category clearly shifts to the lighter values with the decrease of absolute heights i.e from subalpine meadows to spruce-broad-leaved forests. δ13С shift is about 2,49o/oo for trees, 1,75-4,92 o/oo for grasses and ~ 1,8 o/oo for the litter. The

  7. Atomic Weights and Isotopic Compositions

    National Institute of Standards and Technology Data Gateway

    SRD 144 Atomic Weights and Isotopic Compositions (Web, free access)   The atomic weights are available for elements 1 through 111, and isotopic compositions or abundances are given when appropriate.

  8. Advances in the Metrology of Absolute Value Assignments to Isotopic Reference Materials: Consequences from the Avogadro Project

    NASA Astrophysics Data System (ADS)

    Vocke, Robert; Rabb, Savelas

    2015-04-01

    All isotope amount ratios (hereafter referred to as isotope ratios) produced and measured on any mass spectrometer are biased. This unfortunate situation results mainly from the physical processes in the source area where ions are produced. Because the ionized atoms in poly-isotopic elements have different masses, such processes are typically mass dependent and lead to what is commonly referred to as mass fractionation (for thermal ionization and electron impact sources) and mass bias (for inductively coupled plasma sources.) This biasing process produces a measured isotope ratio that is either larger or smaller than the "true" ratio in the sample. This has led to the development of numerous fractionation "laws" that seek to correct for these effects, many of which are not based on the physical processes giving rise to the biases. The search for tighter and reproducible precisions has led to two isotope ratio measurement systems that exist side-by-side. One still seeks to measure "absolute" isotope ratios while the other utilizes an artifact based measurement system called a delta-scale. The common element between these two measurement systems is the utilization of isotope reference materials (iRMs). These iRMs are used to validate a fractionation "law" in the former case and function as a scale anchor in the latter. Many value assignments of iRMs are based on "best measurements" by the original groups producing the reference material, a not entirely satisfactory approach. Other iRMs, with absolute isotope ratio values, have been produced by calibrated measurements following the Atomic Weight approach (AW) pioneered by NBS nearly 50 years ago. Unfortunately, the AW is not capable of calibrating the new generation of iRMs to sufficient precision. So how do we get iRMs with isotope ratios of sufficient precision and without bias? Such a focus is not to denigrate the extremely precise delta-scale measurements presently being made on non-traditional and tradition

  9. Magnesium isotopic composition of the mantle

    NASA Astrophysics Data System (ADS)

    Teng, F.; Li, W.; Ke, S.; Marty, B.; Huang, S.; Dauphas, N.; Wu, F.; Helz, R. L.

    2009-12-01

    Studies of Mg isotopic composition of the Earth not only are important for understanding its geochemistry but also can shed light on the accretion history of the Earth as well as the evolution of the Earth-Moon system. However, to date, the Mg isotopic composition of the Earth is still poorly constrained and highly debated. There is uncertainty in the magnitude of Mg isotope fractionation at mantle temperatures and whether the Earth has a chondritic Mg isotopic composition or not. To constrain further the Mg isotopic composition of the mantle and investigate the behavior of Mg isotopes during igneous differentiation, we report >200 high-precision (δ26Mg < 0.1‰, 2SD) analyses of Mg isotopes on 1) global mid-ocean ridge basalts covering major ridge segments of the world and spanning a broad range in latitudes, chemical and radiogenic isotopic compositions; 2) ocean island basalts from Hawaiian (Koolau, Kilauea and Loihi) and French Polynesian volcanoes (Society island and Cook Austral chain); 3) olivine grains from Hawaiian volcanoes (Kilauea, Koolau and Loihi) and 4) peridotite xenoliths from Australia, China, France, Tanzania and USA. Global oceanic basalts and peridotite xenoliths have a limited (<0.2 ‰) variation in Mg isotopic composition, with an average δ26Mg = -0.25 relative to DSM3. Olivines from Hawaiian lavas have δ26Mg ranging from -0.43 to +0.03, with most having compositions identical to basalts and peridotites. Therefore, the mantle’s δ26Mg value is estimated to be ~ -0.25 ± 0.1 (2SD), different from that reported by Wiechert and Halliday (2007; δ26Mg = ~ 0) but similar to more recent studies (δ26Mg = -0.27 to -0.33) (Teng et al. 2007; Handler et al. 2009; Yang et al., 2009). Moreover, we suggest the Earth, as represented by the mantle, has a Mg isotopic composition similar to chondrites (δ26Mg = ~-0.33). The need for a model such as that of Wiechert and Halliday (2007) that involves sorting of chondrules and calcium

  10. Metal Stable Isotope Tagging: Renaissance of Radioimmunoassay for Multiplex and Absolute Quantification of Biomolecules.

    PubMed

    Liu, Rui; Zhang, Shixi; Wei, Chao; Xing, Zhi; Zhang, Sichun; Zhang, Xinrong

    2016-05-17

    The unambiguous quantification of biomolecules is of great significance in fundamental biological research as well as practical clinical diagnosis. Due to the lack of a detectable moiety, the direct and highly sensitive quantification of biomolecules is often a "mission impossible". Consequently, tagging strategies to introduce detectable moieties for labeling target biomolecules were invented, which had a long and significant impact on studies of biomolecules in the past decades. For instance, immunoassays have been developed with radioisotope tagging by Yalow and Berson in the late 1950s. The later languishment of this technology can be almost exclusively ascribed to the use of radioactive isotopes, which led to the development of nonradioactive tagging strategy-based assays such as enzyme-linked immunosorbent assay, fluorescent immunoassay, and chemiluminescent and electrochemiluminescent immunoassay. Despite great success, these strategies suffered from drawbacks such as limited spectral window capacity for multiplex detection and inability to provide absolute quantification of biomolecules. After recalling the sequences of tagging strategies, an apparent question is why not use stable isotopes from the start? A reasonable explanation is the lack of reliable means for accurate and precise quantification of stable isotopes at that time. The situation has changed greatly at present, since several atomic mass spectrometric measures for metal stable isotopes have been developed. Among the newly developed techniques, inductively coupled plasma mass spectrometry is an ideal technique to determine metal stable isotope-tagged biomolecules, for its high sensitivity, wide dynamic linear range, and more importantly multiplex and absolute quantification ability. Since the first published report by our group, metal stable isotope tagging has become a revolutionary technique and gained great success in biomolecule quantification. An exciting research highlight in this area

  11. Isotopic composition of transpiration and rates of change in leaf water isotopologue storage in response to environmental variables.

    PubMed

    Simonin, Kevin A; Roddy, Adam B; Link, Percy; Apodaca, Randy; Tu, Kevin P; Hu, Jia; Dawson, Todd E; Barbour, Margaret M

    2013-12-01

    During daylight hours, the isotope composition of leaf water generally approximates steady-state leaf water isotope enrichment model predictions. However, until very recently there was little direct confirmation that isotopic steady-state (ISS) transpiration in fact exists. Using isotope ratio infrared spectroscopy (IRIS) and leaf gas exchange systems we evaluated the isotope composition of transpiration and the rate of change in leaf water isotopologue storage (isostorage) when leaves were exposed to variable environments. In doing so, we developed a method for controlling the absolute humidity entering the gas exchange cuvette for a wide range of concentrations without changing the isotope composition of water vapour. The measurement system allowed estimation of (18)O enrichment both at the evaporation site and for bulk leaf water, in the steady state and the non-steady state. We show that non-steady-state effects dominate the transpiration isoflux even when leaves are at physiological steady state. Our results suggest that a variable environment likely prevents ISS transpiration from being achieved and that this effect may be exacerbated by lengthy leaf water turnover times due to high leaf water contents. © 2013 John Wiley & Sons Ltd.

  12. The 238U/235U isotope ratio of the Earth and the solar system: Constrains from a gravimetrically calibrated U double spike and implications for absolute Pb-Pb ages

    NASA Astrophysics Data System (ADS)

    Weyer, Stefan; Noordmann, Janine; Brennecka, Greg; Richter, Stephan

    2010-05-01

    The ratio of 238U and 235U, the two primordial U isotopes, has been assumed to be constant on Earth and in the solar system. The commonly accepted value for the 238U/235U ratio, which has been used in Pb-Pb dating for the last ~ 30 years, was 137.88. Within the last few years, it has been shown that 1) there are considerable U isotope variations (~1.3‰) within terrestrial material produced by isotope fractionation during chemical reactions [1-3] and 2) there are even larger isotope variations (at least 3.5‰) in calcium-aluminum-rich inclusions (CAIs) in meoteorites that define the currently accepted age of the solar system [4]. These findings are dramatic for geochronology, as a known 238U/235U is a requirement for Pb-Pb dating, the most precise dating technique for absolute ages. As 238U/235U variations can greatly affect the reported absolute Pb-Pb age, understanding and accurately measuring variation of the 238U/235U ratio in various materials is critical, With these new findings, the questions also arises of "How well do we know the average U isotope composition of the Earth and the solar system?" and "How accurate can absolute Pb-Pb ages be?" Our results using a gravimetrically calibrated 233U/236U double spike IRMM 3636 [5] indicate that the U standard NBL 950a, which was commonly used to define the excepted "natural" 238U/235U isotope ratio, has a slightly lower 238U/235U of 137.836 ± 0.024. This value is indistinguishable from the U isotope compositions for NBL 960 and NBL112A, which have been determined by several laboratories, also using the newly calibrated U double spike IRMM 3636 [6]. These findings provide new implications about the average U isotope composition of the Earth and the solar system. Basalts display a very tight range of U isotope variations (~0.25-0.32‰ relative to SRM 950a). Their U isotope composition is also very similar to that of chondrites [4], which however appear to show a slightly larger spread. Accepting terrestrial

  13. Miniature Dual-Mode Absolute Scalar Magnetometer Based on the Rubidium Isotope 87Rb

    NASA Astrophysics Data System (ADS)

    Korth, H.; Strohbehn, K.; Kitching, J.

    2016-10-01

    Miniaturized absolute scalar magnetometer based on the rubidium isotope 87Rb takes advantage of recent breakthroughs in micro-fabricated atomic devices, has a total mass of 210 g and uses <1 W of power, and maintains a sensitivity of 0.1 nT rms.

  14. Magnesium isotopic composition of the Earth and chondrites

    NASA Astrophysics Data System (ADS)

    Teng, Fang-Zhen; Li, Wang-Ye; Ke, Shan; Marty, Bernard; Dauphas, Nicolas; Huang, Shichun; Wu, Fu-Yuan; Pourmand, Ali

    2010-07-01

    To constrain further the Mg isotopic composition of the Earth and chondrites, and investigate the behavior of Mg isotopes during planetary formation and magmatic processes, we report high-precision (±0.06‰ on δ 25Mg and ±0.07‰ on δ 26Mg, 2SD) analyses of Mg isotopes for (1) 47 mid-ocean ridge basalts covering global major ridge segments and spanning a broad range in latitudes, geochemical and radiogenic isotopic compositions; (2) 63 ocean island basalts from Hawaii (Kilauea, Koolau and Loihi) and French Polynesia (Society Island and Cook-Austral chain); (3) 29 peridotite xenoliths from Australia, China, France, Tanzania and USA; and (4) 38 carbonaceous, ordinary and enstatite chondrites including 9 chondrite groups (CI, CM, CO, CV, L, LL, H, EH and EL). Oceanic basalts and peridotite xenoliths have similar Mg isotopic compositions, with average values of δ 25Mg = -0.13 ± 0.05 (2SD) and δ 26Mg = -0.26 ± 0.07 (2SD) for global oceanic basalts ( n = 110) and δ 25Mg = -0.13 ± 0.03 (2SD) and δ 26Mg = -0.25 ± 0.04 (2SD) for global peridotite xenoliths ( n = 29). The identical Mg isotopic compositions in oceanic basalts and peridotites suggest that equilibrium Mg isotope fractionation during partial melting of peridotite mantle and magmatic differentiation of basaltic magma is negligible. Thirty-eight chondrites have indistinguishable Mg isotopic compositions, with δ 25Mg = -0.15 ± 0.04 (2SD) and δ 26Mg = -0.28 ± 0.06 (2SD). The constancy of Mg isotopic compositions in all major types of chondrites suggest that primary and secondary processes that affected the chemical and oxygen isotopic compositions of chondrites did not significantly fractionate Mg isotopes. Collectively, the Mg isotopic composition of the Earth's mantle, based on oceanic basalts and peridotites, is estimated to be -0.13 ± 0.04 for δ 25Mg and -0.25 ± 0.07 for δ 26Mg (2SD, n = 139). The Mg isotopic composition of the Earth, as represented by the mantle, is similar to chondrites

  15. Uranium isotope ratios of Muonionalusta troilite and complications for the absolute age of the IVA iron meteorite core

    NASA Astrophysics Data System (ADS)

    Brennecka, Gregory A.; Amelin, Yuri; Kleine, Thorsten

    2018-05-01

    The crystallization ages of planetary crustal material (given by basaltic meteorites) and planetary cores (given by iron meteorites) provide fiducial marks for the progress of planetary formation, and thus, the absolute ages of these objects fundamentally direct our knowledge and understanding of planet formation and evolution. The lone precise absolute age of planetary core material was previously obtained on troilite inclusions from the IVA iron meteorite Muonionalusta. This previously reported Pb-Pb age of 4565.3 ± 0.1 Ma-assuming a 238U/235U =137.88-only post-dated the start of the Solar System by approximately 2-3 million years, and mandated fast cooling of planetary core material. Since an accurate Pb-Pb age requires a known 238U/235U of the sample, we have measured both 238U/235U and Pb isotopic compositions of troilite inclusions from Muonionalusta. The measured 238U/235U of the samples range from ∼137.84 to as low as ∼137.22, however based on Pb and U systematics, terrestrial contamination appears pervasive and has affected samples to various extents for Pb and U. The cause of the relative 235U excess in one sample does not appear to be from terrestrial contamination or the decay of short-lived 247Cm, but is more likely from fractionation of U isotopes during metal-silicate separation during core formation, exacerbated by the extreme U depletion in the planetary core. Due to limited Pb isotopic variation and terrestrial disturbance, no samples of this study produced useful age information; however the clear divergence from the previously assumed 238U/235U of any troilite in Muonionalusta introduces substantial uncertainty to the previously reported absolute age of the sample without knowledge of the 238U/235U of the sample. Uncertainties associated with U isotope heterogeneity do not allow for definition of a robust age of solidification and cooling for the IVA core. However, one sample of this work-paired with previous work using short

  16. Isotopic Compositions of the Elements, 2001

    NASA Astrophysics Data System (ADS)

    Böhlke, J. K.; de Laeter, J. R.; De Bièvre, P.; Hidaka, H.; Peiser, H. S.; Rosman, K. J. R.; Taylor, P. D. P.

    2005-03-01

    The Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry completed its last review of the isotopic compositions of the elements as determined by isotope-ratio mass spectrometry in 2001. That review involved a critical evaluation of the published literature, element by element, and forms the basis of the table of the isotopic compositions of the elements (TICE) presented here. For each element, TICE includes evaluated data from the "best measurement" of the isotope abundances in a single sample, along with a set of representative isotope abundances and uncertainties that accommodate known variations in normal terrestrial materials. The representative isotope abundances and uncertainties generally are consistent with the standard atomic weight of the element Ar(E) and its uncertainty U[Ar(E)] recommended by CAWIA in 2001.

  17. Absolute vibrational numbering from isotope shifts in fragmentary spectroscopic data

    NASA Astrophysics Data System (ADS)

    Pashov, A.; Kowalczyk, P.; Jastrzebski, W.

    2018-05-01

    We discuss application of the isotope effect to establish the absolute vibrational numbering in electronic states of diatomic molecules. This is illustrated by examples of states with potential energy curves of both regular and irregular shape, with one or two potential minima. The minimum number of spectroscopic data (either term values or spectral line positions) necessary to provide a unique numbering is considered. We show that at favourable conditions just four term energies (or spectral lines) in one isotopologue and one term energy in the other suffice.

  18. A Cerenkov-Range analysis of the isotopic composition of cosmic rays with Z from 6 to 26

    NASA Technical Reports Server (NTRS)

    Fisher, A. J.; Hagen, F. A.; Maehl, R.; Ormes, J. F.

    1975-01-01

    High-altitude balloon data on the isotopic composition of heavy cosmic rays are reported. The experiment used a Cerenkov detector, arrays of scintillators, and a digitized wire spark chamber. Peaks assigned to the mono-isotopic elements F and Na indicate that an absolute mass scale can be derived from the data. Even-Z elements in the Z range from 12 through 16 are represented mainly by alpha-particle nuclei. Neutron-rich components dominate in the case of neon present. Mass histograms are plotted for C, O, N, Ne, Mg, and Fe.

  19. Isotopic compositions of the elements, 2001

    USGS Publications Warehouse

    Böhlke, J.K.; De Laeter, J. R.; De Bievre, P.; Hidaka, H.; Peiser, H.S.; Rosman, K.J.R.; Taylor, P.D.P.

    2005-01-01

    The Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry completed its last review of the isotopic compositions of the elements as determined by isotope-ratio mass spectrometry in 2001. That review involved a critical evaluation of the published literature, element by element, and forms the basis of the table of the isotopic compositions of the elements (TICE) presented here. For each element, TICE includes evaluated data from the “best measurement” of the isotope abundances in a single sample, along with a set of representative isotope abundances and uncertainties that accommodate known variations in normal terrestrial materials. The representative isotope abundances and uncertainties generally are consistent with the standard atomic weight of the element Ar(E)">Ar(E)Ar(E) and its uncertainty U[Ar(E)]">U[Ar(E)]U[Ar(E)] recommended by CAWIA in 2001.

  20. Nickel isotopic composition of the mantle

    NASA Astrophysics Data System (ADS)

    Gall, Louise; Williams, Helen M.; Halliday, Alex N.; Kerr, Andrew C.

    2017-02-01

    This paper presents a detailed high-precision study of Ni isotope variations in mantle peridotites and their minerals, komatiites as well as chondritic and iron meteorites. Ultramafic rocks display a relatively large range in δ60 Ni (permil deviation in 60 Ni /58 Ni relative to the NIST SRM 986 Ni isotope standard) for this environment, from 0.15 ± 0.07‰ to 0.36 ± 0.08‰, with olivine-rich rocks such as dunite and olivine cumulates showing lighter isotope compositions than komatiite, lherzolite and pyroxenite samples. The data for the mineral separates shed light on the origin of these variations. Olivine and orthopyroxene display light δ60 Ni whereas clinopyroxene and garnet are isotopically heavy. This indicates that peridotite whole-rock δ60 Ni may be controlled by variations in modal mineralogy, with the prediction that mantle melts will display variable δ60 Ni values due to variations in residual mantle and cumulate mineralogy. Based on fertile peridotite xenoliths and Phanerozoic komatiite samples it is concluded that the upper mantle has a relatively homogeneous Ni isotope composition, with the best estimate of δ60Nimantle being 0.23 ± 0.06‰ (2 s.d.). Given that >99% of the Ni in the silicate Earth is located in the mantle, this also defines the Ni isotope composition of the Bulk Silicate Earth (BSE). This value is nearly identical to the results obtained for a suite of chondrites and iron meteorites (mean δ60 Ni 0.26 ± 0.12‰ and 0.29 ± 0.10‰, respectively) showing that the BSE is chondritic with respect to its Ni isotope composition, with little to no Ni mass-dependent isotope fractionation resulting from core formation.

  1. Calculation and mitigation of isotopic interferences in liquid chromatography-mass spectrometry/mass spectrometry assays and its application in supporting microdose absolute bioavailability studies.

    PubMed

    Gu, Huidong; Wang, Jian; Aubry, Anne-Françoise; Jiang, Hao; Zeng, Jianing; Easter, John; Wang, Jun-sheng; Dockens, Randy; Bifano, Marc; Burrell, Richard; Arnold, Mark E

    2012-06-05

    A methodology for the accurate calculation and mitigation of isotopic interferences in liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS) assays and its application in supporting microdose absolute bioavailability studies are reported for the first time. For simplicity, this calculation methodology and the strategy to minimize the isotopic interference are demonstrated using a simple molecule entity, then applied to actual development drugs. The exact isotopic interferences calculated with this methodology were often much less than the traditionally used, overestimated isotopic interferences simply based on the molecular isotope abundance. One application of the methodology is the selection of a stable isotopically labeled internal standard (SIL-IS) for an LC-MS/MS bioanalytical assay. The second application is the selection of an SIL analogue for use in intravenous (i.v.) microdosing for the determination of absolute bioavailability. In the case of microdosing, the traditional approach of calculating isotopic interferences can result in selecting a labeling scheme that overlabels the i.v.-dosed drug or leads to incorrect conclusions on the feasibility of using an SIL drug and analysis by LC-MS/MS. The methodology presented here can guide the synthesis by accurately calculating the isotopic interferences when labeling at different positions, using different selective reaction monitoring (SRM) transitions or adding more labeling positions. This methodology has been successfully applied to the selection of the labeled i.v.-dosed drugs for use in two microdose absolute bioavailability studies, before initiating the chemical synthesis. With this methodology, significant time and cost saving can be achieved in supporting microdose absolute bioavailability studies with stable labeled drugs.

  2. Sulfur Isotope Composition of Putative Primary Troilite in Chondrules

    NASA Technical Reports Server (NTRS)

    Tachibana, Shogo; Huss, Gary R.

    2002-01-01

    Sulfur isotope compositions of putative primary troilites in chondrules from Bishunpur were measured by ion probe. These primary troilites have the same S isotope compositions as matrix troilites and thus appear to be isotopically unfractionated. Additional information is contained in the original extended abstract.

  3. The silicon isotope composition of the upper continental crust

    NASA Astrophysics Data System (ADS)

    Savage, Paul S.; Georg, R. Bastian; Williams, Helen M.; Halliday, Alex N.

    2013-05-01

    The upper continental crust (UCC) is the major source of silicon (Si) to the oceans and yet its isotopic composition is not well constrained. In an effort to investigate the degree of heterogeneity and provide a robust estimate for the average Si isotopic composition of the UCC, a representative selection of well-characterised, continentally-derived clastic sediments have been analysed using high-precision MC-ICPMS. Analyses of loess samples define a narrow range of Si isotopic compositions (δ30Si = -0.28‰ to -0.15‰). This is thought to reflect the primary igneous mineralogy and predominance of mechanical weathering in the formation of such samples. The average loess δ30Si is -0.22 ± 0.07‰ (2 s.d.), identical to average granite and felsic igneous compositions. Therefore, minor chemical weathering does not resolvably affect bulk rock δ30Si, and loess is a good proxy for the Si isotopic composition of unweathered, crystalline, continental crust. The Si isotopic compositions of shales display much more variability (δ30Si = -0.82‰ to 0.00‰). Shale Si isotope compositions do not correlate well with canonical proxies for chemical weathering, such as CIA values, but do correlate negatively with insoluble element concentrations and Al/Si ratios. This implies that more intensive or prolonged chemical weathering of a sedimentary source, with attendant desilicification, is required before resolvable negative Si isotopic fractionation occurs. Shale δ30Si values that are more positive than those of felsic igneous rocks most likely indicate the presence of marine-derived silica in such samples. Using the data gathered in this study, combined with already published granite Si isotope analyses, a weighted average composition of δ30Si = -0.25 ± 0.16‰ (2 s.d.) for the UCC has been calculated.

  4. Controls on the barium isotope compositions of marine sediments

    NASA Astrophysics Data System (ADS)

    Bridgestock, Luke; Hsieh, Yu-Te; Porcelli, Donald; Homoky, William B.; Bryan, Allison; Henderson, Gideon M.

    2018-01-01

    The accumulation of barium (Ba) in marine sediments is considered to be a robust proxy for export production, although this application can be limited by uncertainty in BaSO4 preservation and sediment mass accumulation rates. The Ba isotope compositions of marine sediments could potentially record insights into past changes in the marine Ba cycle, which should be insensitive to these limitations, enabling more robust interpretation of sedimentary Ba as a proxy. To investigate the controls on the Ba isotope compositions of marine sediments and their potential for paleo-oceanographic applications, we present the first Ba isotope compositions results for sediments, as well as overlying seawater depth profiles collected in the South Atlantic. Variations in Ba isotope compositions of the sediments predominantly reflect changes in the relative contributions of detrital and authigenic Ba sources, with open-ocean sediments constraining the isotope composition of authigenic Ba to be δ 138/134Ba ≈ + 0.1 ‰. This value is consistent with the average isotope composition inferred for sinking particulate Ba using simple mass balance models of Ba in the overlying water column and is hypothesized to reflect the removal of Ba from the upper water column with an associated isotopic fractionation of Δ diss-part 138/134Ba ≈ + 0.4 to +0.5. Perturbations to upper ocean Ba cycling, due to changes in export production and the supply of Ba via upwelling, should therefore be recorded by the isotope compositions of sedimentary authigenic Ba. Such insights will help to improve the reliable application of Ba accumulation rates in marine sediments as a proxy for past changes in export production.

  5. Triple oxygen isotope composition of photosynthetic oxygen

    NASA Astrophysics Data System (ADS)

    van der Meer, Anne; Kaiser, Jan

    2013-04-01

    The measurement of biological production rates is essential for our understanding how marine ecosystems are sustained and how much CO2 is taken up through aquatic photosynthesis. Traditional techniques to measure marine production are laborious and subject to systematic errors. A biogeochemical approach based on triple oxygen isotope measurements in dissolved oxygen (O2) has been developed over the last few years, which allows the derivation of gross productivity integrated over the depth of the mixed layer and the time-scale of O2 gas exchange (Luz and Barkan, 2000). This approach exploits the relative 17O/16O and 18O/16O isotope ratio differences of dissolved O2 compared to atmospheric O2 to work out the rate of biological production. Two parameters are key for this calculation: the isotopic composition of dissolved O2 in equilibrium with air and the isotopic composition of photosynthetic oxygen. Recently, a controversy has emerged in the literature over these parameters (Kaiser, 2011) and one of the goals of this research is to provide additional data to resolve this controversy. In order to obtain more information on the isotopic signature of biological oxygen, laboratory experiments have been conducted to determine the isotopic composition of oxygen produced by different phytoplankton cultures.

  6. Absolute quantitation of intracellular metabolite concentrations by an isotope ratio-based approach

    PubMed Central

    Bennett, Bryson D; Yuan, Jie; Kimball, Elizabeth H; Rabinowitz, Joshua D

    2009-01-01

    This protocol provides a method for quantitating the intracellular concentrations of endogenous metabolites in cultured cells. The cells are grown in stable isotope-labeled media to near-complete isotopic enrichment and then extracted in organic solvent containing unlabeled internal standards in known concentrations. The ratio of endogenous metabolite to internal standard in the extract is determined using mass spectrometry (MS). The product of this ratio and the unlabeled standard amount equals the amount of endogenous metabolite present in the cells. The cellular concentration of the metabolite can then be calculated on the basis of intracellular volume of the extracted cells. The protocol is exemplified using Escherichia coli and primary human fibroblasts fed uniformly with 13C-labeled carbon sources, with detection of 13C-assimilation by liquid chromatography–tandem MS. It enables absolute quantitation of several dozen metabolites over ~1 week of work. PMID:18714298

  7. The carbon isotopic composition of ecosystem breath

    NASA Astrophysics Data System (ADS)

    Ehleringer, J.

    2008-05-01

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

  8. Isotopic composition of atmospheric moisture from pan water evaporation measurements.

    PubMed

    Devi, Pooja; Jain, Ashok Kumar; Rao, M Someshwer; Kumar, Bhishm

    2015-01-01

    A continuous and reliable time series data of the stable isotopic composition of atmospheric moisture is an important requirement for the wider applicability of isotope mass balance methods in atmospheric and water balance studies. This requires routine sampling of atmospheric moisture by an appropriate technique and analysis of moisture for its isotopic composition. We have, therefore, used a much simpler method based on an isotope mass balance approach to derive the isotopic composition of atmospheric moisture using a class-A drying evaporation pan. We have carried out the study by collecting water samples from a class-A drying evaporation pan and also by collecting atmospheric moisture using the cryogenic trap method at the National Institute of Hydrology, Roorkee, India, during a pre-monsoon period. We compared the isotopic composition of atmospheric moisture obtained by using the class-A drying evaporation pan method with the cryogenic trap method. The results obtained from the evaporation pan water compare well with the cryogenic based method. Thus, the study establishes a cost-effective means of maintaining time series data of the isotopic composition of atmospheric moisture at meteorological observatories. The conclusions drawn in the present study are based on experiments conducted at Roorkee, India, and may be examined at other regions for its general applicability.

  9. Mechanisms controlling the silicon isotopic compositions of river waters

    NASA Astrophysics Data System (ADS)

    Georg, R. B.; Reynolds, B. C.; Frank, M.; Halliday, A. N.

    2006-09-01

    It has been proposed that silicon (Si) isotopes are fractionated during weathering and biological activity leading to heavy dissolved riverine compositions. In this study, the first seasonal variations of stable isotope compositions of dissolved riverine Si are reported and compared with concomitant changes in water chemistry. Four different rivers in Switzerland were sampled between March 2004 and July 2005. The unique high-resolution multi-collector ICP-MS Nu1700, has been used to provide simultaneous interference-free measurements of 28Si, 29Si and 30Si abundances with an average limiting precision of ± 0.04‰ on δ 30Si. This precision facilitates the clarification of small temporal variations in isotope composition. The average of all the data for the 40 samples is δ 30Si = + 0.84 ± 0.19‰ (± 1σ SD). Despite significant differences in catchment lithologies, biomass, climate, total dissolved solids and weathering fluxes the averaged isotopic composition of dissolved Si in each river is strikingly similar with means of + 0.70 ± 0.12‰ for the Birs,+ 0.95 ± 0.22‰ for the Saane,+ 0.93 ± 0.12‰ for the Ticino and + 0.79 ± 0.19‰ for the Verzasca. However, the δ 30Si undergoes seasonal variations of up to 0.6‰. Comparisons between δ 30Si and physico-chemical parameters, such as the concentration of dissolved Si and other cations, the discharge of the rivers, and the resulting weathering fluxes, permits an understanding of the processes that control the Si budget and the fate of dissolved Si within these rivers. The main mechanism controlling the Si isotope composition of the mountainous Verzasca River appears to be a two component mixing between the seepage of soil/ground waters, with heavier Si produced by clay formation and superficial runoff associated with lighter Si during high discharge events. A biologically-mediated fractionation can be excluded in this particular river system. The other rivers display increasing complexity with increases

  10. Absolute sulfur isotope amount ratios in two batches of high purity SO2 gas: sulfur isotope reference materials IRMM-2012 and IRMM-2013

    NASA Astrophysics Data System (ADS)

    Valkiers, S.; Ding, T.; Ruße, K.; de Bièvre, P.; Taylor, P. D. P.

    2005-04-01

    SI-traceable ("absolute") values have been obtained for sulfur isotope amount ratios n(33S)/n(32S) and n(34S)/n(32S), in two batches of high purity SO2 gas (IRMM-2012 and IRMM-2013). The SO2 gas was converted at IMR-Beijing to Ag2S, then fluorinated to SF6 gas both at IMR-Beijing and at IRMM-Geel. Yields of different conversion methods exceeded 99%. The sulfur amount-of-substance measurements were performed by gas mass spectrometry on SF5+ ions using "IRMM's amount comparator II". These isotope amount ratios were calibrated by means of gravimetrically prepared synthetic mixtures of highly enriched sulfur isotopes (32S, 33S and 34S) in Ag2S form. The ratio values in the SO2 Secondary Measurement Standard are traceable to the SI system. They can be used in the calibration of field sulfur isotope measurements thus making these metrologically traceable to the SI.

  11. Isotopic compositions of cometary matter returned by Stardust.

    PubMed

    McKeegan, Kevin D; Aléon, Jerome; Bradley, John; Brownlee, Donald; Busemann, Henner; Butterworth, Anna; Chaussidon, Marc; Fallon, Stewart; Floss, Christine; Gilmour, Jamie; Gounelle, Matthieu; Graham, Giles; Guan, Yunbin; Heck, Philipp R; Hoppe, Peter; Hutcheon, Ian D; Huth, Joachim; Ishii, Hope; Ito, Motoo; Jacobsen, Stein B; Kearsley, Anton; Leshin, Laurie A; Liu, Ming-Chang; Lyon, Ian; Marhas, Kuljeet; Marty, Bernard; Matrajt, Graciela; Meibom, Anders; Messenger, Scott; Mostefaoui, Smail; Mukhopadhyay, Sujoy; Nakamura-Messenger, Keiko; Nittler, Larry; Palma, Russ; Pepin, Robert O; Papanastassiou, Dimitri A; Robert, François; Schlutter, Dennis; Snead, Christopher J; Stadermann, Frank J; Stroud, Rhonda; Tsou, Peter; Westphal, Andrew; Young, Edward D; Ziegler, Karen; Zimmermann, Laurent; Zinner, Ernst

    2006-12-15

    Hydrogen, carbon, nitrogen, and oxygen isotopic compositions are heterogeneous among comet 81P/Wild 2 particle fragments; however, extreme isotopic anomalies are rare, indicating that the comet is not a pristine aggregate of presolar materials. Nonterrestrial nitrogen and neon isotope ratios suggest that indigenous organic matter and highly volatile materials were successfully collected. Except for a single (17)O-enriched circumstellar stardust grain, silicate and oxide minerals have oxygen isotopic compositions consistent with solar system origin. One refractory grain is (16)O-enriched, like refractory inclusions in meteorites, suggesting that Wild 2 contains material formed at high temperature in the inner solar system and transported to the Kuiper belt before comet accretion.

  12. Molybdenum Isotopic Composition of Iron Meteorites, Chondrites and Refractory Inclusions

    NASA Technical Reports Server (NTRS)

    Becker, H.; Walker, R. J.

    2003-01-01

    Recent Mo isotopic studies of meteorites reported evidence for differences in isotopic compositions for whole rocks of some primitive and differentiated meteorites relative to terrestrial materials. Enrichments of r- and p-process isotopes of up to 3-4 units (e unit = parts in 10(exp 4) over s-process dominated isotopes are the most prominent features. Certain types of presolar grains show large enrichments in s-process isotopes, however, it was concluded on grounds of mass balance that incomplete digestion of such grains cannot explain the enrichments of r- and p-process isotopes in whole rocks of primitive chondrites. If the reported variability in r- and p-process isotope enrichments reflects the true isotopic characteristics of the whole rocks, the implications are quite profound. It would suggest the presence of large scale Mo isotopic heterogeneity within the solar accretion disk with likely collateral effects for other elements. However, such effects were not found for Ru isotopes, nor for Zr isotopes. Another recent Mo isotopic study by multi collector ICP-MS could not confirm the reported deviations in Allende, Murchison or iron meteorites. Here, we present new results for the Mo isotopic composition of iron meteorites, chondrites and CAIs obtained by negative thermal ionization mass spectrometry (NTIMS). We discuss analytical aspects and the homogeneity of Mo isotopic compositions in solar system materials.

  13. Calcium Isotopic Composition of Bulk Silicate Earth

    NASA Astrophysics Data System (ADS)

    Kang, J.; Ionov, D. A.; Liu, F.; Zhang, C.; Zhang, Z.; Huang, F.

    2016-12-01

    Ca isotopes are used to study the accretion history of the Earth and terrestrial planets, but, Ca isotopic composition of the Bulk Silicate Earth (BSE) remains poorly constrained [1]. To better understand the Ca isotopic composition of BSE, we analyzed 22 well studied peridotite xenoliths from Tariat (Mongolia), Vitim (southern Siberia) and Udachnaya (Siberian Craton). These samples include both fertile and highly depleted garnet and spinel peridotites that show no or only minor post-melting metasomatism or alteration. Ca isotope measurements were done on a Triton-TIMS using double spike method at the Guangzhou Institute of Geochemistry, CAS. The data are reported as δ44/40Ca (relative to NIST SRM 915a). Results for geostandards are consistent with those from other laboratories. 2 standard deviations of SRM 915a analyses are 0.13‰ (n=48). δ44/40Ca of both and fertile and refractory peridotites range from 0.79 to 1.07‰ producing an average of 0.93±0.12‰ (2SD). This value defines the Ca isotopic composition of the BSE, which is consistent with the average δ44/40Ca of oceanic basalts ( 0.90‰)[2,3]. [1] Huang et al (2010) EPSL 292; [2] Valdes et al (2014) EPSL 394; [3]DePaolo (2004) RMG 55.

  14. The Chlorine Isotopic Composition Of Lunar UrKREEP

    NASA Technical Reports Server (NTRS)

    Barnes, J. J.; Tartese, R.; Anand, M.; McCubbin, F. M.; Neal, C. R.; Franchi, I. A.

    2016-01-01

    Since the long standing paradigm of an anhydrous Moon was challenged there has been a renewed focus on investigating volatiles in a variety of lunar samples. However, the current models for the Moon’s formation have yet to fully account for its thermal evolution in the presence of H2O and other volatiles. When compared to chondritic meteorites and terrestrial rocks, lunar samples have exotic chlorine isotope compositions, which are difficult to explain in light of the abundance and isotopic composition of other volatile species, especially H, and the current estimates for chlorine and H2O in the bulk silicate Moon. In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed a comprehensive in situ high precision study of chlorine isotopes, using NanoSIMS (Nanoscale Secondary Ion Mass Spectrometry) of lunar apatite from a suite of Apollo samples covering a range of geochemical characteristics and petrologic types.

  15. Chemical composition of French mimosa absolute oil.

    PubMed

    Perriot, Rodolphe; Breme, Katharina; Meierhenrich, Uwe J; Carenini, Elise; Ferrando, Georges; Baldovini, Nicolas

    2010-02-10

    Since decades mimosa (Acacia dealbata) absolute oil has been used in the flavor and perfume industry. Today, it finds an application in over 80 perfumes, and its worldwide industrial production is estimated five tons per year. Here we report on the chemical composition of French mimosa absolute oil. Straight-chain analogues from C6 to C26 with different functional groups (hydrocarbons, esters, aldehydes, diethyl acetals, alcohols, and ketones) were identified in the volatile fraction. Most of them are long-chain molecules: (Z)-heptadec-8-ene, heptadecane, nonadecane, and palmitic acid are the most abundant, and constituents such as 2-phenethyl alcohol, methyl anisate, and ethyl palmitate are present in smaller amounts. The heavier constituents were mainly triterpenoids such as lupenone and lupeol, which were identified as two of the main components. (Z)-Heptadec-8-ene, lupenone, and lupeol were quantified by GC-MS in SIM mode using external standards and represents 6%, 20%, and 7.8% (w/w) of the absolute oil. Moreover, odorant compounds were extracted by SPME and analyzed by GC-sniffing leading to the perception of 57 odorant zones, of which 37 compounds were identified by their odorant description, mass spectrum, retention index, and injection of the reference compound.

  16. Calcium Isotopic Compositions of Forearc Sediments from DSDP Site 144

    NASA Astrophysics Data System (ADS)

    Zhang, Z.; Zhu, H.; Nan, X.; Li, X.; Huang, F.

    2016-12-01

    It is important to investigate calcium isotopic compositions of reservoirs of the Earth for better application of Ca isotopes into studies of a variety of geochemical problems. Because Ca isotopic compositions for igneous rocks and carbonates are increasingly reported, this maybe bring new requirements on carefully understanding the isotopic compositions of subducted marine sediments. Marine sediments mainly contains carbonates and clays, controlling the compositions of slab-derived materials which are added to the mantle wedge. Obviously, it could have different elemental and calcium isotopic compositions with marine carbonate. Thus, it could also put biases on calcium isotopic signatures of basalts resulted from recycling oceanic carbonate into the mantle. Here, we report calcium isotopic compositions of 17 sediment samples from Deep Sea Drilling Project (DSDP) site 144 (09°27.23' N, 54°20.52' W) which is located about 400 km north of Surinam on the northern flank of the Demerara Rise with a water depth of 2957 meters. These samples have CaO contents ranging from 14.56 wt.% to 41.46 wt.% with an average of 29.61 ± 18.21 (2SD), δ44/40Ca ranges from 0.19 to 0.58 (relative to SRM915a) with an average of 0.40 ± 0.22 (2SD). These carbonate-rich sediments can be used to represent an endmember with high CaO content and low δ44/40Ca, which could modify chemical composition of the upper mantle and subduction zone lavas if they are recycled to the convective mantle during subduction. The positive linear correlation between CaO and δ44/40Ca in the sediments cannot be explained by a simple mixing between marine carbonate and clay. Instead, δ44/40Ca of these samples roughly increase from the Upper Cretaceous to the Early Oligocene, which might reflect the evolution of calcium isotopic compositions of seawater through time.

  17. Osmium Isotope and Highly Siderophile Element Compositions of Lunar Orange and Green Glasses

    NASA Technical Reports Server (NTRS)

    Walker, R. J.; Horan, M. F.; Shearer, C. K.; Papike, J. J.

    2003-01-01

    The absolute and relative abundances of the highly siderophile elements (HSE) present in planetary mantles are primarily controlled by: 1) silicate-metal partitioning during core-mantle differentiation, 2) the subsequent addition of HSE to mantles via continued planetary accretion. Consequently, constraints on the absolute and relative abundances of the HSE in the lunar mantle will provide unique insights to the formation and late accretionary history of not only the Moon, but also Earth. Determining the HSE content of the lunar mantle, however, has proven difficult, because no bona fide mantle rocks have been collected from the moon. The only materials presently available for constraining mantle abundances are lunar volcanic rocks. Lunar basalts typically have very low concentrations of HSE and highly fractionated HSE patterns. Because of our extremely limited understanding of mantle melt partitioning of the HSE, even for terrestrial systems, extrapolations to mantle compositions from basaltic compositions are difficult, except possibly for the less compatible HSE Pt and Pd. Primitive, presumably less fractionated materials, such as picritic glasses are potentially more diagnostic of the lunar interior. Here we report Os isotopic composition data and Re, Os, Ir, Ru, Pt and Pd concentration data for green glass (15426,164) and orange glass (74001,1217). As with previous studies utilizing neutron activation analysis, we are examining different size fractions of the spherules to assess the role of surface condensation in the generation of the HSE abundances.

  18. Long-term data set analysis of stable isotopic composition in German rivers

    NASA Astrophysics Data System (ADS)

    Reckerth, Anne; Stichler, Willibald; Schmidt, Axel; Stumpp, Christine

    2017-09-01

    Stable isotopes oxygen-18 (18O) and deuterium (2H) are commonly used to investigate hydrological processes in catchments. However, only a few isotope studies have been conducted on a large scale and rarely over long time periods. The objective of this study was to identify the spatial and seasonal variability of isotopic composition in river water and how it is affected by geographical and hydrological factors. The stable isotopic composition of river water has been measured in nine large river catchments in Germany for a time period of 12 years or 26 years. We conducted time series and correlation analyses to identify spatial and temporal patterns of the isotopic composition in the rivers. Further, we compared it to isotopic composition in local precipitation and catchments characteristics. In the majority of the rivers, the spatial and temporal patterns of precipitation were directly reflected in river water. The isotopic signals of the river water were time shifted and show attenuated amplitudes. Further deviations from isotopic compositions in local precipitation were observed in catchments with complex flow systems. These deviations were attributed to catchment processes and influences like evaporation, damming and storage. The seasonality of the isotopic composition was mainly determined by the discharge regimes of the rivers. We found correlations between isotopic long-term averages and catchment altitude as well as latitude and longitude, resulting in a northwest-southeast gradient. Furthermore, it was shown that long-term averages of d-excess were inversely related to flow length and catchment size, which indicates that evaporation enrichment has an impact on the isotopic composition even in catchments of humid climates. This study showed that isotopic composition in rivers can serve as a proxy for the local precipitation and can be utilized as an indicator for hydrological processes even in large river basins. In future, such long time series will help to

  19. What is the iron isotope composition of the Moon?

    NASA Astrophysics Data System (ADS)

    Poitrasson, F.; Zambardi, T.; Magna, T.; Neal, C. R.

    2016-12-01

    It is difficult to estimate the bulk chemical and isotopic composition of the Moon because of severe limitations in our sampling. As a result, there is currently a debate on the bulk Fe isotope composition of the Moon despite the constraints on the lunar accretion modes or differentiation processes it may provide. For this, a proper mass balance estimation of essential planetary reservoirs is required. For instance, the dichotomy in δ57Fe between low- and high-Ti mare basalt varieties as a consequence of differences in degree of fractional crystallization of their respective lunar mantle sources should be rigorously tested. To investigate this, we performed new iron isotope measurements of 33 bulk lunar mare basalts and highland rocks, including KREEP-related materials. The new data show significant Fe isotope differences between high-Ti and low-Ti mare basalts, yielding mean δ57FeIRMM-014=0.277±0.020‰ and δ57FeIRMM-014=0.127±0.020‰, respectively. Assuming that lunar basalts mirror the iron isotope composition of their respective mantle protoliths, the estimated relative proportion of the low-Ti and high-Ti mantle source suggests that the lunar upper mantle should be close to δ57Fe=0.14±0.03‰. At present, it is unclear whether the bulk lunar Fe isotope composition is indistinguishable from that of the Earth (δ57FeIRMM-014=0.10±0.03‰), when estimated solely from mare basalts data, or if it is twice as heavy relative to chondrites, as initially proposed. A large scatter at δ57Fe=0.08±0.19‰ for ferroan anorthosites, Mg-suite rocks and a KREEP basalt imparts more complexities for global isotopic view of the Moon. A better understanding of the cause of Fe isotope heterogeneity among the lunar highland rocks will likely allow to better estimate the bulk Moon composition, and possibly to improve our knowledge about the genesis of the lunar crust itself.

  20. Effects of climatic seasonality on the isotopic composition of evaporating soil waters

    NASA Astrophysics Data System (ADS)

    Benettin, Paolo; Volkmann, Till H. M.; von Freyberg, Jana; Frentress, Jay; Penna, Daniele; Dawson, Todd E.; Kirchner, James W.

    2018-05-01

    Stable water isotopes are widely used in ecohydrology to trace the transport, storage, and mixing of water on its journey through landscapes and ecosystems. Evaporation leaves a characteristic signature on the isotopic composition of the water that is left behind, such that in dual-isotope space, evaporated waters plot below the local meteoric water line (LMWL) that characterizes precipitation. Soil and xylem water samples can often plot below the LMWL as well, suggesting that they have also been influenced by evaporation. These soil and xylem water samples frequently plot along linear trends in dual-isotope space. These trend lines are often termed "evaporation lines" and their intersection with the LMWL is often interpreted as the isotopic composition of the precipitation source water. Here we use numerical experiments based on established isotope fractionation theory to show that these trend lines are often by-products of the seasonality in evaporative fractionation and in the isotopic composition of precipitation. Thus, they are often not true evaporation lines, and, if interpreted as such, can yield highly biased estimates of the isotopic composition of the source water.

  1. Zinc isotope fractionation during magmatic differentiation and the isotopic composition of the bulk Earth

    USGS Publications Warehouse

    Chen, Heng; Savage, Paul S.; Teng, Fang-Zehn; Helz, Rosalind T.; Moynier, Frédéric

    2013-01-01

    he zinc stable isotope system has been successfully applied to many and varied fields in geochemistry, but to date it is still not completely clear how this isotope system is affected by igneous processes. In order to evaluate the potential application of Zn isotopes as a proxy for planetary differentiation and volatile history, it is important to constrain the magnitude of Zn isotopic fractionation induced by magmatic differentiation. In this study we present high-precision Zn isotope analyses of two sets of chemically diverse, cogenetic samples from Kilauea Iki lava lake, Hawaii, and Hekla volcano, Iceland, which both show clear evidence of having undergone variable and significant degrees of magmatic differentiation. The Kilauea Iki samples display small but resolvable variations in Zn isotope composition (0.26‰66Zn66Zn defined as the per mille deviation of a sample's 66Zn/64Zn compositional ratio from the JMC-Lyon standard), with the most differentiated lithologies exhibiting more positive δ66Zn values. This fractionation is likely a result of the crystallization of olivine and/or Fe–Ti oxides, which can both host Zn in their crystal structures. Samples from Hekla have a similar range of isotopic variation (0.22‰66Zn66Zn=0.28±0.05‰ (2s.d.).

  2. Dolomite clumped isotope constraints on the oxygen isotope composition of the Phanerozoic Sea

    NASA Astrophysics Data System (ADS)

    Ryb, U.; Eiler, J. M.

    2017-12-01

    The δ18O value of the Phanerozoic Sea has been debated several decades, largely motivated by an 8‰ increase in δ18O of sedimentary carbonates between the Cambrian and the present. Some previous studies have interpreted this increase to be a primary depositional signal, resulting from an increase in the 18O content of ocean water over time, or from a decrease in ocean temperature increasing the oxygen isotope fractionation between seawater and carbonates. In contrast, other studies have interpreted lower δ18O compositions as the products of diagenetic alteration at elevated burial temperatures. Here, we show that the Phanerozoic dolomite δ18O record overlaps with that of well-preserved calcite fossils, and use carbonate clumped isotope measurements of Cambrian to Pleistocene dolomites to calculate their formation temperatures and the isotopic compositions of their parent-waters. The observed variation in dolomite δ18O is largely explained by dolomite formation at burial temperatures of up to 158°C. The δ18O values of dolomite parent-waters range -2 to +12‰ and are correlated with formation temperatures. Such correlation is consistent with the modification of seawater (0±2‰, VSMOW) toward isotopically heavier compositions through water-rock reactions at elevated burial temperatures. The similarity between the dolomite and calcite δ18O records, and published clumped isotope-based calculations of water compositions, suggests that like dolomite, temporal variations of the calcite δ18O record may also be largely driven by diagenetic alteration. Finally, the relationship we observe between temperature of dolomitization and d18O of dolomite suggests platform carbonates generally undergo dolomitization through reaction with modified marine waters, and that there is no evidence those waters were ever significantly lower in d18O than the modern ocean.

  3. Seasonality of Leaf Carbon Isotopic Composition and Leaf Water Isotopic Enrichment in a Mixed Evergreen Forest in Southern California

    NASA Astrophysics Data System (ADS)

    Santiago, L. S.; Sickman, J. O.; Goulden, M.; DeVan, C.; Pasquini, S. C.; Pivovaroff, A. L.

    2011-12-01

    Leaf carbon isotopic composition and leaf water isotopic enrichment reflect physiological processes and are important for linking local and regional scale processes to global patterns. We investigated how seasonality affects the isotopic composition of bulk leaf carbon, leaf sugar carbon, and leaf water hydrogen under a Mediterranean climate. Leaf and stem samples were collected monthly from four tree species (Calocedrus decurrens, Pinus lambertiana, Pinus ponderosa, and Quercus chrysolepis) at the James San Jacinto Mountain Reserve in southern California. Mean monthly bulk leaf carbon isotopic composition varied from -34.5 % in P. ponderosa to -24.7 % in P. lambertiana and became more depleted in 13C from the spring to the summer. Mean monthly leaf sugar varied from -29.3 % in P. ponderosa to -21.8 % in P. lambertiana and was enriched in 13C during the winter, spring and autumn, but depleted during the mid-summer. Leaf water hydrogen isotopic composition was 28.4 to 68.8 % more enriched in deuterium than source water and this enrichment was greater as seasonal drought progressed. These data indicate that leaf carbon and leaf water hydrogen isotopic composition provide sensitive measures that connect plant physiological processes to short-term climatic variability.

  4. Isotope composition and volume of Earth's early oceans.

    PubMed

    Pope, Emily C; Bird, Dennis K; Rosing, Minik T

    2012-03-20

    Oxygen and hydrogen isotope compositions of Earth's seawater are controlled by volatile fluxes among mantle, lithospheric (oceanic and continental crust), and atmospheric reservoirs. Throughout geologic time the oxygen mass budget was likely conserved within these Earth system reservoirs, but hydrogen's was not, as it can escape to space. Isotopic properties of serpentine from the approximately 3.8 Ga Isua Supracrustal Belt in West Greenland are used to characterize hydrogen and oxygen isotope compositions of ancient seawater. Archaean oceans were depleted in deuterium [expressed as δD relative to Vienna standard mean ocean water (VSMOW)] by at most 25 ± 5‰, but oxygen isotope ratios were comparable to modern oceans. Mass balance of the global hydrogen budget constrains the contribution of continental growth and planetary hydrogen loss to the secular evolution of hydrogen isotope ratios in Earth's oceans. Our calculations predict that the oceans of early Earth were up to 26% more voluminous, and atmospheric CH(4) and CO(2) concentrations determined from limits on hydrogen escape to space are consistent with clement conditions on Archaean Earth.

  5. Magnesium isotope evidence that accretional vapour loss shapes planetary compositions

    PubMed Central

    Hin, Remco C.; Coath, Christopher D.; Carter, Philip J.; Nimmo, Francis; Lai, Yi-Jen; Pogge von Strandmann, Philip A.E.; Willbold, Matthias; Leinhardt, Zoë M.; Walter, Michael J.; Elliott, Tim

    2017-01-01

    It has long been recognised that Earth and other differentiated planetary bodies are chemically fractionated compared to primitive, chondritic meteorites and by inference the primordial disk from which they formed. An important question has been whether the notable volatile depletions of planetary bodies are a consequence of accretion1, or inherited from prior nebular fractionation2. The isotopic compositions of the main constituents of planetary bodies can contribute to this debate3–6. Using a new analytical approach to address key issues of accuracy inherent in conventional methods, we show that all differentiated bodies have isotopically heavier magnesium compositions than chondritic meteorites. We argue that possible magnesium isotope fractionation during condensation of the solar nebula, core formation and silicate differentiation cannot explain these observations. However, isotopic fractionation between liquid and vapour followed by vapour escape during accretionary growth of planetesimals generates appropriate residual compositions. Our modelling implies that the isotopic compositions of Mg, Si and Fe and the relative abundances of the major elements of Earth, and other planetary bodies, are a natural consequence of substantial (~40% by mass) vapour loss from growing planetesimals by this mechanism. PMID:28959965

  6. Xenon isotopic composition of the Mid Ocean Ridge Basalt (MORB) source

    NASA Astrophysics Data System (ADS)

    Peto, M. K.; Mukhopadhyay, S.

    2012-12-01

    Although convection models do not preclude preservation of smaller mantle regions with more pristine composition throughout Earth's history, it has been widely assumed that the moon forming giant impact likely homogenizes the whole mantle following a magma ocean that extended all the way to the bottom of the mantle. Recent findings of tungsten and xenon heterogeneities in the mantle [1,2,3,4], however, imply that i) the moon forming giant impact may not have homogenized the whole mantle and ii) plate tectonics was inefficient in erasing early formed compositional differences, particularly for the xenon isotopes. Therefore, the xenon isotope composition in the present day mantle still preserves a memory of early Earth processes. However, determination of the xenon isotopic composition of the mantle source is still scarce, since the mantle composition is overprinted by post-eruptive atmospheric contamination in basalts erupted at ocean islands and mid ocean ridges. The xenon composition of the depleted upper mantle has been defined by the gas rich sample, 2πD43 (also known as "popping rock"), from the North Atlantic (13° 469`N). However, the composition of a single sample is not likely to define the composition of the upper mantle, especially since popping rock has an "enriched" trace element composition. We will present Ne, Ar and Xe isotope data on MORB glass samples with "normal" helium isotope composition (8±1 Ra) from the Southeast Indian Ridge, the South Atlantic Ridge, the Sojourn Ridge, the Juan de Fuca, the East Pacific Rise, and the Gakkel Ridge. Following the approach of [1], we correct for syn- and post-eruptive atmosphere contamination, and determine the variation of Ar and Xe isotope composition of the "normal" MORB source. We investigate the effect of atmospheric recycling in the variation of MORB mantle 40Ar/36Ar and 129Xe/130Xe ratios, and attempt to constrain the average upper mantle argon and xenon isotopic compositions. [1] Mukhopadhyay, Nature

  7. Tooth enamel maturation reequilibrates oxygen isotope compositions and supports simple sampling methods

    NASA Astrophysics Data System (ADS)

    Trayler, Robin B.; Kohn, Matthew J.

    2017-02-01

    Oxygen isotope and major element zoning patterns of several disparate ungulate teeth were collected to evaluate the timing and geometry of enamel formation, records of isotope zoning, and tooth enamel sampling strategies. Isotopic zoning in mammalian tooth enamel encodes a sub-annual time series of isotopic variation of an animal's body water composition, with a damping factor that depends on the specifics of how enamel mineralizes. Enamel formation comprises two stages: precipitation of appositional enamel with a high CO3:PO4 ratio, followed by precipitation of maturational enamel with a lower CO3:PO4. If appositional and maturational enamel both contribute to isotope compositions (but with different CO3:PO4), and if isotope compositions vary seasonally, paired δ18O values from CO3 and PO4 profiles should show a spatial separation. CO3 isotope patterns should be shifted earlier seasonally than PO4 isotope patterns. Such paired profiles for new and published data show no resolvable shifts, i.e. CO3 and PO4 δ18O profiles show coincident maxima and minima. This coincidence suggests that enamel maturation reequilibrates appositional isotope compositions. If enamel maturation establishes enamel isotope compositions, the geometry of maturation, not apposition, should be considered when devising sampling protocols. X-ray maps of Ca zoning show that the majority of enamel (inner and middle layers) mineralizes heavily at a high angle to the external tooth surface and the enamel-dentine junction over length scales of 2-4 mm, while the outer enamel surface mineralizes more slowly. These data suggest that isotopic sampling strategies should parallel maturational geometry and focus on interior enamel to improve data fidelity. The magnitude of isotopic damping is also smaller than implied in previous studies, so tooth enamel zoning more closely reflects original body water isotopic variations than previously assumed.

  8. The oxygen isotope composition of Almahata Sitta

    NASA Astrophysics Data System (ADS)

    Rumble, Douglas; Zolensky, Michael E.; Friedrich, Jon M.; Jenniskens, Peter; Shaddad, Muawia H.

    2010-10-01

    Eleven fragments of the meteorite Almahata Sitta (AHS) have been analyzed for oxygen isotopes. The fragments were separately collected as individual stones from the meteorite's linear strewn field in the Nubian Desert. Each of the fragments represents a sample of a different and distinct portion of asteroid 2008 TC3. Ten of the fragments span the same range of values of δ18O, δ17O, and Δ17O, and follow the same trend along the carbonaceous chondrite anhydrous minerals (CCAM) line as monomict and polymict members of the ureilite family of meteorites. The oxygen isotope composition of fragment #25 is consistent with its resemblance petrographically to an H5 ordinary chondrite. Our results demonstrate that a single small asteroidal parent body, asteroid 2008 TC3, only 4 m in length, encompassed the entire range of variation in oxygen isotope compositions measured for monomict and polymict ureilites.

  9. Zinc Isotopic Compositions of Spinel Peridotites

    NASA Astrophysics Data System (ADS)

    Chen, S.; Huang, F.

    2015-12-01

    Zn isotope geochemistry has shown great potential in exploring planetary differentiation and volatilization history [1,2,3,4]. However, the zinc isotopic composition of the mantle and its fractionation mechanism in high-temperature processes are still unclear. In order to understand Zn isotope composition of the mantle, here we measured Zn isotope data for mantle rocks and minerals, including coexisting olivine, orthopyroxene (Opx), clinopyroxene (Cpx) and spinel from peridotite xenoliths in the Hannuoba (China), Vitim (Siberia), Tariat (central Mongolia), and Dariganga (SE Mongolia). As an accessary mineral, spinels in our study have high Zn contents (500-1400 ppm), accounting for 18%-40% of the total Zn budget in peridotites. Spinels have higher δ66Zn ranging from 0.17 to 0.30‰ than other mantle minerals. For most samples, the δ66Zn of olivines vary from -0.03‰ to 0.19‰, indistinguishable to the value of the coexisting Opx (0.05‰ to 0.20‰). However, we also observed large fractionation between these two minerals, which may reflect disequilibrium fractionation due to kinetic processes. Finally, δ66Zn for peridotites are 0.12-0.21‰, slightly lighter than that of basalts (~0.25±0.05‰), revealing that Zn isotopes can be slightly fractionated during mantle melting. [1] Luck et al., (2005) Geochimica Cosmo Acta, 69, 5351-5363. [2] Paniello et al., (2012) Nature, 490, 376-379. [3] Chen et al., (2013) Meteoritics Planet Sci, 48, 2441-2450. [4] Day and Moynier, (2014) Phil. Transac. of the Royal Society B, 372, 20130259

  10. The Oxygen Isotopic Composition of the Sun

    NASA Astrophysics Data System (ADS)

    McKeegan, K. D.; Kallio, A.; Heber, V. S.; Jarzebinski, G.; Mao, P.; Coath, C.; Kunihiro, T.; Wiens, R. C.; Judith, A.; Burnett, D. S.

    2010-12-01

    An accurate and precise determination of the oxygen isotopic composition of the Sun is the highest priority scientific goal of the Genesis Mission [1] as such data would provide a baseline from which one could interpret the oxygen isotopic anomalies found at all spatial scales in inner solar system materials. We have measured oxygen isotope compositions of implanted solar wind in 40 spots along a radial traverse of the Genesis SiC target sample 60001 by depth profiling with the UCLA MegaSIMS [2]. Mass-dependent fractionation induced by the solar wind concentrator [3] ion optics was corrected by comparison of the concentrator 22Ne/20Ne with that measured in a bulk solar wind target (diamond-like carbon on Si, [4]). The solar wind captured at L1 has an isotopic composition of (δ18O, δ17O) ≈ (-99, -79)‰, a value which is far removed from the terrestrial mass fractionation line. Profiles from the central portion of the target, where solar concentrations are highest and background corrections minimal, yield a mean Δ17O = -28.3 ± 1.8 ‰ indicating that the Earth and other planetary materials from the inner solar system are highly depleted in 16O relative to the solar wind. A mass-dependent fractionation of ~ -20%/amu in the acceleration of solar wind is required if we hypothesize that the photospheric oxygen isotope value, which represents the bulk starting composition of the solar system, is on the 16O-mixing line characteristic of refractory phase in primitive meteorites [5]. With this assumption, our preferred value for the bulk solar oxygen isotope composition is δ18O ≈ δ17O ≈ -57‰. A mechanism is required to fractionate oxygen isotopes in a non-mass-dependent manner to deplete 16O by ~6 to 7% in the rocky materials of the solar nebula. As oxygen is the third most abundant element in the solar system, and the most abundant in the terrestrial planets, this mechanism must operate on a large scale. Isotope-selective photochemistry, for example as in

  11. The mercury isotope composition of Arctic coastal seawater

    NASA Astrophysics Data System (ADS)

    Štrok, Marko; Baya, Pascale Anabelle; Hintelmann, Holger

    2015-11-01

    For the first time, Hg isotope composition of seawater in the Canadian Arctic Archipelago is reported. Hg was pre-concentrated from large volumes of seawater sampling using anion exchange resins onboard the research vessel immediately after collection. Elution of Hg was performed in laboratory followed by isotope composition determination by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). For comparison, seawater from two stations was shipped to the laboratory and processed within it. Results showed negative mass-dependent fractionation in the range from -2.85 to -1.10‰ for δ202Hg, as well as slightly positive mass-independent fractionation of odd Hg isotopes. Positive mass-independent fractionation of 200Hg was also observed. Samples that were pre-concentrated in the laboratory showed different Hg isotope signatures and this is most probably due to the abiotic reduction of Hg in the dark by organic matter during storage and shipment after sampling. This emphasizes the need for immediate onboard pre-concentration.

  12. Fe Isotope Composition of Neoproterozoic Post-Glacial "Cap Dolostones"

    NASA Astrophysics Data System (ADS)

    Halverson, G. P.

    2005-12-01

    The largest variations in the Fe isotope composition in the geological record are found in sedimentary rocks, presumably as the result of redox transformations of iron during mineral precipitation, microbial processing, and diagenesis (Johnson et al., Cont. Min. Petrol., 2003). Systematic trends in the variability of the Fe isotope composition of sulfide minerals formed in ancient marine black shales broadly mirror patterns in sulfur isotope data (Δ33S, Δ34S), which are consistent with geological and other geochemical evidence for the progressive oxidation of the earth's surface during the Precambrian (Rouxel et al., Science, 2005). Therefore, the record of the Fe isotope composition of minerals formed in the marine environment appears to be a promising proxy for the redox evolution of the ocean. We have developed a method to extract the marine Fe isotope composition from carbonates in an attempt to establish higher resolution records of changes in marine redox changes than permitted by black shale geochemistry. We have applied this method to the study of ca. 635 Ma iron-rich dolostones, which are found in Neoproterozoic successions worldwide and immediately post-date a purported snowball (Marinoan) glaciation during which time the deep ocean is thought to have become anoxic (Hoffman et al., Science, 1998), allowing its Fe isotopic composition to evolve towards the composition of relatively light (δ57Fe vs. IRMM-14 ~ -0.6‰) hydrothermal iron (Beard et al., Geology, 2003). Fe isotope compositions were measured relative to IRMM-14 in medium-resolution mode on a Neptune MC-ICP-MS with a long-term external (2σ) reproducibility of < 0.04‰/amu. Preliminary data on dolomite samples from Svalbard, northern Namibia and northwest Canada show a range in δ57Fe values from -0.65 to 0.04‰, similar to the range found in siderite and Fe-rich dolomite in ancient BIFs (Johsnon et al., 2003) and to values for the Namibian cap dolostone reported by Leighton et al

  13. Iron and nickel isotope compositions of presolar silicon carbide grains from supernovae

    NASA Astrophysics Data System (ADS)

    Kodolányi, János; Stephan, Thomas; Trappitsch, Reto; Hoppe, Peter; Pignatari, Marco; Davis, Andrew M.; Pellin, Michael J.

    2018-01-01

    We report the carbon, silicon, iron, and nickel isotope compositions of twenty-five presolar SiC grains of mostly supernova (SN) origin. The iron and nickel isotope compositions were measured with the new Chicago Instrument for Laser Ionization, CHILI, which allows the analysis of all iron and nickel isotopes without the isobaric interferences that plagued previous measurements with the NanoSIMS. Despite terrestrial iron and nickel contamination, significant isotopic anomalies in 54Fe/56Fe, 57Fe/56Fe, 60Ni/58Ni, 61Ni/58Ni, 62Ni/58Ni, and 64Ni/58Ni were detected in nine SN grains (of type X). Combined multi-isotope data of three grains with the largest nickel isotope anomalies (>100‰ or <-100‰ in at least one isotope ratio, when expressed as deviation from the solar value) are compared with the predictions of two SN models, one with and one without hydrogen ingestion in the He shell prior to SN explosion. One grain's carbon-silicon-iron-nickel isotope composition is consistent with the prediction of the model without hydrogen ingestion, whereas the other two grains' isotope anomalies could not be reproduced using either SN models. The discrepancies between the measured isotope compositions and model predictions may indicate element fractionation in the SN ejecta prior to or during grain condensation, and reiterate the need for three-dimensional SN models.

  14. Magnesium stable isotope composition of Earth's upper mantle

    NASA Astrophysics Data System (ADS)

    Handler, Monica R.; Baker, Joel A.; Schiller, Martin; Bennett, Vickie C.; Yaxley, Gregory M.

    2009-05-01

    The mantle is Earth's largest reservoir of Mg containing > 99% of Earth's Mg inventory. However, no consensus exists on the stable Mg isotope composition of the Earth's mantle or how variable it is and, in particular, whether the mantle has the same stable Mg isotope composition as chondrite meteorites. We have determined the Mg isotope composition of olivine from 22 mantle peridotites from eastern Australia, west Antarctica, Jordan, Yemen and southwest Greenland by pseudo-high-resolution MC-ICP-MS on Mg purified to > 99%. The samples include fertile lherzolites, depleted harzburgites and dunites, cryptically metasomatised ('dry') peridotites and modally metasomatised apatite ± amphibole-bearing harzburgites and wehrlites. Olivine from these samples of early Archaean through to Permian lithospheric mantle have δ25Mg DSM-3 = - 0.22 to - 0.08‰. These data indicate the bulk upper mantle as represented by peridotite olivine is homogeneous within current analytical uncertainties (external reproducibility ≤ ± 0.07‰ [2 sd]). We find no systematic δ25Mg variations with location, lithospheric age, peridotite fertility, or degree or nature of mantle metasomatism. Although pyroxene may have slightly heavier δ25Mg than coexisting olivine, any fractionation between mantle pyroxene and olivine is also within current analytical uncertainties with a mean Δ25Mg pyr-ol = +0.06 ± 0.10‰ (2 sd; n = 5). Our average mantle olivine δ25Mg DSM-3 = - 0.14 ± 0.07‰ and δ26Mg DSM-3 = - 0.27 ± 0.14‰ (2 sd) are indistinguishable from the average of data previously reported for terrestrial basalts, confirming that basalts have stable Mg isotope compositions representative of the mantle. Olivine from five pallasite meteorites have δ25Mg DSM-3 = - 0.16 to - 0.11‰ that are identical to terrestrial olivine and indistinguishable from the average δ25Mg previously reported for chondrites. These data provide no evidence for measurable heterogeneity in the stable Mg isotope

  15. The Chlorine Isotopic Composition Of Lunar UrKREEP

    NASA Technical Reports Server (NTRS)

    Barnes, J. J.; Tartese, R.; Anand, M.; McCubbin, F. M.; Neal, C. R.; Franchi, I. A.

    2016-01-01

    Since the long standing paradigm of an anhydrous Moon was challenged there has been a renewed focus on investigating volatiles in a variety of lunar samples. Numerous studies have examined the abundances and isotopic compositions of volatiles in lunar apatite, Ca5(PO4)3(F,Cl,OH). In particular, apatite has been used as a tool for assessing the sources of H2O in the lunar interior. However, current models for the Moon's formation have yet to fully account for its thermal evolution in the presence of H2O and other volatiles. For ex-ample, in the context of the lunar magma ocean (LMO) model, it is anticipated that chlorine (and other volatiles) should have been concentrated in the late-stage LMO residual melts (i.e., the dregs enriched in incompatible elements such as K, REEs (Rare Earth Elements), and P, collectively called KREEP, and in its primitive form - urKREEP, given its incompatibility in mafic minerals like olivine and pyroxene, which were the dominant phases that crystallized early in the cumulate pile of the LMO. When compared to chondritic meteorites and terrestrial rocks, lunar samples have exotic chlorine isotope compositions, which are difficult to explain in light of the abundance and isotopic composition of other volatile species, especially H, and the current estimates for chlorine and H2O in the bulk silicate Moon (BSM). In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed a comprehensive in situ high precision study of chlorine isotopes in lunar apatite from a suite of Apollo samples covering a range of geochemical characteristics and petrologic types.

  16. Variability of Fe isotope compositions of hydrothermal sulfides and oxidation products at mid-ocean ridges

    NASA Astrophysics Data System (ADS)

    Li, Xiaohu; Wang, Jianqiang; Chu, Fengyou; Wang, Hao; Li, Zhenggang; Yu, Xing; Bi, Dongwei; He, Yongsheng

    2018-04-01

    Significant Fe isotopic fractionation occurs during the precipitation and oxidative weathering of modern seafloor hydrothermal sulfides, which has an important impact on the cycling of Fe isotopes in the ocean. This study reports the Fe-isotope compositions of whole-rock sulfides and single-mineral pyrite collected from hydrothermal fields at the South Mid-Atlantic Ridge (SMAR) and the East Pacific Rise (EPR) and discusses the impacts of precipitation and late-stage oxidative weathering of sulfide minerals on Fe isotopic fractionation. The results show large variation in the Fe-isotope compositions of the sulfides from the different hydrothermal fields on the mid-oceanic ridges, indicating that relatively significant isotope fractionation occurs during the sulfide precipitation and oxidative weathering processes. The Fe-isotope compositions of the sulfides from the study area at the SMAR vary across a relatively small range, with an average value of 0.01‰. This Fe-isotope composition is similar to the Fe-isotope composition of mid-oceanic ridge basalt, which suggests that Fe was mainly leached from basalt. In contrast, the Fe-isotope composition of the sulfides from the study area at the EPR are significantly enriched in light Fe isotopes (average value - 1.63‰), mainly due to the kinetic fractionation during the rapid precipitation process of hydrothermal sulfide. In addition, the pyrite from different hydrothermal fields is enriched in light Fe isotopes, which is consistent with the phenomenon in which light Fe isotopes are preferentially enriched during the precipitation of pyrite. The red oxides have the heaviest Fe-isotope compositions (up to 0.80‰), indicating that heavy Fe isotopes are preferentially enriched in the oxidation product during the late-stage oxidation process. The data obtained from this study and previous studies show a significant difference between the Fe-isotope compositions of the sulfides from the SMAR and EPR. The relatively heavy

  17. Variations in Urine Calcium Isotope: Composition Reflect Changes in Bone Mineral Balance in Humans

    NASA Technical Reports Server (NTRS)

    Skulan, Joseph; Anbar, Ariel; Bullen, Thomas; Puzas, J. Edward; Shackelford, Linda; Smith, Scott M.

    2004-01-01

    Changes in bone mineral balance cause rapid and systematic changes in the calcium isotope composition of human urine. Urine from subjects in a 17 week bed rest study was analyzed for calcium isotopic composition. Comparison of isotopic data with measurements of bone mineral density and metabolic markers of bone metabolism indicates the calcium isotope composition of urine reflects changes in bone mineral balance. Urine calcium isotope composition probably is affected by both bone metabolism and renal processes. Calcium isotope. analysis of urine and other tissues may provide information on bone mineral balance that is in important respects better than that available from other techniques, and illustrates the usefulness of applying geochemical techniques to biomedical problems.

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

    PubMed

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

    2016-02-01

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

  19. Tin isotope fractionation during magmatic processes and the isotope composition of the bulk silicate Earth

    NASA Astrophysics Data System (ADS)

    Wang, Xueying; Amet, Quentin; Fitoussi, Caroline; Bourdon, Bernard

    2018-05-01

    Tin is a moderately volatile element whose isotope composition can be used to investigate Earth and planet differentiation and the early history of the Solar System. Although the Sn stable isotope composition of several geological and archaeological samples has been reported, there is currently scarce information about the effect of igneous processes on Sn isotopes. In this study, high-precision Sn isotope measurements of peridotites and basalts were obtained by MC-ICP-MS with a double-spike technique. The basalt samples display small variations in δ124/116Sn ranging from -0.01 ± 0.11 to 0.27 ± 0.11‰ (2 s.d.) relative to NIST SRM 3161a standard solution, while peridotites have more dispersed and more negative δ124Sn values ranging from -1.04 ± 0.11 to -0.07 ± 0.11‰ (2 s.d.). Overall, basalts are enriched in heavy Sn isotopes relative to peridotites. In addition, δ124Sn in peridotites become more negative with increasing degrees of melt depletion. These results can be explained by different partitioning behavior of Sn4+ and Sn2+ during partial melting. Sn4+ is overall more incompatible than Sn2+ during partial melting, resulting in Sn4+-rich silicate melt and Sn2+-rich residue. As Sn4+ has been shown experimentally to be enriched in heavy isotopes relative to Sn2+, the effect of melting is to enrich residual peridotites in relatively more compatible Sn2+, which results in isotopically lighter peridotites and isotopically heavier mantle-derived melts. This picture can be disturbed partly by the effect of refertilization. Similarly, the presence of enriched components such as recycled oceanic crust or sediments could explain part of the variations in Sn isotopes in oceanic basalts. The most primitive peridotite analyzed in this study was used for estimating the Sn isotope composition of the BSE, with δ124Sn = -0.08 ± 0.11‰ (2 s.d.) relative to the Sn NIST SRM 3161a standard solution. Altogether, this suggests that Sn isotopes may be a powerful probe of

  20. Absolute parameters and chemical composition of the binary star OU Gem

    NASA Astrophysics Data System (ADS)

    Glazunova, L. V.; Mishenina, T. V.; Soubiran, C.; Kovtyukh, V. V.

    2014-10-01

    The absolute parameters and chemical composition of the BY Dra-type spectroscopic binary OU Gem (HD 45088) were determined on the basis of 10 high-resolution spectra. A new orbital solution of the binary system was determined, the binary ephemerides were specified, and the main physical and atmospheric parameters of the binary components were obtained. The chemical composition of both components was estimated for the first time for the stars of such type.

  1. Reassessing the stable isotope composition assigned to methane flux from natural wetlands in isotope-constrained budgets

    NASA Astrophysics Data System (ADS)

    Hornibrook, Edward; Maxfield, Peter; Gauci, Vincent; Stott, Andrew

    2013-04-01

    Stable isotope ratios in CH4 preserve information about its origin and history, and are commonly used to constrain global CH4 budgets. Wetlands are key contributors to the atmospheric burden of CH4 and typically are assigned a stable carbon isotope composition of ~-60 permil in isotope-weighted stable isotope models despite the considerable range of δ13C(CH4) values (~ -100 to -40 permil) known to occur in these diverse ecosystems. Kinetic isotope effects (KIEs) associated with the metabolism of CH4-producing microorganisms generate much of the natural variation but highly negative and positive δ13C(CH4) values generally result from secondary processes (e.g., diffusive transport or oxidation by soil methanotrophs). Despite these complexities, consistent patterns exist in the isotope composition of wetland CH4 that can be linked conclusively to trophic status and consequently, natural succession or human perturbations that impact nutrient levels. Another challenge for accurate representation of wetlands in carbon cycle models is parameterisation of sporadic CH4 emission events. Abrupt release of large volumes of CH4-rich bubbles in short periods of time can account for a significant proportion of the annual CH4 flux from a wetland but such events are difficult to detect using conventional methods. New infrared spectroscopy techniques capable of high temporal resolution measurements of CH4 concentration and stable isotope composition can readily quantify short-lived CH4 pulses. Moreover, the isotope data can be used conclusively to determine shifts in the mode of CH4 transport and provide the potential to link initiation of abrupt emission events to forcing by internal or external factors.

  2. Iron isotopic composition of blood serum in anemia of chronic kidney disease.

    PubMed

    Anoshkina, Yulia; Costas-Rodríguez, Marta; Speeckaert, Marijn; Van Biesen, Wim; Delanghe, Joris; Vanhaecke, Frank

    2017-05-24

    Chronic kidney disease (CKD) is a general term for disorders that affect the structure and function of the kidneys. Iron deficiency (ID) and anemia occur in the vast majority of CKD patients, most of whom are elderly. However, establishing the cause of anemia in CKD, and therefore making an informed decision concerning the corresponding therapeutic treatment, is still a challenge. High-precision Fe isotopic analysis of blood serum samples of CKD patients with and without ID/anemia was performed via multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS) for such a purpose. Patients with CKD and/or iron disorders showed a heavier serum Fe isotopic composition than controls. Many clinical parameters used for the diagnosis and follow-up of anemia correlated significantly with the serum Fe isotopic composition. In contrast, no relation was observed between the serum Fe isotopic composition and the estimated glomerular filtration rate as a measure of kidney function. Among the CKD patients, the serum Fe isotopic composition was substantially heavier in the occurrence of ID anemia, while erythropoietin-related anemia did not exert this effect. The Fe isotopic composition can thus be useful for distinguishing these different types of anemias in CKD patients, i.e. ID anemia vs. erythropoietin-related anemia.

  3. The Chlorine Isotope Composition of Earth’s Mantle

    NASA Astrophysics Data System (ADS)

    Bonifacie, M.; Jendrzejewski, N.; Agrinier, P.; Humler, E.; Coleman, M.; Javoy, M.

    2008-03-01

    Chlorine stable isotope compositions (δ37Cl) of 22 mid-ocean ridge basalts (MORBs) correlate with Cl content. The high-δ37Cl, Cl-rich basalts are highly contaminated by Cl-rich materials (seawater, brines, or altered rocks). The low-δ37Cl, Cl-poor basalts approach the composition of uncontaminated, mantle-derived magmas. Thus, most or all oceanic lavas are contaminated to some extent during their emplacement. MORB-source mantle has δ37Cl ≤ 1.6 per mil (‰), which is significantly lower than that of surface reservoirs (~ 0‰). This isotopic difference between the surface and deep Earth results from net Cl isotopic fractionation (associated with removal of Cl from the mantle and its return by subduction over Earth history) and/or the addition (to external reservoirs) of a late volatile supply that is 37Cl-enriched.

  4. Isotopic compositions of the elements 2013 (IUPAC Technical Report)

    USGS Publications Warehouse

    Meija, Juris; Coplen, Tyler B.; Berglund, Michael; Brand, Willi A.; De Bièvre, Paul; Gröning, Manfred; Holden, Norman E.; Irrgeher, Johanna; Loss, Robert D.; Walczyk, Thomas; Prohaska, Thomas

    2016-01-01

    The Commission on Isotopic Abundances and Atomic Weights (ciaaw.org) of the International Union of Pure and Applied Chemistry (iupac.org) has revised the Table of Isotopic Compositions of the Elements (TICE). The update involved a critical evaluation of the recent published literature. The new TICE 2013 includes evaluated data from the “best measurement” of the isotopic abundances in a single sample, along with a set of representative isotopic abundances and uncertainties that accommodate known variations in normal terrestrial materials.

  5. Modelling and intepreting the isotopic composition of water vapour in convective updrafts

    NASA Astrophysics Data System (ADS)

    Bolot, M.; Legras, B.; Moyer, E. J.

    2012-08-01

    The isotopic compositions of water vapour and its condensates have long been used as tracers of the global hydrological cycle, but may also be useful for understanding processes within individual convective clouds. We review here the representation of processes that alter water isotopic compositions during processing of air in convective updrafts and present a unified model for water vapour isotopic evolution within undiluted deep convective cores, with a special focus on the out-of-equilibrium conditions of mixed phase zones where metastable liquid water and ice coexist. We use our model to show that a combination of water isotopologue measurements can constrain critical convective parameters including degree of supersaturation, supercooled water content and glaciation temperature. Important isotopic processes in updrafts include kinetic effects that are a consequence of diffusive growth or decay of cloud particles within a supersaturated or subsaturated environment; isotopic re-equilibration between vapour and supercooled droplets, which buffers isotopic distillation; and differing mechanisms of glaciation (droplet freezing vs. the Wegener-Bergeron-Findeisen process). As all of these processes are related to updraft strength, droplet size distribution and the retention of supercooled water, isotopic measurements can serve as a probe of in-cloud conditions of importance to convective processes. We study the sensitivity of the profile of water vapour isotopic composition to differing model assumptions and show how measurements of isotopic composition at cloud base and cloud top alone may be sufficient to retrieve key cloud parameters.

  6. Modelling and interpreting the isotopic composition of water vapour in convective updrafts

    NASA Astrophysics Data System (ADS)

    Bolot, M.; Legras, B.; Moyer, E. J.

    2013-08-01

    The isotopic compositions of water vapour and its condensates have long been used as tracers of the global hydrological cycle, but may also be useful for understanding processes within individual convective clouds. We review here the representation of processes that alter water isotopic compositions during processing of air in convective updrafts and present a unified model for water vapour isotopic evolution within undiluted deep convective cores, with a special focus on the out-of-equilibrium conditions of mixed-phase zones where metastable liquid water and ice coexist. We use our model to show that a combination of water isotopologue measurements can constrain critical convective parameters, including degree of supersaturation, supercooled water content and glaciation temperature. Important isotopic processes in updrafts include kinetic effects that are a consequence of diffusive growth or decay of cloud particles within a supersaturated or subsaturated environment; isotopic re-equilibration between vapour and supercooled droplets, which buffers isotopic distillation; and differing mechanisms of glaciation (droplet freezing vs. the Wegener-Bergeron-Findeisen process). As all of these processes are related to updraft strength, particle size distribution and the retention of supercooled water, isotopic measurements can serve as a probe of in-cloud conditions of importance to convective processes. We study the sensitivity of the profile of water vapour isotopic composition to differing model assumptions and show how measurements of isotopic composition at cloud base and cloud top alone may be sufficient to retrieve key cloud parameters.

  7. Oxygen Isotopic Compositions of Solar Corundum Grains

    NASA Astrophysics Data System (ADS)

    Makide, Kentaro; Nagashima, Kazuhide; Krot, Alexander N.; Huss, Gary R.

    2009-11-01

    Oxygen is one of the major rock-forming elements in the solar system and the third most abundant element of the Sun. Oxygen isotopic composition of the Sun, however, is not known due to a poor resolution of astronomical spectroscopic measurements. Several Δ17O values have been proposed for the composition of the Sun based on (1) the oxygen isotopic measurements of the solar wind implanted into metallic particles in lunar soil (< -20‰ by Hashizume & Chaussidon and ~ +26‰ by Ireland et al.), (2) the solar wind returned by the Genesis spacecraft (-27‰ ± 6‰ by McKeegan et al.), and (3) the mineralogically pristine calcium-aluminum-rich inclusions (CAIs) (-23.3‰ ± 1.9‰ by Makide et al. and -35‰ by Gounelle et al.). CAIs are the oldest solar system solids, and are believed to have formed by evaporation, condensation, and melting processes in hot nebular region(s) when the Sun was infalling (Class 0) or evolved (Class 1) protostar. Corundum (Al2O3) is thermodynamically the first condensate from a cooling gas of solar composition. Corundum-bearing CAIs, however, are exceptionally rare, suggesting either continuous reaction of the corundum condensates with a cooling nebular gas and their replacement by hibonite (CaAl12O19) or their destruction by melting together with less refractory condensates during formation of igneous CAIs. In contrast to the corundum-bearing CAIs, isolated micrometer-sized corundum grains are common in the acid-resistant residues from unmetamorphosed chondrites. These grains could have avoided multistage reprocessing during CAI formation and, therefore, can potentially provide constraints on the initial oxygen isotopic composition of the solar nebula, and, hence, of the Sun. Here we report oxygen isotopic compositions of ~60 micrometer-sized corundum grains in the acid-resistant residues from unequilibrated ordinary chondrites (Semarkona (LL3.0), Bishunpur (LL3.1), Roosevelt County 075 (H3.2)) and unmetamorphosed carbonaceous

  8. Absolute Calibration of Si iRMs used for Measurements of Si Paleo-nutrient proxies

    NASA Astrophysics Data System (ADS)

    Vocke, R. D., Jr.; Rabb, S. A.

    2016-12-01

    Silicon isotope variations (reported as δ30Si and δ29Si, relative to NBS28) in silicic acid dissolved in ocean waters, in biogenic silica and in diatoms are extremely informative paleo-nutrient proxies. The resolution and comparability of such measurements depend on the quality of the isotopic Reference Materials (iRMs) defining the delta scale. We report new absolute Si isotopic measurements on the iRMs NBS28 (RM 8546 - Silica Sand), Diatomite, and Big Batch using the Avogadro measurement approach and comparing them with prior assessments of these iRMs. The Avogadro Si measurement technique was developed by the German Physikalish-Technische Bundesanstalt (PTB) to provide a precise and highly accurate method to measure absolute isotopic ratios in highly enriched 28Si (99.996%) material. These measurements are part of an international effort to redefine the kg and mole based on the Planck constant h and the Avogadro constant NA, respectively (Vocke et al., 2014 Metrologia 51, 361, Azuma et al., 2015 Metrologia 52 360). This approach produces absolute Si isotope ratio data with lower levels of uncertainty when compared to the traditional "Atomic Weights" method of absolute isotope ratio measurement calibration. This is illustrated in Fig. 1 where absolute Si isotopic measurements on SRM 990, separated by 40+ years of advances in instrumentation, are compared. The availability of this new technique does not say that absolute Si isotopic ratios are or ever will be better for normal Si isotopic measurements when seeking isotopic variations in nature, because they are not. However, by determining the absolute isotopic ratios of all the Si iRM scale artifacts, such iRMs become traceable to the metric system (SI); thereby automatically conferring on all the artifact-based δ30Si and δ29Si measurements traceability to the base SI unit, the mole. Such traceability should help reduce the potential of bias between different iRMs and facilitate the replacement of delta

  9. Baseline shifts in coral skeletal oxygen isotopic composition: a signature of symbiont shuffling?

    NASA Astrophysics Data System (ADS)

    Carilli, J. E.; Charles, C. D.; Garren, M.; McField, M.; Norris, R. D.

    2013-06-01

    Decades-long records of the stable isotopic composition of coral skeletal cores were analyzed from four sites on the Mesoamerican Reef. Two of the sites exhibited baseline shifts in oxygen isotopic composition after known coral bleaching events. Changes in pH at the calcification site caused by a change in the associated symbiont community are invoked to explain the observed shift in the isotopic composition. To test the hypothesis that changes in symbiont clade could affect skeletal chemistry, additional coral samples were collected from Belize for paired Symbiodinium identification and skeletal stable isotopic analysis. We found some evidence that skeletal stable isotopic composition may be affected by symbiont clade and suggest this is an important topic for future investigation. If different Symbiodinium clades leave consistent signatures in skeletal geochemical composition, the signature will provide a method to quantify past symbiont shuffling events, important for understanding how corals are likely to respond to climate change.

  10. Elemental and iron isotopic composition of aerosols collected in a parking structure.

    PubMed

    Majestic, Brian J; Anbar, Ariel D; Herckes, Pierre

    2009-09-01

    The trace metal contents and iron isotope composition of size-resolved aerosols were determined in a parking structure in Tempe, AZ, USA. Particulate matter (PM)<2.5 microm in diameter (the fine fraction) and PM>2.5 microm were collected. Several air toxics (e.g., arsenic, cadmium, and antimony) were enriched above the crustal average, implicating automobiles as an important source. Extremely high levels of fine copper (up to 1000 ng m(-3)) were also observed in the parking garage, likely from brake wear. The iron isotope composition of the aerosols were found to be +0.15+/-0.03 per thousand and +0.18+/-0.03 per thousand for the PM<2.5 microm and PM>2.5 microm fractions, respectively. The similarity of isotope composition indicates a common source for each size fraction. To better understand the source of iron in the parking garage, the elemental composition in four brake pads (two semi-metallic and two ceramic), two tire tread samples, and two waste oil samples were determined. Striking differences in the metallic and ceramic brake pads were observed. The ceramic brake pads contained 10-20% copper by mass, while the metallic brake pads contained about 70% iron, with very little copper. Both waste oil samples contained significant amounts of calcium, phosphorous, and zinc, consistent with the composition of some engine oil additives. Differences in iron isotope composition were observed between the source materials; most notably between the tire tread (average=+0.02 per thousand) and the ceramic brake linings (average=+0.65 per thousand). Differences in isotopic composition were also observed between the metallic (average=+0.18 per thousand) and ceramic brake pads, implying that iron isotope composition may be used to resolve these sources. The iron isotope composition of the metallic brake pads was found to be identical to the aerosols, implying that brake dust is the dominant source of iron in a parking garage.

  11. THE NITROGEN ISOTOPIC COMPOSITION OF METEORITIC HCN

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Pizzarello, Sandra, E-mail: pizzar@asu.edu

    2014-12-01

    HCN is ubiquitous in extraterrestrial environments and is central to current theories on the origin of early solar system organic compounds such as amino acids. These compounds, observed in carbonaceous meteorites, were likely important in the origin and/or evolution of early life. As part of our attempts to understand the origin(s) of meteoritic CN{sup –}, we have analyzed the {sup 15}N/{sup 14}N isotopic composition of HCN gas released from water extracts of the Murchison meteorite and found its value to be near those of the terrestrial atmosphere. The findings, when evaluated viz-a-viz molecular abundances and isotopic data of meteoritic organicmore » compounds, suggest that HCN formation could have occurred during the protracted water alteration processes known to have affected the mineralogy of many asteroidal bodies during their solar residence. This was an active synthetic stage, which likely involved simple gasses, organic molecules, their presolar precursors, as well as mineral catalysts and would have lead to the formation of molecules of differing isotopic composition, including some with solar values.« less

  12. Magnesium Isotopic Composition of Kamchatka Sub-Arc Mantle Peridotites

    NASA Astrophysics Data System (ADS)

    Hu, Y.; Teng, F. Z.; Ionov, D. A.

