Food resources of stream macroinvertebrates determined by natural-abundance stable C and N isotopes and a 15N tracer addition

Treesearch

Patrick J. Mulholland; Jennifer L. Tank; Diane M. Sanzone; Wilfrid M. Wollheim; Bruce J. Peterson; Jackson R. Webster; Judy L. Meyer

2000-01-01

Trophic relationships were examined using natural-abundance 13C and 15N analyses and a 15N-tracer addition experiment in Walker Branch, a 1st-order forested stream in eastern Tennessee. In the 15N-tracer addition experiment, we added 15NH4...

Plant diversity moderates drought stress in grasslands: Implications from a large real-world study on (13)C natural abundances.

PubMed

Klaus, Valentin H; Hölzel, Norbert; Prati, Daniel; Schmitt, Barbara; Schöning, Ingo; Schrumpf, Marion; Solly, Emily F; Hänsel, Falk; Fischer, Markus; Kleinebecker, Till

2016-10-01

Land-use change and intensification play a key role in the current biodiversity crisis. The resulting species loss can have severe effects on ecosystem functions and services, thereby increasing ecosystem vulnerability to climate change. We explored whether land-use intensification (i.e. fertilization intensity), plant diversity and other potentially confounding environmental factors may be significantly related to water use (i.e. drought stress) of grassland plants. Drought stress was assessed using δ(13)C abundances in aboveground plant biomass of 150 grassland plots across a gradient of land-use intensity. Under water shortage, plants are forced to increasingly take up the heavier (13)C due to closing stomata leading to an enrichment of (13)C in biomass. Plants were sampled at the community level and for single species, which belong to three different functional groups (one grass, one herb, two legumes). Results show that plant diversity was significantly related to the δ(13)C signal in community, grass and legume biomass indicating that drought stress was lower under higher diversity, although this relation was not significant for the herb species under study. Fertilization, in turn, mostly increased drought stress as indicated by more positive δ(13)C values. This effect was mostly indirect by decreasing plant diversity. In line with these results, we found similar patterns in the δ(13)C signal of the organic matter in the topsoil, indicating a long history of these processes. Our study provided strong indication for a positive biodiversity-ecosystem functioning relationship with reduced drought stress at higher plant diversity. However, it also underlined a negative reinforcing situation: as land-use intensification decreases plant diversity in grasslands, this might subsequently increases drought sensitivity. Vice-versa, enhancing plant diversity in species-poor agricultural grasslands may moderate negative effects of future climate change. Copyright �

Natural isotope correction of MS/MS measurements for metabolomics and (13)C fluxomics.

PubMed

Niedenführ, Sebastian; ten Pierick, Angela; van Dam, Patricia T N; Suarez-Mendez, Camilo A; Nöh, Katharina; Wahl, S Aljoscha

2016-05-01

Fluxomics and metabolomics are crucial tools for metabolic engineering and biomedical analysis to determine the in vivo cellular state. Especially, the application of (13)C isotopes allows comprehensive insights into the functional operation of cellular metabolism. Compared to single MS, tandem mass spectrometry (MS/MS) provides more detailed and accurate measurements of the metabolite enrichment patterns (tandem mass isotopomers), increasing the accuracy of metabolite concentration measurements and metabolic flux estimation. MS-type data from isotope labeling experiments is biased by naturally occurring stable isotopes (C, H, N, O, etc.). In particular, GC-MS(/MS) requires derivatization for the usually non-volatile intracellular metabolites introducing additional natural isotopes leading to measurements that do not directly represent the carbon labeling distribution. To make full use of LC- and GC-MS/MS mass isotopomer measurements, the influence of natural isotopes has to be eliminated (corrected). Our correction approach is analyzed for the two most common applications; (13)C fluxomics and isotope dilution mass spectrometry (IDMS) based metabolomics. Natural isotopes can have an impact on the calculated flux distribution which strongly depends on the substrate labeling and the actual flux distribution. Second, we show that in IDMS based metabolomics natural isotopes lead to underestimated concentrations that can and should be corrected with a nonlinear calibration. Our simulations indicate that the correction for natural abundance in isotope based fluxomics and quantitative metabolomics is essential for correct data interpretation. © 2015 Wiley Periodicals, Inc.

Carbon and nitrogen biogeochemistry in the ocean: A study using stable isotope natural abundance

NASA Technical Reports Server (NTRS)

Rau, G. H.; Desmarais, David J.

1985-01-01

Determining the biogeochemical pathways traveled by carbon and nitrogen in the ocean is fundamental to the understanding of how the ocean participates in the cycling of these elements within the biosphere. Because biological production, metabolism, and respiration can significantly alter the natural abundance of C-13 and N-15, these abundances can provide important information about the nature of these biological processes and their variability in the marine environment. The research initially seeks to characterize the spatial and temporal patterns of stable isotope abundances in organic matter, and to relate these abundances to C and N biogeochemical processes within selected areas of the northeastern Pacific Ocean.

Ethane C-C clumping in natural gas : a proxy for cracking processes ?

NASA Astrophysics Data System (ADS)

Clog, M. D.; Ferreira, A. A.; Santos Neto, E. V.; Eiler, J. M.

2014-12-01

Ethane (C2H6) is the second-most abundant alkane in most natural gas reservoirs, and is used to produce ethylene for petrochemical industries. It is arguably the simplest molecule that can manifest multiple 13C substitutions. There are several plausible controls on Δ13C2H6in natural gas: thermodynamically controlled homogeneous isotope exchange reactions analogous to those behind carbonate clumped isotope thermometry; inheritance from larger biomolecules that undergo thermal degradation to produce natural gas; mixing of natural gases that differ markedly in bulk isotopic composition; diffusive fractionation; or combinations of these and/or other, less expected fractionations. There is little basis for predicting which of these will control isotopic variations among natural ethanes, but we think it likely that addition of this new isotopic proxy will reveal new insights into the natural chemistry of ethane. We have developed a method to measure the abundance of 13C2H6 in natural samples, using high-resolution mass spectrometry. We define Δ13C2H6 as 1000 . ((13C2H6/12C2H6)measured/(13C2H6/12C2H6)stochastic -1). We studied several suites of natural gas samples and experimentally produced or modified ethane. Natural ethanes, including closely related samples from a single natural gas field, exhibit surprisingly large ranges in Δ13C2H6 (4 ‰ overall; up to 3 ‰ in one gas field). Such ranges cannot be explained by thermodynamic equilibrium at a range of different temperatures, or by diffusive fractionation. Kinetic isotope effects associated with 'cracking' reactions, and/or inheritance of non-equilibrium carbon isotope structures from source organics are more likely causes. We observe a correlation between Δ13C2H6 and the concentration of alkanes other than methane in several suites of natural gases, suggesting the causes of clumped isotope variations are tied to the controls on gas wetness. An experiment examining ethane residual to high-temperature pyrolysis

Sensitivity enhancement in whole-body natural abundance 13C spectroscopy using 13C/1H double-resonance techniques at 4 tesla.

PubMed

Bomsdorf, H; Röschmann, P; Wieland, J

1991-11-01

In vivo 13C spectroscopy experiments were performed using a whole-body MR system at a static field of 4 T. The main goal of the investigations was to evaluate the sensitivity increase achievable by means of 13C/1H double-resonance techniques at 4 T. Spectra from subcutaneous fat as well as muscle glycogen from the lower leg were acquired using frequency selective proton decoupling and the polarization transfer method SINEPT. With respect to measurements on subcutaneous fat, polarization transfer turned out to be more efficient than selective decoupling. About a fourfold enhancement in spectral peak intensity for the C = C line doublet of the unsaturated fatty acid chain was obtained. Combining polarization transfer with decoupling yielded a factor of 6 in signal amplitude. In contrast to that, the signal enhancement observed in measurements on the glycogen C-1 resonance was only around twofold. The lower efficiency is explained by fast T2 relaxation of the proton transition. A T2 value of about 3 ms was derived from the experimental data. Acquisition times as low as 3 min were realized for normal level glycogen in human calf muscle, enabling a time resolution adequate for dynamic studies on muscle glycogen depletion. Aspects of RF power absorption in tissue and the generally higher efficiency make polarization transfer methods preferable to selective decoupling in whole-body 13C spectroscopy at 4 T.

Suppression of Native Soil Organic Matter Decomposition by Post-Fermentation Sludge in Agriculture Soil as Assessed by 13C Natural Abundance

NASA Astrophysics Data System (ADS)

Stelmach, W.; Bieganowski, A.; Kuzyakov, Y.

2016-12-01

Anaerobic digestion of organic wastes results in the production of biogas and post-fermentation sludge. Post-fermentation sludge, which is rich in nutrients and contains more easily accessible inorganic-N than comparable composts, can be used as an alternative fertilizer in organic agriculture systems. While the effects of post fermentation sludge application on crop health and productivity have been extensively studied, little is known about its effects on soil parameters and long-term soil health. Thus, the main aim of this study was to determine the effects of post-fermentation sludge fertilization on agriculture soil quality. Specifically, it examined the efficiency and sequence of sludge utilisation by microorganisms and its influence on the utilisation/stabilization of native soil organic matter (SOM).To determine changes in SOM turnover after the addition of sludge, we utilized a natural stable carbon isotope labelling approach. Sludge produced from C4 plant residues (e.g. maize) was applied to soil under C3 cropping, resulting in distinct stable isotope signatures of fertilizer and SOM. Measuring the carbon isotope composition of CO2 produced in this microcosm experiment permitted accurate determination of the proportion of CO2 fluxes arising from both C sources. The addition of post-fermentation sludge increased the CO2 emissions from the soil by 30%. δ13C analysis of the total CO2 efflux revealed that post-fermentation sludge decreased SOM decomposition by 42% compared to control. Only 34% of the post-fermentation sludge had been mineralized after two months of incubation in the soil.The collective results of our study reveal that application of post-fermentation sludge suppresses SOM decomposition, suggesting its use as a fertilizer could positively influence long-term soil quality. Finally, the success of the natural abundance microcosm labeling approach in our study supports its use as an effective method of analyzing the effects of various

Abundance and δ13C values of fatty acids in lacustrine surface sediments: Relationships with in-lake methane concentrations

NASA Astrophysics Data System (ADS)

Stötter, Tabea; Bastviken, David; Bodelier, Paul L. E.; van Hardenbroek, Maarten; Rinta, Päivi; Schilder, Jos; Schubert, Carsten J.; Heiri, Oliver

2018-07-01

Proxy-indicators in lake sediments provide the only approach by which the dynamics of in-lake methane cycling can be examined on multi-decadal to centennial time scales. This information is necessary to constrain how lacustrine methane production, oxidation and emissions are expected to respond to global change drivers. Several of the available proxies for reconstructing methane cycle changes of lakes rely on interpreting past changes in the abundance or relevance of methane oxidizing bacteria (MOB), either directly (e.g. via analysis of bacterial lipids) or indirectly (e.g. via reconstructions of the past relevance of MOB in invertebrate diet). However, only limited information is available about the extent to which, at the ecosystem scale, variations in abundance and availability of MOB reflect past changes in in-lake methane concentrations. We present a study examining the abundances of fatty acids (FAs), particularly of 13C-depleted FAs known to be produced by MOB, relative to methane concentrations in 29 small European lakes. 39 surface sediment samples were obtained from these lakes and FA abundances were compared with methane concentrations measured at the lake surface, 10 cm above the sediments and 10 cm within the sediments. Three of the FAs in the surface sediment samples, C16:1ω7c, C16:1ω5c/t, and C18:1ω7c were characterized by lower δ13C values than the remaining FAs. We show that abundances of these FAs, relative to other short-chain FAs produced in lake ecosystems, are related with sedimentary MOB concentrations assessed by quantitative polymerase chain reaction (qPCR). We observed positive relationships between methane concentrations and relative abundances of C16:1ω7c, C16:1ω5c/t, and C18:1ω7c and the sum of these FAs. For the full dataset these relationships were relatively weak (Spearman's rank correlation (rs) of 0.34-0.43) and not significant if corrected for multiple testing. However, noticeably stronger and statistically significant

Food webs in Mongolian grasslands: the analysis of 13C and 15N natural abundances.

