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Sample records for 18o 13c 14c

  1. Isotopic analyses (/sup 18/O, /sup 13/C, /sup 14/C) of two meromictic lakes in the Canadian Arctic Archipelago

    SciTech Connect

    Page, P.; Ouellet, M.; Hillaire-Marcel, C.; Dickman, M.

    1984-05-01

    Meromictic Lakes Garrow and Sophia in the Canadian Arctic Archipelago were sampled to establish the origin and age of their water by isotopic studies. /sup 18/O values reflect the permanent stratification of the water in both lakes. The mixolimnia contain waters with an isotopic signal between -13.16 and -21.98%, coherent with the values for precipitation in these high latitudes. In the chemoclines, the delta/sup 18/O values increase to -10% concomitantly with a rise in chloride content to 42 g.liter/sup -1/. In the monimolimnia, hypersaline waters (up to 2.5 times the salinity of seawater) show negative delta/sup 18/O values (ca. -.08%). These waters result from brine production during permafrost growth in the watershed, according to a Rayleigh process. /sup 14/C dating of total inorganic carbon in the Lake Garrow monimolimnion gave an age of 2580 +/- 260 years BP. In Lake Sophia, the deep waters exhibit recent /sup 14/C activity that suggests recent infiltration of seawater into the lake basin.

  2. Isotopic analyses (/sup 18/O, /sup 13/C, /sup 14/C) of two meromictic lakes in the Canadian Arctic Archipelago

    SciTech Connect

    Page, P.; Ouellet, M.; Hillaire-Marcel, C.; Dickman, M.

    1984-05-01

    Meromictic Lakes Garrow and Sophia in the Canadian Arctic Archipelago were sampled to establish the origin and age of their waters by isotopic studies. The sigma/sub SMOW//sup 18/O values reflect the permanent stratification of the waters in both lakes. The mixolimnia contain waters with an isotopic signal between -13.16 and -2.198%, coherent with the values of precipitation in these high latitudes. The short residence time of the water in this layer makes it possible to record episodic variations of the freshwater inputs to the lakes. In the chemoclines, the sigma/sup 18/O values increase to -10% concomitantly with a rise in chloride content to 42 g liter/sup -1/. This corresponds to a conservative mixing of surficial and deep waters. In the monimolimnia, hypersaline waters from brine production during permafrost growth in the watershed, according to a Rayleigh process. The brines drained toward the deepest part of each lake, after postglacial uplift, and became isolated. /sup 14/C dating of total inorganic carbon in the Lake Garrow monimolimnion gave an age of 2580 +/- 260 years B.P. In Lake Sophia, the deep waters exhibit recent /sup 14/C activity (121.4% modern carbon) that suggests recent infiltration of seawater into the lake basin.

  3. A multi-isotopic study (U-series, 14C, 13C, 18O) on growth of Arctic fissure calcretes (endostromatolites) from Northern Canada.

    NASA Astrophysics Data System (ADS)

    Ghaleb, B.; Hillaire-Marcel, C.; Deschamps, P.; Lauriol, B.

    2009-05-01

    The chronology of Arctic terrestrial environments is poorly documented due to the scarcity of representative deposits allowing radiometric age determinations. Endostromatolites are secondary carbonate precipitations filling fractures in karstic carbonate terrains found in various sites in Yukon, North-West Territories. Expectations about their use to document environmental change were high. The specimens studied here originate from the Bear Cave Mountains (Yukon). They fill presently unsaturated fissures along cliffs, above karstic formations, within a few meters from the bedrock surface. They occur on southern oriented surfaces, and systematically develop on the outer side surface of the fractures. These concretions are likely of biogenic origin, and are thought to form during periods with relatively warm conditions in the Arctic (i.e., maximum insolation intervals). We report here on 238U, 234U, 230Th, 226Ra, 14C, 13C and 18O analyses of a few thick specimens (2 cm). A first sample yielded inconsistent 14C- and 230Th-ages (ranging from bottom to top of the concretion10-4 ka and 260-55 ka, respectively). Higher resolution measurements in a second sample better illustrate trends from the layer immediately attached to the host rock (here Paleozoic limestone) and the outer, columnar surface of the concretion: i) 230Th/238U activity ratio decrease from near secular equilibrium values to appr. 0.2; ii) 238U- concentrations increase from ~ 2 to ~ 6 ppm, and iii) 226Ra/230Th activity ratios increase from near secular equilibrium values to 1.2. This pattern suggest a pseudo-Rayleigh fractionation process with redistribution of U-series isotopes from the host-rock into the calcrete growth layers, more or less in function of their relative solubility. Some addition of more soluble elements relating to water fluxes cannot be ruled out. Stable carbon isotopes suggest a similar process with a progressive enrichment in 13C (up to +8.5 vs. VPDB) attributed to kinetic

  4. High Resolution δ18O and δ13C Records of AMS 14C Dated Stalagmites From Jinlun and Yilingyan Caves in Guangxi, China: Climate Variability and Controlling Factors in the Monsoonal Region During the Past 2300 Years

    NASA Astrophysics Data System (ADS)

    Li, H. C.; Lien, W. Y.; Mii, H. S.; Jiang, G. H.; Chou, C. Y.; Chou, P. J.

    2015-12-01

    Jinlun Cave in Mashan County and Yilingyan Cave in Wuming County are ~120km and ~60km north of Nanning in Guangxi Province under influence of both Indian Monsoon and North Western Pacific Monsoon. Several stalagmites have been dated by AMS 14C dating method since 230Th/U is not applicable due to very low U contents. Twenty (20) AMS 14C dates on Stalagmite JL20131005-10 (10-cm long) show "Bomb carbon curve", spanning the past 60 years. Lamination counting further confirms the chronology. Thirty nine (39) AMS 14C dates on Stalagmite JL20131005-12 (33-cm long) reveal 2300-year continuous growth. Stalagmite YLY20130727-12 (10-cm long) from Yilingyan Cave covers a continuous record of past 2300 years. All studied stalagmites in the caves contain low dead carbon fractions. The annual resolution δ18O and δ13C records obtained from the stalagmites allow us to compare the stalagmite δ18O records with the instrumental rainfall and temperature records, Pacific Decadal Oscillation (PDO), Southern Oscillation Index (SOI), and Sunspot variation, etc. The δ18O and δ13C records exhibit relatively good correlation throughout the time, indicating climatic control on vegetation change. Based on the high-resolution δ18O and δ13C records, we interpret that dry climatic conditions and poor vegetation coverage during periods of AD1880~1850, 1700~1600, 1460~1320, 1210~1280, 860~750, 540~420, 300~220, and AD100~0 shown by increased δ18O and δ13C. The δ18O and δ13C were strongly depleted during the Medieval Warm Period (MWP between AD900 and AD1100) and Current Warm Period (CWP, since AD1900), reflecting strongly increased East Asian Summer Monsoon. After AD1900, the δ13C decreased about 6‰, perhaps indicating human impact on surface vegetation. The δ18O records from the study area are comparable to the published WX42B δ18O record of Wanxiang Cave (Zhang et al., 2008) except for the period of AD1400~1850. Our study suggests that AMS 14C dating is an alternative method for

  5. A 2000-yr High-resolution Stalagmite Record From Zhenzhu Cave in Hebei, North China: Interpretations of AMS 14C, 230Th/U, 210Pb Dating, and δ18O, δ13C Results

    NASA Astrophysics Data System (ADS)

    Li, H. C.; Yin, J.; Rao, Z.; Mii, H. S.; Shen, C. C.; Pillutla, R. K.; Li, Y. X.

    2016-12-01

    An 11.1-cm long stalagmite (ZZ12) collected from Zhenzhu cave (38°15'N, 113°42'E, 975m a.s.l.) located at Tiangui mountain of Hebei province, North China. The 230Th/U dates on 12 horizons exhibit large uncertainties with many reversed age sequences due to low U contents and low 230Th/232Th ratios. While the 230Th/U dating is not able to provide the chronology of this stalagmite, AMS 14C dating on 27 samples from various depths of the stalagmite yields a reliable age-depth relationship. Three AMS 14C dates from the top 5 mm appear nuclear bomb carbon indicating that this part was deposited after AD 1950. Seven samples for 210Pb dating were taken from the upper 14 mm with 2 mm intervals, showing exponential decay of excess 210Pb and supporting the AMS 14C dating results. At the base of the stalagmite, charcoal grains were included in the carbonate stalagmite. This charcoal sample has a Calibrated 14C age of 1865±20 a BP. The carbonates at adjacent depths show Calibrated 14C ages of 1900±15 and 2215±75 a BP respectively. The bomb carbon and similar ages between the charcoal and carbonates indicate that dead carbon influence on the 14C dates in some horizons may not be serious. From the 27 AMS 14C dates, we select 17 AMS 14C dates which have minimal influence of dead carbon fraction to construct the chronology. The established chronology shows that slow growth rates occurred prior to 1100 a BP and after 600 a BP. This time interval involves the Medieval Warm Period, while the fast growth rate during this interval may reflect warm and wet climatic conditions. A total of 835 samples were drilled from the stalagmite for δ18O and δ13C analyses. The current 900-year δ18O and δ13C records reveal climate and vegetation changes in the study area. Strong decadal oscillations in the δ18O record reflect variations of monsoonal rain, with relatively dry between AD 1350 and AD 1550 and after AD 1960. The δ13C record appears mainly multi-centennial variations with a 4

  6. Life history of the individuals buried in the St. Benedict Cemetery (Prague, 15th-18th centuries): insights from (14)C dating and stable isotope (δ(13)C, δ(15)N, δ(18)O) analysis.

    PubMed

    Salesse, Kevin; Dufour, Élise; Castex, Dominique; Velemínský, Petr; Santos, Frédéric; Kuchařová, Hedvika; Jun, Libor; Brůžek, Jaroslav

    2013-06-01

    Funerary practices and bioarchaeological (sex and age) data suggest that a mortality crisis linked to an epidemic episode occurred during the fifth phase of the St. Benedict cemetery in Prague (Czech Republic). To identify this mass mortality episode, we reconstructed individual life histories (dietary and mobility factors), assessed the population's biological homogeneity, and proposed a new chronology through stable isotope analysis (δ(13)C, δ(18)O and δ(15)N) and direct radiocarbon dating. Stable isotope analysis was conducted on the bone and tooth enamel (collagen and carbonate) of 19 individuals from three multiple graves (MG) and 12 individuals from individual graves (IG). The δ(15)N values of collagen and the difference between the δ(13)C values of collagen and bone carbonate could indicate that the IG individuals had a richer protein diet than the MG individuals or different food resources. The human bone and enamel carbonate and δ(18)O values suggest that the majority of individuals from MG and all individuals from IG spent most of their lives outside of the Bohemian region. Variations in δ(18)O values also indicate that all individuals experienced residential mobility during their lives. The stable isotope results, biological (age and sex) data and eight (14)C dates clearly differentiate the MG and IG groups. The present work provides evidence for the reuse of the St. Benedict cemetery to bury soldiers despite the funeral protest ban (1635 AD). The Siege of Prague (1742 AD) by French-Bavarian-Saxon armies is identified as the cause of the St. Benedict mass mortality event.

  7. Analysis and theoretical modeling of 18O enriched carbon dioxide spectrum by CRDS near 1.35 μm: (II) 16O13C18O, 16O13C17O, 12C18O2, 17O12C18O, 12C17O2, 13C18O2 and 17O13C18O

    NASA Astrophysics Data System (ADS)

    Karlovets, E. V.; Campargue, A.; Kassi, S.; Tashkun, S. A.; Perevalov, V. I.

    2017-04-01

    This contribution is the second part of the analysis of the room temperature absorption spectrum of 18O enriched carbon dioxide by very high sensitivity Cavity Ring Down spectroscopy between 6977 and 7918 cm-1 (1.43-1.26 μm). Overall, more than 8600 lines belonging to 166 bands of eleven carbon dioxide isotopologues were rovibrationnally assigned. In a first part (Kassi et al. J Quant Spectrosc Radiat Transfer 187 (2017) 414-425, http://dx.doi.org/10.1016/j.jqsrt.2016.09.002), the results relative to mono-substituted isotopologues, 16O12C18O, 16O12C17O, 12C16O2 and 13C16O2, were presented. This second contribution is devoted to the multiply-substituted isotopologues or clumped isotopologues of particular importance in geochemistry: 16O13C18O, 16O13C17O, 12C18O2, 17O12C18O, 12C17O2, 13C18O2 and 17O13C18O. On the basis of the predictions of effective Hamiltonian models, a total of 3195 transitions belonging to 73 bands were rovibrationnally assigned for these seven species. Among the 73 observed bands, 55 are newly reported. All the identified bands correspond to ΔP=10 and 11 series of transitions, where P= 2V1+V2+3V3 is the polyad number (Vi are vibrational quantum numbers). The accurate spectroscopic parameters of 70 bands have been determined from the standard band-by-band analysis. Global fits of the measured line intensities of the ΔP=10 series of transitions of 17O12C18O and 16O13C18O and of the ΔP=11 series of transitions of 12C18O2, 17O12C18O, 16O13C18O and 13C18O2 were performed to determine the corresponding sets of the effective dipole moment parameters.

  8. sup 13 C and sup 18 O isotopic disequilibrium in biological carbonates: I. Patterns

    SciTech Connect

    McConnaughey, T. )

    1989-01-01

    Biological carbonates frequently precipitate out of {sup 18}O and {sup 13}C equilibrium with ambient waters. Two patterns of isotopic disequilibrium are particularly common. Kinetic disequilibria, so designated because they apparently result from kinetic isotope effects during CO{sub 2} hydration and hydroxylation, involve simultaneous depletions of {sup 18}O and {sup 13}C as large as 4{per thousand} and 10 to 15{per thousand}, respectively. Rapid skeletogenesis favors strong kinetic effects, and approximately linear correlations between skeletal {delta}{sup 18}O and {delta}{sup 13}C are common in carbonates showing mainly the kinetic pattern. Metabolic effects involve additional positive or negative modulation of skeletal {delta}{sup 13}C, reflecting changes in the {delta}{sup 13}C of dissolved inorganic carbon, caused mainly by photosynthesis and respiration. Kinetic isotope disequilibria tend to be fairly consistent in rapidly growing parts of photosynthetic corals, and time dependent isotopic variations therefore reflect changes in environmental conditions. {delta}{sup 18}O variations from Galapagos corals yields meaningful clues regarding seawater temperature, while {delta}{sup 13}C variations reflect changes in photosynthesis, modulated by cloudiness.

  9. Large and unexpected enrichment in stratospheric 16O13C18O and its meridional variation

    PubMed Central

    Yeung, Laurence Y.; Affek, Hagit P.; Hoag, Katherine J.; Guo, Weifu; Wiegel, Aaron A.; Atlas, Elliot L.; Schauffler, Sue M.; Okumura, Mitchio; Boering, Kristie A.; Eiler, John M.

    2009-01-01

    The stratospheric CO2 oxygen isotope budget is thought to be governed primarily by the O(1D)+CO2 isotope exchange reaction. However, there is increasing evidence that other important physical processes may be occurring that standard isotopic tools have been unable to identify. Measuring the distribution of the exceedingly rare CO2 isotopologue 16O13C18O, in concert with 18O and 17O abundances, provides sensitivities to these additional processes and, thus, is a valuable test of current models. We identify a large and unexpected meridional variation in stratospheric 16O13C18O, observed as proportions in the polar vortex that are higher than in any naturally derived CO2 sample to date. We show, through photochemical experiments, that lower 16O13C18O proportions observed in the midlatitudes are determined primarily by the O(1D)+CO2 isotope exchange reaction, which promotes a stochastic isotopologue distribution. In contrast, higher 16O13C18O proportions in the polar vortex show correlations with long-lived stratospheric tracer and bulk isotope abundances opposite to those observed at midlatitudes and, thus, opposite to those easily explained by O(1D)+CO2. We believe the most plausible explanation for this meridional variation is either an unrecognized isotopic fractionation associated with the mesospheric photochemistry of CO2 or temperature-dependent isotopic exchange on polar stratospheric clouds. Unraveling the ultimate source of stratospheric 16O13C18O enrichments may impose additional isotopic constraints on biosphere–atmosphere carbon exchange, biosphere productivity, and their respective responses to climate change. PMID:19564595

  10. Large and unexpected enrichment in stratospheric 16O13C18O and its meridional variation.

    PubMed

    Yeung, Laurence Y; Affek, Hagit P; Hoag, Katherine J; Guo, Weifu; Wiegel, Aaron A; Atlas, Elliot L; Schauffler, Sue M; Okumura, Mitchio; Boering, Kristie A; Eiler, John M

    2009-07-14

    The stratospheric CO(2) oxygen isotope budget is thought to be governed primarily by the O((1)D)+CO(2) isotope exchange reaction. However, there is increasing evidence that other important physical processes may be occurring that standard isotopic tools have been unable to identify. Measuring the distribution of the exceedingly rare CO(2) isotopologue (16)O(13)C(18)O, in concert with (18)O and (17)O abundances, provides sensitivities to these additional processes and, thus, is a valuable test of current models. We identify a large and unexpected meridional variation in stratospheric (16)O(13)C(18)O, observed as proportions in the polar vortex that are higher than in any naturally derived CO(2) sample to date. We show, through photochemical experiments, that lower (16)O(13)C(18)O proportions observed in the midlatitudes are determined primarily by the O((1)D)+CO(2) isotope exchange reaction, which promotes a stochastic isotopologue distribution. In contrast, higher (16)O(13)C(18)O proportions in the polar vortex show correlations with long-lived stratospheric tracer and bulk isotope abundances opposite to those observed at midlatitudes and, thus, opposite to those easily explained by O((1)D)+CO(2). We believe the most plausible explanation for this meridional variation is either an unrecognized isotopic fractionation associated with the mesospheric photochemistry of CO(2) or temperature-dependent isotopic exchange on polar stratospheric clouds. Unraveling the ultimate source of stratospheric (16)O(13)C(18)O enrichments may impose additional isotopic constraints on biosphere-atmosphere carbon exchange, biosphere productivity, and their respective responses to climate change.

  11. Factors determining δ13C and δ18O fractionation in aragonitic otoliths of marine fish

    NASA Astrophysics Data System (ADS)

    Thorrold, Simon R.; Campana, Steven E.; Jones, Cynthia M.; Swart, Peter K.

    1997-07-01

    Fish otoliths are aragonitic accretions located within the inner ear of teleost fish. The acellular nature of otoliths, along with taxon-specific shapes, chronological growth increments, and abundance in the fossil record suggest that the stable isotope chemistry of these structures may be unique recorders of environmental conditions experienced by fish in both modern and ancient water masses. To assess the factors determining δ 13C and δ 18O fractionation in fish otoliths, we reared Atlantic croaker ( Micropogonias undulatus) larvae under controlled environmental conditions. Metabolic effects apparently generated large isotopic disequilibria in the δ 13C values of M. undulatus otoliths. We found evidence of a negative regression between δ 13C- carbonate-δ 13C water (δ 13C) and temperature: δ 13C = -1.78 - 0.18 T °C However, this relationship was aliased to a degree by a positive correlation between δ 13C and somatic growth and otolith precipitation rates. Oxygen isotopes were deposited close to equilibrium with the ambient water. The relationship between temperature and the 18O/ 16O fractionation factor (α) was determined empirically to be: 1000 ln α = 18.56(10 3T K -1) - 32.54 The fractionation factor was not affected by either otolith precipitation or fish growth rates. Reconstruction of water temperature histories should, therefore, be possible from the δ 18O values of M. undulatus otoliths with a precision of 1°C, providing the δ 18O of the ambient water can be estimated.

  12. Loggerhead turtle movements reconstructed from 18O and 13C profiles from commensal barnacle shells

    NASA Astrophysics Data System (ADS)

    Killingley, John S.; Lutcavage, Molly

    1983-03-01

    Commensal barnacles, Chelonibia testudinaria, from logger-head turtles have 18O and 13C variations in their calcitic shells that record the environments in which the turtles live. Isotopic profiles from the barnacle shells can thus be interpreted to reconstruct movements of the host turtle between open ocean and brackish-water regimes.

  13. Quantitative analysis of two-neutron correlations in the 12C(18O,16O)14C reaction

    NASA Astrophysics Data System (ADS)

    Cavallaro, M.; Cappuzzello, F.; Bondì, M.; Carbone, D.; Garcia, V. N.; Gargano, A.; Lenzi, S. M.; Lubian, J.; Agodi, C.; Azaiez, F.; De Napoli, M.; Foti, A.; Franchoo, S.; Linares, R.; Nicolosi, D.; Niikura, M.; Scarpaci, J. A.; Tropea, S.

    2013-11-01

    The 12C(18O,16O)14C and 12,13C(18O,17O)13,14C reactions are studied at 84 MeV. Mass distributions and energy spectra of the ejectiles are measured, indicating the selectivity of these reactions to populate two- and one-neutron configurations in the states of the residual nucleus, respectively. The measured absolute cross-section angular distributions are analyzed by exact finite range coupled reaction channel calculations based on a parameter free double-folding optical potential. The form factors for the (18O,16O) reaction are extracted within an extreme cluster and independent particles scheme with shell-model-derived coupling strengths. The results show that the measured cross sections are accurately described for the first time without the need for any arbitrary scaling factor. The (18O,16O) reaction is thus found to be a powerful tool for quantitative spectroscopic studies of pair configurations in nuclear states.

  14. Pre-treatment Effects on Coral Skeletal δ 13C and δ 18O

    NASA Astrophysics Data System (ADS)

    Grottoli, A. G.; Gibb, O.; Wellington, G. M.

    2003-12-01

    Pre-treatment protocols for coral skeletal stable carbon (δ 13C) and oxygen (δ 18O) isotope analyses include no treatment, bleach (NaOH), hydrogen peroxide (H2O2), or vacuum roasting prior to analysis. Such pre-treatments are used to remove organic material prior to isotopic analyses. Researchers that do not pre-treat samples argue that such treatments result in non-linear shifts in coral skeletal δ 13C and δ 18O thus increasing the analytical error in the δ 13C and δ 18O values. Vacuum roasting does cause isotopic shifts and is no longer practiced. However, both no pre-treatment and pre-treatment (with either NaOH or H2O2) coral δ 13C and δ 18O values continue to be published in the literature. In all previous studies of the effects of NaOH and H2O2 pre-treatments on coral δ 13C and δ 18O, the samples sizes were typically small and the exact time interval being sampled and compared was not specifically controlled. Here, we evaluated the effects of NaOH and H2O2 pre-treatments on coral skeletal δ 13C and δ 18O in Pavona clavus and Pavona gigantea from Panama, and Porites compressa from Hawaii. In Panama, at least five coral fragments from five different colonies of each species were stained on November 1978 and April 1979 then collected in November 1979. In Hawaii, at least five coral fragments from five different colonies at 1.7 and 7 m depths were stained on 1 September and 21 November 1996 then collected 2 March 1997. For each fragment, a bulk skeletal sample was extracted representing the entire growth interval between the two stain lines yielding at least 24 mg of material. Sampling between the stain lines ensured that all of the fragments from a given site and species were sampled over the same time interval and avoided any potential contamination from the tissue layer. Eight milligram subsamples from each fragment were subjected to 24 hours of the following treatments: NaOH, H2O2, Milli-Q filtered water (control), or no pre-treatment (control

  15. 13C-18O isotope signatures and ‘clumped isotope’ thermometry in foraminifera and coccoliths

    NASA Astrophysics Data System (ADS)

    Tripati, Aradhna K.; Eagle, Robert A.; Thiagarajan, Nivedita; Gagnon, Alexander C.; Bauch, Henning; Halloran, Paul R.; Eiler, John M.

    2010-10-01

    Accurate constraints on past ocean temperatures and compositions are critical for documenting climate change and resolving its causes. Most proxies for temperature are not thermodynamically based, appear to be subject to biological processes, require regional calibrations, and/or are influenced by fluid composition. As a result, their interpretation becomes uncertain when they are applied in settings not necessarily resembling those in which they were empirically calibrated. Independent proxies for past temperature could provide an important means of testing and/or expanding on existing reconstructions. Here we report measurements of abundances of stable isotopologues of calcitic and aragonitic benthic and planktic foraminifera and coccoliths, relate those abundances to independently estimated growth temperatures, and discuss the possible scope of equilibrium and kinetic isotope effects. The proportions of 13C- 18O bonds in these samples exhibits a temperature dependence that is generally similar to that previously been reported for inorganic calcite and other biologically precipitated carbonate-containing minerals (apatite from fish, reptile, and mammal teeth; calcitic brachiopods and molluscs; aragonitic coral and mollusks). Most species that exhibit non-equilibrium 18O/ 16O (δ 18O) and 13C/ 12C (δ 13C) ratios are characterized by 13C- 18O bond abundances that are similar to inorganic calcite and are generally indistinguishable from apparent equilibrium, with possible exceptions among benthic foraminiferal samples from the Arctic Ocean where temperatures are near-freezing. Observed isotope ratios in biogenic carbonates can be explained if carbonate minerals generally preserve a state of ordering that reflects the extent of isotopic equilibration of the dissolved inorganic carbon species.

  16. 14C and δ13C in Mytilus californianus shells as a proxy of upwelling intensity

    NASA Astrophysics Data System (ADS)

    Ferguson, J. E.; Johnson, K. R.; Santos, G. M.; Meyer, L.; Acaylar, K.; Tripati, A. K.

    2010-12-01

    Along the west coast of North America, climate and marine productivity is strongly affected by seasonal to interannual changes in coastal upwelling intensity. Our understanding of the variability of upwelling on these timescales in the past is limited by the short duration of instrumental records. Changes in upwelling intensity are expected to affect the δ13C and radiocarbon (14C) content of seawater dissolved inorganic carbonate (DIC) due to the variable mixing of old, upwelled seawater into surface waters. If these seasonal variations in the carbon isotope composition of seawater DIC are recorded in marine bivalve shells then they have the potential to provide valuable information about the extent of upwelling in these regions in the past. However, bivalve shell carbon isotope compositions are complicated by a number of factors including the contribution of metabolic carbon. To examine whether the carbon isotope compositions of California mussel (Mytilus californianus) shells could be used to produce records of upwelling intensity we collected living mussels from Newport Beach, CA. Sequential samples were generated from the outer calcite layer of these shells and analyzed for stable isotopes, trace elements and radiocarbon. These geochemical profiles are compared with instrumental records and a nearby timeseries of seawater DIC δ13C and 14C. We show that seasonal Mytilus californianus shell 14C values agree well with seawater DIC 14C measurements. Interpretation of δ13C is more problematic with shell δ13C lower than measured seawater DIC δ13C by up to 1 ‰, consistent with what might be expected due to incorporation of metabolic carbon. Results are also presented from Mytilus californianus shells, collected from Mexico to Oregon following the strong El Niño event of 1997-1998. This event caused a collapse of upwelling and provides an ideal opportunity to examine whether the carbon isotope composition of Mytilus californianus shells show evidence of the

  17. Enhancing the Accuracy of Carbonate δ18O and δ13C Measurements by SIMS

    NASA Astrophysics Data System (ADS)

    Orland, I. J.; Kozdon, R.; Linzmeier, B.; Wycech, J.; Sliwinski, M.; Kitajima, K.; Kita, N.; Valley, J. W.

    2015-12-01

    The precision and accuracy of carbonate δ18O & δ13C analysis by multicollector SIMS is well established if standards match samples in structure and major/minor element chemistry. However, low-T- and bio-carbonates used to construct paleoclimate archives can include complex internal structures and some samples analyzed at WiscSIMS (and other SIMS labs) have a consistent, sample-dependent offset between average SIMS δ18O measurements and bulk δ18O analyses by phosphoric-acid digestion. The offset is typically <1‰, but recent work has discovered samples where the offset is greater — up to 1.8‰ (average SIMS δ18O values < corresponding conventional measurements). Notably, δ13C offsets have not been observed even in samples with a δ18O offset. We conducted tests to characterize the δ18O offset in different low-T carbonate materials. Multiple potential causes were examined: perhaps the measured offset is real and conventional analyses include material that SIMS excludes (and vice versa); analytical errors and inter-lab (mis)calibration; depth-profiling effects; porosity; and the effects of variable minor element composition. One explanation implicates water and/or organic matter within carbonate that is ionized during SIMS analysis, but sometimes removed for bulk analysis. Two diagnostic tools help monitor such contaminants during SIMS analysis: 1) simultaneous measurement of [16O1H], and 2) secondary ion yield. Offsets of 0.3 to 1.8‰ in δ18O correlate to [16O1H] for 7 studies of Nautilus, foraminifera, pteropods and speleothems. Offsets were not observed in all foraminifera. For Nautilus, foraminifera, otoliths, and speleothems we also tested pre-treatment techniques (e.g. vacuum roasting, hydrogen peroxide), for which there is no agreed procedure in conventional bulk analyses. For SIMS analyses, pre-treatments had varied influence on the δ18O value, [16O1H], the concentration of "organic markers" like 12C14N and 31P, and mineralogy (of aragonite

  18. 14C and 13C characteristics of higher plant biomarkers in Washington margin surface sediments

    NASA Astrophysics Data System (ADS)

    Feng, Xiaojuan; Benitez-Nelson, Bryan C.; Montluçon, Daniel B.; Prahl, Fredrick G.; McNichol, Ann P.; Xu, Li; Repeta, Daniel J.; Eglinton, Timothy I.

    2013-03-01

    Plant wax lipids and lignin phenols are the two most common classes of molecular markers that are used to trace vascular plant-derived OM in the marine environment. However, their 13C and 14C compositions have not been directly compared, which can be used to constrain the flux and attenuation of terrestrial carbon in marine environment. In this study, we describe a revised method of isolating individual lignin phenols from complex sedimentary matrices for 14C analysis using high pressure liquid chromatography (HPLC) and compare this approach to a method utilizing preparative capillary gas chromatography (PCGC). We then examine in detail the 13C and 14C compositions of plant wax lipids and lignin phenols in sediments from the inner and mid shelf of the Washington margin that are influenced by discharge of the Columbia River. Plant wax lipids (including n-alkanes, n-alkanoic (fatty) acids, n-alkanols, and n-aldehydes) displayed significant variability in both δ13C (-28.3‰ to -37.5‰) and Δ14C values (-204‰ to +2‰), suggesting varied inputs and/or continental storage and transport histories. In contrast, lignin phenols exhibited similar δ13C values (between -30‰ and -34‰) and a relatively narrow range of Δ14C values (-45‰ to -150‰; HPLC-based measurement) that were similar to, or younger than, bulk OM (-195‰ to -137‰). Moreover, lignin phenol 14C age correlated with the degradation characteristics of this terrestrial biopolymer in that vanillyl phenols were on average ˜500 years older than syringyl and cinnamyl phenols that degrade faster in soils and sediments. The isotopic characteristics, abundance, and distribution of lignin phenols in sediments suggest that they serve as promising tracers of recently biosynthesized terrestrial OM during supply to, and dispersal within the marine environment. Lignin phenol 14C measurements may also provide useful constraints on the vascular plant end member in isotopic mixing models for carbon source

  19. Towards the measurement of the13C(d, p)14C cross section using AMS

    NASA Astrophysics Data System (ADS)

    Murillo-Morales, S.; Barrón-Palos, L.; Chávez, E.; Araujo-Escalona, V.

    2017-07-01

    A plan to study the total cross section for the13C(d, p)14C nuclear reaction has been developed for energies in the center-of-mass frame between 133 and 400 keV. The proposed experiment will use a deuterium beam (1-3 MeV of energy) from the Instituto de Física-UNAM 5.5 MV Van de Graaff accelerator and the produced14C will be afterwards measured by AMS technique in the LEMA-UNAM (HVEE 1 MV Tandetron). One of the main goals is to study the performance of the LEMA-UNAM facility in the cross section measurement in comparison with other data reported in the literature, measured by other techniques. In this work we present the current status of these studies. The relevance of the13C(d, p)14C reaction in the study of compound nucleus formation as well as in some astrophysics scenarios, and the importance of the development of the AMS technique to measure cross sections of nuclear reactions of astrophysical interest in Mixico are also discussed.

  20. 13C 18O clumping in speleothems: Observations from natural caves and precipitation experiments

    NASA Astrophysics Data System (ADS)

    Daëron, M.; Guo, W.; Eiler, J.; Genty, D.; Blamart, D.; Boch, R.; Drysdale, R.; Maire, R.; Wainer, K.; Zanchetta, G.

    2011-06-01

    The oxygen isotope composition of speleothems is an important proxy of continental paleoenvironments, because of its sensitivity to variations in cave temperature and drip water δ 18O. Interpreting speleothem δ 18O records in terms of absolute paleotemperatures and δ 18O values of paleo-precipitation requires quantitative separation of the effects of these two parameters, and correcting for possible kinetic isotope fractionation associated with precipitation of calcite out of thermodynamic equilibrium. Carbonate clumped-isotope thermometry, based on measurements of Δ47 (a geochemical variable reflecting the statistical overabundance of 13C 18O bonds in CO 2 evolved from phosphoric acid digestion of carbonate minerals), potentially provides a method for absolute speleothem paleotemperature reconstructions independent of drip water composition. Application of this new technique to karst records is currently limited by the scarcity of published clumped-isotope studies of modern speleothems. The only modern stalagmite reported so far in the literature yielded a lower Δ47 value than expected for equilibrium precipitation, possibly due to kinetic isotope fractionation. Here we report Δ47 values measured in natural speleothems from various cave settings, in carbonate produced by cave precipitation experiments, and in synthetic stalagmite analogs precipitated in controlled laboratory conditions designed to mimic natural cave processes. All samples yield lower Δ47 and heavier δ 18O values than predicted by experimental calibrations of thermodynamic equilibrium in inorganic calcite. The amplitudes of these isotopic disequilibria vary between samples, but there is clear correlation between the amount of Δ47 disequilibrium and that of δ 18O. Even pool carbonates believed to offer excellent conditions for equilibrium precipitation of calcite display out-of-equilibrium δ 18O and Δ47 values, probably inherited from prior degassing within the cave system. In addition

  1. Mechanisms linking metabolism of Helicobacter pylori to (18)O and (13)C-isotopes of human breath CO2.

    PubMed

    Som, Suman; De, Anulekha; Banik, Gourab Dutta; Maity, Abhijit; Ghosh, Chiranjit; Pal, Mithun; Daschakraborty, Sunil B; Chaudhuri, Sujit; Jana, Subhra; Pradhan, Manik

    2015-06-03

    The gastric pathogen Helicobacter pylori utilize glucose during metabolism, but the underlying mechanisms linking to oxygen-18 ((18)O) and carbon-13 ((13)C)-isotopic fractionations of breath CO2 during glucose metabolism are poorly understood. Using the excretion dynamics of (18)O/(16)O and (13)C/(12)C-isotope ratios of breath CO2, we found that individuals with Helicobacter pylori infections exhibited significantly higher isotopic enrichments of (18)O in breath CO2 during the 2h-glucose metabolism regardless of the isotopic nature of the substrate, while no significant enrichments of (18)O in breath CO2 were manifested in individuals without the infections. In contrast, the (13)C-isotopic enrichments of breath CO2 were significantly higher in individuals with Helicobacter pylori compared to individuals without infections in response to (13)C-enriched glucose uptake, whereas a distinguishable change of breath (13)C/(12)C-isotope ratios was also evident when Helicobacter pylori utilize natural glucose. Moreover, monitoring the (18)O and (13)C-isotopic exchange in breath CO2 successfully diagnosed the eradications of Helicobacter pylori infections following a standard therapy. Our findings suggest that breath (12)C(18)O(16)O and (13)C(16)O(16)O can be used as potential molecular biomarkers to distinctively track the pathogenesis of Helicobacter pylori and also for eradication purposes and thus may open new perspectives into the pathogen's physiology along with isotope-specific non-invasive diagnosis of the infection.

  2. Body temperatures of modern and extinct vertebrates from 13C-18O bond abundances in bioapatite

    PubMed Central

    Eagle, Robert A.; Schauble, Edwin A.; Tripati, Aradhna K.; Tütken, Thomas; Hulbert, Richard C.; Eiler, John M.

    2010-01-01

    The stable isotope compositions of biologically precipitated apatite in bone, teeth, and scales are widely used to obtain information on the diet, behavior, and physiology of extinct organisms and to reconstruct past climate. Here we report the application of a new type of geochemical measurement to bioapatite, a “clumped-isotope” paleothermometer, based on the thermodynamically driven preference for 13C and 18O to bond with each other within carbonate ions in the bioapatite crystal lattice. This effect is dependent on temperature but, unlike conventional stable isotope paleothermometers, is independent from the isotopic composition of water from which the mineral formed. We show that the abundance of 13C-18O bonds in the carbonate component of tooth bioapatite from modern specimens decreases with increasing body temperature of the animal, following a relationship between isotope “clumping” and temperature that is statistically indistinguishable from inorganic calcite. This result is in agreement with a theoretical model of isotopic ordering in carbonate ion groups in apatite and calcite. This thermometer constrains body temperatures of bioapatite-producing organisms with an accuracy of 1–2 °C. Analyses of fossilized tooth enamel of both Pleistocene and Miocene age yielded temperatures within error of those derived from similar modern taxa. Clumped-isotope analysis of bioapatite represents a new approach in the study of the thermophysiology of extinct species, allowing the first direct measurement of their body temperatures. It will also open new avenues in the study of paleoclimate, as the measurement of clumped isotopes in phosphorites and fossils has the potential to reconstruct environmental temperatures. PMID:20498092

  3. Source apportionment of carbonaceous aerosol in Sao Paulo using 13C and 14C measurements

    NASA Astrophysics Data System (ADS)

    Oyama, Beatriz; Andrade, Maria de Fatima; Holzinger, Rupert; Röckmann, Thomas; Meijer, Harro A. J.; Dusek, Ulrike

    2016-04-01

    The Metropolitan Area of Sao Paulo is affected by high aerosol concentrations, which contain a large fraction of organic material. Up to date, not much is known about the composition and origin of the organic aerosol in this city. We present the first source apportionment of the carbonaceous aerosol fraction in Sao Paulo, using stable (13C) and radioactive carbon isotopes (14C). 14C provides a clear-cut distinction between fossil sources, which contain no 14C, and contemporary sources such as biofuels, biomass burning, or biogenic sources, which contain a typical contemporary 14C/12C ratio. 13C can be used to distinguish C3 plants, such as maize and sugarcane, from C4 plants. This can help to identify a possible impact of sugarcane field burning in the rural areas of Sao Paulo State on the aerosol carbon in the city. In the first part of the study, we compare two tunnel studies: Tunnel 1 is frequented only by light duty vehicles, which run mainly on mixtures of gasoline with ethanol (gasohol, 25% ethanol and 85% gasoline) or hydrated ethanol (5% water and 95% ethanol). Tunnel 2 contains a significant fraction of heavy-duty diesel vehicles, and therefore the fraction of biofuels in the average fleet is lower. Comparison of 14C in organic and elemental carbon (OC and EC) shows that in both tunnels there is no significant contribution of biofuels to EC. Combusting ethanol-gasoline fuels in a vehicle engine does apparently not result in significant EC formation from ethanol. Biofuels contribute around 45% to OC in Tunnel 1 an only 20% in Tunnel 2, reflecting a strong impact of diesel vehicles in Tunnel 2. In the second part of the study we conduct a source apportionment of ambient aerosol carbon collected in a field study during winter (July-August) 2012. Ambient EC has two main sources, vehicular emissions and biomass burning. We estimate a contribution of vehicular sources to EC of roughly 90% during weekdays and 80% during weekends, using the 14C values measured in

  4. Mechanisms linking metabolism of Helicobacter pylori to 18O and 13C-isotopes of human breath CO2

    PubMed Central

    Som, Suman; De, Anulekha; Banik, Gourab Dutta; Maity, Abhijit; Ghosh, Chiranjit; Pal, Mithun; Daschakraborty, Sunil B.; Chaudhuri, Sujit; Jana, Subhra; Pradhan, Manik

    2015-01-01

    The gastric pathogen Helicobacter pylori utilize glucose during metabolism, but the underlying mechanisms linking to oxygen-18 (18O) and carbon-13 (13C)-isotopic fractionations of breath CO2 during glucose metabolism are poorly understood. Using the excretion dynamics of 18O/16O and 13C/12C-isotope ratios of breath CO2, we found that individuals with Helicobacter pylori infections exhibited significantly higher isotopic enrichments of 18O in breath CO2 during the 2h-glucose metabolism regardless of the isotopic nature of the substrate, while no significant enrichments of 18O in breath CO2 were manifested in individuals without the infections. In contrast, the 13C-isotopic enrichments of breath CO2 were significantly higher in individuals with Helicobacter pylori compared to individuals without infections in response to 13C-enriched glucose uptake, whereas a distinguishable change of breath 13C/12C-isotope ratios was also evident when Helicobacter pylori utilize natural glucose. Moreover, monitoring the 18O and 13C-isotopic exchange in breath CO2 successfully diagnosed the eradications of Helicobacter pylori infections following a standard therapy. Our findings suggest that breath 12C18O16O and 13C16O16O can be used as potential molecular biomarkers to distinctively track the pathogenesis of Helicobacter pylori and also for eradication purposes and thus may open new perspectives into the pathogen’s physiology along with isotope-specific non-invasive diagnosis of the infection. PMID:26039789

  5. Comparing α-cellulose δ13C and δ18O to regional climate at Big Thicket National Preserve, Texas

    NASA Astrophysics Data System (ADS)

    Lewis, D. B.; Finkelstein, D. B.; Mora, C. I.; Grissino-Mayer, H. D.; Perfect, E.

    2009-12-01

    Few studies have investigated the relationship between tree-ring δ13C, δ18O, and regional climate in the southeastern U.S. In other regions, tree ring δ13C and δ18O have proven useful for analyzing temporal changes in precipitation, temperature, drought, and relative humidity. The purpose of this study was to characterize the relationships of regional climate with seasonally-resolved tree-ring cellulose δ13C and δ18O records from longleaf pine (Pinus palustris Mill.) trees at Big Thicket National Preserve (BTNP), Texas. BTNP is a semi-tropical area along the southeastern Texas Gulf Coast with a MAP of 1300 mm. Increment cores were collected from living trees in the Big Sandy Creek Unit (BSC) of BTNP, and four trees were randomly selected for isotopic analysis. The latewood (LW) portions of annual rings were removed in small slivers using a scalpel, and α-cellulose was extracted for a 26-year period (1982-2007). The δ13C series were compared to δ18O series from the same tree, and correlations ranged from 0.64 (BSC 005) to 0.18 (BSC 010). Single tree LW δ13C and δ18O chronologies were compared to regional climate records (Region 8, Upper Coast). Three of the four LW δ18O series were significantly correlated to fall (August-October) precipitation and the Palmer z-index, a measure of short-term (monthly) drought. BSC 010 δ18O exhibited no relationship with either climate parameter. Two of the δ13C series were correlated to fall precipitation and z-index. BSC 010 and BSC 015 were not significantly correlated. Averaging the four individual LW δ18O series into a single chronology resulted in significant correlations with fall precipitation (r = -0.60, p = 0.002) and z-index (r = -0.58, p = 0.002). Both relationships were slightly improved by removing BSC 010 from the chronology. The average δ13C chronology was also correlated to fall precipitation (r = -0.59, p = 0.001) and z-index (r = -0.57, p = 0.003). Neither isotope chronology was correlated to

  6. delta13C and delta18O trends across overstory environments in whole foliage and cellulose of three Pinus species.

    PubMed

    Powers, Matthew D; Pregitzer, Kurt S; Palik, Brian J

    2008-09-01

    Stable isotope ratios of carbon (delta(13)C) and oxygen (delta(18)O) are increasingly used to investigate environmental influences on plant physiology. Cellulose is often isolated for isotopic studies, but some authors have questioned the value of this process. We studied trends in delta(13)C and delta(18)O of whole foliage and holocellulose from seedlings of three Pinus species across three overstory environments to evaluate the benefits of holocellulose extraction in the context of a traditional ecological experiment. Both tissue types showed increasing delta(13)C from closed-canopy controls to thinned plots to 0.3 ha canopy gaps, and no change in delta(18)O between overstory environments. delta(13)C of P. resinosa and P. strobus was greater than delta(13)C of P. banksiana in whole foliage and holocellulose samples, and there were no differences in delta(18)O associated with species in either tissue type. Our results suggest whole foliage and holocellulose provide similar information about isotopic trends across broad environmental gradients and between species, but holocellulose may be better suited for studying differences in stable isotope composition between multiple species across several treatments.

  7. A New Look at 29Al and 27Mg from the 18O + 14C Reaction

    NASA Astrophysics Data System (ADS)

    Tabor, Samuel; Dungan, Rutger; Volya, Alexander; Tripathi, Vandana; Abromeit, Brittany; Caussyn, David; Kravvaris, Konstantinos; Lubna, Rebeka; Tai, Pei-Luan

    2016-09-01

    It was possible to compare moderately high-spin states in a nearby pair of odd proton and odd neutron s-d shell nuclei by observing proton-gamma-gamma or alpha-gamma-gamma coincidences, respectively, following the fusion of long-lived radioactive 14C with neutron-rich 18O at a beam energy of 40 MeV using the FSU gamma detector array with digital data acquisition. Eight new states were seen in 29Al, all of which decay directly or indirectly to the 9/2 + level, the highest previously known spin in 29Al. Some of the new states form a very likely yrast M1 decay sequence from (15/2 +) down to the 5/2 + ground state. The new states are relatively well described by pure s-d shell model calculations using the USDA interaction. By contrast the 4 new states found in 27Mg are divided between positive and negative parities reaching up to (13/2 +) and (11/2-). Radiative decays of neutron unbound states in 27Mg will be discussed. Supported in part by NSF Grant No. 1401574.

  8. Geochemical disparity of d13C and d18O in gryphaeidae oysters

    NASA Astrophysics Data System (ADS)

    Videt, B.; Bentaleb, I.; Néraudeau, D.

    2003-04-01

    Several geochemical analyses of stable isotopes have been made on the group of the oysters in the past. However the majority of the studies are often focused on the sole family of Ostreidea which constituted a minority in the oyster diversity during Mesozoic times. The purpose of this study is to improve knowledge of the modality of isotopic signal record in the group of Gryphaeidae, notable for its abundance and its omnipresence within the Mesozoic outcropts. In this way, a high resolution isotopic study was carried out on the genera Pycnodonte and Ceratostreon. Each microgrowth increment was sampled with the aim of following the variations of the isotopic ratios during ontogenis. It was then possible to reveal a cyclicity of the signal for these two genera which is ascribable to a saisonnality. With end to test the validity of our results, the studies were lead on individuals coming from two lineage of Cenomanian and Campanian Gryphaeidae. For each period the individuals were obviously collected in the same thin layer, and thus subjected to same the environmental conditions during their life. The respective signal of Ceratostreon flabellatum and Pycnodonte biauriculata of upper Cenomanian are compared and then respectively confronted with Ceratostreon pliciferum and Pycnodonte vesicularis of final Campanian. Thus it is possible to observe a systematic shift of about of 1 per mil for δ13C -relative to PDB- between the two genera. More surprising, range of values of δ18O is strongly exaggerated for Ceratostreon genus. Also, these values could not be directly translated into term of palaeotemperature. An observation of the isotopic curves reveals a progressive shift of about of +0.5 ppm during ontogenesis of the two Ceratostreon species. The previous works showsthat the fossil oysters have a good aptitude to record fluctuation of the environmental conditions. But this study shows too that the previous results are not generalizable. At beyond this study warns

  9. Natural abundance 13C and 14C analysis of water-soluble organic carbon in atmospheric aerosols.

    PubMed

    Kirillova, Elena N; Sheesley, Rebecca J; Andersson, August; Gustafsson, Örjan

    2010-10-01

    Water-soluble organic carbon (WSOC) constitutes a large fraction of climate-forcing organic aerosols in the atmosphere, yet the sources of WSOC are poorly constrained. A method was developed to measure the stable carbon isotope (δ(13)C) and radiocarbon (Δ(14)C) composition of WSOC for apportionment between fossil fuel and different biogenic sources. Synthetic WSOC test substances and ambient aerosols were employed to investigate the effect of both modern and fossil carbon contamination and any method-induced isotope fractionation. The method includes extraction of aerosols collected on quartz filters followed by purification and preparation for off-line δ(13)C and Δ(14)C determination. The preparative freeze-drying step for isotope analysis yielded recoveries of only ∼70% for ambient aerosols and WSOC probes. However, the δ(13)C of the WSOC isolates were in agreement with the δ(13)C of the unprocessed starting material, even for the volatile oxalic acid probe (6.59 ± 0.37‰ vs 6.33 ± 0.31‰; 2 sd). A (14)C-fossil phthalic acid WSOC probe returned a fraction modern biomass of <0.008 whereas a (14)C-modern sucrose standard yielded a fraction modern of >0.999, indicating the Δ(14)C-WSOC method to be free of both fossil and contemporary carbon contamination. Application of the δ(13)C/Δ(14)C-WSOC method to source apportion climate-affecting aerosols was illustrated be constraining that WSOC in ambient Stockholm aerosols were 88% of contemporary biogenic C3 plant origin.

  10. Multi-proxy approaches to isolating low-frequency climate signals from tree-ring δ13C, δ18O and ring-widths

    NASA Astrophysics Data System (ADS)

    Voelker, S. L.; Johnstone, J. A.; Roden, J. S.; Dawson, T. E.

    2013-12-01

    Tree-ring stable isotope records have been increasingly used as climate proxies and have often improved the coherence of climate signals compared to ring-width variability. Here we explore the potential for combining tree ring 13C, 18O and ring-width data to isolate low-frequency climate variation from 1) bur oak trees from mid-continental USA and 2) coastal California redwood trees. For modern mid-continental oaks, Δ13C [carbon isotope discrimination] and Δ18O [isotopic enrichment above source water] are negatively correlated across space and time, conditions representative of the bioclimatic envelope for this species. Correlations with the vapor pressure deficit at the growing season maximum temperature (VPDmax) were greatest for the dual isotopic signal as compared to Δ13C or Δ18O alone (r = 0.79, 0.69 and 0.75, respectively). As applied to 59 sub-fossil oak logs [14C-dated to 9.97-13.64k Cal yrs BP] from Missouri, USA, this dual isotope signal indicates that the Pleistocene-Holocene transition was characterized by an abrupt transition near the end of the Younger-Dryas period from a cold, wet and relatively stable growing season climate to a more variable early Holocene climate characterized by periods of greater growing season VPD and maximum temperatures. Our data further suggest that correlations between Δ13C or Δ18O and ring-width chronologies may provide a record of decadal to multi-decadal variability in VPDmax. For coastal California redwoods, from 1951-2003, we demonstrate drastic differences in both sign and magnitude of 11-year running correlations between northern California regional Δ13C or δ18O chronologies for 'middlewood' or 'latewood' (MW or LW) and a regional ring-width chronology. Comparisons of trends in these correlations to 11-year means of Pacific Decadal Oscillation index (PDO, May-September) show similarities with MW or LW Δ13C (r = 0.70 and 0.53, respectively) and stronger correspondence with inverted MW and LW δ18O (r = 0

  11. Assessing in situ mineralization of recalcitrant organic compounds in vadose zone sediments using delta13C and 14C measurements.

    PubMed

    Kirtland, Brian C; Aelion, C Marjorie; Stone, Peter A

    2005-01-01

    Few techniques exist to measure the biodegradation of recalcitrant organic compounds such as chlorinated hydrocarbons (CHC) in situ, yet predictions of biodegradation rates are needed for assessing monitored natural attenuation. Traditional techniques measuring O2, CO2, or chemical concentrations (in situ respiration, metabolite and soil air monitoring) may not be sufficiently sensitive to estimate biodegradation rates for these compounds. This study combined isotopic measurements (14C and delta13C of CO2 and delta13C of CHCs) in conjunction with traditional methods to assess in situ biodegradation of perchloroethylene (PCE) and its metabolites in PCE-contaminated vadose zone sediments. CHC, ethene, ethane, methane, O2, and CO2 concentrations were measured over 56 days using gas chromatography (GC). delta13C of PCE, trichloroethylene (TCE) and cis-1,2-dichloroethylene (DCE), delta13C and 14C of vadose zone CO2 and sediment organic matter, and delta13C, 14C, and deltaD of methane were measured using a GC-isotope ratio mass spectrometer or accelerator mass spectrometer. PCE metabolites accounted for 0.2% to 18% of CHC concentration suggesting limited reductive dechlorination. Metabolites TCE and DCE were significantly enriched in (13)C with respect to PCE indicating metabolite biodegradation. Average delta13C-CO2 in source area wells (-23.5 per thousand) was significantly lower compared to background wells (-18.4 per thousand) indicating CHC mineralization. Calculated CHC mineralization rates were 0.003 to 0.01 mg DCE/kg soil/day based on lower 14C values of CO2 in the contaminated wells (63% to 107% modern carbon (pMC)) relative to the control well (117 pMC). Approximately 74% of the methane was calculated to be derived from in situ CHC biodegradation based on the 14C measurement of methane (29 pMC). 14C-CO2 analyses was a sensitive measurement for quantifying in situ recalcitrant organic compound mineralization in vadose zone sediments for which limited

  12. δ18O and δ13C Analysis in Tree Rings of Pterocarpus angolensis Growing in Zimbabwe

    NASA Astrophysics Data System (ADS)

    McLeran, K.; Schoof, J. T.; Lefticariu, L.; Therrell, M.

    2015-12-01

    Instrumental weather records in southern Africa are largely limited to the last 100 years and documentary weather-related data are rare prior to the 1800s, hindering our understanding of the natural and/or anthropogenic factors that influence climate variability over this region. Measuring stable isotopes ratios (commonly 13C/12C and 18O/16O) in tree rings can provide a good proxy for extending climate data beyond the instrumental record. The objective of this study is to characterize historical variations in the climatology underlying extreme climatic events in Zimbabwe using instrumental climate records (precipitation and temperature) and a multi-proxy approach (ring width, δ18O, and δ13C) for dendroclimatic proxy reconstructions. A 90-year (1900-1990) δ18O and δ13C tree ring record using four Pterocarpus angolensis samples is being developed and compared to tree ring width, monthly, seasonal, and annual precipitation totals, meteoric water δ18O values, and mean monthly and seasonal temperature. Preliminary results indicate significant correlations between the average δ18O record and the previous year December precipitation totals (r=0.41, p<0.0001), current year January precipitation totals (r=0.45, p<0.0001), and combined total precipitation for the previous year November and December and current year January (r=0.57, p<0.0001). Furthermore, we find that the δ18O values are strongly influenced by maximum temperature during the previous year December (r=0.39, p=0.0001) and current year January (r=0.40, p=0.0001), and average maximum temperature during the months of the previous year December and current year January and February (r=0.47, p<0.001). We thus present one of the first studies to integrate a multi-proxy approach to investigate historical climate variability in southern Africa using ring widths, and tree ring δ18O and δ13C values of trees growing in Zimbabwe.

  13. Biokinetics of (13)C in the human body after oral administration of (13)C-labeled glucose as an index for the biokinetics of (14)C.

    PubMed

    Masuda, Tsuyoshi; Tako, Yasuhiro; Matsushita, Kensaku; Takeda, Hiroshi; Endo, Masahiro; Nakamura, Yuji; Hisamatsu, Shun'ichi

    2016-09-01

    The retention of (13)C in the human body after oral administration of (13)C-labeled glucose was studied in three healthy volunteer subjects to estimate the 50 year cumulative body burden for (13)C as an index of the committed dose of the radioisotope (14)C. After administration of (13)C-labeled glucose, the volunteers ingested controlled diets with a fixed number of calories for 112 d. Samples of breath and urine were collected up to 112 d after administration. Samples of feces were collected up to 14 d after administration. Hair samples were obtained at 119 d after administration and analyzed as a representative index of the rate of excretion of organic (13)C via pathways such as skin cell exfoliation and mucus secretion. All samples were analyzed for (13)C/(12)C atomic ratio to determine the rate of excretion via each pathway. We then constructed a metabolic model with a total of four pathways (breath, urine, feces, and other) comprising seven compartments. We determined the values of the biokinetic parameters in the model by using the obtained excretion data. From 74% to 94% of the (13)C administered was excreted in breath, whereas  <2% was excreted in urine and feces. In the other pathway, the excretion rate constant in the compartment with the longest residence time stretched to hundreds of days but the rate constant for each subject was not statistically significant (P value  >  0.1). In addition, the dataset for one of the three subjects was markedly different from those of the other two. When we estimated the 50 year cumulative body burden for (13)C by using our model and we included non-statistically significant parameters, a considerable cumulative body burden was found in the compartments excreting to the other pathway. Although our results on the cumulative body burden of (13)C from orally administered carbon as glucose were inconclusive, we found that the compartments excreting to the other pathway had a markedly long residence time and

  14. How yield relates to ash content, Δ13C and Δ18O in maize grown under different water regimes

    PubMed Central

    Cabrera-Bosquet, Llorenç; Sánchez, Ciro; Araus, José Luis

    2009-01-01

    Background and Aims Stable isotopes have proved a valuable phenotyping tool when breeding for yield potential and drought adaptation; however, the cost and technical skills involved in isotope analysis limit its large-scale application in breeding programmes. This is particularly so for Δ18O despite the potential relevance of this trait in C4 crops. The accumulation of minerals (measured as ash content) has been proposed as an inexpensive way to evaluate drought adaptation and yield in C3 cereals, but little is known of the usefulness of this measure in C4 cereals such as maize (Zea mays). The present study investigates how yield relates to ash content, Δ13C and Δ18O, and evaluates the use of ash content as an alternative or complementary criterion to stable isotopes in assessing yield potential and drought resistance in maize. Methods A set of tropical maize hybrids developed by CIMMYT were subjected to different water availabilities, in order to induce water stress during the reproductive stages under field conditions. Ash content and Δ13C were determined in leaves and kernels. In addition, Δ18O was measured in kernels. Key Results Water regime significantly affected yield, ash content and stable isotopes. The results revealed a close relationship between ash content in leaves and the traits informing about plant water status. Ash content in kernels appeared to reflect differences in sink–source balance. Genotypic variation in grain yield was mainly explained by the combination of ash content and Δ18O, whilst Δ13C did not explain a significant percentage of such variation. Conclusions Ash content in leaves and kernels proved a useful alternative or complementary criterion to Δ18O in kernels for assessing yield performance in maize grown under drought conditions. PMID:19773272

  15. Harding Iceland spar: a new delta 18O-delta 13C carbonate standard for hydrothermal minerals.

    USGS Publications Warehouse

    Landis, G.P.

    1983-01-01

    An isotopically homogenous calcite, Iceland spar from the Iceberg claim, near the Harding pegmatite of N New Mexico, has delta 18O +11.78 + or - 0.07per mille (=+22.15per mille for CO2) and delta 13C -4.80 + or - 0.02per mille and has been prepared in quantities suitable for use as a working standard in MS.-R.A.H.

  16. Accelerator mass spectrometry measurements of the 13C (n ,γ )14C and 14N(n ,p )14C cross sections

    NASA Astrophysics Data System (ADS)

    Wallner, A.; Bichler, M.; Buczak, K.; Dillmann, I.; Käppeler, F.; Karakas, A.; Lederer, C.; Lugaro, M.; Mair, K.; Mengoni, A.; Schätzel, G.; Steier, P.; Trautvetter, H. P.

    2016-04-01

    The technique of accelerator mass spectrometry (AMS), offering a complementary tool for sensitive studies of key reactions in nuclear astrophysics, was applied for measurements of the 13C (n ,γ )14C and the 14N(n ,p )14C cross sections, which act as a neutron poison in s -process nucleosynthesis. Solid samples were irradiated at Karlsruhe Institute of Technology with neutrons closely resembling a Maxwell-Boltzmann distribution for k T =25 keV, and also at higher energies between En=123 and 182 keV. After neutron irradiation the produced amount of 14C in the samples was measured by AMS at the Vienna Environmental Research Accelerator (VERA) facility. For both reactions the present results provide important improvements compared to previous experimental data, which were strongly discordant in the astrophysically relevant energy range and missing for the comparably strong resonances above 100 keV. For 13C (n ,γ ) we find a four times smaller cross section around k T =25 keV than a previous measurement. For 14N(n ,p ), the present data suggest two times lower cross sections between 100 and 200 keV than had been obtained in previous experiments and data evaluations. The effect of the new stellar cross sections on the s process in low-mass asymptotic giant branch stars was studied for stellar models of 2 M⊙ initial mass, and solar and 1 /10th solar metallicity.

  17. Temporal variations in 13C and 14C concentrations in particulate organic matter from the southern North Sea

    NASA Astrophysics Data System (ADS)

    Megens, L.; van der Plicht, J.; de Leeuw, J. W.

    2001-09-01

    As a new approach for the characterization and determination of the origin of particulate organic matter (POM) in coastal waters, we measured the 14C activity and 13C/12C isotope ratios and applied molecular analysis by means of AMS, IRMS and pyrolysis-GCMS for both bulk samples and isolated fractions of POM from the North Sea off the Dutch coast. The fractions were obtained by a sequence of chemical treatments separating polysaccharides, proteins, lipids and non-hydrolysable resistant compounds. The 13C/12C and 14C/12C isotope ratios, the 14C activities and the polysaccharide/protein contents were high in the spring and summer samples and significantly lower in the autumn and winter samples. This is explained by the high amount of marine phytoplankton in summer and spring, and the presence of detrital material in autumn and winter. It was noted that phytoplankton as found in the spring and summer samples was ca. 20% enriched in 14C with respect to natural values, very likely caused by 14C contamination of the water from the English Channel by the nuclear fuel reprocessing plant at La Hague, Normandy, France. The 13C/12C isotope ratios and 14C activity data show that the winter sample was not a simple mixture of relatively recent marine phytoplankton and POM from the rivers Rhine and Meuse. The main source of both terrestrial and marine organic matter in POM in winter is resuspended organic matter derived from eroded sea floor deposits with relatively low contributions of polysaccharides and proteins.

  18. Two-dimensional infrared spectra of the 13C=18O isotopomers of alanine residues in an alpha-helix.

    PubMed

    Fang, Chong; Hochstrasser, Robin M

    2005-10-06

    The parameters needed to describe the two-dimensional infrared (2D IR) spectra of the isotopically labeled alpha-helix are presented. The 2D IR spectra in the amide-I' spectral region of a series of singly 13C=18O-labeled 25-residue alpha-helices were measured by three-pulse heterodyned spectral interferometry. The dependence of the spectra on the population time was measured. Individual isotopomer levels (residues 11-14) were clearly identified in 2D IR, downshifted by approximately 61 cm(-1) from the main helical band. By analyzing the line shapes of the 13C=18O diagonal peaks that appeared at approximately 1571.3 +/- 0.8 cm(-1) for all four labeled samples, we observed wider structural distributions for residues 14 and 11 than those for 12 and 13. A small fast component in the correlation function was used to estimate the dynamics of these distributions. In all cases, the v = 1 --> 2 transition showed a more Lorentzian-like line shape and also decayed faster than the v = 0 --> 1 transition, indicating that the population relaxation time of the v = 2 state was significantly faster than the v = 1 state. The amide transitions with naturally abundant 13C=16O appeared at approximately 1594 cm(-1), forming very weak and blurred cross-peaks with 13C=18O isotopomer modes. The effects of spectral interferences on the coherence time dependence of the detection frequency spectrum were also investigated. The methods of first moments and Wigner analysis were developed to circumvent the interference effects on the weak isotopomer transitions. The structural origin of the distributions for individual isotopomers was proposed to be an effect of nearby lysine residues on the intrahelical hydrogen-bond network.

  19. Analysis of 14C and 13C in teeth provides precise birth dating and clues to geographical origin

    PubMed Central

    K, Alkass; BA, Buchholz; H, Druid; KL, Spalding

    2011-01-01

    The identification of human bodies in situations when there are no clues as to the person’s identity from circumstantial data, poses a difficult problem to investigators. The determination of age and sex of the body can be crucial in order to limit the search to individuals that are a possible match. We analyzed the proportion of bomb pulse derived carbon-14 (14C) incorporated in the enamel of teeth from individuals from different geographical locations. The ‘bomb pulse’ refers to a significant increase in 14C levels in the atmosphere caused by above ground test detonations of nuclear weapons during the cold war (1955-1963). By comparing 14C levels in enamel with 14C atmospheric levels systematically recorded over time, high precision birth dating of modern biological material is possible. Above ground nuclear bomb testing was largely restricted to a couple of locations in the northern hemisphere, producing differences in atmospheric 14C levels at various geographical regions, particularly in the early phase. Therefore, we examined the precision of 14C birth dating of enamel as a function of time of formation and geographical location. We also investigated the use of the stable isotope 13C as an indicator of geographical origin of an individual. Dental enamel was isolated from 95 teeth extracted from 84 individuals to study the precision of the 14C method along the bomb spike. For teeth formed before 1955 (N = 17), all but one tooth showed negative Δ14C values. Analysis of enamel from teeth formed during the rising part of the bomb-spike (1955-1963, N = 12) and after the peak (>1963, N = 66) resulted in an average absolute date of birth estimation error of 1.9 ±1.4 and 1.3 ± 1.0 years, respectively. Geographical location of an individual had no adverse effect on the precision of year of birth estimation using radiocarbon dating. In 46 teeth, measurement of 13C was also performed. Scandinavian teeth showed a substantially greater depression in average δ13C

  20. Analysis of 14C and 13C in teeth provides precise birth dating and clues to geographical origin.

    PubMed

    Alkass, K; Buchholz, B A; Druid, H; Spalding, K L

    2011-06-15

    The identification of human bodies in situations when there are no clues as to the person's identity from circumstantial data, poses a difficult problem to the investigators. The determination of age and sex of the body can be crucial in order to limit the search to individuals that are a possible match. We analyzed the proportion of bomb pulse derived carbon-14 ((14)C) incorporated in the enamel of teeth from individuals from different geographical locations. The 'bomb pulse' refers to a significant increase in (14)C levels in the atmosphere caused by above ground test detonations of nuclear weapons during the cold war (1955-1963). By comparing (14)C levels in enamel with (14)C atmospheric levels systematically recorded over time, high precision birth dating of modern biological material is possible. Above ground nuclear bomb testing was largely restricted to a couple of locations in the northern hemisphere, producing differences in atmospheric (14)C levels at various geographical regions, particularly in the early phase. Therefore, we examined the precision of (14)C birth dating of enamel as a function of time of formation and geographical location. We also investigated the use of the stable isotope (13)C as an indicator of geographical origin of an individual. Dental enamel was isolated from 95 teeth extracted from 84 individuals to study the precision of the (14)C method along the bomb spike. For teeth formed before 1955 (N=17), all but one tooth showed negative Δ(14)C values. Analysis of enamel from teeth formed during the rising part of the bomb-spike (1955-1963, N=12) and after the peak (>1963, N=66) resulted in an average absolute date of birth estimation error of 1.9±1.4 and 1.3±1.0 years, respectively. Geographical location of an individual had no adverse effect on the precision of year of birth estimation using radiocarbon dating. In 46 teeth, measurement of (13)C was also performed. Scandinavian teeth showed a substantially greater depression in

  1. FT-IR spectra of 18O-, and 13C-enriched CO2 in the ν3 region: High accuracy frequency calibration and spectroscopic constants for 16O12C18O, 18O12C18O, and 16O13C16O

    NASA Astrophysics Data System (ADS)

    Elliott, Ben M.; Sung, Keeyoon; Miller, Charles E.

    2015-06-01

    In this report, we extend our Fourier transform infrared (FT-IR) spectroscopy measurements of CO2 in the ν3 region (2200-2450 cm-1, 65-75 THz) to the 18O-, and 13C-substituted isotopologues, using the JPL Bruker IFS-125HR Fourier Transform Spectrometer (JPL-FTS). High quality (S/N ∼ 2000) spectra were obtained separately for each of the 18O-, and 13C-isotopically enriched samples. The absolute wavenumber accuracies were better than 3 × 10-6 cm-1 (∼100 kHz) for strong, isolated transitions, calibrated against the highest accuracy reported CO and 16O12C16O (626) frequency measurements. The JPL-FTS performance and calibration procedure is shown to be reliable and consistent, achievable through vigorous maintenance of the optical alignment and regular monitoring of its instrumental line shape function. Effective spectroscopic constant fits of the 00011 ← 00001 fundamental bands for 16O12C18O (628), 18O12C18O (828), and 16O13C16O (636) were obtained with RMS residuals of 2.9 × 10-6 cm-1, 2.8 × 10-6 cm-1, and 2.9 × 10-6 cm-1, respectively. The observed bands encompassed 79 lines over the Jmax range of P67/R67, 47 lines over P70/R62, and 60 lines over P70/R70 for 628, 828, and 636, respectively. These results complement our recent work on the 17O-enriched isotopologues (Elliott et al., 2014), providing additional high-quality frequency measurements for atmospheric remote sensing applications.

  2. Wood {delta}13C, {delta}18O and radial growth responses of residual red pine to variable retention harvesting.

    PubMed

    Powers, Matthew D; Pregitzer, Kurt S; Palik, Brian J; Webster, Christopher R

    2010-03-01

    Variable retention harvests are used to enhance the development of structural complexity in managed forests by retaining living trees and other structural legacies from the pre-harvest ecosystem. While harvesting should increase resource availability to residual trees, greater crown exposure may also increase environmental stress, which makes it difficult to predict growth in different structural environments. We used stable carbon isotope ratios (delta(13)C) of annual rings from red pine trees (Pinus resinosa Ait.) as an index of intrinsic water use efficiency (iWUE), the ratio of photosynthetic carbon assimilation (A) to stomatal conductance (g(s)), to better understand how differences in physiological performance relate to growth responses following harvests that left residuals dispersed, aggregated between small (0.1 ha) gaps or aggregated between large (0.3 ha) gaps. Stable oxygen isotope ratios (delta(18)O) were used as an index of g(s) to investigate the drivers behind changes in iWUE. Retention harvesting did not appear to affect delta(13)C or delta(18)O at the stand scale when compared to unharvested control stands, but there was a significant, negative correlation between residual tree delta(13)C and plot basal area in the second and third years after harvesting that suggests declining iWUE as overstory competition increases. Residual tree delta(18)O was similar across treatments and basal areas. Trees in variable retention harvests showed small but positive increases in radial growth from the pre-treatment to post-treatment measurement periods, while radial growth declined in unharvested control stands. There were no significant differences in radial growth among retention treatments. Our results suggest residual red pine in relatively open environments benefit from greater A but do not show evidence of changes in g(s) that would indicate altered water relations.

  3. Correction algorithm for online continuous flow δ13C and δ18O carbonate and cellulose stable isotope analyses

    NASA Astrophysics Data System (ADS)

    Evans, M. N.; Selmer, K. J.; Breeden, B. T.; Lopatka, A. S.; Plummer, R. E.

    2016-09-01

    We describe an algorithm to correct for scale compression, runtime drift, and amplitude effects in carbonate and cellulose oxygen and carbon isotopic analyses made on two online continuous flow isotope ratio mass spectrometry (CF-IRMS) systems using gas chromatographic (GC) separation. We validate the algorithm by correcting measurements of samples of known isotopic composition which are not used to estimate the corrections. For carbonate δ13C18O) data, median precision of validation estimates for two reference materials and two calibrated working standards is 0.05‰ (0.07‰); median bias is 0.04‰ (0.02‰) over a range of 49.2‰ (24.3‰). For α-cellulose δ13C18O) data, median precision of validation estimates for one reference material and five working standards is 0.11‰ (0.27‰); median bias is 0.13‰ (-0.10‰) over a range of 16.1‰ (19.1‰). These results are within the 5th-95th percentile range of subsequent routine runtime validation exercises in which one working standard is used to calibrate the other. Analysis of the relative importance of correction steps suggests that drift and scale-compression corrections are most reliable and valuable. If validation precisions are not already small, routine cross-validated precision estimates are improved by up to 50% (80%). The results suggest that correction for systematic error may enable these particular CF-IRMS systems to produce δ13C and δ18O carbonate and cellulose isotopic analyses with higher validated precision, accuracy, and throughput than is typically reported for these systems. The correction scheme may be used in support of replication-intensive research projects in paleoclimatology and other data-intensive applications within the geosciences.

  4. Reconstruction of last-deglacial palaeoclimate in Northeast Japan using 14C and δ13C records of marsh deposits

    NASA Astrophysics Data System (ADS)

    Shinozaki, T.; Minoura, K.; Kondo, M.; Yasuyuki, S.; Masatoshi, S.; Uchida, M.

    2009-12-01

    Today, global warming has been regarded as a serious problem. High-resolution palaeoclimatic records are needed to be reconstructed to accurately predict climate for the future. From our observations of continuous peat sediment sequences, augmented by a detailed 14C chronology and δ13C, we reconstructed hydrological circulation that related to Asia Monsoon since last 15ka. We used a sediment core (8.8m total thickness) from the Tashiro mire (40°41‧N, 144°55‧, 570m a.s.l.), Northeast Japan. It mostly consisted of peat sediment and four well known dated tephras interbedded. The base of the core is To-H tephra (about 15,000 cal BP), and the other tephras corresponded to the To-Cu (about 6,000 cal BP), To-a (1,000 cal BP) and B-Tm (about AD915) demonstrated by EPMA analysis of volcanic glasses. And we conduct 14C measurement about 50 samples, for sphagnum within peat sediments and bulk organic carbon. Hence, those sediments may have recorded abrupt climatic changes in the last-deglaciation, early-Holocene and late-Holocene. In this study, in order to reconstruct hydrological circulation around the East Asia, we carried out δ13C measurement, from a bulk organic carbon within peat sediments, that indicate for humidity or precipitation variability. So δ13C value, in the Northeast Japan, records humidity fluctuation which is nearly connected with the East Asia Monsoon. We report decadal to centennial scale environmental changes, based on a δ13C records and a detailed 14C chronology, in terrestrial at the Northwest Pacific region for the last-deglaciation.

  5. Tracing the intrusion of fossil carbon into coastal Louisiana macrofauna using natural 14C and 13C abundances

    NASA Astrophysics Data System (ADS)

    Wilson, Rachel M.; Cherrier, Jennifer; Sarkodee-Adoo, Judith; Bosman, Samantha; Mickle, Alejandra; Chanton, Jeffrey P.