    2016-12-01

    Subduction of the oceanic slab may add a crustal isotopic signal to the mantle wedge. The highly variable Mg isotopic compositions (δ26Mg) of the subducted oceanic crust input[1] and arc lava output[2] imply a distinctive Mg isotopic signature of the mantle wedge. Magnesium isotopic data on samples from the sub-arc mantle are still limited, however. To characterize the Mg isotopic composition of typical sub-arc mantle, 17 large and fresh spinel harzburgite xenoliths from Avacha volcano were analyzed. The harzburgites were formed by 30% melt extraction at ≤ 1 2 GPa and fluid fluxing condition, and underwent possible fluid metasomatism as suggested by distinctively high orthopyroxene mode in some samples, the presence of accessory amphibole and highly variable Ba/La ratios[3]. However, their δ26Mg values display limited variation from -0.32 to -0.21, which are comparable to the mantle average at -0.25 ± 0.07[4]. The overall mantle-like and homogenous δ26Mg of Avacha sub-arc peridotites are consistent with their similar chemical compositions and high MgO contents (> 44 wt%) relative to likely crustal fluids. Furthermore, clinopyroxene (-0.24 ± 0.10, 2SD, n = 5), a late-stage mineral exsolved from high-temperature, Ca-rich residual orthopyroxene, is in broad Mg isotopic equilibrium with olivine (-0.27 ± 0.04, 2SD, n = 17) and orthopyroxene (-0.22 ± 0.06, 2SD, n = 17). Collectively, this study finds that the Kamchatka mantle wedge, as represented by the Avacha peridotites, has a mantle-like δ26Mg, and low-degree fluid-mantle interaction does not cause significant Mg isotope fractionation in sub-arc mantle peridotites. [1] Wang et al., EPSL, 2012 [2] Teng et al., PNAS, 2016 [3] Ionov, J. Petrol., 2010, [4] Teng et al., GCA, 2010.

  13. Seasonality of Oxygen isotope composition in cow (Bos taurus) hair and its model interpretation

    NASA Astrophysics Data System (ADS)

    Chen, Guo; Schnyder, Hans; Auerswald, Karl

    2017-04-01

    Oxygen isotopes in animal and human tissues are expected to be good recorders of geographical origin and migration histories based on the isotopic relationship between hair oxygen and annual precipitation and the well-known spatial pattern of oxygen isotope composition in meteoric water. However, seasonal variation of oxygen isotope composition may diminish the origin information in the tissues. Here the seasonality of oxygen isotope composition in tail hair was investigated in a domestic suckler cow (Bos taurus) that underwent different ambient conditions, physiological states, and keeping and feeding strategies during five years. A detailed mechanistic model involving in ambient conditions, soil properties and animal physiology was built to explain this variation. The measured oxygen isotope composition in hair was significantly related (p<0.05) to the isotope composition in meteoric water in a regression analysis. Modelling suggested that this relation was only partly derived from the direct influence of feed moisture. Ambient conditions (temperature, moisture) did not only influence the isotopic signal of precipitation but also affected the animal itself (drinking water demand, transcutaneous vapor etc.). The clear temporal variation thus resulted from complex interactions with multiple influences. The twofold influence of ambient conditions via the feed and via the animal itself is advantageous for tracing the geographic origin because the oxygen isotope composition is then less influenced by variations in moisture uptake; however, it is unfavorable for indicating the production system, e.g. to distinguish between milk produced from fresh grass or from silage.

  14. C-isotope composition of fossil sedges and grasses

    NASA Astrophysics Data System (ADS)

    Kurschner, Wolfram M.

    2010-05-01

    C4 plants differ from C3 plants regarding their anatomy and their C-isotope composition. Both features can be used in the geological record to determine the presence of C4 plants. Yet, the evolution of the C4 pathway in the fossil record is enigmatic as palaeobotanical and geological evidence for C4 plants is sparse. The oldest structural evidence for Kranz anatomy has been found in Late Miocene permineralized grass leaf remains. But studies on the C-isotope composition of sedimentary organic matter indicate that abundant C4 biomass was present in N-America and Asia throughout the Miocene in expanding savannahs and grasslands. The success of C4 plants appears to be related also to an increasing seasonal aridity in the tropical climate belts and the co-evolution of grazers. However, C- isotope composition of palaeosols or vertebrate teeth only allows to estimate the abundance of C4 plant biomass in the vegetation or in the diet without further taxonomical specification which plant groups would have had C4 metabolism. In this contribution the first extensive C-isotope analysis of fossil seeds of sedges and a few grasses are presented. The age of the carpological material ranges from Late Eocene to Pliocene and was collected from several central European brown coal deposits. The 52 different taxa studied include several species of Carex, Cladiocarya, Eriopherum, Eleocharis, Scirpus, Sparganium. Most of them representing herbaceous elements of a (sub)tropical vegetation growing near the edge of a lake. The C-isotope composition of the fossil seeds varies between -30 and -23 o/oo indicating C3 photosynthesis. This first systematic inventory shows that C4 plants were absent in the European (sub)tropical brown coal forming wetland vegetation during the Tertiary. These preliminary data are in agreement with phylogenetic studies which predict the origin of C4 plants outside the European realm.

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

    NASA Astrophysics Data System (ADS)

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

    2004-07-01

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

  16. Isotope composition and volume of Earth’s early oceans

    PubMed Central

    Pope, Emily C.; Bird, Dennis K.; Rosing, Minik T.

    2012-01-01

    Oxygen and hydrogen isotope compositions of Earth’s seawater are controlled by volatile fluxes among mantle, lithospheric (oceanic and continental crust), and atmospheric reservoirs. Throughout geologic time the oxygen mass budget was likely conserved within these Earth system reservoirs, but hydrogen’s was not, as it can escape to space. Isotopic properties of serpentine from the approximately 3.8 Ga Isua Supracrustal Belt in West Greenland are used to characterize hydrogen and oxygen isotope compositions of ancient seawater. Archaean oceans were depleted in deuterium [expressed as δD relative to Vienna standard mean ocean water (VSMOW)] by at most 25 ± 5‰, but oxygen isotope ratios were comparable to modern oceans. Mass balance of the global hydrogen budget constrains the contribution of continental growth and planetary hydrogen loss to the secular evolution of hydrogen isotope ratios in Earth’s oceans. Our calculations predict that the oceans of early Earth were up to 26% more voluminous, and atmospheric CH4 and CO2 concentrations determined from limits on hydrogen escape to space are consistent with clement conditions on Archaean Earth. PMID:22392985

  17. Magnesium isotope compositions of Solar System materials determined by double spiking

    NASA Astrophysics Data System (ADS)

    Hin, R.; Lai, Y. J.; Coath, C.; Elliott, T.

    2015-12-01

    As a major element, magnesium is of interest for investigating large scale processes governing the formation and evolution of rocky planetary bodies. Determining the Mg isotope composition of the Earth and other planetary bodies has hence been a topic of interest ever since mass-dependent fractionation of 'non-traditional' stable isotopes has been used to study high-temperature processes. Published results, however, suffer from disagreement on the Mg isotope compositions of the Earth and chondrites [1-5], which is attributed to residual matrix effects. Nonetheless, most recent studied have converged towards a homogeneous (chondritic) Mg isotope composition in the Solar System [2-5]. However, in several of the recent studies there is a hint of a systematic difference of about 0.02-0.06‰ in the 26Mg/24Mg isotope compositions of chondrites and Earth. Such difference, however, is only resolvable by taking standard errors, which assumes robust data for homogenous sample sets. The discrepancies between various studies unfortunately undermine the confidence in such robustness and homogeneity. The issues with matrix effects during isotopic analyses can be overcome by using a double spike approach. Such methodology generally requires three isotope ratios to solve for three unknowns, a requirement that cannot be met for Mg. However, using a newly developed approach, we present Mg isotope compositions obtained by critical mixture double spiking. This new approach should allow greater confidence in the robustness of the data and hence enable improvement of. Preliminary data indicate that chondrites have a resolvable ~0.04‰ lighter 26Mg/24Mg than (ultra)mafic rocks from Earth, Mars and the eucrite parent body, which appear indistinguishable from each other. It seems implausible that this difference is caused by magmatic process such as partial melting or crystallisation. More likely, Mg isotopes are fractionated by a non-magmatic process during the formation of planets, e

  18. Spatial patterns of throughfall isotopic composition at the event and seasonal timescales

    NASA Astrophysics Data System (ADS)

    Allen, Scott T.; Keim, Richard F.; McDonnell, Jeffrey J.

    2015-03-01

    Spatial variability of throughfall isotopic composition in forests is indicative of complex processes occurring in the canopy and remains insufficiently understood to properly characterize precipitation inputs to the catchment water balance. Here we investigate variability of throughfall isotopic composition with the objectives: (1) to quantify the spatial variability in event-scale samples, (2) to determine if there are persistent controls over the variability and how these affect variability of seasonally accumulated throughfall, and (3) to analyze the distribution of measured throughfall isotopic composition associated with varying sampling regimes. We measured throughfall over two, three-month periods in western Oregon, USA under a Douglas-fir canopy. The mean spatial range of δ18O for each event was 1.6‰ and 1.2‰ through Fall 2009 (11 events) and Spring 2010 (7 events), respectively. However, the spatial pattern of isotopic composition was not temporally stable causing season-total throughfall to be less variable than event throughfall (1.0‰; range of cumulative δ18O for Fall 2009). Isotopic composition was not spatially autocorrelated and not explained by location relative to tree stems. Sampling error analysis for both field measurements and Monte-Carlo simulated datasets representing different sampling schemes revealed the standard deviation of differences from the true mean as high as 0.45‰ (δ18O) and 1.29‰ (d-excess). The magnitude of this isotopic variation suggests that small sample sizes are a source of substantial experimental error.

  19. Oxygen isotope composition of mafic magmas at Vesuvius

    NASA Astrophysics Data System (ADS)

    Dallai, L.; Cioni, R.; Boschi, C.; D'Oriano, C.

    2009-12-01

    The oxygen isotope composition of olivine and clinopyroxene from four plinian (AD 79 Pompeii, 3960 BP Avellino), subplinian (AD 472 Pollena) and violent strombolian (Middle Age activity) eruptions were measured to constrain the nature and evolution of the primary magmas of the last 4000 years of Mt. Vesuvius activity. A large set of mm-sized crystals was accurately separated from selected juvenile material of the four eruptions. Crystals were analyzed for their major and trace element compositions (EPMA, Laser Ablation ICP-MS), and for 18O/16O ratios. As oxygen isotope composition of uncontaminated mantle rocks on world-wide scale is well constrained (δ18Oolivine = 5.2 ± 0.3; δ18Ocpx = 5.6 ± 0.3 ‰), the measured values can be conveniently used to monitor the effects of assimilation/contamination of crustal rocks in the evolution of the primary magmas. Instead, typically uncontaminated mantle values are hardly recovered in Italian Quaternary magmas, mostly due to the widespread occurrence of crustal contamination of the primary magmas during their ascent to the surface (e.g. Alban Hills, Ernici Mts., and Aeolian Islands). Low δ18O values have been measured in olivine from Pompeii eruption (δ18Oolivine = 5.54 ± 0.03‰), whereas higher O-compositions are recorded in mafic minerals from pumices or scoria of the other three eruptions. Measured olivine and clinopyroxene share quite homogeneous chemical compositions (Olivine Fo 85-90 ; Diopside En 45-48, respectively), and represent phases crystallized in near primary mafic magmas, as also constrained by their trace element compositions. Data on melt inclusions hosted in crystals of these compositions have been largely collected in the past demonstrating that they crystallized from mafic melt, basaltic to tephritic in composition. Published data on volatile content of these melt inclusions reveal the coexistence of dissolved water and carbon dioxide, and a minimum trapping pressure around 200-300 MPa, suggesting

  20. Zirconium isotope constraints on the composition of Theia and current Moon-forming theories

    NASA Astrophysics Data System (ADS)

    Akram, W.; Schönbächler, M.

    2016-09-01

    The giant impact theory is the most widely recognized formation scenario of the Earth's Moon. Giant impact models based on dynamical simulations predict that the Moon acquired a significant amount of impactor (Theia) material, which is challenging to reconcile with geochemical data for O, Si, Cr, Ti and W isotopes in the Earth and Moon. Three new giant impact scenarios have been proposed to account for this discrepancy - hit-and-run impact, impact with a fast-spinning protoEarth and massive impactors - each one reducing the proportion of the impactor in the Moon compared to the original canonical giant impact model. The validity of each theory and their different dynamical varieties are evaluated here using an integrated approach that considers new high-precision Zr isotope measurements of lunar rocks, and quantitative geochemical modelling of the isotopic composition of the impactor Theia. All analysed lunar samples (whole-rock, ilmenite and pyroxene separates) display identical Zr isotope compositions to that of the Earth within the uncertainty of 13 ppm for 96Zr/90Zr (2σ weighted average). This 13 ppm upper limit is used to infer the most extreme isotopic composition that Theia could have possessed, relative to the Earth, for each of the proposed giant impact theories. The calculated Theian composition is compared with the Zr isotope compositions of different solar system materials in order to constrain the source region of the impactor. As a first order approximation, we show that all considered models (including the canonical) are plausible, alleviating the initial requirement for the new giant impact models. Albeit, the canonical and hit-and-run models are the most restrictive, suggesting that the impactor originated from a region close to the Earth. The fast-spinning protoEarth and massive impactor models are more relaxed and increase the allowed impactor distance from the Earth. Similar calculations carried out for O, Cr, Ti and Si isotope data support

  1. Verification of the isotopic composition of precipitation simulated by a regional isotope circulation model over Japan.

    PubMed

    Tanoue, Masahiro; Ichiyanagi, Kimpei; Yoshimura, Kei

    2016-01-01

    The isotopic composition (δ(18)O and δ(2)H) of precipitation simulated by a regional isotope circulation model with a horizontal resolution of 10, 30 and 50 km was compared with observations at 56 sites over Japan in 2013. All simulations produced reasonable spatio-temporal variations in δ(18)O in precipitation over Japan, except in January. In January, simulated δ(18)O values in precipitation were higher than observed values on the Pacific side of Japan, especially during an explosively developing extratropical cyclone event. This caused a parameterisation of precipitation formulation about the large fraction of precipitated water to liquid detrained water in the lower troposphere. As a result, most water vapour that transported from the Sea of Japan precipitated on the Sea of Japan side. The isotopic composition of precipitation was a useful verification tool for the parameterisation of precipitation formulation as well as large-scale moisture transport processes in the regional isotope circulation model.

  2. Converting isotope ratios to diet composition - the use of mixing models - June 2010

    EPA Science Inventory

    One application of stable isotope analysis is to reconstruct diet composition based on isotopic mass balance. The isotopic value of a consumer’s tissue reflects the isotopic values of its food sources proportional to their dietary contributions. Isotopic mixing models are used ...

  3. Magnesium Isotopic Compositions of Continental Basalts From Various Tectonic Settings

    NASA Astrophysics Data System (ADS)

    Yang, W.; Li, S.; Tian, H.; Ke, S.

    2016-12-01

    Recycled sedimentary carbonate through subduction is the main light Mg isotopic reservoir in Earth's deep interior, thus Mg isotopic variation of mantle-derived melts provides a fresh perspective on investigating deep carbon cycling. Here we investigate Mg isotopic compositions of continental basalts from various tectonic settings: (1) The Cenozoic basalts from eastern China, coinciding with the stagnant Pacific slab in the mantle transition zone revealed by seismic tomography; (2) The Cenozoic basalts from Tengchong area, southwestern China, which comprises a crucial part of the collision zone between the Indian and Eurasian plates; (3) The Permian basalts from Emeishan large igneous province, related to a mantle plume. The Cenozoic basalts from both eastern China and Tengchong area exhibit light Mg isotopic compositions (δ26Mg = -0.60 to -0.30‰ and -0.51 to -0.33‰), suggesting recycled sedimentary carbonates in their mantle sources. This is supported by their low Fe/Mn, high CaO/Al2O3, low Hf/Hf* and low Ti/Ti* ratios, which are typical features of carbonated peridotite-derived melt. The Tengchong basalts also show high 87Sr/86Sr, high radiogenic Pb and upper crustal-like trace element pattern, indicating contribution of recycled continental crustal materials. By contrast, all Emeishan basalts display a mantle-like Mg isotopic composition, with δ26Mg ranging from -0.35 to -0.19‰. Since the Emeishan basalts derived from a mantle plume, their mantle-like Mg isotopic composition may indicate limited sedimentary carbonated recycled into the lower mantle. This is consistent with a recent experimental study which concluded that direct recycling of carbon into the lower mantle may have been highly restricted throughout most of the Earth's history.

  4. The stable Cr isotopic compositions of chondrites and silicate planetary reservoirs

    NASA Astrophysics Data System (ADS)

    Schoenberg, Ronny; Merdian, Alexandra; Holmden, Chris; Kleinhanns, Ilka C.; Haßler, Kathrin; Wille, Martin; Reitter, Elmar

    2016-06-01

    The depletion of chromium in Earth's mantle (∼2700 ppm) in comparison to chondrites (∼4400 ppm) indicates significant incorporation of chromium into the core during our planet's metal-silicate differentiation, assuming that there was no significant escape of the moderately volatile element chromium during the accretionary phase of Earth. Stable Cr isotope compositions - expressed as the ‰-difference in 53Cr/52Cr from the terrestrial reference material SRM979 (δ53/52CrSRM979 values) - of planetary silicate reservoirs might thus yield information about the conditions of planetary metal segregation processes when compared to chondrites. The stable Cr isotopic compositions of 7 carbonaceous chondrites, 11 ordinary chondrites, 5 HED achondrites and 2 martian meteorites determined by a double spike MC-ICP-MS method are within uncertainties indistinguishable from each other and from the previously determined δ53/52CrSRM979 value of -0.124 ± 0.101‰ for the igneous silicate Earth. Extensive quality tests support the accuracy of the stable Cr isotope determinations of various meteorites and terrestrial silicates reported here. The uniformity in stable Cr isotope compositions of samples from planetary silicate mantles and undifferentiated meteorites indicates that metal-silicate differentiation of Earth, Mars and the HED parent body did not cause measurable stable Cr isotope fractionation between these two reservoirs. Our results also imply that the accretionary disc, at least in the inner solar system, was homogeneous in its stable Cr isotopic composition and that potential volatility loss of chromium during accretion of the terrestrial planets was not accompanied by measurable stable isotopic fractionation. Small but reproducible variations in δ53/52CrSRM979 values of terrestrial magmatic rocks point to natural stable Cr isotope variations within Earth's silicate reservoirs. Further and more detailed studies are required to investigate whether silicate

  5. Spatial patterns of throughfall isotopic composition at the event and seasonal timescales

    Treesearch

    Scott T. Allen; Richard F. Keim; Jeffrey J. McDonnell

    2015-01-01

    Spatial variability of throughfall isotopic composition in forests is indicative of complex processes occurring in the canopy and remains insufficiently understood to properly characterize precipitation inputs to the catchment water balance. Here we investigate variability of throughfall isotopic composition with the objectives: (1) to quantify the spatial variability...

  6. Isotopic Composition of Oxygen in Lunar Zircons

    NASA Technical Reports Server (NTRS)

    Nemchin, A. A.; Whitehouse, M. J.; Pidgeon, R. T.; Meyer, C.

    2005-01-01

    The recent discovery of heavy oxygen in zircons from the Jack Hills conglomerates Wilde et al. and Mojzsis et al. was interpreted as an indication of presence of liquid water on the surface of Early Earth. The distribution of ages of Jack Hills zircons and lunar zircons appears to be very similar and therefore analysis of oxygen in the lunar grains may provide a reference frame for further study of the early history of the Earth as well as give additional information regarding processes that operated on the Moon. In the present study we have analysed the oxygen isotopic composition of zircon grains from three lunar samples using the Swedish Museum of Natural History CAMECA 1270 ion microprobe. The samples were selected as likely tests for variations in lunar oxygen isotopic composition. Additional information is included in the original extended abstract.

  7. The Chlorine Isotope Composition of Martian Meteorites

    NASA Astrophysics Data System (ADS)

    Sharp, Z. D.; Shearer, C. K.; Agee, C.; Burger, P. V.; McKeegan, K. D.

    2014-11-01

    The Cl isotope composition of martian meteorites range from -3.8 to +8.6 per mil. Ol-phyric shergottites are lightest; crustally contaminated samples are heaviest, basaltic shergottites are in-between. The system is explained as two component mixing.

  8. Silicon isotope amount ratios and molar masses for two silicon isotope reference materials: IRMM-018a and NBS28

    NASA Astrophysics Data System (ADS)

    Valkiers, S.; Ding, T.; Inkret, M.; Ruße, K.; Taylor, P.

    2005-04-01

    A new 2 kg batch of SiO2 crystals, IRMM-018a as well as the existing NBS28 silica sand (or RM 8546, obtained by I. Friedman from U.S. Geological Survey) have been characterised for their "absolute" silicon isotope composition and molar mass. The amount-of-substance measurements needed for that purpose were performed on the IRMM amount comparator (Avogadro II) on samples from these batches, which were converted to gaseous silicon tetra-fluoride (SiF4). The isotope amount ratio measurements were calibrated by means of synthesized isotope amount ratios realized in the form of synthetic Si isotope mixtures, the measurement procedure of which makes them SI-traceable. IRMM-018a is intended to be used as Isotope Reference Material for isotope amount measurements in geochemical and other isotope abundance studies of silicon. It is distributed in samples of about 0.1 mol and will replace IRMM-018 (exhausted).

  9. Spacecraft measurements of the elemental and isotopic composition of solar energetic particles

    NASA Technical Reports Server (NTRS)

    Mewaldt, R. A.

    1980-01-01

    Within the past few years, instruments flown on satellites and space probes have made significant progress in measuring the elemental and isotopic composition of energetic heavy nuclei accelerated in solar flares. These new observations are discussed, focusing on: (1) the energy dependence of the elemental composition at energies not greater than 1 MeV/nucleon; (2) flare to flare variations in the composition; and (3) comparisons of the average solar particle abundances (Z not less than 2 and not greater than 28) with other measures of the solar composition, including photospheric, coronal, and solar wind observations. These comparisons have led to the suggestion that solar flares sample the composition of the corona. Isotopic measurements of heavy solar flare nuclei have recently added a new dimension to these studies. In particular, the isotopic composition of solar flare neon has been found to be significantly different from that measured in the solar wind, but consistent with the meteoritic component neon-A.

  10. Hydrogen and oxygen in brine shrimp chitin reflect environmental water and dietary isotopic composition

    NASA Astrophysics Data System (ADS)

    Nielson, Kristine E.; Bowen, Gabriel J.

    2010-03-01

    Hydrogen and oxygen isotope ratios of the common structural biopolymer chitin are a potential recorder of ecological and environmental information, but our understanding of the mechanisms of incorporation of H and O from environmental substrates into chitin is limited. We report the results of a set of experiments in which the isotopic compositions of environmental water and diet were varied independently in order to assess the contribution of these variables to the H and O isotopic composition of Artemia franciscana chitin. Hydrogen isotope ratios of chitin were strongly linearly correlated with both food and water, with approximately 26% of the hydrogen signal reflecting food and approximately 38% reflecting water. Oxygen isotopes were also strongly correlated with the isotopic composition of water and food, but whereas 69% of oxygen in chitin exchanged with environmental water, only 10% was derived from food. We propose that these observations reflect the position-specific, partial exchange of H and O atoms with brine shrimp body water during the processes of digestion and chitin biosynthesis. Comparison of culture experiments with a set of natural samples collected from the Great Salt Lake, UT in 2006 shows that, with some exceptions, oxygen isotope compositions of chitin track those of water, whereas hydrogen isotopes vary inversely with those of lake water. The different behavior of the two isotopic systems can be explained in terms of a dietary shift from allochthonous particulate matter with relatively higher δ 2H values in the early spring to autochthonous particulate matter with significantly lower δ 2H values in the late summer to autumn. These results suggest oxygen in chitin may be a valuable proxy for the oxygen isotopic composition of environmental water, whereas hydrogen isotope values from the same molecule may reveal ecological and biogeochemical changes within lakes.

  11. The neodymium stable isotope composition of the silicate Earth and chondrites

    NASA Astrophysics Data System (ADS)

    McCoy-West, Alex J.; Millet, Marc-Alban; Burton, Kevin W.

    2017-12-01

    The non-chondritic neodymium (Nd) 142Nd/144Nd ratio of the silicate Earth potentially provides a key constraint on the accretion and early evolution of the Earth. Yet, it is debated whether this offset is due to the Earth being formed from material enriched in s-process Nd isotopes or results from an early differentiation process such as the segregation of a late sulfide matte during core formation, collisional erosion or a some combination of these processes. Neodymium stable isotopes are potentially sensitive to early sulfide segregation into Earth's core, a process that cannot be resolved using their radiogenic counterparts. This study presents the first comprehensive Nd stable isotope data for chondritic meteorites and terrestrial rocks. Stable Nd measurements were made using a double spike technique coupled with thermal ionisation mass spectrometry. All three of the major classes of chondritic meteorites, carbonaceous, enstatite and ordinary chondrites have broadly similar isotopic compositions allowing calculation of a chondritic mean of δ146/144Nd = -0.025 ± 0.025‰ (±2 s.d.; n = 39). Enstatite chondrites yield the most uniform stable isotope composition (Δ146/144Nd = 26 ppm), with considerably more variability observed within ordinary (Δ146/144Nd = 72 ppm) and carbonaceous meteorites (Δ146/144Nd = 143 ppm). Terrestrial weathering, nucleosynthetic variations and parent body thermal metamorphism appear to have little measurable effect on δ146/144Nd in chondrites. The small variations observed between ordinary chondrite groups most likely reflect inherited compositional differences between parent bodies, with the larger variations observed in carbonaceous chondrites being linked to varying modal proportions of calcium-aluminium rich inclusions. The terrestrial samples analysed here include rocks ranging from basaltic to rhyolitic in composition, MORB glasses and residual mantle lithologies. All of these terrestrial rocks possess a broadly similar Nd

  12. Isotope-Labeled Composition B for Tracing Detonation Signatures

    NASA Astrophysics Data System (ADS)

    Manner, Virginia; Podlesak, David; Huber, Rachel; Amato, Ronald; Giambra, Anna; Bowden, Patrick; Hartline, Ernest; Dattelbaum, Dana

    2017-06-01

    To better understand how solid carbon forms and evolves during detonation, we have prepared Composition B with 13 C and 15 N-labeled 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and 2,4,6-trinitrotoluene (TNT) in order to trace the formation of soot from the carbon and nitrogen atoms in these explosives. Isotope-labeling of explosives has been performed in the recent past for a variety of reasons, including environmental remediation and reaction mechanism studies. Because it is expensive and time consuming to prepare these materials, and our detection equipment only requires trace amounts of isotopes, we have prepared fully-labeled materials and substituted them into unlabeled RDX and TNT at less than the 1% level. We will discuss the preparation and full characterization of this labeled Composition B, the detonation tests performed, along with the results of the post-detonation soot analysis. Various detonation models predict differing amounts and forms of carbon and nitrogen; these isotopically-labeled precursors have allowed these models to be tested.

  13. Alkali elemental and potassium isotopic compositions of Semarkona chondrules

    USGS Publications Warehouse

    Alexander, C.M. O'D.; Grossman, J.N.

    2005-01-01

    We report measurements of K isotope ratios in 28 Semarkona chondrules with a wide range of petrologic types and bulk compositions as well as the compositions of CPX-mesostasis pairs in 17 type I Semarkona chondrules, including two chondrules with radial alkali zonation and 19 type II chondrules. Despite the wide range in K/Al ratios, no systematic variations in K isotopic compositions were found. Semarkona chondrules do not record a simple history of Rayleigh-type loss of K. Experimentally determined evaporation rates suggest that considerable alkali evaporation would have occurred during chondrule formation. Nevertheless, based on Na CPX-mesostasis distribution coefficients, the alkali contents of the cores of most chondrules in Semarkona were probably established at the time of final crystallization. However, Na CPX-mesostasis distribution coefficients also show that alkali zonation in type I Semarkona chondrules was produced by entry of alkalis after solidification, probably during parent body alteration. This alkali metasomatism may have gone to completion in some chondrules. Our preferred explanation for the lack of systematic isotopic enrichments, even in alkali depleted type I chondrule cores, is that they exchanged with the ambient gas as they cooled. ?? The Meteoritical Society, 2005.

  14. Clumped Isotope Composition of Cold-Water Corals: A Role for Vital Effects?

    NASA Astrophysics Data System (ADS)

    Spooner, P.; Guo, W.; Robinson, L. F.

    2014-12-01

    Measurements on a set of cold-water corals (mainly Desmophyllum dianthus) have suggested that their clumped isotope composition could serve as a promising proxy for reconstructing paleocean temperatures. Such measurements have also offered support for certain isotope models of coral calcification. However, there are differences in the clumped isotope compositions between warm-water and cold-water corals, suggesting that different kinds of corals could have differences in their biocalcification processes. In order to understand the systematics of clumped isotope variations in cold-water corals more fully, we present clumped isotope data from a range of cold-water coral species from the tropical Atlantic and the Southern Ocean.Our samples were either collected live or recently dead (14C ages < 1,000 yrs) with associated temperature data. They include a total of 11 solitary corals and 1 colonial coral from the Atlantic, and 8 solitary corals from the Southern Ocean. The data indicate that coral clumped isotope systematics may be more complicated than previously thought. For example, for the genus Caryophyllia we observe significant variations in clumped isotope compositions for corals which grew at the same temperature with an apparent negative correlation between Δ47 and δ18O, different to patterns previously observed in Desmophyllum. These results indicate that existing isotope models of biocalcification may not apply equally well to all corals. Clumped isotope vital effects may be present in certain cold-water corals as they are in warm-water corals, complicating the use of this paleoclimate proxy.

  15. Antimony isotopic composition in river waters affected by ancient mining activity.

    PubMed

    Resongles, Eléonore; Freydier, Rémi; Casiot, Corinne; Viers, Jérôme; Chmeleff, Jérôme; Elbaz-Poulichet, Françoise

    2015-11-01

    In this study, antimony (Sb) isotopic composition was determined in natural water samples collected along two hydrosystems impacted by historical mining activities: the upper Orb River and the Gardon River watershed (SE, France). Antimony isotope ratio was measured by HG-MC-ICP-MS (Hydride Generation Multi-Collector Inductively Coupled Plasma Mass Spectrometer) after a preconcentration and purification step using a new thiol-cellulose powder (TCP) procedure. The external reproducibility obtained for δ(123)Sb measurements of our in-house Sb isotopic standard solution and a certified reference freshwater was 0.06‰ (2σ). Significant isotopic variations were evident in surface waters from the upper Orb River (-0.06‰≤δ(123)Sb≤+0.11‰) and from the Gardon River watershed (+0.27‰≤δ(123)Sb≤+0.83‰). In particular, streams that drained different former mining sites exploited for Sb or Pb-Zn exhibited contrasted Sb isotopic signature, that may be related to various biogeochemical processes occurring during Sb transfer from rocks, mine wastes and sediments to the water compartment. Nevertheless, Sb isotopic composition appeared to be stable along the Gardon River, which might be attributed to the conservative transport of Sb at distance from mine-impacted streams, due to the relative mobile behavior of Sb(V) in natural oxic waters. This study suggests that Sb isotopic composition could be a useful tool to track pollution sources and/or biogeochemical processes in hydrologic systems. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. Anomalous gain in an isotopically mixed CO2 laser and application to absolute wavelength calibration

    NASA Technical Reports Server (NTRS)

    Hewagama, Tilak; Oppenheim, Uri P.; Mumma, Michael J.

    1991-01-01

    Measurements are reported on a grating-tuned CO2 laser, containing an isotropic mixture of O-16C-12O-16, O-16C-12O-18, and O-18C-12O-18. The P6 and R14 lines of O-16C-12O-16 were found to have anomalously high intensities. These anomalies are produced by the near coincidence of the transition frequencies in two distinct isotopes, permitting them to act as a single indistinguishable population. These two lines can be used to identify the rotational quantum numbers in the P and R branch spectra, thereby permitting absolute wavelength calibration to be achieved.

  17. Isotopic Composition of Barium in Single Presolar Silicon Carbide Grains

    NASA Technical Reports Server (NTRS)

    Savina, M. R.; Tripa, C. E.; Pellin, M. J.; Davis, A. M.; Clayton, R. N.; Lewis, R. S.; Amari, S.

    2002-01-01

    We have measured Ba isotope distributions in individual presolar SiC grains. We find that the Ba isotopic composition in mainstream SiC grains is consistent with models of nucleosynthesis in low to intermediate mass asymptotic giant branch (AGB) stars. Additional information is contained in the original extended abstract.

  18. Oxygen Isotope Composition of Nitrate Produced by Freshwater Nitrification

    NASA Astrophysics Data System (ADS)

    Boshers, D.; Granger, J.; Bohlke, J. K.

    2016-12-01

    Measurements of the naturally occurring nitrogen and oxygen stable isotope ratios of nitrate (NO3-), δ15N and δ18O, can be used to determine the source, dispersal, and fate of natural and contaminant NO3- in aquatic environments. To this end, it is necessary to know the extent to which NO3- isotopologues are modified by biological reactions, as heavy and light isotopes have different reaction rates. The purpose of this study was to determine the influence of the δ18O of ambient water on the isotope composition of NO3- produced during nitrification, the biological oxidation of ammonium (NH4+) to nitrite (NO2-) and then NO3-, which is poorly constrained in freshwater systems. To determine the δ18O of NO3- produced by nitrification in freshwater, we collected water from a stream in New England, which we amended with NH4+ and with increments of 18O-enriched water, to monitor the isotope composition of NO3- produced by a natural consortium of nitrifiers. Added NH4+ was completely oxidized to NO3- over 26 days. The final δ18O of nitrified NO3- revealed sensitivity to the δ18O of water mediated by (a) isotopic equilibration between water and NO2- and (b) kinetic isotope fractionation during O-atom incorporation from water into NO2- and NO3-. Our results concur with nitrifying culture experiments that have demonstrated analogous sensitivity of the δ18O of nitrified NO3- to equilibrium and kinetic O isotope effects (Buchwald et al. 2012), as well as show that these dynamics need to be considered to interpret NO3- isotope distribution in freshwater environments.

  19. 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

  20. Stable isotopic composition of perchlorate and nitrate accumulated in plants: Hydroponic experiments and field data.

    PubMed

    Estrada, Nubia Luz; Böhlke, J K; Sturchio, Neil C; Gu, Baohua; Harvey, Greg; Burkey, Kent O; Grantz, David A; McGrath, Margaret T; Anderson, Todd A; Rao, Balaji; Sevanthi, Ritesh; Hatzinger, Paul B; Jackson, W Andrew

    2017-10-01

    Natural perchlorate (ClO 4 - ) in soil and groundwater exhibits a wide range in stable isotopic compositions (δ 37 Cl, δ 18 O, and Δ 17 O), indicating that ClO 4 - may be formed through more than one pathway and/or undergoes post-depositional isotopic alteration. Plants are known to accumulate ClO 4 - , but little is known about their ability to alter its isotopic composition. We examined the potential for plants to alter the isotopic composition of ClO 4 - in hydroponic and field experiments conducted with snap beans (Phaseolus vulgaris L.). In hydroponic studies, anion ratios indicated that ClO 4 - was transported from solutions into plants similarly to NO 3 - but preferentially to Cl - (4-fold). The ClO 4 - isotopic compositions of initial ClO 4 - reagents, final growth solutions, and aqueous extracts from plant tissues were essentially indistinguishable, indicating no significant isotope effects during ClO 4 - uptake or accumulation. The ClO 4 - isotopic composition of field-grown snap beans was also consistent with that of ClO 4 - in varying proportions from irrigation water and precipitation. NO 3 - uptake had little or no effect on NO 3 - isotopic compositions in hydroponic solutions. However, a large fractionation effect with an apparent ε ( 15 N/ 18 O) ratio of 1.05 was observed between NO 3 - in hydroponic solutions and leaf extracts, consistent with partial NO 3 - reduction during assimilation within plant tissue. We also explored the feasibility of evaluating sources of ClO 4 - in commercial produce, as illustrated by spinach, for which the ClO 4 - isotopic composition was similar to that of indigenous natural ClO 4 - . Our results indicate that some types of plants can accumulate and (presumably) release ClO 4 - to soil and groundwater without altering its isotopic characteristics. Concentrations and isotopic compositions of ClO 4 - and NO 3 - in plants may be useful for determining sources of fertilizers and sources of ClO 4 - in their growth

  1. Stable isotopic composition of perchlorate and nitrate accumulated in plants: Hydroponic experiments and field data

    USGS Publications Warehouse

    Estrada, Nubia Luz; Böhlke, John Karl; Sturchio, Neil C.; Gu, Baohua; Harvey, Greg; Burkey, Kent O.; Grantz, David A.; McGrath, Margaret T.; Anderson, Todd A.; Rao, Balaji; Sevanthi, Ritesh; Hatzinger, Paul B.; Jackson, W. Andrew

    2017-01-01

    Natural perchlorate (ClO4−) in soil and groundwater exhibits a wide range in stable isotopic compositions (δ37Cl, δ18O, and Δ17O), indicating that ClO4− may be formed through more than one pathway and/or undergoes post-depositional isotopic alteration. Plants are known to accumulate ClO4−, but little is known about their ability to alter its isotopic composition. We examined the potential for plants to alter the isotopic composition of ClO4− in hydroponic and field experiments conducted with snap beans (Phaseolus vulgaris L.). In hydroponic studies, anion ratios indicated that ClO4− was transported from solutions into plants similarly to NO3− but preferentially to Cl− (4-fold). The ClO4− isotopic compositions of initial ClO4− reagents, final growth solutions, and aqueous extracts from plant tissues were essentially indistinguishable, indicating no significant isotope effects during ClO4− uptake or accumulation. The ClO4− isotopic composition of field-grown snap beans was also consistent with that of ClO4− in varying proportions from irrigation water and precipitation. NO3− uptake had little or no effect on NO3− isotopic compositions in hydroponic solutions. However, a large fractionation effect with an apparent ε (15N/18O) ratio of 1.05 was observed between NO3− in hydroponic solutions and leaf extracts, consistent with partial NO3− reduction during assimilation within plant tissue. We also explored the feasibility of evaluating sources of ClO4− in commercial produce, as illustrated by spinach, for which the ClO4− isotopic composition was similar to that of indigenous natural ClO4−. Our results indicate that some types of plants can accumulate and (presumably) release ClO4− to soil and groundwater without altering its isotopic characteristics. Concentrations and isotopic compositions of ClO4−and NO3− in plants may be useful for determining sources of fertilizers and sources of ClO4− in their growth environments and

  2. Novel isotopic N, N-Dimethyl Leucine (iDiLeu) Reagents Enable Absolute Quantification of Peptides and Proteins Using a Standard Curve Approach

    NASA Astrophysics Data System (ADS)

    Greer, Tyler; Lietz, Christopher B.; Xiang, Feng; Li, Lingjun

    2015-01-01

    Absolute quantification of protein targets using liquid chromatography-mass spectrometry (LC-MS) is a key component of candidate biomarker validation. One popular method combines multiple reaction monitoring (MRM) using a triple quadrupole instrument with stable isotope-labeled standards (SIS) for absolute quantification (AQUA). LC-MRM AQUA assays are sensitive and specific, but they are also expensive because of the cost of synthesizing stable isotope peptide standards. While the chemical modification approach using mass differential tags for relative and absolute quantification (mTRAQ) represents a more economical approach when quantifying large numbers of peptides, these reagents are costly and still suffer from lower throughput because only two concentration values per peptide can be obtained in a single LC-MS run. Here, we have developed and applied a set of five novel mass difference reagents, isotopic N, N-dimethyl leucine (iDiLeu). These labels contain an amine reactive group, triazine ester, are cost effective because of their synthetic simplicity, and have increased throughput compared with previous LC-MS quantification methods by allowing construction of a four-point standard curve in one run. iDiLeu-labeled peptides show remarkably similar retention time shifts, slightly lower energy thresholds for higher-energy collisional dissociation (HCD) fragmentation, and high quantification accuracy for trypsin-digested protein samples (median errors <15%). By spiking in an iDiLeu-labeled neuropeptide, allatostatin, into mouse urine matrix, two quantification methods are validated. The first uses one labeled peptide as an internal standard to normalize labeled peptide peak areas across runs (<19% error), whereas the second enables standard curve creation and analyte quantification in one run (<8% error).

  3. The Effects of Core Composition on Iron Isotope Fractionation During Planetary Differentiation

    NASA Astrophysics Data System (ADS)

    Elardo, S. M.; Shahar, A.; Caracas, R.; Mock, T. D.; Sio, C. K. I.

    2018-05-01

    High pressure and temperature isotope exchange experiments and density functional theory calculations show how the composition of planetary cores affects the fractionation of iron isotopes during planetary differentiation.

  4. SIMSISH Technique Does Not Alter the Apparent Isotopic Composition of Bacterial Cells

    PubMed Central

    Chapleur, Olivier; Wu, Ting-Di; Guerquin-Kern, Jean-Luc; Mazéas, Laurent; Bouchez, Théodore

    2013-01-01

    In order to identify the function of uncultured microorganisms in their environment, the SIMSISH method, combining in situ hybridization (ISH) and nanoscale secondary ion mass spectrometry (nanoSIMS) imaging, has been proposed to determine the quantitative uptake of specific labelled substrates by uncultured microbes at the single cell level. This technique requires the hybridization of rRNA targeted halogenated DNA probes on fixed and permeabilized microorganisms. Exogenous atoms are introduced into cells and endogenous atoms removed during the experimental procedures. Consequently differences between the original and the apparent isotopic composition of cells may occur. In the present study, the influence of the experimental procedures of SIMSISH on the isotopic composition of carbon in E. coli cells was evaluated with nanoSIMS and compared to elemental analyser-isotopic ratio mass spectrometer (EA-IRMS) measurements. Our results show that fixation and hybridization have a very limited, reproducible and homogeneous influence on the isotopic composition of cells. Thereby, the SIMSISH procedure minimizes the contamination of the sample by exogenous atoms, thus providing a means to detect the phylogenetic identity and to measure precisely the carbon isotopic composition at the single cell level. This technique was successfully applied to a complex sample with double bromine – iodine labelling targeting a large group of bacteria and a specific archaea to evaluate their specific 13C uptake during labelled methanol anaerobic degradation. PMID:24204855

  5. Fossil black smoker yields oxygen isotopic composition of Neoproterozoic seawater.

    PubMed

    Hodel, F; Macouin, M; Trindade, R I F; Triantafyllou, A; Ganne, J; Chavagnac, V; Berger, J; Rospabé, M; Destrigneville, C; Carlut, J; Ennih, N; Agrinier, P

    2018-04-13

    The evolution of the seawater oxygen isotopic composition (δ 18 O) through geological time remains controversial. Yet, the past δ 18 O seawater is key to assess past seawater temperatures, providing insights into past climate change and life evolution. Here we provide a new and unprecedentedly precise δ 18 O value of -1.33 ± 0.98‰ for the Neoproterozoic bottom seawater supporting a constant oxygen isotope composition through time. We demonstrate that the Aït Ahmane ultramafic unit of the ca. 760 Ma Bou Azzer ophiolite (Morocco) host a fossil black smoker-type hydrothermal system. In this system we analyzed an untapped archive for the ocean oxygen isotopic composition consisting in pure magnetite veins directly precipitated from a Neoproterozoic seawater-derived fluid. Our results suggest that, while δ 18 O seawater and submarine hydrothermal processes were likely similar to present day, Neoproterozoic oceans were 15-30 °C warmer on the eve of the Sturtian glaciation and the major life diversification that followed.

  6. Copper and Zinc isotope composition of CR, CB and CH-like meteorites.

    NASA Astrophysics Data System (ADS)

    Russell, S.; Zhu, X.; Guo, Y.; Mullane, E.; Gounelle, M.; Mason, T.; Coles, B.

    2003-04-01

    Copper and zinc isotopes have recently been shown to be variable in isotopic composi-tion among terrestrial and extraterrestrial materials [1-3]. For this study, we have se-lected samples (bulk meteorite and chondrule separates) from the CR meteorite clan: Bencubbin (CB), Renazzo (CR2), NWA 801 (CR2), and HaH237 (CH-like). These meteorites were selected because meteorites from this clan have experienced very little alteration since their initial formation [4] and for their extremely high refrac-tory/volatile element ratios. The latter characteristic may allow a test of the correlation observed by [2] between element ratios and Cu isotope composition. Measurements were performed on NHM/IC Micromass Isoprobe and Oxford Nu MC-ICP-MS using techniques described elsewhere [1,5]. Each of the meteorites measured so far for Cu and Zn are isotopically light compared to the terrestrial mantle. This suggests that the terrestrial value may have been altered from the pristine solar system value, or else there were multiple early solar system components. Zinc isotopic com-positions lie on a fractionation line and range from δ66ZnNIST = -1.4±0.1ppm (bulk NWA801) to -1.9±0.1ppm (separated chondrule, NWA 801). Copper isotope compositions vary from δ65CuNIST976 = -1.5±0.1ppm (bulk Renazzo) to -3.1±0.1ppm (separated chondrule, NWA 801). Two chondrules from NWA 801 have differing Cu isotope values (-3.1±0.1 and -2.0±0.1ppm) and both are lighter than the bulk meteorite (-1.9±0.1ppm), suggesting a lack of equilibration with respect to Cu in this meteorite. The light values for the two separated chondrules, compared the bulk meteorite, hints that chondrules may be isotopically lighter than co-existing matrix, metal and sulphides with respect to Cu. The copper isotope compositions are not as isotopically light as expected for the high refractory/volatile element ratio observed in these chondrites. Thus a model to account for the Cu isotopes in chondrites may require greater com

  7. Non-destructive measurement of carbonic anhydrase activity and the oxygen isotope composition of soil water

    NASA Astrophysics Data System (ADS)

    Jones, Sam; Sauze, Joana; Ogée, Jérôme; Wohl, Steven; Bosc, Alexandre; Wingate, Lisa

    2016-04-01

    Carbonic anhydrases are a group of metalloenzymes that catalyse the hydration of aqueous carbon dioxide (CO2). The expression of carbonic anhydrase by bacteria, archaea and eukarya has been linked to a variety of important biological processes including pH regulation, substrate supply and biomineralisation. As oxygen isotopes are exchanged between CO2 and water during hydration, the presence of carbonic anhydrase in plants and soil organisms also influences the oxygen isotope budget of atmospheric CO2. Leaf and soil water pools have distinct oxygen isotope compositions, owing to differences in pool sizes and evaporation rates, which are imparted on CO2during hydration. These differences in the isotopic signature of CO2 interacting with leaves and soil can be used to partition the contribution of photosynthesis and soil respiration to net terrestrial CO2 exchange. However, this relies on our knowledge of soil carbonic anhydrase activity and currently, the prevalence and function of these enzymes in soils is poorly understood. Isotopic approaches used to estimate soil carbonic anhydrase activity typically involve the inversion of models describing the oxygen isotope composition of CO2 fluxes to solve for the apparent, potentially catalysed, rate of oxygen exchange during hydration. This requires information about the composition of CO2 in isotopic equilibrium with soil water obtained from destructive, depth-resolved soil water sampling. This can represent a significant challenge in data collection given the considerable potential for spatial and temporal variability in the isotopic composition of soil water and limited a priori information with respect to the appropriate sampling resolution and depth. We investigated whether we could circumvent this requirement by constraining carbonic anhydrase activity and the composition of soil water in isotopic equilibrium with CO2 by solving simultaneously the mass balance for two soil CO2 steady states differing only in the

  8. Sulfur-based absolute quantification of proteins using isotope dilution inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Lee, Hyun-Seok; Heun Kim, Sook; Jeong, Ji-Seon; Lee, Yong-Moon; Yim, Yong-Hyeon

    2015-10-01

    An element-based reductive approach provides an effective means of realizing International System of Units (SI) traceability for high-purity biological standards. Here, we develop an absolute protein quantification method using double isotope dilution (ID) inductively coupled plasma mass spectrometry (ICP-MS) combined with microwave-assisted acid digestion for the first time. We validated the method and applied it to certify the candidate protein certified reference material (CRM) of human growth hormone (hGH). The concentration of hGH was determined by analysing the total amount of sulfur in hGH. Next, the size-exclusion chromatography method was used with ICP-MS to characterize and quantify sulfur-containing impurities. By subtracting the contribution of sulfur-containing impurities from the total sulfur content in the hGH CRM, we obtained a SI-traceable certification value. The quantification result obtained with the present method based on sulfur analysis was in excellent agreement with the result determined via a well-established protein quantification method based on amino acid analysis using conventional acid hydrolysis combined with an ID liquid chromatography-tandem mass spectrometry. The element-based protein quantification method developed here can be generally used for SI-traceable absolute quantification of proteins, especially pure-protein standards.

  9. Chemical and isotopic compositions in acid residues from various meteorites

    NASA Technical Reports Server (NTRS)

    Kano, N.; Yamakoshi, K.; Matsuzaki, H.; Nogami, K.

    1993-01-01

    We are planning to carry out systematic isotopic investigations of Ru, Mg, etc., in primordial samples. The investigations will be pursued in the context of a study of the pre-history of the solar system. It is hoped that the study will yield direct evidence for processes of nucleosynthesis in the pre-solar stage and detection of extinct radioactive nuclides. In this paper, we present the results of chemical compositions of acid residues obtained from three types of meteorites: Canyon Diablo (IA), Allende (CV3), and Nuevo Mercuro (H5); and the preliminary results of Ru isotopic compositions.

  10. Sr isotopic composition of Afar volcanics and its implication for mantle evolution

    NASA Astrophysics Data System (ADS)

    Barberi, F.; Civetta, L.; Varet, J.

    1980-10-01

    Investigations of Rb-Sr systematics of basalts from the Afar depression (Ethiopia) indicate the presence of a heterogeneous mantle source region. The Sr isotopic compositions of the basalts from the Afar axial and transverse ranges identify source regions which are enriched in LIL elements and radiogenic Sr (axial ranges) and others which are relatively depleted (transverse ranges). Sr isotopic composition of basalts from the Red Sea, Gulf of Aden and Gulf of Tadjoura, which range from 0.70300 to 0.70340 are also reported and compared with the more radiogenic Afar region, which is characterized by 87Sr/ 86Sr ranging from 0.70328 to 0.70410. Available geochemical and isotopic data suggest that a relation exists between magma composition and the advancement of the rifting process through progressive lithosphere attenuation leading to continental break-up. However, the petrogenetic process is not simple and probably implies a vertically zoned mantle beneath the Afar region. Sr isotopic evidence suggests that the vertically zoned mantle is more radiogenic and enriched in LIL elements in its upper part.

  11. Re-assessing the Molybdenum Isotope Composition of Pre-GOE Seawater: Evidence for Dynamic Ocean Redox

    NASA Astrophysics Data System (ADS)

    Ostrander, C. M.; Kendall, B.; Roy, M.; Romaniello, S. J.; Nunn, S. J.; Gordon, G. W.; Olson, S. L.; Lyons, T. W.; Zheng, W.; Anbar, A. D.

    2016-12-01

    Molybdenum (Mo) isotope compositions of Archean shales can provide important insights into ocean and atmosphere redox dynamics prior to the Great Oxidation Event (GOE). Unfortunately, the relatively limited Mo isotope database and small number of sample sets for Archean shales do not allow for in-depth reconstructions and specifically make it difficult to differentiate global from local effects. To accurately estimate the Mo isotope composition of Archean seawater and better investigate the systematics of local and global redox, more complete sample sets are needed. We carried out a Mo isotope analysis of the euxinic 2.65 Ga Roy Hill Shale sampled in two stratigraphically correlated cores, and revisited the well-studied euxinic 2.5 Ga Mt. McRae Shale in higher resolution. Our data show contrasting Mo isotope values in the 2.65 Ga Roy Hill Shale between near- and offshore depositional environments, with systematically heavier isotope values in the near-shore environment. High-resolution analysis of the Mt. McRae Shale yields oscillating Mo concentrations and isotope values at the cm- to dm-scale during the well-characterized "whiff of O2" interval, with the heaviest isotope values measured during euxinic deposition. Variations in the measured isotope values within each section are primarily associated with redox changes in the local depositional environment and amount of detrital content. Both non-quantitative removal of Mo associated with incorporation into non-euxinic sediments and large detrital Mo contributions shift some measured isotopic compositions toward lighter values. This is readily apparent in the near-shore Roy Hill Shale section and the Mt. McRae Shale, but may not fully explain variations observed in the offshore Roy Hill Shale deposit. Here, euxinic deposition is not accompanied by Mo enrichments or isotopic compositions as heavy as the near-shore equivalent, even after detrital correction. This disparity between the near- and offshore environment

  12. Soil drying effects on the carbon isotope composition of soil respiration

    EPA Science Inventory

    Stable isotopes are used widely as a tool for determining sources of carbon (C) fluxes in ecosystem C studies. Environmental factors that change over time, such as moisture, can create dynamic changes in the isotopic composition of C assimilated by plants, and offers a unique opp...

  13. Variation in the terrestrial isotopic composition and atomic weight of argon

    USGS Publications Warehouse

    Böhlke, John Karl

    2014-01-01

    The isotopic composition and atomic weight of argon (Ar) are variable in terrestrial materials. Those variations are a source of uncertainty in the assignment of standard properties for Ar, but they provide useful information in many areas of science. Variations in the stable isotopic composition and atomic weight of Ar are caused by several different processes, including (1) isotope production from other elements by radioactive decay (radiogenic isotopes) or other nuclear transformations (e.g., nucleogenic isotopes), and (2) isotopic fractionation by physical-chemical processes such as diffusion or phase equilibria. Physical-chemical processes cause correlated mass-dependent variations in the Ar isotope-amount ratios (40Ar/36Ar, 38Ar/36Ar), whereas nuclear transformation processes cause non-mass-dependent variations. While atmospheric Ar can serve as an abundant and homogeneous isotopic reference, deviations from the atmospheric isotopic ratios in other Ar occurrences limit the precision with which a standard atomic weight can be given for Ar. Published data indicate variation of Ar atomic weights in normal terrestrial materials between about 39.7931 and 39.9624. The upper bound of this interval is given by the atomic mass of 40Ar, as some samples contain almost pure radiogenic 40Ar. The lower bound is derived from analyses of pitchblende (uranium mineral) containing large amounts of nucleogenic 36Ar and 38Ar. Within this interval, measurements of different isotope ratios (40Ar/36Ar or 38Ar/36Ar) at various levels of precision are widely used for studies in geochronology, water–rock interaction, atmospheric evolution, and other fields.

  14. The effect of phosphomonoesterases on the oxygen isotope composition of phosphate

    NASA Astrophysics Data System (ADS)

    von Sperber, Christian; Kries, Hajo; Tamburini, Federica; Bernasconi, Stefano M.; Frossard, Emmanuel

    2014-01-01

    Plants and microorganisms under phosphorus (P) stress release extracellular phosphatases as a strategy to acquire inorganic phosphate (Pi). These enzymes catalyze the hydrolysis of phosphoesters leading to a release of Pi. During the enzymatic hydrolysis an isotopic fractionation (ε) occurs leaving an imprint on the oxygen isotope composition of the released Pi which might be used to trace phosphorus in the environment. Therefore, enzymatic assays with acid phosphatases from wheat germ and potato tuber and alkaline phosphatase from Escherichia coli were prepared in order to determine the oxygen isotope fractionation caused by these enzymes. Adenosine 5‧ monophosphate and glycerol phosphate were used as substrates. The oxygen isotope fractionation caused by acid phosphatases is 20-30‰ smaller than for alkaline phosphatases, resulting in a difference of 5-7.5‰ in δ18O of Pi depending on the enzyme. We attribute the enzyme dependence of the isotopic fractionation to distinct reaction mechanisms of the two types of phosphatases. The observed difference is large enough to distinguish between the two enzymatic processes in environmental samples. These findings show that the oxygen isotope composition of Pi can be used to trace different enzymatic processes, offering an analytical tool that might contribute to a better understanding of the P-cycle in the environment.

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

    NASA Astrophysics Data System (ADS)

    Romanek, C.

    2010-12-01

    The stable carbon isotope composition of bivalve shells is a valuable archive of paleobiological and paleoenvironmental information. Previous work has shown that the carbon isotope composition of the shell is related to the carbon isotope composition of dissolved inorganic carbon (DIC) in the ambient water in which a bivalve lives, as well as metabolic carbon derived from bivalve respiration. The contribution of metabolic carbon varies among organisms, but it is generally thought to be relatively low (e.g., <10%) in shells from aquatic organism and high (>90%) in the shells from terrestrial organisms. Because metabolic carbon contains significantly more C-12 than DIC, negative excursions from the expected environmental (DIC) signal are interpreted to reflect an increased contribution of metabolic carbon in the shell. This observation contrasts sharply with modeled carbon isotope compositions for shell layers deposited from the inner extrapallial fluid (EPF). Previous studies have shown that growth lines within the inner shell layer of bivalves are produced during periods of anaerobiosis when acidic metabolic byproducts (e.g., succinic acid) are neutralized (or buffered) by shell dissolution. This requires the pH of EPF to decrease below ambient levels (~7.5) until a state of undersaturation is achieved that promotes shell dissolution. This condition may occur when aquatic bivalves are subjected to external stressors originating from ecological (predation) or environmental (exposure to atm; low dissolved oxygen; contaminant release) pressures; normal physiological processes will restore the pH of EPF when the pressure is removed. As a consequence of this process, a temporal window should also exist in EPF at relatively low pH where shell carbonate is deposited at a reduced saturation state and precipitation rate. For example, EPF chemistry should remain slightly supersaturated with respect to aragonite given a drop of one pH unit (6.5), but under closed conditions

  16. H-Isotopic Composition of Apatite in Northwest Africa 7034

    NASA Technical Reports Server (NTRS)

    McCubbin, F. M.; Barnes, J. J.; Santos, A. R.; Boyce, J. W.; Anand, M.; Franchi, I. A.; Agee, C. B.

    2016-01-01

    Northwest Africa (NWA) 7034 and its pairings comprise a regolith breccia with a basaltic bulk composition [1] that yields a better match than any other martian meteorite to estimates of Mars' bulk crust composition [1]. Given the similarities between NWA 7034 and the martian crust, NWA 7034 may represent an important sample for constraining the crustal composition of components that cannot be measured directly by remote sensing. In the present study, we seek to constrain the H isotopic composition of the martian crust using Cl-rich apatite in NWA 7034.

  17. Pb isotope compositions of modern deep sea turbidites

    NASA Astrophysics Data System (ADS)

    Hemming, S. R.; McLennan, S. M.

    2001-01-01

    Modern deep sea turbidite muds and sands collected from Lamont piston cores represent a large range in age of detrital sources as well as a spectrum of tectonic settings. Pb isotope compositions of all but three of the 66 samples lie to the right of the 4.56 Ga Geochron, and most also lie along a slope consistent with a time-integrated κ ( 232Th/ 238U) between 3.8 and 4.2. Modern deep sea turbidites show a predictable negative correlation between both Pb and Sr isotope ratios and ɛNd and ɛHf, clearly related to the age of continental sources. However, the consistency between Pb and Nd isotopes breaks down for samples with very old provenance ( ɛNd<-20) that are far less radiogenic than predicted by the negative correlation. The correlations among Sr, Nd and Hf isotopes also become more scattered in samples with very old provenance. The unradiogenic Pb isotopic character of modern sediments with Archean Nd model ages is consistent with a model where Th and U abundances of the Archean upper crust are significantly lower than the post-Archean upper crust.

  18. The uranium-isotopic composition of Saharan dust collected over the central Atlantic Ocean

    NASA Astrophysics Data System (ADS)

    Aciego, Sarah M.; Aarons, Sarah M.; Sims, Kenneth W. W.

    2015-06-01

    Uranium isotopic compositions, (234U/238U)activity , are utilized by earth surface disciplines as chronometers and source tracers, including in soil science where aeolian dust is a significant source to the total nutrient pool. However, the (234U/238U)activity composition of dust is under characterized due to material and analytical constraints. Here we present new uranium isotope data measured by high precision MC-ICP-MS on ten airborne dust samples collected on the M55 trans-Atlantic cruise in 2002. Two pairs of samples are presented with different size fractions, coarse (1-30 μm) and fine (<1 μm), and all samples were processed to separate the water soluble component in order to assess the controls on the (234U/238U)activity of mineral aerosols transported from the Sahara across the Atlantic. Our results indicate (234U/238U)activity above one for both the water soluble (1.13-1.17) and the residual solid (1.06-1.18) fractions of the dust; no significant correlation is found between isotopic composition and travel distance. Residual solids indicate a slight dependance of (234U/238U)activity on particle size. Future modeling work that incorporates dust isotopic compositions into mixing or isotopic fractionation models will need to account for the wide variability in dust (234U/238U)activity .

  19. Origin of heavy Fe isotope compositions in high-silica igneous rocks: A rhyolite perspective

    NASA Astrophysics Data System (ADS)

    Du, De-Hong; Wang, Xiao-Lei; Yang, Tao; Chen, Xin; Li, Jun-Yong; Li, Weiqiang

    2017-12-01

    The origin of heavy Fe isotope compositions in high-silica (>70 wt% SiO2) igneous rocks remains a highly controversial topic. Considering that fluid exsolution in eruptive rocks is more straight-forward to constrain than in plutonic rocks, this study addresses the problem of Fe isotope fractionation in high-silica igneous rocks by measuring Fe isotope compositions of representative rhyolitic samples from the Neoproterozoic volcanic-sedimentary basins in southern China and the Triassic Tu Le Basin in northern Vietnam. The samples show remarkably varied δ56FeIRMM014 values ranging from 0.05 ± 0.05‰ to 0.55 ± 0.05‰, which is among the highest values reported from felsic rocks. The extensional tectonic setting and short melt residence time in magma chambers for the studied rhyolites rule out Soret diffusion and thermal migration processes as causes of the high δ56Fe values. Effects of volcanic degassing and fluid exsolution on bulk rock δ56Fe values for the rhyolites are also assessed using bulk rock geochemical indicators and Rayleigh fractionation models, and these processes are found to be insufficient to produce resolvable changes in Fe isotope compositions of the residual melt. The most probable mechanism accounting for heavy Fe isotope compositions in the high-silica rhyolites is narrowed down to fractional crystallization processes in the magma before rhyolite eruption. Removal of isotopically light Fe-bearing minerals (i.e. ulvöspinel-rich titanomagnetite, ilmenite and biotite) is proposed as the main cause of Fe isotope variation in silicic melts during magmatic evolution. This study implies that crystal fractionation is the dominant mechanism that controls Fe isotope fractionation in eruptive rocks and Fe isotopes could be used to study magmatic differentiation of high-silica magmas.

  20. Molybdenum Isotopic Composition of the Archean Mantle As Inferred from Studies of Komatiites

    NASA Astrophysics Data System (ADS)

    Greber, N. D.; Puchtel, I. S.; Nagler, T. F.; Mezger, K.

    2014-12-01

    Molybdenum isotopic composition has been shown to be a powerful tool in studies of planetary processes, e.g. estimating core formation temperatures [1,2]. However, Mo isotope compositions of terrestrial reservoirs are not well constrained. In order to better constrain the Mo isotopic composition of the early Earth's mantle, komatiites from four locations were analyzed for their Mo concentrations and isotopic compositions. Komatiites are particularly appropriate for this type of study because they formed by high degrees of partial melting of the mantle leading to a complete base metal sulfide removal from the residual mantle and the production of sulfur-undersaturated melts and thus a quantitative removal of Mo from the source into the melt. All samples, except for two strongly altered specimens specifically chosen to study the effects of secondary alteration, are very fresh having preserved most of their primary mineralogy. The Mo concentrations in komatiites range from 10 to 120 ng/g. Fresh komatiites have lighter δ98Mo (NIST SRM 3134 = 0.25‰, [3]) than altered samples. The estimated primary Mo isotope compositions of the studied komatiite melts range from 0.02 ± 0.16‰ to 0.19 ± 0.14‰ and are therefore indistinguishable within analytical uncertainty (2SD) from published values for chondritic meteorites (0.09 ± 0.04 ‰; 2SD; [2]) and lighter than the proposed average for Earth's continental crust (0.3 to 0.4‰ [4]). All data combined, although overlapping in errors, show a consistent trend of lighter δ98Mo and lower Mo concentrations in more melt-depleted mantle sources, indicating incompatible behaviour of Mo and preferential mobilization of heavy Mo isotopes during mantle melting. [1] Hin et al. (2013) EPSL, 379 [2] Burkhardt et al. (2014) EPSL, 391 [3] Nägler, et al. (2014) GGR, 38. [4] Voegelin et al. (2014) Lithos, 190-191.

  1. Stable isotope study of a new chondrichthyan fauna (Kimmeridgian, Porrentruy, Swiss Jura): an unusual freshwater-influenced isotopic composition for the hybodont shark Asteracanthus

    NASA Astrophysics Data System (ADS)

    Leuzinger, L.; Kocsis, L.; Billon-Bruyat, J.-P.; Spezzaferri, S.; Vennemann, T.

    2015-12-01

    Chondrichthyan teeth (sharks, rays, and chimaeras) are mineralized in isotopic equilibrium with the surrounding water, and parameters such as water temperature and salinity can be inferred from the oxygen isotopic composition (δ18Op) of their bioapatite. We analysed a new chondrichthyan assemblage, as well as teeth from bony fish (Pycnodontiformes). All specimens are from Kimmeridgian coastal marine deposits of the Swiss Jura (vicinity of Porrentruy, Ajoie district, NW Switzerland). While the overall faunal composition and the isotopic composition of bony fish are generally consistent with marine conditions, unusually low δ18Op values were measured for the hybodont shark Asteracanthus. These values are also lower compared to previously published data from older European Jurassic localities. Additional analyses on material from Solothurn (Kimmeridgian, NW Switzerland) also have comparable, low-18O isotopic compositions for Asteracanthus. The data are hence interpreted to represent a so far unique, freshwater-influenced isotopic composition for this shark that is classically considered a marine genus. While reproduction in freshwater or brackish realms is established for other hybodonts, a similar behaviour for Asteracanthus is proposed here. Regular excursions into lower salinity waters can be linked to the age of the deposits and correspond to an ecological adaptation, most likely driven by the Kimmeridgian transgression and by the competition of the hybodont shark Asteracanthus with the rapidly diversifying neoselachians (modern sharks).

  2. Stable isotope study of a new chondrichthyan fauna (Kimmeridgian, Porrentruy, Swiss Jura): an unusual freshwater-influenced isotopic composition for the hybodont shark Asteracanthus

    NASA Astrophysics Data System (ADS)

    Leuzinger, L.; Kocsis, L.; Billon-Bruyat, J.-P.; Spezzaferri, S.; Vennemann, T.

    2015-08-01

    Chondrichthyan teeth (sharks, rays and chimaeras) are mineralised in isotopic equilibrium with the surrounding water, and parameters such as water temperature and salinity can be inferred from the oxygen isotopic composition (δ18Op) of their bioapatite. We analysed a new chondrichthyan assemblage, as well as teeth from bony fish (Pycnodontiformes). All specimens are from Kimmeridgian coastal marine deposits of the Swiss Jura (vicinity of Porrentruy, Ajoie district, NW Switzerland). While the overall faunal composition and the isotopic composition of bony fish are consistent with marine conditions, unusually low δ18Op values were measured for the hybodont shark Asteracanthus. These values are also lower compared to previously published data from older European Jurassic localities. Additional analyses on material from Solothurn (Kimmeridgian, NW Switzerland) also have comparable, low-18O isotopic compositions for Asteracanthus. The data are hence interpreted to represent a so far unique, freshwater-influenced isotopic composition for this shark that is classically considered as a marine genus. While reproduction in freshwater or brackish realms is established for other hybodonts, a similar behaviour for Asteracanthus is proposed here. Regular excursions into lower salinity waters can be linked to the age of the deposits and correspond to an ecological adaptation, most likely driven by the Kimmeridgian transgression and by the competition of the primitive shark Asteracanthus with the rapidly diversifying neoselachians (modern sharks).

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

    NASA Astrophysics Data System (ADS)

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

    2003-12-01

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

  4. Assessment of shock effects on amphibole water contents and hydrogen isotope compositions: 1. Amphibolite experiments

    NASA Astrophysics Data System (ADS)

    Minitti, Michelle E.; Rutherford, Malcolm J.; Taylor, Bruce E.; Dyar, M. Darby; Schultz, Peter H.

    2008-02-01

    Kaersutitic amphiboles found within a subset of the Martian meteorites have low water contents and variably heavy hydrogen isotope compositions. In order to assess if impact shock-induced devolatilization and hydrogen isotope fractionation were determining factors in these water and isotopic characteristics of the Martian kaersutites, we conducted impact shock experiments on samples of Gore Mountain amphibolite in the Ames Vertical Gun Range (AVGR). A parallel shock experiment conducted on an anorthosite sample indicated that contamination of shocked samples by the AVGR hydrogen propellant was unlikely. Petrographic study of the experimental amphibolite shock products indicates that only ˜ 10% of the shock products experienced levels of damage equivalent to those found in the most highly shocked kaersutite-bearing Martian meteorites (30-35 GPa). Ion microprobe studies of highly shocked hornblende from the amphibolite exhibited elevated water contents (ΔH 2O ˜ 0.1 wt.%) and enriched hydrogen isotope compositions (Δ D ˜ + 10‰) relative to unshocked hornblende. Water and hydrogen isotope analyses of tens of milligrams of unshocked, moderately shocked, and highly shocked hornblende samples by vacuum extraction/uranium reduction and isotope ratio mass spectrometry (IRMS), respectively, are largely consistent with analyses of single grains from the ion microprobe. The mechanisms thought to have produced the excess water in most of the shocked hornblendes are shock-induced reduction of hornblende Fe and/or irreversible adsorption of hydrogen. Addition of the isotopically enriched Martian atmosphere to the Martian meteorite kaersutites via these mechanisms could explain their enriched and variable isotopic compositions. Alternatively, regrouping the water extraction and IRMS analyses on the basis of isotopic composition reveals a small, but consistent, degree of impact-induced devolatilization (˜ 0.1 wt.% H 2O) and H isotope enrichment (Δ D ˜ + 10

  5. Thallium-isotopic compositions of euxinic sediments as a proxy for global manganese-oxide burial

    NASA Astrophysics Data System (ADS)

    Owens, Jeremy D.; Nielsen, Sune G.; Horner, Tristan J.; Ostrander, Chadlin M.; Peterson, Larry C.

    2017-09-01

    Thallium (Tl) isotopes are a new and potentially powerful paleoredox proxy that may track bottom water oxygen conditions based on the global burial flux of manganese oxides. Thallium has a residence time of ∼20 thousand years, which is longer than the ocean mixing time, and it has been inferred that modern oxic seawater is conservative with respect to both concentration and isotopes. Marine sources of Tl have nearly identical isotopic values. Therefore, the Tl sinks, adsorption onto manganese oxides and low temperature oceanic crust alteration (the dominant seawater output), are the primary controls of the seawater isotopic composition. For relatively short-term, ∼million years, redox events it is reasonable to assume that the dominant mechanism that alters the Tl isotopic composition of seawater is associated with manganese oxide burial because large variability in low temperature ocean crust alteration is controlled by long-term, multi-million years, average ocean crust production rates. This study presents new Tl isotope data for an open ocean transect in the South Atlantic, and depth transects for two euxinic basins (anoxic and free sulfide in the water column), the Cariaco Basin and Black Sea. The Tl isotopic signature of open ocean seawater in the South Atlantic was found to be homogeneous with ε205Tl = -6.0 ± 0.3 (±2 SD, n = 41) while oxic waters from Cariaco and the Black Sea are -5.6 and -2.2, respectively. Combined with existing data from the Pacific and Arctic Oceans, our Atlantic data establish the conservatism of Tl isotopes in the global ocean. In contrast, partially- and predominantly-restricted basins reveal Tl isotope differences that vary between open-ocean (-6) and continental material (-2) ε205Tl, scaling with the degree of restriction. Regardless of the differences between basins, Tl is quantitatively removed from their euxinic waters below the chemocline. The burial of Tl in euxinic sediments is estimated to be an order of magnitude

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

    NASA Technical Reports Server (NTRS)

    Lauretta, D. S.

    2004-01-01

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

  7. Origin of isotopically light Zn in lunar samples through vaporization and the Zn isotope composition of the Moon

    NASA Astrophysics Data System (ADS)

    Kato, C.; Valdes, M. C.; Dhaliwal, J.; Day, J. M.; Moynier, F.

    2013-12-01

    the surface of the Moon. This represents secondary effects and mixing with exogenous Zn, explaining the higher abundance of Zn in highland rocks, relative to mare basalts. The pyroclastic green glass (15426) has a higher measured Zn concentration (~50ppm) compared with mare basalts, but is still depleted in Zn relative to most terrestrial basalts (typically >50 to 100 ppm). 15426 is also isotopically light (δ66Zn= -0.98), which is similar to previous measurements of Zn composition made for high-Ti pyroclastic glass beads (74220). We interpret the composition of the lunar pyroclastic glasses to reflect lava fountaining and coating of the surface of the beads by a volatile rich and isotopically light vapor. Thus, we conclude that mare basalts, which are isotopically heavier than the Earth, best represent the lunar silicate composition.

  8. Osmium Isotope Compositions of Komatiite Sources Through Time

    NASA Astrophysics Data System (ADS)

    Walker, R. J.

    2001-12-01

    Extending Os isotopic measurements to ancient plume sources may help to constrain how and when the well-documented isotopic heterogeneities in modern systems were created. Komatiites and picrites associated with plume-related volcanism are valuable tracers of the Os isotopic composition of plumes because of their typically high Os concentrations and relatively low Re/Os. Re-Os data are now available for a variety of Phanerozoic, Proterozoic and Archean komatiites and picrites. As with modern plumes, the sources of Archean and Proterozoic komatiites exhibit a large range of initial 187Os/188Os ratios. Most komatiites are dominated by sources with chondritic Os isotopic compositions (e.g. Song La; Norseman-Wiluna; Pyke Hill; Alexo), though some (e.g. Gorgona) derive from heterogeneous sources. Of note, however, two ca. 2.7 Ga systems, Kostomuksha (Russia) and Belingwe (Zimbabwe), have initial ratios enriched by 2-3% relative to the contemporary convecting upper mantle. These results suggest that if the 187Os enrichment was due to the incorporation of minor amounts of recycled crust into the mantle source of the rocks, the crust formed very early in Earth history. Thus, the Os results could reflect derivation of melt from hybrid mantle whose composition was modified by the addition of mafic crustal material that would most likely have formed between 4.2 and 4.5 Ga. Alternately, the mantle sources of these komatiites may have derived a portion of their Os from the putative 187Os - and 186Os -enriched outer core. For this hypothesis to be applicable to Archean rocks, an inner core of sufficient mass would have to have crystallized sufficiently early in Earth history to generate an outer core with 187Os enriched by at least 3% relative to the chondritic average. Using the Pt-Re-Os partition coefficients espoused by our earlier work, and assuming linear growth of the inner core started at 4.5 Ga and continued to present, would yield an outer core at 2.7 Ga with a gamma Os

  9. NBL CRM 112-A: A new certified isotopic composition

    NASA Astrophysics Data System (ADS)

    Thomas, R. B.; Essex, R. M.; Mason, P.

    2007-12-01

    NBL CRM 112-A Uranium Metal Assay Standard is commonly used as a natural uranium isotopic reference material within the earth science mass spectrometry community. The metal is from the same parent material as NBS SRM 960, the uranyl nitrate solution, CRM 145, and the high-purity uranyl nitrate solution CRM 145-B. Because CRM 112-A has not yet been certified for isotopic composition, it has been assumed that this material has a natural 235U/238U (0.0072527), and the δ234U has been determined by measurement (e.g. -37.1‰; Cheng et al., 2000). These values have been widely used to calibrate the concentration of spikes and standards, and to correct measurements for instrument or mass bias. New, preliminary, isotopic measurements on CRM 145 and CRM 112-A performed at New Brunswick Laboratory suggest that these reference materials have a slightly lower 235U/238U and δ234U than have been commonly used. If this is the case, then data using the accepted values may be slightly biased. The significance of this bias will depend on the uncertainty of the measurement, how the CRM 112-A data is used to correct measurement data, the cited values that were used to correct the data, and the final certified values of the CRM. This fall, New Brunswick Laboratory is certifying the isotopic composition of the CRM 112-A metal using high precision thermal ionization mass spectrometry techniques. Upon completion of certification, the new CRM 112- A standard with certified isotopic ratios will provide the earth science community with a well characterized and traceable reference for calibrating and correcting their mass spectrometry measurement systems.

  10. Lithium contents and isotopic compositions of ferromanganese deposits from the global ocean

    USGS Publications Warehouse

    Chan, L.-H.; Hein, J.R.

    2007-01-01

    To test the feasibility of using lithium isotopes in marine ferromanganese deposits as an indicator of paleoceanographic conditions and seawater composition, we analyzed samples from a variety of tectonic environments in the global ocean. Hydrogenetic, hydrothermal, mixed hydrogenetic–hydrothermal, and hydrogenetic–diagenetic samples were subjected to a two-step leaching and dissolution procedure to extract first the loosely bound Li and then the more tightly bound Li in the Mn oxide and Fe oxyhydroxide. Total leachable Li contents vary from 2 by coulombic force. Hence, the abundant Li in hydrothermal deposits is mainly associated with the dominant phase, MnO2. The surface of amorphous FeOOH holds a slightly positive charge and attracts little Li, as demonstrated by data for hydrothermal Fe oxyhydroxide. Loosely sorbed Li in both hydrogenetic crusts and hydrothermal deposits exhibit Li isotopic compositions that resemble that of modern seawater. We infer that the hydrothermally derived Li scavenged onto the surface of MnO2 freely exchanged with ambient seawater, thereby losing its original isotopic signature. Li in the tightly bound sites is always isotopically lighter than that in the loosely bound fraction, suggesting that the isotopic fractionation occurred during formation of chemical bonds in the oxide and oxyhydroxide structures. Sr isotopes also show evidence of re-equilibration with seawater after deposition. Because of their mobility, Li and Sr in the ferromanganese crusts do not faithfully record secular variations in the isotopic compositions of seawater. However, Li content can be a useful proxy for the hydrothermal history of ocean basins. Based on the Li concentrations of the globally distributed hydrogenetic and hydrothermal samples, we estimate a scavenging flux of Li that is insignificant compared to the hydrothermal flux and river input to the ocean.

  11. Isotopic composition of high-activity particles released in the Chernobyl accident.

    PubMed

    Osuch, S; Dabrowska, M; Jaracz, P; Kaczanowski, J; Le Van Khoi; Mirowski, S; Piasecki, E; Szeflińska, G; Szefliński, Z; Tropiło, J

    1989-11-01

    Gamma spectra were measured and activities of the detected isotopes were analyzed for 206 high-activity particles (hot particles, HPs) found in northeastern Poland after the Chernobyl accident. The isotopic composition of HPs observed in gamma-activity is compared with that of the general fallout and core inventory calculations. Particle formation and a process of depletion in Ru and Cs isotopes are discussed. On the basis of a search performed a year later, some comments on the behavior of HPs in the soil are made.

  12. A non-terrestrial 16O-rich isotopic composition for the protosolar nebula.

    PubMed

    Hashizume, Ko; Chaussidon, Marc

    2005-03-31

    The discovery in primitive components of meteorites of large oxygen isotopic variations that could not be attributed to mass-dependent fractionation effects has raised a fundamental question: what is the composition of the protosolar gas from which the host grains formed? This composition is probably preserved in the outer layers of the Sun, but the resolution of astronomical spectroscopic measurements is still too poor to be useful for comparison with planetary material. Here we report a precise determination of the oxygen isotopic composition of the solar wind from particles implanted in the outer hundreds of nanometres of metallic grains in the lunar regolith. These layers of the grains are enriched in 16O by >20 +/- 4 per thousand relative to the Earth, Mars and bulk meteorites, which implies the existence in the solar accretion disk of reactions--as yet unknown--that were able to change the 17O/16O and 18O/16O ratios in a way that was not dependent strictly on the mass of the isotope. Photochemical self-shielding of the CO gas irradiated by ultraviolet light may be one of these key processes, because it depends on the abundance of the isotopes, rather than their masses.

  13. The isotopic composition of cosmic ray calcium

    NASA Technical Reports Server (NTRS)

    Krombel, K. E.; Wiedenbeck, M. E.

    1985-01-01

    Data from the high energy cosmic ray experiment on the international sun earth explorer 3 (ISEE-3) spacecraft have been used to study the isotopic composition of cosmic ray calcium at an energy of approx. 260 MeV/amu. The arriving calcium is found to consist of (32 + or - 6)%. A propagation model consistent with both the light and the subiron secondary element abundances was used for the interpretation of the observed calcium composition. The measured 42Ca+43Ca+44Ca abundance is consistent with the calculated secondary production, while the 40Ca abundance implies a source ratio of 40Ca/Fe = (7.0 + or - 1.7)%.

  14. Overcoming interference with the detection of a stable isotopically labeled microtracer in the evaluation of beclabuvir absolute bioavailability using a concomitant microtracer approach.

    PubMed

    Jiang, Hao; Titsch, Craig; Zeng, Jianing; Jones, Barry; Joyce, Philip; Gandhi, Yash; Turley, Wesley; Burrell, Richard; Aubry, Anne F; Arnold, Mark E

    2017-09-05

    The oral absolute bioavailability of beclabuvir in healthy subjects was determined using a microdose (100μg) of the stable isotopically labeled tracer via intravenous (IV) infusion started after oral dosing of beclabuvir (150mg). To simultaneously analyze the concentrations of the IV microtracer ([ 13 C 6 ]beclabuvir) and beclabuvir in plasma samples, a liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS) method was initially developed. Surprisingly beclabuvir significantly interfered with the IV microtracer detection when using the selected reaction monitoring (SRM) in the assay. An interfering component from the drug substance was observed using a high resolution mass spectrometer (HRMS). The mass-to-charge (m/z) of the interfering component was -32ppm different from the nominal value for the IV microtracer and thus could not be differentiated in the SRM assay by the unit mass resolution. To overcome this interference, we evaluated two approaches by either monitoring an alternative product ion using the SRM assay or isolating the interfering component using the parallel reaction monitoring (PRM) assay on the HRMS. This case study has demonstrated two practical approaches for overcoming interferences with the detection of stable isotopically labeled IV microtracers in the evaluation of absolute bioavailability, which provides users the flexibility in using either LC-MS/MS or HRMS to mitigate unpredicted interferences in the assay to support microtracer absolute bioavailability studies. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. The distribution of lead concentrations and isotope compositions in the eastern Tropical Atlantic Ocean

    NASA Astrophysics Data System (ADS)

    Bridgestock, Luke; Rehkämper, Mark; van de Flierdt, Tina; Paul, Maxence; Milne, Angela; Lohan, Maeve C.; Achterberg, Eric P.

    2018-03-01

    Anthropogenic emissions have dominated marine Pb sources during the past century. Here we present Pb concentrations and isotope compositions for ocean depth profiles collected in the eastern Tropical Atlantic Ocean (GEOTRACES section GA06), to trace the transfer of anthropogenic Pb into the ocean interior. Variations in Pb concentration and isotope composition were associated with changes in hydrography. Water masses ventilated in the southern hemisphere generally featured lower 206Pb/207Pb and 208Pb/207Pb ratios than those ventilated in the northern hemisphere, in accordance with Pb isotope data of historic anthropogenic Pb emissions. The distributions of Pb concentrations and isotope compositions in northern sourced waters were consistent with differences in their ventilation timescales. For example, a Pb concentration maximum at intermediate depth (600-900 m, 35 pmol kg-1) in waters sourced from the Irminger/Labrador Seas, is associated with Pb isotope compositions (206Pb/207Pb = 1.1818-1.1824, 208Pb/207Pb = 2.4472-2.4483) indicative of northern hemispheric emissions during the 1950s and 1960s close to peak leaded petrol usage, and a transit time of ∼50-60 years. In contrast, North Atlantic Deep Water (2000-4000 m water depth) featured lower Pb concentrations and isotope compositions (206Pb/207Pb = 1.1762-1.184, 208Pb/207Pb = 2.4482-2.4545) indicative of northern hemispheric emissions during the 1910s and 1930s and a transit time of ∼80-100 years. This supports the notion that transient anthropogenic Pb inputs are predominantly transferred into the ocean interior by water mass transport. However, the interpretation of Pb concentration and isotope composition distributions in terms of ventilation timescales and pathways is complicated by (1) the chemical reactivity of Pb in the ocean, and (2) mixing of waters ventilated during different time periods. The complex effects of water mass mixing on Pb distributions is particularly apparent in seawater in the

  16. Clumped isotope composition of cold-water corals: A role for vital effects?

    NASA Astrophysics Data System (ADS)

    Spooner, Peter T.; Guo, Weifu; Robinson, Laura F.; Thiagarajan, Nivedita; Hendry, Katharine R.; Rosenheim, Brad E.; Leng, Melanie J.

    2016-04-01

    The carbonate clumped isotope thermometer is a promising tool for determining past ocean temperatures. It is based on the temperature dependence of rare isotopes 'clumping' into the same carbonate ion group in the carbonate mineral lattice. The extent of this clumping effect is independent of the isotope composition of the water from which carbonate precipitates, providing unique advantages over many other paleotemperature proxies. Existing calibrations of this thermometer in cold-water and warm-water corals suggest clumped isotope 'vital effects' are negligible in cold-water corals but may be significant in warm-water corals. Here, we test the calibration of the carbonate clumped isotope thermometer in cold-water corals with a recently collected and well characterised sample set spanning a range of coral genera (Balanophyllia, Caryophyllia, Dasmosmilia, Desmophyllum, Enallopsammia and Javania). The clumped isotope compositions (Δ47) of these corals exhibit systematic dependences on their growth temperatures, confirming the basis of the carbonate clumped isotope thermometer. However, some cold-water coral genera show Δ47 values that are higher than the expected equilibrium values by up to 0.05‰ (equivalent to underestimating temperature by ∼9 °C) similar to previous findings for some warm-water corals. This finding suggests that the vital effects affecting corals Δ47 are common to both warm- and cold-water corals. By comparison with models of the coral calcification process we suggest that the clumped isotope offsets in these genera are related to the kinetic isotope effects associated with CO2 hydration/hydroxylation reactions in the corals' calcifying fluid. Our findings complicate the use of the carbonate clumped isotope thermometer in corals, but suggest that species- or genus-specific calibrations could be useful for the future application of this paleotemperature proxy.

  17. ISOTOPIC COMPOSITION OF THE COMMON LEAD OF JAPAN

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Sakai, H.; Sato, K.

    1958-11-01

    Lead tetramethyl was synthesized from lead iodide isolated from 14 galenas, 2 anglesites, and 6 pyromorphites of Japan. The mass spectrometric analysis was carried out for the peaks of lead and lead hydride ions. The isotopic compositions of leads from these minerais lie wiyhn a narrow range. The average values for gnlanas are 18.51 O 0.05 for Pb/sup 238//Pb/sup 204/ 15.60 plus or minus 0.05 for Pb/sup 207//Pb/sup 204/8.76 plus or minus 0.15 forPb/ sup 208//Pb/sup 204/ For lead of secondary minerals they are 18.52 plus or minus 0.05, 15.62 plus or minus 0.05, and 38.78 plus or minus 0.15,more » respectively. No detectabla difference was observed between the isotopic compositions of primary and secondary lead ores. The ratios, U/sub 238/Pb/sup 204, and Th/sup 232/ U/sup 238/, in the source magma are estimated from the lead abundances. They are« less

  18. Lead isotopic compositions of common arsenical pesticides used in New England

    USGS Publications Warehouse

    Ayuso, Robert; Foley, Nora; Robinson, Gilpin; Wandless, Gregory; Dillingham, Jeremy

    2004-01-01

    The three most important arsenical pesticides and herbicides that were extensively used on apple, blueberry, and potato crops in New England from mid-1800s to recent times are lead arsenate, calcium arsenate, and sodium arsenate. Lead arsenate was probably the most heavily used of the arsenical pesticides until it was banned in 1988. Other metal-arsenic pesticides were also used but in lesser amounts. A recent report identified areas in New England where arsenical pesticides were used extensively (Robinson and Ayuso, 2004). On the basis of factor analysis of metal concentrations in stream sediment samples, a positive correlation with pesticide use was shown in regions having stream sediment sample populations that contained concentrations of high arsenic and lead. Lead isotope compositions of stream sediments from areas with heavy use of the pesticides could not be entirely explained by lead originating from rock sulfides and their weathering products. An industrial lead contribution (mostly from atmospheric deposition of lead) was suggested in general to explain the lead isotopic distributions of the stream sediments that could not be accounted for by the natural lead in the environment. We concluded that when agricultural land previously contaminated with arsenical pesticides is urbanized, pesticide residues in the soils and stream sediments could be released into the groundwater. No lead isotopic data characterizing the compositions of pesticides were available for comparison. We have determined the lead isotopic compositions of commonly used pesticides in New England, such as lead arsenate, sodium metaarsenite, and calcium arsenate, in order to assist in future isotopic comparisons and to better establish anthropogenic sources of Pb and As. New data are also presented for copper acetoarsenite (or Paris green), methyl arsonic acid and methane arsonic acid, as well as for arsanilic acid, all of which are used as feed additives to promote swine and poultry growth

  19. Absolute Calibration of Si iRMs used for Si Paleo-nutrient proxies

    NASA Astrophysics Data System (ADS)

    Vocke, Robert; Rabb, Savelas

    2016-04-01

    The Avogadro Project is an ongoing international effort, coordinated by the International Bureau of Weights and Measures (BIPM) and the International Avogadro Coordination (IAC) to redefine the SI unit mole in terms of the Avogadro constant and the SI unit kg in terms of the Planck constant. One of the outgrowths of this effort has been the development of a novel, precise and highly accurate method to measure calibrated (absolute) isotopic ratios that are traceable to the SI (Vocke et al., 2014 Metrologia 51, 361, Azuma et al., 2015 Metrologia 52 360). This approach has also been able to produce absolute Si isotope ratio data with lower levels of uncertainty when compared to the traditional "Atomic Weights" method of absolute isotope ratio measurement. Silicon isotope variations (reported as delta(Si30)and delta(Si29)) in silicic acid dissolved in ocean waters, in biogenic silica and in diatoms are extremely informative paleo-nutrient proxies. The utility and comparability of such measurements however depends on calibration with artifact isotopic Reference Materials (iRMs). We will be reporting new measurements on the iRMs NBS-28 (RM 8546 - Silica Sand), Diatomite, Big Batch and SRM 990 using the Avogadro measurement approach, comparing them with prior assessments of these iRMs.

  20. Stable isotope composition of cocoa beans of different geographical origin.

    PubMed

    Perini, Matteo; Bontempo, Luana; Ziller, Luca; Barbero, Alice; Caligiani, Augusta; Camin, Federica

    2016-09-01

    The isotopic profile (δ(13) C, δ(15) N, δ(18) O, δ(2) H, δ(34) S) was used to characterise a wide selection of cocoa beans from different renowned production areas (Africa, Asia, Central and South America). The factors most influencing the isotopic signatures of cocoa beans were climate and altitude for δ(13) C and the isotopic composition of precipitation water for δ(18) O and δ(2) H, whereas δ(15) N and δ(34) S were primarily affected by geology and fertilisation practises. Multi-isotopic analysis was shown to be sufficiently effective in determining the geographical origin of cocoa beans, and combining it with Canonical Discriminant Analysis led to more than 80% of samples being correctly reclassified. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  1. Southern Greenland water vapour isotopic composition at the crossroads of Atlantic and Arctic moisture

    NASA Astrophysics Data System (ADS)

    Bonne, J. L.; Steen-Larsen, H. C.; Risi, C. M.; Werner, M.; Sodemann, H.; Lacour, J. L.; Fettweis, X.; Cesana, G.; Delmotte, M.; Cattani, O.; Clerbaux, C.; Sveinbjörnsdottir, A. E.; Masson-Delmotte, V.

