Science.gov

Sample records for 18o 13c 14c

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. 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

  6. 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.

  7. 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

  8. 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.

  9. 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

  10. 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

  11. 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

  12. 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.

  13. 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

  14. 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

  15. 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

  16. 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

  17. 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.

  18. 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.

  19. 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

  20. 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.

  1. 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

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. 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

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. 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

  15. 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

  16. 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

  17. A study of the carbon dynamics of Japanese grassland and forest using 14C and 13C

    NASA Astrophysics Data System (ADS)

    Katsuno, Kazumi; Miyairi, Yosuke; Tamura, Kenji; Matsuzaki, Hiroyuki; Fukuda, Kenji

    2010-04-01

    We quantified the carbon contents of grassland and forest soil using conventional methods and studied the changes in their dynamics by measuring δ 13C and Δ 14C. Soil samples were taken from a neighboring Miscanthus sinensis grassland and Pinus densiflora forest in central Japan. Both had been maintained as grassland until the 1960s, when the latter was abandoned and became a pine forest by natural succession. The soil carbon content of the forest was much lower than that of the grassland, implying that the soil carbon decreased as the grassland became forest. The δ 13C values were very similar in the grassland and forest, at approximately -20‰, suggesting that M. sinensis (a C4 plant) contributed to carbon storage, whereas there was little carbon accumulation from P. densiflora (a C3 plant) in forest soil. The Δ 14C values and calculated soil carbon mean residence time (MRT) showed that the soil carbon in the upper A horizon was older, and that in the lower A horizon was younger in forest than in grassland. From these results, we conclude that young, fast-MRT soil carbon is decomposed in the upper A horizon, and old, stable soil carbon was decomposed in the lower A horizon after the pine invasion.

  18. 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

  19. 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

  20. 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. 

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. 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

  9. 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

  10. 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

  11. 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.

  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. 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

  15. 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

  16. 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.

  17. 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.

  18. 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

  19. 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

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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

  6. 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

  7. 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).

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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

  16. 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).

  17. 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.

  18. 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.

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. 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

  12. /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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. 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.

  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. 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.

  6. 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

  7. 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.

  8. 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

  9. 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

  10. 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.

  11. 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.

  12. [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).

  13. 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.

  14. 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) .

  15. 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

  16. 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

  17. 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

  18. 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.

  19. 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.

  20. 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

  1. 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.

  2. - 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.

  3. 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.

  4. 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

  5. Utilizing continuous measurements of delta^{13}C_r, delta18O_r, and net ecosystem exchange of CO_2 and H_2O to understand the effects of inter-annual variability in drought on ecosystem functioning

    NASA Astrophysics Data System (ADS)

    Osuna, J. L.; McDowell, N. G.; Shim, J. H.; Rahn, T.; Pockman, W.

    2011-12-01

    In the semi-arid Southwestern US, seasonal drought has strengthened in recent years due to both a decrease in winter precipitation and delayed onset of the summer monsoon. A process-based understanding of ecosystem response to increased drought stress is vital to predicting the long-term stability of semi-arid biomes. To understand the processes responsible for inter-annual and seasonal variability in net ecosystem carbon and water fluxes, we compared nearly continuous measurements of ecosystem scale respiration (R_e) from an eddy covariance system with the stable carbon and oxygen isotope signals in ecosystem respired CO_2 (delta^{13}C_r and delta^{18}O_r) measured continuously by a tunable diode laser spectrometer (TDL) sampling at various canopy heights at the same site. The study site, at Los Alamos National Laboratory, converted from pitilde{n}on juniper woodland to juniper woodland after over 90% of pitilde{n}ons died in 2002-2003 following multiple years of enhanced drought leaving a high necromass at the site. We analyzed the relationships between the Bowen ratio, delta^{18}O_r, daily and annual accumulated NEE, and delta^{13}C_r to understand the (de)coupling between the response of transpiration and respiration under varying degrees of drought stress. Additionally, we explored the variability in the lag and intensity of ecosystem response to precipitation pulses depending on antecedent conditions. The response of delta^{18}O_r was more consistent across years and seasons whereas variability in the contribution of autotrophic versus heterotrophic respiration appeared to cause differing responses of delta^{13}C_r to drought stress and precipitation pulses. This result was supported by the diurnal CO_2 and H_2O fluxes indicating nearly immediate transpirational water loss initiated by most precipitation pulses. Annual accumulated precipitation (versus pulse size) was a better indicator of delta^{13}C_ r response (i.e. relative contributions of autotrophic

  6. 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.

  7. 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

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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

  14. 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.

  15. 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

  16. 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.

  17. 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

  18. 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

  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. 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

  1. 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

  2. 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.

  3. 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.

  4. /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.

  5. 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.

  6. 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

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. 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

  13. 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

  14. (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.

  15. 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.

  16. 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.

  17. 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.

  18. 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%.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. 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

  15. 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

  16. 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

  17. 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

  18. Determination of deoxycholic acid pool size and input rate using (24-/sup 13/C)deoxycholic acid and serum sampling

    SciTech Connect

    Stellard, F.; Paumgartner, G.; van Berge Henegouwen, G.P.; van der Werf, S.D.

    1986-11-01

    We have developed an isotope dilution method for determination of deoxycholic acid pool size and input rate which employs oral administration of 50 mg of (24-/sup 13/C)deoxycholic acid and serum sampling. The method has been validated by classical isotope dilution technique using (24-/sup 14/C)deoxycholic acid and bile sampling in five patients with colonic adenomas. Excellent agreement between pool sizes and input rates determined with /sup 13/C/12C isotope ratio measurements in serum and /sup 14/C measurements in bile was obtained when isotope ratios were measured in the conjugated fraction of deoxycholic acid in serum. We conclude that pool size and input rate of deoxycholic acid can accurately be determined by blood sampling after oral administration of (24-/sup 13/C)deoxycholic acid, therewith eliminating the use of radioactive tracers and the need for bile sampling.

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. 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.

  5. ( 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.

  6. 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.

  7. 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.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. 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.

  15. 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.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  17. 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.

  18. 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.

  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. 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

  1. 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

  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. 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.

  4. Hyperpolarized 13C Metabolic MRI of the Human Heart

    PubMed Central

    Lau, Justin Y.C.; Chen, Albert P.; Geraghty, Benjamin J.; Perks, William J.; Roifman, Idan; Wright, Graham A.; Connelly, Kim A.

    2016-01-01

    Rationale: Altered cardiac energetics is known to play an important role in the progression toward heart failure. A noninvasive method for imaging metabolic markers that could be used in longitudinal studies would be useful for understanding therapeutic approaches that target metabolism. Objective: To demonstrate the first hyperpolarized 13C metabolic magnetic resonance imaging of the human heart. Methods and Results: Four healthy subjects underwent conventional proton cardiac magnetic resonance imaging followed by 13C imaging and spectroscopic acquisition immediately after intravenous administration of a 0.1 mmol/kg dose of hyperpolarized [1-13C]pyruvate. All subjects tolerated the procedure well with no adverse effects reported ≤1 month post procedure. The [1-13C]pyruvate signal appeared within the chambers but not within the muscle. Imaging of the downstream metabolites showed 13C-bicarbonate signal mainly confined to the left ventricular myocardium, whereas the [1-13C]lactate signal appeared both within the chambers and in the myocardium. The mean 13C image signal:noise ratio was 115 for [1-13C]pyruvate, 56 for 13C-bicarbonate, and 53 for [1-13C]lactate. Conclusions: These results represent the first 13C images of the human heart. The appearance of 13C-bicarbonate signal after administration of hyperpolarized [1-13C]pyruvate was readily detected in this healthy cohort (n=4). This shows that assessment of pyruvate metabolism in vivo in humans is feasible using current technology. Clinical Trial Registration: URL: https://www.clinicaltrials.gov. Unique identifier: NCT02648009. PMID:27635086

  5. 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.

  6. 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.

  7. 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.

  8. Radiocarbon, 13C and 15N analysis of fossil bone: Removal of humates with XAD-2 resin

    NASA Astrophysics Data System (ADS)

    Stafford, Thomas W., Jr.; Brendel, Klaus; Duhamel, Raymond C.

    1988-09-01

    Humic acids are the predominant source of error in the 14C and stable isotope analysis of fossil bone organic matter. XAD-2 resin will quantitatively remove humates and give the highest yields of protein from bones with variable types of preservation. Decalcified bone, gelatin and base-leached residues can vary up to 5%. for δ 13C and by 1%. on δ 15N relative to XAD-treated fractions. Simultaneous analysis of 14C age, δ 13C and δ 15N is recommended because each isotope value can be independently affected by the bone's diagenetic history. Radiocarbon analysis is the most sensitive and δ 15N is least sensitive for detecting exogenous organic matter. The uncertainty of analyses on the best pretreated protein is ±0.5%. for both δ 13C and δ 15N and is larger than previous estimates. The accuracy for all isotope analyses will be better assessed by using individual amino acids instead of total collagenous residues. Inaccurate 14C dates on severely degraded bone are an indication that this class of fossils may be unsuitable for any isotopic analysis.

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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

  14. 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.

  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. 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.

  17. 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.

  18. Hyperpolarized 13C MR Markers of Renal Tumor Aggressiveness

    DTIC Science & Technology

    2013-10-01

    reliably distinguish renal cancer aggressiveness for optimal triage of therapies . Hyperpolarized (HP) 13C magnetic resonance spectroscopic imaging (MRSI...reliably distinguish renal cancer aggressiveness for optimal triage of therapies . Hyperpolarized (HP) 13C magnetic resonance spectroscopic imaging (MRSI) is... cancer and normal tissues were obtained from nephrectomy specimens and sliced using Krumdieck slicer. With a precision gauge micrometer, the slice

  19. Functional groups identified by solid state 13C NMR spectroscopy

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  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. 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

  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. 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.

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. 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.

  17. 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.

  18. 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

  19. 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.

  20. 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

  1. 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

  2. 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

  3. 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

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. {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.

  15. 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.

  16. 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.

  17. 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.

  18. 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

  19. 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.

  20. 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

  1. Combining 14C/U-Th Series Geochronology and Stable/Clumped Isotope Geochemistry of MIS 2 Lake Tufas of Lake Chewaucan, Oregon, USA to Reconstruct Deglacial Climate in the Pacific Northwest

    NASA Astrophysics Data System (ADS)

    Hudson, A. M.; Quade, J.; Ali, G.; Boyle, D. P.; Bassett, S.; Huntington, K. W.

    2015-12-01

    Shoreline deposits surrounding closed-basin lake remnants in the Great Basin of North America have been critical to defining the timing and extent of lake highstands during Marine Isotope Stage 2, recording the wettest climate conditions during the last glacial cycle. We present 14C and U-Th series ages and stable and clumped isotope results from MIS 2 microbialite tufas of pluvial Lake Chewaucan, southern Oregon. At ~42.5°N latitude, the Chewaucan basin is the one of the northernmost lake systems in the Great Basin, a critical location for investigating regional climate. Dating of modern tufa and DIC indicates no 14C reservoir effect. Low lake depth is observed for peak LGM conditions (21.0 ka, +11 m above modern), consistent with regional records and climate model results. In contrast with other Great Basin lake reconstructions for deglacial MIS 2, Lake Chewaucan was deepest during the Bølling/Ållerod (B/A; 14.5-13.0 ka, +50 m) and early Holocene (10.9-9.5 ka +15 m) warm periods, with lowstands during Heinrich Event 1 (+0-1 m) and Younger Dryas cold periods (+0 m). This supports previous evidence for wet interstadials in the Pacific Northwest (PNW) during MIS 2-3, the opposite of the central/southern Great Basin, where stadials correlate with wet conditions. δ18O values of tufas (-0.9 to -4.4‰ PDB) reflect high evaporation relative to inflowing meteoric water (-13.6‰ SMOW), and lake water (-6.7 SMOW). δ13C values (+1.7 to +4.5‰ PDB) are consistent with equilibrium with lake DIC (+1.5‰ PDB) and atmospheric CO2, supporting atmospheric 14C equilibrium. Clumped isotope temperatures for modern tufa (20±7°C) are consistent with summer lake surface temperature for modern lake remnant, Abert Lake (17.7-22.0°C), supporting previous clumped isotope results for tufas as summer temperature indicators. Clumped temperatures for the B/A highstand are 19±4°C, indicating near modern lake temperatures during deepest lake conditions. 13±4°C is indicated for the

  2. 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

  3. Metabolic flux analysis using 13C peptide label measurements

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  4. 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.

  5. 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.

  6. 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.

  7. Assessing microbial utilization of free versus sorbed Alanine by using position-specific 13C labeling and 13C-PLFA analysis

    NASA Astrophysics Data System (ADS)

    Herschbach, Jennifer; Apostel, Carolin; Spielvogel, Sandra; Kuzyakov, Yakov; Dippold, Michaela

    2016-04-01

    Microbial utilization is a key transformation process of soil organic matter (SOM). Sorption of low molecular weight organic substances (LMWOS) to soil mineral surfaces blocks or 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 science, combined with 13C-phospholipid fatty acid (PLFA) analysis, to assess microbial utilization of sorbed and non-sorbed Alanine in soil. Alanine has various functional groups enabling different sorption mechanisms via its positive charge (e.g. to clay minerals by cation exchange), as well as via its negative charge (e.g. to iron oxides by ligand exchange). To assess changes in the transformation pathways caused by sorption, we added uniformly and position-specifically 13C and 14C labeled Alanine to the Ap of a loamy Luvisol in a short-term (10 days) incubation experiment. To allow for sorption of the tracer solution to an aliquot of this soil, microbial activity was minimized in this subsample by sterilizing the soil by γ-radiation. After shaking, the remaining solutions were filtered and the non-sorbed Alanine was removed with Millipore water and then added to non-sterilized soil. For the free Alanine treatment, solutions with Alanine of similar amount and isotopic composition were prepared, added to the soil and incubated as well. The respired CO2 was trapped in NaOH and its 14C-activity was determined at increasing times intervals. Microbial utilization of Alanine's individual C positions was evaluated in distinct microbial groups classified by 13C-PLFA analysis. Sorption to soil minerals delayed respiration to CO2 and reduced initial respiration rate by 80%. Irrespective of sorption, the highest amount was respired from the carboxylic position (C-1), whereas the amino-bound (C-2) and the methylic position (C-3) were preferentially incorporated into PLFA of microorganisms due to the

  8. Optical hyperpolarization of 13C nuclear spins in nanodiamond ensembles

    NASA Astrophysics Data System (ADS)

    Chen, Q.; Schwarz, I.; Jelezko, F.; Retzker, A.; Plenio, M. B.

    2015-11-01

    Dynamical nuclear polarization holds the key for orders of magnitude enhancements of nuclear magnetic resonance signals which, in turn, would enable a wide range of novel applications in biomedical sciences. However, current implementations of DNP require cryogenic temperatures and long times for achieving high polarization. Here we propose and analyze in detail protocols that can achieve rapid hyperpolarization of 13C nuclear spins in randomly oriented ensembles of nanodiamonds at room temperature. Our protocols exploit a combination of optical polarization of electron spins in nitrogen-vacancy centers and the transfer of this polarization to 13C nuclei by means of microwave control to overcome the severe challenges that are posed by the random orientation of the nanodiamonds and their nitrogen-vacancy centers. Specifically, these random orientations result in exceedingly large energy variations of the electron spin levels that render the polarization and coherent control of the nitrogen-vacancy center electron spins as well as the control of their coherent interaction with the surrounding 13C nuclear spins highly inefficient. We address these challenges by a combination of an off-resonant microwave double resonance scheme in conjunction with a realization of the integrated solid effect which, together with adiabatic rotations of external magnetic fields or rotations of nanodiamonds, leads to a protocol that achieves high levels of hyperpolarization of the entire nuclear-spin bath in a randomly oriented ensemble of nanodiamonds even at room temperature. This hyperpolarization together with the long nuclear-spin polarization lifetimes in nanodiamonds and the relatively high density of 13C nuclei has the potential to result in a major signal enhancement in 13C nuclear magnetic resonance imaging and suggests functionalized and hyperpolarized nanodiamonds as a unique probe for molecular imaging both in vitro and in vivo.

  9. 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.

  10. 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.

  11. Synthesis of [1-.sup.13C]pyruvic acid], [2-.sup.13C]pyruvic acid], [3-.sup.13C]pyruvic acid] and combinations thereof

    DOEpatents

    Martinez, Rodolfo A. , Unkefer; Clifford J. , Alvarez; Marc, A [Santa Fe, NM

    2012-06-12

    The present invention is directed to the labeled compounds, ##STR00001## wherein C* is each either .sup.13C and .sup.12C where at least one C* is .sup.13C, each hydrogen of the methylene group is hydrogen or deuterium, the methyl group includes either zero or three deuterium atoms, Q is sulfide, sulfinyl, or sulfone, Z is an aryl group such as 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, or a phenyl group ##STR00002## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently either hydrogen, a C.sub.1-C.sub.4 lower alkyl, a halogen, and an amino group such as NH.sub.2, NHR and NRR' where R and R' are each independently either a C.sub.1-C.sub.4 lower alkyl, a phenyl, and an alkoxy group, and the methyl group can include either zero or three deuterium atoms. The present invention is also directed to the labeled compounds ##STR00003##

  12. Synthesis of [1-.sup.13C]pyruvic acid], [2-.sup.13C]pyruvic acid], [3-.sup.13C]pyruvic acid] and combinations thereof

    DOEpatents

    Martinez, Rodolfo A.; Unkefer, Clifford J.; Alvarez, Marc A.

    2009-09-01

    The present invention is directed to labeled compounds, of the formulae ##STR00001## wherein C* is each independently selected from the group consisting of .sup.13C and .sup.12C with the proviso that at least one C* is .sup.13C, each hydrogen of the methylene group can independently be either hydrogen or deuterium, the methyl group includes either zero or three deuterium atoms, Q is from the group of sulfide, sulfinyl, and sulfone, Z is an aryl group from the group of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure ##STR00002## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently from the group of hydrogen, a C.sub.1-C.sub.4 lower alkyl, a halogen, and an amino group from the group of NH.sub.2, NHR and NRR' where R and R' are each independently from the group of a C.sub.1-C.sub.4 lower alkyl, a phenyl, and an alkoxy group, and the methyl group can include either zero or three deuterium atoms.

  13. /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.

  14. Quantification of 13C pyruvate and 13C lactate in dog blood by reversed-phase liquid chromatography-electrospray ionization mass spectrometry after derivatization with 3-nitrophenylhydrazine.

    PubMed

    Uran, Steinar; Landmark, Kristin Eitrem; Hjellum, Gro; Skotland, Tore

    2007-08-15

    Injection of hyperpolarized (13)C-labelled pyruvate ((13)C pyruvate) is under evaluation as an agent for medical metabolic imaging by measuring formation of (13)C lactate using magnetic resonance spectroscopy of the (13)C nuclei. A quantitative method for analysis of these (13)C-labelled substances in dog blood was needed as part of the development of this agent and we here describe a liquid chromatography-mass spectrometry method for that purpose. Immediately after blood collection, the blood proteins were precipitated using methanol added internal standard ([U-(13)C]pyruvate and [U-(13)C]lactate). Prior to analysis, the compounds were derivatized using 3-nitrophenylhydrazine. Following separation on a Supelco Discovery HS C18 column, (13)C pyruvate and (13)C lactate were detected using negative electrospray ionization mass spectrometry. Calibration standards (4.5-4500 microM (13)C pyruvate and 9-9000 microM (13)C lactate) and added internal standard were used to make the calibration curves, which were fitted to a non-linear equation y=a+bx+cx(2) and weighted with a weighting factor of 1/y(2). The analytical lower limit of quantification of (13)C pyruvate and (13)C lactate was 4.5 and 9 microM, respectively. The total precision of the method was below 9.2% for (13)C pyruvate and below 5.8% for (13)C lactate. The accuracy of the method showed a relative error less than 2.4% for (13)C pyruvate and less than 6.3% for (13)C lactate. The recoveries were in the range 93-115% for (13)C pyruvate and 70-111% for (13)C lactate. Both substances were stable in protein-free supernatant when stored for up to 3 weeks in a -20 degrees C freezer, during three freeze/thaw cycles, and when stored in an autosampler for at least 30 h.

  15. Partitioning of Soil Respiration Sources Using 14C-Enriched Leaf Litter and Roots in a Temperate Forest, Oak Ridge, TN

    NASA Astrophysics Data System (ADS)

    Cisneros Dozal, L.; Trumbore, S.; Hanson, P.; Xu, X.

    2002-12-01

    Leaf litter enriched in 14C with values ranging from +952‰ to +1055 ‰ and control leaf litter with Δ14C of +215 ‰ to +230 ‰ were used to establish replicated plots on the Oak Ridge Reservation (ORR), Oak Ridge National Laboratory, Tennessee for tracking of soil carbon cycling. Our goal is to partition the heterotrophic and autotrophic components of total CO2 emission from the soil. Measurements have been carried out in the summer of 2001 and 2002 at two sites (Walker Branch and TVA) that are on the same soil type, but that have different initial levels of 14C resulting from a localized ecosystem-scale 14C release event in 1999. Measurements include total soil respiration rates using a chamber technique, trapping of CO2 evolved from chambers and from root respiration to determine 14C and 13C signatures, and incubations of soil and leaf litter in the laboratory to obtain rates of decomposition and 14C and 13C signatures from heterotrophic CO2 sources. Total C fluxes (mg C/m2-hr) varied among the sites by up to ~40%, with differences between enriched and control plots similar to site-to-site variation between TVA and Walker Branch. In May of 2002, the 14C signature of the total CO2 emitted from the enriched plots was always higher than that of the control plots in both sites, with averaged values of Δ14C of +493 ‰ and +357 ‰ in TVA and of +300 ‰ and +156 ‰ in Walker Branch, for the enriched and control plots respectively. We use the mass balance equation, Δ14Ctotal=FxΔ14C{leaf litter}+(1-F)x(Δ14C{root and soil decomposition} +Δ14C{roots respiration}) to estimate the contribution of leaf litter decomposition to the total CO2 flux (F). Within any one site, the difference in the 14C signature emitted from the soil between the two treatments should be directly proportional to the contribution of leaf litter decomposition only, since the other components (roots and soil decomposition and roots respiration) are assumed to remain the same for enriched

  16. The 13C-excess: a new dual-element stable isotopic approach for detrending the effects of evaporation on lake carbonates

    NASA Astrophysics Data System (ADS)

    Horton, T. W.; Oze, C.