    2016-07-01

    The Deepwater Horizon oil spill released a large volume of 13C and radiocarbon depleted organic matter to the northern Gulf of Mexico. Evidence of petroleum-derived carbon entering the offshore planktonic foodweb, as well as widespread oiling of coastal areas documented in previous studies suggests that hydrocarbons could have entered the near shore foodweb. To test this hypothesis, we measured radiocarbon (Δ14C%) and stable carbon isotopes (δ13C) in an assortment of fish tissue, invertebrate tissue and shell samples collected within a year of the spill at seven sites from Louisiana to Florida USA across the northern Gulf of Mexico. We observed a west-east gradient with the most depleted radiocarbon values found in Terrebonne Bay, Louisana and increasingly enriched radiocarbon values in organisms collected at sites to the east. Depleted radiocarbon values as low as -10% in invertebrate soft tissue from Terrebonne suggest assimilation of fossil carbon (2.8±1.2%), consistent with the hypothesis that organic matter from petrochemical reservoirs released during the Deepwater Horizon spill entered the coastal food web to a limited extent. Further there was a significant correlation between radiocarbon and δ13C values in invertebrate tissue consistent with this hypothesis. Both oyster tissue and hard head catfish tissue collected in impacted areas of coastal Louisiana were significantly depleted in 14C and 13C relative to organisms collected in the unaffected Apalachicola Bay, Florida (p<0.014). Alternative explanations for these results include the influence of chronic hydrocarbon pollution along the western gulf coast or that the organisms ingest carbon derived from 14C depleted organic matter mobilized during the erosion of coastal marshes in southern Louisiana.

  6. Cycles and trends in the δ18O and δ13C records over the Jurassic and Early Cretaceous

    NASA Astrophysics Data System (ADS)

    Martinez, Mathieu; Dera, Guillaume

    2015-04-01

    The million-year fluctuations of the Mesozoic climate are explored through spectral analyses performed on an exhaustive compilation of δ18O and δ13C data measured on belemnite rostra. The data include more than 3500 data points, all coming from Western Tethys and Euro-boreal domains, and covering a time interval spanning 76 Myr from the Sinemurian (~197 Ma; Early Jurassic) to the Aptian (~123 Ma; Early Cretaceous) with an average sample step of ~0.04 Myr. Spectral analyses are performed using the multi-taper method and the evolutive Fast Fourier Transform in order to get an accurate estimate of significant periods and their evolution during geological times. The age uncertainties of the Geological Time Scale 2012 are taken into account to assess the impact of these uncertainties on the identification of the significant periods. After implementing an error model that simulates the uncertainties of the Geological Time Scale, two periods remains significant: the δ13C displays a high-amplitude period at 9.1 Myr, while the δ18O displays a high-amplitude period at 16.4 Myr. The 16.4-Myr period is only expressed in the Early and Middle Jurassic, with maximum amplitudes reached during the 'Toarcian Plateau' (Dera et al., 2011). It is probably a consequence of the activity of the Karoo-Ferrar Large Igneous Province and is an event in the δ18O rather than a true cycle. The 9.1-Myr period displays a spectacular continuity from the Toarcian to the Aptian, and could be related to this intriguing 9.1-Myr cycle observed in the δ13C from the Cenozoic, related to a Myr-amplitude modulation of the eccentricity cycles (Boulila et al., 2012). The δ13C in the Western Tethys thus appears to have a very rhythmic behaviour, interpreted here as a long-term orbital modulation of moisture and heat transfer from equatorial to higher latitudes, modulating in return continental weathering, nutrient and detrital exports to basins, neritic vs. pelagic productivity and finally preservation

  7. Mechanistic studies on the phytylation and methylation steps in bacteriochlorophyll a biosynthesis: an application of the /sup 18/O-induced isotope effect in /sup 13/C NMR

    SciTech Connect

    Emery, V.C.; Akhtar, M.

    1987-02-24

    The high-resolution /sup 13/C NMR spectrum of bacteriochlorophyll a biosynthesized from (1-/sup 13/C,1,1,4-/sup 18/O/sub 3/)-5-aminolevulinic acid by growing cells of Rhodopseudomonas sphaeroides has shown both the C-17/sup 3/ and C-13/sup 3/ resonances consist of three additional components upfield shifted from the -/sup 16/O- /sup 13/C double bond /sup 16/O resonance. By comparison with the /sup 13/C NMR spectrum obtained for phytyl acetate containing /sup 13/C and /sup 18/O selectively in the ester linkage, these components have been identified as the bridge (-/sup 18/O- /sup 13/C double bond /sup 16/O), non bridge (-/sup 16/O-/sup 13/C double bond /sup 18/O), and dual-labeled (-/sup 18/O-/sup 13/C double bond /sup 18/O) isotopomers, These results have been interpreted to suggest that both the ester bonds of bacteriochlorophyll a are produced by a carboxy-alklyl transfer process.

  8. sup 13 C and sup 18 O isotopic disequilibrium in biological carbonates: II. In vitro simulation of kinetic isotope effects

    SciTech Connect

    McConnaughey, T. )

    1989-01-01

    Biological carbonates are built largely from CO{sub 2}, which diffuses across the skeletogenic membrane and reacts to form HCO{sub 3}{sup {minus}}. Kinetic discrimination against the heavy isotopes {sup 18}O and {sup 13}C during CO{sub 2} hydration and hydroxylation apparently causes most of the isotopic disequilibrium observed in biological carbonates. These kinetic isotope effects are expressed when the extracytosolic calcifying solution is thin and alkaline, and HCO{sub 3}{sup {minus}} precipitates fairly rapidly as CaCO{sub 3}. In vitro simulation of the calcifying environment produced heavy isotope depletions qualitatively similar to, but somewhat more extreme than, those seen in biological carbonates. Isotopic equilibration during biological calcification occurs through CO{sub 2} exchange across the calcifying membrane and by admixture ambient waters (containing HCO{sub 3}{sup {minus}}) into the calcifying fluids. Both mechanisms tend to produce linear correlations between skeletal {delta}{sup 13}C and {delta}{sup 18}O.

  9. Using Position-Specific 13C and 14C Labeling and 13C-PLFA Analysis to Assess Microbial Transformations of Free Versus Sorbed Alanine

    NASA Astrophysics Data System (ADS)

    Apostel, C.; Herschbach, J.; Bore, E. K.; Kuzyakov, Y.; Dippold, M. A.

    2015-12-01

    Sorption of charged or partially charged low molecular weight organic substances (LMWOS) to soil mineral surfaces delays microbial uptake and therefore mineralization of LMWOS to CO2, as well as all other biochemical transformations. We used position-specific labeling, a tool of isotope applications novel to soil sciences, to compare the transformation mechanisms of sorbed and non-sorbed alanine in soil. Alanine as an amino acid links C- and N-cycles in soil and therefore is a model substance for the pool of LMWOS. To assess transformations of sorbed alanine, we added position-specific and uniformly 13C and 14C labeled alanine tracer to soil that had previously been sterilized by γ-radiation. The labeled soil was added to non-sterilized soil from the same site and incubated. Soil labeled with the same tracers without previous sorption was prepared and incubated as well. We captured the respired CO2 and determined its 14C-activity at increasing time intervals. The incorporation of 14C into microbial biomass was determined by chloroform fumigation extraction (CFE), and utilization of individual C positions by distinct microbial groups was evaluated by 13C-phospholipid fatty acid analysis (PLFA). A dual peak in the respired CO2 revealed two sorption mechanisms. To compare the fate of individual C atoms independent of their concentration and pool size in soil, we applied the divergence index (DI). The DI reveals the convergent or divergent behavior of C from individual molecule positions during microbial utilization. Alanine C-1 position was mainly oxidized to CO2, while its C-2 and C-3 were preferentially incorporated in microbial biomass and PLFA. This indicates that sorption by the COOH group does not protect this group from preferential oxidation. Microbial metabolism was determinative for the preferential oxidation of individual molecule positions. The use of position-specific labeling revealed mechanisms and kinetics of microbial utilization of sorbed and non

  10. Evaporation induced 18O and 13C enrichment in lake systems: A global perspective on hydrologic balance effects

    NASA Astrophysics Data System (ADS)

    Horton, Travis W.; Defliese, William F.; Tripati, Aradhna K.; Oze, Christopher

    2016-01-01

    Growing pressure on sustainable water resource allocation in the context of global development and rapid environmental change demands rigorous knowledge of how regional water cycles change through time. One of the most attractive and widely utilized approaches for gaining this knowledge is the analysis of lake carbonate stable isotopic compositions. However, endogenic carbonate archives are sensitive to a variety of natural processes and conditions leaving isotopic datasets largely underdetermined. As a consequence, isotopic researchers are often required to assume values for multiple parameters, including temperature of carbonate formation or lake water δ18O, in order to interpret changes in hydrologic conditions. Here, we review and analyze a global compilation of 57 lacustrine dual carbon and oxygen stable isotope records with a topical focus on the effects of shifting hydrologic balance on endogenic carbonate isotopic compositions. Through integration of multiple large datasets we show that lake carbonate δ18O values and the lake waters from which they are derived are often shifted by >+10‰ relative to source waters discharging into the lake. The global pattern of δ18O and δ13C covariation observed in >70% of the records studied and in several evaporation experiments demonstrates that isotopic fractionations associated with lake water evaporation cause the heavy carbon and oxygen isotope enrichments observed in most lakes and lake carbonate records. Modeled endogenic calcite compositions in isotopic equilibrium with lake source waters further demonstrate that evaporation effects can be extreme even in lake records where δ18O and δ13C covariation is absent. Aridisol pedogenic carbonates show similar isotopic responses to evaporation, and the relevance of evaporative modification to paleoclimatic and paleotopographic research using endogenic carbonate proxies are discussed. Recent advances in stable isotope research techniques present unprecedented

  11. Imprint of CO2 emission in atmosphere and biosphere on the basis of 14C and 13C measurements

    NASA Astrophysics Data System (ADS)

    Pazdur, Anna; Gabryś, Alicja; Kuc, Tadeusz; Pawełczyk, Sławomira; Piotrowska, Natalia; Rakowski, Andrzej; Różański, Kazimierz; Sensuła, Barbara

    2015-04-01

    As is shown in the IPCC (Intergovernmental Panel on Climate Change) report, the observed climate changes are caused, among others, by human activity. Mainly emission of CO2 to the atmosphere coming from the burning of fossil fuels, can have dire consequences for life on Earth and development of humankind. The report uses, among others, data obtained from isotopic measurements in the biosphere. Measurements of 14C and 13C concentration in modern atmospheric carbon dioxide and biosphere allow the determination of the decrease of the concentration of this isotope. Furthermore, the magnitude of emission to the atmosphere of carbon dioxide not containing the isotope 14C can be estimated on this basis. Such emission stems from fossil fuel combustion - petroleum, natural gas and black coal. A sensitive bioindicator of the emission are annual tree rings. The measurements of 14C concentration in tree ring material using AMS allow to see its seasonal changes. Trees, treated as an archive of changes in conjunction with information about the isotopic composition of carbon can be used for monitoring of environment as sensitive bioindicators on local, as well as on the global scale. Regular investigations of isotopic composition of carbon in trees have been carried out in the GADAM Centre for the urban areas of both Poland and worldwide. This method can be applied in the study of the emission of CO2 to the atmosphere and its spatial and temporal distribution connected with the production of energy by power plants based on fossil fuel combustion for the area of southern Poland. Modelling of CO2 emission using both 14C and 13C carbon isotopes measured in pine tree rings on the background of climatic changes will be presented. The national ecological policy in the era of global warming requires the manufacturers of energy to get involved in the development of methods suitable for monitoring the state of the environment. Hence, the interest in the area of monitoring the fossil fuel

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

    NASA Astrophysics Data System (ADS)

    Smajgl, Danijela; Stöbener, Nils; Mandic, Magda

    2017-04-01

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

  13. Sub-seasonally resolved δ18O, δ13C, Mg, Sr, Ba, U and Zn records from a Belgian spleothem covering the last 700 years

    NASA Astrophysics Data System (ADS)

    Van Rampelbergh, M.; Verheyden, S.; Cheng, H.; Edwards, R.; Keppens, E.; Claeys, P. F.

    2013-12-01

    Every cave system is unique and every stalagmite has its own behavior. Therefore, when using stalagmites for paleoclimate reconstructions at high-resolution, a good understanding of what the measured proxies are reflecting is required. Generally such information is obtained by cave monitoring and/or by comparing the measured records with other paleoclimate records in the region. A stalagmite from the Han-sur-Lesse cave (Belgium) displays an extremely high growth rate (1mm/y) and annual lamination over the last 700 years allowing the comparison of the measured proxy values with the instrumental record and leading to a robust understanding of their climate transfer functions. The age model is established by layer counting and agrees well with 4 U/Th-ages and one 14C-age, confirming the seasonal character of the layering. A one-year cave monitoring with a two-week cave-visiting frequency monitored the recording of the different proxy signals in the modern calcite and their relationships to the outside cave conditions. Sub-seasonal δ18O and δ13C measurements (3 samples a layer) were carried out on the upper 50 years. The remaining 650 years were sampled for isotopes on a seasonal scale by drilling one sample per layer. LA-ICP-MS measurements for Mg, Sr, Ba, U and Zn concentrations were line tracked on the upper 50 years and are compared with the sub-seasonally resolved isotope records. Cave monitoring results show that the δ18O and δ13C values of fresh glass-slab calcite increase from November to April when the cave temperatures decrease and the drip rate increase. Results from the sub-seasonal isotope sampling show that the δ18O and δ13C values increase within the white more porous layers and decrease in the dark more compact layers. Consequently, white layers are formed during wetter and colder periods while dark layers reflect drier and warmer conditions. Further comparison of the sub-seasonal isotope and trace elemental records with instrumental data will

  14. Insights on Organic Carbon Inputs in the Delaware Estuary from Compound-Specific δ13C and Δ14C

    NASA Astrophysics Data System (ADS)

    Sikes, E. L.; Mollenhauer, G.; Schefuss, E.; Freeman, K. H.; Hermes, A. L.

    2016-02-01

    Land-derived vascular plant particulate organic matter (POM) is delivered to estuaries via rivers, yet its fate is difficult to constrain between land and sea. POM is intricately linked to sediment dynamics, making it susceptible to deposition, resuspension, and trapping. We assessed the spatial and seasonal variation in algal and vascular plant-derived POM for a transect down the Delaware Estuary, using n-alkane and fatty acid biomarkers and their compound specific δ13C values as tracers of organic matter provenance. n-Alkane distributions, and their low δ13C values reveal a markedly higher proportion of terrestrial inputs in bottom waters relative to the overlying surface waters throughout the estuary, and suggest significant marsh POM contributions that were previously undocumented. Fatty acid δ13C distributions indicate similar sources. Bacterial fatty acids from sediments in the estuarine turbidity maximum (ETM) with isotope values of -30 ‰ suggest preferential uptake of terrestrial organic matter by sedimentary bacteria. Lines of evidence from both compound classes highlight marsh contributions to the ETM and in the lower estuary. Compound-specific Δ14C data from ETM sediments indicate both burial and degradation of aged terrestrial POM. Modelling of estuarine circulation suggests input of marsh POM is driven by lateral pumping in the estuary. The input of wetland POM, long recognized as a critical resource for animal ecology, may be geochemically and volumetrically important in the processing and delivery of terrestrial organic carbon to the coastal ocean.

  15. Ontogeny and habitat change in Mesozoic cephalopods revealed by stable isotopes ( δ18O, δ13C)

    NASA Astrophysics Data System (ADS)

    Lukeneder, Alexander; Harzhauser, Mathias; Müllegger, Stefan; Piller, Werner E.

    2010-07-01

    Stable isotope ( δ18O and δ13C) ratios were measured in successive aragonitic shell sequences of ammonoids (class Cephalopoda) to determine whether their depth distributions changed within ontogeny and whether stable isotope values differ in various morphological groups (e.g. Leiostraca vs. Trachyostraca). We concentrate mainly on δ18O for temperature results and added δ13C data to obtain information on the ontogenetic history, for which full spiral measurements were undertaken for the first time. To obtain valid stable isotope data from ammonoid shells, we measured ontogenetic sequences (full shell) within different genera. Data sets from the Jurassic ( Cadoceras) and Cretaceous ( Hypacanthoplites, Nowakites) were chosen due to the pure primary aragonitic shell preservation. The study was designed to extract better information on the habitat and life cycle of fossil cephalopods (e.g. ammonoids) in comparison with recent cephalopods (e.g. Nautilus, Spirula, Sepia) possessing equivalent or comparable hard parts. The data from three genera suggest different modes of life in at least two morphological groups. We detected and established two main groups with different ontogenetic strategies based on the δ18O data. The wcw-type (warm-cool-warm type) of Cadoceras resembles strategies in Nautilus and Sepia, which migrate from shallow into deeper environments and back in ontogeny ( wc-type, warm-cool-type), and the cw-type (cool-warm type) of Hypacanthoplites resembling the first two migration phases of Spirula ( cwc-type), which migrates from deeper into shallower and back again into deeper habitats. The main (three) phases revealed by both δ18O and δ13C data sets most probably reflect diet changes in juvenile to mid-aged individuals, followed by a habitat change for spawning adults. In Cadoceras the temperatures range from 21.2 °C for juveniles down to 12.1 °C for mid-aged individuals and back up 16.9 °C in adults. The cw- type strategy of Hypacanthoplites

  16. The stable isotopic composition of a phosphorite deposit: δ13C, δ34S, and δ18O

    USGS Publications Warehouse

    Piper, D.Z.; Kolodny, Y.

    1987-01-01

    The stable isotopes of carbon and sulfur in a major marine sedimentary phosphate deposit from the northwestern United States (the Phosphoria Formation of Permian age) characterize the chemical properties of the depositional environment. The δ34S and δ13C analyses suggest deposition under conditions of variable redox from a solution the acidity of which was controlled by reaction with carbonate rocks and exchange with seawater. The δ18O concentration of apetite indicates phosphatization in a shallow sea, during three glacial and intervening interglacial stages. These data tend to corroborate the interpretation of field studies by others, that the apatite formed on a continental shelf in an area of intense oceanic upwelling during several episodes of sea level change. 

  17. Microbial transformations of free versus sorbed alanine analyzed by position-specific 13C and 14C labeling and 13C-PLFA analysis

    NASA Astrophysics Data System (ADS)

    Apostel, Carolin; Dippold, Michaela; Bore, Ezekiel; Kuzyakov, Yakov

    2015-04-01

    Sorption of charged or partially charged low molecular weight organic substances (LMWOS) to soil mineral surfaces delays microbial uptake and therefore mineralization of LMWOS to CO2, as well as all other biochemical transformations. We used position-specific labeling, a tool of isotope applications novel to soil sciences, to compare the transformation mechanisms of sorbed and non-sorbed alanine in soil. Alanine as an amino acid links C- and N-cycles in soil and therefore is a model representative for the pool of LMWOS. To assess transformations of sorbed alanine, we combined position-specifically and uniformly 13C and 14C labeled alanine tracer solution with a loamy haplic luvisol that had previously been sterilized by γ-radiation. After shaking the mixtures, the supernatant was removed, as was all non-sorbed alanine by repeated shaking with millipore water. The labeled soil was added to non-sterilized soil from the same site. To compare the effect of sorption, soil labeled with the same position-specifically labeled tracers without previous sorption was prepared and incubated as well. We captured the respired CO2 and determined its 14C-activity at increasing time steps. The incorporation of 14C into microbial biomass was determined by CFE, and utilization of individual C positions by distinct microbial groups was evaluated by 13C-PLFA analysis. A dual peak in the respired CO2 revealed the influence of two sorption mechanisms. Microbial uptake and transformation of the sorbed alanine was 3 times slower compared to non-sorbed alanine. To compare the fate of individual C atoms independent of their concentration and pool size in soil, we introduced the divergence index (DI). The DI reveals the convergent or divergent behaviour of C from individual molecule positions during microbial utilization. The DI revealed, that alanines C-1 position was mainly oxidized to CO2, while its C-2 and C-3 were preferentially incorporated in microbial biomass and PLFAs. This indicates

  18. Quantifying and overcoming bioturbation in marine sediment cores: dual 14C and δ18O analysis on single foraminifera

    NASA Astrophysics Data System (ADS)

    Lougheed, Bryan; Metcalfe, Brett; Wacker, Lukas

    2017-04-01

    Marine sediment cores used in palaeoceanography form the basis of our current understanding of past global climate and ocean chemistry. Precision and accuracy of geochronological control in these sediment cores are crucial in unravelling the timing of rapid shifts in palaeoclimate and, ultimately, the interdependency of global climate mechanisms and their causality. Aware of the problems associated with bioturbation (the mixing of ocean sediments by benthic organisms) palaeoceanographers generally aim to retrieve sediment cores from locations with high sediment accumulation rates, thus minimising the influence of bioturbation as much as possible. However, the practice of concentrating only on areas of the ocean floor with high sedimentation accumulation rates has the potential to introduce a geographical bias into our understanding of global palaeoclimate. For example, global time averaged sediment accumulation rates for the ocean floor (excluding continental margins) indicate that vast areas of the ocean floor have sediment accumulation rates less than the recommended minimum advised sediment accumulation rates of 10 cm/ka or greater. Whilst many studies have focussed on quantifying the impact of bioturbation on our understanding of the past, few have attempted to overcome the problems associated with bioturbation. Recent pioneering developments in 14C AMS at the Laboratory of Ion Beam Physics at ETH Zürich have led to the development of the Mini Carbon Dating System (MICADAS). This compact 14C AMS system can be coupled to a carbonate handling system, thus enabling the direct AMS measurement of gaseous samples, i.e. without graphitisation, allowing for the analysis of carbonate samples of <100 μg. Likewise, while earlier isotope ratio mass spectrometry (IRMS) technology required a minimum of 100 μg of carbonate to produce a successful δ18O measurement, more recent advances in IRMS technology have made routine measurements of as little as 5 μg possible

  19. Climate signals in tree-ring δ(18) O and δ(13) C from southeastern Tibet: insights from observations and forward modelling of intra- to interdecadal variability.

    PubMed

    Zeng, Xiaomin; Liu, Xiaohong; Treydte, Kerstin; Evans, Michael N; Wang, Wenzhi; An, Wenling; Sun, Weizhen; Xu, Guobao; Wu, Guoju; Zhang, Xuanwen

    2017-08-23

    Stable isotopes in tree rings are increasingly used as proxies for climatic and ecophysiological changes. However, uncertainties remain about the strength and consistency of their response to environmental variation at different temporal (i.e. seasonal to inter-decadal) scales. We developed 5 yr of intra-seasonal and 62 yr of early- and late-wood δ(13) C and δ(18) O series of Smith fir (Abies georgei var. smithii) on the southeastern Tibetan Plateau, and used a process-based forward model to examine the relative importance of environmental and physiological controls on the isotopic data. In this temperate high-altitude region, the response, both δ(18) O and δ(13) C, is primarily to variations in relative humidity, but by different processes. In δ(18) O, the response is via source water δ(18) O but also arises from leaf water (18) O enrichment. In δ(13) C, the response is via changes in stomatal conductance but is modified by carry-over effects from prior periods. We conclude that tree-ring δ(18) O may be a more robust climate proxy than δ(13) C, and δ(13) C may be more suited to studies of site-related physiological responses to the local environment. © 2017 The Authors. New Phytologist © 2017 New Phytologist Trust.

  20. Calibration of δ13C and δ18O measurements in CO2 using Off-axis Integrated Cavity Output Spectrometer (ICOS)

    NASA Astrophysics Data System (ADS)

    Joseph, Jobin; Külls, Christoph

    2014-05-01

    The δ13C and δ18O of CO2 has enormous potential as tracers to study and quantify the interaction between the water and carbon cycles. Isotope ratio mass spectrometry (IRMS) being the conventional method for stable isotopic measurements, has many limitations making it impossible for deploying them in remote areas for online or in-situ sampling. New laser based absorption spectroscopy approaches like Cavity Ring Down Spectroscopy (CRDS) and Integrated Cavity Output Spectroscopy (ICOS) have been developed for online measurements of stable isotopes at an expense of considerably less power requirement but with precision comparable to IRMS. In this research project, we introduce a new calibration system for an Off- Axis ICOS (Los Gatos Research CCIA-36d) for a wide range of varying concentrations of CO2 (800ppm - 25,000ppm), a typical CO2 flux range at the plant-soil continuum. The calibration compensates for the concentration dependency of δ13C and δ18O measurements, and was performed using various CO2 standards with known CO2 concentration and δC13 and δO18 values. A mathematical model was developed after the calibration procedure as a correction factor for the concentration dependency of δ13C and δ18O measurements. Temperature dependency of δ13C and δ18O measurements were investigated and no significant influence was found. Simultaneous calibration of δ13C and δ18O is achieved using this calibration system with an overall accuracy of (~ 0.75±0.24 ‰ for δ13C, ~ 0.81 ±0.26‰ for δ18O). This calibration procedure is found to be appropriate for making Off-Axis ICOS suitable for measuring CO2 concentration and δ13C and δ18O measurements at atmosphere-plant-soil continuum.

  1. Water and nitrogen conditions affect the relationships of Delta13C and Delta18O to gas exchange and growth in durum wheat.

    PubMed

    Cabrera-Bosquet, Llorenç; Molero, Gemma; Nogués, Salvador; Araus, José Luis

    2009-01-01

    Whereas the effects of water and nitrogen (N) on plant Delta(13)C have been reported previously, these factors have scarcely been studied for Delta(18)O. Here the combined effect of different water and N regimes on Delta(13)C, Delta(18)O, gas exchange, water-use efficiency (WUE), and growth of four genotypes of durum wheat [Triticum turgidum L. ssp. durum (Desf.) Husn.] cultured in pots was studied. Water and N supply significantly increased plant growth. However, a reduction in water supply did not lead to a significant decrease in gas exchange parameters, and consequently Delta(13)C was only slightly modified by water input. Conversely, N fertilizer significantly decreased Delta(13)C. On the other hand, water supply decreased Delta(18)O values, whereas N did not affect this parameter. Delta(18)O variation was mainly determined by the amount of transpired water throughout plant growth (T(cum)), whereas Delta(13)C variation was explained in part by a combination of leaf N and stomatal conductance (g(s)). Even though the four genotypes showed significant differences in cumulative transpiration rates and biomass, this was not translated into significant differences in Delta(18)O(s). However, genotypic differences in Delta(13)C were observed. Moreover, approximately 80% of the variation in biomass across growing conditions and genotypes was explained by a combination of both isotopes, with Delta(18)O alone accounting for approximately 50%. This illustrates the usefulness of combining Delta(18)O and Delta(13)C in order to assess differences in plant growth and total transpiration, and also to provide a time-integrated record of the photosynthetic and evaporative performance of the plant during the course of crop growth.

  2. Coral skeletal carbon isotopes (δ13C and Δ14C) record the delivery of terrestrial carbon to the coastal waters of Puerto Rico

    USGS Publications Warehouse

    Moyer, R.P.; Grottoli, A.G.

    2011-01-01

    Tropical small mountainous rivers deliver a poorly quantified, but potentially significant, amount of carbon to the world's oceans. However, few historical records of land-ocean carbon transfer exist for any region on Earth. Corals have the potential to provide such records, because they draw on dissolved inorganic carbon (DIC) for calcification. In temperate systems, the stable- (δ13C) and radiocarbon (Δ14C) isotopes of coastal DIC are influenced by the δ13C and Δ14C of the DIC transported from adjacent rivers. A similar pattern should exist in tropical coastal DIC and hence coral skeletons. Here, δ13C and Δ14C measurements were made in a 56-year-old Montastraea faveolata coral growing ~1 km from the mouth of the Rio Fajardo in eastern Puerto Rico. Additionally, the δ13C and Δ14C values of the DIC of the Rio Fajardo and its adjacent coastal waters were measured during two wet and dry seasons. Three major findings were observed: (1) synchronous depletions of both δ13C and Δ14C in the coral skeleton are annually coherent with the timing of peak river discharge, (2) riverine DIC was always more depleted in δ13C and Δ14C than seawater DIC, and (3) the correlation of δ13C and Δ14C was the same in both coral skeleton and the DIC of the river and coastal waters. These results indicate that coral skeletal δ13C and Δ14C are recording the delivery of riverine DIC to the coastal ocean. Thus, coral records could be used to develop proxies of historical land-ocean carbon flux for many tropical regions. Such information could be invaluable for understanding the role of tropical land-ocean carbon flux in the context of land-use change and global climate change.

  3. Coral skeletal carbon isotopes (δ13C and Δ14C) record the delivery of terrestrial carbon to the coastal waters of Puerto Rico

    USGS Publications Warehouse

    Moyer, R.P.; Grottoli, A.G.

    2011-01-01

    Tropical small mountainous rivers deliver a poorly quantified, but potentially significant, amount of carbon to the world's oceans. However, few historical records of land-ocean carbon transfer exist for any region on Earth. Corals have the potential to provide such records, because they draw on dissolved inorganic carbon (DIC) for calcification. In temperate systems, the stable- (??13C) and radiocarbon (??14C) isotopes of coastal DIC are influenced by the ??13C and ??14C of the DIC transported from adjacent rivers. A similar pattern should exist in tropical coastal DIC and hence coral skeletons. Here, ??13C and ??14C measurements were made in a 56-year-old Montastraea faveolata coral growing ~1 km from the mouth of the Rio Fajardo in eastern Puerto Rico. Additionally, the ??13C and ??14C values of the DIC of the Rio Fajardo and its adjacent coastal waters were measured during two wet and dry seasons. Three major findings were observed: (1) synchronous depletions of both ??13C and ??14C in the coral skeleton are annually coherent with the timing of peak river discharge, (2) riverine DIC was always more depleted in ??13C and ??14C than seawater DIC, and (3) the correlation of ??13C and ??14C was the same in both coral skeleton and the DIC of the river and coastal waters. These results indicate that coral skeletal ??13C and ??14C are recording the delivery of riverine DIC to the coastal ocean. Thus, coral records could be used to develop proxies of historical land-ocean carbon flux for many tropical regions. Such information could be invaluable for understanding the role of tropical land-ocean carbon flux in the context of land-use change and global climate change. ?? 2011 United States Geological Survey.

  4. Carbon isotopic composition (δ(13)C and (14)C activity) of plant samples in the vicinity of the Slovene nuclear power plant.

    PubMed

    Sturm, Martina; Vreča, Polona; Krajcar Bronić, Ines

    2012-08-01

    δ(13)C values of various plants (apples, wheat, and maize) collected in the vicinity of the Krško Nuclear Power Plant (Slovenia) during 2008 and 2009 were determined. By measuring dried samples and their carbonized counterparts we showed that no significant isotopic fractionation occurs during the carbonization phase of the sample preparation process in the laboratory. The measured δ(13)C values of the plants were used for δ(13)C correction of their measured (14)C activities.

  5. Effect of photosynthesis on the abundance of 18O13C16O in atmospheric CO2

    NASA Astrophysics Data System (ADS)

    Hofmann, Magdalena E. G.; Pons, Thijs L.; Ziegler, Martin; Lourens, Lucas J.; Röckmann, Thomas

    2016-04-01

    The abundance of the isotopologue 18O13C16O (Δ47) in atmospheric air is a promising new tracer for the atmospheric carbon cycle (Eiler and Schauble, 2004; Affek and Eiler, 2006; Affek et al., 2007). The large gross fluxes in CO2 between the atmosphere and biosphere are supposed to play a major role in controlling its abundance. Eiler and Schauble (2004) set up a box model describing the effect of air-leaf interaction on the abundance of 18O13C16O in atmospheric air. The main assumption is that the exchange between CO2 and water within the mesophyll cells will imprint a Δ47 value on the back-diffusing CO2 that reflects the leaf temperature. Additionally, kinetic effects due to CO2 diffusion into and out of the stomata are thought to play a role. We investigated the effect of photosynthesis on the residual CO2 under controlled conditions using a leaf chamber set-up to quantitatively test the model assumptions suggested by Eiler and Schauble (2004). We studied the effect of photosynthesis on the residual CO2 using two C3 and one C4 plant species: (i) sunflower (Helianthus annuus), a C3 species with a high leaf conductance for CO2 diffusion, (ii) ivy (Hedera hibernica), a C3 species with a low conductance, and (iii), maize (Zea mays), a species with the C4 photosynthetic pathway. We also investigated the effect of different light intensities (photosynthetic photon flux density of 200, 700 and 1800 μmol m2s-1), and thus, photosynthetic rate in sunflower and maize. A leaf was mounted in a cuvette with a transparent window and an adjustable light source. The air inside was thoroughly mixed, making the composition of the outgoing air equal to the air inside. A gas-mixing unit was attached at the entrance of the cuvette that mixed air with a high concentration of scrambled CO2 with a Δ47 value of 0 to 0.1‰ with CO2 free air to set the CO2 concentration of ingoing air at 500 ppm. The flow rate through the cuvette was adjusted to the photosynthetic activity of the leaf

  6. Diamond growth from subducted carbon implied by correlated δ18O13C variations in diamonds and garnet inclusions

    NASA Astrophysics Data System (ADS)

    Ickert, R. B.; Stachel, T.; Harris, J. W.

    2011-12-01

    Much of our knowledge of the deep-Earth carbon cycle is derived from studies of diamond. The sources of carbon in the mantle and the mechanisms of transport and precipitation as diamond, however, are not entirely understood. Due to the chemical purity of diamond, scientific effort has focussed on syngenetic mineral inclusions and their relationship to their diamond hosts. For example, it is well known that, on a worldwide scale, diamonds with eclogitic inclusions have a distinct δ13C distribution when compared to more abundant peridotitic diamonds. Eclogitic diamonds have a distribution that extends from mantle-like δ13C values (ca. -5%), to very light carbon (<-20%). Strong 13C depletion has been explained by either invoking subducted organic carbon, or through high temperature isotopic fractionation of mantle carbon. Here we report high-precision SIMS δ18O measurements (2σ±< 0.3%) of eclogitic garnet inclusions in diamonds from the Damtshaa mine (Orapa cluster, Botswana). The δ13C values of the host diamond were determined to have a wide range (-4.4% to -18%; Deines et al. 2009; Lithos v.112 p776). From 15 inclusions, the δ18O variations range from +4.8 to +8.8 %. The relative 18O abundances are negatively correlated with the δ13C of the host diamonds, suggesting a link between high δ18O host rocks and low δ13C diamonds. Although fractionation of δ13C values is possible at high temperature, δ18O values are susceptible only to very small high temperature fractionations. For example, Cartigny et al. (2001, EPSL v.185 p85) suggested that CO2 degassing from a carbonate-bearing melt prior to diamond precipitation may be responsible for a δ13C distribution of eclogitic diamonds worldwide that is skewed to 13C depleted compositions. Our data place new constraints on that model. Depending on the C/O ratio of the melt, CO2 degassing will either have a negligible effect on the δ18O of the residual melt, or (at high C/O) induce a positive correlation between

  7. Scale dependence of environmental and physiological correlates of δ18O and δ13C in the magnesium calcite skeletons of bamboo corals (Gorgonacea; Isididae)

    NASA Astrophysics Data System (ADS)

    Thresher, Ronald E.; Neil, Helen

    2016-08-01

    We examine in detail δ18O and δ13C in the calcite internodes of bamboo corals as potential proxies of physiological and environmental variability, through (a) a "core top" calibration that includes specimens from a wide range of habitats and environmental conditions and (b) a comparison of high resolution serial point analyses along radial growth axes of a sub-set of specimens with each other, with instrumental temperature and salinity records, with growth rates and with a nominal skeletal proxy for temperature (Mg/Ca) in the same specimens. At the whole-of-specimen level, δ18O and the intercept of the strong within-specimen regression of δ18O against δ13C correlates highly with ambient temperatures at slopes that are identical to those reported for other marine biogenic carbonates (-0.22 per °C). δ13C varies predominantly with apparent specimen-mean growth rate. It also correlates with the slope of the within-specimen covariance between δ18O and δ13C, which in turn is distributed bi-modally among specimens and linked to differences in apparent growth rates. Within-specimens, variability in δ13C, and to a lesser extent δ18O, correlates between specimens collected in the same region and differs between regions, implying an environmental effect, but the factors involved for either isotope ratio are unclear. Correlations between δ18O and temperature (and Mg/Ca) range from positive to negative among specimens and appear to vary over time even within specimens. The mismatch between the consistent temperature-dependence of δ18O at the whole-of-specimen level and the mixed relationship within-specimens can be reconciled by assuming an unknown temperature-dependent factor affecting δ18O during the growth of Isidid calcite. The contrast between the results of the "core top" temperature calibration for δ18O, which are consistent with studies of other carbonates, and the apparently more complex suite of factors affecting both δ13C and δ18O within specimens

  8. Isotopically (δ13C and δ18O) heavy volcanic plumes from Central Andean volcanoes: a field study

    NASA Astrophysics Data System (ADS)

    Schipper, C. Ian; Moussallam, Yves; Curtis, Aaron; Peters, Nial; Barnie, Talfan; Bani, Philipson; Jost, H. J.; Hamilton, Doug; Aiuppa, Alessandro; Tamburello, Giancarlo; Giudice, Gaetano

    2017-08-01

    Stable isotopes of carbon and oxygen in volcanic gases are key tracers of volatile transfer between Earth's interior and atmosphere. Although important, these data are available for few volcanoes because they have traditionally been difficult to obtain and are usually measured on gas samples collected from fumaroles. We present new field measurements of bulk plume composition and stable isotopes (δ13CCO2 and δ18OH2O+CO2) carried out at three northern Chilean volcanoes using MultiGAS and isotope ratio infrared spectroscopy. Carbon and oxygen in magmatic gas plumes of Lastarria and Isluga volcanoes have δ13C in CO2 of +0.76‰ to +0.77‰ (VPDB), similar to slab carbonate; and δ18O in the H2O + CO2 system ranging from +12.2‰ to +20.7‰ (VSMOW), suggesting significant contributions from altered slab pore water and carbonate. The hydrothermal plume at Tacora has lower δ13CCO2 of -3.2‰ and δ18OH2O+CO2 of +7.0‰, reflecting various scrubbing, kinetic fractionation, and contamination processes. We show the isotopic characterization of volcanic gases in the field to be a practical complement to traditional sampling methods, with the potential to remove sampling bias that is a risk when only a few samples from accessible fumaroles are used to characterize a given volcano's volatile output. Our results indicate that there is a previously unrecognized, relatively heavy isotopic signature to bulk volcanic gas plumes in the Central Andes, which can be attributed to a strong influence from components of the subducting slab, but may also reflect some local crustal contamination. The techniques we describe open new avenues for quantifying the roles that subduction zones and arc volcanoes play in the global carbon cycle.

  9. Tracing source, mixing and uptaking processes of carbon in an epikarst spring-pond system in southeastern Guizhou of China by carbon isotopes (13C-14C)

    NASA Astrophysics Data System (ADS)

    Zhao, M.; Chen, B.; Liu, Z.; Li, H. C.; Yang, R.

    2015-12-01

    δ13C and Δ14C of dissolved inorganic carbon (DIC), particulate organic carbon (POC) and aquatic plants from a karst spring and two spring-fed ponds in Laqiao, Maolan County, Guizhou Province in January, July and October of 2013 were measured to understand the roles of aquatic photosynthesis through DIC uptake in karst surface waters. The mean Δ14C and δ13C values of DIC for the spring pool, midstream and downstream ponds are -60.6±26.3‰ and -13.53±1.97‰, -62.8±62.9‰ and -11.72±2.72‰, and -54.2±56.5‰ and -9.40±2.03‰, respectively. Both Δ14C and δ13C show seasonal variations, with lower Δ14C values but heavier δ13C values in dry season and vice versa in summer rainy season. This observation indicates that (1) the main carbon source of the spring DIC is from limestone bedrock dissolution and soil CO2 with higher contribution in summer due to higher productivity; and (2) 13C and 14C have different behaviors during DIC uptake by aquatic plants and during CO2 exchange between DIC and the atmospheric CO2. Biological uptake of CO2 will not affect the Δ14C of DIC, but lead to δ13CDIC enrichment. CO2 exchange between DIC and the atmospheric CO2 should elevate both the Δ14C and δ13C of DIC. In Laqiao spring-pond system, it seems that the effect of biological uptake on the Δ14C and δ13C of DIC is much stronger than that of CO2 exchange with the atmosphere. The mean Δ14C values of POC from the spring pool, midstream and downstream ponds are -308.1 ±64.3‰, -164.4±84.4‰ and -195.1±108.5‰, respectively, indicating mixture of aquatic algae and detrital particle (clay and dust). More aquatic algae were formed in the stream ponds especially in the summer. SEM results of the POC samples support this conclusion. Furthermore, the Δ14C values of the submerged aquatic plants range from -200.0‰ to -51.3 ‰ and were similar to those of the DIC, indicating that the aquatic plants used DIC for photosynthesis. The Δ14C value of an emergent plant

  10. Natural (18)O and (13)C-urea in gastric juice: a new route for non-invasive detection of ulcers.

    PubMed

    Maity, Abhijit; Pal, Mithun; Som, Suman; Maithani, Sanchi; Chaudhuri, Sujit; Pradhan, Manik

    2017-01-01

    The (13)C-urea breath test ((13)C-UBT), developed a few decades ago, is widely used as a non-invasive diagnostic method to detect only the presence of the gastric pathogen Helicobacter pylori infection; however, the actual disease state, i.e. whether the person harbouring H. pylori has peptic ulcer disease (PUD) or non-ulcerous dyspepsia (NUD), is still poorly understood. Nevertheless, the present (13)C-UBT has numerous limitations, drawbacks and pitfalls owing to the ingestion of (13)C-labelled external urea. Here, we show that H. pylori is able to utilize the natural (13)C and (18)O-urea inherently present in the gastric juice in humans for its urease activity which has never been explored before. In vitro measurements of isotopic fractionations of gastric juice urea provide new insights into the actual state of the infection of PUD or NUD. We also provide evidence of the unusual (13)C and (18)O-isotopic fractionations of breath CO2 that are distinctively altered in individuals with PUD encompassing both gastric and duodenal ulcers as well as with NUD by the enzymatic activity of H. pylori in the gastric niche without oral administration of any (13)C-enriched external urea. This deepens our understanding of the UBT exploiting the natural (13)C and (18)O-gastric juice urea in the pathogenesis of H. pylori infection, reveals the actual disease state of PUD or NUD and thus offers novel opportunities for a simple, robust, cost-effective and non-toxic global strategy devoid of any (13)C-enriched urea for treating these common diseases by a single breath test. Graphical Abstract Urea breath test without any external urea.

  11. Exploring tree age-related trends in δ ^{13}C and δ ^{18}O data from North Scandinavia over the last millennium

    NASA Astrophysics Data System (ADS)

    Hartl-Meier, Claudia; Treydte, Kerstin; Schöne, Bernd; Maus, Michael; Esper, Jan

    2017-04-01

    Stable isotope chronologies from tree-rings are increasingly used as estimators for past environmental changes. It is, however, still not fully understood whether trend biases in dendroisotope data are restricted to "juvenile effects" or additional long-term trends associated with tree age are inherent to long carbon (δ13C) and oxygen (δ18O) chronologies. We here develop a new millennium-long chronology from decadally resolved δ13C and δ18O measurements from 70 living and subfossil pine (Pinus sylvestris L.) trees from northern Scandinavia. Our dataset benefits from a consistently high replication of more than five series since 941 AD until present for both δ13C and δ18O. Preliminary results reveal a positive trend in δ13C over the first 150 years of cambial tree age, while a comparable trend is absent in δ18O. Further analyses will focus on time dependent trends, i.e. environmentally induced changes, over the last millennium. The additional availability of tree-ring width and maximum latewood density measurements from the same trees allows a comprehensive evaluation of parameter specific trends, biases and environmental signals.

  12. Synthesis of 3H, 13C,2H3,15N and 14C-labelled SCH 466036, a histamine 3 receptor antagonist.

    PubMed

    Hesk, D; Borges, S; Dumpit, R; Hendershot, S; Koharski, D; Lavey, C; McNamara, P; Voronin, K

    2015-02-01

    The synthesis of [(3)H]SCH 466036, [Me-(3)H3]SCH 466036, [(13)C,(2)H3,(15)N]SCH 466036 and [(14)C]SCH 466036 is described. [(3)H]SCH 466036 was prepared in two steps via Raney Ni-catalysed exchange with tritiated water. [Me-(3)H3]SCH 466036 was prepared in a single step from [(3)H]methyl iodide in 45% yield. [(13)C,(2)H3,(15)N]SCH 466036 was prepared in two steps from [(15)N]hydroxylamine and [(13)C,(2)H3]methyl iodide with an overall yield of 16%. [(14)C]SCH 466036 was prepared in seven steps from [(14)C]potassium cyanide in an overall yield of 13%.

  13. Tree-ring δ13C and δ18O responses to climate change, wildfire, and forest thinning in ponderosa pine ecosystems

    NASA Astrophysics Data System (ADS)

    Wei, L.; Zhang, J.; Marshall, J. D.

    2011-12-01

    We examined the last 200 years of stable carbon and oxygen isotopes in tree rings extracted from >200 year-old ponderosa pine grown at Blacks Mountain Experimental Forest in northeastern California, USA. Thirty six trees were sampled from four stands treated as follows;1) a natural stand without any management activities, 2) a stand with a thinning in 1996 and a prescribed fire in 1997, 3) a stand that were thinned with 55% tree removals in 1938 and a second thinning in 1996-1997, and 4) a stand that was thinned with 75% tree removals in 1938 and a second thinning in 1996-1997. All stands experienced an intense fire in 1840. Exact tree age was determined from each tree ring sample. We combined tree rings of each decade since 1810 and examined the long-term trends of δ13C. The δ13C remained relatively stable until 1950, when δ13C started dropping gradually. In the first decade of the 21st century, the δ13C has dropped ~1.5 per mil compared to pre-1950. Based on the Palmer Drought Severity Index, we compared δ13C and δ18O in tree rings of six dry years and six wet years, and one of each was picked in six ~30 year segments starting in 1820 and ending in 2010. The δ13C in wet years was significantly lower than in dry years, and no clear pattern was found in δ18O.The thinning practices and the fire had clear effects on δ13C and δ18O in tree rings. The δ13C decreased in tree rings following the 1840 fire. The δ13C increased in the following 5-10 years after thinning, while the δ18O decreased in the next two years immediately following the thinning. The results suggest that tree-ring δ13 C tracks climate, fire, and thinning, while the trend of δ18O responses to these variables requires more careful evaluation.

  14. Stable isotopes (δ 18O and δ 13C), trace and minor element compositions of Recent scleractinians and Last Glacial bivalves at the Santa Maria di Leuca deep-water coral province, Ionian Sea

    NASA Astrophysics Data System (ADS)

    Correa, Matthias López; Montagna, Paolo; Vendrell-Simón, Begoña; McCulloch, Malcolm; Taviani, Marco

    2010-03-01

    ' vital effect. The intercept of the δ 13C18O correlation line with the δ 13C DIC-composition permits recognition of δ 18O equilibrium values of aragonite and thus reconstruction of water temperatures despite strong disequilibrium precipitation. Since the environmental parameters ( T, S and δ 18O sw) are stable, the entire isotopic signal of the coral must be driven by biological fractionation and might reflect growth speed variations, potentially related to pH variations and changes in the saturation state of the calcifying fluid or seasonally varying nutrient availability. Laser ablation tracks show a trace element composition dependent to microstructural zones (fibrous aragonite vs. centres of calcification). The parabolic relation of the classical temperature proxies Mg/Ca and U/Ca point to trace element vital effects, rendering them unreliable in L. pertusa. The P/Ca ratio shows similar values as Desmophyllum dianthus, for which a linear dependence with seawater phosphate (DIP) has been previously demonstrated. Consequently L. pertusa might be an additional nutrient recorder at bathyal depths. From the same site we also analysed the stable isotopic composition of the Last Glacial pectinid bivalve Pseudamussium peslutrae, which has been radiocarbon-dated (AMS- 14C) at 26.3 ka 14C yr BP. The isotope values of the shell calcite document a strongly differing glacial temperature-salinity regime preceding the Holocene coral growth above a prominent hiatus.

  15. δ18O and δ13C Values in Living and Holocene Brachiopods and the Relationship with Oceanographic Variability across Australia's Vast Southern Shelf

    NASA Astrophysics Data System (ADS)

    Dhillon, R.

    2015-12-01

    Carbon and oxygen isotopic compositions of brachiopods are commonly used to reconstruct secular changes in ocean chemistry through the Phanerozoic but few studies have focused on the variations that occur laterally and concurrently across a single vast depositional system. Previous studies have identified significant isotopic variability to occur within an individual stratigraphic layer and the scatter in values has been attributed to diagenesis, non-equilibrium fractionation effects, and variability in oceanography. In order to further investigate these hypotheses, this study evaluates the δ18O and δ13C values from 346 living and Holocene brachiopods collected from surficial sediments across the latitude-parallel southern Australian shelf, a lateral distance of ~3000 km. Modern oceanographic measurements were used to calculate the range in δ18O values of calcite precipitated in apparent equilibrium with ambient seawater. A total of 84% of δ18O values from brachiopod samples (n = 684) fall within the range of calculated equilibrium calcite and accurately record a combination of normal shelf water conditions, winter downwelling across the shelf, and local summer upwelling. Most δ18O outliers are attributed to seasonal upwelling (90 of 108 outliers) and imply that either upwelling occurred in an area that has not been well established as an upwelling zone, or it occurred in a known upwelling area but the intensity was greater than previously measured. The δ13C values of brachiopods increase with increasing depth, which is the opposite of what is reported elsewhere. This unusual δ13C trend is caused by deeper slope currents being sourced from surface water southwest of Tasmania, an area with relatively high δ13C of DIC. The δ13C values of living specimens are consistently lower by 0.5-1.0‰ than most dead specimens, which is attributed to the decrease in δ13C values in the carbon cycle due to combustion of isotopically light fossil fuels over the last 200

  16. Stable Oxygen (δ 18O) and Carbon (δ 13C) Isotopes in the Skeleton of Bleached and Recovering Corals From Hawaii

    NASA Astrophysics Data System (ADS)

    Rodrigues, L. J.; Grottoli, A. G.

    2004-12-01

    Coral skeletal stable oxygen isotopes (δ 18O) reflect changes in seawater temperature and salinity, while stable carbon isotopes (δ 13C) reflect a combination of both metabolic (photosynthesis and feeding) and kinetic fractionation. Together, the two isotopic signatures may be used as a proxy for past bleaching events. During bleaching, increased seawater temperatures often contribute to a decline in zooxanthellae and/or chlorophyll concentrations, resulting in a decrease in photosynthesis. We experimentally investigated the effect of bleaching and subsequent recovery on the δ 13C and δ 18O values of coral skeleton. Fragments from two coral species (Montipora capitata and Porites compressa) from Kaneohe Bay, Hawaii were bleached in outdoor tanks by raising the seawater temperature to 30° C. Additional fragments from the same parent colonies were maintained at ambient seawater temperatures (27° C) in separate tanks as controls. After one month in the tanks, a subset of the fragments was frozen and all remaining fragments were placed back on the reef to recover. All coral fragments were analyzed for their skeletal δ 13C and δ 18O compositions at five time intervals: before, immediately after, 1.5, 4, and 8 months after bleaching. In addition, rates of photosynthesis, calcification, and heterotrophy were also measured. Immediately after bleaching, δ 18O decreased in bleached M. capitata relative to controls, reflecting their exposure to increased seawater temperatures. During recovery, δ 18O values in the treatment M. capitata were not different from the controls. In P. compressa, δ 18O did not significantly differ in bleached and control corals at any time during the experiment. Immediately after bleaching, δ 13C decreased in the bleached fragments of both species relative to controls reflecting decreased photosynthetic rates. However, during recovery δ 13C in both species was greater in bleached than control fragments despite photosynthesis remaining

  17. Magma-derived CO 2 emissions recorded in 14C and 13C content of plants growing in Furnas caldera, Azores

    NASA Astrophysics Data System (ADS)

    Pasquier-Cardin, Aline; Allard, Patrick; Ferreira, Teresa; Hatte, Christine; Coutinho, Rui; Fontugne, Michel; Jaudon, Michel

    1999-09-01

    The environmental impact of fumarolic and soil emanations of magma-derived carbon dioxide across Furnas caldera has been investigated by measuring the 14C and 13C content of 40 specimens of different C3 plants (leaves) growing within and outside the degassing areas. The results demonstrate a significant to large 14C depletion in many of the plants due to assimilation of 14C-free endogenous CO 2 during photosynthesis and leading to artificial radiocarbon ageing of up to 4400 years. The extent of 14C ageing broadly correlates with the intensity of gas manifestations at the sampling sites, as inferred from field observations and measurements of excess CO 2 concentrations in the volcanic ground. It also provides a time-integrated measure of the amount of volcanic CO 2 locally admixed to the ambient air; at several sites this accounts for 15 to 40% of total CO 2 (420 to 600 ppm) in enriched air. In some of the plant species ( Azalea, Camellia and fern) 14C depletion is correlated with an enrichment of 13C due to assimilation of magma-derived CO 2 with a 4‰ higher δ 13C than normal atmosphere. The rate of 13C enrichment averages ca. 0.18‰ by percent of volcanic carbon fixed in the plant and includes enhanced 13C discrimination during photosynthesis as a consequence of increased ambient pCO 2 (inferred at -0.0306‰ per added ppm of volcanic CO 2). Furnas is one of the few volcanoes where clear 13C enrichment in plants due to endogenous degassing has been evidenced. Our results can be used to estimate the local intensity of volcanic soil gas fluxes in the emanating areas of Furnas caldera. They also have implications for radiocarbon dating of past eruptive events in the caldera, since plants artificially aged by previous degassing could be trapped in volcanic deposits.

  18. Reconstruction of water mass properties of the Western Mediterranean using stable isotope ratios (δ18O and δ13C) from Pinna nobilis shells

    NASA Astrophysics Data System (ADS)

    Garcia-March, Jose Rafael; Surge, Donna; Tena-Medialdea, Jose; Torres, Javi; Garcia-Martinez, Micaela

    2017-04-01

    We analysed the stable isotope ratios (δ18O and δ13C) from the calcite of the outer prismatic layer of 8 Pinna nobilis shells at a rate of c. 12-16 samples/year for years between 1997 and 2013. These produced 8 time series between 4 and 16 years long. The empty shells had been collected in two Spanish marine protected areas, Tabarca Island in Alicante and Columbretes Islands in Castellón (4 specimens each). For all shells we constrained the time of death within at least a halve year window. The present study completes previous calibrations by using recorded seawater temperature data during at least two years for each site, coinciding with part of the analysed periods in the shells. Our preliminary results clearly reflect the seasonality of the signal in δ18O values for the entire ontogeny of the individuals studied. However, one specimen from Tabarca Island sampled between years 4 and 11 (corresponding to real age) shows a clear ontogenetic change, with an abrupt reduction in the amplitude of the signal from age 6 to 11 for both δ18O and δ13C values. We hypothesize this pattern relates to the onset of first gonad maturation. Values of δ13C track δ18O values in most individuals, but 3 specimens show low amplitude. For all time series, δ13C values show a decreasing slope with ontogeny similar to previous observations in P. nobilis and other bivalves. Estimated seawater temperature from our δ18O time series reveals the potential of P. nobilis shells as valuable archives of Mediterranean temperature reconstructions in the context of climate change.

  19. Environmental significance of 13C/ 12C and 18O/ 16O ratios of modern land-snail shells from the southern great plains of North America

    NASA Astrophysics Data System (ADS)

    Balakrishnan, Meena; Yapp, Crayton J.; Theler, James L.; Carter, Brian J.; Wyckoff, Don G.

    2005-01-01

    13C/ 12C and 18O/ 16O ratios of aragonite shells of modern land snails from the southern Great Plains of North America were measured for samples from twelve localities in a narrow east-west corridor that extended from the Flint Hills in North Central Oklahoma to the foothills of the Sangre de Cristo Mountains in Northern New Mexico, USA. Across the study area, shell δ 18O values (PDB scale) ranged from -4.1‰ to 1.2‰, while δ 13C values ranged from -13.2‰ to 0.0‰. δ 18O values of the shell aragonite were predicted with a published, steady state, evaporative flux balance model. The predicted values differed (with one exception) by less than 1‰ from locality averages of measured δ 18O values. This similarity suggests that relative humidity at the time of snail activity is an important control on the δ 18O values of the aragonite and emphasizes the seasonal nature of the climatic information preserved in the shells. Correlated δ 13C values of coexisting Vallonia and Gastrocopta suggest similar feeding habits and imply that these genera can provide information on variations in southern Great Plains plant ecology. Although there is considerable scatter, multispecies, transect average δ 13C values of the modern aragonite shells are related to variations in the type of photosynthesis (i.e., C 3, C 4) in the local plant communities. The results of this study emphasize the desirability of obtaining isotope ratios representing averages of many shells in a locale to reduce possible biases associated with local variations among individuals, species, etc., and thus better represent the "neighborhood" scale temporal and/or spatial environmental variations of interest in studies of modern and ancient systems.

  20. Toward the Inference of Deglacial Ocean Dynamics from the Spatial Pattern of LGM-to-Modern d13C and d18O Change

    NASA Astrophysics Data System (ADS)

    Gebbie, G.; Peterson, C. D.; Lisiecki, L. E.; Spero, H. J.

    2014-12-01

    Estimates of the whole-ocean d13C change between the Last Glacial Maximum (LGM) and the modern-day are converging to values of about 0.4 per mil, and are of great use in partitioning land versus ocean contributions to the deglacial carbon cycle. To determine which specific oceanic processes are at play, however, knowledge of the spatial pattern of LGM-to-modern d13C and d18O change is critical. Spatial maps have mostly focused on Atlantic d13C, with less progress for d18O and the Pacific and Indian sectors, due to the concentration of sediment-core observations in the Atlantic and the difficulty in making meaningful maps from sparse data. Here, we demonstrate that a state estimation (or data assimilation) method based on recently compiled data and a simple kinematic ocean model simultaneously produces reasonable results for: 1) global maps of d13C and d18O, 2) uncertainty in the estimated properties, and 3) oceanic water-mass geometry. The observations include benthic d13C and d18O data from 493 marine sediment cores that were collected from the scientific literature and NOAA, PANGEA, and Delphi databases. The kinematic model permits each data point to have influence both up- and downstream along a water-mass pathway, typically allowing a larger geographical range than a statistical interpolation method. No assumption regarding the state of the circulation is necessary, and the modern-day circulation need not be assumed to be representative of the LGM. With this method, meridional (or other) sections can be compared between ocean basins. Furthermore, the internally-consistent d18O and d13C maps are used to determine the LGM-to-modern spatial changes that are robust given the uncertainty and sparsity of data. Rather than simply focus on property maps, we suggest that the link between observations and circulation changes (as reflected by the paths that water travels), points the way toward dynamical processes that must be explained. A particular application of our

  1. A field-based method for simultaneous measurements of the δ18O and δ13C of soil CO2 efflux

    NASA Astrophysics Data System (ADS)

    Mortazavi, B.; Prater, J. L.; Chanton, J. P.

    Three approaches for determining the stable isotopic composition (δ13C and δ18O) of soil CO efflux were compared. A new technique employed mini-towers, constructed of open-topped piping, that were placed on the soil surface to collect soil-emitted CO2. Samples were collected along a vertical gradient and analyzed for CO2 concentration and isotopic composition. These data were then used to produce Keeling plots to determine the δ18O and δ13C of CO2 emitted from the soil. These results were then compared to the δ18O and δ13C of soil-respired CO2 measured with two other techniques: (1) flux chambers and (2) estimation from the application of the diffusional fractionation factor to measured values of below ground soil CO2 and to CO2 in equilibrium with soil water δ18O. Mini-tower δ18O Keeling plots were linear and highly significant (0.81< r 2 > 0.96), in contrast to chamber δ18O Keeling plots, which showed significant curvature, necessitating the use of a mass balance to calculate the δ18O of respired CO2. In the chambers, the values determined for the δ18O of soil respired CO2 approached the value of CO2 in equilibrium with surficial soil water, and the results were significantly δ18O enriched relative to the mini-tower results and the δ18O of soil CO2 efflux

  2. Tooth Enamel δ13C and δ18O Variations in Modern and Archaeological Horses From Northern Kazakhstan as Indicators of Regional Climate

    NASA Astrophysics Data System (ADS)

    Sikora, M. T.; Rosenmeier, M. F.; Stacy, E. M.; Olsen, S. L.

    2007-12-01

    In this study, the oxygen and carbon isotope values of tooth enamel were measured in forty-one modern and twenty-three Copper Age (3600 - 3100 B.C.) horse specimens from the grassland steppe region of northern Kazakhstan. Modern tooth enamel δ13C and δ18O values were compared with the carbon isotopic compositions of local vegetation and the δ18O values of meteoric waters. Tooth enamel isotope values within the Copper Age specimens (attributed to the so-called Botai culture) were, in turn, compared with modern samples. Average carbon isotopic values within modern bulk tooth enamel samples ranged between -13.7 and -12.0‰ (VPDB). This suggests that the diet of modern northern Kazakhstani horses is comprised almost entirely of C3 plants (considering enamel-diet fractionation factors) consistent with documented grassland compositions within the region. The observed amplitude of δ13C variations within individual teeth (typically less than ~2‰) suggests only minimal seasonal variation in the δ13C of grasses attributed to heat and water stress. Alternatively, the minimal seasonal changes observed within intra-tooth δ13C values may be the direct result of fodder provisioning. Ingested water δ18O values derived from oxygen isotope ratios within bulk tooth enamel samples appear statistically indistinguishable from estimates of regional precipitation, suggesting that Kazakhstani horse tooth enamel δ18O measurements may be used as a direct estimate of the oxygen isotopic composition of meteoric waters. Intra-tooth oxygen isotopic variations therefore reflect the pronounced seasonal variability in precipitation δ18O values tied to temperature changes and amount effects observed annually within Kazakhstan. However, these intra-tooth isotopic variations exhibit slightly reduced amplitudes relative to meteoric water values, suggesting that horses likely consume water from buffered sources such as lakes and wells. Average bulk tooth enamel δ13C values within

  3. Tequila authenticity assessment by headspace SPME-HRGC-IRMS analysis of 13C/12C and 18O/16O ratios of ethanol.

    PubMed

    Aguilar-Cisneros, Blanca O; López, Mercedes G; Richling, Elke; Heckel, Frank; Schreier, Peter

    2002-12-18

    By use of headspace SPME sampling and a PLOT column, on-line capillary gas chromatography-isotope ratio mass spectrometry was employed in the combustion (C) and the pyrolysis (P) modes (HRGC-C/P-IRMS) to determine the delta(13)C(VPDB) and delta(18)O(VSMOW) values of ethanol in authentic (n = 14) and commercial tequila samples (n = 15) as well as a number of other spirits (n = 23). Whereas with delta(13)C(VPDB) values ranging from -12.1 to -13.2 per thousand and from -12.5 to -14.8 per thousand similar variations were found for 100% agave and mixed tequilas, respectively, the delta(18)O(VSMOW) data differed slightly within these categories: ranges from +22.1 to +22.8 per thousand and +20.8 to +21.7 per thousand were determined for both the authentic 100% agave and mixed products, respectively. The data recorded for commercial tequilas were less homogeneous; delta(13)C(VPDB) data from -10.6 to -13.9 per thousand and delta(18)O(VSMOW) values from +15.5 to +22.7 per thousand were determined in tequilas of both categories. Owing to overlapping data, attempts to differentiate between white, rested, and aged tequilas within each of the two categories failed. In addition, discrimination of tequila samples from other spirits by means of delta(13)C(VPDB) and delta(18)O(VSMOW) data of ethanol was restricted to the products originating from C(3) as well as C(4)/CAM raw materials.

  4. Cycling of high-molecular-weight dissolved organic matter in the Middle Atlantic Bight as revealed by carbon isotopic ({sup 13}C and {sup 14}C) signatures

    SciTech Connect

    Guo, L.; Santschi, P.H.; Cifuentes, L.A.

    1996-09-01

    Carbon isotopes ({sup 13}C and {sup 14}C) and elemental composition (C and N) in two fractions of colloidal organic matter (COM) were measured to study the origin and cycling of dissolved organic matter (DOM) in the Middle Atlantic Bight (MAB). COM{sub 1} (1 kDa-0.2 {mu}m) was 59% of the bulk DOM in surface Chesapeake Bay waters and decreased to 30-35% in water of the MAB. COM{sub 10} (10 kDa-0.2 {mu}m), which was the high-molecular-weight (HMW) component of COM{sub 1}, comprised 3-12% of the bulk DOM, with highest concentrations in Chesapeake Bay waters and the lowest in deep waters in the MAB. {Delta}{sup 14}C values of COM{sub 1} decreased from nearshore (-21 to +12%) to offshore and from surface (-166 to -85{per_thousand}) to bottom waters (-400 to -304{per_thousand}). Although {Delta}{sup 14}C values of surface-water HMW COM{sub 10} were generally high (-2 to -7{per_thousand}), values for bottom-water COM{sub 10} were much lower (-129 to -709{per_thousand}). The high {Delta}{sup 14}C values in the surface water suggest a particulate origin of pelagic COM, consistent with the contemporary {Delta}{sup 14}C values of particulate organic matter (POM). The very low {Delta}{sup 14}C values of bottom-water COM{sub 10} imply that in addition to the pelagic origin, sedimentary organic C may serve as an important source for the benthic colloids in the bottom nepheloid layer. The general flow direction of organic carbon is from POM to HMW and to LMW DOM. Three colloidal end-members were identified in the MAB as well as in the Gulf of Mexico: estuarine colloids with high {Delta}{sup 14}C values, high C:N ratios, and lower {delta}{sup 13}C values; offshore surface water colloids with intermediate {Delta}{sup 14}C values, lower C:N ratios, and higher {delta}{sup 13}C values; and offshore deep-water colloids with low {Delta}{sup 14}C values, intermediate C:N ratios, and variable {delta}{sup 13}C values. 40 refs., 10 figs., 3 tabs.

  5. Sources and Cycling of Dissolved Organic Carbon in the Gulf of Mexico: Insights from Stable (δ13C) and Radiocarbon (Δ14C) Signatures

    NASA Astrophysics Data System (ADS)

    Walker, B. D.; Druffel, E. R. M.; Griffin, S.; Kolasinski, J.; Roberts, B. J.; Xu, X.; Muller-Karger, F. E.; Rosenheim, B. E.

    2016-02-01

    Understanding the production and remineralization of marine dissolved organic carbon (DOC; 662 GtC) is of primary importance to the global carbon cycle. Together, DOC concentrations, stable (δ13C) and radiocarbon (Δ14C) isotopic measurements provide a powerful toolset for evaluating DOC sources and cycling in aquatic environments. However, to date the Δ14C and δ13C composition of total DOC in both the Mississippi River and the Gulf of Mexico (GOM) basin remains largely unconstrained. This has precluded our basic understanding of DOC biogeochemistry, its persistence and contribution to the base of the marine food web in an economically important U.S. ocean region. The Deepwater Horizon (DWH) spill event in 2010 further exemplified the need for understanding the baseline biogeochemistry of DOM across the terrestrial-marine interface in the Northern GOM. In particular, the relative persistence (e.g. biodegradation) and contribution of DWH oil to the DOC reservoir remains largely unknown. Here we present the first DOC Δ14C and δ13C depth profiles taken from five stations in the Northern GOM: 1) the Mississippi River mouth, 2) the shelf bound, aged river plume, 3) the shelf/slope near the Macondo Well site, 4) offshore in the Loop Current and 5) a nearshore mesoscale eddy. We will discuss these DOC Δ14C and δ13C data with three goals in mind. First, we will attempt to disentangle the complex interplay between riverine, coastal, open and deep ocean DOC cycling. Second we will compare these offshore data to a recently measured DOC Δ14C profile from waters feeding the GOM from the Caribbean in order to evaluate DOC cycling and residence time in the deep GOM basin. Finally, we will discuss results suggesting 10-16% of DWH oil has been incorporated into the marine DOC reservoir.

  6. 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

  7. Investigating the influence of sulphur dioxide (SO 2) on the stable isotope ratios (δ 13C and δ 18O) of tree rings

    NASA Astrophysics Data System (ADS)

    Rinne, K. T.; Loader, N. J.; Switsur, V. R.; Treydte, K. S.; Waterhouse, J. S.

    2010-04-01

    This study reports the influence of a 20th century pollution signal recorded in the δ 13C and δ 18O of absolutely dated tree rings from Quercus robur and Pinus sylvestris from southern England. We identify a correspondence between the inter-relationship and climate sensitivity of stable isotope series that appears to be linked to recent trends in local SO 2 emissions. This effect is most clearly exhibited in the broadleaved trees studied but is also observed in the δ 13C values of the (less polluted) pine site at Windsor. The SO 2 induced stomatal closure leads to a maximum increase of 2.5‰ in the isotope values (δ 13C). The combined physiological response to high pollution levels is less in δ 18O than δ 13C. The SO 2 signal also seems to be present as a period of reduced growth in the two ring-width chronologies. Direct, quantitative correction for the SO 2 effect represents a significant challenge owing to the nature of the records and likely local plant response to environmental pollution. Whilst it appears that this signal is both limited to the late industrial period and demonstrates a recovery in line with improvements in air quality, the role of atmospheric pollution during the calibration period should not be underestimated and adequate consideration needs to be taken when calibrating biological environmental proxies in order to avoid development of biased reconstructions.

  8. Physiological and isotopic (delta(13)C and delta(18)O) responses of three tropical tree species to water and nutrient availability.

    PubMed

    Cernusak, Lucas A; Winter, Klaus; Turner, Benjamin L

    2009-10-01

    Water-use efficiency and stable isotope composition were studied in three tropical tree species. Seedlings of Tectona grandis, Swietenia macrophylla and Platymiscium pinnatum were grown at either high or low water supply, and with or without added fertilizer. These three species previously exhibited low, intermediate and high whole-plant water-use efficiency (TE) when grown at high water supply in unfertilized soil. Responses of TE to water and nutrient availability varied among species. The TE was calculated as experiment-long dry matter production divided by cumulative water use. Species-specific offsets were observed in relationships between TE and whole-plant (13)C discrimination (Delta(13)C(p)). These offsets could be attributed to a breakdown in the relationship between Delta(13)C(p) and the ratio of intercellular to ambient CO(2) partial pressures (c(i)/c(a)) in P. pinnatum, and to variation among species in the leaf-to-air vapour pressure difference (v). Thus, a plot of v.TE against c(i)/c(a) showed a general relationship among species. Relationships between delta(18)O of stem dry matter and stomatal conductance ranged from strongly negative for S. macrophylla to no relationship for T. grandis. Results suggest inter-specific variation among tropical tree species in relationships between stable isotope ratios (delta(13)C and delta(18)O) and the gas exchange processes thought to affect them.

  9. Glacial water mass structure and rapid δ18O and δ13C changes during the last glacial termination in the Southwest Pacific

    NASA Astrophysics Data System (ADS)

    Sikes, Elisabeth L.; Elmore, Aurora C.; Allen, Katherine A.; Cook, Mea S.; Guilderson, Thomas P.

    2016-12-01

    Changes in ocean circulation are thought to have contributed to lowering glacial atmospheric CO2 levels by enhancing deep ocean sequestration of carbon that was returned to the atmosphere during glacial terminations. High-resolution benthic foraminiferal δ13C and δ18O records from a depth transect of cores in the Southwest Pacific Ocean presented here provide evidence that both wind- and thermohaline-driven circulation drove CO2 from the ocean during the last deglaciation. Shallow geochemical stratification in the glacial Southern Ocean was followed by a short pulse of rapid δ13C enrichment to intermediate water depths during Heinrich Stadial 1, indicative of better-ventilated intermediate waters co-occurring with documented wind-driven upwelling in the Southern Ocean. Intermediate depth δ13C enrichment paused at the start of the Antarctic Cold Reversal (∼14.7 ka), implying a brief shallow restratification, while deeper layers were progressively flushed of δ13C-depleted and δ18O-enriched waters, likely caused by the increasing influence of deep waters sourced from the North Atlantic. The coincidence of atmospheric CO2 increases with these geochemical shifts in both shallow and deep cores suggests that shifts in both atmospheric and oceanic circulation contributed to the deglacial rise of CO2.

  10. Tree-ring δ13C and δ18O, leaf δ13C and wood and leaf N status demonstrate tree growth strategies and predict susceptibility to disturbance.

    PubMed

    Billings, S A; Boone, A S; Stephen, F M

    2016-05-01

    Understanding how tree growth strategies may influence tree susceptibility to disturbance is an important goal, especially given projected increases in diverse ecological disturbances this century. We use growth responses of tree rings to climate, relationships between tree-ring stable isotopic signatures of carbon (δ(13)C) and oxygen (δ(18)O), wood nitrogen concentration [N], and contemporary leaf [N] and δ(13)C values to assess potential historic drivers of tree photosynthesis in dying and apparently healthy co-occurring northern red oak (Quercus rubra L. (Fagaceae)) during a region-wide oak decline event in Arkansas, USA. Bole growth of both healthy and dying trees responded negatively to drought severity (Palmer Drought Severity Index) and temperature; healthy trees exhibited a positive, but small, response to growing season precipitation. Contrary to expectations, tree-ring δ(13)C did not increase with drought severity. A significantly positive relationship between tree-ring δ(13)C and δ(18)O was evident in dying trees (P < 0.05) but not in healthy trees. Healthy trees' wood exhibited lower [N] than that of dying trees throughout most of their lives (P < 0.05), and we observed a significant, positive relationship (P < 0.05) in healthy trees between contemporary leaf δ(13)C and leaf N (by mass), but not in dying trees. Our work provides evidence that for plants in which strong relationships between δ(13)C and δ(18)O are not evident, δ(13)C may be governed by plant N status. The data further imply that historic photosynthesis in healthy trees was linked to N status and, perhaps, C sink strength to a greater extent than in dying trees, in which tree-ring stable isotopes suggest that historic photosynthesis was governed primarily by stomatal regulation. This, in turn, suggests that assessing the relative dominance of photosynthetic capacity vs stomatal regulation as drivers of trees' C accrual may be a feasible means of predicting tree

  11. Tree-ring δ13C and δ18O, leaf δ13C and wood and leaf N status demonstrate tree growth strategies and predict susceptibility to disturbance

    PubMed Central

    Billings, S.A.; Boone, A.S.; Stephen, F.M.