PubMed

Kohzu, Ayato; Iwata, T; Kato, M; Nishikawa, J; Wada, Eitaro; Amartuvshin, N; Namkhaidorj, B; Fujita, N

2009-09-01

Overgrazing often lowers species richness and productivity of grassland communities. For Mongolian grassland ecosystems, a lack of detailed information about food-web structures makes it difficult to predict the effects of overgrazing on species diversity and community composition. We analysed the delta13C and delta15N signatures of herbaceous plants, arthropods (grouped by feeding habit), wild and domestic mammals, and humans in central Mongolia to understand the predominant food-web pathways in this grassland ecosystem. The delta13C and delta15N values of mammals showed little variation within species, but varied considerably with slope position for arthropods. The apparent isotopic discrimination between body tissue and hair of mammals was estimated as 2.0 per thousand for delta13C and 2.1 per thousand for delta15N, which was large enough to cause overestimation of the trophic level of mammals if not taken into account when using hair samples to measure isotopic enrichment.

Fungal carbon sources in a pine forest: evidence from a 13C-labeled global change experiment

Treesearch

Erik A. Hobbie; Kirsten S. Hofmockel; Linda T.A. Van Diepen; Erik A. Lilleskov; Andrew P. Oiumette; Adrien C. Finzi

2014-01-01

We used natural abundance 13C:12C (δ13C) and 8 yr of labeling with 13C-depleted CO2 in a Pinus taeda Free Air CO2 Enrichment (FACE) experiment to investigate carbon sources of saprotrophic fungi, ectomycorrhizal...

Natural 13C abundance reveals trophic status of fungi and host-origin of carbon in mycorrhizal fungi in mixed forests

PubMed Central

Högberg, Peter; Plamboeck, Agneta H.; Taylor, Andrew F. S.; Fransson, Petra M. A.

1999-01-01

Fungi play crucial roles in the biogeochemistry of terrestrial ecosystems, most notably as saprophytes decomposing organic matter and as mycorrhizal fungi enhancing plant nutrient uptake. However, a recurrent problem in fungal ecology is to establish the trophic status of species in the field. Our interpretations and conclusions are too often based on extrapolations from laboratory microcosm experiments or on anecdotal field evidence. Here, we used natural variations in stable carbon isotope ratios (δ13C) as an approach to distinguish between fungal decomposers and symbiotic mycorrhizal fungal species in the rich sporocarp flora (our sample contains 135 species) of temperate forests. We also demonstrated that host-specific mycorrhizal fungi that receive C from overstorey or understorey tree species differ in their δ13C. The many promiscuous mycorrhizal fungi, associated with and connecting several tree hosts, were calculated to receive 57–100% of their C from overstorey trees. Thus, overstorey trees also support, partly or wholly, the nutrient-absorbing mycelia of their alleged competitors, the understorey trees. PMID:10411910

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

Novel Peak Assignments of in Vivo 13C MRS in Human Brain at 1.5 T

NASA Astrophysics Data System (ADS)

Blüml, Stefan; Hwang, Jong-Hee; Moreno, Angel; Ross, Brian D.

2000-04-01

13C MRS studies at natural abundance and after intravenous 1-13C glucose infusion were performed on a 1.5-T clinical scanner in four subjects. Localization to the occipital cortex was achieved by a surface coil. In natural abundance spectra glucose C3β,5β, myo-inositol, glutamate C1,2,5, glutamine C1,2,5, N-acetyl-aspartate C1-4,Cdbnd O, creatine CH2, CH3, and CCdbnd N, taurine C2,3, bicarbonate HCO-3 were identified. After glucose infusion 13C enrichment of glucose C1α,1β, glutamate C1-4, glutamine C1-4, aspartate C2,3, N-acetyl-aspartate C2,3, lactate C3, alanine C3, and HCO-3 were observed. The observation of 13C enrichment of resonances resonating at >150 ppm is an extension of previously published studies and will provide a more precise determination of metabolic rates and substrate decarboxylation in human brain.

Biosynthetic production of universally (13)C-labelled polyunsaturated fatty acids as reference materials for natural health product research.

PubMed

Le, Phuong Mai; Fraser, Catherine; Gardner, Graeme; Liang, Wei-Wan; Kralovec, Jaroslav A; Cunnane, Stephen C; Windust, Anthony J

2007-09-01

Long-chain polyunsaturated fatty acids (LCPUFA) including eicosapentaenoic acid (EPA, 20:5n-3) and docosahexaenoic acid (DHA, 22:6n-3) have become important natural health products with numerous proven benefits related to brain function and cardiovascular health. Not only are omega-3 fatty acids available in a plethora of dietary supplements, but they are also increasingly being incorporated as triglycerides into conventional foods, including bread, milk, yoghurt and confectionaries. Recently, transgenic oil seed crops and livestock have been developed that enhance omega-3 fatty acid content. This diverse array of matrices presents a difficult analytical challenge and is compounded further by samples generated through clinical research. Stable isotope (13)C-labelled LCPUFA standards offer many advantages as research tools because they may be distinguished from their naturally abundant counterparts by mass spectrometry and directly incorporated as internal standards into analytical procedures. Further, (13)C-labelled LCPUFAs are safe to use as metabolic tracers to study uptake and metabolism in humans. Currently, (13)C-labelled LCPUFAs are expensive, available in limited supply and not in triglyceride form. To resolve these issues, marine heterotrophic microorganisms are being isolated and screened for LCPUFA production with a view to the efficient biosynthetic production of U-(13)C-labelled fatty acids using U-(13)C glucose as a carbon source. Of 37 isolates obtained, most were thraustochytrids, and either DHA or omega-6 docosapentaenoic acid (22:5n-6) were produced as the major LCPUFA. The marine protist Hyalochlorella marina was identified as a novel source of EPA and omega-3 docosapentaenoic acid (22:5n-3). As proof of principle, gram-level production of (13)C-labelled DHA has been achieved with high chemical purity ( >99%) and high (13)C incorporation levels (>90%), as confirmed by NMR and MS analyses. Finally, U-(13)C-DHA was enzymatically re-esterified to

Measurement of starch digestion of naturally 13C-enriched weaning foods, before and after partial digestion with amylase-rich flour, using a 13C breath test.

PubMed

Weaver, L T; Dibba, B; Sonko, B; Bohane, T D; Hoare, S

1995-10-01

Malnutrition in infancy is a global problem which leads to retardation of childhood growth and development. There is a pressing need to improve weaning strategies for infants of the developing world. Traditional Gambian weaning foods are watery and of low energy density, but addition of energy in the form of fat and carbohydrate leads to thick, viscous gruels which are difficult to ingest. Partial digestion with amylase (EC 3.2.1.1)-rich flour reduces their viscosity while retaining their energy density. The aim of the present study was to measure the digestibility of a maize-based weaning food, before and after amylase digestion, in malnourished children using a 13C breath test. Ten children (aged 7-16 months; mean weight-for-age Z score -0.8) received isovolumetric and isoenergetic quantities of a maize-based weaning food naturally abundant with 13C. Breath samples were collected at intervals of 30 min for 5 h thereafter and 13CO2 enrichment was measured by isotope-ratio mass spectrometry. Percentage dose of 13C recovered increased from a mean 13.7 (SD 3.7)% before, to 18.3 (SD 5.6)% after ingestion of amylase-treated weaning foods (P < 0.1). There was a significant inverse relation between age and weight, and percentage dose of 13C recovered in children receiving amylase-treated feeds. There were no differences in concentrations of amylase in saliva of infants or breast milk of their mothers. Partial digestion of supplementary foods may improve the nutrition of undernourished weaning children, not only by reducing their viscosity, thereby increasing ingestion, but also by improving their digestion and thereby their absorption.

Dynamics of shoot vs. root C assessed by natural 13C abundance of their biomarkers

NASA Astrophysics Data System (ADS)

Mendez-Millan, Mercedes; Dignac, Marie-France; Rumpel, Cornelia; Rasse, Daniel P.; Derenne, Sylvie

2010-05-01

Cutins and suberins are biopolyesters that have been suggested to significantly contribute to the stable pool of soil organic matter (SOM). They might be used as tracers for the above- or belowground origin of plant material. The aim of this study was to evaluate the dynamics of shoot and root-derived biomarkers in soils using a wheat/maize (C3/C4) chronosequence. Our results suggest that α,?-alkanedioic acids can be considered as root specific markers and mid-chain hydroxy acids as shoot specific markers of wheat and maize in this agricultural soil. The changes of the 13C isotopic signatures of these markers with years of maize cropping after wheat evidenced their contrasted behaviour in soil. After 12 years of maize cropping, shoot markers present in soils probably originated from old C3 vegetation suggesting that new maize cutin added to soils was mostly degraded within a year. The reasons for long-term stabilisation of shoot biomarkers remain unclear. By contrast, maize root markers were highly incorporated into SOM during the first six years of maize crop, which suggested a selective preservation of root biomass when compared to shoots, possibly due to physical protection. The contrasting distribution of the plant-specific monomers in plants and soils might be explained by different chemical mechanisms leading to selective degradation or stabilization of some biomarkers.