    2014-12-01

    Since September 2011, a continuous water vapour isotopic composition monitoring instrument has been remotely operated in Ivittuut (61.21°N, 48.17°W), southern Greenland. Meteorological parameters are monitored and precipitation has been sampled and analysed for isotopic composition, suggesting equilibrium between surface vapour and precipitation. The data depict small summer diurnal variations. δ18O and deuterium excess (d-excess) are generally anti-correlated and show important seasonal variations (with respective amplitudes of 10 and 20 ‰), and large synoptic variations associated to low-pressure systems (typically +5‰ on δ18O and -15‰ on d-excess). The moisture sources, estimated based on Lagrangian back-trajectories, are primarily influenced by the western North Atlantic, and north-eastern American continent. Notable are important seasonal and synoptic shifts of the moisture sources, and sporadic influences of the Arctic or the eastern North Atlantic. Moisture sources variations can be related to changes in water vapour isotopic composition, and the isotopic fingerprints can be attributed to the areas of moisture origins. Isotopic enabled AGCMs nudged to meteorology (LMDZiso, ECHAM5-wiso), despite biases, correctly capture the δ18O changes, but underestimate the d-excess changes. They allow to identify a high correlation between the southern Greenland d-excess and the simulated relative humidity and d-excess in the moisture source region south of Greenland. An extreme high temperature event in July 2012 affecting all Greenland, similar to ice sheet melt events during the medieval periods and one event in 1889 documented by Greenland ice core records, has been analysed regarding water vapour isotopic composition, using remote sensing (IASI) and in situ observations from Bermuda to northern Greenland (NEEM station). Our southern Greenland observations allow to track the water vapour evolution during this event along the moisture transport path

  2. Potassium Isotopic Compositions of NIST Potassium Standards and 40Ar/39Ar Mineral Standards

    NASA Technical Reports Server (NTRS)

    Morgan, Leah; Tappa, Mike; Ellam, Rob; Mark, Darren; Higgins, John; Simon, Justin I.

    2013-01-01

    Knowledge of the isotopic ratios of standards, spikes, and reference materials is fundamental to the accuracy of many geochronological methods. For example, the 238U/235U ratio relevant to U-Pb geochronology was recently re-determined [1] and shown to differ significantly from the previously accepted value employed during age determinations. These underlying values are fundamental to accurate age calculations in many isotopic systems, and uncertainty in these values can represent a significant (and often unrecognized) portion of the uncertainty budget for determined ages. The potassium isotopic composition of mineral standards, or neutron flux monitors, is a critical, but often overlooked component in the calculation of K-Ar and 40Ar/39Ar ages. It is currently assumed that all terrestrial materials have abundances indistinguishable from that of NIST SRM 985 [2]; this is apparently a reasonable assumption at the 0.25per mille level (1s) [3]. The 40Ar/39Ar method further relies on the assumption that standards and samples (including primary and secondary standards) have indistinguishable 40K/39K values. We will present data establishing the potassium isotopic compositions of NIST isotopic K SRM 985, elemental K SRM 999b, and 40Ar/39Ar biotite mineral standard GA1550 (sample MD-2). Stable isotopic compositions (41K/39K) were measured by the peak shoulder method with high resolution MC-ICP-MS (Thermo Scientific NEPTUNE Plus), using the accepted value of NIST isotopic SRM 985 [2] for fractionation [4] corrections [5]. 40K abundances were measured by TIMS (Thermo Scientific TRITON), using 41K/39K values from ICP-MS measurements (or, for SRM 985, values from [2]) for internal fractionation corrections. Collectively these data represent an important step towards a metrologically traceable calibration of 40K concentrations in primary 40Ar/39Ar mineral standards and improve uncertainties by ca. an order of magnitude in the potassium isotopic compositions of standards.

  3. Osmium Stable Isotope Composition of Chondrites and Iron Meteorites: Implications for Planetary Core Formation

    NASA Astrophysics Data System (ADS)

    Nanne, J. A. M.; Millet, M. A.; Burton, K. W.; Dale, C. W.; Nowell, G. M.; Williams, H. M.

    2016-12-01

    Mass-dependent Os stable isotope fractionation is expected to occur during metal-silicate segregation as well as during crystallization of metal alloys due to the different bonding environment between silicate and metals. As such, Os stable isotopes have the potential to resolve questions pertaining to planetary accretion and differentiation. Here, we present stable Os isotope data for a set of chondrites and iron meteorites to examine the processes associated with core solidification. Carbonaceous, ordinary, and enstatite chondrites show no detectable stable isotope variation with a δ190Os weighted average of +0.12±0.04 (n=37). The uniform composition observed for chondrites implies Os stable isotope homogeneity of the bulk solar nebula. Contrary to chondrites, iron meteorites display a large range in Os stable isotope compositions from δ190Os of +0.05 up to +0.49‰. Variation is only observed in the IIAB and IIIAB irons. Type IVB irons display values similar to chondrites (+0.107±0.047 [n=3]) and IVA compositions are slightly different +0.187±0.004 (n=2). The type IIAB and IIIAB groups show values both within the chondritic range and up to heavier values extending up to +0.49‰. Since core formation in small planetary bodies is expected to quantitatively sequester Os in metal phases, bulk planetary cores are expected to display chondritic δ190Os values. Conversely, samples of the IIAB and IIIAB group display significant variation, possibly indicating that stable isotope fractionation occurred during solidification of the parent-body core. However, no covariation is observed between δ190Os and either Os abundance or radiogenic Os isotope ratios. Instead, liquid immiscibility during core crystallization, where the liquid metal splits into separate S- and P-rich liquids, may be a source of Os stable isotope fractionation.

  4. On the equilibrium isotopic composition of the thorium-uranium-plutonium fuel cycle

    NASA Astrophysics Data System (ADS)

    Marshalkin, V. Ye.; Povyshev, V. M.

    2016-12-01

    The equilibrium isotopic compositions and the times to equilibrium in the process of thorium-uranium-plutonium oxide fuel recycling in VVER-type reactors using heavy water mixed with light water are estimated. It is demonstrated thEhfat such reactors have a capacity to operate with self-reproduction of active isotopes in the equilibrium mode.

  5. On the equilibrium isotopic composition of the thorium–uranium–plutonium fuel cycle

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Marshalkin, V. Ye., E-mail: marshalkin@vniief.ru; Povyshev, V. M.

    2016-12-15

    The equilibrium isotopic compositions and the times to equilibrium in the process of thorium–uranium–plutonium oxide fuel recycling in VVER-type reactors using heavy water mixed with light water are estimated. It is demonstrated thEhfat such reactors have a capacity to operate with self-reproduction of active isotopes in the equilibrium mode.

  6. Chemical and stable-radiogenic isotope compositions of Polatlı-Haymana thermal waters (Ankara, Turkey)

    NASA Astrophysics Data System (ADS)

    Akilli, Hafize; Mutlu, Halim

    2016-04-01

    Complex tectono-magmatic evolution of the Anatolian land resulted in development of numerous geothermal areas through Turkey. The Ankara region in central Anatolia is surrounded by several basins which are filled with upper Cretaceous-Tertiary sediments. Overlying Miocene volcanics and step faulting along the margins of these basins played a significant role in formation of a number of low-enthalpy thermal waters. In this study, chemical and isotopic compositions of Polatlı and Haymana geothermal waters in the Ankara region are investigated. The Polatlı-Haymana waters with a temperature range of 24 to 43 °C are represented by Ca-(Na)-HCO3 composition implying derivation from carbonate type reservoir rocks. Oxygen-hydrogen isotope values of the waters are conformable with the Global Meteoric Water Line and point to a meteoric origin. The carbon isotopic composition in dissolved inorganic carbon (DIC) of the studied waters is between -21.8 and -1.34 permil (vs. VPDB). Marine carbonates and organic rocks are the main sources of carbon. There is a high correlation between oxygen (3.7 to 15.0 permil; VSMOW) and sulfur (-9.2 to 19.5 permil; VCDT) isotope compositions of sulfate in waters. The mixing of sulfate from dissolution of marine carbonates and terrestrial evaporite units is the chief process behind the observed sulfate isotope systematics of the samples. 87Sr/86Sr ratios of waters varying from 0.705883 to 0.707827 are consistent with those of reservoir rocks. The temperatures calculated by SO4-H2O isotope geothermometry are between 81 and 138 °C nearly doubling the estimates from chemical geothermometers.

  7. Light Stable Isotopic Compositions of Enriched Mantle Sources: Resolving the Dehydration Paradox

    NASA Astrophysics Data System (ADS)

    Dixon, J. E.; Bindeman, I. N.; Kingsley, R. H.

    2017-12-01

    An outstanding puzzle in mantle geochemistry has been the origin and evolution of Earth's volatile components. The "dehydration paradox" refers to the following conundrum. Mantle compositions for some enriched mid-ocean ridge (MORB) and ocean island (OIB) basalts basalts require involvement of a mostly dehydrated slab component to explain the trace element ratios and radiogenic isotopic compositions, but a fully hydrated slab component to explain the stable isotopic compositions. Volatile and stable isotopic data on enriched MORB show a diversity of enriched components. Pacific PREMA-type basalts (H2O/Ce = 215 ± 30, δDSMOW = -45 ± 5 ‰) are similar to those in the north Atlantic (H2O/Ce = 220 ± 30; δDSMOW = -30 to -40 ‰). Basalts with EM-type signatures have regionally variable volatile compositions. North Atlantic EM-type basalts are wetter (H2O/Ce = 330 ± 30) and have isotopically heavier hydrogen (δDSMOW = -57 ± 5 ‰) than north Atlantic MORB. South Atlantic EM-type basalts are damp (H2O/Ce = 120 ± 10) with intermediate δDSMOW (-68 ± 2 ‰), similar to dDSMOW for Pacific MORB. North EPR EM-type basalts are dry (H2O/Ce = 110 ± 20) and isotopically light (δDSMOW = -94 ± 3 ‰). Boron and lithium isotopic ratios parallel the trends observed for dDSMOW. A multi-stage metasomatic and melting model accounts for the origin of the enriched components by extending the subduction factory concept down through the mantle transition zone, with slab temperature a key variable. The dehydration paradox is resolved by decoupling of volatiles from lithophile elements, reflecting primary dehydration of the slab followed by secondary rehydration and re-equilibration by fluids derived from subcrustal hydrous phases (e.g., antigorite) in cooler, deeper parts of the slab. The "expanded subduction factory" model includes melting at several key depths, including 1) 180 to 280 km, where EM-type mantle compositions are generated above slabs with average to hot thermal

  8. MAST - A mass spectrometer telescope for studies of the isotopic composition of solar, anomalous, and galactic cosmic ray nuclei

    NASA Technical Reports Server (NTRS)

    Cook, Walter R.; Cummings, Alan C.; Cummings, Jay R.; Garrard, Thomas L.; Kecman, Branislav; Mewaldt, Richard A.; Selesnick, Richard S.; Stone, Edward C.; Von Rosenvinge, T. T.

    1993-01-01

    The Mass Spectrometer Telescope (MAST) on SAMPEX is designed to provide high resolution measurements of the isotopic composition of energetic nuclei from He to Ni (Z = 2 to 28) over the energy range from about 10 to several hundred MeV/nuc. During large solar flares MAST will measure the isotopic abundances of solar energetic particles to determine directly the composition of the solar corona, while during solar quiet times MAST will study the isotopic composition of galactic cosmic rays. In addition, MAST will measure the isotopic composition of both interplanetary and trapped fluxes of anomalous cosmic rays, believed to be a sample of the nearby interstellar medium.

  9. Trihalomethanes formed from natural organic matter isolates: Using isotopic and compositional data to help understand sources

    USGS Publications Warehouse

    Bergamaschi, Brian A.; Fram, Miranda S.; Fujii, Roger; Aiken, George R.; Kendall, Carol; Silva, Steven R.

    2000-01-01

    Over 20 million people drink water from the Sacramento-San Joaquin Delta despite problematic levels of natural organic matter (NOM) and bromide in Delta water, which can form trihalomethanes (THMs) during the treatment process. It is widely believed that NOM released from Delta peat islands is a substantial contributor to the pool of THM precursors present in Delta waters. Dissolved NOM was isolated from samples collected at five channel sites within the Sacramento-San Joaquin Rivers and Delta, California, USA, and from a peat island agricultural drain. To help understand the sources of THM precursors, samples were analyzed to determine their chemical and isotopic composition, their propensity to form THMs, and the isotopic composition of the THMs.The chemical composition of the isolates was quite variable, as indicated by significant differences in carbon-13 nuclear magnetic resonance spectra and carbon-to-nitrogen concentration ratios. The lowest propensity to form THMs per unit of dissolved organic carbon was observed in the peat island agricultural drain isolate, even though it possessed the highest fraction of aromatic material and the highest specific ultraviolet absorbance. Changes in the chemical and isotopic composition of the isolates and the isotopic composition of the THMs suggest that the source of the THMs precursors was different between samples and between isolates. The pattern of variability in compositional and isotopic data for these samples was not consistent with simple mixing of river- and peat-derived organic material.

  10. The initial Hf isotopic composition of the Earth

    NASA Astrophysics Data System (ADS)

    Bouvier, A.; Boyet, M. M.; Vervoort, J. D.; Patchett, P. J.

    2011-12-01

    One area of considerable activity in trying to understand the formation and evolution of Earth's crust is the isotopic analysis of Hf in parallel with Sm-Nd and U-Pb zircon studies, either to constrain early crustal growth and evolution [1], or as a complement to detrital zircon studies [2]. The 176Lu decay constant deduced from early planetary and Earth materials have different values. It has been suggested that a period of irradiation in the early Solar System affected the 176Hf production rate in meteoritic and planetary materials [3,4]. In this scenario, the initial Hf isotopic composition of the Solar System and the Earth would be ~4 ∈Hf units lower, affecting tremendously the interpretation of the differentiation history of the early Earth. We investigated Lu-Hf compositions of calcium-aluminum-rich inclusions, the oldest known objects of the Solar System dated at 4568 Ma [5], to assess the possibility of neutrino irradiation in the solar nebula. Here we report high-precision 176Lu-176Hf systematics of leached and unleached, and spiked and unspiked, bulk fractions and mineral separates of 6 individual CAIs from 2 CV3 chondrites. Isotopic analyses were carried out by Neptune MC-ICPMS at ASU. Analytical details are in [6,7]. The unspiked Hf fractions reveal stable isotope anomalies of μ178Hf= 20 ± 6 and μ180Hf= 31 ± 9 (2SD) for the CAI B4 fractions (n=3) and μ178Hf= -4 ± 10 and μ180Hf= 2 ± 10 (n=2) for BCR-2 relative to the JMC 475 Hf standard. Further high-precision analysis of unspiked Sm and Nd fractions of the samples will be made to correct from nucleosynthetic or neutron capture anomalies [8]. Such Hf stable isotopic anomalies predict no more than 50ppm correction on 176Hf/177Hf. At this stage, we have thus regressed together the spiked and unspiked Hf compositions of CAI fractions (n=13) for isochron calculations. The slope of the Lu-Hf isochron is 0.0882 ± 0.0026 (2SD) which corresponds to a 176Lu decay constant value of 1.852 (± 0.052) ×10

  11. Elemental and isotopic compositions of noble gases in the mantle: Pete's path

    NASA Astrophysics Data System (ADS)

    Moreira, Manuel; Péron, Sandrine; Colin, Aurélia

    2016-04-01

    Noble gases are tracers of the origin of the volatiles on Earth and other terrestrial planets. The determination of their isotopic compositions in oceanic basalts allows discriminating between different possible scenarios for the origin of volatiles (chondritic, solar, cometary). However, oceanic basalts show a ubiquitous component having atmospheric noble gas compositions, which reflects a shallow air contamination. This component masks the mantle composition and only step crushing is able to (partially) remove it. Nevertheless, the exact mantle composition is always unconstrained due to the uncertainty on its complete removal. Developed by Pete Burnard (Burnard et al., 1997; Burnard, 1999), single vesicle analysis using laser ablation is a challenging technique to determine the mantle composition, free of atmospheric contamination. We have used this technique to measure He, Ne, Ar isotopes and CO2 in single vesicles from both MORB and OIB (Galapagos, Iceland). Vesicles are located using microtomography and the noble gases are measured using the Noblesse mass spectrometer from IPGP using an Excimer laser to open the vesicles. Both Galapagos and Iceland samples show that the 20Ne/22Ne ratio is limited to ~12.8 in the primitive mantle, suggesting that the origin of the light noble gases can be attributed to irradiated material instead of a simple dissolution of solar gases into a magma ocean (Moreira and Charnoz, 2016). Such a scenario of incorporation of light noble gases by irradiation also explains the terrestrial argon isotopic composition. However, the Kr and Xe contribution of implanted solar wind is small and these two noble gases were carried on Earth by chondrites and/or cometary material. Burnard, P., D. Graham and G. Turner (1997). "Vesicle-specific noble gas analyses of « popping rock »: implications for primordial noble gases in the Earth." Science 276: 568-571. Burnard, P. (1999). "The bubble-by-bubble volatile evolution of two mid-ocean ridge

  12. Evaluating climate model performance in the tropics with retrievals of water isotopic composition from Aura TES

    NASA Astrophysics Data System (ADS)

    Field, Robert; Kim, Daehyun; Kelley, Max; LeGrande, Allegra; Worden, John; Schmidt, Gavin

    2014-05-01

    Observational and theoretical arguments suggest that satellite retrievals of the stable isotope composition of water vapor could be useful for climate model evaluation. The isotopic composition of water vapor is controlled by the same processes that control water vapor amount, but the observed distribution of isotopic composition is distinct from amount itself . This is due to the fractionation that occurs between the abundant H216O isotopes (isotopologues) and the rare and heavy H218O and HDO isotopes during evaporation and condensation. The fractionation physics are much simpler than the underlying moist physics; discrepancies between observed and modeled isotopic fields are more likely due to problems in the latter. Isotopic measurements therefore have the potential for identifying problems that might not be apparent from more conventional measurements. Isotopic tracers have existed in climate models since the 1980s but it is only since the mid 2000s that there have been enough data for meaningful model evaluation in this sense, in the troposphere at least. We have evaluated the NASA GISS ModelE2 general circulation model over the tropics against water isotope (HDO/H2O) retrievals from the Aura Tropospheric Emission Spectrometer (TES), alongside more conventional measurements. A small ensemble of experiments was performed with physics perturbations to the cumulus and planetary boundary layer schemes, done in the context of the normal model development process. We examined the degree to which model-data agreement could be used to constrain a select group of internal processes in the model, namely condensate evaporation, entrainment strength, and moist convective air mass flux. All are difficult to parameterize, but exert strong influence over model performance. We found that the water isotope composition was significantly more sensitive to physics changes than precipitation, temperature or relative humidity through the depth of the tropical troposphere. Among the

  13. Grosnaja ABCs: Magnesium isotope compositions

    NASA Technical Reports Server (NTRS)

    Goswami, J. N.; Srinivasan, G.; Ulyanov, A. A.

    1993-01-01

    Three CAI's from the Grosnaja CV3 chondrite were analyzed for their magnesium isotopic compositions by the ion microprobe. The selected CAI's represent three distinct types: GR4(compact Type A), GR7(Type B) and GR2(Type C). Petrographic studies indicate that all three Grosnaja inclusions were subjected to secondary alterations. The Type A CAI GR4 is primarily composed of melilite with spinel and pyroxene occurring as minor phases. The rim of the inclusion does not exhibit distinct layered structure and secondary alteration products (garnet, Fe-rich olivine and Na-rich plagioclase) are present in some localized areas near the rim region. The average major element compositions of different mineral phases in GR4 are given. Preliminary REE data suggest a depletion of HREE relative to LREE by about a factor of 3 without any clear indication of interelement fractionation. The CAI GR7 has textural and minerological characteristics similar to Type B inclusions. The REE data show a pattern that is similar to Group 6 with enrichment in Eu and Yb. In addition, a depletion of HREE compared to LREE is also evident in this object. Melilite composition shows a broad range of akermanite content (Ak(sub 15-55)). Detailed petrographic study is in progress. GR2 is a anorthite-rich Type C inclusion with large plagioclase laths intergrown with Ti-rich pyroxene. The average plagioclase composition is close to pure anorthite (An99).

  14. In-Situ Oxygen Isotopic Composition of Tagish Lake: An Ungrouped Type 2 Carbonaceous Chondrite

    NASA Technical Reports Server (NTRS)

    Zolensky, Michael E.; Engrand, Cecile; Gounelle, Matthieu; Zolensky, Mike E.

    2001-01-01

    We have measured the oxygen isotopic composition of several components of Tagish Lake by ion microprobe. This meteorite constitutes the best preserved sample of C2 matter presently available for study. It presents two different lithologies (carbonate-poor and -rich) which have fairly comparable oxygen isotopic composition, with regard to both the primary or secondary minerals. For the olivine and pyroxene grains, their delta O-18 values range from - 10.5% to + 7.4% in the carbonate-poor lithology, with a mean Delta O-17 value of - 3.7 2.4%. In the carbonate-rich lithology, delta O-18 varies from - 7.9% to + 3.3%, and the mean Delta O-17 value is - 4.7 +/- 1.4%. Olivine inclusions (Fo(sub >99)) with extreme O-16-enrichment were found in both lithologies: delta O-18 = - 46.1 %, delta O-187= - 48.3% and delta O-18 = - 40.6%, delta O-17 = - 41.2% in the carbonate-rich lithology; delta O-18 = - 41.5%, delta O-17 = -43.4%0 in the carbonate-poor lithology. Anhydrous minerals in the carbonate-poor lithology are slightly more O-16-rich than in the carbonate-rich one. Four low-iron manganese-rich (LIME) olivine grains do not have an oxygen isotopic composition distinct from the other "normal" olivines. The phyllosilicate matrix presents the same range of oxygen isotopic compositions in both lithologies: delta O-18 from approximately 11 % to approximately 6%, with an average Delta. O-17 approximately 0%. Because the bulk Tagish Lake oxygen isotopic composition given by Brown et al. is on the high end of our matrix analyses, we assume that this "bulk Tagish Lake" composition probably only represents that of the carbonate-rich lithology. Calcium carbonates have delta O-18 values up to 35%, with Delta O-17 approximately 0.5%0. Magnetite grains present very high Delta O-17 values approximately + 3.4%0 +/- 1.2%. Given our analytical uncertainties and our limited carbonate data, the matrix and the carbonate seem to have formed in isotopic equilibrium. In that case, their large

  15. The Dissolved Ca Isotope Composition of Himalayan-Tibetan Waters

    NASA Astrophysics Data System (ADS)

    Tipper, E. T.; Galy, A.; Bickle, M. J.

    2004-12-01

    Determining the relative proportions of carbonate versus silicate weathering in the Himalaya is important for understanding the long-term atmospheric CO2 budget and the marine Sr isotope record. 87Sr/86Sr is not a straightforward proxy of carbonate to silicate weathering in the Himalaya and up to 50% of the dissolved Ca may be removed by the precipitation of secondary calcite. Ca isotopes have the potential to constrain the relative inputs of carbonates to silicates and incongruent dissolution processes in the weathering environment. Ca is the major cation carried by rivers. Thirty four Himalayan rock and water samples from the Nepal Himalaya and Tibet have been analysed for 44/42Ca and 43/42Ca on a Nu-Instruments Multiple Collector -ICP-MS. Unlike the 44/40Ca ratio the 44/42Ca is not susceptible to excess 40Ca production from the decay of K. All samples lie on a single mass fractionation line. There is a total range of 0.4 \\permil variation in \\delta44Ca with values from 0.63 \\permil - 0.21 \\permil relative to the SRM915a standard. This is comparable to that already reported with \\delta44/40Ca for small catchments and global rivers. Small first order catchments from each of the main lithotectonic units of the Himalaya have been analysed to examine the effect of lithology on dissolved Ca isotopic composition. In agreement with previous studies elsewhere there is little correlation between source rock and dissolved composition for small rivers spanning a range of source rock from limestone to various silicates and covering a vegetation range from temperate semi-desert to jungle. \\delta44Ca is not correlated with 87Sr/86Sr or Na/Ca ratios confirming that source rock composition is not the dominant control on the observed range in \\delta44Ca. A time-series has been examined for the Marsyandi River, central Nepal. In spite of significant systematic variations in major element chemistry including Ca concentration and 87Sr/86Sr the variations in \\delta44Ca are

  16. Constraints on Galactic Cosmic-Ray Origins from Elemental and Isotopic Composition Measurements

    NASA Technical Reports Server (NTRS)

    Binns, W. R.; Christian, E. R.; Cummings, A. C.; deNolfo, G. A.; Israel, M. H.; Leske, R. A.; Mewaldt, R. A,; Stone, E. C.; vonRosevinge, T. T.; Wiedenbeck, M. E.

    2013-01-01

    The most recent measurements by the Cosmic Ray Isotope Spectrometer (CRIS) aboard the Advanced Composition Explorer (ACE) satellite of ultra-heavy cosmic ray isotopic and elemental abundances will be presented. A range of isotope and element ratios, most importantly Ne-22/Ne-20, Fe-58/Fe-56, and Ga-31/Ge -32 show that the composition is consistent with source material that is a mix of approx 80% ISM (with Solar System abundances) and 20% outflow/ejecta from massive stars. In addition, our data show that the ordering of refractory and volatile elements with atomic mass is greatly improved when compared to an approx 80%/20% mix rather than pure ISM, that the refractory and volatile elements have similar slopes, and that refractory elements are preferentially accelerated by a factor of approx 4. We conclude that these data are consistent with an OB association origin of GCRs.

  17. The GENESIS Mission: Solar Wind Isotopic and Elemental Compositions and Their Implications

    NASA Astrophysics Data System (ADS)

    Wiens, R. C.; Burnett, D. S.; McKeegan, K. D.; Kallio, A. P.; Mao, P. H.; Heber, V. S.; Wieler, R.; Meshik, A.; Hohenberg, C. M.; Mabry, J. C.; Gilmour, J.; Crowther, S. A.; Reisenfeld, D. B.; Jurewicz, A.; Marty, B.; Pepin, R. O.; Barraclough, B. L.; Nordholt, J. E.; Olinger, C. T.; Steinberg, J. T.

    2008-12-01

    The GENESIS mission was a novel NASA experiment to collect solar wind at the Earth's L1 point for two years and return it for analysis. The capsule crashed upon re-entry in 2004, but many of the solar-wind collectors were recovered, including separate samples of coronal hole, interstream, and CME material. Laboratory analyses of these materials have allowed higher isotopic precision than possible with current in-situ detectors. To date GENESIS results have been obtained on isotopes of O, He, Ne, Ar, Kr, and Xe on the order of 1% accuracy and precision, with poorer uncertainty on Xe isotopes and significantly better uncertainties on the lighter noble gases. Elemental abundances are available for the above elements as well as Mg, Si, and Fe. When elemental abundances are compared with other in situ solar wind measurements, agreement is generally quite good. One exception is the Ne elemental abundance, which agrees with Ulysses and Apollo SWC results, but not with ACE. Neon is of particular interest because of the uncertainty in the solar Ne abundance, which has significant implications for the standard solar model. Helium isotopic results of material from the different solar wind regimes collected by GENESIS is consistent with isotopic fractionation predictions of the Coulomb drag model, suggesting that isotopic fractionation corrections need to be applied to heavier elements as well when extrapolating solar wind to solar compositions. Noble gas isotopic compositions from GENESIS are consistent with those obtained for solar wind trapped in lunar grains, but have for the first time yielded a very precise Ar isotopic result. Most interesting for cosmochemistry is a preliminary oxygen isotopic result from GENESIS which indicates a solar enrichment of ~4% in 16O relative to the planets, consistent with a photolytic self-shielding phenomenon during solar system formation. Analyses of solar wind N and C isotopes may further elucidate this phenomenon. Preliminary results

  18. The vanadium isotope compositions of subduction zone lavas

    NASA Astrophysics Data System (ADS)

    Tian, S.; Huang, F.

    2017-12-01

    Vanadium is a redox sensitive element with multiple oxidation states, and thus it has the potential to trace redox-related processes. With the advancement of analytical method for V isotopes, we are now able to recognize V isotope fractionation for igneous rocks. Subduction zones are critical zones on the Earth for the interaction between crust and mantle where undergo complex geological processes. However, V isotope data of subduction zone lavas are still rare except those reported in [1]. To investigate the V isotope variations of subduction zones and discuss the potential to apply V to trace mantle redox state. In this contribution, we report δ51V for three subduction zone lavas from Kamchatka, Lesser Antilles, and Aleutians which are characterized by well-documented magmatic evolutionary series. 47 arc lava samples have been analyzed and the δ51V data of them range from -0.91‰ to -0.53‰ (2sd = 0.10 ‰). Among these samples, primitive arc basalts with MgO > 6 wt. % have an average δ51V of -0.80 ± 0.15‰ (2sd, n = 20), broadly consistent with δ51V data of MORB [2, 3]. Within the single arc of Kamchatka, δ51V data of primitive basalts from the arc front to the back-arc is almost constant, suggesting limited influences of mantle melting and source heterogeneity on V isotopes. δ51V data of these samples show no correlation with Ba/Nb, suggesting that fluids have little impact on V isotopes. On the other hand, δ51V data of the more involved samples with MgO < 6 wt. % are negatively correlated with MgO contents, indicating that the 50V preferentially enters crystalline minerals, which produces heavier V isotope compositions of residual melts. Distinct to the observation showing 2‰ fractionation reported in [1], the magnitude of V isotope fractionation in arc lavas is much smaller (0.38‰) in this study. Future works are needed for better understanding the V isotope fractionation mechanisms of subduction zone lavas. [1]Prytulak et al., 2017, Geochem

  19. Assessing the ability of isotope-enabled General Circulation Models to simulate the variability of Iceland water vapor isotopic composition

    NASA Astrophysics Data System (ADS)

    Erla Sveinbjornsdottir, Arny; Steen-Larsen, Hans Christian; Jonsson, Thorsteinn; Ritter, Francois; Riser, Camilla; Messon-Delmotte, Valerie; Bonne, Jean Louis; Dahl-Jensen, Dorthe

    2014-05-01

    During the fall of 2010 we installed an autonomous water vapor spectroscopy laser (Los Gatos Research analyzer) in a lighthouse on the Southwest coast of Iceland (63.83°N, 21.47°W). Despite initial significant problems with volcanic ash, high wind, and attack of sea gulls, the system has been continuously operational since the end of 2011 with limited down time. The system automatically performs calibration every 2 hours, which results in high accuracy and precision allowing for analysis of the second order parameter, d-excess, in the water vapor. We find a strong linear relationship between d-excess and local relative humidity (RH) when normalized to SST. The observed slope of approximately -45 o/oo/% is similar to theoretical predictions by Merlivat and Jouzel [1979] for smooth surface, but the calculated intercept is significant lower than predicted. Despite this good linear agreement with theoretical calculations, mismatches arise between the simulated seasonal cycle of water vapour isotopic composition using LMDZiso GCM nudged to large-scale winds from atmospheric analyses, and our data. The GCM is not able to capture seasonal variations in local RH, nor seasonal variations in d-excess. Based on daily data, the performance of LMDZiso to resolve day-to-day variability is measured based on the strength of the correlation coefficient between observations and model outputs. This correlation coefficient reaches ~0.8 for surface absolute humidity, but decreases to ~0.6 for δD and ~0.45 d-excess. Moreover, the magnitude of day-to-day humidity variations is also underestimated by LMDZiso, which can explain the underestimated magnitude of isotopic depletion. Finally, the simulated and observed d-excess vs. RH has similar slopes. We conclude that the under-estimation of d-excess variability may partly arise from the poor performance of the humidity simulations.

  20. Tungsten isotopic compositions of iron meteorites: Chronological constraints vs. cosmogenic effects

    NASA Astrophysics Data System (ADS)

    Markowski, A.; Quitté, G.; Halliday, A. N.; Kleine, T.

    2006-02-01

    High-precision W isotopic compositions are presented for 35 iron meteorites from 7 magmatic groups (IC, IIAB, IID, IIIAB, IIIF, IVA, and IVB) and 3 non-magmatic groups (IAB, IIICD, and IIE). Small but resolvable isotopic variations are present both within and between iron meteorite groups. Variations in the 182W/ 184W ratio reflect either time intervals of metal-silicate differentiation, or result from the burnout of W isotopes caused by a prolonged exposure to galactic cosmic rays. Calculated apparent time spans for some groups of magmatic iron meteorites correspond to 8.5 ± 2.1 My (IID), 5.1 ± 2.3 My (IIAB), and 5.3 ± 1.3 My (IVB). These time intervals are significantly longer than those predicated from models of planetesimal accretion. It is shown that cosmogenic effects can account for a large part of the W isotopic variation. No simple relationship exists with exposure ages, compromising any reliable method of correction. After allowance for maximum possible cosmogenic effects, it is found that there is no evidence that any of the magmatic iron meteorites studied here have initial W isotopic compositions that differ from those of Allende CAIs [ ɛ182W = - 3.47 ± 0.20; [T. Kleine, K. Mezger, H. Palme, E. Scherer and C. Münker, Early core formation in asteroids and late accretion of chondrite parent bodies: evidence from 182Hf- 182W in CAIs, metal-rich chondrites and iron meteorites, Geochim. Cosmochim. Acta (in press)]. Cosmogenic corrections cannot yet be made with sufficient accuracy to obtain highly precise ages for iron meteorites. Some of the corrected ages nevertheless require extremely early metal-silicate segregation no later than 1 My after formation of CAIs. Therefore, magmatic iron meteorites appear to provide the best examples yet identified of material derived from the first planetesimals that grew by runaway growth, as modelled in dynamic simulations. Non-magmatic iron meteorites have a more radiogenic W isotopic composition than magmatic

  1. Stable water isotopic composition of the Antarctic subglacial Lake Vostok: implications for understanding the lake's hydrology.

    PubMed

    Ekaykin, Alexey A; Lipenkov, Vladimir Y; Kozachek, Anna V; Vladimirova, Diana O

    2016-01-01

    We estimated the stable isotopic composition of water from the subglacial Lake Vostok using two different sets of samples: (1) water frozen on the drill bit immediately after the first lake unsealing and (2) water frozen in the borehole after the unsealing and re-drilled one year later. The most reliable values of the water isotopic composition are: -59.0 ± 0.3 ‰ for oxygen-18, -455 ± 1 ‰ for deuterium and 17 ± 1 ‰ for d-excess. This result is also confirmed by the modelling of isotopic transformations in the water which froze in the borehole, and by a laboratory experiment simulating this process. A comparison of the newly obtained water isotopic composition with that of the lake ice (-56.2 ‰ for oxygen-18, -442.4 ‰ for deuterium and 7.2 ‰ for d-excess) leads to the conclusion that the lake ice is very likely formed in isotopic equilibrium with water. In turn, this means that ice is formed by a slow freezing without formation of frazil ice crystals and/or water pockets. This conclusion agrees well with the observed physical and chemical properties of the lake's accreted ice. However, our estimate of the water's isotopic composition is only valid for the upper water layer and may not be representative for the deeper layers of the lake, so further investigations are required.

  2. Factors that control the stable carbon isotopic composition of methane produced in an anoxic marine sediment

    NASA Technical Reports Server (NTRS)

    Alperin, M. J.; Blair, Neal E.; Albert, D. B.; Hoehler, T. M.; Martens, C. S.

    1993-01-01

    The carbon isotopic composition of methane produced in anoxic marine sediment is controlled by four factors: (1) the pathway of methane formation, (2) the isotopic composition of the methanogenic precursors, (3) the isotope fractionation factors for methane production, and (4) the isotope fractionation associated with methane oxidation. The importance of each factor was evaluated by monitoring stable carbon isotope ratios in methane produced by a sediment microcosm. Methane did not accumulate during the initial 42-day period when sediment contained sulfate, indicating little methane production from 'noncompetitive' substrates. Following sulfate depletion, methane accumulation proceeded in three distinct phases. First, CO2 reduction was the dominant methanogenic pathway and the isotopic composition of the methane produced ranged from -80 to -94 per thousand. The acetate concentration increased during this phase, suggesting that acetoclastic methanogenic bacteria were unable to keep pace with acetate production. Second, acetate fermentation became the dominant methanogenic pathway as bacteria responded to elevated acetate concentrations. The methane produced during this phase was progressively enriched in C-13, reaching a maximum delta(C-13) value of -42 per thousand. Third, the acetate pool experienced a precipitous decline from greater than 5 mM to less than 20 micro-M and methane production was again dominated by CO2 reduction. The delta(C-13) of methane produced during this final phase ranged from -46 to -58 per thousand. Methane oxidation concurrent with methane production was detected throughout the period of methane accumulation, at rates equivalent to 1 to 8 percent of the gross methane production rate. Thus methane oxidation was too slow to have significantly modified the isotopic signature of methane. A comparison of microcosm and field data suggests that similar microbial interactions may control seasonal variability in the isotopic composition of methane

  3. The boron and lithium isotopic composition of mid-ocean ridge basalts and the mantle

    NASA Astrophysics Data System (ADS)

    Marschall, Horst R.; Wanless, V. Dorsey; Shimizu, Nobumichi; Pogge von Strandmann, Philip A. E.; Elliott, Tim; Monteleone, Brian D.

    2017-06-01

    A global selection of 56 mid-ocean ridge basalt (MORB) glasses were analysed for Li and B abundances and isotopic compositions. Analytical accuracy and precision of analyses constitute an improvement over previously published MORB data and allow a more detailed discussion of the Li and B systematics of the crust-mantle system. Refined estimates for primitive mantle abundances ([ Li ] = 1.39 ± 0.10 μg/g and [ B ] = 0.19 ± 0.02 μg/g) and depleted mantle abundances ([ Li ] = 1.20 ± 0.10 μg/g and [ B ] = 0.077 ± 0.010 μg/g) are presented based on mass balance and on partial melting models that utilise observed element ratios in MORB. Assimilation of seawater (or brine) or seawater-altered material beneath the ridge, identified by high Cl / K , causes significant elevation of MORB δ11 B and variable elevation in δ7 Li . The B isotope ratio is, hence, identified as a reliable indicator of assimilation in MORB and values higher than -6‰ are strongly indicative of shallow contamination of the magma. The global set of samples investigated here were produced at various degrees of partial melting and include depleted and enriched MORB from slow and fast-spreading ridge segments with a range of radiogenic isotope signatures and trace element compositions. Uncontaminated (low- Cl / K) MORB show no significant boron isotope variation at the current level of analytical precision, and hence a homogenous B isotopic composition of δ11 B = - 7.1 ± 0.9 ‰ (mean of six ridge segments; 2SD). Boron isotope fractionation during mantle melting and basalt fractionation likely is small, and this δ11 B value reflects the B isotopic composition of the depleted mantle and the bulk silicate Earth, probably within ±0.4‰. Our sample set shows a mean δ7 Li = + 3.5 ± 1.0 ‰ (mean of five ridge segments; 2SD), excluding high- Cl / K samples. A significant variation of 1.0-1.5‰ exists among various ridge segments and among samples within individual ridge segments, but this

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

    PubMed

    Leavitt, S W; Long, A

    1985-06-01

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

  5. Isotopic composition of Pb and Th in interplinian volcanics from Somma-Vesuvius volcano, Italy

    USGS Publications Warehouse

    Cortini, M.; Ayuso, R.A.; de Vivo, B.; Holden, P.; Somma, R.

    2004-01-01

    We present a detailed isotopic study of volcanic rocks emitted from Somma-Vesuvius volcano during three periods of interplinian activity: "Protohistoric" (3550 y B.P. to 79 A.D.), "Ancient Historic" (79 to 472 A.D.) and "Medieval" (472 to 1631 A.D.). Pb isotopic compositions of two acid leached fractions and whole rock residues of 37 whole rock samples (determined by Somma et al., 2001) show that each of the three interplinian periods is distinguished by small, systematic, and unique uranogenic and thorogenic Pb isotopic trends. This key and novel feature is compatible with the notion that the Pb isotopic data reflect small-scale source heterogeneity operating over relatively short periods of time. From this representative group of samples, a selected set of nine whole rocks were analysed for Th isotopes. 232Th/238U ratios in the source can be obtained independently from Pb and from Th isotopes. Those obtained from Pb isotopes represent source ratios, time-integrated over the whole age of the Earth; they range from 3.9 to 4.1. 232Th/238U obtained from Th isotopes are those of the present source. They are lower, and cluster around 3.5; this difference probably indicates recent U enrichment of the present source. The behaviour of Pb, as inferred by its isotopic ratios, is quite distinct from that of Sr and Nd isotopes: Pb isotope variations are not correlated to Sr or Nd isotope variations. The isotopic contrast is compatible with the idea that the isotopes were decoupled during magmatic production, evolution, and ascent through the crust. Thus, the Pb isotopes do not reflect the effects of the same processes as in the case of the Sr and Nd isotopes, or, as we also favor, they do not necessarily reflect the same source contributions into the magmas. Moreover, the Pb isotopic evolution of the interplinian rocks chiefly reflects mixing, driven by processes that are superimposed on, and independent of, other source contributions that determine the isotopic compositions

  6. Boron Isotopic Composition of Metasomatized Mantle Xenoliths from the Western Rift, East Africa

    NASA Astrophysics Data System (ADS)

    Hudgins, T.; Nelson, W. R.

    2017-12-01

    The Western Branch of the East African Rift System is known to have a thick lithosphere and sparse, alkaline volcanism associated with a metasomatized mantle source. Recent work investigating the relationship between Western Branch metasomatized mantle xenoliths and associated lavas has suggested that these metasomes are a significant factor in the evolution of the rift. Hydrous/carbonated fluids or silicate melts are potent metasomatic agents, however gaining insight into the source of a metasomatic agent proves challenging. Here we investigate the potential metasomatic fluid sources using B isotope analysis of mineral separates from Western Branch xenoliths. Preliminary SIMS analyses of phlogopite from Katwe Kikorongo and Bufumbira have and average B isotopic composition of -28.2‰ ± 5.1 and -16.4‰ ± 3.6, respectively. These values are are dissimilar to MORB (-7.5‰ ± 0.7; Marschall and Monteleone, 2015), primitive mantle (-10‰ ± 2; Chaussidon and Marty, 1995), and bulk continental crust (-9.1‰ ± 2.4; Marschall et al., 2017) and display significant heterogeneity across a relatively short ( 150km) portion of the Western Branch. Though displaying large variability, these B isotopic compositions are indicative of a metasomatic agent with a more negative B isotopic composition than MORB, PM, or BCC. These results are consistent with fluids that released from a subducting slab and may be related to 700 Ma Pan-African subduction.

  7. Controls on the distribution and isotopic composition of helium in deep ground-water flows

    USGS Publications Warehouse

    Zhao, X.; Fritzel, T.L.B.; Quinodoz, H.A.M.; Bethke, C.M.; Torgersen, T.

    1998-01-01

    The distribution and isotopic composition of helium in sedimentary basins can be used to interpret the ages of very old ground waters. The piston-flow model commonly used in such interpretation, how ever, does not account for several important factors and as such works well only in very simple flow regimes. In this study of helium transport in a hypothetical sedimentary basin, we develop a numerical model that accounts for the magnitude and distribution of the basal helium flux, hydrodynamic dispersion, and complexities in flow regimes such as subregional flow cells. The modeling shows that these factors exert strong controls on the helium distribution and isotopic composition. The simulations may provide a basis for more accurate interpretations of observed helium concentrations and isotopic ratios in sedimentary basins.

  8. The relation between isotopic composition of argon and carbon in natural gases

    NASA Technical Reports Server (NTRS)

    Gavrilov, Y. Y.; Zhurov, Y. A.; Teplinskiy, G. I.

    1977-01-01

    The methods and results of determination of the argon and carbon isotope compositions of hydrocarbon gases of Mezozoic complexes of Western Siberia are presented. Based on the Ar-36, Ar-40, C-12, C-13 content of the various deposits and on the presumed mechanisms of entry of these isotopes into the deposits, it is concluded that formation of natural gas in some deposits included vertical migration from a lower complex.

  9. Boron Isotopic Composition Correlates with Ultra-Structure in a - Sea Coral Lophelia Pertusa: Implications for Biomineralization and - PH

    NASA Astrophysics Data System (ADS)

    Blamart, D.; Rollion-Bard, C.; Meibom, A.; Cuif, J.; Juillet-Leclerc, A.; Dauphin, Y.; Douarin, M.

    2007-12-01

    The geochemistry (stable isotopes and trace elements) of biogenic carbonates has been widely used for more than fifty years to reconstruct past climatic variability. During this time, the studies were mainly based on bulk sampling limiting sometimes the interpretations of the geochemical data as paleoclimatic proxies. Recently, high spatial resolution sampling techniques, such as micro-mill and SIMS, have been employed in the study of C, O and B isotopic compositions and trace elements (Mg, Sr) in the skeletons of a variety of (deep-sea) coral species. These studies have documented dramatic 'vital effects' and uncovered a systematic relationship between skeletal ultra-structure and stable isotopic composition. The formation of skeleton corals follows a universal two-step growth process. At the tips of the skeletal structures, the mineralizing cell layer produces centers of calcification (COC) or, equivalently, Early Mineralization Zone (EMZ). These EMZ are subsequently overgrown by fibrous aragonite(FA) consisting of cyclically added layers. The EMZ are characterized by systematically lighter C and O isotopic compositions compared with the adjacent FA. A number of geochemical models have been proposed, in which this systematic stable isotopic difference between EMZ and FA is ascribed to a biologically induced variation in the pH of a proposed Extra-cytoplasmic Calcifying Fluid (ECF) reservoir. In these models, relatively high pH conditions during the formation of EMZ result in relatively light C and O isotopic compositions compared with FA, which form under generally lower pH conditions. A direct test of such models would be possible if the Boron isotopic composition, which is pH sensitive, of EMZ and FA could be measured. We performed ion microprobe d11B measurements for EMZ and FA in Lophelia pertusa, a deep-sea coral common in the North-East Atlantic Ocean. We observe a systematic difference in B isotopic composition between the EMZ and FA skeleton. In EMZ, the

  10. Neodymium Isotopic Compositions of the Titanite Reference Materials Used in U-Pb Geochronology

    NASA Astrophysics Data System (ADS)

    Ma, Q.; Yang, Y.; Zhao, Z.

    2017-12-01

    Titanite (CaTiSiO5) is a widespread mineral and preferentially incorporates considerable uranium and significant light rare earth elements (LREEs) in its structure. Geochronology based upon U-Pb and Pb-Pb analyses of titanite has proven to be useful for understanding the P-T-t evolution of many igneous, metamorphic and hydrothermally altered rock samples (Scott and St-Onge, 1995). In the meantime, Sm-Nd isotopic composition in single titanite can be used to obtain initial Nd isotope composition at the time of titanite crystallization when combined with its U-Pb age, making titanite the most versatile mineral for dating metamorphism and tracing hydrothermal source (Amelin et al., 2009). The widely utilized in situ analyses by SIMS and LA-(MC)-ICP-MS have emphasized the significance for uniform and homogeneous reference materials for external correction (Liu et al., 2012, Sun et al., 2012, Yang et al., 2014). Here, we present U-Pb ages and Sm-Nd isotope analyses of twelve natural titanite crystals (12YQ82, T004, Ontario, BLR-1, OLT1, Khan, Qinghu, TLS-36, NW-IOA, C253, Pakistan and MKED1) acquired by Agilent 7500a Q-ICP-MS and Neptune MC-ICP-MS, respectively, combined a 193 nm ArF excimer laser ablation system. For U-Pb dating, elemental fractionation and instrumental drift were externally corrected using MKED1 titanite standard, showing results of U-Pb analyses all within error of those recommended values. With respect to Sm-Nd isotopes, we employed the interference-free 147Sm/149Sm to deduct 144Sm isobaric interference on 144Nd, and the fractionation between 147Sm and 144Nd was calibrated using BLR-1 titanite, which is proved homogenous in Sm-Nd isotopic system. The obtained Sm-Nd isotopic compositions for natural titanite samples are all consistent with those values determined by isotope dilution (ID) MC-ICP-MS, demonstrating the precision and accuracy currently available for in situ Sm-Nd analyses. Our results demonstrate that BLR-1, OLT1 and Ontario titanites

  11. Rainfall Type as a Dominant Control of the Isotopic Composition of Precipitation in the South Central United States

    NASA Astrophysics Data System (ADS)

    Sun, C.; Shanahan, T. M.; Partin, J. W.

    2017-12-01

    The processes that control the isotopic composition of precipitation in the mid-latitudes are understudied compared to the high and low latitudes, but are critical for interpreting paleo records using isotope proxies. To better understand these processes, we investigated changes of isotopic composition of rainwater in Central Texas using 20 months of event-based rainwater collection. We find that in both the event-based data and the monthly data from the Waco GNIP station, the dominant control on the isotopic composition of precipitation is the proportion that is derived from convective systems. This finding is consistent with previously reported data largely from tropical localities (Aggarwal et al., 2016), where large organized convective systems lead to high rainfall amounts and isotopically depleted precipitation. Although there are seasonal differences in the dominant rainfall types over the South Central US, with winter precipitation almost entirely stratiform, seasonality plays very little role in the net isotopic composition of precipitation because the total contribution during winter is small compared with spring, summer and fall. We also find that changes of source have little effect on the isotopic composition of rainfall, as the majority of the moisture is derived from the Gulf of Mexico with little influence of reevaporation or mixing. The majority of the warm season precipitation in the South Central US occurs in association with mesoscale convective systems (MCSs) and the development of these systems plays a critical role in the overall isotopic signature of precipitation. MCSs are characterized by a combination of intense, organized convection at their leading edges and trailing stratiform precipitation. Larger MCSs tend to contain higher proportions of stratiform rainfall and as a result, have isotopically depleted values. Proxy records from this region displaying more negative isotope values in the past should therefore be interpreted with

  12. Carbon, nitrogen, magnesium, silicon, and titanium isotopic compositions of single interstellar silicon carbide grains from the Murchison carbonaceous chondrite

    NASA Technical Reports Server (NTRS)

    Hoppe, Peter; Amari, Sachiko; Zinner, Ernst; Ireland, Trevor; Lewis, Roy S.

    1994-01-01

    Seven hundred and twenty SiC grains from the Murchison CM2 chondrite, ranging in size from 1 to 10 micrometers, were analyzed by ion microprobe mass spectrometry for their C-isotopic compositions. Subsets of the grains were also analyzed for N (450 grains), Si (183 grains), Mg (179 grains), and Ti (28 grains) isotopes. These results are compared with previous measurements on 41 larger SiC grains (up to 15 x 26 micrometers) from a different sample of Murchison analyzed by Virag et al. (1992) and Ireland, Zinner, & Amari (1991a). All grains of the present study are isotopically anomalous with C-12/C-13 ratios ranging from 0.022 to 28.4 x solar, N-14/N-15 ratios from 0.046 to 30 x solar, Si-29/Si-28 from 0.54 to 1.20 x solar, Si-30/Si-28 from 0.42 to 1.14 x solar, Ti-49/Ti-48 from 0.96 to 1.95 x solar, and Ti-50/Ti-48 from 0.94 to 1.39 x solar. Many grains have large Mg-26 excesses from the decay of Al-26 with inferred Al-26/Al-27 ratios ranging up to 0.61, or 12,200 x the ratio of 5 x 10(exp -5) inferred for the early solar system. Several groups can be distinguished among the SiC grains. Most of the grains have C-13 and N-14 excesses, and their Si isotopic compositions (mostly excesses in Si-29 and Si-30) plot close to a slope 1.34 line on a Delta Si-29/Si-28 versus Delta Si-30/Si-28 three-isotope plot. Grains with small C-12/C-13 ratios (less than 10) tend to have smaller or no N-14 excesses and high Al-26/Al-27 ratios (up to 0.01). Grains with C-12/C-13 greater than 150 fall into two groups: grains X have N-15 excesses and Si-29 and Si-30 deficits and the highest (0.1 to 0.6) Al-26/Al-27 ratios; grains Y have N-14 excesses and plot on a slope 0.35 line on a Si three-isotope plot. In addition, large SiC grains of the Virag et al. (1992) study fall into three-distinct clusters according to their C-, Si-, and Ti-isotopic compositions. The isotopic diversity of the grains and the clustering of their isotopic compositions imply distinct and multiple stellar sources

  13. Titanium and Oxygen Isotope Compositions of Individual Chondrules from Ordinary Chondrites

    NASA Astrophysics Data System (ADS)

    Bauer, K. K.; Schönbächler, M.; Fehr, M. A.; Vennemann, T.; Chaumard, N.; Zanda, B.

    2016-08-01

    We measured Ti and triple-O isotope compositions of individual chondrules (characterized by CT scanning) from ordinary chondrites. We will discuss correlations between Ti and ∆17O and their implication for the origin of nucleosynthetic anomalies.

  14. Quantifying the isotopic composition of NOx emission sources: An analysis of collection methods

    NASA Astrophysics Data System (ADS)

    Fibiger, D.; Hastings, M.

    2012-04-01

    We analyze various collection methods for nitrogen oxides, NOx (NO2 and NO), used to evaluate the nitrogen isotopic composition (δ15N). Atmospheric NOx is a major contributor to acid rain deposition upon its conversion to nitric acid; it also plays a significant role in determining air quality through the production of tropospheric ozone. NOx is released by both anthropogenic (fossil fuel combustion, biomass burning, aircraft emissions) and natural (lightning, biogenic production in soils) sources. Global concentrations of NOx are rising because of increased anthropogenic emissions, while natural source emissions also contribute significantly to the global NOx burden. The contributions of both natural and anthropogenic sources and their considerable variability in space and time make it difficult to attribute local NOx concentrations (and, thus, nitric acid) to a particular source. Several recent studies suggest that variability in the isotopic composition of nitric acid deposition is related to variability in the isotopic signatures of NOx emission sources. Nevertheless, the isotopic composition of most NOx sources has not been thoroughly constrained. Ultimately, the direct capture and quantification of the nitrogen isotopic signatures of NOx sources will allow for the tracing of NOx emissions sources and their impact on environmental quality. Moreover, this will provide a new means by which to verify emissions estimates and atmospheric models. We present laboratory results of methods used for capturing NOx from air into solution. A variety of methods have been used in field studies, but no independent laboratory verification of the efficiencies of these methods has been performed. When analyzing isotopic composition, it is important that NOx be collected quantitatively or the possibility of fractionation must be constrained. We have found that collection efficiency can vary widely under different conditions in the laboratory and fractionation does not vary

  15. A global algorithm for estimating Absolute Salinity

    NASA Astrophysics Data System (ADS)

    McDougall, T. J.; Jackett, D. R.; Millero, F. J.; Pawlowicz, R.; Barker, P. M.

    2012-12-01

    The International Thermodynamic Equation of Seawater - 2010 has defined the thermodynamic properties of seawater in terms of a new salinity variable, Absolute Salinity, which takes into account the spatial variation of the composition of seawater. Absolute Salinity more accurately reflects the effects of the dissolved material in seawater on the thermodynamic properties (particularly density) than does Practical Salinity. When a seawater sample has standard composition (i.e. the ratios of the constituents of sea salt are the same as those of surface water of the North Atlantic), Practical Salinity can be used to accurately evaluate the thermodynamic properties of seawater. When seawater is not of standard composition, Practical Salinity alone is not sufficient and the Absolute Salinity Anomaly needs to be estimated; this anomaly is as large as 0.025 g kg-1 in the northernmost North Pacific. Here we provide an algorithm for estimating Absolute Salinity Anomaly for any location (x, y, p) in the world ocean. To develop this algorithm, we used the Absolute Salinity Anomaly that is found by comparing the density calculated from Practical Salinity to the density measured in the laboratory. These estimates of Absolute Salinity Anomaly however are limited to the number of available observations (namely 811). In order to provide a practical method that can be used at any location in the world ocean, we take advantage of approximate relationships between Absolute Salinity Anomaly and silicate concentrations (which are available globally).

  16. Coordinated Petrography and Oxygen Isotopic Compositions of Al-Rich Chondrules from CV3 Chondrites

    NASA Astrophysics Data System (ADS)

    Zhang, M. M.; Lin, Y. T.; Tang, G. Q.; Li, X. H.

    2017-07-01

    In this study, we coordinated the petrology, bulk compositions and oxygen isotope compositions of 12 ARCs from Allende and Leoville and Ningqiang chondrites in order to elucidate any potential genetic relationships between ARCs, CAIs and FMCs.

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

    PubMed

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

    2009-03-01

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

  18. Thallium isotope composition of the upper continental crust and rivers - An investigation of the continental sources of dissolved marine thallium

    USGS Publications Warehouse

    Nielsen, S.G.; Rehkamper, M.; Porcelli, D.; Andersson, P.; Halliday, A.N.; Swarzenski, P.W.; Latkoczy, C.; Gunther, D.

    2005-01-01

    The thallium (Tl) concentrations and isotope compositions of various river and estuarine waters, suspended riverine particulates and loess have been determined. These data are used to evaluate whether weathering reactions are associated with significant Tl isotope fractionation and to estimate the average Tl isotope composition of the upper continental crust as well as the mean Tl concentration and isotope composition of river water. Such parameters provide key constraints on the dissolved Tl fluxes to the oceans from rivers and mineral aerosols. The Tl isotope data for loess and suspended riverine detritus are relatively uniform with a mean of ??205Tl = -2.0 ?? 0.3 (??205Tl represents the deviation of the 205Tl/203Tl isotope ratio of a sample from NIST SRM 997 Tl in parts per 104). For waters from four major and eight smaller rivers, the majority were found to have Tl concentrations between 1 and 7 ng/kg. Most have Tl isotope compositions very similar (within ??1.5 ??205Tl) to that deduced for the upper continental crust, which indicates that no significant Tl isotope fractionation occurs during weathering. Based on these results, it is estimated that rivers have a mean natural Tl concentration and isotope composition of 6 ?? 4 ng/kg and ??205Tl = -2.5 ?? 1.0, respectively. In the Amazon estuary, both additions and losses of Tl were observed, and these correlate with variations in Fe and Mn contents. The changes in Tl concentrations have much lower amplitudes, however, and are not associated with significant Tl isotope effects. In the Kalix estuary, the Tl concentrations and isotope compositions can be explained by two-component mixing between river water and a high-salinity end member that is enriched in Tl relative to seawater. These results indicate that Tl can display variable behavior in estuarine systems but large additions and losses of Tl were not observed in the present study. Copyright ?? 2005 Elsevier Ltd.

  19. Stable isotope compositions of gases and vegetation near naturally burning coal

    USGS Publications Warehouse

    Gleason, J.D.; Kyser, T.K.

    1984-01-01

    Our measurements of stable isotope compositions of CO2 issuing from vents produced by naturally burning coal indicate that the coal is oxidized through a kinetic process in which groundwater is the oxidizing agent. The CO2 produced by the oxidation of the coal is extremely depleted in 13C relative to normal atmospheric CO2. The change in the ??13C value of atmospheric CO2 near the vents resulting from the burning coal was not recorded in tree rings from red cedars, but the ??13C values of some C3 and C4 type plants collected from within the area were greatly affected. Our results indicate that the ??13C values of some species of plants may be sensitive indicators of changes in the carbon isotopic composition of atmospheric CO2. ?? 1984 Nature Publishing Group.

  20. Triple oxygen isotope composition of tropospheric carbon dioxide and terrestrial carbonates

    NASA Astrophysics Data System (ADS)

    Hofmann, M. E.; Horváth, B.; Pack, A.

    2011-12-01

    The triple oxygen isotope composition of tropospheric CO2 is a potential new tracer in urban air studies and for biosphere-atmosphere interactions [1]. In this study, we are analyzing CO2 from different provenances in order to trace the influx of anthropogenic CO2 to urban air and to test predictions on the stratosphere-troposphere exchange flux. Since July 2010, we are monitoring the triple oxygen isotope composition of CO2 in urban air in a two-week interval. For this purpose, carbon dioxide was extracted from ~450L of ambient air on the campus of the University of Göttingen using a Russian Doll type cryogenic trap [2]. The CO2 was analyzed by CO2-CeO2 equilibration at 685°C and subsequent IR laser fluorination of CeO2 and CF-irmMS [3]. All triple oxygen isotope data are reported as Δ17OTFL values relative to the terrestrial fractionation line (TFL) with a slope βTFL=0.5251 and an intercept γTFL=-0.014%. On average, the Δ17OTFL value of ambient CO2 was -0.11±0.05% (SD) with a seasonal cycle of 0.04±0.01%. Lower Δ17O values were observed during wintertime. In order to test the potential of Δ17O as a tracer for anthropogenic CO2, we analyzed CO2 from different combustion processes. Our results showed that the Δ17O anomaly of tropospheric O2 [4] is passed on fully, or partially to the combustion CO2 [5]. We estimate that elevated anthropogenic emission during wintertime could be responsible for a decrease in Δ17O of urban air CO2 of -0.02±0.01%. In order to predict the triple oxygen isotope composition of tropospheric CO2 on a global scale, we revised the box model calculation from Hoag et al. [1]. For the exponent β for CO2-water equilibrium, we assume that βCO2-water=0.522±0.001 [6]. Furthermore, we took into account that the Δ17OTFL value of CO2 released from soils is affected by kinetic fractionation. Thus, we obtained a Δ17OTFL value for global tropospheric CO2 of -0.13%. The model calculation agrees well with the Δ17OTFL value determined for

  1. Determination of the isotopic composition of evapotranspiration in a mature oil palm plantation in Jambi province, Indonesia.

    NASA Astrophysics Data System (ADS)

    Bonazza, Mattia; Meijide, Ana; Knohl, Alexander

    2017-04-01

    Evapotranspiration (ET) is defined as the sum of the water vapor fluxes from evaporation (E) and transpiration (T). The relative proportion between these two quantities depends on the species, on their age and on the structure of the stand and canopy. Evaporation represents the fraction of water that doesn't contribute to plants growth hence it often considered as "unused" water by the plants root system. For this reason, in a fast changing environment like Indonesia where, since almost 30 years, tropical rainforests are gradually converted into extensive oil palm plantation, it is important to quantify the amount of evaporated water to improve agricultural practices and water quality. As powerful tracers of the hydrological cycle, water stable isotopes represent an important tool to estimate the isotopic composition of the evapotranspiration flux and they can be used as a starting point for the determination of the T/ET ratio, which can be considered as a plant water uptake efficiency indicator. The isotopic composition (δDvand δ18Ov) and the mixing ratio (qv) of water vapor measured in a stand is the result of the isotopic mixing between two members; ecosystem evapotranspiration (δET) and background air (δa). With the implementation of laser-based isotopic analysers we are now able to improve the measurement frequency of δDvand δ18Ov that leads us to an improved estimation of δET. Here we present the results of a measurement campaign, performed with a Picarro L-2120i and conducted in a mature oil palm plantation in the province of Jambi, Indonesia. We measured the atmospheric water vapor mixing ratio and isotopic composition at 5 sampling heights (21 m, 16 m, 9 m, 3.5 and 0.3 m) along a flux tower throughout the oil palm canopy (average height 10 m). The range of the water vapor isotopic composition was between -19 and -11 and -134 and -82 ‰ for δ18Ov and δDvrespectively. A fairly open canopy structure resulted in small mixing ratio gradients along the

  2. Ca-,Al-rich inclusions in the unique chondrite ALH85085 - Petrology, chemistry, and isotopic compositions

    NASA Technical Reports Server (NTRS)

    Kimura, Makoto; El-Goresy, Ahmed; Palme, Herbert; Zinner, Ernst

    1993-01-01

    A comprehensive study is performed for the Ca-,Al-rich inclusions (CAIs) in the unique chondrite ALH85085. The ALH85085 inclusions are smaller (5-80 microns) and more refractory than their counterparts in carbonaceous chondrites. The study includes 42 inclusions for petrography and mineralogy, 15 for bulk major and minor element chemical composition, six for Mg-Al isotopic systematics, 10 for Ca isotopes, nine for Ti isotopes, and six for trace element abundances. In addition, oxygen-isotopic compositions were determined in minerals from a single inclusion. No correlation is found between mineralogy, major element chemistry, and trace element abundances. It is further shown that the high-temperature geochemical behavior of ultrarefractory trace elements is decoupled from that of the major elements Ca and Ti (Ti is correlated with the relatively volatile elements Nb and Yb) implying that perovskite is of only minor importance as carrier of ultrarefractories.

  3. Spurious and functional correlates of the isotopic composition of a generalist across a tropical rainforest landscape

    PubMed Central

    2009-01-01

    Background The isotopic composition of generalist consumers may be expected to vary in space as a consequence of spatial heterogeneity in isotope ratios, the abundance of resources, and competition. We aim to account for the spatial variation in the carbon and nitrogen isotopic composition of a generalized predatory species across a 500 ha. tropical rain forest landscape. We test competing models to account for relative influence of resources and competitors to the carbon and nitrogen isotopic enrichment of gypsy ants (Aphaenogaster araneoides), taking into account site-specific differences in baseline isotope ratios. Results We found that 75% of the variance in the fraction of 15N in the tissue of A. araneoides was accounted by one environmental parameter, the concentration of soil phosphorus. After taking into account landscape-scale variation in baseline resources, the most parsimonious model indicated that colony growth and leaf litter biomass accounted for nearly all of the variance in the δ15N discrimination factor, whereas the δ13C discrimination factor was most parsimoniously associated with colony size and the rate of leaf litter decomposition. There was no indication that competitor density or diversity accounted for spatial differences in the isotopic composition of gypsy ants. Conclusion Across a 500 ha. landscape, soil phosphorus accounted for spatial variation in baseline nitrogen isotope ratios. The δ15N discrimination factor of a higher order consumer in this food web was structured by bottom-up influences - the quantity and decomposition rate of leaf litter. Stable isotope studies on the trophic biology of consumers may benefit from explicit spatial design to account for edaphic properties that alter the baseline at fine spatial grains. PMID:19930701

  4. Compositional changes in the UCC through time revealed by tungsten isotopes

    NASA Astrophysics Data System (ADS)

    Mundl, A.; Walker, R. J.; Reimink, J. R.; Rudnick, R. L.; Gaschnig, R. M.

    2017-12-01

    During periods of glaciation, ice scrapes off large areas of Earth's surface. The resulting sediments, termed glacial diamictites, are typically little affected by chemical alteration during their accumulation and lithification. The fine-grained matrix of a diamictite can therefore provide important information about the average composition of a portion of the upper continental crust (UCC) preceding the time of its deposition. Major and trace element studies of diamictites have reported compositional changes in the UCC through Earth's history, documenting changes in its average lithology. Short-lived radiogenic isotope systems are useful tools to further study crustal evolution via diamictites, as small-scale 182W (182Hf → 182W, t½ = 8.9 Ma) and 142Nd (146Nd → 142Nd, t½= 103 Ma) anomalies may reflect mantle or crustal processes that occurred very early in Earth history. We have investigated 182W/184W ratios in thirteen glacial diamictite composites from four different continents. These rocks were deposited during the Archean (3.0 Ga), Proterozoic (2.4, 2.3, 2.2, 0.6 Ga) and Paleozoic (0.3 Ga) in South Africa, as well as during the Proterozoic (2.4, 0.7, 0.6 Ga) in North America, and the Paleozoic (0.3 Ga) in South America. Individual glacial diamictites sample multiple crustal sources, so the isotopic compositions of the diamictites are more representative of the UCC at the time of deposition, than the komatiites and early Archean supracrustal rocks, which have been the focus of most prior studies. Tungsten isotope compositions reveal well-resolved deficits in 182W/184W of as much as 14 ppm in three of the four Archean samples from South Africa. By contrast, there are no clearly resolved deficits in Paleoproterozoic diamictites from the same area, although results for multiple analyses of the same samples suggest that a small deficit of 6 ppm may be present. No anomalies are present in younger diamictites. The Archean diamictites provide additional evidence

  5. Coordinated Oxygen Isotopic and Petrologic Studies of CAIS Record Varying Composition of Protosolar

    NASA Technical Reports Server (NTRS)

    Simon, Justin I.; Matzel, J. E. P.; Simon, S. B.; Weber, P. K.; Grossman, L.; Ross, D. K.; Hutcheon, I. D.

    2012-01-01

    Ca-, Al-rich inclusions (CAIs) record the O-isotope composition of Solar nebular gas from which they grew [1]. High spatial resolution O-isotope measurements afforded by ion microprobe analysis across the rims and margin of CAIs reveal systematic variations in (Delta)O-17 and suggest formation from a diversity of nebular environments [2-4]. This heterogeneity has been explained by isotopic mixing between the O-16-rich Solar reservoir [6] and a second O-16-poor reservoir (probably nebular gas) with a "planetary-like" isotopic composition [e.g., 1, 6-7], but the mechanism and location(s) where these events occur within the protoplanetary disk remain uncertain. The orientation of large and systematic variations in (Delta)O-17 reported by [3] for a compact Type A CAI from the Efremovka reduced CV3 chondrite differs dramatically from reports by [4] of a similar CAI, A37 from the Allende oxidized CV3 chondrite. Both studies conclude that CAIs were exposed to distinct, nebular O-isotope reservoirs, implying the transfer of CAIs among different settings within the protoplanetary disk [4]. To test this hypothesis further and the extent of intra-CAI O-isotopic variation, a pristine compact Type A CAI, Ef-1 from Efremovka, and a Type B2 CAI, TS4 from Allende were studied. Our new results are equally intriguing because, collectively, O-isotopic zoning patterns in the CAIs indicate a progressive and cyclic record. The results imply that CAIs were commonly exposed to multiple environments of distinct gas during their formation. Numerical models help constrain conditions and duration of these events.

  6. ISOTOPE CONVERSION DEVICE

    DOEpatents

    Wigner, E.P.; Young, G.J.; Ohlinger, L.A.

    1957-12-01

    This patent relates to nuclear reactors of tbe type utilizing a liquid fuel and designed to convert a non-thermally fissionable isotope to a thermally fissionable isotope by neutron absorption. A tank containing a reactive composition of a thermally fissionable isotope dispersed in a liquid moderator is disposed within an outer tank containing a slurry of a non-thermally fissionable isotope convertible to a thermally fissionable isotope by neutron absorption. A control rod is used to control the chain reaction in the reactive composition and means are provided for circulating and cooling the reactive composition and slurry in separate circuits.

  7. Isotopic composition of hydrogen in insoluble organic matter from cherts

    NASA Technical Reports Server (NTRS)

    Krishnamurthy, R. V.; Epstein, S.

    1991-01-01

    Robert (1989) reported the presence of unusually enriched hydrogen in the insoluble HF-HCl residue extracted from two chert samples of Eocene and Pliocene ages. Since the presence of heavy hydrogen might be due to the incorporation of extraterrestrial materials, we desired to reexamine the same samples to isolate the D-rich components. Our experiments did not reveal any D-rich components, but the hydrogen isotope composition of the insoluble residue of the two chert samples was well within the range expected for terrestrial organic matter. We also describe a protocol that needs to be followed in the hydrogen isotope analysis of any insoluble organic matter.

  8. 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.

  9. Isotopic Composition of Trapped and Cosmogenic Noble Gases in Several Martian Meteorites

    NASA Technical Reports Server (NTRS)

    Garrison, Daniel H.; Bogard, Donald D.

    1997-01-01

    Isotopic abundances of the noble gases were measured in the following Martian meteorites: two shock glass inclusions from EET79001, shock vein glass from Shergotty and Y793605, and whole rock samples of ALH84001 and QUE94201. These glass samples, when combined with literature data on a separate single glass inclusion from EET79001 and a glass vein from Zagami, permit examination of the isotopic composition of Ne, Ar, Kr, and Xe trapped from the Martian atmosphere in greater detail. The isotopic composition of Martian Ne, if actually present in these glasses, remains poorly defined. The Ar-40/Ar-36 ratio of Martian atmospheric Ar may be much less than the ratio measured by Viking and possibly as low as approx. 1900. The atmospheric Ar-36/Ar-38 ratio is less than or equal to 4.0. Martian atmospheric Kr appears to be enriched in lighter isotopes by approx. 0.4%/amu compared to both solar wind Kr and to the Martian composition previously reported. The Martian atmospheric Ar-36/Xe-132 and Kr-84/Xe-132 Xe elemental ratios are higher than those reported by Viking by factors of approx. 3.3 and approx. 2.5, respectively. Cosmogenic gases indicate space exposure ages of 13.9 +/- 1 Myr for ALH84001 and 2.7 +/- 0.6 Myr for QUE94201. Small amounts of Ne-21 produced by energetic solar protons may be present in QUE94201, but are not present in ALH84001 or Y793605. The space exposure age for Y793605 is 4.9 +/- 0.6 Myr and appears to be distinctly older than the ages for basaltic shergottites.

  10. Tungsten residence in silicate rocks: implications for interpreting W isotopic compositions

    NASA Astrophysics Data System (ADS)

    Liu, J.; Pearson, G. D.; Chacko, T.; Luo, Y.

    2015-12-01

    High-precision measurements of W isotopic ratios have boosted recent exploration of early Earth processes from the small W isotope anomalies observable in some Hadean-Archean rocks. However, before applying W isotopic data to understand the geological processes responsible for the formation of these rocks, it is critical to evaluate whether the rocks' present W contents and isotopic compositions reflect that of the protolith or the effects of secondary W addition/mobilization. To investigate this issue, we have carried out in situ concentration measurements of W and other HFSEs in mineral phases and alteration assemblages within a broad spectrum of rocks using LA-ICP-MS. Isotope dilution whole-rock W concentration measurements are used along with modes calculated from mineral and bulk rock major element data to examine the mass balance for W and other elements. In general, W is positively correlated with Nb, Ta, Ti, Sn, Mo and U, indicating similar geochemical behavior. Within granitic gneisses and amphibolites, biotite, hornblende, titanite and ilmenite control the W budget, while plagioclase and k-feldspar have little effect. For granulites, pyroxenites and eclogites, titanite, rutile, ilmenite, magnetite and sulfide, as well as grain boundary alteration assemblages dominate the W budget, while garnet, clinopyroxene, orthopyroxene and plagioclase have little or no W. Within mantle harzburgites and dunites, major phases such as olivine, clinopyroxene, orthopyroxene and spinel/chromite have very low concentrations of W, Nb, Ta, Sn and Mo. Instead, these elements are concentrated along grain boundaries and within sulfide/mss. Mass balance shows that for granitic gneisses and amphibolites, the rock-forming minerals can adequately account for the whole-rock W budget, whereas for ultramafic rocks such as pyroxenites, eclogites and harzburgites and dunites, significant W is hosted along grain boundaries, indicating that metamorphism and melt/fluid metasomatism can

  11. Reassessment of the NH4 NO3 thermal decomposition technique for calibration of the N2 O isotopic composition.

    PubMed

    Mohn, Joachim; Gutjahr, Wilhelm; Toyoda, Sakae; Harris, Eliza; Ibraim, Erkan; Geilmann, Heike; Schleppi, Patrick; Kuhn, Thomas; Lehmann, Moritz F; Decock, Charlotte; Werner, Roland A; Yoshida, Naohiro; Brand, Willi A

    2016-09-08

    In the last few years, the study of N 2 O site-specific nitrogen isotope composition has been established as a powerful technique to disentangle N 2 O emission pathways. This trend has been accelerated by significant analytical progress in the field of isotope-ratio mass-spectrometry (IRMS) and more recently quantum cascade laser absorption spectroscopy (QCLAS). Methods The ammonium nitrate (NH 4 NO 3 ) decomposition technique provides a strategy to scale the 15 N site-specific (SP ≡ δ 15 N α - δ 15 N β ) and bulk (δ 15 N bulk  = (δ 15 N α  + δ 15 N β )/2) isotopic composition of N 2 O against the international standard for the 15 N/ 14 N isotope ratio (AIR-N 2 ). Within the current project 15 N fractionation effects during thermal decomposition of NH 4 NO 3 on the N 2 O site preference were studied using static and dynamic decomposition techniques. The validity of the NH 4 NO 3 decomposition technique to link NH 4 + and NO 3 - moiety-specific δ 15 N analysis by IRMS to the site-specific nitrogen isotopic composition of N 2 O was confirmed. However, the accuracy of this approach for the calibration of δ 15 N α and δ 15 N β values was found to be limited by non-quantitative NH 4 NO 3 decomposition in combination with substantially different isotope enrichment factors for the conversion of the NO 3 - or NH 4 + nitrogen atom into the α or β position of the N 2 O molecule. The study reveals that the completeness and reproducibility of the NH 4 NO 3 decomposition reaction currently confine the anchoring of N 2 O site-specific isotopic composition to the international isotope ratio scale AIR-N 2 . The authors suggest establishing a set of N 2 O isotope reference materials with appropriate site-specific isotopic composition, as community standards, to improve inter-laboratory compatibility. This article is protected by copyright. All rights reserved.

  12. Zinc isotope fractionation during mantle melting and constraints on the Zn isotope composition of Earth's upper mantle

    NASA Astrophysics Data System (ADS)

    Wang, Ze-Zhou; Liu, Sheng-Ao; Liu, Jingao; Huang, Jian; Xiao, Yan; Chu, Zhu-Yin; Zhao, Xin-Miao; Tang, Limei

    2017-02-01

    compositions of MORB. Therefore, preferential melting of spinel in the peridotites may account for the Zn isotopic difference between spinel peridotites and basalts. By contrast, the absence of Zn isotope fractionation between silicate minerals suggests that Zn isotopes are not significantly fractionated during partial melting of spinel-free garnet-facies mantle. If the studied non-metasomatized peridotites represent the refractory upper mantle, mass balance calculation shows that the depleted MORB mantle (DMM) has a δ66Zn value of +0.20 ± 0.05‰ (2SD), which is lighter than the primitive upper mantle (PUM) estimated in previous studies (+0.28 ± 0.05‰, 2SD, Chen et al., 2013b; +0.30 ± 0.07‰, 2SD, Doucet et al., 2016). This indicates that the Earth's upper mantle has a heterogeneous Zn isotopic composition vertically, which is probably due to shallow mantle melting processes.

  13. Natural calcium isotopic composition of urine as a marker of bone mineral balance.

    PubMed

    Skulan, Joseph; Bullen, Thomas; Anbar, Ariel D; Puzas, J Edward; Shackelford, Linda; LeBlanc, Adrian; Smith, Scott M

    2007-06-01

    We investigated whether changes in the natural isotopic composition of calcium in human urine track changes in net bone mineral balance, as predicted by a model of calcium isotopic behavior in vertebrates. If so, isotopic analysis of natural urine or blood calcium could be used to monitor short-term changes in bone mineral balance that cannot be detected with other techniques. Calcium isotopic compositions are expressed as delta(44)Ca, or the difference in parts per thousand between the (44)Ca/(40)Ca of a sample and the (44)Ca/(40)Ca of a standard reference material. delta(44)Ca was measured in urine samples from 10 persons who participated in a study of the effectiveness of countermeasures to bone loss in spaceflight, in which 17 weeks of bed rest was used to induce bone loss. Study participants were assigned to 1 of 3 treatment groups: controls received no treatment, one treatment group received alendronate, and another group performed resistive exercise. Measurements were made on urine samples collected before, at 2 or 3 points during, and after bed rest. Urine delta(44)Ca values during bed rest were lower in controls than in individuals treated with alendronate (P <0.05, ANOVA) or exercise (P <0.05), and lower than the control group baseline (P <0.05, t-test). Results were consistent with the model and with biochemical and bone mineral density data. Results confirm the predicted relationship between bone mineral balance and calcium isotopes, suggesting that calcium isotopic analysis of urine might be refined into a clinical and research tool.

  14. Iron isotope composition of particles produced by UV-femtosecond laser ablation of natural oxides, sulfides, and carbonates.

    PubMed

    d'Abzac, Francois-Xavier; Beard, Brian L; Czaja, Andrew D; Konishi, Hiromi; Schauer, James J; Johnson, Clark M

    2013-12-17

    The need for femtosecond laser ablation (fs-LA) systems coupled to MC-ICP-MS to accurately perform in situ stable isotope analyses remains an open question, because of the lack of knowledge concerning ablation-related isotopic fractionation in this regime. We report the first iron isotope analysis of size-resolved, laser-induced particles of natural magnetite, siderite, pyrrhotite, and pyrite, collected through cascade impaction, followed by analysis by solution nebulization MC-ICP-MS, as well as imaging using electron microscopy. Iron mass distributions are independent of mineralogy, and particle morphology includes both spheres and agglomerates for all ablated phases. X-ray spectroscopy shows elemental fractionation in siderite (C-rich agglomerates) and pyrrhotite/pyrite (S-rich spheres). We find an increase in (56)Fe/(54)Fe ratios of +2‰, +1.2‰, and +0.8‰ with increasing particle size for magnetite, siderite, and pyrrhotite, respectively. Fe isotope differences in size-sorted aerosols from pyrite ablation are not analytically resolvable. Experimental data are discussed using models of particles generation by Hergenröder and elemental/isotopic fractionation by Richter. We interpret the isotopic fractionation to be related to the iron condensation time scale, dependent on its saturation in the gas phase, as a function of mineral composition. Despite the isotopic variations across aerosol size fractions, total aerosol composition, as calculated from mass balance, confirms that fs-LA produces a stoichiometric sampling in terms of isotopic composition. Specifically, both elemental and isotopic fractionation are produced by particle generation processes and not by femtosecond laser-matter interactions. These results provide critical insights into the analytical requirements for laser-ablation-based stable isotope measurements of high-precision and accuracy in geological samples, including the importance of quantitative aerosol transport to the ICP.

  15. [Effect of microorganisms and seasonal factors on the isotope composition of organic carbon from Black Sea suspensions].

    PubMed

    Ivanov, M V; Lein, A Iu; Miller, Iu M; Iusunov, S K; Pimenov, N V; Wehrli, B; Rusanov, I I; Zehnder, A

    2000-01-01

    The isotopic composition of particulate organic carbon (POC) from the Black Sea deep-water zone was studied during a Russian-Swiss expedition in May 1998. POC from the upper part of the hydrogen sulfide zone (the C-layer) was found to be considerably enriched with the 12C isotope, as compared to the POC of the oxycline and anaerobic zone. In the C-layer waters, the concurrent presence of dissolved oxygen and hydrogen sulfide and an increased rate of dark CO2 fixation were recorded, suggesting that the change in the POC isotopic composition occurs at the expense of newly formed isotopically light organic matter of the biomass of autotrophic bacteria involved in the sulfur cycle. In the anaerobic waters below the C-layer, the organic matter of the biomass of autotrophs is consumed by the community of heterotrophic microorganisms; this results in weighting of the POC isotopic composition. Analysis of the data obtained and data available in the literature allows an inference to be made about the considerable seasonable variability of the POC delta 13C value, which depends on the ratio of terrigenic and planktonogenic components in the particulate organic matter.

  16. Uniformity in sulfur isotope composition in the orogenic gold deposits from the Dharwar Craton, southern India

    NASA Astrophysics Data System (ADS)

    Sakthi Saravanan, C.; Mishra, B.

    2009-07-01

    The sulfur isotope composition of sulfides (mainly pyrite and arsenopyrite) from gold deposits/prospects of the Dharwar Craton such as Hutti, Hira-Buddini, Uti, Kolar (Chigargunta), Ajjanahalli, and Jonnagiri has a narrow range (δ34S = +1.1 to +7.1‰). Such craton-scale uniformity of the above gold camps is noteworthy, in spite of the wide diversity in host rock compositions and their metamorphic conditions, and suggests a magmatic or average crustal source of sulfur for all deposits studied. In addition, our study points towards gold precipitation from reduced ore fluids, with near-homogeneous sulfur isotope compositions.

  17. BOREAS TE-5 CO2 Concentration and Stable Isotope Composition

    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 data set contains measurements of the concentration and stable carbon (C-13/C-12 and oxygen (O-18/O-16) isotope ratios of atmospheric CO2 in air samples collected at different heights within forest canopies. The data were collected to determine the influence of photosynthesis and respiration by the forest ecosystems on the concentration and stable isotope ratio of atmospheric CO2 These measurements were collected at the SSA during each 1994 IFC at OJP, OBS, and OA sites. Measurements were also collected at the NSA during each 1994 IFC at the OJP, T6R5S TE UBS, and T2Q6A TE OA sites. The stable isotope ratios are expressed using standard delta notation and in units of per mil. The isotope ratios are expressed relative to the international standard, PDB, for both carbon and oxygen samples. 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 Activity Archive Center (DAAC).

  18. Containing arsenic-enriched groundwater tracing lead isotopic compositions of common arsenical pesticides in a coastal Maine watershed

    USGS Publications Warehouse

    Ayuso, Robert A.; Foley, Nora K.; Robinson, Glipin R.; Colvin, A.S.; Lipfert, G.; Reeve, A.S.

    2006-01-01

    Arsenical pesticides and herbicides were extensively used on apple, blueberry, and potato crops in New England during the first half of the twentieth century. Lead arsenate was the most heavily used arsenical pesticide until it was officially banned. Lead arsenate, calcium arsenate, and sodium arsenate have similar Pb isotope compositions: 208Pb207Pb = 2.3839-2.4722, and 206Pb207Pb = 1.1035-1.2010. Other arsenical pesticides such as copper acetoarsenite (Paris green), methyl arsonic acid and methane arsonic acid, as well as arsanilic acid are widely variable in isotope composition. Although a complete understanding of the effects of historical use of arsenical pesticides is not available, initial studies indicate that arsenic and lead concentrations in stream sediments in New England are higher in agricultural areas that intensely used arsenical pesticides than in other areas. The Pb isotope compositions of pesticides partially overlap values of stream sediments from areas with the most extensive agricultural use. The lingering effects of arsenical pesticide use were tested in a detailed geochemical and isotopic study of soil profiles from a watershed containing arsenic-enriched ground water in coastal Maine. Acid-leach compositions of the soils represent lead adsorbed to mineral surfaces or held in soluble minerals (Fe- and Mn-hydroxides, carbonate, and some micaceous minerals), whereas residue compositions likely reflect bedrock compositions. The soil profiles contain labile Pb (acid-leach) showing a moderate range in 206Pb 207Pb (1.1870-1.2069), and 208Pb207Pb (2.4519-2.4876). Isotope values vary as a function of depth: the lowest Pb isotope ratios (e.g.,208Pb206Pb) representing labile lead are in the uppermost soil horizons. Lead contents decrease with depth in the soil profiles. Arsenic contents show no clear trend with depth. A multi-component mixing scheme that included lead from the local parent rock (Penobscot Formation), lead derived from combustion of

  19. Hydrogen isotope composition of leaf wax n-alkanes in Arabidopsis lines with different transpiration rates

    NASA Astrophysics Data System (ADS)

    Pedentchouk, N.; Lawson, T.; Eley, Y.; McAusland, L.

    2012-04-01

    Stable isotopic compositions of oxygen and hydrogen are used widely to investigate modern and ancient water cycles. The D/H composition of organic compounds derived from terrestrial plants has recently attracted significant attention as a proxy for palaeohydrology. However, the role of various plant physiological and biochemical factors in controlling the D/H signature of leaf wax lipids in extant plants remains unclear. The focus of this study is to investigate the effect of plant transpiration on the D/H composition of n-alkanes in terrestrial plants. This experiment includes 4 varieties of Arabidopsis thaliana that differ with respect to stomatal density and stomatal geometry. All 4 varieties were grown indoors under identical temperature, relative humidity, light and watering regimes and then sampled for leaf wax and leaf water stable isotopic measurements. During growth, stomatal conductance to carbon dioxide and water vapour were also determined. We found that the plants varied significantly in terms of their transpiration rates. Transpiration rates were significantly higher in Arabidopsis ost1 and ost1-1 varieties (2.4 and 3.2 mmol m-2 s-1, respectively) than in Arabidopsis RbohD and Col-0 (1.5 and 1.4). However, hydrogen isotope measurements of n-alkanes extracted from leaf waxes revealed a very different pattern. Varieties ost1, ost1-1, and RbohD have very similar deltaD values of n-C29 alkane (-125, -128, and -127 per mil), whereas the deltaD value of Col-0 is more negative (-137 per mil). The initial results of this work suggest that plant transpiration is decoupled from the D/H composition of n-alkanes. In other words, physical processes that affect water vapour movement between the plant and its environment apparently cannot account for the stable hydrogen isotope composition of organic compounds that comprise leaf waxes. Additional, perhaps biochemical, processes that affect hydrogen isotope fractionation during photosynthesis might need to be invoked

  20. Stable-Carbon Isotopic Composition of Maple Sap and Foliage 1

    PubMed Central

    Leavitt, Steven W.; Long, Austin

    1985-01-01

    The 13C/12C ratios of Acer grandidentatum sap sugar collected during the dormant period are compared to those of buds, leaves, and wood developed over the following growing season. As the primary carbon source for cellulose manufacture at initiation of annual growth in deciduous trees, sap sucrose would be expected to have an isotopic composition similar to first-formed cellulose. Although constancy in concentration and 13C/12C ratios of the maple sap sugar suggests any gains or losses (e.g. to maintenance metabolism) do not appreciably alter composition, the 13C/12C ratios of cellulose of the enlarging buds in the spring are quite distinct from those of the sap sugar, seemingly precluding a simple direct biochemical pathway of sap sucrose→glucose→cellulose in favor of a more complex pathway with greater likelihood of isotopic fractionation. The 13C/12C ratios of the leaves and in the growth ring were initially similar to the sap sugar but decreased steadily over the growing season. PMID:16664259

  1. The Effect of Phytase on the Oxygen Isotope Composition of Phosphate

    NASA Astrophysics Data System (ADS)

    von Sperber, C.; Tamburini, F.; Bernasconi, S. M.; Frossard, E.

    2013-12-01

    Plants and microorganisms under phosphorus (P) stress release extracellular phosphatases as a strategy to acquire inorganic phosphate (Pi) (1-2). These enzymes catalyze the hydrolysis of phosphoesters leading to a release of Pi. The enzymatic hydrolysis leads, via a nucleophilic attack, to the incorporation of one oxygen atom from the water into the newly formed Pi molecule. During the incorporation, an isotopic fractionation occurs, which might be used to identify the origin of Pi in the environment (3-6). While the effect of phosphomonoesterases and phosphodiesterases on the oxygen isotope composition of phosphate has been examined, there are, so far, no studies dealing with the effect of phytases (4-6). Phytases catalyze the hydrolysis of myo-inositol-hexakis-phosphate (IP6), which is an important component of organic P in many ecosystems (7). Enzymatic assays with phytase from wheat germ and Aspergillus niger were prepared under sterile and temperature controlled conditions in order to determine the effect of phytases on the oxygen isotope composition of phosphate, which has been liberated from IP6 via enzymatic hydrolysis. Assays with phytase from wheat germ lead to a turnover of the substrate close to 100%, while assays with phytase from Aspergillus niger lead to a turnover of the substrate close to 80%. In the case of the assays with phytase from wheat germ, our results indicate that one sixth of the total 24 oxygen which are associated to the phosphates in IP6 are exchanged with oxygen from water. From this we conclude that the incorporation of one oxygen atom from water occurs only at four phosphate molecules of IP6, while two phosphate molecules do not experience an incorporation of oxygen. This suggests that during the enzymatic hydrolysis, four P-O bonds and two C-O bonds are broken. Provided that, the isotopic fractionation can be calculated with an isotopic mass balance resulting in -8.4‰ (×3.6 SD). This is a value very similar to those reported

  2. Heterogeneity of the Caribbean plateau mantle source: Sr, O and He isotopic compositions of olivine and clinopyroxene from Gorgona Island

    NASA Astrophysics Data System (ADS)

    Révillon, S.; Chauvel, C.; Arndt, N. T.; Pik, R.; Martineau, F.; Fourcade, S.; Marty, B.