    2016-01-01

    Understanding how tree growth strategies may influence tree susceptibility to disturbance is an important goal, especially given projected increases in diverse ecological disturbances this century. We use growth responses of tree rings to climate, relationships between tree-ring stable isotopic signatures of carbon (δ13C) and oxygen (δ18O), wood nitrogen concentration [N], and contemporary leaf [N] and δ13C values to assess potential historic drivers of tree photosynthesis in dying and apparently healthy co-occurring northern red oak (Quercus rubra L. (Fagaceae)) during a region-wide oak decline event in Arkansas, USA. Bole growth of both healthy and dying trees responded negatively to drought severity (Palmer Drought Severity Index) and temperature; healthy trees exhibited a positive, but small, response to growing season precipitation. Contrary to expectations, tree-ring δ13C did not increase with drought severity. A significantly positive relationship between tree-ring δ13C and δ18O was evident in dying trees (P < 0.05) but not in healthy trees. Healthy trees’ wood exhibited lower [N] than that of dying trees throughout most of their lives (P < 0.05), and we observed a significant, positive relationship (P < 0.05) in healthy trees between contemporary leaf δ13C and leaf N (by mass), but not in dying trees. Our work provides evidence that for plants in which strong relationships between δ13C and δ18O are not evident, δ13C may be governed by plant N status. The data further imply that historic photosynthesis in healthy trees was linked to N status and, perhaps, C sink strength to a greater extent than in dying trees, in which tree-ring stable isotopes suggest that historic photosynthesis was governed primarily by stomatal regulation. This, in turn, suggests that assessing the relative dominance of photosynthetic capacity vs stomatal regulation as drivers of trees’ C accrual may be a feasible means of predicting tree responses to some

  12. The stable isotopic composition of Daphnia ephippia reflects changes in δ13C and δ18O values of food and water

    NASA Astrophysics Data System (ADS)

    Schilder, J.; Tellenbach, C.; Möst, M.; Spaak, P.; van Hardenbroek, M.; Wooller, M. J.; Heiri, O.

    2015-06-01

    The stable isotopic composition of fossil resting eggs (ephippia) of Daphnia spp. is being used to reconstruct past environmental conditions in lake ecosystems. However, the underlying assumption that the stable isotopic composition of the ephippia reflects the stable isotopic composition of the parent Daphnia, of their diet and of the environmental water have yet to be confirmed in a controlled experimental setting. We performed experiments with Daphnia pulicaria cultures, which included a control treatment conducted at 12 °C in filtered lake water and with a diet of fresh algae and three treatments in which we manipulated the stable carbon isotopic composition (δ13C value) of the algae, stable oxygen isotopic composition (δ18O value) of the water and the water temperature, respectively. The stable nitrogen isotopic composition (δ15N value) of the algae was similar for all treatments. At 12 °C, differences in algal δ13C values and in δ18O values of water were reflected in those of Daphnia. The differences between ephippia and Daphnia stable isotope ratios were similar in the different treatments (δ13C: +0.2 ± 0.4 ‰ (standard deviation); δ15N: -1.6 ± 0.4 ‰; δ18O: -0.9 ± 0.4 ‰), indicating that changes in dietary δ13C values and in δ18O values of water are passed on to these fossilizing structures. A higher water temperature (20 °C) resulted in lower δ13C values in Daphnia and ephippia than in the other treatments with the same food source and in a minor change in the difference between δ13C values of ephippia and Daphnia (to -1.3 ± 0.3 ‰). This may have been due to microbial processes or increased algal respiration rates in the experimental containers, which may not affect Daphnia in natural environments. There was no significant difference in the offset between δ18O and δ15N values of ephippia and Daphnia between the 12 and 20 °C treatments, but the δ18O values of Daphnia and ephippia were on average 1.2 ‰ lower at 20 °C than at

  13. Variation of atmospheric CO, δ13C, and δ18O at high northern latitude during 2004-2009: Observations and model simulations

    NASA Astrophysics Data System (ADS)

    Park, Keyhong; Wang, Zhihui; Emmons, Louisa K.; Mak, John E.

    2015-10-01

    Atmospheric CO mixing ratios and stable isotope ratios (δ13C and δ18O) were measured at a high northern latitude site (Westman Islands, Iceland) from January 2004 to March 2010 in order to investigate recent multiyear trends of the sources of atmospheric carbon monoxide in the extratropical Northern Hemisphere. During this period, we observed a decrease of about 2% per year in CO mixing ratios with little significant interannual variability. The seasonal cycles for δ13C and δ18O in CO are similar to that in the CO mixing ratio, and there is a pronounced interannual variation in their seasonal extremes occurring in summer and fall, which is driven by changes in the relative contribution of different sources. Some of the sources of CO are anthropogenic in character (e.g., fossil fuel and biofuel combustion and agricultural waste burning), and some are primarily natural (e.g., oxidation atmospheric methane and other hydrocarbons and wildfires), and distinction among the various major sources can, more or less, be distinguished by the stable isotopic composition of CO. We compare our observations with simulations from a 3-D global chemical transport model (MOZART-4, Model for Ozone and Related Chemical Tracers, version 4). Our results indicate the observed trend of anthropogenic CO emissions is mostly responsible for the observed variation in δ13C and δ18O of CO during 2004-2009. Especially, the δ18O enriched sources such as fossil fuel and biofuel sources are controlling the variation. The modeling results indicate decreasing trends in the fossil fuel and biofuel source contributions at Iceland of -0.61 ± 0.26 ppbv/yr and -0.38 ± 0.10 ppbv/yr, respectively, during the observation period.

  14. Speleothem calcite farmed in situ: Modern calibration of δ 18O and δ 13C paleoclimate proxies in a continuously-monitored natural cave system

    NASA Astrophysics Data System (ADS)

    Tremaine, Darrel M.; Froelich, Philip N.; Wang, Yang

    2011-09-01

    Understanding the relationships between speleothem stable isotopes (δ 13C δ 18O) and in situ cave forcing mechanisms is important to interpreting ancient stalagmite paleoclimate records. Cave studies have demonstrated that the δ 18O of inorganically precipitated (low temperature) speleothem calcite is systematically heavier than the δ 18O of laboratory-grown calcite for a given temperature. To understand this apparent offset, rainwater, cave drip water, groundwater, and modern naturally precipitated calcite (farmed in situ) were grown at multiple locations inside Hollow Ridge Cave in Marianna, Florida. High resolution micrometeorological, air chemistry time series and ventilation regimes were also monitored continuously at two locations inside the cave, supplemented with periodic bi-monthly air gas grab sample transects throughout the cave. Cave air chemistry and isotope monitoring reveal density-driven airflow pathways through Hollow Ridge Cave at velocities of up to 1.2 m s -1 in winter and 0.4 m s -1 in summer. Hollow Ridge Cave displays a strong ventilation gradient in the front of the cave near the entrances, resulting in cave air that is a mixture of soil gas and atmospheric CO 2. A clear relationship is found between calcite δ 13C and cave air ventilation rates estimated by proxies pCO 2 and 222Rn. Calcite δ 13C decreased linearly with distance from the front entrance to the interior of the cave during all seasons, with a maximum entrance-to-interior gradient of Δδ 13C CaCO3 = -7‰. A whole-cave "Hendy test" at multiple contemporaneous farming sites reveals that ventilation induces a +1.9 ± 0.96‰ δ 13C offset between calcite precipitated in a ventilation flow path and calcite precipitated on the edge or out of flow paths. This interpretation of the "Hendy test" has implications for interpreting δ 13C records in ancient speleothems. Calcite δ 13C CaCO3 may be a proxy not only for atmospheric CO 2 or overlying vegetation shifts but also for

  15. Chlorophyll a specific Δ14C, δ13C and δ15N values in stream periphyton: implications for aquatic food web studies

    NASA Astrophysics Data System (ADS)

    Ishikawa, N. F.; Yamane, M.; Suga, H.; Ogawa, N. O.; Yokoyama, Y.; Ohkouchi, N.

    2015-07-01

    We determined the isotopic composition of chlorophyll a in periphytic algae attached to a streambed substrate (periphyton). The samples were collected from a stream flowing on limestone bedrock in the Seri River, central Japan. Stable isotope ratios of carbon (δ13C) and nitrogen (δ15N) and natural radiocarbon abundances (Δ14C) were measured in chlorophyll a (δ13Cchl, δ15Nchl and Δ14Cchl) and bulk (δ13Cbulk, δ15Nbulk and Δ14Cbulk) for periphyton, pure aquatic primary producer (Cladophora sp.) and terrestrial primary producer (Quercus glauca). Periphyton δ13Cbulk and δ13Cchl values did not necessarily correspond to δ13Cbulk for an algal-grazing specialist (Mayfly larva, Epeorus latifolium), suggesting that periphyton δ13C values do not faithfully trace carbon transfer between primary producers and primary consumers. Periphyton Δ14Cchl values (-258 ‰ in April and -190 ‰ in October) were slightly lower than Δ14Cbulk values (-228 ‰ in April and -179 ‰ in October), but were close to the Δ14C value for dissolved inorganic carbon (DIC) (-217 ± 31 ‰), which is a mixture of weathered carbonates (Δ14C = -1000 ‰) and dissolved atmospheric CO2 (Δ14C approximately +30 ‰ in 2013). Δ14Cchl values were also close to Δ14Cbulk for E. latifolium (-215 ‰ in April and -199 ‰ in October) and Cladophora sp. (-210 ‰), whereas the Δ14Cbulk value for Q. glauca (+27 ‰) was closer to Δ14C for atmospheric CO2. Although the bulk isotopic composition of periphyton is recognised as a surrogate for the photosynthetic algal community, natural periphyton is a mixture of aquatic and terrestrial organic materials. Our results indicate that the bulk periphyton matrix at the study site consists of 89 to 95 % algal carbon (derived from 14C-depleted DIC) and 5 to 11 % terrestrial organic carbon (derived from 14C-enriched atmospheric CO2).

  16. Closing an early Miocene astronomical gap with Southern Ocean δ18O and δ13C records: Implications for sea level change

    NASA Astrophysics Data System (ADS)

    Miller, Kenneth G.; Baluyot, Ronidell; Wright, James D.; Kopp, Robert E.; Browning, James V.

    2017-06-01

    We present orbital-scale resolution ( 10 kyr) benthic foraminiferal δ18O and δ13C records from the Kerguelen Plateau (Ocean Drilling Program Sites 751 and 747) from 14.5 to 20.0 Ma spanning the Miocene climate optimum (15-17 Ma). Our records fill a critical gap from 17 to 18 Ma, a time when many other deep-sea records are affected by dissolution. We tested the fidelity of published magnetobiostratigraphic age models for these sites by astronomically tuning to the 405 kyr eccentricity cycle. A comparison of spectral estimates between the untuned and tuned records, as well as coherency with Laskar's (2004) eccentricity solution, revealed quasi-100 kyr cyclicity in δ18O and δ13C. There is only a weak signal associated with the 41 kyr obliquity cycle, likely due to the 10 kyr sampling limiting resolution. The δ18O variations point to persistent 405 and quasi-100 kyr modulations of temperature and sea level changes through the early to middle Miocene as predicted by astronomical solutions, with changing dominance of the 100 and 41 kyr beat. Comparison of δ18O records with early to middle Miocene sequences from the New Jersey shelf, northeast Australian margin, Bahamas, and Maldives suggests that the dominant sea level period preserved is the 1.2 Myr obliquity cycle, with sequence boundaries associated with δ18O increases or maxima. On the New Jersey margin, higher-order sequences reflect the quasi-100 kyr eccentricity cycles as modulated by 405 kyr cycles. We suggest that "nesting" of stratigraphic cycles is a function of the following: (1) pervasive (though changing) Milankovitch forcing of global mean sea level change and (2) preservation that depends on sufficient sediment supply and accommodation.

  17. Bomb-pulse 14C analysis combined with 13C and 15N measurements in blood serum from residents of Malmö, Sweden.

    PubMed

    Georgiadou, Elisavet; Stenström, Kristina Eriksson; Uvo, Cintia Bertacchi; Nilsson, Peter; Skog, Göran; Mattsson, Sören

    2013-05-01

    The (14)C content of 60 human blood serum samples from residents of Malmö (Sweden) in 1978, obtained from a biobank, has been measured to estimate the accuracy of (14)C bomb-pulse dating. The difference between the date estimated using the Calibomb software and sampling date varied between -3 ± 0.4 and +0.2 ± 0.5 years. The average age deviation of all samples was -1.5 ± 0.7 years, with the delay between production and consumption of foodstuffs being probably the dominating cause. The potential influence of food habits on the (14)C date has been evaluated using stable isotope δ(13)C and δ(15)N analysis and information about the dietary habits of the investigated individuals. Although the group consisting of lacto-ovo vegetarians and vegans (pooled group) was not completely separated from the omnivores in a stable isotopic trophic level diagram, this analysis proved to add valuable information on probable dietary habits. The age deviation of the sampling date from the respective Calibomb date was found strongly correlated with the δ(13)C values, probably due to influence from marine diet components. For the omnivore individuals, there were indications of seasonal effects on δ(13)C and the age deviation. No significant correlation was found between the age deviation and the δ(15)N values of any dietary group. No influence of sex or year of birth was found on neither the (14)C nor the δ(13)C and δ(15)N values of the serum samples. The data were also divided into two groups (omnivores and pooled group), based on the level of δ(15)N in the samples. The consumption of high δ(15)N-valued fish and birds can be responsible for this clustering.

  18. Estimation of continuous anthropogenic CO2 using CO2, CO, δ13C(CO2) and Δ14C(CO2)

    NASA Astrophysics Data System (ADS)

    Vardag, S. N.; Gerbig, C.; Janssens-Maenhout, G.; Levin, I.

    2015-07-01

    We investigate different methods for estimating anthropogenic CO2 using modelled continuous atmospheric concentrations of CO2 alone, as well as CO2 in combination with the surrogate tracers CO, δ13C(CO2) and Δ14C(CO2). These methods are applied at three hypothetical stations representing rural, urban and polluted conditions. We find that independent of the tracer used, an observation-based estimate of continuous anthropogenic CO2 is not feasible at rural measurement sites due to the low signal to noise ratio of anthropogenic CO2 estimates at such settings. At urban and polluted sites, potential future continuous Δ14C(CO2) measurements with a precision of 5 ‰ or better are most promising for anthropogenic CO2 determination (precision ca. 10-20%), but the insensitivity against CO2 contributions from biofuel emissions may reduce its accuracy in the future. Other tracers, such as δ13C(CO2) and CO could provide an accurate and already available alternative if all CO2 sources in the catchment area are well characterized with respect to their isotopic signature and CO to anthropogenic CO2 ratio. We suggest a strategy for calibrating these source characteristics on an annual basis using precise Δ14C(CO2) measurements on grab samples. The precision of anthropogenic CO2 determination using δ13C(CO2) is largely determined by the measurement precision of δ13C(CO2) and CO2. The precision when using the CO-method is mainly limited by the variation of natural CO sources and CO sinks. At present, continuous anthropogenic CO2 could be determined using the tracers δ13C(CO2) and/or CO with a precision of about 30 %, a mean bias of about 10 % and without significant diurnal discrepancies. This allows significant improvement, validation and bias reduction of highly resolved emission inventories using atmospheric observation and regional modelling.

  19. Sedimentary rocks as sources of ancient organic carbon to the ocean: An investigation through Δ14C and δ13C signatures of organic compound classes

    NASA Astrophysics Data System (ADS)

    Komada, Tomoko; Druffel, Ellen R. M.; Hwang, Jeomshik

    2005-06-01

    Chemical and isotopic variability of particulate organic carbon (POC) was examined in samples from the Santa Clara River watershed and adjacent shelf to investigate the processing of fossil POC derived from bedrock. The Santa Clara is a small coastal river that drains mountainous terrain in southern California, United States. Organic carbon in shale, river suspended sediment, and coastal marine sediment was separated into three operationally defined organic compound classes: total extractable lipids, acid hydrolyzable material, and the nonhydrolyzable residue. In all samples, the nonhydrolyzable fraction was dominant (˜50% of POC), while lipids and acid hydrolyzable moieties were relatively minor (≤22 and ≤13%, respectively). The Δ14C and δ13C signatures of the isolated fractions varied dramatically, not only across different sample types, but also for a given sample. At the shale exposure, low Δ14C values (<-760‰) indicated dominance of ancient C in all three organic compound classes. In downstream samples, the extractable lipids displayed the lowest Δ14C values (<-500‰), while the acid hydrolyzable fraction was predominantly modern (Δ14C > -30‰). The nonhydrolyzable fraction displayed intermediate Δ14C values (<-190‰) that increased steadily downstream with decreasing δ13C values (-22.2 to -25.0‰), possibly from mixing of shale and surface soil POC. Our results indicate that most of the fossil POC discharged by the Santa Clara is composed of non-acid hydrolyzable material, but its elusive molecular structure and marine-like δ13C signature may render its detection in the ocean difficult. In contrast, fossil lipids may be more amenable to detection if their resistant components (e.g., asphaltic material) are unique to crustal sources.

  20. UV-laser-based microscopic dissection of tree rings - a novel sampling tool for δ(13) C and δ(18) O studies.

    PubMed

    Schollaen, Karina; Heinrich, Ingo; Helle, Gerhard

    2014-02-01

    UV-laser-based microscopic systems were utilized to dissect and sample organic tissue for stable isotope measurements from thin wood cross-sections. We tested UV-laser-based microscopic tissue dissection in practice for high-resolution isotopic analyses (δ(13) C/δ(18) O) on thin cross-sections from different tree species. The method allows serial isolation of tissue of any shape and from millimetre down to micrometre scales. On-screen pre-defined areas of interest were automatically dissected and collected for mass spectrometric analysis. Three examples of high-resolution isotopic analyses revealed that: in comparison to δ(13) C of xylem cells, woody ray parenchyma of deciduous trees have the same year-to-year variability, but reveal offsets that are opposite in sign depending on whether wholewood or cellulose is considered; high-resolution tree-ring δ(18) O profiles of Indonesian teak reflect monsoonal rainfall patterns and are sensitive to rainfall extremes caused by ENSO; and seasonal moisture signals in intra-tree-ring δ(18) O of white pine are weighted by nonlinear intra-annual growth dynamics. The applications demonstrate that the use of UV-laser-based microscopic dissection allows for sampling plant tissue at ultrahigh resolution and unprecedented precision. This new technique facilitates sampling for stable isotope analysis of anatomical plant traits like combined tree eco-physiological, wood anatomical and dendroclimatological studies.

  1. Comparison of δ(18)O and δ(13)C values between tree-ring whole wood and cellulose in five species growing under two different site conditions.

    PubMed

    Weigt, Rosemarie B; Bräunlich, Stephanie; Zimmermann, Lothar; Saurer, Matthias; Grams, Thorsten E E; Dietrich, Hans-Peter; Siegwolf, Rolf T W; Nikolova, Petia S

    2015-12-15

    We investigated the applicability of tree-ring whole-wood material for δ(18)O and δ(13)C analysis in comparison with the more time- and resource-intensive use of cellulose, by considering possible variability between (i) five different tree species (Fagus sylvatica, Quercus robur, Picea abies, Abies alba, Pseudotsuga menziesii), (ii) two sites that differ in soil moisture, and (iii) climate conditions within a 10-year period. Stem cores of 30 individual trees (n = 3 trees per each species and site) were sampled from two sites in south Germany (Bavaria), and tree rings within sapwood of the years 2001-2010 were separated. The δ(18)O and δ(13)C values from homogenized tree-ring whole wood and from extracted cellulose were measured by mass spectrometry. Species-specific offsets in isotope values were analyzed and the responses in isotopic signature to climate variability including a single drought event were compared between whole-wood and cellulose. A constant offset in δ(18)O values of ca 5‰ between wood and cellulose was observed for most species independent of site conditions, with a significant difference between beech and Douglas-fir, while inter-annual variability was only observed in oak. The offset in δ(13)C values ranged between 1.45 and 1.84‰ across species, sites and years. Both materials generally showed similar strength in responses to temperature, precipitation and soil water availability, particularly for conifers. Resistance to severe drought stress--partly more strongly reflected in the δ(13)C values of cellulose--was lower for conifers than for the deciduous species. Wood material from the sapwood of the studied tree species is as useful as cellulose for studying environmental effects on tree-ring δ(18)O and δ(13)C values at a short-term scale as considered in most ecophysiological studies. The more variable response of oak may require further investigations. Copyright © 2015 John Wiley & Sons, Ltd.

  2. Deciphering late Quaternary land snail shell δ18O and δ13C from Franchthi Cave (Argolid, Greece)

    NASA Astrophysics Data System (ADS)

    Colonese, André C.; Zanchetta, Giovanni; Perlès, Catherine; Drysdale, Russell N.; Manganelli, Giuseppe; Baneschi, Ilaria; Dotsika, Elissavet; Valladas, Hélène

    2013-07-01

    This paper investigates the stable isotopic composition from late Pleistocene-Holocene (~ 13 to ~ 10.5 cal ka BP) shells of the land snail Helix figulina, from Franchthi Cave (Greece). It explores the palaeoclimatic and palaeoenvironmental implications of the isotope palaeoecology of archaeological shells at the time of human occupation of the cave. Modern shells from around the cave were also analysed and their isotopic signatures compared with those of the archaeological shells. The carbon isotope composition of modern shells depicts the consumption of C3 vegetation. Shell oxygen isotopic values are consistent with other Mediterranean snail shells from coastal areas. Combining empirical linear regression and an evaporative model, the δ18Os suggest that modern snails in the study area are active during periods of higher relative humidity and lower rainfall δ18O, probably at night. Late glacial and early Holocene δ18Os show lower values compared to modern ones. Early Holocene δ18Os values likely track enhanced moisture and isotopic changes in the precipitation source. By contrast, lower late glacial δ18O could reflect lower temperatures and δ18Op, compared to the present day. Shell carbon isotope values indicate the presence of C3 vegetation as main source of carbon to late glacial and early Holocene snails.

  3. Latest Paleocene benthic extinction event on the southern Tethyan shelf (Egypt): Foraminiferal stable isotopic (δ13C, δ18O) records

    NASA Astrophysics Data System (ADS)

    Schmitz, B.; Speijer, R. P.; Aubry, M.-P.

    1996-04-01

    The dramatic global extinction of 35% 50% of benthic foraminifera species in the deep sea in the latest Paleocene and associated negative excursions in δ13C and δ18O may be related to spreading of warm, saline bottom water from subtropical Tethyan shallow regions over the sea floor worldwide. Our study of neritic sections in Egypt shows that in the southern shallow Tethys, a prominent long-term change in bottom-water chemistry, sedimentation, and benthic foraminifera fauna was initiated at the time when the deep-sea benthic extinction event (BEE) took place. Bottom-water δ13C values on the Tethyan shelf show a sudden 3.0‰ negative shift at this event; however, contrary to the deep sea, in which the δ13C excursion was of short duration, Tethyan δ13C values did not fully return to preboundary values, but remained depressed by ˜1.5‰ for at least 1 m.y. The δ13C values at the Egyptian shelf during the BEE are much lower than would be expected if this was a source region for global deep water. The δ18O values indicate no significant change in bottom-water salinity or temperature at the BEE. The long-lasting environmental changes that began on the Egyptian shelf at the BEE may be related to, for example, gateway reorganization along the Tethyan seaway. Paleogeographic changes possibly also triggered a change in the loci of global deep-water formation; however, these loci must be sought in another part of the Tethys.

  4. Paleocene to Early Eocene paleoceanography of the Middle East: The δ13C and δ18O isotopes from foraminiferal calcite

    NASA Astrophysics Data System (ADS)

    Charisi, Stella D.; Schmitz, Birger

    1998-02-01

    Paleocene to early Eocene benthic foraminiferal δ13C and δ18O records from southern Tethyan sections at Ben Gurion, Israel (paleodepth 500-700 m), and Gebel Aweina, Egypt (paleodepth 150-200 m), show generally similar trends but 1-3‰ more negative values than coeval deep-sea isotopic records. In both Tethyan sections a negative δ13C excursion of 2.5-3‰ marks the benthic extinction event in the latest Paleocene. For at least 1 m.y. after this event, δ13C values were 1.5-2‰ more negative on the shelf than at upper bathyal depths, reflecting a deepening of the oxygen minimum zone, possibly related to an increase or spatial shift in upwelling. Benthic δ18O records indicate a 2-4°C temperature gradient between the shelf and upper bathyal depths. Temperature-salinity reconstructions suggest that upwelling was a dominant mechanism for surface water formation in this part of the southern Tethys during the late Paleocene.

  5. Can tree-ring isotopes (δ18O and δ13C) improve our understanding of hydroclimate variability in the Columbia River Basin?

    NASA Astrophysics Data System (ADS)

    Csank, A. Z.; Wise, E.; McAfee, S. A.

    2015-12-01

    The trajectory of incoming storms from the Pacific Ocean has a strong impact on hydroclimate in the Pacific Northwest. Shifts between zonal and meridional flow are a key influence on drought and pluvial regimes in both the PNW and the western United States as a whole. Circulation-dependent variability in the isotopic composition of precipitation can be recorded and potentially reconstructed using δ18O records derived from tree-rings. Here we present isotopic records of δ18O and δ13C from ponderosa pine (Pinus ponderosa) for the period 1950-2013 from six sites located in the lee of the Cascades in eastern Washington. Because of the orientation of the Cascades, zonal flow will result in an intensified rain shadow whereas meridional flow allows moisture to penetrate at a lower elevation leading to a lower rainout effect. This means zonal flow results in drier conditions in eastern Washington and the converse for meridional flow. We hypothesized that more depleted precipitation δ18O values will occur with periods of more zonal flow across the PNW and will be recorded by trees at our sites. Results show a strong relationship between our δ18O chronologies and winter precipitation (R = -0.50; p<0.001). δ13C chronologies from the same trees showed a relationship to prior fall/winter (pOct-pDec) precipitation (R = -0.46; p<0.005) suggesting a possible link to antecedent moisture conditions. With a focus on years with clear zonal and meridional flow regimes, we regressed the tree-ring δ18O anomaly against the instrumental record of total precipitation and compared the residual series to records of storm track for the period 1978-2008, and we found a detectable signal where the most depleted δ18O was generally associated with zonal flow and the most enriched δ18O with meridional flow. However, there are still some years where the relationship is unclear. Further work is aimed at understanding these anomalous years and extending our record beyond the instrumental

  6. Chlorophyll a-specific Δ14C, δ13C and δ15N values in stream periphyton: implications for aquatic food web studies

    NASA Astrophysics Data System (ADS)

    Ishikawa, N. F.; Yamane, M.; Suga, H.; Ogawa, N. O.; Yokoyama, Y.; Ohkouchi, N.

    2015-11-01

    Periphytic algae attached to a streambed substrate (periphyton) are an important primary producer in stream ecosystems. We determined the isotopic composition of chlorophyll a in periphyton collected from a stream flowing on limestone bedrock in the Seri River, central Japan. Stable isotope ratios of carbon (δ13C) and nitrogen (δ15N) and natural radiocarbon abundances (Δ14C) were measured in chlorophyll a (δ13Cchl, δ15Nchl and Δ14Cchl) and bulk (δ13Cbulk, δ15Nbulk and Δ14Cbulk) for periphyton, a pure aquatic primary producer (Cladophora sp.) and a terrestrial primary producer (Quercus glauca). Periphyton δ13Cbulk and δ13Cchl values did not necessarily correspond to δ13Cbulk for an algal-grazing specialist (Epeorus latifolium). Periphyton Δ14Cchl values (-258 ‰ in April and -190 ‰ in October) were slightly lower than Δ14Cbulk values (-228 ‰ in April and -179 ‰ in October) but were close to the Δ14C value for dissolved inorganic carbon (DIC; -217 ± 31 ‰), which is a mixture of weathered carbonates (Δ14C = -1000 ‰), CO2 derived from aquatic and terrestrial organic matters (variable Δ14C) and dissolved atmospheric CO2 (Δ14C approximately +30 ‰ in 2013). Δ14Cchl values were also close to Δ14Cbulk for E. latifolium (-215 ‰ in April and -199 ‰ in October) and Cladophora sp. (-210 ‰), whereas the Δ14Cbulk value for Q. glauca (+27 ‰) was closer to Δ14C for atmospheric CO2. Although the bulk isotopic composition of periphyton is recognised as a surrogate for the photosynthetic algal community, natural periphyton is a mixture of aquatic and terrestrial organic materials. Our results indicate that the bulk periphyton matrix at the study site consists of 89 to 95 % algal carbon (derived from 14C-depleted DIC) and 5 to 11 % terrestrial organic carbon (derived from 14C-enriched atmospheric CO2).

  7. Neogene climate change and emergence of C 4 grasses in the Namib, southwestern Africa, as reflected in ratite 13C and 18O

    NASA Astrophysics Data System (ADS)

    Ségalen, Loïc; Renard, Maurice; Lee-Thorp, Julia A.; Emmanuel, Laurent; Le Callonnec, Laurence; de Rafélis, Marc; Senut, Brigitte; Pickford, Martin; Melice, Jean-Luc

    2006-04-01

    Stable light isotopes in ratite eggshells have been shown to be reliable indicators of shifts in climate and environmental conditions in the past. Here, we show that δ18O and δ13C values in fossil and modern ratite eggshells collected in the aeolianite deposits of the southern and central Namib Desert track regional distinctions and global climate shifts throughout the Neogene. δ18O values, although variable, are consistently higher in the central compared to the southern Namib throughout the record. δ18O trends during the Miocene differ for the two regions, but track each other post-Miocene. Throughout the Miocene, δ13C values for ratite eggshells from both the central and southern Namib regions are indistinguishable showing that the flora remained C 3 throughout. The overall negative (- 3‰) shift in mean values for Miocene biostratigraphic zones is consistent with the response of C 3 photosynthesis to pCO 2 shifts from 180 to 320 ppmv as estimated from marine alkenone studies and/or evolution of the δ13C of the atmospheric CO 2. Evidence for C 4 plants occurs post-Miocene, with the development of the southern, winter rainfall and central/northern, summer rainfall zonation apparent today. These data provide independent corroboration that the expansion of C 4-dominated ecosystems after ˜ 7 Ma cannot be attributed to a reduction of pCO 2 below a 500 ppmv threshold, as earlier proposed. Proliferation of C 4 plants in the Namib after ˜ 5 Ma and, elsewhere, may be related rather to energy budgets and rainfall seasonality shifts resulting from large-scale atmospheric and oceanic circulation reorganisation.

  8. δ18O and δ13C records from a Cenozoic sedimentary sequence in the Lanzhou Basin, Northwestern China: Implications for palaeoenvironmental and palaeoecological changes

    NASA Astrophysics Data System (ADS)

    Li, Baofeng; Sun, Donghuai; Wang, Xin; Zhang, Yuebao; Hu, Wenwei; Wang, Fei; Li, Zaijun; Ma, Zhiwei; Liang, Baiqing

    2016-08-01

    In northwestern China, carbonate δ18O variation has been closely associated with evaporation and precipitation, whereas the variation of carbonate δ13C generally reflects patterns of palaeovegetation. Located within the transitional zone between the Chinese Loess Plateau and the Tibetan Plateau, the Lanzhou Basin has developed a continuous sequence of Cenozoic sediments which have been subjected to detailed sedimentological and high-resolution magnetostratigraphic analyses. In the present study, pedogenic carbonate O and C isotopic analyses were obtained throughout the entire Cenozoic sequence. The δ18O record exhibits a general positive trend with several abrupt changes. A dramatic positive shift in the δ18O record at ∼33 Ma indicates the initiation of the aridification process within the basin, which was likely associated with the late Eocene westward retreat of the Tethys Sea and global cooling. Two significant positive shifts in the δ18O record at ∼22 Ma and ∼3.5 Ma are synchronous with major increases in aeolian dust deposition on the Chinese Loess Plateau and in the North Pacific Ocean, suggesting the intensified aridity of the Asian interior, which is likely related to the stepwise uplift of the Tibetan Plateau via the blocking of water vapour pathways. The δ13C values exhibit a weak positive trend with a remarkable shift at ∼3.5 Ma. This trend is likely related to a decrease in vegetation density in response to the ongoing Cenozoic aridification, whereas the shift at ∼3.5 Ma may reflect the large-scale expansion of C4 plants.

  9. Synthesizing the Use of Carbon Isotope (14C and 13C) Approaches to Understand Rates and Pathways for Permafrost C Mobilization and Mineralization

    NASA Astrophysics Data System (ADS)

    Estop-Aragones, C.; Olefeldt, D.; Schuur, E.

    2015-12-01

    To better understand the permafrost carbon (C) feedback it is important to synthesize our current knowledge, and knowledge gaps, of how permafrost thaw can cause in situ mineralization or downstream mobilization of aged soil organic carbon (SOC) and the rate of this release. This potential loss of old SOC may occur via gaseous flux of CO2 and CH4 exchanged between soil and the atmosphere and via waterborne flux as DOC, POC (and their subsequent decomposition and release to the atmosphere). Carbon isotope (14C and 13C) approaches have been used to estimate both rates and pathways for permafrost C mobilization and mineralization. Radiocarbon (14C) has been used to estimate the contribution of aged C to overall respiration or waterborne C export. We aim to contrast results from radiocarbon studies, in order to assess differences between ecosystems (contrasting wet and dry ecosystems), thaw histories (active layer deepening or thermokarst landforms), greenhouse gas considered (CO2 and CH4) and seasons. We propose to also contrast methodologies used for assessing the contribution of aged C to overall C balance, and include studies using 13C data. Biological fractionation of 13C during both uptake and decomposition has been taken advantage of both in order to aid the interpretation of 14C data and on its own to assess sources and mineralization pathways. For example, 13C data has been used to differentiate between CH4 production pathways, and the relative contribution of anaerobic CO2 production to overall respiration. Overall, carbon isotope research is proving highly valuable for our understanding of permafrost C dynamics following thaw, and there is a current need to synthesize the available literature.

  10. Seasonal variations in δ13C and δ18O of atmospheric CO2 measured in the urban boundary layer over Vancouver, Canada in relation to fuel emissions.

    NASA Astrophysics Data System (ADS)

    Lee, J.; Christen, A.; Ketler, R.; Nesic, Z.; Schwendenmann, L.; Semmens, C.

    2014-12-01

    Recent advances in techniques to measure carbon dioxide (CO2) in urban plumes show potential for validating and monitoring emission inventories at regional to urban scale. A major challenge remains the attribution of elevated CO2 in urban plumes to different fuel and biogenic sources. Stable isotopes are a promising source of additional information. Here, we report a full year of measurements of CO2 mixing ratios, δ13C and δ18O in CO2 in the urban boundary layer over Vancouver, Canada. The goal of the work is to link seasonally changing isotopic composition to dominant fuel sources and put the urban enhancement into the context of regional background concentrations. Atmospheric composition in the urban atmosphere was measured continuously using a tunable diode laser absorption system (TGA 200, Campbell Scientific, Logan, UT, USA). In addition, end member signatures were determined by means of bag samples from representative fuel emission sources (gasoline, diesel, natural gas). While δ13C depends on the fuel type and origin (for Vancouver in 2013/14: δ13C gasoline 27.2‰; diesel -28.8‰; natural gas -41.6‰), δ18O is fractionated in catalytic converters (d18O gasoline vehicles -12.5‰; diesel -18.6‰; natural gas -22.7‰) and exhibits higher variability between samples. Additional signatures were determined for human, soil and plant respiration. During the study year, monthly mean mixing ratios in the urban atmosphere ranged between 410.5 (Jul) and 425.7 ppm (Dec), which was on average 18 ppm elevated above the regional background. As expected, mean monthly δ13C was lower in winter than summer with seasonally changing intercepts between -33.6‰ (JJF) and -27.7‰ (MJJ). Making the simple assumption that natural gas and gasoline are the only major fuel sources, natural gas would contribute ~45% to emissions in winter and ~3% in early summer, which is lower than the downscaled Local Emissions Inventory (57% in winter and 20% in summer). Mean δ18O showed

  11. Organic and black carbon 13C and 14C through the Santa Monica Basin sediment oxic-anoxic transition

    NASA Astrophysics Data System (ADS)

    Masiello, C. A.; Druffel, E. R. M.

    2003-02-01

    Black carbon (BC) is a significant percentage of sedimentary organic carbon (SOC) at abyssal ocean sites, but its presence in shelf sediments is not well studied. Approximately 1600AD, Santa Monica Basin bottom waters shifted from oxic to very low oxygen (dysoxic) deposition conditions. Under oxic deposition conditions BC was 11 +/- 4% of SOC, whereas after the overlying water became dysoxic (and sediments became anoxic), BC was 5.2 +/- 1.2% of SOC. This shift may reflect the preferential remineralization of non-black SOC under oxic conditions. There is an offset between BC and SOC 14C ages which changes with oxidation conditions, suggesting that BC storage is related to oxygen exposure and confirming a previously published report of the vulnerability of BC to sedimentary oxidation [Middelburg, 1999]. Terrestrial carbon is 17 +/- 5% of total SOC in this core's anoxic region, and 31 +/- 11% of this terrestrial carbon is BC.

  12. Carbon cycling in primary production bottle incubations: inferences from grazing experiments and photosynthetic studies using 14C and 18O in the Arabian Sea

    NASA Astrophysics Data System (ADS)

    Laws, Edward A.; Landry, Michael R.; Barber, Richard T.; Campbell, Lisa; Dickson, Mary-Lynn; Marra, John

    Estimates of photosynthesis based on the incorporation of 14C-labeled inorganic carbon into particulate carbon were compared to estimates of gross photosynthesis based on net O 2 production and the production of 18O2 from H218O during the US Joint Global Ocean Flux Study (US JGOFS) Arabian Sea process cruises. For samples incubated below the surface and at optical depths<3, the 14C uptake : gross photosynthesis ratio averaged 0.45±0.1. This result is in accord with theoretical considerations of the combined effects of the Mehler reaction, photorespiration, dark respiration, excretion, and grazing effects on the two estimates of photosynthesis. The 14C uptake : gross photosynthesis ratio was distinctly higher (0.62) for samples incubated at the surface. This result is likely due to UV light effects, since the O 2 and 14C incubations were done in quartz and polysulfone bottles, respectively. The 14C uptake : gross photosynthesis ratio was lower (0.31) for bottles incubated at optical depths>3. This result probably reflects an increase in the ratio of dark respiration to net photosynthesis in the vicinity of the compensation light level.

  13. A paleothermometer based on abundances of 13C-18O bonds in bioapatite: Calibration and reconstruction of the body temperatures of extinct Cenozoic mammals and Mesozoic dinosaurs

    NASA Astrophysics Data System (ADS)

    Eagle, R.; Schauble, E. A.; Tripati, A. K.; Fricke, H. C.; Tuetken, T.; Eiler, J. M.

    2009-12-01

    The stable isotope compositions of biologically precipitated apatite in bone, teeth, and scales are widely used to obtain information on the diet, behavior, and physiology of extinct organisms, and to reconstruct past climate in terrestrial and marine settings. Here we report the application of a new type of geochemical measurement to bioapatite, a ‘clumped isotope’ thermometer based on the thermodynamically driven preference for 13C and 18O to bond with each other within carbonate ions in the crystal lattice of apatite. This effect is dependent on temperature but unlike conventional stable isotope paleotemperature proxies, is independent from the isotopic composition of water from which the mineral formed. We show that the abundance of 13C-18O bonds in the carbonate component of apatite from modern teeth is proportional to the body temperature of the organism, with an accuracy of 1-2oC, and that the empirical calibration is supported by a theoretical model of isotopic ordering. We also report initial paleothermometry results from analyses of Cenozoic fossil mammal teeth and Mesozoic dinosaur teeth. Therefore, clumped isotope analysis of bioapatite represents a new approach in the study of the physiology of extinct species by allowing the first relatively assumption-free measurement of their body temperatures. It will also open new avenues in the study of paleoclimate, as the measurements of clumped isotopes in apatite from fossils, such as conodonts and brachiopods, as well as phosphorites, have the potential to record environmental temperatures.

  14. 14C and 13C Contents of Dissolved Organic Matter in the St. Lawrence Estuary and in a Hydroelectric Reservoir From the Boreal Forest (Quebec)

    NASA Astrophysics Data System (ADS)

    Lamontagne, J.; Hélie, J.; Hillaire-Marcel, C.

    2004-05-01

    In this study we examine the 14C and 13C contents of Dissolved Organic Matter (DOM) in the St. Lawrence River, at its outlet near Quebec City, and in a large hydroelectric reservoir, from the Canadian Boreal forest (Robert-Bourassa reservoir) as a mean to document the origin and residence time of DOM in such large catchments. Samples of DOM were collected bi-weekly at the Quebec City station from November 2001 until November 2002, as part of a geochemical monitoring program of the river, carried out since 1997. At the Robert-Bourassa reservoir, sampling operations took place from July 15 to July 26, 2001. All samples were filtered and acidified on site, and preserved in brown glass bottles at 4° C. Prior to their isotopic analysis, DOM samples were freeze-dried. 13C analyses were made at GEOTOP whereas 14C measurements were performed at the Lawrence Livermore National Laboratory, for samples coming from the St. Lawrence River, and at the Laboratoire d'Hydrologie et de géochimie isotopique of University Paris XI for samples originating from the Robert-Bourassa reservoir. Results are expressed respectively in ‰ vs. V-PDB and in % of modern carbon (% MC; i.e. 13.56 dpm/g C in 1950, for d13C=-25 ‰ ). D13C values averaging -26.3 ± 0.2 ‰ in the St. Lawrence, and -27.1 ± 0.2 ‰ at the Robert-Bourassa reservoir, indicate that DOC originates from terrestrial production, although a slight influence of aquatic DOC is seen in the St. Lawrence river during low water level episodes. In the river, DOC-14C activities range from 97.7 to 106.7 ± 0.5 %, with a mean value of 103.9 ± 0.5 %, whereas samples from Robert-Bourassa reservoir show a range of values between 108.5 and 110.5 ± 0.9 %, with a mean of 109.5 ± 0.9 %. In comparison, measurements made during the late 80's, in a small brook of Ontario, yielded 14C-DOM activities ranging from 113 to 118 % MC (Schiff et al., 1990). Meanwhile, 14C-activity of atmospheric CO2 has decreased of approximately the same

  15. Characterization of terrestrial organic matter transported through the Lena River Delta (NE Siberia) to its adjacent nearshore zone using lignin phenols, δ13C and ∆14C

    NASA Astrophysics Data System (ADS)

    Winterfeld, M.; Goni, M. A.; Just, J.; Hefter, J.; Han, P.; Mollenhauer, G.

    2014-12-01

    The Lena River in central Siberia is one of the major pathways translocating terrestrial organic matter (OMterr) from its southernmost reaches near Lake Baikal to the coastal zone of the Laptev Sea and the Arctic Ocean. Permafrost soils from its vast catchment area store huge amounts of pre-aged OM, which is expected to be remobilized due to climate warming. To characterize the composition and vegetation sources of OM discharged by the Lena River, we analyzed the lignin phenol and carbon isotopic composition (δ13C and ∆14C) in total suspended matter (TSM) from surface waters collected in spring and summer, surface sediments from the Buor Khaya Bay along with soils from the Lena Delta. A simple linear mixing model based on the lignin phenol distributions indicates OM in TSM samples from the delta and Buor Khaya Bay surface sediments contains comparable contributions from gymnosperm sources, which are primarily from the taiga forests south of the delta, and angiosperm material typical for tundra vegetation. Considering the small area covered by tundra (~12% of total catchment), the input of tundra-derived OM input is substantial and likely to increase in a warming Arctic. Radiocarbon compositions (∆14C) of bulk OM in TSM samples varied from -55 to -391‰, i.e. 14C ages of 395 to 3920 yrs BP. Using δ13C compositions to estimate the fraction of phytoplankton-derived OM and assuming that this material has a modern 14C signature, we inferred the ∆14C compositions of OMterr in TSM exported by the Lena River to range between -190 and -700‰. Such variability in the ages of OMTERR (i.e. 1640 to 9720 14C yrs BP) reflects the heterogeneous composition and residence time of OM in the Lena River catchment soils (Holocene to Pleistocene ages). Lignin phenol and ∆14C compositions of surface sediments from the adjacent Buor Khaya Bay suggest that OMTERR deposited there is older and more degraded than materials present in river particles and catchment soils. Stronger

  16. Thawing permafrost increases old soil and autotrophic respiration in tundra: partitioning ecosystem respiration using δ(13) C and ∆(14) C.

    PubMed

    Hicks Pries, Caitlin E; Schuur, Edward A G; Crummer, Kathryn G

    2013-02-01

    Ecosystem respiration (Reco ) is one of the largest terrestrial carbon (C) fluxes. The effect of climate change on Reco depends on the responses of its autotrophic and heterotrophic components. How autotrophic and heterotrophic respiration sources respond to climate change is especially important in ecosystems underlain by permafrost. Permafrost ecosystems contain vast stores of soil C (1672 Pg) and are located in northern latitudes where climate change is accelerated. Warming will cause a positive feedback to climate change if heterotrophic respiration increases without corresponding increases in primary production. We quantified the response of autotrophic and heterotrophic respiration to permafrost thaw across the 2008 and 2009 growing seasons. We partitioned Reco using Δ(14) C and δ(13) C into four sources-two autotrophic (above - and belowground plant structures) and two heterotrophic (young and old soil). We sampled the Δ(14) C and δ(13) C of sources using incubations and the Δ(14) C and δ(13) C of Reco using field measurements. We then used a Bayesian mixing model to solve for the most likely contributions of each source to Reco . Autotrophic respiration ranged from 40 to 70% of Reco and was greatest at the height of the growing season. Old soil heterotrophic respiration ranged from 6 to 18% of Reco and was greatest where permafrost thaw was deepest. Overall, growing season fluxes of autotrophic and old soil heterotrophic respiration increased as permafrost thaw deepened. Areas with greater thaw also had the greatest primary production. Warming in permafrost ecosystems therefore leads to increased plant and old soil respiration that is initially compensated by increased net primary productivity. However, barring large shifts in plant community composition, future increases in old soil respiration will likely outpace productivity, resulting in a positive feedback to climate change.

  17. Reconstruction of Atmospheric [CO] and Stable CO Isotopes delta 13C and delta18O Over the Last 250 Years

    NASA Astrophysics Data System (ADS)

    Mullaley, Alicia

    Carbon monoxide (CO) is a trace gas that influences atmospheric chemical reactions. CO is relatively short-lived (weeks to months) in the atmosphere and therefore spatially variable with a modern concentration range from 35 parts per billion (ppb) to 150 ppb (Globalview-CO, 2009). Because of its lifetime, atmospheric carbon monoxide is a good tracer for hemispheric processes; it is long enough to be transported over hemispheric distances but is short enough where there can be large seasonal and interannual variations. Therefore, measuring the variations in CO from bubbles trapped in Antarctic ice can reveal processes that occur in the Southern Hemisphere (SH). CO is the principal sink for the hydroxyl radical (OH) which is the most important oxidant in the atmosphere. The abundance of atmospheric OH can impact the lifetime of various atmospheric constituents such as the greenhouse gas methane (CH4), hydrofluorocarbons (HCFCs), non-methane hydrocarbons (NMHCs) and tropospheric ozone. In particular, because CO is the main loss mechanism for OH, increased concentrations of CO can cause a build-up of methane therefore affecting the global radiative budget and thus Earth's climate. Once CO concentration is determined, the isotopes of CO provide valuable information on the source of CO. These new data will better constrain the sources and sinks of CO and thus its global cycle, helping to resolve uncertainties in climate models by providing additional constraints. Here I present a detailed investigation to determine atmospheric [CO] and stable CO isotopes 13CO and C18O from 1950-1700 AD as recorded in bubbles trapped in ice cores from West Antarctic Ice Sheet Divide (WAIS D), Antarctica. This study better constrains the sources of atmospheric CO in the Southern Hemisphere during the late Holocene, including the contribution from biomass burning. The relationship between CO and CH4 over this time period is constructed based on these new observations and previously

  18. Investigations of (Delta)14C, (delta)13C, and (delta)15N in vertebrae of white shark (Carcharodon carcharias) from the eastern North Pacific Ocean

    SciTech Connect

    Kerr, L A; Andrews, A H; Cailliet, G M; Brown, T A; Coale, K H

    2006-06-08

    The white shark (Carcharodon carcharias) has a complex life history that is characterized by large scale movements and a highly variable diet. Estimates of age and growth for the white shark from the eastern North Pacific Ocean indicate they have a slow growth rate and a relatively high longevity. Age, growth, and longevity estimates useful for stock assessment and fishery models, however, require some form of validation. By counting vertebral growth band pairs, ages can be estimated, but because not all sharks deposit annual growth bands and many are not easily discernable, it is necessary to validate growth band periodicity with an independent method. Radiocarbon ({sup 14}C) age validation uses the discrete {sup 14}C signal produced from thermonuclear testing in the 1950s and 1960s that is retained in skeletal structures as a time-specific marker. Growth band pairs in vertebrae, estimated as annual and spanning the 1930s to 1990s, were analyzed for {Delta}{sup 14}C and stable carbon and nitrogen isotopes ({delta}{sup 13}C and {delta}{sup 15}N). The aim of this study was to evaluate the utility of {sup 14}C age validation for a wide-ranging species with a complex life history and to use stable isotope measurements in vertebrae as a means of resolving complexity introduced into the {sup 14}C chronology by ontogenetic shifts in diet and habitat. Stable isotopes provided useful trophic position information; however, validation of age estimates was confounded by what may have been some combination of the dietary source of carbon to the vertebrae, large-scale movement patterns, and steep {sup 14}C gradients with depth in the eastern North Pacific Ocean.

  19. Molecular, 13C, and 14C evidence for the allochthonous and ancient origin of C 16C 18n-alkanes in modern soils

    NASA Astrophysics Data System (ADS)

    Lichtfouse, Éric; Bardoux, Gerard; Mariotti, Andre; Balesdent, Jerome; Ballentine, Donna C.; Macko, Stephen A.

    1997-05-01

    The heterogeneous isotopic composition of C 3 and C 4 plants can be used to to follow the fate of plant carbon into soil organic molecules. Thus, after 23 years of maize cropping (C 4) on a soil which was previously under C 3 vegetation, C 25C 33 soil n-alkanes are 13C-enriched up to 9ℵ. relatively to the initial C 3 soil, reflecting the input of 13C-enriched n-alkanes from maize waxes. In sharp contrast, C 16C 18 soil n-alkanes do not show any significant 13C/ 12C variation over the same time interval. This absence of isotopic variation, along with consideration of their relative concentration, absolute concentration, and biodegradability, demonstrate that these substances must represent a regular input from an external source. Evidence of a large contribution of an ancient source, amounting to more than 65% of the alkane fraction, is given by a 14C-age of 8510 yrs BP. Moreover, short-chain n-alkanes from soils, diesel fuel, diesel automobile exhaust, and petroleum products exhibit similar distributions and δ 13C values. These findings suggests that C 16C 18 soil n-alkanes represent a non-point source pollution of ancient hydrocarbons either carried by aerosols or entering the soil via continuous hydrocarbon seepage from the deep sedimentary rocks of the Paris basin.

  20. Straightforward preparation of labeled potassium cyanate by ozonation and application to the synthesis of [13C] or [14C]ureidocarboxylic acids.

    PubMed

    Loreau, Olivier; Marlière, Philippe

    2013-06-15

    The development of new efficient syntheses of labeled reagents is a great challenge. Avoidance of overcomplicated procedures, availability and cost of starting materials are important considerations in choosing the synthetic route. In this report, we describe a facile and rapid preparation of labeled cyanate by ozonation of cyanide, a basic precursor. The crude cyanate was used without purification for the synthesis of various [(13)C] or [(14)C]ureidocarboxylic acids (20-68% yield from potassium cyanide). According to these results, cyanide ozonation may prove to be a promising alternative to traditional preparations of labeled cyanate.

  1. The curved 14C vs. δ13C relationship in dissolved inorganic carbon: A useful tool for groundwater age- and geochemical interpretations

    USGS Publications Warehouse

    Han, Liang-Feng; Plummer, Niel; Aggarwal, Pradeep

    2014-01-01

    Determination of the 14C content of dissolved inorganic carbon (DIC) is useful for dating of groundwater. However, in addition to radioactive decay, the 14C content in DIC (14CDIC) can be affected by many geochemical and physical processes and numerous models have been proposed to refine radiocarbon ages of DIC in groundwater systems. Changes in the δ13C content of DIC (δ13CDIC) often can be used to deduce the processes that affect the carbon isotopic composition of DIC and the 14C value during the chemical evolution of groundwater. This paper shows that a curved relationship of 14CDIC vs. δ13CDIC will be observed for groundwater systems if (1) the change in δ13C value in DIC is caused by a first-order or pseudo-first-order process, e.g. isotopic exchange between DIC and solid carbonate, (2) the reaction/process progresses with the ageing of the groundwater, i.e. with decay of 14C in DIC, and (3) the magnitude of the rate of change in δ13C of DIC is comparable with that of 14C decay. In this paper, we use a lumped parameter method to derive a model based on the curved relationship between 14CDICand δ13CDIC. The derived model, if used for isotopic exchange between DIC and solid carbonate, is identical to that derived by Gonfiantini and Zuppi (2003). The curved relationship of 14CDIC vs. δ13CDIC can be applied to interpret the age of the DIC in groundwater. Results of age calculations using the method discussed in this paper are compared with those obtained by using other methods that calculate the age of DIC based on adjusted initial radiocarbon values for individual samples. This paper shows that in addition to groundwater age interpretation, the lumped parameter method presented here also provides a useful tool for geochemical interpretations, e.g. estimation of apparent rates of geochemical reactions and revealing the complexity of the geochemical environment.

  2. Nuclear potentials for sub-barrier fusion and cluster decay in {sup 14}C, {sup 18}O+{sup 208}Pb systems

    SciTech Connect

    Sagaidak, R. N.; Tretyakova, S. P.; Khlebnikov, S. V.; Ogloblin, A. A.; Rowley, N.; Trzaska, W. H.

    2007-09-15

    Near-barrier fusion excitation functions for the {sup 14}C and {sup 18}O+{sup 208}Pb reactions have been analyzed in the framework of the barrier-passing model using different forms of the nuclear potential and the phenomenology of a fluctuating barrier. The best-fit fusion potentials were used to estimate cluster decay probabilities from the corresponding ground states of Ra and Th (i.e., for the inverse decay process). The analysis supports the ''{alpha}-decay-like'' scenario for carbon and oxygen emission from these nuclei.

  3. Multipolarity analysis for {sup 14}C high-energy resonance populated by ({sup 18}O,{sup 16}O) two-neutron transfer reaction

    SciTech Connect

    Carbone, D. Cavallaro, M.; Bondì, M.; Agodi, C.; Cunsolo, A.; Cappuzzello, F.; Azaiez, F.; Franchoo, S.; Khan, E.; Bonaccorso, A.; Fortunato, L.; Foti, A.; Linares, R.; Lubian, J.; Scarpaci, J. A.; Vitturi, A.

    2015-10-15

    The {sup 12}C({sup 18}O,{sup 16}O){sup 14}C reaction at 84 MeV incident energy has been explored up to high excitation energy of the residual nucleus thanks to the use of the MAGNEX spectrometer to detect the ejectiles. In the region above the two-neutron separation energy, a resonance has been observed at 16.9 MeV. A multipolarity analysis of the cross section angular distribution indicates an L = 0 character for such a transition.

  4. Apportioning carbon sources of authigenic carbonate of extremely 13C-depleted foraminifera from the western North Pacific sediments: Implication from the coupled 13C and 14C isotopic mass balance approach

    NASA Astrophysics Data System (ADS)

    Uchida, M.; Ohkushi, K.; Ahagon, N.; Kimoto, K.; Inagaki, F.; Shibata, Y.

    2005-12-01

    Recently, Uchida et al. (G-cubed, 2004) and Ohkushi et al. (G-cubed, 2005) interprete /delta 13C variations of planktonic and benthic foraminifera found in Last Glacial sediments in off Shimokita Peninsula and Tokachi as evidence for periodic releases of methane, arising from the dissociation of methane hydrate, and its subsequent oxidation in bottom- and/or surface-water environments. According to recent observations of anomalous bottom-simulating reflections, northwest Pacific marginal sediments around Japan main islands bear large abundances of methane hydrate. In this study, analyzed piston cores (42° 21.42' N, 144° 13.36' E) at a water depth 1066-m was retrieved from the off Tokachi continental slope in the Oyashio current region, where recently is found to bear immense amounts of methane hydrate. The piston core covered past 22 ka with high-resolution. Here we showed that carbon isotope signals indicated that planktonic and benthic foraminifera in several glacial sediment layers in the core were highly depleted in13 C; both the planktonic and benthic foraminiferal /delta 13C values ranged from about -10/permil to -2/permil. Most foraminiferal tests in these horizons were brown as a result of postdepositional alteration. Foraminiferal oxygen isotopes fluctuated abnormally in the glacial sediment layers, showing small (about 0.5/permil) positive shifts relative to normal glacial values. We attributed the positive shifts to authigenic carbonate formation in the foraminiferal tests. In order to decipher the relation between foraminifera carbon isotopic signal and methane release from the seafloor, we have apportioned carbon sources (methane from methane hydrate or not) of foraminiferal carbon isotopic anomalies using dual mass balance isotopic model (14C/ 12C and 13C/ 12C). It has been suggested that sulfate-dependent anaerobic methane oxidation (AOM) dominates carbon oxidation and attendant authigenic carbonate precipitation to foraminifera. To this assumption

  5. 2H NMR and 13C-IRMS analyses of acetic acid from vinegar, 18O-IRMS analysis of water in vinegar: international collaborative study report.

    PubMed

    Thomas, Freddy; Jamin, Eric

    2009-09-01

    An international collaborative study of isotopic methods applied to control the authenticity of vinegar was organized in order to support the recognition of these procedures as official methods. The determination of the 2H/1H ratio of the methyl site of acetic acid by SNIF-NMR (site-specific natural isotopic fractionation-nuclear magnetic resonance) and the determination of the 13C/12C ratio, by IRMS (isotope ratio mass spectrometry) provide complementary information to characterize the botanical origin of acetic acid and to detect adulterations of vinegar using synthetic acetic acid. Both methods use the same initial steps to recover pure acetic acid from vinegar. In the case of wine vinegar, the determination of the 18O/16O ratio of water by IRMS allows to differentiate wine vinegar from vinegars made from dried grapes. The same set of vinegar samples was used to validate these three determinations. The precision parameters of the method for measuring delta13C (carbon isotopic deviation) were found to be similar to the values previously obtained for similar methods applied to wine ethanol or sugars extracted from fruit juices: the average repeatability (r) was 0.45 per thousand, and the average reproducibility (R) was 0.91 per thousand. As expected from previous in-house study of the uncertainties, the precision parameters of the method for measuring the 2H/1H ratio of the methyl site were found to be slightly higher than the values previously obtained for similar methods applied to wine ethanol or fermentation ethanol in fruit juices: the average repeatability was 1.34 ppm, and the average reproducibility was 1.62 ppm. This precision is still significantly smaller than the differences between various acetic acid sources (delta13C and delta18O) and allows a satisfactory discrimination of vinegar types. The precision parameters of the method for measuring delta18O were found to be similar to the values previously obtained for other methods applied to wine and

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

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

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

  7. /sup 18/O isotope effect in /sup 13/C nuclear magnetic resonance spectroscopy. Part 9. Hydrolysis of benzyl phosphate by phosphatase enzymes and in acidic aqueous solutions

    SciTech Connect

    Parente, J.E.; Risley, J.M.; Van Etten, R.L.

    1984-12-26

    The /sup 18/O isotope-induced shifts in /sup 13/C and /sup 31/P nuclear magnetic resonance (NMR) spectroscopy were used to establish the position of bond cleavage in the phosphatase-catalyzed and acid-catalyzed hydrolysis reactions of benzyl phosphate. The application of the /sup 18/O-isotope effect in NMR spectroscopy affords a continuous, nondestructive assay method for following the kinetics and position of bond cleavage in the hydrolytic process. The technique provides advantages over most discontinuous methods in which the reaction components must be isolated and converted to volatile derivatives prior to analysis. In the present study, (..cap alpha..-/sup 13/C,ester-/sup 18/O)benzyl phosphate and (ester-/sup 18/O)benzyl phosphate were synthesized for use in enzymatic and nonenzymatic studies. Hydrolysis reactions catalyzed by the alkaline phosphatase from E. coli and by the acid phosphatases isolated from human prostate and human liver were all accompanied by cleavage of the substrate phosphorus-oxygen bond consistent with previously postulated mechanisms involving covalent phosphoenzyme intermediates. An extensive study of the acid-catalyzed hydrolysis of benzyl phosphate at 75/sup 0/C revealed that the site of bond cleavage is dependent on pH. At pH less than or equal to 1.3, the hydrolysis proceeds with C-O bond cleavage; at 1.3 < pH < 2.0, there is a mixture of C-O and P-O bond scission, the latter progressively predominating as the pH is raised; at pH greater than or equal to 2.0, the hydrolysis proceeds with exclusive P-O bond scission. (S)-(+)-(..cap alpha..-/sup 2/H)Benzyl phosphate was also synthesized. Hydrolysis of this chiral benzyl derivative demonstrated that the acid-catalyzed C-O bond scission of benzyl phosphate proceeds by an A-1 (S/sub N/1) mechanism with 70% racemization and 30% inversion at carbon. 37 references, 4 figures, 2 tables.

  8. Stable isotope values (δ18O & δ13C) of multiple ostracode species in a large Neotropical lake as indicators of past changes in hydrology

    NASA Astrophysics Data System (ADS)

    Pérez, Liseth; Curtis, Jason; Brenner, Mark; Hodell, David; Escobar, Jaime; Lozano, Socorro; Schwalb, Antje

    2013-04-01

    Modern lake hydrodynamics, ostracode species autecology, stable isotopes (δ18O and δ13C) of multiple ostracode species, ostracode taphonomy and sediment geochemistry were studied to improve interpretation of the late Pleistocene-early Holocene (˜24-10 ka) stable isotope record of ostracodes in sediment core PI-6 from Lago Petén Itzá, northern Guatemala. Oxygen and carbon stable isotopes in modern and fossil species assemblages of Lago Petén Itzá were used as indicators of changes in the balance between evaporation and precipitation, past lake level and carbon source. Ostracode taphonomy was used to detect past periods of strong currents, high-energy environments, and possible partial or full mixing of the lake. The modern lake water isotopic composition displays clear seasonal differences that are independent of lake level fluctuations. Modern benthic species displayed lower δ18O and δ13C values than nektobenthic species, with differences of 3.0‰ and 5.3‰, respectively. Valves of nektobenthic species display higher values of δ13C because these ostracodes live in shallower environments among abundant algae and aquatic plants, where productivity is high. The benthic species Limnocythere opesta Brehm, 1939 displayed the smallest average offset from δ18O water (+0.3‰) and the largest offset from δ13CDIC values (-4.1‰) among studied ostracode species. Nektobenthic species Heterocypris punctata Keyser, 1975 displayed the smallest difference relative to the δ13CDIC values (-0.1‰). Late Pleistocene-early Holocene climate conditions and water levels in Lago Petén Itzá can be summarized as follows: 1) high lake levels and cold conditions (Last Glacial Maximum [LGM], ˜24-19 ka), 2) fluctuating lake levels and cold conditions (Heinrich Stadial 1 [HS1], ˜19-15 ka), 3) high lake levels and warm and wetter conditions (Bølling-Allerød [BA], ˜15-13 ka), 4) low lake levels and dry conditions (Younger Dryas [YD], ˜13-11.5 ka) and 5) high lake levels and

  9. 18O/16O, 30Si/28Si, D/H, and 13C/12C Studies of Lunar Rocks and Minerals.

    PubMed

    Epstein, S; Taylor, H P

    1970-01-30

    The delta (18)O of minerals from lunar gabbros and basalts are: plgioclases +6.06 to +6.33), pyroxenes (+5.70 to +5.95), and ilmenites (+3.85 to +4.12). The uniformity of these results indicates isotopic equilibrium in the mineral assemblages. Estimated plagioclase-ilmenite temperautres range from 1150 degrees C to 1340 degrees C. The bulk (18)/ (16)O and (30)Si/ (28)Si ratios of these lunar rocks are identical with ratios of terrestrial basalts, but the lunar glass, breccia, and dust are slightly enriched in the heavier isotopes. The lunar hydrogen (formed from solar wind) has a delta D/H of less than-873 per mil and the value may be even lower, as it is probably contaminated with terrestrial hydrogen. The delta (13)C of lunar dust and breccia is unusually high relative to reduced carbon in meteorites or on earth.

  10. Predicting Effects of Cations (Mg, Ca, Na, and K) on 13C-18O Clumping in Dissolved Inorganic Carbon Species and Implications for Carbonate Geothermometry

    NASA Astrophysics Data System (ADS)

    Hill, P. S.; Tripati, A.; Schauble, E. A.

    2014-12-01

    13C-18O bond abundance in carbonates is becoming more widely used as a geothermometer; this proxy is affected by various environmental factors. Here we report the influence of cations (Mg2+, Ca2+, Na+, and K+) at high concentrations (~2 mol/liter) on the isotopologue composition of the DIC pool. Clumped isotope fractionation in CO32- groups of dissolved species and carbonate minerals is reported using the notation Δ63 corresponding mainly to the enrichment in per mil of Hx13C18O16O2x-2 (plus Hx12C18O17O 16Ox-2, Hx12C17O17O 17Ox-2, and Hx13C17O17O 16Ox-2) above the amount expected for a random distribution of isotopes among all CO32-, HCO3- and H2CO3 isotopologues. The Δ63 of a solution of dissolved inorganic carbon (DIC) depends upon the relative abundances of each DIC species (CO2(aq) or H2CO3, HCO3-, and CO32-) since each DIC species has a distinct equilibrium clumped isotope signature. These abundances depend primarily upon solution pH and secondarily upon temperature and salinity (fresh water vs. sea water vs. brine). Solvated DIC species with additional ions and the composite DIC solutions were modeled as a series of supermolecular clusters, each with a single DIC molecule, an added cation, and 21 to 32 surrounding H2O molecules. As in our previous work (Hill et al., 2014, GCA 125, 610-652), we developed electronic structure models at different levels of theory to ensure the best possible reliability at reasonable computational efficiency. Overall, the models predict that common aqueous cations will slightly increase the 13C-18O clumping signature of both individual DIC species and the total DIC pool at a given pH, salinity, and temperature. Predicted Δ63values are also dependent upon cation concentration. The perturbing effect of Mg2+ > Ca2+ > K+ > Na+. Dissolved cations increase the clumped crossover pH (pH at which the composite Δ63 of the DIC pool equals the Δ63 of calcite at equilibrium). Our models predict that a DIC solution of low to moderate p

  11. Experimental assessment of the purity of α-cellulose produced by variations of the Brendel method: Implications for stable isotope (δ13C, δ18O) dendroclimatology

    NASA Astrophysics Data System (ADS)

    Brookman, Tom; Whittaker, Thomas

    2012-09-01

    Stable isotope dendroclimatology using α-cellulose has unique potential to deliver multimillennial-scale, sub-annually resolved, terrestrial climate records. However, lengthy processing and analytical methods often preclude such reconstructions. Variants of the Brendel extraction method have reduced these limitations, providing fast, easy methods of isolating α-cellulose in some species. Here, we investigate application of Standard Brendel (SBrendel) variants to resinous soft-woods by treating samples of kauri (Agathis australis), ponderosa pine (Pinus ponderosa) and huon pine (Lagarastrobus franklinii), varying reaction vessel, temperature, boiling time and reagent volume. Numerous samples were visibly `under-processed' and Fourier Transform infrared spectroscopic (FTIR) investigation showed absorption peaks at 1520 cm-1 and ˜1600 cm-1 in those fibers suggesting residual lignin and retained resin respectively. Replicate analyses of all samples processed at high temperature yielded consistent δ13C and δ18O despite color and spectral variations. Spectra and isotopic data revealed that α-cellulose δ13C can be altered during processing, most likely due to chemical contamination from insufficient acetone removal, but is not systematically affected by methodological variation. Reagent amount, temperature and extraction time all influence δ18O, however, and our results demonstrate that different species may require different processing methods. FTIR prior to isotopic analysis is a fast and cost effective way to determine α-cellulose extract purity. Furthermore, a systematic isotopic test such as we present here can also determine sensitivity of isotopic values to methodological variables. Without these tests, isotopic variability introduced by the method could obscure or `create' climatic signals within a data set.

  12. UV-laser microdissection system - A novel approach for the preparation of high-resolution stable isotope records (δ13C18O) from tree rings

    NASA Astrophysics Data System (ADS)

    Schollaen, Karina; Helle, Gerhard

    2013-04-01

    Intra-annual stable isotope (δ13C and δ18O) studies of tree rings at various incremental resolutions have been attempting to extract valuable seasonal climatic and environmental information or assessing plant ecophysiological processes. For preparing high-resolution isotope samples normally wood segments or cores are mechanically divided in radial direction or cut in tangential direction. After mechanical dissection, wood samples are ground to a fine powder and either cellulose is extracted or bulk wood samples are analyzed. Here, we present a novel approach for the preparation of high-resolution stable isotope records from tree rings using an UV-laser microdissection system. Firstly, tree-ring cellulose is directly extracted from wholewood cross-sections largely leaving the wood anatomical structure intact and saving time as compared to the classical procedure. Secondly, micro-samples from cellulose cross-sections are dissected with an UV-Laser dissection microscope. Tissues of interest from cellulose cross-sections are identified and marked precisely with a screen-pen and dissected via an UV-laser beam. Dissected cellulose segments were automatically collected in capsules and are prepared for stable isotope (δ13C and δ18O) analysis. The new techniques facilitate inter- and intra-annual isotope analysis on tree-ring and open various possibilities for comparisons with wood anatomy in plant eco-physiological studies. We describe the design and the handling of this novel methodology and discuss advantages and constraints given by the example of intra-annual oxygen isotope analysis on tropical trees.

  13. sup 18 O/ sup 16 O and sup 13 C/ sup 12 C in lower Paleozoic articulate brachiopods: Implications for the isotopic composition of seawater

    SciTech Connect

    Wadleigh, M.A. ); Veizer, J. Ruhr Univ., Bochum )

    1992-01-01

    Three hundred and eleven articulate brachiopods, with extensive geographic coverage, spanning the Cambrian to Silurian stratigraphic interval, were analyzed for oxygen and carbon isotopic composition. Cambrian samples have {delta}{sup 18}O {le} {minus}7{per thousand}, Ordovician samples {le} {minus}2.4{per thousand}, and Silurian samples {le} {minus}1.9{per thousand}, confirming the previously established trend towards lighter isotopic compositions with increasing age throughout the Lower Paleozoic. Forty-nine best preserved' Ordovician and Silurian samples were identified based on scanning electron microscopy and trace element analysis. They were found to bracket the isotopic compositions of over 85% of specimens from these stratigraphic intervals supporting widespread preservation of the isotopic signal. Some latest Ordovician and Lower Ludlovian samples associated with shale sequences are apparently enriched' in {sup 18}O. These are interpreted as an environmental phenomenon, perhaps related to water temperature and glaciation. A number of Silurian samples of varying genera and stratigraphic levels are highly enriched in {sup 13}C, up to +6{per thousand}. Some are shale related, but some are associated with carbonate-bearing basins. These are also thought to represent near-original' compositions, but a single environmental cause is unknown. The present data show that luminescence is not a decisive criterion for evaluating the degree of brachiopod preservation. Whole-shell values were isotopically similar to their nonluminescent portions for both oxygen and carbon.

  14. Chemical weathering and the role of sulfuric and nitric acids in carbonate weathering: Isotopes (13C, 15N, 34S, and 18O) and chemical constraints

    NASA Astrophysics Data System (ADS)

    Li, Cai; Ji, Hongbing

    2016-05-01

    Multiple isotopes (13C-DIC, 34S and 18O-SO42-, 15N and 18O-NO3-) and water chemistry were used to evaluate weathering rates and associated CO2 consumption by carbonic acid and strong acids (H2SO4 and HNO3) in a typical karst watershed (Wujiang River, Southwest China). The dual sulfate isotopes indicate that sulfate is mainly derived from sulfide oxidation in coal stratum and sulfide-containing minerals, and dual nitrate isotopes indicate that nitrate is mainly derived from soil N and nitrification. The correlation between isotopic compositions and water chemistry suggests that sulfuric and nitric acids, in addition to carbonic acid, are involved in carbonate weathering. The silicate and carbonate weathering rates are 7.2 t km-2 yr-1 and 76 t km-2 yr-1, respectively. In comparison with carbonate weathering rates (43 t km-2 yr-1) by carbonic acid alone, the subsequent increase in rates indicates significant enhancement of weathering when combined with sulfuric and nitric acids. Therefore, the role of sulfuric and nitric acids in the rock weathering should be considered in the global carbon cycle.

  15. Differential modulation of host plant delta13C and delta18O by native and nonnative arbuscular mycorrhizal fungi in a semiarid environment.

    PubMed

    Querejeta, J I; Allen, M F; Caravaca, F; Roldán, A

    2006-01-01

    Native, drought-adapted arbuscular mycorrhizal fungi (AMF) often improve host-plant performance to a greater extent than nonnative AMF in dry environments. However, little is known about the physiological basis for this differential plant response. Seedlings of Olea europaea and Rhamnus lycioides were inoculated with either a mixture of eight native Glomus species or with the nonnative Glomus claroideum before field transplanting in a semiarid area. Inoculation with native AMF produced the greatest improvement in nutrient and water status as well as in long-term growth for both Olea and Rhamnus. Foliar delta18O measurements indicated that native AMF enhanced stomatal conductance to a greater extent than nonnative AMF in Olea and Rhamnus.delta13C data showed that intrinsic water-use efficiency in Olea was differentially stimulated by native AMF compared with nonnative AMF. Our results suggest that modulation of leaf gas exchange by native, drought-adapted AMF is critical to the long-term performance of host plants in semiarid environments. delta18O can provide a time-integrated measure of the effect of mycorrhizal infection on host-plant water relations.

  16. Oscillator Strengths and Predissociation Rates for W-X Bands and the 4P5P Complex in 13C16O and 12C18O

    NASA Astrophysics Data System (ADS)

    Eidelsberg, Michele; Lemaire, Jean Louis; Federman, Steven; Stark, Glenn; Heays, Alan; Gavilan, Lisseth; Lyons, James R.; Smith, Peter L.; de Oliveira, Nelson; Joyeux, Denis

    2014-06-01

    We are conducting experiments on the DESIRS beam-line at the SOLEIL Synchrotron to acquire the necessary data on oscillator strengths and predissociation rates for modeling CO photochemistry in astronomical environments. A VUV Fourier Transform Spectrometer provides a resolving power of about 350,000, allowing us to discern individual lines in electronic transitions. Here we focus on results obtained from absorption spectra of 13C16O and 12C18O for the W ^1Π - X ^1Σ^+ bands with v'=0-3 and v"=0 and the four overlapping bands (three resolved and one diffuse) observed between 92.97 and 93.35 nm. The three resolved bands are transitions to the upper levels 4pπ(2), 5pπ(0), and 5pσ(0) of the 4p(2) and 5p(0) complexes, and the diffuse band is associated with a non Rydberg level I ^1Π; weak features in 13C16O are likely associated with absorption to the 4pσ(2) and II ^1Π levels. Several perturbations are also revealed in the high-resolution spectra. We compare our results with earlier determinations for these isotopologues of CO, as well as our SOLEIL measurements on 12C16O.