THE GALACTIC R CORONAE BOREALIS STARS: THE C{sub 2} SWAN BANDS, THE CARBON PROBLEM, AND THE {sup 12}C/{sup 13}C RATIO

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

Hema, B. P.; Pandey, Gajendra; Lambert, David L., E-mail: hema@iiap.res.in, E-mail: pandey@iiap.res.in, E-mail: dll@astro.as.utexas.edu

2012-03-10

Observed spectra of R Coronae Borealis (RCB) and hydrogen-deficient carbon (HdC) stars are analyzed by synthesizing the C{sub 2} Swan bands (1, 0), (0, 0), and (0, 1) using our detailed line list and the Uppsala model atmospheres. The (0, 1) and (0, 0) C{sub 2} bands are used to derive the {sup 12}C abundance, and the (1, 0) {sup 12}C{sup 13}C band to determine the {sup 12}C/{sup 13}C ratios. The carbon abundance derived from the C{sub 2} Swan bands is about the same for the adopted models constructed with different carbon abundances over the range 8.5 (C/He = 0.1%)more » to 10.5 (C/He = 10%). Carbon abundances derived from C I lines are about a factor of four lower than the carbon abundance of the adopted model atmosphere over the same C/He interval, as reported by Asplund et al., who dubbed the mismatch between adopted and derived C abundance as the 'carbon problem'. In principle, the carbon abundances obtained from C{sub 2} Swan bands and that assumed for the model atmosphere can be equated for a particular choice of C/He that varies from star to star. Then, the carbon problem for C{sub 2} bands is eliminated. However, such C/He ratios are in general less than those of the extreme helium stars, the seemingly natural relatives to the RCB and HdC stars. A more likely solution to the C{sub 2} carbon problem may lie in a modification of the model atmosphere's temperature structure. The derived carbon abundances and the {sup 12}C/{sup 13}C ratios are discussed in light of the double degenerate and the final flash scenarios.« less

Measurement and significance of the equilibrium reaction C-13/+/ + /C-12/O yields C-12/+/ + /C-13/O for alteration of the C-13/C-12 ratio in interstellar molecules

NASA Technical Reports Server (NTRS)

Watson, W. D.; Anicich, V. G.; Huntress, W. T., Jr.

1976-01-01

Laboratory measurements using the ion-cyclotron resonance technique yield a rate constant of 2 by 10 to the -10th power cu cm/sec at 300 K for the isotope exchange C-13(+) + (C-12)O yields C-12(+) + (C-13)O. According to the usual ideas about ion-molecule reactions, this rate constant should also be appropriate at temperatures not exceeding about 100 K. Then the observed C-13/C-12 ratio obtained from radio observation of interstellar molecules may be either larger or smaller than the actual value in the interstellar medium by factors of 2 or so. If the ratio is altered from the actual interstellar value, it will not be the same in all molecules, and CO will tend to have the highest value. The chief astronomical uncertainty for the occurrence of this isotope fractionation is the abundance of 'unobservable' molecules which can react rapidly with C(+): e.g., O2, H2O, CO2, and CH4. If their abundance is greater than about one-tenth that of CO, the isotope fractionation will be inhibited.

Microwave Spectra for the Three 13C_1 Isotopologues of Propene and New Rotational Constants for Propene and its 13C_1 Isotopologues

NASA Astrophysics Data System (ADS)

Craig, Norman C.; Groner, Peter; Conrad, Andrew R.; Gurusinghe, Ranil M.; Tubergen, Michael

2016-06-01

New measurements of microwave lines (A and E) of propene and its three 13C_1 isotopologues have been made in the 10-22 GHz region with FT accuracy. The revised lines for propene along with many hundreds from the literature were fitted with the ERHAM program for internal rotors to give improved rotational constants. The new constants for propene are A_0 = 46280.2904(16), B_0 = 9305.24260(30), and C_0 = 8134.22685(28) MHz. Lines for the 3-13C_1 species were observed in a pure sample; lines for the 1-13C_1 and 2-13C_1 species were observed in natural abundance. In fitting the limited sets of lines for the 13C_1 species, many of the centrifugal distortion constants and most of the tunneling parameters were transferred from the fit of propene itself with 27 parameters. Improved rotational constants for the 13C_1 species are reported.

Detection of C-13O radio emission from C-13-rich carbon stars

NASA Technical Reports Server (NTRS)

Jura, M.; Kahane, C.; Omont, A.

1988-01-01

A high ratio of C-13O radio emission in the J = 1-0 rotational line has been detected from three mass-losing carbon stars which optical data indicate have high C-13/C12 ratios. Since chemical fractionation, isotope-dependent photodissociation and opacity in the rotational and vibrational lines may not raise significantly the C-13O ratio above the actual C-13/C-12 ratio in these circumstellar envelopes, the relative abundance of C-13 in these stars might be even greater by perhaps a factor of two than previously believed. About 15 percent of all luminous carbon stars are C-13-rich, and these stars may play a significant role in the enhancement in the C-13/C12 ratio that has occurred during the past 4.6 billion years since the formation of the sun.

13C Natural Abundance of Serum Retinol Is a Novel Biomarker for Evaluating Provitamin A Carotenoid-Biofortified Maize Consumption in Male Mongolian Gerbils.

PubMed

Gannon, Bryan M; Pungarcher, India; Mourao, Luciana; Davis, Christopher R; Simon, Philipp; Pixley, Kevin V; Tanumihardjo, Sherry A

2016-07-01

Crops such as maize, sorghum, and millet are being biofortified with provitamin A carotenoids to ensure adequate vitamin A (VA) intakes. VA assessment can be challenging because serum retinol concentrations are homeostatically controlled and more sensitive techniques are resource-intensive. We investigated changes in serum retinol relative differences of isotope amount ratios of (13)C/(12)C (δ(13)C) caused by natural (13)C fractionation in C3 compared with C4 plants as a biomarker to detect provitamin A efficacy from biofortified (orange) maize and high-carotene carrots. The design was a 2 × 2 × 2 maize (orange compared with white) by carrot (orange compared with white) by a VA fortificant (VA+ compared with VA-) in weanling male Mongolian gerbils (n = 55), which included a 14-d VA depletion period and a 62-d treatment period (1 baseline and 8 treatment groups; n = 5-7/group). Liver VA and serum retinol were quantified, purified by HPLC, and analyzed by GC combustion isotope ratio mass spectrometry for (13)C. Treatments affected liver VA concentrations (0.048 ± 0.039 to 0.79 ± 0.24 μmol/g; P < 0.0001) but not overall serum retinol concentrations (1.38 ± 0.22 μmol/L). Serum retinol and liver VA δ(13)C were significantly correlated (R(2) = 0.92; P < 0.0001). Serum retinol δ(13)C differentiated control groups that consumed white maize and white carrots (-27.1 ± 1.2 δ(13)C‰) from treated groups that consumed orange maize and white carrots (-21.6 ± 1.4 δ(13)C‰ P < 0.0001) and white maize and orange carrots (-30.6 ± 0.7 δ(13)C‰ P < 0.0001). A prediction model demonstrated the relative contribution of orange maize to total dietary VA for groups that consumed VA from mixed sources. Provitamin A efficacy and quantitative estimation of the relative contribution to dietary VA were demonstrated with the use of serum retinol δ(13)C. This method could be used for maize efficacy or effectiveness studies and with other C4 crops biofortified with provitamin A

Determination of Natural 14C Abundances in Dissolved Organic Carbon in Organic-Rich Marine Sediment Porewaters by Thermal Sulfate Reduction

NASA Astrophysics Data System (ADS)

Johnson, L.; Komada, T.

2010-12-01

The abundances of natural 14C in dissolved organic carbon (DOC) in the marine environment hold clues regarding the processes that influence the biogeochemical cycling of this large carbon reservoir. At present, UV irradiation is the widely accepted method for oxidizing seawater DOC for determination of their 14C abundances. This technique yields precise and accurate values with low blanks, but it requires a dedicated vacuum line, and hence can be difficult to implement. As an alternative technique that can be conducted on a standard preparatory vacuum line, we modified and tested a thermal sulfate reduction method that was previously developed to determine δ13C values of marine DOC (Fry B. et al., 1996. Analysis of marine DOC using a dry combustion method. Mar. Chem., 54: 191-201.) to determine the 14C abundances of DOC in marine sediment porewaters. In this method, the sample is dried in a 100 ml round-bottom Pyrex flask in the presence of excess oxidant (K2SO4) and acid (H3PO4), and combusted at 550 deg.C. The combustion products are cryogenically processed to collect and quantify CO2 using standard procedures. Materials we have oxidized to date range from 6-24 ml in volume, and 95-1500 μgC in size. The oxidation efficiency of this method was tested by processing known amounts of reagent-grade dextrose and sucrose (as examples of labile organic matter), tannic acid and humic acid (as examples of complex natural organic matter), and porewater DOC extracted from organic-rich nearshore sediments. The carbon yields for all of these materials averaged 99±4% (n=18). The 14C abundances of standard materials IAEA C-6 and IAEA C-5 processed by this method using >1mgC aliquots were within error of certified values. The size and the isotopic value of the blank were determined by a standard dilution technique using IAEA C-6 and IAEA C-5 that ranged in size from 150 to 1500 μgC (n=4 and 2, respectively). This yielded a blank size of 6.7±0.7 μgC, and a blank isotopic

Natural 13C abundance: a tool to trace the incorporation of dung-derived carbon into soil particle-size fractions.

PubMed

Amelung, W; Bol, R; Friedrich, C

1999-01-01

During the decay of 13C enriched dung patches, the; delta 13C signal of surface soil (1-5 cm) increased with a temporary maximum after 42 d. To understand the underlying processes, we investigated the incorporation of dung-derived C into soil particle-size fractions. Dung, collected from beef steers fed on maize (delta 13C = -15.36/1000) or ryegrass (delta 13C = -25.67/1000), was applied in circular patches to a C3 pasture at North Wyke, UK. Triplicates were sampled from surface soil (1-5 cm) at 14, 28, 42, and 70 d after application, pooled, separated into fine (< 0.2 micron) and coarse clay (0.2-2 microns), silt plus fine sand (2-250 microns), and coarse sand (250-2000 microns), and analyzed for total C, N, and delta 13C. As particle-size diameter decreased, the C/N ratios decreased and delta 13C values increased at all plots due to increasing microbial alteration of soil organic matter. After dung application, ca. 60% of dung-derived C in soil was recovered in the 0.2-250 microns fractions during the whole experiment. The proportion of dung-derived C in the fine clay peaked 42 d after dung application, coinciding with the delta 13C maximum in the bulk soil and the maximum leaching rate measured in lysimeters at this time in another study at the same sites. The percentage of dung-derived C as particulate C in the coarse sand fraction increased until the end of the experiment. We conclude that incorporation of C into soil from decomposing dung patches involved both temporary sorption of leached dung C to < 0.2 micron fractions and continuous accumulation of particulate C (> 250 microns).