    2012-12-01

    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. Here, we show that globally distributed Quaternary 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 hydrological conditions and water source effects such as the strength of prevailing air-mass trajectory, >3km errors in paleoelevation estimates, unrealistic shifts in lake water temperature, and misleading interpretations of local carbon cycle 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 detrend lake carbonate compositions for the effects of surface water evaporation using a parameter we define here 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. To demonstrate the potential strength of the 13C-excess approach over single element methods, we compare the paleoelevation estimates derived from lake carbonate compositions using both approaches. When Tibetan lakes are excluded from the dataset, 13C-excess values are significantly correlated with mean up-slope hypsometric altitude with

  17. Imaging pH with hyperpolarized 13C.

    PubMed

    Gallagher, Ferdia A; Kettunen, Mikko I; Brindle, Kevin M

    2011-10-01

    pH is a fundamental physiological parameter that is tightly controlled by endogenous buffers. The acid-base balance is altered in many disease states, such as inflammation, ischemia and cancer. Despite the importance of pH, there are currently no routine methods for imaging the spatial distribution of pH in humans. The enormous gain in sensitivity afforded by dynamic nuclear polarization (DNP) has provided a novel way in which to image tissue pH using MR, which has the potential to be translated into the clinic. This review explores the advantages and disadvantages of current pH imaging techniques and how they compare with DNP-based approaches for the measurement and imaging of pH with hyperpolarized (13)C. Intravenous injection of hyperpolarized (13)C-labeled bicarbonate results in the rapid production of hyperpolarized (13)CO(2) in the reaction catalyzed by carbonic anhydrase. As this reaction is close to equilibrium in the body and is pH dependent, the ratio of the (13)C signal intensities from H(13)CO(3)(-) and (13)CO(2), measured using MRS, can be used to calculate pH in vivo. The application of this technique to a murine tumor model demonstrated that it measured predominantly extracellular pH and could be mapped in the animal using spectroscopic imaging techniques. A second approach has been to use the production of hyperpolarized (13)CO(2) from hyperpolarized [1-(13)C]pyruvate to measure predominantly intracellular pH. In tissues with a high aerobic capacity, such as the heart, the hyperpolarized [1-(13)C]pyruvate undergoes rapid oxidative decarboxylation, catalyzed by intramitochondrial pyruvate dehydrogenase. Provided that there is sufficient carbonic anhydrase present to catalyze the rapid equilibration of the hyperpolarized (13)C label between CO(2) and bicarbonate, the ratio of their resonance intensities may again be used to estimate pH, which, in this case, is predominantly intracellular. As both pyruvate and bicarbonate are endogenous molecules they

  18. δ18O anchoring to VPDB: calcite digestion with 18O-adjusted ortho-phosphoric acid.

    PubMed

    Wendeberg, Magnus; Richter, Jürgen M; Rothe, Michael; Brand, Willi A

    2011-04-15

    For anchoring CO(2) isotopic measurements on the δ(18)O(VPD-CO2) scale, the primary reference material (NBS 19 calcite) needs to be digested using concentrated ortho-phosphoric acid. During this procedure, great care must be taken to ensure that the isotopic composition of the liberated gas is accurate. Apart from controlling the reaction temperature to ±0.1 °C, the potential for oxygen isotope exchange between the produced CO(2) and water must be kept to a minimum. The water is usually assumed to reside on the walls in the headspace of the reaction vessel. We demonstrate here that a large fraction of the exchange may also occur with water inside the acid. Our results indicate that both exchange reactions have a significant impact on the results and may have largely been responsible for scale inconsistencies between laboratories in the past. The extent of CO(2)/H(2)O oxygen exchange depends on the concentration (amount of free water) in the acid. For acids with a nominal H(3)PO(4) mass fraction of less than 102%, oxygen isotope exchange can create a substantial isotopic bias during high-precision measurements with the degree of the alteration being proportional to the effective isotopic contrast between the acid and the CO(2) released from the calcite. Water evaporating from the acid at 25 °C has a δ(18)O value of -34.5‰ relative to the isotopic composition of the whole acid. This large fractionation is likely to occur in two steps; by exchange with phosphate, water inside the acid is decreased in oxygen-18 relative to the bulk acid by ∼ -22‰. This water is then fractionated further during evaporation. Oxygen exchange with both water inside the acid and water condensate in the headspace can contribute to the measured isotopic signature depending on the experimental parameters. The system employed for this study has been specifically designed to minimize oxygen exchange with water. However, the amount of altered CO(2) for a 95% H(3)PO(4) at 25 °C still

  19. Intramolecular labelling of sucrose made by leaves from [14C)carbon dioxide or [3-14C]serine.

    PubMed Central

    Bird, I F; Cornelius, M J; Keys, A J; Whittingham, C P

    1978-01-01

    Pea leaves were illuminated in air containing 150 or 1000p.p.m. of 14CO2 for various times. Alternatively, segments of wheat leaves were supplied with [3-14C]serine for 40 min in the light in air with 145, 326 or 944p.p.m. of 12CO2. Sucrose was extracted from the leaf material, hydrolysed with invertase, and 14C in the pairs of carbon atoms C-3+C-4, C-2+C-5 and C-1+C-6 in the glucose moiety was measured. The results obtained after metabolism of 14CO2 were consistent with the operation of the photosynthetic carbon-reduction cycle; the effects of CO2 concentration on distribution of 14C in the carbon chain of glucose after metabolism of [3-14C]serine is more easily explained by metabolism through the glycollate pathway than by the carbon-reduction cycle. PMID:656073

  20. Identification of Biodegradation Pathways in a Multi-Process Phytoremediation System (MPPS) Using Natural Abundance 14C Analysis of PLFA

    NASA Astrophysics Data System (ADS)

    Cowie, B. R.; Greenberg, B. M.; Slater, G. F.

    2008-12-01

    Optimizing remediation of petroleum-contaminated soils requires thorough understanding of the mechanisms and pathways involved in a proposed remediation system. In many engineered and natural attenuation systems, multiple degradation pathways may contribute to observed contaminant mass losses. In this study, biodegradation in the soil microbial community was identified as a major pathway for petroleum hydrocarbon removal in a Multi-Process Phytoremediation System (MPPS) using natural abundance 14C analysis of Phospholipid Fatty Acids (PLFA). In contaminated soils, PLFA were depleted in Δ14C to less than -800‰, directly demonstrating microbial uptake and utilization of petroleum derived carbon (Δ14C = -992‰) during bioremediation. Mass balance indicated that more than 80% of microbial carbon was derived from petroleum hydrocarbons and a maximum of 20% was produced from metabolism of modern carbon sources. In contrast, in a nearby uncontaminated control soil, the microbial community maintained a nearly modern 14C signature, suggesting preferential degradation of more labile, recent carbon. Mass balance using δ13C and Δ14C of soil CO2 demonstrated that mineralization of petroleum carbon contributed 60-65% of soil CO2 at the contaminated site. The remainder was derived from atmospheric (27-30%) and decomposition of non- petroleum natural organic carbon (5-10%). The clean control exhibited substantially lower CO2 concentrations that were derived from atmospheric (55%) and natural organic carbon (45%) sources. This study highlights the value of using multiple carbon isotopes to identify degradation pathways in petroleum- contaminated soils undergoing phytoremediation and the power of natural abundance 14C to detect petroleum metabolism in natural microbial communities.

  1. 14C BOMB-PULSE DATING AND STABLE ISOTOPE ANALYSIS FOR GROWTH RATE AND DIETARY INFORMATION IN BREAST CANCER?

    PubMed

    Lång, K; Eriksson Stenström, K; Rosso, A; Bech, M; Zackrisson, S; Graubau, D; Mattsson, S

    2016-06-01

    The purpose of this study was to perform an initial investigation of the possibility to determine breast cancer growth rate with (14)C bomb-pulse dating. Tissues from 11 breast cancers, diagnosed in 1983, were retrieved from a regional biobank. The estimated average age of the majority of the samples overlapped the year of collection (1983) within 3σ Thus, this first study of tumour tissue has not yet demonstrated that (14)C bomb-pulse dating can obtain information on the growth of breast cancer. However, with further refinement, involving extraction of cell types and components, there is a possibility that fundamental knowledge of tumour biology might still be gained by the bomb-pulse technique. Additionally, δ (13)C and δ (15)N analyses were performed to obtain dietary and metabolic information, and to serve as a base for improvement of the age determination.

  2. 14C BOMB-PULSE DATING AND STABLE ISOTOPE ANALYSIS FOR GROWTH RATE AND DIETARY INFORMATION IN BREAST CANCER?

    PubMed Central

    Lång, K.; Eriksson Stenström, K.; Rosso, A.; Bech, M.; Zackrisson, S.; Graubau, D.; Mattsson, S.

    2016-01-01

    The purpose of this study was to perform an initial investigation of the possibility to determine breast cancer growth rate with 14C bomb-pulse dating. Tissues from 11 breast cancers, diagnosed in 1983, were retrieved from a regional biobank. The estimated average age of the majority of the samples overlapped the year of collection (1983) within 3σ. Thus, this first study of tumour tissue has not yet demonstrated that 14C bomb-pulse dating can obtain information on the growth of breast cancer. However, with further refinement, involving extraction of cell types and components, there is a possibility that fundamental knowledge of tumour biology might still be gained by the bomb-pulse technique. Additionally, δ 13C and δ 15N analyses were performed to obtain dietary and metabolic information, and to serve as a base for improvement of the age determination. PMID:27179119

  3. Peripheral elastic and inelastic scattering of {sup 17,18}O on light targets at 12 MeV/nucleon

    SciTech Connect

    Carstoiu, F.; Al-Abdullah, T.; Gagliardi, C. A.; Trache, L.

    2015-02-24

    The elastic and inelastic scattering of {sup 17,18}O with light targets has been undertaken at 12 MeV/nucleon in order to determine the optical potentials needed for the transfer reaction {sup 13}C({sup 17}O,{sup 18}O){sup 12}C. Optical potentials in both incoming and outgoing channels have been determined in a single experiment. This transfer reaction was used to infer the direct capture rate to the {sup 17}F(p,γ){sup 18}Ne which is essential to estimate the production of {sup 18}F at stellar energies in ONe novae. We demonstrate the stability of the ANC method and OMP results using good quality elastic and inelastic scattering data with stable beams. The peripherality of our reaction is inferred from a semiclassical decomposition of the total scattering amplitude into barrier and internal barrier components. Comparison between elastic scattering of {sup 17}O, {sup 18}O and {sup 16}O projectiles is made.

  4. δ18O Record of the Last Deglaciation Measured in the Tyrrhenian Deep-Sea Core CT85-5

    NASA Astrophysics Data System (ADS)

    Taricco, Carla; Mancuso, Salvatore; Hajdas, Irka; Rubinetti, Sara; Bernasconi, Stefano M.

    2014-05-01

    We present the δ18O measurements corresponding to the upper 450 cm of the Central Mediterranean deep-sea core CT85-5. The detailed radiocarbon chronology of this core, which is based on the analysis of foraminifera shells, is reported in Hajdas et al. (2011). This chronology shows regular features, but a reversal in 14C ages appears, corresponding to a layer containing the deposit of the Campanian Ignimbrite (~ 40 kyr cal BP) that overlaps with the layer where an enhanced 10Be concentration in sediment was found (Castagnoli et al. 1995). Due to this feature of the core, a reliable calibration of δ18O profile was obtained only for the last 270 cm. The comparison between our δ18O profile and Mediterranean and high latitudes records, including North Atlantic sediments and Greenland ice cores, will be discussed. I. Hajdas, C. Taricco, G. Bonani, J. Beer, S. M. Bernasconi, L. Wacker, Anomalous radiocarbon ages found in Campanian Ignimbrite deposit of the Mediterranean deep-sea core CT85-5, Radiocarbon, 53, n. 4, 575, 2011. Castagnoli G.C., Albrecht A., Beer J., Bonino G., Shen C., Callegari E., Taricco C., Dittrich-Hannen B., Kubik P.,Suter M., Zhu G.M., Evidence for enhanced 10Be deposition in Mediterranean sediments 35 kyr BP, Geophysical Research Letters, 22(6), 707, 1995.

  5. 13C Tracer Studies of Metabolism in Mouse Tumor Xenografts

    PubMed Central

    Lane, Andrew N.; Yan, Jun; Fan, Teresa W-M.

    2015-01-01

    Mice are widely used for human tumor xenograft studies of cancer development and drug efficacy and toxicity. Stable isotope tracing coupled with metabolomic analysis is an emerging approach for assaying metabolic network activity. In mouse models there are several routes of tracer introduction, which have particular advantages and disadvantages that depend on the model and the questions addressed. This protocol describes the bolus i.v. route via repeated tail vein injections of solutions of stable isotope enriched tracers including 13C6-glucose and 13C5,15N2-glutamine. Repeated injections give higher enrichments and over longer labeling periods than a single bolus. Multiple injections of glutamine are necessary to achieve adequate enrichment in engrafted tumors. PMID:26693168

  6. 14C Analysis of Protein Extracts from Bacillus Spores

    PubMed Central

    Cappucio, Jenny A.; Sarachine Falso, Miranda J.; Kashgarian, Michaele; Buchholz, Bruce A.

    2014-01-01

    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 F14C (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 F14C values of biological materials and has been used to date the synthesis of biomaterials over the bomb pulse era (1955 to present). The F14C 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 F14C 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 14C 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 14C bomb-pulse dating. Since media is contemporary, 14C bomb-pulse dating of isolated soluble proteins can be used to distinguish between historical archives of bioagents and those produced from recent media. PMID:24814329

  7. Characterization of 14C in Swedish light water reactors.

    PubMed

    Magnusson, Asa; Aronsson, Per-Olof; Lundgren, Klas; Stenström, Kristina

    2008-08-01

    This paper presents the results of a 4-y investigation of 14C in different waste streams of both boiling water reactors (BWRs) and pressurized water reactors (PWRs). Due to the potential impact of 14C on human health, minimizing waste and releases from the nuclear power industry is of considerable interest. The experimental data and conclusions may be implemented to select appropriate waste management strategies and practices at reactor units and disposal facilities. Organic and inorganic 14C in spent ion exchange resins, process water systems, ejector off-gas and replaced steam generator tubes were analyzed using a recently developed extraction method. Separate analysis of the chemical species is of importance in order to model and predict the fate of 14C within process systems as well as in dose calculations for disposal facilities. By combining the results of this investigation with newly calculated production rates, mass balance assessments were made of the 14C originating from production in the coolant. Of the 14C formed in the coolant of BWRs, 0.6-0.8% was found to be accumulated in the ion exchange resins (core-specific production rate in the coolant of a 2,500 MWth BWR calculated to be 580 GBq GW(e)(-1) y(-1)). The corresponding value for PWRs was 6-10% (production rate in a 2,775 MWth PWR calculated to be 350 GBq GW(e)(-1) y(-1)). The 14C released with liquid discharges was found to be insignificant, constituting less than 0.5% of the production in the coolant. The stack releases, routinely measured at the power plants, were found to correspond to 60-155% of the calculated coolant production, with large variations between the BWR units.

  8. Galactose oxidation using (13)C in healthy and galactosemic children.

    PubMed

    Resende-Campanholi, D R; Porta, G; Ferrioli, E; Pfrimer, K; Ciampo, L A Del; Junior, J S Camelo

    2015-03-01

    Galactosemia is an inborn error of galactose metabolism that occurs mainly as the outcome of galactose-1-phosphate uridyltransferase (GALT) deficiency. The ability to assess galactose oxidation following administration of a galactose-labeled isotope (1-(13)C-galactose) allows the determination of galactose metabolism in a practical manner. We aimed to assess the level of galactose oxidation in both healthy and galactosemic Brazilian children. Twenty-one healthy children and seven children with galactosemia ranging from 1 to 7 years of age were studied. A breath test was used to quantitate (13)CO2 enrichment in exhaled air before and at 30, 60, and 120 min after the oral administration of 7 mg/kg of an aqueous solution of 1-(13)C-galactose to all children. The molar ratios of (13)CO2 and (12)CO2 were quantified by the mass/charge ratio (m/z) of stable isotopes in each air sample by gas-isotope-ratio mass spectrometry. In sick children, the cumulative percentage of (13)C from labeled galactose (CUMPCD) in the exhaled air ranged from 0.03% at 30 min to 1.67% at 120 min. In contrast, healthy subjects showed a much broader range in CUMPCD, with values from 0.4% at 30 min to 5.58% at 120 min. The study found a significant difference in galactose oxidation between children with and without galactosemia, demonstrating that the breath test is useful in discriminating children with GALT deficiencies.

  9. 13C NMR of Nephila clavipes major ampullate silk gland.

    PubMed

    Hijirida, D H; Do, K G; Michal, C; Wong, S; Zax, D; Jelinski, L W

    1996-12-01

    The major ampullate glands of the spider Nephila clavipes contain approximately 0.2 microliter each of a highly concentrated (approximately 50%) solution of silk fibroin. Therefore, the reservoir of silk in these glands presents an ideal opportunity to observe prefolded conformations of a protein in its native state. To this end, the structure and conformation of major ampullate gland silk fibroin within the glands of the spider N. clavipes were examined by 13C NMR spectroscopy. These results were compared to those from silk protein first drawn from the spinneret and then denatured. The 13C NMR chemical shifts, along with infrared and circular dichroism data, suggest that the silk fibroin in the glands exists in dynamically averaged helical conformations. Furthermore, there is no evidence of proline residues in U-(13)C-D-glucose-labeled silk. This transient prefolded "molten fibril" state may correspond to the silk I form found in Bombyx mori silk. There is no evidence of the final beta-sheet structure in the ampullate gland silk fibroin before final silk processing. However, the conformation of silk in the glands appears to be in a highly metastable state, as plasticization with water produces the beta-sheet structure. Therefore, the ducts connecting the ampullate glands to the spinnerets play a larger role in silk processing than previously thought.

  10. Millimeter and submillimeter wave spectra of 13C methylamine

    NASA Astrophysics Data System (ADS)

    Motiyenko, R. A.; Margulès, L.; Ilyushin, V. V.; Smirnov, I. A.; Alekseev, E. A.; Halfen, D. T.; Ziurys, L. M.

    2016-03-01

    Context. Methylamine (CH3NH2) is a light molecule of astrophysical interest, which has an intensive rotational spectrum that extends in the submillimeter wave range and far beyond, even at temperatures characteristic for the interstellar medium. It is likely for 13C isotopologue of methylamine to be identified in astronomical surveys, but there is no information available for the 13CH3NH2 millimeter and submillimeter wave spectra. Aims: In this context, to provide reliable predictions of 13CH3NH2 spectrum in millimeter and submillimeter wave ranges, we have studied rotational spectra of the 13C methylamine isotopologue in the frequency range from 48 to 945 GHz. Methods: The spectrum of 13C methylamine was recorded using conventional absorption spectrometers. The analysis of the rotational spectrum of 13C methylamine in the ground vibrational state was performed on the basis of the group-theoretical high-barrier tunneling Hamiltonian that was developed for methylamine. The available multiple observations of the parent methylamine species toward Sgr B2(N) at 1, 2, and 3 mm using the Submillimeter Telescope and the 12 m antenna of the Arizona Radio Observatory were used to make a search for interstellar 13CH3NH2. Results: In the recorded spectra, we have assigned 2721 rotational transitions that belong to the ground vibrational state of the 13CH3NH2. These measurements were fitted to the Hamiltonian model that uses 75 parameters to achieve an overall weighted rms deviation of 0.73. On the basis of these spectroscopic results, predictions of transition frequencies in the frequency range up to 950 GHz with J ≤ 50 and Ka ≤ 20 are presented. The search for interstellar 13C methylamine in available observational data was not successful and therefore only an upper limit of 6.5 × 1014 cm-2 can be derived for the column density of 13CH3NH2 toward Sgr B2(N), assuming the same source size, temperature, linewidth, and systemic velocity as for parent methylamine isotopic

  11. Exploring Organic Matter Sources Through δ13C Depletion of Lipid Biomarkers at Lake El'gygytgyn, NE Siberia

    NASA Astrophysics Data System (ADS)

    Holland, A. R.; Wilkie, K. M.; Petsch, S.; Brigham-Grette, J.; Lake El'Gygytgyn Scientific Party

    2010-12-01

    Through studies of compound-specific δ13C, Lake El’gygytgyn pilot core LZ1029 has revealed unexpected information regarding organic matter source and carbon cycling in the lake throughout the past 50 kyr. Compound-specific δ13C of alkanes, fatty acids, and alcohols were analyzed to determine the changing sources of organic matter as well as the cause of a strong negative isotopic shift in the bulk sediment δ13C (-26‰ to -33‰) over the past 50 kyr. Compounds indicative of terrestrial, aquatic, bacterial, and archaeal sources were identified. An increase in lipid concentrations during the local last glacial maximum (LLGM) is interpreted to represent increased preservation due to decreasing dissolved oxygen in the water column and sediments. The majority of alkanes, fatty acids, and alcohols are long chain compounds consistent with a terrestrial plant origin, with a slight increase in aquatic (mid-chain) contribution during the LLGM. However, isotopic results indicate that long chain fatty acids (except C30) and alcohols cannot be entirely associated with terrestrial sources, as demonstrated by an average 5‰ carbon isotope excursion from interglacial to LLGM conditions. Both mid-chain (C19-C23) and short-chain (C14-C18) fatty acids display a 10‰ excursion, but mid-chain fatty acids are consistently ~7‰ depleted compared with short-chain fatty acids. Long chain n-alkanes and the C30 fatty acid demonstrate constant isotopic values throughout the LLGM, as expected from a terrestrial source. The strongest δ13C excursion from autochthonous mid- and short-chain fatty acids (average LLGM mid-chain fatty acid δ13C = -43‰) is interpreted to result from recycling of oxidized carbon within the lake with little or no exchange with atmospheric carbon. If the lake is permanently covered by ice, isotopically depleted dissolved carbon might build up in the water column from either oxidized organic matter or oxidized methane. The presence of diplopterol (LLGM δ13C

  12. Rapid, high-resolution 14C chronology of ooids

    NASA Astrophysics Data System (ADS)

    Beaupré, Steven R.; Roberts, Mark L.; Burton, Joshua R.; Summons, Roger E.

    2015-06-01

    Ooids are small, spherical to ellipsoidal grains composed of concentric layers of CaCO3 that could potentially serve as biogeochemical records of the environments in which they grew. Such records, however, must be placed in the proper temporal context. Therefore, we developed a novel acidification system and employed an accelerator mass spectrometer (AMS) with a gas accepting ion source to obtain radiocarbon (14C) chronologies extending radially through ooids within one 8-h workday. The method was applied to ooids from Highborne Cay, Bahamas and Shark Bay, Australia, yielding reproducible 14C chronologies, as well as constraints on the rates and durations of ooid growth and independent estimates of local 14C reservoir ages.

  13. Metabolism of [1-14C]glyoxylate, [1-14C]-glycollate, [1-14C]glycine and [2-14C]-glycine by homogenates of kidney and liver tissue from hyperoxaluric and control subjects

    PubMed Central

    Dean, Betty M.; Watts, R. W. E.; Westwick, Wendy J.