    2002-12-01

    The composition of the mantle plumes that created large oceanic plateaus such as Ontong Java or the Caribbean is still poorly known. Geochemical and isotopic studies on accreted portions of the Caribbean plateau have shown that the plume source was heterogeneous and contained isotopically depleted and relatively enriched portions. A distinctive feature of samples from the Caribbean plateau is their unusual Sr isotopic compositions, which, at a given Nd isotopic ratio, are far higher than in samples from other oceanic plateaus. Sr, O and He isotopic compositions of whole rocks and magmatic minerals (clinopyroxene or olivine) separated from komatiites, gabbros and peridotites from Gorgona Island in Colombia were determined to investigate the origin of these anomalously radiogenic compositions. Sequentially leached clinopyroxenes have Sr isotopic compositions in the range 87Sr/ 86Sr=0.70271-0.70352, systematically lower than those of leached and unleached whole rocks. Oxygen isotopic ratios of clinopyroxene vary within the range δ 18O=5.18-5.35‰, similar to that recorded in oceanic island basalts. He isotopic ratios are high ( R/ Ra=8-19). The lower 87Sr/ 86Sr ratios of most of the clinopyroxenes shift the field of the Caribbean plateau in Nd-Sr isotope diagrams toward more 'normal' values, i.e. a position closer to the field defined by mid-ocean ridge basalts and oceanic-island basalts. Three clinopyroxenes have slightly higher 87Sr/ 86Sr ratios that cannot be explained by an assimilation model. The high 87Sr/ 86Sr and variations of 143Nd/ 144Nd are interpreted as a source characteristic. Trace-element ratios, however, are controlled mainly by fractionation during partial melting. We combine these isotopic data in a heterogeneous plume source model that accounts for the diversity of isotopic signatures recorded on Gorgona Island and throughout the Caribbean plateau. The heterogeneities are related to old recycled oceanic lithosphere in the plume source; the high 3

  3. 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

  4. Spectroscopic metrology for isotope composition measurements and transfer standards

    NASA Astrophysics Data System (ADS)

    Anyangwe Nwaboh, Javis; Balslev-Harder, David; Kääriäinen, Teemu; Richmond, Craig; Manninen, Albert; Mohn, Joachim; Kiseleva, Maria; Petersen, Jan C.; Werhahn, Olav; Ebert, Volker

    2017-04-01

    The World Meteorological Organization (WMO) has identified greenhouse gases such as CO2, CH4 and N2O as critical for global climate monitoring. Other molecules such as CO that has an indirect effect of enhancing global warming are also monitored. WMO has stated compatibility goals for atmospheric concentration and isotope ratio measurements of these gases, e.g. 0.1 ppm for CO2 concentration measurements in the northern hemisphere and 0.01 ‰ for δ13C-CO2. For measurements of the concentration of greenhouse gases, gas analysers are typically calibrated with static gas standards e.g. traceable to the WMO scale or to the International System of Units (SI) through a national metrology institute. However, concentrations of target components, e.g. CO, in static gas standards have been observed to drift, and typically the gas matrix as well as the isotopic composition of the target component does not always reflect field gas composition, leading to deviations of the analyser response, even after calibration. The deviations are dependent on the measurement technique. To address this issue, part of the HIGHGAS (Metrology for high-impact greenhouse gases) project [1] focused on the development of optical transfer standards (OTSs) for greenhouse gases, e.g. CO2 and CO, potentially complementing gas standards. Isotope ratio mass spectrometry (IRMS) [2] is currently used to provide state-of-the-art high precision (in the 0.01 ‰ range) measurements for the isotopic composition of greenhouse gases. However, there is a need for field-deployable techniques such as optical isotope ratio spectroscopy (OIRS) that can be combined with metrological measurement methods. Within the HIGHGAS project, OIRS methods and procedures based on e.g. cavity enhanced spectroscopy (CES) and tunable diode laser absorption spectroscopy (TDLAS), matched to metrological principles have been established for the measurement of 13C/12C and 18O/16O ratios in CO2, 15N/14N ratios in N2O, and 13C/12C and 2H

  5. The silicon isotopic composition of fine-grained river sediments and its relation to climate and lithology

    NASA Astrophysics Data System (ADS)

    Bayon, G.; Delvigne, C.; Ponzevera, E.; Borges, A. V.; Darchambeau, F.; De Deckker, P.; Lambert, T.; Monin, L.; Toucanne, S.; André, L.

    2018-05-01

    The δ30Si stable isotopic composition of silicon in soils and fine-grained sediments can provide insights into weathering processes on continents, with important implications on the Si budget of modern and past oceans. To further constrain the factors controlling the distribution of Si isotopes in sediments, we have analysed a large number (n = 50) of separate size-fractions of sediments and suspended particulate materials collected near the mouth of rivers worldwide. This includes some of the world's largest rivers (e.g. Amazon, Congo, Mackenzie, Mississippi, Murray-Darling, Nile, Yangtze) and rivers from the case study areas of the Congo River Basin and Northern Ireland. Silt-size fractions exhibit a mean Si isotopic composition (δ30Si = -0.21 ± 0.19‰; 2 s.d.) similar to that previously inferred for the upper continental crust. In contrast, clay-size fractions display a much larger range of δ30Si values from -0.11‰ to -2.16‰, which yield a global δ30Siclay of -0.57 ± 0.60‰ (2 s.d.) representative of the mean composition of the average weathered continental crust. Overall, these new data show that the Si isotopic signature transported by river clays is controlled by the degree of chemical weathering, as inferred from strong relationships with Al/Si ratios. At a global scale, the clay-bound Si isotopic composition of the world's largest river systems demonstrates a link with climate, defining a general correlation with mean annual temperature (MAT) in corresponding drainage basins. While the distribution of Si isotopes in river sediments also appears to be influenced by the tectonic setting, lithological effects and sediment recycling from former sedimentary cycles, our results pave the way for their use as paleo-weathering and paleo-climate proxies in the sedimentary record.

  6. Lead isotope studies of the Guerrero composite terrane, west-central Mexico: implications for ore genesis

    NASA Astrophysics Data System (ADS)

    Potra, Adriana; Macfarlane, Andrew W.

    2014-01-01

    New thermal ionization mass spectrometry and multi-collector inductively coupled plasma mass spectrometry Pb isotope analyses of three Cenozoic ores from the La Verde porphyry copper deposit located in the Zihuatanejo-Huetamo subterrane of the Guerrero composite terrane are presented and the metal sources are evaluated. Lead isotope ratios of 3 Cenozoic ores from the El Malacate and La Esmeralda porphyry copper deposits located in the Zihuatanejo-Huetamo subterrane and of 14 ores from the Zimapan and La Negra skarn deposits from the adjoining Sierra Madre terrane are also presented to look for systematic differences in the lead isotope trends and ore metal sources among the proposed exotic tectonostratigraphic terranes of southern Mexico. Comparison among the isotopic signatures of ores from the Sierra Madre terrane and distinct subterranes of the Guerrero terrane supports the idea that there is no direct correlation between the distinct suspect terranes of Mexico and the isotopic signatures of the associated Cenozoic ores. Rather, these Pb isotope patterns are interpreted to reflect increasing crustal contribution to mantle-derived magmas as the arc advanced eastward onto a progressively thicker continental crust. The lead isotope trend observed in Cenozoic ores is not recognized in the ores from Mesozoic volcanogenic massive sulfide and sedimentary exhalative deposits. The Mesozoic ores formed prior to the amalgamation of the Guerrero composite terrane to the continental margin, which took place during the Late Cretaceous, in intraoceanic island arc and intracontinental marginal basin settings, while the Tertiary deposits formed after this event in a continental arc setting. Lead isotope ratios of the Mesozoic and Cenozoic ores appear to reflect these differences in tectonic setting of ore formation. Most Pb isotope values of ores from the La Verde deposit (206Pb/204Pb = 18.674-18.719) are less radiogenic than those of the host igneous rocks, but plot within the

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

    NASA Astrophysics Data System (ADS)

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

    1986-09-01

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

  8. The influence of kinetics on the oxygen isotope composition of calcium carbonate

    NASA Astrophysics Data System (ADS)

    Watkins, James M.; Nielsen, Laura C.; Ryerson, Frederick J.; DePaolo, Donald J.

    2013-08-01

    Paleotemperature reconstructions rely on knowledge of the equilibrium separation of oxygen isotopes between aqueous solution and calcium carbonate. Although oxygen isotope separation is expected on theoretical grounds, the temperature-dependence remains uncertain because other factors, such as slow exchange of isotopes between dissolved CO2-species and water, can obscure the temperature signal. This is problematic for crystal growth experiments on laboratory timescales and for interpreting the oxygen isotope composition of crystals formed in natural settings. We present results from experiments in which inorganic calcite is precipitated in the presence of 0.25 μM dissolved bovine carbonic anhydrase (CA). The presence of dissolved CA accelerates oxygen isotope equilibration between the dissolved carbon species CO2, H2CO3, HCO3-, CO32- and water, thereby eliminating this source of isotopic disequilibrium during calcite growth. The experimental results allow us to isolate, for the first time, kinetic oxygen isotope effects occurring at the calcite-water interface. We present a framework of ion-by-ion growth of calcite that reconciles our new measurements with measurements of natural cave calcites that are the best candidate for having precipitated under near-equilibrium conditions. Our findings suggest that isotopic equilibrium between calcite and water is unlikely to have been established in laboratory experiments or in many natural settings. The use of CA in carbonate precipitation experiments offers new opportunities to refine oxygen isotope-based geothermometers and to interrogate environmental variables other than temperature that influence calcite growth rates.

  9. Variable Isotopic Compositions of Host Plant Populations Preclude Assessment of Aphid Overwintering Sites

    PubMed Central

    Voegtlin, David J.; Hamilton, Krista L.; Hogg, David B.

    2017-01-01

    Soybean aphid (Aphis glycines Matsumura) is a pest of soybean in the northern Midwest whose migratory patterns have been difficult to quantify. Improved knowledge of soybean aphid overwintering sites could facilitate the development of control efforts with exponential impacts on aphid densities on a regional scale. In this preliminary study, we explored the utility of variation in stable isotopes of carbon and nitrogen to distinguish soybean aphid overwintering origins. We compared variation in bulk 13C and 15N content in buckthorn (Rhamnus cathartica L.) and soybean aphids in Wisconsin, among known overwintering locations in the northern Midwest. Specifically, we looked for associations between buckthorn and environmental variables that could aid in identifying overwintering habitats. We detected significant evidence of correlation between the bulk 13C and 15N signals of soybean aphids and buckthorn, despite high variability in stable isotope composition within and among buckthorn plants. Further, the 15N signal in buckthorn varied predictably with soil composition. However, lack of sufficient differentiation of geographic areas along axes of isotopic and environmental variation appears to preclude the use of carbon and nitrogen isotopic signals as effective predictors of likely aphid overwintering sites. These preliminary data suggest the need for future work that can further account for variability in 13C and 15N within/among buckthorn plants, and that explores the utility of other stable isotopes in assessing likely aphid overwintering sites. PMID:29206134

  10. Soil moisture effects on the carbon isotopic composition of soil respiration

    EPA Science Inventory

    The carbon isotopic composition ( 13C) of recently assimilated plant carbon is known to depend on water-stress, caused either by low soil moisture or by low atmospheric humidity. Air humidity has also been shown to correlate with the 13C of soil respiration, which suggests indir...

  11. Hydrogen Isotopic Composition of Apatite in Northwest Africa 7034: A Record of the "Intermediate" H-Isotopic Reservoir in the Martian Crust?

    NASA Technical Reports Server (NTRS)

    McCubbin, F. M.; Barnes, J. J.; Santos, A. R.; Boyce, J. W.; Anand, M.; Franchi, I. A.; Agee, C. B.

    2016-01-01

    Northwest Africa (NWA) 7034 and its pairings comprise a regolith breccia with a basaltic bulk composition [1] that yields a better match than any other martian meteorite to visible-infrared reflectance spectra of the martian surface measured from orbit [2]. The composition of the fine-grained matrix within NWA 7034 bears a striking resemblance to the major element composition estimated for the martian crust, with several exceptions. The NWA 7034 matrix is depleted in Fe, Ti, and Cr and enriched in Al, Na, and P [3]. The differences in Al and Fe are the most substantial, but the Fe content of NWA 7034 matrix falls within the range reported for the southern highlands crust [6]. It was previously suggested by [4] that NWA 7034 was sourced from the southern highlands based on the ancient 4.4 Ga ages recorded in NWA 7034/7533 zircons [4, 5]. In addition, the NWA 7034 matrix material is enriched in incompatible trace elements by a factor of 1.2-1.5 [7] relative to estimates of the bulk martian crust. The La/Yb ratio of the bulk martian crust is estimated to be approximately 3 [7], and the La/Yb of the NWA 7034 matrix materials ranges from approximately 3.9 to 4.4 [3, 8], indicating a higher degree of LREE enrichment in the NWA 7034 matrix materials. This elevated La/Yb ratio and enrichment in incompatible lithophile trace elements is consistent with NWA 7034 representing a more geochemically enriched crustal terrain than is represented by the bulk martian crust, which would be expected if NWA 7034 represents the bulk crust from the southern highlands. Given the similarities between NWA 7034 and the martian crust, NWA 7034 may represent an important sample for constraining the composition of the martian crust, particularly the ancient highlands. In the present study, we seek to constrain the H isotopic composition of the martian crust using Cl-rich apatite in NWA 7034. Usui et al., [9] recently proposed that a H isotopic reservoir exists within the martian crust that has

  12. Extreme Hf-Os Isotope Compositions in Hawaiian Peridotite Xenoliths: Evidence for an Ancient Recycled Lithosphere

    NASA Astrophysics Data System (ADS)

    Bizimis, M.; Lassiter, J. C.; Salters, V. J.; Sen, G.; Griselin, M.

    2004-12-01

    We report on the first combined Hf-Os isotope systematics of spinel peridotite xenoliths from the Salt Lake Crater (SLC), Pali and Kaau (PK) vents from the island of Oahu, Hawaii. These peridotites are thought to represent the Pacific oceanic lithosphere beneath Oahu, as residues of MORB-type melting at a paleo-ridge some 80-100Ma ago. Clinopyroxene mineral separates in these peridotites have very similar Nd and Sr isotope compositions with the post erosional Honolulu Volcanics (HV) lavas that bring these xenoliths to the surface. This and their relatively elevated Na and LREE contents suggest that these peridotites are not simple residues of MORB-type melting but have experience some metasomatic enrichment by the host HV lavas. However, the SLC and PK xenoliths show an extreme range in Hf isotope compositions towards highly radiogenic values (ɛ Hf= 7-80), at nearly constant Nd isotope compositions (ɛ Nd= 7-10), unlike any OIB or MORB basalt. Furthermore, these Oahu peridotites show a bimodal distribution in their bulk rock 187Os/186Os ratios: the PK peridotites have similar ratios to the abyssal peridotites (0.130-0.1238), while the SLC peridotites have highly subchondritic ratios (0.1237-0.1134) that yield 500Ma to 2Ga Re-depletion ages. Hf-Os isotopes show a broad negative correlation whereby the samples with the most radiogenic 176Hf/177Hf have the most unradiogenic 187Os/186Os ratios. Based on their combined Hf-Os-Nd isotope and major element compositions, the PK peridotites can be interpreted as fragments of the Hawaiian lithosphere, residue of MORB melting 80-100Ma ago, that have been variably metasomatized by the host HV lavas. In contrast, the extreme Hf-Os isotope compositions of the SLC peridotites suggest that they cannot be the source nor residue of any kind of Hawaiian lavas, and that Hf and Os isotopes survived the metasomatism or melt-rock reaction that has overprinted the Nd and Sr isotope compositions of these peridotites. The ancient (>1Ga

  13. [Quantitative estimation source of urban atmospheric CO2 by carbon isotope composition].

    PubMed

    Liu, Wei; Wei, Nan-Nan; Wang, Guang-Hua; Yao, Jian; Zeng, You-Shi; Fan, Xue-Bo; Geng, Yan-Hong; Li, Yan

    2012-04-01

    To effectively reduce urban carbon emissions and verify the effectiveness of currently project for urban carbon emission reduction, quantitative estimation sources of urban atmospheric CO2 correctly is necessary. Since little fractionation of carbon isotope exists in the transportation from pollution sources to the receptor, the carbon isotope composition can be used for source apportionment. In the present study, a method was established to quantitatively estimate the source of urban atmospheric CO2 by the carbon isotope composition. Both diurnal and height variations of concentrations of CO2 derived from biomass, vehicle exhaust and coal burning were further determined for atmospheric CO2 in Jiading district of Shanghai. Biomass-derived CO2 accounts for the largest portion of atmospheric CO2. The concentrations of CO2 derived from the coal burning are larger in the night-time (00:00, 04:00 and 20:00) than in the daytime (08:00, 12:00 and 16:00), and increase with the increase of height. Those derived from the vehicle exhaust decrease with the height increase. The diurnal and height variations of sources reflect the emission and transport characteristics of atmospheric CO2 in Jiading district of Shanghai.

  14. Stable isotope composition of waters in the Great Basin, United States 1. Air-mass trajectories

    USGS Publications Warehouse

    Friedman, I.; Harris, J.M.; Smith, G.I.; Johnson, C.A.

    2002-01-01

    Isentropic trajectories, calculated using the NOAA/Climate Monitoring and Diagnostics Laboratory's isentropic transport model, were used to determine air-parcel origins and the influence of air mass trajectories on the isotopic composition of precipitation events that occurred between October 1991 and September 1993 at Cedar City, Utah, and Winnemucca, Nevada. Examination of trajectories that trace the position of air parcels backward in time for 10 days indicated five distinct regions of water vapor origin: (1) Gulf of Alaska and North Pacific, (2) central Pacific, (3) tropical Pacific, (4) Gulf of Mexico, and (5) continental land mass. Deuterium (??D) and oxygen-18 (??18O) analyses were made of precipitation representing 99% of all Cedar City events. Similar analyses were made on precipitation representing 66% of the precipitation falling at Winnemucca during the same period. The average isotopic composition of precipitation derived from each water vapor source was determined. More than half of the precipitation that fell at both sites during the study period originated in the tropical Pacific and traveled northeast to the Great Basin; only a small proportion traversed the Sierra Nevada. The isotopic composition of precipitation is determined by air-mass origin and its track to the collection station, mechanism of droplet formation, reequilibration within clouds, and evaporation during its passage from cloud to ground. The Rayleigh distillation model can explain the changes in isotopic composition of precipitation as an air mass is cooled pseudo-adiabatically during uplift. However, the complicated processes that take place in the rapidly convecting environment of cumulonimbus and other clouds that are common in the Great Basin, especially in summer, require modification of this model because raindrops that form in the lower portion of those clouds undergo isotopic change as they are elevated to upper levels of the clouds from where they eventually drop to the

  15. Detection of phosphohydrolytic enzyme activity through the oxygen isotope composition of dissolved phosphate

    NASA Astrophysics Data System (ADS)

    Colman, A. S.

    2016-02-01

    Phosphohydrolytic enzymes play an important role in phosphorus remineralization. As they release phosphate (Pi) from various organophosphorus compounds, these enzymes facilitate the transfer of oxygen atoms from water to the phosphoryl moieties. Most such enzymatic reactions impart a significant isotopic fractionation to the oxygen transferred. If this reaction occurs within a cell, then the resultant oxygen isotope signal is overprinted by continued recycling of the Pi. However, if this reaction occurs extracellularly, then the isotopic signal will be preserved until the Pi is transported back into a cell. Thus, the oxygen isotope composition of Pi (δ18Op) in an aquatic ecosystem can serve as a useful indicator of the mechanisms by which P is remineralized. We develop a time-dependent model illustrating the sensitivity of the δ18O of dissolved phosphate to various modes of P remineralization. The model is informed by cell lysis experiments that reveal the relative proportions of P­i that are directly liberated from cytosol vs. regenerated from co-liberated dissolved organic phosphorus compounds via extracellular hydrolysis. By incorporating both cellular uptake and release fluxes of P, we show that the degree of isotopic disequilibrium in an aquatic ecosystem can be a strong indicator of P remineralization mode. Apparent oxygen isotope equilibrium between Pi and water arises in this model as a steady-state scenario in which fractionation upon cellular uptake of Pi counterbalances the hydrolytic source flux of disequilibrated Pi. Low and high rates of extracellular phosphohydrolase activity are shown to produce steady-state δ18Op values that are respectively above or below thermodynamic equilibrium compositions.

  16. About Tagish Lake as a Potential Parent Body for Polar Micrometeorites; Clues from their Hydrogen Isotopic Compositions

    NASA Technical Reports Server (NTRS)

    Engrand, C.; Gounelle, M.; Zolensky, M. E.; Duprat, J.

    2003-01-01

    The origin of the Antarctic micrometeorites (AMMs) is still a matter of debate. Their closest meteoritic counterparts are the C2 chondrites, but the match is not perfect, and the parent body(ies) of the AMMs is(are) still to be identified. Tagish Lake is a new meteorite fall which bears similarity with CI1 and CM2 chondrites, but is distinct from both. Based on the mineralogy of phyllosilicates, Noguchi et al. proposed that the phyllosilicate-rich AMMs and the Tagish Lake meteorites could derive from similar asteroids. The hydrogen isotopic compositions of extra-terrestrial samples can be used to get some insight on their origin. The D/H ratios of AMMs and of Tagish Lake have been measured, but using different analytical techniques. They are therefore not directly comparable. We performed additional hydrogen isotopic analyses of fragments of Tagish Lake using the same experimental setup previously used for the measurement of the hydrogen isotopic composition of AMMs. In this work, we could also analyze separately both lithologies of Tagish Lake (carbonate-poor and -rich). The distributions of delta D values measured in the two lithologies of Tagish Lake are very similar, indicating that fluids with similar hydrogen isotopic compositions altered the meteorite on the parent body for the two lithologies. Yet, the hydrogen isotopic composition of Tagish Lake is different from that of AMMs, suggesting that they do not derive from the same parent body.

  17. Controls on the iron isotopic composition of global arc magmas

    NASA Astrophysics Data System (ADS)

    Foden, John; Sossi, Paolo A.; Nebel, Oliver

    2018-07-01

    We determined the iron isotope composition of 130 mafic lavas from 15 arcs worldwide with the hypothesis that the results would reflect the relatively high oxidation state of arc magmas. Although this expectation was not realized, this Fe isotope data set reveals important insights into the geodynamic controls and style of the melting regimes in the sub-arc mantle. Samples are from oceanic arcs from the circum-Pacific, the Indonesian Sunda-Banda islands, Scotia and the Lesser Antilles as well as from the eastern Pacific Cascades. Their mean δ57Fe value is +0.075 ± 0.05‰, significantly lighter than MORB (+0.15 ± 0.03‰). Western Pacific arcs extend to very light δ57Fe (Kamchatka = -0.11 ± 0.04‰). This is contrary to expectation, because Fe isotope fractionation factors (Sossi et al., 2016, 2012) and the incompatibility of ferric versus ferrous iron during mantle melting, predict that melts of more oxidized sources will be enriched in heavy Fe isotopes. Subducted oxidation capacity flux may correlate with hydrous fluid release from the slab. If so, a positive correlation between each arc's thermal parameter (ϕ) and δ57Fe is predicted. On the contrary, the sampled arcs mostly contribute to a negative array with the ϕ value. High ϕ arcs, largely in the western Pacific, have primary magmas with lower δ57Fe values than the low ϕ, eastern Pacific arcs. Arcs with MORB-like Sr-, Nd- and Pb-isotopes, show a large range of δ57Fe from heavy MORB-like values (Scotia or the Cascades) to very light values (Kamchatka, Tonga). Although all basalts with light δ57Fe values have MORB-like Pb-, Nd- and Sr-isotope ratios some, particularly those from eastern Indonesia, have heavier δ57Fe and higher Pb- and Sr- and lower Nd-isotope ratios reflecting sediment contamination of the mantle wedge. Because basalts with MORB-like radiogenic isotopes range all the way from heavy to light δ57Fe values this trend is process-, not source composition-driven. Neither the slab

  18. Investigation of magnesium isotope fractionation during basalt differentiation: Implications for a chondritic composition of the terrestrial mantle

    USGS Publications Warehouse

    Teng, F.-Z.; Wadhwa, M.; Helz, R.T.

    2007-01-01

    To investigate whether magnesium isotopes are fractionated during basalt differentiation, we have performed high-precision Mg isotopic analyses by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) on a set of well-characterized samples from Kilauea Iki lava lake, Hawaii, USA. Samples from the Kilauea Iki lava lake, produced by closed-system crystal-melt fractionation, range from olivine-rich cumulates to highly differentiated basalts with MgO content ranging from 2.37 to 26.87??wt.%. Our results demonstrate that although these basalts have diverse chemical compositions, mineralogies, crystallization temperatures and degrees of differentiation, their Mg isotopic compositions display no measurable variation within the limits of our external precision (average ??26Mg = - 0.36 ?? 0.10 and ??25Mg = - 0.20 ?? 0.07; uncertainties are 2SD). This indicates that Mg isotopic fractionation during crystal-melt fractionation at temperatures of ??? 1055????C is undetectable at the level of precision of the current investigation. Calculations based on our data suggest that at near-magmatic temperatures the maximum fractionation in the 26Mg/24Mg ratio between olivine and melt is 0.07???. Two additional oceanic basalts, two continental basalts (BCR-1 and BCR-2), and two primitive carbonaceous chondrites (Allende and Murchison) analyzed in this study have Mg isotopic compositions similar to the Kilauea Iki lava lake samples. In contrast to a recent report [U. Wiechert, A.N. Halliday, Non-chondritic magnesium and the origins of the inner terrestrial planets, Earth and Planetary Science Letters 256 (2007) 360-371], the results presented here suggest that the Bulk Silicate Earth has a chondritic Mg isotopic composition. ?? 2007.

  19. Isotopic composition of water vapor near the air-water interface

    NASA Astrophysics Data System (ADS)

    Zannoni, Daniele; Bergamasco, Andrea; Peschiutta, Mirco; Rampazzo, Giancarlo; Stenni, Barbara

    2017-04-01

    Evaporation is a key process in water cycle that links liquid water to the atmosphere. In the last fifty years stable isotopes of hydrogen and oxygen have been intensively used to describe climate processes related to evaporation and precipitation, ranging in different spatial and temporal scales. Evaporation introduces large isotopic effects in the phases involved. The well known Craig-Gordon model (Craig & Gordon, 1965) describes those isotopic effects involving several steps and different processes, moving from the air-water interface to the free atmosphere. However, very few works in literature have tested the vertical behavior of the Craig-Gordon model in natural conditions on both fresh and marine waters. In this work we present the results from four field experiments aimed to describe the vertical variability of δ18O and δD in the first few meters over a large water body (the coastal lagoon of Venice, northern Italy) and to test the Craig-Gordon model in such conditions. Each experiment involved cryotrapping of water vapor at different height over the water surface (0.1m, 2m and 4m) and the sampling of the liquid water at two depth (surface and 0.5m). During the experiments, water vapor was also sampled in the nearest mainland (˜2.5 km from gradient measurements) to determine the isotopic composition of background water vapor. Liquid samples were then analyzed with a Picarro L1102-i and Thermo-Fisher Delta Plus Advantage for water vapor and lagoon water, respectively. The last two experiments have also involved simultaneous measurements of relative humidity using commercially-available humidity probes at each height. This approach was used to determine a reference scale in order to compare observations to modeled estimates. Despite the coarse time resolution due to cryotrapping method (measurements are averaged over 1.5 hours), preliminary results show measurable differences in the isotopic composition of water vapor along the vertical gradient and good

  20. A paired apatite and calcite clumped isotope thermometry approach to estimating Cambro-Ordovician seawater temperatures and isotopic composition

    NASA Astrophysics Data System (ADS)

    Bergmann, Kristin D.; Finnegan, Seth; Creel, Roger; Eiler, John M.; Hughes, Nigel C.; Popov, Leonid E.; Fischer, Woodward W.

    2018-03-01

    The secular increase in δ18O values of both calcitic and phosphatic marine fossils through early Phanerozoic time suggests either that (1) early Paleozoic surface temperatures were high, in excess of 40 °C (tropical MAT), (2) the δ18O value of seawater has increased by 7-8‰ VSMOW through Paleozoic time, or (3) diagenesis has altered secular trends in early Paleozoic samples. Carbonate clumped isotope analysis, in combination with petrographic and elemental analysis, can deconvolve fluid composition from temperature effects and therefore determine which of these hypotheses best explain the secular δ18O increase. Clumped isotope measurements of a suite of calcitic and phosphatic marine fossils from late Cambrian- to Middle-late Ordovician-aged strata-the first paired fossil study of its kind-document tropical sea surface temperatures near modern temperatures (26-38 °C) and seawater oxygen isotope ratios similar to today's ratios.

  1. Correlated silicon and titanium isotopic compositions of presolar SiC grains from the Murchison CM2 chondrite

    NASA Astrophysics Data System (ADS)

    Gyngard, Frank; Amari, Sachiko; Zinner, Ernst; Marhas, Kuljeet Kaur

    2018-01-01

    We report correlated Si, and Ti isotopic compositions and elemental concentrations of 238 presolar SiC grains from the Murchison CM2 meteorite. Combined with measurements of the C and N isotopic compositions of these 238 grains, 220 were determined to be of type mainstream, 10 type AB, 4 type Y and 4 type Z. SiC grains of diameter ≳2.5 μm, to ensure enough material to attempt Ti measurements, were randomly chosen without any other prejudice. The Ti isotopic compositions of the majority of the grains are characterized by enrichments in 46Ti, 47Ti, 49Ti, and 50Ti relative to 48Ti, and show linear isotopic correlations indicative of galactic chemical evolution and neutron capture of the grains parent stars. The variability in the observed Ti signal as a function of depth in most of the grains indicates the presence of distinct subgrains, likely TiC that have been previously observed in TEM studies. Vandium-51 concentrations correlate with those of Ti, indicating V substitutes for Ti in the TiC matrix in many of the grains. No isotopic anomalies in 52Cr/53Cr ratios were observed, and Cr concentrations did not correlate with those of either Ti or V.

  2. Lead isotope compositions as guides to early gold mineralization: The North Amethyst vein system, Creede district, Colorado

    USGS Publications Warehouse

    Foley, Nora K.; Ayuso, Robert A.

    1994-01-01

    Pb isotope compositions from the late stage of the North Amethyst vein system and from the Bondholder and central and southern Creede mining districts are more radiogenic than the host volcanic rocks of the central cluster of the San Juan volcanic field. Our Pb isotope results indicate that early Au mineralization of the North Amethyst area may represent the product of an older and relatively local hydrothermal system distinct from that of the younger base metal and Ag mineralization found throughout the region. Fluids that deposited Au minerals may have derived their Pb isotope composition by a greater degree of interaction with shallow, relatively less radiogenic volcanic wall rocks. The younger, base metal and Ag-rich mineralization that overprints the Au mineralization in the North Amethyst area clearly has a more radiogenic isotopic signature, which implies that the later mineralization derived a greater component of its Pb from Proterozoic source rocks, or sediments derived from them.Paragenetically early sulfide-rich vein assemblages have the least radiogenic galenas and generally also have the highest Au contents. Thus, identification of paragenetically early vein assemblages with relatively unradiogenic Pb isotope compositions similar to those of the North Amethyst area provides an additional exploration tool for Au in the central San Juan Mountains area.

  3. Efficient mixing of the solar nebula from uniform Mo isotopic composition of meteorites.

    PubMed

    Becker, Harry; Walker, Richard J

    2003-09-11

    The abundances of elements and their isotopes in our Galaxy show wide variations, reflecting different nucleosynthetic processes in stars and the effects of Galactic evolution. These variations contrast with the uniformity of stable isotope abundances for many elements in the Solar System, which implies that processes efficiently homogenized dust and gas from different stellar sources within the young solar nebula. However, isotopic heterogeneity has been recognized on the subcentimetre scale in primitive meteorites, indicating that these preserve a compositional memory of their stellar sources. Small differences in the abundance of stable molybdenum isotopes in bulk rocks of some primitive and differentiated meteorites, relative to terrestrial Mo, suggest large-scale Mo isotopic heterogeneity between some inner Solar System bodies, which implies physical conditions that did not permit efficient mixing of gas and dust. Here we report Mo isotopic data for bulk samples of primitive and differentiated meteorites that show no resolvable deviations from terrestrial Mo. This suggests efficient mixing of gas and dust in the solar nebula at least to 3 au from the Sun, possibly induced by magnetohydrodynamic instabilities. These mixing processes must have occurred before isotopic fractionation of gas-phase elements and volatility-controlled chemical fractionations were established.

  4. Using semi-continuous, in-situ measurements of nitrous oxide isotopic composition at a suburban site to track emission processes

    NASA Astrophysics Data System (ADS)

    Harris, Eliza; Henne, Stephan; Christoph, Hüglin; Christoph, Zellweger; Béla, Tuzson; Erkan, Ibraim; Lukas, Emmenegger; Joachim, Mohn

    2017-04-01

    Nitrous oxide (N2O) is a potent greenhouse gas and the strongest ozone-destroying substance emitted this century. The atmospheric N2O mole fraction has been increasing at a rate of 0.2-0.3% per year over the past decades due to anthropogenic emissions; in addition, recent results suggest that the rate of increase is rising - therefore effective mitigation of N2O emissions is a critical point for environmental policy. However, N2O sources are poorly defined and disperse, complicating the development of targeted mitigation strategies. Online isotopic measurements using preconcentration and laser spectroscopy [1,2,3] have great potential to unravel spatial and temporal variations in sources, sinks and chemistry of trace gases such as N2O. Semi-continuous, real-time measurements of N2O isotopic composition (δ18O, site preference [SP = 14N15N16O - 15N14N16O] and δ15Nbulk) were performed at the suburban site of Dübendorf, Switzerland, for 19 months between July 2014 and February 2016. The data precision reached 0.1‰ in the final months, thus the results could clearly identify nocturnal build-up of N2O, with a corresponding decrease in δ18O, SP and δ15Nbulk due to isotopically depleted anthropogenic sources. Daily mean source isotopic composition was calculated by considering the measured and the background mole fraction and isotopic composition. Delta values of the mean emission source were highest in winter, with a seasonal cycle of 12, 8 and 5‰ for δ18O, SP and δ15Nbulk respectively. The chemical and meteorological parameters controlling source isotopic composition were considered using data from the Swiss National Air Pollution Monitoring Network (NABEL) as well as a transport regime cluster analysis. A clear spatial distribution for source isotopic composition was observed for δ18O, as well as a significant relationship with the level of urban pollution, indicating δ18O may be a strong indicator of combustion/industrial vs. agricultural N2O. In contrast

  5. Isotopic composition of atmospheric nitrate in a tropical marine boundary layer.

    PubMed

    Savarino, Joel; Morin, Samuel; Erbland, Joseph; Grannec, Francis; Patey, Matthew D; Vicars, William; Alexander, Becky; Achterberg, Eric P

    2013-10-29

    Long-term observations of the reactive chemical composition of the tropical marine boundary layer (MBL) are rare, despite its crucial role for the chemical stability of the atmosphere. Recent observations of reactive bromine species in the tropical MBL showed unexpectedly high levels that could potentially have an impact on the ozone budget. Uncertainties in the ozone budget are amplified by our poor understanding of the fate of NOx (= NO + NO2), particularly the importance of nighttime chemical NOx sinks. Here, we present year-round observations of the multiisotopic composition of atmospheric nitrate in the tropical MBL at the Cape Verde Atmospheric Observatory. We show that the observed oxygen isotope ratios of nitrate are compatible with nitrate formation chemistry, which includes the BrNO3 sink at a level of ca. 20 ± 10% of nitrate formation pathways. The results also suggest that the N2O5 pathway is a negligible NOx sink in this environment. Observations further indicate a possible link between the NO2/NOx ratio and the nitrogen isotopic content of nitrate in this low NOx environment, possibly reflecting the seasonal change in the photochemical equilibrium among NOx species. This study demonstrates the relevance of using the stable isotopes of oxygen and nitrogen of atmospheric nitrate in association with concentration measurements to identify and constrain chemical processes occurring in the MBL.

  6. Isotopic composition of atmospheric nitrate in a tropical marine boundary layer

    PubMed Central

    Savarino, Joel; Morin, Samuel; Erbland, Joseph; Grannec, Francis; Patey, Matthew D.; Vicars, William; Alexander, Becky; Achterberg, Eric P.

    2013-01-01

    Long-term observations of the reactive chemical composition of the tropical marine boundary layer (MBL) are rare, despite its crucial role for the chemical stability of the atmosphere. Recent observations of reactive bromine species in the tropical MBL showed unexpectedly high levels that could potentially have an impact on the ozone budget. Uncertainties in the ozone budget are amplified by our poor understanding of the fate of NOx (= NO + NO2), particularly the importance of nighttime chemical NOx sinks. Here, we present year-round observations of the multiisotopic composition of atmospheric nitrate in the tropical MBL at the Cape Verde Atmospheric Observatory. We show that the observed oxygen isotope ratios of nitrate are compatible with nitrate formation chemistry, which includes the BrNO3 sink at a level of ca. 20 ± 10% of nitrate formation pathways. The results also suggest that the N2O5 pathway is a negligible NOx sink in this environment. Observations further indicate a possible link between the NO2/NOx ratio and the nitrogen isotopic content of nitrate in this low NOx environment, possibly reflecting the seasonal change in the photochemical equilibrium among NOx species. This study demonstrates the relevance of using the stable isotopes of oxygen and nitrogen of atmospheric nitrate in association with concentration measurements to identify and constrain chemical processes occurring in the MBL. PMID:23431201

  7. Isotopic Composition of the Neolithic Alpine Iceman's Tooth Enamel and Clues to his Origin

    NASA Astrophysics Data System (ADS)

    Muller, W.; Muller, W.; Halliday, A. N.

    2001-12-01

    Five small enamel fragments from three teeth of the upper right jaw from the mummy of the Neolithic Alpine Iceman have been investigated for their isotopic composition in order to shed light on his geographic origins. Soils from approximately contemporaneous sites were sampled for comparison. Tooth enamel forms ontogenetically very early and is not re-mineralized during later lifetime (unlike with bone material). Therefore, unique insights into the Iceman's childhood can be acquired. Enamel also is the densest tissue of a human body and is thus less susceptible to post-mortem alteration. Both radiogenic (Sr, Pb, Nd) and stable isotopes (O, C) are investigated. Radiogenic isotopes allow reconstruction of the local geological background, because humans incorporate Sr, Pb and Nd from their local environment by eating local food. Stable isotopes provide information about altitude and/or position relative to the main Alpine watershed. High spatial-resolution laser-ablation ICPMS profiles reveal that most elements are distributed in a manner that is essentially similar to modern human teeth except of that La, Ce, Nd (LREE) show up to a 100-fold enrichment towards the outer enamel surface. These uptake-profiles may reflect interaction with melt water, consistent with data for the composition of samples of the Iceman's skin. Biogenic apatites (enamel, bone) have very low in-vivo LREE concentrations, but take up LREEs post-mortem from the burial environment. Ice core samples from the finding site show concentrations up to 400 ppt Ce. Such high uptake of the LREEs precludes the derivation of an in-vivo Nd isotopic signal, but both other radiogenic tracers, Sr and Pb, show pristine (in-vivo) concentrations of 87 ppm and 0.1 ppm, respectively. Strontium isotopic compositions were determined on fragments from the canine, the first and second premolar (1 - 9 mg) and two hip bone samples, utilizing three sequential leaching steps for each sample to detect possible alteration

  8. Mercury emissions and stable isotopic compositions at Vulcano Island (Italy)

    NASA Astrophysics Data System (ADS)

    Zambardi, T.; Sonke, J. E.; Toutain, J. P.; Sortino, F.; Shinohara, H.

    2009-01-01

    Sampling and analyses methods for determining the stable isotopic compositions of Hg in an active volcanic system were tested and optimized at the volcanic complex of Vulcano (Aeolian Islands, Italy). Condensed gaseous fumarole Hg (fum)T, plume gaseous elemental Hg (g)0 and plume particulate Hg (p)II were obtained at fumaroles F0, F5, F11, and FA. The average total Hg emissions, based on Hg T/SO 2 in condensed fumarolic gases and plumes, range from 2.5 to 10.1 kg y - 1 , in agreement with published values [Ferrara, R., Mazzolai, B., Lanzillotta, E., Nucaro, E., Pirrone, N., 2000. Volcanoes as emission sources of atmospheric mercury in the Mediterranean Basin. Sci. Total Environ. 259(1-3), 115-121; Aiuppa, A., Bagnato, E., Witt, M.L.I., Mather, T.A., Parello, F., Pyle, D.M., Martin, R.S., 2007. Real-time simultaneous detection of volcanic Hg and SO 2 at La Fossa Crater, Vulcano (Aeolian Islands, Sicily). Geophys. Res. Lett. 34(L21307).]. Plume Hg (p)II increases with distance from the fumarole vent, at the expense of Hg (g)0 and indicates significant in-plume oxidation and condensation of fumarole Hg (fum)T. Relative to the NIST SRM 3133 Hg standard, the stable isotopic compositions of Hg are δ 202Hg (fum)T = - 0.74‰ ± 0.18 (2SD, n = 4) for condensed gaseous fumarole Hg (fum)T, δ 202Hg (g)0 = - 1.74‰ ± 0.36 (2SD, n = 1) for plume gaseous elemental Hg (g)0 at the F0 fumarole, and δ 202Hg (p)II = - 0.11‰ ± 0.18 (2SD, n = 4) for plume particulate Hg (p)II. The enrichment of Hg (p)II in the heavy isotopes and Hg (g)0 in the light isotopes relative to the total condensed fumarolic Hg (fum)T gas complements the speciation data and demonstrates a gas-particle fractionation occurring after the gas expulsion in ambient T° atmosphere. A first order Rayleigh equilibrium condensation isotope fractionation model yields a fractionation factor α cond-gas of 1.00135 ± 0.00058.

  9. Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide

    NASA Astrophysics Data System (ADS)

    Wiegel, Aaron A.; Cole, Amanda S.; Hoag, Katherine J.; Atlas, Elliot L.; Schauffler, Sue M.; Boering, Kristie A.

    2013-10-01

    We report observations of stratospheric CO2 that reveal surprisingly large anomalous enrichments in 17O that vary systematically with latitude, altitude, and season. The triple isotope slopes reached 1.95 ± 0.05(1σ) in the middle stratosphere and 2.22 ± 0.07 in the Arctic vortex versus 1.71 ± 0.03 from previous observations and a remarkable factor of 4 larger than the mass-dependent value of 0.52. Kinetics modeling of laboratory measurements of photochemical ozone-CO2 isotope exchange demonstrates that non-mass-dependent isotope effects in ozone formation alone quantitatively account for the 17O anomaly in CO2 in the laboratory, resolving long-standing discrepancies between models and laboratory measurements. Model sensitivities to hypothetical mass-dependent isotope effects in reactions involving O3, O(1D), or CO2 and to an empirically derived temperature dependence of the anomalous kinetic isotope effects in ozone formation then provide a conceptual framework for understanding the differences in the isotopic composition and the triple isotope slopes between the laboratory and the stratosphere and between different regions of the stratosphere. This understanding in turn provides a firmer foundation for the diverse biogeochemical and paleoclimate applications of 17O anomalies in tropospheric CO2, O2, mineral sulfates, and fossil bones and teeth, which all derive from stratospheric CO2.

  10. The formation and alteration of the Renazzo-like carbonaceous chondrites I: Implications of bulk-oxygen isotopic composition

    NASA Astrophysics Data System (ADS)

    Schrader, Devin L.; Franchi, Ian A.; Connolly, Harold C., Jr.; Greenwood, Richard C.; Lauretta, Dante S.; Gibson, Jenny M.

    2011-01-01

    To better understand the role of aqueous alteration on the CR chondrite parent asteroid, a whole-rock oxygen isotopic study of 20 meteorites classified as Renazzo-like carbonaceous chondrites (CR) was conducted. The CR chondrites analyzed for their oxygen isotopes were Dhofar 1432, Elephant Moraine (EET) 87770, EET 92042, EET 96259, Gao-Guenie (b), Graves Nunataks (GRA) 95229, GRA 06100, Grosvenor Mountains (GRO) 95577, GRO 03116, LaPaz Ice Field (LAP) 02342, LAP 04720, Meteorite Hills (MET) 00426, North West Africa (NWA) 801, Pecora Escarpment (PCA) 91082, Queen Alexandra Range (QUE) 94603, QUE 99177, and Yamato-793495 (Y-793495). Three of the meteorites, Asuka-881595 (A-881595), GRA 98025, and MET 01017, were found not to be CR chondrites. The remaining samples concur petrographically and with the well-established oxygen-isotope mixing line for the CR chondrites. Their position along this mixing line is controlled both by the primary oxygen-isotopic composition of their individual components and their relative degree of aqueous alteration. Combined with literature data and that of this study, we recommend the slope for the CR-mixing line to be 0.70 ± 0.04 (2σ), with a δ 17O-intercept of -2.23 ± 0.14 (2σ). Thin sections of Al Rais, Shişr 033, Renazzo, and all but 3 samples analyzed for oxygen isotopes were studied petrographically. The abundance of individual components is heterogeneous among the CR chondrites, but FeO-poor chondrules and matrix are the most abundant constituents and therefore, dominate the whole-rock isotopic composition. The potential accreted ice abundance, physico-chemical conditions of aqueous alteration (e.g. temperature and composition of the fluid) and its duration control the degree of alteration of individual CR chondrites. Combined with literature data, we suggest that LAP 02342 was exposed to lower temperature fluid during alteration than GRA 95229. With only two falls, terrestrial alteration of the CR chondrites complicates the

  11. In situ observations of the isotopic composition of methane at the Cabauw tall tower site

    NASA Astrophysics Data System (ADS)

    Röckmann, Thomas; Eyer, Simon; van der Veen, Carina; Popa, Maria E.; Tuzson, Béla; Monteil, Guillaume; Houweling, Sander; Harris, Eliza; Brunner, Dominik; Fischer, Hubertus; Zazzeri, Giulia; Lowry, David; Nisbet, Euan G.; Brand, Willi A.; Necki, Jaroslav M.; Emmenegger, Lukas; Mohn, Joachim

    2016-08-01

    High-precision analyses of the isotopic composition of methane in ambient air can potentially be used to discriminate between different source categories. Due to the complexity of isotope ratio measurements, such analyses have generally been performed in the laboratory on air samples collected in the field. This poses a limitation on the temporal resolution at which the isotopic composition can be monitored with reasonable logistical effort. Here we present the performance of a dual isotope ratio mass spectrometric system (IRMS) and a quantum cascade laser absorption spectroscopy (QCLAS)-based technique for in situ analysis of the isotopic composition of methane under field conditions. Both systems were deployed at the Cabauw Experimental Site for Atmospheric Research (CESAR) in the Netherlands and performed in situ, high-frequency (approx. hourly) measurements for a period of more than 5 months. The IRMS and QCLAS instruments were in excellent agreement with a slight systematic offset of (+0.25 ± 0.04) ‰ for δ13C and (-4.3 ± 0.4) ‰ for δD. This was corrected for, yielding a combined dataset with more than 2500 measurements of both δ13C and δD. The high-precision and high-temporal-resolution dataset not only reveals the overwhelming contribution of isotopically depleted agricultural CH4 emissions from ruminants at the Cabauw site but also allows the identification of specific events with elevated contributions from more enriched sources such as natural gas and landfills. The final dataset was compared to model calculations using the global model TM5 and the mesoscale model FLEXPART-COSMO. The results of both models agree better with the measurements when the TNO-MACC emission inventory is used in the models than when the EDGAR inventory is used. This suggests that high-resolution isotope measurements have the potential to further constrain the methane budget when they are performed at multiple sites that are representative for the entire European domain.

  12. In-situ observations of the isotopic composition of methane at the Cabauw tall tower site

    NASA Astrophysics Data System (ADS)

    Röckmann, Thomas; Eyer, Simon; van der Veen, Carina; E Popa, Maria; Tuzson, Béla; Monteil, Guillaume; Houweling, Sander; Harris, Eliza; Brunner, Dominik; Fischer, Hubertus; Zazzeri, Giulia; Lowry, David; Nisbet, Euan G.; Brand, Willi A.; Necki, Jaroslav M.; Emmenegger, Lukas; Mohn, Joachim

    2017-04-01

    High precision analyses of the isotopic composition of methane in ambient air can potentially be used to discriminate between different source categories. Due to the complexity of isotope ratio measurements, such analyses have generally been performed in the laboratory on air samples collected in the field. This poses a limitation on the temporal resolution at which the isotopic composition can be monitored with reasonable logistical effort. Here we present the performance of a dual isotope ratio mass spectrometric system (IRMS) and a quantum cascade laser absorption spectroscopy (QCLAS) based technique for in-situ analysis of the isotopic composition of methane under field conditions. Both systems were deployed at the Cabauw experimental site for atmospheric research (CESAR) in the Netherlands and performed in-situ, high-frequency (approx. hourly) measurements for a period of more than 5 months. The IRMS and QCLAS instruments were in excellent agreement with a slight systematic offset of +0.05 ± 0.03 ‰ for δ13C-CH4 and -3.6 ± 0.4 ‰ for δD-CH4. This was corrected for, yielding a combined dataset with more than 2500 measurements of both δ13C and δD. The high precision and temporal resolution dataset does not only reveal the overwhelming contribution of isotopically depleted agricultural CH4 emissions from ruminants at the Cabauw site, but also allows the identification of specific events with elevated contributions from more enriched sources such as natural gas and landfills. The final dataset was compared to model calculations using the global model TM5 and the mesoscale model FLEXPART-COSMO. The results of both models agree better with the measurements when the TNO-MACC emission inventory is used in the models than when the EDGAR inventory is used. This suggests that high-resolution isotope measurements have the potential to further constrain the methane budget, when they are performed at multiple sites that are representative for the entire European

  13. The isotopic composition of CO in vehicle exhaust

    NASA Astrophysics Data System (ADS)

    Naus, S.; Röckmann, T.; Popa, M. E.

    2018-03-01

    We investigated the isotopic composition of CO in the exhaust of individual vehicles. Additionally, the CO2 isotopes, and the CO:CO2, CH4:CO2 and H2:CO gas ratios were measured. This was done under idling and revving conditions, and for three vehicles in a full driving cycle on a testbench. The spread in the results, even for a single vehicle, was large: for δ13 C in CO ∼ -60 to 0‰, for δ18 O in CO ∼ +10 to +35‰, and for all gas ratios several orders of magnitude. The results show an increase in the spread of isotopic values for CO compared to previous studies, suggesting that increasing complexity of emission control in vehicles might be reflected in the isotopic composition. When including all samples, we find a weighted mean for the δ13 C and δ18 O in CO of -28.7 ± 0.5‰ and +24.8 ± 0.3‰ respectively. This result is dominated by cold petrol vehicles. Diesel vehicles behaved as a distinct group, with CO enriched in 13C and depleted in 18O, compared to petrol vehicles. For the H2:CO ratio of all vehicles, we found a value of 0.71 ± 0.31 ppb:ppb. The CO:CO2 ratio, with a mean of 19.4 ± 6.8 ppb:ppm, and the CH4:CO2 ratio, with a mean of 0.26 ± 0.05 ppb:ppm, are both higher than recent literature indicates. This is likely because our sampling distribution was biased towards cold vehicles, and therefore towards higher emission situations. The CH4:CO2 ratio was found to behave similarly to the CO:CO2 ratio, suggesting that the processes affecting CO and CH4 are similar. The δ13 C values in CO2 were close to the expected δ13 C in fuel, with no significant difference between petrol and diesel vehicles. The δ18 O values in CO2 for petrol vehicles covered a range of 20-35‰, similar to the δ18 O of CO. The δ18 O values in CO2 for diesel vehicles were close to the δ18 O in atmospheric oxygen. A set of polluted atmospheric samples, taken near a highway and inside parking garages, showed an isotopic signature of CO and a H2:CO ratio that were

  14. The isotopic composition of uranium and lead in Allende inclusions and meteoritic phosphates

    NASA Technical Reports Server (NTRS)

    Chen, J. H.; Wasserburg, G. J.

    1981-01-01

    The isotopic compositions of uranium and lead in Ca-Al-rich inclusions from the Allende chondrite and in whitlockite from the St. Severin chondrite and the Angra dos Reis achondrite are reported. Isoptopic analysis of acid soluble fractions of the Allende inclusions and the meteoritic whitlockite, which show isotopic anomalies in other elements, reveals U-235/U-238 ratios from 1/137.6 to 1/138.3, within 20 per mil of normal terrestrial U abundances. The Pb isotopic compositions of five coarse-grained Allende inclusions give a mean Pb-207/Pb-206 model age of 4.559 + or - 0.015 AE, in agreement with the U results. Pb isotope ratios of two fine-grained inclusions and a coarse-grained inclusion with strong mass fractionation and some nonlinear isotopic anomalies indicate that the U-Pb systems of these inclusions have evolved differently from the rest of Allende. Th/U abundance ratios in the Allende inclusions and meteoritic phosphate are found to range from 3.8 to 96, presumably indicating an optimal case for Cm/U fractionation, although the normal U concentrations do not support claims of abundant live Cm-247 or Cm-247/U-238 fractionation at the time of meteorite formation, in contrast to previous results. A limiting Cm-247/U-235 ratio of 0.004 at the time of meteorite formation is calculated which implies that the last major r process contribution at the protosolar nebula was approximately 100 million years prior to Al-26 formation and injection.

  15. Isotope pattern deconvolution for peptide mass spectrometry by non-negative least squares/least absolute deviation template matching

    PubMed Central

    2012-01-01

    Background The robust identification of isotope patterns originating from peptides being analyzed through mass spectrometry (MS) is often significantly hampered by noise artifacts and the interference of overlapping patterns arising e.g. from post-translational modifications. As the classification of the recorded data points into either ‘noise’ or ‘signal’ lies at the very root of essentially every proteomic application, the quality of the automated processing of mass spectra can significantly influence the way the data might be interpreted within a given biological context. Results We propose non-negative least squares/non-negative least absolute deviation regression to fit a raw spectrum by templates imitating isotope patterns. In a carefully designed validation scheme, we show that the method exhibits excellent performance in pattern picking. It is demonstrated that the method is able to disentangle complicated overlaps of patterns. Conclusions We find that regularization is not necessary to prevent overfitting and that thresholding is an effective and user-friendly way to perform feature selection. The proposed method avoids problems inherent in regularization-based approaches, comes with a set of well-interpretable parameters whose default configuration is shown to generalize well without the need for fine-tuning, and is applicable to spectra of different platforms. The R package IPPD implements the method and is available from the Bioconductor platform (http://bioconductor.fhcrc.org/help/bioc-views/devel/bioc/html/IPPD.html). PMID:23137144

  16. Compilation of minimum and maximum isotope ratios of selected elements in naturally occurring terrestrial materials and reagents

    USGS Publications Warehouse

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

    2002-01-01

    laboratories comparable. The minimum and maximum concentrations of a selected isotope in naturally occurring terrestrial materials for selected chemical elements reviewed in this report are given below: Isotope Minimum mole fraction Maximum mole fraction -------------------------------------------------------------------------------- 2H 0 .000 0255 0 .000 1838 7Li 0 .9227 0 .9278 11B 0 .7961 0 .8107 13C 0 .009 629 0 .011 466 15N 0 .003 462 0 .004 210 18O 0 .001 875 0 .002 218 26Mg 0 .1099 0 .1103 30Si 0 .030 816 0 .031 023 34S 0 .0398 0 .0473 37Cl 0 .240 77 0 .243 56 44Ca 0 .020 82 0 .020 92 53Cr 0 .095 01 0 .095 53 56Fe 0 .917 42 0 .917 60 65Cu 0 .3066 0 .3102 205Tl 0 .704 72 0 .705 06 The numerical values above have uncertainties that depend upon the uncertainties of the determinations of the absolute isotope-abundance variations of reference materials of the elements. Because reference materials used for absolute isotope-abundance measurements have not been included in relative isotope abundance investigations of zinc, selenium, molybdenum, palladium, and tellurium, ranges in isotopic composition are not listed for these elements, although such ranges may be measurable with state-of-the-art mass spectrometry. This report is available at the url: http://pubs.water.usgs.gov/wri014222.

  17. Nd and Sm isotopic composition of spent nuclear fuels from three material test reactors

    DOE PAGES

    Sharp, Nicholas; Ticknor, Brian W.; Bronikowski, Michael; ...

    2016-11-17

    Rare earth elements such as neodymium and samarium are ideal for probing the neutron environment that spent nuclear fuels are exposed to in nuclear reactors. The large number of stable isotopes can provide distinct isotopic signatures for differentiating the source material for nuclear forensic investigations. The rare-earth elements were isolated from the high activity fuel matrix via ion exchange chromatography in a shielded cell. The individual elements were then separated using cation exchange chromatography. In conclusion, the neodymium and samarium aliquots were analyzed via MC–ICP–MS, resulting in isotopic compositions with a precision of 0.01–0.3%.

  18. Nd and Sm isotopic composition of spent nuclear fuels from three material test reactors

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Sharp, Nicholas; Ticknor, Brian W.; Bronikowski, Michael

    Rare earth elements such as neodymium and samarium are ideal for probing the neutron environment that spent nuclear fuels are exposed to in nuclear reactors. The large number of stable isotopes can provide distinct isotopic signatures for differentiating the source material for nuclear forensic investigations. The rare-earth elements were isolated from the high activity fuel matrix via ion exchange chromatography in a shielded cell. The individual elements were then separated using cation exchange chromatography. In conclusion, the neodymium and samarium aliquots were analyzed via MC–ICP–MS, resulting in isotopic compositions with a precision of 0.01–0.3%.

  19. Stable bromine isotopic composition of methyl bromide released from plant matter

    NASA Astrophysics Data System (ADS)

    Horst, Axel; Holmstrand, Henry; Andersson, Per; Thornton, Brett F.; Wishkerman, Asher; Keppler, Frank; Gustafsson, Örjan

    2014-01-01

    Methyl bromide (CH3Br) emitted from plants constitutes a natural source of bromine to the atmosphere, and is a component in the currently unbalanced global CH3Br budget. In the stratosphere, CH3Br contributes to ozone loss processes. Studies of stable isotope composition may reduce uncertainties in the atmospheric CH3Br budget, but require well-constrained isotope fingerprints of the source end members. Here we report the first measurements of stable bromine isotopes (δ81Br) in CH3Br from abiotic plant emissions. Incubations of both KBr-fortified pectin, a ubiquitous cell-stabilizing macromolecule, and of a natural halophyte (Salicornia fruticosa), yielded an enrichment factor (ε) of -2.00 ± 0.23‰ (1σ, n = 8) for pectin and -1.82 ± 0.02‰ (1σ, n = 4) for Salicornia (the relative amount of the heavier 81Br was decreased in CH3Br compared to the substrate salt). For short incubations, and up to 10% consumption of the salt substrate, this isotope effect was similar for temperatures from 30 up to 300 °C. For longer incubations of up to 90 h at 180 °C the δ81Br values increased from -2‰ to 0‰ for pectin and to -1‰ for Salicornia. These δ81Br source signatures of CH3Br formation from plant matter combine with similar data for carbon isotopes to facilitate multidimensional isotope diagnostics of the CH3Br budget.

  20. Isotopic compositions and probable origins of organic molecules in the Eocene Messel shale

    NASA Technical Reports Server (NTRS)

    Hayes, J. M.; Takigiku, Ray; Ocampo, Ruben; Callot, Enry J.; Albrecht, Pierre

    1987-01-01

    It is shown here that the carbon isotopic compositions of biomarkers from the Eocene Messel shale, accumulated 47 + or - 2 million years ago in anaerobic waters at the bottom of a lake, allow identification of specific sources for some materials and reconstruction of carbon flows within the lake and its sediments. The C-13 content of organic matter synthesized by lacustrine primary producers can be estimated from the observed C-13 content of the geoporphyrins derived from their chlorophylls. Total organic material in the shale is depleted in C-13 by six parts per thousand relative to that input. This difference cannot be explained by selective loss of components enriched in C-13, nor, as shown by isotopic compositions of other biomarkers, by inputs from land plants surrounding the lake or from methanogenic bacteria.

  1. High temporal resolution measurements of the isotopic composition of CH4 at the Lutjewad station, The Netherlands

    NASA Astrophysics Data System (ADS)

    Röckmann, Thomas; van der Veen, Carina; Chen, Huilin; Scheeren, Bert

    2017-04-01

    Isotope measurements can help constraining the atmospheric budget of the greenhouse gas methane (CH4) because different sources emit CH4 with slightly different isotopic composition. In the past, high precision isotope measurements have primarily been carried out by isotope ratio mass spectrometry on flask samples that are usually collected at relatively low temporal resolution. We have recently developed a fully automated gas chromatography - isotope ratio mass spectrometry system (GC-IRMS) for autonomous and unattended CH4 isotope measurements (δD and δ13C) in the field. The first deployment at the Cabauw Experimental Site for Atmospheric Research (CESAR) indicated that CH4 emissions from fossil fuel sources are overestimated in this region [1]. To further exploit the potential of this approach, the in situ system has been installed in November 2016 at the Lutjewad atmospheric monitoring and sampling site in the North of the Netherlands. This site is expected to sample also emissions from the large Groningen gas fields. The isotope measurements are expected to allow distinguishing these emissions from the agricultural emissions, which are also strong in this region. We will present the results from these ongoing measurements of δD and δ13C in CH4.. 1. Röckmann, T., et al., In situ observations of the isotopic composition of methane at the Cabauw tall tower site, Atmos. Chem. Phys., 2016. 16: 10469-10487.

  2. Silicon isotope fractionation by marine sponges and the reconstruction of the silicon isotope composition of ancient deep water

    NASA Astrophysics Data System (ADS)

    de La Rocha, Christina L.

    2003-05-01

    The silicon isotope composition (δ30Si) of biogenic opal provides a view of the silica cycle at times in the past. Reconstructions require the knowledge of silicon isotope fractionation during opal biomineralization. The δ30Si of specimens of hexactinellid sponges and demosponges growing in the modern ocean ranged from -1.2‰ to -3.7‰ (n = 6), corresponding to the production of opal that has a δ30Si value 3.8‰ ± 0.8‰ more negative than seawater silicic acid and a fractionation factor (α) of 0.9964. This is three times the fractionation observed during opal formation by marine diatoms and terrestrial plants and is the largest fractionation of silicon isotopes observed for any natural process on Earth. The δ30Si values of sponge spicules across the Eocene-Oligocene boundary at Ocean Drilling Program Site 689 on Maud Rise range from -1.1‰ to -3.0‰, overlapping the range observed for sponges growing in modern seawater.

  3. A model composition for Mars derived from the oxygen isotopic ratios of martian/SNC meteorites. [Abstract only

    NASA Technical Reports Server (NTRS)

    Delaney, J. S.

    1994-01-01

    Oxygen is the most abundant element in most meteorites, yet the ratios of its isotopes are seldom used to constrain the compositional history of achondrites. The two major achondrite groups have O isotope signatures that differ from any plausible chondritic precursors and lie between the ordinary and carbonaceous chondrite domains. If the assumption is made that the present global sampling of chondritic meteorites reflects the variability of O reservoirs at the time of planetessimal/planet aggregation in the early nebula, then the O in these groups must reflect mixing between known chondritic reservoirs. This approach, in combination with constraints based on Fe-Mn-Mg systematics, has been used previously to model the composition of the basaltic achondrite parent body (BAP) and provides a model precursor composition that is generally consistent with previous eucrite parent body (EPB) estimates. The same approach is applied to Mars exploiting the assumption that the SNC and related meteorites sample the martian lithosphere. Model planet and planetesimal compositions can be derived by mixing of known chondritic components using O isotope ratios as the fundamental compositional constraint. The major- and minor-element composition for Mars derived here and that derived previously for the basaltic achondrite parent body are, in many respects, compatible with model compositions generated using completely independent constraints. The role of volatile elements and alkalis in particular remains a major difficulty in applying such models.

  4. Spatial, seasonal, and source variability in the stable oxygen and hydrogen isotopic composition of tap waters throughout the USA

    USGS Publications Warehouse

    Landwehr, Jurate M.; Coplen, Tyler B.; Stewart, David W.

    2013-01-01

    To assess spatial, seasonal, and source variability in stable isotopic composition of human drinking waters throughout the entire USA, we have constructed a database of δ18O and δ2H of US tap waters. An additional purpose was to create a publicly available dataset useful for evaluating the forensic applicability of these isotopes for human tissue source geolocation. Samples were obtained at 349 sites, from diverse population centres, grouped by surface hydrologic units for regional comparisons. Samples were taken concurrently during two contrasting seasons, summer and winter. Source supply (surface, groundwater, mixed, and cistern) and system (public and private) types were noted. The isotopic composition of tap waters exhibits large spatial and regional variation within each season as well as significant at-site differences between seasons at many locations, consistent with patterns found in environmental (river and precipitation) waters deriving from hydrologic processes influenced by geographic factors. However, anthropogenic factors, such as the population of a tap’s surrounding community and local availability from diverse sources, also influence the isotopic composition of tap waters. Even within a locale as small as a single metropolitan area, tap waters with greatly differing isotopic compositions can be found, so that tap water within a region may not exhibit the spatial or temporal coherence predicted for environmental water. Such heterogeneities can be confounding factors when attempting forensic inference of source water location, and they underscore the necessity of measurements, not just predictions, with which to characterize the isotopic composition of regional tap waters. Published 2013. This article is a U.S. Government work and is in the public domain in the USA.

  5. Stable calcium isotope composition of a pedogenic carbonate in forested ecosystem: the case of the needle fibre calcite (NFC).

    NASA Astrophysics Data System (ADS)

    Milliere, Laure; Verrecchia, Eric; Gussone, Nikolaus

    2014-05-01

    Calcium (Ca), carbon (C) and oxygen (O) are important elements in terrestrial environment, as their biogeochemical cycles are directly related to the storage of atmospheric carbon. Nevertheless, contrarily to C and O, Ca isotope composition has been only poorly studied in the terrestrial carbonates. Needle Fibre Calcite (NFC) is one of the most common pedogenic carbonates, unless its origin is still under debate. Recent studies explain its formation by precipitation inside fungal hyphae. Due to this possible biogenic origin, NFC can be considered as a potential bridge between the biochemistry (precipitation inside organic structure) and geochemistry (pedogenic carbonate related to soil conditions) of the Ca. Thus, the study of the Ca isotope composition of NFC seem to be of first interest in order to shed light on the behaviour of Ca in terrestrial environment, especially when precipitation of secondary carbonates is involved. The sampling site is situated in the Swiss Jura Mountains and has been chosen due to a previous complete study of the C and O isotope composition of NFC in relation to the ecosystem, which represent a good precondition for the understanding of the NFC Ca isotope signatures in this context. In this study, the implication of the fungi in the origin of NFC is investigated, by comparing the Ca isotope composition of NFC and a purely physicochemical calcite cement (LCC), both precipitated in the same environment. The δ44Ca signature of NFC and LCC crystals were used to determine possible differences of the precipitation rate during their formation. NFC and LCC have similar δ18O composition and are supposed to precipitate at the same temperature (Milliere et al., 2011a). Thus the study of Ca isotope composition of NFC seems to demonstrate that the elongated shape of the calcite needle can be explained by different precipitation processes than the rhombohedric calcite crystals precipitated in the same environment; and more precisely, the specific

  6. Box-modeling of bone and tooth phosphate oxygen isotope compositions as a function of environmental and physiological parameters.

    PubMed

    Langlois, C; Simon, L; Lécuyer, Ch

    2003-12-01

    A time-dependent box model is developed to calculate oxygen isotope compositions of bone phosphate as a function of environmental and physiological parameters. Input and output oxygen fluxes related to body water and bone reservoirs are scaled to the body mass. The oxygen fluxes are evaluated by stoichiometric scaling to the calcium accretion and resorption rates, assuming a pure hydroxylapatite composition for the bone and tooth mineral. The model shows how the diet composition, body mass, ambient relative humidity and temperature may control the oxygen isotope composition of bone phosphate. The model also computes how bones and teeth record short-term variations in relative humidity, air temperature and delta18O of drinking water, depending on body mass. The documented diversity of oxygen isotope fractionation equations for vertebrates is accounted for by our model when for each specimen the physiological and diet parameters are adjusted in the living range of environmental conditions.

  7. Amino acid compositions in heated carbonaceous chondrites and their compound-specific nitrogen isotopic ratios

    NASA Astrophysics Data System (ADS)

    Chan, Queenie Hoi Shan; Chikaraishi, Yoshito; Takano, Yoshinori; Ogawa, Nanako O.; Ohkouchi, Naohiko

    2016-01-01

    A novel method has been developed for compound-specific nitrogen isotope compositions with an achiral column which was previously shown to offer high precision for nitrogen isotopic analysis. We applied the method to determine the amino acid contents and stable nitrogen isotopic compositions of individual amino acids from the thermally metamorphosed (above 500 °C) Antarctic carbonaceous chondrites Ivuna-like (CI)1 (or CI-like) Yamato (Y) 980115 and Ornans-like (CO)3.5 Allan Hills (ALH) A77003 with the use of gas chromatography/combustion/isotope ratio mass spectrometry. ALHA77003 was deprived of amino acids due to its extended thermal alteration history. Amino acids were unambiguously identified in Y-980115, and the δ15N values of selected amino acids (glycine +144.8 ‰; α-alanine +121.2 ‰) are clearly extraterrestrial. Y-980115 has experienced an extended period of aqueous alteration as indicated by the presence of hydrous mineral phases. It has also been exposed to at least one post-hydration short-lived thermal metamorphism. Glycine and alanine were possibly produced shortly after the accretion event of the asteroid parent body during the course of an extensive aqueous alteration event and have abstained from the short-term post-aqueous alteration heating due to the heterogeneity of the parent body composition and porosity. These carbonaceous chondrite samples are good analogs that offer important insights into the target asteroid Ryugu of the Hayabusa-2 mission, which is a C-type asteroid likely composed of heterogeneous materials including hydrated and dehydrated minerals.

  8. Soil moisture effects on the carbon isotope composition of soil respiration

    Treesearch

    Claire L. Phillips; Nick Nickerson; David Risk; Zachary E. Kayler; Chris Andersen; Alan Mix; Barbara J. Bond

    2010-01-01

    The carbon isotopic composition (δ13C) of recently assimilated plant carbon is known to depend on water-stress, caused either by low soil moisture or by low atmospheric humidity. Air humidity has also been shown to correlate with the δ13C of soil respiration, which suggests indirectly that recently fixed photosynthates...

  9. Perchlorate in the Great Lakes: isotopic composition and origin.

    PubMed

    Poghosyan, Armen; Sturchio, Neil C; Morrison, Candice G; Beloso, Abelardo D; Guan, Yunbin; Eiler, John M; Jackson, W Andrew; Hatzinger, Paul B

    2014-10-07

    Perchlorate is a persistent and mobile contaminant in the environment with both natural and anthropogenic sources. Stable isotope ratios of oxygen (δ(18)O, Δ(17)O) and chlorine (δ(37)Cl) along with the abundance of the radioactive isotope (36)Cl were used to trace perchlorate sources and behavior in the Laurentian Great Lakes. These lakes were selected for study as a likely repository of recent atmospheric perchlorate deposition. Perchlorate concentrations in the Great Lakes range from 0.05 to 0.13 μg per liter. δ(37)Cl values of perchlorate from the Great Lakes range from +3.0‰ (Lake Ontario) to +4.0‰ (Lake Superior), whereas δ(18)O values range from -4.1‰ (Lake Superior) to +4.0‰ (Lake Erie). Great Lakes perchlorate has mass-independent oxygen isotopic variations with positive Δ(17)O values (+1.6‰ to +2.7‰) divided into two distinct groups: Lake Superior (+2.7‰) and the other four lakes (∼+1.7‰). The stable isotopic results indicate that perchlorate in the Great Lakes is dominantly of natural origin, having isotopic composition resembling that measured for indigenous perchlorate from preindustrial groundwaters of the western USA. The (36)Cl/Cl ratio of perchlorate varies widely from 7.4 × 10(-12) (Lake Ontario) to 6.7 × 10(-11) (Lake Superior). These (36)ClO4(-) abundances are consistent with an atmospheric origin of perchlorate in the Great Lakes. The relatively high (36)ClO4(-) abundances in the larger lakes (Lakes Superior and Michigan) could be explained by the presence of (36)Cl-enriched perchlorate deposited during the period of elevated atmospheric (36)Cl activity following thermonuclear bomb tests in the Pacific Ocean.

  10. Statistical clumped isotope signatures

    PubMed Central

    Röckmann, T.; Popa, M. E.; Krol, M. C.; Hofmann, M. E. G.

    2016-01-01

    High precision measurements of molecules containing more than one heavy isotope may provide novel constraints on element cycles in nature. These so-called clumped isotope signatures are reported relative to the random (stochastic) distribution of heavy isotopes over all available isotopocules of a molecule, which is the conventional reference. When multiple indistinguishable atoms of the same element are present in a molecule, this reference is calculated from the bulk (≈average) isotopic composition of the involved atoms. We show here that this referencing convention leads to apparent negative clumped isotope anomalies (anti-clumping) when the indistinguishable atoms originate from isotopically different populations. Such statistical clumped isotope anomalies must occur in any system where two or more indistinguishable atoms of the same element, but with different isotopic composition, combine in a molecule. The size of the anti-clumping signal is closely related to the difference of the initial isotope ratios of the indistinguishable atoms that have combined. Therefore, a measured statistical clumped isotope anomaly, relative to an expected (e.g. thermodynamical) clumped isotope composition, may allow assessment of the heterogeneity of the isotopic pools of atoms that are the substrate for formation of molecules. PMID:27535168

  11. Stardust in STARDUST - the C, N, and O Isotopic Compositions of Wild 2 Cometary Matter in Al foil Impacts

    NASA Technical Reports Server (NTRS)

    Stadermann, Frank J.; Hoppe, Peter; Floss, Christine; Hoerz, Friedrich; Huth, Joachim; Kearsley, Anton T.; Leitner, Jan; Marhas, Kuljeet K.; McKeegan, Kevin D.; Stephan, Thomas; hide

    2007-01-01

    In January 2006, the STARDUST mission successfully returned dust samples from the tail of comet 81P/Wild 2 in two principal collection media, low density silica aerogel and Al foil. While hypervelocity impacts at 6.1 km/s, the encounter velocity of STARDUST, into Al foils are generally highly disruptive for natural, silicate-dominated impactors, previous studies have shown that many craters retain sufficient residue to allow a determination of the elemental and isotopic compositions of the original projectile. We have used the NanoSIMS to perform C, N, and O isotope imaging measurements on four large (59-370 microns diameter) and on 47 small (0.32-1.9 microns diameter) Al foil impact craters as part of the STARDUST Preliminary Examination. Most analyzed residues in and around these craters are isotopically normal (solar) in their C, N, and O isotopic compositions. However, the debris in one large crater shows an average 15N enrichment of approx. 450 %, which is similar to the bulk composition of some isotopically primitive interplanetary dust particles. A 250 nm grain in another large crater has an O-17 enrichment with approx. 2.65 times the solar O-17/O-16 ratio. Such an O isotopic composition is typical for circumstellar oxide or silicate grains from red giant or asymptotic giant branch stars. The discovery of this circumstellar grain clearly establishes that there is authentic stardust in the cometary samples returned by the STARDUST mission. However, the low apparent abundance of circumstellar grains in Wild 2 samples and the preponderance of isotopically normal material indicates that the cometary matter is a diverse assemblage of presolar and solar system materials.

  12. Primitive helium isotopic compositions associated with Miocene lavas from Northwest Iceland

    NASA Astrophysics Data System (ADS)

    Jackson, M. G.; Reinhard, A.; Blichert-Toft, J.; Price, A. A.; Kurz, M. D.; Halldorsson, S. A.

    2016-12-01

    Elevated 3He/4He ratios identified in hotspots globally are associated with an early-formed, less degassed mantle reservoir that resides in the deep mantle, but the origin and mechanism for the long-term preservation of this mantle domain are not well understood. The highest known terrestrial mantle-derived 3He/4He ratios (49.5 Ra) have been measured in 62 million year old lavas from Baffin Island and West Greenland, associated with the proto-Iceland plume [1]. Mid-Miocene lavas from northwest Iceland have 3He/4He ratios of up to 37 Ra [2]. Thus, the Iceland plume has tapped a high-3He/4He mantle source over much of the Cenozoic. This is important, as 182W [3] and 129Xe [4] data indicate that the high 3He/4He domain sampled by the Iceland plume formed in the early Hadean. We report new 3He/4He measurements on magmatic olivine in mid-Miocene lavas from Northwest Iceland. Fusion experiments indicate that the new, high 3He/4He ratios do not have a cosmogenic 3He contribution. New Sr, Nd, Hf, and Pb isotopic data place important constraints on the isotopic composition of the highest 3He/4He mantle domain sampled by mid-Miocene Iceland lavas. An important question is whether the highest 3He/4He lavas from Iceland have Sr-Nd-Hf-Pb isotopic compositions that overlap with those found in the high-3He/4He lavas from Baffin Island. If not, it will be important to understand the mechanism responsible for the offset in Sr-Nd-Hf-Pb isotopic compositions, and whether this also explains the lower maximum 3He/4He in mid-Miocene Icelandic lavas relative to their counterparts in Baffin Island. The new data will have implications for the preservation of primitive reservoirs in the deep mantle. [1] Stuart et al., Nature, v. 424, 2003. [2] Hilton et al., Earth Planet Sci. Lett., v. 173, 1999. [3] Rizo et al., Science, v. 352, 2016. [4] Mukhopadhyay, Nature, v. 486, 2012.

  13. Isotopic composition of Mg and Fe in garnet peridotites from the Kaapvaal and Siberian cratons

    NASA Astrophysics Data System (ADS)

    An, Yajun; Huang, Jin-Xiang; Griffin, W. L.; Liu, Chuanzhou; Huang, Fang

    2017-03-01

    We present Mg and Fe isotopic data for whole rocks and separated minerals (olivine, clinopyroxene, orthopyroxene, garnet, and phlogopite) of garnet peridotites that equilibrated at depths of 134-186 km beneath the Kaapvaal and Siberian cratons. There is no clear difference in δ26Mg and δ56Fe of garnet peridotites from these two cratons. δ26Mg of whole rocks varies from -0.243‰ to -0.204‰ with an average of -0.225 ± 0.037‰ (2σ, n = 19), and δ56Fe from -0.038‰ to 0.060‰ with an average of -0.003 ± 0.068‰ (2σ, n = 19). Both values are indistinguishable from the fertile upper mantle, indicating that there is no significant Mg-Fe isotopic difference between the shallow and deep upper mantle. The garnet peridotites from ancient cratons show δ26Mg similar to komatiites and basalts, further suggesting that there is no obvious Mg isotopic fractionation during different degrees of partial melting of deep mantle peridotites and komatiite formation. The precision of the Mg and Fe isotope data (⩽±0.05‰ for δ26Mg and δ56Fe, 2σ) allows us to distinguish inter-mineral isotopic fractionations. Olivines are in equilibrium with opx in terms of Mg and Fe isotopes. Garnets have the lowest δ26Mg and δ56Fe among the coexisting mantle minerals, suggesting the dominant control of crystal structure on the Mg-Fe isotopic compositions of garnets. Elemental compositions and mineralogy suggest that clinopyroxene and garnet were produced by later metasomatic processes as they are not in chemical equilibrium with olivine or orthopyroxene. This is consistent with the isotopic disequilibrium of Mg and Fe isotopes between orthopyroxene/olivine and garnet/clinopyroxene. Combined with one sample showing slightly heavy δ26Mg and much lighter δ56Fe, these disequilibrium features in the garnet peridotites reveal kinetic isotopic fractionation due to Fe-Mg inter-diffusion during reaction between peridotites and percolating melts in the Kaapvaal craton.

  14. Selective recharge and isotopic composition of shallow groundwater within temperate, epigenic carbonate aquifers

    NASA Astrophysics Data System (ADS)

    Florea, Lee J.

    2013-05-01

    This paper considers the variation of δ18O and δ2H (VSMOW) in precipitation and shallow groundwater from carbonate aquifers that lend insight into the source and timing of recharge within temperate, epigenic karst. The shallow groundwater collected during 2010 and 2011 at Stream Cave (SC) and Natural Bridge Caverns (NBC) represent one input to and the primary output from the Redmond Creek karst aquifer in the Cumberland Plateau of southeast Kentucky, respectively. These data are compared with the isotopic composition of concurrent samples of precipitation from the same watershed that covers some 1900 ha. Values of δ18O and δ2H at SC and NBC are statistically similar and cluster at the midpoint of the local meteoric water line. These values remain surprisingly constant despite seasonal changes in temperature regimens and discharge. Samples in 2012 from regional springs that include Redmond Creek are more depleted in the heavier isotope and similarly stable despite coming from aquifers of a range of sizes and physical characteristics. Applying a Priestly-Taylor model for daily values of potential evapotranspiration, only 43% of the 1.10 m of precipitation in the 2010-2011 dataset remains as potential recharge, primarily during cooler months with lower solar insolation. Weighting δ18O and δ2H values of precipitation by potential recharge creates a better match with the isotopic composition of shallow groundwater than by weighting by precipitation amount. The isotopic composition and deuterium excess of precipitation samples are directly and inversely proportional to temperature, respectively. Deuterium excess in this study and displays intra- and inter-annual variation that ranges from a minimum of +11.1‰ to a maximum of +29.5‰ that demonstrate the higher-than-average deuterium excess in greater Appalachia and the shifting latitude of moisture sources, including a significant winter component of re-evaporated, continental moisture.

  15. Isotopic and Trace Element Compositions of Antarctic Micrometeorites and Comparison with IDPs

    NASA Astrophysics Data System (ADS)

    Stadermann, F. J.; Olinger, C. T.

    1992-07-01

    Antarctic micrometeorites (AMMs) show resemblances and differences to both stratospheric interplanetary dust particles (IDPs) and chondritic meteorites, but the exact nature of this relationship has yet to be established. We measured Ne, H, C, and N isotopic compositions, as well as trace element abundances in several AMMs in order to compare the results to similar measurements of IDPs (Stadermann, 1991). AMMs for this study were collected near Cap-Prudhomme (Maurette et al., 1989), and optically selected (Olinger et al., 1990). Noble gases of 23 selected AMMs were extracted through laser vaporization. Nine of these particles contained implanted solar Ne and one showed a clear signature from spallogenic Ne, confirming their extraterrestrial origin. We selected fragments from 6 of these particles, plus 2 containing apparent Ne excess and one with a roughly chondritic bulk chemistry but immeasurably low Ne, for further analyses. Secondary ion mass spectrometry (SIMS) was used to measure the H, C, and N isotopic compositions. These measurements turned out to be difficult, since the concentrations of H and C in the analyzed samples were significantly lower than in IDPs. The low concentration of C also affected the N isotopic measurements because N could only be measured as CN-. We were able to measure H in 9, as well as C and N in 3 AMMs. All measurements yielded isotopically normal results. Previous determinations of the O isotopic compositions of the same samples (Virag, pers. comm.) also gave no indication of isotopic anomalies. These results are significantly different from measurements of IDPs, where isotopic anomalies in H and N were found in roughly 1/2 and 1/3 of the particles, respectively. SIMS was also used to measure the rare earth and trace element abundances in up to 4 different fragments of 6 AMMs. Although most particles had roughly chondritic abundances, anomalous concentrations were found for Ca, Li, Co, Ni, and Ba. Significant Ca depletions up to 0

  16. Experimental constraints on reconstruction of Archean seawater Ni isotopic composition from banded iron formations

    NASA Astrophysics Data System (ADS)

    Wang, Shui-Jiong; Wasylenki, Laura E.

    2017-06-01

    The Ni isotopic systematics in banded iron formations (BIFs) potentially recorded the Ni isotopic composition of ancient seawater over Precambrian geological history. However, the utility of BIFs as proxies requires quantitative knowledge of how Ni isotopes fractionated as dissolved Ni was initially incorporated into iron-rich sediments and how diagenesis may have affected the Ni isotopic systematics. Here we report results of synthesis experiments to investigate the behavior of Ni isotopes during Ni coprecipitation with ferrihydrite and then transformation of ferrihydrite to hematite. Ferrihydrite coprecipitation experiments at neutral pH demonstrated that the dissolved Ni was variably heavier than coprecipitated Ni (likely a mixture of surface-adsorbed and structurally incorporated Ni), with the isotope fractionation becoming larger as the fraction of Ni associated with solid increased (Δ60/58Nisolution-solid = +0.08 to +0.50‰). Further experiments at lower pH (3.7-6.7), in which structurally incorporated Ni likely dominated in solids, documented a decrease in Δ60/58Nisolution-solid from +0.44‰ to -0.18‰ as the pH decreased. The negative value for Δ60/58Nisolution-solid at low pH indicates the enrichment of heavier isotopes in incorporated Ni relative to dissolved and adsorbed Ni, possibly as a result of the presence of a small amount of tetrahedral Ni2+ in addition to octahedral Ni2+ in the ferrihydrite structure. The results of the ferrihydrite experiments thus reflect equilibrium isotope fractionation between three pools of Ni, with δ60/58Ni values in the order of incorporated > dissolved > adsorbed. Hematite was synthesized by transformation of Ni-bearing ferrihydrite in aqueous solution at ∼100 °C. A significant amount of Ni (up to 60%) was released (desorbed) from solids into solutions as pH dropped from ∼7 to 4.5-5.5 upon phase transformation. Rinsing of the synthesized hematite in 2 M acetic acid released only very small amounts of Ni (<4

  17. [Tracing Sources of Sulfate Aerosol in Nanjing Northern Suburb Using Sulfur and Oxygen Isotopes].

    PubMed

    Wei, Ying; Guo, Zhao-bing; Ge, Xin; Zhu, Sheng-nan; Jiang, Wen-juan; Shi, Lei; Chen, Shu

    2015-04-01

    Abstract: To trace the sources of sulfate contributing to atmospheric aerosol, PM2.5 samples for isotopic analysis were collected in Nanjing northern suburb during January 2014. The sulfur and oxygen isotopic compositions of sulfate from these samples were determined by EA-IRMS. Source identification and apportionment were carried out using stable isotopic and chemical evidences, combined with absolute principal component analysis (APCA) method. The Δ34S values of aerosol sulfate ranged from 2.7 per thousand to 6.4 per thousand, with an average of 5.0 per thousand ± 0.9 per thousand, while the Δ18O values ranged from 10.6 per thousand to 16.1 per thousand, with an average of 12.5 per thousand ± 1.37 per thousand. In conjunction with air mass trajectories, the results suggested that aerosol sulfates were controlled by a dominance of local anthropogenic sulfate, followed by the contributions of long-distance transported sulfate. There was a minor effect of some other low-Δ34S valued sulfates, which might be expected from biogenic sources. Absolute principal component analysis results showed that the contributions of anthropogenic sulfate and long-distance transported sulfate were 46.74% and 31.54%, respectively.

  18. Isotopic composition of cosmic ray nitrogen at 1.5 GeV/amu

    NASA Technical Reports Server (NTRS)

    Dwyer, R.; Meyer, P.

    1975-01-01

    For any location, the earth's magnetic field acts as a filter for incoming cosmic rays, allowing only particles above a certain rigidity. The relative isotopic composition of abundant elements can be measured with a detector sensitive to the velocity of particles in the penumbra of the earth's magnetic field. In this paper, the nitrogen velocity spectrum is compared with that of carbon plus oxygen as a reference, since in this case Z-dependent effects are minimal. The form of the energy spectrum of carbon, nitrogen, and oxygen, needed for proper correction, was measured in the same experiment. The results were obtained using a scintillator-Cerenkov counter telescope with a geometric factor of 0.25 sq in sr, flown twice on high-altitude balloons from Palestine, Texas, obtaining an exposure factor of 20 sq m sr hr. Results are presented on the isotopic composition of nitrogen at about 1.5GeV/amu.

  19. Identification of cellular MMP substrates using quantitative proteomics: isotope-coded affinity tags (ICAT) and isobaric tags for relative and absolute quantification (iTRAQ).

    PubMed

    Butler, Georgina S; Dean, Richard A; Morrison, Charlotte J; Overall, Christopher M

    2010-01-01

    Identification of protease substrates is essential to understand the functional consequences of normal proteolytic processing and dysregulated proteolysis in disease. Quantitative proteomics and mass spectrometry can be used to identify protease substrates in the cellular context. Here we describe the use of two protein labeling techniques, Isotope-Coded Affinity Tags (ICAT and Isobaric Tags for Relative and Absolute Quantification (iTRAQ), which we have used successfully to identify novel matrix metalloproteinase (MMP) substrates in cell culture systems (1-4). ICAT and iTRAQ can label proteins and protease cleavage products of secreted proteins, protein domains shed from the cell membrane or pericellular matrix of protease-transfected cells that have accumulated in conditioned medium, or cell surface proteins in membrane preparations; isotopically distinct labels are used for control cells. Tryptic digestion and tandem mass spectrometry of the generated fragments enable sequencing of differentially labeled but otherwise identical pooled peptides. The isotopic tag, which is unique for each label, identifies the peptides originating from each sample, for instance, protease-transfected or control cells, and comparison of the peak areas enables relative quantification of the peptide in each sample. Thus proteins present in altered amounts between protease-expressing and null cells are implicated as protease substrates and can be further validated as such.

  20. Nitrogen isotopic baselines and implications for estimating foraging habitat and trophic position of yellowfin tuna in the Indian and Pacific Oceans

    NASA Astrophysics Data System (ADS)

    Lorrain, Anne; Graham, Brittany S.; Popp, Brian N.; Allain, Valérie; Olson, Robert J.; Hunt, Brian P. V.; Potier, Michel; Fry, Brian; Galván-Magaña, Felipe; Menkes, Christophe E. R.; Kaehler, Sven; Ménard, Frédéric

    2015-03-01

    Assessment of isotopic compositions at the base of food webs is a prerequisite for using stable isotope analysis to assess foraging locations and trophic positions of marine organisms. Our study represents a unique application of stable-isotope analyses across multiple trophic levels (primary producer, primary consumer and tertiary consumer) and over a large spatial scale in two pelagic marine ecosystems. We found that δ15N values of particulate organic matter (POM), barnacles and phenylalanine from the muscle tissue of yellowfin tuna all showed similar spatial patterns. This consistency suggests that isotopic analysis of any of these can provide a reasonable proxy for isotopic variability at the base of the food web. Secondly, variations in the δ15N values of yellowfin tuna bulk-muscle tissues paralleled the spatial trends observed in all of these isotopic baseline proxies. Variation in isotopic composition at the base of the food web, rather than differences in tuna diet, explained the 11‰ variability observed in the bulk-tissue δ15N values of yellowfin tuna. Evaluating the trophic position of yellowfin tuna using amino-acid isotopic compositions across the western Indian and equatorial Pacific Oceans strongly suggests these tuna occupy similar trophic positions, albeit absolute trophic positions estimated by this method were lower than expected. This study reinforces the importance of considering isotopic baseline variability for diet studies, and provides new insights into methods that can be applied to generate nitrogen isoscapes for worldwide comparisons of top predators in marine ecosystems.

  1. Changes in erosion and ocean circulation recorded in the Hf isotopic compositions of North Atlantic and Indian Ocean ferromanganese crusts

    USGS Publications Warehouse

    Piotrowski, Alexander M.; Lee, Der-Chuen; Christensen, John N.; Burton, Kevin W.; Halliday, Alex N.; Hein, James R.; Günther, Detlef

    2000-01-01

    High-resolution Hf isotopic records are presented for hydrogenetic Fe–Mn crusts from the North Atlantic and Indian Oceans. BM1969 from the western North Atlantic has previously been shown to record systematically decreasing Nd isotopic compositions from about 60 to ∼4 Ma, at which time both show a rapid decrease to unradiogenic Nd composition, thought to be related to the increasing influence of NADW or glaciation in the northern hemisphere. During the Oligocene, North Atlantic Hf became progressively less radiogenic until in the mid-Miocene (∼15 Ma) it reached +1. It then shifted gradually back to an ϵHf value of +3 at 4 Ma, since when it has decreased rapidly to about −1 at the present day. The observed shifts in the Hf isotopic composition were probably caused by variation in intensity of erosion as glaciation progressed in the northern hemisphere. Ferromanganese crusts SS663 and 109D are from about 5500 m depth in the Indian Ocean and are now separated by ∼2300 km across the Mid-Indian Ridge. They display similar trends in Hf isotopic composition from 20 to 5 Ma, with the more northern crust having a composition that is consistently more radiogenic (by ∼2 ϵHf units). Paradoxically, during the last 20 Ma the Hf isotopic compositions of the two crusts have converged despite increased separation and subsidence relative to the ridge. A correlatable negative excursion at ∼5 Ma in the two records may reflect a short-term increase in erosion caused by the activation of the Himalayan main central thrust. Changes to unradiogenic Hf in the central Indian Ocean after 5 Ma may alternatively have been caused by the expanding influence of NADW into the Mid-Indian Basin via circum-Antarctic deep water or a reduction of Pacific flow through the Indonesian gateway. In either case, these results illustrate the utility of the Hf isotope system as a tracer of paleoceanographic changes, capable of responding to subtle changes in erosional regime not readily resolved

  2. V isotope composition in modern marine hydrothermal sediments

    NASA Astrophysics Data System (ADS)

    Wu, F.; Owens, J. D.; Nielsen, S.; German, C. R.; Rachel, M.