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.

Methane Provenance Determined by CH2D2 and 13CH3D Abundances

NASA Astrophysics Data System (ADS)

Kohl, I. E.; Giunta, T.; Warr, O.; Ash, J. L.; Ruffine, L.; Sherwood Lollar, B.; Young, E. D.

2017-12-01

Determining the provenance of naturally occurring methane gases is of major interest to energy companies and atmospheric climate modelers, among others. Bulk isotopic compositions and other geochemical tracers sometimes fail to provide definitive determinations of sources of methane due to complications from mixing and complicated chemical pathways of origin. Recent measurements of doubly-substituted isotopologues of methane, CH2D2 (UCLA) and 13CH3D (UCLA, CalTech, and MIT) have allowed for major improvements in sourcing natural methane gases. Early work has focused on formation temperatures obtained when the relative abundances of both doubly-substituted mass-18 species are consistent with internal equilibrium. When methane gases do not plot on the thermodynamic equilibrium curve in D12CH2D2 vs D13CH3D space, temperatures determined from D13CH3D values alone are usually spurious, even when appearing reasonable. We find that the equilibrium case is actually rare and almost exclusive to thermogenic gases produced at temperatures exceeding 100°C. All other relevant methane production processes appear to generate gases that are not in isotopologue-temperature equilibrium. When gases show departures from equilibrium as determined by the relationship between CH2D2 and 13CH3D abundances, data fall within empirically defined fields representing formation pathways. These fields are thus far consistent between different geological settings and and between lab experiments and natural samples. We have now defined fields for thermogenic gas production, microbial methanogenesis, low temperature abiotic (Sabatier) synthesis and higher temperature FTT synthesis. The majority of our natural methane data can be explained by mixing between end members originating within these production fields. Mixing can appear complex, resulting in both hyper-clumped and anti-clumped isotopologue abundances. In systems where mixtures dominate and end-members are difficult to sample, mixing models

Late-Quaternary variation in C3 and C4 grass abundance in southeastern Australia as inferred from δ13C analysis: Assessing the roles of climate, pCO2, and fire

NASA Astrophysics Data System (ADS)

Nelson, David M.; Urban, Michael A.; Kershaw, A. Peter; Hu, Feng Sheng

2016-05-01

Climate, atmospheric pCO2, and fire all may exert major influences on the relative abundance of C3 and C4 grasses in the present-day vegetation. However, the relative role of these factors in driving variation in C3 and C4 grass abundances in the paleorecord is uncertain, and C4 abundance is often interpreted narrowly as a proxy indicator of aridity or pCO2. We measured δ13C values of individual grains of grass (Poaceae) pollen in the sediments of two sites in southeastern Australia to assess changes in the proportions of C3 and C4 grasses during the past 25,000 years. These data were compared with shifts in pCO2, temperature, moisture balance, and fire to assess how these factors were related to long-term variation of C4 grass abundance during the late Quaternary. At Caledonia Fen, a high-elevation site in the Snowy Mountains, C4 grass abundance decreased from an average of 66% during the glacial period to 11% during the Holocene, primarily in response to increased pCO2 and temperature. In contrast, this pattern did not exist in low-elevation savannah woodlands around Tower Hill Northwest Crater, where C4 grass abundance instead varied in response to shifts in regional aridity. Fire did not appear to have strongly influenced the proportions of C3 and C4 grasses on the landscape at millennial timescales at either site. These patterns are similar to those of a recent study in East Africa, suggesting that elevation-related climatic differences influence how the abundance of C3 and C4 grasses responds to shifts in climate and pCO2. These results caution against using C4 plant abundance as a proxy indicator of either climate or pCO2 without an adequate understanding of key controlling factors.

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 instrument was satisfactory, correction factors for each carbon in vanillin could be calculated to harmonize the results. Copyright © 2013 Elsevier B.V. All rights reserved.

Implications of new measurements of O-16 + p + C-12,13, N-14,15 for the abundances of C, N isotopes at the cosmic ray source

NASA Technical Reports Server (NTRS)

Guzik, T. G.; Wefel, J. P.; Crawford, H. J.; Greiner, D. E.; Lindstrom, P. J.; Schimmerling, W.; Symons, T. J. M.

1985-01-01

The fragmentation of a 225 MeV/n O-16 beam was investigated at the Bevalac. Preliminary cross sections for mass = 13, 14, 15 fragments are used to constrain the nuclear excitation functions employed in galactic propagation calculations. Comparison to cosmic ray isotonic data at low energies shows that in the cosmic ray source C-13/C approximately 2% and N-14/0=3-6%. No source abundance of N-15 is required with the current experimental results.

High-precision optical measurements of 13C/12C isotope ratios in organic compounds at natural abundance

PubMed Central

Zare, Richard N.; Kuramoto, Douglas S.; Haase, Christa; Tan, Sze M.; Crosson, Eric R.; Saad, Nabil M. R.

2009-01-01

A continuous-flow cavity ring-down spectroscopy (CRDS) system integrating a chromatographic separation technique, a catalytic combustor, and an isotopic 13C/12C optical analyzer is described for the isotopic analysis of a mixture of organic compounds. A demonstration of its potential is made for the geochemically important class of short-chain hydrocarbons. The system proved to be linear over a 3-fold injection volume dynamic range with an average precision of 0.95‰ and 0.67‰ for ethane and propane, respectively. The calibrated accuracy for methane, ethane, and propane is within 3‰ of the values determined using isotope ratio mass spectrometry (IRMS), which is the current method of choice for compound-specific isotope analysis. With anticipated improvements, the low-cost, portable, and easy-to-use CRDS-based instrumental setup is poised to evolve into a credible challenge to the high-cost and complex IRMS-based technique. PMID:19564619

Natural abundance high-resolution solid state 2 H NMR spectroscopy

NASA Astrophysics Data System (ADS)

Aliev, Abil E.; Harris, Kenneth D. M.; Apperley, David C.

1994-08-01

We report for the first time an approach for natural abundance solid state 2 H NMR spectroscopy involving magic angle sample spinning (MAS), high-power 1 H decoupling (HPPD) and 1 H- 2 H cross polarization (CP). Taking tetrakis(trimethylsilyl)silane (TTMSS), adamantane, 1-chloroadamantane, hexamethylbenzene (HMB), 2,2-dimethyl-1,3-propanediol (DMPD) and 2-hydroxymethyl-2-methyl-1,3-propanediol (HMPD) as examples, it has been shown that the combination of HPPD and MAS can be applied readily to study rotator phase solids, allowing isotropic peaks arising from chemically inequivalent 2 H nuclei to be resolved. For natural abundance samples of TTMSS and chloroadamantane, it has been shown that 2 H CP/HPPD/MAS NMR experiments, involving polarization transfer from 1 H to 2 H, may provide considerable sensitivity enhancement in comparison with single pulse experiments.

Natural abundance high-resolution solid state 2 H NMR spectroscopy

NASA Astrophysics Data System (ADS)

Aliev, Abil E.; Harris, Kenneth D. M.; Apperley, David C.

1994-08-01

We report for the first time an approach for natural abundance solid state 2H NMR spectroscopy involving magic angle sample spinning (MAS), high-power 1H decoupling (HPPD) and 1H- 2H cross polarization (CP). Taking tetrakis(trimethylsilyl)silane (TTMSS), adamantane, 1-chloroadamantane, hexamethylbenzene (HMB), 2,2-dimethyl-1,3-propanediol (DMPD) and 2-hydroxymethyl-2-methyl-1,3-propanediol (HMPD) as examples, it has been shown that the combination of HPPD and MAS can be applied readily to study rotator phase solids, allowing isotropic peaks arising from chemically inequivalent 2H nuclei to be resolved. For natural abundance samples of TTMSS and chloroadamantane, it has been shown that 2H CP/HPPD/MAS NMR experiments, involving polarization transfer from 1H to 2H, may provide considerable sensitivity enhancement in comparison with single pulse experiments.

Short-Term Effects of Tillage Practices on Soil Organic Carbon Turnover Assessed by δ 13C Abundance in Particle-Size Fractions of Black Soils from Northeast China

PubMed Central

Zhang, Xiaoping; Chen, Xuewen

2014-01-01

The combination of isotope trace technique and SOC fractionation allows a better understanding of SOC dynamics. A five-year tillage experiment consisting of no-tillage (NT) and mouldboard plough (MP) was used to study the changes in particle-size SOC fractions and corresponding δ 13C natural abundance to assess SOC turnover in the 0–20 cm layer of black soils under tillage practices. Compared to the initial level, total SOC tended to be stratified but showed a slight increase in the entire plough layer under short-term NT. MP had no significant impacts on SOC at any depth. Because of significant increases in coarse particulate organic carbon (POC) and decreases in fine POC, total POC did not remarkably decrease under NT and MP. A distinct increase in silt plus clay OC occurred in NT plots, but not in MP plots. However, the δ 13C abundances of both coarse and fine POC increased, while those of silt plus clay OC remained almost the same under NT. The C derived from C3 plants was mainly associated with fine particles and much less with coarse particles. These results suggested that short-term NT and MP preferentially enhanced the turnover of POC, which was considerably faster than that of silt plus clay OC. PMID:25162052

Fourier transform C-13 NMR analysis of some free and potassium-ion complexed antibiotics.

NASA Technical Reports Server (NTRS)

Ohnishi, M.; Fedarko, M.-C.; Baldeschwieler, J. D.; Johnson, L. F.

1972-01-01

Fourier transforms of the noise-decoupled, natural abundance C-13 NMR free induction decays of the cyclic antibiotic valinomycin and its potassium-ion complex have been obtained at 25.2 MHz. Comparisons are made with C-13 NMR spectra taken at 22.6 MHz of the cyclic antibiotic nonactin and the synthetic polyether dicyclohexyl-18-crown-6 and their potassium complexes. The results obtained suggest that conformational rearrangements of the molecule as a whole can compete with direct interactions between carbons and the potassium ion in determining C-13 chemical shift differences between the free and complexed species.

Determination of 13C isotopic enrichment of valine and threonine by GC-C-IRMS after formation of the N(O,S)-ethoxycarbonyl ethyl ester derivatives of the amino acids.