  17. Diagenetic mineralization in Pennsylvanian coals from Indiana, USA: 13C/12C and 18O/16O implications for cleat origin and coalbed methane generation

    USGS Publications Warehouse

    Solano-Acosta, W.; Schimmelmann, A.; Mastalerz, Maria; Arango, I.

    2008-01-01

    Cleats and fractures in southwestern Indiana coal seams are often filled with authigenic kaolinite and/or calcite. Carbon- and oxygen-stable isotope ratios of kaolinite, calcite, and coalbed CO2 were evaluated in combination with measured values and published estimates of ??18O of coalbed paleowaters that had been present at the time of mineralization. ??18Omineral and ??18Owater values jointly constrain the paleotemperature of mineralization. The isotopic evidence and the thermal and tectonic history of this part of the Illinois Basin led to the conclusion that maximum burial and heat-sterilization of coal seams approximately 272??Ma ago was followed by advective heat redistribution and concurrent precipitation of kaolinite in cleats at a burial depth of < 1600??m at ??? 78 ?? 5????C. Post-Paleozoic uplift, the development of a second generation of cleats, and subsequent precipitation of calcite occurred at shallower burial depth between ??? 500 to ??? 1300??m at a lower temperature of 43 ?? 6????C. The available paleowater in coalbeds was likely ocean water and/or tropical meteoric water with a ??18Owater ??? - 1.25??? versus VSMOW. Inoculation of coalbeds with methanogenic CO2-reducing microbes occurred at an even later time, because modern microbially influenced 13C-enriched coalbed CO2 (i.e., the isotopically fractionated residue of microbial CO2 reduction) is out of isotopic equilibrium with 13C-depleted calcite in cleats. ?? 2007 Elsevier B.V. All rights reserved.

  18. Air-Broadened Line Parameters for the 2←0 Bands of 13C16O and 12C18O at 2.3 μm

    NASA Astrophysics Data System (ADS)

    Devi, V. Malathy; Benner, D. Chris; Smith, M. A. H.; Mantz, A. W.; Sung, K.; Brown, L. R.

    2012-06-01

    Air-broadened line shape parameters were determined for the first time in the 2←0 bands of 13C16O near 4166.8 cm-1 and 12C18O near 4159.0 cm-1. Spectra were recorded at 0.005 cm-1 resolution using a coolable absorption cell in the sample compartment of the Bruker IFS 125HR Fourier transform spectrometer at Jet Propulsion Laboratory. Gas temperatures and pressures ranged from 150 to 298 K and 20 to 700 Torr, respectively. Line parameters were determined by broad-band multispectrum least-squares fitting of the 4000-4360 cm-1 region in 16 spectra simultaneously; each set included 4 isotope-enriched pure sample scans and 12 air+CO samples (13CO or C18O, as appropriate). The air-broadened parameters measured were Lorentz half-width coefficients, their temperature dependence exponents; pressure-induced shift coefficients, their temperature dependences; and off-diagonal relaxation matrix elements. Speed dependence parameters were included to minimize the fit residuals. For both isotopologues the individual line positions and intensities were constrained to their theoretical relationships in order to obtain the rovibrational (G, B, D, and H) and band intensity parameters, including Herman-Wallis coefficients. The results for 13C16O and 12C18O are compared with those for the 12C16O 2←0 band and discussed. K. Sung, A. W. Mantz, M. A. H. Smith, et al., JMS 262 (2010) 122-134. D. C. Benner, C. P. Rinsland, V. Malathy Devi, M. A. H. Smith and D. A. Atkins, JQSRT 53 (1995) 705-721. V. Malathy Devi, D. C. Benner, L. R. Brown, C. E. Miller and R. A. Toth, JMS 242 (2007) 90-117. V. Malathy Devi, D. C. Benner, M. A. H. Smith, et al., JQSRT (2012) in press. Research described in this paper was performed at Connecticut College, the College of William and Mary, NASA Langley Research Center and the Jet Propulsion Laboratory, California Institute of Technology, under contracts and cooperative agreements with the National Aeronautics and Space Administration.

  19. Isotopic signatures ( 14C, 13C, 15N) as tracers of sources and cycling of soluble and particulate organic matter in the Santa Monica Basin, California

    NASA Astrophysics Data System (ADS)

    Williams, P. M.; Robertson, K. J.; Soutar, A.; Griffin, S. M.; Druffel, E. R. M.

    Measurements of Δ 14C, δ 13C and δ 15N are reported for dissolved (plus colloidal), suspended and sinking particulate, and total sedimentary organic matter in the Santa Monica Basin (mid-basin and shelf sites) on CaBS cruises 1, 3, 4, 7, 8 and 10. These isotopic signatures were indicative of the following processes occurring within the basin regime: (1) terrestrial inputs of organic matter to the sinking and suspended particulate organic matter were of the order of 10% or less, and as high as 25% for the sedimentary organic matter; (2) Δ 14C values of the UV-oxidizable dissolved organic matter below 5m were similar to those measured in open ocean waters, while the Δ 14C values in the suspended, and, to a lesser degree, in the sinking organic matter decreased markedly with depth. This latter decrease was primarily attributed to episodic resuspension of shelf and slope sedimentary organic matter, and secondarily to natural and/or anthropogenic petroleum inputs; and (3) the isotopic signatures of the UV-oxidizable dissolved organic matter, coupled with total dissolved carbon and amino acid and carbohydrate concentrations were strikingly similar in the deep basin and at an open-ocean site, suggesting a common history for the subsurface (>300m) and deep water at both sites. In addition, total mass and organic carbon and nitrogen fluxes from five particle trap deployments are described in detail. Mass fluxes increased with depth, especially on the shelf, suggesting that particle input from the basin slopes may reach the mid-basin site. We conclude that there is minimal perturbation of all organic phases in the basin from terrestrial sources, and that the properties of the UV-oxidizable dissolved organic matter are not greatly influenced by particles of local origin.

  20. Distributions and Transformations of Natural Abundance 14C and 13C in Dissolved and Particulate Lipids in a Major Temperate Estuary

    NASA Astrophysics Data System (ADS)

    Bauer, J. E.; Canuel, E. A.; McIntosh, H.; Barrett, A.; Ferer, E.; Hossler, K.

    2013-12-01

    Limited previous studies have shown major differences in the natural 14C and 13C isotopic signatures and radiocarbon ages of different biochemical classes (e.g., proteins, carbohydrates, lipid, etc.) in river, estuarine and marine dissolved and particulate organic matter (DOM and POM, respectively). Of particular note are the much greater radiocarbon ages of lipophilic materials than other compound classes. Possible explanations for these findings include greater-than-expected inputs of fossil and highly aged lipid-containing organic matter to rivers and estuaries, extended sorptive-protection of lipophilic materials from degradation and/or lower overall reactivities of lipids vs. other major biochemical classes. We measured the Delta 14C and del 13C signatures and 14C ages of lipid classes in DOM and POM in a major temperate estuary, Delaware Bay (USA) over two years. Changes in DOM were also followed during large volume dark and light incubations to assess the microbial and photochemical reactivity and processing of DOM and lipids. Neutral lipids in DOM were among the most highly aged (> 30,000 yrs BP) of any materials measured in natural waters to date, and were significantly older than co-occurring polar lipids (~4,000-5,000 yrs BP). In general, DOM lipid ages were significantly greater than POM lipid ages across the river-estuary transect, arguing against sorptive protection as the major factor explaining greater ages of lipid than those of other compound classes. Both dark and light incubations of DOM resulted in losses of very highly aged material (30-50,000 y BP), with the remnant exported lipids being correspondingly younger. The microbial and photochemical alterations were most pronounced for lipids from freshwater reaches of the system (i.e., the Delaware River). These findings suggest that a) dissolved vs. particulate lipids have fundamentally different sources and/or physico-chemical partitioning, b) different lipid classes (e.g., neutral vs. polar

  1. Assessing the impact of diagenesis on δ11B, δ13C, δ18O, Sr/Ca and B/Ca values in fossil planktic foraminiferal calcite

    NASA Astrophysics Data System (ADS)

    Edgar, Kirsty M.; Anagnostou, Eleni; Pearson, Paul N.; Foster, Gavin L.

    2015-10-01

    The geochemical composition of foraminiferal tests is a valuable archive for the reconstruction of paleo-climatic, -oceanographic and -ecological changes. However, dissolution of biogenic calcite and precipitation of inorganic calcite (overgrowth and recrystallization) at the seafloor and in the sediment column can potentially alter the original geochemical composition of the foraminiferal test, biasing any resulting paleoenvironmental reconstruction. The δ11B of planktic foraminiferal calcite is a promising ocean pH-proxy but the effect of diagenesis is still poorly known. Here we present new δ11B, δ13C, δ18O, Sr/Ca and B/Ca data from multiple species of planktic foraminifera from time-equivalent samples for two low latitude sites: clay-rich Tanzanian Drilling Project (TDP) Site 18 from the Indian Ocean containing well-preserved ('glassy') foraminifera and carbonate-rich Ocean Drilling Program (ODP) Site 865 from the central Pacific Ocean hosting recrystallized ('frosty') foraminifera. Our approach makes the assumption that environmental conditions were initially similar at both sites so most chemical differences are attributable to diagenesis. Planktic foraminiferal δ18O and δ13C records show offsets in both relative and absolute values between the two sites consistent with earlier findings that these isotopic ratios are strongly influenced by diagenetic alteration. Sr/Ca and B/Ca ratios in planktic foraminiferal calcite are also offset between the two sites but there is little change in the relative difference between surface and deep dwelling taxa. In contrast, δ11B values indicate no large differences between well-preserved and recrystallized foraminifera suggesting that despite extensive diagenetic alteration the δ11B of biogenic calcite appears robust, potentially indicative of a lack of free exchange of boron between pore fluids and the recrystallizing CaCO3. Our finding may remove one potential source of uncertainty in δ11B based p

  2. Growth decline and divergent tree ring isotopic composition (δ(13) C and δ(18) O) contradict predictions of CO2 stimulation in high altitudinal forests.

    PubMed

    Gómez-Guerrero, Armando; Silva, Lucas C R; Barrera-Reyes, Miguel; Kishchuk, Barbara; Velázquez-Martínez, Alejandro; Martínez-Trinidad, Tomás; Plascencia-Escalante, Francisca Ofelia; Horwath, William R

    2013-06-01

    Human-induced changes in atmospheric composition are expected to affect primary productivity across terrestrial biomes. Recent changes in productivity have been observed in many forest ecosystems, but low-latitude upper tree line forests remain to be investigated. Here, we use dendrochronological methods and isotopic analysis to examine changes in productivity, and their physiological basis, in Abies religiosa (Ar) and Pinus hartwegii (Ph) trees growing in high-elevation forests of central Mexico. Six sites were selected across a longitudinal transect (Transverse Volcanic Axis), from the Pacific Ocean toward the Gulf of Mexico, where mature dominant trees were sampled at altitudes ranging from 3200 to 4000 m asl. A total of 60 Ar and 84 Ph trees were analyzed to describe changes in growth (annual-resolution) and isotopic composition (decadal-resolution) since the early 1900s. Our results show an initial widespread increase in basal area increment (BAI) during the first half of the past century. However, BAI has decreased significantly since the 1950s with accentuated decline after the 1980s in both species and across sites. We found a consistent reduction in atmosphere to wood (13) C discrimination, resulting from increasing water use efficiency (20-60%), coinciding with rising atmospheric CO2 . Changes in (13) C discrimination were not followed, however, by shifts in tree ring δ(18) O, indicating site- and species-specific differences in water source or uptake strategy. Our results indicate that CO2 stimulation has not been enough to counteract warming-induced drought stress, but other stressors, such as progressive nutrient limitation, could also have contributed to growth decline. Future studies should explore the distinct role of resource limitation (water vs. nutrients) in modulating the response of high-elevation ecosystems to atmospheric change.

  3. Effect of in-stream physicochemical processes on the seasonal variations in δ13C and δ18O values in laminated travertine deposits in a mountain stream channel

    NASA Astrophysics Data System (ADS)

    Yan, Hao; Liu, Zaihua; Sun, Hailong

    2017-04-01

    Travertines are potential archives of continental paleoclimate. Records of stable carbon and oxygen isotopic composition (δ13C and δ18O) in laminated travertine deposits from endogene spring waters show regular cyclic patterns which may be due to seasonal change in climate determinants such as temperature and rainfall. In this study, δ13C and δ18O measurements of three travertine specimens that grew naturally over the eight years, 2004-2011, at upstream, middle and downstream sites in a canal at Baishuitai, SW China, are presented. They exhibit clear seasonal variations that generally correlate with biannual laminations. Specifically, δ13C and δ18O values show significant positive correlation with each other for the three travertine specimens, with the correlation coefficients increasing downstream along the canal. To reveal the factors governing the seasonal and spatial variations in δ13C and δ18O values, newly formed travertines precipitated on Plexiglas substrates are also examined. Both δ13C and δ18O of the substrate travertines are low in the summer/rainy season and high in the winter/dry season, showing a great consistency with the patterns in the natural travertines. Spatially, isotope values increase downstream in both seasons, with higher increase rates in winter that are related to removal of larger fractions of dissolved inorganic carbon (DIC) from the solution and stronger kinetic isotopic fractionation in winter. Due to in-stream physicochemical processes, including CaCO3 precipitation and the associated degassing of CO2, seasonal changes in δ13C and δ18O in the travertines are amplified by two times between the upstream and downstream sites: this is opposite to trends for epigene (meteogene) tufas whose seasonal changes in stable isotope compositions are reduced downstream. We suggest in-stream physicochemical processes are a potential reason for underestimation of annual temperature ranges that are inferred from epigene tufa δ18O data.

  4. Change of Tree-ring δ13C, δ18O and Water Use Efficiency of Loblolly Pine in Southeastern US in Response to Drought

    NASA Astrophysics Data System (ADS)

    Lin, W.; Noormets, A.; King, J.; Sun, G.; McNulty, S. G.; Domec, J. C.

    2015-12-01

    As a key parameter in carbon and water cycles of terrestrial ecosystems, water use efficiency is affected by isotopic signatures of the sources, climate, species- and site-specific characteristics such as mesophyll conductance(Barbour et al., 2010) and stand structure (Moreno-GutiÉRrez et al., 2012) . However, the magnitude of their effects and interactions are not well understood. Contributing to 36% of the sequestered forest carbon in the conterminous United States, the southern forests of USA are dominated by loblolly pine plantations. The objective of this study is to understand the response of loblolly pines to drought in terms of intrinsic water use efficiency and water source. We analyzed the δ13C and δ18O of α-cellulose extracted from latewood (summerwood) of tree rings produced in wet and dry years in 50 sites from southeastern USA and found that loblolly pines from different locations responded differently to droughts. Here we present our primary results in evaluating the effects of local climate variables, progeny of loblolly pines, and geographic locations on intrinsic water use efficiency.

  5. Linkages Between Upwelling and Shell Characteristics of Mytilus californianus: Morphology and Stable Isotope (δ13C, δ18O) Signatures of a Carbonate Archive from the California Current

    NASA Astrophysics Data System (ADS)

    Hosfelt, J. D.; Hill, T. M.; Russell, A. D.; Bean, J. R.; Sanford, E.; Gaylord, B.

    2014-12-01

    Many calcareous organisms are known to record the ambient environmental conditions in which they grow, and their calcium carbonate skeletons are often valuable archives of climate records. Mytilus californianus, a widely distributed species of intertidal mussel, experiences a spatial mosaic of oceanographic conditions as it grows within the California Current System. Periodic episodes of upwelling bring high-CO2 waters to the surface, during which California coastal waters are similar to projected conditions and act as a natural analogue to future ocean acidification. To examine the link between upwelling and shell characteristics of M. californianus, we analyzed the morphology and stable isotope (δ13C, δ18O) signatures of mussel specimens collected live from seven study sites within the California Current System. Morphometric analyses utilized a combination of elliptic Fourier analysis and shell thickness measurements to determine the influence of low pH waters on the growth morphology and ecological fitness of M. californianus. These geochemical and morphological analyses were compared with concurrent high-resolution environmental (T, S, pH, TA, DIC) records from these seven study sites from 2010-2013. With appropriate calibration, new archives from modern M. californianus shells could provide a valuable tool to enable environmental reconstructions within the California Current System. These archives could in turn be used to predict the future consequences of continuing ocean acidification, as well as reconstruct past (archeological) conditions.

  6. Reassessment of the 13C/12C and 14C/12C isotopic fractionation ratio and its impact on high-precision radiocarbon dating

    NASA Astrophysics Data System (ADS)

    Fahrni, Simon M.; Southon, John R.; Santos, Guaciara M.; Palstra, Sanne W. L.; Meijer, Harro A. J.; Xu, Xiaomei

    2017-09-01

    The vast majority of radiocarbon measurement results (14C/12C isotopic ratios or sample activities) are corrected for isotopic fractionation processes (measured as 13C/12C isotopic ratios) that occur in nature, in sample preparation and measurement. In 1954 Harmon Craig suggested a value of 2.0 for the fractionation ratio b that is used to correct 14C/12C ratios for shifts in the 13C/12C ratios and this value has been applied by the radiocarbon community ever since. While theoretical considerations suggest moderate deviations of b from 2.0, some measurements have suggested larger differences (e.g. b = 2.3, measured by Saliège and Fontes in 1984). With the high precision attained in radiocarbon measurements today (±2‰), even a relatively small deviation of b from 2.0 can impact the accuracy of radiocarbon data, and it is, therefore, of interest to re-evaluate the fractionation corrections. In the present study, the fractionation ratio b was determined by independent experiments on the chemical reduction of carbon dioxide (CO2) to elemental carbon (graphitization reaction) and on the photosynthetic uptake of CO2 by C3 and C4 plants. The results yielded b = 1.882 ± 0.019 for the reduction of CO2 to solid graphite and b = 1.953 ± 0.025 for the weighted mean of measurements involving C3 and C4 photosynthesis pathways. In addition, the analysis of over 9600 full-sized OX-I and OX-II normalizing standards measured between 2002 and 2012 confirms b values lower than 2.0. The obtained values are in good agreement with quantum mechanical estimates of the equilibrium fractionation and classic kinetic fractionation as well as with results from other light three-isotope systems (oxygen, magnesium, silicon and sulfur). While the value of the fractionation ratio varies with the relative importance of kinetic and equilibrium fractionation, the values obtained in the present study cluster around b = 1.9. Our findings suggest that a significant fraction of all samples

  7. Evaluating climate signal recorded in tree ring δ(13) C and δ(18) O values from bulk wood and α-cellulose for six species across four sites in the northeastern US.

    PubMed

    Guerrieri, Rossella; Jennings, Katie; Belmecheri, Soumaya; Asbjornsen, Heidi; Ollinger, Scott

    2017-09-22

    We evaluated the applicability of tree ring δ(13) C and δ(18) O values in bulk wood - instead of the more time and lab-consuming α-cellulose δ(13) C and δ(18) O values, for assessing climate and physiological signals across multiple sites and for six tree species along a latitudinal gradient (35°97(') N to 45°20(') N) of the northeastern United States. Wood cores (n=4 per tree) were sampled from ten trees per species. Cores were cross-dated within and across trees at each site, and for the last 30 years. Seven years, including the driest on record, were selected for this study. The δ(13) C and δ(18) O values were measured on two of the ten trees from the bulk wood and the α-cellulose. The offsets between materials in δ(13) C and δ(18) O values were assessed. Correlation and multiple regression analyses were used to evaluate the strength of the climate signal across sites. Finally the relationship between δ(13) C and δ(18) O values in bulk wood vs α-cellulose was analyzed to assess the consistency of the interpretation, in terms of CO2 assimilation and stomatal conductance, from both materials. We found an offset of 1.1‰ and 5.6‰ between bulk and α-cellulose for δ(13) C and δ(18) O values, respectively, consistent with offset values reported in the literature. Bulk wood showed similar or stronger correlations to climate parameters than α-cellulose for the investigated sites. In particular, temperature and vapour pressure deficit and SPEI were the most visible climate signals recorded in δ(13) C and δ(18) O values, respectively. For most of the species, there was no relationship between δ(13) C and δ(18) O values, regardless of the wood material considered. α-cellulose extraction was not necessary to detect climate signals in tree rings across the four investigated sites. Furthermore, the physiological information inferred from the dual isotope approach was similar for most of the species regardless of the material considered. This article

  8. Seasonal variations recorded in cave monitoring results and a 10 year monthly resolved speleothem δ18O and δ13C record from the Han-sur-Lesse cave, Belgium

    NASA Astrophysics Data System (ADS)

    Van Rampelbergh, M.; Verheyden, S.; Allan, M.; Quinif, Y.; Keppens, E.; Claeys, P.

    2014-04-01

    Speleothems provide paleoclimate information on multi-millennial to decadal scales in the Holocene. However seasonal or even monthly resolved records remain scarce. They require fast growing stalagmites and a good understanding of the proxy transfer function on very short time scales. The Proserpine stalagmite from the Han-sur-Less cave (Belgium) displays seasonal layers of 0.5 to 2 mm thickness that reconstruct paleoclimates at a monthly scale. Through a regular cave monitoring, we acquired a good understanding of how δ18O and δ13C signals in modern calcite reflect climate variations on sub-seasonal scale. Cave parameters vary seasonally in response to the activity of the vegetation cover and outside air temperature. From December to June, the cave remains in "winter-mode". Outside temperatures are cold inducing low cave air and water temperatures. Bio-productivity in the soil is limited leading to low pCO2, higher δ13C composition of the CO2 in the cave air and high discharge due to the inactivity of the plant coverage. From June to December, the cave switches to "summer-mode" and the measured factors display an opposite behavior. The δ18O and δ13C signals of fresh calcite precipitated on glass slabs vary seasonally. Lowest δ18O values occur during the summer-mode when the δ13C values are high. The δ18O composition of the calcite is in equilibrium with the drip water δ18O and display seasonal variations due to changes in the cave air and water temperature. In contrast to the δ18O signal, δ13C values of the calcite precipitated on the glass slabs do not reflect equilibrium conditions. Highest δ13C values occur during summer, when discharge rates are low increasing the evaporation effect on the thin water film covering the stalagmite. This same antithetical behavior of the δ18O vs. the δ13C signals is seen in the monthly resolved speleothem record that covers the period between 1976 and 1985 AD. Dark layers are formed during summer, while light layers

  9. A new mechanism of phosphoric acid digestion reaction and theoretical re-calibration on the carbonate 13C-18O clumped isotope thermometry

    NASA Astrophysics Data System (ADS)

    Tang, M.; Liu, Y.

    2016-12-01

    The carbonate 13C-18O clumped isotope thermometry has been widely used for surface temperature systems. However, the existing D47-T relationships calibrated by different groups are incompatible, generating substantial confusions in the community. Here we propose a new molecular-level mechanism of the kinetic isotope effect (KIE) produced in the phosphoric acid digestion reaction of carbonates. We will show why the previous mechanism won't work and why this new one is reasonable, especially based on experimental evidences. This new mechanism, which suggests that there are three parallel pathways undergoing for the phosphoric acid digestion process, can explain well the discrepancies of the D47-T relationships obtained by different groups at slightly different experimental conditions (Fig.1). Based on the new mechanism and sophisticated quantum chemistry calculations, we show that the clumped isotope enrichments (i.e., Δ*47) can be significantly different from those provided by Guo et al. (2009) if considering the change of individual contributions of the three parallel pathways. Consequently, if we use these new Δ*47 values to plot the D47-T figure under the absolute reference frame (ARF), all the calibration lines conducted at 90°C (e.g., Dennis et al. (2011)) will be relocated. They can be much closer to those calibration lines conducted at 25°C than before in the low temperature range (Fig.1). In another word, there may not be much difference between these two groups of calibration lines. However, we obtain a slope very close to those conducted at 90°C but with distinct difference to that of Ghosh et al. (2006). Finally, we provide molecular-level explanations on the changes of calibration lines if the experiments are conducted under slightly different conditions. We show why the temperature of phosphoric acid digestion, the reaction time and the amount of sample can affect the position of calibration line but not the slope of it. This new mechanism not only

  10. A conifer-friendly high-throughput α-cellulose extraction method for δ13C and δ18O stable isotope ratio analysis

    NASA Astrophysics Data System (ADS)

    Lin, W.; Noormets, A.; domec, J.; King, J. S.; Sun, G.; McNulty, S.

    2012-12-01

    Wood stable isotope ratios (δ13C and δ18O) offer insight to water source and plant water use efficiency (WUE), which in turn provide a glimpse to potential plant responses to changing climate, particularly rainfall patterns. The synthetic pathways of cell wall deposition in wood rings differ in their discrimination ratios between the light and heavy isotopes, and α-cellulose is broadly seen as the best indicator of plant water status due to its local and temporal fixation and to its high abundance within the wood. To use the effects of recent severe droughts on the WUE of loblolly pine (Pinus taeda) throughout Southeastern USA as a harbinger of future changes, an effort has been undertaken to sample the entire range of the species and to sample the isotopic composition in a consistent manner. To be able to accommodate the large number of samples required by this analysis, we have developed a new high-throughput method for α-cellulose extraction, which is the rate-limiting step in such an endeavor. Although an entire family of methods has been developed and perform well, their throughput in a typical research lab setting is limited to 16-75 samples per week with intensive labor input. The resin exclusion step in conifersis is particularly time-consuming. We have combined the recent advances of α-cellulose extraction in plant ecology and wood science, including a high-throughput extraction device developed in the Potsdam Dendro Lab and a simple chemical-based resin exclusion method. By transferring the entire extraction process to a multiport-based system allows throughputs of up to several hundred samples in two weeks, while minimizing labor requirements to 2-3 days per batch of samples.

  11. Re-evaluation of the ;elevated epifauna; as indicator of Mediterranean Outflow Water in the Gulf of Cadiz using stable isotopes (δ13C, δ18O)

    NASA Astrophysics Data System (ADS)

    García-Gallardo, Ángela; Grunert, Patrick; Voelker, Antje H. L.; Mendes, Isabel; Piller, Werner E.

    2017-08-01

    The presence and high abundances of the benthic foraminiferal group ;elevated epifauna; has been proposed as indicator of the existence of Mediterranean Outflow Water (MOW) in the Gulf of Cadiz. Here we intend to use this potential proxy to reconstruct MOW in the early Pliocene at the Integrated Ocean Drilling Program (IODP) Hole U1387C. Cibicides lobatulus, Planulina ariminensis and Cibicides refulgens were found at this site, but high abundances of C. lobatulus and C. refulgens coincide with increases of shelf taxa and grain size, related to episodes of downslope transport. This issue calls into question the applicability of these species as MOW proxies. The present study therefore reassesses the role of these three elevated epifaunal species by means of stable isotope analyses (δ18O, δ13C) by contrasting their isotopic signature with that of shelf dwellers and deep-water taxa from Pliocene and Recent sediments from the Gulf of Cadiz and the western Iberian margin. Since foraminiferal calcite does not always precipitate in equilibrium with seawater, substantial efforts have been taken in order to determine species-specific offset values and to correct the isotopic signature for vital effects. Our corrected results demonstrate that C. lobatulus and C. refulgens are isotopically similar to the shelf dwellers in the Pliocene data-set, eliminating them as MOW indicators. Recent samples from the Gulf of Cadiz and the western Portugal shelf corroborate the wide bathymetric range of C. lobatulus from the shelf to the slope. Our results thus warrant for caution when considering C. lobatulus and C. refulgens as indicators of bottom current strength in unstable slope settings, particularly when co-occurring with allochthonous shelf dwellers. In contrast, P. ariminensis shows a signature close to deep-water taxa, corroborating its reliability as indicator of MOW.

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

    PubMed

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

    2013-03-30

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

  13. 13C, 18O, and D fractionation effects in the reactions of CH3OH isotopologues with Cl and OH radicals.

    PubMed

    Feilberg, Karen L; Gruber-Stadler, Margret; Johnson, Matthew S; Mühlhäuser, Max; Nielsen, Claus J

    2008-11-06

    A relative rate experiment is carried out for six isotopologues of methanol and their reactions with OH and Cl radicals. The reaction rates of CH2DOH, CHD2OH, CD3OH, (13)CH3OH, and CH3(18)OH with Cl and OH radicals are measured by long-path FTIR spectroscopy relative to CH3OH at 298 +/- 2 K and 1013 +/- 10 mbar. The OH source in the reaction chamber is photolysis of ozone to produce O((1)D) in the presence of a large excess of molecular hydrogen: O((1)D) + H2 --> OH + H. Cl is produced by the photolysis of Cl2. The FTIR spectra are fitted using a nonlinear least-squares spectral fitting method with measured high-resolution infrared spectra as references. The relative reaction rates defined as alpha = k(light)/k(heavy) are determined to be: k(OH + CH3OH)/k(OH + (13)CH3OH) = 1.031 +/- 0.020, k(OH + CH3OH)/k(OH + CH3(18)OH) = 1.017 +/- 0.012, k(OH + CH3OH)/k(OH + CH2DOH) = 1.119 +/- 0.045, k(OH + CH3OH)/k(OH + CHD2OH) = 1.326 +/- 0.021 and k(OH + CH3OH)/k(OH + CD3OH) = 2.566 +/- 0.042, k(Cl + CH3OH)/k(Cl + (13)CH3OH) = 1.055 +/- 0.016, k(Cl + CH3OH)/k(Cl + CH3(18)OH) = 1.025 +/- 0.022, k(Cl + CH3OH)/k(Cl + CH2DOH) = 1.162 +/- 0.022 and k(Cl + CH3OH)/k(Cl + CHD2OH) = 1.536 +/- 0.060, and k(Cl + CH3OH)/k(Cl + CD3OH) = 3.011 +/- 0.059. The errors represent 2sigma from the statistical analyses and do not include possible systematic errors. Ground-state potential energy hypersurfaces of the reactions were investigated in quantum chemistry calculations at the CCSD(T) level of theory with an extrapolated basis set. The (2)H, (13)C, and (18)O kinetic isotope effects of the OH and Cl reactions with CH3OH were further investigated using canonical variational transition state theory with small curvature tunneling and compared to experimental measurements as well as to those observed in CH4 and several other substituted methane species.

  14. Glacial- interglacial temperature change based on 13C18O carbonate bond with in fish bone otoliths from Red Sea sediments

    NASA Astrophysics Data System (ADS)

    Ghosh, P.; Eiler, J.; Feeney, R.

    2006-12-01

    Determining the past record of temperature and salinity of ocean surface waters is essential for understanding past changes in climate, such as those which occur across glacial-interglacial transitions. As a useful proxy, the clumped isotope of CO2 in carbonate (13C18O16O or ?47) from inorganic precipitation experiment has been shown to reflect surface temperature with high degree of confidence (Ghosh et al., 2006). The last glacial cycle was characterized by climate fluctuations, but the extent of any associated changes in global sea level (or, equivalently, ice volume) remains elusive. High stands of sea level can be reconstructed from dated fossil and isotopic analyses of foraminifera and terapods, and these data are complemented by a compilation of global sea-level estimates based on deep-sea oxygen isotope ratios. Salinity derived from the records of oxygen isotopes ratios, however, contains uncertainties due to lack of information about the sea surface temperature change. Here we used combination of clumped isotopes technique and oxygen isotope measurement from fish otoliths (Myctophiformes; lanternfishes) extracted from two piston cores (Ku et al., 1969) (CH-154 and CH-153) to understand the temperature evolution and salinity variation of Red Sea water (300-800m) during the last 70 k.y. We analyzed well preserved unaltered otoliths from 7 different stratigraphic horizons from sediment core CH-154. Our preliminary observation suggests ~20 degree Celsius differences in sea water temperatures between glacial and interglacial time. We showed that the region has experienced fluctuation in climatic and tectonic processes during glacial interglacial time and the otoliths developed within the fishes captured the information about temperature change and salinity variation. Our results indicate a drop in temperature and restricted exchange of water with the open ocean during glaciations. The Red Sea environment was also highly saline even during the interglacial event

  15. Discerning the interactions between environmental parameters reflected in δ13C and δ18O of recent fluvial tufas: Lessons from a Mediterranean climate region

    NASA Astrophysics Data System (ADS)

    Osácar, M. Cinta; Arenas, Concha; Auqué, Luis; Sancho, Carlos; Pardo, Gonzalo; Vázquez-Urbez, Marta

    2016-11-01

    δ13C and δ18O of recent, continuous tufa records, obtained during a monitoring period spanning 3 to 13 years, are compared with the corresponding, known environmental conditions. Three rivers in NE Iberia (located along a 200-km N-S transect) are used for this comparison. The isotopic variations through space and time are discussed in terms of the environmental and geological parameters that operate on different scales, focusing on discerning the interactions between these parameters and providing examples of possible misinterpretation of climatic conditions, which is important to past climate studies based on isotopic data. The calculation of the actual isotopic fractionation coefficients, and the comparison with the literature-derived coefficients, demonstrates that the studied tufa formation was close to isotopic equilibrium to reflect the water temperature. The difference between mean measured water temperature (Tw) and mean calculated Tw (based on δ18Ocalcite and measured δ18Owater) is less than 2.7 °C. Tendencies of these calculated Tw are similar to the regional air temperature (Tair) tendencies through time, in particular in the case of the 13-year record, although certain deviations exist over shorter time spans. The best agreement between measured and calculated Tw and between δ18Ocalcite-based Tw tendencies and Tair tendencies corresponds to the tufa stromatolite facies. Differences between the δ18Ocalcite records of the three rivers cannot be attributed to temperature changes, but to the varying influences of groundwater inputs and isotopic rainfall composition in each river. Without considering these parameters, δ18Ocalcite-based Tw calculations yield inaccurate results when comparing the study sites. δ13Ccalcite values do not exhibit distinct patterns over time, and δ13Ccalcite variations are likely caused by local processes that do not reflect general environmental changes. These findings underscore the significance of accounting for both

  16. The pharmacokinetics and metabolism of 14C/13C-labeled ortho-phenylphenol formation following dermal application to human volunteers.

    PubMed

    Timchalk, C; Selim, S; Sangha, G; Bartels, M J

    1998-08-01

    1. The pharmacokinetics and metabolism of uniformly labeled 14C/13C-ortho-phenylphenol (OPP) were followed in six human male volunteers given a single 8 h dermal dose of 6 microg OPP/kg body weight formulated as a 0.4% (w/v) solution in isopropyl alcohol. The application site was covered with a non-occlusive dome allowing free movement of air, but preventing the loss of radioactivity due to physical contact. At 8 h post-exposure the non-occlusive dome was removed, the dose site was wiped with isopropyl alcohol containing swabs and the skin surface repeatedly stripped with tape. Blood specimens, urine, and feces were collected from each volunteer over a 5 day post-exposure period and were analyzed for radioactivity and metabolites (urine only). 2. Following dermal application, peak plasma levels of radioactivity were obtained within 4 h post-exposure and rapidly declined with virtually all of the absorbed dose rapidly excreted into the urine within 24 h post-exposure. A one-compartment pharmacokinetic model was used to describe the time-course of OPP absorption and clearance in male human volunteers. Approximately 43% of the dermally applied dose was absorbed through the skin with an average absorption half-life of 10 h. Once absorbed the renal clearance of OPP was rapid with an average half-life of 0.8 h. The rate limiting step for renal clearance was the relatively slower rate of dermal absorption; therefore the pharmacokinetics of OPP in humans was described by a 'flip-flop' single compartment model. Overall, the pharmacokinetics were similar between individuals, and the model parameters were in excellent agreement with the experimental data. 3. Approximately 73% of the total urinary radioactivity was accounted for as free OPP, OPP-sulfate and OPP-glucuronide conjugates. The sulfate conjugate was the major metabolite (approximately 69%). Therefore, total urinary OPP equivalents (acid-labile conjugates+free OPP) can be used to estimate the systemically absorbed

  17. Geochemistry of Cambro-Ordovician Arbuckle limestone, Oklahoma: Implications for diagenetic. delta. sup 18 O alteration and secular. delta. sup 13 C and sup 87 Sr/ sup 86 Sr variation

    SciTech Connect

    Gao, Guoqiu; Land, L.S. )

    1991-10-01

    Isotopic analyses of 227 limestone samples from the Cambro-Ordovician Arbuckle Group, Oklahoma, document slow secular changes in the chemistry of the limestones. From late Cambrian to early Ordovician, the {delta}{sup 18}O values of the limestones increase from {minus}10{per thousand} to {minus}7{per thousand} (PDB); {delta}{sup 13}C values decrease from 0{per thousand} to {minus}2{per thousand} (PDB); and {sup 87}Sr/{sup 86}Sr ratios decrease from 0.7091 to 0.7088. The light {delta}{sup 18}O values suggest that all Arbuckle limestones underwent diagenetic alteration, probably caused by meteoric water recharged during the development of the overlying, pre-middle Ordovician unconformity. The gradual {delta}{sup 18}O increase from late Cambrian to early Ordovician reflects reduced {sup 18}O depletion with decreasing burial temperature during alteration, although the presence of additional primary secular {delta}{sup 18}O variation cannot be ruled out. The {delta}{sup 13}C and {sup 87}Sr/{sup 86}Sr variations, in accord with {delta}{sup 13}C and {sup 87}Sr/{sup 86}Sr variations in the literature, represent primary secular variations. The variations indicate that the {delta}{sup 13}C value and {sup 87}Sr/{sup 86}Sr ratio of early Paleozoic surface seawater decreased from late Cambrian to early Ordovician. The {delta}{sup 13}C variation during this time period seems to correlate with sea-level variation. Specifically, during sea-level fall, an increase in the rate of oxidation of organic matter caused {sup 13}C depletion of inorganic bicarbonate in seawater. As a result, early Ordovician carbonates, probably deposited during the regression stage of the latest Precambrian to latest early Ordovician cycle, became {sup 13}C depleted, relative to late Cambrian carbonates. The decrease of seawater {sup 87}Sr/{sup 86}Sr ratio from late Cambrian to early Ordovician may have resulted from decreased riverine Sr input caused by decreased rate of continental weathering.

  18. The Impact of Climate, Sulfur Dioxide, and Industrial Dust on δ(18)O and δ(13)C in Glucose from Pine Tree Rings Growing in an Industrialized Area in the Southern Part of Poland.

    PubMed

    Sensuła, Barbara M

    The mass spectrometric analysis of the impact of sulfur dioxide and dust emission on carbon and oxygen stable isotopic compositions of glucose hydrolysed from α-cellulose samples extracted from Scots pine growing in the vicinity of "Huta Katowice" steelworks was the main aim of this study. The annual rings covered the time span from 1975 to 2012 AD. The relationships between climatic conditions, sulfur dioxide, and industrial dust emission and oxygen and carbon isotopic compositions were analyzed using correlation function methods. This study shows the first analysis of carbon and oxygen stable isotopes in glucose as the bio-indicators of CO2, sulfur dioxide, and industrial dust emission. The anticoincidence trend of δ(18)O and δ(13)C and dust and sulfur dioxide confirms that the decreases of dust and sulfur dioxide industrial emission increase δ(18)O and δ(13)C values in glucose.

  19. MEASUREMENTS OF PAST 14C LEVELS AND 13C/12C RATIOS IN THE SURFACE WATERS OF THE WORLD'S SUBPOLAR OCEANS.

    SciTech Connect

    Brown, T A

    2010-04-22

    Under this project we have developed methods that allow the reconstruction of past {sup 14}C levels of the surface waters of the subpolar North Pacific Ocean by measuring the {sup 14}C contents of archived salmon scales. The overall goal of this research was to reduce of the uncertainty in the uptake of fossil CO{sub 2} by the oceans and thereby improve the quantification of the global carbon cycle and to elucidate the fate of anthropogenic CO{sub 2}. Ocean General Circulation Models (OGCMs), with their three dimensional global spatial coverage and temporal modeling capabilities, provide the best route to accurately calculating the total uptake of CO{sub 2} by the oceans and, hence, to achieving the desired reduction in uncertainty. {sup 14}C has played, and continues to play, a central role in the validation of the OGCMs calculations, particularly with respect to those model components which govern the uptake of CO{sub 2} from the atmosphere and the transport of this carbon within the oceans. Under this project, we have developed time-series records of the {sup 14}C levels of the surface waters of three areas of the subpolar North Pacific Ocean. As the previously available data on the time-history of oceanic surface water {sup 14}C levels are very limited, these time-series records provide significant new {sup 14}C data to constrain and validate the OGCMs.

  20. An extractive removal step optimized for a high-throughput α-cellulose extraction method for δ 13 C and δ 18 O stable isotope ratio analysis in conifer tree rings

    Treesearch

    Wen Lin; Asko Noormets; John S. King; Ge Sun; Steve McNulty; Jean-Christophe Domec; Lucas Cernusak

    2017-01-01

    Stable isotope ratios (δ13C and δ18O) of tree-ring α-cellulose are important tools in paleoclimatology, ecology, plant physiology and genetics. The Multiple Sample Isolation System for Solids (MSISS) was a major advance in the tree-ring α-cellulose extraction methods, offering greater throughput and reduced labor input compared to traditional alternatives. However, the...

  1. [sup 13]C and [sup 18]O of wood from the Roman siege rampart in Masada, Israel (AD 70-73): Evidence for a less arid climate for the region

    SciTech Connect

    Yakir, D.; Gat, J. ); Issar, A.; Adar, E. ); Trimborn, P.; Lipp, J. )

    1994-08-01

    The isotopic ratios [sup 13]C/[sup 12]C and [sup 18]O/[sup 16]O of cellulose from tamarix trees which were used by the Roman army as a groundwork of the siege-rampart of Masada (AD 70-73) were compared with ratios measured in present-day tamarix trees growing in the Masada region and in central Israel. The ancient tamarix cellulose is depleted in both [sup 13]C and [sup 18]O compared to cellulose from trees growing in the Masada region today. Similar trends were observed on comparing modern tamarix trees growing in the Negev Desert with those growing in the temperate climate of central Israel. Considering the factors that can contribute to the observed changes in isotopic composition, the authors conclude that the ancient trees enjoyed less arid environmental conditions during their growth compared to contemporary trees in this desert region. This report demonstrates the potential in using combined [sup 18]O and [sup 13]C analyses of archeological plant material as independent indication of regional climate change in desert areas (where conventional isotopic analyses, such as in tree rings, are impractical).

  2. Comparison of δ(13)C and δ(18)O from cellulose, whole wood, and resin-free whole wood from an old high elevation Pinus uncinata in the Spanish central Pyrenees.

    PubMed

    Riechelmann, Dana F C; Maus, Michael; Dindorf, Willi; Konter, Oliver; Schöne, Bernd R; Esper, Jan

    2016-12-01

    δ(13)C and δ(18)O values from sapwood of a single Pinus uncinata tree, from a high elevation site in the Spanish Pyrenees, were determined to evaluate the differences between whole wood and resin-free whole wood. This issue is addressed for the first time with P. uncinata over a 38-year long period. Results are also compared with published isotope values of α-cellulose samples from the same tree. The differences in δ(13)C and δ(18)O between whole wood and resin-free whole wood vary within the analytical uncertainty of 0.3 and 0.5 ‰, respectively, indicating that resin extraction is not necessary for sapwood of P. uncinata. Mean differences between cellulose and whole wood are 0.9 ‰ (δ(13)C) and 5.0 ‰ (δ(18)O), respectively. However, further analyses of different species and other sites are needed to evaluate whether the findings reported here are coherent more generally.

  3. High-resolution study of oscillator strengths and predissociation rates for 13C18O . W-X bands and Rydberg complexes between 92.9 and 93.5 nm

    NASA Astrophysics Data System (ADS)

    Eidelsberg, M.; Lemaire, J. L.; Federman, S. R.; Heays, A. N.; Stark, G.; Lyons, J. R.; Gavilan, L.; de Oliveira, N.

    2017-06-01

    We carried out experiments at the SOLEIL synchrotron facility to acquire data for modelling CO photochemistry in the vacuum ultraviolet. We report oscillator strengths and predissociation rates for four vibrational bands associated with transitions from the v = 0 level of the X1Σ+ ground state to the v = 0-3 vibrational levels of the core excited W1Π Rydberg state, and for three overlapping bands associated with the 4pπ, 5pπ, and 5pσ Rydberg states between 92.9 and 93.4 nm in 13C18O. These results complete those obtained in the same conditions for 12C16O, 13C16O, and 12C18O recently published by us, and extend the development of a comprehensive database of line positions, oscillator strengths, and linewidths of photodissociating transitions for CO isotopologues. Absorption spectra were recorded using the Vacuum UltraViolet Fourier Transform Spectrometer (VUV-FTS) installed on the Dichroïsme Et Spectroscopie par Interaction avec le Rayonnement Synchrotron (DESIRS) beamline at SOLEIL. The resolving power of the measurements, R = 300 000 to 400 000, allows the analysis of individual line strengths and widths within the bands. Gas column densities in the differentially pumped system were calibrated using the B-X (0-0) band at 115.1 nm in 13C18O.

  4. Leaf functional response to increasing atmospheric CO(2) concentrations over the last century in two northern Amazonian tree species: a historical δ(13) C and δ(18) O approach using herbarium samples.

    PubMed

    Bonal, Damien; Ponton, Stéphane; Le Thiec, Didier; Richard, Béatrice; Ningre, Nathalie; Hérault, Bruno; Ogée, Jérôme; Gonzalez, Sophie; Pignal, Marc; Sabatier, Daniel; Guehl, Jean-Marc

    2011-08-01

    We assessed the extent of recent environmental changes on leaf morphological (stomatal density, stomatal surface, leaf mass per unit area) and physiological traits (carbon isotope composition, δ(13)C(leaf) , and discrimination, Δ(13)C(leaf) , oxygen isotope composition, δ(18)O(leaf) ) of two tropical rainforest species (Dicorynia guianensis; Humiria balsamifera) that are abundant in the Guiana shield (Northern Amazonia). Leaf samples were collected in different international herbariums to cover a 200 year time-period (1790-2004) and the whole Guiana shield. Using models describing carbon and oxygen isotope fractionations during photosynthesis, different scenarios of change in intercellular CO(2) concentrations inside the leaf (C(i)), stomatal conductance (g), and photosynthesis (A) were tested in order to understand leaf physiological response to increasing air CO(2) concentrations (C(a)). Our results confirmed that both species displayed physiological response to changing C(a) . For both species, we observed a decrease of about 1.7‰ in δ(13)C(leaf) since 1950, without significant change in Δ(13)C(leaf) and leaf morphological traits. Furthermore, there was no clear change in δ(18)O(leaf) for Humiria over this period. Our simulation approach revealed that an increase in A, rather than a decrease in g, explained the observed trends for these tropical rainforest species, allowing them to maintain a constant ratio of C(i)/C(a) .

  5. A dynamic soil chamber system coupled with a tunable diode laser for online measurements of delta-13C, delta-18O, and efflux rate of soil respired CO2

    SciTech Connect

    Powers, Heath H; Mcdowell, Nate; Hanson, David; Hunt, John

    2009-01-01

    High frequency observations of the stable isotopic composition of CO(2) effluxes from soil have been sparse due in part to measurement challenges. We have developed an open-system method that utilizes a flow-through chamber coupled to a tunable diode laser (TDL) to quantify the rate of soil CO(2) efflux and its delta(13)C and delta(18)O values (delta(13)C(R) and delta(18)O(R), respectively). We tested the method first in the laboratory using an artificial soil test column and then in a semi-arid woodland. We found that the CO(2) efflux rates of 1.2 to 7.3 micromol m(-2) s(-1) measured by the chamber-TDL system were similar to measurements made using the chamber and an infrared gas analyzer (IRGA) (R(2) = 0.99) and compared well with efflux rates generated from the soil test column (R(2) = 0.94). Measured delta(13)C and delta(18)O values of CO(2) efflux using the chamber-TDL system at 2 min intervals were not significantly different from source air values across all efflux rates after accounting for diffusive enrichment. Field measurements during drought demonstrated a strong dependency of CO(2) efflux and isotopic composition on soil water content. Addition of water to the soil beneath the chamber resulted in average changes of +6.9 micromol m(-2) s(-1), -5.0 per thousand, and -55.0 per thousand for soil CO(2) efflux, delta(13)C(R) and delta(18)O(R), respectively. All three variables initiated responses within 2 min of water addition, with peak responses observed within 10 min for isotopes and 20 min for efflux. The observed delta(18)O(R) was more enriched than predicted from temperature-dependent H(2)O-CO(2) equilibration theory, similar to other recent observations of delta(18)O(R) from dry soils (Wingate L, Seibt U, Maseyk K, Ogee J, Almeida P, Yakir D, Pereira JS, Mencuccini M. Global Change Biol. 2008; 14: 2178). The soil chamber coupled with the TDL was found to be an effective method for capturing soil CO(2) efflux and its stable isotope composition at high

  6. A dynamic soil chamber system coupled with a tunable diode laser for online measurements of delta13C, delta18O, and efflux rate of soil-respired CO2.

    PubMed

    Powers, Heath H; Hunt, John E; Hanson, David T; McDowell, Nate G

    2010-02-01

    High frequency observations of the stable isotopic composition of CO(2) effluxes from soil have been sparse due in part to measurement challenges. We have developed an open-system method that utilizes a flow-through chamber coupled to a tunable diode laser (TDL) to quantify the rate of soil CO(2) efflux and its delta(13)C and delta(18)O values (delta(13)C(R) and delta(18)O(R), respectively). We tested the method first in the laboratory using an artificial soil test column and then in a semi-arid woodland. We found that the CO(2) efflux rates of 1.2 to 7.3 micromol m(-2) s(-1) measured by the chamber-TDL system were similar to measurements made using the chamber and an infrared gas analyzer (IRGA) (R(2) = 0.99) and compared well with efflux rates generated from the soil test column (R(2) = 0.94). Measured delta(13)C and delta(18)O values of CO(2) efflux using the chamber-TDL system at 2 min intervals were not significantly different from source air values across all efflux rates after accounting for diffusive enrichment. Field measurements during drought demonstrated a strong dependency of CO(2) efflux and isotopic composition on soil water content. Addition of water to the soil beneath the chamber resulted in average changes of +6.9 micromol m(-2) s(-1), -5.0 per thousand, and -55.0 per thousand for soil CO(2) efflux, delta(13)C(R) and delta(18)O(R), respectively. All three variables initiated responses within 2 min of water addition, with peak responses observed within 10 min for isotopes and 20 min for efflux. The observed delta(18)O(R) was more enriched than predicted from temperature-dependent H(2)O-CO(2) equilibration theory, similar to other recent observations of delta(18)O(R) from dry soils (Wingate L, Seibt U, Maseyk K, Ogee J, Almeida P, Yakir D, Pereira JS, Mencuccini M. Global Change Biol. 2008; 14: 2178). The soil chamber coupled with the TDL was found to be an effective method for capturing soil CO(2) efflux and its stable isotope composition at high

  7. A 500-year seasonally resolved δ18O and δ13C, layer thickness and calcite aspect record from a speleothem deposited in the Han-sur-Lesse cave, Belgium

    NASA Astrophysics Data System (ADS)

    Van Rampelbergh, M.; Verheyden, S.; Allan, M.; Quinif, Y.; Cheng, H.; Edwards, L. R.; Keppens, E.; Claeys, P.

    2015-06-01

    Speleothem δ18O and δ13C signals enable climate reconstructions at high resolution. However, scarce decadal and seasonally resolved speleothem records are often difficult to interpret in terms of climate due to the multitude of factors that affect the proxy signals. In this paper, a fast-growing (up to 2 mm yr-1) seasonally laminated speleothem from the Han-sur-Lesse cave (Belgium) is analyzed for its δ18O and δ13C values, layer thickness and changes in calcite aspect. The studied record covers the period between AD 2001 and 1479 as indicated by layer counting and confirmed by 20 U / Th ages. The Proserpine proxies are seasonally biased and document drier (and colder) winters on multidecadal scales. Higher δ13C signals reflect increased prior calcite precipitation (PCP) and lower soil activity during drier (and colder) winters. Thinner layers and darker calcite relate to slower growth and exist during drier (and colder) winter periods. Exceptionally dry (and cold) winter periods occur from 1565 to 1610, at 1730, from 1770 to 1800, from 1810 to 1860, and from 1880 to 1895 and correspond to exceptionally cold periods in historical and instrumental records as well as European winter temperature reconstructions. More relative climate variations, during which the four measured proxies vary independently and display lower amplitude variations, occur between 1479 and 1565, between 1610 and 1730, and between 1730 and 1770. The winters during the first and last periods are interpreted as relatively wetter (and warmer) and correspond to warmer periods in historical data and in winter temperature reconstructions in Europe. The winters in the period between 1610 and 1730 are interpreted as relatively drier (and cooler) and correspond to generally colder conditions in Europe. Interpretation of the seasonal variations in δ18O and δ13C signals differs from that on a decadal and multidecadal scale. Seasonal δ18O variations reflect cave air temperature variations and

  8. The effects of Paraloid B-72 and Butvar B-98 treatment and organic solvent removal on δ(13)C, δ(15)N, and δ(18)O values of collagen and hydroxyapatite in a modern bone.

    PubMed

    France, Christine A M; Giaccai, Jennifer A; Doney, Charlotte R

    2015-06-01

    Stable isotopes in bones are a powerful tool for diet, provenance, climate, and physiological reconstructions, but necessarily require well-preserved specimens unaltered by postmortem diagenesis or conservation practices. This study examines the effects of Paraloid B-72 and Butvar B-98, two common consolidants used in field and museum conservation, on δ(13)C, δ(15)N, and δ(18)O values from bone collagen and hydroxyapatite. The effects of solvent removal (100% acetone, 100% ethanol, 9:1 acetone:xylenes, 9:1 ethanol:xylenes) and drying methods (ambient air, vacuum, oven drying at 80°C) were also examined to determine if bones treated with these consolidants can successfully be cleaned and used for stable isotope analyses. Results show that introduction of Paraloid B-72 or Butvar B-98 in 100% acetone or 100% ethanol, respectively, with subsequent removal by the same solvents and drying at 80°C facilitates the most successful removal of consolidants and solvents. The δ(13)C values in collagen, δ(15)N in collagen, δ(18)O in hydroxyapatite phosphate, and δ(13)C in hydroxyapatite structural carbonate were unaltered by treatments with Paraloid or Butvar and subsequent solvent removal. The δ(18)O in hydroxyapatite structural carbonate showed nonsystematic variability when bones were treated with Paraloid and Butvar, which is hypothesized to be a result of hydroxyl exchange when bones are exposed to consolidants in solution. It is therefore recommended that δ(18)O in hydroxyapatite structural carbonate should not be used in stable isotope studies if bones have been treated with Paraloid or Butvar.

  9. Using dual carbon isotopes, 13C and 14C, to resolve the origin, mixing and alteration of major carbon pools in shallow-water CO2 vents (Kueishantao hydrothermal field, offshore Taiwan)

    NASA Astrophysics Data System (ADS)

    Wang, Shing-Lin; Lin, Yu-Shih; Burr, George; Wang, Chau-Chang

    2017-04-01

    Submarine hydrothermal vents at convergent boundaries tend to emit CO2-rich fluids due to the subduction of marine sediment. In the shallow-water hydrothermal field, the carbon dioxide gas bubbles can reach to the surface seawater and may alter the surface seawater chemistry and the planktonic microbial community. We use duel carbon isotopes, 13C and 14C, to evaluate the effect of additional CO2 input on the major carbon pools in ambient seawater of hydrothermal vents. Radiocarbon (14C) is undetectable in hydrothermal CO2 (Δ14C ˜-1000‰), so this "radiocarbon-dead" CO2 can be used as an end-member to constrain the carbon sources in the hydrothermal field. Here we report δ13C and Δ14C values of CO2(g), dissolved inorganic carbon (DIC) and particulate organic carbon (POC) within and above two vents, yellow vent (YV) and white vent (WV), in the Kueishantao shallow-water hydrothermal field, northeastern offshore Taiwan. The results show that the δ13C value of vent CO2 gas is around -6‰ within the range of mantle source. DIC was 13C-depleted (around -9‰) than CO2 gas and POC were more 13C-depleted in YV (-25.7‰) and in WV (-22.4‰). The Δ14C values of vent CO2 are slightly higher than -1000 ‰ with -949.2±16.0 ‰ in YV (Temp. = 116°C) and -890.7±7.6‰ in WV (Temp. = 58°C). It suggests the radiocarbon composition is more than 90% radiocarbon-dead carbon mixed with less than 10% modern carbon. Our result clearly indicates the main component in vent CO2 gas is the mantle-derived carbon and it is supported by helium isotopic compositions (YV, 7.5±0.1 Ra; WV, 7.1±0.2 Ra). We expect the Δ14C values of DIC and POC above the two vents will also reflect the mantle-derive signal and it will also reveal how much the carbon is emitted from hydrothermal vents and exchanged within these major carbon pools in the ambient seawater.

  10. Multi-isotope labelling of organic matter by diffusion of 2H/18O-H2O vapour and 13C-CO2 into the leaves and its distribution within the plant

    NASA Astrophysics Data System (ADS)

    Studer, M. S.; Siegwolf, R. T. W.; Leuenberger, M.; Abiven, S.

    2015-03-01

    Isotope labelling is a powerful tool to study elemental cycling within terrestrial ecosystems. Here we describe a new multi-isotope technique to label organic matter (OM). We exposed poplars (Populus deltoides × nigra) for 14 days to an atmosphere enriched in 13CO2 and depleted in 2H218O. After 1 week, the water-soluble leaf OM (δ13C = 1346 ± 162‰) and the leaf water were strongly labelled (δ18O = -63 ± 8, δ2H = -156 ± 15‰). The leaf water isotopic composition was between the atmospheric and stem water, indicating a considerable back-diffusion of vapour into the leaves (58-69%) in the opposite direction to the net transpiration flow. The atomic ratios of the labels recovered (18O/13C, 2H/13C) were 2-4 times higher in leaves than in the stems and roots. This could be an indication of the synthesis of more condensed compounds in roots and stems (e.g. lignin vs. cellulose) or might be the result of O and H exchange and fractionation processes during phloem transport and biosynthesis. We demonstrate that the three major OM elements (C, O, H) can be labelled and traced simultaneously within the plant. This approach could be of interdisciplinary interest in the fields of plant physiology, palaeoclimatic reconstruction or soil science.

  11. Estimation of continuous anthropogenic CO2: model-based evaluation of CO2, CO, δ13C(CO2) and Δ14C(CO2) tracer methods

    NASA Astrophysics Data System (ADS)

    Vardag, S. N.; Gerbig, C.; Janssens-Maenhout, G.; Levin, I.

    2015-11-01

    We investigate different methods for estimating anthropogenic CO2 using modeled continuous atmospheric concentrations of CO2 alone, as well as CO2 in combination with the surrogate tracers CO, δ13C(CO2) and Δ14C(CO2). These methods are applied at three hypothetical stations representing rural, urban and polluted conditions. We find that, independent of the tracer used, an observation-based estimate of continuous anthropogenic CO2 is not yet feasible at rural measurement sites due to the low signal-to-noise ratio of anthropogenic CO2 estimates at such settings. The tracers δ13C(CO2) and CO provide an accurate possibility to determine anthropogenic CO2 continuously, only if all CO2 sources in the catchment area are well characterized or calibrated with respect to their isotopic signature and CO to anthropogenic CO2 ratio. We test different calibration strategies for the mean isotopic signature and CO to CO2 ratio using precise Δ14C(CO2) measurements on monthly integrated as well as on grab samples. For δ13C(CO2), a calibration with annually averaged 14C(CO2) grab samples is most promising, since integrated sampling introduces large biases into anthropogenic CO2 estimates. For CO, these biases are smaller. The precision of continuous anthropogenic CO2 determination using δ13C(CO2) depends on measurement precision of δ13C(CO2) and CO2, while the CO method is mainly limited by the variation in natural CO sources and sinks. At present, continuous anthropogenic CO2 could be determined using the tracers δ13C(CO2) and/or CO with a precision of about 30 %, a mean bias of about 10 % and without significant diurnal discrepancies. Hypothetical future measurements of continuous Δ14C(CO2) with a precision of 5 ‰ are promising for anthropogenic CO2 determination (precision ca. 10-20 %) but are not yet available. The investigated tracer-based approaches open the door to improving, validating and reducing biases of highly resolved emission inventories using atmospheric

  12. - and Air-Broadening of 12C16O, 13C16O and 12C18O at 2.3 μm

    NASA Astrophysics Data System (ADS)

    Devi, V. Malathy; Benner, D. Chris; Smith, Mary Ann H.; Mantz, Arlan W.; Sung, Keeyoon; Brown, Linda R.

    2011-06-01

    High resolution (0.005 Cm-1) absorption spectra of CO and two of its isotopologues (13CO and C18O) were recorded between 3550 and 5250 Cm-1 using the Bruker IFS-125HR Fourier transform spectrometer (FTS) located at the Jet Propulsion Laboratory (JPL) and a specially designed and built coolable 20.38 cm long absorption cell placed within the sample compartment of the FTS. More than 50 spectra of both pure and air-broadened samples of CO, 13CO and C18O were recorded at various temperatures from 150 K to 298 K, with maximum total pressures up to ˜700 Torr. A multispectrum nonlinear least squares spectrum fitting technique was used to determine the spectral line shape parameters including speed dependence, Lorentz halfwidth coefficients, pressure-induced shift coefficients, and off-diagonal relaxation matrix element coefficients for line mixing. These line shape parameters were obtained for both self- and air-broadening, and temperature dependences of these parameters were determined where possible. As previously done in studies of CO_2, rather than retrieving individual line positions and intensities, we constrained them to their theoretical relationships, including Herman-Wallis terms, determining only the band intensities and rovibrational constants. The results are discussed and compared with values reported in the literature. K. Sung, A. W. Mantz, M. A. H. Smith, L. R. Brown, T. J. Crawford, V. Malathy Devi and D. C. Benner, JMS 262 (2010) 122-134. D. C. Benner, C. P. Rinsland, V. Malathy Devi, M. A. H. Smith and D. A. Atkins, JQSRT 53 (1995) 705-721. V. Malathy Devi, D. C. Benner, L. R. Brown, C. E. Miller and R. A. Toth, JMS 242 (2007) 90-117. Research described in this paper was performed at Connecticut College, the College of William and Mary, NASA Langley Research Center and the Jet Propulsion Laboratory, California Institute of Technology, under contracts and cooperative agreements with the National Aeronautics and Space Administration.

  13. Foliar delta(13)C and delta(18)O reveal differential physiological responses of canopy foliage to pre-planting weed control in a young spotted gum (Corymbia citriodora subsp. Variegata) plantation.

    PubMed

    Huang, Zhiqun; Xu, Zhihong; Blumfield, Timothy J; Bubb, Ken

    2008-10-01

    Weed control may improve the growth of forest plantations by influencing soil water and nutrient availability, but our knowledge of leaf-level physiological responses to weed control at different within-canopy positions is limited for tropical and subtropical plantations. Foliar carbon (delta(13)C) and oxygen (delta(18)O) isotope compositions, gas exchange, and nitrogen (N(mass)) and phosphorus (P(mass)) concentrations at four canopy positions were assessed in a young spotted gum (Corymbia citriodora subsp. Variegata (F. Muell.) A.R. Bean & M.W. McDonald) plantation subjected to either weed control or no weed control treatment, to test if leaves at different positions within the tree canopy had the same physiological responses to the weed control treatment. Weed control increased foliar delta(13)C but lowered delta(18)O in the upper-outer and upper-inner canopy, indicating that weed control resulted in a higher foliar photosynthetic capacity at upper-canopy positions, a conclusion confirmed by gas exchange measurements. The increased photosynthetic capacity resulting from weed control can be explained by an increase in foliar N(mass). In the lower-outer canopy, weed control reduced foliar delta(13)C while lowering delta(18)O even more than in the upper-canopy, suggesting strong enhancement of the partial pressure of CO(2) in the leaf intercellular spaces and of foliar stomatal conductance in lower-canopy foliage. This conclusion was supported by gas exchange measurements. Foliar photosynthesis in the lower-inner canopy showed no significant response to weed control. The finding that leaves at different canopy positions differ in their physiological responses to weed control highlights the need to consider the canopy position effect when examining competition for soil nutrient and water resources between weeds and trees.

  14. A Column Experiment To Determine Black Shale Degradation And Colonization By Means of δ13C and 14C Analysis Of Phospholipid Fatty Acids And DNA Extraction

    NASA Astrophysics Data System (ADS)

    Seifert, A.; Gleixner, G.

    2008-12-01

    We investigated the degradation of black shale organic matter by microbial communities. We inoculated two columns respectively, with the fungi Schizophyllum commune, the gram-positive bacterium Pseudomonas putida and the gram-negative bacteria Streptomyces griseus and Streptomyces chartreusis. These microorganisms are known to degrade a wide variety of organic macromolecules. Additionally, we had two sets of control columns. To one set the same nutrient solution was added as to the inoculated columns and to the other set only sterile deionised water was supplied. All columns contained 1.5 kg of freshly crushed not autoclaved black shale material with a particle size of 0.63-2 mm. The columns were incubated at 28° C and 60% humidity in the dark. The aim was to investigate, which microorganisms live on black shales and if these microorganisms are able to degrade ancient organic matter. We used compound specific stable isotope measurement techniques and compound specific 14C-dating methods. After 183 days PLFAs were extracted from the columns to investigate the microbial community, furthermore we extracted on one hand total-DNA of column material and on the other hand DNA from pure cultures isolates which grew on Kinks-agar B, Starch-casein-nitrate-agar (SCN) and on complete-yeast-medium-agar (CYM). According to the PLFA analysis bacteria dominated in the columns, whereas in pure cultures more fungi were isolated. A principal component analysis revealed differences between the columns in accordance with the inoculation, but it seems that the inoculated microorganisms were replaced by the natural population. For AMS measurements palmitic acid (C 16:0) was re-isolated from total-PLFA-extract with a preparative fraction collector (PFC). Preliminary results of the study revealed that microorganisms are able to degrade black shale material and that PLFA analysis are useful methods to be combined with analysis of stable isotope and 14C measurements to study microbial

  15. Influence of different organic fertilizers on quality parameters and the delta(15)N, delta(13)C, delta(2)H, delta(34)S, and delta(18)O values of orange fruit (Citrus sinensis L. Osbeck).

    PubMed

    Rapisarda, Paolo; Camin, Federica; Fabroni, Simona; Perini, Matteo; Torrisi, Biagio; Intrigliolo, Francesco

    2010-03-24

    To investigate the influence of different types of fertilizers on quality parameters, N-containing compounds, and the delta(15)N, delta(13)C, delta(2)H, delta (34)S, and delta(18)O values of citrus fruit, a study was performed on the orange fruit cv. 'Valencia late' (Citrus sinensis L. Osbeck), which was harvested in four plots (three organic and one conventional) located on the same farm. The results demonstrated that different types of organic fertilizers containing the same amount of nitrogen did not effect important changes in orange fruit quality parameters. The levels of total N and N-containing compounds such as synephrine in fruit juice were not statistically different among the different treatments. The delta(15)N values of orange fruit grown under fertilizer derived from animal origin as well as from vegetable compost were statistically higher than those grown with mineral fertilizer. Therefore, delta(15)N values can be used as an indicator of citrus fertilization management (organic or conventional), because even when applied organic fertilizers are of different origins, the natural abundance of (15)N in organic citrus fruit remains higher than in conventional ones. These treatments also did not effect differences in the delta(13)C, delta(2)H, delta(34)S, and delta(18)O values of fruit.

  16. Microbial carbon cycling in oligotrophic regional aquifers near the Tono Uranium Mine, Japan as inferred from δ 13C and Δ 14C values of in situ phospholipid fatty acids and carbon sources

    NASA Astrophysics Data System (ADS)

    Mills, Christopher T.; Amano, Yuki; Slater, Gregory F.; Dias, Robert F.; Iwatsuki, Teruki; Mandernack, Kevin W.

    2010-07-01

    Microorganisms are ubiquitous in deep subsurface environments, but their role in the global carbon cycle is not well-understood. The natural abundance δ 13C and Δ 14C values of microbial membrane phospholipid fatty acids (PLFAs) were measured and used to assess the carbon sources of bacteria in sedimentary and granitic groundwaters sampled from three boreholes in the vicinity of the Tono Uranium Mine, Gifu, Japan. Sample storage experiments were performed and drill waters analyzed to characterize potential sources of microbial contamination. The most abundant PLFA structures in all waters sampled were 16:0, 16:1ω7 c, cy17:0, and 18:1ω7 c. A PLFA biomarker for type II methanotrophs, 18:1ω8 c, comprised 3% and 18% of total PLFAs in anoxic sedimentary and granitic waters, respectively, sampled from the KNA-6 borehole. The presence of this biomarker was unexpected given that type II methanotrophs are considered obligate aerobes. However, a bacterium that grows aerobically with CH 4 as the sole energy source and which also produces 56% of its total PLFAs as 18:1ω8 c was isolated from both waters, providing additional evidence for the presence of type II methanotrophs. The Δ 14C values determined for type II methanotroph PLFAs in the sedimentary (-861‰) and granite (-867‰) waters were very similar to the Δ 14C values of dissolved inorganic carbon (DIC) in each water (˜-850‰). This suggests that type II methanotrophs ultimately derive all their carbon from inorganic sources, whether directly from DIC and/or from CH 4 produced by the reduction of DIC. In contrast, δ 13C values of type II PLFAs in the sedimentary (-93‰) and granite (-60‰) waters indicate that these organisms use different carbon assimilation schemes in each environment despite very similar δ13C values (˜-95‰) for each water. The δ 13C PLFA values (-28‰ to -45‰) of non-methanotrophic bacteria in the KNA-6 LTL water do not clearly distinguish between heterotrophic and autotrophic

  17. Thermal evolution of Site U1414 by stable isotopes δ13C and δ18O, 87Sr/86Sr and fluid inclusion analyses, IODP Expedition 344

    NASA Astrophysics Data System (ADS)

    Brandstätter, Jennifer; Kurz, Walter; Krenn, Kurt; Richoz, Sylvain

    2017-04-01

    IODP Expedition 344 is the second expedition in course of the Costa Rica Seismogenesis Project (Program A), that was designed to reveal processes that effect nucleation and seismic rupture of large earthquakes at erosional subduction zones. Site 344-U1414, located 1 km seaward of the deformation front offshore Costa Rica, serves to evaluate fluid-rock interaction and geochemical processes linked with the tectonic evolution of the incoming Cocos Plate from the Early Miocene up to recent times. Combined isotope analyses and microthermometric analyses of fluid inclusions of hydrothermal veins within lithified sediments and the igneous basement (Cocos Ridge basalt), was used to reveal the thermal history of Site 344-U1414. Veins in the sedimentary rocks are mainly filled by coarse-grained calcite and subordinately by quartz. Veins within the basalt show polymineralic filling of clay minerals, calcite, aragonite and quartz. Blocky veins with embedded wall rock fragments, appearing in the sediments and in the basalt, indicate hydraulic fracturing. The carbon isotopic composition of the vein calcite suggest the influence of a CO2 -rich fluid mixed with seawater (-3.0 to -0.4‰ V-PDB) and the δ18O values can be differentiated in two groups, depending on the formation temperature (-13.6 to -9.3‰ and -10.8 to -4.7‰ V-PDB). 87Sr/86Sr ratios from the veins confirm the results of the stable isotope analyses, with a higher 87Sr/86Sr ratio close to seawater composition and lower ratios indicating the influence of basalt alteration. The hydrothermal veins contain different types of fluid inclusions with high and low entrapment temperatures and low saline fluids. The occurrence of decrepitated fluid inclusions, formed by increased internal overpressure, is related to isobaric heating. Elongated fluid inclusion planes, arc-like fluid inclusions and low homogenization temperatures suggest subsequent isobaric cooling. The stable isotopic content, strontium isotopic composition

  18. Combined δ11B, δ13C, and δ18O analyses of coccolithophore calcite constrains the response of coccolith vesicle carbonate chemistry to CO2-induced ocean acidification

    NASA Astrophysics Data System (ADS)

    Liu, Yi-Wei; Tripati, Robert; Aciego, Sarah; Gilmore, Rosaleen; Ries, Justin

    2016-04-01

    Coccolithophorid algae play a central role in the biological carbon pump, oceanic carbon sequestration, and in marine food webs. It is therefore important to understand the potential impacts of CO2-induced ocean acidification on these organisms. Differences in the regulation of carbonate chemistry, pH, and carbon sources of the intracellular compartments where coccolith formation occurs may underlie the diverse calcification and growth responses to acidified seawater observed in prior experiments. Here we measured stable isotopes of boron (δ11B), carbon (δ13C) and oxygen (δ18O) within coccolith calcite, and δ13C of algal tissue to constrain carbonate system parameters in two strains of Pleurochrysis carterae (P. carterae). The two strains were cultured under variable pCO2, with water temperature, salinity, dissolved inorganic carbon (DIC), and alkalinity monitored. Notably, PIC, POC, and PIC/POC ratio did not vary across treatments, indicating that P. carterae is able to calcify and photosynthesize at relatively constant rates irrespective of pCO2 treatment. The δ11B data indicate that mean pH at the site of coccolith formation did not vary significantly in response to elevated CO2. These results suggest that P. carterae regulates calcifying vesicle pH, even amidst changes in external seawater pH. Furthermore, δ13C and δ18O data suggest that P. carterae may utilize carbon from a single internal DIC pool for both calcification and photosynthesis, and that a greater proportion of dissolved CO2 relative to HCO3- enters the internal DIC pool under acidified conditions. These results suggest that P. carterae is able to calcifyand photosynthesize at relatively constant rates across pCO2 treatments by maintaining pH homeostasis at their site of calcification and utilizing a greater proportion of aqueous CO2.