    2017-12-01

    Vanadium is multivalence transition metal with two isotopes (51V and 50V). Recent work has shown that large V isotope variations occur with oxygen variations in modern sediments (Wu et al., 2016 and 2017 Goldschmidt Abstracts), providing its potential as a promising proxy for determining low oxygen conditions. However, the development of V isotopes as a proxy to probe past redox conditions requires a comprehensive understanding of the modern oceanic isotopic mass balance. Therein, the scavenging of V from the hydrous iron oxides in hydrothermal fluid has been shown to be an important removal process from seawater (Rudnicki and Elderfield, 1993 GCA) but remains unquantified. In this study, we analyzed V isotopic compositions of metalliferous sediments around the active TAG hydrothermal mound from the mid-Atlantic Ridge (26° degrees North) and the Eastern Pacific Zonal Transect (GEOTRACES EPZT cruise GP16). The TAG sediments deposited as Fe oxyhydroxides from plume fall-out, and have δ51V values between -0.3 to 0‰. The good correlation between Fe and V for these metalliferous sediments indicate that the accumulation of V in these samples is directly related to the deposition of Fe oxyhydroxides, which also control their V isotope signature. The EPZT samples cover 8,000 km in the South Pacific Ocean with sedimentary areas that underlie the Peru upwelling region and the well-oxygenated deep South Pacific Ocean influenced by hydtorthermal plume material from southern East Pacific Rise (EPR). The sediments collected at the east of the EPR have δ51V values between -1.2 to -0.7‰, similar to previous δ51V of oxic sediments. In contrast, the sediments from the west of the EPR have δ51V values (-0.4 to 0‰) similar to hydrothermal sediments from the mid-Atlantic Ridge, indicating the long transportation (more than 4,000 km, Fitzsimmons et al., 2017 NG) of Fe and Mn from hydrothermal plume and their incorporation into sediments have a major impact on the cycle of V

  3. Interrogating trees for isotopic archives of atmospheric sulphur deposition and comparison to speleothem records.

    PubMed

    Wynn, P M; Loader, N J; Fairchild, I J

    2014-04-01

    Palaeorecords which depict changes in sulphur dynamics form an invaluable resource for recording atmospheric pollution. Tree rings constitute an archive that are ubiquitously available and can be absolutely dated, providing the potential to explore local- to regional-scale trends in sulphur availability. Rapid isotopic analysis by a novel "on-line" method using elemental analyser isotope ratio mass spectrometry (EA-IRMS) is developed, achieving sample precision of <0.4‰ using sample sizes of 40 mg wood powder. Tree cores from NE Italy show trends in pollution, evidenced through increasing concentrations of sulphur towards the youngest growth, and inverse trends in sulphur isotopes differentiating modern growth with light sulphur isotopes (+0.7‰) from pre-industrial growth (+7.5‰) influenced by bedrock composition. Comparison with speleothem records from the same location demonstrate replication, albeit offset in isotopic value due to groundwater storage. Using EA-IRMS, tree ring archives form a valuable resource for understanding local- to regional-scale sulphur pollution dynamics. Copyright © 2013 Elsevier Ltd. All rights reserved.

  4. Standardization approaches in absolute quantitative proteomics with mass spectrometry.

    PubMed

    Calderón-Celis, Francisco; Encinar, Jorge Ruiz; Sanz-Medel, Alfredo

    2017-07-31

    Mass spectrometry-based approaches have enabled important breakthroughs in quantitative proteomics in the last decades. This development is reflected in the better quantitative assessment of protein levels as well as to understand post-translational modifications and protein complexes and networks. Nowadays, the focus of quantitative proteomics shifted from the relative determination of proteins (ie, differential expression between two or more cellular states) to absolute quantity determination, required for a more-thorough characterization of biological models and comprehension of the proteome dynamism, as well as for the search and validation of novel protein biomarkers. However, the physico-chemical environment of the analyte species affects strongly the ionization efficiency in most mass spectrometry (MS) types, which thereby require the use of specially designed standardization approaches to provide absolute quantifications. Most common of such approaches nowadays include (i) the use of stable isotope-labeled peptide standards, isotopologues to the target proteotypic peptides expected after tryptic digestion of the target protein; (ii) use of stable isotope-labeled protein standards to compensate for sample preparation, sample loss, and proteolysis steps; (iii) isobaric reagents, which after fragmentation in the MS/MS analysis provide a final detectable mass shift, can be used to tag both analyte and standard samples; (iv) label-free approaches in which the absolute quantitative data are not obtained through the use of any kind of labeling, but from computational normalization of the raw data and adequate standards; (v) elemental mass spectrometry-based workflows able to provide directly absolute quantification of peptides/proteins that contain an ICP-detectable element. A critical insight from the Analytical Chemistry perspective of the different standardization approaches and their combinations used so far for absolute quantitative MS-based (molecular and

  5. The stable isotope composition of nitrogen and carbon and elemental contents in modern and fossil seabird guano from Northern Chile - Marine sources and diagenetic effects.

    PubMed

    Lucassen, Friedrich; Pritzkow, Wolfgang; Rosner, Martin; Sepúlveda, Fernando; Vásquez, Paulina; Wilke, Hans; Kasemann, Simone A

    2017-01-01

    Seabird excrements (guano) have been preserved in the arid climate of Northern Chile since at least the Pliocene. The deposits of marine organic material in coastal areas potentially open a window into the present and past composition of the coastal ocean and its food web. We use the stable isotope composition of nitrogen and carbon as well as element contents to compare the principal prey of the birds, the Peruvian anchovy, with the composition of modern guano. We also investigate the impact of diagenetic changes on the isotopic composition and elemental contents of the pure ornithogenic sediments, starting with modern stratified deposits and extending to fossil guano. Where possible, 14C systematics is used for age information. The nitrogen and carbon isotopic composition of the marine prey (Peruvian anchovy) of the birds is complex as it shows strong systematic variations with latitude. The detailed study of a modern profile that represents a few years of guano deposition up to present reveals systematic changes in nitrogen and carbon isotopic composition towards heavier values that increase with age, i.e. depth. Only the uppermost, youngest layers of modern guano show compositional affinity to the prey of the birds. In the profile, the simultaneous loss of nitrogen and carbon occurs by degassing, and non-volatile elements like phosphorous and calcium are passively enriched in the residual guano. Fossil guano deposits are very low in nitrogen and low in carbon contents, and show very heavy nitrogen isotopic compositions. One result of the study is that the use of guano for tracing nitrogen and carbon isotopic and elemental composition in the marine food web of the birds is restricted to fresh material. Despite systematic changes during diagenesis, there is little promise to retrieve reliable values of marine nitrogen and carbon signatures from older guano. However, the changes in isotopic composition from primary marine nitrogen isotopic signatures towards very

  6. Fe isotope composition of bulk chondrules from Murchison (CM2): Constraints for parent body alteration, nebula processes and chondrule-matrix complementarity

    NASA Astrophysics Data System (ADS)

    Hezel, Dominik C.; Wilden, Johanna S.; Becker, Daniel; Steinbach, Sonja; Wombacher, Frank; Harak, Markus

    2018-05-01

    Chondrules are a major constituent of primitive meteorites. The formation of chondrules is one of the most elusive problems in cosmochemistry. We use Fe isotope compositions of chondrules and bulk chondrites to constrain the conditions of chondrule formation. Iron isotope compositions of bulk chondrules are so far only known from few studies on CV and some ordinary chondrites. We studied 37 chondrules from the CM chondrite Murchison. This is particularly challenging, as CM chondrites contain the smallest chondrules of all chondrite groups, except for CH chondrites. Bulk chondrules have δ56Fe between -0.62 and +0.24‰ relative to the IRMM-014 standard. Bulk Murchison has as all chondrites a δ56Fe of 0.00‰ within error. The δ56Fe distribution of the Murchison chondrule population is continuous and close to normal. The width of the δ56Fe distribution is narrower than that of the Allende chondrule population. Opaque modal abundances in Murchison chondrules is in about 67% of the chondrules close to 0 vol.%, and in 33% typically up to 6.5 vol.%. Chondrule Al/Mg and Fe/Mg ratios are sub-chondritic, while bulk Murchison has chondritic ratios. We suggest that the variable bulk chondrule Fe isotope compositions were established during evaporation and recondensation prior to accretion in the Murchison parent body. This range in isotope composition was likely reduced during aqueous alteration on the parent body. Murchison has a chondritic Fe isotope composition and a number of chondritic element ratios. Chondrules, however, have variable Fe isotope compositions and chondrules and matrix have complementary Al/Mg and Fe/Mg ratios. In combination, this supports the idea that chondrules and matrix formed from a single reservoir and were then accreted in the parent body. The formation in a single region also explains the compositional distribution of the chondrule population in Murchison.

  7. Isotopic composition analysis and age dating of uranium samples by high resolution gamma ray spectrometry

    NASA Astrophysics Data System (ADS)

    Apostol, A. I.; Pantelica, A.; Sima, O.; Fugaru, V.

    2016-09-01

    Non-destructive methods were applied to determine the isotopic composition and the time elapsed since last chemical purification of nine uranium samples. The applied methods are based on measuring gamma and X radiations of uranium samples by high resolution low energy gamma spectrometric system with planar high purity germanium detector and low background gamma spectrometric system with coaxial high purity germanium detector. The ;Multigroup γ-ray Analysis Method for Uranium; (MGAU) code was used for the precise determination of samples' isotopic composition. The age of the samples was determined from the isotopic ratio 214Bi/234U. This ratio was calculated from the analyzed spectra of each uranium sample, using relative detection efficiency. Special attention is paid to the coincidence summing corrections that have to be taken into account when performing this type of analysis. In addition, an alternative approach for the age determination using full energy peak efficiencies obtained by Monte Carlo simulations with the GESPECOR code is described.

  8. Stardust in STARDUST - the C, N, and O Isotopic Compositions of Wild 2 Cometary Matter in Al Foil Impacts

    NASA Technical Reports Server (NTRS)

    Stadermann, Frank J.; Hoppe, Peter; Floss, Christine; Heck, Philipp R.; Hoerz, Friedrich; Huth, Joachim; Kearsley, Anton T.; Leitner, Jan; Marhas, Kuljeet K.; McKeegan, Kevin D.; hide

    2007-01-01

    In January 2006, the Stardust mission successfully returned dust samples from the tail of comet 81P/Wild 2 in two principal collection media, low density silica aerogel and Al foil. While hypervelocity impacts at the Stardust encounter velocity of 6.1 kilometers per second into Al foils are generally highly disruptive for natural, silicate-dominated impactors, previous studies have shown that many craters retain sufficient residue to allow a determination of the elemental and isotopic compositions of the original projectile. We have used two NanoSIMS ion microprobes to perform C, N, and O isotope imaging measurements on four large (59-295 micrometer diameter) and on 47 small (0.32-1.9 micrometer diameter) Al foil impact craters as part of the Stardust Preliminary Examination. Most analyzed residues in and around these craters are isotopically normal (solar) in their C, N, and O isotopic compositions. However, the debris in one large crater shows an average N-15 enrichment of approx. 450%o, which is similar to the bulk composition of some isotopically primitive interplanetary dust particles and to components of some primitive meteorites. A 250 nm grain in another large crater has an O-17 enrichment with approx. 2.65 times the solar O-17/O-16 ratio. Such an O isotopic composition is typical for circumstellar oxide or silicate grains from red giant or asymptotic giant branch stars. The discovery of this circumstellar grain clearly establishes that there is authentic stardust in the cometary samples returned by the Stardust mission. However, the low apparent abundance of circumstellar grains in Wild 2 samples and the preponderance of isotopically normal material indicates that the cometary matter is a diverse assemblage of presolar and solar system materials.

  9. The effects of magmatic processes and crustal recycling on the molybdenum stable isotopic composition of Mid-Ocean Ridge Basalts

    NASA Astrophysics Data System (ADS)

    Bezard, Rachel; Fischer-Gödde, Mario; Hamelin, Cédric; Brennecka, Gregory A.; Kleine, Thorsten

    2016-11-01

    Molybdenum (Mo) stable isotopes hold great potential to investigate the processes involved in planetary formation and differentiation. However their use is currently hampered by the lack of understanding of the dominant controls driving mass-dependent fractionations at high temperature. Here we investigate the role of magmatic processes and mantle source heterogeneities on the Mo isotope composition of Mid-Ocean Ridges Basalts (MORBs) using samples from two contrasting ridge segments: (1) the extremely fast spreading Pacific-Antarctic (66-41°S) section devoid of plume influence and; (2) the slow spreading Mohns-Knipovich segment (77-71°N) intercepted by the Jan Mayen Plume (71°N). We show that significant variations in Mo stable isotope composition exist in MORBs with δ98/95Mo ranging from - 0.24 ‰ to + 0.15 ‰ (relative to NIST SRM3134). The absence of correlation between δ98/95Mo and indices of magma differentiation or partial melting suggests a negligible impact of these processes on the isotopic variations observed. On the other hand, the δ98/95Mo variations seem to be associated with changes in radiogenic isotope signatures and rare earth element ratios (e.g., (La/Sm)N), suggesting mantle source heterogeneities as a dominant factor for the δ98/95Mo variations amongst MORBs. The heaviest Mo isotope compositions correspond to the most enriched signatures, suggesting that recycled crustal components are isotopically heavy compared to the uncontaminated depleted mantle. The uncontaminated depleted mantle shows slightly sub-chondritic δ98/95Mo, which cannot be produced by core formation and, therefore, more likely result from extensive anterior partial melting of the mantle. Consequently, the primitive δ98/95Mo composition of the depleted mantle appears overprinted by the effects of both partial melting and crustal recycling.

  10. Measurement of the Carbon Isotopic Composition of Methane Using Helicoidal Laser Eigenstates

    NASA Astrophysics Data System (ADS)

    Jacob, D.; Le Floch, A.; Bretenaker, F.; Guenot, P.

    1996-06-01

    The spatially generalized Jones matrix formalism is used to design a laser cavity to make intracavity measurements of the carbon isotopic composition of methane. the method is based on a double optical lever effect for helicoidally polarized eigenstates, permitting to measure successively the ^{12}CH_4 and ^{13}CH_4 concentrations. To choose the probed isotope, one simply tunes the frequency of the laser by Zeeman effect. The experiment exhibits a good agreement with the predictions and permits to measure the ^{13}CH4/^{12}CH_4 composition ratio of methane with an uncertainty of the order of ± 0.07% for a sample containing only 6× 10^{-9} mole of methane. On utilise le formalisme des matrices de Jones généralisées spatialement pour concevoir une cavité laser permettant la mesure intra-cavité de la composition isotopique du carbone présent dans le méthane. La méthode est fondée sur une double application de l'effet de levier optique pour les états propres hélicoïdaux, permettant de mesurer successivement les concentrations de ^{12}CH_4 et de ^{13}CH_4. Pour passer d'un isotope à l'autre, on ajuste simplement la fréquence du laser par effet Zeeman. L'expérience est en bon accord avec les prédictions et permet d'effectuer la mesure du rapport isotopique ^{13}CH4/^{12}CH_4 avec une fourchette d'incertitude de ± 0,07% pour des échantillons de gaz ne contenant que 6× 10^{-9} mole de méthane.

  11. Variation in the isotopic composition of striped weakfish Cynoscion guatucupa of the Southwest Atlantic Ocean in response to dietary shifts.

    PubMed

    Viola, M N Paso; Riccialdelli, L; Jaureguizar, A; Panarello, H O; Cappozzo, H L

    2018-05-01

    The aim of this study was to analyze the isotopic composition in muscle of striped weakfish Cynoscion guatucupa from Southwest Atlantic Ocean in order to evaluate a possible variation in δ13C and δ15N in response to dietary shifts that occur as animals grow. We also explored for isotopic evidence of differences between sample locations. The results showed an agreement between isotope analysis and previous conventional studies. Differences in the isotope composition between sampling location were not observed. A positive relation exists between isotope values and total body length of the animals. The Cluster analysis defined three groups of size classes, validated by the MDS. Differences in the relative consumption of prey species in each size class were also observed performing isotope mixing models (SIAR). Variation in δ15N among size classes would be associated with the consumption of a different type of prey as animals grow. Small striped weakfish feed on small crustaceans and progressively increase their consumption of fish (anchovy, Engraulis anchoita), increasing by this way their isotope values. On the other hand, differences in δ13C values seemed to be related to age-class specific spatial distribution patterns. Therefore, large and small striped weakfish remain specialized but feeding on different prey at different trophic levels. These results contribute to the study of the diet of striped weakfish, improve the isotopic ecology models and highlight on the importance of accounting for variation in the isotopic composition in response to dietary shifts with the size of one of the most important fishery resources in the region.

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

    NASA Technical Reports Server (NTRS)

    Blum, J. D.; Klaue, Bjorn

    2005-01-01

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

  13. Methane flux and carbon isotope composition correlate to shifting plant and microbial communities along a permafrost thaw gradient

    NASA Astrophysics Data System (ADS)

    McCalley, C. K.; Mondav, R.; Chanton, J.; Crill, P. M.; Hodgkins, S. B.; Kim, E.; Rich, V. I.; Wehr, R.; Woodcroft, B. J.; Tyson, G. W.; Saleska, S. R.

    2012-12-01

    Methane flux from high latitude wetlands is a critical component of the global carbon budget and is highly sensitive to climate change, with observed and predicted increases as permafrost thaws. Microorganisms mediate wetland methane cycling, but connections between ecosystem-scale flux and underlying microbial dynamics are poorly understood. To address this gap we used isotopic (laser absorption spectrometry) and molecular (16S rRNA gene amplicon sequencing) techniques in a high latitude (68° N) wetland to investigate the relationship between microbial community composition and methane emissions across a permafrost thaw gradient. The transition from permafrost dominated, well drained palsas, through intermediate thaw sites dominated by Sphagnum spp., to wet sites with no underlying permafrost dominated by Eriophorum angustifolium is associated with substantial increases in methane emission. Across this thaw progression the carbon isotopic composition of emitted methane increased from -79.5 ‰ in the intermediate-thawing site to -66.4 ‰ in the thawed site, indicating a relative shift from CO2-reductive towards acetoclastic methanogenesis. Increases in methane flux under thaw were correlated with increasing abundance of methane-producing archaeal clades and increases in methane isotopic composition were associated with shifts in the archaeal community. While CO2 reducing methanogens were found throughout thawing and thawed sites, methanogens of the Methanosarcina (the order of Archaea that contains all known acetoclastic methanogens) were most associated with the fully thawed site. These results directly link microbial community composition to ecosystem scale changes in the magnitude and isotopic composition of methane emissions under permafrost thaw. If isotopic shifts of this magnitude are characteristic of methane dynamics under permafrost loss they should also become detectable in global atmospheric methane observations, providing a global scale tracer of

  14. Sulfide in the core and the Nd isotopic composition of the silicate Earth

    NASA Astrophysics Data System (ADS)

    McCoy-West, A.; Millet, M. A.; Nowell, G. M.; Wohlers, A.; Wood, B. J.; Burton, K. W.

    2016-12-01

    The chemical composition of the Earth is traditionally explained in terms of evolution from a solar-like composition, similar to that found in primitive chondritic meteorites. It now appears, however, that the silicate Earth is not chondritic, but depleted in incompatible elements and a resovable 20 ppm excess is observed in 142Nd relative to chondirtes [1, 2]. This anomaly requires a process that occurred within 30 Myr of solar system formation and has been variably ascribed to: a complementary enriched reservoir in the deep Earth [1]; loss to space through collisional erosion [3]; or the inhertence of nucleosynthetic anomalies [4]. Sulfide in the core may provide a reservoir capable of balancing the composition of the silicate Earth. Recent experimental work suggests that the core contains a significant proportion of sulfide, added during the final stages of accretion and new data suggests that at high pressures sulfide can incorporate a substantial amount of refractory lithophile and heat-producing elements [5]. The drawback of the short-lived 146Sm-142Nd radiogenic isotope system is that it is not possible to distinguish between fractionations of Sm/Nd that occurs during silicate melting or segregation of a sulfide-melt. Neodymium stable isotopes have the potential to provide just such a tracer of sulfide segregation, because there is a significant contrast in bonding environment between sulfide and silicate, where heavy isotopes should be preferentially incorporated into high force-constant bonds involving REE3+ (i.e. the silicate mantle). Preliminary data indicate that mantle rocks do indeed possess heavier 146Nd/144Nd values than chondritic meteorites by 0.3 ‰, consistent with the removal of light Nd into sulfide in the core, driving the residual mantle to heavier values. Overall, our isotope and elemental data indicate that the rare earths and other incompatible elements are substantially incorporated into sulfide. While Nd stable isotope data for

  15. Stable isotope compositions of waters in the Great Basin, United States 3. Comparison of groundwaters with modern precipitation

    USGS Publications Warehouse

    Smith, G.I.; Friedman, I.; Veronda, G.; Johnson, C.A.

    2002-01-01

    Groundwater samples from wells and springs, scattered over most of the Great Basin province, were collected and analyzed for their isotopic makeup. They were augmented by previously published isotopic data on groundwaters from southeast California and by several hundred unpublished isotopic analyses. The ratio of 2H (deuterium, D) to 1H, in water samples from valleys in parts of California, Idaho, Nevada, Oregon, and Utah, are here compared with the winter, summer, and annual isotopic compositions of precipitation falling in or near the sampled areas. The main goal of this study was to identify basins where the groundwaters have isotopic compositions that are "lighter" (depleted in the heavier isotope, D) relative to modern winter precipitation. Where these basins do not adjoin substantially higher terrain, we consider those light groundwaters to be of Pleistocene age and thus more than 10,000 years old. Where the groundwater is 10 to 19??? lighter than local winter precipitation, we consider it to be possibly an indication of Pleistocene water; where the ??D makeup is >20??? lighter, we consider it to be probably Pleistocene water. More than 80 sites underlain by waters of possible or probable Pleistocene age were identified.

  16. Experimental Constraints on Reconstruction of Archean Seawater Ni Isotopic Composition from Banded Iron Formations

    NASA Astrophysics Data System (ADS)

    Wang, S.; Wasylenki, L.

    2016-12-01

    Ni isotope systematics in banded iron formations (BIFs) potentially recorded the Ni isotopic composition of ancient seawater during the Precambrian Eon[1]. The use of BIFs as seawater proxies requires knowing how Ni isotopes fractionated during initial incorporation into iron-rich sediments and during early diagenesis. We conducted experiments to investigate Ni isotope behavior during coprecipitation with ferrihydrite and transformation of ferrihydrite to hematite. Ferrihydrite synthesis at neutral pH demonstrated that dissolved Ni was variably heavier than coprecipitated Ni (Δ60/58Ni = +0.08 to +0.50 ‰), in contrast to the constant offset observed earlier during adsorption to pre-existing ferrihydrite[2]. Experiments at lower pH (<7) yielded negative values of Δ60/58Ni ( -0.18 ‰), suggesting enrichment in heavier isotopes of structurally incorporated Ni relative to dissolved and adsorbed Ni, possibly due to the presence of a small amount of highly fractionated tetrahedral Ni2+ in the ferrihydrite structure. We model our results as equilibrium fractionation among three pools of Ni with systematically varied proportions. We synthesized hematite by transforming Ni-bearing ferrihydrite in aqueous solution at 100 °C and observed significant Ni release from solids (up to 60 %) as pH dropped from 7 to 4.5 - 5.5 during phase transformation. Rinsing hematite with acetic acid released very little Ni (presumably surface-adsorbed) compared to the amounts remaining in solid residues (presumably incorporated). We infer that Δ60/58Ni values (-0.04 to +0.77 ‰) observed in hematite experiments likely reflect Rayleigh fractionation between incorporated and dissolved Ni. The final hematite was slightly lighter than the ferrihydrite had been (by 0.08 ‰), indicating that this phase transformation results in very limited change in Ni isotopic composition, given current analytical uncertainty of ± 0.09 ‰. [1] Wasylenki and Wang (2016) Goldschmidt; [2] Wasylenki et al

  17. Characterisation of methane isotope composition over the Silesian Coal Basin, Poland.

    NASA Astrophysics Data System (ADS)

    Necki, Jaroslaw; Zimnoch, Miroslaw; Jasek, Alina; Chmura, Lukasz; Galkowski, Michal; Wolkowicz, Wojciech

    2017-04-01

    Methane emissions from Silesian Coal Basin (SCB), one of European regions associated with coal excavation industry constitute an important component of the continental anthropogenic flux of this gas into the atmosphere. It is estimated by different methodology that SCB is responsible for between 450 - 1350 Gg CH4 of atmospheric methane releases annually, making it one of the most significant sources of this gas in Europe. In this region, active or restructuring coal mining methane emissions may lead to elevated concentrations of this gas in near-ground atmosphere. Observed methane mixing ratio in pbl during nighttime over the specific areas of SCB is elevated by up to 50ppm with carbon isotope source ratio -46‰ to -52‰ with occasionally lighter methane (-58) form particular coal beds. Numbers were derived from direct measurement of samples taken from ventilation shafts (concentration 1.5% to 4% of CH4, subsequently diluted to 2ppm with zero air and measured by Picarro CRDS analyzer). Measurements of CH4 mixing ratios and isotopic composition were performed along latitudinal transects (ca. 50oN), typically extending from ca. 15oE to 20oE, covering the Upper Silesia and bordering regions on the public roads in vicinity of the mine ventilation shafts. Apart from CH4 emissions associated with coal production, other sources of anthropogenic methane are also active over SCB. These include city gas networks leakages that enrich the air by up to 5ppm (in the city centers, carbon isotope ratio on average -52). Most of the numerous landfills, not yet equipped with appropriate CH4 uptake installations, also contribute to substantial anthropogenic flux of this gas to the atmosphere. Values of methane mixing ratio recorded during the in-situ measurements close to the landfill sites reached 15ppm (with carbon isotope ratio -56‰ to -60). The transects of methane concentration over Silesian area, assisted by analysis of its stable isotopic composition has been performed in

  18. A new method and application for determining the nitrogen isotopic composition of NOx

    NASA Astrophysics Data System (ADS)

    Hastings, M. G.; Miller, D. J.; Wojtal, P.; O'Connor, M.

    2015-12-01

    Atmospheric nitrogen oxides (NOx = NO + NO2) play key roles in atmospheric chemistry, air quality, and radiative forcing, and contribute to nitric acid deposition. Sources of NOx include both natural and anthropogenic emissions, which vary significantly in space and time. NOx isotopic signatures offer a potentially valuable tool to trace source impacts on atmospheric chemistry and regional acid deposition. Previous work on NOx isotopic signatures suggests large ranges in values, even from the same emission source, as well as overlapping ranges amongst different sources, making it difficult to use the isotopic composition as a quantitative tracer of source influences. These prior measurements have utilized a variety of methods for collecting the NOx as nitrate or nitrite for isotopic analysis, and testing of some of these methods (including active and passive collections) reveal inconsistencies in efficiency of collection, as well as issues related to changes in conditions such as humidity, temperature, and NOx fluxes. A recently developed method allows for accurately measuring the nitrogen isotopic composition of NOx (NOx = NO + NO2) after capturing the NOx in a potassium permanganate/sodium hydroxide solution as nitrate (Fibiger et al., Anal. Chem., 2014). The method has been thoroughly tested in the laboratory and field, and efficiently collects NO and NO2 under a variety of conditions. There are several advantages to collecting NOx actively, including the ability to collect over minutes to hourly time scales, and the ability to collect in environments with highly variable NOx sources and concentrations. Challenges include a nitrate background present in potassium permanganate (solid and liquid forms), accurately deriving ambient NOx concentrations based upon flow rate and solution concentrations above this variable background, and potential interferences from other nitrogen species. This method was designed to collect NOx in environments with very different

  19. Methane clumped isotopes: Progress and potential for a new isotopic tracer

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Douglas, Peter M. J.; Stolper, Daniel A.; Eiler, John M.

    The isotopic composition of methane is of longstanding geochemical interest, with important implications for understanding hydrocarbon systems, atmospheric greenhouse gas concentrations, the global carbon cycle, and life in extreme environments. Recent analytical developments focusing on multiply substituted isotopologues (‘clumped isotopes’) are opening a potentially valuable new window into methane geochemistry. When methane forms in internal isotopic equilibrium, clumped isotopes can provide a direct record of formation temperature, making this property particularly valuable for identifying different methane origins. However, it has also become clear that in certain settings methane clumped isotope measurements record kinetic rather than equilibrium isotope effects. Here wemore » present a substantially expanded dataset of methane clumped isotope analyses, and provide a synthesis of the current interpretive framework for this parameter. We review different processes affecting methane clumped isotope compositions, describe the relationships between conventional isotope and clumped isotope data, and summarize the types of information that this measurement can provide in different Earth and planetary environments.« less

  20. An Approach for Validating Actinide and Fission Product Burnup Credit Criticality Safety Analyses-Isotopic Composition Predictions

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Radulescu, Georgeta; Gauld, Ian C; Ilas, Germina

    2011-01-01

    The expanded use of burnup credit in the United States (U.S.) for storage and transport casks, particularly in the acceptance of credit for fission products, has been constrained by the availability of experimental fission product data to support code validation. The U.S. Nuclear Regulatory Commission (NRC) staff has noted that the rationale for restricting the Interim Staff Guidance on burnup credit for storage and transportation casks (ISG-8) to actinide-only is based largely on the lack of clear, definitive experiments that can be used to estimate the bias and uncertainty for computational analyses associated with using burnup credit. To address themore » issues of burnup credit criticality validation, the NRC initiated a project with the Oak Ridge National Laboratory to (1) develop and establish a technically sound validation approach for commercial spent nuclear fuel (SNF) criticality safety evaluations based on best-available data and methods and (2) apply the approach for representative SNF storage and transport configurations/conditions to demonstrate its usage and applicability, as well as to provide reference bias results. The purpose of this paper is to describe the isotopic composition (depletion) validation approach and resulting observations and recommendations. Validation of the criticality calculations is addressed in a companion paper at this conference. For isotopic composition validation, the approach is to determine burnup-dependent bias and uncertainty in the effective neutron multiplication factor (keff) due to bias and uncertainty in isotopic predictions, via comparisons of isotopic composition predictions (calculated) and measured isotopic compositions from destructive radiochemical assay utilizing as much assay data as is available, and a best-estimate Monte Carlo based method. This paper (1) provides a detailed description of the burnup credit isotopic validation approach and its technical bases, (2) describes the application of the

  1. [High-precision in situ analysis of the lead isotopic composition in copper using femtosecond laser ablation MC-ICP-MS and the application in ancient coins].

    PubMed

    Chen, Kai-Yun; Fan, Chao; Yuan, Hong-Lin; Bao, Zhi-An; Zong, Chun-Lei; Dai, Meng-Ning; Ling, Xue; Yang, Ying

    2013-05-01

    In the present study we set up a femtosecond laser ablation MC-ICP-MS method for lead isotopic analysis. Pb isotopic composition of fifteen copper (brass, bronze) standard samples from the National Institute of Standards Material were analyzed using the solution method (MC-ICP-MS) and laser method (fLA-MC-ICPMS) respectively, the results showed that the Pb isotopic composition in CuPb12 (GBW02137) is very homogeneous, and can be used as external reference material for Pb isotopic in situ analysis. On CuPb12 112 fLA-MC-ICPMS Pb isotope analysis, the weighted average values of the Pb isotopic ratio are in good agreement with the results analyzed by bulk solution method within 2sigma error, the internal precision RSEs of the 208 Pb/204 Pb ratio and 207 Pb/206 Pb ratio are less than 90 and 40 ppm respectively, and the external precision RSDs of them are less than 60 and 30 ppm respectively. Pb isotope of thirteen ancient bronze coins was analyzed via fLA-MC-ICPMS, the results showed that the Pb isotopic composition of ancient coins of different dynasties is significantly different, and not all the Pb isotopic compositions in the coins even from the same dynasty are in agreement with each other.

  2. Using Nitrogen and Oxygen Isotope Compositions of Nitrate to Distinguish Contaminant Sources in Hanford Soil and Groundwater

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Conrad, Mark; Bill, Markus

    2008-08-01

    The nitrogen ({delta}{sup 15}N) and oxygen ({delta}{sup 18}O) isotopic compositions of nitrate in the environment are primarily a function of the source of the nitrate. The ranges of isotopic compositions for nitrate resulting from common sources are outlined in Figure 1 from Kendall (1998). As noted on Figure 1, processes such as microbial metabolism can modify the isotopic compositions of the nitrate, but the effects of these processes are generally predictable. At Hanford, nitrate and other nitrogenous compounds were significant components of most of the chemical processes used at the site. Most of the oxygen in nitrate chemicals (e.g., nitricmore » acid) is derived from atmospheric oxygen, giving it a significantly higher {delta}{sup 18}O value (+23.5{per_thousand}) than naturally occurring nitrate that obtains most of its oxygen from water (the {delta}{sup 18}O of Hanford groundwater ranges from -14{per_thousand} to -18{per_thousand}). This makes it possible to differentiate nitrate from Hanford site activities from background nitrate at the site (including most fertilizers that might have been used prior to the Department of Energy plutonium production activities at the site). In addition, the extreme thermal and chemical conditions that occurred during some of the waste processing procedures and subsequent waste storage in select single-shell tanks resulted in unique nitrate isotopic compositions that can be used to identify those waste streams in soil and groundwater at the site (Singleton et al., 2005; Christensen et al., 2007). This report presents nitrate isotope data for soil and groundwater samples from the Hanford 200 Areas and discusses the implications of that data for potential sources of groundwater contamination.« less

  3. SRS-sensor 13C/12C isotops measurements for detecting Helicobacter Pylori

    NASA Astrophysics Data System (ADS)

    Grishkanich, Aleksandr; Chubchenko, Yan; Elizarov, Valentin; Zhevlakov, Aleksandr; Konopelko, Leonid

    2018-02-01

    We developed SRS-sensor 13C/12C isotops measurements detecting Helicobacter Pylori for medical diagnostics of human health. Measuring of absolute 13C/12C isotope amount ratios allows to explore the topical problems of the modern world, alcoholic beverages and tobacco, medical diagnostics of human health. SRS method is used to measure the ratio of carbon isotopes in the exhaled carbon dioxide, which is used to diagnose the human infection of Helicobacter pylori and the influence of the Helicobacter pylori bacterium on the occurrence of gastritis, gastric and duodenal ulcers. A method for the analysis of human infection with Helicobacter pylori was developed on the basis of measurements of the ratio of 13C / 12C carbon isotopes in human exhaled air with a high level of measurement accuracy. The article reviews the work in the field of provision comparability of absolute 13C/12C isotope amount ratios in the environment and food. The analysis of the technical and metrological characteristics of traditional and perspective instruments for measuring isotope ratios is presented. The provision of comparability of absolute 13C/12C isotope amount ratios is carried by gravimetrically prepared reference standards. The key features and emerging issues are discussed.

  4. Reconstruction of the Nd isotope composition of seawater on epicontinental seas: Testing the potential of Fe-Mn oxyhydroxide coatings on foraminifera tests for deep-time investigations

    NASA Astrophysics Data System (ADS)

    Charbonnier, Guillaume; Pucéat, Emmanuelle; Bayon, Germain; Desmares, Delphine; Dera, Guillaume; Durlet, Christophe; Deconinck, Jean-François; Amédro, Francis; Gourlan, Alexandra T.; Pellenard, Pierre; Bomou, Brahimsamba

    2012-12-01

    The Fe-Mn oxide fraction leached from deep-sea sediments has been increasingly used to reconstruct the Nd isotope composition of deep water masses, that can be used to track changes in oceanic circulation with a high temporal resolution. Application of this archive to reconstruct the Nd isotope composition of bottom seawater in shallow shelf environments remained however to be tested. Yet as the Nd isotope composition of seawater on continental margins is particularly sensitive to changes in erosional inputs, establishment of neritic seawater Nd isotope evolution around areas of deep water formation would be useful to discriminate the influence of changes in oceanic circulation and in isotopic composition of erosional inputs on the Nd isotope record of deep waters. The purpose of this study is to test the potential of Fe-Mn coatings leached from foraminifera tests to reconstruct the Nd isotope composition of seawater in shelf environments for deep-time intervals. Albian to Turonian samples from two different outcrops have been recovered, from the Paris Basin (Wissant section, northern France) and from the Western Interior Seaway (Hot Spring, South Dakota, USA), that were deposited in epicontinental seas. Rare Earth Element (REE) spectra enriched in middle REEs in the foraminifera leach at Wissant highlight the presence of Fe-Mn oxides. The similarity of the Nd isotopic signal of the Fe-Mn oxide fraction leached from foraminifera tests with that of fish teeth suggests that Fe-Mn oxides coating foraminifera can be good archives of shelf bottom seawater Nd isotopic composition. Inferred bottom shelf water Nd isotope compositions at Wissant range from -8.5 to -9.7 ɛ-units, about 1.5-2 ɛ-units higher than that of the contemporaneous local detrital fraction. At Hot Spring, linear REE spectra characterizing foraminifera leach may point to an absence of authigenic marine Fe-Mn oxide formation in this area during the Late Cenomanian-Early Turonian, consistent with dysoxic

  5. The stable isotope composition of nitrogen and carbon and elemental contents in modern and fossil seabird guano from Northern Chile – Marine sources and diagenetic effects

    PubMed Central

    Pritzkow, Wolfgang; Rosner, Martin; Sepúlveda, Fernando; Vásquez, Paulina; Wilke, Hans; Kasemann, Simone A.

    2017-01-01

    Seabird excrements (guano) have been preserved in the arid climate of Northern Chile since at least the Pliocene. The deposits of marine organic material in coastal areas potentially open a window into the present and past composition of the coastal ocean and its food web. We use the stable isotope composition of nitrogen and carbon as well as element contents to compare the principal prey of the birds, the Peruvian anchovy, with the composition of modern guano. We also investigate the impact of diagenetic changes on the isotopic composition and elemental contents of the pure ornithogenic sediments, starting with modern stratified deposits and extending to fossil guano. Where possible, 14C systematics is used for age information. The nitrogen and carbon isotopic composition of the marine prey (Peruvian anchovy) of the birds is complex as it shows strong systematic variations with latitude. The detailed study of a modern profile that represents a few years of guano deposition up to present reveals systematic changes in nitrogen and carbon isotopic composition towards heavier values that increase with age, i.e. depth. Only the uppermost, youngest layers of modern guano show compositional affinity to the prey of the birds. In the profile, the simultaneous loss of nitrogen and carbon occurs by degassing, and non-volatile elements like phosphorous and calcium are passively enriched in the residual guano. Fossil guano deposits are very low in nitrogen and low in carbon contents, and show very heavy nitrogen isotopic compositions. One result of the study is that the use of guano for tracing nitrogen and carbon isotopic and elemental composition in the marine food web of the birds is restricted to fresh material. Despite systematic changes during diagenesis, there is little promise to retrieve reliable values of marine nitrogen and carbon signatures from older guano. However, the changes in isotopic composition from primary marine nitrogen isotopic signatures towards very

  6. Isotopic composition of zinc, copper, and iron in lunar samples

    NASA Astrophysics Data System (ADS)

    Moynier, F.; Albarède, F.; Herzog, G. F.

    2006-12-01

    We determined by ICP-MS the concentrations and isotopic ratios of Fe, Cu, and Zn in the Ti-rich lunar basalt 74275, in the lunar orange glass 74220, and in up to 10 lunar soils, namely, 14163, 15231, 64501, 66041, 68841, 69941, 70011, 72501, 75081, and 76501. Two analyses of zinc in lunar basalt 74275 give δ 66Zn = 0.17‰ and 0.75‰, values within the range of those measured in terrestrial basalts; copper in lunar basalt 74275 has δ 65Cu ˜ +1.4‰, which is isotopically heavier than values observed in terrestrial basalts. In the orange glass, we measured δ 56Fe = -0.24‰, δ 65Cu = -0.42‰, and δ 66Zn ˜ -3.6‰. These values of δ are more negative than those obtained for 74275 and for typical lunar basalts, but for Cu, comparable to those observed in terrestrial sulfides and meteorites. In lunar soils we found 0.11‰ ⩽ δ 56Fe ⩽ 0.51‰, 2.6‰ ⩽ δ 65Cu ⩽ 4.5‰, and 2.2‰ ⩽ δ 66Zn ⩽ 6.4‰. Insofar as we can generalize from a small sample set, S, Fe, Cu, Zn, and Cd show similar trends in isotopic fractionation on the Moon. Lunar basalts have nearly terrestrial isotopic ratios. Relative to the lunar basalt 74275, the pyroclastic glass 74220 is enriched in the lighter isotopes of Fe, Cu, and Zn, and the soils are enriched in the heavier isotopes of Fe, Cu, and Zn. The patterns in the basalts are likely inherited from the source material; the light-isotope enrichments seen in the orange glass originated during lava fountaining or, less probably, during partial condensation of vapor; and the heavy-isotope enrichments in the lunar soils were likely created by a combination of processes that included micrometeorite vaporization and sputtering. In the orange glass, the light-isotope enrichments (relative to lunar basalts) of Zn are larger than those of Cu. If these enrichments reflect accurately the isotopic composition of the gas, they suggest that Cu is more volatile than Zn in the liquid from which the gas derived. A simple model built on

  7. Oxygen and nitrogen isotopic composition of nitrate in commercial fertilizers, nitric acid, and reagent salts.

    PubMed

    Michalski, Greg; Kolanowski, Michelle; Riha, Krystin M

    2015-01-01

    Nitrate is a key component of synthetic fertilizers that can be beneficial to crop production in agro-ecosystems, but can also cause damage to natural ecosystems if it is exported in large amounts. Stable isotopes, both oxygen and nitrogen, have been used to trace the sources and fate of nitrate in various ecosystems. However, the oxygen isotope composition of synthetic and organic nitrates is poorly constrained. Here, we present a study on the N and O isotope composition of nitrate-based fertilizers. The δ(15)N values of synthetic and natural nitrates were 0 ± 2 ‰ similar to the air N2 from which they are derived. The δ(18)O values of synthetic nitrates were 23 ± 3 ‰, similar to air O2, and natural nitrate fertilizer δ(18)O values (55 ± 5 ‰) were similar to those observed in atmospheric nitrate. The Δ(17)O values of synthetic fertilizer nitrate were approximately zero following a mass-dependent isotope relationship, while natural nitrate fertilizers had Δ(17)O values of 18 ± 2 ‰ similar to nitrate produced photochemically in the atmosphere. These narrow ranges of values can be used to assess the amount of nitrate arising from fertilizers in mixed systems where more than one nitrate source exists (soil, rivers, and lakes) using simple isotope mixing models.

  8. The effect of environmental factors on stable isotopic composition of n-alkanes in Mediterranean olive oils

    NASA Astrophysics Data System (ADS)

    Pedentchouk, Nikolai; Mihailova, Alina; Abbado, Dimitri

    2014-05-01

    Traceability of the geographic origin of olive oils is an important issue from both commercial and health perspectives. This study evaluates the impact of environmental factors on stable C and H isotope compositions of n-alkanes in extra virgin olive oils from Croatia, France, Greece, Italy, Morocco, Portugal, Slovenia, and Spain. The data are used to investigate the applicability of stable isotope methodology for olive oil regional classification in the Mediterranean region. Analysis of stable C isotope composition of n-C29 alkane showed that extra virgin olive oils from Portugal and Spain have the most positive n-C29 alkane delta13C values. Conversely, olive oils from Slovenia, northern and central Italy are characterized by the most negative values. Overall, the n-C29 alkane delta13C values show a positive correlation with the mean air temperature during August-December and a negative correlation with the mean relative humidity during these months. Analysis of stable H isotope composition of n-C29 alkane revealed that the deltaD values are the most positive in olive oils from Greece and Morocco and the most negative in oils from northern Italy. The deltaD values of oils show significant correlation with all the analyses geographical parameters: the mean air temperature and relative humidity during August-December, the total amount of rainfall (the same months) and the annual deltaD values of precipitation. As predictor variables in the Categorical Data Analysis, the n-C29 alkane deltaD values show the most significant discriminative power, followed by the n-C29 alkane delta13C values. Overall, 93.4% of olive oil samples have been classified correctly into one of the production regions. Our findings suggest that an integrated analysis of C and H isotope compositions of n-alkanes extracted from extra virgin olive oil could become a useful tool for geographical provenancing of this highly popular food commodity.

  9. Summer precipitation influences the stable oxygen and carbon isotopic composition of tree-ring cellulose in Pinus ponderosa.

    PubMed

    Roden, John S; Ehleringer, James R

    2007-04-01

    The carbon and oxygen isotopic composition of tree-ring cellulose was examined in ponderosa pine (Pinus ponderosa Dougl.) trees in the western USA to study seasonal patterns of precipitation inputs. Two sites (California and Oregon) had minimal summer rainfall inputs, whereas a third site (Arizona) received as much as 70% of its annual precipitation during the summer months (North American monsoon). For the Arizona site, both the delta(18)O and delta(13)C values of latewood cellulose increased as the fraction of annual precipitation occurring in the summer (July through September) increased. There were no trends in latewood cellulose delta(18)O with the absolute amount of summer rain at any site. The delta(13)C composition of latewood cellulose declined with increasing total water year precipitation for all sites. Years with below-average total precipitation tended to have a higher proportion of their annual water inputs during the summer months. Relative humidity was negatively correlated with latewood cellulose delta(13)C at all sites. Trees at the Arizona site produced latewood cellulose that was significantly more enriched in (18)O compared with trees at the Oregon or California site, implying a greater reliance on an (18)O-enriched water source. Thus, tree-ring records of cellulose delta(18)O and delta(13)C may provide useful proxy information about seasonal precipitation inputs and the variability and intensity of the North American monsoon.

  10. Importance of depth and intensity of convection on the isotopic composition of water vapor as seen from IASI and TES δD observations

    NASA Astrophysics Data System (ADS)

    Lacour, Jean-Lionel; Risi, Camille; Worden, John; Clerbaux, Cathy; Coheur, Pierre-François

    2018-01-01

    We use tropical observations of the water vapor isotopic composition, derived from IASI and TES spaceborne measurements, to show that the isotopic composition of water vapor in the free troposphere is sensitive to both the depth and the intensity of convection. We find that for any given precipitation intensity, vapor associated with deep convection is isotopically depleted relative to vapor associated with shallow convection. The intensity of precipitation also plays a role as for any given depth of convection, the relative enrichment of water vapor decreases as the intensity of precipitation increases. Shallow convection, via the uplifting of enriched boundary layer air into the free troposphere and the convective detrainment, enriches the free troposphere. In contrast, deep convection is associated with processes that deplete the water vapor in the free troposphere, such as rain re-evaporation. The results of this study allow for a better identification of the parameters controlling the isotopic composition of the free troposphere and indicate that the isotopic composition of water vapor can be used to evaluate the relative contributions of shallow and deep convection in global models.

  11. Calcium isotopic fractionation in mantle peridotites by melting and metasomatism and Ca isotope composition of the Bulk Silicate Earth

    NASA Astrophysics Data System (ADS)

    Kang, Jin-Ting; Ionov, Dmitri A.; Liu, Fang; Zhang, Chen-Lei; Golovin, Alexander V.; Qin, Li-Ping; Zhang, Zhao-Feng; Huang, Fang

    2017-09-01

    To better constrain the Ca isotopic composition of the Bulk Silicate Earth (BSE) and explore the Ca isotope fractionation in the mantle, we determined the Ca isotopic composition of 28 peridotite xenoliths from Mongolia, southern Siberia and the Siberian craton. The samples are divided in three chemical groups: (1) fertile, unmetasomatized lherzolites (3.7-4.7 wt.% Al2O3); (2) moderately melt-depleted peridotites (1.3-3.0 wt.% Al2O3) with no or very limited metasomatism (LREE-depleted cpx); (3) strongly metasomatized peridotites (LREE-enriched cpx and bulk rock) further divided in subgroups 3a (harzburgites, 0.1-1.0% Al2O3) and 3b (fertile lherzolites, 3.9-4.3% Al2O3). In Group 1, δ44/40Ca of fertile spinel and garnet peridotites, which experienced little or no melting and metasomatism, show a limited variation from 0.90 to 0.99‰ (relative to SRM 915a) and an average of 0.94 ± 0.05‰ (2SD, n = 14), which defines the Ca isotopic composition of the BSE. In Group 2, the δ44/40Ca is the highest for three rocks with the lowest Al2O3, i.e. the greatest melt extraction degrees (average 1.06 ± 0.04 ‰, i.e. ∼0.1‰ heavier than the BSE estimate). Simple modeling of modal melting shows that partial melting of the BSE with 103 ln ⁡αperidotite-melt ranging from 0.10 to 0.25 can explain the Group 2 data. By contrast, δ44/40Ca in eight out of nine metasomatized Group 3 peridotites are lower than the BSE estimate. The Group 3a harzburgites show the greatest δ44/40Ca variation range (0.25-0.96‰), with δ44/40Ca positively correlated with CaO and negatively correlated with Ce/Eu. Chemical evidence suggests that the residual, melt-depleted, low-Ca protoliths of the Group 3a harzburgites were metasomatized, likely by carbonate-rich melts/fluids. We argue that such fluids may have low (≤0.25‰) δ44/40Ca either because they contain recycled crustal components or because Ca isotopes, similar to trace elements and their ratios, may be fractionated by kinetic and

  12. Rubidium Isotope Composition of the Earth and the Moon: Evidence for the Origin of Volatile Loss During Planetary Accretion

    NASA Astrophysics Data System (ADS)

    Pringle, E. A.; Moynier, F.

    2016-12-01

    The Earth-Moon system has a variety of chemical and isotopic characteristics that provide clues to understanding the mechanism of lunar formation. One important observation is the depletion in moderately volatile elements in the Moon compared to the Earth. This volatile element depletion may be a signature of volatile loss during the Moon-forming Giant Impact. Stable isotopes are powerful tracers of such a process, since volatile loss via evaporation enriches the residue in heavy isotopes. However, early studies searching for the fingerprint of volatile loss failed to find any resolvable variations [1]. Recent work has now revealed heavy isotope enrichments in the Moon relative to the Earth for the moderately volatile elements Zn [2,3] and K [4]. The purely lithophile nature of Rb (in contrast to the chalcophile/lithophile nature of Zn) and the higher volatility of Rb compared to K make Rb an ideal element with which to study the origin of lunar volatile element depletion. We have developed a new method for the high-precision measurement of Rb isotope ratios by MC-ICP-MS. The Rb isotope compositions of terrestrial rocks define a narrow range, indicating that Rb isotope fractionation during igneous differentiation is limited (<30 ppm/amu). There is a clear signature of Rb loss during evaporation in volatile-depleted achondrites and lunar rocks. In particular, eucrites are significantly enriched in 87Rb (up to several per mil) relative to chondrites. Similarly, lunar basalts are enriched in 87Rb compared to terrestrial basalts, by 200 ppm for 87Rb/85Rb. These data are the first measurements of a resolvable difference in Rb isotope composition between the Earth and the Moon. The variations in Rb isotope composition between the Earth and the Moon are consistent with Rb isotope fractionation due to evaporation. References: [1] Humayun & Clayton GCA 1995. [2] Paniello et al. Nature 2012. [3] Kato et al. Nat. Comm. 2015. [4] Wang and Jacobsen Nature in press.

  13. Constraining late stage melt-peridotite interaction in the lithospheric mantle of southern Ethiopia: evidence from lithium elemental and isotopic compositions

    NASA Astrophysics Data System (ADS)

    Alemayehu, Melesse; Zhang, Hong-Fu; Seitz, Hans-Michael

    2017-10-01

    Lithium (Li) elemental and isotopic compositions for mineral separates of coexisting olivine, orthopyroxene and clinopyroxene of mantle xenoliths from the Quaternary volcanic rocks of southern Ethiopian rift (Dillo and Megado) reveal the influence of late stage melt-peridotite interaction on the early depleted and variably metasomatized lithospheric mantle. Two types of lherzolites are reported (LREE-depleted La/Sm(N) = 0.11-0.37 × Cl and LREE-enriched, La/Sm(N) = 1.88-15.72 × Cl). The depleted lherzolites have variable range in Li concentration (olivine: 2.1-5.4 ppm; opx: 1.1-2.3 ppm; cpx: 1.0-1.8 ppm) and in Li isotopic composition (δ7Li in olivine: -9.4 to 1.5‰; in opx: -4.5 to 3.6‰; in cpx: -17.0 to 4.8‰), indicating strong disequilibrium in Li partitioning and Li isotope fractionation between samples. The enriched lherzolites have limited range in both Li abundances (olivine: 2.7-3.0 ppm; opx: 1.1-3.1 ppm; cpx: 1.1-2.3 ppm) and Li isotopic compositions (δ7Li in olivine: -1.3 to +1.3‰; in opx: -2.0 to +5.0‰; in cpx: -7.5 to +4.8‰), suggest that the earlier metasomatic event which lead to LREE enrichment could also homogenize the Li contents and its isotopes. The enriched harzburgite and clinopyroxenite minerals show limited variation in Li abundances and variable Li isotopic compositions. The Li enrichments of olivine and clinopyroxene correlate neither with the incompatible trace element enrichment nor with the Sr-Nd isotopic compositions of clinopyroxene. These observations indicate that the metasomatic events which are responsible for the LREE enrichment and for the Li addition are distinct, whereby the LREE-enrichment pre-dates the influx of Li. The presence of large Li isotopic disequilibria within and between minerals of depleted and enriched peridotites suggest that the lithospheric mantle beneath the southern Ethiopian rift has experienced recent melt-peridotite interaction. Thus, the Li data set reported in this study offer new

  14. Temporal variations of methane concentration and isotopic composition in groundwater of the St. Lawrence Lowlands, eastern Canada

    NASA Astrophysics Data System (ADS)

    Rivard, Christine; Bordeleau, Geneviève; Lavoie, Denis; Lefebvre, René; Malet, Xavier

    2018-03-01

    Dissolved methane concentrations in shallow groundwater are known to vary both spatially and temporally. The extent of these variations is poorly documented although this knowledge is critical for distinguishing natural fluctuations from anthropogenic impacts stemming from oil and gas activities. This issue was addressed as part of a groundwater research project aiming to assess the risk of shale gas development for groundwater quality over a 500-km2 area in the St. Lawrence Lowlands (Quebec, Canada). A specific study was carried out to define the natural variability of methane concentrations and carbon and hydrogen isotope ratios in groundwater, as dissolved methane is naturally ubiquitous in aquifers of this area. Monitoring was carried out over a period of up to 2.5 years in seven monitoring wells. Results showed that for a given well, using the same sampling depth and technique, methane concentrations can vary over time from 2.5 to 6 times relative to the lowest recorded value. Methane isotopic composition, which is a useful tool to distinguish gas origin, was found to be stable for most wells, but varied significantly over time in the two wells where methane concentrations are the lowest. The use of concentration ratios, as well as isotopic composition of methane and dissolved inorganic carbon (DIC), helped unravel the processes responsible for these variations. This study indicates that both methane concentrations and isotopic composition, as well as DIC isotopes, should be regularly monitored over at least 1 year to establish their potential natural variations prior to hydrocarbon development.

  15. Variability in magnesium, carbon and oxygen isotope compositions, and trace element contents of brachiopod shells: implications for paleoceanographic studies

    NASA Astrophysics Data System (ADS)

    Rollion-Bard, Claire; Saulnier, Ségolène; Vigier, Nathalie; Schumacher, Aimryc; Chaussidon, Marc; Lécuyer, Christophe

    2016-04-01

    Magnesium content in the ocean is ≈ 1290 ppm and is one of the most abundant elements. It is involved in the carbon cycle via the dissolution and precipitation of carbonates, especially Mg-rich carbonates as dolomites. The Mg/Ca ratio of the ocean is believed to have changed through time. The causes of these variations, i.e. hydrothermal activity change or enhanced precipitation of dolomite, could be constrained using the magnesium isotope composition (δ26Mg) of carbonates. Brachiopods, as marine environmental proxies, have the advantage to occur worldwide in a depth range from intertidal to abyssal, and have been found in the geological record since the Cambrian. Moreover, as their shell is in low-Mg calcite, they are quite resistant to diagenetic processes. Here we report δ26Mg, δ18O, δ13C values along with trace element contents of one modern brachiopod specimen (Terebratalia transversa) and one fossil specimen (Terebratula scillae, 2.3 Ma). We combined δ26Mg values with oxygen and carbon isotope compositions and trace element contents to look for possible shell geochemical heterogeneities in order to investigate the processes that control the Mg isotope composition of brachiopod shells. We also evaluate the potential of brachiopods as a proxy of past seawater δ26Mg values. The two investigated brachiopod shells present the same range of δ26Mg variation (up to 2 ‰)). This variation cannot be ascribed to changes in environmental parameters, i.e. temperature or pH. As previously observed, the primary layer of calcite shows the largest degree of oxygen and carbon isotope disequilibrium relative to seawater. In contrast, the δ26Mg value of this layer is comparable to that of the secondary calcite layer value. In both T. scillae and T. transversa, negative trends are observable between magnesium isotopic compositions and oxygen and carbon isotopic compositions. These trends, combined to linear relationships between δ26Mg values and REE contents, are best

  16. FE and MG Isotopic Analyses of Isotopically Unusual Presolar Silicate Grains

    NASA Technical Reports Server (NTRS)

    Nguyen, A. N.; Messenger, S.; Ito, M.; Rahman, Z.

    2011-01-01

    Interstellar and circumstellar silicate grains are thought to be Mg-rich and Fe-poor, based on astronomical observations and equilibrium condensation models of silicate dust formation in stellar outflows. On the other hand, presolar silicates isolated from meteorites have surprisingly high Fe contents and few Mg-rich grains are observed. The high Fe contents in meteoritic presolar silicates may indicate they formed by a non-equilibrium condensation process. Alternatively, the Fe in the stardust grains could have been acquired during parent body alteration. The origin of Fe in presolar silicates may be deduced from its isotopic composition. Thus far, Fe isotopic measurements of presolar silicates are limited to the Fe-54/Fe-56 ratios of 14 grains. Only two slight anomalies (albeit solar within error) were observed. However, these measurements suffered from contamination of Fe from the adjacent meteorite matrix, which diluted any isotopic anomalies. We have isolated four presolar silicates having unusual O isotopic compositions by focused ion beam (FIB) milling and obtained their undiluted Mg and Fe isotopic compositions. These compositions help to identify the grains stellar sources and to determine the source of Fe in the grains.

  17. The impact of moisture sources on the oxygen isotope composition of precipitation at a continental site in central Europe

    NASA Astrophysics Data System (ADS)

    Krklec, Kristina; Domínguez-Villar, David; Lojen, Sonja

    2018-06-01

    The stable isotope composition of precipitation records processes taking place within the hydrological cycle. Potentially, moisture sources are important controls on the stable isotope composition of precipitation, but studies focused on this topic are still scarce. We studied the moisture sources contributing to precipitation at Postojna (Slovenia) from 2009 to 2013. Back trajectory analyses were computed for the days with precipitation at Postojna. The moisture uptake locations were identified along these trajectories using standard hydrometeorological formulation. The moisture uptake locations were integrated in eight source regions to facilitate its comparison to the monthly oxygen isotope composition (δ18O values) of precipitation. Nearly half of the precipitation originated from continental sources (recycled moisture), and >40% was from central and western Mediterranean. Results show that moisture sources do not have a significant impact on the oxygen isotope composition at this site. We suggest that the large proportion of recycled moisture originated from transpiration rather than evaporation, which produced water vapour with less negative δ18O values. Thus the difference between the oceanic and local vapour source was reduced, which prevented the distinction of the moisture sources based on their oxygen isotope signature. Nevertheless, δ18O values of precipitation are partially controlled by climate parameters, which is of major importance for paleoclimate studies. We found that the main climate control on Postojna δ18O values of precipitation is the surface temperature. Amount effect was not recorded at this site, and the winter North Atlantic Oscillation (NAO) does not impact the δ18O values of precipitation. The Western Mediterranean Oscillation (WeMO) was correlated to oxygen stable isotope composition, although this atmospheric pattern was not a control. Instead we found that the link to δ18O values results from synoptic scenarios affecting We

  18. The tungsten isotopic composition of the Earth's mantle before the terminal bombardment.

    PubMed

    Willbold, Matthias; Elliott, Tim; Moorbath, Stephen

    2011-09-07

    Many precious, 'iron-loving' metals, such as gold, are surprisingly abundant in the accessible parts of the Earth, given the efficiency with which core formation should have removed them to the planet's deep interior. One explanation of their over-abundance is a 'late veneer'--a flux of meteorites added to the Earth after core formation as a 'terminal' bombardment that culminated in the cratering of the Moon. Some 3.8 billion-year-old rocks from Isua, Greenland, are derived from sources that retain an isotopic memory of events pre-dating this cataclysmic meteorite shower. These Isua samples thus provide a window on the composition of the Earth before such a late veneer and allow a direct test of its importance in modifying the composition of the planet. Using high-precision (less than 6 parts per million, 2 standard deviations) tungsten isotope analyses of these rocks, here we show that they have a isotopic tungsten ratio (182)W/(184)W that is significantly higher (about 13 parts per million) than modern terrestrial samples. This finding is in good agreement with the expected influence of a late veneer. We also show that alternative interpretations, such as partial remixing of a deep-mantle reservoir formed in the Hadean eon (more than four billion years ago) or core-mantle interaction, do not explain the W isotope data well. The decrease in mantle (182)W/(184)W occurs during the Archean eon (about four to three billion years ago), potentially on the same timescale as a notable decrease in (142)Nd/(144)Nd (refs 3 and 6). We speculate that both observations can be explained if late meteorite bombardment triggered the onset of the current style of mantle convection.

  19. Establishing Ion Ratio Thresholds Based on Absolute Peak Area for Absolute Protein Quantification using Protein Cleavage Isotope Dilution Mass Spectrometry

    PubMed Central

    Loziuk, Philip L.; Sederoff, Ronald R.; Chiang, Vincent L.; Muddiman, David C.

    2014-01-01

    Quantitative mass spectrometry has become central to the field of proteomics and metabolomics. Selected reaction monitoring is a widely used method for the absolute quantification of proteins and metabolites. This method renders high specificity using several product ions measured simultaneously. With growing interest in quantification of molecular species in complex biological samples, confident identification and quantitation has been of particular concern. A method to confirm purity or contamination of product ion spectra has become necessary for achieving accurate and precise quantification. Ion abundance ratio assessments were introduced to alleviate some of these issues. Ion abundance ratios are based on the consistent relative abundance (RA) of specific product ions with respect to the total abundance of all product ions. To date, no standardized method of implementing ion abundance ratios has been established. Thresholds by which product ion contamination is confirmed vary widely and are often arbitrary. This study sought to establish criteria by which the relative abundance of product ions can be evaluated in an absolute quantification experiment. These findings suggest that evaluation of the absolute ion abundance for any given transition is necessary in order to effectively implement RA thresholds. Overall, the variation of the RA value was observed to be relatively constant beyond an absolute threshold ion abundance. Finally, these RA values were observed to fluctuate significantly over a 3 year period, suggesting that these values should be assessed as close as possible to the time at which data is collected for quantification. PMID:25154770

  20. Evaluating the Historical Importance of Impact Induced Hydrothermal Systems on Mars Using the Stable Isotopic Composition of Martian Water

    NASA Technical Reports Server (NTRS)

    Niles, Paul B.

    2010-01-01

    The importance of impact events during the early history of Mars is obvious through a simple examination of the character of the martian surface. This ancient, heavily cratered terrain has been shown to be associated with extensive phyllosilicate deposits. This geologic link could suggest that the extensive phyllosilicate-forming alteration may have occurred during early martian history through impact-induced hydrothermal alteration. However, examination of the oxygen isotopic composition of water on Mars suggests that the extensive phyllosilicate deposits were formed primarily through low temperature (<30 C) interactions, and that high temperature weathering in impact-induced hydrothermal systems have not been a dominant process on Mars. The average oxygen isotopic composition of water on Earth is dictated by the nature of water-rock interactions. If these interactions occur at higher temperatures then the water will contain a higher proportion of 18O, while lower temperature interactions will result in water with a lower proportion of 18O. Water on Earth today contains a higher proportion of 18O because of plate tectonics and hydrothermal interaction at mid-ocean ridges. The oxygen isotopic composition of water on early earth, however, may have been quite different, containing a smaller proportion of 18O suggesting much less hydrothermal interaction. Because there are not yet any direct measurements of the oxygen isotopic composition of water on Mars, it needs to be inferred through examination of carbonates preserved in martian meteorites and the isotopic composition of atmospheric CO2. This can be done because the oxygen incorporated into carbonates and CO2 is easily exchanged with liquid water if it is present. Independently, both measurements provide an estimate for the (Sigma)18O of water on Mars to be near -16%. This composition is consistent with low temperature weathering of the silicate crust, and indicates that impact hydrothermal systems did not play

  1. Stable water isotope patterns in a climate change hotspot: the isotope hydrology framework of Corsica (western Mediterranean).

    PubMed

    van Geldern, Robert; Kuhlemann, Joachim; Schiebel, Ralf; Taubald, Heinrich; Barth, Johannes A C

    2014-06-01

    The Mediterranean is regarded as a region of intense climate change. To better understand future climate change, this area has been the target of several palaeoclimate studies which also studied stable isotope proxies that are directly linked to the stable isotope composition of water, such as tree rings, tooth enamel or speleothems. For such work, it is also essential to establish an isotope hydrology framework of the region of interest. Surface waters from streams and lakes as well as groundwater from springs on the island of Corsica were sampled between 2003 and 2009 for their oxygen and hydrogen isotope compositions. Isotope values from lake waters were enriched in heavier isotopes and define a local evaporation line (LEL). On the other hand, stream and spring waters reflect the isotope composition of local precipitation in the catchment. The intersection of the LEL and the linear fit of the spring and stream waters reflect the mean isotope composition of the annual precipitation (δP) with values of-8.6(± 0.2) ‰ for δ(18)O and-58(± 2) ‰ for δ(2)H. This value is also a good indicator of the average isotope composition of the local groundwater in the island. Surface water samples reflect the altitude isotope effect with a value of-0.17(± 0.02) ‰ per 100 m elevation for oxygen isotopes. At Vizzavona Pass in central Corsica, water samples from two catchments within a lateral distance of only a few hundred metres showed unexpected but systematic differences in their stable isotope composition. At this specific location, the direction of exposure seems to be an important factor. The differences were likely caused by isotopic enrichment during recharge in warm weather conditions in south-exposed valley flanks compared to the opposite, north-exposed valley flanks.

  2. Isotopic composition of reduced and oxidized sulfur in the Canary Islands: implications for the mantle S cycle

    NASA Astrophysics Data System (ADS)

    Beaudry, P.; Longpre, M. A.; Wing, B. A.; Bui, T. H.; Stix, J.

    2017-12-01

    The Earth's mantle contains distinct sulfur reservoirs, which can be probed by sulfur isotope analyses of volcanic rocks and gases. We analyzed the isotopic composition of reduced and oxidized sulfur in a diverse range of volcanically derived materials spanning historical volcanism in the Canary Islands. Our sample set consists of subaerial volcanic tephras from three different islands, mantle and sedimentary xenoliths, as well as lava balloon samples from the 2011-2012 submarine El Hierro eruption and associated crystal separates. This large sample set allows us to differentiate between the various processes responsible for sulfur isotope heterogeneity in the Canary archipelago. Our results define an array in triple S isotope space between the compositions of the MORB and seawater sulfate reservoirs. Specifically, the sulfide values are remarkably homogeneous around d34S = -1 ‰ and D33S = -0.01 ‰, while sulfate values peak at d34S = +4 ‰ and D33S = +0.01 ‰. Lava balloons from the El Hierro eruption have highly enriched sulfate d34S values up to +19.3 ‰, reflecting direct interaction between seawater sulfate and the erupting magma. Several sulfate data points from the island of Lanzarote also trend towards more positive d34S up to +13.8 ‰, suggesting interaction with seawater sulfate-enriched lithologies or infiltration of seawater within the magmatic system. On the other hand, the modal values and relative abundances of S2- and S6+ in crystal separates suggest that the Canary Island mantle source has a d34S around +3 ‰, similar to the S-isotopic composition of a peridotite xenolith from Lanzarote. We infer that the S2- and S6+ modes reflect isotopic equilibrium between those species in the magmatic source, which requires 80 % of the sulfide to become oxidized after melting, consistent with measured S speciation. This 34S enrichment of the source could be due to the recycling of hydrothermally-altered oceanic crust, which has been previously suggested

  3. Seasonality of stable isotope composition of atmospheric water input at the southern slopes of Mt. Kilimanjaro, Tanzania

    USGS Publications Warehouse

    Otte, Insa; Detsch, Florian; Gutlein, Adrian; Scholl, Martha A.; Kiese, Ralf; Appelhans, Tim; Nauss, Thomas

    2017-01-01

    To understand the moisture regime at the southern slopes of Mt. Kilimanjaro, we analysed the isotopic variability of oxygen (δ18O) and hydrogen (δD) of rainfall, throughfall, and fog from a total of 2,140 samples collected weekly over 2 years at 9 study sites along an elevation transect ranging from 950 to 3,880 m above sea level. Precipitation in the Kilimanjaro tropical rainforests consists of a combination of rainfall, throughfall, and fog. We defined local meteoric water lines for all 3 precipitation types individually and the overall precipitation, δDprec = 7.45 (±0.05) × δ18Oprec + 13.61 (±0.20), n = 2,140, R2 = .91, p < .001. We investigated the precipitation-type-specific stable isotope composition and analysed the effects of amount, altitude, and temperature. Aggregated annual mean values revealed isotope composition of rainfall as most depleted and fog water as most enriched in heavy isotopes at the highest elevation research site. We found an altitude effect of δ18Orain = −0.11‰ × 100 m−1, which varied according to precipitation type and season. The relatively weak isotope or altitude gradient may reveal 2 different moisture sources in the research area: (a) local moisture recycling and (b) regional moisture sources. Generally, the seasonality of δ18Orain values follows the bimodal rainfall distribution under the influences of south- and north-easterly trade winds. These seasonal patterns of isotopic composition were linked to different regional moisture sources by analysing Hybrid Single Particle Lagrangian Integrated Trajectory backward trajectories. Seasonality of dexcess values revealed evidence of enhanced moisture recycling after the onset of the rainy seasons. This comprehensive dataset is essential for further research using stable isotopes as a hydrological tracer of sources of precipitation that contribute to water resources of the Kilimanjaro region.

  4. Isotopic composition of carbonaceous-chondrite kerogen Evidence for an interstellar origin of organic matter in meteorites

    NASA Technical Reports Server (NTRS)

    Kerridge, J. F.

    1983-01-01

    Stepwise combustion has revealed systematic patterns of isotopic heterogeneity for C, H and N in the insoluble organic fraction (m-kerogen) from the Orgueil and Murray carbonaceous chondrites. Those patterns are essentially identical for both meteorites, indicating a common source of m-kerogen. The data cannot be reconciled with a single mass-fractionation process acting upon a single precursor composition. This indicates either a multi-path history of mass-dependent processing or a significant nucleogenetic contribution, or both. If mass-fractionation were the dominant process, the magnitude of the observed isotopic variability strongly suggests that ion-molecule reactions at very low temperatures, probably in interstellar clouds, were responsible. In any case, an interstellar, rather than solar nebular, origin for at least some of the meteoritic organic matter is indicated. This has interesting implications for the origin of prebiotic molecules, temperatures in the early solar system, and the isotopic compositions of volatiles accreted by the terrestrial planets.

  5. The O and H stable isotope composition of freshwaters in the British Isles. 2. Surface waters and groundwater

    NASA Astrophysics Data System (ADS)

    Darling, W. G.; Bath, A. H.; Talbot, J. C.

    The utility of stable isotopes as tracers of the water molecule has a long pedigree. The study reported here is part of an attempt to establish a comprehensive isotopic "baseline" for the British Isles as background data for a range of applications. Part 1 of this study (Darling and Talbot, 2003) considered the isotopic composition of rainfall in Britain and Ireland. The present paper is concerned with the composition of surface waters and groundwater. In isotopic terms, surface waters (other than some upland streams) are poorly characterised in the British Isles; their potential variability has yet to be widely used as an aid in hydrological research. In what may be the first study of a major British river, a monthly isotopic record of the upper River Thames during 1998 was obtained. This shows high damping of the isotopic variation compared to that in rainfall over most of the year, though significant fluctuations were seen for the autumn months. Smaller rivers such as the Stour and Darent show a more subdued response to the balance between runoff and baseflow. The relationship between the isotopic composition of rainfall and groundwater is also considered. From a limited database, it appears that whereas Chalk groundwater is a representative mixture of weighted average annual rainfall, for Triassic sandstone groundwater there is a seasonal selection of rainfall biased towards isotopically-depleted winter recharge. This may be primarily the result of physical differences between the infiltration characteristics of rock types, though other factors (vegetation, glacial history) could be involved. In the main, however, groundwaters appear to be representative of bulk rainfall within an error band of 0.5‰ δ18O. Contour maps of the δ18O and δ2H content of recent groundwaters in the British Isles show a fundamental SW-NE depletion effect modified by topography. The range of measured values, while much smaller than those for rainfall, still covers some ‰ for δ18

  6. The chlorine isotope composition of the moon and implications for an anhydrous mantle.

    PubMed

    Sharp, Z D; Shearer, C K; McKeegan, K D; Barnes, J D; Wang, Y Q

    2010-08-27

    Arguably, the most striking geochemical distinction between Earth and the Moon has been the virtual lack of water (hydrogen) in the latter. This conclusion was recently challenged on the basis of geochemical data from lunar materials that suggest that the Moon's water content might be far higher than previously believed. We measured the chlorine isotope composition of Apollo basalts and glasses and found that the range of isotopic values [from -1 to +24 per mil (per thousand) versus standard mean ocean chloride] is 25 times the range for Earth. The huge isotopic spread is explained by volatilization of metal halides during basalt eruption--a process that could only occur if the Moon had hydrogen concentrations lower than those of Earth by a factor of approximately 10(4) to 10(5), implying that the lunar interior is essentially anhydrous.

  7. Isotopic composition of low-latitude paleoprecipitation during the Early Cretaceous

    USGS Publications Warehouse

    Suarez, M.B.; Gonzalez, Luis A.; Ludvigson, Greg A.; Vega, F.J.; Alvarado-Ortega, J.

    2009-01-01

    The response of the hydrologic cycle in global greenhouse conditions is important to our understanding of future climate change and to the calibration of global climate models. Past greenhouse conditions, such as those of the Cretaceous, can be used to provide empirical data with which to evaluate climate models. Recent empirical studies have utilized pedogenic carbonates to estimate the isotopic composition of meteoric waters and calculate precipitation rates for the AptianAlbian. These studies were limited to data from mid(35??N) to high (75??N) paleolatitudes, and thus future improvements in accuracy will require more estimates of meteoric water compositions from numerous localities around the globe. This study provides data for tropical latitudes (18.5??N paleolatitude) from the Tlayua Formation, Puebla, Mexico. In addition, the study confirms a shallow nearshore depositional environment for the Tlayua Formation. Petrographic observations of fenestral fabrics, gypsum crystal molds, stromatolitic structures, and pedogenic matrix birefringence fabric support the interpretation that the strata represent deposition in a tidal flat environment. Carbonate isotopic data from limestones of the Tlayua Formation provide evidence of early meteoric diagenesis in the form of meteoric calcite lines. These trends in ??18O versus ??13C were used to calculate the mean ??18O value of meteoric water, which is estimated at -5.46 ?? 0.56??? (Vienna Standard Mean Ocean Water [VSMOW]). Positive linear covariant trends in oxygen and carbon isotopic values from some horizons were used to estimate evaporative losses of vadose groundwater from tropical exposure surfaces during the Albian, and the resulting values range from 8% to 12%. However, the presence of evaporative mineral molds indicates more extensive evaporation. The added tropical data improve latitudinal coverage of paleoprecipitation ??18O estimates. The data presented here imply that earlier isotope mass balance models most

  8. Isotopic Composition of Molybdenum and Barium in Single Presolar Silicon Carbide Grains of Type A+B

    NASA Technical Reports Server (NTRS)

    Savina, M. R.; Tripa, C. E.; Pellin, M. J.; Davis, A. M.; Clayton, R. N.; Lewis, R. S.; Amari, S.

    2003-01-01

    Presolar SiC grains fall into several groups based on C, N, and Si isotopic compositions. Approximately 93% are defined as mainstream, having 10 less than C-12/C-13 less than 100 and N-14/N-15 ranging from 50 to 20,000. A number of studies have shown that the most likely sources of mainstream grains are low mass asymptotic giant branch stars. Models of nucleosynthesis in AGB stars reproduce the s-process enhancements seen in the heavy elements in mainstream SiC grains. Among the less common grains, A+B grains, which comprise approximately 3-4% of presolar SiC, are perhaps the least well understood. Recent studies by Amari et al. show that A+B grains can be divided into at least 4 groups based on their trace element concentration patterns. Of 20 grains studied, 7 showed trace element patterns consistent with condensation from a gas of solar system composition, while the rest had varying degrees of process enhancements. Our previous measurements on 3 A+B grains showed Mo of solar isotopic composition, but Zr with a strong enhancement in 96Zr, which is an r-process isotope but can be made in an sprocess if the neutron density is high enough to bridge the unstable Zr-95 (T(sub 1/2)= 64 d). The observation of Mo with solar system isotopic composition in the same grains is puzzling however. Meyer et al. have recently shown that a neutron burst mechanism can produce a high Zr-96/Zr-94 without enhancing Mo-100, however this model leads to enhancements in Mo-95 and Mo-97 not observed in A+B grains. We report here results of Mo measurements on 7 additional A+B grains, and Ba measurements on 2 A+B grains, and compare these to the previous studies.

  9. Bulk Chemistry and Oxygen Isotopic Compositions of Lunar Meteorites Dhofar 025 and Dhofar 026

    NASA Astrophysics Data System (ADS)

    Taylor, L. A.; Nazarov, M. A.; Cohen, B. A.; Warren, P. H.; Barsukova, L. D.; Clayton, R. N.; Mayeda, T. K.

    2001-03-01

    The major- and trace-element composition of highlands meteorites Dh25 and Dh26 show that both are dominated by a FAN component. Incompatible element depletion and low Ti abundances suggest a farside origin. O-isotopes are typical for lunar meteorites.

  10. Determination of chemical purity and isotopic composition of natural and carbon-13-labeled arsenobetaine bromide standards by quantitative(1)H-NMR.

    PubMed

    Le, Phuong-Mai; Ding, Jianfu; Leek, Donald M; Mester, Zoltan; Robertson, Gilles; Windust, Anthony; Meija, Juris

    2016-10-01

    In this study, we report the characterization of three arsenobetaine-certified reference materials by quantitative NMR. We have synthesized an arsenobetaine bromide high-purity standard of natural isotopic composition (ABET-1) and two carbon-13-labeled isotopic standards (BBET-1 and CBET-1). Assignments of the chemical purity and isotopic composition are not trivial in the case of arsenobetaine, and in this study we utilized quantitative(1)H-NMR techniques for the determination of the mass fractions (chemical purity). The isotopic purity of all three standards was also assessed by NMR from the carbon-13 satellite signals. The standards are non-hygroscopic, high-purity (ca. 0.99 g/g), and the carbon-13 enrichment for both isotopic standards is x((13)C)≈0.99. These standards are designed for use as primary calibrators for mass spectrometric determination of arsenobetaine in environmental samples.

  11. Relationship between the trajectory of mid-latitude cyclones in the eastern Pacific Ocean and the isotopic composition of snowfall in the Sierra Nevada, California

    NASA Astrophysics Data System (ADS)

    Vasquez, K. T.; Sickman, J. O.; Heard, A.; Lucero, D.

    2013-12-01

    Diatoms, preserved in lake sediments, provide a potential archive of snowfall variability in the Sierra Nevada through their sensitivity to changes in water chemistry (a proxy for runoff volume) and by recording the isotopic composition of snow-melt (potentially a proxy for sources of atmospheric moisture). In the Sierra Nevada, we hypothesize that the oxygen isotopic composition of diatom silica is principally controlled by snow and that the isotopic composition of snow varies as a function of the tracks of mid-latitude cyclonic storms in the eastern Pacific Ocean. Snow samples from discrete storms were collected from December 2012 to March 2013 at 2042 meters a.s.l. in Sequoia National Park. The δ18O and δ2H values of the snow samples were measured using a temperature-conversion elemental analyzer coupled to a Delta V isotope ratio mass spectrometer. The isotopic measurements were then coupled to 3, 5 and 7-day air mass back trajectories using the NOAA HYSPLIT model. The measured δ18O values ranged from -17.6 to -7.8 per mil and the δ2H ranged from -119.8 to -73.3 per mil. Both δ18O and δ2H were inversely related to the latitude of the storm origin (R^2 values of 0.67 and 0.57, respectively). Winter storms from the Gulf of Alaska were the most isotopically depleted while storms originating in the subtropical/tropical Pacific were the most isotopically enriched, reflecting the overall latitudinal pattern of ocean-water isotope composition in the Pacific Ocean. Our results suggest that the isotopic composition of Sierra Nevada snowfall is influenced by storm track trajectory and this relationship could be useful in interpreting the climatic significance of δ18O of diatom silica preserved in lake cores.

  12. Investigating the Relationship Between Soil Water Mobility and Stable Isotope Composition with Implications for the Ecohydrologic Separation Hypothesis

    NASA Astrophysics Data System (ADS)

    Shuler, J.; McNamara, J. P.; Benner, S. G.; Kohn, M. J.; Evans, S.

    2017-12-01

    The ecohydrologic separation (ES) hypothesis states that streams and plants return different soil water compartments to the atmosphere and that these compartments bear distinct isotopic compositions that can be used to infer soil water mobility. Recent studies have found isotopic evidence for ES in a variety of ecosystems, though interpretations of these data vary. ES investigations frequently suffer from low sampling frequencies as well as incomplete or missing soil moisture and matric potential data to support assumptions of soil water mobility. We sampled bulk soil water every 2-3 weeks in the upper 1 m of a hillslope profile from May 2016 to July 2017 in a semi-arid watershed outside Boise, ID. Twig samples of three plant species were also collected concurrently. Plant and soil water samples extracted via cryogenic vacuum distillation were analyzed for δ2H and δ18O composition. Soil moisture and soil matric potential sensors were installed at five and four depths in the profile, respectively. Shallow bulk soil water was progressively enriched in both isotopes over the growing season and plotted along a soil evaporation line in a plot of δ2H versus δ18O. Plant water during the growing season plotted below both the Local Meteoric Water Line and soil evaporation line. Plant water isotopic composition could not be traced to any source sampled in this study. Additionally, soil moisture and matric potential data revealed that soils were well-drained and that mobile soil water was unavailable throughout most of the growing season at the depths sampled. Soil water isotopic composition alone failed to predict mobility as observed in soil moisture and matric potential data. These results underscore the need for standard hydrologic definitions for the mobile and immobile compartments of soil water in future studies of the ES hypothesis and ecohydrologic processes in general.

  13. Uranium isotopic compositions of the crust and ocean: Age corrections, U budget and global extent of modern anoxia

    NASA Astrophysics Data System (ADS)

    Tissot, François L. H.; Dauphas, Nicolas

    2015-10-01

    The 238U/235U isotopic composition of uranium in seawater can provide important insights into the modern U budget of the oceans. Using the double spike technique and a new data reduction method, we analyzed an array of seawater samples and 41 geostandards covering a broad range of geological settings relevant to low and high temperature geochemistry. Analyses of 18 seawater samples from geographically diverse sites from the Atlantic and Pacific oceans, Mediterranean Sea, Gulf of Mexico, Persian Gulf, and English Channel, together with literature data (n = 17), yield a δ238U value for modern seawater of -0.392 ± 0.005‰ relative to CRM-112a. Measurements of the uranium isotopic compositions of river water, lake water, evaporites, modern coral, shales, and various igneous rocks (n = 64), together with compilations of literature data (n = 380), allow us to estimate the uranium isotopic compositions of the various reservoirs involved in the modern oceanic uranium budget, as well as the fractionation factors associated with U incorporation into those reservoirs. Because the incorporation of U into anoxic/euxinic sediments is accompanied by large isotopic fractionation (ΔAnoxic/Euxinic-SW = +0.6‰), the size of the anoxic/euxinic sink strongly influences the δ238U value of seawater. Keeping all other fluxes constant, the flux of uranium in the anoxic/euxinic sink is constrained to be 7.0 ± 3.1 Mmol/yr (or 14 ± 3% of the total flux out of the ocean). This translates into an areal extent of anoxia into the modern ocean of 0.21 ± 0.09% of the total seafloor. This agrees with independent estimates and rules out a recent uranium budget estimate by Henderson and Anderson (2003). Using the mass fractions and isotopic compositions of various rock types in Earth's crust, we further calculate an average δ238U isotopic composition for the continental crust of -0.29 ± 0.03‰ corresponding to a 238U/235U isotopic ratio of 137.797 ± 0.005. We discuss the implications of

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

    NASA Technical Reports Server (NTRS)

    Boehme, Susan E.

    1993-01-01

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

  15. Mass-independent sulfur isotopic compositions in stratospheric volcanic eruptions.

    PubMed

    Baroni, Mélanie; Thiemens, Mark H; Delmas, Robert J; Savarino, Joël

    2007-01-05

    The observed mass-independent sulfur isotopic composition (Delta33S) of volcanic sulfate from the Agung (March 1963) and Pinatubo (June 1991) eruptions recorded in the Antarctic snow provides a mechanism for documenting stratospheric events. The sign of Delta33S changes over time from an initial positive component to a negative value. Delta33S is created during photochemical oxidation of sulfur dioxide to sulfuric acid on a monthly time scale, which indicates a fast process. The reproducibility of the results reveals that Delta33S is a reliable tracer to chemically identify atmospheric processes involved during stratospheric volcanism.

  16. Calcium Isotopic Compositions of Normal Mid-Ocean Ridge Basalts From the Southern Juan de Fuca Ridge

    NASA Astrophysics Data System (ADS)

    Zhu, Hongli; Liu, Fang; Li, Xin; Wang, Guiqin; Zhang, Zhaofeng; Sun, Weidong

    2018-02-01

    Mantle peridotites show that Ca is isotopically heterogeneous in Earth's mantle, but the mechanism for such heterogeneity remains obscure. To investigate the effect of partial melting on Ca isotopic fractionation and the mechanism for Ca isotopic heterogeneity in the mantle, we report high-precision Ca isotopic compositions of the normal Mid-Ocean Ridge Basalts (N-MORB) from the southern Juan de Fuca Ridge. δ44/40Ca of these N-MORB samples display a small variation ranging from 0.75 ± 0.05 to 0.86 ± 0.03‰ (relative to NIST SRM 915a, a standard reference material produced by the National Institute of Standards and Technology), which are slightly lower than the estimated Upper Mantle value of 1.05 ± 0.04‰ and the Bulk Silicate Earth (BSE) value of 0.94 ± 0.05‰. This phenomenon cannot be explained by fractional crystallization, because olivine and orthopyroxene fractional crystallization has limited influence on δ44/40Ca of N-MORB due to their low CaO contents, while plagioclase fractional crystallization cannot lead to light Ca isotopic compositions of the residue magma. Instead, the lower δ44/40Ca of N-MORB samples compared to their mantle source is most likely caused by partial melting. The offset in δ44/40Ca between N-MORB and BSE indicates that at least 0.1-0.2‰ fractionation would occur during partial melting and light Ca isotopes are preferred to be enriched in magma melt, which is in accordance with the fact that δ44/40Ca of melt-depleted peridotites are higher than fertile peridotites in literature. Therefore, partial melting is an important process that can decrease δ44/40Ca in basalts and induce Ca isotopic heterogeneity in Earth's mantle.

  17. The Boron Isotopic Composition of Elephant Dung: Inputs to the Global Boron Budget

    NASA Astrophysics Data System (ADS)

    Williams, L. B.; Hervig, R. L.

    2011-12-01

    A survey of boron in kerogen showed isotopically light δ11B values (0 to -50%) that are distinctly different from most mineral and natural water B reservoirs. Diagenesis releases this isotopically light B into pore fluids when hydrocarbons are generated, thus enriching oilfield brines in 10B. This observation suggests that borated biomolecules (BM) are primarily tetrahedral favoring 10B, whereas 11B is preferred in trigonal coordination. Plants, with optimal concentrations up to 100ppm, contribute more B than animal remains to sediment. Elephants are one of the largest herbivores on earth, consuming 200 - 250 kg of plant material/day and producing 50 kg of manure/day. They are inefficient at digestion, thus the manure contains >50% undigested plant material. Dung samples are therefore ideal for studying the δ11B of both the food input and digested output of a significant B supply to sedimentary systems. Horse and rabbit manure were studied for comparison to evaluate B isotope variations in the food supply and potential vital effects on the output. B-content and isotopic composition of dung plant material and digested fractions were measured in the solid state by secondary ion mass spectrometry. The digests were rinsed in 1.8% mannitol, a B-complexing agent, to remove surface adsorbed-B, then air dried and Au-coated for charge compensation. Results showed that the elephant diet contains 3-13 ppm B, with an average δ11B of -20 ± 0.8% (1σ), while rabbit food had 88 ppm B with a δ11B of -50 ± 1.3 %. The digested fraction of the elephant dung contains 4-10ppm B with average δ11B values of -12 ± 1.2%. In comparison, horse manure with 11-21 ppm B has a δ11B of -10.7 ± 0.5% and rabbit manure contains 2-3 ppm B with a δ11B of -8.8 ± 1%. Boron isotope compositions of these manures are indistinguishable (within error). Clearly plant material is a major contributor of isotopically light B to sediments. The herbivores studied fractionate their total B intake in

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

    PubMed

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

    2016-05-01

    The natural carbon isotope composition of individual amino acids from plant leaf proteins has been measured to establish potential sources of variability. The plant leaves studied, taken from a range of plant groups (forbs, trees, grasses, and freshwater aquatic plants), showed no significant influence of either season or environment (water and light availability) on their Δδ(13)C values. Plant groups did, however, differ in carbon isotope composition, although no consistent differences were identified at the species level. A discriminant analysis model was constructed which allowed leaves from (1) nettles, (2) Pooideae, (3) other Poales, (4) trees and (5) freshwater higher plants to be distinguished from each other on the basis of their natural abundance (13)C/(12)C ratios of individual amino acids. Differences in carbon isotope composition are known to be retained, to some extent, in the tissues of their consumers, and hence an understanding of compound-specific variation in (13)C/(12)C fractional abundance in plants has the potential to provide dietary insights of value in archaeological and ecological studies. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. What controls the stable isotope composition of precipitation in the Mekong Delta? A model-based statistical approach

    NASA Astrophysics Data System (ADS)

    Le Duy, Nguyen; Heidbüchel, Ingo; Meyer, Hanno; Merz, Bruno; Apel, Heiko

    2018-02-01

    This study analyzes the influence of local and regional climatic factors on the stable isotopic composition of rainfall in the Vietnamese Mekong Delta (VMD) as part of the Asian monsoon region. It is based on 1.5 years of weekly rainfall samples. In the first step, the isotopic composition of the samples is analyzed by local meteoric water lines (LMWLs) and single-factor linear correlations. Additionally, the contribution of several regional and local factors is quantified by multiple linear regression (MLR) of all possible factor combinations and by relative importance analysis. This approach is novel for the interpretation of isotopic records and enables an objective quantification of the explained variance in isotopic records for individual factors. In this study, the local factors are extracted from local climate records, while the regional factors are derived from atmospheric backward trajectories of water particles. The regional factors, i.e., precipitation, temperature, relative humidity and the length of backward trajectories, are combined with equivalent local climatic parameters to explain the response variables δ18O, δ2H, and d-excess of precipitation at the station of measurement. The results indicate that (i) MLR can better explain the isotopic variation in precipitation (R2 = 0.8) compared to single-factor linear regression (R2 = 0.3); (ii) the isotopic variation in precipitation is controlled dominantly by regional moisture regimes (˜ 70 %) compared to local climatic conditions (˜ 30 %); (iii) the most important climatic parameter during the rainy season is the precipitation amount along the trajectories of air mass movement; (iv) the influence of local precipitation amount and temperature is not significant during the rainy season, unlike the regional precipitation amount effect; (v) secondary fractionation processes (e.g., sub-cloud evaporation) can be identified through the d-excess and take place mainly in the dry season, either

  20. Magnesium and Titanium Isotopic Compositions of an Unusual Hibonite-Perovskite Refractory Inclusion from Allende: It Is Fun

    NASA Technical Reports Server (NTRS)

    Liu, M.-C.; Keller, L. P.; McKeegan, K. D.