PubMed

Godin, Jean-Philippe; Faure, Magali; Breuille, Denis; Hopfgartner, Gérard; Fay, Laurent-Bernard

2007-06-01

We describe a new method of assessing, in a single run, (13)C isotopic enrichment of both Val and Thr by gas chromatography-combustion-isotope-ratio mass spectrometry (GC-C-IRMS). This method characterised by a rapid one-step derivatisation procedure performed at room temperature to form the N(O,S)-ethoxycarbonyl ethyl ester derivatives, and a polar column for GC. The suitability of this method for Val and Thr in in-vivo samples (mucosal hydrolysate) was demonstrated by studying protein metabolism with two tracers ((13)C-valine or (13)C-threonine). The intra-day and inter-day repeatability were both assessed either with standards or with in-vivo samples at natural abundance and at low (13)C isotopic enrichment. For inter-day repeatability CVs were between 0.8 and 1.5% at natural abundance and lower than 5.5% at 0.112 and 0.190 atom% enrichment for Val and Thr, respectively. Overall isotopic precision was studied for eleven standard amino acid derivatives (those of Val, Ala, Leu, Iso, Gly, Pro, Asp, Thr, Ser, Met, and Phe) and was assessed at 0.32 per thousand. The (13)C isotopic measurement was then extended to the other amino acids (Ala, Val, Leu, Iso, Gly, Pro, Thr, and Phe) at natural abundance for in-vivo samples. The isotopic precision was better than 0.002 atom% per amino acid (for n = 4 rats). This analytical method was finally applied to an animal study to measure Thr utilization in protein synthesis.

Measurement of 13CO2 in expired air as an index of compliance to a high carbohydrate diet naturally enriched in 13C.

PubMed

Gay, L J; Schutz, Y; DiVetta, V; Schneiter, P; Tappy, L; Jéquier, E

1994-09-01

The aim of this study was to determine whether breath 13CO2 measurements could be used to assess the compliance to a diet containing carbohydrates naturally enriched in 13C. The study was divided into two periods: Period 1 (baseline of 4 days) with low 13C/12C ratio carbohydrates. Period 2 (5 days) isocaloric diet with a high 13C/12C ratio (corn, cane sugar, pineapple, millet) carbohydrates. Measurements were made of respiratory gas exchange by indirect calorimetry, urinary nitrogen excretion and breath 13CO2 every morning in post-absorptive conditions, both in resting state and during a 45-min low intensity exercise (walking on a treadmill). The subjects were 10 healthy lean women (BMI 20.4 +/- 1.7 kg/m2, % body fat 24.4 +/- 1.3%), the 13C enrichment of oxidized carbohydrate and breath 13CO2 were compared to the enrichment of exogenous dietary carbohydrates. At rest the enrichment of oxidized carbohydrate increased significantly after one day of 13C carbohydrate enriched diet and reached a steady value (103 +/- 16%) similar to the enrichment of exogenous carbohydrates. During exercise, the 13C enrichment of oxidized carbohydrate remained significantly lower (68 +/- 17%) than that of dietary carbohydrates. The compliance to a diet with a high content of carbohydrates naturally enriched in 13C may be assessed from the measurement of breath 13CO2 enrichment combined with respiratory gas exchange in resting, postabsorptive conditions.

Abundances in the red giants of M13 and M22

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

Lehnert, M.D.; Bell, R.A.; Cohen, J.G.

Abundances of Ca, Na, and Fe are derived for 10 red giant branch stars in the globular clusters M13 and M22, by means of model atmosphere analyses of high-dispersion spectra. It was found that M13 and M22 represent two different types of globular clusters. M13 is similar to M92 and many other globular clusters in that it displays variations in CH and CN band strengths, while showing no variation in either Ca or Fe abundance. The Na abundance was found to vary and its variation correlates with CN band strengths. This suggests that the source of the observed CN bandmore » strength variation is the same as that of the Na variation. M22, on the other hand, is similar to Omega Cen, in that it displays variations in Ca, Na, and Fe abundances, and these variations correlate with variations in CH and CN band strengths. These correlations suggest that the cause of the variations in M22 is largely primordial, and that mixing may only make a relatively small contribution to the C and N variations observed. 61 refs.« less

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

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

NASA Technical Reports Server (NTRS)

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

1987-01-01

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

Metal abundance of Tal 13

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

Zinn, R.; Diaz, A.I.

1982-08-01

Low-resolution spectrograms have been obtained of the three RR Lyrae variables in the distant and very sparse globular cluster Pal 13. A comparison of these spectrograms with similar ones of several RR Lyrae variables in the globular clusters M4, M5, and M22 reveals that Pal 13 is intermediate to M5 and M22 in metal abundance. A value of (Fe/H) = -1.67 +- 0.15 is obtained for Pal 13 by adopting Zinn's (1980a (Astrophys. J. Suppl. 42,19)) values of (Fe/H) for these other clusters. Pal 13 is another example of a distant halo object that is not extremely metal poor.

Carbon-13 natural abundance signatures of long-chain fatty acids to determinate sediment origin: A case study in northeast Austria

NASA Astrophysics Data System (ADS)

Mabit, Lionel; Gibbs, Max; Meusburger, Katrin; Toloza, Arsenio; Resch, Christian; Klik, Andreas; Swales, Andrew; Alewell, Christine

2016-04-01

- Several recently published information from scientific research have highlighted that compound-specific stable isotope (CSSI) signatures of fatty acids (FAs) based on the measurement of carbon-13 natural abundance signatures showed great promises to identify sediment origin. The authors have used this innovative isotopic approach to investigate the sources of sediment in a three hectares Austrian sub-watershed (i.e. Mistelbach). Through a previous study using the Cs-137 technique, Mabit et al. (Geoderma, 2009) reported a local maximum sedimentation rate reaching 20 to 50 t/ha/yr in the lowest part of this watershed. However, this study did not identify the sources. Subsequently, the deposited sediment at its outlet (i.e. the sediment mixture) and representative soil samples from the four main agricultural fields - expected to be the source soils - of the site were investigated. The bulk delta carbon-13 of the samples and two long-chain FAs (i.e. C22:0 and C24:0) allowed the best statistical discrimination. Using two different mixing models (i.e. IsoSource and CSSIAR v1.00) and the organic carbon content of the soil sources and sediment mixture, the contribution of each source has been established. Results suggested that the grassed waterway contributed to at least 50% of the sediment deposited at the watershed outlet. This study, that will require further validation, highlights that CSSI and Cs-137 techniques are complementary as fingerprints and tracers for establishing land sediment redistribution and could provide meaningful information for optimized decision-making by land managers.

Influence of the 13C-enrichment of the habitual diet on a 13CO2 breath test used as an index of liver glycogen oxidation: a validation study in western Europe and Africa.

PubMed

Tanis, A A; Rietveld, T; Van den Berg, J W; Wattimena, J L; Swart, G R

2000-01-01

A diet containing naturally 13C-enriched carbohydrate combined with a 13CO2 breath-test analysis can be used to monitor liver glycogen oxidation in persons used to a diet low in 13C, e.g., the Western European diet. In this study, we evaluated this test principle further by changing the way we label the glycogen pool. The 13C enrichment of exhaled CO2 was studied in two groups, one in Europe and one in Africa. The European group (n = 12) was accustomed to a diet low in 13C, and they went on a 13C-enriched study diet to identify liver glycogen. The African group (n = 6) was accustomed to a diet naturally high in 13C, and they went on a diet low in 13C. The basal 13C abundance in exhaled CO2 was higher in the African group (1.0879 At%; atmospheric 1.1 atom percent) than in the European group (1.0821 At%). During the study period, the parameters for liver glycogen oxidation--the 13CO2 enrichment plateau, the plateau duration, and the return to baseline time--did not differ between groups. The abundance of 13CO2 in exhaled CO2 over time in the two groups was similar but inverse. This study confirms the use of a 13CO2 breath test to monitor liver glycogen oxidation and demonstrates how to use such a test in persons accustomed to a diet high in 13C.

Position-specific 13C distributions within propane from experiments and natural gas samples

NASA Astrophysics Data System (ADS)

Piasecki, Alison; Sessions, Alex; Lawson, Michael; Ferreira, A. A.; Santos Neto, E. V.; Ellis, Geoffrey S.; Lewan, Michael D.; Eiler, John M.

2018-01-01

Site-specific carbon isotope measurements of organic compounds potentially recover information that is lost in a conventional, 'bulk' isotopic analysis. Such measurements are useful because isotopically fractionating processes may have distinct effects at different molecular sites, and thermodynamically equilibrated populations of molecules tend to concentrate heavy isotopes in one molecular site versus another. Most recent studies of site-specific 13C in organics use specialized Nuclear Magnetic Resonance (NMR) techniques or complex chemical degradations prior to mass spectrometric measurements. Herein we present the first application of a new mass spectrometric technique that reconstructs the site-specific carbon isotope composition of propane based on measurements of the 13C/12C ratios of two or more fragment ions that sample different proportions of the terminal and central carbon sites. We apply this method to propane from laboratory experiments and natural gas samples to explore the relationships between site-specific carbon isotope composition, full-molecular δ13C, thermal maturity, and variation in organic matter precursors. Our goal is to advance the understanding of the sources and histories of short-chain alkanes within geologic systems. Our findings suggest that propane varies in its site-specific carbon isotope structure, which is correlated with increasing thermal maturity, first increasing in terminal position δ13C and then increasing in both center and terminal position δ13C. This pattern is observed in both experimental and natural samples, and is plausibly explained by a combination of site-specific, temperature-dependent isotope effects associated with conversion of different precursor molecules (kerogen, bitumen, and/or oil) to propane, differences in site-specific isotopic contents of those precursors, and possibly distillation of reactive components of those precursors with increasing maturity. We hypothesize that the largest changes in

Position-specific 13C distributions within propane from experiments and natural gas samples

USGS Publications Warehouse

Piasecki, Alison; Sessions, Alex L.; Lawson, Michael; Ferreira, A.A.; Santos Neto, E. V.; Ellis, Geoffrey S.; Lewan, Michael; Eilers, J.M.