    1967-01-01

    1. The metabolism of [1-14C]glyoxylate to carbon dioxide, glycine, oxalate, serine, formate and glycollate was investigated in hyperoxaluric and control subjects' kidney and liver tissue in vitro. 2. Only glycine and carbon dioxide became significantly labelled with 14C, and this was less in the hyperoxaluric patients' kidney tissue than in the control tissue. 3. Liver did not show this difference. 4. The metabolism of [1-14C]glycollate was also studied in the liver tissue; glyoxylate formation was demonstrated and the formation of 14CO2 from this substrate was likewise unimpaired in the hyperoxaluric patients' liver tissue in these experiments. 5. Glycine was not metabolized by human kidney, liver or blood cells under the conditions used. 6. These observations show that glyoxylate metabolism by the kidney is impaired in primary hyperoxaluria. PMID:5584012

  14. Oxygen isotopes in tree rings record variation in precipitation δ18O and amount effects in the south of Mexico

    PubMed Central

    Brienen, Roel J W; Hietz, Peter; Wanek, Wolfgang; Gloor, Manuel

    2013-01-01

    [1] Natural archives of oxygen isotopes in precipitation may be used to study changes in the hydrological cycle in the tropics, but their interpretation is not straightforward. We studied to which degree tree rings of Mimosa acantholoba from southern Mexico record variation in isotopic composition of precipitation and which climatic processes influence oxygen isotopes in tree rings (δ18Otr). Interannual variation in δ18Otr was highly synchronized between trees and closely related to isotopic composition of rain measured at San Salvador, 710 km to the southwest. Correlations with δ13C, growth, or local climate variables (temperature, cloud cover, vapor pressure deficit (VPD)) were relatively low, indicating weak plant physiological influences. Interannual variation in δ18Otr correlated negatively with local rainfall amount and intensity. Correlations with the amount of precipitation extended along a 1000 km long stretch of the Pacific Central American coast, probably as a result of organized storm systems uniformly affecting rainfall in the region and its isotope signal; episodic heavy precipitation events, of which some are related to cyclones, deposit strongly 18O-depleted rain in the region and seem to have affected the δ18Otr signal. Large-scale controls on the isotope signature include variation in sea surface temperatures of tropical north Atlantic and Pacific Ocean. In conclusion, we show that δ18Otr of M. acantholoba can be used as a proxy for source water δ18O and that interannual variation in δ18Oprec is caused by a regional amount effect. This contrasts with δ18O signatures at continental sites where cumulative rainout processes dominate and thus provide a proxy for precipitation integrated over a much larger scale. Our results confirm that processes influencing climate-isotope relations differ between sites located, e.g., in the western Amazon versus coastal Mexico, and that tree ring isotope records can help in disentangling the processes

  15. Oxygen isotopes in tree rings record variation in precipitation δ(18)O and amount effects in the south of Mexico.

    PubMed

    Brienen, Roel J W; Hietz, Peter; Wanek, Wolfgang; Gloor, Manuel

    2013-12-01

    [1] Natural archives of oxygen isotopes in precipitation may be used to study changes in the hydrological cycle in the tropics, but their interpretation is not straightforward. We studied to which degree tree rings of Mimosa acantholoba from southern Mexico record variation in isotopic composition of precipitation and which climatic processes influence oxygen isotopes in tree rings (δ(18)Otr). Interannual variation in δ(18)Otr was highly synchronized between trees and closely related to isotopic composition of rain measured at San Salvador, 710 km to the southwest. Correlations with δ(13)C, growth, or local climate variables (temperature, cloud cover, vapor pressure deficit (VPD)) were relatively low, indicating weak plant physiological influences. Interannual variation in δ(18)Otr correlated negatively with local rainfall amount and intensity. Correlations with the amount of precipitation extended along a 1000 km long stretch of the Pacific Central American coast, probably as a result of organized storm systems uniformly affecting rainfall in the region and its isotope signal; episodic heavy precipitation events, of which some are related to cyclones, deposit strongly (18)O-depleted rain in the region and seem to have affected the δ(18)Otr signal. Large-scale controls on the isotope signature include variation in sea surface temperatures of tropical north Atlantic and Pacific Ocean. In conclusion, we show that δ(18)Otr of M. acantholoba can be used as a proxy for source water δ(18)O and that interannual variation in δ(18)Oprec is caused by a regional amount effect. This contrasts with δ(18)O signatures at continental sites where cumulative rainout processes dominate and thus provide a proxy for precipitation integrated over a much larger scale. Our results confirm that processes influencing climate-isotope relations differ between sites located, e.g., in the western Amazon versus coastal Mexico, and that tree ring isotope records can help in

  16. Oxygen isotopes in tree rings record variation in precipitation δ18O and amount effects in the south of Mexico

    NASA Astrophysics Data System (ADS)

    Brienen, Roel J. W.; Hietz, Peter; Wanek, Wolfgang; Gloor, Manuel

    2013-12-01

    Natural archives of oxygen isotopes in precipitation may be used to study changes in the hydrological cycle in the tropics, but their interpretation is not straightforward. We studied to which degree tree rings of Mimosa acantholoba from southern Mexico record variation in isotopic composition of precipitation and which climatic processes influence oxygen isotopes in tree rings (δ18Otr). Interannual variation in δ18Otr was highly synchronized between trees and closely related to isotopic composition of rain measured at San Salvador, 710 km to the southwest. Correlations with δ13C, growth, or local climate variables (temperature, cloud cover, vapor pressure deficit (VPD)) were relatively low, indicating weak plant physiological influences. Interannual variation in δ18Otr correlated negatively with local rainfall amount and intensity. Correlations with the amount of precipitation extended along a 1000 km long stretch of the Pacific Central American coast, probably as a result of organized storm systems uniformly affecting rainfall in the region and its isotope signal; episodic heavy precipitation events, of which some are related to cyclones, deposit strongly 18O-depleted rain in the region and seem to have affected the δ18Otr signal. Large-scale controls on the isotope signature include variation in sea surface temperatures of tropical north Atlantic and Pacific Ocean. In conclusion, we show that δ18Otr of M. acantholoba can be used as a proxy for source water δ18O and that interannual variation in δ18Oprec is caused by a regional amount effect. This contrasts with δ18O signatures at continental sites where cumulative rainout processes dominate and thus provide a proxy for precipitation integrated over a much larger scale. Our results confirm that processes influencing climate-isotope relations differ between sites located, e.g., in the western Amazon versus coastal Mexico, and that tree ring isotope records can help in disentangling the processes

  17. Characterization of 14C in Neutron-Irradiated Graphite

    NASA Astrophysics Data System (ADS)

    LaBrier, Daniel Patrick

    A long-term radiological concern regarding irradiated graphite waste is the presence of the radionuclide 14C. Recent studies suggest that a significant portion of 14C contamination present in reactor-irradiated graphite is concentrated on the surface and within near-surface layers. Methods for treating irradiated graphite waste (e.g. pyrolysis, oxidation) in order to remove 14C-bearing species from the bulk graphite are being investigated to lend guidance in optimizing long-term disposal strategies. Characterization studies were performed in order to determine the chemical nature of 14C on irradiated graphite surfaces. Samples of the nuclear-grade graphite NBG-25 were irradiated in a neutron flux of 10 14 n/cm2-s for 360 days at the Advanced Test Reactor (at the Idaho National Laboratory). Surface-sensitive analysis techniques (XPS, ToF-SIMS, SEM/EDS and Raman) were employed to determine the type, location and quantity of specific chemical species and bonds that were present on the surfaces of irradiated graphite samples. Several 14C precursor species were identified on the surfaces of irradiated NBG-25; the quantities of these species decrease at sub-surface depths, which, is consistent with the observation of high concentrations of 14C on the surfaces of graphite reactor components. The elevated presence of surface oxide complexes on irradiated NBG-25 surfaces was attributed directly to neutron irradiation. Pathways for the release of 14C were identified for irradiated NBG-25: carboxyls and lactones (14CO 2), and carbonyls, ethers and quinones (14CO). Increased amounts of C-O and C=O bonding were observed on irradiated NBG-25 surfaces (when compared to unirradiated samples) in the form of interlattice (e.g. ether) and dangling (e.g. carboxyl or quinone) bonds; the quantities of these bond types also decrease at sub-surface depths. The results of this study are consistent with thermal treatment studies that indicate that the primary candidates for the release of

  18. A simplified In Situ cosmogenic 14C extraction system

    USGS Publications Warehouse

    Pigati, J.S.; Lifton, N.A.; Timothy, Jull A.J.; Quade, Jay

    2010-01-01

    We describe the design, construction, and testing of a new, simplified in situ radiocarbon extraction system at the University of Arizona. Blank levels for the new system are low ((234 ?? 11) ?? 103 atoms (1 ??; n = 7)) and stable. The precision of a given measurement depends on the concentration of 14C, but is typically <5% for concentrations of 100 ?? 103 atoms g-1 or more. The new system is relatively small and easy to construct, costs significantly less than the original in situ 14C extraction system at Arizona, and lends itself to future automation. ?? 2010 by the Arizona Board of Regents on behalf of the University of Arizona.

  19. Laboratory Precision Measurements of the Rotational Spectrum of 12C17O and 13C17O

    NASA Astrophysics Data System (ADS)

    Klapper, Gabriele; Surin, Leonid; Lewen, Frank; Müller, Holger S. P.; Pak, Igor; Winnewisser, Gisbert

    2003-01-01

    High-precision millimeter and submillimeter wave measurements were performed on two 17O isotopically substituted carbon monoxide species, i.e., 12C17O and 13C17O. Covering the frequency region from 100 GHz to 1 THz, the accuracy achievable is estimated to be +/-5 kHz in the Doppler-limited mode and +/-1 kHz for sub-Doppler-resolution measurements. From a weighted least-squares fit, the following molecular rotational parameters for 12C17O and 13C17O were obtained: for 12C17O,B0=56,179.99110(28)MHz,D0=174.330(6)kHzand for 13C17O,B0=53,644.7906(29)MHz,D0=158.918(19)kHzin both instances, the H0 values were kept fixed to IR data. The oxygen 17O nucleus exhibits a sizeable electric nuclear quadrupole moment, which has been measured for both isotopomers, i.e., eQq(12C17O)=4.298(44)MHz and eQq(13C17O)=4.355(182)MHz. The high precision of the Lamb dip measurements allowed us to observe additional small hyperfine effects caused by the magnetic moment of the 17O nucleus. These precision measurements allowed the determination of the nuclear spin-rotation constant CI(17O)=-31.60(72)Hz for 12C17O, solely from the Cologne data set. The highly precise transition frequencies reported here should warrant deep interstellar searches for the two molecules 12C17O and 13C17O. The latter has not been detected in space until very recently. On the basis of our laboratory data, we were able to report the discovery of 13C17O (by Bensch and coworkers) along with the observations of two additionalrare CO isotopomers including 12C17O and 12C18O toward core C of the ρ Ophiucus molecular cloud.

  20. In vivo investigation of cardiac metabolism in the rat using MRS of hyperpolarized [1-13C] and [2-13C]pyruvate.

    PubMed

    Josan, Sonal; Park, Jae Mo; Hurd, Ralph; Yen, Yi-Fen; Pfefferbaum, Adolf; Spielman, Daniel; Mayer, Dirk

    2013-12-01

    Hyperpolarized (13)C MRS allows the in vivo assessment of pyruvate dehydrogenase complex (PDC) flux, which converts pyruvate to acetyl-coenzyme A (acetyl-CoA). [1-(13)C]pyruvate has been used to measure changes in cardiac PDC flux, with demonstrated increase in (13)C-bicarbonate production after dichloroacetate (DCA) administration. With [1-(13)C]pyruvate, the (13)C label is released as (13 CO2 /(13)C-bicarbonate, and, hence, does not allow us to follow the fate of acetyl-CoA. Pyruvate labeled in the C2 position has been used to track the (13)C label into the TCA (tricarboxylic acid) cycle and measure [5-(13)C]glutamate as well as study changes in [1-(13)C]acetylcarnitine with DCA and dobutamine. This work investigates changes in the metabolic fate of acetyl-CoA in response to metabolic interventions of DCA-induced increased PDC flux in the fed and fasted state, and increased cardiac workload with dobutamine in vivo in rat heart at two different pyruvate doses. DCA led to a modest increase in the (13)C labeling of [5-(13)C]glutamate, and a considerable increase in [1-(13)C]acetylcarnitine and [1,3-(13)C]acetoacetate peaks. Dobutamine resulted in an increased labeling of [2-(13)C]lactate, [2-(13)C]alanine and [5-(13)C]glutamate. The change in glutamate with dobutamine was observed using a high pyruvate dose but not with a low dose. The relative changes in the different metabolic products provide information about the relationship between PDC-mediated oxidation of pyruvate and its subsequent incorporation into the TCA cycle compared with other metabolic pathways. Using a high dose of pyruvate may provide an improved ability to observe changes in glutamate.

  1. Stratigraphic significance and global distribution of the δ13C Suess effect during the Anthropocene

    NASA Astrophysics Data System (ADS)

    Paul, André; Mulitza, Stefan

    2015-04-01

    The Anthropocene is the proposed term for the present geological epoch (from the time of the Industrial Revolution onwards), during which human influence significantly impacts the environment. We argue that the burning of isotopically light fossil fuel that causes the so-called 'δ13C Suess effect' leaves such a strong imprint on marine sediments that it may serve to define the onset of this geological epoch, at least since the so-called 'Great Acceleration', i.e., the second half of the 20th century. Sediment data with high temporal resolution from the recent past indeed reveal a trend that corresponds to a negative carbon isotope excursion of the order of one permil, comparable to carbon isotope excursions in the deep past that define stratigraphic boundaries such as the Paleocene-Eocene Thermal Maximum (PETM). A global carbon cycle model based on the MIT general circulation model (MITgcm), fitted with carbon isotopes 13C and 14C and forced with observed changes in the atmospheric carbon dioxide partial pressure and carbon isotopic ratio 13C/12C, allows to investigate the temporal evolution and three-dimensional structure of the anomaly. We show the carbon isotopic ratios of fossil shells of benthic foraminifera (δ13Cc) from two ocean sediment cores GeoB6008 (31° N) und GeoB9501 (17° N) over the Anthropocene (mainly the 20th century). The decrease in δ13Cc at 31° N is about 0.8 permil; off Mauretania (at 17° N in the shadow zone of the subtropical gyre) it still amounts to about 0.4 permil. While the magnitude of the change in the global carbon cycle model is similar, the difference is smaller: The decrease in the model is around 0.9 permil near the location of the northern core and around 0.8 permil near the location of the southern core. The smaller difference of only about 0.1 permil points to a bias in the simulated as opposed to the observed ventilation of the thermocline. We further use a carbon cycle multi-box model to extrapolate this change in δ13

  2. The 13C nuclear magnetic resonance in graphite intercalation compounds

    NASA Technical Reports Server (NTRS)

    Tsang, T.; Resing, H. A.

    1985-01-01

    The (13)C NMR chemical shifts of graphite intercalation compounds were calculated. For acceptor types, the shifts come mainly from the paramagnetic (Ramsey) intra-atomic terms. They are related to the gross features of the two-dimensional band structures. The calculated anisotropy is about -140 ppm and is independent of the finer details such as charge transfer. For donor types, the carbon 2p pi orbitals are spin-polarized because of mixing with metal conduction electrons, thus there is an additional dipolar contribution which may be correlated with the electronic specific heat. The general agreement with experimental data is satisfactory.

  3. Forward modeling of δ18O in Andean ice cores

    NASA Astrophysics Data System (ADS)

    Hurley, J. V.; Vuille, M.; Hardy, D. R.

    2016-08-01

    Tropical ice core archives are among the best dated and highest resolution from the tropics, but a thorough understanding of processes that shape their isotope signature as well as the simulation of observed variability remain incomplete. To address this, we develop a tropical Andean ice core isotope forward model from in situ hydrologic observations and satellite water vapor isotope measurements. A control simulation of snow δ18O captures the mean and seasonal trend but underestimates the observed intraseasonal variability. The simulation of observed variability is improved by including amount effects associated with South American cold air incursions, linking synoptic-scale disturbances and monsoon dynamics to tropical ice core δ18O. The forward model was calibrated with and run under present-day conditions but can also be driven with past climate forcings to reconstruct paleomonsoon variability. The model is transferable and may be used to render a (paleo)climatic context at other ice core locations.

  4. /sup 18/O + /sup 12/C fusion-evaporation reaction

    SciTech Connect

    Heusch, B; Beck, C; Coffin, J P; Freeman, R M; Gallmann, A; Haas, F; Rami, F; Wagner, P; Alburger, D E

    1980-01-01

    A study of the /sup 18/O + /sup 12/C fusion evaporation reaction has been undertaken for 2 reasons: to make a systematic study of the formation cross section for each individual evaporation residue over a broad excitation energy region in the compound nucleus /sup 30/Si:30 to 62 MeV; and to compare all results to fusion-evaporation calculations done in the framework of the Hauser-Feschbach statistical model.

  5. Applications of AMS {sup 14}C on Climate and Archaeology

    SciTech Connect

    Gomes, P. R. S.

    2007-10-26

    We describe the Accelerator Mass Spectrometry (AMS) technique and two distinct applications of its use with {sup 14}C to study environmental problems in Brazil, such as forest fires and climate changes in the Amazon region and archaeological studies on the early settlements in the Southeast Brazilian coast.

  6. Excretion of radioactivity following the intraperitoneal administration of /sup 14/C-DDT, /sup 14/C-DDD, /sup 14/C-DDE and /sup 14/C-DDMU to the rat and Japanese Quail

    SciTech Connect

    Fawcett, S.C.; Bunyan, P.J.; Huson, L.W.; King, L.J.; Stanley, P.I.

    1981-09-01

    A study in progress to examine the metabolic fate of DDT in birds and mammals is discussed. The first phase of the study, which is reported in this article, has been to establish the rate of excretion of ratioactivity following the intraperitoneal administrations of /sup 14/C-DDT, /sup 14/C-DDE, /sup 14/C-DDD, and /sup 14/C-DDMU to male rats and male Japanese quail. The mean values from the three animals in each experimental group for the amount of radioactivity excreted daily are given, and it was found that the rats excreted the radioactivity administered as DDT, DDD, and DDE substantially faster than did the quail. DDMU was excreted relatively rapidly and at similar rates. This finding suggests that apparent differences in the rates of excretion of DDT by birds and mammals probably arise from differences in the conversion of DDT to DDD or DDE or in the degradation of these metabolites to DDMU. The Japanese quail differ from the rats in excreting substantial amounts of unchanged DDT, DDE, and DDD, which probably reflects the inability of the Japanese quail to readily metabolise these compounds.

  7. 17 CFR 240.14c-1 - Definitions.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... director or officer of the registrant or any of its parents or subsidiaries. (b) Employee benefit plan. For purposes of § 240.14c-7, the term “employee benefit plan” means any purchase, savings, option, bonus..., trustees or officers. (c) Entity that exercises fiduciary powers. The term “entity that exercises...

  8. Convenient preparative synthesis of ( sup 14 C)trehalose from ( sup 14 C)glucose by intact Escherichia coli cells

    SciTech Connect

    Brand, B.; Boos, W. )

    1989-09-01

    At high osmolarity, Escherichia coli synthesizes trehalose intracellularly, irrespective of the nature of the carbon source. Synthesis proceeds via the transfer of UDP-glucose to glucose 6-phosphate, yielding trehalose 6-phosphate, followed by its dephosphorylation to trehalose. This reaction was exploited to preparatively synthesize ({sup 14}C)trehalose from exogenous ({sup 14}C)glucose by using intact bacteria of a mutant (DF214) that could not metabolize glucose. The total yield of radiochemically pure trehalose from glucose was routinely more than 50%.

  9. Extraction of in situ cosmogenic 14C from olivine

    USGS Publications Warehouse

    Pigati, J.S.; Lifton, N.A.; Timothy, Jull A.J.; Quade, Jay

    2010-01-01

    Chemical pretreatment and extraction techniques have been developed previously to extract in situ cosmogenic radiocarbon (in situ 14C) from quartz and carbonate. These minerals can be found in most environments on Earth, but are usually absent from mafic terrains. To fill this gap, we conducted numerous experiments aimed at extracting in situ 14C from olivine ((Fe,Mg)2SiO4). We were able to extract a stable and reproducible in situ 14C component from olivine using stepped heating and a lithium metaborate (LiBO2) flux, following treatment with dilute HNO3 over a variety of experimental conditions. However, measured concentrations for samples from the Tabernacle Hill basalt flow (17.3 ?? 0.3 ka4) in central Utah and the McCarty's basalt flow (3.0 ?? 0.2 ka) in western New Mexico were significantly lower than expected based on exposure of olivine in our samples to cosmic rays at each site. The source of the discrepancy is not clear. We speculate that in situ 14C atoms may not have been released from Mg-rich crystal lattices (the olivine composition at both sites was ~Fo65Fa35). Alternatively, a portion of the 14C atoms released from the olivine grains may have become trapped in synthetic spinel-like minerals that were created in the olivine-flux mixture during the extraction process, or were simply retained in the mixture itself. Regardless, the magnitude of the discrepancy appears to be inversely proportional to the Fe/(Fe+Mg) ratio of the olivine separates. If we apply a simple correction factor based on the chemical composition of the separates, then corrected in situ 14C concentrations are similar to theoretical values at both sites. At this time, we do not know if this agreement is fortuitous or real. Future research should include measurement of in situ 14C concentrations in olivine from known-age basalt flows with different chemical compositions (i.e. more Fe-rich) to determine if this correction is robust for all olivine-bearing rocks. ?? 2010 by the Arizona

  10. Reconstructing Ocean Circulation using Coral (triangle)14C Time Series

    SciTech Connect

    Kashgarian, M; Guilderson, T P

    2001-02-23

    We utilize monthly {sup 14}C data derived from coral archives in conjunction with ocean circulation models to address two questions: (1) how does the shallow circulation of the tropical Pacific vary on seasonal to decadal time scales and (2) which dynamic processes determine the mean vertical structure of the equatorial Pacific thermocline. Our results directly impact the understanding of global climate events such as the El Nino-Southern Oscillation (ENSO). To study changes in ocean circulation and water mass distribution involved in the genesis and evolution of ENSO and decadal climate variability, it is necessary to have records of climate variables several decades in length. Continuous instrumental records are limited because technology for continuous monitoring of ocean currents (e.g. satellites and moored arrays) has only recently been available, and ships of opportunity archives such as COADS contain large spatial and temporal biases. In addition, temperature and salinity in surface waters are not conservative and thus can not be independently relied upon to trace water masses, reducing the utility of historical observations. Radiocarbon in sea water is a quasi-conservative water mass tracer and is incorporated into coral skeletal material, thus coral {sup 14}C records can be used to reconstruct changes in shallow circulation that would be difficult to characterize using instrumental data. High resolution {Delta}{sup 14}C timeseries such as ours, provide a powerful constraint on the rate of surface ocean mixing and hold great promise to augment one time oceanographic surveys. {Delta}{sup 14}C timeseries such as these, not only provide fundamental information about the shallow circulation of the Pacific, but can also be directly used as a benchmark for the next generation of high resolution ocean models used in prognosticating climate. The measurement of {Delta}{sup 14}C in biological archives such as tree rings and coral growth bands is a direct record of

  11. 13C metabolic flux analysis in complex systems.

    PubMed

    Zamboni, Nicola

    2011-02-01

    Experimental determination of in vivo metabolic rates by methods of (13)C metabolic flux analysis is a pivotal approach to unravel structure and regulation of metabolic networks, in particular with microorganisms grown in minimal media. However, the study of real-life and eukaryotic systems calls for the quantification of fluxes also in cellular compartments, rich media, cell-wide metabolic networks, dynamic systems or single cells. These scenarios drastically increase the complexity of the task, which is only partly dealt by existing approaches that rely on rigorous simulations of label propagation through metabolic networks and require multiple labeling experiments or a priori information on pathway inactivity to simplify the problem. Albeit qualitative and largely driven by human interpretation, statistical analysis of measured (13)C-patterns remains the exclusive alternative to comprehensively handle such complex systems. In the future, this practice will be complemented by novel modeling frameworks to assay particular fluxes within a network by stable isotopic tracer for targeted validation of well-defined hypotheses.

  12. Glucogenesis in an insect, Manduca sexta L., estimated from the 13C isotopomer distribution in trehalose synthesized from [1,3-13C2]glycerol.