  19. Intra-seasonal dynamics in metabolic processes of 13C/12C and 18O/16O in components of Scots pine twigs from southern Siberia interpreted with a conceptual framework based on the Carbon Metabolism Oscillatory Model

    PubMed Central

    2012-01-01

    Background Carbon isotope data from conifer trees play an important role in research on the boreal forest carbon reservoir in the global carbon cycle. Carbon isotopes are routinely used to study interactions between the environment and tree growth. Moreover, carbon isotopes became an essential tool for the evaluation of carbon assimilation and transport from needles into reserve pools, as well as the allocation of stored assimilates within a tree. The successful application and interpretation of carbon isotopes rely on the coherence of isotopic fractionation modeling. This study employs a new Carbon Metabolism Oscillatory Model (CMOM) to interpret the experimental data sets on metabolic seasonal dynamics of 13C/12 C and 18O/16O ratios measured in twig components of Scots pine growing in southern Siberia (Russia). Results The dynamics of carbon isotopic variables were studied in components of Pinus sylvestris L. in light and in dark chambers during the vegetation period from 14 June to 28 July 2006. At the beginning of this period water-soluble organic matter, mostly labile sugars (including sucrose as the main component) and newly formed bulk needle material, displayed relatively “light” δ13C values (depletion in 13 C). Then, 13 C content increased again with noticeable “depletion” events in the middle of the growth period. A gradual 13 C accumulation took place in the second half of the vegetation period. Similar effects were observed both in the light and in the dark with some temporal shifts. Environmental factors did not influence the δ13C values. A gradual 12C-depletion effect was noticed in needles of the previous year. The δ13C values of sucrose and proteins from needle biomass altered independently from each other in the light chamber. A distinct negative correlation between δ13C and δ18O values was revealed for all studied variables. Conclusions The abrupt 13C depletion recorded by all tested trees for the period from June to July

  20. A new set-up for simultaneous high-precision measurements of CO2, δ13C-CO2 and δ18O-CO2 on small ice core samples

    NASA Astrophysics Data System (ADS)

    Jenk, Theo Manuel; Rubino, Mauro; Etheridge, David; Ciobanu, Viorela Gabriela; Blunier, Thomas

    2016-08-01

    Palaeoatmospheric records of carbon dioxide and its stable carbon isotope composition (δ13C) obtained from polar ice cores provide important constraints on the natural variability of the carbon cycle. However, the measurements are both analytically challenging and time-consuming; thus only data exist from a limited number of sampling sites and time periods. Additional analytical resources with high analytical precision and throughput are thus desirable to extend the existing datasets. Moreover, consistent measurements derived by independent laboratories and a variety of analytical systems help to further increase confidence in the global CO2 palaeo-reconstructions. Here, we describe our new set-up for simultaneous measurements of atmospheric CO2 mixing ratios and atmospheric δ13C and δ18O-CO2 in air extracted from ice core samples. The centrepiece of the system is a newly designed needle cracker for the mechanical release of air entrapped in ice core samples of 8-13 g operated at -45 °C. The small sample size allows for high resolution and replicate sampling schemes. In our method, CO2 is cryogenically and chromatographically separated from the bulk air and its isotopic composition subsequently determined by continuous flow isotope ratio mass spectrometry (IRMS). In combination with thermal conductivity measurement of the bulk air, the CO2 mixing ratio is calculated. The analytical precision determined from standard air sample measurements over ice is ±1.9 ppm for CO2 and ±0.09 ‰ for δ13C. In a laboratory intercomparison study with CSIRO (Aspendale, Australia), good agreement between CO2 and δ13C results is found for Law Dome ice core samples. Replicate analysis of these samples resulted in a pooled standard deviation of 2.0 ppm for CO2 and 0.11 ‰ for δ13C. These numbers are good, though they are rather conservative estimates of the overall analytical precision achieved for single ice sample measurements. Facilitated by the small sample requirement

  1. Using stable isotope (delta18O, delta13C) on lacustrine mollusks as palaeoclimate tools in Chilean Patagonian Lakes: A case study from Lago Cisnes (47°S)

    NASA Astrophysics Data System (ADS)

    Alvarez, Denisse; Fagel, Nathalie; Keppens, Eddy; Arraneda, Alberto; Urrutia, Roberto

    2010-05-01

    Understanding the past climatic changes in the Southern Hemisphere (SH), are important to know the global climatic system on natural conditions, before the anthropogenic forcing became significant. However the knowledge in this Hemisphere still is not well developed comparatively with the Northern Hemisphere (NH); due in part to the used of climatic indicators still is limited. The carbon and oxygen stable isotope composition of biogenic carbonates precipitated in a lake have been successfully applied in several investigations of past climate and environment in the NH contrary to SH, where just few studies have applied stable isotopes in lakes. In this study, stable isotopes (delta18O, delta13C) were analyzed on lacustrine mollusk shells present in a short sediment core (34 cm) from a small Patagonian lake in order to assess if the isotopic signal on biogenic carbonates reflects environmental and climatic changes in this area. The analyses were made in three mollusk species, one bivalve (Musculium sp.) and two gastropods (Lymnaea sp. and Biomphalaria sp.) using isotope ratio mass spectrometry (IRMS). Additionally sedimentological and geochemical analyses were conducted (LOI 550 and 950°C, TON, TOC, C/N ratio and bulk X-ray diffraction). The results indicated that both delta18O and delta13C showed significantive fluctuations along the core, but with different trends, probably due to different physiological behavior between bivalves and gastropods. Gastropods are air-breathing pulmonates that discriminate against heavy isotopes of 18O and 13C, leading a significant fractionation between light and heavy isotopes of those elements. Only the isotopical signals of the Musculium sp. give similar trends with the sedimentological and geochemical records, suggesting this species could be a good indicator of climatic and environment changes in Cisnes lake. All sedimentological, geochemical and carbon and oxygen stable isotopes (from Musculium sp.) records indicated that

  2. An automated GC-C-GC-IRMS setup to measure palaeoatmospheric δ13C-CH4, δ15N-N2O and δ18O-N2O in one ice core sample

    NASA Astrophysics Data System (ADS)

    Sperlich, P.; Buizert, C.; Jenk, T. M.; Sapart, C. J.; Prokopiou, M.; Röckmann, T.; Blunier, T.

    2013-08-01

    Air bubbles in ice core samples represent the only opportunity to study the mixing ratio and isotopic variability of palaeoatmospheric CH4 and N2O. The highest possible precision in isotope measurements is required to maximize the resolving power for CH4 and N2O sink and source reconstructions. We present a new setup to measure δ13C-CH4, δ15N-N2O and δ18O-N2O isotope ratios in one ice core sample and with one single IRMS instrument, with a precision of 0.09, 0.6 and 0.7‰, respectively, as determined on 0.6-1.6 nmol CH4 and 0.25-0.6 nmol N2O. The isotope ratios are referenced to the VPDB scale (δ13C-CH4), the N2-air scale (δ15N-N2O) and the VSMOW scale (δ18O-N2O). Ice core samples of 200-500 g are melted while the air is constantly extracted to minimize gas dissolution. A helium carrier gas flow transports the sample through the analytical system. We introduce a new gold catalyst to oxidize CO to CO2 in the air sample. CH4 and N2O are then separated from N2, O2, Ar and CO2 before they get pre-concentrated and separated by gas chromatography. A combustion unit is required for δ13C-CH4 analysis, which is equipped with a constant oxygen supply as well as a post-combustion trap and a post-combustion GC column (GC-C-GC-IRMS). The post-combustion trap and the second GC column in the GC-C-GC-IRMS combination prevent Kr and N2O interferences during the isotopic analysis of CH4-derived CO2. These steps increase the time for δ13C-CH4 measurements, which is used to measure δ15N-N2O and δ18O-N2O first and then δ13C-CH4. The analytical time is adjusted to ensure stable conditions in the ion source before each sample gas enters the IRMS, thereby improving the precision achieved for measurements of CH4 and N2O on the same IRMS. The precision of our measurements is comparable to or better than that of recently published systems. Our setup is calibrated by analysing multiple reference gases that were injected over bubble-free ice samples. We show that our measurements

  3. Short-term natural δ13C and δ18O variations in pools and fluxes in a beech forest: the transfer of isotopic signal from recent photosynthates to soil respired CO2

    NASA Astrophysics Data System (ADS)

    Gavrichkova, O.; Proietti, S.; Moscatello, S.; Portarena, S.; Battistelli, A.; Matteucci, G.; Brugnoli, E.

    2011-10-01

    The fate of photosynthetic products within the plant-soil continuum determines how long the reduced carbon resides within the ecosystem and when it returns back to the atmosphere in the form of respiratory CO2. We have tested the possibility of measuring natural variation in δ13C and δ18O to disentangle the potential times needed to transfer carbohydrates produced by photosynthesis down to trunk, roots and, in general, to belowground up to its further release in the form of soil respiration into the atmosphere in a beech (Fagus sylvatica) forest. We have measured the variation in stable carbon and oxygen isotope compositions in plant material and in soil respired CO2 every three hours for three consecutive days. Possible steps and different signs of post-photosynthetic fractionation during carbon translocation were also identified. A 12 h-periodicity was observed for variation in δ13C in soluble sugars in the top crown leaves and it can be explained by starch day/night dynamics in synthesis and breakdown and by stomatal limitations under elevated vapour pressure deficits. Photosynthetic products were transported down the trunk and mixed with older carbon pools, therefore causing the dampening of the δ13C signal variation. The strongest periodicity of 24 h was found in δ13C in soil respiration indicating changes in root contribution to the total CO2 efflux. Other non-biological causes like diffusion fractionation and advection induced by gas withdrawn from the measurement chamber complicate data interpretation on this step of C transfer path. Nevertheless, it was possible to identify the speed of carbohydrates' translocation from the point of assimilation to the trunk breast height because leaf-imprinted enrichment of δ18O in soluble sugars was less modified along the downward transport and was well related to environmental parameters potentially linked to stomatal conductance. The speed of carbohydrates translocation from the site of assimilation to the trunk

  4. Middle Holocene Bison diet and mobility in the eastern Great Plains (USA) based on δ13C, δ18O, and 87Sr/ 86Sr analyses of tooth enamel carbonate

    NASA Astrophysics Data System (ADS)

    Widga, Chris; Walker, J. Douglas; Stockli, Lisa D.

    2010-05-01

    During the Holocene, bison ( Bison bison) were key components of the Great Plains landscape. This study utilizes serial stable isotope analyses (tooth enamel carbonate) of 29 individuals from five middle Holocene (˜ 7-8.5 ka) archaeological sites to address seasonal variability in movement patterns and grazing behavior of bison populations in the eastern Great Plains. Stable carbon isotopes ( δ13C) indicate a bison diet that is similar to the C3/C4 composition of modern tallgrass prairies, while 87Sr/ 86Sr values generally indicate very little seasonal movement (< 50 km) and relatively limited inter-annual movement (< 500 km) over the course of 4-5 yr. Analyses of variability in serial stable oxygen isotope samples ( δ18O) further substantiate a model of localized bison herds that adhered to upland areas of the eastern Plains and prairie-forest border.

  5. Microscopic cluster model for the description of new experimental results on the 13C(18O,16O) 15C two-neutron transfer at 84 MeV incident energy

    NASA Astrophysics Data System (ADS)

    Carbone, D.; Ferreira, J. L.; Cappuzzello, F.; Lubian, J.; Agodi, C.; Cavallaro, M.; Foti, A.; Gargano, A.; Lenzi, S. M.; Linares, R.; Santagati, G.

    2017-03-01

    The 13C(18O,16O) 15C reaction is studied at 84 MeV incident energy. Excitation energy spectra and absolute cross-section angular distributions for the strongest transitions are measured with good energy and angular resolutions. Strong selectivity for two-neutron configurations in the states of the residual nucleus is found. The measured cross-section angular distributions are analyzed by exact finite-range coupled reaction channel calculations. The two-particle wave functions are extracted using the extreme cluster and the independent coordinate scheme with shell-model derived coupling strengths. A new approach also is introduced, the microscopic cluster, in which the spectroscopic amplitudes in the center-of-mass reference frame are derived from shell-model calculations using the Moshinsky transformation brackets. This new model is able to describe well the experimental cross section and to highlight cluster configurations in the involved wave functions.

  6. An extractive removal step optimized for a high-throughput α-cellulose extraction method for δ13C and δ18O stable isotope ratio analysis in conifer tree rings.

    PubMed

    Lin, Wen; Noormets, Asko; King, John S; Sun, Ge; McNulty, Steve; Domec, Jean-Christophe

    2016-09-26

    Stable isotope ratios (δ(13)C and δ(18)O) of tree-ring α-cellulose are important tools in paleoclimatology, ecology, plant physiology and genetics. The Multiple Sample Isolation System for Solids (MSISS) was a major advance in the tree-ring α-cellulose extraction methods, offering greater throughput and reduced labor input compared to traditional alternatives. However, the usability of the method for resinous conifer species may be limited by the need to remove extractives from some conifer species in a separate pretreatment step. Here we test the necessity of pretreatment for α-cellulose extraction in loblolly pine (Pinus taeda L.), and the efficiency of a modified acetone-based ambient-temperature step for the removal of extractives (i) in loblolly pine from five geographic locations representing its natural range in the southeastern USA, and (ii) on five other common coniferous species (black spruce (Picea mariana Mill.), Fraser fir (Abies fraseri (Pursh) Poir.), Douglas fir (Pseudotsuga menziesii (Mirb.) Franco), Norway spruce (Picea abies (L.) Karst) and ponderosa pine (Pinus ponderosa D.)) with contrasting extractive profiles. The differences of δ(13)C values between the new and traditional pretreatment methods were within the precision of the isotope ratio mass spectrometry method used (±0.2‰), and the differences between δ(18)O values were not statistically significant. Although some unanticipated results were observed in Fraser fir, the new ambient-temperature technique was deemed as effective as the more labor-consuming and toxic traditional pretreatment protocol. The proposed technique requires a separate acetone-inert multiport system similar to MSISS, and the execution of both pretreatment and main extraction steps allows for simultaneous treatment of up to several hundred microsamples from resinous softwood, while the need of additional labor input remains minimal.

  7. Analysis and theoretical modeling of the 18O enriched carbon dioxide spectrum by CRDS near 1.35 μm: (I) 16O12C18O, 16O12C17O, 12C16O2 and 13C16O2

    NASA Astrophysics Data System (ADS)

    Kassi, S.; Karlovets, E. V.; Tashkun, S. A.; Perevalov, V. I.; Campargue, A.

    2017-01-01

    The room temperature absorption spectrum of 18O enriched carbon dioxide has been recorded by very high-sensitivity Cavity Ring Down spectroscopy between 6977 and 7918 cm-1 (1.43-1.26 μm). The achieved sensitivity (noise equivalent absorption αmin 8×10-11 cm-1) has allowed for the detection of more than 8600 lines belonging to 166 bands of eleven carbon dioxide isotopologues. Line intensities of the weakest observed transitions are on the order of 2×10-30 cm/molecule. In this first part, we present the results relative to the 16O12C18O, 16O12C17O, 12C16O2 and 13C16O2 isotopologues. Their absorption lines were rovibrationally assigned on the basis of the predictions of their respective effective Hamiltonian model. Overall 5476 lines were measured and assigned to 93 bands. Forty nine of them, all belonging to 16O12C18O and 16O12C17O, are reported for the first time. The studied spectral region is formed by ΔP=10-12 series of transitions, where P=2V1+V2+3V3 is the polyad number (Vi are vibrational quantum numbers). The spectroscopic parameters of 58 bands of 16O12C18O and 16O12C17O were determined from a fit of the measured line positions. An inter- and an intrapolyad resonance perturbation were identified and analyzed in the 16O12C18O spectrum. The comparison with the line positions and line intensities included in the AMES line list is discussed. Global fits of the line intensities were performed in order to (i) improve the ΔP=10 and 11 sets of the effective dipole moment parameters of 16O12C18O and the ΔP=11 set of parameters of 16O12C17O and (ii) derive for the first time the ΔP=10 and 12 parameters of 16O12C17O and 16O12C18O, respectively.

  8. A New Substrate Cycle in Plants. Evidence for a High Glucose-Phosphate-to-Glucose Turnover from in Vivo Steady-State and Pulse-Labeling Experiments with [13C]Glucose and [14C]Glucose1

    PubMed Central

    Alonso, Ana Paula; Vigeolas, Hélène; Raymond, Philippe; Rolin, Dominique; Dieuaide-Noubhani, Martine

    2005-01-01

    Substrate (futile) cycling involving carbohydrate turnover has been widely reported in plant tissues, although its extent, mechanisms, and functions are not well known. In this study, two complementary approaches, short and steady-state labeling experiments, were used to analyze glucose metabolism in maize (Zea mays) root tips. Unidirectional rates of synthesis for storage compounds (starch, Suc, and cell wall polysaccharides) were determined by short labeling experiments using [U-14C]glucose and compared with net synthesis fluxes to determine the rate of glucose production from these storage compounds. Steady-state labeling with [1-13C]glucose and [U-13C]glucose showed that the redistribution of label between carbon C-1 and C-6 in glucose is close to that in cytosolic hexose-P. These results indicate a high resynthesis flux of glucose from hexose-P that is not accounted for by glucose recycling from storage compounds, thus suggesting the occurrence of a direct glucose-P-to-glucose conversion. An enzyme assay confirmed the presence of substantial glucose-6-phosphatase activity in maize root tips. This new glucose-P-to-glucose cycle was shown to consume around 40% of the ATP generated in the cell, whereas Suc cycling consumes at most 3% to 6% of the ATP produced. The rate of glucose-P cycling differs by a factor of 3 between a maize W22 line and the hybrid maize cv Dea, and is significantly decreased by a carbohydrate starvation pretreatment. PMID:16024683

  9. Simultaneous determination of stable isotopic compositions of nitrous oxide (δ15N and δ18O of N2O) and methane (δ13C of CH4) in nanomolar quantities from a single water sample

    NASA Astrophysics Data System (ADS)

    Hirota, A.; Tsunogai, U.; Komatsu, D. D.; Nakagawa, F.

    2010-12-01

    The stable isotopic compositions of nitrous oxide (δ15N of N2O and δ18O of N2O, respectively) and methane (δ13C of CH4) have provided us with some interesting geochemical insights. We have developed a rapid, sensitive, and automated analytical system to simultaneously determine the concentrations and stable isotopic compositions of nanomolar quantities of N2O and CH4 in the environmental water, by combining continuous-flow isotope-ratio mass spectrometry and a He-sparging system to extract and purify the dissolved gases. Our system, which is composed of a sparging bottle, a chemical trap, four cold traps and a capillary gas chromatograph that use ultra-pure helium as the carrier gas, achieves complete extraction of N2O and CH4 in a water sample and separation among N2O, CH4, and the other component gases. The flow path subsequent to gas chromatograph was periodically changed to pass the gases through the combustion furnace to convert CH4 and the other hydrocarbons into CO2, or to bypass the combustion furnace for the direct introduction of eluted N2O into the mass spectrometer, for determining the stable isotopic compositions through monitoring m/z = 44, 45, and 46, on the bases of CO2+ and N2O+, respectively. The analytical system can be operated automatically with sequential software programmed on a personal computer. The analytical precisions (the standard deviation of a single measurement) were better than 0.2‰ for δ15N of N2O and 0.3‰ for δ18O of N2O, in the case of more than 6.7 nmol N2O injection and better than 1.4‰ for δ15N of N2O and 2.6‰ for δ18O of N2O, in the case of more than 0.2 nmol N2O injection, respectively. Simultaneously, the analytical precisions were better than 0.07‰ for δ13C of CH4, in the case of more than 5.5 nmol CH4 infection and better than 2.1‰ for δ13C of CH4, when more than 0.024 nmol CH4 injection. In this manner, we can simultaneously determine stable isotopic compositions of a 120 mL water sample having

  10. Automated simultaneous measurement of the δ(13) C and δ(2) H values of methane and the δ(13) C and δ(18) O values of carbon dioxide in flask air samples using a new multi cryo-trap/gas chromatography/isotope ratio mass spectrometry system.

    PubMed

    Brand, Willi A; Rothe, Michael; Sperlich, Peter; Strube, Martin; Wendeberg, Magnus

    2016-07-15

    The isotopic composition of greenhouse gases helps to constrain global budgets and to study sink and source processes. We present a new system for high-precision stable isotope measurements of carbon, hydrogen and oxygen in atmospheric methane and carbon dioxide. The design is intended for analyzing flask air samples from existing sampling programs without the need for extra sample air for methane analysis. CO2 and CH4 isotopes are measured simultaneously using two isotope ratio mass spectrometers, one for the analysis of δ(13) C and δ(18) O values and the second one for δ(2) H values. The inlet carousel delivers air from 16 sample positions (glass flasks 1-5 L and high-pressure cylinders). Three 10-port valves take aliquots from the sample stream. CH4 from 100-mL air aliquots is preconcentrated in 0.8-mL sample loops using a new cryo-trap system. A precisely calibrated working reference air is used in parallel with the sample according to the Principle of Identical Treatment. It takes about 36 hours for a fully calibrated analysis of a complete carousel including extractions of four working reference and one quality control reference air. Long-term precision values, as obtained from the quality control reference gas since 2012, account for 0.04 ‰ (δ(13) C values of CO2 ), 0.07 ‰ (δ(18) O values of CO2 ), 0.11 ‰ (δ(13) C values of CH4 ) and 1.0 ‰ (δ(2) H values of CH4 ). Within a single day, the system exhibits a typical methane δ(13) C standard deviation (1σ) of 0.06 ‰ for 10 repeated measurements. The system has been in routine operation at the MPI-BGC since 2012. Consistency of the data and compatibility with results from other laboratories at a high precision level are of utmost importance. A high sample throughput and reliability of operation are important achievements of the presented system to cope with the large number of air samples to be analyzed. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  11. Conifers, Angiosperm Trees, and Lianas: Growth, Whole-Plant Water and Nitrogen Use Efficiency, and Stable Isotope Composition (δ13C and δ18O) of Seedlings Grown in a Tropical Environment1[W][OA

    PubMed Central

    Cernusak, Lucas A.; Winter, Klaus; Aranda, Jorge; Turner, Benjamin L.

    2008-01-01

    Seedlings of several species of gymnosperm trees, angiosperm trees, and angiosperm lianas were grown under tropical field conditions in the Republic of Panama; physiological processes controlling plant C and water fluxes were assessed across this functionally diverse range of species. Relative growth rate, r, was primarily controlled by the ratio of leaf area to plant mass, of which specific leaf area was a key component. Instantaneous photosynthesis, when expressed on a leaf-mass basis, explained 69% of variation in r (P < 0.0001, n = 94). Mean r of angiosperms was significantly higher than that of the gymnosperms; within angiosperms, mean r of lianas was higher than that of trees. Whole-plant nitrogen use efficiency was also significantly higher in angiosperm than in gymnosperm species, and was primarily controlled by the rate of photosynthesis for a given amount of leaf nitrogen. Whole-plant water use efficiency, TEc, varied significantly among species, and was primarily controlled by ci/ca, the ratio of intercellular to ambient CO2 partial pressures during photosynthesis. Instantaneous measurements of ci/ca explained 51% of variation in TEc (P < 0.0001, n = 94). Whole-plant 13C discrimination also varied significantly as a function of ci/ca (R2 = 0.57, P < 0.0001, n = 94), and was, accordingly, a good predictor of TEc. The 18O enrichment of stem dry matter was primarily controlled by the predicted 18O enrichment of evaporative sites within leaves (R2 = 0.61, P < 0.0001, n = 94), with some residual variation explained by mean transpiration rate. Measurements of carbon and oxygen stable isotope ratios could provide a useful means of parameterizing physiological models of tropical forest trees. PMID:18599645

  12. Assessing methane oxidation under landfill covers and its contribution to the above atmospheric CO{sub 2} levels: The added value of the isotope ({delta}{sup 13}C and {delta}{sup 18}O CO{sub 2}; {delta}{sup 13}C and {delta}D CH{sub 4}) approach

    SciTech Connect

    Widory, D.; Proust, E.; Bellenfant, G.; Bour, O.

    2012-09-15

    Highlights: Black-Right-Pointing-Pointer Comparison of the isotope and mass balance approaches to evaluate the level of methane oxidation within a landfill. Black-Right-Pointing-Pointer The level of methane oxidation is not homogenous under the landfill cover and is strongly correlated to the methane flux. Black-Right-Pointing-Pointer Isotope tracking of the contribution of the methane oxidation to the CO{sub 2} concentrations in the ambient air. - Abstract: We are presenting here a multi-isotope approach ({delta}{sup 13}C and {delta}{sup 18}O of CO{sub 2}; {delta}{sup 13}C and {delta}D of CH{sub 4}) to assess (i) the level(s) of methane oxidation during waste biodegradation and its migration through a landfill cover in Sonzay (France), and (ii) its contribution to the atmospheric CO{sub 2} levels above the surface. The isotope approach is compared to the more conventional mass balance approach. Results from the two techniques are comparable and show that the CH{sub 4} oxidation under the landfill cover is heterogenous, with low oxidation percentages in samples showing high biogas fluxes, which was expected in clay covers presenting fissures, through which CH{sub 4} is rapidly transported. At shallow depth, more immobile biogas pockets show a higher level of CH{sub 4} oxidation by the methanotrophic bacteria. {delta}{sup 13}C of CO{sub 2} samples taken at different heights (from below the cover up to 8 m above the ground level) were also used to identify and assess the relative contributions of its main sources both under the landfill cover and in the surrounding atmosphere.

  13. An isotopic (Δ14C, δ13C, and δ15N) investigation of particulate organic matter and zooplankton biomass in Lake Superior and across a size-gradient of aquatic systems

    NASA Astrophysics Data System (ADS)

    Zigah, P. K.; Minor, E. C.; Werne, J. P.; McCallister, S. Leigh

    2012-04-01

    Food webs in aquatic systems can be supported both by carbon from recent local primary productivity and by carbon subsidies, such as material from terrestrial ecosystems or past in situ primary productivity. The importance of these subsidies to respiration and biomass production remains a topic of debate, but they may play major roles in determining the fate of organic carbon and in sustaining upper trophic levels, including those contributing to economically important fisheries. While some studies have reported that terrigenous organic carbon supports disproportionately high zooplankton production, others have suggested that phytoplankton preferentially supports zooplankton production in aquatic ecosystems. Here we apply natural abundance radiocarbon (Δ14C) and stable isotope (δ13C, δ15N) analyses to show that zooplankton in Lake Superior selectively incorporate recently-fixed, locally-produced (autochthonous) organic carbon even though other carbon sources are readily available. Estimates from Bayesian isotopic modeling based on Δ14C values show that the average lakewide median contributions of recent in situ algal, terrestrial, sedimentary, and bacterial organic carbon to the bulk POM in Lake Superior were 23%, 28%, 15%, and 25%, respectively. However, the isotopic modeling estimates show that recent in situ production (algae) contributed a disproportionately large amount (median, 40-89%) of the carbon in zooplankton biomass in Lake Superior. Although terrigenous organic carbon and old organic carbon from resuspended sediments were significant portions of the available basal food resources, these contributed only a small amount to zooplankton biomass (average lakewide median, 2% from sedimentary organic carbon and 9% from terrigenous organic carbon). Comparison of zooplankton food sources based on their radiocarbon composition showed that terrigenous organic carbon was relatively more important in rivers and small lakes, and the proportion of terrestrially

  14. Physiological responses of a young Picea Sitchensis stand to long-term nitrogen and sulphur deposition: a lesson from d13C, d18O and d15N in tree rings

    NASA Astrophysics Data System (ADS)

    Guerrieri, Rossella; Mencuccini, Maurizio; Borghetti, Marco; Levy, Peter; Perks, Mike; Saurer, Matthias; Sheppard, Lucy; Sutton, Mark

    2010-05-01

    deposition on tree physiological traits were investigated in a young Picea Sitchensis (Bong.) Carr. plantation on an acid peat soil (Deepsyke forest, Scotland, UK). The Deepsyke experiment is unique in providing the opportunity to evaluate the long-term effects of frequent aerial N and S spraying onto a forest canopy for a period of 5 to 8 years. The adopted approach was based on the measurements of stable carbon (d13C), oxygen (d18O) and nitrogen (d15N) isotope composition in tree rings. We used d13C for assessing changes in WUEi, while the degree of photosynthetic and stomatal responses to the different treatments were investigated using a conceptual model, combining variations of d13C and d18O. The differences between canopy vs. soil N applications were evaluated as magnitude of changes in WUEi and underlying mechanisms involved. Furthermore, physiological responses were also assessed in relation to leaf nutrient status. Finally, changes in tree internal N cycle in relation to canopy nitrogen uptake and the relative contribution to variation of WUEi were detected by d15N in tree rings.

  15. Chemical dynamics of the "St. Lawrence" riverine system: δD H 2O, δ 18O H 2O, δ 13C DIC, δ 34S sulfate, and dissolved 87Sr/ 86Sr

    NASA Astrophysics Data System (ADS)

    Yang, Chao; Telmer, Kevin; Veizer, Ján

    1996-03-01

    Chemical and stable isotope analyses of the St. Clair, Detroit, Niagara, and St. Lawrence rivers ("St. Lawrence" system) and their tributaries show that the chemical and isotopic compositions of the waters are strongly controlled by the geology of their drainage basins. Tributaries draining the Canadian Shield have very low TDS, HCO 3-, SO 42-, Ca 2+, Mg 2+, NO 3-, Sr 2+, higher Si and Fe total, and high 87Sr/ 86Sr ratios (0.710-0.713). The Grand and Thames rivers that drain Paleozoic limestones, dolostones, and evaporites are characterized by opposite attributes. The "St. Lawrence" and the tributaries draining the Canadian Appalachians fall between these two endmembers. The St. Clair, Detroit, and Niagara rivers do not show any pronounced seasonal variations in major component chemistry due to buffering by the Great Lakes. In contrast, pronounced seasonal variations characterize the lower St. Lawrence mainly because of significant tributary inputs into the overall water budget. The δD and δ18O in the "St. Lawrence" range from -60.9 to -44.5‰ and from -8.5 to -6.1‰ SMOW, respectively, much heavier than the comparative values measured for the tributaries (-92.8 to -58.3‰ and -13.1 to -8.5‰). This is a consequence of evaporative loss that, over the residence time of water of 10 2 years, equals about 7% of the water volume in the Great Lakes. The strontium and sulfur isotopic values for the "St. Lawrence" system are relatively uniform, with measured values from 0.70927 to 0.71112 for 87Sr/ 86Sr and from 4.3 to 5.6‰ for sulfate δ34S. Their seasonal variations are also minor. The strontium and sulfur fluxes of the St. Lawrence river are calculated to be 7.84 × 10 8 and 1.09 × 10 11 mol/a, respectively. The relative contributions of the Great Lakes, tributaries, and other sources to these fluxes are 73:16:11% for strontium and 64:13:23% for sulfur. Isotopic composition of dissolved inorganic carbon ( δ13C DIC) in the "St. Lawrence" system ranges from -4

  16. Biotic and geochemical (δ18O, δ13C, Mg/Ca, Ba/Ca) responses of Globigerinoides ruber morphotypes to upper water column variations during the last deglaciation, Gulf of Mexico

    NASA Astrophysics Data System (ADS)

    Antonarakou, A.; Kontakiotis, G.; Mortyn, P. G.; Drinia, H.; Sprovieri, M.; Besiou, E.; Tripsanas, E.

    2015-12-01

    Within the Gulf of Mexico (GOM), the Bryant Canyon is exceptional in that rapid sedimentation sustained by high rates of terrigenous sediment delivery and surface marine productivity make this basin an excellent recorder of paleoenvironmental and paleoclimatic conditions. We present a new 21-kyr record of sea surface temperature (SST) and local salinity changes from the NW GOM (core JPC-26) approximated from combined Globigerinoides ruber morphotype-specific δ18O and Mg/Ca, as well as Ba/Ca, which reflect the subtropical GOM hydrographic dynamics and their relationship to both Mississippi River discharges and climate evolution during the last deglaciation. Overall, the reconstructed SST and SSS-related patterns reveal notable variations in amplitude between the analyzed morphotypes, adding valuable insights to previously published G. ruber (w, mixed) GOM records. Especially during the deglaciation, Bryant Canyon meltwater flooding events (BCDFs) and associated sea surface freshening seem to be more pronounced than the SST reduction. Our Mg/Ca-derived SST records of both morphotypes (G. ruber sensu stricto (s.s.) and G. ruber sensu lato (s.l.)) show comparable general trends, but with important SST differences (ΔT). We interpret down-core ΔT as a record of changing upper water column hydrography, with particular influence from the deglacial meltwater (BCDFs) or Holocene (BCHFs) flooding events. During the warm intervals, the deeper, thicker and probably more seasonally persistent mixed layer led to more uniform thermal conditions for both G. ruber morphotypes and therefore to a minimum ΔT. On the contrary, during the cold and low salinity periods, the shallower mixed layer favored more habitat divergence, and caused a maximum thermal gradient in the well-stratified upper water column. Overall, this supports the notion that G. ruber s.s. is consistently calcifying in warmer waters than G. ruber s.l., either due to a shallower depth habitat or to a more summer

  17. Assessing the Resilience of a Blue Carbon Store: Characterizing the Lateral Flux of DIC from an East Coast U.S. Saltmarsh using Δ14C and δ13C

    NASA Astrophysics Data System (ADS)

    Felgate, S. L.; Gonneea, M. E.; Kroeger, K. D.; Chu, S. N.; Wang, A. Z.

    2016-12-01

    Intertidal saltmarshes are highly productive coastal habitats and important blue carbon stores. They commonly exhibit high salinity, low oxygen environmental regimes which lend themselves towards reduced rates of microbial respiration, and the assimilation of atmospheric CO2 into plant biomass tends to outpace the rate at which that biomass is broken down. As a result, a relatively high proportion of CO2 entering the system can be expected to become incorporated into marsh sediment before it can be metabolised, potentially entering storage for thousands of years and providing a sizeable natural carbon sink. However, the rate at which these habitats are now being degraded is substantial and growing: the combined impacts of stressors such as increasing temperature and sea level rise are predicted to reduce global saltmarsh coverage by 30-40% by the end of the century, and many saltmarsh carbon stores can be expected to shift from net sinks to sources within the same time frame. Based on high resolution measurements and modelling in a northeastern U.S. saltmarsh, a recent study reported a marsh DIC export of 414g C m2 yr-1. This is more than twice that put forward in previous estimates, and is larger than the total uptake by plant biomass. This translates into one of the largest carbon fluxes to the coastal ocean found along the U.S. East Coast. Additionally it is possible that the marsh carbon budget is not in balance, with export exceeding carbon fixation rates. Here we characterise this carbon flux using Δ14C and δ13C data to age and source the exported dissolved carbon pools. Carbon isotope mixing models between surface (modern) and porewater (old) carbon sources are constrained by creek samples and porewaters from multiple depths and locations within the marsh. We determine the age of exported carbon to see if carbon stored over the lifetime of the marsh (c. 2000 years) continues to be respired, thereby evaluating the long term resilience of the carbon sink.

  18. Stepped Acid Extractions of CO2 from Ancient Carbonates in Martian Nakhlites (MIL 03346, 090030, 090032, 090036) Show Distinct δ18O and δ13C Isotopic Values Compared to Secondary Terrestrial Carbonates Formed on Ordinary Chondrites (OC) Collected from Antarctica

    NASA Astrophysics Data System (ADS)

    Evans, M. E.; Niles, P. B.

    2016-12-01

    This study finds that 1) Martian Nakhlite meteorites contain insitu carbonates with distinctive δ13C from terrestrial carbonates formed on Antarctic Ordinary Chondrites (OCs), and 2) Martian carbonate formation δ18O values for atmospheric CO2 and meteoric water can be predicted with a mixing model created from Antarctic OC carbonate data. Nakhlite and OC meteorites collected in Antarctica contain both calcites and non-calcite carbonates. Rock samples were crushed, dissolved in pure phosphoric acid, and allowed to react at the following conditions: 1 hr@30°C (Rx0, fine calcite), 18 hr@30°C (Rx1, course calcite), and 3 hr@150°C (Rx2, siderite and/or magnesite). The collected CO2 was purified with a Thermo Trace GC and analyzed on a Thermo MAT 253 IRMS in dual inlet mode. Ten OC meteorite samples collected from three different Antarctic regions (RBT, ALH, MIL) were analyzed. These samples had no pre-terrestrial aqueous alterations, yet evaporite minerals were visible on the fusion crust. It is deduced these OC carbonates were completely terrestrial. These calcites have δ13C=+6‰ and are consistent with equilibrium formation to Earth atmospheric CO2 δ13C=-7‰ at 0°C to 10°C. Siderite or magnesite fractionation may create slightly heavier δ13C as seen in the Rx2 results. The range of δ18O from +3‰ to +30‰ is heavier than expected if carbonate forms in equilibrium with only meteoric water. A δ18O mixing model is created with Earth atmospheric CO2 and meteoric water as end members. This model predicts the OC calcites form with 60%-90% contribution from atmospheric CO2 at 0°C, and the non-calcites form with 40-60% contribution from atmospheric CO2. Four martian Nakhlites collected from the Antarctic Miller Range were analyzed. These samples contain low carbonate concentrations (avg. 0.007% by weight) with distinctly heavier δ13C = +7‰ to +59‰. In general, these carbonates are lighter than expected if formed in equilibrium with the modern martian

  19. δ13C and δ18O isotopic composition of CaCO3 measured by continuous flow isotope ratio mass spectrometry: statistical evaluation and verification by application to Devils Hole core DH-11 calcite

    USGS Publications Warehouse

    Revesz, Kinga M.; Landwehr, Jurate M.

    2002-01-01

    A new method was developed to analyze the stable carbon and oxygen isotope ratios of small samples (400 ± 20 µg) of calcium carbonate. This new method streamlines the classical phosphoric acid/calcium carbonate (H3PO4/CaCO3) reaction method by making use of a recently available Thermoquest-Finnigan GasBench II preparation device and a Delta Plus XL continuous flow isotope ratio mass spectrometer. Conditions for which the H3PO4/CaCO3 reaction produced reproducible and accurate results with minimal error had to be determined. When the acid/carbonate reaction temperature was kept at 26 °C and the reaction time was between 24 and 54 h, the precision of the carbon and oxygen isotope ratios for pooled samples from three reference standard materials was ≤0.1 and ≤0.2 per mill or ‰, respectively, although later analysis showed that materials from one specific standard required reaction time between 34 and 54 h for δ18O to achieve this level of precision. Aliquot screening methods were shown to further minimize the total error. The accuracy and precision of the new method were analyzed and confirmed by statistical analysis. The utility of the method was verified by analyzing calcite from Devils Hole, Nevada, for which isotope-ratio values had previously been obtained by the classical method. Devils Hole core DH-11 recently had been re-cut and re-sampled, and isotope-ratio values were obtained using the new method. The results were comparable with those obtained by the classical method with correlation = +0.96 for both isotope ratios. The consistency of the isotopic results is such that an alignment offset could be identified in the re-sampled core material, and two cutting errors that occurred during re-sampling then were confirmed independently. This result indicates that the new method is a viable alternative to the classical reaction method. In particular, the new method requires less sample material permitting finer resolution and allows

  20. Evolution of the geothermal fluids at Los Azufres, Mexico, as traced by noble gas isotopes, δ18O, δD, δ13C and 87Sr/86Sr

    NASA Astrophysics Data System (ADS)

    Pinti, D. L.; Castro, M. C.; Shouakar-Stash, O.; Tremblay, A.; Garduño, V. H.; Hall, C. M.; Hélie, J.-F.; Ghaleb, B.

    2013-01-01

    Isotopes of noble gases, CO2, H2O and Sr were measured in 10 geothermal wells and 8 hot springs, fumaroles and mud volcanoes at Los Azufres, the second most important geothermal field in Mexico. The aim of this study is to provide additional information on fluid circulation in the field and surrounding areas (Araró hot springs), as well as on physical processes such as boiling, steam separation and invasion of re-injected brines following over 25 years of geothermal fluid exploitation. Mantle helium dominates in fluids from the northern production zone of Marítaro, with measured 3He/4He ratios up to 7 Ra (where Ra is the atmospheric ratio of 1.386 × 10- 6). 3He/4He ratios are positively correlated with 87Sr/86Sr ratios and with δD and δ18O. These relationships suggest that Los Azufres fluids represent a mixing between primary magmatic 3He-rich fluids and groundwater currently discharging at Araró hot springs and enriched in radiogenic 4He acquired from Miocene andesites. Unusually high He ratios together with radiogenic Sr isotopic ratios suggest that thermal waters acquired mantle He from deep-seated parent magmas and radiogenic Sr possibly during their uprising through the metamorphic basement. 40Ar/36Ar ratios of 366 to 429 measured in two wells indicate either mantle-derived argon or a radiogenic 40Ar in situ component, suggesting the local presence of an older crustal fluid component in the northern part of the field. Ne, Kr and Xe are entirely of atmospheric origin, but processes of boiling, steam separation and re-injection of used brines have led to fractionation of their elemental abundances. Comparison with previous studies suggests that the boiling zone in the northern production zone is currently extending further north (Marítaro hot springs). In the southwestern productive zone, re-injected brines might account for more than 90% of the exploited fluids.

  1. Three whole-wood isotopic reference materials, USGS54, USGS55, and USGS56, for δ2H, δ13C, δ15N, and δ18O measurements

    USGS Publications Warehouse

    Qi, Haiping; Coplen, Tyler B.; Jordan, James A.

    2016-01-01

    Comparative measurements of stable hydrogen and oxygen isotopes in wood are hampered by the lack of proper reference materials (RMs). The U.S. Geological Survey (USGS) has prepared three powdered, whole-wood RMs, USGS54 (Pinus contorta, Canadian lodgepole pine), USGS55 (Cordia cf. dodecandra, Mexican ziricote), and USGS56 (Berchemia cf. zeyheri, South African red ivorywood). The stable isotopes of hydrogen, oxygen, carbon, and nitrogen in these RMs span ranges as δ2HVSMOW from –150.4 to –28.2 mUr or ‰, as δ18OVSMOW from + 17.79 to + 27.23 mUr, as δ13CVPDB from –27.13 to –24.34 mUr, and as δ15N AIR-N2 from –2.42 to + 1.8 mUr. These RMs will enable users to normalize measurements of wood samples to isotope–delta scales, and they are intended primarily for the normalization of δ2H and δ18O measurements of unknown wood samples. However, they also are suitable for normalization of stable isotope measurements of carbon and nitrogen in wood samples. In addition, these RMs are suitable for inter-laboratory calibration for the dual-water suilibration procedure for the measurements of δ2HVSMOW values of non-exchangeable hydrogen. The isotopic compositions with 1-σ uncertainties, mass fractions of each element, and fractions of exchangeable hydrogen of these materials are:USGS54 (Pinus contorta, Canadian Lodgepole pine)δ2HVSMOW = –150.4 ± 1.1 mUr (n = 29), hydrogen mass fraction = 6.00 ± 0.04 % (n = 10)Fraction of exchangeable hydrogen = 5.4 ± 0.6 % (n = 29)δ18OVSMOW = + 17.79 ± 0.15 mUr (n = 18), oxygen mass fraction = 40.4 ± 0.2 % (n = 6)δ13CVPDB = –24.43 ± 0.02 mUr (n = 18), carbon mass fraction = 48.3 ± 0.4 % (n = 12)δ15NAIR-N2 = –2.42 ± 0.32 mUr (n = 17), nitrogen mass fraction = 0.05 % (n = 4)USGS55 (Cordia cf. dodecandra, Mexican ziricote)δ2HVSMOW = –28.2 ± 1.7 mUr (n = 30), hydrogen mass fraction = 5.65 ± 0.06 % (n = 10)Fraction of exchangeable

  2. The evolution of 13C and 18O isotope composition of DIC in a calcite depositing film of water with isotope exchange between the DIC and a CO2 containing atmosphere, and simultaneous evaporation of the water. Implication to climate proxies from stalagmites: A theoretical model

    NASA Astrophysics Data System (ADS)

    Dreybrodt, Wolfgang; Romanov, Douchko

    2016-12-01

    The most widely applied climate proxies in speleothems are the isotope compositions of carbon and oxygen expressed by δ13C and δ18O values. However, mechanisms, which are not related to climate changes, overlay the climate signal. One is the temporal increase of both, δ13C and δ18O values by kinetic processes during precipitation of calcite. Isotope exchange between DIC in the water and the CO2 in the surrounding cave atmosphere can also change isotope composition. Here we present a theoretical model of the temporal isotope evolution of DIC in a thin water layer during precipitation of calcite and simultaneous isotope exchange with the cave atmosphere, and simultaneous evaporation of water. The exchange of oxygen isotopes in the DIC with those in the water is also considered. For drip times for Tdrip < 0.2τ, where τ is the precipitation time, we find for the change of the δ13C and δ18O values, respectively, after the time Tdrip ΔDIC(Tdrip) = ((λ + ɛ)Ceq/C0 - ɛ) Tdrip/τ + ((δeqatm - δ0) Tdrip/τinatm) + (δeqwater - δ0 - ɛw Tdrip/Tev) Tdrip/Twater The first term on the right hand side is the contribution from precipitation of calcite, the second stems from isotope exchange with the CO2 of the cave atmosphere, and the third results from isotope exchange between oxygen in the DIC and the oxygen in the water. λ, ε are kinetic parameters, τ is the time scale of precipitation, (δeqatm -δ0) and (δeqwater -δ0) are the differences between the corresponding initial δ-value δ0 and the value δeqatm,water if DIC were in isotope equilibrium with the atmosphere or in the case of oxygen with the water, respectively. τinatm and τwater are the time scales of approach to isotope equilibrium by the exchange reactions. Ceq is the concentration of DIC in chemical equilibrium with the CO2 in the cave atmosphere and C0 is the initial concentration, when the water drips to the stalagmite. Tev is the time needed for complete evaporation of the water layer. ε

  3. High-resolution spectroscopy of the {A}^{1}{\\rm{\\Pi }}(v^{\\prime} =0{--}10){--}{X}^{1}{{\\rm{\\Sigma }}}^{+}(v^{\\prime\\prime} =0) bands in 13C18O: term values, ro-vibrational oscillator strengths and Hönl-London corrections

    NASA Astrophysics Data System (ADS)

    Lemaire, J. L.; Eidelsberg, M.; Heays, A. N.; Gavilan, L.; Federman, S. R.; Stark, G.; Lyons, J. R.; de Oliveira, N.; Joyeux, D.

    2016-08-01

    Our knowledge of astronomical environments containing CO depends on accurate molecular data to reproduce and interpret observations. The constant improvement in UV space instrumentation, both in sensitivity and resolution, requires increasingly detailed laboratory data. Following a long-term experimental campaign at the SOLEIL Synchrotron facility, we have acquired complete datasets on the CO isotopologues in the vacuum ultraviolet. Absorption spectra were recorded using the Fourier-transform spectrometer installed on the DESIRS beamline, providing a resolving power R > 106 in the 8-12 eV range. Such resolution allows the analysis of individual line positions and strengths in electronic transitions and the location of perturbations. We continue our previous work on A-X bands of 12C16O and 13C16O, reporting here measurements for the 13C18O isotopologue. Gas column densities in the differentially-pumped system were calibrated using the B {}1{{{Σ }}}+-X {}1{{{Σ }}}+({v}\\prime =0,v\\prime\\prime =0) band. Absorption bands are analyzed by synthesizing line and band profiles and fitting them to measured spectra. New results for A {}1{{\\Pi }}({v}\\prime =0{--}10)-X {}1{{{Σ }}}+(v\\prime\\prime =0) bands include precise line assignments, term values, band-integrated oscillator strengths as well as individual ro-vibrational oscillator strengths and Hönl-London corrections. For ({v}\\prime =1) our results are compared with earlier studies. The interpretation of mixed perturbing bands, complementing an earlier study, is also presented as well as precise line assignments and term values for the B {}1{{{Σ }}}+-X {}1{{{Σ }}}+(0-0) band calibrator, and the nearby B-X (1-0) and C {}1{{{Σ }}}+-X {}1{{{Σ }}}+(0-0) bands.

  4. Cross-checking groundwater age by 4He and 14C dating in a granite, Tono area, central Japan

    NASA Astrophysics Data System (ADS)

    Hasegawa, Takuma; Nakata, Kotaro; Tomioka, Yuichi; Goto, Kazuyuki; Kashiwaya, Koki; Hama, Katsuhiro; Iwatsuki, Teruki; Kunimaru, Takanori; Takeda, Masaki

    2016-11-01

    groundwater flow in the Tono area may be several tens of thousands of years, and the groundwater age calculated from the 4He and 14C ages appears to be consistent with geochemical information such as groundwater types, δD and δ18O.

  5. Isotopic paleoecology of the Pleistocene megamammals from the Brazilian Intertropical Region: Feeding ecology (δ13C), niche breadth and overlap

    NASA Astrophysics Data System (ADS)

    Dantas, Mário André Trindade; Cherkinsky, Alexander; Bocherens, Hervé; Drefahl, Morgana; Bernardes, Camila; França, Lucas de Melo

    2017-08-01

    The extinct megamammals Eremotherium laurillardi (weight 6550 kg), Notiomastodon platensis (w = 6000 kg), Toxodon platensis (w = 3090 kg), Valgipes bucklandi (w = 980 kg) and Equus (Amerhippus) neogaeus (w = 370 kg) are recorded for the late Pleistocene of the Brazilian Intertropical Region. In order to evaluate the isotopic paleoecology (feeding diet, niche breadth and overlap) of these species, 14C dates, δ13C and δ18O analyzes were performed. Our results suggest that E. laurillardi (μδ13C = -4.35 ± 2.87‰; μBA = 0.77 ± 0.25), T. platensis (μδ13C = -5.74 ± 4.80‰; μBA = 0.57 ± 0.40) and N. platensis (μδ13C = -1.17 ± 2.76‰; μBA = 0.56 ± 0.20) were mixed feeders with a wide niche breadth, while E. (A.) neogaeus (μδ13C = 0.73 ± 1.19‰; μBA = 0.38 ± 0.22) was a grazer, and V. bucklandi (δ13C = -10.17‰; BA = 0.13) was a specialist browser. A narrow niche overlap occurred between V. bucklandi and the species that fed principally on C4 plants (>70%; O = 0.24-0.43). In contrast, there was a high niche overlap between E. neogaeus and N. platensis (O = 0.75) and between E. laurillardi and T. platensis (O = 0.86). Therefore, E. laurillardi was probably a key species in this Pleistocene community due to its high body weight and wide niche breadth, suggesting that E. laurillardi was a great competitor for resources in the BIR.

  6. /sup 13/C nuclear magnetic resonance studies of cardiac metabolism

    SciTech Connect

    Seeholzer, S.H.

    1985-01-01

    The last decade has witnessed the increasing use of Nuclear Magnetic Resonance (NMR) techniques for following the metabolic fate of compounds specifically labeled with /sup 13/C. The goals of the present study are: (1) to develop reliable quantitative procedures for measuring the /sup 13/C enrichment of specific carbon sites in compounds enriched by the metabolism of /sup 13/C-labeled substrates in rat heart, and (2) to use these quantitative measurements of fractional /sup 13/C enrichment within the context of a mathematical flux model describing the carbon flow through the TCA cycle and ancillary pathways, as a means for obtaining unknown flux parameters. Rat hearts have been perfused in vitro with various combinations of glucose, acetate, pyruvate, and propionate to achieve steady state flux conditions, followed by perfusion with the same substrates labeled with /sup 13/C in specific carbon sites. The hearts were frozen at different times after addition of /sup 13/C-labeled substrates and neutralized perchloric acid extracts were used to obtain high resolution proton-decoupled /sup 13/C NMR spectra at 90.55 MHz. The fractional /sup 13/C enrichment (F.E.) of individual carbon sites in different metabolites was calculated from the area of the resolved resonances after correction for saturation and nuclear Overhauser effects. These F.E. measurements by /sup 13/C NMR were validated by the analysis of /sup 13/C-/sup 1/H scalar coupling patterns observed in /sup 1/H NMR spectra of the extracted metabolites. The results obtained from perfusion of hearts glucose plus either (2-/sup 13/C) acetate or (3-/sup 13/C) pyruvate are similar to those obtained by previous investigators using /sup 14/C-labeled substrates.

  7. FINE PARTICULATE MATTER SOURCE ATTRIBUTION FOR SOUTHEAST TEXAS USING 14C/13C RATIOS

    EPA Science Inventory

    Radiocarbon analyses of fine particulate matter samples collected during the summer of 2000 in southeast Texas indicate that a substantial fraction of the aerosol carbon at an urban/suburban site (27% to 73%) and at a rural, forested site (44% to 77%) was modern carbon. Data fr...

  8. O18O and C18O observations of ρ Ophiuchi A

    NASA Astrophysics Data System (ADS)

    Liseau, R.; Larsson, B.; Bergman, P.; Pagani, L.; Black, J. H.; Hjalmarson, Å.; Justtanont, K.

    2010-02-01

    Context. Contrary to theoretical expectation, surprisingly low concentrations of molecular oxygen, O2, have been found in the interstellar medium. Telluric absorption makes ground based O2 observations essentially impossible and observations had to be done from space. Millimetre-wave telescopes on space platforms were necessarily small, which resulted in large, several arcminutes wide, beam patterns. Observations of the (NJ = 11-10) ground state transition of O2 with the Odin satellite resulted in a ≳ 5σ detection toward the dense core ρ {Oph A}. At the frequency of the line, 119 GHz, the Odin telescope has a beam width of 10', larger than the size of the dense core. Aims: The precise nature of the emitting source and its exact location and extent are therefore unknown. The current investigation is intended to remedy this. Methods: Although the Earth's atmosphere is entirely opaque to low-lying O2 transitions, it allows ground based observations of the much rarer 16O18O in favourable conditions and at much higher angular resolution with larger telescopes. In addition, ρ {Oph A} exhibits both multiple radial velocity systems and considerable velocity gradients. Extensive mapping of the region in the proxy C18O (J = 3-2) line can be expected to help identify the O2 source on the basis of its line shape and Doppler velocity. Line opacities were determined from observations of optically thin 13C18O (J = 3-2). During several observing periods, two C18O intensity maxima in ρ {Oph A} were searched for O18O in the (21-01) line at 234 GHz with the 12 m APEX telescope. These positions are associated also with peaks in the mm-continuum emission from dust. Results: Our observations resulted in an upper limit on the integrated O18O intensity of int T*A d\\upsilon < 0.01 K km s-1 (3 σ) into the 26.6 arcsec beam. Together with the C18O data, this leads to a ratio of N(C18O)/N(O18O) > 16. Combining Odin's O2 with the present O18O observations we infer an O2 abundance 5

  9. Pyrolysis-combustion 14C dating of soil organic matter

    USGS Publications Warehouse

    Wang, Hongfang; Hackley, Keith C.; Panno, S.V.; Coleman, D.D.; Liu, J.C.-L.; Brown, J.

    2003-01-01

    Radiocarbon (14C) dating of total soil organic matter (SOM) often yields results inconsistent with the stratigraphic sequence. The onerous chemical extractions for SOM fractions do not always produce satisfactory 14C dates. In an effort to develop an alternative method, the pyrolysis-combustion technique was investigated to partition SOM into pyrolysis volatile (Py-V) and pyrolysis residue (Py-R) fractions. The Py-V fractions obtained from a thick glacigenic loess succession in Illinois yielded 14C dates much younger but more reasonable than the counterpart Py-R fractions for the soil residence time. Carbon isotopic composition (??13C) was heavier in the Py-V fractions, suggesting a greater abundance of carbohydrate- and protein-related constituents, and ??13C was lighter in the Py-R fractions, suggesting more lignin- and lipid-related constituents. The combination of 14C dates and ??13C values indicates that the Py-V fractions are less biodegradation resistant and the Py-R fractions are more biodegradation resistant. The pyrolysis-combustion method provides a less cumbersome approach for 14C dating of SOM fractions. With further study, this method may become a useful tool for analyzing unlithified terrestrial sediments when macrofossils are absent. ?? 2003 University of Washington. Published by Elsevier Inc. All rights reserved.

  10. High-precision measurements of 17O18O and 18O18O in air

    NASA Astrophysics Data System (ADS)

    Yeung, L. Y.; Young, E. D.; Schauble, E. A.

    2011-12-01

    The isotopic composition of atmospheric O2 reflects the balance between photosynthesis, respiration, the hydrologic cycle, and stratospheric photochemistry on decadal to millennial timescales. The quaternary oxygen-isotope budget in atmospheric O2, however, is under-constrained, and measurements of the 17O18O and 18O18O content in the atmosphere will provide additional information. In particular, relative proportions of 17O18O and 18O18O (i.e., Δ35 and Δ36, respectively, defined as Δm = [Rmmeasured/Rmstochastic - 1] × 1000) in the atmosphere will be insensitive to changes in the hydrologic cycle and in glacial ice cover; therefore, natural variations in Δ35 and Δ36 should primarily reflect a balance between stratospheric photochemistry and oxygen consumption mechanisms such as respiration. The Δ35 and Δ36 tracers will have applications both for global and oceanic biogeochemistry. We report preliminary measurements of Δ35 and Δ36 in air using the MAT 253 isotope ratio mass spectrometer (IRMS) at UCLA. We address three major analytical challenges: (1) isotopic recombination and exchange in the IRMS source, (2) 36Ar mass interference, and (3) establishing a stochastic reference frame for determining absolute Δ35 and Δ36 values. Isotope exchange in our IRMS source was found to be 1% under typical analytical conditions. We also demonstrate a method to separate 99.997% of the argon from 50 - 75 μmol samples of air. At this level of O2 purity, the 36Ar interference is still measurable, but it can be accounted for by an ion correction. To establish a stochastic reference frame for O2, we developed a method to generate high-temperature, argon-free O2 standards using metal peroxides. These techniques allow us to measure Δ35 and Δ36 with external precisions of ±0.1 - 0.2% (1σ). Our initial measurements of atmospheric O2 yield Δ35 ~ 1% and Δ36 ~ 2%; these values are consistent with stratospheric dominance of the 17O18O and 18O18O budgets via O(3P) + O2

  11. 13C metabolic flux analysis.

    PubMed

    Wiechert, W

    2001-07-01

    Metabolic flux analysis using 13C-labeled substrates has become an important tool in metabolic engineering. It allows the detailed quantification of all intracellular fluxes in the central metabolism of a microorganism. The method has strongly evolved in recent years by the introduction of new experimental procedures, measurement techniques, and mathematical data evaluation methods. Many of these improvements require advanced skills in the application of nuclear magnetic resonance and mass spectrometry techniques on the one hand and computational and statistical experience on the other hand. This minireview summarizes these recent developments and sketches the major practical problems. An outlook to possible future developments concludes the text.

  12. A high resolution method for 14C analysis of a coral from South China Sea: Implication for "AD 775" 14C event

    NASA Astrophysics Data System (ADS)

    Ding, Ping; Shen, Chengde; Yi, Weixi; Wang, Ning; Ding, Xingfang; Liu, Kexin; Fu, Dongpo; Liu, Weiguo; Liu, Yi

    2015-10-01

    A pre-heating method that improves the background and precision of 14C dating significantly was applied for fossil coral dating with high resolution in our lab in Guangzhou Institute of Geochemistry, Chinese Academy of Sciences (GIGCAS). The reaction tube is heated under 300 °C in a vacuum line before it is used for graphitization. The method can reduce the contamination absorbed in TiH2, Zn and Fe power placed in the graphitization tube. With the pre-heating and average drilling method, bi-weekly resolution 14C dating in a fossil coral is carried out to investigate the "AD 775 14C spike event". Different from the tree ring 14C archives with the 14C spike of ∼15‰ (Δ14C), the 14C spike in the coral shows an abrupt peak of 45‰ and two smaller spikes of Δ14C > 20‰ in half a year in AD 776. And then, the 14C content in coral decreases gradually in AD 777. The peak time of the 14C spike event likely occurs in the summer of AD 776 according to the δ18O variation in coral. High-resolution dating of 14C in coral provides not only a more detail process of the event than that from tree rings, but also the first report of the event from sea ecosystem. Both of them suggest an extraterrestrial origin of the event cause.

  13. Estimate of recharge of a rising water table in semiarid Niger from 3H and 14C modeling.

    PubMed

    Favreau, Guillaume; Leduc, Christian; Marlin, Christelle; Dray, Martial; Taupin, Jean-Denis; Massault, Marc; Le, GalLaSalleCorinne; Babic, Milanka

    2002-01-01

    A hydrodynamic survey carried out in semiarid southwest Niger revealed an increase in the unconfined ground water reserves of approximately 10% over the last 50 years due to the clearing of native vegetation. Isotopic samplings (3H, 18O, 2H for water and 14C, 13C for the dissolved inorganic carbon) were performed on about 3500 km2 of this silty aquifer to characterize recharge. Stable isotope analyses confirmed the indirect recharge process that had already been shown by hydrodynamic surveys and suggested the tracers are exclusively of atmospheric origin. An analytical model that takes into account the long-term rise in the water table was used to interpret 3H and 14C contents in ground water. The natural, preclearing median annual renewal rate (i.e., recharge as a fraction of the saturated aquifer volume) lies between 0.04% and 0.06%. For representative characteristics of the aquifer (30 m of saturated thickness, porosity between 10% and 25%), this implies a recharge of between 1 and 5 mm/year, which is much lower than the estimates of 20 to 50 mm/year for recent years, obtained using hydrological and hydrodynamic methods and the same aquifer parameters. Our study, therefore, reveals that land clearing in semiarid Niger increased ground water recharge by about one order of magnitude.

  14. Does the Shuram δ13C excursion record Ediacaran oxygenation?

    NASA Astrophysics Data System (ADS)

    Husson, J. M.; Maloof, A. C.; Schoene, B.; Higgins, J. A.

    2013-12-01

    The most negative carbon isotope excursion in Earth history is found in carbonate rocks of the Ediacaran Period (635-542 Ma). Known colloquially as the the 'Shuram' excursion, workers have long noted its tantalizing, broad concordance with the rise of abundant macro-scale fossils in the rock record, variously interpreted as animals, giant protists, macro-algae and lichen, and known as the 'Ediacaran Biota.' Thus, the Shuram excursion has been interpreted by many in the context of a dramatically changing redox state of the Ediacaran oceans - e.g., a result of methane cycling in a low O2 atmosphere, the final destruction of a large pool of recalcitrant dissolved organic carbon (DOC), and the step-wise oxidation of the Ediacaran oceans. More recently, diagenetic interpretations of the Shuram excursion - e.g. sedimentary in-growth of very δ13C depleted authigenic carbonates, meteoric alteration of Ediacaran carbonates, late-stage burial diagenesis - have challenged the various Ediacaran redox models. A rigorous geologic context is required to discriminate between these explanatory models, and determine whether the Shuram excursion can be used to evaluate terminal Neoproterozoic oxygenation. Here, we present chemo-stratigraphic data (δ13C, δ18O, δ44/42Ca and redox sensitive trace element abundances) from 12 measured sections of the Ediacaran-aged Wonoka Formation (Fm.) of South Australia that require a syn-depositional age for the extraordinary range of δ13C values (-12 to +4‰) observed in the formation. In some locations, the Wonoka Fm. is ~700 meters (m) of mixed shelf limestones and siliclastics that record the full 16 ‰ δ13C excursion in a remarkably consistent fashion across 100s of square kilometers of basin area. Fabric-altering diagenesis, where present, occurs at the sub-meter vertical scale, only results in sub-permil offsets in δ13C and cannot be used to explain the full δ13C excursion. In other places, the Wonoka Fm. is host to deep (1 km

  15. Synthesis of exemestane labelled with (13)C.

    PubMed

    Fontana, Erminia; Pignatti, Alberto; Giribone, Danilo; Di Salle, Enrico

    2008-08-01

    The synthesis of exemestane Aromasin, an irreversible steroidal aromatase inhibitor, specifically labelled with (13)C is reported. The preparation of [(13)C(3)]exemestane was achieved according to an eight-step procedure starting from the commercially available testosterone.

  16. 13C-labeled D-ribose: chemi-enzymic synthesis of various isotopomers.

    PubMed

    Serianni, A S; Bondo, P B

    1994-04-01

    Current interest in the use of heteronuclear multidimensional NMR methods to assess the structures, conformations and/or dynamics of oligonucleotides in solution has created an immediate need for nucleosides and their derivatives labeled in various ways with stable isotopes (13C, 2H, 15N and/or 17,18O). This short review focuses exclusively on chemienzymic methods to introduce one or more 13C labels into D-ribose, a precursor to ribo- and 2'-deoxyribonucleosides. It will be demonstrated that five convenient reactions, applied in specific sequences, provide access to 26 of the 32 13C-labeled isotopomers of D-ribose in acceptable yields. While not explicitly discussed herein, these same reactions, appropriately modified, can also be used to insert one or more 2H and/or 17,18O isotopes into this aldopentose.

  17. Large spatial variations in coastal 14C reservoir age - a case study from the Baltic Sea

    NASA Astrophysics Data System (ADS)

    Lougheed, B. C.; Filipsson, H. L.; Snowball, I.

    2013-05-01

    Coastal locations are highly influenced by input from freshwater river runoff, including sources of terrestrial carbon, which can be expected to modify the 14C reservoir age, or R (t), associated with marine water. In this Baltic Sea case study, pre-bomb museum collection mollusc shells of known calendar age, from 30 locations across a strategic salinity transect of the Baltic Sea, were analysed for 14C, δ13C and δ18O. R (t) was calculated for all 30 locations. Seven locations, of which six are within close proximity of the coast, were found to have relatively higher R (t) values, indicative of hard-water effects. Whenever possible, the Macoma genus of mollusc was selected from the museum collections, in order to exclude species specific reservoir age effects as much as possible. When the Macoma samples are exclusively considered, and samples from hard-water locations excluded, a statistically significant correlation between Macoma R (t) and average salinity is found, indicating a two end-member linear mixing model between 14Cmarine and 14Crunoff. A map of Baltic Sea Macoma aragonite R (t) for the late 19th and early 20th centuries is produced. Such a map can provide an estimate for contemporary Baltic Sea Macoma R (t), although one must exercise caution when applying such estimates back in time or to 14C dates obtained from different sample material. A statistically significant correlation is found between δ18Oaragonite and Macoma R (t), suggesting that δ18Oaragonite can be used to estimate Macoma palaeo-R (t), due to the δ18Oaragonite signal being dominated by the salinity gradient of the Baltic Sea. A slightly increased correlation can be expected when δ18Oaragonite is corrected for temperature fractionation effects. The results of this Baltic Sea case study, which show that R (t) is affected by hydrographic conditions and local carbon inputs, have important consequences for other coastal and estuarine locations, where R (t) is also likely to significantly

  18. High-Resolution ∂18O record of middle-late Holocene hydrologic variability from the central Peruvian Andes (Invited)

    NASA Astrophysics Data System (ADS)

    Rodbell, D. T.; Abbott, M.; Bird, B. W.; Stansell, N.

    2009-12-01

    Laguna Yuraicocha in the western cordillera of the central Peruvian Andes (12.53°S; 75.50°W; 4460 masl) is dammed by late glacial moraines and is underlain and surrounded by Jurassic and Cretaceous limestone interbedded with siliciclastic rocks. A 6.9 meter-long sediment core from the distal end of the lake is dominated by authigenic calcite (marl) with a mean concentration of 82 weight percent that has accumulated at a rate of ~ 1 mm yr-1 for the past 6200 years. The age model for the core is based on a combination of 210Pb and AMS 14C ages from charcoal; modern lake water is ~1‰ evaporatively enriched from mean regional precipitation. Marl samples were taken with an average sampling interval of 8 years; samples were treated to remove organic matter, sieved to concentrate the <75 µm fraction, and the clay fraction was removed by repeated pipette withdrawal. The <75 µm fraction contains abundant euhedral grains of calcite that are not abraded or corroded, thus reflecting their authigenic origin in Laguna Yuraicocha. The 18O and 13C stratigraphy reveals decadal, century, and millennial-scale variability that is comparable to isotope records from other carbonate lakes and ice cores in the region. The 18O and 13C records generally covary with similar amplitudes; δ13C ranges from -0.5 to 3.5 ‰ (PDB). A pronounced linear trend of δ18O depletion (from -10.5 to -14.5 ‰) spans the length of record and likely reflects a progressive increase in hydrologic balance (i.e., the ratio of precipitation/evaporation) through the middle and late Holocene. This interpretation is consistent with basal core sediment that records pronounced lake low stands, and possible periodic dessication in the early-middle Holocene. The last 1200 yr of record reveals a 2‰ depletion culminating with the most depleted isotopes on record ~ AD 1800 followed by an abrupt 1.5 ‰ enrichment that began ~AD 1900 and continues to the present. These trends match closely the 18O record from the

  19. (13)C NMR Metabolomics: INADEQUATE Network Analysis.

    PubMed

    Clendinen, Chaevien S; Pasquel, Christian; Ajredini, Ramadan; Edison, Arthur S

    2015-06-02

    The many advantages of (13)C NMR are often overshadowed by its intrinsically low sensitivity. Given that carbon makes up the backbone of most biologically relevant molecules, (13)C NMR offers a straightforward measurement of these compounds. Two-dimensional (13)C-(13)C correlation experiments like INADEQUATE (incredible natural abundance double quantum transfer experiment) are ideal for the structural elucidation of natural products and have great but untapped potential for metabolomics analysis. We demonstrate a new and semiautomated approach called INETA (INADEQUATE network analysis) for the untargeted analysis of INADEQUATE data sets using an in silico INADEQUATE database. We demonstrate this approach using isotopically labeled Caenorhabditis elegans mixtures.

  20. Estimating 14C groundwater ages in a methanogenic aquifer

    USGS Publications Warehouse

    Aravena, Ramon; Wassenaar, Leonard I; Plummer, L. Niel

    1995-01-01

    This paper addresses the problem of 14C age dating of groundwaters in a confined regional aquifer affected by methanogenesis. Increasing CH4 concentrations along the groundwater flow system and 13C and 14C isotopic data for dissolved inorganic carbon, dissolved organic carbon, and CH4 clearly show the effect of methanogenesis on groundwater chemistry. Inverse reaction path modeling using NETPATH indicates the predominant geochemical reactions controlling the chemical evolution of groundwater in the aquifer are incongruent dissolution of dolomite, ion exchange, methanogenesis, and oxidation of sedimentary organic matter. Modeling of groundwater 14C ages using NETPATH indicates that a significant part of groundwater in the Alliston aquifer is less than 13,000 years old; however, older groundwater in the range of 15,000–23,000 years is also present in the aquifer. This paper demonstrates that 14C ages calculated using NETPATH, incorporating the effects of methanogenesis on the carbon pools, provide reasonable groundwater ages that were not possible by other isotopic methods.

  1. The CW-CRDS spectra of the 16O/18O isotopologues of ozone between 5930 and 6340 cm-1—Part 3: 16O18O18O and 18O16O18O

    NASA Astrophysics Data System (ADS)

    De Backer, M.-R.; Barbe, A.; Starikova, E.; Tyuterev, Vl. G.; Mondelain, D.; Kassi, S.; Campargue, A.

    2013-09-01

    Our systematic investigation of the high sensitivity CW-Cavity Ring Down Spectra of 16O/18O ozone isotopologues at high vibrational excitation continues with the study of the 16O18O18O and 18O16O18O species. The first two papers of this series were devoted to the analysis of the same four bands of the 16O16O18O and 16O18O16O species in the 5930-6340 cm-1domain. Here, after a brief reminder of relevant experiment and theory, we report the analyses of two bands of 16O18O18O, vibrationally assigned as 2ν2+5ν3 and 2ν1+2ν2+3ν3_2 and three bands of 18O16O18O, assigned to 2ν1+2ν2+3ν3_1, 5ν1+ν3 and 3ν1+ν2+3ν3.They correspond to the highest vibration excitations observed so far for the 16O18O18O and 18O16O18O isotopologues. Altogether for the two new bands of 16O18O18O, 1214 rovibrational transitions were assigned up to Jmax=29 and for the three new bands of 18O16O18O, 948 rovibrational transitions were assigned up to Jmax=27. Observed line positions were fitted with root-mean squares deviations ranging from 0.005 to 0.011 cm-1, using effective Hamiltonian models accounting for dark state perturbations. The derived band centres and rotational constants are in good agreement with new theoretical calculations from the molecular potential function. The corresponding lists of 3365 lines are provided as Supplementary material.

  2. The δ18O record of phanerozoic abiotic marine calcite cements

    NASA Astrophysics Data System (ADS)

    Lohmann, Kyger C.; Walker, James C. G.

    Monomineralic, abiotic marine cements formed in low-latitude Phanerozoic reefs provide the direction and amplitude of secular variation of δ13C and δ18O in marine calcite and defines two end member compositions — 580 to 360 my (-7 to -5‰ δ18OPDB) and 360 to present (-3 to 0‰ δ18OPDB). Sampling of the Devono-Carboniferous transition (375-320 my) at several global sites reveals a rapid change in carbonate isotopic compositions. Bracketed within Fammenian to Early Visean-aged strata, a 7 to 15 my time interval, this shift corresponds to a 2‰ offset in mean δ13C and 3-4‰ offset in δ18O. The abruptness of such change, and its overall correlation with variations in 87Sr/86Sr, δ34S, δ13C, and Li/Al ratios in marine sediments suggests a primary offset in marine water composition.

  3. New guidelines for δ13C measurements

    USGS Publications Warehouse

    Coplen, Tyler B.; Brand, Willi A.; Gehre, Matthias; Groning, Manfred; Meijer, Harro A. J.; Toman, Blaza; Verkouteren, R. Michael

    2006-01-01

    Consistency of δ13C measurements can be improved 39−47% by anchoring the δ13C scale with two isotopic reference materials differing substantially in 13C/12C. It is recommended thatδ13C values of both organic and inorganic materials be measured and expressed relative to VPDB (Vienna Peedee belemnite) on a scale normalized by assigning consensus values of −46.6‰ to L-SVEC lithium carbonate and +1.95‰ to NBS 19 calcium carbonate. Uncertainties of other reference material values on this scale are improved by factors up to two or more, and the values of some have been notably shifted:  the δ13C of NBS 22 oil is −30.03%.