2018-01-01

Site-specific carbon isotope measurements of organic compounds potentially recover information that is lost in a conventional, ‘bulk’ isotopic analysis. Such measurements are useful because isotopically fractionating processes may have distinct effects at different molecular sites, and thermodynamically equilibrated populations of molecules tend to concentrate heavy isotopes in one molecular site versus another. Most recent studies of site-specific 13C in organics use specialized Nuclear Magnetic Resonance (NMR) techniques or complex chemical degradations prior to mass spectrometric measurements. Herein we present the first application of a new mass spectrometric technique that reconstructs the site-specific carbon isotope composition of propane based on measurements of the 13C/12C ratios of two or more fragment ions that sample different proportions of the terminal and central carbon sites. We apply this method to propane from laboratory experiments and natural gas samples to explore the relationships between site-specific carbon isotope composition, full-molecular δ13C, thermal maturity, and variation in organic matter precursors. Our goal is to advance the understanding of the sources and histories of short-chain alkanes within geologic systems. Our findings suggest that propane varies in its site-specific carbon isotope structure, which is correlated with increasing thermal maturity, first increasing in terminal position δ13C and then increasing in both center and terminal position δ13C. This pattern is observed in both experimental and natural samples, and is plausibly explained by a combination of site-specific, temperature-dependent isotope effects associated with conversion of different precursor molecules (kerogen, bitumen, and/or oil) to propane, differences in site-specific isotopic contents of those precursors, and possibly distillation of reactive components of those precursors with increasing maturity. We hypothesize that the largest changes in

15N and 13C abundances in the Antartic Ocean with emphasis on the biogeochemical structure of the food web

NASA Astrophysics Data System (ADS)

Wada, Eitaro; Terazaki, Makoto; Kabaya, Yuko; Nemoto, Takahisa

1987-06-01

Distributions of δ 15N and δ 13C for biogenic substances in the Antarctic Ocean were investigated to construct a biogeochemical framework for assessing the Antarctic ecosystem. Phytoplankton exhibited particularly low δ 15N (0.5%) and 13C (-26.9%) values in pelagic plankton samples. High nitrate concentrations, and high PCO 2 in the surface waters on the southern side of the polar front and the resulting slow growth rate of phytoplankton under low light intensity are suggested as possible factors in causing the low isotopic compositions. Mean fractionation factors of 1.029 and 1.006 were estimated for photosynthetic carbon fixation and for the assimilation of inorganic nitrogeneous compounds (ammonium plus nitrate) during algal growth, respectively. Enrichment of 15N with increasing trophic level was confirmed for Antarctic ecosystems: δ15N animal% = 3.3 (trophic level -1) + δ5N algae, whereas 13C content did not increase in the same manner. Differences in lipid content among animals may be the main factor in causing this δ 13C anomaly. 15N and 13C abundance of sedimentary organic nitrogen differed from phytoplankton and settling particles. An exact mechanism for explaining the high δ 15N (around 5%) is not known. The very high δ 13C value of -20.5% at Sta. 3B may originate in ice algae that had grown under CO 2-limited conditions. Particles collected by sediment traps gave characteristically low δ 15N values (-3.0 to 0.9%), strongly suggesting a phytoplankton origin. The δ 15N and δ 13C values of settling material showed similar vertical profiles with depth which might arise from temporal variation of algal growth.

Detection of (C-13)-ethane in Jupiter's atmosphere

NASA Technical Reports Server (NTRS)

Wiedemann, Guenter; Bjoraker, Gordon L.; Jennings, Donald E.

1991-01-01

High-resolution (C-12)- and (C-13)-ethane spectra of Jupiter were acquired with the Kitt Peak 4 m Fourier spectrometer and the Goddard postdisperser in June 1987. A relative abundance ratio (C-12/C-13) of 94 +/- 12 was derived from the measurements. This nearly terrestrial value indicates little or no fractionation of carbon isotopes when ethane is produced in the photolysis of methane in Jupiter's atmosphere.

Optimized slice-selective 1H NMR experiments combined with highly accurate quantitative 13C NMR using an internal reference method.

PubMed

Jézéquel, Tangi; Silvestre, Virginie; Dinis, Katy; Giraudeau, Patrick; Akoka, Serge

2018-04-01

Isotope ratio monitoring by 13 C NMR spectrometry (irm- 13 C NMR) provides the complete 13 C intramolecular position-specific composition at natural abundance. It represents a powerful tool to track the (bio)chemical pathway which has led to the synthesis of targeted molecules, since it allows Position-specific Isotope Analysis (PSIA). Due to the very small composition range (which represents the range of variation of the isotopic composition of a given nuclei) of 13 C natural abundance values (50‰), irm- 13 C NMR requires a 1‰ accuracy and thus highly quantitative analysis by 13 C NMR. Until now, the conventional strategy to determine the position-specific abundance x i relies on the combination of irm-MS (isotopic ratio monitoring Mass Spectrometry) and 13 C quantitative NMR. However this approach presents a serious drawback since it relies on two different techniques and requires to measure separately the signal of all the carbons of the analyzed compound, which is not always possible. To circumvent this constraint, we recently proposed a new methodology to perform 13 C isotopic analysis using an internal reference method and relying on NMR only. The method combines a highly quantitative 1 H NMR pulse sequence (named DWET) with a 13 C isotopic NMR measurement. However, the recently published DWET sequence is unsuited for samples with short T 1 , which forms a serious limitation for irm- 13 C NMR experiments where a relaxing agent is added. In this context, we suggest two variants of the DWET called Multi-WET and Profiled-WET, developed and optimized to reach the same accuracy of 1‰ with a better immunity towards T 1 variations. Their performance is evaluated on the determination of the 13 C isotopic profile of vanillin. Both pulse sequences show a 1‰ accuracy with an increased robustness to pulse miscalibrations compared to the initial DWET method. This constitutes a major advance in the context of irm- 13 C NMR since it is now possible to perform

Optimized slice-selective 1H NMR experiments combined with highly accurate quantitative 13C NMR using an internal reference method

NASA Astrophysics Data System (ADS)

Jézéquel, Tangi; Silvestre, Virginie; Dinis, Katy; Giraudeau, Patrick; Akoka, Serge

2018-04-01

Isotope ratio monitoring by 13C NMR spectrometry (irm-13C NMR) provides the complete 13C intramolecular position-specific composition at natural abundance. It represents a powerful tool to track the (bio)chemical pathway which has led to the synthesis of targeted molecules, since it allows Position-specific Isotope Analysis (PSIA). Due to the very small composition range (which represents the range of variation of the isotopic composition of a given nuclei) of 13C natural abundance values (50‰), irm-13C NMR requires a 1‰ accuracy and thus highly quantitative analysis by 13C NMR. Until now, the conventional strategy to determine the position-specific abundance xi relies on the combination of irm-MS (isotopic ratio monitoring Mass Spectrometry) and 13C quantitative NMR. However this approach presents a serious drawback since it relies on two different techniques and requires to measure separately the signal of all the carbons of the analyzed compound, which is not always possible. To circumvent this constraint, we recently proposed a new methodology to perform 13C isotopic analysis using an internal reference method and relying on NMR only. The method combines a highly quantitative 1H NMR pulse sequence (named DWET) with a 13C isotopic NMR measurement. However, the recently published DWET sequence is unsuited for samples with short T1, which forms a serious limitation for irm-13C NMR experiments where a relaxing agent is added. In this context, we suggest two variants of the DWET called Multi-WET and Profiled-WET, developed and optimized to reach the same accuracy of 1‰ with a better immunity towards T1 variations. Their performance is evaluated on the determination of the 13C isotopic profile of vanillin. Both pulse sequences show a 1‰ accuracy with an increased robustness to pulse miscalibrations compared to the initial DWET method. This constitutes a major advance in the context of irm-13C NMR since it is now possible to perform isotopic analysis with high

Identification of natural metabolites in mixture: a pattern recognition strategy based on (13)C NMR.

PubMed

Hubert, Jane; Nuzillard, Jean-Marc; Purson, Sylvain; Hamzaoui, Mahmoud; Borie, Nicolas; Reynaud, Romain; Renault, Jean-Hugues

2014-03-18

Because of their highly complex metabolite profile, the chemical characterization of bioactive natural extracts usually requires time-consuming multistep purification procedures to achieve the structural elucidation of pure individual metabolites. The aim of the present work was to develop a dereplication strategy for the identification of natural metabolites directly within mixtures. Exploiting the polarity range of metabolites, the principle was to rapidly fractionate a multigram quantity of a crude extract by centrifugal partition extraction (CPE). The obtained fractions of simplified chemical composition were subsequently analyzed by (13)C NMR. After automatic collection and alignment of (13)C signals across spectra, hierarchical clustering analysis (HCA) was performed for pattern recognition. As a result, strong correlations between (13)C signals of a single structure within the mixtures of the fraction series were visualized as chemical shift clusters. Each cluster was finally assigned to a molecular structure with the help of a locally built (13)C NMR chemical shift database. The proof of principle of this strategy was achieved on a simple model mixture of commercially available plant secondary metabolites and then applied to a bark extract of the African tree Anogeissus leiocarpus Guill. & Perr. (Combretaceae). Starting from 5 g of this genuine extract, the fraction series was generated by CPE in only 95 min. (13)C NMR analyses of all fractions followed by pattern recognition of (13)C chemical shifts resulted in the unambiguous identification of seven major compounds, namely, sericoside, trachelosperogenin E, ellagic acid, an epimer mixture of (+)-gallocatechin and (-)-epigallocatechin, 3,3'-di-O-methylellagic acid 4'-O-xylopyranoside, and 3,4,3'-tri-O-methylflavellagic acid 4'-O-glucopyranoside.

Isotopically Enriched C-13 Diamond Anvil as a Stress Sensor in High Pressure Experiments

NASA Astrophysics Data System (ADS)

Vohra, Yogesh; Qiu, Wei; Kondratyev, Andreiy; Velisavljevic, Nenad; Baker, Paul

2004-03-01

The conventional high pressure diamond anvils were modified by growing an isotopically pure C-13 diamond layer by microwave plasma chemical vapor deposition using methane/hydrogen/oxygen chemistry. The isotopically pure C-13 nature of the culet of the diamond anvil was confirmed by the Raman spectroscopy measurements. This isotopically engineered diamond anvil was used against a natural abundance diamond anvil for high pressure experiments in a diamond anvil cell. Spatial resolved Raman spectroscopy was used to measure the stress induced shift in the C-13 layer as well as the undelying C-12 layer to ultra high pressures. The observed shift and splitiing of the diamond first order Raman spectrum was correlated with the stress distribution in the diamond anvil cell. The experimental results will be compared with the finite element modeling results using NIKE-2D software in order to create a mathematical relationship between sets of the following parameters: vertical (z axis) distance; horizontal (r axis) distance; max shear stress, and pressure. The isotopically enriched diamond anvils offer unique opportunities to measure stress distribution in the diamond anvil cell devices.

The 12C/13C Isotopic Ratio in Planetary Nebulae as Deduced from IUE Data

NASA Astrophysics Data System (ADS)

Miskey, C. L.; Feibelman, W. A.; Bruhweiler, F. C.