    PubMed

    Thompson, S N

    1997-07-19

    Glucogenesis from [3-13C]alanine and [1,3-13C2]glycerol was demonstrated in the insect Manduca sexta by examining the 13C enrichment of trehalose, a non-reducing disaccharide of glucose synthesized in the insect fat body and released into the blood or hemolymph. In insects maintained on a low carbohydrate diet, trehalose synthesized from [3-13C]alanine was selectively enriched at C1 and C6, and C2 and C5. The 13C-labelling pattern indicated the carboxylation of [3-13C]pyruvate, formed by transamination of the [3-13C]alanine followed by randomization of the label at the fumarate step of the tricarboxylic acid cycle and glucose synthesis via the gluconeogenic pathway. 13C enrichment of trehalose was absent in similarly maintained insect larvae administered 3-mercaptopicolinic acid, an inhibitor of hepatic phosphoenolpyruvate carboxykinase. Insects on the low carbohydrate diet also synthesized trehalose from [1,3-13C2]glycerol. 13C multiplets were observed in trehalose C3 and C4 demonstrating the synthesis of three 13C enriched glucose isotopomers from the 13C-labelled glycerol. The relative contributions of 13C-labelled glycerol and unlabelled 3 carbon substrates to the synthesis of the 13C enriched trehalose isotopomers were determined from the multiplet structure at C3, and calculation of minimal rates of glucogenesis were based on the 13C enrichment of C4. The C4/C3 13C enrichment ratio in trehalose synthesized from [1,3-13C2]glycerol was close to unity, and total glucogenesis was calculated after estimation of the expected contribution of unlabelled trehalose synthesis from 3 carbon substrates by comparison of the ratio of unlabelled and labelled contributions to the 13C enriched trehalose isotopomers with the 13C enrichment of [1,3-13C2]glycerol-3-phosphate. The estimated total rates of glucogenesis varied from 0.33 to 2.80 micromol glucose/g fresh weight/h. The blood sugar level of M. sexta was also highly variable. Although the potential importance of

  13. Application of δ(18)O, δ(13)CDIC, and major ions to evaluate micropollutant sources in the Bay of Vidy, Lake Geneva.

    PubMed

    Halder, Janine; Pralong, Charles; Bonvin, Florence; Lambiel, Frederic; Vennemann, Torsten W

    2016-01-01

    Waters were sampled monthly from a profile at the wastewater outlet and a reference point in the Bay of Vidy (Lake Geneva) for a year. The samples were analyzed for (18)O/(16)O of water, (13)C/(12)C of dissolved inorganic carbon (DIC), major ions, and selected micropollutant concentrations. δ(18)O values, combined with the major ion concentrations, allowed discharged waste and storm-drainage water to be traced within the water column. On the basis of δ(18)O values, mole fractions of wastewater (up to 45 %), storm-drainage (up to 16 %), and interflowing Rhône River water (up to 34 %) could be determined. The results suggest that the stormwater fractions do not influence micropollutant concentrations in a measurable way. In contrast, the Rhône River interflow coincides with elevated concentrations of Rhône River-derived micropollutants in some profiles. δ(13)C values of DIC suggest that an increase in micropollutant concentrations at the sediment-water interface could be related to remineralization processes or resuspension.

  14. Measuring changes in substrate utilization in the myocardium in response to fasting using hyperpolarized [1-13C]butyrate and [1-13C]pyruvate

    PubMed Central

    Bastiaansen, Jessica A. M.; Merritt, Matthew E.; Comment, Arnaud

    2016-01-01

    Cardiac dysfunction is often associated with a shift in substrate preference for ATP production. Hyperpolarized (HP) 13C magnetic resonance spectroscopy (MRS) has the unique ability to detect real-time metabolic changes in vivo due to its high sensitivity and specificity. Here a protocol using HP [1-13C]pyruvate and [1-13C]butyrate is used to measure carbohydrate versus fatty acid metabolism in vivo. Metabolic changes in fed and fasted Sprague Dawley rats (n = 36) were studied at 9.4 T after tail vein injections. Pyruvate and butyrate competed for acetyl-CoA production, as evidenced by significant changes in [13C]bicarbonate (−48%), [1-13C]acetylcarnitine (+113%), and [5-13C]glutamate (−63%), following fasting. Butyrate uptake was unaffected by fasting, as indicated by [1-13C]butyrylcarnitine. Mitochondrial pseudoketogenesis facilitated the labeling of the ketone bodies [1-13C]acetoacetate and [1-13C]β-hydroxybutyryate, without evidence of true ketogenesis. HP [1-13C]acetoacetate was increased in fasting (250%) but decreased during pyruvate co-injection (−82%). Combining HP 13C technology and co-administration of separate imaging agents enables noninvasive and simultaneous monitoring of both fatty acid and carbohydrate oxidation. This protocol illustrates a novel method for assessing metabolic flux through different enzymatic pathways simultaneously and enables mechanistic studies of the changing myocardial energetics often associated with disease. PMID:27150735

  15. Rapid radiosynthesis of [11C] and [14C]azelaic, suberic, and sebacic acids for in vivo mechanistic studies of systemic acquired resistance in plants

    SciTech Connect

    Best M.; Fowler J.; Best, M.; Gifford, A.N.; Kim, S.W.; Babst, B.; Piel, M.; Roesch, F.; Fowler, J.S.

    2011-11-25

    A recent report that the aliphatic dicarboxylic acid, azelaic acid (1,9-nonanedioic acid) but not related acids, suberic acid (1,8-octanedioic acid) or sebacic (1,10-decanedioic acid) acid induces systemic acquired resistance to invading pathogens in plants stimulated the development of a rapid method for labeling these dicarboxylic acids with {sup 11}C and {sup 14}C for in vivo mechanistic studies in whole plants. {sup 11}C-labeling was performed by reaction of ammonium [{sup 11}C]cyanide with the corresponding bromonitrile precursor followed by hydrolysis with aqueous sodium hydroxide solution. Total synthesis time was 60 min. Median decay-corrected radiochemical yield for [{sup 11}C]azelaic acid was 40% relative to trapped [{sup 11}C]cyanide, and specific activity was 15 GBq/{micro}mol. Yields for [{sup 11}C]suberic and sebacic acids were similar. The {sup 14}C-labeled version of azelaic acid was prepared from potassium [{sup 14}C]cyanide in 45% overall radiochemical yield. Radiolabeling procedures were verified using {sup 13}C-labeling coupled with {sup 13}C-NMR and liquid chromatography-mass spectrometry analysis. The {sup 11}C and {sup 14}C-labeled azelaic acid and related dicarboxylic acids are expected to be of value in understanding the mode-of-action, transport, and fate of this putative signaling molecule in plants.

  16. Online Determination of 18O Fractionation Between CO2 and Soil-Water during Soil Dessication by a Novel Mid-Infrared CO2 Isotope Analyzer Coupled to an Dynamic Chamber Incubation System

    NASA Astrophysics Data System (ADS)

    Nowak, A.

    2015-12-01

    The stable oxygen isotope composition of CO2 is an important tracer for quantifying gas interactions between soils and atmosphere. Soils impact atmospheric 18O-CO2 signatures by CO2-H2O equilibration during diffusion of CO2 through the soil column. However, recent research has revealed that also catalytic reactions by carbonic anhydrase, an enzyme used by microorganisms for triggering the conversion of CO2 and water to bicarbonate and protons, is an important factor influencing the oxygen isotopic signature of CO2. In order to study the importance of biotic and abiotic factors for 18O-CO2, we used a novel mid infrared 18O/13C-CO2 analyser coupled to a dynamic chamber system, which allowed us to measure online 18O and 13C of a continuous CO2 stream percolating through soil samples while drying out from fully water saturated to air dry. Our results indicate that changes in CO2- 18O signatures peak at certain soil moistures levels, which is most probably catalysed by the activity of certain microbial groups under optimum growth conditions. More analyses with different soil types and depths, combined with molecular analyses are planned in order to understand the importance of microbial processes and dynamics for influencing soil-CO2 interactions.

  17. The ({sup 18}O, {sup 16}O) reaction as a probe for nuclear spectroscopy

    SciTech Connect

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

    2014-11-11

    The response of nuclei to the ({sup 18}O, {sup 16}O) two-neutron transfer reaction at 84 MeV incident energy has been systematically studied at the Catania INFN-LNS laboratory. The experiments were performed using several solid targets from light ({sup 9}Be, {sup 11}B, {sup 12,13}C, {sup 16}O, {sup 28}Si) to heavy ones ({sup 58,64}Ni, {sup 120}Sn, {sup 208}Pb). The {sup 16}O ejectiles were detected at forward angles by the MAGNEX magnetic spectrometer. Exploiting the large momentum acceptance (−10%, +14%) and solid angle (50 msr) of the spectrometer, energy spectra were obtained with a relevant yield up to about 20 MeV excitation energy. The application of the powerful trajectory reconstruction technique did allow to get energy spectra with energy resolution of about 150 keV and angular distributions with angular resolution better than 0.3°. A common feature observed with light nuclei is the appearance of unknown resonant structures at high excitation energy. The strong population of these latter together with the measured width can reveal the excitation of a collective mode connected with the transfer of a pair.

  18. UV/vis, 1H, and 13C NMR spectroscopic studies to determine mangiferin pKa values.

    PubMed

    Gómez-Zaleta, Berenice; Ramírez-Silva, María Teresa; Gutiérrez, Atilano; González-Vergara, Enrique; Güizado-Rodríguez, Marisol; Rojas-Hernández, Alberto

    2006-07-01

    The acid constants of mangiferin (a natural xanthonoid) in aqueous solution were determined through an UV/vis spectroscopic study employing the SQUAD program as a computational tool. A NMR study complements the pK(a) values assignment and evidences a H-bridge presence on 1-C. The chemical model used was consistent with the experimental data obtained. The pK(a) values determined with this procedure were as follows: H(4)(MGF)=H(3)(MGF)(-)+H(+), pKa1 (6-H)=6.52+/-0.06; H(3)(MGF)(-)=H(2)(MGF)(2-)+H(+), pKa2 (3-H)=7.97+/-0.06; H(2)(MGF)(2-)=H(MGF)(3-)+H(+), pKa3 (7-H)=9.44+/-0.04; H(MGF)(3-)=(MGF)(4-)+H(+), pKa4 (1-H)=12.10+/-0.01; where it has been considered mangiferin C(19)H(18)O(11) as H(4)(MGF). Mangiferin UV/vis spectral behavior, stability study in aqueous solution as well as NMR spectroscopy studies: one-dimensional (1)H,(13)C, 2D correlated (1)H/(13)C performed by (g)-HSQC and (g)-HMBC methods; are also presented. pK(a) values determination of H(4)(MGF) in aqueous solution is a necessary contribution to subsequent pharmacokinetic study, and a step towards the understanding of its biological effects.

  19. Improved ground state and ν12 = 1 state rovibrational constants for ethylene-13C2 (13C2H4)

    NASA Astrophysics Data System (ADS)

    Gabona, M. G.; Tan, T. L.

    2014-05-01

    The Fourier transform infrared (FTIR) absorption spectrum of the ν12 fundamental band of ethylene-13C2 (13C2H4) was recorded in the frequency range of 1350-1550 cm-1 with unapodized resolution of 0.0063 cm-1. Improved upper state (ν12 = 1) rovibrational constants consisting of three rotational, five quartic and five sextic constants were derived by assigning and fitting 1731 infrared transitions using Watson's A-reduced Hamiltonian in the Ir representation. The root-mean-square deviation of the fit was 0.00030 cm-1. More higher-order upper state (ν12 = 1) constant were derived in the present analysis than previously reported. Improved ground state rovibrational constants were also determined from the fit of 1104 ground state combination differences (GSCD) with a root-mean-square deviation of 0.00029 cm-1. The A-type ν12 band centered at 1436.65409 ± 0.00002 cm-1 has a calculated inertial defect Δ12 is 0.242896 ± 0.000007 μÅ2. No indications of perturbation were found in the analysis of the band.

  20. Degradation of /sup 14/C-labeled lignins and /sup 14/C-labeled aromatic acids by fusarium solani

    SciTech Connect

    Norris, D.M.

    1980-08-01

    Abilities of isolate AF-W1 of Fusarium solani to degrade the side chain and the ring structure of synthetic dehydrogenative polymerizates, aromatic acids, or lignin in sound wood were investigated under several conditions of growth substrate or basal medium and pH. Significant transformations of lignins occurred in 50 days in both unextracted and extracted sound wood substrances with 3% malt as the growth substrate and the pH buffered initially at 4.0 with 2,2-dimethylsuccinate. Degradation of lignin in such woods also occurred under unbuffered pH conditions when a basal medium of either 3% malt or powdered cellulose in deionized water was present. Decomposition of the lignin in these woods did not occur in cultures where D-glucose was present as a growth substrate. F. solani significantly transformed, as measured as evolved /sup 14/CO/sub 2/, both synthetic side chain (beta, gamma)-/sup 14/C- and U-ring-/sup 14/C-labeled lignins in 30 days under liquid culture conditions of only distilled deionized water and no pH adjustment. Degradation of dehydrogenative polymerizates by F. solani was reduced drastically when D2 was the liquid medium. AF-W1 also cleaved the alpha-/sup 14/C from p- hydroxybenzoic acid and evolved /sup 14/CO/sub 2/ from the substrace, (3-/sup 14/C) cinnamic acid. Thus, the fungus cleaved side chain carbon from substrate that originally lacked hydroxyl substitution on the aromatic nucleus. Surprisingly, small amounts of /sup 14/C cleaved from aromatic acids by F. solani were incorporated into cell mass. Initial buffering of the culture medium to pH 4.0 or 5.0 with 0.1 M2,2-dimethylsuccinate significantly increased F. solani degradation of all lignins or aromatic acids. Results indicated that AF-W1 used lignin as a sole carbon source.

  1. Nucleosynthesis in AGB stars traced by oxygen isotopic ratios. I. Determining the stellar initial mass by means of the 17O/18O ratio

    NASA Astrophysics Data System (ADS)

    De Nutte, R.; Decin, L.; Olofsson, H.; Lombaert, R.; de Koter, A.; Karakas, A.; Milam, S.; Ramstedt, S.; Stancliffe, R. J.; Homan, W.; Van de Sande, M.

    2017-03-01

    Aims: We seek to investigate the 17O/18O ratio for a sample of AGB stars containing M-, S-, and C-type stars. These ratios are evaluated in relation to fundamental stellar evolution parameters: the stellar initial mass and pulsation period. Methods: Circumstellar 13C16O, 12C17O, and 12C18O line observations were obtained for a sample of nine stars with various single-dish long-wavelength facilities. Line intensity ratios are shown to relate directly to the surface 17O/18O abundance ratio. Results: Stellar evolution models predict the 17O/18O ratio to be a sensitive function of initial mass and to remain constant throughout the entire TP-AGB phase for stars initially less massive than 5 M⊙. This makes the measured ratio a probe of the initial stellar mass. Conclusions: Observed 17O/18O ratios are found to be well in the range predicted by stellar evolution models that do not consider convective overshooting. From this, accurate initial mass estimates are calculated for seven sources. For the remaining two sources, there are two mass solutions, although there is a larger probability that the low-mass solution is correct. Finally, we present hints at a possible separation between M/S- and C-type stars when comparing the 17O/18O ratio to the stellar pulsation period. The reduced spectra are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/600/A71

  2. Carbon isotopes profiles of human whole blood, plasma, red blood cells, urine and feces for biological/biomedical 14C-accelerator mass spectrometry applications.

    PubMed

    Kim, Seung-Hyun; Chuang, Jennifer C; Kelly, Peter B; Clifford, Andrew J

    2011-05-01

    Radiocarbon ((14)C) is an ideal tracer for in vivo human ADME (absorption, distribution, metabolism, elimination) and PBPK (physiological-based pharmacokinetic) studies. Living plants peferentially incorporate atmospheric (14)CO(2) versus (13)CO(2) versus (12)CO(2), which result in unique signature. Furthermore, plants and the food chains they support also have unique carbon isotope signatures. Humans, at the top of the food chain, consequently acquire isotopic concentrations in the tissues and body fluids depending on their dietary habits. In preparation of ADME and PBPK studies, 12 healthy subjects were recruited. The human baseline (specific to each individual and their diet) total carbon (TC) and carbon isotope (13)C (δ(13)C) and (14)C (F(m)) were quantified in whole blood (WB), plasma, washed red blood cell (RBC), urine, and feces. TC (mg of C/100 μL) in WB, plasma, RBC, urine, and feces were 11.0, 4.37, 7.57, 0.53, and 1.90, respectively. TC in WB, RBC, and feces was higher in men over women, P < 0.05. Mean δ(13)C were ranked low to high as follows: feces < WB = plasma = RBC = urine, P < 0.0001. δ(13)C was not affected by gender. Our analytic method shifted δ(13)C by only ±1.0 ‰ ensuring our F(m) measurements were accurate and precise. Mean F(m) were ranked low to high as follows: plasma = urine < WB = RBC = feces, P < 0.05. F(m) in feces was higher for men over women, P < 0.05. Only in WB, (14)C levels (F(m)) and TC were correlated with one another (r = 0.746, P < 0.01). Considering the lag time to incorporate atmospheric (14)C into plant foods (vegetarian) and or then into animal foods (nonvegetarian), the measured F(m) of WB in our population (recruited April 2009) was 1.0468 ± 0.0022 (mean ± SD), and the F(m) of WB matched the (extrapolated) atmospheric F(m) of 1.0477 in 2008. This study is important in presenting a procedure to determine a baseline for a study group for human ADME and PBPK studies using (14)C as a tracer.

  3. Determination of microbial carbon sources and cycling during remediation of petroleum hydrocarbon impacted soil using natural abundance (14)C analysis of PLFA.

    PubMed

    Cowie, Benjamin R; Greenberg, Bruce M; Slater, Gregory F

    2010-04-01

    In a petroleum impacted land-farm soil in Sarnia, Ontario, compound-specific natural abundance radiocarbon analysis identified biodegradation by the soil microbial community as a major pathway for hydrocarbon removal in a novel remediation system. During remediation of contaminated soils by a plant growth promoting rhizobacteria enhanced phytoremediation system (PEPS), the measured Delta(14)C of phospholipid fatty acid (PLFA) biomarkers ranged from -793 per thousand to -897 per thousand, directly demonstrating microbial uptake and utilization of petroleum hydrocarbons (Delta(14)C(PHC) = -1000 per thousand). Isotopic mass balance indicated that more than 80% of microbial PLFA carbon was derived from petroleum hydrocarbons (PHC) and a maximum of 20% was obtained from metabolism of more modern carbon sources. These PLFA from the contaminated soils were the most (14)C-depleted biomarkers ever measured for an in situ environmental system, and this study demonstrated that the microbial community in this soil was subsisting primarily on petroleum hydrocarbons. In contrast, the microbial community in a nearby uncontaminated control soil maintained a more modern Delta(14)C signature than total organic carbon (Delta(14)C(PLFA) = +36 per thousand to -147 per thousand, Delta(14)C(TOC) = -148 per thousand), indicating preferential consumption of the most modern plant-derived fraction of soil organic carbon. Measurements of delta(13)C and Delta(14)C of soil CO(2) additionally demonstrated that mineralization of PHC contributed to soil CO(2) at the contaminated site. The CO(2) in the uncontaminated control soil exhibited substantially more modern Delta(14)C values, and lower soil CO(2) concentrations than the contaminated soils, suggesting increased rates of soil respiration in the contaminated soils. In combination, these results demonstrated that biodegradation in the soil microbial community was a primary pathway of petroleum hydrocarbon removal in the PEPS system. This study

  4. Revision of Fontes & Garnier's model for the initial 14C content of dissolved inorganic carbon used in groundwater dating

    USGS Publications Warehouse

    Han, Liang-Feng; Plummer, L. Niel

    2013-01-01

    The widely applied model for groundwater dating using 14C proposed by Fontes and Garnier (F&G) (Fontes and Garnier, 1979) estimates the initial 14C content in waters from carbonate-rock aquifers affected by isotopic exchange. Usually, the model of F&G is applied in one of two ways: (1) using a single 13C fractionation factor of gaseous CO2 with respect to a solid carbonate mineral, εg/s, regardless of whether the carbon isotopic exchange is controlled by soil CO2 in the unsaturated zone, or by solid carbonate mineral in the saturated zone; or (2) using different fractionation factors if the exchange process is dominated by soil CO2 gas as opposed to solid carbonate mineral (typically calcite). An analysis of the F&G model shows an inadequate conceptualization, resulting in underestimation of the initial 14C values (14C0) for groundwater systems that have undergone isotopic exchange. The degree to which the 14C0 is underestimated increases with the extent of isotopic exchange. Examples show that in extreme cases, the error in calculated adjusted initial 14C values can be more than 20% modern carbon (pmc). A model is derived that revises the mass balance method of F&G by using a modified model conceptualization. The derivation yields a “global” model both for carbon isotopic exchange dominated by gaseous CO2 in the unsaturated zone, and for carbon isotopic exchange dominated by solid carbonate mineral in the saturated zone. However, the revised model requires different parameters for exchange dominated by gaseous CO2 as opposed to exchange dominated by solid carbonate minerals. The revised model for exchange dominated by gaseous CO2 is shown to be identical to the model of Mook (Mook, 1976). For groundwater systems where exchange occurs both in the unsaturated zone and saturated zone, the revised model can still be used; however, 14C0 will be slightly underestimated. Finally, in carbonate systems undergoing complex geochemical reactions, such as oxidation of

  5. Hepatic albumin and urea synthesis: The mathematical modelling of the dynamics of [14C]carbonate-derived guanidine-labelled arginine in the isolated perfused rat liver.

    PubMed Central

    Tavill, A S; Nadkarni, D; Metcalfe, J; Black, E; Hoffenberg, R; Carson, E R

    1975-01-01

    A mathematical model was constructed to define the dynamics of incorporation of radioactivity into urea carbon and the guanidine carbon of arginine in plasma albumin after the rapid intraportal-venous administration of Na214CO3 in the isolated perfused rat liver. 2. The model was formulated in terms of compartmental analysis and additional experiments were designed to provide further information on subsystem dynamics and to discriminate between alternative model structures. 3. Evidence for the rapid-time-constant of labelling of intracellular arginine was provided by precursor-product analysis of precursor [14C]carboante and product [14C]urea in the perfusate. 4. Compartmental analysis of the dynamics of newly synthesized urea was based on the fate of exogenous [13C]urea, endogenous [14C]urea and the accumulation of [12C]urea in perfusate water, confirming the early completion of urea carbon labelling, the absence of continuing synthesis of labelled urea, and the presence of a small intrahepatic urea-delay pool. 5. Analysis of the perfusate dynamics of endogenously synthesized and exogenously administered [6-14C]arginine indicated that although the capacity for extrahepatic formation of [14C]-urea exists, little or no arginine formed within the intrahepatic urea cycle was transported out of the liver. However, the presence of a rapidly turning-over intrahepatic arginine pool was confirmed. 6. On the basis of these subsystem analyses it was possible to offer feasible estimations for the parameters of the mathematical model. However, it was not possible to stimulate the form and magnitude of the dynamics of newly synthesized labelled urea and albumin which were simultaneously observed after administration of [14C]carbonate on the basis of a preliminary model which postulated that both products were derived from a single hepatic pool of [16-14C]arginine. On the other hand these observed dynamics could be satisfied to a two-compartment arginine model, which also

  6. 13C Metabolomics: NMR and IROA for Unknown Identification

    PubMed Central

    Clendinen, Chaevien S.; Stupp, Gregory S.; Wang, Bing; Garrett, Timothy J.; Edison, Arthur S.