    2016-01-01

    Introduction: Hibonite-rich refractory inclusions are among the first solids that formed in the solar nebula, and thus provide constraints on the earliest environment in the Solar System. An unusual hibonite-perovskite inclusion from Allende, SHAL, consists of a large (approximately 500 by 200 microns) single hibonite crystal and coexisting blocky perovskite (approximately 200 microns in size). The hibonite is characterized by chemical and oxygen isotopic compositions similar to those in the FUN (Fractionated and Unknown Nuclear anomalies) inclusion HAL. However, the rare earth element (REE) patterns measured at different spots of SHAL hibonite are highly variable, ranging from Group II-like (light REEs enriched relative to heavy REEs) to Group III-like (relatively flat with slight Eu depletions), but overall contrast largely with that of HAL, especially in the Ce and Yb abundances. This implies that SHAL hibonite formed and underwent distillation processes under more reducing conditions. Interestingly, the accompanying perovskite has uniform, unfractionated oxygen isotopic compositions (averaging delta (sup 17) O equals delta (sup 18) O equals -7 per mille) and REE abundances that are completely different from those of SHAL hibonite. This has been interpreted that perovskite and hibonite may not be co-genetic. Here we performed Al-Mg and Ti isotopic measurements of SHAL hibonite and perovskite to determine if the FUN characteristics are observed in these two isotope systems, and to further constrain the origin and evolution of SHAL. Results: Isotopic measurements of Al-Mg and Ti in SHAL were performed on the UCLA CAMECA ims-1290 ion microprobe by following the analytical protocols described in [1]. The Al-Mg and Ti data obtained in both terrestrial standards and SHAL hibonite and perovskite are shown below. Both SHAL hibonite and perovskite, despite very high (sup 27) Al to (sup 24) Mg ratios, are devoid of (sup 26) Mg excesses that can be attributed to the decay

  1. Altitude effect on leaf wax carbon isotopic composition in humid tropical forests

    NASA Astrophysics Data System (ADS)

    Wu, Mong Sin; Feakins, Sarah J.; Martin, Roberta E.; Shenkin, Alexander; Bentley, Lisa Patrick; Blonder, Benjamin; Salinas, Norma; Asner, Gregory P.; Malhi, Yadvinder

    2017-06-01

    The carbon isotopic composition of plant leaf wax biomarkers is commonly used to reconstruct paleoenvironmental conditions. Adding to the limited calibration information available for modern tropical forests, we analyzed plant leaf and leaf wax carbon isotopic compositions in forest canopy trees across a highly biodiverse, 3.3 km elevation gradient on the eastern flank of the Andes Mountains. We sampled the dominant tree species and assessed their relative abundance in each tree community. In total, 405 sunlit canopy leaves were sampled across 129 species and nine forest plots along the elevation profile for bulk leaf and leaf wax n-alkane (C27-C33) concentration and carbon isotopic analyses (δ13C); a subset (76 individuals, 29 species, five forest plots) were additionally analyzed for n-alkanoic acid (C22-C32) concentrations and δ13C. δ13C values display trends of +0.87 ± 0.16‰ km-1 (95% CI, r2 = 0.96, p < 0.01) for bulk leaves and +1.45 ± 0.33‰ km-1 (95% CI, r2 = 0.94, p < 0.01) for C29n-alkane, the dominant chain length. These carbon isotopic gradients are defined in multi-species sample sets and corroborated in a widespread genus and several families, suggesting the biochemical response to environment is robust to taxonomic turnover. We calculate fractionations and compare to adiabatic gradients, environmental variables, leaf wax n-alkane concentrations, and sun/shade position to assess factors influencing foliar chemical response. For the 4 km forested elevation range of the Andes, 4-6‰ higher δ13C values are expected for upland versus lowland C3 plant bulk leaves and their n-alkyl lipids, and we expect this pattern to be a systematic feature of very wet tropical montane environments. This elevation dependency of δ13C values should inform interpretations of sedimentary archives, as 13C-enriched values may derive from C4 grasses, petrogenic inputs or upland C3 plants. Finally, we outline the potential for leaf wax carbon isotopes to trace biomarker

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

    NASA Technical Reports Server (NTRS)

    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.

  3. Historical variations in the stable isotope composition of mercury in Arctic lake sediments.

    PubMed

    Jackson, Togwell A; Muir, Derek C G; Vincent, Warwick F

    2004-05-15

    The stable isotope composition of mercury (Hg) in a dated core from the anoxic zone of a saline, meromictic Arctic lake was found to vary as a complex function of the age and chemical composition of the sediment. Throughout the stratigraphic sequence, which spans the years 1899-1997, the ratios 198Hg/202Hg, 199Hg/202Hg, 200Hg/202Hg, 201Hg/202Hg, and 204Hg/202Hg expressed as delta-values (per mil deviations relative to a standard) reveal enrichment in 198Hg, 199Hg, 200Hg, and 201Hg, with depletion in 204Hg, the degree of enrichment varying inversely with atomic mass. A plot of delta198Hg, delta199Hg, delta200Hg, and delta201Hg against depth gave parallel profiles characterized by large, regular undulations superimposed on an overall trend toward increase with depth (i.e. age), and the delta204Hg profile is a mirror image of them. The delta198Hg, delta199Hg, delta200Hg, and delta201Hg values of the oldest (1899-1929) strata vary inversely with NH2OH.HCl/HNO3-extractable manganese concentration, but those of the youngest (1963-1997) strata give a positive correlation; intermediate (1936-1956) strata show no correlation and negligible variation in delta-values, possibly signifying a transition phase in which the two opposite trends offset each other. The delta-values show similar but weaker relationships with organic carbon. The results strongly suggest fractionation of Hg isotopes by microbial activities linked to oxidation-reduction reactions in the lake, although effects of isotopic signatures indicative of the sources of the Hg have not been ruled out. The radical change in the nature of the relationship between 6-values and sediment chemistry over time may reflect environmental and biotic changes that altered the isotope-fractionating processes. These findings imply that variations in the isotopic makeup of Hg, together with related physical, chemical, and biological data, could yield important new information about the biogeochemical cycle of Hg.

  4. Isotopic composition of inorganic mercury and methylmercury downstream of a historical gold mining region

    USGS Publications Warehouse

    Donovan, Patrick M.; Blum, Joel D.; Singer, Michael B.; Marvin-DiPasquale, Mark C.; Tsui, Martin T.K.

    2016-01-01

    We measured total mercury (THg) and monomethyl mercury (MMHg) concentrations and mercury (Hg) isotopic compositions in sediment and aquatic organisms from the Yuba River (California, USA) to identify Hg sources and biogeochemical transformations downstream of a historical gold mining region. Sediment THg concentrations and δ202Hg decreased from the upper Yuba Fan to the lower Yuba Fan and the Feather River. These results are consistent with the release of Hg during gold mining followed by downstream mixing and dilution. The Hg isotopic composition of Yuba Fan sediment (δ202Hg = −0.38 ± 0.17‰ and Δ199Hg = 0.04 ± 0.03‰; mean ± 1 SD, n = 7) provides a fingerprint of inorganic Hg (IHg) that could be methylated locally or after transport downstream. The isotopic composition of MMHg in the Yuba River food web was estimated using biota with a range of %MMHg (the percent of THg present as MMHg) and compared to IHg in sediment, algae, and the food web. The estimated δ202Hg of MMHg prior to photodegradation (−1.29 to −1.07‰) was lower than that of IHg and we suggest this is due to mass-dependent fractionation (MDF) of up to −0.9‰ between IHg and MMHg. This result is in contrast to net positive MDF (+0.4 to +0.8‰) previously observed in lakes, estuaries, coastal oceans, and forests. We hypothesize that this unique relationship could be due to differences in the extent or pathway of biotic MMHg degradation in stream environments.

  5. Isotopic Composition of Inorganic Mercury and Methylmercury Downstream of a Historical Gold Mining Region.

    PubMed

    Donovan, Patrick M; Blum, Joel D; Singer, Michael Bliss; Marvin-DiPasquale, Mark; Tsui, Martin T K

    2016-02-16

    We measured total mercury (THg) and monomethyl mercury (MMHg) concentrations and mercury (Hg) isotopic compositions in sediment and aquatic organisms from the Yuba River (California, USA) to identify Hg sources and biogeochemical transformations downstream of a historical gold mining region. Sediment THg concentrations and δ(202)Hg decreased from the upper Yuba Fan to the lower Yuba Fan and the Feather River. These results are consistent with the release of Hg during gold mining followed by downstream mixing and dilution. The Hg isotopic composition of Yuba Fan sediment (δ(202)Hg = -0.38 ± 0.17‰ and Δ(199)Hg = 0.04 ± 0.03‰; mean ± 1 SD, n = 7) provides a fingerprint of inorganic Hg (IHg) that could be methylated locally or after transport downstream. The isotopic composition of MMHg in the Yuba River food web was estimated using biota with a range of %MMHg (the percent of THg present as MMHg) and compared to IHg in sediment, algae, and the food web. The estimated δ(202)Hg of MMHg prior to photodegradation (-1.29 to -1.07‰) was lower than that of IHg and we suggest this is due to mass-dependent fractionation (MDF) of up to -0.9‰ between IHg and MMHg. This result is in contrast to net positive MDF (+0.4 to +0.8‰) previously observed in lakes, estuaries, coastal oceans, and forests. We hypothesize that this unique relationship could be due to differences in the extent or pathway of biotic MMHg degradation in stream environments.

  6. Effect of amino acids on the precipitation kinetics and Ca isotopic composition of gypsum

    NASA Astrophysics Data System (ADS)

    Harouaka, Khadouja; Kubicki, James D.; Fantle, Matthew S.

    2017-12-01

    Stirred gypsum (CaSO4 · 2H2O) precipitation experiments (initial Ωgypsum = 2.4 ± 0.14, duration ≈ 1.0-1.5 h) were conducted in the presence of the amino acids glycine (190 μM), L-alanine (190 μM), D- and L-arginine (45 μM), and L-tyrosine (200 μM) to investigate the effect of simple organic compounds on both the precipitation kinetics and Ca isotopic composition of gypsum. Relative to abiotic controls, glycine, tyrosine, and alanine inhibited precipitation rates by ∼22%, 27%, and 29%, respectively, while L- and D-arginine accelerated crystal growth by ∼8% and 48%, respectively. With the exception of tyrosine, amino acid induced inhibition resulted in fractionation factors (αs-f) associated with precipitation that were no more than 0.3‰ lower than amino acid-free controls. In contrast, the tyrosine and D- and L-arginine experiments had αs-f values associated with precipitation that were similar to the controls. Our experimental results indicate that Ca isotopic fractionation associated with gypsum precipitation is impacted by growth inhibition in the presence of amino acids. Specifically, we propose that the surface-specific binding of amino acids to gypsum can change the equilibrium fractionation factor of the bulk mineral. We investigate the hypothesis that amino acids can influence the growth of gypsum at specific crystal faces via adsorption and that different faces have distinct fractionation factors (αface-fluid). Accordingly, preferential sorption of amino acids at particular faces changes the relative, face-specific mass fluxes of Ca during growth, which influences the bulk isotopic composition of the mineral. Density functional theory (DFT) calculations suggest that the energetic favorability of glycine sorption onto gypsum crystal faces occurs in the order: (1 1 0) > (0 1 0) > (1 2 0) > (0 1 1), while glycine sorption onto the (-1 1 1) face was found to be energetically unfavorable. Face-specific fractionation factors constrained by

  7. [Determination of deuterium concentration in foods and influence of water with modified isotopic composition on oxidation parameters and heavy hydrogen isotopes content in experimental animals].

    PubMed

    Basov, A A; Bykov, I M; Baryshev, M G; Dzhimak, S S; Bykov, M I

    2014-01-01

    The article presents the results of the study of the deuterium (D) content in food products as well as the influence of deuterium depleted water (DDW) on the concentration of heavy hydrogen isotopes in the blood and lyophilized tissues of rats. The most significant difference in the content of D was found between potato and pork fat, which indexes the standard delta notation (δ) D in promille, related to the international standard SMOW (Standard Mean Ocean of Water) amounted to -83,2 per thousand and -250,7 per thousand, respectively (p<0,05). Among the investigated samples of water deuterium concentration ranged from -75,5 per thousand (Narzan) to +72,1 per thousand (Kubai), that indicates the ability of some food products to increase the concentration of heavy hydrogen atoms in the body. The data obtained in the experimental modeling of the diet of male Wistar rats in the age of 5-6 mo (weight 235 ± 16 g) using DDW (δD = -743,2 per thousand) instead of drinking water (δD = -37,0 per thousand) with identical mineral composition showed that after 2 weeks significant (p <0,05) formation of isotopic (deuterium-protium, D/H) gradient in the body is possible. Changing the direction of isotopic D/H gradient in laboratory animals in comparison with its physiological indicators (72-127 per thousand, "plasma>tissue") is due to different rates ofisotopic exchange reactions in plasma and tissues (liver, kidney, heart), which can be explained by entering into the composition of a modified diet of organic substrates with more than DDW concentration D, which are involved in the construction of cellular structures and eventually lead to a redistribution of D and change direction of D/H gradient "plasmaisotopic composition, aimed at reducing the level of heavy non-radioactive atoms will

  8. A revision in hydrogen isotopic composition of USGS42 and USGS43 human-hair stable isotopic reference materials for forensic science

    USGS Publications Warehouse

    Coplen, Tyler B.; Qi, Haiping

    2016-01-01

    The hydrogen isotopic composition (δ2HVSMOW-SLAP) of USGS42 and USGS43 human hair stable isotopic reference materials, normalized to the VSMOW (Vienna-Standard Mean Ocean Water)–SLAP (Standard Light Antarctic Precipitation) scale, was originally determined with a high temperature conversion technique using an elemental analyzer (TC/EA) with a glassy carbon tube and glassy carbon filling and analysis by isotope-ratio mass spectrometer (IRMS). However, the TC/EA IRMS method can produce inaccurate δ2HVSMOW-SLAPresults when analyzing nitrogen-bearing organic substances owing to the formation of hydrogen cyanide (HCN), leading to non-quantitative conversion of a sample into molecular hydrogen (H2) for IRMS analysis. A single-oven, chromium-filled, elemental analyzer (Cr-EA) coupled to an IRMS substantially improves the measurement quality and reliability of hydrogen isotopic analysis of hydrogen- and nitrogen-bearing organic material because hot chromium scavenges all reactive elements except hydrogen. USGS42 and USGS43 human hair isotopic reference materials have been analyzed with the Cr-EA IRMS method, and the δ2HVSMOW-SLAP values of their non-exchangeable hydrogen fractions have been revised:where mUr = 0.001 = ‰. On average, these revised δ2HVSMOW-SLAP values are 5.7 mUr more positive than those previously measured. It is critical that readers pay attention to the δ2HVSMOW-SLAP of isotopic reference materials in publications as they may need to adjust the δ2HVSMOW–SLAP measurement results of human hair in previous publications to ensure all results are on the same isotope-delta scale.

  9. A revision in hydrogen isotopic composition of USGS42 and USGS43 human-hair stable isotopic reference materials for forensic science.

    PubMed

    Coplen, Tyler B; Qi, Haiping

    2016-09-01

    The hydrogen isotopic composition (δ(2)HVSMOW-SLAP) of USGS42 and USGS43 human hair stable isotopic reference materials, normalized to the VSMOW (Vienna-Standard Mean Ocean Water)-SLAP (Standard Light Antarctic Precipitation) scale, was originally determined with a high temperature conversion technique using an elemental analyzer (TC/EA) with a glassy carbon tube and glassy carbon filling and analysis by isotope-ratio mass spectrometer (IRMS). However, the TC/EA IRMS method can produce inaccurate δ(2)HVSMOW-SLAP results when analyzing nitrogen-bearing organic substances owing to the formation of hydrogen cyanide (HCN), leading to non-quantitative conversion of a sample into molecular hydrogen (H2) for IRMS analysis. A single-oven, chromium-filled, elemental analyzer (Cr-EA) coupled to an IRMS substantially improves the measurement quality and reliability of hydrogen isotopic analysis of hydrogen- and nitrogen-bearing organic material because hot chromium scavenges all reactive elements except hydrogen. USGS42 and USGS43 human hair isotopic reference materials have been analyzed with the Cr-EA IRMS method, and the δ(2)HVSMOW-SLAP values of their non-exchangeable hydrogen fractions have been revised: [Formula: see text] [Formula: see text] where mUr=0.001=‰. On average, these revised δ(2)HVSMOW-SLAP values are 5.7mUr more positive than those previously measured. It is critical that readers pay attention to the δ(2)HVSMOW-SLAP of isotopic reference materials in publications as they may need to adjust the δ(2)HVSMOW-SLAP measurement results of human hair in previous publications to ensure all results are on the same isotope-delta scale. Published by Elsevier Ireland Ltd.

  10. Tracing the secular evolution of the UCC using the iron isotope composition of ancient glacial diamictites

    NASA Astrophysics Data System (ADS)

    Liu, X. M.; Gaschnig, R. M.; Rudnick, R. L.; Hazen, R. M.; Shahar, A.

    2014-12-01

    Iron is the fourth most abundant element in the continental crust and influences global climate and biogeochemical cycles in the ocean1. Continental inputs, including river waters, sediments and atmospheric dust are dominant sources (>95%) of iron into the ocean2. Therefore, understanding how continental inputs may have changed through time is important in understanding the secular evolution of the marine Fe cycle. We analysed the Fe isotopic composition of twenty-four glacial diamictite composites, upper continental crust (UCC) proxies, with ages ranging from the Mesoarchean to the Paleozoic eras to characterize the secular evolution of the UCC. The diamictites all have elevated chemical index of alteration (CIA) and other characteristics of weathered regolith (e.g., strong depletion in soluble elements such as Sr), which they inherited from their upper crustal source region3. δ56Fe in the diamictite composites range from -0.59 to +0.23‰, however, most diamictites cluster with an average δ56Fe of 0.11± 0.20 (2s), overlapping juvenile continental material such as island arc basalts (IABs), which show a narrow range in δ56Fe from -0.04 to +0.14 ‰4. There is no obvious correlation between δ56Fe of the glacial diamictites and the CIA, except that the diamictite with the lowest δ56Fe at -0.59 ‰ also has the highest CIA = 89 (the Paleoproterozoic Makganyene Fm.). The data suggest that the Fe isotope compositions in the upper continental crust did not vary throughout Earth history. Interestingly, chemical weathering and sedimentary transport likely play only a minor role in producing Fe isotope variations in the upper continental crust. Anoxic weathering pre-GOE (Great Oxidation Event) does not seem to generate different Fe isotopic signatures from the post-GOE oxidative weathering environment in the upper continental crust. Therefore, large Fe isotopic fractionations observed in various marine sedimentary records are likely due to other processes occurring

  11. Tracing the secular evolution of the UCC using the iron isotope composition of ancient glacial diamictites

    NASA Astrophysics Data System (ADS)

    Liu, X. M.; Gaschnig, R. M.; Rudnick, R. L.; Hazen, R. M.; Shahar, A.

    2015-12-01

    Iron is the fourth most abundant element in the continental crust and influences global climate and biogeochemical cycles in the ocean1. Continental inputs, including river waters, sediments and atmospheric dust are dominant sources (>95%) of iron into the ocean2. Therefore, understanding how continental inputs may have changed through time is important in understanding the secular evolution of the marine Fe cycle. We analysed the Fe isotopic composition of twenty-four glacial diamictite composites, upper continental crust (UCC) proxies, with ages ranging from the Mesoarchean to the Paleozoic eras to characterize the secular evolution of the UCC. The diamictites all have elevated chemical index of alteration (CIA) and other characteristics of weathered regolith (e.g., strong depletion in soluble elements such as Sr), which they inherited from their upper crustal source region3. δ56Fe in the diamictite composites range from -0.59 to +0.23‰, however, most diamictites cluster with an average δ56Fe of 0.11± 0.20 (2s), overlapping juvenile continental material such as island arc basalts (IABs), which show a narrow range in δ56Fe from -0.04 to +0.14 ‰4. There is no obvious correlation between δ56Fe of the glacial diamictites and the CIA, except that the diamictite with the lowest δ56Fe at -0.59 ‰ also has the highest CIA = 89 (the Paleoproterozoic Makganyene Fm.). The data suggest that the Fe isotope compositions in the upper continental crust did not vary throughout Earth history. Interestingly, chemical weathering and sedimentary transport likely play only a minor role in producing Fe isotope variations in the upper continental crust. Anoxic weathering pre-GOE (Great Oxidation Event) does not seem to generate different Fe isotopic signatures from the post-GOE oxidative weathering environment in the upper continental crust. Therefore, large Fe isotopic fractionations observed in various marine sedimentary records are likely due to other processes occurring

  12. EasyDelta: A spreadsheet for kinetic modeling of the stable carbon isotope composition of natural gases

    NASA Astrophysics Data System (ADS)

    Zou, Yan-Rong; Wang, Lianyuan; Shuai, Yanhua; Peng, Ping'an

    2005-08-01

    A new kinetic model and an Excel © spreadsheet program for modeling the stable carbon isotope composition of natural gases is provided in this paper. The model and spreadsheet could be used to describe and predict the variances in stable carbon isotope of natural gases under both experimental and geological conditions with heating temperature or geological time. It is a user-friendly convenient tool for the modeling of isotope variation with time under experimental and geological conditions. The spreadsheet, based on experimental data, requires the input of the kinetic parameters of gaseous hydrocarbons generation. Some assumptions are made in this model: the conventional (non-isotope species) kinetic parameters represent the light isotope species; the initial isotopic value is the same for all parallel chemical reaction of gaseous hydrocarbons generation for simplicity, the re-exponential factor ratio, 13A/ 12A, is a constant, and both heavy and light isotope species have similar activation energy distribution. These assumptions are common in modeling of isotope ratios. The spreadsheet is used for searching the best kinetic parameters of the heavy isotope species to reach the minimum errors compared with experimental data, and then extrapolating isotopic changes to the thermal history of sedimentary basins. A short calculation example on the variation in δ13C values of methane is provided in this paper to show application to geological conditions.

  13. Linking the isotopic composition of monthly precipitation, cave drip water and tree ring cellulose - 15 years of monitoring and data-model comparison

    NASA Astrophysics Data System (ADS)

    Labuhn, Inga; Genty, Dominique; Daux, Valérie; Bourges, François; Hoffmann, Georg

    2013-04-01

    The isotopic composition of proxies used for palaeoclimate reconstruction, like tree ring cellulose or speleothem calcite, is controlled to a large extent by the isotopic composition of precipitation. In order to calibrate and interpret these proxies in terms of climate, it is necessary to study water isotopes in rainfall and their link with the proxies' source water. We present 10 to 15-year series of stable hydrogen and oxygen isotopes in monthly precipitation from three sites in the south of France, along with corresponding REMOiso model simulations, a monitoring of cave drip water from two of these sites (Villars cave in the south-west and Chauvet cave in the south-east), as well as measurements of oxygen isotopes in tree ring cellulose from oak trees growing in the same area. The isotopic composition of monthly precipitation at the three sites displays a typical annual cycle. At the south-west sites, under Atlantic influence, the interannual variability is much more pronounced during the winter months than during the summer, whereas the south-eastern Mediterranean site shows the same variability throughout the year. The model simulations are able to reproduce the annual cycle of monthly precipitation δ18O as well as the intra-seasonal variability. Compared to the data, however, the modelled average isotopic values and the seasonal amplitude are overestimated. Correlations between temperature and precipitation δ18O are generally weak at all our sites, on both the monthly and the annual scale, even when using temperature averages weighted by the amount of precipitation. Consequently, a proxy which is controlled by the δ18O of precipitation cannot be directly interpreted in terms of temperature in this region. The isotopic composition of cave drip water in both caves remains stable throughout the monitoring period. By calculating different weighted averages of precipitation δ18O for time periods ranging from months to years, we demonstrate that the cave drip

  14. Tracing the distribution of erosion in the Brahmaputra watershed from isotopic compositions of stream sediments

    NASA Astrophysics Data System (ADS)

    Singh, Sunil K.; France-Lanord, Christian

    2002-09-01

    Bank sediments and suspended loads of the Brahmaputra River and its important tributaries were collected from the Himalayan front to Bangladesh along with most of the important tributaries. Chemical and isotopic compositions of the sediments are used to trace sediment provenance and to understand erosion patterns in the basin. Overall isotopic compositions range from 0.7053 to 0.8250 for Sr and ɛNd from -20.5 to -6.9. This large range derives from the variable proportions of sediments from Himalayan formations with high Sr isotopic ratios and low ɛNd, and Transhimalayan plutonic belt with lower Sr isotopic ratios and higher ɛNd. The latter are exposed to erosion in the Tsangpo and in the eastern tributary drainages. Overall erosion of the Himalayan rocks is dominant, representing ca 70% of the detrital influx. Compositions of the Brahmaputra main channel are rather stable between 0.7177 and 0.7284 for Sr and between -14.4 and -12.5 for ɛNd throughout its course in the plain from the Siang-Tsangpo at the foot of the Himalayan range down to the delta. This stability, despite the input of large Himalayan rivers suggests that the Siang-Tsangpo River represents the major source of sediment to the whole Brahmaputra. Geochemical budget implies that erosion of the Namche Barwa zone represents about 45% of the total flux at its outflow before confluence with the Ganga from only 20% of the mountain area. Higher erosion rates in the eastern syntaxis compared to the other Himalayan ranges is related to the rapid exhumation rates of this region, possibly triggered by higher precipitation over the far-eastern Himalaya and the high incision potential of the Tsangpo River due to its very high water discharge.

  15. Variations in the isotopic composition of stable mercury isotopes in typical mangrove plants of the Jiulong estuary, SE China.

    PubMed

    Sun, Lumin; Lu, Bingyan; Yuan, Dongxing; Hao, Wenbo; Zheng, Ying

    2017-01-01

    Variations in the composition of stable isotopes of mercury contained in tissues (root, stem, leaf, and hypocotyl or flower) of three typical mangrove plants (Kandelia candel, Aegiceras corniculata, and Bruguiera gymnorhiza), collected from the mangrove wetland of Jiulong estuary, SE China, were used to investigate the sources and transformation of mercury in the mangrove plants. Tissue samples from the plants were digested and mercury in the solution was pre-concentrated with purge-trap method and then analyzed by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The results showed that the mass dependent fractionation (MDF) of mercury ranged from -2.67 to -0.87 ‰ for δ 202 Hg while the mass independent fractionation (MIF) of mercury isotopes ranged from -0.16 to 0.09 and -0.19 to 0.05 ‰ for Δ 199 Hg and Δ 201 Hg, respectively, relative to the standard NIST SRM 3133. The ratio of Δ 199 Hg/Δ 201 Hg was 0.991, indicating that the mercury had been photo-reduced before being accumulated in mangrove plants. Analyses of the data from MIF studies revealed that the major portion of the mercury measured in leaves (∼90 %) originated from the atmosphere while the source of over half of the mercury present in roots was the surficial sediment. This study, the first of its kind investigating the variations in isotopic composition of mercury in the tissues of mangrove plants, could be helpful to identify the source of mercury contamination in mangroves and understand the biogeochemical cycle of mercury in the estuarine mangrove wetlands.

  16. High precision isotope ratio measurements of mercury isotopes in cinnabar ores using multi-collector inductively coupled plasma mass spectrometry.

    PubMed

    Hintelmann, Holger; Lu, ShengYong

    2003-06-01

    Variations in Hg isotope ratios in cinnabar ores obtained from different countries were detected by high precision isotope ratio measurements using multi-collector inductively coupled mass spectrometry (MC-ICP-MS). Values of delta198/202Hg varied from 0.0-1.3 percent per thousand relative to a NIST SRM 1641d Hg solution. The typical external uncertainty of the delta values was 0.06 to 0.26 percent per thousand. Hg was introduced into the plasma as elemental Hg after reduction by sodium borohydride. A significant fractionation of lead isotopes was observed during the simultaneous generation of lead hydride, preventing normalization of the Hg isotope ratios using the measured 208/206Pb ratio. Hg ratios were instead corrected employing the simultaneously measured 205/203T1 ratio. Using a 10 ng ml(-1) Hg solution and 10 min of sampling, introducing 60 ng of Hg, the internal precision of the isotope ratio measurements was as low as 14 ppm. Absolute Hg ratios deviated from the representative IUPAC values by approximately 0.2% per u. This observation is explained by the inadequacy of the exponential law to correct for mass bias in MC-ICP-MS measurements. In the absence of a precisely characterized Hg isotope ratio standard, we were not able to determine unambiguously the absolute Hg ratios of the ore samples, highlighting the urgent need for certified standard materials.

  17. High-resolution food webs based on nitrogen isotopic composition of amino acids

    PubMed Central

    Chikaraishi, Yoshito; Steffan, Shawn A; Ogawa, Nanako O; Ishikawa, Naoto F; Sasaki, Yoko; Tsuchiya, Masashi; Ohkouchi, Naohiko

    2014-01-01

    Food webs are known to have myriad trophic links between resource and consumer species. While herbivores have well-understood trophic tendencies, the difficulties associated with characterizing the trophic positions of higher-order consumers have remained a major problem in food web ecology. To better understand trophic linkages in food webs, analysis of the stable nitrogen isotopic composition of amino acids has been introduced as a potential means of providing accurate trophic position estimates. In the present study, we employ this method to estimate the trophic positions of 200 free-roaming organisms, representing 39 species in coastal marine (a stony shore) and 38 species in terrestrial (a fruit farm) environments. Based on the trophic positions from the isotopic composition of amino acids, we are able to resolve the trophic structure of these complex food webs. Our approach reveals a high degree of trophic omnivory (i.e., noninteger trophic positions) among carnivorous species such as marine fish and terrestrial hornets.This information not only clarifies the trophic tendencies of species within their respective communities, but also suggests that trophic omnivory may be common in these webs. PMID:25360278

  18. Determining absolute protein numbers by quantitative fluorescence microscopy.

    PubMed

    Verdaasdonk, Jolien Suzanne; Lawrimore, Josh; Bloom, Kerry

    2014-01-01

    Biological questions are increasingly being addressed using a wide range of quantitative analytical tools to examine protein complex composition. Knowledge of the absolute number of proteins present provides insights into organization, function, and maintenance and is used in mathematical modeling of complex cellular dynamics. In this chapter, we outline and describe three microscopy-based methods for determining absolute protein numbers--fluorescence correlation spectroscopy, stepwise photobleaching, and ratiometric comparison of fluorescence intensity to known standards. In addition, we discuss the various fluorescently labeled proteins that have been used as standards for both stepwise photobleaching and ratiometric comparison analysis. A detailed procedure for determining absolute protein number by ratiometric comparison is outlined in the second half of this chapter. Counting proteins by quantitative microscopy is a relatively simple yet very powerful analytical tool that will increase our understanding of protein complex composition. © 2014 Elsevier Inc. All rights reserved.

  19. Size scales over which ordinary chondrites and their parent asteroids are homogeneous in oxidation state and oxygen-isotopic composition

    NASA Astrophysics Data System (ADS)

    Rubin, Alan E.; Ziegler, Karen; Young, Edward D.

    2008-02-01

    Literature data demonstrate that on a global, asteroid-wide scale (plausibly on the order of 100 km), ordinary chondrites (OC) have heterogeneous oxidation states and O-isotopic compositions (represented, respectively, by the mean olivine Fa and bulk Δ 17O compositions of equilibrated samples). Samples analyzed here include: (a) two H5 chondrite Antarctic finds (ALHA79046 and TIL 82415) that have the same cosmic-ray exposure age (7.6 Ma) and were probably within ˜1 km of each other when they were excavated from the H-chondrite parent body, (b) different individual stones from the Holbrook L/LL6 fall that were probably within ˜1 m of each other when their parent meteoroid penetrated the Earth's atmosphere, and (c) drill cores from a large slab of the Estacado H6 find located within a few tens of centimeters of each other. Our results indicate that OC are heterogeneous in their bulk oxidation state and O-isotopic composition on 100-km-size scales, but homogeneous on meter-, decimeter- and centimeter-size scales. (On kilometer size scales, oxidation state is heterogeneous, but O isotopes appear to be homogeneous.) The asteroid-wide heterogeneity in oxidation state and O-isotopic composition was inherited from the solar nebula. The homogeneity on small size scales was probably caused in part by fluid-assisted metamorphism and mainly by impact-gardening processes (which are most effective at mixing target materials on scales of ⩽1 m).

  20. Pan-derived isotopic composition of atmospheric vapour in a Mediterranean wetland (Rhône River Delta, France).

    PubMed

    Vallet-Coulomb, Christine; Cartapanis, Olivier; Radakovitch, Olivier; Sonzogni, Corinne; Pichaud, Marc

    2010-03-01

    A continuous record of atmospheric vapour isotopic composition (delta(A)) can be derived from the isotope mass balance of a water body submitted to natural evaporation. In this paper, we present preliminary results of the application of this method to a drying evaporation pan, located in a Mediterranean wetland, during a two-month summer period. Results seem consistent with few atmospheric vapour data based on the assumption of isotopic equilibrium with precipitation, but we observed a shift between pan-derived delta(A) and the composition of vapour samples collected by cold trapping. These results suggest that further investigations are necessary to evaluate the effect of diurnal variations of atmospheric conditions on the applicability of the pan-evaporation method, and on the representative of grab atmospheric samples. We also propose a sensitivity analysis for evaluating the impact of the different measured components on delta(A) calculation, and show an improvement in the method efficiency as the pan is drying.

  1. Asian anthropogenic lead contamination in the North Pacific Ocean as evidenced by stable lead isotopic compositions

    NASA Astrophysics Data System (ADS)

    Zurbrick, Cheryl M.

    This dissertation work determined the changing scope of lead (Pb) contamination in the North Pacific Ocean since the phase-out of leaded gasoline in most of the world. Chapters 1 and 2 consisted of validating our method for determining Pb concentrations and isotopic compositions in seawater. Chapter 3 established a baseline of Pb isotopic compositions (PbICs) in the western and central North Pacific in 2002. This was an ideal time to establish such a baseline because China had recently (mid-2000) ceased their use of leaded gasoline and simultaneously began consuming increasingly large amounts of coal, known to have relatively high Pb concentrations. We found subsurface waters were contaminated with Asian industrial Pb, predominantly Chinese coal emissions. In contrast, the abyssal waters were a mix of Asian industrial Pb and background (i.e., natural) Pb. Chapter 4 revisited the western and central North Pacific in 2009 -- 2011 to determine what, if any, changes had occurred in this short time period. We found that Pb in subsurface and abyssal waters of the western North Pacific were similar to Chinese aerosols. Such a large change in the PbICs of abyssal water in 9 years was unanticipated and attributed to the relatively large flux of particle-bound Pb from the euphotic zone to the deep ocean, which was in isotopic equilibrium with the reservoir of dissolved Pb. In contrast, the central North Pacific abyssal water PbICs were similar to values previously reported because of the relatively lower particulate export. Based on comparisons to baseline PbIC data, we determined that abyssal waters in the western and central North Pacific would be isotopically indistinguishable from surface waters in the next three decades. Sources of Pb to coastal California waters were reevaluated in Chapter 5. Prior studies had found that surface waters of the California Current System (CCS) were isotopically consistent with both Asian industrial Pb and US leaded gasoline, still in use

  2. Iron isotope composition of depleted MORB

    NASA Astrophysics Data System (ADS)

    Labidi, J.; Sio, C. K. I.; Shahar, A.

    2015-12-01

    In terrestrial basalts, iron isotope ratios are observed to weakly fractionate as a function of olivine and pyroxene crystallization. However, a ~0.1‰ difference between chondrites and MORB had been reported (Dauphas et al. 2009, Teng et al. 2013 and ref. therein). This observation could illustrate an isotope fractionation occurring during partial melting, as a function of the Fe valence in melt versus crystals. Here, we present high-precision Fe isotopic data measured by MC-ICP-MS on well-characterized samples from the Pacific-Antarctic Ridge (PAR, n=9) and from the Garrett Transform Fault (n=8). These samples allow exploring the Fe isotope fractionation between melt and magnetite, and the role of partial melting on Fe isotope fractionation. Our average δ56Fe value is +0.095±0.013‰ (95% confidence, n=17), indistinguishable from a previous estimate of +0.105±0.006‰ (95% confidence, n=43, see ref. 2). Our δ56Fe values correlate weakly with MgO contents, and correlate positively with K/Ti ratios. PAC1 DR10 shows the largest Ti and Fe depletion after titanomagnetite fractionation, with a δ56Fe value of +0.076±0.036‰. This is ~0.05‰ below other samples at a given MgO. This may illustrate a significant Fe isotope fractionation between the melt and titanomagnetite, in agreement with experimental determination (Shahar et al. 2008). GN09-02, the most incompatible-element depleted sample, has a δ56Fe value of 0.037±0.020‰. This is the lowest high-precision δ56Fe value recorded for a MORB worldwide. This basalt displays an incompatible-element depletion consistent with re-melting beneath the transform fault of mantle source that was depleted during a first melting event, beneath the ridge axis (Wendt et al. 1999). The Fe isotope observation could indicate that its mantle source underwent 56Fe depletion after a first melting event. It could alternatively indicate a lower Fe isotope fractionation during re-melting, if the source was depleted of its Fe3

  3. The isotope composition of inorganic germanium in seawater and deep sea sponges

    NASA Astrophysics Data System (ADS)

    Guillermic, Maxence; Lalonde, Stefan V.; Hendry, Katharine R.; Rouxel, Olivier J.

    2017-09-01

    Although dissolved concentrations of germanium (Ge) and silicon (Si) in modern seawater are tightly correlated, uncertainties still exist in the modern marine Ge cycle. Germanium stable isotope systematics in marine systems should provide additional constraints on marine Ge sources and sinks, however the low concentration of Ge in seawater presents an analytical challenge for isotopic measurement. Here, we present a new method of pre-concentration of inorganic Ge from seawater which was applied to measure three Ge isotope profiles in the Southern Ocean and deep seawater from the Atlantic and Pacific Oceans. Germanium isotopic measurements were performed on Ge amounts as low as 2.6 ng using a double-spike approach and a hydride generation system coupled to a MC-ICP-MS. Germanium was co-precipitated with iron hydroxide and then purified through anion-exchange chromatography. Results for the deep (i.e. >1000 m depth) Pacific Ocean off Hawaii (nearby Loihi Seamount) and the deep Atlantic off Bermuda (BATS station) showed nearly identical δ74/70Ge values at 3.19 ± 0.31‰ (2SD, n = 9) and 2.93 ± 0.10‰ (2SD, n = 2), respectively. Vertical distributions of Ge concentration and isotope composition in the deep Southern Ocean for water depth > 1300 m yielded an average δ74/70Ge = 3.13 ± 0.25‰ (2SD, n = 14) and Ge/Si = 0.80 ± 0.09 μmol/mol (2SD, n = 12). Significant variations in δ74/70Ge, from 2.62 to 3.71‰, were measured in the first 1000 m in one station of the Southern Ocean near Sars Seamount in the Drake Passage, with the heaviest values measured in surface waters. Isotope fractionation by diatoms during opal biomineralization may explain the enrichment in heavy isotopes for both Ge and Si in surface seawater. However, examination of both oceanographic parameters and δ74/70Ge values suggest also that water mass mixing and potential contribution of shelf-derived Ge also could contribute to the variations. Combining these results with new Ge isotope data

  4. Microscale determination of the spectral characteristics and carbon-isotopic compositions of porphyrins

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

    Molar extinction coefficients for band III of Ni porphyrins are calculated from results of spectrophotometric and manometric analyses of individual etioporphyrins, DPEP, cyclic, and diDPEP porphyrins known to initially be pure from mass spectrometry, 1H NMR, and analytical HPLC studies. A method for determining carbon-isotopic compositions and purity of micromolar quantities of individual porphyrins using combined spectrophotometric and manometric techniques is presented.

  5. Investigating the source, transport, and isotope composition of water vapor in the planetary boundary layer

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Griffis, Timothy J.; Wood, Jeffrey D.; Baker, John M.

    Increasing atmospheric humidity and convective precipitation over land provide evidence of intensification of the hydrologic cycle – an expected response to surface warming. The extent to which terrestrial ecosystems modulate these hydrologic factors is important to understand feedbacks in the climate system. We measured the oxygen and hydrogen isotope composition of water vapor at a very tall tower (185 m) in the upper Midwest, United States, to diagnose the sources, transport, and fractionation of water vapor in the planetary boundary layer (PBL) over a 3-year period (2010 to 2012). These measurements represent the first set of annual water vapor isotopemore » observations for this region. Several simple isotope models and cross-wavelet analyses were used to assess the importance of the Rayleigh distillation process, evaporation, and PBL entrainment processes on the isotope composition of water vapor. The vapor isotope composition at this tall tower site showed a large seasonal amplitude (mean monthly δ 18O v ranged from –40.2 to –15.9 ‰ and δ 2H v ranged from –278.7 to –113.0 ‰) and followed the familiar Rayleigh distillation relation with water vapor mixing ratio when considering the entire hourly data set. However, this relation was strongly modulated by evaporation and PBL entrainment processes at timescales ranging from hours to several days. The wavelet coherence spectra indicate that the oxygen isotope ratio and the deuterium excess ( d v) of water vapor are sensitive to synoptic and PBL processes. According to the phase of the coherence analyses, we show that evaporation often leads changes in d v, confirming that it is a potential tracer of regional evaporation. Isotope mixing models indicate that on average about 31 % of the growing season PBL water vapor is derived from regional evaporation. However, isoforcing calculations and mixing model analyses for high PBL water vapor mixing ratio events ( > 25 mmol mol –1) indicate that

  6. Investigating the source, transport, and isotope composition of water vapor in the planetary boundary layer

    DOE PAGES

    Griffis, Timothy J.; Wood, Jeffrey D.; Baker, John M.; ...

    2016-04-25

    Increasing atmospheric humidity and convective precipitation over land provide evidence of intensification of the hydrologic cycle – an expected response to surface warming. The extent to which terrestrial ecosystems modulate these hydrologic factors is important to understand feedbacks in the climate system. We measured the oxygen and hydrogen isotope composition of water vapor at a very tall tower (185 m) in the upper Midwest, United States, to diagnose the sources, transport, and fractionation of water vapor in the planetary boundary layer (PBL) over a 3-year period (2010 to 2012). These measurements represent the first set of annual water vapor isotopemore » observations for this region. Several simple isotope models and cross-wavelet analyses were used to assess the importance of the Rayleigh distillation process, evaporation, and PBL entrainment processes on the isotope composition of water vapor. The vapor isotope composition at this tall tower site showed a large seasonal amplitude (mean monthly δ 18O v ranged from –40.2 to –15.9 ‰ and δ 2H v ranged from –278.7 to –113.0 ‰) and followed the familiar Rayleigh distillation relation with water vapor mixing ratio when considering the entire hourly data set. However, this relation was strongly modulated by evaporation and PBL entrainment processes at timescales ranging from hours to several days. The wavelet coherence spectra indicate that the oxygen isotope ratio and the deuterium excess ( d v) of water vapor are sensitive to synoptic and PBL processes. According to the phase of the coherence analyses, we show that evaporation often leads changes in d v, confirming that it is a potential tracer of regional evaporation. Isotope mixing models indicate that on average about 31 % of the growing season PBL water vapor is derived from regional evaporation. However, isoforcing calculations and mixing model analyses for high PBL water vapor mixing ratio events ( > 25 mmol mol –1) indicate that

  7. Lead isotopic composition of trinitite melt glass: evidence for the presence of Canadian industrial lead in the first atomic weapon test.

    PubMed

    Bellucci, Jeremy J; Simonetti, Antonio; Wallace, Christine; Koeman, Elizabeth C; Burns, Peter C

    2013-08-06

    The Pb isotopic compositions for 51 spots of melt glass in 11 samples of trinitite have been determined by laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS). Trinitite glass yields a large range of Pb isotopic compositions (i.e., (206)Pb/(204)Pb = 17.08-19.04), which reflect mixing between industrial Pb from materials used in the Trinity test and natural geologic components. Areas within trinitite melt glass containing high concentrations of both Cu and Pb, which are derived from the bomb and blast site-related components, were used for delineating the Pb isotopic composition corresponding to the anthropogenic Pb component. Comparison between the isotopic composition estimated here for the industrial Pb used in the Trinity test and those from known Pb deposits worldwide indicates close agreement with ore from the Buchans mine (Newfoundland, Canada). The Buchans mine was active during the time of the Trinity test and was operated by the American Smelting and Refining Company, which could have provided the Pb used in the test. The industrial Pb used in the Trinity test materials is not documented in the literature (or declassified) but could have been present in bricks, solder, pigs, or some other anthropogenic component related to the experiment.

  8. Controls over spatial and seasonal variations on isotopic composition of the precipitation along the central and eastern portion of Brazil.

    PubMed

    Gastmans, Didier; Santos, Vinícius; Galhardi, Juliana Aparecida; Gromboni, João Felipe; Batista, Ludmila Vianna; Miotlinski, Konrad; Chang, Hung Kiang; Govone, José Silvio

    2017-10-01

    Based on Global Network Isotopes in Precipitation (GNIP) isotopic data set, a review of the spatial and temporal variability of δ 18 O and δ 2 H in precipitation was conducted throughout central and eastern Brazil, indicating that dynamic interactions between Intertropical and South Atlantic Convergence Zones, Amazon rainforest, and Atlantic Ocean determine the variations on the isotopic composition of precipitation over this area. Despite the seasonality and latitude effects observed, a fair correlation with precipitation amount was found. In addition, Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) air mass back trajectories were used to quantify the factors controlling daily variability in stable isotopes in precipitation. Through a linear multiple regression analysis, it was observed that temporal variations were consistent with the meteorological parameters derived from HYSPLIT, particularly precipitation amount along the trajectory and mix depth, but are not dependent on vapour residence time in the atmosphere. These findings also indicate the importance of convective systems to control the isotopic composition of precipitation in tropical and subtropical regions.

  9. Coffee seeds isotopic composition as a potential proxy to evaluate Minas Gerais, Brazil seasonal variations during seed maturation

    NASA Astrophysics Data System (ADS)

    Rodrigues, Carla; Maia, Rodrigo; Brunner, Marion; Carvalho, Eduardo; Prohaska, Thomas; Máguas, Cristina

    2010-05-01

    Plant seeds incorporate the prevailing climate conditions and the physiological response to those conditions (Rodrigues et al., 2009; Rodrigues et al., submitted). During coffee seed maturation the biochemical compounds may either result from accumulated material in other organs such as leafs and/or from new synthesis. Accordingly, plant seeds develop in different stages along a particular part of the year, integrating the plant physiology and seasonal climatic conditions. Coffee bean is an extremely complex matrix, rich in many products derived from both primary and secondary metabolism during bean maturation. Other studies (De Castro and Marraccini, 2006) have revealed the importance of different coffee plant organs during coffee bean development as transfer tissues able to provide compounds (i.e. sugars, organic acids, etc) to the endosperm where several enzymatic activities and expressed genes have been reported. Moreover, it has been proved earlier on that green coffee bean is a particularly suitable case-study (Rodrigues et al., 2009; Rodrigues et al., submitted), not only due to the large southern hemispheric distribution but also because of this product high economic interest. The aim of our work was to evaluate the potential use of green coffee seeds as a proxy to seasonal climatic conditions during coffee bean maturation, through an array of isotopic composition determinations. We have determined carbon, nitrogen, oxygen and sulfur isotopic composition (by IRMS - Isotope Ratio Mass Spectrometry) as well as strontium isotope abundance (by MC-ICP-MS; Multicollector Inductively Coupled Plasma Mass Spectrometry), of green coffee beans harvested at different times at Minas Gerais, Brazil. The isotopic composition data were combined with air temperature and relative humidity data registered during the coffee bean developmental period, and with the parent rock strontium isotopic composition. Results indicate that coffee seeds indeed integrate the interactions

  10. Barium isotopic compositions of oceanic basalts from São Miguel, Azores Archipelago

    NASA Astrophysics Data System (ADS)

    Yu, H.; Nan, X.; Huang, F.

    2016-12-01

    Oceanic island basalts (OIB) provide important information to decipher the processes of mantle convection and crustal material recycling1. OIBs from São Miguel, Azores Archipelago have extreme radiogenic isotope compositions2-3, representing an enriched component in their mantle source. However, the origins of the enriched mantle are still in debate. Previous studies proposed that the enriched component could be subducted terrigenous sediments2,4, delaminated subcontinental lithosphere5-6, recycled oceanic crust with evolved compositions (such as a subducted seamount)7, or enriched (E-MORB type) under-plated basalts which infiltrated the oceanic mantle lithosphere8. In this study, we use Ba isotopes to constrain the origin of enriched component beneath São Miguel because Ba isotopes can be significantly fractionated at the Earth's surface with low temperature environment than in the mantle with high temperature9-10. We analyzed Ba isotopes of 15 basalts from São Miguel. Although these samples have large variations of 87Sr/86Sr (0.703440-0.705996), 206Pb/204Pb (19.319-20.095) and 187Os/188Os (0.127-0.161), they have limited variation of 137Ba/134Ba (-0.003 to +0.048‰). The average 137Ba/134Ba of São Miguel basalts is 0.019±0.033‰ (n=15, 2SD), which is in the range of mantle (0.026±0.090‰, n=32, 2SD)9, indicating there is no surface material in the mantle source of São Miguel. The enriched source of São Miguel could be evolved material from the mantle. 1. Hofmann, 1997, Nature; 2. Hawkesworth et al., 1979, Nature; 3. White et al., 1979, CMP; 4. Turner et al., 1997, CG; 5. Widom et al., 1997, CG; 6. Moreira et al., 1999, EPSL; 7. Beier et al., 2007, EPSL; 8. Elliott et al., 2007, GCA; 9. Huang et al., 2015, Goldschmidt abs 1331; 10. Nan et al., 2016, Goldschmidt abs 2246.

  11. Isotope reference materials

    USGS Publications Warehouse

    Coplen, Tyler B.

    2010-01-01

    Measurement of the same isotopically homogeneous sample by any laboratory worldwide should yield the same isotopic composition within analytical uncertainty. International distribution of light element isotopic reference materials by the International Atomic Energy Agency and the U.S. National Institute of Standards and Technology enable laboratories to achieve this goal.

  12. Isotopic composition and identification of the origins of individuals buried in a Neolithic collective grave at Bronocice (southern Poland).

    PubMed

    Szostek, K; Haduch, E; Stepańczak, B; Kruk, J; Szczepanek, A; Pawlyta, J; Głąb, H; Milisauskas, S

    2014-04-01

    The oxygen present in a human organism comes from numerous sources, but the major factor that causes variation in the isotopic composition of this element in a tissue is available drinking water. The isotopic ratio of oxygen in an organism's tissue, including that found in bones and teeth, reflects the isotopic oxygen composition typical for the area where a given individual developed and lived. Of particular interest with regard to this issue were a series of skeletons from the multiple grave discovered at the Funnel Beaker-Baden settlement at Bronocice (southern Poland). The question therefore arose whether the specimens buried in this grave were part of the local community. The oxygen isotope level was established using apatite isolated from bones or teeth. A femur and root dentine samples taken from permanent teeth were subjected to oxygen isotope analysis. The oxygen isotope level of the site was established on the basis of local water precipitation and measurements taken from the oxygen isotope concentration in apatite samples isolated from the bones of animals co-occurring with the studied human group. It has been found that the oxygen isotope levels in the bones and dentine of almost all the analysed specimens from the excavated site at Bronocice were within the established range for the area's environment, providing evidence for their local origin. Thus, it can be assumed that the analysed group inhabiting the macrosettlement at Bronocice during the Funnel Beaker phase of the Baden culture was most probably of local origin. Copyright © 2013 Elsevier GmbH. All rights reserved.

  13. Lead isotope compositions of Late Cretaceous and early Tertiary igneous rocks and sulfide minerals in Arizona: Implications for the sources of plutons and metals in porphyry copper deposits

    USGS Publications Warehouse

    Bouse, R.M.; Ruiz, J.; Titley, S.R.; Tosdal, R.M.; Wooden, J.L.

    1999-01-01

    Porphyry copper deposits in Arizona are genetically associated with Late Cretaceous and early Tertiary igneous complexes that consist of older intermediate volcanic rocks and younger intermediate to felsic intrusions. The igneous complexes and their associated porphyry copper deposits were emplaced into an Early Proterozoic basement characterized by different rocks, geologic histories, and isotopic compositions. Lead isotope compositions of the Proterozoic basement rocks define, from northwest to southeast, the Mojave, central Arizona, and southeastern Arizona provinces. Porphyry copper deposits are present in each Pb isotope province. Lead isotope compositions of Late Cretaceous and early Tertiary plutons, together with those of sulfide minerals in porphyry copper deposits and of Proterozoic country rocks, place important constraints on genesis of the magmatic suites and the porphyry copper deposits themselves. The range of age-corrected Pb isotope compositions of plutons in 12 Late Cretaceous and early Tertiary igneous complexes is 206Pb/204Pb = 17.34 to 22.66, 207Pb/204Pb = 15.43 to 15.96, and 208Pb/204Pb = 37.19 to 40.33. These Pb isotope compositions and calculated model Th/U are similar to those of the Proterozoic rocks in which the plutons were emplaced, thereby indicating that Pb in the younger rocks and ore deposits was inherited from the basement rocks and their sources. No Pb isotope differences distinguish Late Cretaceous and early Tertiary igneous complexes that contain large economic porphyry copper deposits from less rich or smaller deposits that have not been considered economic for mining. Lead isotope compositions of Late Cretaceous and early Tertiary plutons and sulfide minerals from 30 metallic mineral districts, furthermore, require that the southeastern Arizona Pb province be divided into two subprovinces. The northern subprovince has generally lower 206Pb/204Pb and higher model Th/U, and the southern subprovince has higher 206Pb/204Pb and

  14. Essential Oils, Part VI: Sandalwood Oil, Ylang-Ylang Oil, and Jasmine Absolute.

    PubMed

    de Groot, Anton C; Schmidt, Erich

    In this article, some aspects of sandalwood oil, ylang-ylang oil, and jasmine absolute are discussed including their botanical origin, uses of the plants and the oils and absolute, chemical composition, contact allergy to and allergic contact dermatitis from these essential oils and absolute, and their causative allergenic ingredients.

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

    NASA Technical Reports Server (NTRS)

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

    2012-01-01

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

  16. Partitioning understory evapotranspiration in semi-arid ecosystems in Namibia using the isotopic composition of water vapour

    NASA Astrophysics Data System (ADS)

    de Blécourt, Marleen; Gaj, Marcel; Holtorf, Kim-Kirsten; Gröngröft, Alexander; Brokate, Ralph; Himmelsbach, Thomas; Eschenbach, Annette

    2016-04-01

    In dry environments with a sparse vegetation cover, understory evapotranspiration is a major component of the ecosystem water balance. Consequently, knowledge on the size of evapotranspiration fluxes and the driving factors is important for our understanding of the hydrological cycle. Understory evapotranspiration is made up of soil evaporation and plant transpiration. Soil evaporation can be measured directly from patches free of vegetation. However, when understory vegetation is present distinguishing between soil evaporation and plant transpiration is challenging. In this study, we aim to partition understory evapotranspiration based on an approach that combines the measurements of water-vapour fluxes using the closed chamber method with measurements of the isotopic composition of water vapour. The measurements were done in the framework of SASSCAL (Southern African Science Service Centre for Climate Change and Adaptive Land Management). The study sites were located in three different semi-arid ecosystems in Namibia: thornbush savanna, Baikiaea woodland and shrubland. At each site measurements were done under tree canopies as well as at unshaded areas between the canopies. We measured evaporation from the bare soil and evapotranspiration from patches covered with herbaceous species and shrubs using a transparent chamber connected with an infrared gas analyser (LI-8100A, LICOR Inc.). The stable isotope composition of water vapour inside the chamber and depth profiles of soil water stable isotopes were determined in-situ using a tuneable off-axis integrated cavity output spectroscope (OA-ICOS, Los Gatos Research, DLT 100). Xylem samples were extracted using the cryogenic vacuum extraction method and the isotopic composition of the extracted water was measured subsequently with a cavity-ring-down spectrometer (CRDS L2120-i, Picarro Inc.). We will present the quantified fluxes of understory evapotranspiration measured in the three different ecosystems, show the

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

    NASA Technical Reports Server (NTRS)

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

    2014-01-01

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

  18. [Identification of using organic carbon isotopic composition of soil pollution process].

    PubMed

    Guo, Qing-Jun; Chen, Tong-Bin; Yang, Jun; Strauss, Harald; Lei, Mei; Zhu, Guang-Xu; Li, Yan-Mei; Zhou, Xiao-Yong; Li, Xiao-Yan

    2011-10-01

    This study has taken advantage of the characteristics of concentration of soil organic matter (SOC) and delta13 C(SOC) values to provide proofs for environment quality assessment and to know more about polluted sources, sizes and processes in Beijing steel company area. delta13C values of SOC is good for tracing sources and documenting shifts in community composition and distribution. Two sections (Beijing steel company area and Yongledian, Tongzhou) which belong to two different soil types collected in Beijing, and organic carbon isotopic composition and total soil organic carbon were analyzed. These results shows that SOC of soil samples from Beijing steel company area are quite high, and even 9.7% at the surface sample, however SOC from unpolluted area (Yongledian area) is lower than those of industrial area. delta13 C(SOC) from soils of Beijing steel company area and Yongledian area respectively vary from -24.8 per thousand to -23.1 per thousand and -26.4 per thousand to -20.5 per thousand, the results are quite different. The results reflect that there are different organic carbon sources in different types' soil: Organic carbon from Beijing steel company area has been mainly affected by coal burning, soil organic carbon concentrations are quite high, and pollution can affect on soils 70 cm deep underground; and soils from Yongledian area, have been not polluted, and organic matter is from natural litter (C3 plants). Although there are different soil organic carbon concentrations and isotope compositions, two soil sections have similar variation trends. This study provides proofs for environment quality assessment and know more about polluted and natural sources, sizes in Beijing.

  19. Characterizing the oxygen isotopic composition of phosphate sources to aquatic ecosystems

    USGS Publications Warehouse

    Young, M.B.; McLaughlin, K.; Kendall, C.; Stringfellow, W.; Rollog, M.; Elsbury, K.; Donald, E.; Paytan, A.

    2009-01-01

    The oxygen isotopic composition of dissolved inorganic phosphate (δ18Op) in many aquatic ecosystems is not in isotopic equilibrium with ambient water and, therefore, may reflect the source δ18Op. Identification of phosphate sources to water bodies is critical for designing best management practices for phosphate load reduction to control eutrophication. In order for δ18O p to be a useful tool for source tracking, the δ18Op of phosphate sources must be distinguishable from one another; however, the δ18Op of potential sources has not been well characterized. We measured the δ18O p of a variety of known phosphate sources, including fertilizers, semiprocessed phosphorite ore, particulate aerosols, detergents, leachates of vegetation, soil, animal feces, and wastewater treatment plant effluent. We found a considerable range of δ18Op values (from +8.4 to +24.9‰) for the various sources, and statistically significant differences were found between several of the source types. δ18Op measured in three different fresh water systems was generally not in equilibrium with ambient water. Although there is overlap in δ18Op values among the groups of samples, our results indicate that some sources are isotopically distinct and δ18Op can be used for identifying phosphate sources to aquatic systems.

  20. Age, compositional, and isotopic evidence for crustal recycling in a Late Archean arc, Beartooth Mountains

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wooden, J.L.; Mueller, P.A.; Graves, M.A.

    1985-01-01

    Late Archean rocks of the eastern Beartooth Mountains range in composition from basaltic andesite to granite and were emplaced 2.73-2.80 Ga ago in a middle to early Archean terrane as indicated by U-Pb zircon studies. Although trace element abundances are extremely variable for this group of rocks, their initial Pb, Sr, and Nd isotopic compositions are remarkably homogenous. A composite Rb-Sr isochron (>30 samples) yield an age of 2.79/plus minus/0.04 Ga with an initial ratio of 0.7022/plus minus/2 while /epsilon/Nd 2.78 Ga ago ranges from -1.5 to -3.1 (av. -2.2). Whole-rock Pb data for these rocks scatter about a 2.75more » Ga isochron and feldspar Pb data suggest initial 206/204 = 13.88, 207/204 = 14.96, and 208/204 = 34.3. These values lie well above values for average crustal leads 2.78 Ga ago as modeled by Stacey and Kramer (1975) and would require development in a reservior with /mu/= 12 from 3.7-2.8 Ga (/mu/= 7.2, 4.5-3.7 Ga). The marked differences between these values and those of the late Archean mantle require that an early to middle Archean crust played a role in the genesis of these rocks. The compositional variety and isotopic homogeneity may have developed as the result of crust-mantle mixing similar to that observed in modern volcanic-plutonic arcs along continental margins where crustal materials can be subducted, and fluids derived from these materials added to the overlying mantle wedge and lower crust. During this period, contaminated mantle may have been generated on a regional scale as evidenced by the isotopic systematics of young mafic volcanics from the northwestern U.S. (e.g. Snake River Plain, Yellowstone, Columbia River).« less

  1. The influence of leaf-atmosphere NH3(g ) exchange on the isotopic composition of nitrogen in plants and the atmosphere.

    PubMed

    Johnson, Jennifer E; Berry, Joseph A

    2013-10-01

    The distribution of nitrogen isotopes in the biosphere has the potential to offer insights into the past, present and future of the nitrogen cycle, but it is challenging to unravel the processes controlling patterns of mixing and fractionation. We present a mathematical model describing a previously overlooked process: nitrogen isotope fractionation during leaf-atmosphere NH3(g ) exchange. The model predicts that when leaf-atmosphere exchange of NH3(g ) occurs in a closed system, the atmospheric reservoir of NH3(g ) equilibrates at a concentration equal to the ammonia compensation point and an isotopic composition 8.1‰ lighter than nitrogen in protein. In an open system, when atmospheric concentrations of NH3(g ) fall below or rise above the compensation point, protein can be isotopically enriched by net efflux of NH3(g ) or depleted by net uptake. Comparison of model output with existing measurements in the literature suggests that this process contributes to variation in the isotopic composition of nitrogen in plants as well as NH3(g ) in the atmosphere, and should be considered in future analyses of nitrogen isotope circulation. The matrix-based modelling approach that is introduced may be useful for quantifying isotope dynamics in other complex systems that can be described by first-order kinetics. © 2013 John Wiley & Sons Ltd.

  2. Chemical and isotopic composition of secondary organic aerosol generated by α-pinene ozonolysis

    NASA Astrophysics Data System (ADS)

    Meusinger, Carl; Dusek, Ulrike; King, Stephanie M.; Holzinger, Rupert; Rosenørn, Thomas; Sperlich, Peter; Julien, Maxime; Remaud, Gerald S.; Bilde, Merete; Röckmann, Thomas; Johnson, Matthew S.

    2017-05-01

    Secondary organic aerosol (SOA) plays a central role in air pollution and climate. However, the description of the sources and mechanisms leading to SOA is elusive despite decades of research. While stable isotope analysis is increasingly used to constrain sources of ambient aerosol, in many cases it is difficult to apply because neither the isotopic composition of aerosol precursors nor the fractionation of aerosol forming processes is well characterised. In this paper, SOA formation from ozonolysis of α-pinene - an important precursor and perhaps the best-known model system used in laboratory studies - was investigated using position-dependent and average determinations of 13C in α-pinene and advanced analysis of reaction products using thermal-desorption proton-transfer-reaction mass spectrometry (PTR-MS). The total carbon (TC) isotopic composition δ13C of the initial α-pinene was measured, and the δ13C of the specific carbon atom sites was determined using position-specific isotope analysis (PSIA). The PSIA analysis showed variations at individual positions from -6.9 to +10. 5 ‰ relative to the bulk composition. SOA was formed from α-pinene and ozone in a constant-flow chamber under dark, dry, and low-NOx conditions, with OH scavengers and in the absence of seed particles. The excess of ozone and long residence time in the flow chamber ensured that virtually all α-pinene had reacted. Product SOA was collected on two sequential quartz filters. The filters were analysed offline by heating them stepwise from 100 to 400 °C to desorb organic compounds that were (i) detected using PTR-MS for chemical analysis and to determine the O : C ratio, and (ii) converted to CO2 for 13C analysis. More than 400 ions in the mass range 39-800 Da were detected from the desorbed material and quantified using a PTR-MS. The largest amount desorbed at 150 °C. The O : C ratio of material from the front filter increased from 0.18 to 0.25 as the desorption temperature was

  3. Continental paleothermometry and seasonality using the isotopic composition of aragonitic otoliths of freshwater fishes

    NASA Astrophysics Data System (ADS)

    Patterson, William P.; Smith, Gerald R.; Lohmann, Kyger C.

    To investigate the applicability of oxygen isotope themometry using fish aragonite, the δ18O values of paired otolith and water samples were analyzed from six large modem temperate lakes. Otoliths are accretionaiy aragonitic structures which are precipitated within the sacculus of fish ears. Deep-water obligate benthic species from the hypolimnion of the Laurentian Great Lakes of North America and Lake Baikal, Siberia, provided cold-water end member values for aragonite δ18O. Warm-water values were obtained from naturally grown warm-water stenothermic species and from fish grown in aquaria under controlled conditions. These two groups, which represent growth over a temperature range of 3.2-30.3°C. were employed to determine the oxygen isotope temperature fractionation relationship for aragonite-water: 103lnα = 18.56 (±0.319)·(103)T-1 K -33.49 (±0.307). Empirical calibration of a fish aragonite thennometry equation allows its direct application to studies of paleoclimate. For example, high-resolution sampling of shallow-water eurythermic species coupled with a knowledge of the isotopic composition of meteoric waters can be used to determine seasonal temperature variation. This approach was tested using a modem shallow-water eurythermic species from Sandusky Bay, Lake Erie. Temperatures calculated from carbonate composition agree with meteorological records from the Sandusky Bay weather station for the same time period.

  4. Tracing Altiplano-Puna plateau surface uplift via radiogenic isotope composition of Andean arc lavas

    NASA Astrophysics Data System (ADS)

    Scott, E. M.; Allen, M. B.; Macpherson, C.; McCaffrey, K. J. W.; Davidson, J.; Saville, C.

    2016-12-01

    We have compiled published geochemical data for Jurassic to Holocene Andean arc lavas from 5oN to 47oS, covering the current extent of the northern, central and southern volcanic zones. Using this dataset we evaluate the spatial and temporal evolution of age corrected Sr- and Nd-radiogenic isotopes in arc lavas at a continental-scale, in order to understand the tectonic and surface uplift histories of the Andean margin. It has long been noted that baseline 87Sr/86Sr and 143Nd/144Nd ratios of Quaternary lavas from the central volcanic zone, located within the Altiplano-Puna plateau, are distinct from volcanic rocks to the north and south. This is commonly attributed to greater crustal thickness, which increases to roughly twice that of the average continental crust within the Altiplano-Puna plateau. By comparing 87Sr/86Sr and 143Nd/144Nd ratios in Quaternary lavas to published crustal thickness models, present day topography and the compositions of basement terranes, we note that Sr- and Nd-isotope values of Quaternary lavas are an effective proxy for present day regional elevation. In contrast, variation in basement terranes has only a small, second order effect on isotopic composition at the scale of our study. Using this isotopic proxy, we infer the spatial extent of the plateau and its surface uplift history from the Jurassic to the present. Our results concur with a crustal thickening model of continued surface uplift, which initiated in the Altiplano, with deformation propagating southwards into the Puna throughout the Neogene and then continuing in central Chile and Argentina up to the present day.

  5. Isotopic Analysis and Evolved Gases

    NASA Technical Reports Server (NTRS)

    Swindle, Timothy D.; Boynton, William V.; Chutjian, Ara; Hoffman, John H.; Jordan, Jim L.; Kargel, Jeffrey S.; McEntire, Richard W.; Nyquist, Larry

    1996-01-01

    Precise measurements of the chemical, elemental, and isotopic composition of planetary surface material and gases, and observed variations in these compositions, can contribute significantly to our knowledge of the source(s), ages, and evolution of solar system materials. The analyses discussed in this paper are mostly made by mass spectrometers or some other type of mass analyzer, and address three broad areas of interest: (1) atmospheric composition - isotopic, elemental, and molecular, (2) gases evolved from solids, and (3) solids. Current isotopic data on nine elements, mostly from in situ analysis, but also from meteorites and telescopic observations are summarized. Potential instruments for isotopic analysis of lunar, Martian, Venusian, Mercury, and Pluto surfaces, along with asteroid, cometary and icy satellites, surfaces are discussed.

  6. Distribution of stable isotopes in arid storms . I. Relation between the distribution of isotopic composition in rainfall and in the consequent runoff

    NASA Astrophysics Data System (ADS)

    Adar, E. M.; Dody, A.; Geyh, M. A.; Yair, A.; Yakirevich, A.; Issar, A. S.

    Temporal distributions of the isotopic composition in arid rain storms and in the associated runoff were investigated in a small arid rocky basin in Israel. Customized rain and runoff samplers provided sequential water samples hermetically sealed in high-density PVC bags. In several storms where the runoff was isotopically depleted, compared with the rainfall, the difference could not be explained by fractionation effects occurring during overland flow. A water-balance study relating the runoff discharge to rainfall over a rocky watershed showed that the entire discharge is produced by a very small segment (1-2mm) of the rain storm. The major objective, therefore, was to provide quantitative relations between segments of rainfall (rain showers and rain spells) and runoff. The time distribution of the composition of stable isotopes (oxygen and hydrogen) was used to quantify the correlation between the rain spell's amount and the consequent runoff. The aim of this work was to (a) utilize the dynamic variations in the isotopic composition in rainfall and runoff and model the magnitude of surface-storage capacity associated with runoff processes of overland flow, and (b) characterize the isotopic composition of the percolating water with respect to the isotopic distribution in rainfall and runoff events. The conceptual model postulates an isotopic mixing of overland flow with water within the depression storage. A transport model was then formulated in order to estimate the physical watershed parameters that control the development of overland flow from a certain rainfall period. Part I (this paper) presents the results and the assessment of the relative depression storage obtained from oxygen-18 and deuterium analyses that lead to the physical and mathematical formulation of a double-component model of kinematic-wave flow and transport, which is presented in Part II (accompanying paper). Résumé Les variations temporelles, en zone aride, de la composition isotopique

  7. Tetrathionate and Elemental Sulfur Shape the Isotope Composition of Sulfate in Acid Mine Drainage

    PubMed Central

    Balci, Nurgul; Brunner, Benjamin; Turchyn, Alexandra V.

    2017-01-01

    Sulfur compounds in intermediate valence states, for example elemental sulfur, thiosulfate, and tetrathionate, are important players in the biogeochemical sulfur cycle. However, key understanding about the pathways of oxidation involving mixed-valance state sulfur species is still missing. Here we report the sulfur and oxygen isotope fractionation effects during the oxidation of tetrathionate (S4O62−) and elemental sulfur (S°) to sulfate in bacterial cultures in acidic conditions. Oxidation of tetrathionate by Acidithiobacillus thiooxidans produced thiosulfate, elemental sulfur and sulfate. Up to 34% of the tetrathionate consumed by the bacteria could not be accounted for in sulfate or other intermediate-valence state sulfur species over the experiments. The oxidation of tetrathionate yielded sulfate that was initially enriched in 34S (ε34SSO4−S4O6) by +7.9‰, followed by a decrease to +1.4‰ over the experiment duration, with an average ε34SSO4−S4O6 of +3.5 ± 0.2‰ after a month of incubation. We attribute this significant sulfur isotope fractionation to enzymatic disproportionation reactions occurring during tetrathionate decomposition, and to the incomplete transformation of tetrathionate into sulfate. The oxygen isotope composition of sulfate (δ18OSO4) from the tetrathionate oxidation experiments indicate that 62% of the oxygen in the formed sulfate was derived from water. The remaining 38% of the oxygen was either inherited from the supplied tetrathionate, or supplied from dissolved atmospheric oxygen (O2). During the oxidation of elemental sulfur, the product sulfate became depleted in 34S between −1.8 and 0‰ relative to the elemental sulfur with an average for ε34SSO4−S0 of −0.9 ± 0.2‰ and all the oxygen atoms in the sulfate derived from water with an average normal oxygen isotope fractionation (ε18OSO4−H2O) of −4.4‰. The differences observed in δ18OSO4 and the sulfur isotope composition of sulfate (δ34SSO4), acid

  8. Uncoupling between soil and xylem water isotopic composition: how to discriminate mobile and tightly-bound water?

    NASA Astrophysics Data System (ADS)

    Martín Gómez, Paula; Aguilera, Mònica; Pemán, Jesús; Gil Pelegrín, Eustaquio; Ferrio, Juan Pedro

    2014-05-01

    As a general rule, no isotopic fractionation occurs during water uptake and water transport, thus, xylem water reflects source water. However, this correspondence does not always happen. Isotopic enrichment of xylem water has been found in several cases and has been either associated to 'stem processes' like cuticular evaporation 1 and xylem-phloem communication under water stress 2,3 or to 'soil processes' such as species-specific use of contrasting water sources retained at different water potential forces in soil. In this regard, it has been demonstrated that mobile and tightly-bound water may show different isotopic signature 4,5. However, standard cryogenic distillation does not allow to separate different water pools within soil samples. Here, we carried out a study in a mixed adult forest (Pinus sylvestris, Quercus subpyrenaica and Buxus sempervirens) growing in a relatively deep loamy soil in the Pre-Pyrenees. During one year, we sampled xylem from twigs and soil at different depths (10, 30 and 50 cm). We also sampled xylem from trunk and bigger branches to assess whether xylem water was enriched in the distal parts of the tree. We found average deviations in the isotopic signature from xylem to soil of 4o 2o and 2.4o in δ18O and 18.3o 7.3o and 8.9o in δ2H, for P.sylvestris, Q.subpyrenaica and B.sempervirens respectively. Xylem water was always enriched compared to soil. In contrast, we did not find clear differences in isotopic composition between xylem samples along the tree. Declining the hypothesis that 'stem processes' would cause these uncoupling between soil and xylem isotopic values, we tested the possibility to separate mobile and tightly-bound water by centrifugation. Even though we could separate two water fractions in soils close to saturation, we could not recover a mobile fraction in drier soils. In this regard, we welcome suggestions on alternatives to separate different soil fractions in order to find the correspondence between soil and

  9. Iron mineral structure, reactivity, and isotopic composition in a South Pacific Gyre ferromanganese nodule over 4 Ma

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Marcus, Matthew A.; Edwards, Katrina J.; Gueguen, Bleuenn

    Deep-sea ferromanganese nodules accumulate trace elements from seawater and underlying sediment porewaters during the growth of concentric mineral layers over millions of years. These trace elements have the potential to record past ocean geochemical conditions. The goal of this study was to determine whether Fe mineral alteration occurs and how the speciation of trace elements responds to alteration over ~3.7Ma of marine ferromanganese nodule (MFN) formation, a timeline constrained by estimates from 9 Be/ 10 Be concentrations in the nodule material. We determined Fe-bearing phases and Fe isotope composition in a South Pacific Gyre (SPG) nodule. Specifically, the distribution patternsmore » and speciation of trace element uptake by these Fe phases were investigated. The time interval covered by the growth of our sample of the nodule was derived from 9 Be/ 10 Be accelerator mass spectrometry (AMS). The composition and distribution of major and trace elements were mapped at various spatial scales, using micro-X-ray fluorescence (μXRF), electron microprobe analysis (EMPA), and inductively coupled plasma mass spectrometry (ICP-MS). Fe phases were characterized by micro-extended X-ray absorption fine structure (μEXAFS) spectroscopy and micro-X-ray diffraction (μXRD). Speciation of Ti and V, associated with Fe, was measured using micro-X-ray absorption near edge structure (μXANES) spectroscopy. Iron isotope composition (δ 56/54 Fe) in subsamples of 1-3mm increments along the radius of the nodule was determined with multiple-collector ICP-MS (MC-ICP-MS). The SPG nodule formed through primarily hydrogeneous inputs at a rate of 4.0±0.4mm/Ma. The nodule exhibited a high diversity of Fe mineral phases: feroxyhite (δ-FeOOH), goethite (α-FeOOH), lepidocrocite (γ-FeOOH), and poorly ordered ferrihydrite-like phases. These findings provide evidence that Fe oxyhydroxides within the nodule undergo alteration to more stable phases over millions of years. Trace Ti and V

  10. Iron mineral structure, reactivity, and isotopic composition in a South Pacific Gyre ferromanganese nodule over 4 Ma

    DOE PAGES

    Marcus, Matthew A.; Edwards, Katrina J.; Gueguen, Bleuenn; ...

    2015-09-05

    Deep-sea ferromanganese nodules accumulate trace elements from seawater and underlying sediment porewaters during the growth of concentric mineral layers over millions of years. These trace elements have the potential to record past ocean geochemical conditions. The goal of this study was to determine whether Fe mineral alteration occurs and how the speciation of trace elements responds to alteration over ~3.7Ma of marine ferromanganese nodule (MFN) formation, a timeline constrained by estimates from 9 Be/ 10 Be concentrations in the nodule material. We determined Fe-bearing phases and Fe isotope composition in a South Pacific Gyre (SPG) nodule. Specifically, the distribution patternsmore » and speciation of trace element uptake by these Fe phases were investigated. The time interval covered by the growth of our sample of the nodule was derived from 9 Be/ 10 Be accelerator mass spectrometry (AMS). The composition and distribution of major and trace elements were mapped at various spatial scales, using micro-X-ray fluorescence (μXRF), electron microprobe analysis (EMPA), and inductively coupled plasma mass spectrometry (ICP-MS). Fe phases were characterized by micro-extended X-ray absorption fine structure (μEXAFS) spectroscopy and micro-X-ray diffraction (μXRD). Speciation of Ti and V, associated with Fe, was measured using micro-X-ray absorption near edge structure (μXANES) spectroscopy. Iron isotope composition (δ 56/54 Fe) in subsamples of 1-3mm increments along the radius of the nodule was determined with multiple-collector ICP-MS (MC-ICP-MS). The SPG nodule formed through primarily hydrogeneous inputs at a rate of 4.0±0.4mm/Ma. The nodule exhibited a high diversity of Fe mineral phases: feroxyhite (δ-FeOOH), goethite (α-FeOOH), lepidocrocite (γ-FeOOH), and poorly ordered ferrihydrite-like phases. These findings provide evidence that Fe oxyhydroxides within the nodule undergo alteration to more stable phases over millions of years. Trace Ti and V

  11. Modification of Ca isotope and trace metal composition of the major matrices involved in shell formation of Mytilus edulis

    NASA Astrophysics Data System (ADS)

    Heinemann, Agnes; Fietzke, Jan; Eisenhauer, Anton; Zumholz, Karsten

    2008-01-01

    In this study we present the first combined investigation into the composition of the major matrices involved in calcification processes (surrounding water, extrapallial fluid, aragonite, and calcite) of Mytilus edulis with respect to their calcium isotope (δ44/40Ca) and elemental compositions (Sr/Ca and Mg/Ca). Our aim was to examine the suitability of Mytilus edulis as a proxy archive and to contribute to the understanding of the process of biomineralization. Mytilus edulis specimens were live collected from the Schwentine Estuary, Kiel Fjord, and North Sea (Sylt). δ44/40Ca was determined by thermal ionization mass spectrometry (TIMS) accompanied by measurements of Mg/Ca and Sr/Ca using inductively coupled plasma-optical emission spectroscopy (ICP-OES). The elemental and isotopic compositions of the investigated matrices showed systematic offsets. The carbonates are strongly depleted in their magnesium and strontium concentrations and fractionated toward lighter calcium isotope compositions relative to the surrounding Schwentine Estuary water. The opposite is observed for the extrapallial fluid (EPF). Our findings extend the results of previous studies reporting a strong biological control and the interaction of different environmental conditions influencing biomineralization. Future studies should focus on the temporal development of the interrelation between the different matrices.

  12. Preservation of Earth-forming events in the tungsten isotopic composition of modern flood basalts.

    PubMed

    Rizo, Hanika; Walker, Richard J; Carlson, Richard W; Horan, Mary F; Mukhopadhyay, Sujoy; Manthos, Vicky; Francis, Don; Jackson, Matthew G

    2016-05-13

    How much of Earth's compositional variation dates to processes that occurred during planet formation remains an unanswered question. High-precision tungsten isotopic data from rocks from two large igneous provinces, the North Atlantic Igneous Province and the Ontong Java Plateau, reveal preservation to the Phanerozoic of tungsten isotopic heterogeneities in the mantle. These heterogeneities, caused by the decay of hafnium-182 in mantle domains with high hafnium/tungsten ratios, were created during the first ~50 million years of solar system history, indicating that portions of the mantle that formed during Earth's primary accretionary period have survived to the present. Copyright © 2016, American Association for the Advancement of Science.

  13. Production waters associated with the Ferron coalbed methane fields, central Utah: Chemical and isotopic composition and volumes

    USGS Publications Warehouse

    Rice, C.A.

    2003-01-01

    This study investigated the composition of water co-produced with coalbed methane (CBM) from the Upper Cretaceous Ferron Sandstone Member of the Mancos Shale in east-central Utah to better understand coalbed methane reservoirs. The Ferron coalbed methane play currently has more than 600 wells producing an average of 240 bbl/day/well water. Water samples collected from 28 wellheads in three fields (Buzzards Bench, Drunkards Wash, and Helper State) of the northeast-southwest trending play were analyzed for chemical and stable isotopic composition.Water produced from coalbed methane wells is a Na-Cl-HCO3 type. Water from the Drunkards Wash field has the lowest total dissolved solids (TDS) (6300 mg/l) increasing in value to the southeast and northeast. In the Helper State field, about 6 miles northeast, water has the highest total dissolved solids (43,000 mg/l), and major ion abundance indicates the possible influence of evaporite dissolution or mixing with a saline brine. In the southern Buzzards Bench field, water has variable total dissolved solids that are not correlated with depth or spatial distance. Significant differences in the relative compositions are present between the three fields implying varying origins of solutes and/or different water-rock interactions along multiple flow paths.Stable isotopic values of water from the Ferron range from +0.9??? to -11.4??? ?? 18O and -32??? to -90??? ?? 2H and plot below the global meteoric water line (GMWL) on a line near, but above values of present-day meteoric water. Isotopic values of Ferron water are consistent with modification of meteoric water along a flow path by mixing with an evolved seawater brine and/or interaction with carbonate minerals. Analysis of isotopic values versus chloride (conservative element) and total dissolved solids concentrations indicates that recharge water in the Buzzards Bench area is distinct from recharge water in Drunkards Wash and is about 3 ??C warmer. These variations in

  14. Supernova graphite in the NanoSIMS: Carbon, oxygen and titanium isotopic compositions of a spherule and its TiC sub-components

    NASA Astrophysics Data System (ADS)

    Stadermann, F. J.; Croat, T. K.; Bernatowicz, T. J.; Amari, S.; Messenger, S.; Walker, R. M.; Zinner, E.

    2005-01-01

    Presolar graphite spherules from the Murchison low-density separate KE3 contain a large number of internal TiC crystals that range in size from 15 to 500 nm. We have studied one such graphite grain in great detail by successive analyses with SEM, ims3f SIMS, TEM and NanoSIMS. Isotopic measurements of the 'bulk' particle in the ims3f indicate a supernova origin for this graphite spherule. The NanoSIMS measurements of C, N, O and Ti isotopes were performed directly on TEM ultramicrotome sections of the spherule, allowing correlated studies of the isotopic and mineralogical properties of the graphite grain and its internal crystals. We found isotopic gradients in 12C/ 13C and 16O/ 18O from the core of the graphite spherule to its perimeter, with the most anomalous compositions being present in the center. These gradients may be the result of isotopic exchange with isotopically normal material, either in the laboratory or during the particle's history. No similar isotopic gradients were found in the 16O/ 17O and 14N/ 15N ratios, which are normal within analytical uncertainty throughout the graphite spherule. Due to an unusually high O signal, internal TiC crystals were easily located during NanoSIMS imaging measurements. It was thus possible to determine isotopic compositions of several internal TiC grains independent of the surrounding graphite matrix. These TiC crystals are significantly more anomalous in their O isotopes than the graphite, with 16O/ 18O ratios ranging from 14 to 250 (compared to a terrestrial value of 499). Even the most centrally located TiC grains show significant variations in their O isotopic compositions from crystal to crystal. Measurement of the Ti isotopes in three TiC grains found no variations among them and no large differences between the compositions of the different crystals and the 'bulk' graphite spherule. However, the same three TiC crystals vary by a factor of 3 in their 16O/ 18O ratios. It is not clear in what form the O is

  15. Cadmium cycling in the water column of the Kuroshio-Oyashio Extension region: Insights from dissolved and particulate isotopic composition

    NASA Astrophysics Data System (ADS)

    Yang, Shun-Chung; Zhang, Jing; Sohrin, Yoshiki; Ho, Tung-Yuan

    2018-07-01

    We measured dissolved and particulate Cd isotopic composition in the water column of a meridional transect across the Kuroshio-Oyashio Extension region in a Japanese GEOTRACES cruise to investigate the relative influence of physical and biogeochemical processes on Cd cycling in the Northwestern Pacific Ocean. Located at 30-50°N along 165°E, the transect across the extension region possesses dramatic hydrographic contrast. Cold surface water and a relatively narrow and shallow thermocline characterizes the Oyashio Extension region in contrast to a relatively warm and highly stratified surface water and thermocline in the Kuroshio Extension region. The contrasting hydrographic distinction at the study site provides us with an ideal platform to investigate the spatial variations of Cd isotope fractionation systems in the ocean. Particulate samples demonstrated biologically preferential uptake of light Cd isotopes, and the fractionation effect varied dramatically in the surface water of the two regions, with relatively large fractionation factors in the Oyashio region. Based on the relationship of dissolved Cd concentrations and isotopic composition, we found that a closed system fractionation model can reasonably explain the relationship in the Kuroshio region. However, using dissolved Cd isotopic data, either a closed system or steady-state open system fractionation model may explain the relationship in the surface water of the Oyashio region. Particulate δ114/110Cd data further supports that the surface water of the Oyashio region matches a steady-state open system model more closely. Contrary to the surface water, the distribution of potential density exhibits comparable patterns with Cd elemental and isotopic composition in the thermocline and deep water in the two extension regions, showing that physical processes are the dominant forcing controlling Cd cycling in the deep waters. The results demonstrate that Cd isotope fractionation can match either a closed

  16. Gradients in seasonality and seawater oxygen isotopic composition along the early Permian Gondwanan coast, SE Australia

    NASA Astrophysics Data System (ADS)

    Beard, J. Andrew; Ivany, Linda C.; Runnegar, Bruce

    2015-09-01

    Oxygen isotope compositions of marine carbonates are commonly employed for understanding ancient temperatures, but this approach is complicated in the very distant past due to uncertainties about the effects of diagenesis and the isotopic composition of seawater, both locally and globally. Microsampled accretionary calcite from two species of the fossil bivalve Eurydesma Sowerby and Morris 1845 collected from sediments of Cisuralian age in high latitude marine sediments along the SE coast of Australia records cyclic seasonal fluctuations in shell δ18O values during growth, demonstrating the primary nature of the isotope signal and thus allowing investigation of early Permian seawater isotopic composition and water temperature in the high southern latitudes. The mean and seasonal range of δ18Ocarb decreases poleward across about 10° of paleolatitude (∼67°S-77°S). The presence of co-occurring dropstones and stratigraphically associated glendonites constrains winter temperatures across the region to near-freezing, thus permitting calculation of realistic estimates of water composition and summer temperatures. Summer δ18Ocarb values indicate water temperatures between 5 °C and 12 °C, with warmer values at lower latitudes. The decrease in both mean sea surface temperature and seasonal amplitude with increasing latitude on the Gondwanan coast is much like that observed along high-latitude coastlines today. Calculated δ18Owater decreases toward the pole, likely associated with an increasing contribution of isotopically light fresh water derived from summer snow-melt. The gradient in δ18Owater is similar to that documented over a similar span of latitude on the modern SE Greenland coast. We infer the presence of a north-flowing coastal current of cold, O18-depleted water that entrains progressively greater amounts of more typical seawater as it moves away from the pole. δ18O values in SE Australia, however, are about 3‰ lower than those off Greenland

  17. Characterization of a customized calibration unit for continuous measurements of the isotopic composition of water vapor

    NASA Astrophysics Data System (ADS)

    Moro, Giovanni; Zannoni, Daniele; Dreossi, Giuliano; Stenni, Barbara

    2017-04-01

    The objective of this work is the development, standardization and creation of a method to carry out continuous measurement of oxygen and hydrogen isotopic composition of the atmospheric water vapor using a wavelength-scanned cavity ring down spectroscopy (WS-CRDS) instrument produced by Picarro, L1102-i model. Some technical improvements of the standard instrument configuration have been made to create three different inlet gas lines: a "standard" line, a calibration line and a line connected with the external sampler. The calibration line is composed of a syringe-pump that continuously injects standard water into a steel tee heated at the temperature of 170°C and flushed with dry nitrogen gas. In this way, instantaneous and complete vaporization of the standard water takes place. The resulting steam is characterized by a well-defined composition in δD e δ18O values. To allow comparison with other international data, we have characterized the individual instrumental response to variation of the isotopic composition of the water vapor. Several humidity-isotope response functions (6000-26000 ppmv) have been estimated with three different internal standards (0.35‰ -8.75‰ -29.11‰ and -40.28‰ for δ18O; 2.31‰ -58.91‰ -222.19‰ and -317.78‰ for δD). Moreover, we have measured the instrumental drift at regular time intervals to apply the opportune corrections to instrument data. The setup has been tested using a 3.5 day continuous measurements carried out with the Picarro sampling the water vapor outside our campus in Venice and parallel sampling using the classical cryogenic trapping procedure, obtaining excellent results. Furthermore, our analysis technique has given good results for the standards with values which are similar to those obtained with the isotope ratio mass spectrometry (IRMS) technique.

  18. Global patterns of the isotopic composition of soil and plant nitrogen

    USGS Publications Warehouse

    Amundson, Ronald; Austin, A.T.; Schuur, E.A.G.; Yoo, K.; Matzek, V.; Kendall, C.; Uebersax, A.; Brenner, D.; Baisden, W.T.

    2003-01-01

    We compiled new and published data on the natural abundance N isotope composition (??15N values) of soil and plant organic matter from around the world. Across a broad range of climate and ecosystem types, we found that soil and plant ??15N values systematically decreased with increasing mean annual precipitation (MAP) and decreasing mean annual temperature (MAT). Because most undisturbed soils are near N steady state, the observations suggest that an increasing fraction of ecosystem N losses are 15N-depleted forms (NO3, N2O, etc.) with decreasing MAP and increasing MAT. Wetter and colder ecosystems appear to be more efficient in conserving and recycling mineral N. Globally, plant ??15N values are more negative than soils, but the difference Nitrogen isotopes reflect time integrated measures of the controls on N storage that are critical for predictions of how these ecosystems will respond to human-mediated disturbances of the global N cycle.

  19. Universal absolute quantification of biomolecules using element mass spectrometry and generic standards.

    PubMed

    Calderón-Celis, Francisco; Sanz-Medel, Alfredo; Encinar, Jorge Ruiz

    2018-01-23

    We present a novel and highly sensitive ICP-MS approach for absolute quantification of all important target biomolecule containing P, S, Se, As, Br, and/or I (e.g., proteins and phosphoproteins, metabolites, pesticides, drugs), under the same simple instrumental conditions and without requiring any specific and/or isotopically enriched standard.

  20. Organic and inorganic components of aerosols over the central Himalayas: winter and summer variations in stable carbon and nitrogen isotopic composition.