2000-05-01

The relative abundances of C, N, and O and the isotopic ratio of 12C/13C represent tracers of nucleosynthesis in intermediate stars with main-sequence masses between 0.6 and 8.0 solar masses in our Galaxy. Determining these abundances and the isotopic 12C/13C ratio in planetary nebulae (PNe) represent perhaps the best means to discern exactly how the ISM is enriched by CNO stellar nucleosynthesis. Walsh et al. (1996) and Clegg et al. (1997), using the Hubble Space Telescope, have derived the isotopic 12C/13C abundance ratio in the galactic carbon-rich PN, NGC 3918, and placed marginal constraints on it for the Magellanic PNe, N2 (SMC) and N122 (LMC). This was done using the well-known 12C 3P-1S (J=1-0 and J=2-0) transitions of C+2 at 1906.68 Angstroms and 1908.77 Angstroms and a J=0-0 transition at 1909.6 Angstroms, which is strictly forbidden in 12C. The finite nuclear spin of 13C (I=1/2) permits a corresponding F=1/2-1/2 electric dipole transition not seen in 12C. Since the 1909.6 Angstroms line is well separated from the other two 12C transitions, it provides an important means of determining 12C/13C in planetary nebulae. We have just completed a search of archival International Ultraviolet Explorer (IUE) high-dispersion spectra of approximately three dozen PNe, and derived 12C/13C ratios of 39 and 23 for the galactic PNe, NGC 2440 and NGC 6302, respectively. These are values much lower than the solar value of 89. In the other objects, the limited S/N of the IUE data indicate 12C/13C ratio upper limits much higher than 50. The implications of these results and their pertinence to stellar evolution are discussed.

Measurement of δ13C values of soil amino acids by GC-C-IRMS using trimethylsilylation: a critical assessment.

PubMed

Rubino, Mauro; Milin, Sylvie; D'Onofrio, Antonio; Signoret, Patrick; Hatté, Christine; Balesdent, Jérôme

2014-01-01

In this study, we evaluated trimethylsilyl (TMS) derivatives as derivatization reagents for the compound-specific stable carbon isotope analysis of soil amino acids by gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). We used non-proteinogenic amino acids to show that the extraction-derivatization-analysis procedure provides a reliable method to measure δ(13)C values of amino acids extracted from soil. However, we found a number of drawbacks that significantly increase the final total uncertainty. These include the following: production of multiple peaks for each amino acid, identified as di-, tri- and tetra-TMS derivatives; a number of TMS-carbon (TMS-C) atoms added lower than the stoichiometric one, possibly due to incomplete combustion; different TMS-C δ(13)C for di-, tri- and tetra-TMS derivatives. For soil samples, only four amino acids (leucine, valine, threonine and serine) provide reliable δ(13)C values with a total average uncertainty of 1.3 ‰. We conclude that trimethylsilyl derivatives are only suitable for determining the (13)C incorporation in amino acids within experiments using (13)C-labelled tracers but cannot be applied for amino acids with natural carbon isotope abundance until the drawbacks described here are overcome and the measured total uncertainty significantly decreased.

Priming of Soil Carbon Decomposition in Two Inner Mongolia Grassland Soils following Sheep Dung Addition: A Study Using 13C Natural Abundance Approach

PubMed Central

Ma, Xiuzhi; Ambus, Per; Wang, Shiping; Wang, Yanfen; Wang, Chengjie

2013-01-01

To investigate the effect of sheep dung on soil carbon (C) sequestration, a 152 days incubation experiment was conducted with soils from two different Inner Mongolian grasslands, i.e. a Leymus chinensis dominated grassland representing the climax community (2.1% organic matter content) and a heavily degraded Artemisia frigida dominated community (1.3% organic matter content). Dung was collected from sheep either fed on L. chinensis (C3 plant with δ13C = −26.8‰; dung δ13C = −26.2‰) or Cleistogenes squarrosa (C4 plant with δ13C = −14.6‰; dung δ13C = −15.7‰). Fresh C3 and C4 sheep dung was mixed with the two grassland soils and incubated under controlled conditions for analysis of 13C-CO2 emissions. Soil samples were taken at days 17, 43, 86, 127 and 152 after sheep dung addition to detect the δ13C signal in soil and dung components. Analysis revealed that 16.9% and 16.6% of the sheep dung C had decomposed, of which 3.5% and 2.8% was sequestrated in the soils of L. chinensis and A. frigida grasslands, respectively, while the remaining decomposed sheep dung was emitted as CO2. The cumulative amounts of C respired from dung treated soils during 152 days were 7–8 times higher than in the un-amended controls. In both grassland soils, ca. 60% of the evolved CO2 originated from the decomposing sheep dung and 40% from the native soil C. Priming effects of soil C decomposition were observed in both soils, i.e. 1.4 g and 1.6 g additional soil C kg−1 dry soil had been emitted as CO2 for the L. chinensis and A. frigida soils, respectively. Hence, the net C losses from L. chinensis and A. frigida soils were 0.6 g and 0.9 g C kg−1 soil, which was 2.6% and 7.0% of the total C in L. chinensis and A. frigida grasslands soils, respectively. Our results suggest that grazing of degraded Inner Mongolian pastures may cause a net soil C loss due to the positive priming effect, thereby accelerating soil deterioration. PMID:24236024

Abundance Profiles for C3 Hydrocarbons in Titan's Atmosphere

NASA Astrophysics Data System (ADS)

Lombardo, Nicholas; Nixon, Conor A.; Achterberg, Richard; Jolly, Antoine; Sung, Keeyoon; Irwin, Patrick; Flasar, F. Michael

2017-10-01

The atmosphere of Titan is of astrobiological importance. Its highly reducing composition and prebiotic chemistry make it analogous to that of the early Earth. Since the Voyager era, several complex hydrocarbons and nitriles have been detected, in some cases making Titan the only known planetary body where these gasses occur naturally. In this work, we report abundance profiles of four major C3 gasses expected to occur in Titan’s atmosphere, derived from Cassini/Composite Infrared Spectrometer (CIRS) data.Using the NEMESIS iterative radiative transfer module, we retrieved vertical abundance profiles for propane (C3H8) and propyne (CHCCH3), both initially detected by the Voyager IRIS instrument. Using newly available line data, we were also able to determine the first vertical abundance profiles for propene (C3H6), initially detected in 2013. We present profiles for several latitudes and times and compare to photochemical model predictions and previous observations. We also discuss our efforts to further the search for allene (CH2CCH2), an isomer of propyne. The abundances we retrieved will help to further our understanding of the chemical pathways that occur in Titan's atmosphere.

The relative isotopic abundance (δ13C, δ15N) during composting of agricultural wastes in relation to compost quality and feedstock.

PubMed

Inácio, Caio T; Magalhães, Alberto M T; Souza, Paulo O; Chalk, Phillip M; Urquiaga, Segundo

2018-05-01

Variations in the relative isotopic abundance of C and N (δ 13 C and δ 15 N) were measured during the composting of different agricultural wastes using bench-scale bioreactors. Different mixtures of agricultural wastes (horse bedding manure + legume residues; dairy manure + jatropha mill cake; dairy manure + sugarcane residues; dairy manure alone) were used for aerobic-thermophilic composting. No significant differences were found between the δ 13 C values of the feedstock and the final compost, except for dairy manure + sugarcane residues (from initial ratio of -13.6 ± 0.2 ‰ to final ratio of -14.4 ± 0.2 ‰). δ 15 N values increased significantly in composts of horse bedding manure + legumes residues (from initial ratio of +5.9 ± 0.1 ‰ to final ratio of +8.2 ± 0.5 ‰) and dairy manure + jatropha mill cake (from initial ratio of +9.5 ± 0.2 ‰ to final ratio of +12.8 ± 0.7 ‰) and was related to the total N loss (mass balance). δ 13 C can be used to differentiate composts from different feedstock (e.g. C 3 or C 4 sources). The quantitative relationship between N loss and δ 15 N variation should be determined.

Structure of thin diamond films: A 1H and 13C nuclear-magnetic-resonance study

NASA Astrophysics Data System (ADS)

Pruski, M.; Lang, D. P.; Hwang, Son-Jong; Jia, H.; Shinar, J.

1994-04-01

The 1H and 13C nuclear magnetic resonance (NMR) of thin diamond films deposited from naturally abundant (1.1 at. %) as well as 50% and 100% 13enriched CH4 heavily diluted in H2 is described and discussed. Less than 0.6 at. % of hydrogen is found in the films which contain crystallites up to ~15 μm across. The 1H NMR consists of a broad 50-65-kHz-wide Gaussian line attributed to H atoms bonded to carbon and covering the crystallite surfaces. A narrow Lorentzian line was only occasionally observed and is found not to be intrinsic to the diamond structure. The 13C NMR demonstrates that >99.5% of the C atoms reside in a quaternary diamondlike configuration. 1-13C cross-polarization measurement indicates that, at the very least, the majority of 13C nuclei cross polarized by 1H, i.e., within three bond distances from a 1H at a crystallite surface, reside in sp3 diamondlike coordinated sites. The 13C relaxation rates of the films are four orders of magnitude faster than that of natural diamond and believed to be due to 13C spin diffusion to paramagnetic centers, presumably carbon dangling bonds. Analysis of the measured relaxation rates indicates that within the 13C spin-diffusion length of √DTc1 ~0.05 μm, these centers are uniformly distributed in the diamond crystallites. The possibility that the dangling bonds are located at internal nanovoid surfaces is discussed.

The 13C-Pocket Structure In AGB Models: Constraints From Zirconium Isotope Abundances In Single Mainstream SiC Grains

DOE PAGES

Liu, Nan; Gallino, Roberto; Bisterzo, Sara; ...

2014-06-04

In this paper, we present postprocess asymptotic giant branch (AGB) nucleosynthesis models with different 13C-pocket internal structures to better explain zirconium isotope measurements in mainstream presolar SiC grains by Nicolussi et al. and Barzyk et al. We show that higher-than-solar 92Zr/ 94Zr ratios can be predicted by adopting a 13C-pocket with a flat 13C profile, instead of the previous decreasing-with-depth 13C profile. Finally, the improved agreement between grain data for zirconium isotopes and AGB models provides additional support for a recent proposal of a flat 13C profile based on barium isotopes in mainstream SiC grains by Liu et al.

(13)C-Breath testing in animals: theory, applications, and future directions.

PubMed

McCue, Marshall D; Welch, Kenneth C

2016-04-01

The carbon isotope values in the exhaled breath of an animal mirror the carbon isotope values of the metabolic fuels being oxidized. The measurement of stable carbon isotopes in carbon dioxide is called (13)C-breath testing and offers a minimally invasive method to study substrate oxidation in vivo. (13)C-breath testing has been broadly used to study human exercise, nutrition, and pathologies since the 1970s. Owing to reduced use of radioactive isotopes and the increased convenience and affordability of (13)C-analyzers, the past decade has witnessed a sharp increase in the use of breath testing throughout comparative physiology--especially to answer questions about how and when animals oxidize particular nutrients. Here, we review the practical aspects of (13)C-breath testing and identify the strengths and weaknesses of different methodological approaches including the use of natural abundance versus artificially-enriched (13)C tracers. We critically compare the information that can be obtained using different experimental protocols such as diet-switching versus fuel-switching. We also discuss several factors that should be considered when designing breath testing experiments including extrinsic versus intrinsic (13)C-labelling and different approaches to model nutrient oxidation. We use case studies to highlight the myriad applications of (13)C-breath testing in basic and clinical human studies as well as comparative studies of fuel use, energetics, and carbon turnover in multiple vertebrate and invertebrate groups. Lastly, we call for increased and rigorous use of (13)C-breath testing to explore a variety of new research areas and potentially answer long standing questions related to thermobiology, locomotion, and nutrition.