    2016-01-01

    Abstract: Background Isotopic Ratio Outlier Analysis (IROA) is an untargeted metabolomics method that uses stable isotopic labeling and LC-HRMS for identification and relative quantification of metabolites in a biological sample under varying experimental conditions. Objective We demonstrate a method using high-sensitivity 13C NMR to identify an unknown metabolite isolated from fractionated material from an IROA LC-HRMS experiment. Methods IROA samples from the nematode Caenorhabditis elegans were fractionated using LC-HRMS using 5 repeated injections and collecting 30 sec fractions. These were concentrated and analyzed by 13C NMR. Results We isotopically labeled samples of C. elegans and collected 2 adjacent LC fractions. By HRMS, one contained at least 2 known metabolites, phenylalanine and inosine, and the other contained tryptophan and an unknown feature with a monoisotopic mass of m/z 380.0742 [M+H]+. With NMR, we were able to easily verify the known compounds, and we then identified the spin system networks responsible for the unknown resonances. After searching the BMRB database and comparing the molecular formula from LC-HRMS, we determined that the fragments were a modified anthranilate and a glucose modified by a phosphate. We then performed quantum chemical NMR chemical shift calculations to determine the most likely isomer, which was 3’-O-phospho-β-D-glucopyranosyl-anthranilate. This compound had previously been found in the same organism, validating our approach. Conclusion We were able to dereplicate previously known metabolites and identify a metabolite that was not in databases by matching resonances to NMR databases and using chemical shift calculations to determine the correct isomer. This approach is efficient and can be used to identify unknown compounds of interest using the same material used for IROA. PMID:28090435

  7. Millimeter and submillimeter wave spectra of 13C-glycolaldehydes

    NASA Astrophysics Data System (ADS)

    Haykal, I.; Motiyenko, R. A.; Margulès, L.; Huet, T. R.

    2013-01-01

    Context. Glycolaldehyde (CH2OHCHO) is the simplest sugar and an important intermediate in the path toward forming more complex biologically relevant molecules. Astronomical surveys of interstellar molecules, such as those available with the very sensitive ALMA telescope, require preliminary laboratory investigations of the microwave and submillimeter-wave spectra of molecular species including new isotopologs - to identify these in the interstellar media. Aims: To achieve the detection of the 13C isotopologs of glycolaldehyde in the interstellar medium, their rotational spectra in the millimeter and submillimeter-wave regions were studied. Methods: The spectra of 13CH2OHCHO and CH2OH13CHO were recorded in the 150-945 GHz spectral range in the laboratory using a solid-state submillimeter-wave spectrometer in Lille. The observed line frequencies were measured with an accuracy of 30 kHz up to 700 GHz and of 50 kHz above 700 GHz. We analyzed the spectra with a standard Watson Hamiltonian. Results: About 10 000 new lines were identified for each isotopolog. The spectroscopic parameters were determined for the ground- and the three lowest vibrational states up to 945 and 630 GHz. Previous microwave assignments of 13CH2OHCHO were not confirmed. Conclusions: The provided line-lists and sets of molecular parameters meet the needs for a first astrophysical search of 13C-glycolaldehydes. Full Tables 3 and 4 are only available at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/549/A96

  8. Cluster Structure and 3-body decay in 14C

    NASA Astrophysics Data System (ADS)

    Carpenter, Lisa; Bazin, D.; Mittig, W.; Ayyad, Y.; Beceiro Novo, S.; Bradt, J.; Ahn, T.; Kolata, J. J.; Becchetti, F. D.; Fritsch, A.

    2016-09-01

    Recent model calculations with most advanced methods for cluster states have shown the need of experimental data to probe the structure of light exotic nuclei, including those with α-clustering, such as 14C. The Prototype Active Target Time Projection Chamber (PAT-TPC) allows us to investigate these types of structures, giving access to the full excitation function with a single beam energy. This type of experiment measures resonances in 14C that can be compared to the models. With an improved Micromegas pad plane with a circular backgammon design we are able to investigate 3-body decays in addition to 2-body scattering. The measurements were carried out by resonant alpha-scattering on 10Be beam delivered by the TwinSol facility at the University of Notre Dame. This work is supported by the National Science Foundation.

  9. The behaviour of (14)C profiles in Helianthus seedlings.

    PubMed

    Whittle, C M

    1971-06-01

    The log. (14)C activity/distance profile in the stems of Helianthus seedlings consists of two main parts: region 1, the linear advancing front and region 2, which is also linear but with a less steep slope. As the front passes down the stem, the slope of region 1 remains constant but the amplitude of the front becomes attenuated. The attenuation increases with temperature. The apparent velocity of the profile, which can be derived from the position of the front, is also temperature dependent. Small amounts of (14)C occur in the stem ahead of the profile; these amounts increase with a rise of temperature. Region 2 behaves differently: its slope decreases steadily with time but it is insensitive to temperature. The behaviour of this region is dependent on the movement of tracer into an immobile fraction as well as on the longitudinal movement of tracer in the translocation stream.

  10. May 14C be used to date contemporary art?

    NASA Astrophysics Data System (ADS)

    Fedi, M. E.; Caforio, L.; Mandò, P. A.; Petrucci, F.; Taccetti, F.

    2013-01-01

    The use of radiocarbon in forensics is by now widespread, thanks to the so-called bomb peak, which makes it possible to perform high-precision dating. Since 1955, 14C concentration in the atmosphere had strongly increased due to nuclear explosions, reaching its maximum value in 1963-1965. After the Nuclear Test Ban Treaty, 14C started to decrease as a consequence of the exchanges between atmosphere and the other natural carbon reservoirs. Nowadays, it is still slightly above the pre-bomb value. The work presented in this paper is based on the idea of exploiting the bomb peak to “precisely” date works of contemporary art, with the aim at identifying possible fakes. We analysed two kinds of materials from the 20th century: newspapers and painting canvases. Newspaper samples were taken because they might in principle be considered to represent dated samples (considering the date on the issues). Our data (28 samples) show a trend similar to atmospheric data in the literature, although with some differences; the paper peak is flatter and shifted towards more recent years (about five years) with respect to the atmospheric data. This can be explained by taking paper manufacturing processes into account. As to the canvas samples, the measured 14C concentrations were generally reasonably consistent with the expected concentrations (based on the year on the paintings). However, this does not indicate that the interpretation of the results is simpler and more straightforward. Obviously, we only measure the 14C concentration of the fibre used for the canvas, which does not necessarily measure the date the painting was manufactured. In this paper, sample preparation and experimental results will be discussed, in order to show the potential as well as the limitations of radiocarbon to date contemporary art.

  11. A dipseudoacid, C 16H 18O 6

    NASA Astrophysics Data System (ADS)

    Liskin, Dmitriy V.; Valente, Edward J.

    2008-04-01

    Pseudoacids, or cyclic oxocarboxylic acids commonly form non-planar, complementary and non-cooperative, dimeric hydrogen-bonds. A dehydration resistant arylpyran dipseudoacid, C 16H 18O 6, has been synthesized and characterized. Crystals of trans-4,4,8,8-tetramethyl-3,7-dihydroxy-1,2,3,4,5,6,7,8-octahydro-2,6-dioxaanthracen-1,5-dione occur in the monoclinic system and form linear hydrogen-bonded chains; it has an elevated melting point without decomposition at 574.6 K.

  12. 14C content in aerosols in Mexico City

    NASA Astrophysics Data System (ADS)

    Gómez, V.; Solís, C.; Chávez, E.; Andrade, E.; Ortiz, M. E.; Huerta, A.; Aragón, J.; Rodríguez-Ceja, M.; Martínez, M. A.; Ortiz, E.

    2016-03-01

    14C-AMS of total carbon was determined in aerosols (PM10 fraction), collected in Mexico City during two weeks from 21 November to 3 December 2012. Other tracers such as total carbon (TC), organic carbon (OC), elemental carbon (EC) and trace element contents were also determined. F14C values varied from 0.39 to 0.48 with an average of 0.43. These values are slightly lower than those previously obtained for PM2.5 in 2003 and 2006 and reflect a high contribution of fossil CO2 to the carbonaceous matter in aerosols from Mexico City. In contrast, from 2006 to 2012 PM10 increased; EC, Ca, Ti and Fe concentrations remained constant, while OC, TC and K concentrations decreased. The use of potassium as an indicator of biomass burning showed that this source was negligible during this campaign. Combined analytical approaches allowed us to distinguish temporal variations of anthropogenic and natural inputs to the F14C.

  13. Airy structure in 16O+14C nuclear rainbow scattering

    NASA Astrophysics Data System (ADS)

    Ohkubo, S.; Hirabayashi, Y.

    2015-08-01

    The Airy structure in 16 O +14 C rainbow scattering is studied with an extended double-folding (EDF) model that describes all the diagonal and off-diagonal coupling potentials derived from the microscopic realistic wave functions for 16 O by using a density-dependent nucleon-nucleon force. The experimental angular distributions at EL=132 , 281, and 382.2 MeV are well reproduced by the calculations. By studying the energy evolution of the Airy structure, the Airy minimum around θ =76∘ in the angular distribution at EL=132 MeV is assigned as the second-order Airy minimum A 2 in contrast to the recent literature which assigns it as the third order A 3 . The Airy minima in the 90∘ excitation function is investigated in comparison with well-known 16 O +16 O and 12 C +12 C systems. Evolution of the Airy structure into the molecular resonances with the 16 O +14 C cluster structure in the low-energy region around Ec .m .=30 MeV is discussed. It is predicted theoretically for the first time for a non-4 N 16O +14 C system that Airy elephants in the 90∘ excitation function are present.

  14. Disposition of (/sup 14/C)dimercaptosuccinic acid in mice

    SciTech Connect

    Liang, Y.Y.; Marlowe, C.; Waddell, W.J.

    1986-04-01

    Dimercaptosuccinic acid labeled with /sup 14/C ((/sup 14/C)DMSA) was administered to mice iv; the mice were frozen by immersion in dry ice/hexane at 6 and 20 min and 1, 3, 9, and 24 hr after injection. The frozen mice were sectioned and processed for whole-body autoradiography for soluble substances. The radioactivity was highly localized in extracellular fluids such as the subcutaneous, intrapleural, intraperitoneal, and periosteal spaces. There was a pronounced accumulation in the periosteal fluid above that in other fluids during the first hour after injection. Most of the radioactivity was eliminated by the kidney and liver. Pretreatment of a mouse with HgCl/sub 2/ subcutaneously 1 hr before (/sup 14/C)DMSA produced an increase in radioactivity in the liver and a decrease in the lungs. A high concentration of radioactivity was seen at the subcutaneous site of injection of the HgCl/sub 2/. The results are interpreted to indicate that most of the DMSA is in the extracellular space but that it can cross cellular membranes to some extent. The pronounced accumulation in periosteal fluid may be an interaction of DMSA with Ca2+ in this space. No tissue had a pronounced retention of the compound, but the lungs retained more than most other tissues.

  15. Carbon cycle dynamics and solar activity embedded in a high-resolution 14C speleothem record from Belize, Central America

    NASA Astrophysics Data System (ADS)

    Lechleitner, Franziska A.; Breitenbach, Sebastian F. M.; McIntyre, Cameron; Asmerom, Yemane; Prufer, Keith M.; Polyak, Victor; Culleton, Brendan J.; Kennett, Douglas J.; Eglinton, Timothy I.; Baldini, James U. L.

    2015-04-01

    of old recalcitrant carbon to the soil water, and resulting in closer coupling between atmosphere and cave environment. The resolution of the record (0.3-0.7 mm/sample) permits identification of the dominant drivers of stalagmite 14C during different intervals. For example, hydrologic control on 14C appears dominant during the 11th century drought, while in the 16th to 18th century a clear solar influence exists. Solar activity is reflected in YOK-I as lower a14Cinit, reflecting the atmospheric a14C. We apply simple hydrological models to investigate the different factors influencing 14C in YOK-I. We estimate the importance of mean SOM age to signal dampening, and quantify the strength of the solar influence and the global carbon cycle on the record. References: Genty, D., Baker, A., Massault, M., Proctor, C., Gilmour, M., Pons-Branchu, E., Hamelin, B. (2001) Dead carbon in stalagmites: carbonate bedrock paleodissolution vs. ageing of soil organic matter. Implications for 13C variations in speleothems, GCA, 65 Griffiths, M.L., Fohlmeister, J., Drysdale, R.N., Hua, Q., Johnson, K.R., Hellstrom, J.C., Gagan, M.K., Zhao, J.-x. (2012) Hydrological control of the dead carbon fraction in a Holocene tropical speleothem, Quat. Geochron. 14 Ridley, H.E., Baldini, J.U.L., Prufer, K.M., Walczak, I.W., Breitenbach, S.F.M. (in press) High resolution monitoring of a tropical cave system reveals dynamic ventilation and hydrologic resilience to seismic activity, Journal of Cave and Karst Studies

  16. The First in Vivo Observation of 13C- 15N Coupling in Mammalian Brain

    NASA Astrophysics Data System (ADS)

    Kanamori, Keiko; Ross, Brian D.

    2001-12-01

    [5-13C,15N]Glutamine, with 1J(13C-15N) of 16 Hz, was observed in vivo in the brain of spontaneously breathing rats by 13C MRS at 4.7 T. The brain [5-13C]glutamine peak consisted of the doublet from [5-13C,15N]glutamine and the center [5-13C,14N]glutamine peak, resulting in an apparent triplet with a separation of 8 Hz. The time course of formation of brain [5-13C,15N]glutamine was monitored in vivo with a time resolution of 20-35 min. This [5-13C,15N]glutamine was formed by glial uptake of released neurotransmitter [5-13C]glutamate and its reaction with 15NH3 catalyzed by the glia-specific glutamine synthetase. The neurotransmitter glutamate C5 was selectively13C-enriched by intravenous [2,5-13C]glucose infusion to 13C-label whole-brain glutamate C5, followed by [12C]glucose infusion to chase 13C from the small and rapidly turning-over glial glutamate pool, leaving 13C mainly in the neurotransmitter [5-13C]glutamate pool, which is sequestered in vesicles until release. Hence, the observed [5-13C,15N]glutamine arises from a coupling between 13C of neuronal origin and 15N of glial origin. Measurement of the rate of brain [5-13C,15N]glutamine formation provides a novel noninvasive method of studying the kinetics of neurotransmitter uptake into glia in vivo, a process that is crucial for protecting the brain from glutamate excitotoxicity.

  17. Reaction cross sections for. nu. sup 13 C r arrow e sup minus sup 13 N and. nu. sup 13 C r arrow. nu. prime sup 13 C sup * for low energy neutrinos

    SciTech Connect

    Fukugita, M. ); Kohyama, Y.; Kubodera, K.; Kuramoto, T. )

    1990-04-01

    Cross sections for {nu}+{sup 13}C reactions are calculated both for charged- and neutral-current reactions in order to estimate the efficiency of a {sup 13}C target as a solar neutrino detector. The relevant transition matrix elements are obtained using the semiphenomenological effective-operator approach for {ital p}-shell nuclei.

  18. Amount and identity of (/sup 14/C) residues in bluegills (Lepomis macrochirus) exposed to (/sup 14/C)triclopyr

    SciTech Connect

    Lickly, T.D.; Murphy, P.G.

    1987-01-01

    The level and identity of (/sup 14/C) residues in bluegills (Lepomis macrochirus) exposed to 2.5 mg/L (/sup 14/C) triclopyr (3,5,6-trichloro-2-pyridinyloxyacetic acid) have been determined. The highest level of radioactivity observed in the flesh of a fish at any time point (0.13 mg/kg, calculated as equivalent mg triclopyr/kg fish) was less than 5% of the fish exposure level of 2.5 mg/L, while the maximum level in the remainder (head, skin, and viscera) was about 95% (2.33 mg/kg) of the fish exposure level, indicating no concentrating effect. The principal components observed in the fish tissues were triclopyr, 3,5,6-trichloro-2-pyridinol, 2-methoxy-3,5,6-trichloropyridine and a conjugate. These components accounted for greater than 75% of all the residues observed.

  19. The fate of {sup 14}C-pyrene and {sup 14}C-chrysene in soils amended with a PAH mixture

    SciTech Connect

    Guthrie, E.; Thompkins, J.; Pfaender, F.

    1995-12-31

    Polycyclic Aromatic Hydrocarbons (PAH) are ubiquitous environmental contaminants at many hazardous waste sites. Microbial processes are known to influence the fate of PAH in soils and can effect PAH structure, toxicity, bioavailability, and association with soil organic matter (SOM). Experiments were conducted to determine the extent of {sup 14}C-pyrene or {sup 14}C-chrysene associations with soil organic matter (SOM) in soils amended with a PAH mixture and either a [4,5,9,10-{sup 14}C]pyrene or [5,6,11,12-{sup 14}C] chrysene tracer. Changes in microbial respiration ({sup 14}CO{sub 2} efflux), {sup 14}C-volatile organics, {sup 14}C-water soluble metabolites, and {sup 14}C-SOM were measured over time in continuously, aerated microcosms. The bioavailability of {sup 14}C-products in SOM fractions was determined using a mineralization endpoint assay. Extracts of {sup 14}C products in SOM fractions were tested for acute and chronic toxicity using Microtox{trademark}. The {sup 14}C-products associated with residual soil fractions were further extracted with HF/HCI and methylene chloride and then analyzed with LC-MS. The presence of a PAH mixture enhanced {sup 14}C-pyrene mineralization in non-adapted, pristine soils to a greater extent than {sup 14}C-pyrene mineralization observed in pristine soils amended with a known PAH-mineralizing, microbial community. Mineralization of {sup 14}C-chrysene in non-adapted, pristine soils was greater than NaN{sup 3} abiotic, control soils, but significantly less than {sup 14}C-chrysene mineralization in pristine soils amended with a known PAH-mineralizing, microbial community. The major fate of {sup 14}C-pyrene, {sup 14}C-chrysene, and PAH mixtures is association with SOM.

  20. Comparisons of observed and modelled lake δ18O variability

    NASA Astrophysics Data System (ADS)

    Jones, Matthew D.; Cuthbert, Mark O.; Leng, Melanie J.; McGowan, Suzanne; Mariethoz, Gregoire; Arrowsmith, Carol; Sloane, Hilary J.; Humphrey, Kerenza K.; Cross, Iain

    2016-01-01

    With the substantial number of lake sediment δ18O records published in recent decades, a quantitative, process-based understanding of these systems can increase our understanding of past climate change. We test mass balance models of lake water δ18O variability against five years of monthly monitoring data from lakes with different hydrological characteristics, in the East-Midlands region of the UK, and the local isotope composition of precipitation. These mass balance models can explain up to 74% of the measured lake water isotope variability. We investigate the sensitivity of the model to differing calculations of evaporation amount, the amount of groundwater, and to different climatic variables. We show there is only a small range of values for groundwater exchange flux that can produce suitable lake water isotope compositions and that variations in evaporation and precipitation are both required to produce recorded isotope variability in lakes with substantial evaporative water losses. We then discuss the potential for this model to be used in a long-term, palaeo-scenario. This study demonstrates how long term monitoring of a lake system can lead to the development of robust models of lake water isotope compositions. Such systematics-based explanations allow us to move from conceptual, to more quantified reconstructions of past climates and environments.

  1. Glacial-interglacial shifts in global and regional precipitation δ18O

    NASA Astrophysics Data System (ADS)

    Jasechko, S.; Lechler, A.; Pausata, F. S. R.; Fawcett, P. J.; Gleeson, T.; Cendón, D. I.; Galewsky, J.; LeGrande, A. N.; Risi, C.; Sharp, Z. D.; Welker, J. M.; Werner, M.; Yoshimura, K.

    2015-03-01

    Previous analyses of past climate changes have often been based on site-specific isotope records from speleothems, ice cores, sediments and groundwaters. However, in most studies these dispersed records have not been integrated and synthesized in a comprehensive manner to explore the spatial patterns of precipitation isotope changes from the last ice age to more recent times. Here we synthesize 88 globally-distributed groundwater, cave calcite, and ice core isotope records spanning the last ice age to the late-Holocene. Our data-driven review shows that reconstructed precipitation δ18O changes from the last ice age to the late-Holocene range from -7.1‰ (ice age δ18O < late-Holocene δ18O) to +1.8‰ (ice age δ18O > late-Holocene δ18O) with wide regional variability. The majority (75%) of reconstructions have lower ice age δ18O values than late-Holocene δ18O values. High-magnitude, negative glacial-interglacial precipitation δ18O shifts (ice age δ18O < late-Holocene δ18O by more than 3‰) are common at high latitudes, high altitudes and continental interiors. Conversely, lower-magnitude, positive glacial-interglacial precipitation δ18O shifts (ice age δ18O > late-Holocene δ18O by less than 2‰) are most common along subtropical coasts. Broad, global patterns of glacial-interglacial precipitation δ18O shifts are consistent with stronger-than-modern isotopic distillation of air masses during the last ice age, likely impacted by larger global temperature differences between the tropics and the poles. Further, to complement our synthesis of proxy-record precipitation δ18O, we compiled isotope enabled general circulation model simulations of recent and last glacial maximum climate states. Simulated precipitation δ18O from five general circulation models show better inter-model and model-observation agreement in the sign of δ18O changes from the last ice age to present day in temperate and polar regions than in the tropics. Further model precipitation

  2. Influence of selected pesticides on the microbial degradation of 14C-triallate and 14C-diallate in soil.

    PubMed

    Anderson, J P; Domsch, K H

    1980-01-01

    Degradation in soil of [allyl-2-14C]triallate and [carbonyl-14C]diallate herbicides, as affected by other selected pesticides, was studied in an incubation system that allowed recovery of 95 to 100% of added 14C. The amount and sequence of pesticide additions simulated field use in the protection of wheat (triallate) and sugar beets (diallate). Neither the rate nor the pattern of triallate degradation in soil was influenced by the following sequence of formulated pesticides: dinoseb acetate, (bentazon + dichlorprop + 2,4,5-T), 2,4-D, (chlorcholinchloride + cholinchloride), tridemorph, and thiophanate. Similarly, diallate degradation was unaffected by pyrazon, dimethoate, and thiophanate. The effect of azinphosmethyl was unclear. In contrast, chlorpyrifos reduced diallate degradation by approximately 14% relative to the occurring in the insecticide's absence. This effect was caused by chlorpyrifos and not its formulation components. Chlorpyrifos was also found to partially inhibit degradation of triallate in soil. Inhibition of neither herbicide was considered to be of ecological significance. Triallate, diallate, and thiophanate were applied at 1 microgram/g; all others were at 2 microgram/g.

  3. Autoradiographic disposition of (1-methyl-/sup 14/C)- and (2-/sup 14/C)caffeine in mice

    SciTech Connect

    Lachance, M.P.; Marlowe, C.; Waddell, W.J.

    1983-11-01

    Male, C57B1/6J mice received either (1-methyl-14C)caffeine or (2-14C)caffeine via the tail vein at a dose of 0.7 or 11 mg/kg, respectively. At 0.1, 0.33, 1, 3, 9, and 24 hr after treatment, the mice were anesthetized with ether and frozen by immersion in dry ice/hexane. The mice were processed for whole-body autoradiography by the Ullberg technique; this procedure does not allow thawing or contact with solvents. All autoradiographs revealed some retention of radioactivity at early time intervals in the lacrimal glands, seminal vesicle fluid, nasal and olfactory epithelium, and retinal melanocytes. The remaining portion of the animal was densitometrically uniform except for the lower levels noted in the CNS and adipose tissues. Excretion of radioactivity by the liver and kidneys seems to be the major routes of elimination. Localization in the liver at late time intervals was confined principally to the centrilobular region. Late sites of retention, observed only after (1-methyl-14C)caffeine administration, included the pancreas, minor and major salivary glands, splenic red pulp, thymal cortex, bone marrow, and gastrointestinal epithelium. Sites of localization present in both studies included the olfactory epithelium, lacrimal glands, hair follicles, and retinal melanocytes. Further studies are needed to determine whether the localization at these various sites is due to metabolic degradation, active transport, or possibly a specific receptor interaction.