  4. Temperature signal instability of tree-ring δ13C chronology in the northeastern Qinghai-Tibetan Plateau

    NASA Astrophysics Data System (ADS)

    Wang, Wenzhi; Liu, Xiaohong; Xu, Guobao; Zeng, Xiaomin; Wu, Guoju; Zhang, Xuanwen; Qin, Dahe

    2016-04-01

    Tree ring δ13C as a climate proxy is widely used for palaeoclimate research, however, its temporal stability response to the climate change remains unclear under more than one limited factors on tree growth. Here, we used a millennium tree-ring δ13C chronology combining two annual-resolution δ13C chronologies since 1800 from long-lived Qilian juniper (Sabina przewalskii) to assess its instability of the climate signal in the northeastern Qinghai-Tibetan Plateau. Tree-ring δ13C chronologies were strongly correlated with the regional mean April to August temperature from 1956 to 2008, but the associations were absent within the period 1901 to 1955 values in the CRU TS dataset. Comparison of the millennium-long δ13C series with reconstructed Asian temperatures also demonstrated that the δ13C chronology exhibited climate signal temporal instability. Substantial oscillations were revealed using a frequency-dependent analysis and 51-year running correlation analysis from the millennium-long tree-ring δ13C and δ18O series. Dual-isotope approach indicated that stomatal limitations created a statistical significant positive correlation between tree-ring δ13C and δ18O, but photosynthetic rate may be dominant when the correlations were not significant. Our results suggest that tree-ring δ13C series in the northeastern Qinghai-Tibetan Plateau is responded instability to temperature variations in the past 1000 years.

  5. The. delta. sup 18 O record of Phanerozoic abiotic marine calcite cements

    SciTech Connect

    Lohmann, K.C.; Walker, J.C.G. )

    1989-04-01

    Monomineralic, abiotic marine cements formed in low-latitude Phanerozoic reefs provide the direction and amplitude of secular variation of {delta}{sup 13}C and {delta}{sup 18}O in marine calcite and defines two end member compositions - 580 to 360 my ({minus}7 to {minus}5{per thousand}{delta}{sup 18}O{sub PDB}) and 360 to present ({minus}3 to 0{per thousand}{delta}{sup 18}O{sub PDB}). Sampling of the Devono-Carboniferous transition (375-320 my) at several global sites reveals a rapid change in carbonate isotopic compositions. Bracketed within Fammenian to Early Visean-aged strata, a 7 to 15 my time interval, this shift corresponds to a 2% offset in mean {delta}{sup 13}C and 3-4% offset in {delta}{sup 18}O. The abruptness of such change, and its overall correlation with variations in {sup 87}Sr/{sup 86}Sr, {delta}{sup 34}S, {delta}{sup 13}C, and Li/Al ratios in marine sediments suggests a primary offset in marine water composition.

  6. Estimation of groundwater residence time using environmental radioisotopes (14C,T) in carbonate aquifers, southern Poland.

    PubMed

    Samborska, Katarzyna; Różkowski, Andrzej; Małoszewski, Piotr

    2013-01-01

    Triassic carbonate aquifers in the Upper Silesia region, affected by intense withdrawal, have been investigated by means of isotopic analyses of (14)C, δ(13)C, δ(2)H, δ(18)O and (3)H. The isotopic examinations were carried out in the 1970s and in the early 1980s, and it was the first application of tracers to estimate age and vulnerability for the contamination of groundwater in this region. Similar isotopic analyses were conducted in 2007 and 2008 with the same Triassic carbonate formation. The isotopic examinations were performed within the confined part of the carbonate formation, wherein aquifers are covered by semi-permeable deposits. The direct recharge of the aquifer occurs in the outcrop areas, but it mainly takes place due to percolation of the water through aquitards and erosional windows. The Triassic aquifer has been intensively drained by wells and by lead-zinc mines. Nowadays, the declining water demand and closure of some mines have induced a significant increase in the water table level. The detailed analysis of the results, including the radiocarbon age corrections and the comparison of radioisotope activities, has made it possible to estimate the range of residence time within the carbonate Triassic aquifer. This range from several tens to several tens of thousands indicates that the recharge of aquifers might have occurred between modern times and the Pleistocene. The apparent age of the water estimated on the basis of (14)C activity was corrected considering the carbon isotope exchange and the diffusion between mobile water in fractures and stagnant water in micropores. The obtained corrected period of recharge corresponds to the result of investigations of noble gases, which were carried out in the 1990s. In almost half of the cases, groundwater is a mixture of young and old water. The mixing processes occur mainly in areas of heavy exploitation of the aquifer.

  7. 13C NMR of tunnelling methyl groups

    NASA Astrophysics Data System (ADS)

    Detken, A.

    The dipolar interactions between the protons and the central 13C nucleus of a 13CH3 group are used to study rotational tunnelling and incoherent dynamics of such groups in molecular solids. Single-crystal 13C NMR spectra are derived for arbitrary values of the tunnel frequency upsilon t. Similarities to ESR and 2H NMR are pointed out. The method is applied to three different materials. In the hydroquinone/acetonitrile clathrate, the unique features in the 13C NMR spectra which arise from tunnelling with a tunnel frequency that is much larger than the dipolar coupling between the methyl protons and the 13C nucleus are demonstrated, and the effects of incoherent dynamics are studied. The broadening of the 13C resonances is related to the width of the quasi-elastic line in neutron scattering. Selective magnetization transfer experiments for studying slow incoherent dynamics are proposed. For the strongly hindered methyl groups of L-alanine, an upper limit for upsilon is derived from the 13C NMR spectrum. In aspirinTM (acetylsalicylic acid), incoherent reorientations dominate the spectra down to the lowest temperatures studied; their rate apparently increases with decreasing temperature below 25K.

  8. Global ocean climatology of the 13C Suess effect and preindustrial δ13C

    NASA Astrophysics Data System (ADS)

    Eide, Marie; Olsen, Are; Ninnemann, Ulysses; Eldevik, Tor; Johannessen, Truls

    2017-04-01

    We present the first observationally based estimate of the full global ocean 13C Suess effect since preindustrial times. This was constructed by using Olsen and Ninnemann's [2010] back-calculation method to calculate the 13C Suess effect with data from 29 cruises spanning the world ocean. We find a strong 13C Suess effect in the upper 1000 m of all basins, with strongest decrease in the Subtropical Gyres of the Northern Hemisphere, where δ13C has decreased by more than 0.8‰ since the industrial revolution. At greater depths, a significant 13C Suess effect can only be detected in the northern parts of the North Atlantic Ocean. The magnitude of the 13C Suess effect is correlated with the concentration of anthropogenic carbon, but their relationship varying strongly between water masses, reflecting the degree to which source waters are equilibrated with the atmospheric 13C Suess effect before sinking. From the 13C Suess effect estimates, we have estimated the preindustrial δ13C (δ13CPI) along the 29 sections. Further, we developed regional multilinear regression equations, which were applied on the World Ocean Atlas data to construct the δ13CPI climatology, which reveals the natural δ13C distribution in the global ocean. Compared to the modern distribution, the preindustrial δ13C spans a larger range of values, and we find that in some regions in the high northern latitudes, the gradient in modern ocean δ13C is completely reversed compared to the preindustrial. Maximum δ13CPI, of up to 1.8‰, are found in the subtropical gyres of all basins, in the upper and intermediate waters of the North Atlantic, as well as in mode waters with a Southern Ocean origin. Particularly strong gradients occur at intermediate depths, revealing a strong potential for using δ13C as a tracer for changes in water mass geometry at these levels. Further, we identify a much tighter relationship between δ13C and Apparent Oxygen Utilization (AOU) than between δ13C and phosphate that

  9. Delta Ray Road Trip: Measuring δ13C, δ18O and concentration of CO2 across Canada

    NASA Astrophysics Data System (ADS)

    Jost, Hansjurg; Stow, Peter; Mandic, Luka

    2016-04-01

    The Delta Ray Road Trip was conceived to demonstrate that there is now an instrument capable of being taken to the sample collection point and in fact taken to the samples along an 8000 km route across Canada. The concept was to drive a Thermo Scientific Delta Ray Isotope Ratio Infrared Spectrometer from coast to coast across the 2nd largest country in the world. This route took the Delta Ray from a coastal environment, through forests, arable farm land, urban and industrial centres, across prairies and over mountains. The vehicle was a standard RV with as few modifications as possible. Along the way there were stops at most of the major universities in Canada as well as the AGU-GAC-MAC conference in Montreal, where indoor measurements were performed. Date was uploaded in quasi realtime to a website. We will present data acquired during the trip and discuss the lessons learned.

  10. Relationships between δ18O and δ13C of the of living Radix sp. shells and its ambient water

    NASA Astrophysics Data System (ADS)

    Hu, H. P.; Feng, J. L.; Chen, F.

    2016-12-01

    Radix sp. is widespread on the Tibetan Plateau. Living Radix sp. was collected from rivers, swamp, through-flow lakes and closed lakes. We measured the δ18Oshell and δ13Cshell values of living and fossil Radix sp. shells, and the δ18Owater and δ13CDIC values of the ambient water. The δ18Oshell values of living Radix sp. from different water bodies are significant related to the δ18Owater of the ambient water. The δ18Oshell values of living Radix sp. shells depend on the δ18Owater of the ambient water. Thus, δ18Oshell of fossil Radix sp. shells can be utilized to rebuild δ18Owater of the paleo-water body. Moreover, the δ18Oshell values of Radix sp. shells in the rivers are very low, the values from the swamp are bit higher, probably due to weak evaporation. The δ18Oshell values for the through-flow lakes ranging within a wide range, while values for the closed lakes are higher. It is possible that intensive evaporation may be the cause of the lake's isotopic characteristics. Therefore, the δ18Oshell values of living Radix sp. can be used to determine its hydrological status. In contrast, we do not observe a significant positive correlation between the δ13Cshell value of living Radix sp. and the δ13CDIC values of the ambient water. The δ13CDIC value of a water body is determined by many factors; in addition, δ13CDIC is more variable in the river, swamp and through-flow lake than in the closed lake. Consequently, the δ13CDIC values at the time of sampling cannot reflect the δ13CDIC values of the ambient water during the entire life span of Radix sp.. Moreover, the δ13Cshell values of living Radix sp. do not appear to have a close relationship with the hydrological status of the water body.

  11. Ostracode δ18O and δ13C evidence of Holocene environmental changes in the sediments of two Minnesota lakes

    USGS Publications Warehouse

    Schwalb, Antje; Locke, Sharon M.; Dean, Walter E.

    1995-01-01

    Stable oxygen and carbon isotope geochemistry of ostracode valves, abundance and assemblages of ostracode species, and sedimentological parameters from cores taken in Williams and Shingobee Lakes in north-central Minnesota show changes in climatic and hydrologic history during the Holocene. Isotopic records are consistent with the following scenario: Before 9800 yr B.P. the two lakes were connected. Increasing evaporation through the jack/red pine period (9800-7700 yr B.P.) led to lower lake levels, leaving small separated basins. The prairie period (7700-4000 yr B.P.) reflects high aridity, and lake levels reached low stands shortly before 6500 yr B.P. Low lake levels are associated with groundwater discharge between 6500 and 6000 yr B.P. The hardwood period (4000-3200 yr B.P.) corresponds to long cold winters and warm to cool summers with lower evaporation rates and slower sedimentation. During the white pine period (<3200 yr B.P.) evaporation increased and/or precipitation shifted to the summer months. These changes can be related to shifting atmospheric circulation patterns. Zonal flow was probably dominant during the early Holocene until the end of the prairie period (c. 4000 yr B.P.). During the hardwood period a combination of zonal and meridional flow patterns caused long and cold winters and wetter summers. During the white pine period wintners were shorter and the meridional flow pattern more significant. Today meridional flow dominates the circulation pattern. ?? 1995 Kluwer Academic Publishers.

  12. The suitability of the dual isotope approach (δ13C and δ18O) in tree ring studies

    NASA Astrophysics Data System (ADS)

    Siegwolf, Rolf; Saurer, Matthias

    2016-04-01

    The use of stable isotopes, complementary to tree ring width data in tree ring research has proven to be a powerful tool in studying the impact of environmental parameters on tree physiology and growth. These three proxies are thus instrumental for climate reconstruction and improve the understanding of underlying causes of growth changes. In various cases, however, their use suggests non-plausible interpretations. Often the use of one isotope alone does not allow the detection of such "erroneous isotope responses". A careful analysis of these deviating results shows that either the validity of the carbon isotope discrimination concept is no longer true (Farquhar et al. 1982) or the assumptions for the leaf water enrichment model (Cernusak et al., 2003) are violated and thus both fractionation models are not applicable. In this presentation we discuss such cases when the known fractionation concepts fail and do not allow a correct interpretation of the isotope data. With the help of the dual isotope approach (Scheidegger et al.; 2000) it is demonstrated, how to detect and uncover the causes for such anomalous isotope data. The fractionation concepts and their combinations before the background of CO2 and H2O gas exchange are briefly explained and the specific use of the dual isotope approach for tree ring data analyses and interpretations are demonstrated. References: Cernusak, L. A., Arthur, D. J., Pate, J. S. and Farquhar, G. D.: Water relations link carbon and oxygen isotope discrimination to phloem sap sugar concentration in Eucalyptus globules, Plant Physiol., 131, 1544-1554, 2003. Farquhar, G. D., O'Leary, M. H. and Berry, J. A.: On the relationship between carbon isotope discrimination and the intercellular carbon dioxide concentration in leaves, Aust. J. Plant Physiol., 9, 121-137, 1982. Scheidegger, Y., Saurer, M., Bahn, M. and Siegwolf, R.: Linking stable oxygen and carbon isotopes with stomatal conductance and photosynthetic capacity: A conceptual model, Oecologia, 125, 350-357, 2000.

  13. Reaction-dependent spin population and evidence of breakup in {sup 18}O

    SciTech Connect

    Hojman, D.; Pacheco, A.J.; Testoni, J.E.; Davidson, J.; Davidson, M.; Cardona, M.A.; Fernandez-Niello, J.O.; Kreiner, A.J.; Arazi, A.; Capurro, O.A.; Marti, G.V.; Bazzacco, D.; Lenzi, S.M.; Lunardi, S.; Alvarez, C. Rossi; Ur, C.; Burlon, A.; Debray, M.E.; De Angelis, G.; De Poli, M.

    2006-04-15

    Angular distributions and angular correlations have been measured for the emission of one and two {alpha}-particles in the {sup 18}O+{sup 207,208}Pb,{sup 209}Bi reactions at several beam energies above the Coulomb barrier. The results rule out fusion evaporation as the main reaction mechanism for the channels involving {alpha}-particle emission and support the interpretation of the breakup of the {sup 18}O projectiles into at least {sup 14}C+{alpha} and {sup 10}Be+{sup 8}Be before fusion.

  14. Stable C, O and clumped isotope systematics and 14C geochronology of carbonates from the Quaternary Chewaucan closed-basin lake system, Great Basin, USA: Implications for paleoenvironmental reconstructions using carbonates

    NASA Astrophysics Data System (ADS)

    Hudson, Adam M.; Quade, Jay; Ali, Guleed; Boyle, Douglas; Bassett, Scott; Huntington, Katharine W.; De los Santos, Marie G.; Cohen, Andrew S.; Lin, Ke; Wang, Xiangfeng

    2017-09-01

    Isotopic compositions of lacustrine carbonates are commonly used for dating and paleoenvironmental reconstructions. Here we use carbonate δ13C and δ18O, clumped (Δ47), and 14C compositions to better understand the carbonate isotope system in closed-basin lakes and trace the paleohydrologic and temperature evolution in the Chewaucan closed-basin lake system, northern Great Basin, USA, over the Last Glacial/Holocene transition. We focus on shorezone tufas to establish that they form in isotopic equilibrium with lake water and DIC, they can be dated reliably using 14C, and their clumped isotope composition can be used to reconstruct past lake temperature. Calculations of the DIC budget and reservoir age for the lake indicate residence time is short, and dominated by exchange with atmospheric CO2 at all past lake levels. Modern lake DIC and shorezone tufas yield δ13C and 14C values consistent with isotopic equilibrium with recent fossil fuel and bomb-influenced atmospheric CO2, supporting these calculations. δ13C values of fossil tufas are also consistent with isotopic equilibrium with pre-industrial atmospheric CO2 at all shoreline elevations. This indicates that the 14C reservoir effect for this material is negligible. Clumped isotope (Δ47) results indicate shorezone tufas record mean annual lake temperature. Modern (average 13 ± 2 °C) and 18 ka BP-age tufas (average 6 ± 2 °C) have significantly different temperatures consistent with mean annual temperature lowering of 7 ± 3 °C (1 SE) under full glacial conditions. For shorezone tufas and other lake carbonates, including spring mounds, mollusk shells, and ostracod tests, overall δ13C and δ18O values co-vary according to the relative contribution of spring and lacustrine end member DIC and water compositions in the drainage system, but specific isotope values depend strongly upon sample context and are not well correlated with past lake depth. This contrasts with the interpretation that carbonate

  15. Stable C, O and clumped isotope systematics and 14C geochronology of carbonates from the Quaternary Chewaucan closed-basin lake system, Great Basin, USA: Implications for paleoenvironmental reconstructions using carbonates

    USGS Publications Warehouse

    Hudson, Adam; Quade, Jay; Ali, Guleed; Boyle, Douglas P.; Bassett, Scott; Huntington, Katharine W.; De los Santos, Marie G.; Cohen, Andrew S.; Lin, Ke; Wang, Xiangfeng

    2017-01-01

    Isotopic compositions of lacustrine carbonates are commonly used for dating and paleoenvironmental reconstructions. Here we use carbonate δ13C and δ18O, clumped (Δ47), and 14C compositions to better understand the carbonate isotope system in closed-basin lakes and trace the paleohydrologic and temperature evolution in the Chewaucan closed-basin lake system, northern Great Basin, USA, over the Last Glacial/Holocene transition. We focus on shorezone tufas to establish that they form in isotopic equilibrium with lake water and DIC, they can be dated reliably using 14C, and their clumped isotope composition can be used to reconstruct past lake temperature. Calculations of the DIC budget and reservoir age for the lake indicate residence time is short, and dominated by exchange with atmospheric CO2 at all past lake levels. Modern lake DIC and shorezone tufas yield δ13C and 14C values consistent with isotopic equilibrium with recent fossil fuel and bomb-influenced atmospheric CO2, supporting these calculations. δ13C values of fossil tufas are also consistent with isotopic equilibrium with pre-industrial atmospheric CO2 at all shoreline elevations. This indicates that the 14C reservoir effect for this material is negligible. Clumped isotope (Δ47) results indicate shorezone tufas record mean annual lake temperature. Modern (average 13 ± 2 °C) and 18 ka BP-age tufas (average 6 ± 2 °C) have significantly different temperatures consistent with mean annual temperature lowering of 7 ± 3 °C (1 SE) under full glacial conditions. For shorezone tufas and other lake carbonates, including spring mounds, mollusk shells, and ostracod tests, overall δ13C and δ18O values co-vary according to the relative contribution of spring and lacustrine end member DIC and water compositions in the drainage system, but specific isotope values depend strongly upon sample context and are not well correlated with past lake depth. This contrasts with the interpretation that carbonate

  16. Electric dipole moment of 13C

    NASA Astrophysics Data System (ADS)

    Yamanaka, Nodoka; Yamada, Taiichi; Hiyama, Emiko; Funaki, Yasuro

    2017-06-01

    We calculate for the first time the electric dipole moment (EDM) of 13C generated by the isovector charge conjugation-parity (CP)-odd pion exchange nuclear force in the α -cluster model, which describes well the structures of low-lying states of the 13C nucleus. The linear dependence of the EDM of 13C on the neutron EDM and the isovector CP-odd nuclear coupling is found to be d13C=-0.33 dn-0.0020 G¯π(1 ) . The linear enhancement factor of the CP-odd nuclear coupling is smaller than that of the deuteron, due to the difference of the structure between the 1 /21- state and the opposite-parity (1 /2+ ) states. We clarify the role of the structure played in the enhancement of the EDM. This result provides good guiding principles to search for other nuclei with large enhancement factor. We also mention the role of the EDM of 13C in determining the new physics beyond the standard model.

  17. Measurement of fecal /sup 14/C excretion

    SciTech Connect

    Kumaran, K.A.; Wiener, N.S.; Katz, J.B.

    1982-11-01

    Simultaneous measurements of fecal /sup 14/C and expired /sup 14/CO/sub 2/ in the breath are necessary to evaluate patients with various ileal abnormalities and bile salt malabsorption. Following the oral ingestion of the labeled bile acid, glycine-(I-/sup 14/C)cholic acid, detection of increased fecal /sup 14/C without abnormal expiration of /sup 14/CO/sub 2/ identifies patients with ileal resection. This contrasts with the normal fecal /sup 14/C content and abnormal expired /sup 14/CO/sub 2/ found in patients with bacterial overgrowth. Fecal /sup 14/C content was determined by utilizing Van Slyke combustion of the specimen and trapping the liberated /sup 14/CO/sub 2/ with Scintisorb C. The method is simple, rapid, and accurate, and expands the diagnostic usefulness of the bile salt absorption test.

  18. A 10,300 14C yr Record of Climate and Vegetation Change from Haiti

    NASA Astrophysics Data System (ADS)

    Higuera-Gundy, Antonia; Brenner, Mark; Hodell, David A.; Curtis, Jason H.; Leyden, Barbara W.; Binford, Michael W.

    1999-09-01

    Pleistocene and Holocene vegetation dynamics in the American tropics are inferred largely from pollen in continental lake sediments. Maritime influences may have moderated climate and vegetation changes on Caribbean islands. Stable isotope (δ18O) study of a 7.6-m core from Lake Miragoane, Haiti, provided a high-resolution record of changing evaporation/precipitation (E/P) since ∼10,300 14C yr B.P. The Miragoane pollen record documents climate influences and human impacts on vegetation in Hispaniola. The δ18O and pollen data near the base of the core indicate cool, dry conditions before ∼10,000 14C yr B.P. Lake Miragoane filled with water in the early Holocene as E/P declined and the freshwater aquifer rose. Despite increasing early Holocene moisture, shrubby, xeric vegetation persisted. Forest expanded ∼7000 14C yr B.P. in response to greater effective moisture and warming. The middle Holocene (∼7000-3200 14C yr B.P.) was characterized by high lake levels and greatest relative abundance of pollen from moist forest taxa. Climatic drying that began ∼3200 14C yr B.P. may have driven some mesophilic animal species to extinction. The pollen record of the last millennium reflects pre-Columbian (Taino) and European deforestation. Long-term, Holocene vegetation trends in southern Haiti are comparable to trends from continental, lowland circum-Caribbean sites, suggesting a common response to regional climate change.

  19. 14C-carbaryl residues in hazelnut.

    PubMed

    Yücel, Ulkü; Ilim, Murat; Aslan, Nazife

    2006-01-01

    A hazelnut ocak (shrub growing form) in the field in Black Sea region of Turkey was treated with commercial carbaryl insecticide spiked with 14C-carbaryl. Three months later, the harvested hazelnuts were separated into husk, shell, and kernel components, then homogenized and analyzed. The total and unextractable (bound) 14C-residues were determined by combustion and the extractable 14C-residues were obtained by extracting the samples with methanol. Concentrated extracts were first analyzed by thin layer chromatography (TLC). The extracts were also subjected to a series of liquid-liquid extraction procedures for clean-up and the final extracts were analyzed by high performance liquid chromatography (HPLC). Crude hazelnut oil was also extracted with hexane and analyzed for total 14C-residue. A total of 1.3% of applied radioactivity was recovered from the total nut harvested, with 0.04%, 0.06%, and 1.2% present in shell, kernel, and husk, respectively. The results show that the inedible husk and shell contained 95.7% 14C, whereas the edible kernel contained 4.3% of the total 14C recovered. The terminal 14C-residue in hazelnut kernel and oil did not contain carbaryl and/or its metabolite naphthol.

  20. Evidence for anthropogenic 14C-enrichment in estuarine waters adjacent to the North Sea

    NASA Astrophysics Data System (ADS)

    Ahad, Jason M. E.; Ganeshram, Raja S.; Spencer, Robert G. M.; Uher, Günther; Gulliver, Pauline; Bryant, Charlotte L.

    2006-04-01

    The isotopic composition (δ13C and Δ14C) of high molecular weight dissolved organic carbon (HMW DOC) was studied in the Tyne and Tweed estuaries, NE England. Despite significant removal of terrigenous HMW DOC in the low salinity regions (S < 15), Δ14C remained modern with little variation around 115‰. This lack of apparent age discrimination was attributed to either non-oxidative removal or the absence of a significant proportion of old refractory C in the HMW DOC pool. At S > 15, we observed seaward increases in δ13C and Δ14C. With no documented local 14C inputs, we attributed non-bomb related 14C-enrichment at S > 15 to a possible `lingering effect' of distal anthropogenic sources in near-coastal North Sea HMW DOC. Given the global distribution of potential sources, we propose that anthropogenic 14C should be considered in assigning ages of DOC pools in near-coastal waters and suggest its possible use as a tracer for DOC transformations.

  1. Comparative absorption of [13C]glucose and [13C]lactose by premature infants.

    PubMed

    Murray, R D; Boutton, T W; Klein, P D; Gilbert, M; Paule, C L; MacLean, W C

    1990-01-01

    Oxidation of orally administered [13C]glucose and [13C]lactose and fecal recovery of malabsorbed substrates were determined in two groups of premature infants. Eighteen studies were performed with six infants at Johns Hopkins Hospital (JHH); 24 studies were performed with nine infants at Columbus Children's Hospital (CCH). The two groups differed in that JHH infants had shorter gestations but were older when studied. Fecal 13C loss after [13C]glucose administration did not differ between the two groups. Compared with glucose, the metabolism of lactose appeared to involve more malabsorption and colonic fermentation in JHH infants than in CCH infants and resulted in higher fecal losses of substrate carbon. Maturation appeared to involve increased proximal intestinal absorption and greater retention of absorbed carbohydrate. Simultaneous absorption of substrate from the small and large intestine may limit the usefulness of breath tests for 13C in the premature infant.

  2. Application of 13C-labeling and 13C-13C COSY NMR experiments in the structure determination of a microbial natural product.

    PubMed

    Kwon, Yun; Park, Sunghyouk; Shin, Jongheon; Oh, Dong-Chan

    2014-08-01

    The elucidation of the structures of complex natural products bearing many quaternary carbons remains challenging, even in this advanced spectroscopic era. (13)C-(13)C COSY NMR spectroscopy shows direct couplings between (13)C and (13)C, which comprise the backbone of a natural product. Thus, this type of experiment is particularly useful for natural products bearing consecutive quaternary carbons. However, the low sensitivity of (13)C-based NMR experiments, due to the low natural abundance of the (13)C nucleus, is problematic when applying these techniques. Our efforts in the (13)C labeling of a microbial natural product, cyclopiazonic acid (1), by feeding (13)C-labeled glucose to the fungal culture, enabled us to acquire (13)C-(13)C COSY NMR spectra on a milligram scale that clearly show the carbon backbone of the compound. This is the first application of (13)C-(13)C COSY NMR experiments for a natural product. The results suggest that (13)C-(13)C COSY NMR spectroscopy can be routinely used for the structure determination of microbial natural products by (13)C-enrichment of a compound with (13)C-glucose.

  3. Synthesis Of [2h, 13c] And [2h3, 13c]Methyl Aryl Sulfides

    DOEpatents

    Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.

    2004-03-30

    The present invention is directed to labeled compounds, [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2, .sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfides wherein the .sup.13 C methyl group attached to the sulfur of the sulfide includes exactly one, two or three deuterium atoms and the aryl group is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 are each independently, hydrogen, a C.sub.1 -C.sub.4 lower alkyl, a halogen, an amino group from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each a C.sub.1 -C.sub.4 lower alkyl, a phenyl, or an alkoxy group. The present invention is also directed to processes of preparing [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2,.sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfides wherein the .sup.13 C methyl group attached to the sulfur of the sulfide includes exactly one, two or three deuterium atoms. The present invention is also directed to the labeled compounds of [.sup.2 H.sub.1, .sup.13 C]methyl iodide and [.sup.2 H.sub.2, .sup.13 C]methyl iodide.

  4. Evolution of low-18O Icelandic crust

    NASA Astrophysics Data System (ADS)

    Pope, Emily C.; Bird, Dennis K.; Arnórsson, Stefán

    2013-07-01

    The Krafla central volcano in the neovolcanic zone of Iceland hosts a chemically diverse suite of magmas characterized by anomalously low δ18O values. A rhyolite magma intercepted by the Iceland Deep Drilling Project (IDDP) exploratory well at 2.1 km depth provided a unique opportunity to investigate the origins of an unerupted rhyolite melt in the primarily basaltic central volcano at Krafla. Here we compare whole rock hydrogen and oxygen isotopes of this melt to those of lavas within and near the caldera of the Krafla central volcano ranging from recent fissure eruptions to Plio--Pleistocene age (including analyses of 18 new samples, plus previously published values) in order to evaluate the petrogenesis of low-18O magmas within the neovolcanic zone of Iceland. Oxygen isotope values of the IDDP-1 melt (δ18O=+3.2±0.2‰) are within the range of Krafla eruptives that have a bimodal composition of olivine-tholeiite and rhyolite (δ18O=+1.6‰ to +4.5‰). Lavas show significantly more variability in hydrogen isotope values (δD=-161‰ to -92‰) than the IDDP-1 melt (-121±2‰), whose δD is comparable to local hydrothermal epidote (-127 to -108‰), and show significantly lower water contents than IDDP-1 (0.1-1.1 wt%, in contrast to ~1.8 wt%). Basaltic to dacitic lavas from the proximal Heidarspordur ridge volcanic zone have δ18O between +3.4‰ and +4.2‰ and δD between -105‰ and -99‰. Uniformity of oxygen isotopes in the Heidarspordur ridge lavas suggests that their magmatic compositional variations are a consequence of fractional crystallization. The δD of the glass sampled by IDDP-1 unequivocally identifies the source of silicic low-18O melts like those erupted from within the caldera of the Krafla volcano as anatexis of meteoric-hydrothermally altered basalts resulting from the intrusion of mantle-derived basaltic magma. Finally, mantle-derived basalts in both the Krafla central volcano and Heidarspordur ridge (MgO>5 wt%) have δ18O values lower

  5. Accurate determinations of one-bond 13C-13C couplings in 13C-labeled carbohydrates

    NASA Astrophysics Data System (ADS)

    Azurmendi, Hugo F.; Freedberg, Darón I.

    2013-03-01

    Carbon plays a central role in the molecular architecture of carbohydrates, yet the availability of accurate methods for 1DCC determination has not been sufficiently explored, despite the importance that such data could play in structural studies of oligo- and polysaccharides. Existing methods require fitting intensity ratios of cross- to diagonal-peaks as a function of the constant-time (CT) in CT-COSY experiments, while other methods utilize measurement of peak separation. The former strategies suffer from complications due to peak overlap, primarily in regions close to the diagonal, while the latter strategies are negatively impacted by the common occurrence of strong coupling in sugars, which requires a reliable assessment of their influence in the context of RDC determination. We detail a 13C-13C CT-COSY method that combines a variation in the CT processed with diagonal filtering to yield 1JCC and RDCs. The strategy, which relies solely on cross-peak intensity modulation, is inspired in the cross-peak nulling method used for JHH determinations, but adapted and extended to applications where, like in sugars, large one-bond 13C-13C couplings coexist with relatively small long-range couplings. Because diagonal peaks are not utilized, overlap problems are greatly alleviated. Thus, one-bond couplings can be determined from different cross-peaks as either active or passive coupling. This results in increased accuracy when more than one determination is available, and in more opportunities to measure a specific coupling in the presence of severe overlap. In addition, we evaluate the influence of strong couplings on the determination of RDCs by computer simulations. We show that individual scalar couplings are notably affected by the presence of strong couplings but, at least for the simple cases studied, the obtained RDC values for use in structural calculations were not, because the errors introduced by strong couplings for the isotropic and oriented phases are very

  6. Accurate determinations of one-bond 13C-13C couplings in 13C-labeled carbohydrates.

    PubMed

    Azurmendi, Hugo F; Freedberg, Darón I

    2013-03-01

    Carbon plays a central role in the molecular architecture of carbohydrates, yet the availability of accurate methods for (1)D(CC) determination has not been sufficiently explored, despite the importance that such data could play in structural studies of oligo- and polysaccharides. Existing methods require fitting intensity ratios of cross- to diagonal-peaks as a function of the constant-time (CT) in CT-COSY experiments, while other methods utilize measurement of peak separation. The former strategies suffer from complications due to peak overlap, primarily in regions close to the diagonal, while the latter strategies are negatively impacted by the common occurrence of strong coupling in sugars, which requires a reliable assessment of their influence in the context of RDC determination. We detail a (13)C-(13)C CT-COSY method that combines a variation in the CT processed with diagonal filtering to yield (1)J(CC) and RDCs. The strategy, which relies solely on cross-peak intensity modulation, is inspired in the cross-peak nulling method used for J(HH) determinations, but adapted and extended to applications where, like in sugars, large one-bond (13)C-(13)C couplings coexist with relatively small long-range couplings. Because diagonal peaks are not utilized, overlap problems are greatly alleviated. Thus, one-bond couplings can be determined from different cross-peaks as either active or passive coupling. This results in increased accuracy when more than one determination is available, and in more opportunities to measure a specific coupling in the presence of severe overlap. In addition, we evaluate the influence of strong couplings on the determination of RDCs by computer simulations. We show that individual scalar couplings are notably affected by the presence of strong couplings but, at least for the simple cases studied, the obtained RDC values for use in structural calculations were not, because the errors introduced by strong couplings for the isotropic and

  7. Towards 14C-free liquid scintillator

    NASA Astrophysics Data System (ADS)

    Enqvist, T.; Barabanov, I. R.; Bezrukov, L. B.; Gangapshev, A. M.; Gavrilyuk, Y. M.; Grishina, V. Yu; Gurentsov, V. I.; Hissa, J.; Joutsenvaara, J.; Kazalov, V. V.; Krokhaleva, S.; Kutuniva, J.; Kuusiniemi, P.; Kuzminov, V. V.; Kurlovich, A. S.; Loo, K.; Lubsandorzhiev, B. K.; Lubsandorzhiev, S.; Morgalyuk, V. P.; Novikova, G. Y.; Pshukov, A. M.; Sinev, V. V.; lupecki, M. S.; Trzaska, W. H.; Umerov, Sh I.; Veresnikova, A. V.; Virkajärvi, A.; Yanovich, Y. A.; Zavarzina, V. P.

    2017-09-01

    A series of measurements has been started where the 14C concentration is determined from several liquid scintillator samples. A dedicated setup has been designed and constructed with the aim of measuring concentrations smaller than 10‑18. Measurements take place in two underground laboratories: in the Baksan Neutrino Observatory, Russia, and in the new Callio Lab in the Pyhäsalmi mine, Finland. Low-energy neutrino detection with a liquid scintillator requires that the intrinsic 14C concentration in the liquid is extremely low. In the Borexino CTF detector the concentration of 2 × 10‑18 has been achieved being the lowest value ever measured. In principle, the older the oil or gas source that the liquid scintillator is derived from and the deeper it situates, the smaller the 14C concentration is supposed to be. This, however, is not generally the case and the concentration is probably due to the U and Th content of the local environment.

  8. Thermophilic Anaerobic Biodegradation of [14C]Lignin, [14C]Cellulose, and [14C]Lignocellulose Preparations

    PubMed Central

    Benner, Ronald; Hodson, Robert E.

    1985-01-01

    Thermophilic (55°C) anaerobic enrichment cultures were incubated with [14C-lignin]lignocellulose, [14C-polysaccharide]lignocellulose, and kraft [14C]lignin prepared from slash pine, Pinus elliottii, and 14C-labeled preparations of synthetic lignin and purified cellulose. Significant but low percentages (2 to 4%) of synthetic and natural pine lignin were recovered as labeled methane and carbon dioxide during 60-day incubations, whereas much greater percentages (13 to 23%) of kraft lignin were recovered as gaseous end products. Percentages of label recovered from lignin-labeled substrates as dissolved degradation products were approximately equal to percentages recovered as gaseous end products. High-pressure liquid chromatographic analyses of CuO oxidation products of sound and degraded pine lignin indicated that no substantial chemical modifications of the remaining lignin polymer, such as demethoxylation and dearomatization, occurred during biodegradation. The polysaccharide components of pine lignocellulose and purified cellulose were relatively rapidly mineralized to methane and carbon dioxide; 31 to 37% of the pine polysaccharides and 56 to 63% of the purified cellulose were recovered as labeled gaseous end products. An additional 10 to 20% of the polysaccharide substrates was recovered as dissolved degradation products. Overall, these results indicate that elevated temperatures can greatly enhance rates of anaerobic degradation of lignin and lignified substrates to methane and low-molecular-weight aromatic compounds. PMID:16346924

  9. Diagenetic overprinting of the sphaerosiderite palaeoclimate proxy: are records of pedogenic groundwater δ18O values preserved?

    USGS Publications Warehouse

    Ufnar, David F.; Gonzalez, Luis A.; Ludvigson, Greg A.; Brenner, Richard L.; Witzkes, Brian J.

    2004-01-01

    Meteoric sphaerosiderite lines (MSLs), defined by invariant ??18O and variable ??13C values, are obtained from ancient wetland palaeosol sphaerosiderites (millimetre-scale FeCO3 nodules), and are a stable isotope proxy record of terrestrial meteoric isotopic compositions. The palaeoclimatic utility of sphaerosiderite has been well tested; however, diagenetically altered horizons that do not yield simple MSLs have been encountered. Well-preserved sphaerosiderites typically exhibit smooth exteriors, spherulitic crystalline microstructures and relatively pure (> 95 mol% FeCO3) compositions. Diagenetically altered sphaerosiderites typically exhibit corroded margins, replacement textures and increased crystal lattice substitution of Ca2+, Mg2+ and Mn2+ for Fe2+. Examples of diagenetically altered Cretaceous sphaerosiderite-bearing palaeosols from the Dakota Formation (Kansas), the Swan River Formation (Saskatchewan) and the Success S2 Formation (Saskatchewan) were examined in this study to determine the extent to which original, early diagenetic ??18O and ??13C values are preserved. All three units contain poikilotopic calcite cements with significantly different ??18O and ??13C values from the co-occurring sphaerosiderites. The complete isolation of all carbonate phases is necessary to ensure that inadvertent physical mixing does not affect the isotopic analyses. The Dakota and Swan River samples ultimately yield distinct MSLs for the sphaerosiderites, and MCLs (meteoric calcite lines) for the calcite cements. The Success S2 sample yields a covariant ??18O vs. ??13C trend resulting from precipitation in pore fluids that were mixtures between meteoric and modified marine phreatic waters. The calcite cements in the Success S2 Formation yield meteoric ??18O and ??13C values. A stable isotope mass balance model was used to produce hyperbolic fluid mixing trends between meteoric and modified marine end-member compositions. Modelled hyperbolic fluid mixing curves for the

  10. Global-mean marine δ13C and its uncertainty in a glacial state estimate

    NASA Astrophysics Data System (ADS)

    Gebbie, Geoffrey; Peterson, Carlye D.; Lisiecki, Lorraine E.; Spero, Howard J.

    2015-10-01

    A paleo-data compilation with 492 δ13C and δ18O observations provides the opportunity to better sample the Last Glacial Maximum (LGM) and infer its global properties, such as the mean δ13C of dissolved inorganic carbon. Here, the paleo-compilation is used to reconstruct a steady-state water-mass distribution for the LGM, that in turn is used to map the data onto a 3D global grid. A global-mean marine δ13C value and a self-consistent uncertainty estimate are derived using the framework of state estimation (i.e., combining a numerical model and observations). The LGM global-mean δ13C is estimated to be 0.14‰ ± 0.20‰ at the two standard error level, giving a glacial-to-modern change of 0.32‰ ± 0.20‰. The magnitude of the error bar is attributed to the uncertain glacial ocean circulation and the lack of observational constraints in the Pacific, Indian, and Southern Oceans. To halve the error bar, roughly four times more observations are needed, although strategic sampling may reduce this number. If dynamical constraints can be used to better characterize the LGM circulation, the error bar can also be reduced to 0.05 to 0.1‰, emphasizing that knowledge of the circulation is vital to accurately map δ13C in three dimensions.

  11. In Vivo13C Spectroscopy in the Rat Brain using Hyperpolarized [1-13C]pyruvate and [2-13C]pyruvate

    PubMed Central

    Marjańska, Małgorzata; Iltis, Isabelle; Shestov, Alexander A.; Deelchand, Dinesh K.; Nelson, Christopher; Uğurbil, Kâmil; Henry, Pierre-Gilles

    2010-01-01

    The low sensitivity of 13C spectroscopy can be enhanced using dynamic nuclear polarization. Detection of hyperpolarized [1-13C]pyruvate and its metabolic products has been reported in kidney, liver, and muscle. In this work, the feasibility of measuring 13C signals of hyperpolarized 13C metabolic products in the rat brain in vivo following the injection of hyperpolarized [1-13C]pyruvate and [2-13C]pyruvate is investigated. Injection of [2-13C]pyruvate led to the detection of [2-13C]lactate, but no other downstream metabolites such as TCA cycle intermediates were detected. Injection of [1-13C]pyruvate enabled the detection of both [1-13C]lactate and [13C]bicarbonate. A metabolic model was used to fit the hyperpolarized 13C time courses obtained during infusion of [1-13C]pyruvate and to determine the values of VPDH and VLDH. PMID:20685141

  12. Late Holocene monsoon climate of northeastern Taiwan inferred from elemental (C, N) and isotopic (δ13C, δ15N) data in lake sediments

    NASA Astrophysics Data System (ADS)

    Selvaraj, Kandasamy; Wei, Kuo-Yen; Liu, Kon-Kee; Kao, Shuh-Ji

    2012-03-01

    Little information exists about centennial-scale climate variability on oceanic islands in the western Pacific where the East Asian monsoon (EAM) strongly influences the climate, mountain ecosystem and the society. In this study, we investigate a 168 cm long sediment core recovered from Emerald Peak Lake in subalpine NE Taiwan for the contents of grain size, total organic carbon (TOC), C/N ratio, and stable isotopes (δ13C and δ15N) to reconstruct the monsoon climate and vegetation density during the late Holocene. Six radiocarbon (14C) ages obtained on plant remains used for the chronology indicate that the sediment core has been accumulated since ˜3770 cal BP with a mean sedimentation rate of 44.6 cm/ka. The sub-centennial resolution of our proxy records reveals strong fluctuations of the EAM and vegetation density for the past ˜3770 cal BP. The greater contents of coarse and medium sediments with overall decreasing trends from 3770 to 2000 cal BP suggest an increasing fine sediment influx from the catchment likely due to an increasing lake water level. Although low TOC content, C/N ratio, and enriched δ13C values in bulk and fine sediments during this interval suggest a sparsely vegetated catchment, increasing trends of TOC content and C/N ratio together with decreasing trends of δ13C and δ15N values indicate a strengthening pattern of summer monsoon. This is in contrast to a decreasing monsoon strength inferred from Dongge Cave δ18O record at that time, supporting the idea of anti-phasing of summer EAM and Indian summer monsoon. Since 2000 cal BP, higher content of fine sediments with high TOC content and C/N ratio but relatively depleted δ13C and low δ15N values suggest a high but stable lake water level and dense C3 plants, consistent with a stronger summer monsoon in a wet climate. Within this general trend, we interpret a prominent change of proxy parameters in sediments from ˜560 to 150 cal BP, as subtropical evidence for the Little Ice Age in NE

  13. 14C Analysis via Intracavity Optogalvanic Spectroscopy

    PubMed Central

    Murnick, Daniel; Dogru, Ozgur; Ilkmen, Erhan

    2010-01-01

    A new ultra sensitive laser-based analytical technique, intracavity optogalvanic spectroscopy (ICOGS), allowing extremely high sensitivity for detection of 14C-labeled carbon dioxide has recently been demonstrated. Capable of replacing accelerator mass spectrometers (AMS) for many applications, the technique quantifies zeptomoles of 14C in sub micromole CO2 samples. Based on the specificity of narrow laser resonances coupled with the sensitivity provided by standing waves in an optical cavity, and detection via impedance variations, limits of detection near 10−15 14C/12C ratios have been obtained with theoretical limits much lower. Using a 15 W 14CO2 laser, a linear calibration with samples from 5 × 10−15 to >1.5 × 10−12 in 14C/12C ratios, as determined by AMS, was demonstrated. Calibration becomes non linear over larger concentration ranges due to interactions between CO2 and buffer gas, laser saturation effects and changes in equilibration time constants. The instrument is small (table top), low maintenance and can be coupled to GC or LC input. The method can also be applied to detection of other trace entities. Possible applications include microdosing studies in drug development, individualized sub therapeutic tests of drug metabolism, carbon dating and real time monitoring of atmospheric radiocarbon. PMID:20448803

  14. Isotopomer studies of gluconeogenesis and the Krebs cycle with 13C-labeled lactate.

    PubMed

    Katz, J; Wals, P; Lee, W N

    1993-12-05

    Fasted rats were intragastrically infused with either [2,3-13C]lactate or [1,2,3-13C]lactate. The infusate also contained 14C-labeled lactate and [3-3H]glucose. Glucose, alanine, glutamate, and glutamine were isolated from liver and blood. There was near complete equilibration of lactate and alanine, and the relative specific activities and relative enrichments were the same in blood and liver. Glucose was cleaved enzymatically to lactate. The compounds were examined by gas chromatography-mass spectroscopy. From the mass isotopomer spectra of the lactate, glutamate, and glutamine and their cleavage fragments the positional isotopomer composition of these compounds was obtained. The enrichment and isotopomer pattern in the lactate from cleaved glucose represents that in phosphoenolpyruvate (PEP). When [1,2,3-13C]lactate was infused the mass isotopomer spectrum of glutamates consisted only of compounds containing either one, two, or three 13C carbons per molecule (m1, m2, and m3). There was little 13C in C-4 and C-5 of glutamate. The rate of pyruvate decarboxylation is low, and 3-4% of the acetyl-CoA flux in the Krebs cycle is contributed by lactate carbon. The major isotopomers in lactate, alanine, and PEP were m3 and m2 with 13C in C-2 and C-3. The predominant isotopomer in PEP from [2,3-13C]lactate was m2 with 13C in C-2 and C-3. There was much more of m1 isotopomer with 13C in C-3 and C-2 than the m1 isotopomer with 13C in C-1. There was very little m3, the isotopomer with 13C in all three carbons. Most of the 13C in C-3 and C-4 of glucose and C-1 of glutamate was introduced via 13CO2 fixation. From the isotopomer distribution and the rate of glucose turnover we deduced, applying the analysis described in the "Appendix," the absolute rates of gluconeogenic pathways, recycling of PEP and the Cori cycle, and flux in the Krebs cycle. The flux from oxaloacetate (OAA)-->PEP was seven times that of OAA-->citrate, and about half of PEP was recycled to pyruvate via

  15. Optoacoustic 13C-breath test analyzer

    NASA Astrophysics Data System (ADS)

    Harde, Hermann; Helmrich, Günther; Wolff, Marcus

    2010-02-01

    The composition and concentration of exhaled volatile gases reflects the physical ability of a patient. Therefore, a breath analysis allows to recognize an infectious disease in an organ or even to identify a tumor. One of the most prominent breath tests is the 13C-urea-breath test, applied to ascertain the presence of the bacterium helicobacter pylori in the stomach wall as an indication of a gastric ulcer. In this contribution we present a new optical analyzer that employs a compact and simple set-up based on photoacoustic spectroscopy. It consists of two identical photoacoustic cells containing two breath samples, one taken before and one after capturing an isotope-marked substrate, where the most common isotope 12C is replaced to a large extent by 13C. The analyzer measures simultaneously the relative CO2 isotopologue concentrations in both samples by exciting the molecules on specially selected absorption lines with a semiconductor laser operating at a wavelength of 2.744 μm. For a reliable diagnosis changes of the 13CO2 concentration of 1% in the exhaled breath have to be detected at a concentration level of this isotope in the breath of about 500 ppm.

  16. Late Holocene hydroclimate change inferred from δ18O of lake sediments, Lost River Range, Idaho

    NASA Astrophysics Data System (ADS)

    Krueger, C. R.; Finney, B. P.; Shapley, M.

    2012-12-01

    High-resolution paleohydrological records are needed to assess the frequency and magnitude of past droughts in Idaho and the northern Rocky Mountain region, but are scarce in this semi-arid region. Sediments from Lost Keys Pond (LKP) can be used to reconstruct hydroclimate. LKP is closed to surface outflow and is therefore sensitive to precipitation minus evaporation; surface water is enriched in δ18O compared to the local meteoric waters. In summer 2011 several sediment cores were collected from LKP using a square rod piston corer; the focus of this analysis is an 82-cm Bolivia core. This core contains thinly banded to laminated, authigenic carbonate mud, a recorder of lake δ18O at the time of deposition. This core was sampled for δ18O and /δ13C at 0.5 cm intervals, and the <20 um fraction was isolated to avoid any detrital carbonate. Based on the current age model, sampling at this interval records sub-decadal (5-10 year) hydroclimate variability. The δ18O signal recovered has 5‰ variability over the length of the record, including several major fluctuations in last 1,000 years. During this period, several major dry and wet periods have been recorded occurring over multidecadal timescales, with a trend toward increasing aridity. The δ18O and δ13C records in the lowest decimeter are divergent and mirror each other, above this interval isotopic records have strong covariance. This pattern may be indicative of a change from surface outflow to no surface outflow conditions. The age model is being refined to better assess how this record correlates with other regional records, and ultimately improve our understanding of past atmospheric circulation.

  17. Using 16O/18O to Determine the Evolutionary History of the R Coronae Borealis Stars

    NASA Astrophysics Data System (ADS)

    Clayton, Geoffrey; Geballe, Tom; Welch, Douglas; Tisserand, Patrick

    2014-08-01

    All of the Galactic hydrogen-deficient carbon (HdC) and R Coronae Borealis (RCB) stars for which oxygen isotopic ratios can be measured, show 16O/18O < 5, values that are orders of magnitude lower than measured in other stars (the Solar value is 500). This suggests that most if not all HdC and RCB stars are highly enriched in 18O. This is an important clue to determining the evolutionary pathways of HdC and RCB stars, for which two models have been proposed: the double degenerate (white dwarf (WD) merger), and the final helium-shell flash (FF). No overproduction of 18O is expected in the FF scenario. However, some RCB stars also show characteristics, such as 13C and Lithium, seen in FF stars. Therefore, we are conducting a survey of all the RCB stars in the LMC and SMC for the characteristics of a WD merger or a FF. Most of the stars have been surveyed for 13C already, and we are also planning to survey them for Lithium. But no RCB star in the Magellanic Clouds has been observed for 18O. The Magellanic Clouds provide an unbiased, relatively complete sample of RCB stars which are at a known distance so their bolometric luminosities can be used in our stellar evolution models. This proposal is to use Gemini/Flamingos-2 to survey all of the Magellanic Cloud stars, which are cool enough to show CO bands, for the presence of 18O near 2.3 micron. This survey, combined with our stellar evolution models, will reveal the true fraction of RCB stars formed by each of the proposed scenarios.

  18. Metabolism of (14)C-octamethylcyclotetrasiloxane ([(14)C]D4) or (14)C-decamethylcyclopentasiloxane ([(14)C]D5) orally gavaged in rainbow trout (Oncorhynchus mykiss).

    PubMed

    Domoradzki, Jeanne Y; Sushynski, Jacob M; Thackery, Lisa M; Springer, Timothy A; Ross, Timothy L; Woodburn, Kent B; Durham, Jeremy A; McNett, Debra A

    2017-04-21

    Critical factors (uptake, distribution, metabolism and elimination) for understanding the bioaccumulation/biomagnification potential of Octamethylcyclotetrasiloxane (D4) and Decamethylcyclopentasiloxane (D5) siloxanes in fish were investigated to address whether these chemicals meet the "B" criteria of the Persistent, Bioaccumulative, and Toxic (PBT) classification. A metabolism study was conducted in rainbow trout whereby a 15mg [(14)C]D4/kg bw or [(14)C]D5/kg bw as a single bolus oral dose was administered via gavage. Of the administered dose, 79% (D4) and 78% (D5) was recovered by the end of the study (96-h). Eighty-two percent and 25% of the recovered dose was absorbed based on the percentage of recovered dose in carcass (69% and 17%), tissues, bile and blood (12% and 8%) and urine (1%) for D4 and D5, respectively. A significant portion of the recovered dose (i.e. 18% for D4 and 75% for D5) was eliminated in feces. Maximum blood concentrations were 1.6 and 1.4μg D4 or D5/g blood at 24h post-dosing, with elimination half-lives of 39h (D4) and 70h (D5). Modeling of parent and metabolite blood concentrations resulted in estimated metabolism rate constants (km(blood)) of 0.15 (D4) and 0.17day(-1)(D5). Metabolites in tissues, bile, blood, and urine totaled a minimum of 2% (D4) and 14% (D5) of the absorbed dose. The highest concentration of (14)C-activity in the fish following D4 administration was in mesenteric fat followed by bile, but the opposite was true for D5. Metabolites were not detected in fat, only parent chemical. In bile, 94% (D4) and 99% (D5) of the (14)C-activity was due to metabolites. Metabolites were also detected in the digestive tract, liver and gonads. Approximately 40% of the (14)C-activity detected in the liver was due to the presence of metabolites. Urinary elimination represented a minor pathway, but all the (14)C-activity in the urine was associated with metabolites. Clearance may occur via enterohepatic circulation of metabolic products in

  19. Estimating past leaf-to-air vapour pressure deficit from terrestrial plant 13C

    NASA Astrophysics Data System (ADS)

    Turney, Chris S. M.; Barringer, James; Hunt, John E.; McGlone, Matt S.

    1999-08-01

    13C was determined in lignin extracted from present-day cladodes of Phyllocladus alpinus (a small coniferous tree) from seven well-lit sites across New Zealand. The 13C values ranged from -30.9 to -23.6 and were compared with monthly means of temperature, precipitation, relative humidity and vapour pressure deficit from the nearest recording stations. Of these parameters, the leaf-to-air vapour pressure deficit of the first month of cladode growth and expansion proved to be the most significantly correlated with lignin 13C, over a range of 0.3 to 0.8 kPa, confirming the importance of atmospheric moisture content on stomatal conductance. The carbon isotopic signature of lignin from fossilised cladodes preserved under the Kawakawa Tephra (22.6 k 14C yr BP) on the North Island is identical to that of the whole tissue, suggesting that for this species at least, fossil material can be used to approximate the lignin 13C. The 13C of species- and organ-specific fossil terrestrial plant material therefore provides an excellent method to quantify past changes in leaf-to-air vapour pressure deficit.

  20. 14C analysis via intracavity optogalvanic spectroscopy

    NASA Astrophysics Data System (ADS)

    Murnick, Daniel; Dogru, Ozgur; Ilkmen, Erhan

    2010-04-01

    A new ultra sensitive laser-based analytical technique, intracavity optogalvanic spectroscopy (ICOGS), allowing extremely high sensitivity for detection of 14C-labeled carbon dioxide has recently been demonstrated. Capable of replacing accelerator mass spectrometers (AMS) for many applications, the technique quantifies zeptomoles of 14C in sub micromole CO 2 samples. Based on the specificity of narrow laser resonances coupled with the sensitivity provided by standing waves in an optical cavity, and detection via impedance variations, limits of detection near 10 -1514C/ 12C ratios have been obtained with theoretical limits much lower. Using a 15 W 14CO 2 laser, a linear calibration with samples from 5 × 10 -15 to >1.5 × 10 -12 in 14C/ 12C ratios, as determined by AMS, was demonstrated. Calibration becomes non-linear over larger concentration ranges due to interactions between CO 2 and buffer gas, laser saturation effects and changes in equilibration time constants. The instrument is small (table top), low maintenance and can be coupled to GC or LC input. The method can also be applied to detection of other trace entities. Possible applications include microdosing studies in drug development, individualized sub-therapeutic tests of drug metabolism, carbon dating and real time monitoring of atmospheric radiocarbon.

  1. An improved 13C-tracer method for the study of lignin structure and reactions : differential 13C-NMR

    Treesearch

    Noritsugu Terashima; Dmitry Evtuguin; Carlos Pascoal Neto; Jim Parkas; Magnus Paulsson; Ulla Westermark; Sally Ralph; John Ralph

    2003-01-01

    The technique of selective 13C-enrichment of specific carbons in lignin combined with 13C-NMR differential spectrometry between spectra of 13C-enriched and unenriched lignins (Ä13C-NMR) provides definitive information on the structure of the lignin macromolecule. Improvements were made on, (1) specific 13C-enrichment of almost all carbons involved in inter-unit bonds...

  2. Towards hyperpolarized 13C-succinate imaging of brain cancer

    NASA Astrophysics Data System (ADS)

    Bhattacharya, Pratip; Chekmenev, Eduard Y.; Perman, William H.; Harris, Kent C.; Lin, Alexander P.; Norton, Valerie A.; Tan, Chou T.; Ross, Brian D.; Weitekamp, Daniel P.

    2007-05-01

    We describe a novel 13C enriched precursor molecule, sodium 1- 13C acetylenedicarboxylate, which after hydrogenation by PASADENA (Parahydrogen and Synthesis Allows Dramatically Enhanced Nuclear Alignment) under controlled experimental conditions, becomes hyperpolarized 13C sodium succinate. Fast in vivo 3D FIESTA MR imaging demonstrated that, following carotid arterial injection, the hyperpolarized 13C-succinate appeared in the head and cerebral circulation of normal and tumor-bearing rats. At this time, no in vivo hyperpolarized signal has been localized to normal brain or brain tumor. On the other hand, ex vivo samples of brain harvested from rats bearing a 9L brain tumor, 1 h or more following in vivo carotid injection of hyperpolarized 13C sodium succinate, contained significant concentrations of the injected substrate, 13C sodium succinate, together with 13C maleate and succinate metabolites 1- 13C-glutamate, 5- 13C-glutamate, 1- 13C-glutamine and 5- 13C-glutamine. The 13C substrates and products were below the limits of NMR detection in ex vivo samples of normal brain consistent with an intact blood-brain barrier. These ex vivo results indicate that hyperpolarized 13C sodium succinate may become a useful tool for rapid in vivo identification of brain tumors, providing novel biomarkers in 13C MR spectral-spatial images.

  3. Towards hyperpolarized 13C-succinate imaging of brain cancer

    PubMed Central

    Bhattacharya, Pratip; Chekmenev, Eduard Y.; Perman, William H.; Harris, Kent C.; Lin, Alexander P.; Norton, Valerie A.; Tan, Chou T.; Ross, Brian D.; Weitekamp, Daniel P.

    2009-01-01

    We describe a novel 13C enriched precursor molecule, sodium 1-13C acetylenedicarboxylate, which after hydrogenation by PASADE-NA (Parahydrogen and Synthesis Allows Dramatically Enhanced Nuclear Alignment) under controlled experimental conditions, becomes hyperpolarized 13C sodium succinate. Fast in vivo 3D FIESTA MR imaging demonstrated that, following carotid arterial injection, the hyperpolarized 13C-succinate appeared in the head and cerebral circulation of normal and tumor-bearing rats. At this time, no in vivo hyperpolarized signal has been localized to normal brain or brain tumor. On the other hand, ex vivo samples of brain harvested from rats bearing a 9L brain tumor, 1 h or more following in vivo carotid injection of hyperpolarized 13C sodium succinate, contained significant concentrations of the injected substrate, 13C sodium succinate, together with 13C maleate and succinate metabolites 1-13C-glutamate, 5-13C-glutamate, 1-13C-glutamine and 5-13C-glutamine. The 13C substrates and products were below the limits of NMR detection in ex vivo samples of normal brain consistent with an intact blood–brain barrier. These ex vivo results indicate that hyperpolarized 13C sodium succinate may become a useful tool for rapid in vivo identification of brain tumors, providing novel biomarkers in 13C MR spectral-spatial images. PMID:17303454

  4. In vivo dynamic turnover of cerebral 13C isotopomers from [U- 13C]glucose

    NASA Astrophysics Data System (ADS)

    Xu, Su; Shen, Jun

    2006-10-01

    An INEPT-based 13C MRS method and a cost-effective and widely available 11.7 Tesla 89-mm bore vertical magnet were used to detect dynamic 13C isotopomer turnover from intravenously infused [U- 13C]glucose in a 211 μL voxel located in the adult rat brain. The INEPT-based 1H → 13C polarization transfer method is mostly adiabatic and therefore minimizes signal loss due to B 1 inhomogeneity of the surface coils used. High quality and reproducible data were acquired as a result of combined use of outer volume suppression, ISIS, and the single-shot three-dimensional localization scheme built in the INEPT pulse sequence. Isotopomer patterns of both glutamate C4 at 34.00 ppm and glutamine C4 at 31.38 ppm are dominated first by a doublet originated from labeling at C4 and C5 but not at C3 (with 1JC4C5 = 51 Hz) and then by a quartet originated from labeling at C3, C4, and C5 (with 1JC3C4 = 35 Hz). A lag in the transition of glutamine C4 pattern from doublet-dominance to quartet dominance as compared to glutamate C4 was observed, which provides an independent verification of the precursor-product relationship between neuronal glutamate and glial glutamine and a significant intercompartmental cerebral glutamate-glutamine cycle between neurons and glial cells.

  5. Calculation of total meal d13C from individual food d13C.

    USDA-ARS?s Scientific Manuscript database

    Variations in the isotopic signature of carbon in biological samples can be used to distinguish dietary patterns and monitor shifts in metabolism. But for these variations to have meaning, the isotopic signature of the diet must be known. We sought to determine if knowledge of the 13C isotopic abund...

  6. Measurements of 18O18O and 17O18O in the atmosphere and the role of isotope-exchange reactions

    NASA Astrophysics Data System (ADS)

    Yeung, Laurence Y.; Young, Edward D.; Schauble, Edwin A.

    2012-09-01

    Of the six stable isotopic variants of O2, only three are measured routinely. Observations of natural variations in 16O18O/16O16O and 16O17O/16O16O ratios have led to insights in atmospheric, oceanographic, and paleoclimate research. Complementary measurements of the exceedingly rare 18O18O and 17O18O isotopic variants might therefore broaden our understanding of oxygen cycling. Here we describe a method to measure natural variations in these multiply substituted isotopologues of O2. Its accuracy is demonstrated by measuring isotopic effects for Knudsen diffusion and O2 electrolysis in the laboratory that are consistent with theoretical predictions. We then report the first measurements of 18O18O and 17O18O proportions relative to the stochastic distribution of isotopes (i.e., Δ36 and Δ35 values, respectively) in tropospheric air. Measured enrichments in 18O18O and 17O18O yield Δ36 = 2.05 ± 0.24‰ and Δ35 = 1.4 ± 0.5‰ (2σ). Based on the results of our electrolysis experiment, we suggest that autocatalytic O(3P) + O2 isotope exchange reactions play an important role in regulating the distribution of 18O18O and 17O18O in air. We constructed a box model of the atmosphere and biosphere that includes the effects of these isotope exchange reactions, and we find that the biosphere exerts only a minor influence on atmospheric Δ36 and Δ35 values. O(3P) + O2 isotope exchange in the stratosphere and troposphere is therefore expected to govern atmospheric Δ36 and Δ35 values on decadal timescales. These results suggest that the `clumped' isotopic composition of atmospheric O2in ice core records is sensitive to past variations in atmospheric dynamics and free-radical chemistry.

  7. Determination of the δ13C of dissolved inorganic carbon in water; RSIL lab code 1710

    USGS Publications Warehouse

    Singleton, Glenda L.; Revesz, Kinga; Coplen, Tyler B.

    2012-01-01

    The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 1710 is to present a method to determine the δ13C of dissolved inorganic carbon (DIC) of water. The DIC of water is precipitated using ammoniacal strontium chloride (SrCl2) solution to form strontium carbonate (SrCO3). The δ13C is analyzed by reacting SrCO3 with 100-percent phosphoric acid (H3PO4) to liberate carbon quantitatively as carbon dioxide (CO2), which is collected, purified by vacuum sublimation, and analyzed by dual inlet isotope-ratio mass spectrometry (DI-IRMS). The DI-IRMS is a DuPont double-focusing mass spectrometer. One ion beam passes through a slit in a forward collector and is collected in the rear collector. The other measurable ion beams are collected in the front collector. By changing the ion-accelerating voltage under computer control, the instrument is capable of measuring mass/charge (m/z) 45 or 46 in the rear collector and m/z 44 and 46 or 44 and 45, respectively, in the front collector. The ion beams from these m/z values are as follows: m/z 44 = CO2 = 12C16O16O, m/z 45 = CO2 = 13C16O16O primarily, and m/z 46 = CO2 = 12C16O18O primarily. The data acquisition and control software calculates δ13C values.

  8. Deglacial 14C plateau suites recalibrated by Suigetsu atmospheric 14C record - Revised 14C reservoir ages from three ocean basins corroborate extreme surface water variations

    NASA Astrophysics Data System (ADS)

    Sarnthein, M.; Balmer, S.; Grootes, P. M.

    2013-12-01

    Radiocarbon (14C) reservoir/ventilation ages (Δ14C) provide unique insights into the dynamics of ocean water masses over LGM and deglacial times. The 14C plateau-tuning technique enables us to derive both an absolute chronology for marine sediment records and a high-resolution record of changing Δ14C values for deglacial surface and deep waters (Sarnthein et al., 2007; AGU Monogr. 173, 175). We designate as 14C plateau a sediment section in the age-depth profile with several almost constant planktic 14C ages - variation less than ×100 to ×300 yr - which form a plateau-shaped scatter band that extends over ~5 to 50 and up to 200 cm in sediment cores with sedimentation rates of >10 cm/ky. Previously, a suite of >15 plateau boundary ages were calibrated to a joint reference record of U/Th-dated 14C time series measured on coral samples, the Cariaco sediment record, and speleothems (Fairbanks et al., 2005, QSR 24; Hughen et al., 2006, QSR 25; Beck et al., 2001, Science 292). We now used the varve-counted atmospheric 14C record of Lake Suigetsu (Ramsey et al., 2012, Science 338, 370) to recalibrate the boundary ages and average ages of 14C plateaus and apply the amended plateau-tuning technique to a dozen Δ14C records from the Atlantic and Indo-Pacific. Main results are: (1) The Suigetsu atmospheric 14C record reflects all 14C plateaus, their internal structures and relative length previously identified, but implies a rise in the average plateau age by <200 14C yr during the LGM, >700 yr at its end, and <200 yr in the Bølling-Allerød. (2) Based on different 14C ages of coeval atmospheric and planktic 14C plateaus surface water Δ14C may have temporarily dropped to an equivalent of 200 yr in low-latitude stratified waters, such as off northwestern South America, and in turn reached values corresponding to an age difference of >2500 14C yr in stratified subpolar regions and upwelled waters such as in the South China Sea, values that differ significantly from a

  9. ( sup 14 C)urea breath test for diagnosis of Helicobacter pylori

    SciTech Connect

    Ormand, J.E.; Talley, N.J.; Carpenter, H.A.; Shorter, R.G.; Conley, C.R.; Wilson, W.R.; DiMagno, E.P.; Zinsmeister, A.R.; Phillips, S.F. )

    1990-07-01

    H. pylori is a potent urease producer, a characteristic that has been exploited in the development of the (14C)- and (13C)urea breath tests. The prevalence of H. pylori infection also is known to increase with advancing age; however, the individual patient's age has not routinely been considered when interpreting urea breath test results. The aim of this study was to validate a short, age-adjusted (14C)urea breath test for use in diagnosing H. pylori infections. Forty-one subjects (28 volunteers, 13 patients) underwent esophagogastroduodenoscopy with biopsies. Subjects were defined as being H. pylori-positive if histology or culture was positive. In addition, all subjects completed a 120-min (14C)urea breath test. A logistic regression analysis adjusting for age was used to estimate the probability of H. pylori positivity as a function of the 14C values generated. Sixteen subjects were H. pylori-positive, and 25 were H. pylori-negative. The 14C values generated between 15 and 80 min were found to be equally predictive in identifying H. pylori-positive subjects. Advancing age was associated with a higher probability of H. pylori-positivity. By taking advantage of the statistical probabilities, older patients could be accurately diagnosed with H. pylori at lower 14C values. We found that (14C)urea breath test to be both a sensitive and specific test that can be abbreviated to a 30-min examination (total test time). Moreover, our mathematical model indicates that a patient's age should be considered in order to optimize interpretation of the (14C)urea breath test, although further observations are needed to confirm this model.

  10. Constraining carbon sources and growth rates of freshwater microbialites in Pavilion Lake using (14)C analysis.

    PubMed

    Brady, A L; Slater, G; Laval, B; Lim, D S

    2009-12-01

    This study determined the natural abundance isotopic compositions ((13)C, (14)C) of the primary carbon pools and microbial communities associated with modern freshwater microbialites located in Pavilion Lake, British Columbia, Canada. The Delta(14)C of dissolved inorganic carbon (DIC) was constant throughout the water column and consistent with a primarily atmospheric source. Observed depletions in DIC (14)C values compared with atmospheric CO(2) indicated effects due either to DIC residence time and/or inputs of (14)C-depleted groundwater. Mass balance comparisons of local and regional groundwater indicate that groundwater DIC could contribute a maximum of 9-13% of the DIC. (14)C analysis of microbial phospholipid fatty acids from microbialite communities had Delta(14)C values comparable with lake water DIC, demonstrating that lake water DIC was their primary carbon source. Microbialite carbonate was also primarily derived from DIC. However, some depletion in microbialite carbonate (14)C relative to lake water DIC occurred, due either to residence time or mixing with a (14)C-depleted carbon source. A detrital branch covered with microbialite growth was used to estimate a microbialite growth rate of 0.05 mm year(-1) for the past 1000 years, faster than previous estimates for this system. These results demonstrate that the microbialites are actively growing and that the primary carbon source for both microbial communities and recent carbonate is DIC originating from the atmosphere. While these data cannot conclusively differentiate between abiotic and biotic formation mechanisms, the evidence for minor inputs of groundwater-derived DIC is consistent with the previously hypothesized biological origin of the Pavilion Lake microbialites.

  11. Synthesis of 2H- and 13C-substituted dithanes

    DOEpatents

    Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.

    2003-01-01

    The present invention is directed to labeled compounds, [2-.sup.13 C]dithiane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to processes of preparing [2-.sup.13 C]dithiane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to labeled compounds, e.g., [.sup.2 H.sub.1-2, .sup.13 C]methanol (arylthio)-, acetates wherein the .sup.13 C atom is directly bonded to exactly one or two deuterium atoms.

  12. Synthesis Of 2h- And 13c-Substituted Dithanes

    DOEpatents

    Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.

    2004-05-04

    The present invention is directed to labeled compounds, [2-.sup.13 C]dithane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to processes of preparing [2-.sup.13 C]dithane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to labeled compounds, e.g., [.sup.2 H.sub.1-2, .sup.13 C]methanol (arylthio)-, acetates wherein the .sup.13 C atom is directly bonded to exactly one or two deuterium atoms.

  13. Intermediate water 14C evidence for the mechanism of deglacial CO2 increase

    NASA Astrophysics Data System (ADS)

    Marchitto, T. M.; Lehman, S. J.; Ortiz, J. D.; van Geen, A.

    2006-12-01

    Carbon sequestration in the ocean is widely considered to be the proximate cause of glacial CO2 lowering. The 14C activity of the atmosphere during the last glacial period appears to have been too high to be explained by increased cosmogenic production alone, implying that exchange of CO2 with the deep ocean must have been reduced. In other words, there must have been a relatively isolated deep ocean carbon reservoir. Likewise there was a sharp drop in atmospheric 14C activity coincident with the Termination I atmospheric CO2 increase, suggesting that the deep isolated reservoir, and therefore the carbon released from the ocean, was extremely depleted in 14C. Both the CO2 and 14C changes occurred in step with Antarctic warming, implicating the Southern Ocean as the main locus of carbon release. We therefore hypothesize that 14C-depleted waters should have spread to the intermediate/upper ocean via Antarctic Intermediate Water and Subantarctic Mode Water during the last deglaciation. We show that at ~700 m water depth off of southern Baja California, very 14C-depleted waters appeared in two stages during the last deglaciation, closely coincident with the atmospheric CO2 rise. The spectral reflectance record from our sediment core bears a remarkable resemblance to Greenland ice δ 18O, allowing us to assign calendar ages to our samples. Radiocarbon activity of paleo-waters is then calculated by age-correcting our benthic foraminiferal 14C measurements. During most of the 40,000 year record, intermediate water activity was ~100-200‰ lower than the atmosphere (like today), but during deglaciation this depletion increased to as much as 450‰. We suggest that this transient drop reflects the mixing of `old' carbon to the Southern Ocean surface, with spreading to the North Pacific via Antarctic Intermediate Water.

  14. Using 16O/18O to Determine the Evolutionary History of the R Coronae Borealis Stars

    NASA Astrophysics Data System (ADS)

    Clayton, Geoffrey; Geballe, Tom; Welch, Douglas; Tisserand, Patrick

    2013-08-01

    Of the Galactic hydrogen-deficient carbon (HdC) and R Coronae Borealis (RCB) stars for which oxygen isotopic ratios can be measured, all of them show 16O/18O < 5, values that are orders of magnitude lower than measured in other stars (the Solar value is 500). This suggests that most if not all HdC and RCB stars are highly enriched in 18O. This is an important clue in determining the evolutionary pathways of HdC and RCB stars, for which two models have been proposed: the double degenerate (white dwarf (WD) merger), and the final helium-shell flash (FF). No overproduction of 18O is expected in the FF scenario. However, some RCB stars also show characteristics, such as 13C and Lithium, seen in FF stars. Therefore, we are conducting a survey all the RCB stars in the LMC and SMC for the characteristics of a WD merger or a FF. Most of the stars have been surveyed for 13C already and we plan to survey them for Lithium in the future. This proposal is to use Gemini/Flamingos-2 to survey all the stars, which are cool enough to show CO bands, for the presence of 18O near 2.3 micron. The Magellanic Clouds provide an unbiased, relatively complete sample of RCB stars which are at a known distance so their bolometric luminosities can be used in our stellar evolution models. This survey, combined with our models, will reveal the true fraction of RCB stars formed by each of the proposed scenarios.

  15. Searching for ^16^O^18^O.

    NASA Astrophysics Data System (ADS)

    Marechal, P.; Pagani, L.; Langer, W. D.; Castets, A.

    1997-02-01

    After our first tentative detection of the molecular oxygen ^16^O^18^O isotopomer obtained during the winter '92/93 (Pagani et al. 1993), we attempted to confirm our results by making a deep search in other sources and in other positions in L134N. We have not been able to confirm the original detection in any other place in L134N but we obtain good upper limits towards NGC 2264(IRS2), TMC2, OMC3 and L134N (4', -1') and (5.2', -1) which give an O_2_/CO ratio upper limit near 0.1 -- the lowest yet obtained toward galactic sources -- instead of 0.3-0.4 as predicted by gas phase chemical equilibrium models. As our sample consists of eight cold or lukewarm dark clouds, the low abundance of O_2_ with respect to CO seems to be a general characteristic of dark clouds.