    PubMed

    Hegde, Prashant; Kawamura, Kimitaka; Joshi, H; Naja, M

    2016-04-01

    The aerosol samples were collected from a high elevation mountain site, Nainital, in India (1958 m asl) during September 2006 to June 2007 and were analyzed for water-soluble inorganic species, total carbon, nitrogen, and their isotopic composition (δ(13)C and δ(15)N, respectively). The chemical and isotopic composition of aerosols revealed significant anthropogenic influence over this remote free-troposphere site. The amount of total carbon and nitrogen and their isotopic composition suggest a considerable contribution of biomass burning to the aerosols during winter. On the other hand, fossil fuel combustion sources are found to be dominant during summer. The carbon aerosol in winter is characterized by greater isotope ratios (av. -24.0‰), mostly originated from biomass burning of C4 plants. On the contrary, the aerosols in summer showed smaller δ(13)C values (-26.0‰), indicating that they are originated from vascular plants (mostly of C3 plants). The secondary ions (i.e., SO4 (2-), NH4 (+), and NO3 (-)) were abundant due to the atmospheric reactions during long-range transport in both seasons. The water-soluble organic and inorganic compositions revealed that they are aged in winter but comparatively fresh in summer. This study validates that the pollutants generated from far distant sources could reach high altitudes over the Himalayan region under favorable meteorological conditions.

  1. Long-term enrichment of the stable isotopic composition of stream water due to the release of groundwater recharge from extreme precipitation events

    NASA Astrophysics Data System (ADS)

    Boutt, D. F.

    2017-12-01

    The isotopic composition of surface and groundwater is impacted by a multitude of hydrologic processes. The long-term response of these systems to hydrologic change is critical for appropriately interpreting isotopic information for streamflow generation, stream-aquifer-coupling, sources of water to wells, and understanding recharge processes. To evaluate the response time of stream-aquifer systems to extreme precipitation events we use a long-term isotope dataset from Western Massachusetts with drainage areas ranging from 0.1 to > 800 km2. The year of 2011 was the wettest calendar year on record and the months of August and September of 2011 were the wettest consecutive two-month period in the 123 year record. Stable isotopic composition of surface waters of catchments ranging from 1 - 1000 km2 show an enrichment due to summertime and Tropical Storm precipitation. Enrichment in potential recharge water is shown to have a significant long-term impact (> 3 hydrologic years) on the isotopic composition of both surface and groundwater. This highlights the importance of groundwater sources of baseflow to streams and the transient storage and release mechanisms of shallow groundwater storage. The length of isotopic recession of stream water are also a strong function of watershed area. It is concluded that the stream water isotopes are consistent with a large pulse of water being stored and released from enriched groundwater emplaced during this period of above-average precipitation. Ultimately the results point to the importance of considering hydrological processes of streamflow generation and their role in hydrologic processes beyond traditional catchment response analysis.

  2. Nitrogen Isotopic Ratio in Jupiter's Atmosphere from Observations by Composite Infrared Spectrometer (CIRS) on the Cassini Spacecraft

    NASA Technical Reports Server (NTRS)

    Abbas, M. M.; LeClair, A.; Owen, T.; Conrath, B. J.; Flasar, F. M.; Kunde, V. G.; Nixon, C. A..; Achterberg, R. K.; Bjoraker, G.; Jennings, D. J.

    2003-01-01

    The Composite Infrared Spectrometer (CIRS) on the Cassini spacecraft made infrared observations of Jupiter's atmosphere during the flyby in December 2000 to January 2001. The unique database in the 600-1400/cm region with 0.53 and 2.8/cm spectral resolutions obtained from the observations permits retrieval of global maps of the thermal structure and composition of Jupiter's atmosphere including the distributions of (14)NH3 and (15)NH3. Analysis of Jupiter's ammonia distributions from three isolated (15)NH3 spectral lines in eight latitudes is presented for evaluation of the nitrogen isotopic ratio. The nitrogen isotopic ratio (14)N/(15)N (or (15)N/(14)N) in Jupiter's atmosphere in this analysis is calculated to be: 448 +/- 62 ((2.23 +/- 0.31) x 10(exp -3)). This value of the ratio determined from CIRS data is found to be in very close agreement with the value previously obtained from the measurements by the Galileo Probe Mass Spectrometer. Some possible mechanisms to account for the variation of Jupiter's observed isotopic ratio relative to various astrophysical environments are discussed.

  3. Intracellular Cadmium Isotope Fractionation

    NASA Astrophysics Data System (ADS)

    Horner, T. J.; Lee, R. B.; Henderson, G. M.; Rickaby, R. E.

    2011-12-01

    Recent stable isotope studies into the biological utilization of transition metals (e.g. Cu, Fe, Zn, Cd) suggest several stepwise cellular processes can fractionate isotopes in both culture and nature. However, the determination of fractionation factors is often unsatisfactory, as significant variability can exist - even between different organisms with the same cellular functions. Thus, it has not been possible to adequately understand the source and mechanisms of metal isotopic fractionation. In order to address this problem, we investigated the biological fractionation of Cd isotopes within genetically-modified bacteria (E. coli). There is currently only one known biological use or requirement of Cd, a Cd/Zn carbonic anhydrase (CdCA, from the marine diatom T. weissfloggii), which we introduce into the E. coli genome. We have also developed a cleaning procedure that allows for the treating of bacteria so as to study the isotopic composition of different cellular components. We find that whole cells always exhibit a preference for uptake of the lighter isotopes of Cd. Notably, whole cells appear to have a similar Cd isotopic composition regardless of the expression of CdCA within the E. coli. However, isotopic fractionation can occur within the genetically modified E. coli during Cd use, such that Cd bound in CdCA can display a distinct isotopic composition compared to the cell as a whole. Thus, the externally observed fractionation is independent of the internal uses of Cd, with the largest Cd isotope fractionation occurring during cross-membrane transport. A general implication of these experiments is that trace metal isotopic fractionation most likely reflects metal transport into biological cells (either actively or passively), rather than relating to expression of specific physiological function and genetic expression of different metalloenzymes.

  4. Isotopic composition of a sample enriched in 93Zr

    DOE PAGES

    Fujii, Toshiyuki; Hori, Jun-ichi; Du, Miting; ...

    2015-10-22

    A project to determine the neutron-capture cross section of long lived fission products and minor actinides has been started by using a beam-line at Japan Proton Accelerator Research Complex (J-PARC). We prepared one of the target nuclides is Zr-93, which in Oak Ridge National Laboratory. Qualitative and quantitative analyses on the sample were performed at Kyoto University. The isotopic composition of (m) Zr (m 90, 91, 92, 93, 94, and 96) was precisely determined by multi-collector thermal ionization mass spectrometry with < 0.1 % of 2 sigma uncertainty. We determined that the atomic abundance of Zr-93 in the sample tomore » be 18.86 ± A 0.05 %.« less

  5. The stable isotopic and chemical composition of pedogenic carbonate in the Minusinsk Basin, South Siberia

    NASA Astrophysics Data System (ADS)

    Vasilchuk, Jessica; Ivanova, Elena; Krechetov, Pavel; Litvinskiy, Vladimir; Budantseva, Nadine; Chizhova, Julia; Vasil'chuk, Yurij

    2017-04-01

    Stable isotope composition of carbonate neoformations can be used as a proxy for the reconstructons of environmental conditions of the past. Carbonate coatings on coarse rock framents are studied in order to indicate the climatic conditions and predominant vegetation under which they were formed. Such coatings commonly occur in different types of soils and paleosols of South Siberian intermountain basins mainly in relatively dry modern conditions. The purpose of the research is to characterize the isotopic composition and chemical composition of carbonate pedofeatures in soils of Minusink Hollow and estimate its correlation with defferent factors. The samples of pedogenic carbonates, vegetation, carbonate parent material, soil water and precipitation water were analyzed using the Delta-V mass spectrometer with options of a gas bench and element analyser. The soils we studied are mainly Kastanozems that are poorly moisturized; therefore, soil pore water was extracted by ethanol. Minor and major elements content was also measured by ICP-MS. Carbonates mostly contain calcuim (37-45%) and highly enriched in Pb, Tl and Ba. Oxygen and carbon isotopic composition of pedogenic carbonates was analyzed in 3 key sites. Kazanovka Khakass state national reserve, Hankul salt lake, region of Sayanogorsk aluminum smelter. Vegetation photosynthetic pathway in the region is mainly C3. δ18O values of carbonate coatings in soils of Kazanovka vary in a range from -7.49 to -10.5‰ (vs V-PDB). The lowest values corresponds the coatings found between two buried mid-Holocene soil horizons. That may indicate cooler conditions of late Holocene than nowadays. In Sayanogorsk carbonates' δ18O values' range is -8.3...-11.1‰ and near the Hankul Lake is -9.0...-10.2‰ all ranges are quite similar and may indicate close conditions of pendants formation. δ13C values of carbonate coatings in Kazanovka vary from -2.5 to -6.7‰, the highest values correspond to the soils of Askiz and Syglygkug

  6. Absolute measurements and certified reference material for iron isotopes using multiple-collector inductively coupled mass spectrometry.

    PubMed

    Zhou, Tao; Zhao, Motian; Wang, Jun; Lu, Hai

    2008-01-01

    Two enriched isotopes, 99.94 at.% 56Fe and 99.90 at.% 54Fe, were blended under gravimetric control to prepare ten synthetic isotope samples whose 56Fe isotope abundances ranged from 95% to 20%. For multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) measurements typical polyatomic interferences were removed by using Ar and H2 as collision gas and operating the MC-ICP-MS system in soft mode. Thus high-precision measurements of the Fe isotope abundance ratios were accomplished. Based on the measurement of the synthetic isotope abundance ratios by MC-ICP-MS, the correction factor for mass discrimination was calculated and the results were in agreement with results from IRMM014. The precision of all ten correction factors was 0.044%, indicating a good linearity of the MC-ICP-MS method for different isotope abundance ratio values. An isotopic reference material was certified under the same conditions as the instrument was calibrated. The uncertainties of ten correction factors K were calculated and the final extended uncertainties of the isotopic certified Fe reference material were 5.8363(37) at.% 54Fe, 91.7621(51) at.% 56Fe, 2.1219(23) at.% 57Fe, and 0.2797(32) at.% 58Fe.

  7. Barium isotope composition of altered oceanic crust from the IODP Site 1256 at the East Pacific Rise

    NASA Astrophysics Data System (ADS)

    Nan, X.; Yu, H.; Gao, Y.

    2017-12-01

    To understand the behavior of Ba isotopes in the oceanic crust during seawater alteration, we analyzed Ba isotopes for altered oceanic crust (AOC) from the IODP Site 1256 at the East Pacific Rise (EPR). The samples include 33 basalts, 5 gabbros, and 1 gabbronorite. This drill profile has four sections from top to bottom, including the volcanic section, transition zone, sheeted dyke complex, and plutonic complex. They display various degrees of alteration with obviously variable temperatures and water/rock ratios (Gao et al., 2012). The volcanic section is slightly to moderately altered by seawater at 100 to 250°; the transition zone is a mixing zone between upwelling hydrothermal fluids and downwelling seawater; and the sheeted dyke complex and plutonic complex are highly altered by hydrothermal fluids (˜250°). Ba isotopes were analyzed on a Neptune Plus MC-ICP-MS at the University of Science and Technology of China. The long-term precision of δ137/134Ba is better than 0.04‰ (2SD). The δ137/134Ba of the volcanic section and the top of the transition zone range between -0.01 and 0.30‰, higher than the δ137/134Ba of fresh MORB and upper mantle (0.020 ± 0.021‰, 2SE, Huang et al., 2015). Similarly, the δ137/134Ba of the sheeted dyke complex ranges from 0.05 to 0.28‰. The plutonic section has δ137/134Ba from -0.17 to -0.05‰, which is lower than the upper mantle, with one exception that has δ137/134Ba of 0.19‰. No correlation exists between Ba contents and δ137/134Ba. The weighted average δ137/134Ba of the AOC samples is 0.13±0.04‰ (2SE), significantly higher than that of the upper mantle. In all, our AOC data reveal obvious Ba isotopic fractionation, reflecting alteration of the AOC by hydrothermal fluids and seawater. The obvious difference of Ba isotope composition between the AOC and the upper mantle further indicates that recycling of the AOC could result in Ba isotope heterogeneity of the mantle. References: Gao Y, Vils F, Cooper K M, et

  8. Osmium Isotopic Composition of the Sumbar Cretaceous- Tertiary Boundary, Turkmenia

    NASA Astrophysics Data System (ADS)

    Meisel, T.; Krahenbuhl, U.; Nazarov, M. A.

    1992-07-01

    Turekian (1982) propagated the use of the osmium isotopic composition as a cosmic indicator for the origin of the high osmium (and iridium) layers at the K/T boundaries. He did not consider the osmium isotopic signature of the terrestrial mantle, which also has a chondritic evolution of the Re-Os system. Osmium cannot serve alone as an infallible indicator of the impact theory, but interesting results can be obtained from their investigation. Different K/T boundary section have been analyzed so far for ^187Os/^186Os. An overview of the values is presented in the table. Boundary Clay layer Os ratio Reference Stevns Klint fish clay 1.66 Luck and Turekian, 1983 Woodside Creek 1.12 Lichte et al., 1986 Raton Basin 1.23 Kraehenbuehl et al., 1988 Raton Basin (several) 1.15-1.23 Esser and Turekian, 1989 Sumbar (0-1 cm) 1.16 This work We obtained a complete marine section of the K/T boundary in southern Turkmenia (decribed by Alekseyev, 1988). It shows a very high Ir concentration (66 ppb) at the boundary layer and a remarkable Ir enrichment over crustal rocks continuing up to 30 cm above the boundary. Our aim of this investigation is to analyze several samples from above and below the boundary for the ^187Os/^186Os ratio to obtain a complete picture of the isotopic evolution of the section. We want to evaluate mixing of Os with chondritic ratios with Os from upper crustal rocks. Another goal is to investigate a mobilization of Os. So far only one sample has been analyzed with NTI-MS after fire assay digestion of the sample. The sample 0 to 1 cm has an ^187Os/^186Os ratio of 1.162 +- 13, which is quite low. We expect an even lower value for the boundary clay (0 cm) itself not taking into account a contribution of radiogenic osmium from the decay of terrestrial rhenium. This might put this K/T boundary section closest of all to the present day chondritic value (approx. 1.05). Further analysis will be presented at the meeting. References Alekseyev A. S., Nazarov M. A

  9. Geochemical and NdSr isotopic composition of deep-sea turbidites: Crustal evolution and plate tectonic associations

    NASA Astrophysics Data System (ADS)

    McLennan, S. M.; Taylor, S. R.; McCulloch, M. T.; Maynard, J. B.

    1990-07-01

    Petrographic, geochemical, and isotopic data for turbidites from a variety of tectonic settings exhibit considerable variability that is related to tectonic association. Passive margin turbidites (Trailing Edge, Continental Collision) display high framework quartz (Q) content in sands, evolved major element compositions (high Si/Al, K/Na), incompatible element enrichments (high Th/Sc, La/Sc, La/Yb), negative Eu-anomalies and variable Th/U ratios. They have low 143Nd /144Nd and high 87Sr /86Sr ( ɛNd = -26 to -10; 87Sr /86Sr = 0.709 to 0.734 ), indicating a dominance of old upper crustal sources. Active margin settings (Fore Arc, Continental Arc, Back Arc, Strike Slip) commonly exhibit quite different compositions. Th/Sc varies from <0.01 to 1.8, and ɛNd varies from -13.8 to +8.3. Eu-anomalies range from no anomaly ( Eu/Eu ∗ = 1.0 ) to Eu-depletions typical of post-Archean shales ( Eu/Eu ∗ = 0.65 ). Active margin data are explained by mixtures of young arc-derived material, with variable composition and old upper crustal sources. Major element data indicate that passive margin turbidites have experienced more severe weathering histories than those from active settings. Most trace elements are enriched in muds relative to associated sands because of dilution effects from quartz and calcite and concentration of trace elements in clays. Exceptions include Zr, Hf (heavy mineral influence) and Tl (enriched in feldspar) which display enrichments in sands. Active margin sands commonly exhibit higher Eu/Eu ∗ than associated muds, resulting from concentration of plagioclase during sorting. Some associated sands and muds, especially from active settings, have systematic differences in Th/Sc ratios and Nd-isotopic composition, indicating that various provenance components may separate into different grain-size fractions during sedimentary sorting processes. Trace element abundances of modern turbidites, from both active and passive settings, differ from Archean

  10. Isotopic coherence of refractory inclusions from CV and CK meteorites: Evidence from multiple isotope systems

    NASA Astrophysics Data System (ADS)

    Shollenberger, Quinn R.; Borg, Lars E.; Render, Jan; Ebert, Samuel; Bischoff, Addi; Russell, Sara S.; Brennecka, Gregory A.

    2018-05-01

    Calcium-aluminum-rich inclusions (CAIs) are the oldest dated materials in the Solar System and numerous previous studies have revealed nucleosynthetic anomalies relative to terrestrial rock standards in many isotopic systems. However, most of the isotopic data from CAIs has been limited to the Allende meteorite and a handful of other CV3 chondrites. To better constrain the isotopic composition of the CAI-forming region, we report the first Sr, Mo, Ba, Nd, and Sm isotopic compositions of two CAIs hosted in the CK3 desert meteorites NWA 4964 and NWA 6254 along with two CAIs from the CV3 desert meteorites NWA 6619 and NWA 6991. After consideration of neutron capture processes and the effects of hot-desert weathering, the Sr, Mo, Ba, Nd, and Sm stable isotopic compositions of the samples show clearly resolvable nucleosynthetic anomalies that are in agreement with previous results from Allende and other CV meteorites. The extent of neutron capture, as manifested by shifts in the observed 149Sm-150Sm isotopic composition of the CAIs is used to estimate the neutron fluence experienced by some of these samples and ranges from 8.40 × 1013 to 2.11 × 1015 n/cm2. Overall, regardless of CAI type or host meteorite, CAIs from CV and CK chondrites have similar nucleosynthetic anomalies within analytical uncertainty. We suggest the region that CV and CK CAIs formed was largely uniform with respect to Sr, Mo, Ba, Nd, and Sm isotopes when CAIs condensed and that CAIs hosted in CV and CK meteorites are derived from the same isotopic reservoir.

  11. Uranium isotope composition of a laterite profile during extreme weathering of basalt in Guangdong, South China

    NASA Astrophysics Data System (ADS)

    Huang, J.; Zhou, Z.; Gong, Y.; Lundstrom, C.; Huang, F.

    2015-12-01

    Rock weathering and soil formation in the critical zone are important for material cycle from the solid Earth to superficial system. Laterite is a major type of soil in South China forming at hot-humid climate, which has strong effect on the global uranium cycle. Uranium is closely related to the environmental redox condition because U is stable at U(Ⅳ) in anoxic condition and U(Ⅵ) as soluble uranyl ion (UO22+) under oxic circumstance. In order to understand the behavior of U isotopes during crust weathering, here we report uranium isotopic compositions of soil and base rock samples from a laterite profile originated from extreme weathering of basalt in Guangdong, South China. The uranium isotopic data were measured on a Nu Plasma MC-ICP-MS at the University of Illinois at Urbana-Champaign using the double spike method. The δ238U of BCR-1 is -0.29±0.03‰ (relative to the international standard CRM-112A), corresponding to a 238U/235U ratio of 137.911±0.004. Our result of BCR-1 agrees with previous analyses (e.g., -0.28‰ in Weyer et al. 2008) [1]. U contents of the laterite profile decrease from 1.9 ppm to 0.9 ppm with depth, and peak at 160 - 170 cm (2.3 ppm), much higher than the U content of base rocks (~0.5 ppm). In contrary, U/Th of laterites is lower than that of base rock (0.27) except the peak at the depth of 160-170 cm (0.38), indicating significant U loss during weathering. Notably, U isotope compositions of soils show a small variation from -0.38 to -0.28‰, consistent with the base rock within analytical error (0.05‰ to 0.08‰, 2sd). Such small variation can be explained by a "rind effect" (Wang et al., 2015) [2], by which U(Ⅳ) can be completely oxidized to U(VI) layer by layer during basalt weathering by dissolved oxygen. Therefore, our study indicates that U loss during basalt weathering at the hot-humid climate does not change U isotope composition of superficial water system. [1] Weyer S. et al. (2008) Natural fractionation of 238U/235

  12. Bioapatite Recrystallization During Burning and its Effects on Phosphate Stable Oxygen Isotope Composition

    NASA Astrophysics Data System (ADS)

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

    2003-04-01

    Stable oxygen isotopic compositions of phosphate from mammal bones are commonly used in palaeoenvironmental reconstructions. However, preservation of the primary bone oxygen isotopic composition is of concern during post-mortem alteration. Particularly in studies of archaeological interest, bone samples are often obtained from contexts where they have been heated, either in middens, or near hearths. Hence, in addition to alteration resulting from natural diagenetic processes, burning may also have contributed to modification of the primary oxygen isotopic signal. Various techniques can be employed to evaluate the degree of preservation of bone during burning. Anthropologists commonly use colour comparisons (Munsell Colour Chart) to assess the temperature of burning. Recrystallization of the carbonated hydroxyapatite, i.e., bioapatite, in bone is more rigorously assessed using X-ray diffraction and infra-red spectroscopy. In this study, freshly deceased (6<8 months) white-tailed deer leg bones (Odocoileus virginianus) were collected from Pinery Provincial Park, Ontario, Canada. Each long bone was sectioned, incrementally burned, colour-typed, ground to a standardized grain-size (45<63mm), and analysed using differential thermal analysis (DTA), thermogravimetric analysis (TGA), rotating anode X-ray diffraction (XRD), and Fourier transform infra-red spectroscopy (FTIR). Heating temperatures ranged from 25 to 900^oC, increasing in intervals of 25^oC. Two major stages of weight loss were recorded in the DTA/TGA data, 25-260^oC representing dehydration, and 270-600^oC reflecting incineration of organic matter. The end-product (900^oC) resembled pure hydroxyapatite. XRD patterns of the bioapatite remained virtually unchanged from 25-250^oC, after which peak intensity, sharpness and the XRD crystallinity index (XRD CI) increased from 0.80 at 250^oC to 1.26 at 900^oC. FTIR patterns showed analogous behaviour, demonstrating minimal fluctuations in the FTIR crystallinity

  13. Gas chromatographic/mass spectrometric determination of carbon isotope composition in unpurified samples: methamphetamine example.

    PubMed

    Low, I A; Liu, R H; Legendre, M G; Piotrowski, E G; Furner, R L

    1986-10-01

    A gas chromatograph/quadrupole mass spectrometer system, operated in electron impact/selected ion monitoring mode, is used to determine the intensity ratio of the m/z 59 and the m/z 58 ions of the [C3H8N]+ fragment derived from methamphetamine samples synthesized with varying amounts of 13C-labeled methylamine. Crude products are introduced into the gas chromatograph without prior cleanup. The ratios measured were in excellent agreement with those calculated. A change in 0.25% use of 13C-methylamine is sufficient for product differentiation. The feasibility of using isotope labeling and subsequent mass spectrometric isotope ratio measurement as the basis of a compound tracing mechanism is discussed. Specifically, if methamphetamine samples manufactured from legal sources are asked to incorporate distinct 13C compositions, their sources can be traced when samples are diverted into illegal channels. Samples derived from illicit preparations can also be traced if the manufacturers of a precursor (methylamine in this case) incorporate distinct 13C compositions in their products.

  14. Limitations of the isotopic composition of nitrates as a tracer of their origin

    NASA Astrophysics Data System (ADS)

    Kloppmann, Wolfram; Mayer, Bernhard; Otero, Neus; Sebilo, Mathieu; Gooddy, Daren; Lapworth, Dan; Surridge, Ben; Petelet Giraud, Emmanuelle; Flehoc, Christine; Baran, Nicole

    2017-04-01

    Nitrogen and oxygen isotopes are traditionally considered and frequently used as tracers of nitrate sources in watersheds used for drinking water production. The enrichment of synthetic nitrate-containing fertilizers in 18O due to the contribution of atmospheric oxygen in the production process confers a specific isotopic fingerprint to mineral fertilizers. In spite of the still widespread use on nitrate-containing synthetic fertilizers, their characteristic N and O isotope signatures are rarely unambiguously observed in nitrate-contaminated groundwater. We postulate, in line with Mengis et al. (2001), that fertilizer-derived nitrate is not directly and rapidly transferred to groundwater but rather retained in the soil-plant system as organic N and then mineralized and re-oxidized (termed the mineralization-immobilization turnover, MIT) thereby re-setting the oxygen isotope composition of nitrate and also changing its N isotope ratios. We show examples from watersheds on diverse alluvial/clastic and carbonate aquifers in eastern and northern France where, in spite of the use of mineral fertilizers, evidenced also through other isotopic tracers (boron isotopes), both N and O-isotope ratios are very homogeneous and compatible with nitrification of ammonium where 2/3 of oxygen is derived from soil water and 1/3 from atmospheric O2. These field data are corroborated by lysimeter data from Canada. Even if in areas where ammonium is derived from chemical fertilizers, N values still tend to be lower than in areas where ammonium is derived from manure/sewage, this is clearly a limitation to the dual isotope method (N, O) for nitrate source identification, but has important implications for the nitrogen mobility and residence time in soils amended with synthetic fertilizers (Sebilo et al., 2013). Mengis M., Walther U., Bernasconi S. M., Wehrli B. (2001) Limitations of Using δ18O for the Source Identification of Nitrate in Agricultural Soils. Environmental Science

  15. Isotope specific arbitrary material flow meter

    DOEpatents

    Barty, Christopher P. J.; Post, John C.; Jones, Edwin

    2016-10-25

    A laser-based mono-energetic gamma-ray source is used to provide non-destructive and non-intrusive, quantitative determination of the absolute amount of a specific isotope contained within pipe as part of a moving fluid or quasi-fluid material stream.

  16. Calcium and Oxygen Isotopic Composition of Calcium Carbonates

    NASA Astrophysics Data System (ADS)

    Niedermayr, Andrea; Eisenhauer, Anton; Böhm, Florian; Kisakürek, Basak; Balzer, Isabelle; Immenhauser, Adrian; Jürgen Köhler, Stephan; Dietzel, Martin

    2016-04-01

    Different isotopic systems are influenced in multiple ways corresponding to the crystal structure, dehydration, deprotonation, adsorption, desorption, isotope exchange and diffusion processes. In this study we investigated the structural and kinetic effects on fractionation of stable Ca- and O-isotopes during CaCO3 precipitation. Calcite, aragonite and vaterite were precipitated using the CO2 diffusion technique[1]at a constant pH of 8.3, but various temperatures (6, 10, 25 and 40° C) and precipitation rates R (101.5 to 105 μmol h-1 m-2). The calcium isotopic fractionation between solution and vaterite is lower (Δ44/40Ca= -0.10 to -0.55 ‰) compared to calcite (-0.69 to -2.04 ‰) and aragonite (-0.91 to -1.55 ‰). In contrast the fractionation of oxygen isotopes is highest for vaterite (32.1 ‰), followed by aragonite (29.2 ‰) and calcite (27.6 ‰) at 25° C and equilibrium. The enrichment of 18O vs. 16O in all polymorphs decreases with increasing precipitation rate by around -0.7 ‰ per log(R). The calcium isotopic fractionation between calcite/ vaterite and aqueous Ca2+ increases with increasing precipitation rate by ˜0.45 ‰ per log(R) and ˜0.1 ‰ per log(R) at 25° C and 40° C, respectively. In contrast the fractionation of Ca-isotopes between aragonite and aqueous Ca2+ decreases with increasing precipitation rates. The large enrichment of 18O vs. 16O isotopes in carbonates is related to the strong bond of oxygen to the small and highly charged C4+-ion. In contrast equilibrium isotopic fractionation between solution and calcite or vaterite is nearly zero as the Ca-O bond length is similar for calcite, vaterite and the hydrated Ca. Aragonite incorporates preferentially the lighter 40Ca isotope as it has very large Ca-O bonds in comparison to the hydrated Ca. At the crystal surface the lighter 40Ca isotopes are preferentially incorporated as dehydration and diffusion of lighter isotopes are faster. Consequently, the surface becomes enriched in 40

  17. Isotopically distinct reservoirs in the solar nebula: Isotope anomalies in Vigarano meteorite inclusions

    NASA Technical Reports Server (NTRS)

    Loss, R. D.; Lugmair, G. W.; Davis, A. M.; Macpherson, G. J.

    1994-01-01

    The isotopic compositions of Mg, Ca, Ti, Cr, Zn, Sr, Ba, Nd, and Sm were measured in four relatively unaltered refractory inclusions from the Vigarano carbonaceous chondrite meteorite. Three of the inclusions (USNM 1623-2, 1623-3, and 1623-8) show similar Mg, Ca, Ti, and Cr isotopic compositions to those found in most inclusions in the Allende carbonaceous chondrite. This indicates that these Vigarano inclusions sampled the same isotopic reservoirs as the majority of the Allende inclusions that isotope signatures in the latter were not significantly modified by the secondary alteration that permeates most Allende inclusions. In contrast, inclusion 1623-5 has large deficits in Mg-26, Ca-48, and Ti-50 and small but distinct Cr-54, Zn-66, Sr-84, Ba-135, Ba-137, and Sm-144 anomalies. The magnitudes of these unusual anomalies in the refractory elements are within analytical uncertainty of those found in the Allende 'FUN" inclusion C1, yet 1623-5 has a very different bulk chemical composition from C1. The fact that 1623-5 and C1 have identical isotopic anomalies yet have significantly distinct major and trace element contents provide convincing evidence for the presence of isotopically distinct reservoirs in the early solar system.

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

    PubMed

    Pang, Jiaping; Wen, Xuefa; Sun, Xiaomin

    2016-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

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

  20. Monitoring water stable isotope composition in soils using gas-permeable tubing and infrared laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Rothfuss, Youri; Vereecken, Harry; Brüggemann, Nicolas

    2013-04-01

    The water stable isotopologues 1H2H16O and 1H218O are powerful tracers of processes occurring in nature. Their slightly different masses as compared to the most abundant water isotopologue (1H216O) affect their thermodynamic (e.g. during chemical equilibrium reactions or physical phase transitions with equilibration) and kinetic (liquid and vapor phases transport processes and chemical reactions without equilibration) properties. This results in measurable differences of the isotopic composition of water within or between the different terrestrial ecosystem compartments (i.e. sub-soil, soil, surface waters, plant, and atmosphere). These differences can help addressing a number of issues, among them water balance closure and flux partitioning from the soil-plant-atmosphere continuum at the field to regional scales. In soils particularly, the isotopic composition of water (δ2H and δ18O) provides qualitative information about whether water has only infiltrated or already been re-evaporated since the last rainfall event or about the location of the evaporation front. From water stable isotope composition profiles measured in soils, it is also possible, under certain hypotheses, to derive quantitative information such as soil evaporation flux and the identification of root water uptake depths. In addition, water stable isotopologues have been well implemented into physically based Soil-Vegetation-Atmosphere Transfer models (e.g. SiSPAT-Isotope; Soil-Litter iso; TOUGHREACT) and have demonstrated their potential. However, the main disadvantage of the isotope methodology is that, contrary to other soil state variables that can be monitored over long time periods, δ2H and δ18O are typically analyzed following destructive sampling. Here, we present a non-destructive method for monitoring soil liquid water δ2H and δ18O over a wide range of water availability conditions and temperatures by sampling and measuring water vapor equilibrated with soil water using gas

  1. Calcium isotopic composition of mantle xenoliths and minerals from Eastern China

    NASA Astrophysics Data System (ADS)

    Kang, Jin-Ting; Zhu, Hong-Li; Liu, Yu-Fei; Liu, Fang; Wu, Fei; Hao, Yan-Tao; Zhi, Xia-Chen; Zhang, Zhao-Feng; Huang, Fang

    2016-02-01

    This study presents calcium isotope data for co-existing clinopyroxenes (cpx), orthopyroxenes (opx), and olivine (ol) in mantle xenoliths to investigate Ca isotopic fractionation in the upper mantle. δ44/40Ca (δ44/40Ca (‰) = (44Ca/40Ca)SAMPLE/(44Ca/40Ca)SRM915a - 1) in opx varies from 0.95 ± 0.05‰ to 1.82 ± 0.01‰ and cpx from 0.71 ± 0.06‰ to 1.03 ± 0.12‰ (2se). δ44/40Ca in ol (P-15) is 1.16 ± 0.08‰, identical to δ44/40Ca of the co-existing opx (1.12 ± 0.09‰, 2se). The Δ44/40Caopx-cpx (Δ44/40Caopx-cpx = δ44/40Caopx-δ44/40Cacpx) shows a large variation ranging from -0.01‰ to 1.11‰ and it dramatically increases with decreasing of Ca/Mg (atomic ratio) in opx. These observations may reflect the effect of opx composition on the inter-mineral equilibrium fractionation of Ca isotopes, consistent with the theoretical prediction by first-principles theory calculations (Feng et al., 2014). Furthermore, Δ44/40Caopx-cpx decreases when temperature slightly increases from 1196 to 1267 K. However, the magnitude of such inter-mineral isotopic fractionation (1.12‰) is not consistent with the value calculated by the well-known correlation between inter-mineral isotope fractionation factors and 1/T2 (Urey, 1947). Instead, it may reflect the temperature control on crystal chemistry of opx (i.e., Ca content), which further affects Δ44/40Caopx-cpx. The calculated δ44/40Ca of bulk peridotites and pyroxenites range from 0.76 ± 0.06‰ to 1.04 ± 0.12‰ (2se). Notably, δ44/40Ca of bulk peridotites are positively correlated with CaO and negatively with MgO content. Such correlations can be explained by mixing between a fertile mantle end-member and a depleted one with low δ44/40Ca, indicating that Ca isotopes could be a useful tool in studying mantle evolution.

  2. Isotopic, Chemical and Mineralogical Investigation's of Extraterrestrial Materials

    NASA Technical Reports Server (NTRS)

    Lugmair, G. W.

    2003-01-01

    During the grant period we have concentrated on the following main topics: 1. Enstatite meteorites and original heterogeneity of Mn-53 distribution in the solar nebula. We have completed our studies of the enstatite chondrites. 2. Processes of planetary differentiation. We have completed our study of silicate clasts from the mesosiderite Vaca Muerta and found that the global Mn/Cr fractionation event that established mantle source reservoirs on the parent body of the Vaca Muerta silicate clasts occurred approx. 2 Ma after a similar event on the howardite-eucrite-diogenite (HED) parent body. 3. Carbonaceous chondrites. Much effort has been devoted during the last three years to the investigation of this important class of meteorites. 4. Early solar system timescales. Based on the studies of the Mn-53 - Cr-53 isotope system in various meteorites and using results obtained with other isotope chronometers we constructed an absolute time-scale for events in the early solar system. 5.Unusual meteorites. We have studied the anomalous pallasite Eagle Station. 6. The chromium isotopic composition as a tracer for extraterrestrial material on Earth. Based on the observed difference in the Cr-53/Cr-52 ratios between Earth and the other solar system objects we developed a method for detecting cosmic materials on Earth using the Cr-53/Cr-52 ratio as a tracer.

  3. Stable isotope composition (δ(13)C and δ(15)N values) of slime molds: placing bacterivorous soil protozoans in the food web context.

    PubMed

    Tiunov, Alexei V; Semenina, Eugenia E; Aleksandrova, Alina V; Tsurikov, Sergey M; Anichkin, Alexander E; Novozhilov, Yuri K

    2015-08-30

    Data on the bulk stable isotope composition of soil bacteria and bacterivorous soil animals are required to estimate the nutrient and energy fluxes via bacterial channels within detrital food webs. We measured the isotopic composition of slime molds (Myxogastria, Amoebozoa), a group of soil protozoans forming macroscopic spore-bearing fruiting bodies. An analysis of largely bacterivorous slime molds can provide information on the bulk stable isotope composition of soil bacteria. Fruiting bodies of slime molds were collected in a monsoon tropical forest of Cat Tien National Park, Vietnam, and analyzed by continuous-flow isotope ratio mass spectrometry. Prior to stable isotope analysis, carbonates were removed from a subset of samples by acidification. To estimate the trophic position of slime molds, their δ(13) C and δ(15) N values were compared with those of plant debris, soil, microbial destructors (litter-decomposing, humus-decomposing, and ectomycorrhizal fungi) and members of higher trophic levels (oribatid mites, termites, predatory macroinvertebrates). Eight species of slime molds represented by at least three independent samples were 3-6‰ enriched in (13) C and (15) N relative to plant litter. A small but significant difference in the δ(13) C and δ(15) N values suggests that different species of myxomycetes can differ in feeding behavior. The slime molds were enriched in (15) N compared with litter-decomposing fungi, and depleted in (15) N compared with mycorrhizal or humus-decomposing fungi. Slime mold sporocarps and plasmodia largely overlapped with oribatid mites in the isotopic bi-plot, but were depleted in (15) N compared with predatory invertebrates and humiphagous termites. A comparison with reference groups of soil organisms suggests strong trophic links of slime molds to saprotrophic microorganisms which decompose plant litter, but not to humus-decomposing microorganisms or to mycorrhizal fungi. Under the assumption that slime molds are

  4. Natural Ca Isotope Composition of Urine as a Rapid Measure of Bone Mineral Balance

    NASA Astrophysics Data System (ADS)

    Skulan, J.; Gordon, G. W.; Morgan, J.; Romaniello, S. J.; Smith, S. M.; Anbar, A. D.

    2011-12-01

    Naturally occurring stable Ca isotope variations in urine are emerging as a powerful tool to detect changes in bone mineral balance. Bone formation depletes soft tissue of light Ca isotopes while bone resorption releases isotopically light Ca into soft tissue. Previously published work found that variations in Ca isotope composition could be detected at 4 weeks of bed rest in a 90-day bed rest study (data collected at 4, 8 and 12 weeks). A new 30-day bed rest study involved 12 patients on a controlled diet, monitored for 7 days prior to bed rest and 7 days post bed rest. Samples of urine, blood and food were collected throughout the study. Four times daily blood samples and per void urine samples were collected to monitor diurnal or high frequency variations. An improved chemical purification protocol, followed by measurement using multiple collector inductively coupled plasma mass spectrometry (MC-ICP-MS) allowed accurate and precise determinations of mass-dependent Ca isotope variations in these biological samples to better than ±0.2% (δ44/42Ca) on <25 μg of Ca. Results from this new study show that Ca isotope ratios shift in a direction consistent with net bone loss after just 7 days, long before detectible changes in bone density by X-ray measurements occur. Consistent with this interpretation, the Ca isotope variations track changes observed in N-teleopeptide, a bone resorption biomarker. Bone-specific alkaline phosphatase, a bone formation biomarker, is unchanged over this period. Ca isotopes can in principle be used to quantify net changes in bone mass. Using a mass-balance model, our results indicate an average loss of 0.62 ± 0.16 % in bone mass over the course of this 30-day study. This is consistent with the rate of bone loss in longer-term studies as seen by X-ray measurements. This Ca isotope technique should accelerate the pace of discovery of new treatments for bone disease and provide novel insights into the dynamics of bone metabolism.

  5. Study of the dynamics of Zn, Fe, and Cu in the soil-plant system during leaf litter decomposition using isotopic compositions

    NASA Astrophysics Data System (ADS)

    Pichat, S.; Fekiacova, Z.

    2013-12-01

    Litter decomposition is a key process in the cycle of the elements in the soil-plant system. We have investigated the dynamics of three essential micronutrients (Zn, Fe, and Cu) in the vegetal cover, litter, organic horizons, and upper soil horizon (0-2 and 5-10 cm) using both element concentrations and isotopic compositions. The study was conducted on the O3HP (Oak Observatory at the Haute-Provence Observatory) experimental field site in southern France. O3HP is located far from pollution sources. It has been a fallow land for 70 years with the tree cover represented mainly by oak trees (Quercus pubescens). The soil is a thin layer of Calcisol developed under Mediterranean climate. The area has been subdivided in four zones as a function of plant cover. The results for two of these zones, dominated by respectively Poaceae and Genista hispanica, are reported here. We found that the concentrations of the three elements increase from the Ol to the Of horizon. Copper concentration in the Of horizon is close to that of the soil, whereas it is lower for Fe and Zn. For isotopic compositions, the behavior of the three elements is, however, different, which suggests different processes of redistribution for these elements. An enrichment in light Fe isotopes was observed from the Ol to the Of horizon, the latter having an isotopic composition similar to that of the soil. Zinc isotopic compositions are also similar in the Of horizon and the soil but they are isotopically heavier than in the Ol horizon. For Cu, the O horizons are isotopically heavier than the soil, with Of being the heaviest horizon. In addition, for Cu and Zn, the profiles in the O-horizons in the Poaceae-dominated and Genista hispanica-dominated areas are similar but their values are offset, suggesting an influence of the vegetal cover. The increase in concentration for Cu, Zn and Fe with age/depth in the O horizons is in agreement with what is commonly observed in litter-bag experiments, e.g. 1,2. Two

  6. Isotopic measurements (C,N,O) of detonation soot produced from labeled and unlabeled Composition B-3 indicate source of solid carbon residues

    NASA Astrophysics Data System (ADS)

    Podlesak, David; Manner, Virginia; Amato, Ronald; Dattelbaum, Dana; Gusavsen, Richard; Huber, Rachel

    2017-06-01

    Detonation of HE is an exothermic process whereby metastable complex molecules are converted to simple stable molecules such as H2 O, N2, CO, CO2, and solid carbon. The solid carbon contains various allotropes such as detonation nanodiamonds, graphite, and amorphous carbon. It is well known that certain HE formulations such as Composition B (60% RDX, 40% TNT) produce greater amounts of solid carbon than other more oxygen-balanced formulations. To develop a greater understanding of how formulation and environment influence solid carbon formation, we synthesized TNT and RDX with 13 C and 15 N at levels slightly above natural abundance levels. Synthesized RDX and TNT were mixed at a ratio of 60:40 to form Composition B and solid carbon residues were collected from detonations of isotopically-labeled as well as un-labelled Composition B. The raw HE and detonation residues were analyzed isotopically for C, N, O isotopic compositions. We will discuss differences between treatments groups as a function of formulation and environment. LA-UR - 17-21266.

  7. Constraints on Earth degassing history from the argon isotope composition of Devonian atmosphere

    NASA Astrophysics Data System (ADS)

    Stuart, F. M.; Mark, D.

    2012-04-01

    The primordial and radiogenic isotopes of the noble gases combine to make them a powerful tool for determining the time and tempo of the outgassing of the Earth's interior. The outgassing history of the Earth is largely constrained from measurements of the isotopic composition of He, Ne, Ar and Xe in samples of modern mantle, crust and atmosphere. There have been few unequivocal measurement of the isotopic composition of noble gases in ancient atmosphere. We have re-visited whether ancient Ar is trapped in the ~400 Ma Rhynie chert [1]. We have analysed samples of pristine Rhynie chert using the ARGUS multi-collector mass spectrometer calibrated against the new determination of atmospheric Ar isotope ratios [2]. 40Ar/36Ar ratios are low, with many lower than the modern air value (298.8). Importantly these are accompanied by atmospheric 38Ar/36Ar ratios indicating that the low 40Ar/36Ar are not due to mass fractionation. We conclude that the Rhynie chert has captured Devonian atmosphere-derived Ar. The data indicate that the Devonian atmosphere 40Ar/36Ar was at least 3 % lower than the modern air value. Thus the Earth's atmosphere has accumulated at least 5 ± 0.2 x 1016 moles of 40Ar in the last 400 million years, at an average rate of 1.24 ± 0.06 x 108 mol 40Ar/year. This overlaps the rate determined from ice cores for the last 800,000 years [3] and implies that there has been no resolvable temporal change in Earth outgassing rate since mid-Palaeozoic times. The new data require the Earth outgassed early, and suggests that pristine samples of Archaean and Proterozoic chert may prove useful as palaeo-atmosphere tracers. [1] G. Turner, J. Geol. Soc. London 146, 147-154 (1989) [2] D. Mark, F.M. Stuart, M. de Podesta, Geochim. Cosmochim. Acta 75, 7494-7501 [3] M. Bender et al., Proc. Nat. Acad. Sci. 105, 8232-8237 (2008)

  8. Tracing mantle processes with Fe isotopes

    NASA Astrophysics Data System (ADS)

    Weyer, S.; Ionov, D.

    2006-12-01

    High precision Fe isotope measurements have been performed on various mantle peridotites (fertile lherzolites, harzburgites, metasomatised Fe-enriched rocks) and volcanic rocks (mainly oceanic basalts) from different localities and tectonic settings. Pimitive peridotites (Mg# = 0.894) yield delta56Fe = 0.02 and are significantly lighter than the basalts (average delta56Fe = 0.11). Furthermore, the peridotites display a negative correlation of iron isotopes with Mg#. Taken together, these findings imply that Fe isotopes fractionate during partial melting, with heavy isotopes preferentially entering the melt [1, 2]. A particularly good correlation of the Fe isotope composition and Mg# shown by poorly metasomatised spinel lherzolites of three localities (Horoman, Kamchatka and Lherz) was used to model Fe isotope fractionation during partial melting, resulting in alphamantle-melt = 1.0003. This value implies higher Fe isotope fractionation between residual mantle and mantle-derived melts (i.e. Delta56Femantle-melt = 0.2-0.3) than the observed difference between the peridotites and the basalts in this study. Our data on plagioclase lherzolites from Horoman and spinel lherzolites from other localities indicate that the difference in Fe isotope composition between mantle and basalts may be reduced by partial re-equilibration between the isotopically heavy basalts and the isotopically light depleted lithospheric mantle during melt ascent. Besides partial melting, the Fe isotope composition of mantle peridotites can also be significantly modified by metasomatic events. At two localities (Tok, Siberia and Tariat, Mongolia) Fe isotopes correlates with the Fe concentration of the peridotites, which was increased up to 14.5% FeO by melt percolation. Such processes can be accompanied by chromatographic effects and produce a range of Fe isotope compositions in the percolation columns, from extremely light to heavy (delta56Fe = -0.42 to +0.17). We propose that Fe isotopes can be

  9. Experimental evaporation of hyperacid brines: Effects on chemical composition and chlorine isotope fractionation

    NASA Astrophysics Data System (ADS)

    Rodríguez, Alejandro; van Bergen, Manfred J.; Eggenkamp, H. G. M.

    2018-02-01

    Hyperacid brines from active volcanic lakes are some of the chemically most complex aqueous solutions on Earth. Their compositions provide valuable insights into processes of elemental transfer from a magma body to the surface and interactions with solid rocks and the atmosphere. This paper describes changes in chemical and δ37Cl signatures observed in a 1750 h isothermal evaporation experiment on hyperacid (pH 0.1) sulphate-chloride brine water from the active lake of Kawah Ijen volcano (Indonesia). Although gypsum was the only evaporite mineral identified in the evolving brine, decreasing Si concentrations may ultimately result in amorphous silica precipitation. Geochemical simulations predict the additional formation of elemental sulphur at lower water activities (aH2O ≤ 0.65) that were not reached in the experiment. Absence of other sulphates and halides despite the high load of dissolved elements (initial TDS ca. 100 g/kg) can be attributed to increased solubility of metals, promoted by extensive formation of complexes between the variety of cations and the major anions (HSO4-, Cl-, F-) present. Chlorine deviations from a conservative behaviour point to losses of gaseous hydrogen chloride (HCl(g)) and consequently an increase in Br/Cl ratios. Chlorine isotope fractionation that accompanied the escape of HCl(g) showed a marked change in sign and magnitude in the course of progressive evaporation of the brine. The calculated factor of fractionation between HCl(g) and dissolved Cl for the initial interval (before 500 h) is positive (1000lnαHCl(g)-Cldiss. = + 1.55 ± 0.49‰to + 3.37 ± 1.11‰), indicating that, at first, the escaping HCl(g) was isotopically heavier than the dissolved Cl remaining in the brine. Conversely, fractionation shifted to the opposite direction in the subsequent interval (1000lnαHCl(g)-Cldiss. = 5.67 ± 0.17‰to - 5.64 ± 0.08‰), in agreement with values reported in literature. It is proposed that Cl isotopic fractionation in

  10. Assessment of oceanic productivity with the triple-isotope composition of dissolved oxygen.

    PubMed

    Luz, B; Barkan, E

    2000-06-16

    Plant production in the sea is a primary mechanism of global oxygen formation and carbon fixation. For this reason, and also because the ocean is a major sink for fossil fuel carbon dioxide, much attention has been given to estimating marine primary production. Here, we describe an approach for estimating production of photosynthetic oxygen, based on the isotopic composition of dissolved oxygen of seawater. This method allows the estimation of integrated oceanic productivity on a time scale of weeks.

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

    NASA Astrophysics Data System (ADS)

    Gellatly, Anne M.; Lyons, Timothy W.

    2005-08-01

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

  12. Stable isotopes in mineralogy

    USGS Publications Warehouse

    O'Neil, J.R.

    1977-01-01

    Stable isotope fractionations between minerals are functions of the fundamental vibrational frequencies of the minerals and therefore bear on several topics of mineralogical interest. Isotopic compositions of the elements H, C, O, Si, and S can now be determined routinely in almost any mineral. A summary has been made of both published and new results of laboratory investigations, analyses of natural materials, and theoretical considerations which bear on the importance of temperature, pressure, chemical composition and crystal structure to the isotopic properties of minerals. It is shown that stable isotope studies can sometimes provide evidence for elucidating details of crystal structure and can be a powerful tool for use in tracing the reaction paths of mineralogical reactions. ?? 1977 Springer-Verlag.

  13. Isotopic compositions of carbonates and organic carbon from upper Proterozoic successions in Namibia: stratigraphic variation and the effects of diagenesis and metamorphism

    NASA Technical Reports Server (NTRS)

    Kaufman, A. J.; Hayes, J. M.; Knoll, A. H.; Germs, G. J.

    1991-01-01

    The carbon isotope geochemistry of carbonates and organic carbon in the late Proterozoic Damara Supergroup of Namibia, including the Nama, Witvlei, and Gariep groups on the Kalahari Craton and the Mulden and Otavi groups on the Congo Craton, has been investigated as an extension of previous studies of secular variations in the isotopic composition of late Proterozoic seawater. Subsamples of microspar and dolomicrospar were determined, through petrographic and cathodoluminescence examination, to represent the "least-altered" portions of the rock. Carbon-isotopic abundances in these phases are nearly equal to those in total carbonate, suggesting that 13C abundances of late Proterozoic fine-grained carbonates have not been significantly altered by meteoric diagenesis, although 18O abundances often differ significantly. Reduced and variable carbon-isotopic differences between carbonates and organic carbon in these sediments indicate that isotopic compositions of organic carbon have been altered significantly by thermal and deformational processes, likely associated with the Pan-African Orogeny. Distinctive stratigraphic patterns of secular variation, similar to those noted in other, widely separated late Proterozoic basins, are found in carbon-isotopic compositions of carbonates from the Nama and Otavi groups. For example, in Nama Group carbonates delta 13C values rise dramatically from -4 to +5% within a short stratigraphic interval. This excursion suggests correlation with similar excursions noted in Ediacaran-aged successions of Siberia, India, and China. Enrichment of 13C (delta 13C> +5%) in Otavi Group carbonates reflects those in Upper Riphean successions of the Akademikerbreen Group, Svalbard, its correlatives in East Greenland, and the Shaler Group, northwest Canada. The widespread distribution of successions with comparable isotopic signatures supports hypotheses that variations in delta 13C reflect global changes in the isotopic composition of late

  14. Intramolecular Isotopic Studies: Chemical Enhancements and Alternatives

    NASA Astrophysics Data System (ADS)

    Hayes, J. M.

    2016-12-01

    As mass spectroscopic and NMR-based methods now appropriately flourish, chemical techniques should not be forgotten. First, the methods developed by pioneering intramolecular analysts can be reapplied to new samples. Second, they can be extended. The synthesis of intramolecular isotopic standards is particularly important and straightforward. It requires only that a chemical reaction has no secondary products. An example is provided by the addition of carbon dioxide to a Grignard reagent. The reaction proceeds with an isotope effect. The isotopic composition of the carboxyl group in the acid which is produced is thus not equal to that of the starting carbon dioxide but the unconsumed CO2 can be recovered and analyzed. A simple titration can show that all the rest of the CO2 is in the product acid. The isotopic composition of the carboxyl group can then be calculated by difference. The product is an intramolecular isotopic standard, an organic molecule in which the isotopic composition of a specific carbon position is known accurately. Both analysts and reviewers can thus gain invaluable confidence in the accuracy of instrumental results. A second example: the haloform reaction quantitatively degrades methyl ketones, producing a carboxylic acid which can be decarboxylated to determine the isotopic composition of the parent carbonyl and a haloform (CHI3, for example) that can be combusted to determine the isotopic composition of the methyl group. Ketones thus analyzed can be combined with Grignard reagents to yield carbon skeletons in which the isotopic compositions of internal and terminal -CH2- and -CH3 groups are known accurately. In general, analysts accustomed to demanding quantitative reactions should remember the power of mass balances and recognize that many organic-chemical reactions, while not quantitative, lack side products and can be driven to the total consumption of at least one reactant.

  15. SULFUR ISOTOPIC COMPOSITIONS OF SUBMICROMETER SiC GRAINS FROM THE MURCHISON METEORITE

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Xu, Yuchen; Zinner, Ernst; Gallino, Roberto

    2015-02-01

    We report C, Si, N, S, Mg-Al, and Ca-Ti isotopic compositions of presolar silicon carbide (SiC) grains from the SiC-rich KJE size fraction (0.5-0.8 μm) of the Murchison meteorite. One thousand one hundred thirteen SiC grains were identified based on their C and Si isotopic ratios. Mainstream, AB, C, X, Y, and Z subtypes of SiC, and X-type silicon nitride (Si{sub 3}N{sub 4}) account for 81.4%, 5.7%, 0.1%, 1.5%, 5.8%, 4.9%, and 0.4%, respectively. Twenty-five grains with unusual Si isotopic ratios, including one C grain, 16 X grains, 1 Y grain, 5 Z grains, and 2 X-type Si{sub 3}N{sub 4} grainsmore » were selected for N, S, Mg-Al, and Ca-Ti isotopic analysis. The C grain is highly enriched in {sup 29}Si and {sup 30}Si (δ{sup 29}Si = 1345‰ ± 19‰, δ{sup 30}Si = 1272‰ ± 19‰). It has a huge {sup 32}S excess, larger than any seen before, and larger than that predicted for the Si/S supernova (SN) zone, providing evidence against the elemental fractionation model by Hoppe et al. Two SN models investigated here present a more satisfying explanation in terms of a radiogenic origin of {sup 32}S from the decay of short-lived {sup 32}Si (τ{sub 1/2} = 153 yr). Silicon-32 as well as {sup 29}Si and {sup 30}Si can be produced in SNe by short neutron bursts; evidence for initial {sup 44}Ti (τ{sub 1/2} = 60 yr) in the C grain is additional evidence for an SN origin. The X grains have marginal {sup 32}S excesses, much smaller than expected from their large {sup 28}Si excesses. Similarly, the Y and Z grains do not show the S-isotopic anomalies expected from their large Si isotopic anomalies. Low intrinsic S contents and contamination with isotopically normal S are the most likely explanations.« less

  16. Triple oxygen isotope composition of leaf waters in Mpala, central Kenya

    NASA Astrophysics Data System (ADS)

    Li, Shuning; Levin, Naomi E.; Soderberg, Keir; Dennis, Kate J.; Caylor, Kelly K.

    2017-06-01

    Variations in triple oxygen isotopes have been used in studies of atmospheric photochemistry, global productivity and increasingly in studies of hydroclimate. Understanding the distribution of triple oxygen isotopes in plant waters is critical to studying the fluxes of oxygen isotopes between the atmosphere and hydrosphere, in which plants play an important role. In this paper we report triple oxygen isotope data for stem and leaf waters from Mpala, Kenya and explore how Δ17 O, the deviation from an expected relationship between 17O /16O and 18O /16O ratios, in plant waters vary with respect to relative humidity and deuterium excess (d-excess). We observe significant variation in Δ17 O among waters in leaves and stems from a single plant (up to 0.16‰ range in Δ17 O in leaf water in a plant over the course of a signal day), which correlates to changes in relative humidity. A steady state model for evaporation in leaf water reproduces the majority of variation in Δ17 O and d-excess we observed in leaf waters, except for samples that were collected in the morning, when relative humidity is high and the degree of fractionation in the system is minimal. The data and the steady state model indicate that the slope, λtransp, that links δ17 O and δ18 O values of stem and leaf waters and characterizes the fractionation during transpiration, is strongly influenced by the isotopic composition of ambient vapor when relative humidity is high. We observe a strong, positive relationship between d-excess and Δ17 O, with a slope 2.2 ± 0.2 per meg ‰-1, which is consistent with the observed relationship in tropical rainfall and in water in an evaporating open pan. The strong linear relationship between d-excess and Δ17 O should be typical for any process involving evaporation or any other fractionation that is governed by kinetic effects.

  17. Regulation of Isotopic Composition of Water - way of Improvement of Cosmonauts Drinking Water Functional Properties

    NASA Astrophysics Data System (ADS)

    Kulikova, Ekaterina; Utina, Dina; Vorozhtsova, Svetlana; Severyuhin, Yuri; Abrosimova, Anna; Sinyak, Yuri; Ivanov, Alexander

    The problem in providing drinking water to cosmonauts is solved - at this moment there is a task to improve the functional properties of the water. One of the perspectives of this trend is the use of light isotopic water. The animal studies have shown that long-term consumption of water with a depletion of deuterium and oxygen heavy isotopes accelerates the rise of mass non-irradiated mice, the phase fluctuations reducing or increasing hematological parameters were having adaptive nature. These fluctuations didn’t overcome values beyond the physiological norm of this type of animal. It is established that the therapeutic use of light isotopic water with 35 - 90 ppm in deuterium increases the survival of irradiated mice by an average of 30%, contributes to the preservation of irradiated animals body weight. Treatment of acute radiation sickness with light isotopic water stimulates hematopoietic recovery. At the same time, keeping mice drinking light isotopic water for 7 - 8 days before the irradiation (from 4 to 8.5 Gr) has no effect on the level of radio resistance. Longer keeping mice on light isotopic water, for 14 -21 days - reduction in life expectancy, animal mass, bone marrow cellularity and the level of white blood cells in irradiated animals is noted. It was established that keeping mice on light isotopic water for 14 days before exposure in experimental animals causes an increase in the mitotic index and the frequency of formation of aberrant mitosis after 24 hours of Co(60) gamma radiation in doses of 1 , 2, and 4 Gr. Thus, it is clear that the regulation of the isotopic composition of drinking water - way to improve its functional properties.

  18. Stable Cl isotope composition of the Changjiang River water

    NASA Astrophysics Data System (ADS)

    Lang, Y.; Liu, C. Q.; LI, S. L.; Aravena, R.; Ding, H.; WANG, B.; Benjamin, C.

    2017-12-01

    To understand chemical wreathing, nutrient cycling, and the impact of human activities on eco-environments of the Changjiang River (Yangtze River) Basin, we carried out a geochemical study on water chemistry and multiple isotopes (C, N, S, Sr…...) of Changjiang River water in the summer season. Some of the research results about the water chemistry, boron isotope geochemistry and suspended matter have been published (Chetelat et al., 2008; Li et al., 2010). Ten samples were selected for the measurement of δ37Cl values, among which 7 samples were collected from main stream and 3 samples from tributaries. The range of δ37Cl values varies between 0.02‰ and 0.33‰ in the main stream and between 0.16‰ and 0.71‰ in the tributary waters. The δ37Cl values in general are negatively correlated with Cl- concentrations for both main stream and tributary waters. δ37Cl value of Wujiang, which is one of the large tributaries in the upper reach of Changjiang and dominated by carbonate rocks in lithology of the watershed, has the maximum value but minimum value of Cl- concentration in this study. The lowest δ37Cl value was measured for the water collected from the estuary of Changjiang River. The variation of δ37Cl values in the waters would be attributed to mixing of different sources of chlorine, which most likely include rain water, ground water, seawater, and pollutants. Systematic characterization of different Cl sources in terms of their chlorine isotope composition is imperative for better understanding of sources and processes of chlorine cycling. Acknowledgements: This work was financially supported by NSFC through project 41073099. (Omit references)

  19. A Procedure to Determine the Coordinated Chromium and Calcium Isotopic Composition of Astromaterials Including the Chelyabinsk Meteorite

    NASA Technical Reports Server (NTRS)

    Tappa, M. J.; Mills, R. D.; Ware, B.; Simon, J. I.

    2014-01-01

    The isotopic compositions of elements are often used to characterize nucelosynthetic contributions in early Solar System objects. Coordinated multiple middle-mass elements with differing volatilities may provide information regarding the location of condensation of early Solar System solids. Here we detail new procedures that we have developed to make high-precision multi-isotope measurements of chromium and calcium using thermal ionization mass spectrometry, and characterize a suite of chondritic and terrestrial material including two fragments of the Chelyabinsk LL-chondrite.

  20. Impact of contamination and pre-treatment on stable carbon and nitrogen isotopic composition of charred plant remains

    PubMed Central

    Vaiglova, Petra; Snoeck, Christophe; Nitsch, Erika; Bogaard, Amy; Lee-Thorp, Julia

    2014-01-01

    Rationale Stable isotope analysis of archaeological charred plants has become a useful tool for interpreting past agricultural practices and refining ancient dietary reconstruction. Charred material that lay buried in soil for millennia, however, is susceptible to various kinds of contamination, whose impact on the grain/seed isotopic composition is poorly understood. Pre-treatment protocols have been adapted in distinct forms from radiocarbon dating, but insufficient research has been carried out on evaluating their effectiveness and necessity for stable carbon and nitrogen isotope analysis. Methods The effects of previously used pre-treatment protocols on the isotopic composition of archaeological and modern sets of samples were investigated. An archaeological sample was also artificially contaminated with carbonates, nitrates and humic acid and subjected to treatment aimed at removing the introduced contamination. The presence and removal of the contamination were investigated using Fourier transform infrared spectroscopy (FTIR) and δ13C and δ15N values. Results The results show a ca 1‰ decrease in the δ15N values of archaeological charred plant material caused by harsh acid treatments and ultra-sonication. This change is interpreted as being caused by mechanical distortion of the grains/seeds rather than by the removal of contamination. Furthermore, specific infrared peaks have been identified that can be used to detect the three types of contaminants studied. We argue that it is not necessary to try to remove humic acid contamination for stable isotope analysis. The advantages and disadvantages of crushing the grains/seeds before pre-treatment are discussed. Conclusions We recommend the use of an acid-only procedure (0.5 M HCl for 30 min at 80°C followed by three rinses in distilled water) for cleaning charred plant remains. This study fills an important gap in plant stable isotope research that will enable future researchers to evaluate potential

  1. Habitat use and trophic position effects on contaminant bioaccumulation in fish indicated by stable isotope composition

    EPA Science Inventory

    The objective of our study was to determine the relationship between fish tissue stable isotope composition and total mercury or polychlorinated biphenyl (PCB) concentrations in a Great Lakes coastal food web. We sampled two resident fishes, Yellow Perch (Perca flavescens) and Bl...

  2. Isotopic variability of cave bears (δ15N, δ13C) across Europe during MIS 3

    NASA Astrophysics Data System (ADS)

    Krajcarz, Magdalena; Pacher, Martina; Krajcarz, Maciej T.; Laughlan, Lana; Rabeder, Gernot; Sabol, Martin; Wojtal, Piotr; Bocherens, Hervé

    2016-01-01

    Collagen, the organic fraction of bone, records the isotopic parameters of consumed food for carbon (δ13C) and nitrogen (δ15N). This relationship of isotopic signature between diet and tissue is an important tool for the study of dietary preferences of modern and fossil animal species. Since the first information on the isotopic signature of cave bear was reported, numerous data from Europe have become available. The goal of this work is to track the geographical variation of cave bear collagen isotopic values in Europe during Marine Isotopic Stage 3 (about 60,000-25,000 yr BP). In this study the results of new δ13C and δ15N isotopic analyses of cave bear collagen from four Central-Eastern European sites are presented, as well as a review of all published isotopic data for cave bears of the same period. The main conclusion is a lack of geographical East-West pattern in the variations of δ13C and δ15N values of cave bear collagen. Moreover, no relationship was found between cave bear taxonomy and isotopic composition. The cave bears from Central-Eastern Europe exhibit δ13C and δ15N values near the average of the range of Central, Western and Southern European cave bears. Despite the fact that most cave bear sites follow an altitudinal gradient, separate groups of sites exhibit shift in absolute values of δ13C, what disturbs an altitude-related isotopic pattern. The most distinct groups are: high Alpine sites situated over 1500 m a.s.l. - in terms of δ13C; and two Romanian sites Peştera cu Oase and Urşilor - in case of δ15N. Although the cave bear isotopic signature is driven by altitude, the altitudinal adjustment of isotopic data is not enough to explain the isotopic dissimilarity of these cave bears. The unusually high δ15N signature of mentioned Romanian sites is an isolated case in Europe. Cave bears from relatively closely situated Central-Eastern European sites and other Romanian sites are more similar to Western European than to Romanian

  3. The He isotope composition of the earliest picrites erupted by the Ethiopia plume, implications for mantle plume source

    NASA Astrophysics Data System (ADS)

    Stuart, Finlay; Rogers, Nick; Davies, Marc

    2016-04-01

    The earliest basalts erupted by mantle plumes are Mg-rich, and typically derived from mantle with higher potential temperature than those derived from the convecting upper mantle at mid-ocean ridges and ocean islands. The chemistry and isotopic composition of picrites from CFB provide constraints on the composition of deep Earth and thus the origin and differentiation history. We report new He-Sr-Nd-Pb isotopic composition of the picrites from the Ethiopian flood basalt province from the Dilb (Chinese Road) section. They are characterized by high Fe and Ti contents for MgO = 10-22 wt. % implying that the parent magma was derived from a high temperature low melt fraction, most probably from the Afar plume head. The picrite 3He/4He does not exceed 21 Ra, and there is a negative correlation with MgO, the highest 3He/4He corresponding to MgO = 15.4 wt. %. Age-corrected 87Sr/86Sr (0.70392-0.70408) and 143Nd/144Nd (0.512912-0.512987) display little variation and are distinct from MORB and OIB. Age-corrected Pb isotopes display a significant range (e.g. 206Pb/204Pb = 18.70-19.04) and plot above the NHRL. These values contrast with estimates of the modern Afar mantle plume which has lower 3He/4He and Sr, Nd and Pb isotope ratios that are more comparable with typical OIB. These results imply either interaction between melts derived from the Afar mantle plume and a lithospheric component, or that the original Afar mantle plume had a rather unique radiogenic isotope composition. Regardless of the details of the origins of this unusual signal, our observations place a minimum 3He/4He value of 21 Ra for the Afar mantle plume, significantly greater than the present day value of 16 Ra, implying a significant reduction over 30 Myr. In addition the Afar source was less degassed than convecting mantle but more degassed than mantle sampled by the proto-Iceland plume (3He/4He ~50 Ra). This suggests that the largest mantle plumes are not sourced in a single deep mantle domain with a

  4. Evidence for rapid climate change in North America during the latest Paleocene thermal maximum: oxygen isotope compositions of biogenic phosphate from the Bighorn Basin (Wyoming)

    NASA Astrophysics Data System (ADS)

    Fricke, Henry C.; Clyde, William C.; O'Neil, James R.; Gingerich, Philip D.

    1998-07-01

    Oxygen isotope records of Cenozoic sea water temperatures indicate that a rapid warming event known as the Latest Paleocene Thermal Maximum (LPTM) occurred during the otherwise gradual increase in world temperatures during the Late Paleocene and Early Eocene. Oxygen isotope analysis of the carbonate and phosphate components of hydroxyapatite found in mammalian tooth enamel and body scales of river-dwelling fish from the Bighorn Basin in Wyoming were made to investigate corresponding changes in the terrestrial climate. A comparison of carbonate and phosphate isotope data from modern and fossil material indicates that some diagenetic alteration of the fossil material has occurred, although systematically larger intra-tooth ranges in the oxygen isotope composition of carbonate indicate that it is more likely to have been affected than phosphate. Carbonate and phosphate from the ecologically diverse mammals and fishes both record a shift to higher oxygen isotope ratios at the same time and of the same duration as the LPTM. These shifts reflect a change in the isotopic composition of regional precipitation, which in turn provides the first evidence for continental climate change during the LPTM. Assuming the present-day relation between the oxygen isotope composition of precipitation and temperature applies to conditions in the past, and that animal physiology and behavior is relatively invariant over time, the isotopic shift is equivalent to an increase of surface temperature in western North America of several degrees. This result is consistent with the magnitude of high-latitude ocean warming, and provides a basis for relating marine and terrestrial oxygen isotope records to records of terrestrial biotic change.

  5. Isotopic compositions and sources of nitrate in ground water from western Salt River Valley, Arizona

    USGS Publications Warehouse

    Gellenbeck, D.J.

    1994-01-01

    Isotopic and chemical compositions of ground water from western Salt River Valley near Phoenix, Arizona, were used to develop identification tech- niques for sources of nitrate in ground water. Four possible sources of nitrate were studied: dairies and feedlots, sewage-treatment plants, agricultural activities, and natural source. End members that represent these sources were analyzed for a variety of chemical and isotopic constituents; contents of the end-member and the ground water were compared to identify nitrate from these sources. Nitrate from dairies and feedlots was identified by delta 15N values higher than +9.0 per mil. Nitrate from sewage treatment plants was identified by some chemical constituents and values of delta 15N, delta 34S, delta 7Li, and delta 11B that were lighter than the values determined for ground water not affected by sewage-treatment plants. Nitrate from agricultural activities was identified by delta 15N, 3H, and delta 34S compositions. Natural nitrate derived from decomposing plants and accumulated by biological fixation was identified by delta 15N values that range between +2 and +8 per mil. In addition to identifying nitrate sources, some chemical and isotopic charabteristics of ground water were determined on the basis of data collected during this study. Concentrations of major ions, lithium, and boron and delta 7Li, delta 11B, 3H, delta D, and delta 18O data identify ground water in different geographic regions in the study area. These differences probably are related to different sources of ground water, geochemical processes, or geologic deposits. The Luke salt body and a geothermal anomaly alter the chemical and isotopic content of some ground water.

  6. Significance of the air moisture source on the stable isotope composition of the precipitation in Hungary

    NASA Astrophysics Data System (ADS)

    Czuppon, György; Bottyán, Emese; Krisztina, Krisztina; Weidinger, Tamás; Haszpra, László

    2017-04-01

    In the last few years, the analysis of backward trajectories has become a common use for identifying moisture uptake regions for the precipitation of various regions. Hungary is influenced by meteorological (climatological) conditions of Atlantic, Mediterranean and North/East regions therefore this area is sensitive to detect changes in the atmospheric circulation. In this study we present the result of the investigation about the determination of air moisture source regions for six localities in Hungary for more than four years. To reconstruct the path of the air moisture from the source region, we ran the NOAA HYSPLIT trajectory model using the GDAS database with 1° spatial and 6 hours temporal resolution for every precipitation event, for heights of 500, 1500 and 3000 m. We determined the location where water vapour entered into the atmosphere by calculating specific humidity along the trajectories. Five possible moisture source regions for precipitation were defined: Atlantic, North European, East European, Mediterranean and continental (local/convective). Additionally, this study evaluates the regional differences in stable isotope compositions of precipitation based on hydrogen and oxygen isotope analyses of daily rainwater samples. Stable isotope variations show systematic and significant differences between the regions. The variability of moisture source shows also systematic seasonal and spatial distribution. Interestingly, the most dominant among the identified source regions in all stations is the Mediterranean area; while the second is the Atlantic region. The ratio of the precipitations originated in Eastern and Northern Europe seem to correlate with the geographic position of the meteorological station. Furthermore, the ratios of the different moisture sources show intra annual variability. In each location, the amount weighted d-excess values were calculated for the identified moisture sources. The precipitation originated in the Mediterranean

  7. Chromium isotope heterogeneity in the mantle

    NASA Astrophysics Data System (ADS)

    Xia, Jiuxing; Qin, Liping; Shen, Ji; Carlson, Richard W.; Ionov, Dmitri A.; Mock, Timothy D.

    2017-04-01

    To better constrain the Cr isotopic composition of the silicate Earth and to investigate potential Cr isotopic fractionation during high temperature geological processes, we analyzed the Cr isotopic composition of different types of mantle xenoliths from diverse geologic settings: fertile to refractory off-craton spinel and garnet peridotites, pyroxenite veins, metasomatised spinel lherzolites and associated basalts from central Mongolia, spinel lherzolites and harzburgites from North China, as well as cratonic spinel and garnet peridotites from Siberia and southern Africa. The δ53CrNIST 979 values of the peridotites range from - 0.51 ± 0.04 ‰ (2SD) to + 0.75 ± 0.05 ‰ (2SD). The results show a slight negative correlation between δ53Cr and Al2O3 and CaO contents for most mantle peridotites, which may imply Cr isotopic fractionation during partial melting of mantle peridotites. However, highly variable Cr isotopic compositions measured in Mongolian peridotites cannot be caused by partial melting alone. Instead, the wide range in Cr isotopic composition of these samples most likely reflects kinetic fractionation during melt percolation. Chemical diffusion during melt percolation resulted in light Cr isotopes preferably entering into the melt. Two spinel websterite veins from Mongolia have extremely light δ53Cr values of - 1.36 ± 0.04 ‰ and - 0.77 ± 0.06 ‰, respectively, which are the most negative Cr isotopic compositions yet reported for mantle-derived rocks. These two websterite veins may represent crystallization products from the isotopically light melt that may also metasomatize some peridotites in the area. The δ53Cr values of highly altered garnet peridotites from southern Africa vary from - 0.35 ± 0.04 ‰ (2SD) to + 0.12 ± 0.04 ‰ (2SD) and increase with increasing LOI (Loss on Ignition), reflecting a shift of δ53Cr to more positive values by secondary alteration. The Cr isotopic composition of the pristine, fertile upper mantle is

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

    NASA Technical Reports Server (NTRS)

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

    2001-01-01

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

  9. Oxygen isotopic composition of chondritic interplanetary dust particles: A genetic link between carbonaceous chondrites and comets

    NASA Astrophysics Data System (ADS)

    Aléon, J.; Engrand, C.; Leshin, L. A.; McKeegan, K. D.

    2009-08-01

    Oxygen isotopes were measured in four chondritic hydrated interplanetary dust particles (IDPs) and five chondritic anhydrous IDPs including two GEMS-rich particles (Glass embedded with metal and sulfides) by a combination of high precision and high lateral resolution ion microprobe techniques. All IDPs have isotopic compositions tightly clustered around that of solar system planetary materials. Hydrated IDPs have mass-fractionated oxygen isotopic compositions similar to those of CI and CM carbonaceous chondrites, consistent with hydration of initially anhydrous protosolar dust. Anhydrous IDPs have small 16O excesses and depletions similar to those of carbonaceous chondrites, the largest 16O variations being hosted by the two GEMS-rich IDPs. Coarse-grained forsteritic olivine and enstatite in anhydrous IDPs are isotopically similar to their counterparts in comet Wild 2 and in chondrules suggesting a high temperature inner solar system origin. The small variations in the 16O content of GEMS-rich IDPs suggest that most GEMS either do not preserve a record of interstellar processes or the initial interstellar dust is not 16O-rich as expected by self-shielding models, although a larger dataset is required to verify these conclusions. Together with other chemical and mineralogical indicators, O isotopes show that the parent-bodies of carbonaceous chondrites, of chondritic IDPs, of most Antarctic micrometeorites, and comet Wild 2 belong to a single family of objects of carbonaceous chondrite chemical affinity as distinct from ordinary, enstatite, K- and R-chondrites. Comparison with astronomical observations thus suggests a chemical continuum of objects including main belt and outer solar system asteroids such as C-type, P-type and D-type asteroids, Trojans and Centaurs as well as short-period comets and other Kuiper Belt Objects.

  10. Development of particle induced gamma-ray emission methods for nondestructive determination of isotopic composition of boron and its total concentration in natural and enriched samples.

    PubMed

    Chhillar, Sumit; Acharya, Raghunath; Sodaye, Suparna; Pujari, Pradeep K

    2014-11-18

    We report simple particle induced gamma-ray emission (PIGE) methods using a 4 MeV proton beam for simultaneous and nondestructive determination of the isotopic composition of boron ((10)B/(11)B atom ratio) and total boron concentrations in various solid samples with natural isotopic composition and enriched with (10)B. It involves measurement of prompt gamma-rays at 429, 718, and 2125 keV from (10)B(p,αγ)(7)Be, (10)B(p, p'γ)(10)B, and (11)B(p, p'γ)(11)B reactions, respectively. The isotopic composition of boron in natural and enriched samples was determined by comparing peak area ratios corresponding to (10)B and (11)B of samples to natural boric acid standard. An in situ current normalized PIGE method, using F or Al, was standardized for total B concentration determination. The methods were validated by analyzing stoichiometric boron compounds and applied to samples such as boron carbide, boric acid, carborane, and borosilicate glass. Isotopic compositions of boron in the range of 0.247-2.0 corresponding to (10)B in the range of 19.8-67.0 atom % and total B concentrations in the range of 5-78 wt % were determined. It has been demonstrated that PIGE offers a simple and alternate method for total boron as well as isotopic composition determination in boron based solid samples, including neutron absorbers that are important in nuclear technology.

  11. Isotope effects on the optical spectra of semiconductors

    NASA Astrophysics Data System (ADS)

    Cardona, Manuel; Thewalt, M. L. W.

    2005-10-01

    Since the end of the cold war, macroscopic amounts of separated stable isotopes of most elements have been available “off the shelf” at affordable prices. Using these materials, single crystals of many semiconductors have been grown and the dependence of their physical properties on isotopic composition has been investigated. The most conspicuous effects observed have to do with the dependence of phonon frequencies and linewidths on isotopic composition. These affect the electronic properties of solids through the mechanism of electron-phonon interaction, in particular, in the corresponding optical excitation spectra and energy gaps. This review contains a brief introduction to the history, availability, and characterization of stable isotopes, including their many applications in science and technology. It is followed by a concise discussion of the effects of isotopic composition on the vibrational spectra, including the influence of average isotopic masses and isotopic disorder on the phonons. The final sections deal with the effects of electron-phonon interaction on energy gaps, the concomitant effects on the luminescence spectra of free and bound excitons, with particular emphasis on silicon, and the effects of isotopic composition of the host material on the optical transitions between the bound states of hydrogenic impurities.

  12. Late Quaternary Environmental Changes Inferred from the stable Oxygen Isotope Composition of Aquatic Insects (Chironomidae: Diptera) and Stable Hydrogen Isotope Composition of bulk sediments from Idavain Lake, Southwest Alaska

    NASA Astrophysics Data System (ADS)

    Wang, Y.; Finney, B.; Wooller, M. J.

    2007-12-01

    Several techniques are available to examine the isotopic composition of historic lake waters, providing data that can subsequently be used to examine environmental changes. Recently-developed techniques are the stable oxygen isotope analysis of subfossil chironomid (Diptera: Chironomidae) head capsules (mostly chitin) preserved in lake sediments and stable hydrogen isotope analyses directly on bulk sediments. An advantage of using δ18O of chironomids is that the chitinous chironomid headcapsules preserve well in lake sediments, retaining the stable oxygen isotope signature of the lake in which they lived. An advantage of δD analyses of bulk sediments is that a sediment core can be analyzed relatively easily and when the %C (total organic carbon) and %H profiles correlate the data can be used to infer past δD changes of the organics in the sediments. We present results from these analyses of a lake sediment core from Idavain Lake (58°46'N, 155°57'W, 223m above sea level) in southwest Alaska in concert with other paleolimnological proxies, including δ15N, δ13C, LOI, magnetic susceptibility, organic content and opal concentrations for a better understanding of paleolimnological changes since deglaciation for the region. Our preliminilary result shows that downcore shifts of δ18O analyzed from chironomid head capsules coincide well with LOI and pollen changes. The δD of sediments and TOM showed large magnitude changes and reflected the relative lake level changes during the record. This study aim to test the correlation between stable isotope analyese on chiornomid head capsules, lake water, and bulk sediments. In the addition, our study will add to the relatively small database of paleoenvironmental reconstructions from terrestrial sites in Southwest Alaska.

  13. X-ray diffraction characterization of epitaxial CVD diamond films with natural and isotopically modified compositions

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Prokhorov, I. A., E-mail: igor.prokhorov@mail.ru; Voloshin, A. E.; Ralchenko, V. G.

    2016-11-15

    Comparative investigations of homoepitaxial diamond films with natural and modified isotopic compositions, grown by chemical vapor deposition (CVD) on type-Ib diamond substrates, are carried out using double-crystal X-ray diffractometry and topography. The lattice mismatch between the substrate and film is precisely measured. A decrease in the lattice constant on the order of (Δa/a){sub relax} ∼ (1.1–1.2) × 10{sup –4} is recorded in isotopically modified {sup 13}C (99.96%) films. The critical thicknesses of pseudomorphic diamond films is calculated. A significant increase in the dislocation density due to the elastic stress relaxation is revealed by X-ray topography.

  14. Stable isotope and chemical compositions of European and Australasian ciders as a guide to authenticity.

    PubMed

    Carter, James F; Yates, Hans S A; Tinggi, Ujang

    2015-01-28

    This paper presents a data set derived from the analysis of bottled and canned ciders that may be used for comparison with suspected counterfeit or substitute products. Isotopic analysis of the solid residues from ciders (predominantly sugar) provided a means to determine the addition of C4 plant sugars. The added sugars were found to comprise cane sugar, high-fructose corn syrup, glucose, or combinations. The majority of ciders from Australia and New Zealand were found to contain significant amounts of added sugar, which provided a limited means to distinguish these ciders from European ciders. The hydrogen and oxygen isotopic compositions of the whole ciders (predominantly water) were shown to be controlled by two factors, the water available to the parent plant and evaporation. Analysis of data derived from both isotopic and chemical analysis of ciders provided a means to discriminate between regions and countries of manufacture.

  15. Impact of topography, climate and moisture sources on isotopic composition (δ18O &δD) of rivers in the Pyrenees: Implications for topographic reconstructions in small orogens

    NASA Astrophysics Data System (ADS)

    Huyghe, Damien; Mouthereau, Frédéric; Sébilo, Mathieu; Vacherat, Arnaud; Ségalen, Loïc; Richard, Patricia; Biron, Philippe; Bariac, Thierry

    2018-02-01

    Understanding how orogenic topography controls the spatial distribution and isotopic composition of precipitation is critical for paleoaltitudinal reconstructions. Here, we determine the isotopic composition (δ18O and δD) of 82 small rivers and springs from small catchments in the Pyrenees. Calculation of the deuterium excess (d-excess) parameter allows the distinction of four distinct isotopic provinces with d-excess values of between 15 and 22‰ in the northwest, between 7 and 14‰ in the central northern Pyrenees and between 3 and 11‰ in the northeast. The southern Pyrenees have a homogenous d-excess signature ranging from 7 to 14‰. Our results show significant local moisture recycling and/or rain amount effect in the northwestern Pyrenees, and control by evaporation processes during rainfall events in the southern Pyrenees and for low elevated samples of the northeast of the range. Based on the distribution of d-excess values, we estimate contrasting isotope lapse rates of -2.9/-21.4‰/km (δ18O/δD) in the northwest, -2.7/-21.4‰/km (δ18O/δD) in the north central and -3.7/-31.7‰/km (δ18O/δD) in the northeastern Pyrenees. The southern Pyrenees show distinctly higher lapse rates of -9.5/-77.5‰/km (δ18O/δD), indicating that in this area the altitudinal effect in not the only parameter driving isotopic composition of rivers. Despite their relatively low topographic gradient, the Pyrenees exert a direct control on the isotopic composition of river waters, especially on their northern side. The variations in isotopic composition-elevation relationships documented along the strike of the range are interpreted to reflect an increasing continentality effect driven by wind trajectories parallel to the range, and mixing with Mediterranean air masses. Despite these effects, the measurable orographic effect on precipitation in the Pyrenees proves that the isotopic composition approach for reconstructing past topography is applicable to low

  16. Chemistry and Ni-isotope composition of ureilites and their components

    NASA Astrophysics Data System (ADS)

    Gabriel, A. D.; Quitté, G.; Pack, A.

    2008-09-01

    Ureilites are olivine-pigeonite bearing achondrites with interstitial carbonaceous material and metal. The latter is present as <1 μm metal inclusions in reduced rims of silicate grains, 5-20 μm spherical inclusions in clear silicate grains, and in association with interstitial carbonaceous material. We have studied the composition of metal and silicates in 9 ureilites with a fayalite content of Fa2 to Fa21. Vein metal contains 3.7 to 5.4 wt% Ni and 0.35 to 0.54 wt% Co. Cobalt and Ni contents in vein metal and fayalite in olivine do not correlate. Mass balance calculations assuming a chondritic parent body yield a metal core with 7 to 11 wt% Ni and 0.3 to 0.55 wt% Co. Thermodynamic calculations of Fe-Ni and Fe-Co exchange between olivine and vein metal show that vein metal cannot be in equilibrium with the olivine at any temperature. We conclude that the vein metal is genetically not linked to the ureilite olivine and may have been injected into the parent body by an impactor. Recently published data show a deficit in 60Ni of - 0.24+/-0.02 ɛ-units for various achondrites including ureilites [1]. This has been interpreted as evidence for a late injection of 60Fe after formation of these achondrites. However, our chemical data for vein metal, which is the dominant Ni host in ureilites, demonstrate that bulk Ni isotope data have little meaning with respect to the formation of ureilite silicates. In this work we present Ni isotope data for bulk samples but also vein material and the silicate phase of 4 ureilites (ALHA77257, EET87157, EET96041, Kenna). Bulk ureilites have a ɛ60 between -0.05+/-0.12 and 0.08+/-0.12; the vein metal gives ɛ60 = -0.05+/-0.13 to 0.11+/-0.16. No resolvable deficit in ɛ60 was found, in disagreement with results reported in Bizzarro et al. (2007). The vein material and the bulk samples have, within uncertainty, the same isotopic composition, confirming that the global Ni budget is controlled by the vein material. In ureilite silicates

  17. Isotope variations of dissolved Zn in the Rio Grande watershed, USA: The role of adsorption on Zn isotope composition

    NASA Astrophysics Data System (ADS)

    Szynkiewicz, Anna; Borrok, David M.

    2016-01-01

    In order to better understand the factors influencing zinc (Zn) isotope composition in hydrological systems, we analyzed the δ66Zn of dissolved Zn in the streams and groundwater of the Upper and Middle Rio Grande watershed in Colorado and New Mexico, United States. The stream water samples have a wider variation of δ66Zn (-0.57 to + 0.41 ‰ relative to the JMC 3-0749-Lyon standard) than groundwater samples (-0.13 to + 0.12 ‰) and than samples from streams that are in close proximity to abandoned mining sites (+0.24 to + 0.40 ‰). Regional changes of bedrock geology, from primarily igneous rocks to primarily sedimentary rocks, have no resolvable effect on the δ66Zn of aqueous samples. Instead, an increase in water pH from 7.5 to 8.5 corresponds to a considerable decrease in the δ66Zn of dissolved Zn (R2 = - 0.37, p = 0.003, n = 22). Consequently, we link the observed Zn isotope variations to the process of adsorption of Zn onto suspended sediment and bedrock minerals (average Δ66Znadsorbed-dissolved = + 0.31 ‰). Our results are in good agreement with previous experimental and empirical studies suggesting that Zn adsorption leads to a residual dissolved pool enriched in light Zn isotopes. Given that anthropogenic Zn sources can also be responsible for lowering of δ66Zn, and may overlap with the pH/adsorption effect on δ66Zn, the latter needs to be carefully considered in future studies to differentiate between natural and anthropogenic factors influencing Zn isotopes in this and other aquatic systems.

  18. Hafnium isotope stratigraphy of ferromanganese crusts

    PubMed

    Lee; Halliday; Hein; Burton; Christensen; Gunther

    1999-08-13

    A Cenozoic record of hafnium isotopic compositions of central Pacific deep water has been obtained from two ferromanganese crusts. The crusts are separated by more than 3000 kilometers but display similar secular variations. Significant fluctuations in hafnium isotopic composition occurred in the Eocene and Oligocene, possibly related to direct advection from the Indian and Atlantic oceans. Hafnium isotopic compositions have remained approximately uniform for the past 20 million years, probably reflecting increased isolation of the central Pacific. The mechanisms responsible for the increase in (87)Sr/(86)Sr in seawater through the Cenozoic apparently had no effect on central Pacific deep-water hafnium.

  19. A 15N-poor isotopic composition for the solar system as shown by Genesis solar wind samples.

    PubMed

    Marty, B; Chaussidon, M; Wiens, R C; Jurewicz, A J G; Burnett, D S

    2011-06-24

    The Genesis mission sampled solar wind ions to document the elemental and isotopic compositions of the Sun and, by inference, of the protosolar nebula. Nitrogen was a key target element because the extent and origin of its isotopic variations in solar system materials remain unknown. Isotopic analysis of a Genesis Solar Wind Concentrator target material shows that implanted solar wind nitrogen has a (15)N/(14)N ratio of 2.18 ± 0.02 × 10(-3) (that is, ≈40% poorer in (15)N relative to terrestrial atmosphere). The (15)N/(14)N ratio of the protosolar nebula was 2.27 ± 0.03 × 10(-3), which is the lowest (15)N/(14)N ratio known for solar system objects. This result demonstrates the extreme nitrogen isotopic heterogeneity of the nascent solar system and accounts for the (15)N-depleted components observed in solar system reservoirs.

  20. The bulk isotopic composition of hydrocarbons in subaerial volcanic-hydrothermal emissions from different tectonic settings

    NASA Astrophysics Data System (ADS)

    Fiebig, J.; Tassi, F.; Vaselli, O.; Viveiros, M. F.; Silva, C.; Lopez, T. M.; D'Alessandro, W.; Stefansson, A.

    2015-12-01

    Assuming that methane and its higher chain homologues derive from a common source, carbon isotope patterns have been applied as a criterion to identify occurrences of abiogenic hydrocarbons. Based on these, it has been postulated that abiogenic hydrocarbon production occurs within several (ultra)mafic environments. More evolved volcanic-hydrothermal systems may also provide all the prerequisites necessary for abiogenic hydrocarbon production, such as availability of inorganic CO2, hydrogen and heat. We have investigated the chemical and isotopic composition of n-alkanes contained within subaerial hydrothermal discharges emitted from a range of hot spot, subduction and rift-related volcanoes to determine the origin of hydrocarbons in these systems. Amongst these are Nisyros (Greece), Vesuvio, Campi Flegrei, Ischia, Pantelleria and Vulcano (all Italy), Mt. Mageik and Trident (USA), Copahue (Argentina), Teide (Spain), Furnas and Fogo (Portugal). The carbon isotopic composition of methane emitted from these sites varies from -65 to -8‰ , whereas δ13C of ethane and propane exhibit a much narrower variation from -17‰ to -31‰. Methane that occurs most enriched in 13C is also characterized by relatively positive δD values ranging up to -80‰. Carbon isotope reversals between methane and ethane are only observed for locations exhibiting δ13C-CH4 values > -20‰, such as Teide, Pantelleria, Trident and Furnas. At Furnas, δ13C-CH4 varies by 50‰ within a relatively short distance of <50m between two vents, whereas δ13C-C2H6 varies by less than 2‰ only. For some of the investigated locations apparent carbon isotopic temperatures between methane and CO2 are in agreement with those derived from gas concentration geothermometers. At these locations methane, however seems to be in disequilibrium with ethane and propane. These findings imply that methane on the one hand and the C2+ hydrocarbons on the other hand often might derive from distinct sources.

  1. Stable Isotope Analysis of Chlorate

    NASA Astrophysics Data System (ADS)

    Brundrett, M.; Jackson, W. A.; Sturchio, N. C.; Bohlke, J. K.; Hatzinger, P.