  4. How Reliable is the Bulk δ13C value of Soil Organic Matter in Paleovegetational Reconstruction?

    NASA Astrophysics Data System (ADS)

    Sanyal, P.; Rakshit, S.

    2015-12-01

    Carbon isotope ratios of soil/paleosol organic matter (δ13CSOM) have been used to reconstruct abundance of C3-C4 plants survived in the landscape as the δ13C value of C3 (-27‰) and C4 (-12.5 ‰) plants are distinctly different. In an attempt to reconstruct the abundance of C3 and C4 plants, δ13CSOM have been measured from three soil profiles developed on flood plain of the Gangetic plain, Mohanpur, West Bengal, India. Satellite images reveal that the investigated sediments have been deposited in an oxbow lake setting of the river Ganges. The total organic carbon content of the profile ranges from 0.9% to 0.1%. The δ13CSOM values mostly range from -19.2‰ to -22‰ except a rapid positive excursions of ~5‰ at 1.5 m depth showing enriched value (-14.2‰) in all the three profiles. Based on mass balance calculation using the δ13C values of C3 and C4 plants, the δ13CSOM in the Gangetic plain indicate presence of both C3 and C4 plants in the floodplain. However, characterization of alkanes separated from lipids extracted from the same soil organic matter reveals dominant preferences in short carbon chain (C14, C16, C18, C20) with a little preferences for higher chain (C29, C31, C33). Interestingly, n-alkanes at 1.5 m depth shows very high concentration in short chain n-alkanes. Since the lower chain n-alkane represents aquatic productivity or intense bacterial decomposition and higher chain indicates the contribution from C3-C4 plants, the data from the investigated sedimentary profile shows contribution mostly from aquatic vegetation with a little contribution from terrestrial plants. This implies that before using bulk δ13CSOM value for reconstruction of C3-C4 plants from soil/paleosol, characterization (molecular level) of soil organic matter is required

  5. Vertical variation of δ13C of sphagnum in the four peat cores collected from both the hemispheres

    NASA Astrophysics Data System (ADS)

    Ooki, S.; Akagi, T.; Franzen, L.; McCulloch, R.; Skrzypek, G. D.

    2009-12-01

    The carbon isotope profiles of the organic burials in several peat lands have been reported and have been discussed in terms of some local climatic and/or environmental conditions such as moistness, local CO2 supply from fossil carbon combustion, etc. In order to discuss the influence of some global environmental factors on the carbon isotope composition of sphagnum, we have sampled four peat cores from the world: two high latitudinal location in the Northern hemisphere (Fallahogy, Northern Ireland and Suche Bagno, Poland), one medium latitudinal site in the Northern hemisphere (Oze, Japan), and one high latitudinal site in the Southern hemisphere (Harbarton, Argentina). Here we report the vertical profiles of δ13C of sphagnum in the four peat cores. The peat core samples were divided to 2-5cm and dried. After drying we separated only sphagnum tissues with tweezers. The waxes and oils in the collected sphagnum material were removed with a mixture solvent of benzene and ethanol by soxhlet extraction and then lignin and cellulose components were isolated from the treated samples and the recovered components were weighed. The δ13C of the three components (the treated sample, lignin and cellulose components) were measured with EA-IRMS. The 14C ages were also measured using some of the treated samples. The δ13C variations of the cores showed a similar general tend to become greater with time and it is very interesting that the range of the δ13C changes were equally 2.5-3‰. Although the possibility of the diagensis of organic materials cannot be ruled out as the cause of the changes at the moment, a global factor, such as gradual increase in atmospheric carbon dioxide concentration during the last ten millennia years, may be one of the candidates for the cause. Besides some simultaneous changes, some minor local changes are also noticeable. It has been reported that the δ13C of sphagnum varies with several factors: species, tissue, lignin/cellulose ratio, water

  6. PASADENA hyperpolarization of 13C biomolecules: equipment design and installation

    PubMed Central

    Hövener, Jan-Bernd; Chekmenev, Eduard Y.; Harris, Kent C.; Perman, William H.; Robertson, Larry W.; Bhattacharya, Pratip

    2009-01-01

    Object The PASADENA method has achieved hyperpolarization of 16–20% (exceeding 40,000-fold signal enhancement at 4.7 T), in liquid samples of biological molecules relevant to in vivo MRI and MRS. However, there exists no commercial apparatus to perform this experiment conveniently and reproducibly on the routine basis necessary for translation of PASADENA to questions of biomedical importance. The present paper describes equipment designed for rapid production of six to eight liquid samples per hour with high reproducibility of hyperpolarization. Materials and methods Drawing on an earlier, but unpublished, prototype, we provide diagrams of a delivery circuit, a laminar-flow reaction chamber within a low field NMR contained in a compact, movable housing. Assembly instructions are provided from which a computer driven, semiautomated PASADENA polarizer can be constructed. Results Together with an available parahydrogen generator, the polarizer, which can be operated by a single investigator, completes one cycle of hyperpolarization each 52 s. Evidence of efficacy is presented. In contrast to competing, commercially available devices for dynamic nuclear polarization which characteristically require 90 min per cycle, PASADENA provides a low-cost alternative for high throughput. Conclusions This equipment is suited to investigators who have an established small animal NMR and wish to explore the potential of heteronuclear (13C and 15N) MRI, MRS, which harnesses the enormous sensitivity gain offered by hyperpolarization. PMID:19067008

  7. New optical analyzer for 13C-breath test

    NASA Astrophysics Data System (ADS)

    Harde, Hermann; Dressler, Matthias; Helmrich, Günther; Wolff, Marcus; Groninga, Hinrich

    2008-04-01

    Medical breath tests are well established diagnostic tools, predominantly for gastroenterological inspections, but also for many other examinations. Since the composition and concentration of exhaled volatile gases reflect the physical condition of a patient, a breath analysis allows one 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 is based on photoacoustic spectroscopy and uses a DFB diode laser at 2.744 μm. The concentration ratio of the CO II isotopologues is determined by measuring the absorption on a 13CO II line in comparison to a 12CO II line. In the specially selected spectral range the lines have similar strengths, although the concentrations differ by a factor of 90. Therefore, the signals are well comparable. Due to an excellent signal-noise-ratio isotope variations of less than 1% can be resolved as required for the breath test.

  8. 17 CFR 240.14c-3 - Annual report to be furnished security holders.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... security holders. 240.14c-3 Section 240.14c-3 Commodity and Securities Exchanges SECURITIES AND EXCHANGE... Section 14(c) § 240.14c-3 Annual report to be furnished security holders. (a) If the information statement... such meeting, of security holders at which directors of the registrant, other than an...

  9. 17 CFR 240.14c-3 - Annual report to be furnished security holders.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... security holders. 240.14c-3 Section 240.14c-3 Commodity and Securities Exchanges SECURITIES AND EXCHANGE... Section 14(c) § 240.14c-3 Annual report to be furnished security holders. (a) If the information statement... such meeting, of security holders at which directors of the registrant, other than an...

  10. 17 CFR 240.14c-3 - Annual report to be furnished security holders.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... security holders. 240.14c-3 Section 240.14c-3 Commodity and Securities Exchanges SECURITIES AND EXCHANGE... Section 14(c) § 240.14c-3 Annual report to be furnished security holders. (a) If the information statement... such meeting, of security holders at which directors of the registrant, other than an...

  11. 17 CFR 240.14c-3 - Annual report to be furnished security holders.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... security holders. 240.14c-3 Section 240.14c-3 Commodity and Securities Exchanges SECURITIES AND EXCHANGE... Section 14(c) § 240.14c-3 Annual report to be furnished security holders. (a) If the information statement... such meeting, of security holders at which directors of the registrant, other than an...

  12. Human folate metabolism using 14C-accelerator mass spectrometry

    SciTech Connect

    Clifford, A. J.; Arjomand, A.; Duecker, S. R.; Johnson, H.; Schneider, P. D.; Zulim, R. A.; Bucholz, B. A.; Vogel, J. S.

    1999-03-25

    Folate is a water soluble vitamin required for optimal health, growth and development. It occurs naturally in various states of oxidation of the pteridine ring and with varying lengths to its glutamate chain. Folates function as one-carbon donors through methyl transferase catalyzed reactions. Low-folate diets, especially by those with suboptimal methyltransferase activity, are associated with increased risk of neural tube birth defects in children, hyperhomocysteinemic heart disease, and cancer in adults. Rapidly dividing (neoplastic) cells have a high folate need for DNA synthesis. Chemical analogs of folate (antifolates) that interfere with folate metabolism are used as therapeutic agents in cancer treatment. Although much is known about folate chemistry, metabolism of this vitamin in vivo in humans is not well understood. Since folate levels in blood and tissues are very low and methods to measure them are inadequate, the few previous studies that have examined folate metabolism used large doses of radiolabeled folic acid in patients with Hodgkin's disease and cancer (Butterworth et al. 1969, Krumdieck et al. 1978). A subsequent protocol using deuterated folic acid was also insufficiently sensitive to trace a physiologic folate dose (Stites et al. 1997). Accelerator mass spectrometry (AMS) is an emerging bioanalytical tool that overcomes the limitations of traditional mass spectrometry and of decay counting of long lived radioisotopes (Vogel et al. 1995). AMS can detect attomolar concentrations of 14 C in milligram-sized samples enabling in vivo radiotracer studies in healthy humans. We used AMS to study the metabolism of a physiologic 80 nmol oral dose of 14 C-folic acid (1/6 US RDA) by measuring the 14 C-folate levels in serial plasma, urine and feces samples taken over a 150-day period after dosing a healthy adult volunteer.

  13. Benthic ostracode δ13C as sensor for early Holocene establishment of modern circulation patterns in Central Europe

    NASA Astrophysics Data System (ADS)

    Schwalb, Antje; Dean, Walter; Güde, Hans; Hanisch, Sabine; Sobek, Sebastian; Wessels, Martin

    2013-04-01

    Shells from adult specimen of the benthic ostracodes Limnocytherina sanctipatricii and Leucocythere mirabilis selected from a 8.7 m long piston core provide continuous stable oxygen and carbon records for the past approximately 16 ka. Oxygen isotopes from both species show identical values and track the general North Atlantic and European temperature history since deglaciation in great detail. Values of ostracode δ18O values suggest that about 16 cal ka the average annual air temperatures were about 11 °C colder than today. Carbon isotopic values from both species of ostracodes are similar during the Lateglacial and early Holocene, and show an overall decrease from -4‰ to -7‰ that is probably related to an increase in photosynthetic productivity in the water column, as suggested by an increase in organic carbon, delivering 13C-depleted organic matter to the bottom waters (carbon pump). About 9 cal ka only L. mirabilis δ13C values decreased about -2.5‰ within 300 years. Higher δ13C variability and ecological evidence suggests that L. mirabilis represents a summer signal, whereas L. sanctipatricii displays a more subdued annual average. After about 7 cal ka another -1.5% decrease for both species, accompanied by an increase in magnetic susceptibility, a decrease in carbonate content, and more positive bulk carbonate isotope values followed, suggesting higher detrital-clastic input into the lake. In order to provide a possible mechanism explaining the negative L. mirabilis δ13C-values, sediment pore water profiles of O2 and CH4 in short cores collected from sites distal to proximal to the Alpine Rhine River delta, were inspected. Sediments in cores from more proximal sites to the Rhine delta become anoxic at shallower sediment depth due to the decay of high allochthonous organic carbon input to the sediment, which greatly increases concentrations of methane in pore waters closer to the Rhine inflow. When methane is oxidized close to the sediment

  14. Effect of seasonal changes in the pathways of methanogenesis on the δ13C values of pore water methane in a Michigan peatland

    NASA Astrophysics Data System (ADS)

    Avery, G. Brooks; Shannon, Robert D.; White, Jeffrey R.; Martens, Christopher S.; Alperin, Marc J.

    1999-06-01

    The δ13C value of pore water methane produced in a Michigan peatland varied by 11‰ during the year. This isotopic shift resulted from large seasonal changes in the pathways of methane production. On the basis of mass balance calculations, the δ13C value of methane from CO2 reduction (average = -71.4 ± 1.8‰) was depleted in 13C compared to that produced from acetate (-44.4 ± 8.2‰). The dissolved methane at the site remained heavy (approximately -51‰) during most of the year. Tracer experiments using 14C-labeled CO2 indicated that during January 110 ± 25% of the methane was produced by CO2 reduction. Because of low-methane production rates during the winter, this 13C-depleted methane had only a slight effect on the isotopic composition of the methane pool. In early spring when peat temperatures and methane production rates increased, the δ13C value of the dissolved methane in shallow peat was influenced by the isotopically light methane and approached -61‰. Peat incubation experiments conducted at 15°C in May and June (when the peat reaches its maximum temperature) indicated that an average of 84 ± 9% of the methane production was from acetate and had an average δ13C value of -48.7 ± 5.6‰. Rising acetate concentrations during April-May (approaching 1 mmol L-1(mM)) followed by a rapid decrease in acetate concentrations during May-June reflected the shift toward methane production dominated by acetate fermentation. During this period, dissolved methane in shallow peat at the site returned to heavier values (approximately -51‰) similar to that produced in the incubation experiments.

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

    SciTech Connect

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

    2014-09-21

    Application of sets of {sup 13}C-{sup 13}C 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 {sup 13}C-{sup 13}C distances in uniformly {sup 13}C-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 ({sup 13}C′) and aliphatic ({sup 13}C{sub aliphatic}) 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 {sup 13}C,{sup 15}N-labeled-L-isoleucine. In a more challenging biological application, FOLD 2D experiments are used to determine a large number of {sup 13}C′-{sup 13}C{sub aliphatic} distances in amyloid fibrils formed by the SNNFGAILSS fibrillating core of the human islet amyloid polypeptide with uniform {sup 13}C,{sup 15}N-labeling on the FGAIL fragment.

  16. 40 CFR 721.6505 - Polymers of C13C15 oxoalcohol ethoxolates.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Polymers of C13C15 oxoalcohol... Specific Chemical Substances § 721.6505 Polymers of C13C15 oxoalcohol ethoxolates. (a) Chemical substance... polymers of C13C15 oxoalcohol ethoxolates (PMNs P-96-950/951) are subject to reporting under this...

  17. 40 CFR 721.6505 - Polymers of C13C15 oxoalcohol ethoxolates.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Polymers of C13C15 oxoalcohol... Specific Chemical Substances § 721.6505 Polymers of C13C15 oxoalcohol ethoxolates. (a) Chemical substance... polymers of C13C15 oxoalcohol ethoxolates (PMNs P-96-950/951) are subject to reporting under this...

  18. 40 CFR 721.6505 - Polymers of C13C15 oxoalcohol ethoxolates.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Polymers of C13C15 oxoalcohol... Specific Chemical Substances § 721.6505 Polymers of C13C15 oxoalcohol ethoxolates. (a) Chemical substance... polymers of C13C15 oxoalcohol ethoxolates (PMNs P-96-950/951) are subject to reporting under this...

  19. 40 CFR 721.6505 - Polymers of C13C15 oxoalcohol ethoxolates.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Polymers of C13C15 oxoalcohol... Specific Chemical Substances § 721.6505 Polymers of C13C15 oxoalcohol ethoxolates. (a) Chemical substance... polymers of C13C15 oxoalcohol ethoxolates (PMNs P-96-950/951) are subject to reporting under this...

  20. 40 CFR 721.6505 - Polymers of C13C15 oxoalcohol ethoxolates.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Polymers of C13C15 oxoalcohol... Specific Chemical Substances § 721.6505 Polymers of C13C15 oxoalcohol ethoxolates. (a) Chemical substance... polymers of C13C15 oxoalcohol ethoxolates (PMNs P-96-950/951) are subject to reporting under this...

  1. Terahertz spectroscopy of ground state HD18O

    NASA Astrophysics Data System (ADS)

    Yu, Shanshan; Pearson, John C.; Drouin, Brian J.; Miller, Charles E.; Kobayashi, Kaori; Matsushima, Fusakazu

    2016-10-01

    Terahertz absorption spectroscopy was employed to measure the ground state pure rotational transitions of the water isotopologue HD18O . A total of 105 pure rotational transitions were observed in the 0.5-5.0 THz region with ∼ 100 kHz accuracy for the first time. The observed positions were fit to experimental accuracy using the Euler series expansion of the asymmetric-top Hamiltonian together with the literature Microwave, Far-IR and IR data in the ground state and ν2 . The new measurements and predictions reported here support the analysis of astronomical observations by high-resolution spectroscopic telescopes such as SOFIA and ALMA where laboratory rest frequencies with uncertainties of 1 MHz or less are required for proper analysis of velocity resolved astrophysical data.

  2. Enhancing the [13C]bicarbonate signal in cardiac hyperpolarized [1-13C]pyruvate MRS studies by infusion of glucose, insulin and potassium.

    PubMed

    Lauritzen, Mette Hauge; Laustsen, Christoffer; Butt, Sadia Asghar; Magnusson, Peter; Søgaard, Lise Vejby; Ardenkjær-Larsen, Jan Henrik; Åkeson, Per

    2013-11-01

    A change in myocardial metabolism is a known effect of several diseases. MRS with hyperpolarized (13)C-labelled pyruvate is a technique capable of detecting changes in myocardial pyruvate metabolism, and has proven to be useful for the evaluation of myocardial ischaemia in vivo. However, during fasting, the myocardial glucose oxidation is low and the fatty acid oxidation (β-oxidation) is high, which complicates the interpretation of pyruvate metabolism with the technique. The aim of this study was to investigate whether the infusion of glucose, insulin and potassium (GIK) could increase the myocardial glucose oxidation in the citric acid cycle, reflected as an increase in the [(13)C]bicarbonate signal in cardiac hyperpolarized [1-(13)C]pyruvate MRS measurements in fasted rats. Two groups of rats were infused with two different doses of GIK and investigated by MRS after injection of hyperpolarized [1-(13)C]pyruvate. No [(13)C]bicarbonate signal could be detected in the fasted state. However, a significant increase in the [(13)C]bicarbonate signal was observed by the infusion of a high dose of GIK. This study demonstrates that a high [(13)C]bicarbonate signal can be achieved by GIK infusion in fasted rats. The increased [(13)C]bicarbonate signal indicates an increased flux of pyruvate through the pyruvate dehydrogenase enzyme complex and an increase in myocardial glucose oxidation through the citric acid cycle.

  3. 13C nuclear magnetic resonance data of lanosterol derivatives—Profiling the steric topology of the steroid skeleton via substituent effects on its 13C NMR

    NASA Astrophysics Data System (ADS)

    Dias, Jerry Ray; Gao, Hongwu

    2009-12-01

    The 13C NMR spectra of over 24 tetracyclic triterpenoid derivatives have been structurally analyzed. The 13C NMR chemical shifts allow one to probe the steric topology of the rigid steroid skeleton and inductive effects of its substituents. Use of deuterium labeling in chemical shift assignment and B-ring aromatic terpenoids are also featured.

  4. 2H and 18O Freshwater Isoscapes of Scotland

    NASA Astrophysics Data System (ADS)

    Meier-Augenstein, Wolfram; Hoogewerff, Jurian; Kemp, Helen; Frew, Danny

    2013-04-01

    Scotland's freshwater lochs and reservoirs provide a vital resource for sustaining biodiversity, agriculture, food production as well as for human consumption. Regular monitoring of freshwaters by the Scottish Environment Protection Agency (SEPA) fulfils legislative requirements with regards to water quality but new scientific methods involving stable isotope analysis present an opportunity combining these mandatory monitoring schemes with fundamental research to inform and deliver on current and nascent government policies [1] through gaining a greater understanding of Scottish waters and their importance in the context of climate change, environmental sustainability and food security. For example, 2H and 18O isoscapes of Scottish freshwater could be used to underpin research and its applications in: • Climate change - Using longitudinal changes in the characteristic isotope composition of freshwater lochs and reservoirs as proxy, isoscapes will provide a means to assess if and how changes in temperature and weather patterns might impact on precipitation patterns and amount. • Scottish branding - Location specific stable isotope signatures of Scottish freshwater have the potential to be used as a tool for provenancing and thus protecting premium Scottish produce such as Scottish beef, Scottish soft fruit and Scottish Whisky. During 2011 and 2012, with the support of SEPA more than 110 samples from freshwater lochs and reservoirs were collected from 127 different locations across Scotland including the Highlands and Islands. Here we present the results of this sampling and analysis exercise isotope analyses in form of 2H and 18O isoscapes with an unprecedented grid resolution of 26.5 × 26.5 km (or 16.4 × 16.4 miles). [1] Adaptation Framework - Adapting Our Ways: Managing Scotland's Climate Risk (2009): Scotland's Biodiversity: It's in Your Hands - A strategy for the conservation and enhancement of biodiversity in Scotland (2005); Recipe For Success - Scotland

  5. Geochemical Approach to Archaeal Ecology: δ13C of GDGTs

    NASA Astrophysics Data System (ADS)

    Lichtin, S.; Warren, C.; Pearson, A.; Pagani, M.

    2015-12-01

    Over the last decade and a half, glycerol dialkyl glycerol tetraethers (GDGTs) have increasingly been used to reconstruct environmental temperatures; proxies like TEX86 that correlate the relative abundance of these archaeal cell membrane lipids to sea surface temperature are omnipresent in paleoclimatology literature. While it has become common to make claims about past temperatures using GDGTs, our present understanding of the organisms that synthesize the compounds is still quite limited. The generally accepted theory states that microorganisms like the Thaumarchaeota modify the structure of membrane lipids to increase intermolecular interactions, strengthening the membrane at higher temperatures. Yet to date, culture experiments have been largely restricted to a single species, Nitrosopumilus maritimes, and recent studies on oceanic archaeal rRNA have revealed that these biomarkers are produced in diverse, heterogeneous, and site-specific communities. This brings up questions as to whether different subclasses of GDGTs, and all subsequent proxies, represent adaptation within a single organismal group or a shift in community composition. To investigate whether GDGTs with different chain structures, from the simple isoprenoidal GDGT-0 to Crenarchaeol with its many cyclopentane groups, are sourced from archaea with similar or disparate metabolic pathways—and if that information is inherited in GDGTs trapped in marine sediments—this study examines the stable carbon isotope values (δ13C) of GDGTs extracted from the uppermost meters of sediment in the Orca Basin, Gulf of Mexico, using spooling-wire microcombustion isotope-ratio mass spectrometer (SWiM-IRMS), tackling a fundamental assumption of the TEX86 proxy that influences the way we perceive the veracity of existing temperature records.

  6. 14C Concentrations in the Northern Atlantic and Nordic Seas

    NASA Astrophysics Data System (ADS)

    Nadeau, M.-J.; Grootes, P. M.; Erlenkeuser, H.