  16. Accurate measurements of 13C-13C distances in uniformly 13C-labeled proteins using multi-dimensional four-oscillating field solid-state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Straasø, Lasse Arnt; Nielsen, Jakob Toudahl; Bjerring, Morten; Khaneja, Navin; Nielsen, Niels Chr.

    2014-09-01

    Application of sets of 13C-13C internuclear distance restraints constitutes a typical key element in determining the structure of peptides and proteins by magic-angle-spinning solid-state NMR spectroscopy. Accurate measurements of the structurally highly important 13C-13C distances in uniformly 13C-labeled peptides and proteins, however, pose a big challenge due to the problem of dipolar truncation. Here, we present novel two-dimensional (2D) solid-state NMR experiments capable of extracting distances between carbonyl (13C') and aliphatic (13Caliphatic) spins with high accuracy. The method is based on an improved version of the four-oscillating field (FOLD) technique [L. A. Straasø, M. Bjerring, N. Khaneja, and N. C. Nielsen, J. Chem. Phys. 130, 225103 (2009)] which circumvents the problem of dipolar truncation, thereby offering a base for accurate extraction of internuclear distances in many-spin systems. The ability to extract reliable accurate distances is demonstrated using one- and two-dimensional variants of the FOLD experiment on uniformly 13C,15N-labeled-L-isoleucine. In a more challenging biological application, FOLD 2D experiments are used to determine a large number of 13C'-13Caliphatic distances in amyloid fibrils formed by the SNNFGAILSS fibrillating core of the human islet amyloid polypeptide with uniform 13C,15N-labeling on the FGAIL fragment.

  17. Measurement of {alpha} and neutron decay widths of excited states of {sup 14}C

    SciTech Connect

    Haigh, P. J.; Ashwood, N. I.; Bloxham, T.; Curtis, N.; Freer, M.; McEwan, P.; Price, D.; Ziman, V.; Bohlen, H. G.; Kokalova, Tz.; Schulz, Ch.; Torabi, R.; Oertzen, W. von; Wheldon, C.; Catford, W.; Harlin, C.; Kalpakchieva, R.; Massey, T. N.

    2008-07-15

    The {sup 12}C({sup 16}O,{sup 14}O){sup 14}C reaction was studied at a beam energy of 234 MeV. The {sup 14}O ejectile was detected by a Q3D spectrometer at forward angles. The energies and angles of the excited {sup 14}C recoil break-up fragments were measured in coincidence with the {sup 14}O ejectile using a double sided silicon strip detector array at backward angles. A complete kinematic reconstruction of the reaction was performed to reconstruct the {sup 14}C*{yields}{sup 10}Be+{alpha} and {sup 14}C*{yields}{sup 13}C+n decay channels and the branching ratios and widths of these decays were calculated. Theoretical decay branches were calculated using barrier penetrability factors and were compared to the measured ratios to provide information on the spins, parities, and configurations of the states. Neutron emission was found to be favored for the 11.73, 12.96, 14.87, 16.72, and 18.6 MeV states. The 14.87, 18.6, and 21.4 MeV states were found to have a considerable width for {alpha}-decay and are candidates for the three bodied molecular cluster structure of {sup 14}C.

  18. C14-C15 single bond isomerizations of the retinal chromophore involved in the proton-pumping mechanism of bacteriorhodopsin

    SciTech Connect

    Smith, S.O.; Hornung, I.; van der Steen, R.; Pardoen, J.A.; Braiman, M.S.; Lugtenburg, J.; Mathies, R.A.

    1986-02-01

    Resonance Raman spectroscopy is used to examine the possibility that C14-C15 single bond isomerizations of the retinal prosthetic group are involved in the photochemical reactions of bacteriorhodopsin. Normal mode calculations show that the vibration that contains predominantly C14-C15 stretch character is approximately equal to 70 cm-1 lower in frequency in the 14-s-cis conformer than in the s-trans case. This geometric effect is insensitive to out-of-plane twists and should be observed in the sterically hindered 13-cis, 14-s-cis retinal protonated Schiff base, which has been proposed as the chromophore in the K and L intermediates of bacteriorhodopsin. Resonance Raman spectra were obtained of K625 by using the low temperature (77 K) spinning-cell technique. Isotopic substitutions with 13C and 2H show that significant C14-C15 stretch character is observed in normal modes at approximately equal to 1185-1195 cm-1. The relatively high frequency of the C14-C15 stretch argues that K625 contains a 13-cis, 14-s-trans chromophore. Similarly, isotopic derivatives show that L550 has a localized C14-C15 stretch at 1172 cm-1, consistent with a 14-s-trans chromophore. These results argue that the primary step in bacteriorhodopsin is a C13=C14 trans----cis photoisomerization that does not involve C14-C15 s-cis structures.

  19. Two-neutron stripping in ({sup 18}O, {sup 16}O) and (t,p) reactions

    SciTech Connect

    Cavallaro, M.; Agodi, A.; Carbone, D.; Cunsolo, A.; Bondì, M.; Cappuzzello, F.; Nicolosi, D.; Tropea, S.; Borello-Lewin, T.; Rodrigues, M. R. D.; De Napoli, M.; Garcia, V. N.

    2014-11-11

    The {sup 12}C({sup 18}O,{sup 16}O){sup 14}C reactions has been investigated at 84 MeV incident energy. The charged ejectiles produced in the reaction have been momentum analyzed and identified by the MAGNEX magnetic spectrometer. Q-value spectra have been extracted with an energy resolution of 160 keV (Full Width at Half Maximum) and several known bound and resonant states of {sup 14}C have been identified up to 15 MeV. In particular, excited states with dominant 2p - 4h configuration are the most populated. The absolute values of the cross sections have been extracted showing a striking similarity with those measured for the same transitions by (t,p) reactions. This indicates that the effect of the {sup 16}O core is negligible in the reaction mechanism.

  20. Design and operation of a continuous 13C and 15N labeling chamber for uniform or differential, metabolic and structural, plant tissue isotope labeling

    USDA-ARS?s Scientific Manuscript database

    Tracing heavy stable isotopes from plant material through the ecosystem provides the most sensitive information about ecosystem processes; from CO2 fluxes and soil organic matter formation to small-scale stable-isotope biomarker probing. Coupling multiple stable isotopes such as 13C with 15N, 18O o...

  1. 13C isotopic fractionation during biodegradation of agricultural wastes.

    PubMed

    Chalk, Phillip M; Inácio, Caio T; Urquiaga, Segundo; Chen, Deli

    2015-01-01

    Significant differences in δ(13)C signatures occur within and between plant tissues and their constituent biochemical entities, and also within and between heterotrophic bacteria and fungi and their metabolic products. Furthermore, (13)C isotopic fractionation occurs during the biodegradation of organic molecules as seen in the substrate, respired CO(2) and the microbial biomass, which could be related to substrate composition and/or microbial metabolism. The (13)C isotopic fractionation observed during the decomposition of a single defined C substrate appears to be due to the intra-molecular heterogeneity in (13)C in the substrate and to (13)C isotopic fractionation during microbial metabolism. Very limited data suggest that the latter may be quantitatively more important than the former. Studies with defined fungi in culture media have highlighted the complexities associated with the interpretation of the observed patterns of (13)C isotopic fractionation when a single defined C source is added to the culture medium which itself contains one or more C sources. Techniques involving (13)C enrichment or paired treatments involving an equivalent C(3)- and C(4)-derived substrate have been devised to overcome the problem of background C in the culture medium and (13)C isotopic fractionation during metabolism. Studies with complex substrates have shown an initial (13)C depletion phase in respired CO(2) followed by a (13)C enrichment phase which may or may not be followed by another (13)C depletion phase. Basic studies involving an integrated approach are required to gain a new insight into (13)C isotopic fractionation during organic residue decomposition, by simultaneous measurements of δ(13)C in all C moieties. New analytical tools to measure real-time changes in δ(13)CO(2) and the intra-molecular δ(13)C distribution within plant biochemical entities offer new opportunities for unravelling the complex interactions between substrate and microbial metabolism with

  2. Forensic applications of 14C at CIRCE

    NASA Astrophysics Data System (ADS)

    Marzaioli, F.; Fiumano, V.; Capano, M.; Passariello, I.; Cesare, N. De.; Terrasi, F.

    2011-12-01

    The decreasing trend of the radiocarbon pulse produced during the atmospheric tests of nuclear weapons (bomb-carbon) coupled with high sensitivity accelerator mass spectrometry (AMS) measurements, drastically increased the precision of radiocarbon age determinations since the second part of the sixties, allowing the application of radiocarbon AMS to a wide range of studies previously not directly involving conventional radiocarbon dating (i.e. food authenticity, forensic, biochemistry). In the framework of authenticity evaluation of artworks, high precision radiocarbon ( 14C) AMS measurements (Δ R/ R < 0.3%) reduce the conventional uncertainty of the dating to few decades, allowing precise age estimation of materials containing carbon (C). The Centre for Isotopic Research on Cultural and Environmental heritage (CIRCE) during its activity on AMS 14C dating achieved high precision measurements opening the opportunity to these kinds of applications. This paper presents the main results obtained from radiocarbon measurements on a set of bone samples analyzed for the determination of the post-mortem interval in the framework of an unsolved case investigated by the Rome prosecutor office. The chronological characterization of the wooden support of the "Acerenza portrait" is also presented with the aim to evaluate its age and to further investigate the possibility to attribute this artwork to Leonardo da Vinci. Bomb- 14C dating on the lipid and collagen fractions of bones allows the evaluation of the year of the death of the individuals by means of ad hoc calibration data sheet with the typical few years precision and difference between collagen apparent age and the year of death appeared in agreement with the age of one individual estimated by dating of tooth collagen. Conventional radiocarbon dating on both wood and wood extracted cellulose leads to an estimation of the portrait wood board age (2σ) of 1459-1524 AD (57% relative probability), 1571-1631 AD interval (42

  3. Carbon and 14C distribution in tropical and subtropical agricultural soils

    NASA Astrophysics Data System (ADS)

    Prastowo, Erwin; Grootes, Pieter; Nadeau, Marie

    2016-04-01

    Paddy soil management affects, through the alternating anoxic and oxic conditions it creates, the transport and stabilisation of soil organic matter (SOM). Irrigation water may percolate more organic materials - dissolved (DOM) and colloidal - into the subsoil during anoxic conditions. Yet a developed ploughpan tends to prevent C from going deeper in the subsoil and partly decouple C distribution in top and sub soil. We investigate the influence of different soil type and environment. We observed the C and 14C distribution in paddy and non-paddy soil profiles in three different soil types from four different climatic regions of tropical Indonesia, and subtropical China. Locations were Sukabumi (Andosol, ca. 850 m a.s.l), Bogor (clayey Alisol, ca. 240 m a.s.l), and Ngawi (Vertisol, ca. 70 m a.s.l) in Jawa, Indonesia, and Cixi (Alisol(sandy), ca. 4 - 6 m a.s.l) in Zhejiang Province, China. We compared rice paddies with selected neighbouring non-paddy fields and employed AMS 14C as a tool to study C dynamics from bulk, alkali soluble-humic, and insoluble humin samples, and macrofossils (plant remains, charcoal). Our data suggest that vegetation type determines the quantity and quality of biomass introduced as litter and root material in top and subsoil, and thus contributes to the soil C content and profile, which fits the 14C signal distribution, as well as 13C in Ngawi with C4 sugar cane as upland crop. 14C concentrations for the mobile humic acid fraction were generally higher than for bulk samples from the same depth, except when recent plant and root debris led to high 14C levels in near-surface samples. The difference in sampling, - averaged layer for bulk sample and 1-cm layer thickness for point sample - shows gradients in C and 14C across the layers, which could be a reason for discrepancies between the two. High 14C concentrations - in Andosol Sukabumi up to 111 pMC - exceed the atmospheric 14CO2concentration in the sampling year in 2012 (˜ 103 pMC) and

  4. To live or to die? Evidence of variable drivers of wood d13C reveal different responses to disturbance in co-occurring oaks

    NASA Astrophysics Data System (ADS)

    Reed, A. S.; Stephen, F. M.; Billings, S. A.

    2011-12-01

    A major oak decline event in recent decades in Northwest Arkansas permits insight into disturbance impacts on forests, which is important for understanding global carbon, nutrient and climate cycles given projections of increasing disturbance event frequency in the future. The decline event, associated with an increase in population of a native, wood-boring insect, followed a cycle of droughts and resulted in a mosaic of apparently healthy red oaks (Quercus rubra) neighboring severely declining trees of the same species. Tree-ring evidence suggests decreased growth rates following increases in the insect's population decades prior to visible external decline symptoms (i.e. decreased crown coverage, mortality), but only in trees destined to die during the insect outbreak. Reasons why some trees experienced mortality and some remained healthy are unclear. Through analysis of stable isotopes of carbon (δ13C) and oxygen (δ18O) in wood and leaf δ13C and nitrogen among co-occurring trees, we can infer differential responses of red oaks to disturbance and associated resilience to mortality. Tree-ring a-cellulose δ13C varied from -27.3to -23.0%, and δ18O values varied from 27.5 to 31.8%. Neither δ13C nor δ18O exhibited signficant differences between healthy and declining trees. However, declining trees exhibited a significant, positive relationship between δ13C and δ18O (p <0.05, r2=0.15) prior to peak insect infestation. In contrast, apparently healthy individuals did not exhibit a significant relationship between these parameters, but exhibited significant, positive relationships between current year leaf δ13C and nitrogen content (p<0.05, r2=0.77). These results suggest that healthy and declining trees had different strategies for coping with insect infestation. Correlation between tree-ring δ13C and δ18O in dying trees suggests that trees destined to die during the infestation regulated their δ13C values primarily via stomatal conductance, a mechanism that

  5. Diachronous benthic δ18O responses during late Pleistocene terminations

    NASA Astrophysics Data System (ADS)

    Lisiecki, Lorraine E.; Raymo, Maureen E.

    2009-09-01

    Benthic δ18O is often used as a stratigraphic tool to place marine records on a common age model and as a proxy for the timing of ice volume/sea level change. However, Skinner and Shackleton (2005) found that the timing of benthic δ18O change at the last termination differed by 3900 years between one Atlantic site and one Pacific site. These results suggest that benthic δ18O change may not always accurately record the timing of deglaciation. We compare benthic δ18O records from 20 Atlantic sites and 14 Pacific sites to evaluate systematic differences in the timing of terminations in benthic δ18O. Analysis of sedimentation rates derived from the alignment of benthic δ18O suggests a statistically significant Atlantic lead over Pacific benthic δ18O change during the last six terminations. We estimate an average Pacific benthic δ18O lag of 1600 years for Terminations 1-5, slightly larger than the delay expected from ocean mixing rates given that most glacial meltwater probably enters the North Atlantic. We additionally find evidence of ˜4000-year Pacific δ18O lags at approximately 128 ka and 330 ka, suggesting that stratigraphic correlation of δ18O has the potential to generate age model errors of several thousand years during terminations. A simple model demonstrates that these lags can be generated by diachronous temperature changes and do not require slower circulation rates. Most importantly, diachronous benthic δ18O responses must be taken into account when comparing Atlantic and Pacific benthic δ18O records or when using benthic δ18O records as a proxy for the timing of ice volume change.

  6. 17 CFR 240.14c-101 - Schedule 14C. Information required in information statement.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ...): No fee required Fee computed on table below per Exchange Act Rules 14c-5(g) and 0-11 (1) Title of... Act Rule 0-11 (set forth the amount on which the filing fee is calculated and state how it was... 0-11(a)(2) and identify the filing for which the offsetting fee was paid previously. Identify the...

  7. 17 CFR 240.14c-101 - Schedule 14C. Information required in information statement.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ...): No fee required Fee computed on table below per Exchange Act Rules 14c-5(g) and 0-11 (1) Title of... Act Rule 0-11 (set forth the amount on which the filing fee is calculated and state how it was... 0-11(a)(2) and identify the filing for which the offsetting fee was paid previously. Identify the...

  8. 17 CFR 240.14c-101 - Schedule 14C. Information required in information statement.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ...): No fee required Fee computed on table below per Exchange Act Rules 14c-5(g) and 0-11 (1) Title of... Act Rule 0-11 (set forth the amount on which the filing fee is calculated and state how it was... 0-11(a)(2) and identify the filing for which the offsetting fee was paid previously. Identify the...

  9. 17 CFR 240.14c-101 - Schedule 14C. Information required in information statement.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ...): No fee required Fee computed on table below per Exchange Act Rules 14c-5(g) and 0-11 (1) Title of... Act Rule 0-11 (set forth the amount on which the filing fee is calculated and state how it was... 0-11(a)(2) and identify the filing for which the offsetting fee was paid previously. Identify the...

  10. 17 CFR 240.14c-101 - Schedule 14C. Information required in information statement.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... Exchange Act Rules 14c-5(g) and 0-11 (1) Title of each class of securities to which transaction applies: (2... transaction computed pursuant to Exchange Act Rule 0-11 (set forth the amount on which the filing fee is... as provided by Exchange Act Rule 0-11(a)(2) and identify the filing for which the offsetting fee was...

  11. Distribution of labeled products from (1-/sup 14/C), (U-/sup 14/C) and (16-/sup 14/C)-palmitate in isolated rat hepatocytes and liver mitochondria

    SciTech Connect

    Chatzidakis, C.; Otto, D.A.

    1986-05-01

    Fatty acids (FA) labeled in different carbon positions are used to study the distribution of labeled oxidation products. With rat hepatocytes (Hep) the authors observed significant differences in the distribution of label into products from (1-/sup 14/C) and (U-/sup 14/C)-palmitate (P). The total recovery of label in products (/sup 14/CO/sub 2/ + acid soluble fraction (ASF)) was identical between the two labeled FA. However, /sup 14/CO/sub 2/ production from (U-/sup 14/C)-P was only 40% of that from (1-/sup 14/C)-P. A recent report showed that approximately = 95% of succinate (Suc) utilized by Hep does not complete one full turn through the citric acid cycle. The authors observed that /sup 14/CO/sub 2/ evolution from (2,3-/sup 14/C)-Suc was approximately = 9% of that from (1,4-/sup 14/C)-Suc, indicating that the differences in label distribution between (1-/sup 14/C) and (U-/sup 14/C)-P are partially due to less /sup 14/CO/sub 2/ production from label in the even carbon positions of the FA with consequently more label remaining in the ASF. The /sup 14/CO/sub 2/ production from (16-/sup 14/C)-P was only 4% of that from (1-/sup 14/C)-P a value less than expected from the Suc experiments. Ketone bodies (KB) comprised 78% of total labeled products from (16-/sup 14/C)-P as compared to 28% from (1-/sup 14/C)-P and 41% from (U-/sup 14/C)-P, giving support to the previously reported preferential use of the omega-C/sub 2/ unit for KB synthesis without entry into the acetyl-CoA pool. Studies with isolated rat liver mitochondria gave results similar to those with Hep, indicating minimal involvement of perioxisomal ..beta..-oxidation.

  12. Synthesis Of [2h, 13c]M [2h2m 13c], And [2h3,, 13c] Methyl Aryl Sulfones And Sulfoxides

    DOEpatents

    Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.; Schmidt, Jurgen G.

    2004-07-20

    The present invention is directed to labeled compounds, [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2, .sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfones and [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2, .sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfoxides, wherein the .sup.13 C methyl group attached to the sulfur of the sulfone or sulfoxide includes exactly one, two or three deuterium atoms and the aryl group is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure: ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently, hydrogen, a C.sub.1 -C.sub.4 lower alkyl, a halogen, an amino group from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each a C.sub.1 -C.sub.4 lower alkyl, a phenyl, or an alkoxy group. The present invention is also directed to processes of preparing methyl aryl sulfones and methyl aryl sulfoxides.

  13. Primary Productivity Rates at Station ALOHA Determined by 18O Labeling and the Triple Isotope Composition of Dissolved Oxygen

    NASA Astrophysics Data System (ADS)

    Juranek, L. W.; Quay, P. D.; Karl, D. M.

    2002-12-01

    Although knowledge of accurate Primary Productivity (PPr) rates is essential to the understanding of ocean carbon cycling, the standard method of determining ocean productivity, 14C labeling, often yields uncertain results. Typically, 14C-derived PPr rates fall ambiguously between gross and net productivity because the method is sensitive to recycling of a relatively small POC pool. Bottle incubations using labeled oxygen produced from 18O-enriched water have shown promise in giving a more consistent measure of gross productivity, since the pool of dissolved oxygen is less sensitive to recycling than POC. Typically this method gives gross PPr rates that are 2-3 times 14C-derived rates. Recently Luz and Barkan (2001) have pioneered a new technique to determine PPr rates using the triple isotope composition of dissolved oxygen as an in situ tracer. This relies on the observation that a signature of mass-independent fractionation originating in the stratosphere and imparted to the surface ocean by air-sea exchange is diminished by biological oxygen production. In February 2002 we measured gross productivity using both the 18O-labeling and triple isotope in situ methods at Hawaii Ocean Time-Series station ALOHA in the N. Pacific subtropical gyre. We found the in situ oxygen isotope method yielded double the 14C-derived PPr rates while 18O bottle incubations yielded similar rates as 14C. In addition, comparison of in situ isotope measurements with the biological oxygen saturation state indicate that community respiration is approximately equal to gross photosynthesis in the upper 60 m while from 80-200 m respiration exceeds photosynthesis by at most 10 %. We will present these results along with new results from upcoming measurements at station ALOHA.

  14. Chironomid δ 18O as a proxy for past lake water δ 18O: a Lateglacial record from Rotsee (Switzerland)

    NASA Astrophysics Data System (ADS)

    Verbruggen, F.; Heiri, O.; Reichart, G.-J.; Lotter, A. F.

    2010-08-01

    We explored whether the stable oxygen isotope composition (δ 18O) of fossil chironomid remains can be used to reconstruct past variations in lake water δ 18O from Lateglacial and early Holocene sediments from Rotsee (Switzerland). A sediment core from the former littoral zone of the lake was examined since it contained both high concentrations of chironomid remains and abundant authigenic carbonates and therefore allowed a direct comparison of chironomid δ 18O with values measured on bulk carbonates. Since carbonate particles adhering to chironomid remains potentially affect 18O measurements we tested two methods to chemically remove residual carbonates. Trials with isotopically heavy and light acid solutions indicated that treatment with hydrochloric acid promoted oxygen exchange between chironomid remains and the water used during pretreatment. In contrast, a buffered 2 M ammonium chloride (NH 4Cl) solution did not seem to affect chironomid δ 18O to a significant extent. Fossil chironomid δ 18O was analyzed for the Rotsee record both using standard palaeoecological methods and after pretreatment with NH 4Cl. Samples prepared using standard techniques showed a poor correlation with δ 18O of bulk carbonate ( r2 = 0.14) suggesting that carbonate contamination of the chironomid samples obscured the chironomid δ 18O signature. Samples pretreated with NH 4Cl correlated well with bulk carbonate δ 18O ( r2 = 0.67) and successfully tracked the well-known Lateglacial changes in δ 18O. Chironomid δ 18O indicated depleted lake water δ 18O during the Oldest Dryas period, the Aegelsee and Gerzensee Oscillations, and the Younger Dryas, whereas enriched δ 18O values were associated with sediments deposited during the Lateglacial interstadial and the early Holocene. Differences in the amplitude of variations in bulk carbonate and chironomid δ 18O are attributed to differential temperature effects on oxygen isotope fractionation during the formation of carbonates and

  15. Pharmacokinetics of 14C CDP-choline.

    PubMed

    Dinsdale, J R; Griffiths, G K; Rowlands, C; Castelló, J; Ortiz, J A; Maddock, J; Aylward, M

    1983-01-01

    The absorption, metabolism and excretion of cytidine diphosphate choline (CDP-choline, citicoline, Somazina) were investigated in six adult healthy subjects after a single oral dose of 300 mg of the 14C-labelled compound. The compound was well tolerated by the subjects. Absorption was virtually complete with less than 1% of the dose being found in the faeces during the 5-day collection period. Two peaks were found in the plasma radioactivity time profile: the first at 1 h, and a second larger peak at 24 h post-dose. Elimination of the ingested dose occurred via respiratory CO2 and through urinary excretion; the former predominating, and both routes exhibited biphasic patterns characterized by an early phase followed by slower decline. It is postulated that in the healthy human subject CDP-choline is metabolized in the gut wall and in the liver; the products arising from the compound's extensive hepatic metabolism being subsequently available for diverse biosynthetic pathways, tissue metabolism, and excretion.

  16. Changes in14c activity over time during vacuum distillation of carbon from rock pore water

    USGS Publications Warehouse

    Davidson, G.R.; Yang, I.C.

    1999-01-01

    The radiocarbon activity of carbon collected by vacuum distillation from a single partially saturated tuff began to decline after approximately 60% of the water and carbon had been extracted. Disproportionate changes in 14C activity and ??13C during distillation rule out simple isotopic fractionation as a causative explanation. Additional phenomena such as matrix diffusion and ion exclusion in micropores may play a role in altering the isotopic value of extracted carbon, but neither can fully account for the observed changes. The most plausible explanation is that distillation recovers carbon from an adsorbed phase that is depleted in 14C relative to DIC in the bulk pore water. ?? 1999 by the Arizona Board of Regents on behalf of the University of Arizona.

  17. Variability of 13C-labeling in plant leaves.

    PubMed

    Nguyen Tu, Thanh Thuy; Biron, Philippe; Maseyk, Kadmiel; Richard, Patricia; Zeller, Bernd; Quénéa, Katell; Alexis, Marie; Bardoux, Gérard; Vaury, Véronique; Girardin, Cyril; Pouteau, Valérie; Billiou, Daniel; Bariac, Thierry

    2013-09-15

    Plant tissues artificially labeled with (13)C are increasingly used in environmental studies to unravel biogeochemical and ecophysiological processes. However, the variability of (13)C-content in labeled tissues has never been carefully investigated. Hence, this study aimed at documenting the variability of (13)C-content in artificially labeled leaves. European beech and Italian ryegrass were subjected to long-term (13)C-labeling in a controlled-environment growth chamber. The (13)C-content of the leaves obtained after several months labeling was determined by isotope ratio mass spectrometry. The (13)C-content of the labeled leaves exhibited inter- and intra-leaf variability much higher than those naturally occurring in unlabeled plants, which do not exceed a few per mil. This variability was correlated with labeling intensity: the isotope composition of leaves varied in ranges of ca 60‰ and 90‰ for experiments that led to average leaf (13)C-content of ca +15‰ and +450‰, respectively. The reported variability of isotope composition in (13)C-enriched leaves is critical, and should be taken into account in subsequent experimental investigations of environmental processes using (13)C-labeled plant tissues. Copyright © 2013 John Wiley & Sons, Ltd.

  18. 13C NMR Metabolomics: Applications at Natural Abundance

    PubMed Central

    2015-01-01

    13C NMR has many advantages for a metabolomics study, including a large spectral dispersion, narrow singlets at natural abundance, and a direct measure of the backbone structures of metabolites. However, it has not had widespread use because of its relatively low sensitivity compounded by low natural abundance. Here we demonstrate the utility of high-quality 13C NMR spectra obtained using a custom 13C-optimized probe on metabolomic mixtures. A workflow was developed to use statistical correlations between replicate 1D 13C and 1H spectra, leading to composite spin systems that can be used to search publicly available databases for compound identification. This was developed using synthetic mixtures and then applied to two biological samples, Drosophila melanogaster extracts and mouse serum. Using the synthetic mixtures we were able to obtain useful 13C–13C statistical correlations from metabolites with as little as 60 nmol of material. The lower limit of 13C NMR detection under our experimental conditions is approximately 40 nmol, slightly lower than the requirement for statistical analysis. The 13C and 1H data together led to 15 matches in the database compared to just 7 using 1H alone, and the 13C correlated peak lists had far fewer false positives than the 1H generated lists. In addition, the 13C 1D data provided improved metabolite identification and separation of biologically distinct groups using multivariate statistical analysis in the D. melanogaster extracts and mouse serum. PMID:25140385

  19. Changes in Atmospheric 14C Between 55 and 42 ky BP Recorded in a Stalagmite From Socotra Island, Indian Ocean

    NASA Astrophysics Data System (ADS)

    Weyhenmeyer, C. E.; Burns, S. J.; Fleitmann, D.; Kramers, J. D.; Matter, A.; Waber, H. N.; Reimer, P. J.

    2003-12-01

    A record of atmospheric radiocarbon (14C) variations for a part of the last glacial period was obtained from a 1.7 m long stalagmite, M1-2, from Socotra Island in the Indian Ocean. The stalagmite radiocarbon values were corrected for 14C-free carbon added by water-rock interaction (dead carbon fraction), by using del 13C values of the calcite as a constraint. An age-depth model was developed from 25 high-precision U/Th measurements. The base of the stalagmite dates to 54.7 ky BP and it stopped growing around 42.2 ky BP. The difference between U/Th and 14C ages shows a smooth, steady increase from about 5,000 years at the base of the stalagmite to about 8,000 years at its top. Correspondingly, Delta 14C values increase from 500 per mil to about 1300 per mil, which indicates that concentrations of atmospheric 14C steadily increased between 55 and 42 yr BP. The record from Socotra Island does not show the large and rapid D14C changes previously recorded in a stalagmite from the Bahamas (Beck et al, Science 2001). The D14C values estimated from M1-2 are significantly higher than those estimated from a marine 14C record (foraminifera) from Cariaco Basin for the same time period (Hughen et al. in prep). In the latter, D14C values decrease to near 0 at about 44 ky BP. The most likely reason for this discrepancy are the two different time scales used; the Cariaco Basin is matched to the GISP2 timescale, which is approximately 5000 years younger than indicated by the stalagmite U/Th chronology (Burns et al, Science 2003). When the Cariaco basin record is adjusted to the M1-2 timescale, the D14C values for both datasets are similar.

  20. Determination of sup 13 C labeling pattern of citric acid cycle intermediates by gas chromatography-mass spectrometry

    SciTech Connect

    Di Donato, L.; Montgomery, J.A.; Des Rosiers, C.; David, F.; Garneau, M.; Brunengraber, H. )

    1990-02-26

    Investigations of the regulation of the citric acid cycle require determination of labeling patterns of cycle intermediates. These were assayed to date, using infusion of: (i) ({sup 14}C)tracer followed by chemical degradation of intermediates and (ii) ({sup 13}C)tracer followed by NMR analysis of intermediates. The authors developed a strategy to analyze by GC-MS the ({sup 13}C) labeling pattern of {mu}mole samples of citrate (CIT), isocitrate (ICIT), 2-ketoglutarate (2-KG), glutamate (GLU) and glutamine (GLN). These are enzymatically or chemically converted to 2-KG, ICIT, 4-aminobutyrate (GABA) and 2-hydroxyglutarate (2-OHG). GC-MS analyses of TMS or TBDMS derivatives of these compounds yield the enrichment of each carbon. The authors confirmed the identity of each fragment using the spectra of (1-{sup 13}C), (5-{sup 13}C), (2,3,3,4,4-{sup 2}H{sub 5})glutamate and (1-{sup 13}C), (1,4-{sup 13}C)GABA.

  1. Radiolabelling of humic substances with (14)C by azo coupling [(14)C]phenyldiazonium ions.

    PubMed

    Mansel, A; Kupsch, H

    2007-07-01

    For the first time, natural and synthetic humic substances were radiolabelled by azo coupling [U-(14)C]phenyldiazonium ions onto the aromatic fragments of their macromolecules under mild reaction conditions. The radiolabelling procedure was optimized with respect to pH, reaction temperature and the molar ratio of the humic substance to the labelling compound. The labelled humic substances were purified by precipitation or ultrafiltration. The chemical yields were in the range between 23% and 95%, and the specific radioactivities varied between 68 and 206MBq (14)C per gram of the humic substance, depending on the origin of the humic substance and the purification method. With the (14)C-labelled humic compounds thus obtained, we were able to detect humic substances at concentrations as low as 5microg/L. These radiolabelled compounds can be used in long-term studies because, according to size exclusion chromatography data, there are no signs of their decomposition even after 5 months of storage.

  2. Chemistry and rotational excitation of O_2 in interstellar clouds. II. The 16O^18O isotopomer

    NASA Astrophysics Data System (ADS)

    Marechal, P.; Viala, Y. P.; Pagani, L.

    1997-12-01

    Although molecular oxygen O_2 is predicted to be an important constituent of the interstellar gas, it has not yet been observed in Galactic interstellar clouds. While ongoing O_2 observation projects in our Galaxy have to use stratospheric balloons or satellites, several teams have already tried to observe its isotopomer (16) O(18) O with ground-based telescopes. In this paper, a chemical model of interstellar clouds including (18) O and (13) C isotopic reactions with a non-LTE calculation of (16) O(18) O rotational population has been used to predict the intensity of the 3 (16) O(18) O lines observable from the ground, namely the 234, 298 and 402 GHz lines. These predictions are compared to the upper limits obtained by Marechal et al. (1997a) and to the tentative detection obtained by Pagani et al. (1993) towards L134N. We show that only the 234 GHz line is observable with today's receivers and that the strong upper limits we have reported are not compatible with a standard steady-state model. Clumpiness, high (0.7) C/O ratio or other non-standard models are required to explain our observations. The consequence of the (18) O isotopic fractionation is also discussed. The Table 4 is only available in electronic form at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsweb.u-strasbg.fr/Abstract.html

  3. 18O-Labeled Proteome Reference as Global Internal Standards for Targeted Quantification by Selected Reaction Monitoring-Mass Spectrometry

    SciTech Connect

    Kim, Jong Seo; Fillmore, Thomas L.; Liu, Tao; Robinson, Errol W.; Hossain, Mahmud; Champion, Boyd L.; Moore, Ronald J.; Camp, David G.; Smith, Richard D.; Qian, Weijun

    2011-10-11

    Selected reaction monitoring-mass spectrometry (SRM-MS) is an emerging technology for high throughput targeted protein quantification and verification in biological and biomarker discovery studies; however, the cost associated with the use of stable isotope labeled synthetic peptides as internal standards is prohibitive for quantitatively screening large numbers of candidate proteins as often required in the pre-verification phase of biomarker discovery. Herein we present the proof-of-concept experiments of using an 18O-labeled 'universal' reference as comprehensive internal standards for quantitative SRM-MS analysis. With an 18O-labeled whole proteome sample as reference, every peptide of interest will have its own corresponding heavy isotope labeled internal standard, thus providing an ideal approach for quantitative screening of a large number of candidates using SRM-MS. Our results showed that the 18O incorporation efficiency using a recently improved protocol was >99.5% for most peptides investigated, a level comparable to 13C/15N labeled synthetic peptides in terms of heavy isotope incorporation. The accuracy, reproducibility, and linear dynamic range of quantification were further assessed based on known ratios of standard proteins spiked into mouse plasma with an 18O-labeled mouse plasma reference. A dynamic range of four orders of magnitude in relative concentration was obtained with high reproducibility (i.e., coefficient of variance <10%) based on the 16O/18O peak area ratios. Absolute and relative quantification of C-reactive protein and prostate-specific antigen were demonstrated by coupling an 18O-labeled reference with standard additions of protein standards. Collectively, our results demonstrated that the use of 18O-labeled reference provides a convenient and effective strategy for quantitative SRM screening of large number of candidate proteins.

  4. Correction for the 17O interference in δ(13C) measurements when analyzing CO2 with stable isotope mass spectrometry

    USGS Publications Warehouse

    Coplen, Tyler B.; Brand, Willi A.; Assonov, Sergey S.

    2010-01-01

    Measurements of δ(13C) determined on CO2 with an isotope-ratio mass spectrometer (IRMS) must be corrected for the amount of 17O in the CO2. For data consistency, this must be done using identical methods by different laboratories. This report aims at unifying data treatment for CO2 IRMS by proposing (i) a unified set of numerical values, and (ii) a unified correction algorithm, based on a simple, linear approximation formula. Because the oxygen of natural CO2 is derived mostly from the global water pool, it is recommended that a value of 0.528 be employed for the factor λ, which relates differences in 17O and 18O abundances. With the currently accepted N(13C)/N(12C) of 0.011 180(28) in VPDB (Vienna Peedee belemnite) reevaluation of data yields a value of 0.000 393(1) for the oxygen isotope ratio N(17O)/N(16O) of the evolved CO2. The ratio of these quantities, a ratio of isotope ratios, is essential for the 17O abundance correction: [N(17O)/N(16O)]/[N(13C)/N(12C)] = 0.035 16(8). The equation [δ(13C) ≈ 45δVPDB-CO2 + 2 17R/13R (45δVPDB-CO2 – λ46δVPDB-CO2)] closely approximates δ(13C) values with less than 0.010 ‰ deviation for normal oxygen-bearing materials and no more than 0.026 ‰ in extreme cases. Other materials containing oxygen of non-mass-dependent isotope composition require a more specific data treatment. A similar linear approximation is also suggested for δ(18O). The linear approximations are easy to implement in a data spreadsheet, and also help in generating a simplified uncertainty budget.

  5. Functional groups identified by solid state 13C NMR spectroscopy

    USDA-ARS?s Scientific Manuscript database

    Animal manure is generally high in organic matter intensity so it is well suitable for 13C nuclear magnetic resonance (NMR) analysis. Solid-state 13C NMR techniques used in characterizing organic matter and its components include, but are not limited to, cross-polarization /magic angle spinning (CP...

  6. Polymeric proanthocyanidins 13C NMR studies of procyanidins

    Treesearch

    Lawrence J. Porter; Roger H. Newman; Lai Yeap Foo; Herbert Wong; Richard W. Hemingway

    1982-01-01

    Proanthocyanidin polymers have been shown to consist entirely of flavan-3-ol units by a combination of techniques including 13C n.m.r. spectroscopy. The 13C n.m.r. spectra of the polymers and related molecules are now considered in more detail. Prior to this study UC n.m.r. data has been published of procyanidins and...

  7. 18O enrichment in phosphorus pools extracted from soybean leaves.

    PubMed

    Pfahler, Verena; Dürr-Auster, Thilo; Tamburini, Federica; Bernasconi, M Stefano; Frossard, Emmanuel

    2013-01-01

    The objective of this study was to investigate the isotopic composition of oxygen bound to phosphate (δ(18)O-PO(4)) in different phosphorus (P) pools in plant leaves. As a model plant we used soybean (Glycine max cv Toliman) grown in the presence of ample P in hydroponic cultures. The leaf blades were extracted with 0.3 M trichloroacetic acid (TCA) and with 10 M nitric acid. These extractions allowed measurement of the TCA-soluble reactive P (TCA P) that is rapidly cycled within the cell and the total leaf P. The difference between total leaf P and TCA P yielded the structural P which includes organic P compounds not extractable by TCA. P uptake and its translocation and transformation within the soybean plants lead to an (18)O enrichment of TCA P (δ(18)O-PO(4) between 16.9 and 27.5‰) and structural P (δ(18)O-PO(4) between 42.6 and 68.0 ‰) compared with 12.4‰ in the phosphate in the nutrient solution. δ(18)O values of phosphate extracted from soybean leaves grown under optimal conditions are greater than the δ(18)O-PO(4) values of the provided P source. Furthermore, the δ(18)O-PO(4) of TCA P seems to be controlled by the δ(18)O of leaf water and the activity of inorganic pyrophosphatase or other pyrophosphatases.

  8. Paleoclimate record from Zidita Cave (Romania) using guano-derived δ13C isotopic data

    NASA Astrophysics Data System (ADS)

    Forray, Ferenc L.; Giurgiu, Alexandra; Onac, Bogdan P.; Tămaş, Tudor

    2014-05-01

    In this study, we measured the carbon isotopic composition of a core taken from a bat guano deposit in Zidita Cave (Metaliferi Mountains, Romania). The cave develops in Late Jurassic limestones, has a total length of 547 m, and its entrance was fortified during the XIV - XVIII centuries. The cave is a fossil maze with a filling represented by limestone blocks, clay sediments, and scarce calcite speleothems. The guano accumulation, 1.5 m thick, is located in a small room towards the end of the cave, under a Rhinolophus euryale roost site.The core was recovered with a Russian peat corer. 14C dating performed on the guano indicates a continuous deposition since ca. 500 years BP, but however, the upper first meter of the core has a modern age and high radiocarbon activity acquired from atmospheric radiocarbon bomb pulse. The core was sampled at 2 cm ± 2 mm intervals for δ13C analyses (76 samples) and at 5 cm for pollen. The investigations were carried out using a Picarro G2121-i δ13C analyzer (Combustion Module coupled with a Cavity Ring Down Spectroscopy technique) at the Stable Isotope Laboratory of the Department of Geology, Babes-Bolyai University (Cluj-Napoca, Romania). The result shows that guano δ13C range from -24.07 to -27.61 o‰The carbon isotopic profile indicates two major wet periods and 2 to 3 shorter periods characterized by drier climate.

  9. Determination of the delta(18O/16O)of Water: RSIL Lab Code 489

    USGS Publications Warehouse

    Revesz, Kinga; Coplen, Tyler

    2008-01-01

    The purpose of the technique described by the Reston Stable Isotope Laboratory (RSIL) lab code 489 is to present a method to determine the delta(180/160), abbreviated as delta-180, of water. This delta-18O measurement of water also is a component of National Water Quality Laboratory (NWQL in USGS) schedules 1142 and 1172. Water samples are loaded into glass sample containers on a vacuum manifold to equilibrate gaseous CO2 at constant temperature (25 deg C) with water samples. After loading water samples on the vacuum manifold, air is evacuated through capillary to avoid evaporation, and CO2 is added. The samples are shaken to increase the equilibration rate of water and CO2. When isotopic equilibrium has been attained, an aliquot of CO2 is extracted sequentially from each sample container, separated from water vapor by means of a dry ice trap, and introduced into a dual-inlet isotope-ratio mass spectrometer (DI-IRMS) for determination of the delta-18O value. There is oxygen isotopic fractionation between water and CO2, but it is constant at constant temperature. The DI-IRMS is a DuPont double-focusing mass spectrometer. It has a double collector. One ion beam passes through a slit in a forward collector and is collected in the rear collector. The other ion beams are collected in the front collector. The instrument is capable of measuring mass/charge (m/z) 44 and 45 or 44 and 46 by changing the ion-accelerating voltage under computer control. The ion beams from these m/z values are as follows: m/z 44=CO2=12C16O16O, m/z 45=CO2=13C16O16O primarily, and m/z 46 = CO2=12C16O18O primarily. The data acquisition and control software calculates delta-18O values.

  10. Linking Biogeochemistry to Microbial Diversity Using New 13C Approaches

    NASA Astrophysics Data System (ADS)

    Baggs, E. M.

    2005-12-01

    The use of 13C enables us to overcome uncertainties associated with soil C processes and to assess the links between species diversity and ecosystem function. Recent advances in stable isotope techniques enable determination of process rates, for example CH4 oxidation by direct measurement of 13C-CH4 and 13C-CO2. This overcomes uncertainties associated with reliance on changes in net CH4 emission, which may have compromised some earlier studies as both methanogenesis and CH4 oxidation may occur simultaneously in soil, providing significant advances in our understanding of the process of CH4 oxidation. These stable isotope techniques can be combined with molecular techniques (analysis of gene expression, stable isotope probing (SIP)) to relate the measured process to the microbial populations responsible. Here we will give a synthesis of results from experiments in which we applied 13C-CH4 to accurately determine CH4 oxidation rates in soils, and also present results of 13C-SIP from which we can identify the key players in the microbial population that are using the applied 13C substrate. With the 13C-CH4 technique we were able to provide direct evidence of inhibition of CH4 oxidation following fertiliser application (50-300 kg N ha-1) that was less under elevated pCO2, and evidence for anaerobic CH4 oxidation occurring in soil at 75% soil water filled pore space that would not have been apparent from changes in net CH4 emissions. 13C-SIP both through plants (using 13C-CO2) and directly into soil (using 13C-methane and -organic substrates) has revealed how key players in C utilisation vary under different soil conditions, for example, under improved and unimproved grasslands.

  11. Towards an inhalative 13C breath test method.

    PubMed

    Krumbiegel, P; Rolle-Kampczyk, U; Liebergeld, P; Herbarth, O; Köbrich, R

    2002-06-01

    Customary 13CO2 breath tests--and also 15N urine tests--always start with an oral administration of a test substrate. The test person swallows a stable isotope labelled diagnostic agent. This technique has been used to study several pathophysiological changes in gastrointestinal organs. However, to study pathophysiological changes of the bronchial and lung epithelium, the inhalative administration of a stable isotope labelled agent appeared more suitable to us. [1-13C]Hexadecanol and [1-13C]glucose were chosen. Inhaled [1-13C]hexadecanol did not yield 13CO2 in the exhaled air, but [1-13C]glucose did. To study the practicability of the [1-13C]glucose method and the reproducibility of the results, 18 inhalation tests were performed with healthy subjects. In 6 self-tests, the optimum inhalative dose of [13C]glucose was determined to be 205 mg. Using the APS aerosol provocation system with the nebulizer 'Medic Aid' (Erich Jaeger Würzburg), a 25% aqueous solution was inhaled. Then, breath samples were collected at 15 min. intervals and analysed for 13CO2. 75-120 min after the end of inhalation a well-reproducible maximum delta13C value of 6%o over baseline (DOB) was detected for 12 healthy probands. Speculating that the pulmonary resorption of the [13C]glucose is the rate-limiting step of elimination, decompensations in the epithelium ought to be reflected in changed [1-13C]glucose resorption rates and changed 13CO2 output. Therefore, we speculate that the inhalation of suitable 13C-labelled substrates will pave the way for a new group of 13CO2 breath tests aiding investigations of specific pathophysiological changes in the pulmonary tract, such as inflammations of certain sections and decompensations of cell functions.

  12. Distinct fungal and bacterial δ13C signatures can drive the increase in soil δ13C with depth

    NASA Astrophysics Data System (ADS)

    Kohl, Lukas; Laganièrea, Jérôme; Edwards, Kate A.; Billings, Sharon A.; Morrill, Penny L.; Van Biesen, Geert; Ziegler, Susan E.

    2015-04-01

    Soil microbial biomass is a key precursor of soil organic carbon (SOC), and the enrichment in 13C during SOC diagenesis has been purported to be driven by increasing proportions of microbially derived SOC. Yet, little is known about how the δ13C of soil microbial biomass - and by extension the δ13C of microbial inputs to SOC - vary in space, time, or with the composition of the microbial community. Phospholipid fatty acids (PLFA) can be analyzed to measure the variation of the natural abundance δ13C values of both individual groups of microorganisms and the microbial community as a whole. Here, we show how variations of δ13CPLFA within the soil profile provides insight into C fluxes in undisturbed soils and demonstrate that distinct δ13C of fungal and bacterial biomass and their relative abundance can drive the increase of bulk δ13CSOC with depth. We studied the variation in natural abundance δ13C signatures of PLFA in podzolic soil profiles from mesic boreal forests in Atlantic Canada. Samples from the organic horizons (L,F,H) and the mineral (B; top 10 cm) horizons were analyzed for δ13C values of PLFA specific to fungi, G+ bacteria, or G- bacteria as proxies for the δ13C of the biomass of these groups, and for δ13C values of PLFA produced by a wide range of microorganisms (e.g. 16:0) as a proxy for the δ13C value of microbial biomass as a whole. Results were compared to fungi:bacteria ratios (F:B) and bulk δ13CSOC values. The δ13C values of group-specific PLFA were driven by differences among source organisms, with fungal PLFA consistently depleted (2.1 to 6.4‰) relative to and G+ and G- bacterial PLFA in the same sample. All group-specific PLFA, however, exhibited nearly constant δ13C values throughout the soil profile, apparently unaffected by the over 2.8‰ increase in δ13CSOC with depth from the L to B horizons. This indicates that bulk SOC poorly represents the substrates actually consumed by soil microorganisms in situ. Instead, our

  13. Influence of food supply on the δ13C signature of mollusc shells: implications for palaeoenvironmental reconstitutions

    NASA Astrophysics Data System (ADS)

    Lartaud, Franck; Emmanuel, Laurent; de Rafelis, Marc; Pouvreau, Stephane; Renard, Maurice

    2010-02-01

    Compared to oxygen isotopes, the carbon isotope composition of biogenic carbonates is less commonly used as proxy for palaeoenvironmental reconstructions because shell δ13C is derived from both dissolved inorganic (seawater) and organic carbon sources (food), and interactions between these two pools make it difficult to unambiguously identify any independent effect of either. The main purpose of this study was to demonstrate any direct impact of variable food supply on bivalve shell δ13C signatures, using low/high rations of a 13C-light mixed algal diet fed to 14-month-old (adult) cultured Japanese Crassostrea gigas under otherwise essentially identical in vitro conditions during 3 summer months (May, June and July 2003, seawater temperature means at 16, 18 and 20 °C respectively) in experimental tanks at the Argenton laboratory along the Brittany Atlantic coast of France. At a daily ration of 12% (versus 4%) oyster dry weight, the newly grown part of the shells (hinge region) showed significantly lower δ13C values, by 3.5‰ (high ration: mean of -5.8 ± 1.1‰, n = 10; low ration: mean of -2.3 ± 0.7‰, n = 6; ANOVA Scheffe's test, p < 0.0001). This can be explained by an enhanced metabolic activity at higher food supply, raising 13C-depleted respiratory CO2 in the extrapallial cavity. Based on these δ13C values and data extracted from the literature, and assuming no carbon isotope fractionation between food and shell, the proportion of shell metabolic carbon would be 26 ± 7 and 5 ± 5% for the high- and low-ration C. gigas shells respectively; with carbon isotope fractionation (arguably more realistic), the corresponding values would be 69 ± 14 and 24 ± 9%. Both groups of cultured shells exhibited lower δ13C values than did wild oysters from Marennes-Ol éron Bay in the study region, which is not inconsistent with an independent influence of diet type. Although there was no significant difference between the two food regimes in terms of δ18O shell

  14. Uptake and distribution of /sup 14/C during and following exposure to (/sup 14/C)methyl isocyanate

    SciTech Connect

    Ferguson, J.S.; Kennedy, A.L.; Stock, M.F.; Brown, W.E.; Alarie, Y.

    1988-06-15

    Guinea pigs were exposed to (/sup 14/C)methyl isocyanate (/sup 14/CH/sub 3/-NCO, /sup 14/C MIC) for periods of 1 to 6 hr at concentrations of 0.5 to 15 ppm. Arterial blood samples taken during exposure revealed immediate and rapid uptake of /sup 14/C. Clearance of /sup 14/C was then gradual over a period of 3 days. Similarly /sup 14/C was present in urine and bile immediately following exposure, and clearance paralleled that observed in blood. Guinea pigs fitted with a tracheal cannula and exposed while under anesthesia showed a reduced /sup 14/C uptake in blood indicating that most of the /sup 14/C MIC uptake in normal guinea pigs occurred from retention of this agent in the upper respiratory tract passages. In exposed guinea pigs /sup 14/C was distributed to all examined tissues. In pregnant female mice similarly exposed to /sup 14/C MIC, /sup 14/C was observed in all tissues examined following exposure including the uterus, placenta, and fetus. While the form of /sup 14/C distributed in blood and tissues has not yet been identified, these findings may help to explain the toxicity of MIC or MIC reaction products on organs other than the respiratory tract, as noted by several investigators.

  15. NMR structure analysis of uniformly 13C-labeled carbohydrates.

    PubMed

    Fontana, Carolina; Kovacs, Helena; Widmalm, Göran

    2014-06-01

    In this study, a set of nuclear magnetic resonance experiments, some of them commonly used in the study of (13)C-labeled proteins and/or nucleic acids, is applied for the structure determination of uniformly (13)C-enriched carbohydrates. Two model substances were employed: one compound of low molecular weight [(UL-(13)C)-sucrose, 342 Da] and one compound of medium molecular weight ((13)C-enriched O-antigenic polysaccharide isolated from Escherichia coli O142, ~10 kDa). The first step in this approach involves the assignment of the carbon resonances in each monosaccharide spin system using the anomeric carbon signal as the starting point. The (13)C resonances are traced using (13)C-(13)C correlations from homonuclear experiments, such as (H)CC-CT-COSY, (H)CC-NOESY, CC-CT-TOCSY and/or virtually decoupled (H)CC-TOCSY. Based on the assignment of the (13)C resonances, the (1)H chemical shifts are derived in a straightforward manner using one-bond (1)H-(13)C correlations from heteronuclear experiments (HC-CT-HSQC). In order to avoid the (1) J CC splitting of the (13)C resonances and to improve the resolution, either constant-time (CT) in the indirect dimension or virtual decoupling in the direct dimension were used. The monosaccharide sequence and linkage positions in oligosaccharides were determined using either (13)C or (1)H detected experiments, namely CC-CT-COSY, band-selective (H)CC-TOCSY, HC-CT-HSQC-NOESY or long-range HC-CT-HSQC. However, due to the short T2 relaxation time associated with larger polysaccharides, the sequential information in the O-antigen polysaccharide from E. coli O142 could only be elucidated using the (1)H-detected experiments. Exchanging protons of hydroxyl groups and N-acetyl amides in the (13)C-enriched polysaccharide were assigned by using HC-H2BC spectra. The assignment of the N-acetyl groups with (15)N at natural abundance was completed by using HN-SOFAST-HMQC, HNCA, HNCO and (13)C-detected (H)CACO spectra.

  16. Whole-core analysis by sup 13 C NMR

    SciTech Connect

    Vinegar, H.J.; Tutunjian, P.N. ); Edelstein, W.A.; Roemer, P.B. )

    1991-06-01

    This paper reports on a whole-core nuclear magnetic resonance (NMR) system that was used to obtain natural abundance {sup 13}C spectra. The system enables rapid, nondestructive measurements of bulk volume of movable oil, aliphatic/aromatic ratio, oil viscosity, and organic vs. carbonate carbon. {sup 13}C NMR can be used in cores where the {sup 1}H NMR spectrum is too broad to resolve oil and water resonances separately. A 5 1/4-in. {sup 13}C/{sup 1}H NMR coil was installed on a General Electric (GE) CSI-2T NMR imager/spectrometer. With a 4-in.-OD whole core, good {sup 13}C signal/noise ratio (SNR) is obtained within minutes, while {sup 1}H spectra are obtained in seconds. NMR measurements have been made of the {sup 13}C and {sup 1}H density of crude oils with a wide range of API gravities. For light- and medium-gravity oils, the {sup 13}C and {sup 1}H signal per unit volume is constant within about 3.5%. For heavy crudes, the {sup 13}C and {sup 1}H density measured by NMR is reduced by the shortening of spin-spin relaxation time. {sup 13}C and {sup 1}H NMR spin-lattice relaxation times were measured on a suite of Cannon viscosity standards, crude oils (4 to 60{degrees} API), and alkanes (C{sub 5} through C{sub 16}) with viscosities at 77{degrees}F ranging from 0.5 cp to 2.5 {times} 10{sup 7} cp. The {sup 13}C and {sup 1}H relaxation times show a similar correlation with viscosity from which oil viscosity can be estimated accurately for viscosities up to 100 cp. The {sup 13}C surface relaxation rate for oils on water-wet rocks is very low. Nonproton decoupled {sup 13}C NMR is shown to be insensitive to kerogen; thus, {sup 13}C NMR measures only the movable hydrocarbon content of the cores. In carbonates, the {sup 13}C spectrum also contains a carbonate powder pattern useful in quantifying inorganic carbon and distinguishing organic from carbonate carbon.

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

    PubMed

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

    2017-10-09

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

  18. Metabolism of uniformly labeled (13)C-eicosapentaenoic acid and (13)C-arachidonic acid in young and old men.

    PubMed

    Léveillé, Pauline; Chouinard-Watkins, Raphaël; Windust, Anthony; Lawrence, Peter; Cunnane, Stephen C; Brenna, J Thomas; Plourde, Mélanie

    2017-08-01

    Background: Plasma eicosapentaenoic acid (EPA) and arachidonic acid (AA) concentrations increase with age.Objective: The aim of this study was to evaluate EPA and AA metabolism in young and old men by using uniformly labeled carbon-13 ((13)C) fatty acids.Design: Six young (∼25 y old) and 6 old (∼75 y old) healthy men were recruited. Each participant consumed a single oral dose of 35 mg (13)C-EPA and its metabolism was followed in the course of 14 d in the plasma and 28 d in the breath. After the washout period of ≥28 d, the same participants consumed a single oral dose of 50 mg (13)C-AA and its metabolism was followed for 28 d in plasma and breath.Results: There was a time × age interaction for (13)C-EPA (Ptime × age = 0.008), and the shape of the postprandial curves was different between young and old men. The (13)C-EPA plasma half-life was ∼2 d for both young and old men (P = 0.485). The percentage dose recovered of (13)C-EPA per hour as (13)CO2 and the cumulative β-oxidation of (13)C-EPA did not differ between young and old men. At 7 d, however, old men had a >2.2-fold higher plasma (13)C-DHA concentration synthesized from (13)C-EPA compared with young men (Page = 0.03). (13)C-AA metabolism was not different between young and old men. The (13)C-AA plasma half-life was ∼4.4 d in both young and old participants (P = 0.589).Conclusions: The metabolism of (13)C-AA was not modified by age, whereas (13)C-EPA metabolism was slightly but significantly different in old compared with young men. The higher plasma (13)C-DHA seen in old men may be a result of slower plasma DHA clearance with age. This trial was registered at clinicaltrials.gov as NCT02957188. © 2017 American Society for Nutrition.

  19. Quality assurance of PASADENA hyperpolarization for 13C biomolecules

    PubMed Central

    Hövener, Jan-Bernd; Chekmenev, Eduard Y.; Harris, Kent C.; Perman, William H.; Tran, Thao T.; Bhattacharya, Pratip

    2009-01-01

    Object Define MR quality assurance procedures for maximal PASADENA hyperpolarization of a biological 13C molecular imaging reagent. Materials and methods An automated PASADENA polarizer and a parahydrogen generator were installed. 13C enriched hydroxyethyl acrylate, 1-13C, 2,3,3-d3 (HEA), was converted to hyperpolarized hydroxyethyl propionate, 1-13C, 2,3,3-d3 (HEP) and fumaric acid, 1-13C, 2,3-d2 (FUM) to hyperpolarized succinic acid, 1-13C, 2,3-d2 (SUC), by reaction with parahydrogen and norbornadiene rhodium catalyst. Incremental optimization of successive steps in PASADENA was implemented. MR spectra and in vivo images of hyperpolarized 13C imaging agents were acquired at 1.5 and 4.7 T. Results Application of quality assurance (QA) criteria resulted in incremental optimization of the individual steps in PASADENA implementation. Optimal hyperpolarization of HEP of P = 20% was achieved by calibration of the NMR unit of the polarizer (B0 field strength ± 0.002 mT). Mean hyperpolarization of SUC, P = [15.3 ± 1.9]% (N = 16) in D2O, and P = [12.8 ± 3.1]% (N = 12) in H2O, was achieved every 5–8 min (range 13–20%). An in vivo 13C succinate image of a rat was produced. Conclusion PASADENA spin hyperpolarization of SUC to 15.3% in average was demonstrated (37,400 fold signal enhancement at 4.7 T). The biological fate of 13C succinate, a normally occurring cellular intermediate, might be monitored with enhanced sensitivity. PMID:19067009

  20. Study of Urban environmental quality through Isotopes δ13C

    NASA Astrophysics Data System (ADS)

    González-Sosa, E.; Mastachi-Loza, C.; Becerril-Piña, R.; Ramos-Salinas, N. M.

    2012-04-01

    Usually, trees with similar pH values on their bark develop epiphytes of similar species, the acidity to be a factor for growth. The aim of the study was evaluate the air quality through isotope δ13C in order to define the levels of environmental quality in the city of Queretaro, Mexico. In this work were collected at least 4 epiphytes positioned in trees of the species Prosopis Laevigata at 25 sites of Queretaro City. The samples were analyzed for trace elements with an inductively coupled plasma atomic emission spectroscopy (ICP). The collecting took place during dry period, in May and early rain June 2011 period, and on four sectors to identify the spatial distribution of pollution, using isotopic analysis of concentration of δ 13C. According with the results there are significant differences among the species in each of the sampled areas. The 5 February Avenue presented greater diversity and richness of δ13C, followed by those who were surveyed in the proximity of the UAQ and finally in the middle-east area. An average value of δ13C-17.92%, followed by those surveyed in the vicinity of the UAQ that correspond to sector I and II with an concentration of δ13C-17.55% and δ13C-17.22%, and finally the samples collected in trees scattered in the East-Sector II and IV with a value of δ13C-17.02% and δ13C-15.62%, respectively. Also were observed differences between the dry and wet period. It is likely that these results of δ 13C in moist period reflect the drag of the isotopes due to rain events that could mark a trend in the dilution of this element, however there is a trend in terms of abundance and composition of finding more impact in those species sampled in dry period, in May and early June 2011.

  1. First results from a novel methodological approach for δ18O analyses of sugars using GC-Py-IRMS

    NASA Astrophysics Data System (ADS)

    Zech, Michael; Saurer, Matthias; Tuthorn, Mario; Rinne, Katja; Werner, Roland; Juchelka, Dieter; Siegwolf, Rolf; Glaser, Bruno

    2013-04-01

    statistically not significant) for δ18O of sucrose (n = 7) and bulk δ18O (R = 0.62), δ13C of sucrose (R = 0.55) and maximum day temperature (R = 0.58) and negative correlation for δ18O of sucrose and cloudiness (R = -0.80). This highlights the great potential of compound-specific δ18O analyses of sucrose for (paleo-) plimate studies. Zech, M., Glaser, B., 2009. Compound-specific d18O analyses of neutral sugars in soils using GC-Py-IRMS: problems, possible solutions and a first application. RCM 23, 3522-3532. Zech, M., Tuthorn, M., Glaser, B., Amelung, W., Huwe, B., Zech, W., Zöller, L., Löffler, J., 2013. Natural abundance of 18O of sugar biomarkers in topsoils along a climate transect over the Central Scandinavian Mountains, Norway. JPNSS, in press. Zech, M., Werner, R., Juchelka, D., Kalbitz, K., Buggle, B., Glaser, B., 2012. Absence of oxygen isotope fractionation/exchange of (hemi-) cellulose derived sugars during litter decomposition. Org Geochem 42, 1470-1475.

  2. C14-C15 single bond isomerizations of the retinal chromophore involved in the proton-pumping mechanism of bacteriorhodopsin

    SciTech Connect

    Smith, S.O.; Hornung, I.; van der Steen, R.; Pardoen, J.A.; Braiman, M.S.; Lugtenburg, J.; Mathies, R.A.

    1986-02-01

    Resonance Raman spectroscopy is used to examine the possibility that C14-C15 single bond isomerizations of the retinal prosthetic group are involved in the photochemical reactions of bacteriorhodopsin. Normal mode calculations show that the vibration that contains predominantly C14-C15 stretch character is approx. = 70 cm lower in frequency in the 14-s-cis conformer than in the s-trans case. This geometric effect is insensitive to out-of-plane twists and should be observed in the sterically hindered 13-cis, 14-s-cis retinal protonated Schiff base, which has been proposed as the chromophore in the K and L intermediates of bacteriorhodopsin. Resonance Raman spectra were obtained of K625 by using the low temperature (77 K) spinning-cell technique. Isotopic substitutions with T and SH show that significant C14-C15 stretch character is observed in normal modes at approx. = 1185-1195 cm . The relatively high frequency of the C14-C15 stretch argues that K625 contains a 13-cis, 14-s-trans chromophore. Similarly, isotopic derivatives show that L550 has a localized C14-C15 stretch at 1172 cm , consistent with a 14-s-trans chromophore. These results argue that the primary step in bacteriorhodopsin is a C13=C14 trans cis photoisomerization that does not involve C14-C15 s-cis structures.

  3. Decadal patterns in δ18O of atmospheric CO2

    NASA Astrophysics Data System (ADS)

    Zakem, E.; White, J. W.

    2010-12-01

    The stable oxygen isotope 18O is unique to isotope ecology in that it links the hydrosphere to the carbon cycle. Since land biosphere fluxes are the dominant influences on 18O of atmospheric CO2, particularly on shorter times scales, analysis of atmospheric δ18O trends can provide useful insight into the terrestrial carbon cycle. The isotopic values imprinted by leaf water and soil water exchanges with CO2 out-compete those from ocean exchange, fossil fuel and biomass burning, and stratospheric reactions. The opposing isotopic imprints of photosynthesis and ecosystem respiration therefore control the majority of atmospheric 18O concentration. The resulting seasonal cycle in δ18O data of peaks during early summer, when photosynthesis dominates, and lows during early winter, when respiration dominates, has been clearly established. However, the reasons for the interannual variability of atmospheric 18O remain unknown. Studies have shown that the size and isotopic value of the “retrodiffusion” flux- the CO2 that enters and exits leaves without being fixed by photosynthesis- is a function of stomatal conductance, which is affected by the relative humidity in the surrounding atmosphere. We observe that data from numerous global sites shows a global decadal oscillation in δ18O, suggesting a climatological forcing. We compare decadal trends in δ18O with climate oscillations and the 11-year solar cycle, as well as relative humidity records, examining correlations and proposing associated mechanisms. Understanding the decadal patterns in atmospheric 18O of CO2 will shed light on global terrestrial carbon fluxes and the carbon-water interaction on decadal time scales, potentially helping to scale human versus natural impacts on this coupled system.

  4. (13)C isotopic abundances in natural nutrients: a newly formulated test meal for non-invasive diagnosis of type 2 diabetes.

    PubMed

    Ghosh, Chiranjit; Mandal, Santanu; Pal, Mithun; Mukhopadhyay, Prabuddha; Ghosh, Shibendu; Pradhan, Manik

    2017-06-01

    A new method to replace commercially prepared (13)C-labelled glucose with naturally available (13)C-enriched substrates could result in promotion of the clinical applicability of the isotopic breath test for detection of type 2 diabetes (T2D). Variation of the carbon-13 isotope in human breath depends on the (13)C enrichment in the diet taken by subjects. Here, we formulated a new test meal comprising naturally available (13)C-enriched foods and subsequently administered it to non-diabetic control (NDC) subjects and those with T2D. We found that the new test meal-derived (13)C enrichment of breath CO2 was significantly lower in T2D compared with NDC. Furthermore, from our observations T2D exhibited higher isotopic enrichment of oxygen-18 ((18)O) in breath CO2 compared with NDC following ingestion of the new meal. We determined the optimal diagnostic cut-off values of (13)C (i.e. δ (13)C‰ = 7.5‰) and (18)O (i.e. δ (18)O‰ = 3.5‰) isotopes in breath CO2 for precise classification of T2D and NDC. Our new method involving the administration of naturally (13)C-abundant nutrients showed a typical diagnostic sensitivity and specificity of about 95%, suggesting a valid and potentially robust global method devoid of any synthetically manufactured commercial (13)C-enriched glucose which thus may serve as an alternative diagnostic tool for routine clinical applications.

  5. Histamine formation from 14C-L-histidine in man

    PubMed Central

    Berg, B.; Granerus, G.; Johansson, Maj-Britt; Westling, H.; White, T.

    1972-01-01

    1. 14C-L-histidine was given i.v. to one normal subject and two patients with chronic myelocytic leukaemia. Urinary excretion of histamine and two of its metabolites methylhistamine and methylimidazoleacetic acid, total as well as 14C-labelled, was measured, as well as blood 14C-histamine. In addition the total urinary and pulmonary elimination of 14C was followed. 2. Total 14C elimination was high during the first days, then declined slowly except for a plateau at the 10th-14th day in the two patients. There was a measurable elimination even after some months. 3. 14C-histamine appeared in the blood of the leukaemic patient, whereas in the normal subjects the values were hardly measurable. 4. The leukaemic patients excreted much more of the two 14C-labelled histamine metabolites than the normal subject. The difference in excretion of the 14C-labelled metabolites was largest around the 12th day after the infusion of 14C-L-histidine. 5. The results indicate that the leukaemic patients formed at least 20 times more histamine daily than the normal subject. PMID:4510213

  6. 13C isotope effects on 1H chemical shifts: NMR spectral analysis of 13C-labelled D-glucose and some 13C-labelled amino acids.

    PubMed

    Tiainen, Mika; Maaheimo, Hannu; Soininen, Pasi; Laatikainen, Reino

    2010-02-01

    The one- and two-bond (13)C isotope shifts, typically -1.5 to -2.5 ppb and -0.7 ppb respectively, in non-cyclic aliphatic systems and up to -4.4 ppb and -1.0 ppb in glucose cause effects that need to be taken into account in the adaptive NMR spectral library-based quantification of the isotopomer mixtures. In this work, NMR spectral analyses of some (13)C-labelled amino acids, D-glucose and other small compounds were performed in order to obtain rules for prediction of the (13)C isotope effects on (1)H chemical shifts. It is proposed that using the additivity rules, the isotope effects can be predicted with a sufficient accuracy for amino acid isotopomer applications. For glucose the effects were found strongly non-additive. The complete spectral analysis of fully (13)C-labelled D-glucose made it also possible to assign the exocyclic proton signals of the glucose. Copyright 2009 John Wiley & Sons, Ltd.

  7. Detection of inflammatory cell function using 13C magnetic resonance spectroscopy of hyperpolarized [6-13C]-arginine

    PubMed Central

    Najac, Chloé; Chaumeil, Myriam M.; Kohanbash, Gary; Guglielmetti, Caroline; Gordon, Jeremy W.; Okada, Hideho; Ronen, Sabrina M.

    2016-01-01

    Myeloid-derived suppressor cells (MDSCs) are highly prevalent inflammatory cells that play a key role in tumor development and are considered therapeutic targets. MDSCs promote tumor growth by blocking T-cell-mediated anti-tumoral immune response through depletion of arginine that is essential for T-cell proliferation. To deplete arginine, MDSCs express high levels of arginase, which catalyzes the breakdown of arginine into urea and ornithine. Here, we developed a new hyperpolarized 13C probe, [6-13C]-arginine, to image arginase activity. We show that [6-13C]-arginine can be hyperpolarized, and hyperpolarized [13C]-urea production from [6-13C]-arginine is linearly correlated with arginase concentration in vitro. Furthermore we show that we can detect a statistically significant increase in hyperpolarized [13C]-urea production in MDSCs when compared to control bone marrow cells. This increase was associated with an increase in intracellular arginase concentration detected using a spectrophotometric assay. Hyperpolarized [6-13C]-arginine could therefore serve to image tumoral MDSC function and more broadly M2-like macrophages. PMID:27507680

  8. Constraining 3-PG with a new δ13C submodel: a test using the δ13C of tree rings.

    PubMed

    Wei, Liang; Marshall, John D; Link, Timothy E; Kavanagh, Kathleen L; DU, Enhao; Pangle, Robert E; Gag, Peter J; Ubierna, Nerea

    2014-01-01

    A semi-mechanistic forest growth model, 3-PG (Physiological Principles Predicting Growth), was extended to calculate δ(13)C in tree rings. The δ(13)C estimates were based on the model's existing description of carbon assimilation and canopy conductance. The model was tested in two ~80-year-old natural stands of Abies grandis (grand fir) in northern Idaho. We used as many independent measurements as possible to parameterize the model. Measured parameters included quantum yield, specific leaf area, soil water content and litterfall rate. Predictions were compared with measurements of transpiration by sap flux, stem biomass, tree diameter growth, leaf area index and δ(13)C. Sensitivity analysis showed that the model's predictions of δ(13)C were sensitive to key parameters controlling carbon assimilation and canopy conductance, which would have allowed it to fail had the model been parameterized or programmed incorrectly. Instead, the simulated δ(13)C of tree rings was no different from measurements (P > 0.05). The δ(13)C submodel provides a convenient means of constraining parameter space and avoiding model artefacts. This δ(13)C test may be applied to any forest growth model that includes realistic simulations of carbon assimilation and transpiration.

  9. Synthesis of Site-Specifically (13)C Labeled Linoleic Acids.

    PubMed

    Offenbacher, Adam R; Zhu, Hui; Klinman, Judith P

    2016-10-12

    Soybean lipoxygenase-1 (SLO-1) catalyzes the C-H abstraction from the reactive carbon (C-11) in linoleic acid as the first and rate-determining step in the formation of alkylhydroperoxides. While previous labeling strategies have focused on deuterium labeling to ascertain the primary and secondary kinetic isotope effects for this reaction, there is an emerging interest and need for selectively enriched (13)C isotopologues. In this report, we present synthetic strategies for site-specific (13)C labeled linoleic acid substrates. We take advantage of a Corey-Fuchs formyl to terminal (13)C-labeled alkyne conversion, using (13)CBr4 as the labeling source, to reduce the number of steps from a previous fatty acid (13)C synthetic labeling approach. The labeled linoleic acid substrates are useful as nuclear tunneling markers and for extracting active site geometries of the enzyme-substrate complex in lipoxygenase.

  10. (13)C metabolic flux analysis of recombinant expression hosts.

    PubMed

    Young, Jamey D

    2014-12-01

    Identifying host cell metabolic phenotypes that promote high recombinant protein titer is a major goal of the biotech industry. (13)C metabolic flux analysis (MFA) provides a rigorous approach to quantify these metabolic phenotypes by applying isotope tracers to map the flow of carbon through intracellular metabolic pathways. Recent advances in tracer theory and measurements are enabling more information to be extracted from (13)C labeling experiments. Sustained development of publicly available software tools and standardization of experimental workflows is simultaneously encouraging increased adoption of (13)C MFA within the biotech research community. A number of recent (13)C MFA studies have identified increased citric acid cycle and pentose phosphate pathway fluxes as consistent markers of high recombinant protein expression, both in mammalian and microbial hosts. Further work is needed to determine whether redirecting flux into these pathways can effectively enhance protein titers while maintaining acceptable glycan profiles.

  11. Anomalous 13C enrichment in modern marine organic carbon

    USGS Publications Warehouse

    Arthur, M.A.; Dean, W.E.; Claypool, G.E.

    1985-01-01

    Marine organic carbon is heavier isotopically (13C enriched) than most land-plant or terrestrial organic C1. Accordingly, ??13C values of organic C in modern marine sediments are routinely interpreted in terms of the relative proportions of marine and terrestrial sources of the preserved organic matter2,3. When independent geochemical techniques are used to evaluate the source of organic matter in Cretaceous or older rocks, those rocks containing mostly marine organic C are found typically to have lighter (more-negative) ??13C values than rocks containing mostly terrestrial organic C. Here we conclude that marine photosynthesis in mid-Cretaceous and earlier oceans generally resulted in a greater fractionation of C isotopes and produced organic C having lighter ??13C values. Modern marine photosynthesis may be occurring under unusual geological conditions (higher oceanic primary production rates, lower PCO2) that limit dissolved CO2 availability and minimize carbon isotope fractionation4. ?? 1985 Nature Publishing Group.