    2016-12-01

    Studies have confirmed the presence of chlorate (ClO3-) throughout terrestrial and extraterrestrial systems generally in excess of perchlorate (ClO4-) [1, 2]. ClO3- occurrence, production, and post depositional transformation has significant implications to our understanding of atmospheric Cl cycling and potential biogeochemical reactions on Earth and Mars. The isotopic composition of oxyanions can be used to evaluate their production mechanisms and post-depositional alteration [3, 4]. However, no information is available on the natural isotopic composition of ClO3-. The objective of this study was to develop a method to measure the stable isotope composition (δ18O, δ17O and δ37Cl) of ClO3- and to determine the isotopic composition of ClO3- in natural desert salt accumulations that have been studied previously for NO3- and ClO4- isotopic composition. The process of ClO3- purification and analysis of δ18O, δ 17O and δ37Cl is problematic but has recently been resolved by adapting previously published methods for ClO4-. Competitive anions (e.g. NO3-, Cl-, ClO4-, and SO4-2) are removed through a series of processes including biological reduction, solid phase extraction, and anion or cation exchange. Initial results for control samples treated with the above method have a maximum variation of ± 2 ‰. These methods are being applied to representative samples to determine if various sources of natural and synthetic ClO3- have distinctive isotopic compositions, as reported previously for ClO4- [3, 4]. Establishing the range of isotopic composition of natural ClO3- also could provide information about atmospheric ClO3- production mechanisms and post-depositional processing, with implications for the atmospheric chemistry of oxychlorine compounds and the global biogeochemical cycling of Cl. [1] Jackson et al. (2015) EPSL 430, 470-476. [2] Rao et al. (2010) ES&T 44, 8429-8434. [3] Jackson et al. (2010) ES&T 44, 4869-4876. [4] Bao and Gu (2004) ES&T 38, 5073-5077.

  2. 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.

  3. Relationship between the trajectory of mid-latitude cyclones in the eastern Pacific Ocean and the isotopic composition of snowfall in the Sierra Nevada, California

    NASA Astrophysics Data System (ADS)

    Vasquez, K. T.; Sickman, J. O.; Lucero, D. M.; Heard, A. M.

    2014-12-01

    Climate change has caused a change in the Sierra Nevada snowpack and the timing of its snowmelt, threatening a valuable water resource that provides for 25 million people and 5 million hectares of irrigated land. Understanding past and future variations in the snowpack is crucial in order to plan future water management. Of particular importance would be an archive of the variability of past snowfall, which can be recorded through the isotopic records found in local paleoproxies (e.g., diatoms). We propose to quantify the relationship between sources of atmospheric moisture in the Sierra Nevada and the isotopic composition of its snowpack to uncover whether isotopic variations recorded in paloearchives are a result of the isotopic composition of the precipitation, thereby showing whether these archives could serve as a reliable source of atmospheric moisture. Preliminary analysis conducted from December 2012 to March 2013 at Sequoia National Park resulted in statistically significant correlations between the isotopic composition of the winter snowfall and storm track trajectories. It was observed that storms originating from more northern latitudes had predominantly lighter isotopes (more negative δ 2H and δ18O) and sub-tropical/tropical Pacific storms showed more positive δ 2H and δ18O. This pattern reflects the isotopic gradient of the Pacific Ocean and can prove useful when interpreting the climatic significance of the δ2H and δ18O values in analyzed proxies. While our initial investigation was promising, the winter of 2012 -2013 was abnormally dry compared to long-term averages. Before directing our investigation to known paleoproxies, we aim to determine if the correlation between storm tracks and isotopic composition of precipitation holds in years with average and above average precipitation through analysis of archived samples from calendar years 2007 - 2011 from Giant Forest in Sequoia National Park (southern sierra) and Manzanita Lake in Lassen

  4. Isotopic composition of recent shark teeth as a proxy for environmental conditions

    NASA Astrophysics Data System (ADS)

    Vennemann, T. W.; Hegner, E.; Cliff, G.; Benz, G. W.

    2001-05-01

    The O, C, and Sr isotope compositions of teeth from ten species, belonging to five families, and three orders of sharks were measured to determine the influence of habitat, diet, and possible species-specific fractionation effects on the isotopic composition of biogenic phosphate from fish. The sharks were recently caught in subtropical waters off the KwaZulu-Natal (KZN) coast of South Africa, as well as from cold waters in Prince William Sound (PWS), Alaska, and Victor Bay (VB), Nunavut, Canada. δ 18O values of tooth phosphate (δ 18O P) range from 20.9 to 23.5‰ for the KZN sharks. For most species the range in measured δ 18O P values is about 0.6‰, but it may be as high as 1.1‰ for different teeth from a single shark. Dentine and enameloid within individual teeth have no apparent differences in δ 18O P values. The δ 18O P values of the KZN shark teeth reflect the typical habitat of the studied species, primarily the thermal structure of the water column off KZN at depths between 20 and 280 m. The δ 18O P values of teeth from different Greenland sharks from VB and Pacific sleeper sharks from PWS are very homogeneous, averaging 25.8 and 24.7‰, respectively. These values appear to be in equilibrium with deep (>500 m) ocean waters in each case at temperatures of about -0.3°C or less. There is little discernable evidence for species-specific fractionation effects for the oxygen isotope composition of phosphate in the studied marine fish. The oxygen isotope composition of carbonate in apatite averages about 9.1‰ higher than corresponding δ 18O P values, in agreement with equilibrium fractionation between carbonate and phosphate, but with a large variance (1σ = ±1.5‰). δ 18O C values also vary by up to 1‰ between enameloid and dentine within single teeth, but in a non-systematic way. Differences in δ 13C values between carbonate in enameloid and dentine is also large (up to 8‰) but the δ 13C values vary systematically. Enameloid is always

  5. Atmospheric CO2 effect on stable carbon isotope composition of terrestrial fossil archives.

    PubMed

    Hare, Vincent J; Loftus, Emma; Jeffrey, Amy; Ramsey, Christopher Bronk

    2018-01-17

    The 13 C/ 12 C ratio of C 3 plant matter is thought to be controlled by the isotopic composition of atmospheric CO 2 and stomatal response to environmental conditions, particularly mean annual precipitation (MAP). The effect of CO 2 concentration on 13 C/ 12 C ratios is currently debated, yet crucial to reconstructing ancient environments and quantifying the carbon cycle. Here we compare high-resolution ice core measurements of atmospheric CO 2 with fossil plant and faunal isotope records. We show the effect of pCO 2 during the last deglaciation is stronger for gymnosperms (-1.4 ± 1.2‰) than angiosperms/fauna (-0.5 ± 1.5‰), while the contributions from changing MAP are -0.3 ± 0.6‰ and -0.4 ± 0.4‰, respectively. Previous studies have assumed that plant 13 C/ 12 C ratios are mostly determined by MAP, an assumption which is sometimes incorrect in geological time. Atmospheric effects must be taken into account when interpreting terrestrial stable carbon isotopes, with important implications for past environments and climates, and understanding plant responses to climate change.

  6. New perspectives on the Li isotopic composition of the upper continental crust and its weathering signature

    NASA Astrophysics Data System (ADS)

    Sauzéat, Lucie; Rudnick, Roberta L.; Chauvel, Catherine; Garçon, Marion; Tang, Ming

    2015-10-01

    Lithium isotopes are increasingly used to trace both present-day and past weathering processes at the surface of the Earth, and could potentially be used to evaluate the average degree of past weathering recorded by the upper continental crust (UCC). Yet the previous estimate of average δ7Li of the UCC has a rather large uncertainty, hindering the use of Li isotopes for this purpose. New δ7Li for desert and periglacial loess deposits (windblown dust) from several parts of the world (Europe, Argentina, China and Tajikistan) demonstrate that the former are more homogeneous than the latter, and may therefore serve as excellent proxies of the average composition of large tracts of the UCC. The Li isotopic compositions and concentrations of desert loess samples are controlled by eolian sorting that can be quantified by a binary mixing between a weathered, fine-grained end-member, dominated by phyllosilicates and having low δ7Li, and an unweathered, coarse-grained end-member, that is a mixture of quartz and plagioclase having higher δ7Li. We use correlations between insoluble elements (REE, Nd/Hf and Fe2O3/SiO2), Li concentrations (henceforth referred as [Li]), and δ7Li to estimate a new, more precise, average Li isotopic composition and concentration for the UCC: [ Li ] = 30.5 ± 3.6 (2 σ) ppm, and δ7Li = + 0.6 ± 0.6 (2 σ). The δ7Li for desert loess deposits is anti-correlated with the chemical index of alteration (CIA). Using this relationship, along with our average δ7Li, we infer that (1) the present-day CIA of the average UCC is 61-2+4 (2 σ), higher than the common reference value of 53, and (2) the average proportion of chemically weathered components is as high as 37-10+17 (2 σ)% at the surface of the Earth.

  7. Isotopic composition of water in a deep unsaturated zone beside a radioactive-waste disposal area near Beatty, Nevada

    USGS Publications Warehouse

    Stonestrom, David A.; Prudic, David E.; Striegl, Robert G.; Morganwalp, David W.; Buxton, Herbert T.

    1999-01-01

    The isotopic composition of water in deep unsaturated zones is of interest because it provides information relevant to hydrologic processes and contaminant migration. Profiles of oxygen-18 (18O), deuterium (D), and tritium (3H) from a 110-meter deep unsaturated zone, together with data on the isotopic composition of ground water and modern-day precipitation, are interpreted in the context of water-content, water-potential, and pore-gas profiles. At depths greater than about three meters, water vapor and liquid water are in approximate equilibrium with respect to D and 18O. The vapor-phase concentrations of D and 18O have remained stable through repeated samplings. Vapor-phase 3H concentrations have generally increased with time, requiring synchronous sampling of liquid and vapor to assess equilibrium. Below 30 meters, concentrations of D and 18O in pore water become approximately equal to the composition of ground water, which is isotopically lighter than modern precipitation and has a carbon-14 (14C) concentration of about 26 percent modern carbon. These data indicate that net gradients driving fluxes of water, gas, and heat are directed upwards for undisturbed conditions at the Amargosa Desert Research Site (ADRS). Superimposed on the upward-directed flow field, tritium is migrating away from waste in response to gradients in tritium concentrations.

  8. Isotopic anomalies - Chemical memory of Galactic evolution

    NASA Technical Reports Server (NTRS)

    Clayton, Donald D.

    1988-01-01

    New mechanisms for the chemical memory of isotopic anomalies are proposed which are based on the temporal change during the chemical evolution of the Galaxy of the isotopic composition of the mean ejecta from stars. Because of the differing temporal evolution of primary and secondary products of nucleosynthesis, the isotopic composition of the bulk interstellar medium changes approximately linearly with time, and thus any dust component having an age different from that of average dust will be isotopically anomalous. Special attention is given to C, O, Mg, Si, and isotopically heavy average-stellar condensates of SiC.

  9. 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.

  10. Influence of the balance of the intertropical front on seasonal variations of the isotopic composition in rainfall at Kisiba Masoko (Rungwe Volcanic Province, SW, Tanzania).

    PubMed

    Nivet, Fantine; Bergonzini, Laurent; Mathé, Pierre-Etienne; Noret, Aurélie; Monvoisin, Gaël; Majule, Amos; Williamson, David

    2018-08-01

    Tropical rainfall isotopic composition results from complex processes. The climatological and environmental variability in East Africa increases this complexity. Long rainfall isotope datasets are needed to fill the lack of observations in this region. At Kisiba Masoko, Tanzania, rainfall and rain isotopic composition have been monitored during 6 years. Mean year profiles allow to analyse the seasonal variations. The mean annual rainfall is 2099 mm with a rain-weighted mean composition of -3.2 ‰ for δ 18 O and -11.7 ‰ for δ 2 H. The results are consistent with available data although they present their own specificity. Thus, if the local meteoric water line is δ 2 H = 8.6 δ 18 O + 14.8, two seasonal lines are observed. The seasonality of the isotopic composition in rain and deuterium excess has been compared with precipitating air masses backtracking trajectories to characterize a simple scheme of vapour histories. The three major oceanic sources have two moisture signatures with their own trajectory histories: one originated from the tropical Indian Ocean at the beginning of the rainy season and one from the Austral Ocean at its end. The presented isotopic seasonality depends on the balance of the intertropical front and provides a useful dataset to improve the knowledge about local processes.

  11. Hydrogen and Oxygen Isotope Ratios in Body Water and Hair: Modeling Isotope Dynamics in Nonhuman Primates

    PubMed Central

    O’Grady, Shannon P.; Valenzuela, Luciano O.; Remien, Christopher H.; Enright, Lindsey E.; Jorgensen, Matthew J.; Kaplan, Jay R.; Wagner, Janice D.; Cerling, Thure E.; Ehleringer, James R.

    2012-01-01

    The stable isotopic composition of drinking water, diet, and atmospheric oxygen influence the isotopic composition of body water (2H/1H, 18O/16O expressed as δ2H and δ18O). In turn, body water influences the isotopic composition of organic matter in tissues, such as hair and teeth, which are often used to reconstruct historical dietary and movement patterns of animals and humans. Here, we used a nonhuman primate system (Macaca fascicularis) to test the robustness of two different mechanistic stable isotope models: a model to predict the δ2H and δ18O values of body water and a second model to predict the δ2H and δ18O values of hair. In contrast to previous human-based studies, use of nonhuman primates fed controlled diets allowed us to further constrain model parameter values and evaluate model predictions. Both models reliably predicted the δ2H and δ18O values of body water and of hair. Moreover, the isotope data allowed us to better quantify values for two critical variables in the models: the δ2H and δ18O values of gut water and the 18O isotope fractionation associated with a carbonyl oxygen-water interaction in the gut (αow). Our modeling efforts indicated that better predictions for body water and hair isotope values were achieved by making the isotopic composition of gut water approached that of body water. Additionally, the value of αow was 1.0164, in close agreement with the only other previously measured observation (microbial spore cell walls), suggesting robustness of this fractionation factor across different biological systems. PMID:22553163

  12. Nucleosynthetic Heterogeneity Controls Vanadium Isotope Variations in Bulk Chondrites

    NASA Technical Reports Server (NTRS)

    Nielsen, S. G.; Righter, K.; Wu, F.; Owens, J. D.; Prytulak, J.; Burton, K.; Parkinson, I.; Davis, D.

    2018-01-01

    The vanadium (V) isotope composition of early solar system materials have been hypothesized to be sensitive to high energy irradiation that originated from the young Sun. Vanadium has two isotopes with masses 50 and 51 that have (51)V/(50)V ratio of approximately 410. High energy irradiation produces (50)V from various target isotopes of Ti, Cr and Fe, which would result in light V isotope compositions (expressed as delta (51)V in per mille = 1000 x (((51)V/(50)V(sub sample)/(51)V/(50)V(sub AlfaAesar)) - 1)) relative to a presumably chondritic starting composition. Recently published V isotope data for calcium aluminium inclusions (CAIs) has revealed some very negative values relative to chondrites (by almost -4 per mille) that were indeed interpreted to reflect irradiation processes despite the fact that the studied CAIs all exhibited significant initial abundances of (10)Be, while only a few CAIs displayed light V isotope compositions. It is difficult to relate V isotope variations directly to a singular process because V only possesses two isotopes. Therefore, V isotope variations can principally be produced both mass dependent and independent processes. Mass dependent kinetic stable isotope fractionation is common in CAIs for refractory elements due to partial condensation/evaporation processes. The element strontium (Sr) has an almost identical condensation temperature to V and studies of stable Sr isotope compositions in CAIs reveal both heavy and light values relative to chondrites of several permil. These variations are similar in magnitude to those reported for V isotopes in CAIs, which suggests it is possible that some of the V isotope variation in CAIs could be due to kinetic stable isotope fractionation during condensation/evaporation processes.

  13. Isotopic composition of sulfate accumulations, Northern Calcareous Alps, Austria

    NASA Astrophysics Data System (ADS)

    Bojar, Ana-Voica; Halas, Stanislaw; Bojar, Hans-Peter; Trembaczowski, Andrzej

    2015-04-01

    The Eastern Alps are characterised by the presence of three main tectonic units, such as the Lower, Middle and Upper Austroalpine, which overlie the Penninicum (Tollmann, 1977). The Upper Austroalpine unit consists of the Northern Calcareous Alps (NCA) overlying the Greywacke zone and corresponding to the Graz Paleozoic, Murau Paleozoic and the Gurktal Nappe. Evaporitic rocks are lacking in the later ones. The Northern Calcareous Alps are a detached fold and thrust belt. The sedimentation started in the Late Carboniferous or Early Permian, the age of the youngest sediments being Eocene. The NCA are divided into the Bajuvaric, Tirolic and Juvavic nappe complexes. The evaporitic Haselgebirge Formation occurs in connection with the Juvavic nappe complex at the base of the Tirolic units (Leitner et al., 2013). The Haselgebirge Formation consists mainly of salt, shales, gypsum and anhydrite and includes the oldest sediments of the NCA. The age of the Haselgebirge Formation, established by using spors and geochronological data, is Permian to Lower Triassic. For the Northern Calcareous Alps, the mineralogy of sulphate accumulations consists mainly of gypsum and anhydrite and subordonates of carbonates. The carbonates as magnesite, dolomite and calcite can be found either as singular crystals or as small accumulations within the hosting gypsum. Sulfides (sphalerite, galena, pyrite), sulfarsenides (enargite, baumhauerite) and native sulphur enrichments are known from several deposits (Kirchner, 1987; Postl, 1990). The investigated samples were selected from various gypsum and halite rich deposits of the Northern Calcareous Alps. A total of over 20 samples were investigated, and both oxygen and sulfur isotopic composition were determined for anhydrite, gyps, polyhalite, blödite and langbeinite. The sulfur isotopic values vary between 10.1 to 14 ‰ (CDT), with three values higher than 14 ‰. The Oxygen isotopic values show a range from 9 to 23 ‰ (SMOW). The sulfur

  14. Application of stable isotope (δ13C and δ18O) composition of mollusc shells in palaeolimnological studies - possibilities and limitations

    NASA Astrophysics Data System (ADS)

    Apolinarska, Karina; Pełechaty, Mariusz; Kossler, Annette; Pronin, Eugeniusz; Noskowiak, Daria

    2017-04-01

    Carbon (δ13C) and oxygen (δ18O) stable isotope analyses are among the standard methods applied in the studies of past environment, including climate. In lacustrine sediments, δ13C and δ18O values can be measured in fine carbonate fraction (carbonate mud), in charophyte encrustations, ostracod carapaces and mollusc shells. Application of the stable isotope record of each of the above-mentioned components of the lake sediment requires knowledge about possibilities and limitations of the method. The present research discusses the most important results of the studies carried out between 2011 and 2013, concentrated on the stable isotope composition of snail shells, primarily, the species commonly preserved in central European Quaternary lacustrine sediments. The stable isotope studies involved also, the zebra mussel (Dreissena polymorpha), one of the most invasive freshwater species in the world. The research involved shell isotope studies of both recent (Apolinarska, 2013; Apolinarska et al., 2016; Apolinarska and Pełechaty, in press) and fossil molluscs derived from the Holocene sediments (Apolinarska et al., 2015a, b). Shell δ13C values were species-specific and among the gastropods studied the same order of species from the most to the least 13C-depleted was observed at all sites sampled. Shell δ18O values were more uniform. The wide range of δ13C and δ18O values were observed in population and subpopulation, i.e. when live snails were sampled live from restricted area within the lake littoral zone. Carbon and oxygen stable isotope values of the mono-specific shells sampled from 1 cm thick sediment samples were highly variable. Those intra-specific differences (n=20) were as large as several permill. Such significant variability in δ13C and δ18O values indicates that stable isotope composition of single shells is unlikely to be representative of the sediment sample. In conclusion, samples of freshwater molluscs for stable isotope analyses should be

  15. NanoSIMS Determination of Carbon and Oxygen Isotopic Compositions of Presolar Graphites from the Murchison Meteorite

    NASA Technical Reports Server (NTRS)

    Stadermann, F. J.; Croat, T. K.; Bernatowicz, T.

    2004-01-01

    Graphite from the Murchison density separate KFC1 (2.15 - 2.20 g/cu cm) has previously been studied by combined SEM/EDX and ion microprobe analysis. These studies found several distinct morphological types of graphites and C isotopic compositions that vary over more than 3 orders of magnitude, clearly establishing their presolar origin. Subsequent TEM measurements of a subset of these particles found abundant embedded crystals of metal (Zr, Mo, Ti, Ru) carbides which were incorporated during the growth of the graphites. A new TEM study of a large set of KFC1 graphites led to the discovery of another type of presolar material, Ru-Fe metal. Here we report results of the C and O isotopic measurements in the same graphite sections, which makes it possible for the first time to directly correlate isotopic and TEM data of KFC1 grains.

  16. Compound Specific Hydrogen Isotope Composition of Type II and III Kerogen Extracted by Pyrolysis-GC-MS-IRMS

    NASA Technical Reports Server (NTRS)

    Socki, Richard A.; Pernia, Denet; Evans, Michael; Fu, Qi; Bissada, Kadry K.; Curiale, Joseph A.; Niles, Paul B.

    2013-01-01

    The use of Hydrogen (H) isotopes in understanding oil and gas resource plays is in its infancy. Described here is a technique for H isotope analysis of organic compounds pyrolyzed from oil and gas shale-derived kerogen. Application of this technique will progress our understanding. This work complements that of Pernia et al. (2013, this meeting) by providing a novel method for the H isotope analysis of specific compounds in the characterization of kerogen extracted by analytically diverse techniques. Hydrogen isotope analyses were carried out entirely "on-line" utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC Ultra interfaced with a Thermo MAT 253 IRMS. Also, a split of GC-separated products was sent to a DSQ II quadrupole MS to make semi-quantitative compositional measurements of the extracted compounds. Kerogen samples from five different basins (type II and III) were dehydrated (heated to 80 C overnight in vacuum) and analyzed for their H isotope compositions by Pyrolysis-GC-MS-TC-IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C) which quantitatively forms H2, following a modified method of Burgoyne and Hayes, (1998, Anal. Chem., 70, 5136-5141). Samples ranging from approximately 0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. Compounds were separated on a Poraplot Q GC column. Hydrogen isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight compounds. Water (H2O) average deltaD = -215.2 (V-SMOW), ranging from -271.8 for the Marcellus Shale to -51.9 for the Polish Shale. Higher molecular weight compounds like toluene (C7H8) have an average deltaD of -89.7 0/00, ranging from -156.0 for the Barnett Shale to -50.0 for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during formation within each basin. Since hydrocarbon H isotopes

  17. Deciphering the iron isotope message of the human body

    NASA Astrophysics Data System (ADS)

    Walczyk, Thomas; von Blanckenburg, Friedhelm

    2005-04-01

    Mass-dependent variations in isotopic composition are known since decades for the light elements such as hydrogen, carbon or oxygen. Multicollector-inductively coupled plasma mass spectrometry (MC-ICP-MS) and double-spike thermal ionization mass spectrometry (TIMS) permit us now to resolve small variations in isotopic composition even for the heavier elements such as iron. Recent studies on the iron isotopic composition of human blood and dietary iron sources have shown that lighter iron isotopes are enriched along the food chain and that each individual bears a certain iron isotopic signature in blood. To make use of this finding in biomedical research, underlying mechanisms of isotope fractionation by the human body need to be understood. In this paper available iron isotope data for biological samples are discussed within the context of isotope fractionation concepts and fundamental aspects of human iron metabolism. This includes evaluation of new data for body tissues which show that blood and muscle tissue have a similar iron isotopic composition while heavier iron isotopes are concentrated in the liver. This new observation is in agreement with our earlier hypothesis of a preferential absorption of lighter iron isotopes by the human body. Possible mechanisms for inducing an iron isotope effect at the cellular and molecular level during iron uptake are presented and the potential of iron isotope effects in human blood as a long-term measure of dietary iron absorption is discussed.

  18. Distinct 238U/235U ratios and REE patterns in plutonic and volcanic angrites: Geochronologic implications and evidence for U isotope fractionation during magmatic processes

    NASA Astrophysics Data System (ADS)

    Tissot, François L. H.; Dauphas, Nicolas; Grove, Timothy L.

    2017-09-01

    Angrites are differentiated meteorites that formed between 4 and 11 Myr after Solar System formation, when several short-lived nuclides (e.g., 26Al-26Mg, 53Mn-53Cr, 182Hf-182W) were still alive. As such, angrites are prime anchors to tie the relative chronology inferred from these short-lived radionuclides to the absolute Pb-Pb clock. The discovery of variable U isotopic composition (at the sub-permil level) calls for a revision of Pb-Pb ages calculated using an ;assumed; constant 238U/235U ratio (i.e., Pb-Pb ages published before 2009-2010). In this paper, we report high-precision U isotope measurement for six angrite samples (NWA 4590, NWA 4801, NWA 6291, Angra dos Reis, D'Orbigny, and Sahara 99555) using multi-collector inductively coupled plasma mass-spectrometry and the IRMM-3636 U double-spike. The age corrections range from -0.17 to -1.20 Myr depending on the samples. After correction, concordance between the revised Pb-Pb and Hf-W and Mn-Cr ages of plutonic and quenched angrites is good, and the initial (53Mn/55Mn)0 ratio in the Early Solar System (ESS) is recalculated as being (7 ± 1) × 10-6 at the formation of the Solar System (the error bar incorporates uncertainty in the absolute age of Calcium, Aluminum-rich inclusions - CAIs). An uncertainty remains as to whether the Al-Mg and Pb-Pb systems agree in large part due to uncertainties in the Pb-Pb age of CAIs. A systematic difference is found in the U isotopic compositions of quenched and plutonic angrites of +0.17‰. A difference is also found between the rare earth element (REE) patterns of these two angrite subgroups. The δ238U values are consistent with fractionation during magmatic evolution of the angrite parent melt. Stable U isotope fractionation due to a change in the coordination environment of U during incorporation into pyroxene could be responsible for such a fractionation. In this context, Pb-Pb ages derived from pyroxenes fraction should be corrected using the U isotope composition

  19. Multiple stable isotope fronts during non-isothermal fluid flow

    NASA Astrophysics Data System (ADS)

    Fekete, Szandra; Weis, Philipp; Scott, Samuel; Driesner, Thomas

    2018-02-01

    Stable isotope signatures of oxygen, hydrogen and other elements in minerals from hydrothermal veins and metasomatized host rocks are widely used to investigate fluid sources and paths. Previous theoretical studies mostly focused on analyzing stable isotope fronts developing during single-phase, isothermal fluid flow. In this study, numerical simulations were performed to assess how temperature changes, transport phenomena, kinetic vs. equilibrium isotope exchange, and isotopic source signals determine mineral oxygen isotopic compositions during fluid-rock interaction. The simulations focus on one-dimensional scenarios, with non-isothermal single- and two-phase fluid flow, and include the effects of quartz precipitation and dissolution. If isotope exchange between fluid and mineral is fast, a previously unrecognized, significant enrichment in heavy oxygen isotopes of fluids and minerals occurs at the thermal front. The maximum enrichment depends on the initial isotopic composition of fluid and mineral, the fluid-rock ratio and the maximum change in temperature, but is independent of the isotopic composition of the incoming fluid. This thermally induced isotope front propagates faster than the signal related to the initial isotopic composition of the incoming fluid, which forms a trailing front behind the zone of transient heavy oxygen isotope enrichment. Temperature-dependent kinetic rates of isotope exchange between fluid and rock strongly influence the degree of enrichment at the thermal front. In systems where initial isotope values of fluids and rocks are far from equilibrium and isotope fractionation is controlled by kinetics, the temperature increase accelerates the approach of the fluid to equilibrium conditions with the host rock. Consequently, the increase at the thermal front can be less dominant and can even generate fluid values below the initial isotopic composition of the input fluid. As kinetics limit the degree of isotope exchange, a third front may

  20. 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.

  1. An evaporite-based high-resolution sulfur isotope record of Late Permian and Triassic seawater sulfate

    NASA Astrophysics Data System (ADS)

    Bernasconi, Stefano M.; Meier, Irene; Wohlwend, Stephan; Brack, Peter; Hochuli, Peter A.; Bläsi, Hansruedi; Wortmann, Ulrich G.; Ramseyer, Karl

    2017-05-01

    Variations in the sulfur isotope composition of dissolved marine sulfate through time reflect changes in the global sulfur cycle and are intimately related to changes in the carbon and oxygen cycles. A large shift in the sulfur isotope composition of sulfate at the Permian/Triassic boundary has been recognized for long time and a number of studies were carried out to understand the causes and significance of this shift. However, data for the Middle and Late Triassic are very sparse and the stratigraphic evolution of the sulfur isotope composition of seawater is poorly constrained due to the small number of samples analyzed and/or due to the limited stratigraphic intervals studied. Moreover, in the last few years the Triassic timescale has significantly changed due to a wealth of new radiometric and stratigraphic data. In this study we show that for the Late Permian and the Triassic it is possible to obtain a precise reconstruction of the evolution of the sulfur cycle, for parts of it at sub-million year resolution, by analyzing exclusively gypsum and anhydrite deposits. We base our reconstruction on new data from the Middle and Late Triassic evaporites of Northern Switzerland and literature data from evaporites from Germany, Austria, Italy and the Middle East. We propose a revised correlation between the well-dated marine Tethyan sections in northern Italy and the evaporites from Northern Switzerland and from the Germanic Basin calibrated to the newest radiometric absolute age scale. This new correlation allows for a precise dating of the evaporites and constructing a composite sulfur isotope evolution of seawater sulfate from the latest Permian (Lopingian Epoch) to the Norian. We show that a rapid positive shift of approximately 24‰ at the Permian-Triassic boundary can be used to constrain seawater sulfate concentrations in the range of 2-6 mM, thus higher than previous estimates but with less rapid changes. Finally, we discuss two possible evolution scenarios

  2. Modes of planetary-scale Fe isotope fractionation

    NASA Astrophysics Data System (ADS)

    Schoenberg, Ronny; von Blanckenburg, Friedhelm

    2006-12-01

    A comprehensive set of high-precision Fe isotope data for the principle meteorite types and silicate reservoirs of the Earth is used to investigate iron isotope fractionation at inter- and intra-planetary scales. 14 chondrite analyses yield a homogeneous Fe isotope composition with an average δ56Fe/ 54Fe value of - 0.015 ± 0.020‰ (2 SE) relative to the international iron standard IRMM-014. Eight non-cumulate and polymict eucrite meteorites that sample the silicate portion of the HED (howardite-eucrite-diogenite) parent body yield an average δ56Fe/ 54Fe value of - 0.001 ± 0.017‰, indistinguishable to the chondritic Fe isotope composition. Fe isotope ratios that are indistinguishable to the chondritic value have also been published for SNC meteorites. This inner-solar system homogeneity in Fe isotopes suggests that planetary accretion itself did not significantly fractionate iron. Nine mantle xenoliths yield a 2 σ envelope of - 0.13‰ to + 0.09‰ in δ56Fe/ 54Fe. Using this range as proxy for the bulk silicate Earth in a mass balance model places the Fe isotope composition of the outer liquid core that contains ca. 83% of Earth's total iron to within ± 0.020‰ of the chondritic δ56Fe/ 54Fe value. These calculations allow to interprete magmatic iron meteorites ( δ56Fe/ 54Fe = + 0.047 ± 0.016‰; N = 8) to be representative for the Earth's inner metallic core. Eight terrestrial basalt samples yield a homogeneous Fe isotope composition with an average δ56Fe/ 54Fe value of + 0.072 ± 0.016‰. The observation that terrestrial basalts appear to be slightly heavier than mantle xenoliths and that thus partial mantle melting preferentially transfers heavy iron into the melt [S. Weyer, A.D. Anbar, G.P. Brey, C. Munker, K. Mezger and A.B. Woodland, Iron isotope fractionation during planetary differentiation, Earth and Planetary Science Letters 240(2), 251-264, 2005.] is intriguing, but also raises some important questions: first it is questionable whether the

  3. Determination of the total oxygen isotopic composition of nitrate and the calibration of a Δ17Ο nitrate reference material

    USGS Publications Warehouse

    Michalski, Greg; Savarino, Joel; Böhlke, J.K.; Thiemens , Mark

    2002-01-01

    A thermal decomposition method was developed and tested for the simultaneous determination of δ18O and δ17Ο in nitrate. The thermal decomposition of AgNO3 allows for the rapid and accurate determination of 18O/16O and 17O/16O isotopic ratios with a precision of ±1.5‰ for δ18O and ±0.11‰ for Δ17Ο (Δ17Ο = δ17Ο − 0.52 × δ18O). The international nitrate isotope reference material IAEA-NO3 yielded a δ18O value of +23.6‰ and Δ17Ο of −0.2‰, consistent with normal terrestrial mass-dependent isotopic ratios. In contrast, a large sample of NaNO3 from the Atacama Desert, Chile, was found to have Δ17Ο = 21.56 ± 0.11‰ and δ18O = 54.9 ± 1.5‰, demonstrating a substantial mass-independent isotopic composition consistent with the proposed atmospheric origin of the desert nitrate. It is suggested that this sample (designated USGS-35) can be used to generate other gases (CO2, CO, N2O, O2) with the same Δ17Ο to serve as measurement references for a variety of applications involving mass-independent isotopic compositions in environmental studies.

  4. Climate in the Great Lakes Region between 14,000 and 4000 years ago from isotopic composition of conifer wood

    Treesearch

    Steven W. Leavitt; Irina P. Panyushkina; Todd Lange; Alex Wiedenhoeft; Li Cheng; R. Douglas Hunter; John Hughes; Frank Pranschke; Allan F. Schneider; Joseph Moran; Ron Stieglitz

    2006-01-01

    The isotopic composition of ancient wood has the potential to provide information about past environments. We analyzed the ä13C, ä18O, and ä2H of cellulose of conifer trees from several cross-sections at each of 9 sites around the Great Lakes region ranging from ~4000 to 14,000 cal BP. Isotopic values of Picea, Pinus, and Thuja species seem inter-changeable for ä18O...

  5. Argon isotopic composition of Archaean atmosphere probes early Earth geodynamics.

    PubMed

    Pujol, Magali; Marty, Bernard; Burgess, Ray; Turner, Grenville; Philippot, Pascal

    2013-06-06

    Understanding the growth rate of the continental crust through time is a fundamental issue in Earth sciences. The isotopic signatures of noble gases in the silicate Earth (mantle, crust) and in the atmosphere afford exceptional insight into the evolution through time of these geochemical reservoirs. However, no data for the compositions of these reservoirs exists for the distant past, and temporal exchange rates between Earth's interior and its surface are severely under-constrained owing to a lack of samples preserving the original signature of the atmosphere at the time of their formation. Here, we report the analysis of argon in Archaean (3.5-billion-year-old) hydrothermal quartz. Noble gases are hosted in primary fluid inclusions containing a mixture of Archaean freshwater and hydrothermal fluid. Our analysis reveals Archaean atmospheric argon with a (40)Ar/(36)Ar value of 143 ± 24, lower than the present-day value of 298.6 (for which (40)Ar has been produced by the radioactive decay of the potassium isotope (40)K, with a half-life of 1.25 billion years; (36)Ar is primordial in origin). This ratio is consistent with an early development of the felsic crust, which might have had an important role in climate variability during the first half of Earth's history.

  6. Uncovering trophic positions and food resources of soil animals using bulk natural stable isotope composition.

    PubMed

    Potapov, Anton M; Tiunov, Alexei V; Scheu, Stefan

    2018-06-19

    Despite the major importance of soil biota in nutrient and energy fluxes, interactions in soil food webs are poorly understood. Here we provide an overview of recent advances in uncovering the trophic structure of soil food webs using natural variations in stable isotope ratios. We discuss approaches of application, normalization and interpretation of stable isotope ratios along with methodological pitfalls. Analysis of published data from temperate forest ecosystems is used to outline emerging concepts and perspectives in soil food web research. In contrast to aboveground and aquatic food webs, trophic fractionation at the basal level of detrital food webs is large for carbon and small for nitrogen stable isotopes. Virtually all soil animals are enriched in 13 C as compared to plant litter. This 'detrital shift' likely reflects preferential uptake of 13 C-enriched microbial biomass and underlines the importance of microorganisms, in contrast to dead plant material, as a major food resource for the soil animal community. Soil organic matter is enriched in 15 N and 13 C relative to leaf litter. Decomposers inhabiting mineral soil layers therefore might be enriched in 15 N resulting in overlap in isotope ratios between soil-dwelling detritivores and litter-dwelling predators. By contrast, 13 C content varies little between detritivores in upper litter and in mineral soil, suggesting that they rely on similar basal resources, i.e. little decomposed organic matter. Comparing vertical isotope gradients in animals and in basal resources can be a valuable tool to assess trophic interactions and dynamics of organic matter in soil. As indicated by stable isotope composition, direct feeding on living plant material as well as on mycorrhizal fungi is likely rare among soil invertebrates. Plant carbon is taken up predominantly by saprotrophic microorganisms and channelled to higher trophic levels of the soil food web. However, feeding on photoautotrophic microorganisms and non

  7. High Precision Iron Isotope Compositions in Components From the Allende CV3 Meteorite by MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Mullane, E.; Russell, S. S.; Weiss, D.; Mason, T. F.; Gounelle, M.

    2001-12-01

    Four chondrules and one matrix sample of Allende were examined for Fe-isotope frac-tionation, using multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS). Iron is the most volatile major constituent of chondrules and a recent study [1] suggested that solar system Fe was initially isotopically homogeneous. Thus, any isotopic variation is likely due to mass fractionation during nebular process-ing. The chondrule samples were split. One portion was subject to a standard acid dis-solution whilst the other was polished, ena-bling textural and compositional characteri-zation. Fe, Cu and Zn are separated from the remaining matrix elements [2], removing potential interfering ions from the solution. 100 % elemental recovery (within error) is achieved, ensuring that chromatographic fractionation does not occur [2]. Hydrogen is bled into the collision cell, minimising Ar polyatomic species interferences. Typical precisions of 0.1‰ (2σ ) for 54Fe/56Fe ratios are achieved for 75 replicates. Instrumental mass bias is assessed using (1) sample-standard brack-eting and (2) doping with Cu. A variation of 0.8‰ /amu is observed, which is approximately 18 times the analyti-cal uncertainty at the 2σ level. Our high precision data show that: (1) Allende chondrules and matrix exhibit clear isotopic variation in iron. (2) δ 54Fe val-ues appear to be correlated to the bulk FeO content, with the more iron rich samples enriched in the lighter 54Fe isotope. (3) δ 54Fe values appear to be unre-lated to texture, and consequently to the temperature of chondrule formation. Bulk Fe-content may be a proxy for the amount of volatilisation experienced, and volatilisation of Fe in chondrule precursor material has resulted in a residue of the heavier Fe isotopes. Chondrules are known to have often experienced several heating events, and their texture primarily reflects the nature of the last event. Thus, the lack of correlation between the δ 54Fe value and chondrule texture

  8. Evaluating the influence of chemical weathering on the composition of the continental crust using lithium and its isotopes

    NASA Astrophysics Data System (ADS)

    Rudnick, R. L.; Liu, X.

    2011-12-01

    The continental crust has an "intermediate" bulk composition that is distinct from primary melts of peridotitic mantle (basalt or picrite). This mismatch between the "building blocks" and the "edifice" of the continental crust points to the operation of processes that preferentially remove mafic to ultramafic material from the continents. Such processes include lower crustal recycling (via density foundering or lower crustal subduction - e.g., relamination, Hacker et al., 2011, EPSL), generation of evolved melts via slab melting, and/or chemical weathering. Stable isotope systems document the influence of chemical weathering on the bulk crust composition: the oxygen isotope composition of the bulk crust is distinctly heavier than that of primary, mantle-derived melts (Simon and Lecuyer, 2005, G-cubed) and the Li isotopic composition of the bulk crust is distinctly lighter than that of mantle-derive melts (Teng et al., 2004, GCA; 2008, Chem. Geol.). Both signatures mark the imprint of chemical weathering on the bulk crust composition. Here, we use a simple mass balance model for lithium inputs and outputs from the continental crust to quantify the mass lost due to chemical weathering. We find that a minimum of 15%, a maximum of 60%, and a best estimate of ~40% of the original juvenile rock mass may have been lost via chemical weathering. The accumulated percentage of mass loss due to chemical weathering leads to an average global chemical weathering rate (CWR) of ~ 8×10^9 to 2×10^10 t/yr since 3.5 Ga, which is about an order of magnitude higher than the minimum estimates based on modern rivers (Gaillardet et al., 1999, Chem. Geol.). While we cannot constrain the exact portion of crustal mass loss via chemical weathering, given the uncertainties of the calculation, we can demonstrate that the weathering flux is non-zero. Therefore, chemical weathering must play a role in the evolution of the composition and mass of the continental crust.

  9. The isotopic composition and concentration of Ag in iron meteorites and the origin of exotic silver

    NASA Technical Reports Server (NTRS)

    Kaiser, T.; Wasserburg, G. J.

    1983-01-01

    The isotopic composition of Ag and the concentration of Ag and Pd in Canyon Diablo (IA), Grant (IIIB), Santa Clara, Tlacotepec and Warburton Range (IVB), Pinon and Deep Springs (anom) were analyzed. Troilite from Santa Clara and from Grant was also studied. With the exception of IA, all the meteorites were enriched in Ag-107 by about 2%-212% and the ratio of Ag-107/Ag-109 in the metal phase was found to be greater than the terrestrial value. Ag of anomalous isotopic composition was found to be common in all IVB and anomalous meteorites. A correlation of Ag-107/Ag-109 with Pd/Ag was established except for the iron meteorite of Santa Clara. The excess Ag-107 is thought to result from the decay of Pd-107. The Grant data appear to represent a Pd-107-Ag-107 isochron and indicate that the cooling rate at elevated temperatures was rapid enough to preserve the isotopic differences between metal and troilite. The data suggest that Ag in Santa Clara is made up of almost pure Ag-107 produced from Pd-107 decay and Ag-109 produced by nuclear reactions with only a small amount of 'normal' Ag. This indicates an intense energetic particle bombardment history in the early solar system which occurred after the formation of small planetary bodies.

  10. Tracing of ca 800 yr old mining activity in peat bog using Pb elemental concentrations and isotope compositions.

    NASA Astrophysics Data System (ADS)

    Baron, S.; Carignan, J.; Ploquin, A.

    2003-04-01

    Sixty sites of slags have been documented on the Mont-Lozère in southern France. The petrographic analysis shows that slags are metallurgical wastes (800 to 850 yr BP) which certainly result from smelting activity for lead and silver extraction (Ploquin et al., 2001). The aims of this study are: 1) to trace the source of Pb ores which supplied the smelting sites, by using the Pb isotopic composition of several surrounding Pb deposits, 2) to evaluate the actual pollution caused by these slags, by using elemental and isotopic compositions of soils, water and vegetation, and 3) to document the pollution history of the region, by using elemental and isotopic compositions of peat bog cores collected in the neighbourhood of the historical smelting sites. The lead isotopic composition of galena collected in most surrounding ores is very similar to that of different slag samples. On the other hand, the high precision of the results allowed us to select the mineralised areas which were probably the ore sources. The Pb isotopic composition of slags is even more homogeneous: 208/206 Pb: 2.092±0.002; 206/207 Pb: 1.179±0.001; 208/204 Pb: 38.663±0.025; 207/204 Pb: 15.665±0.006; 206/204 Pb: 18.476±0.023, and will allow source tracing in the environment. The "Narses Mortes" peat bog, around which two smelting sites have been reported, is strongly minerotrophic and contains 8 to 60% ash. A 1.40 m core have been retrieved and divided into 58 individual samples. Minerotrophic peat bog records both atmospheric deposition, soils leaching and the grounwater influence. The measured metal concentrations are normalised to Al contents of peat bog samples and the metal/Al ratios are compared to that of the Mont-Lozère granite: relative excess in metal concentrations are found in peat bog samples. An increasing excess of most metals (Pb, Zn, Cd...) was measured for surface samples, from 55 cm depth to the top of the core (23 cm depth). This profil might be attributed to atmospheric

  11. The role of soil biogeochemistry in wine taste: Soil factors influencing grape elemental composition, photosynthetic biomarkers and Cu/Zn isotopic signature of Vitis vinifera

    NASA Astrophysics Data System (ADS)

    Blotevogel, Simon; Oliva, Priscia; Darrozes, José; Viers, Jérôme; Audry, Stéphane; Courjault-Radé, Pierre; Orgogozo, Laurent; Le Guedard, Marina; Schreck, Eva

    2015-04-01

    Understanding the influence of soil composition in wine taste is of great economic and environmental interest in France and around the world. Nevertheless the impact of soil composition on wine taste is still controversially discussed. Since inorganic soil components do not have a proper taste and do not enter the plant anyway, their influence needs to be induced by nutrient absorption and its impact on plant functioning and grape composition. Indeed recent development of geological tracers of origin proof the existence of soil chemical and isotopic signatures in wine. However, type and scale of the impact of soil composition on wine taste are not well understood yet, and little experimental evidence exists due to the complexity of mechanisms involved. Thus, to provide evidence for the impact of soil composition on grape composition and potentially wine taste, we studied soil and plant material from two relevant vineyards (Soave, Italia). On those two directly adjacent vineyards, two different wines are produced with the same plant material and cultivation techniques. The vineyards only differ by their underlying bedrock - limestone versus basaltic rock - and thus present suitable conditions for investigating the impact of soil composition on grapes and wine. Pedological and mineralogical parameters were analyzed for the two vineyards whereas chemical extractions (citrate, CaCl2) were performed to determine nutrient bioavailability in both soils. Elemental compositions were determined by ICP-MS analyses in different compartments (soils, vine leaves and grapes). Isotopic fractionation of Cu and Zn was investigated in various samples as source tracers and in order to better understand fractionation mechanisms involved. Finally, plant health was studied using the Omega-3 biomarker which determines the fatty acid composition in vine leaves, directly involved in photosynthetic processes. Results show that the vineyards are characterized by two different soil types due

  12. Measurement of the oxygen isotopic composition of nitrate in seawater and freshwater using the denitrifier method

    USGS Publications Warehouse

    Casciotti, K.L.; Sigman, D.M.; Hastings, M. Galanter; Böhlke, J.K.; Hilkert, A.

    2002-01-01

    We report a novel method for measurement of the oxygen isotopic composition (18O/16O) of nitrate (NO3-) from both seawater and freshwater. The denitrifier method, based on the isotope ratio analysis of nitrous oxide generated from sample nitrate by cultured denitrifying bacteria, has been described elsewhere for its use in nitrogen isotope ratio (15N/14N) analysis of nitrate.1Here, we address the additional issues associated with 18O/16O analysis of nitrate by this approach, which include (1) the oxygen isotopic difference between the nitrate sample and the N2O analyte due to isotopic fractionation associated with the loss of oxygen atoms from nitrate and (2) the exchange of oxygen atoms with water during the conversion of nitrate to N2O. Experiments with 18O-labeled water indicate that water exchange contributes less than 10%, and frequently less than 3%, of the oxygen atoms in the N2O product for Pseudomonas aureofaciens. In addition, both oxygen isotope fractionation and oxygen atom exchange are consistent within a given batch of analyses. The analysis of appropriate isotopic reference materials can thus be used to correct the measured 18O/16O ratios of samples for both effects. This is the first method tested for 18O/16O analysis of nitrate in seawater. Benefits of this method, relative to published freshwater methods, include higher sensitivity (tested down to 10 nmol and 1 μM NO3-), lack of interference by other solutes, and ease of sample preparation.

  13. A comparison of chemical compositions of reported altered oceanic crusts and global MORB data set: implication for isotopic heterogeneity of recycled materials

    NASA Astrophysics Data System (ADS)

    Shimoda, G.; Kogiso, T.

    2017-12-01

    Chemical composition of altered oceanic crust is one of important constraints to delineate chemical heterogeneity of the mantle. Accordingly, many researchers have been studied to determine bulk chemical composition of altered oceanic crust mainly based on chemical compositions of old oceanic crusts at Site 801 and Site 417/418, and young crust at Site 504 (e.g., Staudigel et al., 1996; Bach et al. 2003; Kuo et al., 2016). Their careful estimation provided reliable bulk chemical compositions of these Sites and revealed common geochemical feature of alteration. To assess effect of recycling of altered oceanic crust on chemical evolution of the mantle, it might be meaningful to discuss whether the reported chemical compositions of altered oceanic crusts can represent chemical composition of globally subducted oceanic crusts. Reported chemical compositions of fresh glass or less altered samples from Site 801, 417/418 and 504 were highly depleted compared to that of global MORB reported by Gale et al. (2013), suggesting that there might be sampling bias. Hence, it could be important to consider chemical difference between oceanic crusts of these three Sites and global MORB to discuss effect of recycling of oceanic crust on isotopic heterogeneity of the mantle. It has been suggested that one of controlling factors of chemical variation of oceanic crust is crustal spreading rate because different degree of partial melting affects chemical composition of magmas produced at a mid-ocean ridge. Crustal spreading rate could also affect intensity of alteration. Namely, oceanic crusts produced at slow-spreading ridges may prone to be altered due to existence of larger displacement faults compared to fast spreading ridges which have relatively smooth topography. Thus, it might be significant to evaluate isotopic evolution of oceanic crusts those were produced at different spreading rates. In this presentation, we will provide a possible chemical variation of altered oceanic

  14. Isotope Geochemistry for Comparative Planetology of Exoplanets

    NASA Technical Reports Server (NTRS)

    Mandt, K. E.; Atreya, S.; Luspay-Kuti, A.; Mousis, O.; Simon, A.; Hofstadter, M. D.

    2017-01-01

    Isotope geochemistry has played a critical role in understanding processes at work in and the history of solar system bodies. Application of these techniques to exoplanets would be revolutionary and would allow comparative planetology with the formation and evolution of exoplanet systems. The roadmap for comparative planetology of the origins and workings of exoplanets involves isotopic geochemistry efforts in three areas: (1) technology development to expand observations of the isotopic composition of solar system bodies and expand observations to isotopic composition of exoplanet atmospheres; (2) theoretical modeling of how isotopes fractionate and the role they play in evolution of exoplanetary systems, atmospheres, surfaces and interiors; and (3) laboratory studies to constrain isotopic fractionation due to processes at work throughout the solar system.

  15. Seasonal and ENSO Influences on the Stable Isotopic Composition of Galápagos Precipitation

    NASA Astrophysics Data System (ADS)

    Martin, N. J.; Conroy, J. L.; Noone, D.; Cobb, K. M.; Konecky, B. L.; Rea, S.

    2018-01-01

    The origin of stable isotopic variability in precipitation over time and space is critical to the interpretation of stable isotope-based paleoclimate proxies. In the eastern equatorial Pacific, modern stable isotope measurements in precipitation (δ18Op and δDp) are sparse and largely unevaluated in the literature, although insights from such analyses would benefit the interpretations of several regional isotope-based paleoclimate records. Here we present a new 3.5 year record of daily-resolved δ18Op and δDp from Santa Cruz, Galápagos. With a prior 13 year record of monthly δ18Op and δDp from the island, these new data reveal controls on the stable isotopic composition of regional precipitation on event to interannual time scales. Overall, we find Galápagos δ18Op is significantly correlated with precipitation amount on daily and monthly time scales. The majority of Galápagos rain events are drizzle, or garúa, derived from local marine boundary layer vapor, with corresponding high δ18Op values due to the local source and increased evaporation and equilibration of smaller drops with boundary layer vapor. On monthly time scales, only precipitation in very strong, warm season El Niño months has substantially lower δ18Op values, as the sea surface temperature threshold for deep convection (28°C) is only surpassed at these times. The 2015/2016 El Niño event did not produce strong precipitation or δ18Op anomalies due to the short period of warm SST anomalies, which did not extend into the peak of the warm season. Eastern Pacific proxy isotope records may be biased toward periods of high rainfall during strong to very strong El Niño events.

  16. Hydrogen and oxygen isotope ratios in body water and hair: modeling isotope dynamics in nonhuman primates.

    PubMed

    O'Grady, Shannon P; Valenzuela, Luciano O; Remien, Christopher H; Enright, Lindsey E; Jorgensen, Matthew J; Kaplan, Jay R; Wagner, Janice D; Cerling, Thure E; Ehleringer, James R

    2012-07-01

    The stable isotopic composition of drinking water, diet, and atmospheric oxygen influence the isotopic composition of body water ((2)H/(1)H, (18)O/(16)O expressed as δ(2) H and δ(18)O). In turn, body water influences the isotopic composition of organic matter in tissues, such as hair and teeth, which are often used to reconstruct historical dietary and movement patterns of animals and humans. Here, we used a nonhuman primate system (Macaca fascicularis) to test the robustness of two different mechanistic stable isotope models: a model to predict the δ(2)H and δ(18)O values of body water and a second model to predict the δ(2)H and δ(18)O values of hair. In contrast to previous human-based studies, use of nonhuman primates fed controlled diets allowed us to further constrain model parameter values and evaluate model predictions. Both models reliably predicted the δ(2)H and δ(18)O values of body water and of hair. Moreover, the isotope data allowed us to better quantify values for two critical variables in the models: the δ(2)H and δ(18)O values of gut water and the (18)O isotope fractionation associated with a carbonyl oxygen-water interaction in the gut (α(ow)). Our modeling efforts indicated that better predictions for body water and hair isotope values were achieved by making the isotopic composition of gut water approached that of body water. Additionally, the value of α(ow) was 1.0164, in close agreement with the only other previously measured observation (microbial spore cell walls), suggesting robustness of this fractionation factor across different biological systems. © 2012 Wiley Periodicals, Inc.

  17. The isotopic composition of authigenic chromium in anoxic marine sediments: A case study from the Cariaco Basin

    NASA Astrophysics Data System (ADS)

    Reinhard, Christopher T.; Planavsky, Noah J.; Wang, Xiangli; Fischer, Woodward W.; Johnson, Thomas M.; Lyons, Timothy W.

    2014-12-01

    Chromium (Cr) isotopes are an emerging proxy for tracking redox processes at the Earth's surface. However, there has been limited exploration of the Cr isotope record of modern and recent marine sediments. The basic inorganic chemistry of Cr suggests that anoxic marine basins should factor prominently in the global Cr cycle and that sediments deposited within anoxic basins may offer a valuable Cr isotope archive throughout Earth's history. Here, we present δ53Cr data from sediments of the Cariaco Basin, Venezuela-a 'type' environment for large, perennially anoxic basins with a relatively strong hydrological connection to the global oceans. We document a marked positive shift in bulk δ53Cr values following the termination of the Last Glacial Maximum, followed by relative stasis. Based on a suite of independent redox proxies, this transition marks a switch from oxic to persistently anoxic and sulfidic (euxinic) depositional conditions within the basin. We find good agreement between two independent approaches toward estimating the δ53Cr composition of authigenic Cr in euxinic Cariaco Basin sediments and that these estimates are very similar to the δ53Cr composition of modern open Atlantic Ocean seawater. These data, together with considerations of reaction kinetics and mass balance within the Cariaco Basin, are consistent with the hypothesis that anoxic marine settings can serve as a chemical archive of first-order trends in seawater δ53Cr composition. Additionally, the Cariaco Basin data suggest that there has been secular stability in the average δ53Cr value of Atlantic seawater over the last ∼15 kyr.

  18. Sr isotopic composition as a tracer of Ca sources in two forest ecosystems in Belgium.

    NASA Astrophysics Data System (ADS)

    Drouet, T.; Herbauts, J.; Demaiffe, D.

    2003-04-01

    The two main sources of Ca in forest ecosystem are the mineral weathering release and atmospheric inputs. We use the 87Sr/86Sr isotopic ratio (Sr is a proxy for Ca) to determine the Ca contribution from rain input in two forest ecosystems (beech stands) growing on soils formed from parent materials with distinct total Ca contents and contrasted isotopic ratios: Pleistocene loess in Central Belgium (leached brown soil) with present-day 87Sr/86Sr =0.72788 and Lower Devonian shales and sandstones in Ardennes (ochreous brown earth) with 87Sr/86Sr = 0.76913. The 87Sr/86Sr ratios and the Ca and Sr contents were measured in rainwater, vegetation (beech wood growth rings and leaves) and main soil horizons (total, labile and HCl 0.1 M soluble forms). The relative contributions of atmospheric input and soil mineral weathering to vegetation were calculated using mixing equations. Calculations based on the Sr isotope ratios of rainwater (endmember 1; 87Sr/86Sr close to seawater: 0.7090), labile soil fraction (endmember 2; 87Sr/86Sr: 0.71332 to 0.71785) and beech wood (mixing compartment) indicate that about 50 % (Central Belgium) to 35 % (Ardennes) of Ca uptake originate from atmospheric inputs. The choice of the appropriate 87Sr/86Sr ratio for the weathering endmember is however critical. The isotopic composition of the mineral source is theoretically determined by the mineralogical composition of the soil and the relative weatherability of the Sr-bearing minerals. Due to soil processes (weathering and clay illuviation), the distribution of minerals in both soil profiles is not homogeneous and varies from horizon to horizon. Which horizons are relevant and which kind of soil extract (labile soil fraction, acid soluble fraction, total soil,...) should be selected for isotopic measurement of weathering endmember, is therefore questionable. The different ways of estimation are discussed. Quantitative mineralogical reconstitutions of soil horizons and isotopic data indicate

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

    PubMed Central

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

    2016-01-01

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

  20. On the progressive enrichment of the oxygen isotopic composition of water along a leaf.

    PubMed

    Farquhar, G. D.; Gan, K. S.

    2003-06-01

    A model has been derived for the enrichment of heavy isotopes of water in leaves, including progressive enrichment along the leaf. In the model, lighter water is preferentially transpired leaving heavier water to diffuse back into the xylem and be carried further along the leaf. For this pattern to be pronounced, the ratio of advection to diffusion (Péclet number) has to be large in the longitudinal direction, and small in the radial direction. The progressive enrichment along the xylem is less than that occurring at the sites of evaporation in the mesophyll, depending on the isolation afforded by the radial Péclet number. There is an upper bound on enrichment, and effects of ground tissue associated with major veins are included. When transpiration rate is spatially nonuniform, averaging of enrichment occurs more naturally with transpiration weighting than with area-based weighting. This gives zero average enrichment of transpired water, the modified Craig-Gordon equation for average enrichment at the sites of evaporation and the Farquhar and Lloyd (In Stable Isotopes and Plant Carbon-Water Relations, pp. 47-70. Academic Press, New York, USA, 1993) prediction for mesophyll water. Earlier results on the isotopic composition of evolved oxygen and of retro-diffused carbon dioxide are preserved if these processes vary in parallel with transpiration rate. Parallel variation should be indicated approximately by uniform carbon isotope discrimination across the leaf.

  1. Isotope compositions of C and O of magmatic calcites from the Udachnaya-East pipe kimberlite, Yakutia

    NASA Astrophysics Data System (ADS)

    Tomilenko, A. A.; Dublyansky, Yu. V.; Kuzmin, D. V.; Sobolev, N. V.

    2017-07-01

    It has been demonstrated for the first time that the isotopic compositions of carbon (δ13C) in magmatic calcites from the Udachnaya-East pipe kimberlite groundmass varies from-2.5 to-1.0‰ (V-PDB), while those of oxygen (δ18O) range from 15.0 to 18.2‰ (V-SMOW). The obtained results imply that during the terminal late magmatic and postmagmatic stages of the kimberlite pipe formation, the carbonates in the kimberlite groundmass became successively heavier isotopically, which indicates the hybrid nature of the carbonate component of the kimberlite: it was formed with contributions from mantle and sedimentary marine sources.

  2. Calcium Isotope (δ44/40Ca) Composition of Morozovella Velascoensis During the Paleocene Eocene Thermal Maximum Ocean Acidification Event

    NASA Astrophysics Data System (ADS)

    Kitch, G. D.; Jacobson, A. D.; Hurtgen, M.; Sageman, B. B.; Harper, D. T.; Zachos, J. C.

    2017-12-01

    Ocean acidification (OA) events are transient disruptions to the carbonate chemistry of seawater that involve decreases in pH, [CO32-] and carbonate mineral saturation states (Ω). Numerical modeling studies predict that the Ca isotope (δ44/40Ca) composition of primary marine carbonate should be sensitive to OA1, and recent evidence from the rock record may support this hypothesis2. Boron isotope (δ11B) data for the planktonic foraminifera Morozovella velascoensis indicate that the Paleocene-Eocene Thermal Maximum (PETM; 55 Mya) was an interval of pronounced OA3, although the Ca isotope composition of the bulk carbonate record appears to show post-burial diagenetic effects4. To further evaluate the Ca isotope proxy, we used a high-precision (2σSD=±0.04‰), double-spike (43Ca-42Ca) TIMS method5 to measure δ44/40Ca values of well-preserved M. velascoensis tests spanning the PETM. M. velascoensis tests (250-355 µm) were picked from samples recovered during ODP Leg 198, Site 1209 on Shatsky Rise in the equatorial Pacific. Five M. velascoensis tests were combined per sample, dissolved, spiked, and analyzed using a Triton TIMS. Repeat dissolutions of ten samples gave δ44/40Ca values within ±0.04‰ of the original measurements. Method and procedural blanks were negligible. δ44/40Ca values are elevated, even before the negative carbon isotope excursion (CIE) that marks the PETM. When δ11/10B values decrease during the CIE, δ44/40Ca values remain elevated, but then decrease by 0.10‰ as δ11B values return to pre-CIE levels. The apparent inverse correlation between δ44/40Ca and δ11B values suggests that Ca isotope fractionation by M. velascoensis was sensitive to OA. A decrease in pH indicated by lower δ11B values is consistent with higher δ44/40Ca values (decreased fractionation) due to elevated [Ca2+]/[CO32-] ratios and reduced W. The Ca isotope composition of pristine foraminiferal calcite may have potential for reconstructing [CO32-]. The current

  3. Determining the isotopic compositions of uranium and fission products in radioactive environmental microsamples using laser ablation ICP-MS with multiple ion counters.

    PubMed

    Boulyga, Sergei F; Prohaska, Thomas

    2008-01-01

    This paper presents the application of a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS)--a Nu Plasma HR--equipped with three ion-counting multipliers and coupled to a laser ablation system (LA) for the rapid and sensitive determination of the 235U/238U, 236U/238U, 145Nd/143Nd, 146Nd/143Nd, 101Ru/(99Ru+99Tc) and 102Ru/(99Ru+99Tc) isotope ratios in microsamples collected in the vicinity of Chernobyl. Microsamples with dimensions ranging from a hundred mum to about 1 mm and with surface alpha activities of 3-38 mBq were first identified using nuclear track radiography. U, Nd and Ru isotope systems were then measured sequentially for the same microsample by LA-MC-ICP-MS. The application of a zoom ion optic for aligning the ion beams into the ion counters allows fast switching between different isotope systems, which enables all of the abovementioned isotope ratios to be measured for the same microsample within a total analysis time of 15-20 min (excluding MC-ICP-MS optimization and calibration). The 101Ru/(99Ru+99Tc) and 102Ru/(99Ru+99Tc) isotope ratios were measured for four microsamples and were found to be significantly lower than the natural ratios, indicating that the microsamples were contaminated with the corresponding fission products (Ru and Tc). A slight depletion in 146Nd of about 3-5% was observed in the contaminated samples, but the Nd isotopic ratios measured in the contaminated samples coincided with natural isotopic composition within the measurement uncertainty, as most of the Nd in the analyzed samples originates from the natural soil load of this element. The 235U/238U and 236U/238U isotope ratios were the most sensitive indicators of irradiated uranium. The present work yielded a significant variation in uranium isotope ratios in microsamples, in contrast with previously published results from the bulk analysis of contaminated samples originating from the vicinity of Chernobyl. Thus, the 235U/238U ratios measured in ten

  4. Impact of moisture source regions on the isotopic composition of precipitation events at high-mountain continental site Kasprowy Wierch, southern Poland

    NASA Astrophysics Data System (ADS)

    Rozanski, Kazimierz; Chmura, Lukasz; Dulinski, Marek

    2016-04-01

    Five-year record of deuterium and oxygen-18 isotope composition of precipitation events collected on top of the Kasprowy Wierch mountain (49° 14'N, 19° 59'E, 1989 m a.s.l.) located in north-western High Tatra mountain ridge, southern Poland, is presented and discussed. In total 670 precipitation samples have been collected and analysed. Stable isotope composition of the analysed precipitation events varied in a wide range, from -2.9 to -26.6‰ for δ18O and from -7 to -195 ‰ for δ2H. The local meteoric water line (LMWL) defined by single events data (δ2H=(7.86±0.05)δ18O+(12.9±0.6) deviate significantly from the analogous line defined by monthly composite precipitation data available for IAEA/GNIP station Krakow-Balice (50o04'N, 19o55'E, 220 m a.s.l.), located ca. 100 km north of Kasprowy Wierch ((δ2H=(7.82±0.11)δ18O+(6.9±1.1). While slopes of those two LMWLs are statistically indistinguishable, the intercept of Kasprowy Wierch line is almost two times higher that that characterizing Krakow monthly precipitation. This is well-documented effect associated with much higher elevation of Kasprowy Wierch sampling site when compared to Krakow. The isotope data for Kasprowy Wierch correlate significantly with air temperature, with the slope of the regression line being equal 0.35±0.02 ‰oC for δ18O, whereas no significant correlation with precipitation amount could be established. The impact of moisture source regions on the isotopic composition of precipitation events collected at Kasprowy Wierch site was analysed using HYSPLITE back trajectory model. Five-days back trajectories were calculated for all analysed precipitation events and seasonal maps of trajectory distribution were produced. They illustrate changes in the prevailing transport patterns of air masses bringing precipitation to the sampling site. Back trajectories for the events yielding extreme isotopic composition of precipitation collected at Kasprowy Wierch were analyzed in detail

  5. Absolute quantification of protein NP24 in tomato fruit by liquid chromatography/tandem mass spectrometry using stable isotope-labelled tryptic peptide standard.

    PubMed

    Ippoushi, Katsunari; Sasanuma, Motoe; Oike, Hideaki; Kobori, Masuko; Maeda-Yamamoto, Mari

    2015-04-15

    Protein NP24 is a thaumatin-like protein contained in tomato (Lycopersicon esculentum Mill.). This protein is reported to be a putative tomato allergen and is listed as a food allergen in Structural Database of Allergenic Proteins (SDAP). In this research, we developed the quantitative analysis of NP24 by employing the protein absolute quantification (AQUA) technology composed of stable isotope-labelled internal standard (SIIS) peptide (GQTWVINAPR[(13)C6,(15)N4]) and liquid chromatography/tandem mass spectrometry (LC/MS/MS). A linear relationship (r(2)>0.99) was found throughout the concentration range (2.0-500 fmol/μL). The coefficients of variation (CVs) measured on each of the five days when NP24 contained in the tomato skin was analysed did not exceed 13%. Our developed assay of NP24 will contribute to the allergological examination of tomato and its derived products. Copyright © 2014 Elsevier Ltd. All rights reserved.

  6. Isotopic composition (oxygen and hydrogen) of groundwater in Norway - a review of current knowledge and future perspectives

    NASA Astrophysics Data System (ADS)

    Kracht, O.

    2012-04-01

    A review of current knowledge and available data covering the stable isotope composition of groundwater in Norway is presented. Furthermore, the future challenge of obtaining systematic background datasets and of integrating isotopes into the mainstream of hydrogeological observation programmes is discussed. I will summarize our experiences gained from different preliminary studies and will try to identify relationships to existing datasets, historical registrations, and networks on precipitation data. The study of transient effects in hydrological cycles is highly topical as these are supposed to provide means for investigating the effects of climate change and increasing human activities. From a hydrogeological point of view, is critical to establish suitable tools for the large scale observation of changes in groundwater recharge and depletion, their likely controls, and the expected nature of responses to changing climate, urbanization and other human activities. In this context, stable isotopes (δ18O and δ2H of water) can provide an expedient instrument to investigate the general hydrological setting, connections, and pathways of various scale aquifer systems. However, we are up to now missing an expedient background dataset on hydrogeological and hydrological stable isotopes observations for mainland Norway. Against this background, during years 2010 and 2011 the Geological Survey of Norway (NGU) organized two nation-wide sampling campaigns on the stable isotope composition of modern groundwater. These pilot studies aimed to obtain a first overview about the data ranges and natural variations to be expected. We used stations from the existing Norwegian Groundwater Monitoring Network (Landsomfattende Grunnvannsnett, LGN) to collect samples of groundwater at 55 different locations throughout Norway. As a main characteristic of these two datasets, all δ18O and δ2H values of the "LGN series" were well correlated and plotted close to the global meteoric water

  7. Carbon and nitrogen isotope composition of core catcher samples from the ICDP deep drilling at Laguna Potrok Aike (Patagonia, Argentina)

    NASA Astrophysics Data System (ADS)

    Luecke, Andreas; Wissel, Holger; Mayr*, Christoph; Oehlerich, Markus; Ohlendorf, Christian; Zolitschka, Bernd; Pasado Science Team

    2010-05-01

    The ICDP project PASADO aims to develop a detailed paleoclimatic record for the southern part of the South American continent from sediments of Laguna Potrok Aike (51°58'S, 70°23'W), situated in the Patagonian steppe east of the Andean cordillera and north of the Street of Magellan. The precursor project SALSA recovered the Holocene and Late Glacial sediment infill of Laguna Potrok Aike and developed the environmental history of the semi-arid Patagonian steppe by a consequent interdisciplinary multi-proxy approach (e.g. Haberzettl et al., 2007). From September to November 2008 the ICDP deep drilling took place and successfully recovered in total 510 m of sediments from two sites resulting in a composite depth of 106 m for the selected main study Site 2. A preliminary age model places the record within the last 50.000 years. During the drilling campaign, the core catcher content of each drilled core run (3 m) was taken as separate sample to be shared and distributed between involved laboratories long before the main sampling party. A total of 70 core catcher samples describe the sediments of Site 2 and will form the base for more detailed investigations on the palaeoclimatic history of Patagonia. We here report on the organic carbon and nitrogen isotope composition of bulk sediment and plant debris of the core catcher samples. Similar investigations were performed for Holocene and Late Glacial sediments of Laguna Potrok Aike revealing insights into the organic matter dynamics of the lake and its catchment as well as into climatically induced hydrological variations with related lake level fluctuations (Mayr et al., 2009). The carbon and nitrogen content of the core catcher fine sediment fraction (<200 µm) is low to very low (around 1 % and 0.1 %, respectively) and requires particular attention in isotope analysis. The carbon isotope composition shows comparably little variation around a value of -26.0 per mil. The positive values of the Holocene and the Late

  8. Changes in stable isotope composition in Lake Michigan trout ...

    EPA Pesticide Factsheets

    Researchers have frequently sought to use environmental archives of sediment, peat and glacial ice to try and assess historical trends in atmospheric mercury (Hg) deposition to aquatic ecosystems. While this information is valuable in the context of identifying temporal source trends, these types of assessments cannot account for likely changes in bioavailability of Hg sources that are tied to the formation of methylmercury (MeHg) and accumulation in fish tissues. For this study we propose the use of long-term fish archives and Hg stable isotope determination as an improved means to relate temporal changes in fish Hg levels to varying Hg sources in the Great Lakes. For this study we acquired 180 archived fish composites from Lake Michigan over a 40-year time period (1975 to 2014) from the Great Lakes Fish Monitoring and Surveillance Program, which were analyzed for their total Hg content and Hg isotope abundances. The results reveal that Hg sources to Lake Michigan trout (Salvelinus namaycush) have encountered considerable changes as well as a large shift in the food web trophic position as a result of the introduction of several invasive species, especially the recent invasion of dreissenid mussels. Total Hg concentrations span a large range (1,600 to 150 ng g-1) and exhibit large variations from 1975 to 1985. Ä199Hg signatures similarly exhibit large variation (3.2 to 6.9‰) until 1985, followed by less variation through the end of the data record in 2014.

  9. Volatile Concentrations and H-Isotope Composition of Unequilibrated Eucrites

    NASA Technical Reports Server (NTRS)

    Sarafian, Adam R.; Nielsen, Sune G.; Marschall, Horst R.; Gaetani, Glenn A.; Hauri, Erik H.; Righter, Kevin; Berger, Eve L.

    2017-01-01

    Eucrites are among the oldest and best studied asteroidal basalts (1). They represent magmatism that occurred on their parent asteroid, likely 4-Vesta, starting at 4563 Ma and continuing for approx. 30 Myr. Two hypotheses are debated for the genesis of eucrites, a magma ocean model (2), and a mantle partial melting model. In general, volatiles (H, C, F, Cl) have been ignored for eucrites and 4-Vesta, but solubility of wt% levels of H2O are possible at Vestan interior PT conditions. Targeted measurements on samples could aid our understanding considerably. Recent studies have found evidence of volatile elements in eucrites, but quantifying the abundance of volatiles remains problematic (6). Volatile elements have a disproportionately large effect on melt properties and phase stability, relative to their low abundance. The source of volatile elements can be elucidated by examining the hydrogen isotope ratio (D/H), as different H reservoirs have drastically different H isotope compositions. Recent studies of apatite in eucrites have shown that the D/H of 4-Vesta matches that of Earth and carbonaceous chondrites, however, the D/H of apatites may not represent the D/H of a primitive 4-Vesta melt due to the possibility of degassing prior to the crystallization of apatite. Therefore, the D/H of early crystallizing phases must be measured to determine if the D/H of 4-Vesta is equal to that of the Earth and carbonaceous chondrites.

  10. Isotopic signals of denitrification in a northern hardwood forested catchment

    NASA Astrophysics Data System (ADS)

    Wexler, Sarah; Goodale, Christine

    2013-04-01

    Water samples from streams, groundwater and precipitation were collected during summer from the hydrologic reference watershed (W3) at Hubbard Brook Experimental Forest in the White Mountains, New Hampshire, and analysed for d15N-NO3 and d18O-NO3. Despite very low nitrate concentrations (<0.5 to 8.8 uM NO3-) dual-isotopic signals of sources and processes were clearly distinguishable. The isotopic composition of nitrate from shallow groundwater showed evidence of dual isotopic fractionation in line with denitrification, with a positive relationship between nitrogen and oxygen isotopic composition, a regression line slope of 0.76 (r2 = 0.68), and an empirical isotope enrichment factor of ɛP-S 15N-NO3 -12.7%. The isotopic composition of riparian groundwater nitrate from time-series samples showed variation in processes over a small spatial scale. The expected isotopic composition of nitrate sources in the watershed was used to distinguish nitrate in rain and nitrate from nitrification of both rainfall ammonium and ammonium from mineralised soil organic nitrogen. Evidence of oxygen exchange with water during nitrification was seen in the isotopic composition of stream and shallow groundwater nitrate. The isotopic composition of streamwater nitrate following a period of storms indicated that 25% of nitrate in the streamwater was of atmospheric origin. This suggests rapid infiltration of rainfall via vertical bypass flow to the saturated zone, enabling transport of atmospheric nitrate to the stream channels. Across the Hubbard Brook basin, the isotopic composition of nitrate from paired samples from watersheds 4-7 indicated a switch between a nitrification and assimilation dominated system, to a system influenced by rainfall nitrogen inputs and denitrification. The dual isotope approach has revealed evidence of denitrification of nitrate from different sources at low concentrations at Hubbard Brook during summer. This isotopic evidence deepens our understanding of the

  11. Isotope fractionation by multicomponent diffusion (Invited)

    NASA Astrophysics Data System (ADS)

    Watkins, J. M.; Liang, Y.; Richter, F. M.; Ryerson, F. J.; DePaolo, D. J.

    2013-12-01

    Isotope fractionation by multicomponent diffusion The isotopic composition of mineral phases can be used to probe the temperatures and rates of mineral formation as well as the degree of post-mineralization alteration. The ability to interpret stable isotope variations is limited by our knowledge of three key parameters and their relative importance in determining the composition of a mineral grain and its surroundings: (1) thermodynamic (equilibrium) partitioning, (2) mass-dependent diffusivities, and (3) mass-dependent reaction rate coefficients. Understanding the mechanisms of diffusion and reaction in geological liquids, and how these mass transport processes discriminate between isotopes, represents an important problem that is receiving considerable attention in the geosciences. Our focus in this presentation will be isotope fractionation by chemical diffusion. Previous studies have documented that diffusive isotope effects vary depending on the cation as well as the liquid composition, but the ability to predict diffusive isotope effects from theory is limited; for example, it is unclear whether the magnitude of diffusive isotopic fractionations might also vary with the direction of diffusion in composition space. To test this hypothesis and to further guide the theoretical treatment of isotope diffusion, two chemical diffusion experiments and one self diffusion experiment were conducted at 1250°C and 0.7 GPa. In one experiment (A-B), CaO and Na2O counter-diffuse rapidly in the presence of a small SiO2 gradient. In the other experiment (D-E), CaO and SiO2 counter-diffuse more slowly in a small Na2O gradient. In both chemical diffusion experiments, Ca isotopes become fractionated by chemical diffusion but by different amounts, documenting for the first time that the magnitude of isotope fractionation by diffusion depends on the direction of diffusion in composition space. The magnitude of Ca isotope fractionation that develops is positively correlated with

  12. Monitoring concentration and isotopic composition of methane in groundwater in the Utica Shale hydraulic fracturing region of Ohio.

    PubMed

    Claire Botner, E; Townsend-Small, Amy; Nash, David B; Xu, Xiaomei; Schimmelmann, Arndt; Miller, Joshua H

    2018-05-03

    Degradation of groundwater quality is a primary public concern in rural hydraulic fracturing areas. Previous studies have shown that natural gas methane (CH 4 ) is present in groundwater near shale gas wells in the Marcellus Shale of Pennsylvania, but did not have pre-drilling baseline measurements. Here, we present the results of a free public water testing program in the Utica Shale of Ohio, where we measured CH 4 concentration, CH 4 stable isotopic composition, and pH and conductivity along temporal and spatial gradients of hydraulic fracturing activity. Dissolved CH 4 ranged from 0.2 μg/L to 25 mg/L, and stable isotopic measurements indicated a predominantly biogenic carbonate reduction CH 4 source. Radiocarbon dating of CH 4 in combination with stable isotopic analysis of CH 4 in three samples indicated that fossil C substrates are the source of CH 4 in groundwater, with one 14 C date indicative of modern biogenic carbonate reduction. We found no relationship between CH 4 concentration or source in groundwater and proximity to active gas well sites. No significant changes in CH 4 concentration, CH 4 isotopic composition, pH, or conductivity in water wells were observed during the study period. These data indicate that high levels of biogenic CH 4 can be present in groundwater wells independent of hydraulic fracturing activity and affirm the need for isotopic or other fingerprinting techniques for CH 4 source identification. Continued monitoring of private drinking water wells is critical to ensure that groundwater quality is not altered as hydraulic fracturing activity continues in the region. Graphical abstract A shale gas well in rural Appalachian Ohio. Photo credit: Claire Botner.

  13. Variations of geothermometry and chemical-isotopic compositions of hot spring fluids in the Rehai geothermal field, southwestern China

    NASA Astrophysics Data System (ADS)

    Du, Jianguo; Liu, Congqiang; Fu, Bihong; Ninomiya, Yoshiki; Zhang, Youlian; Wang, Chuanyuan; Wang, Hualiu; Sun, Zigang

    2005-04-01

    Geothermal variations, origins of carbon-bearing components and reservoir temperatures in the Rehai geothermal field (RGF) of Tengchong volcanic area, Yunnan Province, southwestern China, are discussed on the basis of carbon isotope compositions, combined with helium isotope ratios and geothermal data from 1973 to 2000. δ 13C values of CO 2, CH 4, HCO 3-, CO 3= and travertine in the hot springs range from -7.6‰ to -1.18‰, -56.9‰ to -19.48‰, -6.7‰ to -4.2‰, -6.4‰ to -4.2‰ and -27.1‰ to +0.6‰, respectively. The carbon dioxide probably has a mantle/magma origin, but CH 4 and He have multiple origins. HCO 3- and CO 3= in RGF thermal fluids are predominantly derived from igneous carbon dioxide, but other ions originate from rocks through which the fluids circulate. The 13C values of CO 2, HCO 3- (aq) and CO 3= (aq) illustrate that isotopic equilibriums between CO 2 and HCO 3- (aq), and CO 3= (aq) and between DIC and travertine were not achieved, and no carbon isotope fractionation between HCO 3- (aq) and CO 3= (aq) of the hot springs in RGF was found. Using various geothermometers, temperatures of the geothermal reservoirs are estimated in a wide range from 69 °C to 450 °C that fluctuated from time to time. The best estimate of subsurface reservoir temperature may be 250-300 °C. Contributions of mantle fluids and shallow crust fluids in Rehai geothermal field varied with time, which resulted in variations of chemical and isotopic compositions and reservoir temperatures.

  14. Composition of Hydrothermal Vent Microbial Communities as Revealed by Analyses of Signature Lipids, Stable Carbon Isotopes and Aquificales Cultures

    NASA Technical Reports Server (NTRS)

    Jahnke, L. L.; Eder, W.; Huber, Robert; Hinrichs, K-U.; Hayes, J. M.; DesMarais, D. J.; Cady, S. L.; Hope, J. M.; Summons, R. E.

    2001-01-01

    This paper describes a study of lipid biomarker composition and carbon isotopic fractionation in cultured Aquificales and natural analogues from Yellowstone National Park. Additional information is contained in the original extended abstract.

  15. Magnesium isotope systematics in Martian meteorites

    NASA Astrophysics Data System (ADS)

    Magna, Tomáš; Hu, Yan; Teng, Fang-Zhen; Mezger, Klaus

    2017-09-01

    Magnesium isotope compositions are reported for a suite of Martian meteorites that span the range of petrological and geochemical types recognized to date for Mars, including crustal breccia Northwest Africa (NWA) 7034. The δ26Mg values (per mil units relative to DSM-3 reference material) range from -0.32 to -0.11‰; basaltic shergottites and nakhlites lie to the heavier end of the Mg isotope range whereas olivine-phyric, olivine-orthopyroxene-phyric and lherzolitic shergottites, and chassignites have slightly lighter Mg isotope compositions, attesting to modest correlation of Mg isotopes and petrology of the samples. Slightly heavier Mg isotope compositions found for surface-related materials (NWA 7034, black glass fraction of the Tissint shergottite fall; δ26Mg > -0.17‰) indicate measurable Mg isotope difference between the Martian mantle and crust but the true extent of Mg isotope fractionation for Martian surface materials remains unconstrained. The range of δ26Mg values from -0.19 to -0.11‰ in nakhlites is most likely due to accumulation of clinopyroxene during petrogenesis rather than garnet fractionation in the source or assimilation of surface material modified at low temperatures. The rather restricted range in Mg isotope compositions between spatially and temporally distinct mantle-derived samples supports the idea of inefficient/absent major tectonic cycles on Mars, which would include plate tectonics and large-scale recycling of isotopically fractionated surface materials back into the Martian mantle. The cumulative δ26Mg value of Martian samples, which are not influenced by late-stage alteration processes and/or crust-mantle interactions, is - 0.271 ± 0.040 ‰ (2SD) and is considered to reflect δ26Mg value of the Bulk Silicate Mars. This value is robust taking into account the range of lithologies involved in this estimate. It also attests to the lack of the Mg isotope variability reported for the inner Solar System bodies at current

  16. Lead and strontium isotopic evidence for crustal interaction and compositional zonation in the source regions of Pleistocene basaltic and rhyolitic magmas of the Coso volcanic field, California

    USGS Publications Warehouse

    Bacon, C.R.; Kurasawa, H.; Delevaux, M.H.; Kistler, R.W.; Doe, B.R.

    1984-01-01

    The isotopic compositions of Pb and Sr in Pleistocene basalt, high-silica rhyolite, and andesitic inclusions in rhyolite of the Coso volcanic field indicate that these rocks were derived from different levels of compositionally zoned magmatic systems. The 2 earliest rhyolites probably were tapped from short-lived silicic reservoirs, in contrast to the other 36 rhyolite domes and lava flows which the isotopic data suggest may have been leaked from the top of a single, long-lived magmatic system. Most Coso basalts show isotopic, geochemical, and mineralogic evidence of interaction with crustal rocks, but one analyzed flow has isotopic ratios that may represent mantle values (87Sr/86Sr=0.7036,206Pb/204Pb=19.05,207Pb/204Pb=15.62,208Pb/204Pb= 38.63). The (initial) isotopic composition of typical rhyolite (87Sr/86Sr=0.7053,206Pb/204Pb=19.29,207Pb/204Pb= 15.68,208Pb/204Pb=39.00) is representative of the middle or upper crust. Andesitic inclusions in the rhyolites are evidently samples of hybrid magmas from the silicic/mafic interface in vertically zoned magma reservoirs. Silicic end-member compositions inferred for these mixed magmas, however, are not those of erupted rhyolite but reflect the zonation within the silicic part of the magma reservoir. The compositional contrast at the interface between mafic and silicic parts of these systems apparently was greater for the earlier, smaller reservoirs. ?? 1984 Springer-Verlag.

  17. Hf isotope compositions In detrital zircons as a new tool for provenance studies

    NASA Astrophysics Data System (ADS)

    Jacobsen, Y. J.; Münker, C.; Mezger, K.

    2003-04-01

    Identifying the provenance of continental sediments is a major issue in palaeo-tectonic studies, providing important information for paleogeographic reconstructions. Isotope studies, e.g. those of whole rock Sm-Nd or detrital zircon U-Pb dating, have widely been used for this purpose. Here we assess the potential of combined Lu-Hf data and U-Pb ages determined on the same single detrital zircons as a new tool for provenance studies. Due to the low Lu/Hf ratios in zircons the Hf isotope composition of a zircon changes insignificantly after its crystallization. Thus each particular grain preserves information on the Hf-siotpe composition of its source and the age of this source. Provided that both the U-Pb and Lu-Hf isotope systems have not been disturbed, this information can be used to constrain the sources of each individual zircon. In order to demonstrate the capability of Hf isotope studies on detrital zircons for provenance studies, we obtained combined U-Pb ages and Lu-Hf isotope data for zircons from the Cambrian Junction Formation in New Zealand. The Junction Formation was deposited on the (present) SE margin of Gondwana near the Australian continent and consists of turbidites, siltstones and conglomerates [1]. Typical continent derived Paleozoic sediments in SE Gondwana generally show characteristic age maxima at 500-600 Ma, 1000-1200 Ma (Grenvillian) and additional older peaks (early Proterozoic to Archean) [2]. We focused on two groups of detrital zircons with Grenvillian and Proterozoic to Late Archean ages. The initial ɛHf values for these zircons range from 0.7 to -15.5 for the Grenvillian and from -5.2 to -14.1 for the Proterozoic/Archean zircons. Corresponding two stage Hf model ages range from ca. 1500 to 2500 Ma for the Grenvillian and from ca. 3200 to 3600 Ma for the Proterozoic/Archean zircons. Furthermore it can be shown that the Grenvillian zircons must have been derived from recycled Grenvillian provinces. Comparison of these Hf model ages

  18. Tracing subducted crustal materials in the mantle by using magnesium isotopes

    NASA Astrophysics Data System (ADS)

    Teng, F. Z.

    2016-12-01

    Recent studies show that some continental basalt, mantle-metasomatised peridotite and cratonic eclogite have heterogeneous Mg isotopic compositions. These isotopically distinct Mg isotopic compositions have been explained by the incorporation of subducted materials in their mantle sources though the detailed mechanisms are still not well understood. In particular, how Mg-poor crustal materials can modify Mg isotopic systematics of Mg-rich mantle is unknown. Subduction zones are the most efficient sites for crust and mantle interactions, hence should be where the most prominent Mg isotopic variation occurs. However, to date, little is known on Mg isotope systematics in the subduction factory. Here I first review and report new Mg isotopic data for arc lava, subarc peridotite and the subducted slab (marine sediment, altered basalt and abyssal peridotite), then use them to constrain the origins of mantle Mg isotopic heterogeneity and lay the foundation for using Mg isotopes as new tools for tracing crust-mantle interactions. The main conclusions are 1) fluid-rock interactions can modify Mg isotopic systematics of abyssal peridotites; 2) island arc lavas have non-MORB Mg isotopic compositions, reflecting distinct surbarc mantle Mg isotopic signature; 3) continental arcs have non-MORB Mg isotopic compositions, likely resulting from crustal contamination and 4) the isotopically heterogeneous continental basalts are mainly produced by mixing of isotopically distinct magmas instead of being partial melting products of metasomatised mantle peridotites.

  19. Human drinking water compared with river waters throughout the United States with respect to their stable hydrogen and oxygen isotopic composition

    NASA Astrophysics Data System (ADS)

    Landwehr, J. M.; Coplen, T. B.; Qi, H.

    2009-04-01

    The composition of stable isotopes of hydrogen (^2H) and oxygen (^18O) in animal tissues, such as hair, nail, teeth and bone, has been used to trace migrations and geographic origin of individuals. Variations of these isotopic ratios in tissue are known to show significant correlations with the isotopic composition of ingested water, as well as with diet and other oxygen sources. Drinking water in natural ecosystems is defined by what is locally available for animal consumption, primarily surface waters such as streams, ponds, lakes, seeps, springs, etc. Tap water provides the drinking water in many human ecosystems. It may derive from local sources but can also draw on more diverse sources, such as large rivers with watersheds larger than those of local creeks, deep ground waters or even imported supplies, which may be isotopically distinct from local ecosystem supplies. Because of the potentially complex hydrologic pathways of water sources available in either animal or human ecosystems, the stable isotopic composition of these supplies may differ significantly from that of the (weighted average) local precipitation which is sometimes used to represent local water supplies. For example, water samples taken from three different taps in Washington, D.C., USA, on August 15, 2007, had measured ^2H and ^18O values of -41.7 per mill and -6.13 per mill, -41.7 per mill and -6.06 per mill, and -42.2 per mill and -6.22 per mill, respectively. A water sample taken on the same day from the Potomac River, which is the source of the D.C. water supply, had ^2H and ^18O values of -41.7 per mill and -6.06 per mill, respectively, consistent with that of the urban tap water. However, precipitation samples collected locally in Reston, Virginia, USA, had ^2H and ^18O values of -16.1 per mill and -3.13 per mill, respectively, for the week ending on August 15, 2007; -17.5 per mill and -3.40 per mill, respectively, for the month preceding August 15, 2007; and -13.6 per mill and -3

  20. Reconstructing lake evaporation history and the isotopic composition of precipitation by a coupled δ18O-δ2H biomarker approach

    NASA Astrophysics Data System (ADS)

    Hepp, Johannes; Tuthorn, Mario; Zech, Roland; Mügler, Ines; Schlütz, Frank; Zech, Wolfgang; Zech, Michael

    2015-10-01

    Over the past decades, δ18O and δ2H analyses of lacustrine sediments became an invaluable tool in paleohydrology and paleolimnology for reconstructing the isotopic composition of past lake water and precipitation. However, based on δ18O or δ2H records alone, it can be challenging to distinguish between changes of the precipitation signal and changes caused by evaporation. Here we propose a coupled δ18O-δ2H biomarker approach that provides the possibility to disentangle between these two factors. The isotopic composition of long chain n-alkanes (n-C25, n-C27, n-C29, n-C31) were analyzed in order to establish a 16 ka Late Glacial and Holocene δ2H record for the sediment archive of Lake Panch Pokhari in High Himalaya, Nepal. The δ2Hn-alkane record generally corroborates a previously established δ18Osugar record reporting on high values characterizing the deglaciation and the Older and the Younger Dryas, and low values characterizing the Bølling and the Allerød periods. Since the investigated n-alkane and sugar biomarkers are considered to be primarily of aquatic origin, they were used to reconstruct the isotopic composition of lake water. The reconstructed deuterium excess of lake water ranges from +57‰ to -85‰ and is shown to serve as proxy for the evaporation history of Lake Panch Pokhari. Lake desiccation during the deglaciation, the Older Dryas and the Younger Dryas is affirmed by a multi-proxy approach using the Hydrogen Index (HI) and the carbon to nitrogen ratio (C/N) as additional proxies for lake sediment organic matter mineralization. Furthermore, the coupled δ18O and δ2H approach allows disentangling the lake water isotopic enrichment from variations of the isotopic composition of precipitation. The reconstructed 16 ka δ18Oprecipitation record of Lake Panch Pokhari is well in agreement with the δ18O records of Chinese speleothems and presumably reflects the Indian Summer Monsoon variability.