    2003-04-01

    We report here more than 450 new Δ14C results from water samples from the North Atlantic and the Nordic Seas measured at the Leibniz-Labor, Christian-Albrechts Universität, Kiel, using accelerator mass spectrometry. The water samples were collected during three cruises of the RV Meteor: M36 in 1996 (65 measurements, 6 stations), M39 in 1997 (217 measurements, 11 stations) and M50 in 2001 (189 measurements, 10 stations). These results are compared to those of previous sampling campaigns: GEOSECS (1972) and TTO (1981) and of samples obtained from previous cruises of the RV Meteor (M18 in 1991 and M30 in 1994) measured by decay counting at the Institut für Umweltphysik in Heidelberg. Several stations from the cruise M50 are located along the WOCE A02 line from the western entrance of the English Channel to the tip of Newfoundland/Grand Banks. This transect also analysed during the M30 (1994) campaign provides the evolution of the penetration of atmospheric bomb 14C into these waters over a seven year period. Other samples were taken in the Labrador Sea, and North and South of Iceland. Comparison with CFC measurements, for some of the stations, also provides an insight in the penetration of both tracers into the ocean.

  7. NOTE The effect of 13C enrichment in the glassing matrix on dynamic nuclear polarization of [1-13C]pyruvate

    NASA Astrophysics Data System (ADS)

    Lumata, Lloyd; Kovacs, Zoltan; Malloy, Craig; Sherry, A. Dean; Merritt, Matthew

    2011-03-01

    Dimethyl sulfoxide (DMSO) can effectively form a glassy matrix necessary for dynamic nuclear polarization (DNP) experiments. We tested the effects of 13C enrichment in DMSO on DNP of [1-13C]pyruvate doped with trityl radical OX063Me. We found that the polarization build-up time τ of pyruvate in 13C-labeled DMSO glassing solution is twice as fast as the unenriched DMSO while the nuclear magnetic resonance enhancement was unchanged. This indicates that 13C-13C spin diffusion is a limiting factor in the kinetics of DNP in this system, but it has a minimal effect on the absolute value of polarization achievable for the target.

  8. The effect of 13C enrichment in the glassing matrix on dynamic nuclear polarization of [1-13C]pyruvate

    NASA Astrophysics Data System (ADS)

    Lumata, Lloyd; Kovacs, Zoltan; Malloy, Craig; Sherry, A. Dean; Merritt, Matthew

    2011-03-01

    Dimethyl sulfoxide (DMSO) can effectively form a glassy matrix necessary for dynamic nuclear polarization (DNP) experiments. We tested the effects of 13C enrichment in DMSO on DNP of [1-13C]pyruvate doped with trityl radical OX063Me. We found that the polarization build-up time τ of pyruvate in 13C-labeled DMSO glassing solution is twice as fast as the unenriched DMSO while the nuclear magnetic resonance enhancement was unchanged. This indicates that 13C-13C spin diffusion is a limiting factor in the kinetics of DNP in this system, but it has a minimal effect on the absolute value of polarization achievable for the target.

  9. The use of 13C labeling to enhance the sensitivity of 13C solid-state CPMAS NMR to study polymorphism in low dose solid formulations.

    PubMed

    Booy, Kees-Jan; Wiegerinck, Peter; Vader, Jan; Kaspersen, Frans; Lambregts, Dorette; Vromans, Herman; Kellenbach, Edwin

    2005-02-01

    (13)C labeling was used to enhance the sensitivity of (13)C solid-state NMR to study the effect of tabletting on the polymorphism of a steroidal drug. The steroidal drug Org OD 14 was (13)C labeled and formulated into tablets containing only 0.5-2.5% active ingredient. The tablets were subsequently studied by solid-state (13)C CPMAS NMR. The crystalline form present in tablets could readily be analyzed in tablets. No change in crystalline form was observed as a result of formulation or in subsequent stability studies. Solid-state NMR in combination with (13)C labeling can, in suitable cases, be used as a strategy to study the effect of formulation on the polymorphism of low dose drugs.

  10. A 16 ka lacustrine 18O record from High Himalaya reflecting the Indian Monsoon variability

    NASA Astrophysics Data System (ADS)

    Zech, M.; Tuthorn, M.; Zech, R.; Schlütz, F.; Zech, W.; Glaser, B.

    2012-04-01

    Establishing 18O records using organic matter of lake sediments is so far complicated due to analytical challenges. Based on the results obtained by a novel analytical method, the so-called compound-specific delta18O-analysis of hemicellulose monosaccharides (Zech, M. and Glaser, B., 2009. Rapid Communications in Mass Spectrometry 23, 3522-3532), we here present a first well-dated continuous late glacial lacustrine 18O record from High Himalayan lake sediments. Our 18O record, which reflects a coupled hydrological and thermal control, reveals the late glacial Indian Summer Monsoon variability depicting the Bölling/Alleröd and the Younger Dryas. Thus, it closely resembles the 18O records of South Asian speleothems and Greenland ice cores. We hence conclude that our novel 18O method enables regional paleoclimate reconstructions and that our 18O record highlights the previously suggested teleconnections between the Indian and the East Asian Monsoon and Greenland temperatures.

  11. Methods for metabolic evaluation of prostate cancer cells using proton and 13C HR-MAS spectroscopy and [3-13C] pyruvate as a metabolic substrate

    PubMed Central

    Levin, Yakir S.; Albers, Mark J.; Butler, Thomas N.; Spielman, Daniel; Peehl, Donna M.; Kurhanewicz, John

    2009-01-01

    Prostate cancer has been shown to undergo unique metabolic changes associated with neoplastic transformation, with associated changes in citrate, alanine, and lactate concentrations. 13C HR-MAS spectroscopy provides an opportunity to simultaneously investigate the metabolic pathways implicated in these changes by using 13C labeled substrates as metabolic probes. In this work, a method to reproducibly interrogate metabolism in prostate cancer cells in primary culture was developed using HR-MAS spectroscopy. Optimization of cell culture protocols, labeling parameters, harvesting, storage, and transfer was performed. Using [3-13C] pyruvate as a metabolic probe, 1H and 13C HR-MAS spectroscopy were used to quantify the net amount and fractional enrichment of several labeled metabolites that evolved in multiple cell samples from each of five different prostate cancers. Average enrichment across all cancers was 32.4±5.4% for [3-13C] alanine, 24.5±5.4% for [4-13C] glutamate, 9.1±2.5% for [3-13C] glutamate, 25.2±5.7% for [3-13C] aspartate, and 4.2±1.0% for [3-13C] lactate. Cell samples from the same parent population demonstrated reproducible fractional enrichments of alanine, glutamate, and aspartate to within 12%, 10%, and 10%, respectively. Furthermore, the cells produced a significant amount of [4-13C] glutamate, which supports the bioenergetic theory for prostate cancer. These methods will allow further characterization of metabolic properties of prostate cancer cells in the future. PMID:19780158

  12. Determination of fructose metabolic pathways in normal and fructose-intolerant children: A sup 13 C NMR study using (U- sup 13 C)fructose

    SciTech Connect

    Gopher, A.; Lapidot, A. ); Vaisman, N. ); Mandel, H. )

    1990-07-01

    An inborn deficiency in the ability of aldolase B to split fructose 1-phosphate is found in humans with hereditary fructose intolerance (HFI). A stable isotope procedure to elucidate the mechanism of conversion of fructose to glucose in normal children and in HFI children has been developed. A constant infusion of D-(U-{sup 13}C)fructose was given nasogastrically to control and to HFI children. Hepatic fructose conversion to glucose was estimated by examination of {sup 13}C NMR spectra of plasma glucose. Significantly lower values ({approx}3-fold) for fructose conversion to glucose were obtained for the HFI patients as compared to the controls. A quantitative determination of the metabolic pathways of fructose conversion to glucose was derived from {sup 13}C NMR measurement of plasma ({sup 13}C)glucose isotopomer populations. The finding of isotopomer populations of three adjacent {sup 13}C atoms at glucose C-4 ({sup 13}C{sub 3}-{sup 13}C{sub 4}-{sup 13}C{sub 5}) suggests that there is a direct pathway from fructose, by-passing fructose-1-phosphate aldolase, to fructose 1,6-bisphosphate. The metabolism of fructose by fructose-1-phosphate aldolase activity accounts for only {approx}50% of the total amount of hepatic fructose conversion to glucose. In view of the marked decline by 67% in synthesis of glucose from fructose in HFI subjects found in this study, the extent of ({sup 13}C)glucose formation from a trace amount of (U-{sup 13}C)fructose infused into the patient can be used as a safe and noninvasive diagnostic test for inherent faulty fructose metabolism.

  13. A 240 ka terrestrial 18O record from a NE-Siberian loess-like permafrost paleosol-sequence based on a novel analytical 18O method

    NASA Astrophysics Data System (ADS)

    Tuthorn, M.; Zech, M.; Detsch, F.; Juchelka, D.; Kalbitz, K.; Mayr, C.; Werner, R.; Zech, R.; Zech, W.; Glaser, B.

    2012-04-01

    Recently, we developed a novel analytical tool for paleoclimate research based on compound-specific delta18O analyses of hemicellulose-derived monosaccharides using gas chromatography-pyrolysis-isotope ratio mass spectrometry (GC-Py-IRMS) (Zech and Glaser, 2009. Rapid Communications in Mass Spectrometry 23, 3522-3532). This method overcomes extraction, purification and hygroscopicity problems of so far applied cellulose methods based on TC/EA-IRMS delta18O analyses and allows establishing 18O records from sedimentary organic matter. Taking advantage of plant samples from a climate chamber experiment we can demonstrate that our novel method yields similar results like cellulose for plant material. Furthermore, we demonstrate using 18O-enriched water that the hydroxyl-groups of hemicelluloses are not prone to oxygen exchange reactions (Zech et al., 2012. Organic Geochemistry 42, 1470-1475). Ongoing methodological improvements will be shortly reported. By applying our novel 18O method to a loess-like permafrost paleosol-sequence we established a presumably 240 ka terrestrial 18O record for NE-Siberia. While the modern topsoil and the interglacial/-stadial paleosols reveal more positive delta18O values, the glacial paleosols reveal more negative delta18O values. The 18O variability is generally confirmed by a respective deltaD record which is based on sedimentary plant leafwax-derived n-alkanes. This finding suggests that our high-latitude 240 ka terrestrial 18O and D/H record from NE-Siberia reflects the temperature-dependent isotopic composition of precipitation and the increased isotopic enrichment of leaf-water during interglacials/-stadials.

  14. Meteoric diagenesis below a submerged platform: implications for δ13C compositions prior to pre-vascular plant evolution, Middle Ordovician, Alabama, U.S.A.

    NASA Astrophysics Data System (ADS)

    Tobin, Kenneth J.; Walker, Kenneth R.

    1994-04-01

    The Middle Ordovician "Chickamauga" Formation at Red Mountain Expressway (RME) and Tidwell Hollow (TWH) sections in Alabama (U.S.A) has a complex early diagenetic history. Early diagenetic history of the buildup facies consisted of two phases of marine cementation separated by two generations of meteoric, equant calcite with moldic dissolution separating equant calcite generations. A third generation of meteoric, equant (drusy) calcite is present after secondary marine diagenesis. Equant (drusy) calcite is interpreted as meteoric because its stable isotopic composition ( δ 13C = -0.1 to -1.6‰ , δ 18O = -4.8 to -7.3‰ ) is too variable to be accounted for by marine or mixing zone precipitation. Equant (drusy) calcite from buildup facies is mostly non-luminescent and non-ferroan. This is unlike early, ferroan equant calcite (dull to bright luminescent) from below the unconformity that overlies the "Chickamauga" Formation at RME. Meteoric diagenesis below the unconformity is unrelated to early diagenesis in the underlying buildup facies. Equant (drusy) calcite from the buildup facies at RME has a covariation of δ13C and δ18O values that forms a truncated inverted "J" and has elevated Mg values. These geochemical signatures indicate precipitation at a site that was distal from the recharge zone. Meteoric diagenesis at RME occurred during rising relative sea level and flow of meteoric fluids under a submerged platform is the only mechanism able to reconcile available stratigraphic, petrologic, and geochemical data. Ordovician meteoric δ13C values (from TWH and other formations) are slightly depleted (2-4‰) relative to coeval marine carbonate, especially when compared with post-Silurian meteoric carbonate. Minor depletion of Ordovician carbonate is the result of limited generation of light soil-gas CO 2 before the development of vascular plants.

  15. Accelerator mass spectrometry analysis of 14C-oxaliplatin concentrations in biological samples and 14C contents in biological samples and antineoplastic agents

    NASA Astrophysics Data System (ADS)

    Toyoguchi, Teiko; Kobayashi, Takeshi; Konno, Noboru; Shiraishi, Tadashi; Kato, Kazuhiro; Tokanai, Fuyuki

    2015-10-01

    Accelerator mass spectrometry (AMS) is expected to play an important role in microdose trials. In this study, we measured the 14C concentration in 14C-oxaliplatin-spiked serum, urine and supernatant of fecal homogenate samples in our Yamagata University (YU) - AMS system. The calibration curves of 14C concentration in serum, urine and supernatant of fecal homogenate were linear (the correlation coefficients were ⩾0.9893), and the precision and accuracy was within the acceptance criteria. To examine a 14C content of water in three vacuum blood collection tubes and a syringe were measured. 14C was not detected from water in these devices. The mean 14C content in urine samples of 6 healthy Japanese volunteers was 0.144 dpm/mL, and the intra-day fluctuation of 14C content in urine from a volunteer was little. The antineoplastic agents are administered to the patients in combination. Then, 14C contents of the antineoplastic agents were quantitated. 14C contents were different among 10 antineoplastic agents; 14C contents of paclitaxel injection and docetaxel hydrate injection were higher than those of the other injections. These results indicate that our quantitation method using YU-AMS system is suited for microdosing studies and that measurement of baseline and co-administered drugs might be necessary for the studies in low concentrations.

  16. Synthesis and solid-state NMR structural characterization of 13C-labeled graphite oxide.

    PubMed

    Cai, Weiwei; Piner, Richard D; Stadermann, Frank J; Park, Sungjin; Shaibat, Medhat A; Ishii, Yoshitaka; Yang, Dongxing; Velamakanni, Aruna; An, Sung Jin; Stoller, Meryl; An, Jinho; Chen, Dongmin; Ruoff, Rodney S

    2008-09-26

    The detailed chemical structure of graphite oxide (GO), a layered material prepared from graphite almost 150 years ago and a precursor to chemically modified graphenes, has not been previously resolved because of the pseudo-random chemical functionalization of each layer, as well as variations in exact composition. Carbon-13 (13C) solid-state nuclear magnetic resonance (SSNMR) spectra of GO for natural abundance 13C have poor signal-to-noise ratios. Approximately 100% 13C-labeled graphite was made and converted to 13C-labeled GO, and 13C SSNMR was used to reveal details of the chemical bonding network, including the chemical groups and their connections. Carbon-13-labeled graphite can be used to prepare chemically modified graphenes for 13C SSNMR analysis with enhanced sensitivity and for fundamental studies of 13C-labeled graphite and graphene.

  17. Local deposition of 13C tracer in the JET MKII-HD divertor

    NASA Astrophysics Data System (ADS)

    Likonen, Jari; Airila, M. I.; Coad, J. P.; Hakola, A.; Koivuranta, S.; Ahonen, E.; Alves, E.; Barradas, N.; Widdowson, A.; Rubel, M.; Brezinsek, S.; Groth, M.; JET-EFDA Contributors

    2013-07-01

    Migration and deposition of 13C have been investigated at JET by injecting 13C-labelled methane at the outer divertor base at the end of the 2009 campaign. The 13C deposition profile was measured with enhanced proton scattering (EPS) and secondary ion mass spectrometry (SIMS) techniques. A strong toroidal deposition band for 13C was observed experimentally on each of the analysed four outer divertor floor tiles. In addition, 13C was also found on the vertical edge of load bearing tile (LBT) and at the bottom of the LBT tile facing the puffing hole. Local 13C migration in the vicinity of the injection location was modelled by the ERO code. The ERO simulations also produced the strong toroidal 13C deposition band but there is strong deposition also on the vertical edge of the LBT tile and elsewhere on the horizontal part of the outer divertor floor tile.

  18. [Measuring 14C-glucose and 14C-acetate oxidation in tumour cells and tumorous host organism].

    PubMed

    Hujber, Zoltán; Jeney, András; Oláh, Júlia; Szoboszlai, Norbert; Baranyai, Lajos; Környei, József; Petõvári, Gábor; Sebestyén, Anna

    2015-12-01

    Tumour cell metabolism can be influenced by alterations of the extracellular microenvironment and the tumour-promoting genetically changed mechanisms. There is increasing interest to introduce appropriate bioenergetic assays to describe the therapeutic effect and metabolic subtypes of tumours in clinical oncology. The analysis of 14C-glucose and 14C-acetate oxidation could be a suitable method to examine the metabolic/bioenergetic profiles of tumour cells and tumorous host organisms. The metabolic activity of tumour cells (in vitro cell lines, primary human lymphocytes and leukaemia cells) and the tumourous host organism were examined in vitro and in vivo by detecting the released CO2 levels derived from the radioactive carbon atom labelled energy substrates. We have found that the most cancer cells of solid tumours oxidised glucose more intensively than acetate. It was interesting that AML, CML and CLL cells isolated from blood preferred acetate as an energy substrate in vitro. Furthermore, based on our observations, tumours affected the glucose or acetate oxidation of the organism when applying bioenergetic substrates per os or iv. We provided the first data about the alterations in metabolic profiles of the tumour bearing organism in xenograft models. In summary, according to our results, comparison of the energy substrate oxidation can be an indicative method related to the metabolic profile analysis of tumour cells in vitro and tumorous host organism in vivo.

  19. Propionate metabolism in the rat heart by 13C n.m.r. spectroscopy.

    PubMed Central

    Sherry, A D; Malloy, C R; Roby, R E; Rajagopal, A; Jeffrey, F M

    1988-01-01

    High-resolution 13C n.m.r. spectroscopy has been used to examine propionate metabolism in the perfused rat heart. A number of tricarboxylic acid (TCA) cycle intermediates are observable by 13C n.m.r. in hearts perfused with mixtures of pyruvate and propionate. When the enriched 13C-labelled nucleus originates with pyruvate, the resonances of the intermediates appear as multiplets due to formation of multiply-enriched 13C-labelled isotopomers, whereas when the 13C-labelled nucleus originates with propionate, these same intermediates appear as singlets in the 13C spectrum since entry of propionate into the TCA cycle occurs via succinyl-CoA. An analysis of the isotopomer populations in hearts perfused with [3-13C]pyruvate plus unlabelled propionate indicates that about 27% of the total pyruvate pool available to the heart is derived directly from unlabelled propionate. This was substantiated by perfusing a heart for 2 h with [3-13C]propionate as the only available exogenous substrate. Under these conditions, all of the propionate consumed by the heart, as measured by conventional chemical analysis, ultimately entered the oxidative pathway as [2-13C] or [3-13C]pyruvate. This is consistent with entry of propionate into the TCA cycle intermediate pools as succinyl-CoA and concomitant disposal of malate to pyruvate via the malic enzyme. 13C resonances arising from enriched methylmalonate and propionylcarnitine are also detected in hearts perfused with [3-13C] or [1-13C]propionate which suggests that 13C n.m.r. may be useful as a non-invasive probe in vivo of metabolic abnormalities involving the propionate pathway, such as methylmalonic aciduria or propionic acidaemia. PMID:3178775

  20. Characterization of uniformly and atom-specifically 13C-labeled heparin and heparan sulfate polysaccharide precursors using 13C NMR spectroscopy and ESI mass spectrometry

    PubMed Central

    Nguyen, Thao K. N.; Tran, Vy M.; Victor, Xylophone V.; Skalicky, Jack J.; Kuberan, Balagurunathan

    2010-01-01

    The biological actions of heparin and heparan sulfate, two structurally related glycosaminoglycans, depend on the organization of the complex heparanome. Due to the structural complexity of the heparanome, the sequence of variably sulfonated uronic acid and glucosamine residues is usually characterized by the analysis of smaller oligosaccharide and disaccharide fragments. Even characterization of smaller heparin/heparan sulfate oligosaccharide or disaccharide fragments using simple 1D 1H NMR spectroscopy is often complicated by the extensive signal overlap. 13C NMR signals, on the other hand, overlap less and therefore, 13C NMR spectroscopy can greatly facilitate the structural elucidation of the complex heparanome and provide finer insights into the structural basis for biological functions. This is the first report of the preparation of anomeric carbon-specific 13C-labeled heparin/heparan sulfate precursors from the Escherichia coli K5 strain. Uniformly 13C- and 15N-labeled precursors were also produced and characterized by 13C NMR spectroscopy. Mass spectrometric analysis of enzymatically fragmented disaccharides revealed that anomeric carbon-specific labeling efforts resulted in a minor loss/scrambling of 13C in the precursor backbone, whereas uniform labeling efforts resulted in greater than 95% 13C isotope enrichment in the precursor backbone. These labeled precursors provided high-resolution NMR signals with great sensitivity and set the stage for studying the heparanome–proteome interactions. PMID:20832774

  1. 13C MRS of Human Brain at 7 Tesla Using [2-13C]Glucose Infusion and Low Power Broadband Stochastic Proton Decoupling

    PubMed Central

    Li, Shizhe; An, Li; Yu, Shao; Araneta, Maria Ferraris; Johnson, Christopher S.; Wang, Shumin; Shen, Jun

    2015-01-01

    Purpose 13C magnetic resonance spectroscopy (MRS) of human brain at 7 Tesla (T) may pose patient safety issues due to high RF power deposition for proton decoupling. The purpose of present work is to study the feasibility of in vivo 13C MRS of human brain at 7 T using broadband low RF power proton decoupling. Methods Carboxylic/amide 13C MRS of human brain by broadband stochastic proton decoupling was demonstrated on a 7 T scanner. RF safety was evaluated using the finite-difference time-domain method. 13C signal enhancement by nuclear Overhauser effect (NOE) and proton decoupling was evaluated in both phantoms and in vivo. Results At 7 T, the peak amplitude of carboxylic/amide 13C signals was increased by a factor of greater than 4 due to the combined effects of NOE and proton decoupling. The 7 T 13C MRS technique used decoupling power and average transmit power of less than 35 W and 3.6 W, respectively. Conclusion In vivo 13C MRS studies of human brain can be performed at 7 T well below the RF safety threshold by detecting carboxylic/amide carbons with broadband stochastic proton decoupling. PMID:25917936

  2. Transformation of ENSO-related rainwater to dripwater δ18O variability by vadose water mixing

    NASA Astrophysics Data System (ADS)

    Moerman, Jessica W.; Cobb, Kim M.; Partin, Judson W.; Meckler, A. Nele; Carolin, Stacy A.; Adkins, Jess F.; Lejau, Syria; Malang, Jenny; Clark, Brian; Tuen, Andrew A.

    2014-11-01

    Speleothem oxygen isotopes (δ18O) are often used to reconstruct past rainfall δ18O variability, and thereby hydroclimate changes, in many regions of the world. However, poor constraints on the karst hydrological processes that transform rainfall signals into cave dripwater add significant uncertainty to interpretations of speleothem-based reconstructions. Here we present several 6.5 year, biweekly dripwater δ18O time series from northern Borneo and compare them to local rainfall δ18O variability. We demonstrate that vadose water mixing is the primary rainfall-to-dripwater transformation process at our site, where dripwater δ18O reflects amount-weighted rainfall δ18O integrated over the previous 3-10 months. We document large interannual dripwater δ18O variability related to the El Niño-Southern Oscillation (ENSO), with amplitudes inversely correlated to dripwater residence times. According to a simple stalagmite forward model, asymmetrical ENSO extremes produce significant offsets in stalagmite δ18O time series given different dripwater residence times. Our study highlights the utility of generating multiyear, paired time series of rainfall and dripwater δ18O to aid interpretations of stalagmite δ18O reconstructions.