  12. THz and Ft-Ir Study of 18-O Isotopologues of Sulfur Dioxide: 32S16O18O and 32S18O_2

    NASA Astrophysics Data System (ADS)

    Margulès, L.; Motiyenko, R. A.; Demaison, J.; Perrin, Agnes; Kwabia Tchana, F.; Manceron, Laurent

    2016-06-01

    Sulfur dioxide is a molecule that have a great interest in different domains: for atmospheric and planetology chemistry, it is also ubiquitous and abundant in interstellar medium. If the 16O species were extensively studied, this is not the case of the 18O isotopologues. The aim of this study is first to complete the rotational spectra of the ground state with these new measurements up to 1.5 THz, previous measurements are up to 1050 GHz for the 32S16O18O species, and 145 GHz concerning the 32S18O_2 species. The second part is making a global fit of the rotational and vibrational transitions for the excited vibrational states. For the v_2 band, we will complete the recent I.R. analysis. About the triad (v_1, 2v_2, v_3): 32S18O_2 species was studied, but not the 32S16O18O one. and 145 GHz concerning the 32S18O_2 species. The second part is making a global fit of the rotational and vibrational transitions for the excited vibrational states. For the v_2 band, we will complete the recent I.R. analysis. About the triad (v_1, 2v_2, v_3): 32S18O_2 species was studied, but not the 32S16O18O one. The FT-IR spectra were recorded on the AILES Beamline at Synchrotron SOLEIL using the Synchrotron light source, coupled to the Bruker IFS125HR Fourier transform spectrometer. The THz spectra were obtained from 150 to 1500 GHz using the Lille's solid state spectrometer. The analysis is in progress, the latest results will be presented. Support from the French Laboratoire d'Excellence CaPPA (Chemical and Physical Properties of the Atmosphere) through contract ANR-10-LABX-0005 of the Programme d'Investissements d'Avenir is acknowledged Belov, S. P.; et al., 1998, J. Mol. Spectrosc. 191, 17 Lindermayer, J.; et al., 1985, J. Mol. Spectrosc. 110, 357 Gueye, F.; et al. Mol. Phys. in press Ulenikov, O. N.; et al., 2015, JQSRT 166, 13 Brubach, J.; et al., 2010, AIP Conf. Proc. 1214, 81 Zakharenko, O.; et al., 2015, J. Mol. Spectrosc. 317, 41

  13. An in Vivo 13C NMR Analysis of the Anaerobic Yeast Metabolism of 1-13C-Glucose

    NASA Astrophysics Data System (ADS)

    Giles, Brent J.; Matsche, Zenziwe; Egeland, Ryan D.; Reed, Ryan A.; Morioka, Scott S.; Taber, Richard L.

    1999-11-01

    A biochemistry laboratory experiment that studies the dynamics of the anaerobic yeast metabolism of 1-13C-D-glucose via NMR is described. Fleischmann's Active Dry yeast, under anaerobic conditions, produces primarily 2-13C-ethanol and some 1-13C-glycerol as end products. An experiment is described in which the yeast is subjected to osmotic shock from an increasing sodium chloride concentration. Under these conditions, the yeast increases the ratio of glycerol to ethanol. The experiment can be accomplished in a single laboratory period.

  14. TEX 86 and stable δ 18O paleothermometry of early Cretaceous sediments: Implications for belemnite ecology and paleotemperature proxy application

    NASA Astrophysics Data System (ADS)

    Mutterlose, Jörg; Malkoc, Matthias; Schouten, Stefan; Sinninghe Damsté, Jaap S.; Forster, Astrid

    2010-10-01

    Recent studies have cast doubt on the unadjusted usage of Jurassic and Cretaceous δ 18O paleotemperature data derived from belemnites, since the latter data often reflect cooler paleotemperature estimates than would be expected. In this study we address this problem by analysing rocks of Barremian to early Aptian age from two outcrops in northern Germany using TEX 86 paleothermometry, along with 142 belemnite guards studied for their stable isotope (δ 13C, δ 18O) and trace element composition (magnesium, strontium, iron, and manganese). Both TEX 86 and δ 18O Bel indicate very warm water temperatures for a distinctive black shale sequence of late early Barremian age ("Hauptblätterton") with temperatures of up to 29 °C and 23 °C, respectively. We observe a constant offset of TEX 86 temperatures versus the 4 to 5 °C cooler δ 18O belemnite signal for this interval. The late Barremian sequence shows an increase of the δ 18O Bel values from - 1‰ to 0‰ reflecting temperatures around 16 to 12 °C, while the contemporaneous TEX 86 temperatures vary between 26 and 32 °C. The common occurrence of belemnites in the anoxic sediments of the early Barremian implies, however, clearly a nektonic way of life similar to that of recent teuthids, rather than a nektobenthic one like Sepia. This in turn suggests that the belemnites investigated here (genera Praeoxyteuthis, Aulacoteuthis, Oxyteuthis, and Neohibolites) were active swimmers, which inhabited a deeper habitat below the thermocline in an epicontinental sea of perhaps 100 to 250 m water depth. The offset of the TEX 86 and δ 18O Bel data is therefore interpreted to reflect temperature signals from two different depth habitats, i.e. the TEX 86 is selectively derived from warm sea-surface waters, and the belemnites likely occupied deeper and cooler waters with relative increasing salinities in the late Barremian. This study stresses the importance that the taxonomy, paleobiology and ecology of the belemnite taxa

  15. Source and age of carbon in peatland surface waters: new insights from 14C analysis

    NASA Astrophysics Data System (ADS)

    Billett, Michael; Garnett, Mark; Dinsmore, Kerry; Leith, Fraser

    2013-04-01

    Peatlands are a significant source of carbon to the aquatic environment which is increasingly being recognised as an important flux pathway (both lateral and vertical) in total landscape carbon budgets. Determining the source and age of the carbon (in its various forms) is a key step to understanding the stability of peatland systems as well as the connectivity between the soil carbon pool and the freshwater environment. Novel analytical and sampling methods using molecular sieves have been developed for (1) within-stream, in situ sampling of CO2 in the field and (2) for the removal/separation of CO2 in the laboratory prior to 14C analysis of CH4. Here we present dual isotope (δ13C and 14C) data from freshwater systems in UK and Finnish peatlands to show that significant differences exist in the source and age of CO2, DOC (dissolved organic carbon) and POC (particulate organic carbon). Individual peatlands clearly differ in terms of their isotopic freshwater signature, suggesting that carbon cycling may be "tighter" in some systems compared to others. We have also measured the isotopic signature of different C species in peatland pipes, which appear to be able to tap carbon from different peat depths. This suggests that carbon cycling and transport within "piped-peatlands" may be more complex than previously thought. Some of our most recent work has focussed on the development of a method to measure the 14C component of CH4 in freshwaters. Initial results suggest that CH4 in peatland streams is significantly older than CO2 and derived from a much deeper source. We have also shown that the age (but not the source) of dissolved CO2 changes over the hydrological year in response to seasonal changes in discharge and temperature. Radiocarbon measurements in the peat-riparian-stream system suggest that a significant degree of connectivity exists in terms of C transport and cycling, although the degree of connectivity differs for individual C species. In summary, 14C

  16. Methanogenesis in Peat Bogs - Insights from 14C Data Synthesis and Modeling

    NASA Astrophysics Data System (ADS)

    Hoyt, A.; Pangala, S. R.; Gandois, L.; Cobb, A.; Kai, F. M.; Xu, X.; Gauci, V.; Mahmud, Y.; Kamariah, A. S.; Eri, J. A.; Harvey, C. F.

    2015-12-01

    Depth profiles of Δ14C found in peat bogs are similar across latitudes. Solid peat radiocarbon ages increase with depth, young or modern DOC is found in porewater at all depths, and dissolved methane has an intermediate age. Using traditional mixing models, this pattern has been explained as methane produced from roughly half peat and half DOC. However, these models do not account for the advection and diffusion of dissolved gases, which plays an important role in peatlands. We develop a model that includes these transport pathways and individually models 12C, 13C and 14C during the transformation and transport of DOC, DIC, and methane. We test the model against existing data from several field sites, in bogs as disparate as the Glacial Lake Aggasiz Peatlands and Brunei Darussalam. Our model suggests that in bogs with typical Δ14C profiles, where the methane age is intermediate between that of peat and DOC, DOC advected from the surface does not contribute significantly to methane production. Instead, peat decomposition is the primary carbon source. The younger apparent ages of methane compared to peat at the same depth result from vertical advection of the dissolved gases, rather than consumption of DOC for methanogenesis. This is consistent with the finding that DOC found in these bogs is recalcitrant. The model reproduces vertical patterns of DOC, DIC and methane found in both tropical peatlands and northern bogs, emphasizing the similarities in hydrological and geochemical processes across latitudes.

  17. Ultrathin W18O49 nanowire assemblies for electrochromic devices.

    PubMed

    Liu, By Jian-Wei; Zheng, Jing; Wang, Jin-Long; Xu, Jie; Li, Hui-Hui; Yu, Shu-Hong

    2013-08-14

    Ordered W18O49 nanowire thin films were fabricated by Langmuir-Blodgett (LB) technique in the presence of poly(vinyl pyrrolidone) coating. The well-organized monolayer of W18O49 nanowires with periodic structures can be readily used as electrochromic sensors, showing reversibly switched electrochromic properties between the negative and positive voltage. Moreover, the electrochromism properties of the W18O49 nanowire films exhibit significant relationship with their thickness. The coloration/bleaching time was around 2 s for the W18O49 nanowire monolayer, which is much faster than the traditional tungsten oxide nanostructures. Moreover, the nanowire devices display excellent stability when color switching continues, which may provide a versatile and promising platform for electrochromism device, smart windows, and other applications.

  18. Direct Synthesis of ESBO Derivatives-18O Labelled with Dioxirane

    PubMed Central

    Tommasi, Immacolata; Fusco, Caterina

    2013-01-01

    This work addresses a new approach developed in our laboratory, consisting in the application of isolated dimethyldioxirane (DDO, 1a) labelled with 18O for synthesis of epoxidized glyceryl linoleate (Gly-LLL, 2). We expect that this work could contribute in improving analytical methods for the determination of epoxidized soybean oil (ESBO) in complex food matrices by adopting an 18O-labelled-epoxidized triacylglycerol as an internal standard. PMID:24163617

  19. Micron-scale intra-ring analyses of δ13C in early Eocene Arctic wood from Ellesmere Island

    NASA Astrophysics Data System (ADS)

    Schubert, B.; Jahren, H.; Eberle, J.; Sternberg, L.

    2009-12-01

    Early Eocene (ca. 53 Ma) fossil assemblages on Ellesmere Island (75 oN paleolatitude), provide rich information about the plant and animal life of the lush polar ecosystems of the time. Fossil wood recovered from Ellesmere Island is abundant and not permineralized; however, morphological features such as growth rings and resin canals have been obliterated by compression. We report on exceptionally high-resolution intra-ring analyses of δ13C within fossil wood, sampled at ~30 micron intervals across several centimeters of wood sample. Clear patterns in systematic seasonal increases and decreases in wood δ13C allowed us to identify at least 5 annual cycles in the wood. The patterns of increase and decrease in δ13C were consistent with patterns observed for evergreen wood, and distinct from the deciduous patterns we have observed for Metasequoia fossil wood from the middle Eocene (ca. 45 Ma) Arctic site on Axel Heiberg Island. We believe that the high point in the δ13C value of wood seen in each cycle corresponds to the highest environmental temperatures during the annual cycle, as has been seen for modern evergreens (e.g., Barbour et al., 2002). Modern studies have also noted that high temperature periods are correlated with the highest vapor-pressure and soil-water deficits of the annual cycle; these environmental factors would cause the plant to change its discrimination during photosynthesis. We will discuss the relatively low amplitude of δ13C fluctuations (0.5-1.0 ‰) clearly defined by Ellesmere fossil wood, in comparison to observations on modern common evergreens (2.0-4.0 ‰), and speculate that this difference implies greatly dampened seasonal temperature fluctuations in Eocene polar environments, relative to today. Barbour M.M., Walcroft A.S., Farquhar G.D., 2002, Seasonal variation in δ13C and δ18O of cellulose from growth rings of Pinus radiata. Plant, Cell and Environment: v. 25, p. 1483-1499.

  20. High epibenthic foraminiferal δ13C in the Recent deep Arctic Ocean: Implications for ventilation and brine release during stadials

    NASA Astrophysics Data System (ADS)

    Mackensen, Andreas

    2013-09-01

    Low planktic and benthic δ18O and δ13C values in sediments from the Nordic seas of cold stadials of the last glaciation have been attributed to brines, formed similar to modern ones in the Arctic Ocean. To expand on the carbon isotopes of this hypothesis, I investigated benthic δ13C from the modern Arctic Ocean. I show that mean δ13C values of live epibenthic foraminifera from the deep Arctic basins are higher than mean δ13C values of upper slope epibenthic foraminifera. This agrees with mean high δ13C values of dissolved inorganic carbon (DIC) in Arctic Bottom Water (ABW), which are higher than mean δ13CDIC values from shallower water masses of mainly Atlantic origin. However, adjustments for oceanic 13C Suess depletion raise subsurface and intermediate water δ13CDIC values over ABW δ13CDIC ones. Accordingly, during preindustrial Holocene times, the δ13CDIC of ABW was as high or even higher than today but lower than the δ13CDIC of younger subsurface and intermediate water. If brine-enriched water significantly ventilated ABW, brines should have had high δ13CDIC values. Analogously, high-δ13CDIC brines may have been formed in the Nordic seas during warm interstadials. During cold stadials, when most of the Arctic Ocean was perennially sea ice covered, a cessation of high-δ13CDIC brine rejection may have lowered δ13CDIC values of ABW, and ultimately the δ13CDIC in Nordic seas intermediate and deep water. So in contrast to the idea of enhanced brine formation during cold stadials, the results of this investigation imply that a cessation of brine rejection would be more likely.

  1. Influence of Changing Atmospheric Circulation on Precipitation δ 18O-Temperature Relations in Canada during the Holocene

    NASA Astrophysics Data System (ADS)

    Edwards, Thomas W. D.; Wolfe, Brent B.; Macdonald, Glen M.

    1996-11-01

    Postglacial precipitation δ 18O history has been reconstructed for two regions of Canada. Long-term shifts in the oxygen-isotope composition of annual precipitation (δ 18O p) in southern Ontario appear to have occurred with a consistent isotope-temperature relation throughout the past 11,500 14C yr. The modern isotope-temperature relation in central Canada near present boreal treeline evidently became established between 5000 and 4000 years ago, although the relation during the last glacial maximum and deglaciation may also have been similar to present. In the early Holocene, however, unusually high δ 18O papparently persisted, in spite of low temperature locally, probably associated with high zonal index. A rudimentary sensitivity analysis suggests that a small reduction in distillation of moisture in Pacific air masses traversing the western Cordillera, perhaps accompanied by a higher summer:winter precipitation ratio, could have been responsible for the observed effect. Equivalent isotope-temperature "anomalies" apparently occurred elsewhere in western North America in response to changing early-Holocene atmospheric circulation patterns, suggesting that a time-slice map of δ 18O pfor North America during this period might provide a useful target for testing and validation of atmospheric general circulation model simulations using isotopic water tracers.

  2. Evidence for Biomass Burning from 14C and 13C/12C Measurements at T-0 and T-1 during MILAGRO.

    NASA Astrophysics Data System (ADS)

    Gaffney, J. S.; Marley, N. A.; Tackett, M. J.; Sturchio, N. C.; Heraty, L. J.; Martinez, N.; Hardy, K.; Guilderson, T.

    2007-12-01

    Both stable carbon isotopic and radiocarbon characterizations of aerosols can yield important information regarding the sources of carbonaceous aerosols in urban and regional environments. Biomass derived materials are labeled due to their recent photochemical activity in radiocarbon and vary depending upon the photochemical pathway (either C-4 or C-3) in stable carbon-13 content. C-4 being enriched over C-3. During the MILAGRO campaign, quartz filter samples were taken at 12 hour intervals from 5 am to 5 pm (day) and from 5 pm to 5 am (night) during the month of March 2006. These samples were taken at the two super-sites, T-0 (Instituto Mexicano de Petroleo in Mexico City) and T-1 (Universidad Technologica de Tecamac, State of Mexico). The total carbon content was analyzed for stable carbon isotopic composition as well as for radiocarbon. Stable isotope mass spectroscopy was used to determine the carbon-13 to carbon-12 isotopic ratios on carbon dioxide. The carbon dioxide was then converted to graphite for analysis by accelerator mass spectrometry at the Center for Accelerator Mass Spectrometry at Lawrence Livermore National Laboratory. Results are presented for the carbon-13 content relative to the PDB standard and radiocarbon is given relative to recent carbon. The results for total radiocarbon content show that the carbonaceous aerosol content in Mexico City has more than half of the carbon coming from biomass derived sources. These can include inflow of biomass burning aerosols into the T-0 site as well as the input from local burning of biofuels and trash containing biomass derived materials (paper, boxes, etc.). Data also indicate that at the T-1 site biomass burning of C-4 grasses appears to be significant in that the carbon-13 values observed are enriched. Also at T-1 the radiocarbon levels are also found to be slightly higher indicating regional biomass burning as a significant contributor to aerosol carbon in the 0.1 to 1.0 micron size fraction. Some day and night differences were observed that indicate secondary organic aerosols are contributing and that a significant fraction of these aerosols are biomass derived. Further analyses of organic carbon and elemental carbon fractions are underway. This work was performed as part of the Department of Energy's Megacity Aerosol Experiment - Mexico City (MAX- Mex) under the support of the Atmospheric Science Program. This research was supported by the Office of Science (BER), U.S. Department of Energy, Grant No. DE-FG02-07ER64328.

  3. Implications for chloro- and pheopigment synthesis and preservation from combined compound-specific δ13C, δ15N, and Δ14C analysis

    NASA Astrophysics Data System (ADS)

    Kusch, S.; Kashiyama, Y.; Ogawa, N. O.; Altabet, M.; Butzin, M.; Friedrich, J.; Ohkouchi, N.; Mollenhauer, G.

    2010-12-01

    Chloropigments and their derivative pheopigments preserved in sediments can directly be linked to photosynthesis. Their carbon and nitrogen stable isotopic compositions have been shown to be a good recorder of recent and past surface ocean environmental conditions tracing the carbon and nitrogen sources and dominant assimilation processes of the phytoplanktonic community. In this study we report results from combined compound-specific radiocarbon and stable carbon and nitrogen isotope analysis to examine the time-scales of synthesis and fate of chlorophyll-a and its degradation products pheophytin-a, pyropheophytin-a, and 132,173-cyclopheophorbide-a-enol until burial in Black Sea core-top sediments. The pigments are mainly of marine phytoplanktonic origin as implied by their stable isotopic compositions. Pigment δ15N values indicate nitrate as the major uptake substrate but 15N-depletion towards the open marine setting indicates either contribution from N2-fixation or direct uptake of ammonium from deeper waters. Radiocarbon concentrations translate into minimum and maximum pigment ages of approximately 40 to 1200 years. This implies that protective mechanisms against decomposition such as association with minerals, storage in deltaic anoxic environments, or eutrophication-induced hypoxia and light limitation are much more efficient than previously thought. Moreover, seasonal variations of nutrient source, growth period, and habitat and their associated isotopic variability are likely at least as strong as long-term trends. Combined triple isotope analysis of sedimentary chlorophyll and its primary derivatives is a powerful tool to delineate biogeochemical and diagenetic processes in the surface water and sediments, and to assess their precise time-scales.

  4. Implications for chloro- and pheopigment synthesis and preservation from combined compound-specific δ13C, δ15N, and Δ14C analysis

    NASA Astrophysics Data System (ADS)

    Kusch, S.; Kashiyama, Y.; Ogawa, N. O.; Altabet, M.; Butzin, M.; Friedrich, J.; Ohkouchi, N.; Mollenhauer, G.

    2010-08-01

    Chloropigments and their derivative pheopigments preserved in sediments can directly be linked to photosynthesis. Their carbon and nitrogen stable isotopic compositions have been shown to be a good recorder of recent and past surface ocean environmental conditions tracing the carbon and nitrogen sources and dominant assimilation processes of the phytoplanktonic community. In this study we report results from combined compound-specific radiocarbon and stable carbon and nitrogen isotopic analysis to examine the timescales of synthesis and fate of chlorophyll-a and its degradation products pheophytin-a, pyropheophytin-a, and 132,173-cyclopheophorbide-a-enol until burial in Black Sea surface sediments. The pigments are mainly of marine phytoplanktonic origin as implied by their stable isotopic compositions. Pigment δ15N values indicate nitrate as the major uptake substrate but 15N-depletion towards the open marine setting indicates contribution from N2-fixation. Radiocarbon concentrations translate into minimum and maximum pigment ages of approximately 40 to 1200 years. This implies that protective mechanisms against decomposition such as association with minerals or eutrophication-induced hypoxia and light limitation are much more efficient than previously thought. However, seasonal variations of nutrient source, growth period, and habitat and their associated isotopic variability are likely at least as strong as long-term trends. Combined triple isotopic analysis of sedimentary chlorophyll and its primary derivatives is a powerful tool to delineate biogeochemical and diagenetic processes in the surface water and assess their precise timescales.

  5. Two-phase diagenesis of Quaternary carbonates, Arabian Gulf: Insights from {delta}{sup 13}C and {delta}{sup 18}O data

    SciTech Connect

    Chafetz, H.S.; Rush, P.F.

    1995-04-03

    Diagenesis of the top 25 m of Quaternary sediment and rock samples from the shallow subsurface under the nearshore part of the Arabian Gulf is the primary subject of this study. During the last forty years, since this area was recognized as a site of extensive carbonate deposition, the origin, distribution, and dolomitization of modern sediments in the Arabian Gulf region have been intensively studied. However, few geoscientists have studied the Quaternary deposits below the top few meters of accumulation. As a complement to previous work, this study is primarily concerned with the diagenesis of aragonitic and high-magnesium calcitic sediments to sediments composing a low-magnesium calcitic facies. The samples studied, intercalated carbonate and siliciclastic sediments and rocks, were collected from a series of borings offshore of Al Jubayl, Saudi Arabia. The lowermost part of the section is predominantly Pleistocene dolomite. The middle part is composed of intercalated low-magnesium calcite and siliciclastics and is herein interpreted as Pleistocene.

  6. Implications of high-precision measurements of 13C-18O bond ordering in CO2 for thermometry in modern bivalved mollusc shells

    NASA Astrophysics Data System (ADS)

    Petrizzo, Daniel A.; Young, Edward D.; Runnegar, Bruce N.

    2014-10-01

    We report a temperature calibration for Δ47 from bivalve carbonate that lies within error of theoretical predictions (Schauble et al., 2006; Guo et al., 2009). The temperature sensitivity of this calibration is lower than several different earlier calibrations determined using either inorganic calcite, corals, foraminiferans and coccoliths, or brachiopods and bivalved molluscs, but it agrees with more recent Δ47-temperature relationships determined from measurements of clumped-isotopes in mollusc and brachiopod shells. We demonstrate that mollusc shell temperature calibrations originating from different laboratories that have not been corrected for instrument backgrounds may differ by as much as ∼0.07‰ in Δ47 over the ∼0 to 30 °C temperature range even where dΔ47/dT agree. Because recent calibrations for Δ47 vs. T from several different laboratories agree for bivalved mollusc shells, yet differ from an early calibration for bivalved molluscs, we suggest it is unlikely that temperature-Δ47 variability is attributable to phylum-specific vital effects, and instead conclude that differences in calibration slope between phyla and/or inorganic calcite are more easily explained by variability in measurements made in different laboratories. Discrepancies in both calibration slopes and/or intercepts indicate that Δ47 values measured in natural materials may be more significantly influenced by instrument-specific effects, as well as effects from sample preparation and handling and purification of CO2 than current techniques are able to correct for, and therefore, temperatures obtained by comparing measurements of Δ47 to independently determined calcite calibrations may err by a far greater amount than acknowledged in previous studies.

  7. Larix decidua δ(18)O tree-ring cellulose mainly reflects the isotopic signature of winter snow in a high-altitude glacial valley of the European Alps.

    PubMed

    Leonelli, Giovanni; Battipaglia, Giovanna; Cherubini, Paolo; Saurer, Matthias; Siegwolf, Rolf T W; Maugeri, Maurizio; Stenni, Barbara; Fusco, Stella; Maggi, Valter; Pelfini, Manuela

    2017-02-01

    We analyzed the chronologies of cellulose stable isotopes (δ(13)C and δ(18)O) and tree-ring widths from European larch (Larix decidua) in a high-altitude site (2190ma.s.l.) at the bottom of a glacial valley in the Italian Alps, and investigated their dependence on monthly meteorological variables and δ(18)O precipitation values. The δ(18)O of tree-ring cellulose appears to be strongly driven by the δ(18)O of winter snowfall (November to March), which suggests that larch trees mostly use the snow-melt water of the previous winter during the growing season. This water, which also comes from the slope streams and from the underground flow of nearby steep slopes, infiltrates the soil in the valley bottom. The tree-ring cellulose δ(18)O values were also found to be influenced by the August precipitation δ(18)O and mean temperature. The associated regression model shows that the δ(18)O chronology from the tree rings explains up to 34% of the variance in the winter precipitation δ(18)O record, demonstrating the potential for reconstructing the δ(18)O isotopic composition of past winter precipitation in the study region. Unlike most other tree-ring studies that focus on growing season signals, in our study the summer signal was small and the winter signal dominant due to the special conditions of the glacial valley. Site topography, geomorphology and soil characteristics in particular influence the stable isotope signal in tree-ring cellulose. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. 3D 13C- 13C- 13C correlation NMR for de novo distance determination of solid proteins and application to a human α-defensin

    NASA Astrophysics Data System (ADS)

    Li, Shenhui; Zhang, Yuan; Hong, Mei

    2010-02-01

    The de novo structure of an antimicrobial protein, human α-defensin 1 (HNP-1), is determined by combining a 3D 13C- 13C- 13C (CCC) magic-angle spinning (MAS) correlation experiment with standard resonance assignment experiments. Using a short spin diffusion mixing time to assign intra-residue cross peaks and a long mixing time to detect inter-residue correlation peaks, we show that the 3D CCC experiment not only reduces the ambiguity of resonance assignment, but more importantly yields two orders of magnitude more long-range distances without recourse to existing crystal structures. Most of these distance constraints could not be obtained in a de novo fashion from 2D correlation spectra due to significant resonance overlap. Combining the distance constraints from the 3D CCC experiment and the chemical-shift-derived torsion angles, we obtained a de novo high-resolution NMR structure of HNP-1, with a heavy-atom RMSD of 3.4 Å from the crystal structure of the analogous HNP-3. The average energy of the minimum-energy ensemble is less than of 40 kcal/mol. Thus, the 3D CCC experiment provides a reliable means of restraining the three-dimensional structure of insoluble proteins with unknown conformations.

  9. 3D (13)C-(13)C-(13)C correlation NMR for de novo distance determination of solid proteins and application to a human alpha-defensin.

    PubMed

    Li, Shenhui; Zhang, Yuan; Hong, Mei

    2010-02-01

    The de novo structure of an antimicrobial protein, human alpha-defensin 1 (HNP-1), is determined by combining a 3D (13)C-(13)C-(13)C (CCC) magic-angle spinning (MAS) correlation experiment with standard resonance assignment experiments. Using a short spin diffusion mixing time to assign intra-residue cross peaks and a long mixing time to detect inter-residue correlation peaks, we show that the 3D CCC experiment not only reduces the ambiguity of resonance assignment, but more importantly yields two orders of magnitude more long-range distances without recourse to existing crystal structures. Most of these distance constraints could not be obtained in a de novo fashion from 2D correlation spectra due to significant resonance overlap. Combining the distance constraints from the 3D CCC experiment and the chemical-shift-derived torsion angles, we obtained a de novo high-resolution NMR structure of HNP-1, with a heavy-atom RMSD of 3.4A from the crystal structure of the analogous HNP-3. The average energy of the minimum-energy ensemble is less than of 40kcal/mol. Thus, the 3D CCC experiment provides a reliable means of restraining the three-dimensional structure of insoluble proteins with unknown conformations. Copyright 2009 Elsevier Inc. All rights reserved.

  10. The effect of composition on stability ((14)C activity) of soil organic matter fractions from the albic and black soils.

    PubMed

    Jin, Jie; Sun, Ke; Wang, Ziying; Han, Lanfang; Wu, Fengchang; Xing, Baoshan

    2016-01-15

    The importance of the composition of soil organic matter (SOM) for carbon (C) cycling is still under debate. Here a single soil source was used to examine the specific influence of its composition on stability ((14)C activity) of SOM fractions while constraining other influential C turnover factors such as mineral, climate and plant input. The following SOM fractions were isolated from two soil samples: four humic acids, two humins, non-hydrolyzable carbon, and the demineralized fraction. We examined the isotope ratios of SOM fractions in relation to composition (such as aliphatic and aromatic C content) using solid state (13)C nuclear magnetic resonance (NMR) and thermal analysis. The Δ(14)C values of the fractions isolated from both an albic soil (SOMs-A) and a black soil (SOMs-B) correlated negatively with their peak temperature of decomposition and the temperature where half of the total heat of reaction was evolved, implying a potential link between thermal and biogeochemical stability of SOM fractions. Aryl C contents of SOMs-A determined using (13)C NMR varied inversely with δ(15)N values and directly with δ(13)C values, suggesting that part of aryl C of SOMs-A might be fire-derived. The Δ(14)C values of SOMs-A correlated positively with aliphatic C content and negatively with aromatic C content. We therefore concluded that fire-derived aromatic C in SOMs-A appeared to be more stable than microbially-derived aliphatic C. The greater decomposition of SOMs-B fractions weakened the relationship of their Δ(14)C values with alkyl and aryl C contents. Hence, the role of the composition of SOM fractions in regulating stability might be dependent on the source of specific C forms and their stage of decomposition.

  11. 13C-based metabolic flux analysis: fundamentals and practice.

    PubMed

    Yang, Tae Hoon

    2013-01-01

    Isotope-based metabolic flux analysis is one of the emerging technologies applied to system level metabolic phenotype characterization in metabolic engineering. Among the developed approaches, (13)C-based metabolic flux analysis has been established as a standard tool and has been widely applied to quantitative pathway characterization of diverse biological systems. To implement (13)C-based metabolic flux analysis in practice, comprehending the underlying mathematical and computational modeling fundamentals is of importance along with carefully conducted experiments and analytical measurements. Such knowledge is also crucial when designing (13)C-labeling experiments and properly acquiring key data sets essential for in vivo flux analysis implementation. In this regard, the modeling fundamentals of (13)C-labeling systems and analytical data processing are the main topics we will deal with in this chapter. Along with this, the relevant numerical optimization techniques are addressed to help implementation of the entire computational procedures aiming at (13)C-based metabolic flux analysis in vivo.

  12. A scientific workflow framework for (13)C metabolic flux analysis.

    PubMed

    Dalman, Tolga; Wiechert, Wolfgang; Nöh, Katharina

    2016-08-20

    Metabolic flux analysis (MFA) with (13)C labeling data is a high-precision technique to quantify intracellular reaction rates (fluxes). One of the major challenges of (13)C MFA is the interactivity of the computational workflow according to which the fluxes are determined from the input data (metabolic network model, labeling data, and physiological rates). Here, the workflow assembly is inevitably determined by the scientist who has to consider interacting biological, experimental, and computational aspects. Decision-making is context dependent and requires expertise, rendering an automated evaluation process hardly possible. Here, we present a scientific workflow framework (SWF) for creating, executing, and controlling on demand (13)C MFA workflows. (13)C MFA-specific tools and libraries, such as the high-performance simulation toolbox 13CFLUX2, are wrapped as web services and thereby integrated into a service-oriented architecture. Besides workflow steering, the SWF features transparent provenance collection and enables full flexibility for ad hoc scripting solutions. To handle compute-intensive tasks, cloud computing is supported. We demonstrate how the challenges posed by (13)C MFA workflows can be solved with our approach on the basis of two proof-of-concept use cases.

  13. Synthesis and applications of {sup 13}C glycerol

    SciTech Connect

    Stocking, E.; Khalsa, O.; Martinez, R.A.; Silks, L.A. III

    1994-12-01

    Due in part to the use of labeled glycerol for the {sup 13}C enrichment of biomolecules, we are currently developing new synthetic routes to various isotopomers of glycerol. Judging from our experience, traditional methods of glycerol synthesis are not easily adapted for isotopic enrichment and/or have poor overall yields (12 to 15%). Furthermore, the use of glycerol for enrichment can be prohibitively expensive and its availability is limited by the level of demand. We are presently developing a short de novo synthesis of glycerol from carbon dioxide ({approximately}53% overall yield for four steps) and are examining the feasibility of synthesizing site-specific {sup 13}C-labeled glycerol and dihydroxyacetone (DHA) from labeled methanol and carbon dioxide. One application of {sup 13}C glycerol we have examined is enzymatic conversion of glycerol to glyceraldehyde-3-monophosphate or dihydroxyacetone monophosphate (DHAP) with yields ranging from 25 to 50% (as determined by NMR spectroscopy). We are also pursuing the chemical conversion of {sup 13}C-labeled DHA to DHAP. We are especially interested in {sup 13}C-labeled DHAP because we are investigating its use as a chemo-enzymatic precursor for both labeled 2-deoxyribose and 2-deoxyribonucleic acids.

  14. The 13C-excess: a new dual element stable isotopic approach for de-trending the effects of evaporation on lake carbonates

    NASA Astrophysics Data System (ADS)

    Horton, T. W.; Oze, C.

    2013-12-01

    Stable isotope based proxy methods enhance our ability to interpret paleohydrology, paleoelevation, climate change, and biogeochemical cycles. In ancient carbonate lakes, these methods often require that the unmodified isotopic composition of meteoric water or local carbon reservoirs, or both, are recorded by authigenic minerals. Surprisingly, these critical assumptions have not been tested across wide-ranging environmental contexts. A review of globally distributed Quaternary records reveals that lake carbonate oxygen isotope compositions are not strongly, nor significantly, correlated with local meteoric-derived water compositions due to the modification of in-flow waters following entry into the lake environment. These modifications are largely caused by surface water evaporation, and can result in dubious reconstructions of ancient environmental conditions if not accounted for. However, our analysis suggests that positive shifts in surface water δ18O are accompanied by similar magnitude shifts in δ13C-DIC during lake residence. This positive co-variation in δ18O and δ13C may be used to de-trend lake carbonate compositions for the effects of surface water evaporation using a parameter we define as the ';13C-excess'. This approach uses the isotopic covariant trend between in-flow waters and lake waters, rather than lacustrine covariation alone, to better constrain ancient meteoric-derived water compositions. In Quaternary lake systems, 13C-excess values are significantly correlated with modern mean up-slope hypsometric altitude with an error of ×500m. Application of the 13C-excess approach to Cenozoic lake carbonate records from the western U.S. Cordillera both challenges and reinforces previous paleoelevational interpretations based on δ18O alone, while application of the 13C-excess approach to Middle Miocene laminated lacustrine carbonates from California and New Zealand provides important insights into the paleohydrologies of these two highly debated

  15. A Multi-Isotope (B, Sr, O, H, C) and Age Dating (3H-3He, 14C) Study of Ground Water From Salinas Valley, California: Hydrochemistry, Dynamics, and Contamination Processes

    SciTech Connect

    Vengosh, A; Gill, J; Davisson, M L; Hudson, B G

    2001-08-01

    The chemical and isotopic ({sup 11}B/{sup 10}B, {sup 87}Sr/{sup 86}Sr, {sup 18}O/{sup 16}O, {sup 2}H/H, {sup 13}C/{sup 12}C, {sup 14}C, {sup 3}He/{sup 3}H) compositions of groundwater from the upper aquifer system of the Salinas Valley in coastal central California were investigated in order to delineate the origin and processes of groundwater contamination in this complex system. The Salinas Valley has a relatively deep, confined ''400-foot'' aquifer, overlain by a ''180-foot'' aquifer, and a shallower perched aquifer, all made up of alluvial sand, gravel, and clay deposits. Groundwater from the aquifers have different {sup 14}C ages; fossil ({sup 14}C = 21.3 pmc) for the 400-foot, and modern ({sup 14}C = 72.2 to 98.2 pmc) for the 180-foot. Fresh groundwater in all aquifers is recharged naturally and artificially and through the Salinas River. The two modes of recharge can be distinguished chemically. We identified several different saline components with distinguishable chemical and isotopic fingerprints. (1) Salt-water intrusion in the northern basin has Cl concentrations up to 1700 mg/l, a Na/Cl ratio seawater, {delta}{sup 11}B between +17 and +38 per mil, and {sup 87}Sr/{sup 86}Sr between 0.7088 and 0.7096. Excess dissolved Ca, relative to the expected concentration for simple dilution of seawater, correlates with {sup 87}Sr/{sup 86}Sr ratios, suggesting base exchange reaction with clay minerals. (2) Agriculture return flow is high in NO{sub 3} and SO{sub 4}, with a {sup 87}Sr/{sup 86}Sr = 0.7082, {delta}{sup 11}B = 19 per mil; and {delta}{sup 13}C between -23 and -17 per mil. The {sup 3}H-{sup 3}He ages (5-17 years) and {sup 14}C data suggest vertical infiltration rates of irrigation water of 3 to 10 m/yr. (3) Non-marine saline water in the southern part of the valley has high TDS up to 3800 mg/l, high SO{sub 4}, Na/Cl ratio >1, {delta}{sup 11}B between +24 and +30 per mil, and {sup 87}Sr/{sup 86}Sr = 0

  16. A multi-isotope (B, Sr, O, H, and C) and age dating (3H-3He and 14C) study of groundwater from Salinas Valley, California: Hydrochemistry, dynamics, and contamination processes

    NASA Astrophysics Data System (ADS)

    Vengosh, Avner; Gill, Jim; Lee Davisson, M.; Bryant Hudson, G.

    2002-01-01

    The chemical and isotope (11B/10B, 87Sr/86Sr, 18O/16O, 2H/H, 13C/12C, 14C, and 3He/3H) compositions of groundwater from the upper aquifer system of the Salinas Valley in coastal central California were investigated in order to delineate the origin and processes of groundwater contamination in this complex system. The Salinas Valley has a relatively deep, confined ``400-foot'' aquifer, overlain by a ``180-foot'' aquifer and a shallower perched aquifer, all made up of alluvial sand, gravel and clay deposits. Groundwater from the aquifers have different 14C ages: fossil (14C = 21.3 percent modern carbon (pmc) for the 400-foot aquifer and modern (14C = 72.2-98.2 pmc) for the 180-foot aquifer. Fresh groundwater in all aquifers is recharged naturally and artificially through the Salinas River. The two modes of recharge can be distinguished chemically. We identified several different saline components with distinguishable chemical and isotopic fingerprints. (1) Saltwater intrusion in the northern basin has C1 concentrations up to 1700 mg/L, a Na/Cl ratio less than seawater, a marine Br/Cl ratio, a Ca/Cl ratio greater than seawater, δ11B between +17 and +38‰ and 87Sr/86Sr between 0.7088 and 0.7096. Excess dissolved Ca, relative to the expected concentration for simple dilution of seawater, correlates with 87Sr/86Sr ratios, suggesting base exchange reaction with clay materials. (2) Agriculture return flow is high in NO3 and SO4, with a 87Sr/86Sr = 0.7082,δ11B =19‰and δ13C between -23 and -17‰. The 3H-3He ages (5-17 years) and 14C data suggest vertical infiltration rates of irrigation water of 3-10 m/yr. (3) Nonmarine saline water in the southern part of the valley has high total dissolved solids up to 3800 mg/L, high SO4, Na/Cl ratio >1, δ11B between +24 and +30‰, and 87Sr/86Sr = 0.70852. This groundwater may have acquired its geochemical signature from leaching of sedimentary rocks associated with the Coast Range marine deposits of Mesozoic to early Cenozoic

  17. 14C Analysis of protein extracts from Bacillus spores.

    PubMed

    Cappuccio, Jenny A; Falso, Miranda J Sarachine; Kashgarian, Michaele; Buchholz, Bruce A

    2014-07-01

    Investigators of bioagent incidents or interdicted materials need validated, independent analytical methods that will allow them to distinguish between recently made bioagent samples versus material drawn from the archives of a historical program. Heterotrophic bacteria convert the carbon in their food sources, growth substrate or culture media, into the biomolecules they need. The F(14)C (fraction modern radiocarbon) of a variety of media, Bacillus spores, and separated proteins from Bacillus spores was measured by accelerator mass spectrometry (AMS). AMS precisely measures F(14)C values of biological materials and has been used to date the synthesis of biomaterials over the bomb pulse era (1955 to present). The F(14)C of Bacillus spores reflects the radiocarbon content of the media in which they were grown. In a survey of commercial media we found that the F(14)C value indicated that carbon sources for the media were alive within about a year of the date of manufacture and generally of terrestrial origin. Hence, bacteria and their products can be dated using their (14)C signature. Bacillus spore samples were generated onsite with defined media and carbon free purification and also obtained from archived material. Using mechanical lysis and a variety of washes with carbon free acids and bases, contaminant carbon was removed from soluble proteins to enable accurate (14)C bomb-pulse dating. Since media is contemporary, (14)C bomb-pulse dating of isolated soluble proteins can be used to distinguish between historical archives of bioagents and those produced from recent media.

  18. TMEM14C is required for erythroid mitochondrial heme metabolism

    PubMed Central

    Yien, Yvette Y.; Robledo, Raymond F.; Schultz, Iman J.; Takahashi-Makise, Naoko; Gwynn, Babette; Bauer, Daniel E.; Dass, Abhishek; Yi, Gloria; Li, Liangtao; Hildick-Smith, Gordon J.; Cooney, Jeffrey D.; Pierce, Eric L.; Mohler, Kyla; Dailey, Tamara A.; Miyata, Non; Kingsley, Paul D.; Garone, Caterina; Hattangadi, Shilpa M.; Huang, Hui; Chen, Wen; Keenan, Ellen M.; Shah, Dhvanit I.; Schlaeger, Thorsten M.; DiMauro, Salvatore; Orkin, Stuart H.; Cantor, Alan B.; Palis, James; Koehler, Carla M.; Lodish, Harvey F.; Kaplan, Jerry; Ward, Diane M.; Dailey, Harry A.; Phillips, John D.; Peters, Luanne L.; Paw, Barry H.

    2014-01-01

    The transport and intracellular trafficking of heme biosynthesis intermediates are crucial for hemoglobin production, which is a critical process in developing red cells. Here, we profiled gene expression in terminally differentiating murine fetal liver-derived erythroid cells to identify regulators of heme metabolism. We determined that TMEM14C, an inner mitochondrial membrane protein that is enriched in vertebrate hematopoietic tissues, is essential for erythropoiesis and heme synthesis in vivo and in cultured erythroid cells. In mice, TMEM14C deficiency resulted in porphyrin accumulation in the fetal liver, erythroid maturation arrest, and embryonic lethality due to profound anemia. Protoporphyrin IX synthesis in TMEM14C-deficient erythroid cells was blocked, leading to an accumulation of porphyrin precursors. The heme synthesis defect in TMEM14C-deficient cells was ameliorated with a protoporphyrin IX analog, indicating that TMEM14C primarily functions in the terminal steps of the heme synthesis pathway. Together, our data demonstrate that TMEM14C facilitates the import of protoporphyrinogen IX into the mitochondrial matrix for heme synthesis and subsequent hemoglobin production. Furthermore, the identification of TMEM14C as a protoporphyrinogen IX importer provides a genetic tool for further exploring erythropoiesis and congenital anemias. PMID:25157825

  19. Study of molecular interactions with 13C DNP-NMR

    NASA Astrophysics Data System (ADS)

    Lerche, Mathilde H.; Meier, Sebastian; Jensen, Pernille R.; Baumann, Herbert; Petersen, Bent O.; Karlsson, Magnus; Duus, Jens Ø.; Ardenkjær-Larsen, Jan H.

    2010-03-01

    NMR spectroscopy is an established, versatile technique for the detection of molecular interactions, even when these interactions are weak. Signal enhancement by several orders of magnitude through dynamic nuclear polarization alleviates several practical limitations of NMR-based interaction studies. This enhanced non-equilibrium polarization contributes sensitivity for the detection of molecular interactions in a single NMR transient. We show that direct 13C NMR ligand binding studies at natural isotopic abundance of 13C gets feasible in this way. Resultant screens are easy to interpret and can be performed at 13C concentrations below μM. In addition to such ligand-detected studies of molecular interaction, ligand binding can be assessed and quantified with enzymatic assays that employ hyperpolarized substrates at varying enzyme inhibitor concentrations. The physical labeling of nuclear spins by hyperpolarization thus provides the opportunity to devise fast novel in vitro experiments with low material requirement and without the need for synthetic modifications of target or ligands.

  20. δ(13)C values of some succulent plants from Madagascar.

    PubMed

    Winter, Klaus

    1979-01-01

    δ(13)C values were determined in 20 succulents from Madagascar. The values were indicative of Crassulacean Acid Metabolism in 10 species of the Didiereaceae, 4 species of the Euphorbiaceae, 2 species of the Crassulaceae and 1 species of the Cucurbitaceae. The Didiereaceae and Euphorbiaceae studied are major components of a high biomass xerophytic flora in the semi-arid southwest and south of Madagascar. Three species of the Euphorbiaceae with succulent stems and non-succulent leaves, which were cultivated outdoors in the Tananarive Botanic Garden, showed C3 like δ(13)C values for both leaves and stems. δ(13)C values of leaf and stem material from a similar species, collected in the south of Madagascar, indicated Crassulacean Acid Metabolism.

  1. {sup 13}C relaxation in an RNA hairpin

    SciTech Connect

    King, G.C. |; Akratos, C.; Xi, Z.; Michnica, M.J.

    1994-12-01

    This initial survey of {sup 13}C relaxation in the {triangle}TAR RNA element has generated a number of interesting results that should prove generally useful for future studies. The most readily comparable study in the literature monitored {sup 13}C relaxation of the methyl groups from unusual bases in tRNA{sup Phe}. The study, which used T{sub 1} and NOE data only, reported order parameters for the methyl group axis that ranged between 0.51 and 0.97-a range similar to that observed here. However, they reported a breakdown of the standard order parameter analysis at higher (118-MHz {sup 13}C) frequencies, which should serve to emphasize the need for a thorough exploration of suitable motional models.

  2. Hyperpolarized 13C Metabolic Magnetic Resonance Spectroscopy and Imaging.

    PubMed

    Kubala, Eugen; Muñoz-Álvarez, Kim A; Topping, Geoffrey; Hundshammer, Christian; Feuerecker, Benedikt; Gómez, Pedro A; Pariani, Giorgio; Schilling, Franz; Glaser, Steffen J; Schulte, Rolf F; Menzel, Marion I; Schwaiger, Markus

    2016-12-30

    In the past decades, new methods for tumor staging, restaging, treatment response monitoring, and recurrence detection of a variety of cancers have emerged in conjunction with the state-of-the-art positron emission tomography with (18)F-fluorodeoxyglucose ([(18)F]-FDG PET). (13)C magnetic resonance spectroscopic imaging ((13)CMRSI) is a minimally invasive imaging method that enables the monitoring of metabolism in vivo and in real time. As with any other method based on (13)C nuclear magnetic resonance (NMR), it faces the challenge of low thermal polarization and a subsequent low signal-to-noise ratio due to the relatively low gyromagnetic ratio of (13)C and its low natural abundance in biological samples. By overcoming these limitations, dynamic nuclear polarization (DNP) with subsequent sample dissolution has recently enabled commonly used NMR and magnetic resonance imaging (MRI) systems to measure, study, and image key metabolic pathways in various biological systems. A particularly interesting and promising molecule used in (13)CMRSI is [1-(13)C]pyruvate, which, in the last ten years, has been widely used for in vitro, preclinical, and, more recently, clinical studies to investigate the cellular energy metabolism in cancer and other diseases. In this article, we outline the technique of dissolution DNP using a 3.35 T preclinical DNP hyperpolarizer and demonstrate its usage in in vitro studies. A similar protocol for hyperpolarization may be applied for the most part in in vivo studies as well. To do so, we used lactate dehydrogenase (LDH) and catalyzed the metabolic reaction of [1-(13)C]pyruvate to [1-(13)C]lactate in a prostate carcinoma cell line, PC3, in vitro using (13)CMRSI.

  3. ESR Investigations on 13C enriched Sc3@C82

    NASA Astrophysics Data System (ADS)

    Rahmer, J.; Mehring, M.; Dorn, H. C.

    2002-10-01

    13C enrichment of Sc3@C82 for the first time allows the resolution of 13C hyperfine satellite lines in the electron spin resonance (ESR) spectra of this material. A simple model is proposed to simulate the spectra. The ESR data is well reproduced under the assumption that two or three carbon atoms have a significantly stronger hyperfine coupling than all other atoms. Relating this result to the geometry of the C3υ cage leads to the conclusion that the electron density is concentrated on the upper hemisphere of the C82 cage.

  4. Stable isotope and 14C study of biogenic calcrete in a termite mound, Western Cape, South Africa, and its palaeoenvironmental significance

    NASA Astrophysics Data System (ADS)

    Potts, Alastair J.; Midgley, Jeremy J.; Harris, Chris

    2009-09-01

    Late Quaternary terrestrial climate records from the semi-arid zone of the Western Cape of South Africa are rare. However, palaeoenvironmental information may be inferred from ancient termite mounds of the region. Calcrete lenses in these mounds have δ 13C and δ 18O values that show systematic changes with radiocarbon dates, which range from 33,629-36,709 to 21,676-23,256 cal yr BP. These dates confirm that these heuweltjies had been present in the landscape since the last glacial period. The decrease in δ 13C and δ 18O from 33,629-36,709 to 21,676-23,256 cal yr BP indicates that climate information is recorded by the calcretes. It is suggested that a progressive decline in air temperature and an increase in moisture availability, and a decline in abundance of C 4 or CAM plants, occurred in the region during the time heuweltjie calcite precipitated.

  5. Structure of uniaxially aligned 13C labeled silk fibroin fibers with solid state 13C-NMR

    NASA Astrophysics Data System (ADS)

    Demura, Makoto; Yamazaki, Yasunobu; Asakura, Tetsuo; Ogawa, Katsuaki

    1998-01-01

    Carbon-13 isotopic labeling of B. mori silk fibroin was achieved biosynthetically with [1- 13C] glycine in order to determine the carbonyl bond orientation angle of glycine sites with the silk fibroin. Angular dependence of 13C solid state NMR spectra of uniaxially oriented silk fibroin fiber block sample due to the carbonyl 13C chemical shift anisotropy was simulated according to the chemical shift transformation with Euler angles, αF and βF, from principal axis system (PAS) to fiber axis system (FAS). The another Euler angles, αDCO and βDCO, for transformation from PAS to the molecular symmetry axis were determined from the [1- 13C] glycine sequence model compounds for the silk fibroin. By the combination of these Euler angles, the carbonyl bond orientation angle with respect to FAS of the [1- 13C] glycine sites of the silk fibroin was determined to be 90 ± 5°. This value is in agreement with the X-ray diffraction and our previous solid state NMR data of B. mori silk fibroin fiber (a typical β-pleated sheet) within experimental error.

  6. Influence of 13C isotopic labeling location of 13C DNP of acetate using TEMPO free radical

    NASA Astrophysics Data System (ADS)

    Parish, Christopher; Niedbalski, Peter; Lumata, Lloyd

    2015-03-01

    Dynamic nuclear polarization (DNP) via the dissolution method enhances the liquid-state magnetic resonance (NMR or MRI) signals of insensitive nuclear spins by at least 10,000-fold. The basis for all these signal enhancements at room temperature is the polarization transfer from the electrons to nuclear spins at cryogenic temperature and high magnetic field. In this work, we have studied the influence of the location of 13C isotopic labeling on the DNP of sodium acetate at 3.35 T and 1.4 K using a wide ESR linewidth free radical 4-oxo-TEMPO. The carbonyl [1-13C]acetate spins produced a polarization level that is almost twice that of the methyl [2-13C]acetate spins. On the other hand, the polarization of the methyl 13C spins doubled to reach the level of [1-13C]acetate when the methyl group was deuterated. Meanwhile, the solid-state nuclear relaxation of these samples are the same and do not correlate with the polarization levels. These behavior implies that the nuclear relaxation for these samples is dominated by the contribution from the free radicals and the polarization levels can be explained by a thermodynamic picture of DNP.

  7. High-resolution 14C dating of a 25,000-year lake-sediment record from equatorial East Africa

    NASA Astrophysics Data System (ADS)

    Blaauw, Maarten; van Geel, Bas; Kristen, Iris; Plessen, Birgit; Lyaruu, Anna; Engstrom, Daniel R.; van der Plicht, Johannes; Verschuren, Dirk

    2011-10-01

    We dated a continuous, ˜22-m long sediment sequence from Lake Challa (Mt. Kilimanjaro area, Kenya/Tanzania) to produce a solid chronological framework for multi-proxy reconstructions of climate and environmental change in equatorial East Africa over the past 25,000 years. The age model is based on a total of 168 AMS 14C dates on bulk-organic matter, combined with a 210Pb chronology for recent sediments and corrected for a variable old-carbon age offset. This offset was estimated by i) pairing bulk-organic 14C dates with either 210Pb-derived time markers or 14C dates on grass charcoal, and ii) wiggle-matching high-density series of bulk-organic 14C dates. Variation in the old-carbon age offset through time is relatively modest, ranging from ˜450 yr during glacial and late glacial time to ˜200 yr during the early and mid-Holocene, and increasing again to ˜250 yr today. The screened and corrected 14C dates were calibrated sequentially, statistically constrained by their stratigraphical order. As a result their constrained calendar-age distributions are much narrower, and the calibrated dates more precise, than if each 14C date had been calibrated on its own. The smooth-spline age-depth model has 95% age uncertainty ranges of ˜50-230 yr during the Holocene and ˜250-550 yr in the glacial section of the record. The δ 13C values of paired bulk-organic and grass-charcoal samples, and additional 14C dating on selected turbidite horizons, indicates that the old-carbon age offset in Lake Challa is caused by a variable contribution of old terrestrial organic matter eroded from soils, and controlled mainly by changes in vegetation cover within the crater basin.

  8. Identification of /sup 13/C depleted mantle carbon in diamonds from the Roberts Victor Kimberlite, South Africa

    SciTech Connect

    Deines, P.

    1985-01-01

    The Roberts Victor Kimberlite is known for the abundance of eclogite xenoliths, some of which show an unusual depletion in /sup 18/O. The question whether the observed oxygen isotope variations can be related to carbon isotopic composition variations has been investigated. Peridotite-suite diamons (X = -5.4 per thousand vs. PDB, s = +/-0.9 per thousand, n = 65) and sulfide containing diamonds (X = -4.9, s = +/-0.9, n = 20) do not differ in their /sup 13/C content. For these samples, delta/sup 13/C is not related to diamond shape, color, minerals occluded, or the inclusion chemistry. Eclogite suite diamonds (11) can be subdivided into two groups, GI and GII, based on delta/sup 13/C : GI = (X = -15.4, s = +/-0.4, n = 8); GII = (X = -5.9, s = +/-0.4, n = 3). The composition of the gt and cpx inclusions of the two groups is distinct; e.g. cpx of GI is significantly depleted in SiO/sub 2/, MgO, and CaO, and significantly enriched in Al/sub 2/O/sub 3/, FeO and MnO, compared to cpx of GII. Comparison of the chemical composition of the inclusions in E-type diamonds with those of eclogite xenoliths showing /sup 18/O depletion suggests that /sup 13/C and /sup 18/O depletion are not likely to be related. Evaluation of compositional trends of gt and cpx in eclogite xenoliths indicates that GI and GII are not related by a single fractionation event, but represent products from different reservoirs. Equilibration conditions deduced from coexisting gt and cpx demonstrate that GI diamonds come from larger depths than eclogite xenoliths and by inference GII diamonds. The high FeO and MnO content of a gt inclusion in cpx of an eclogite xenolith is used to argue for the existence of two separate events responsible for the formation of GI and GII diamonds.

  9. Directly Measured Clumped Isotope Temperatures From Known And Proposed Paleozoic Glacial Intervals Suggest That Oceans Were Depleted in 18O

    NASA Astrophysics Data System (ADS)

    Petrizzo, D. A.; Runnegar, B.; Ivany, L.; Young, E. D.

    2011-12-01

    Oceans enriched in 13C are thought to result from atmospheric CO2 drawdown and concomitant global cooling resulting from increased burial of organic matter. We investigated ocean temperatures during two times when the oceans were exceptionally heavy in 13C, the Lau Event of the late Silurian and the Late Paleozoic Ice Age (LPIA), using both δ18O and "directly measured" clumped isotope (Δ47) temperatures. We report a tropical ocean temperature of 16 ± 3°C at the peak of the Lau Event, confirm seasonality at a high-latitude LPIA site, and raise the possibility that some degradation of 13C-18O bonds may be widespread in apparently unaltered carbonates that have seen temperatures higher than 100-150°C. Silurian conodonts from Gotland, Sweden, are almost unaltered (CAI ~ 0) indicating burial temperatures of <50°C. We measured atrypid brachiopod calcite from the peak of the late Silurian Lau event, the largest positive carbon isotope excursion (+8%) since the Cambrian, and obtained Δ47 = 0.687 ± 0.014, giving a low latitude water temperature of 16 ± 3°C. This is significantly cooler than tropical temperatures reported from pentamerid brachiopod calcite of the early Silurian greenhouse period (35°C, Came et al., 2007) and those derived from rugose corals during the Hirnantian (Ordovician) positive carbon isotope excursion (+5%) and accompanying glaciation (27-32°C, Finnegan et al., 2010). We also measured Δ47 in two shells of the Australian Permian bivalve Eurydesma, a circumpolar genus associated with cold water indicators. Ivany and Runnegar (2010) found high-amplitude annual cycles in δ18O in one of these specimens but the calculated temperatures seemed too warm for the periglacial conditions indicated by approximately coeval dropstones and glendonites unless Permian ocean water δ18O was lighter than ~ -3%. Our Δ47 results also give unrealistically warm winter (~12°C) and summer (~23°C) temperatures for this high-latitude site, raising the possibility

  10. Thermophilic anaerobic biodegradation of (/sup 14/C)lignin, (/sup 14/C)cellulose, and (/sup 14/C)lignocellulose preparations

    SciTech Connect

    Benner, R.; Hodson, R.E.

    1985-10-01

    Thermophilic (55/sup 0/C) anaerobic enrichment cultures were incubated with (/sup 14/C-lignin)lignocellulose, (/sup 14/C- polysaccharide)lignocellulose, and kraft (/sup 14/C)lignin prepared from slash pine, Pinus elliotti, and /sup 14/C-labeled preparations of synthetic lignin and purified cellulose. Significant but low percentages (2 to 4%) of synthetic and natural pine lignin were recovered as labeled methane and carbon dioxide during 60-day incubations, whereas much greater percentages (13 to 23%) of kraft lignin were recovered as gaseous end products. Percentages of label recovered from lignin-labeled substrates as dissolved degradation products were approximately equal to percentages recovered as gaseous end products. High-pressure liquid chromatographic analyses of CuO oxidation products of sound and degraded pine lignin indicated that no substantial chemical modifications of the remaining lignin polymer, such as demethoxylation and dearomatization, occurred during biodegradation. The polysaccharide components of pine lignocellulose and purified cellulose were relatively rapidly mineralized to methane and carbon dioxide; 31% to 37% of the pine polysaccharides and 56% to 63% of the purified cellulose were recovered as labeled gaseous end products. An additional 10% to 20% of the polysaccharide substrates was recovered as dissolved degradation products. Overall, these results indicate that elevated temperatures can greatly enhance rates of anaerobic degradation of lignin and lignified substrates to methane and low-molecular-weight aromatic compounds.

  11. Kinetics of metabolism of organic and inorganic 14C compounds.

    PubMed

    Vasilenko IYa; Bugryshev, P F; Istomina, A G; Turova, V I

    1982-01-01

    Results of experimental studies on the dynamics of metabolism of various inorganic (NA2CO3, K2CO3, CaCO3) and organic (glucose, glycine, palmitic and succinic acids, ethanol and methanol) compounds of 14C after its single and long-term administration into the organism of rats are presented. The values of the corresponding rates of accumulation of 14C and the onset of the state of equilibrium after long-term administration of the radionuclide were elucidated for a number of compounds. Results of the studies can find practical application in norm-setting. The corresponding rate of accumulation in man of 14C taken in the diet was determined by extrapolation of the experimental data. It was found to be approximately 30. The state of practical 14C equilibrium in man occurs approximately 11/2 years after the beginning of the intake.

  12. Forensic applications of 14C bomb-pulse dating

    NASA Astrophysics Data System (ADS)

    Zoppi, U.; Skopec, Z.; Skopec, J.; Jones, G.; Fink, D.; Hua, Q.; Jacobsen, G.; Tuniz, C.; Williams, A.

    2004-08-01

    After a brief review of the basics of 14C bomb-pulse dating, this paper presents two unique forensic applications. Particular attention is dedicated to the use of the 14C bomb-pulse to establish the time of harvest of illicit drugs such as heroin and opium. Preliminary measurements of 14C concentrations in milligram samples taken from seized drugs are presented. 14C bomb-pulse dating can determine whether drug distribution originates from stockpiles or recent manufacture, and support the action of law enforcement authorities against criminal organisations involved in drug trafficking. In addition, we describe the dating of wine vintages for a number of authenticated single label vintage red wines from the Barossa Valley - South Australia. Our results show that radiocarbon dating can be used to accurately determine wine vintages and therefore reveal the addition of unrelated materials of natural and synthetic origin.

  13. Effect of HF leaching on 14C dates of pottery

    NASA Astrophysics Data System (ADS)

    Goslar, Tomasz; Kozłowski, Janusz; Szmyt, Marzena; Czernik, Justyna

    2013-01-01

    This paper presents the experiments with 14C dating of two potsherds, which contained carbon dispersed rather homogeneously in their clay fabric. After AAA treatment, the potsherds still appeared to be contaminated with young carbon, presumably connected with humic acids. To make removal of humic acids more effective, we treated the sherds with HF acid of different concentration. The 14C results obtained demonstrate that HF treatment indeed helps to remove humic contaminants, but it also mobilizes carbon bound to raw clay, which may make 14C dates too old. We conclude therefore, that using a simple combination of HF and AAA treatment seems insufficient in reliable 14C dating of carbon homogeneously dispersed in the volume of potsherds.

  14. 13C/Palynological evidence of differential residence times of organic carbon prior to its sedimentation in East African Rift Lakes and peat bogs

    NASA Astrophysics Data System (ADS)

    Hillaire-Marcel, Claude; Aucour, Anne-Marie; Bonnefille, Raymonde; Riollet, Guy; Vincens, Annie; Williamson, David

    Most terrestrial plants producing large amounts of organic matter in the East African Rift follow the Calvin (C3) photosynthetic pathway. Their end products have δ13C values of ca. -27 ± 2‰ (vs. PDB). On the contrary, most Cyperaceae (notably Cyperus papyrus and C. latifolius) are characterized by higher 13C contents ° 13C = -10.5 ± 1‰ ) in relation to their Hatch and Slack (C4) photosynthetic cycle. In consequence, δ13C values in total organic matter (TOM) from peat bog or lake cores essentially responded to the proportion of detritus from C4-Cyperaceae. Immediate evidence of the development or disappearance of Cyperaceae around lake margins or in peat bogs can be found in pollen assemblages. Lag times between pollen signals and correlative ° 13C shifts in TOM from cores are therefore indicative of the residence time of organic matter prior to its sedimentation. Delayed sedimentation of TOM will result in 14C anomalies which depend on several parameters, most of them being site specific as shown by examples from a peat bog in Burundi and from southern Lake Tanganyika. An independent assessment of the chronology by high resolution paleomagnetic correlations indicates a ca. 1.5 ka apparent 14C age of TOM in Lake Tanganyika at the Pleistocene-Holocene transition.

  15. Holocene climate and vegetation change in the Main Ethiopian Rift Valley, inferred from the composition (C/N and δ 13C) of lacustrine organic matter

    NASA Astrophysics Data System (ADS)

    Lamb, Angela L.; Leng, Melanie J.; Umer Mohammed, Mohammed; Lamb, Henry F.

    2004-04-01

    In order to track changes in the relative abundance of C 3 and C 4 plants in savanna vegetation, C/N and δ 13C values were measured on bulk organic material in an 8840 14C-year record from Lake Tilo, Ethiopia. Between 8840 and 2500 BP, high C/N ratios suggest that input to the lake was predominantly from terrestrial plants. The corresponding δ 13C values thus provide a proxy for changes in catchment vegetation that are supported by pollen data. δ 13C values in the early Holocene are relatively low, reflecting the dominance of C 3 vegetation (woody plants) and a more humid climate. δ 13C shows no response to a known regional arid interval at 7800 yr BP, suggesting that woody vegetation was able to survive relatively prolonged dry periods. A gradual, rather than sharp, δ 13C response to the end of the early Holocene humid interval at ˜4500 yr BP further supports this. Higher δ 13C values at ˜2800-2300 and ˜1000 yr BP correspond to increases in sedge pollen, thought to be growing in freshwater springs, exposed as lake-level fell. The C/N and δ 13C composition of bulk organic material complements the pollen evidence and may be useful in other lakes in savanna regions as indicators of terrestrial vegetation change.

  16. High Resolution deglacial monsoon δ18O record from a new stalagmite from the Kailash Cave, Central India

    NASA Astrophysics Data System (ADS)

    Allu C, Narayana; Pawan K, Gautam; Shraddha, Band; Madhusudan G, Yadava; Rengaswamy, Ramesh; Shen, Chuan-Chou

    2016-04-01

    High resolution δ18O and δ13C data from absolutely dated stalagmites have been useful for reconstructing the Asian monsoon variability (e.g., Yadava et al., 2004; Laskar et al., 2013; Allu et al., 2014; Lone et al., 2014; Sinha et al., 2015). However, many studies lack high resolution spatial and temporal records leaving significant gaps which need to be filled for a vivid understanding of monsoonal variability. We report here the first high resolution stalagmite δ18O isotope results during the last deglacial obtained from the Kailash cave located from the core monsoon region. The length of stalagmite was 480 mm, with an average diameter of 120 mm. The sample was cut for continuous micro milling at 400μm intervals along the growth axis (using new wave research micro-mill-101288) for the analyses of stable oxygen and carbon isotopes using a Delta V plus IRMS at the Physical Research Laboratory, Ahmedabad. The physical appearance of the sample section reveals very fine, straight and clear laminations from the top to 310 mm from below, which have thick laminae. U-Th dates obtained from a Thermo Fisher NEPTUNE multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS) at High-Precision Mass Spectrometry and Environment Change Laboratory (HISPEC), National Taiwan University, Taiwan (Shen et al., 2012) showed the record spanned ~2400 years from ~14.6 ka to ~12.2 ka. Linear Age-Depth model constructed from dates suggests that the sample grew for ~2.400 years from ~14.6 ka to ~12.2 ka with varying resolutions from ~6 months to ~8 years. Hendy's test from 8 distinct layers shows poor correlation between δ18O and δ13C suggesting the isotopic equilibrium conditions at the time of crystallization. δ18O and δ13C results appear to be cyclic in nature varying in the range from +0.37‰ to -6.07‰ and -1.59‰ to -10.59‰ respectively. Enriched δ18O in top portion represents poor monsoon during the onset of Younger Drayas. Later, the δ18O signals

  17. Quantitative 13C NMR characterization of fast pyrolysis oils

    DOE PAGES

    Happs, Renee M.; Lisa, Kristina; Ferrell, III, Jack R.

    2016-10-20

    Quantitative 13C NMR analysis of model catalytic fast pyrolysis (CFP) oils following literature procedures showed poor agreement for aromatic hydrocarbons between NMR measured concentrations and actual composition. Furthermore, modifying integration regions based on DEPT analysis for aromatic carbons resulted in better agreement. Solvent effects were also investigated for hydrotreated CFP oil.

  18. Modeling of the 2007 JET ^13C migration experiments

    NASA Astrophysics Data System (ADS)

    Strachan, J. D.; Likonen, J.; Hakola, A.; Coad, J. P.; Widdowson, A.; Koivuranta, S.; Hole, D. E.; Rubel, M.

    2010-11-01

    Using the last run day of the 2007 JET experimental campaign, ^13CH4 was introduced repeatedly from the vessel top into a single plasma type (H-mode, Ip= 1.6 MA, Bt= 1.6 T). Similar experiments were performed in 2001 (vessel top into L-Mode) and 2004 (outer divertor into H-Mode). Divertor and wall tiles were removed and been analysed using secondary ion mass spectrometry (SIMS) and Rutherford backscattering (RBS) to determine the ^13C migration. ^13C was observed to migrate both to the inner (largest deposit), outer divertor (less) , and the floor tiles (least). This paper reports the EDGE2D/NIMBUS based modelling of the carbon migration. The emphasis is on the comparison of the 2007 results with the 2001 results where both injections were from the machine top but ELMs were present in 2007 but not present in 2001. The ELMs seemed to cause more ^13C re-erosion near the inner strike point. Also of interest is the difference in the Private Flux Region deposits where the changes in divertor geometry between 2004 and 2007 caused differences in the deposits. In 2007, the tilting of the load bearing tile caused regions of the PFR to be shadowed from the inner strike point which were not shadowed in 2004, indicating ^13C neutrals originated from the OSP.

  19. Metabolic flux analysis using 13C peptide label measurements

    USDA-ARS?s Scientific Manuscript database

    13C metabolic flux analysis (MFA) has become the experimental method of choice to investigate cellular metabolism. MFA has established flux maps of central metabolism for dozens of microbes, cell cultures, and plant seeds. Steady-state MFA utilizes isotopic labeling measurements of amino acids obtai...

  20. Complete 1H and 13C spectral assignment of floridoside.

    PubMed

    Simon-Colin, Christelle; Kervarec, Nelly; Pichon, Roger; Deslandes, Eric

    2002-02-11

    Floridoside (2-O-alpha-D-galactopyranosylglycerol) was extracted from the red marine alga Rhodymenia palmata, and purified by ion-exchange chromatography: 1D and 2D NMR spectroscopy experiments were used to unambiguously assign the complete 1H and 13C spectra.

  1. Gram-scale synthesis and efficient purification of 13C-labeled levoglucosan from 13C glucose.

    PubMed

    Alexander, Lisa; Hoyt, Caroline; Michalczyk, Ryszard; Wu, Ruilian; Thorn, Dave L; Silks, L A Pete

    2013-01-01

    (13)C-Labeled levoglucosan has been synthesized and purified in good yield, and on the gram scale in one step from commercially available (13)C glucose. This one-step protocol uses 2-chloro-1,3-dimethylimidazolinium chloride that serves to selectively activate the anomeric carbon toward substitution reactions. The labeled glucose is then smoothly converted to the anhydroglucose. Purification is efficiently achieved on large scale by chromatography on silica gel. Published 2012. This article is a US Government work and is in the public domain in the USA.

  2. Recent insights into intramolecular 13C isotope composition of biomolecules

    NASA Astrophysics Data System (ADS)

    Gilbert, A.; Yamada, K.; Julien, M.; Yoshida, N.; Remaud, G.; Robins, R.

    2016-12-01

    In 1961 Abelson & Hoering shown that the intramolecular 13C distribution in amino acids was not homogeneous, namely the carboxylic acid positions were 13C-enriched compared with the mean of the remaining C-atoms in the molecule [1]. Nearly 20 years later, Monson & Hayes were able to demonstrate that even and odd positions in acetogenic fatty acids also showed non-statistical 13C isotope distributions, and that the pattern varied depending on the organism [2]. It took a further decade for the intramolecular 13C distribution in the key metabolite, glucose, to be defined [3]. Although informative, much of this work was incomplete, a number of positions having to be deduced by difference. This limitation arose mainly due to the lack of techniques enabling the separation and quantification of 13C isotopomers of the target molecule. In the past decade, quantitative 13C NMR has been developed for the determination of the intramolecular isotope composition of a given molecule with a precision of 1‰ or better [4]. This breakthrough has made possible a comprehensive view of the determinants governing intramolecular isotope composition of biological molecules. In particular, it can be shown that intramolecular pattern in sugars is influenced by the C-assimilation pathway and by post-photosynthetic fractionation associated with carbohydrate metabolism [5]. In addition, analysis by NMR of the alkyl chain of acetogenic lipids (fatty acids, n-alkanes) shows an alternation between odd and even C-atom positions, as observed by Monson& Hayes [2], throughout the molecule [6]. Overall, it is becoming apparent that this pattern is influenced by two principal metabolic factors: (i) the 13C pattern extant in the starting compounds; (ii) isotope fractionation associated with the enzymes involved in the biosynthetic pathway. On the whole, the determination of intramolecular isotope patterns in biomolecules allows better insights into the conditions and pathways by which they are formed

  3. /sup 14/C distribution in the Atlantic Ocean

    SciTech Connect

    Stuiver, M.

    1980-05-20

    The amount of /sup 14/C produced by nuclear bomb testing that entered the Atlantic Ocean by late 1972 was 1.71 x 10/sup -8/ ..mu..mol/cm/sup 2/ of ocean surface area for the west Atlantic (36/sup 0/S-45/sup 0/N) and 1.18 x 10/sup -8/ ..mu..mol/cm/sup 2/ for the east Atlantic (50/sup 0/S-28/sup 0/N) Geochemical Ocean Sections Study stations. There are strong latitudinal differences in the integrated amount of bomb /sup 14/C content in Atlantic waters. Bomb-produced /sup 14/C is mostly encountered near the center of the large mid-latitude gyres, whereas the equatorial region has a lower /sup 14/C inventory. The average ocean wide vertical distribution of bomb /sup 14/C in the Atlantic can be explained by a vertical eddy diffusion coefficient of 4.0 cm/sup 2//s in the surface mixed layer plus thermocline gyre reservoirs. The average /sup 14/C activity per unit area measured in the Atlantic yields an atmosphere-ocean CO/sub 2/ exchange rate of 23 mol/m/sup 2/ yr, which is equivalent with an atmospheric CO/sub 2/ residence time of 6.8 years.