  3. The in vitro biological activities of synthetic 18-O-methyl mycalamide B, 10-epi-18-O-methyl mycalamide B and pederin.

    PubMed

    Richter, A; Kocienski, P; Raubo, P; Davies, D E

    1997-04-01

    Mycalamides A and B, which were originally isolated from a marine sponge, show close structural similarity to the insect toxin pederin, and exhibit potent cytotoxicity and antitumour activity. Detailed investigation of the clinical potential of these compounds has been hampered because they are available in only minute quantities from natural sources. We now describe the biological activities of 18-O-methyl mycalamide B, 10-epi-18-O-methyl mycalamide and pederin, all prepared by total synthesis. The activities of 18-O-methyl mycalamide B and pederin were virtually indistinguishable when evaluated in DNA or protein synthesis assays, and in cytotoxicity assays using human carcinoma cell lines (IC50s 0.2-0.6 nM). In all assays, 10-epi-18-O-methyl mycalamide B was 10(3) times less toxic than its diastereoisomer, demonstrating that the cytotoxicity of 18-O-methyl mycalamide B is inseparable from its ability to inhibit protein synthesis. Short-term exposure of squamous carcinoma cells to 18-O-methyl mycalamide B or pederin caused an irreversible inhibition of cellular proliferation and induced cellular necrosis. In contrast, the antiproliferative effects of the compounds on human fibroblasts were reversible and there was no evidence of necrosis. Demonstration that 18-O-methyl mycalamide B and the synthetically less complex molecule, pederin, show some tumour cell toxicity indicates that this novel class of compounds should be subjected to preclinical evaluation.

  4. A new metabolically trapped agent by brain monoamine oxidase: N-methyl labeled (14C) N-methylphenylethylamine (14C-MPEA).

    PubMed

    Osamu, I

    1983-01-01

    A new type of metabolically trapped agent for measuring regional brain function was designed and evaluated. N-methylphenylethylamine (14C-MPEA) was synthesized with trifluoroacetylphenylethylamine and 14C-methyl iodide. A high concentration of 14C-MPEA accumulated in mouse brain 1 min after injection, and radioactivities in the brain remained for a long period. By radiochemical analysis, it was found 14C-MPEA was metabolized in the brain to 14C-methylamine. 14C-methylamine was trapped by the blood-brain barrier because of its cationic charge at physiological pH. When the mouse was pretreated with a MAO inhibitor (pargyline hydrochloride 100 mg/kg IP) the radioactivity was rapidly excreted from the brain with a half-life of about 45 min. These results indicate that 11C-MPEA has potential for the measurement of brain MAO activity.

  5. 13C metabolic flux analysis at a genome-scale.

    PubMed

    Gopalakrishnan, Saratram; Maranas, Costas D

    2015-11-01

    Metabolic models used in 13C metabolic flux analysis generally include a limited number of reactions primarily from central metabolism. They typically omit degradation pathways, complete cofactor balances, and atom transition contributions for reactions outside central metabolism. This study addresses the impact on prediction fidelity of scaling-up mapping models to a genome-scale. The core mapping model employed in this study accounts for (75 reactions and 65 metabolites) primarily from central metabolism. The genome-scale metabolic mapping model (GSMM) (697 reaction and 595 metabolites) is constructed using as a basis the iAF1260 model upon eliminating reactions guaranteed not to carry flux based on growth and fermentation data for a minimal glucose growth medium. Labeling data for 17 amino acid fragments obtained from cells fed with glucose labeled at the second carbon was used to obtain fluxes and ranges. Metabolic fluxes and confidence intervals are estimated, for both core and genome-scale mapping models, by minimizing the sum of square of differences between predicted and experimentally measured labeling patterns using the EMU decomposition algorithm. Overall, we find that both topology and estimated values of the metabolic fluxes remain largely consistent between core and GSM model. Stepping up to a genome-scale mapping model leads to wider flux inference ranges for 20 key reactions present in the core model. The glycolysis flux range doubles due to the possibility of active gluconeogenesis, the TCA flux range expanded by 80% due to the availability of a bypass through arginine consistent with labeling data, and the transhydrogenase reaction flux was essentially unresolved due to the presence of as many as five routes for the inter-conversion of NADPH to NADH afforded by the genome-scale model. By globally accounting for ATP demands in the GSMM model the unused ATP decreased drastically with the lower bound matching the maintenance ATP requirement. A non

  6. Oxygen isotopes of Pacific seawater, 0-40 kyr, based on d18O and Mg/Ca of benthic and planktic foraminifera: relation to deglacial sealevel rise.

    NASA Astrophysics Data System (ADS)

    Mix, A. C.; Klinkhammer, G. P.

    2007-12-01

    Combining high resolution (~200 year sample resolution) oxygen and carbon isotope measurements and Mg/Ca analyses in planktic (G. ruber and N. dutertrei) and benthic foraminifera (Uvigerina sp.; use of infaunal benthics minimizes likely CO3= effects) from the mid-depth eastern Pacific provides for detailed estimates of changing d18O of seawater over the past 40 kyr at ODP Site 1242. The key to this analysis is improved precision of the Mg/Ca analyses based on a new generation of high precision flow-through time-resolved analysis (FT-TRA) (e.g., average internal precision for Mg/Ca is now +/-0.005 benthic, and +/-0.015 planktic). This method is relatively insensitive to mild dissolution of heterogeneous shells, and thus requires no corrections for preservation. The change in seawater d18O (at 1364 m depth) between the Holocene and Last Glacial Maximum is 1.2 +/- 0.04 permil when averaged over the stages, consistent with pore-water diffusion estimates; however, millennial scale events (which the pore-water data cannot detect) bring the total range up to about 1.6 permil. Are such short-term events related to sealevel change, or do they reflect changing watermasses? Measurements of d13C data (C. wuellerstorfi), sensitive to modern subsurface watermass gradients, are not highly correlated to short- term changes in d18Oseawater suggesting a transient response to ice volume changes. Glacial weakening of AAIW (salty, high d18O, high d13C) relative to north Pacific watermasses (fresher, lower d18O, low d13C) suggest that the benthic d18Oseawater may underestimate total local changes related to ice volume (with a caveat regarding proper scaling of benthic Mg/Ca to temperature). Benthic d18Oseawater falls through the deglaciation in steps, starting at 18 cal ka, with maximum rates of change at 14-15 ka, and with secondary rapid steps at 16-17 ka and 10-11 kar. Planktic foraminifera yield smaller glacial-interglacial d18Oseawater values, with Holocene-to-LGM stage- average

  7. Effect of endomycorrhizae on the bioavailability of bound sup 14 C residues to onion plants from an organic soil treated with ( sup 14 C)fonofos

    SciTech Connect

    Nelson, S.D.; Khan, S.U. )

    1990-03-01

    Uptake of bound {sup 14}C residues from an organic soil treated with radiolabeled fonofos (O-ethyl S-phenyl ethylphosphonodithioate) by selected Glomus endomycorrhiza and onion roots was studied. The hyphae of endomycorrhizal associations were capable of removing {sup 14}C residues from the soil and transporting them to onion plants. Bioavailability of soil-bound {sup 14}C residues, as measured by {sup 14}C residue content in onion, was increased 32 and 40% over that of nonmycorrhizal plants by hyphae of Glomus intraradices and Glomus vesiculiferium, respectively. The data suggest that under field conditions endomycorrhizal infection may greatly increase the bioavailability of soil-bound pesticide residues to plants.

  8. Percutaneous absorption of ( sup 14 C)DDT and ( sup 14 C)benzo(a)pyrene from soil

    SciTech Connect

    Wester, R.C.; Maibach, H.I.; Bucks, D.A.; Sedik, L.; Melendres, J.; Liao, C.; DiZio, S. )

    1990-10-01

    The objective was to determine percutaneous absorption of DDT and benzo(a)pyrene in vitro and in vivo from soil into and through skin. Soil (Yolo County 65-California-57-8; 26% sand, 26% clay, 48% silt) was passed through 10-, 20-, and 48-mesh sieves. Soil then retained by 80-mesh was mixed with (14C)-labeled chemical at 10 ppm. Acetone solutions at 10 ppm were prepared for comparative analysis. Human cadaver skin was dermatomed to 500 microns and used in glass diffusion cells with human plasma as the receptor fluid (3 ml/hr flow rate) for a 24-hr skin application time. With acetone vehicle, DDT (18.1 +/- 13.4%) readily penetrated into human skin. Significantly less DDT (1.0 +/- 0.7%) penetrated into human skin from soil. DDT would not partition from human skin into human plasma in the receptor phase (less than 0.1%). With acetone vehicle, benzo(a)pyrene (23.7 +/- 9.7%) readily penetrated into human skin. Significantly less benzo(a)pyrene (1.4 +/- 0.9%) penetrated into human skin from soil. Benzo(a)pyrene would not partition from human skin into human plasma in the receptor phase (less than 0.1%). Substantivity (skin retention) was investigated by applying 14C-labeled chemical to human skin in vitro for only 25 min. After soap and water wash, 16.7 +/- 13.2% of DDT applied in acetone remained absorbed to skin. With soil only 0.25 +/- 0.11% of DDT remained absorbed to skin. After soap and water wash 5.1 +/- 2.1% of benzo(a)pyrene applied in acetone remained absorbed to skin. With soil only 0.14 +/- 0.13% of benzo(a)pyrene remained absorbed to skin.

  9. Pentose cycling and the distribution of 13C in trehalose during glucogenesis from 13C-labelled substrates in an insect.

    PubMed

    Thompson, S N; Scales, V M; Bochardt, D B

    1995-07-26

    Redistribution of 13C in trehalose (Tre) due to pentose cycling was observed in vivo in Manduca sexta during glucogenesis from [3-13C]alanine (Ala) and [2-13C]glycerol (Gly). The extent of cycling was affected by dietary composition. Larvae maintained on a low-carbohydrate diet (LCD) exhibited approximately 13% cycling, while those on a complete-balanced diet (CBD) or low-fat diet (LFD) displayed much higher rates of cycling. Significant incorporation of 13C via reversal of the non-oxidative phase was evident on all diets but was greatest on the CBD and LFD. In contrast to conclusions from previous studies with insects, the present results indicate that under normal conditions the pentose pathway is not the principal source of triose phosphates for oxidative catabolism during larval development.

  10. Isotopic 13C NMR spectrometry to assess counterfeiting of active pharmaceutical ingredients: site-specific 13C content of aspirin and paracetamol.

    PubMed

    Silvestre, Virginie; Mboula, Vanessa Maroga; Jouitteau, Catherine; Akoka, Serge; Robins, Richard J; Remaud, Gérald S

    2009-10-15

    Isotope profiling is a well-established technique to obtain information about the chemical history of a given compound. However, the current methodology using IRMS can only determine the global (13)C content, leading to the loss of much valuable data. The development of quantitative isotopic (13)C NMR spectrometry at natural abundance enables the measurement of the (13)C content of each carbon within a molecule, thus giving simultaneous access to a number of isotopic parameters. When it is applied to active pharmaceutical ingredients, each manufactured batch can be characterized better than by IRMS. Here, quantitative isotopic (13)C NMR is shown to be a very promising and effective tool for assessing the counterfeiting of medicines, as exemplified by an analysis of aspirin (acetylsalicylic acid) and paracetamol (acetaminophen) samples collected from pharmacies in different countries. It is proposed as an essential complement to (2)H NMR and IRMS.

  11. δ 18O values, 87Sr /86Sr and Sr/Mg ratios of Late Devonian abiotic marine calcite: Implications for the composition of ancient seawater

    NASA Astrophysics Data System (ADS)

    Carpenter, Scott J.; Lohmann, K. C.; Holden, Peter; Walter, Lynn M.; Huston, Ted J.; Halliday, Alex N.

    1991-07-01

    Late Devonian (Frasnian) abiotic marine calcite has been microsampled and analyzed for 87Sr /86Sr ratios, δ 18O and δ 13C values, and minor element concentrations. Portions of marine cement crystals from the Alberta and Canning Basins have escaped diagenetic alteration and preserve original marine δ 18O values (-4.8%. ± 0.5, PDB), δ 13C values (+2.0 to +3.0%., PDB), 87Sr /86Sr ratios (0.70805 ± 3), and Sr/Mg weight ratios (0.04 to 0.05). Marine 87Sr /86Sr ratios are globally consistent and can be correlated within the Alberta Basin, and among the Alberta, Canning, and Williston Basins. Correlation of isotopic and chemical data strengthen the conclusion that marine cements from the Leduc Formation preserve original marine δ 18O values which are 3 to 4%. lower than those of modern marine cements. These low δ 18O values are best explained by precipitation from 18O-depleted seawater and not by elevated seawater temperature or diagenetic alteration. For comparison with Devonian data, analogous data were collected from Holocene Mg-calcite and aragonite marine cements from Enewetak Atoll, Marshall Islands. Mg-calcite and aragonite marine cements are in isotopic equilibrium with ambient seawater, and Mg-calcite cements are homogeneous with respect to Sr and Mg contents. Empirically derived homogeneous distribution coefficients for Mg and Sr in modern, abiotic Mg-calcite from Enewetak Atoll are 0.034 and 0.15, respectively. An equation describing the dependence of DSr on Mg content was based on a compilation of Sr and Mg data from Holocene abiotic marine calcite ( DSr = 3.52 × 10 -6 (ppm Mg) + 6.20 × 10 -3). Unlike that derived from experimental data, this Sr-Mg relation is consistent over a range of 4 to 20 mol% MgCO 3 and may represent precipitation phenomena which are minimally controlled by kinetic effects. Comparison of Sr and Mg contents of analogous Devonian and Holocene marine cements suggests that the Mg/Ca ratio of Late Devonian seawater was

  12. The next chapter of direct phytolith 14C dating: debunking the myth of occluded photosynthetic carbon exclusivity

    NASA Astrophysics Data System (ADS)

    Santos, G.; Harutyunyan, A.; Alexandre, A. E.; Reyerson, P. E.; Gallagher, K. L.; Isabelle, B. D.

    2014-12-01

    Radiocarbon dating of carbon (C) encapsulated in phytoliths (phytC) is currently used in many Earth Science disciplines for absolute chronologies and paleoclimatic reconstructions; however, the usefulness of phytC has been hampered by inadequate extraction methods[1] and uncertainties regarding its origin as purely photosynthetic [2,3,4]. An early investigation measuring isotopes from Gramineae spp. grown in free-air C enrichment experiments (FACE), showed that part of of its phytC is from a non-photosynthetic source, thus indicating a dual origin[5]. To demonstrate that non-photosynthetic sources within phytC could be from soil C stocks, we measured 14C-AMS phytC extracted from a set of Sorghum bicolor growing on known 14C and d13C bulk substrates and hydroponic solutions. The phytolith concentrates and a silica blank were extracted at UCI, CEREGE and Wisconsin using an improved protocol [1,2]. We also measured CO2 fluxes and isotopic signatures of microbial respiration, percentage of biomass and phytolith extracts produced, and isotopic signatures of the local air and bulk-plant during the growing season of 2012. This allowed comparison of the belowground substrate and nutrient C contributions to phytC 14C results. Meanwhile, NanoSIMS analyses of phytolith polished sections was used to locate phytC in the phytolith siliceous structure [6]. These results will be shown and discussed. [1] Corbineau et al. 2013 R. Paleobot. Palyn. 197: 179 [2] Santos et al. 2010 T. Radiocarbon 52:113 [3] Santos et al. 2012a Biogeosci. 9:1873 [4] Santos et al. 2012b Biogeosci. Discussion 9:C6114 [5] Reyerson et al. 2013 AGU Fall meeting 2013 (Abstract ID: 1803125). [6] Alexandre, et al., submitted.

  13. Metabolic pathways for ketone body production. /sup 13/C NMR spectroscopy of rat liver in vivo using /sup 13/C-multilabeled fatty acids

    SciTech Connect

    Pahl-Wostl, C.; Seelig, J.

    1986-11-04

    The hormonal regulation of ketogenesis in the liver of living rat has been studied noninvasively with /sup 13/C nuclear magnetic resonance. The spatial selection for the liver was better than 90%, with extrahepatic adipose tissue contribution only a very small amount of signal. The metabolic activities of the liver were investigated by infusion of /sup 13/C-labeled butyrate in the jugular vein of the anesthetized rat. The rate of butyrate infusion was chosen to be close to the maximum oxidative capacity of the rat liver, and the /sup 13/C signal intensities were enhanced by using doubly labeled (1,3-/sup 13/C)butyrate as a substrate. Different /sup 13/C NMR spectra and hence different metabolites were observed depending on the hormonal state of the animal. The /sup 13/C NMR studies demonstrate that even when rate of acetyl-CoA production are high, the disposal of this compound is not identical in fasted and diabetic animals. This supports previous suggestions that the redox state of the mitochondrion represents the most important factor in regulation. For a given metabolic state of the animal, different signal intensities were obtained depending on whether butyrate was labeled at C-1, C-3, or C-1,3. From the ratios of incorporation of /sup 13/C label into the carbons of 3-hydroxybutyrate, it could be estimated that a large fraction of butyrate evaded ..beta..-oxidation to acetyl-CoA but was converted directly to acetoacetyl-CoA. /sup 13/C-labeled glucose could be detected in vivo in the liver of diabetic rats.

  14. Defective (U-14 C) palmitic acid oxidation in Duchenne muscular dystrophy

    SciTech Connect

    Carroll, J.E.; Norris, B.J.; Brooke, M.H.

    1985-01-01

    Compared with normal skeletal muscle, muscle from patients with Duchenne dystrophy had decreased (U-14 C) palmitic acid oxidation. (1-14 C) palmitic acid oxidation was normal. These results may indicate a defect in intramitochondrial fatty acid oxidation.

  15. Carbonates in leaching reactions in context of 14C dating

    NASA Astrophysics Data System (ADS)

    Michalska, Danuta; Czernik, Justyna

    2015-10-01

    Lime mortars as a mixture of binder and aggregate may contain carbon of various origins. If the mortars are made of totally burnt lime, radiocarbon dating of binder yields the real age of building construction. The presence of carbonaceous aggregate has a significant influence on the 14C measurements results and depending on the type of aggregate and fraction they may cause overaging. Another problem, especially in case of hydraulic mortars that continue to be chemically active for a very long time, is the recrystallization usually connected with rejuvenation of the results but also, depending on local geological structures, with so called reservoir effect yielding apparent ages. An attempt in separating the binder from other carbonaceous components successfully was made for samples from Israel by Nawrocka-Michalska et al. (2007). The same preparation procedure, after taking into account the petrographic composition, was used for samples coming from Poland, Nawrocka et al. (2009). To verify the procedure used previously for non-hydraulic samples determination an experimental tests on carbonaceous mortars with crushed bricks from Novae in Bulgaria were made. Additionally, to identify different carbonaceous structures and their morphology, a cathodoluminescence and scanning electron microscope with electron dispersive spectrometer were applied. The crushed bricks and brick dust used in mortars production process have been interpreted as an alternative use to other pozzolanic materials. The reaction between lime and pozzolanic additives take place easily and affects the rate and course of carbonates decomposition in orthophosphric acid, during the samples pretreatment for dating. The composition of the Bulgarian samples together with influence of climate conditions on mortar carbonates do not allow for making straightforward conclusions in chronology context, but gives some new guidelines in terms of hydraulic mortars application for dating. This work has mainly

  16. 14C-NaVP and 14C-PEV repeated dose study in rat. Pharmacokinetic study in rats after repeated oral administrations of 14C-valproic acid sodium salt and 14C-valproic acid pivaloyl oxymethyl ester.

    PubMed

    Bertolino, M; Acerbi, D; Canali, S; Giachetti, C; Poli, G; Ventura, P; Zanolo, G

    1998-01-01

    The absorption, excretion and tissue distribution of radioactivity after repeated oral equimolar doses of 14C-valproic acid sodium salt (NaVP) or 14C-valproic acid pivaloyl oxymethyl ester (PEV) was investigated in male rats treated once a day for 14 consecutive days. The 14th day plasma time-course of radioactivity after PEV administrations was characterised by a slow absorption rate with a delayed peak (tmax 2 h, Cmax 7.52 +/- 1.35 microg eq./ml), followed by a plateau lasting up to 8 h. After NaVP treatment, the main peak of radioactivity was observed 0.5 h after administration (Cmax 8.30 +/- 1.26 microg eq./ml) followed by a secondary peak due to biliary enterohepatic recycling. Starting from 4 h onwards, radioactivity levels after PEV treatment were higher than those after NaVP (AUCtau = 113.3 h.microg eq./ml after PEV vs 71.9 h.microg eq./ml after NaVP), but concentrations declined with similar terminal half-lives (52.8 h for PEV and 49.7 h for NaVP). Radioactivity recovered (0-432 h interval) in urine accounted for 79.3% (PEV) and 56.1% (NaVP) while, in faeces accounted for 9.1% (PEV) and 26.1% (NaVP) of total administered dose (14 days). The difference is attributable to a higher excretion of radioactivity in the bile for NaVP. The missing fraction in the total radioactivity balance is probably excreted in expired air, as observed in single dose studies. Radioactivity excreted in bile (0-8 h interval of the last 14th day) accounted for 5.1% (NaVP) and 0.23% (PEV) of the total administered dose (14 days). A possible explanation of this difference may be a different metabolism pattern for the two compounds. The negligible biliary excretion observed after PEV administration is probably due to an inhibition of the glucuronation of valproic acid (or other metabolites) caused by the pivalic acid. Due to the presence of the enterohepatic recycle, the radioactivity levels in intestine, 0.5 and 2 h after administration, were higher after NaVP administration

  17. Site-specific 13C content by quantitative isotopic 13C nuclear magnetic resonance spectrometry: a pilot inter-laboratory study.

    PubMed

    Chaintreau, Alain; Fieber, Wolfgang; Sommer, Horst; Gilbert, Alexis; Yamada, Keita; Yoshida, Naohiro; Pagelot, Alain; Moskau, Detlef; Moreno, Aitor; Schleucher, Jürgen; Reniero, Fabiano; Holland, Margaret; Guillou, Claude; Silvestre, Virginie; Akoka, Serge; Remaud, Gérald S

    2013-07-25

    Isotopic (13)C NMR spectrometry, which is able to measure intra-molecular (13)C composition, is of emerging demand because of the new information provided by the (13)C site-specific content of a given molecule. A systematic evaluation of instrumental behaviour is of importance to envisage isotopic (13)C NMR as a routine tool. This paper describes the first collaborative study of intra-molecular (13)C composition by NMR. The main goals of the ring test were to establish intra- and inter-variability of the spectrometer response. Eight instruments with different configuration were retained for the exercise on the basis of a qualification test. Reproducibility at the natural abundance of isotopic (13)C NMR was then assessed on vanillin from three different origins associated with specific δ (13)Ci profiles. The standard deviation was, on average, between 0.9 and 1.2‰ for intra-variability. The highest standard deviation for inter-variability was 2.1‰. This is significantly higher than the internal precision but could be considered good in respect of a first ring test on a new analytical method. The standard deviation of δ (13)Ci in vanillin was not homogeneous over the eight carbons, with no trend either for the carbon position or for the configuration of the spectrometer. However, since the repeatability for each in