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

PubMed Central

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

2008-01-01

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

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

Soil Carbon-Fixation Rates and Associated Bacterial Diversity and Abundance in Three Natural Ecosystems.

PubMed

Lynn, Tin Mar; Ge, Tida; Yuan, Hongzhao; Wei, Xiaomeng; Wu, Xiaohong; Xiao, Keqing; Kumaresan, Deepak; Yu, San San; Wu, Jinshui; Whiteley, Andrew S

2017-04-01

CO 2 assimilation by autotrophic microbes is an important process in soil carbon cycling, and our understanding of the community composition of autotrophs in natural soils and their role in carbon sequestration of these soils is still limited. Here, we investigated the autotrophic C incorporation in soils from three natural ecosystems, i.e., wetland (WL), grassland (GR), and forest (FO) based on the incorporation of labeled C into the microbial biomass. Microbial assimilation of 14 C ( 14 C-MBC) differed among the soils from three ecosystems, accounting for 14.2-20.2% of 14 C-labeled soil organic carbon ( 14 C-SOC). We observed a positive correlation between the cbbL (ribulose-1,5-bisphosphate carboxylase/oxygenase (RubisCO) large-subunit gene) abundance, 14 C-SOC level, and 14 C-MBC concentration confirming the role of autotrophic bacteria in soil carbon sequestration. Distinct cbbL-bearing bacterial communities were present in each soil type; form IA and form IC RubisCO-bearing bacteria were most abundant in WL, followed by GR soils, with sequences from FO soils exclusively derived from the form IC clade. Phylogenetically, the diversity of CO 2 -fixing autotrophs and CO oxidizers differed significantly with soil type, whereas cbbL-bearing bacterial communities were similar when assessed using coxL. We demonstrate that local edaphic factors such as pH and salinity affect the C-fixation rate as well as cbbL and coxL gene abundance and diversity. Such insights into the effect of soil type on the autotrophic bacterial capacity and subsequent carbon cycling of natural ecosystems will provide information to enhance the sustainable management of these important natural ecosystems.

Theoretical estimates of equilibrium 13C-18O clumping in carbonates and organic acids

NASA Astrophysics Data System (ADS)

Schauble, E. A.; Eiler, J. M.

2004-12-01

The development of techniques for measuring small gas-phase molecules containing more than one rare stable isotope (e.g., 13C18O16O) at natural, ppm-level abundances1,2 has made it possible to track sources and sinks of atmospheric gases from a new perspective. Similar measurements of 13C-18O clumping in ancient samples could improve our understanding of ancient climates, if the abundances of `clumped' rare stable isotopes in materials that retain isotopic signatures over geologic time can be measured with sufficient precision. This theoretical study estimates the abundances of such 13C-18O `clumps' in carbonates and organic acids and discusses their potential applications. Accompanying abstracts by Eiler et al. and Ghosh et al. will present the analytical methods and some initial data for carbonate minerals to examine the applicability of our theoretical models. Equilibrium isotopic speciations in carbonate minerals and organic acids are calculated from the reduced partition function ratios of isotopically substituted crystals and molecules. Vibrational frequencies used as input for these calculations come from ab initio force fields, determined using density functional theory. Our calculations indicate that carbonate minerals, including calcite, dolomite, and aragonite, when equilibrated at earth-surface temperatures, will have a slight overabundance of CO32- groups containing both 13C and 18O (i.e., 13C18O16O22-) relative to what would be expected if carbon and oxygen isotopes were distributed randomly in the crystal lattice. Calcite and dolomite crystals are predicted to have 0.4‰ excesses of 13C18O16O22- at 298 K; in aragonite the excess will be about 0.05‰ larger. The excesses are smaller for crystals formed or equilibrated at higher temperatures, decreasing by 0.003\\permil/oC at room temperature and essentially disappearing at temperatures of 1000 K or higher. Similarly, there is an excess of both 13C18O16OH and 13C16O18OH groups in organic acids like

Early-stage changes in natural (13)C and (15)N abundance and nutrient dynamics during different litter decomposition.

PubMed

Gautam, Mukesh Kumar; Lee, Kwang-Sik; Song, Byeong-Yeol; Lee, Dongho; Bong, Yeon-Sik

2016-05-01

Decomposition, nutrient, and isotopic (δ(13)C and δ(15)N) dynamics during 1 year were studied for leaf and twig litters of Pinus densiflora, Castanea crenata, Erigeron annuus, and Miscanthus sinensis growing on a highly weathered soil with constrained nutrient supply using litterbags in a cool temperate region of South Korea. Decay constant (k/year) ranged from 0.58 to 1.29/year, and mass loss ranged from 22.36 to 58.43 % among litter types. The results demonstrate that mass loss and nutrient dynamics of decomposing litter were influenced by the seasonality of mineralization and immobilization processes. In general, most nutrients exhibited alternate phases of rapid mineralization followed by gradual immobilization, except K, which was released throughout the field incubation. At the end of study, among all the nutrients only N and P showed net immobilization. Mobility of different nutrients from decomposing litter as the percentage of initial litter nutrient concentration was in the order of K > Mg > Ca > N ≈ P. The δ(13)C (0.32-6.70 ‰) and δ(15)N (0.74-3.90 ‰) values of residual litters showed nonlinear increase and decrease, respectively compared to initial isotopic values during decomposition. Litter of different functional types and chemical quality converged toward a conservative nutrient use strategy through mechanisms of slow decomposition and slow nutrient mobilization. Our results indicate that litter quality and season, are the most important regulators of litter decomposition in these forests. The results revealed significant relationships between litter decomposition rates and N, C:N ratio and P, and seasonality (temperature). These results and the convergence of different litters towards conservative nutrient use in these nutrient constrained ecosystems imply optimization of litter management because litter removal can have cascading effects on litter decomposition and nutrient availability in these systems.

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

PubMed

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

2017-01-01

The 13 C-urea breath test ( 13 C-UBT), developed a few decades ago, is widely used as a non-invasive diagnostic method to detect only the presence of the gastric pathogen Helicobacter pylori infection; however, the actual disease state, i.e. whether the person harbouring H. pylori has peptic ulcer disease (PUD) or non-ulcerous dyspepsia (NUD), is still poorly understood. Nevertheless, the present 13 C-UBT has numerous limitations, drawbacks and pitfalls owing to the ingestion of 13 C-labelled external urea. Here, we show that H. pylori is able to utilize the natural 13 C and 18 O-urea inherently present in the gastric juice in humans for its urease activity which has never been explored before. In vitro measurements of isotopic fractionations of gastric juice urea provide new insights into the actual state of the infection of PUD or NUD. We also provide evidence of the unusual 13 C and 18 O-isotopic fractionations of breath CO 2 that are distinctively altered in individuals with PUD encompassing both gastric and duodenal ulcers as well as with NUD by the enzymatic activity of H. pylori in the gastric niche without oral administration of any 13 C-enriched external urea. This deepens our understanding of the UBT exploiting the natural 13 C and 18 O-gastric juice urea in the pathogenesis of H. pylori infection, reveals the actual disease state of PUD or NUD and thus offers novel opportunities for a simple, robust, cost-effective and non-toxic global strategy devoid of any 13 C-enriched urea for treating these common diseases by a single breath test. Graphical Abstract Urea breath test without any external urea.

Transport of 13C-oleate in adipocytes measured using multi imaging mass spectrometry.

PubMed

Kleinfeld, Alan M; Kampf, J Patrick; Lechene, Claude

2004-11-01

The mechanism of long chain free fatty acid (FFA) transport across cell membranes is under active investigation. Here we describe the use of multi imaging mass spectrometry (MIMS) to monitor intracellular concentrations of FFA and provide new insight into FFA transport in cultured adipocytes. Cells were incubated with 13C-oleate:BSA and either dried directly or dried after washing with a medium deprived of 13C-oleate:BSA. Cells were analyzed with MIMS using a scanning primary Cs+ ion beam and 12C-, 13C-, 12C14N-, 13C14N-) (or 12C 15N-) were imaged simultaneously. From these quantitative images the values of the 13C/ 12C ratios were determined in the intracellular lipid droplets, in the cytoplasm and outside the 3T3F442A adipocytes. The results indicate that after incubation with 13C-oleate:BSA the droplet 13C/ 12C ratio was 15 +/- 6%. This value is about 14-fold higher than the 13C/ 12C terrestrial ratio (1.12%). After washing the 13C-oleate:BSA, the droplet 13C/ 12C ratios decreased to 1.6 +/- 0.1%, about 40% greater than the natural abundance. Results for washed cells indicate that relatively little FFA was esterified. The unwashed cell results, together with the value of the lipid water partition coefficient, reveal that intracellular unbound FFA (FFAu) concentrations were on average about 4.5-fold greater than the extracellular FFAu concentrations. These results are consistent with the possibility that FFA may be pumped into adipocytes against their electro-chemical potential. This work demonstrates that MIMS can be used to image and quantitate stable isotope labeled fatty acid in intracellular lipid droplets.

[Humus composition and stable carbon isotope natural abundance in paddy soil under long-term fertilization].

PubMed

Ma, Li; Yang, Lin-Zhang; Ci, En; Wang, Yan; Yin, Shi-Xue; Shen, Ming-Xing

2008-09-01

Soil samples were collected from an experimental paddy field with long-term (26 years) fertilization in Taihu Lake region of Jiangsu Province to study the effects of different fertilization on the organic carbon distribution and stable carbon isotope natural abundance (delta 13C) in the soil profile, and on the humus composition. The results showed that long-term fertilization increased the organic carbon content in top soil significantly, and there was a significantly negative exponential correlation between soil organic carbon content and soil depth (P < 0.01). The organic carbon content in 10-30 cm soil layer under chemical fertilizations and in 20-40 cm soil layer under organic fertilizations was relatively stable. Soil delta 13C increased gradually with soil depth, its variation range being from -24% per thousand to -28 per thousand, and had a significantly negative linear correlation with soil organic carbon content (P < 0.05). In 0-20 cm soil layer, the delta 13C in treatments organic manure (M), M + NP, M + NPK, M + straw (R) + N, and R + N decreased significantly; while in 30-50 cm soil layer, the delta 13C in all organic fertilization treatments except R + N increased significantly. Tightly combined humus (humin) was the main humus composition in the soil, occupying 50% or more, and the rest were loosely and stably combined humus. Long-term fertilization increased the content of loosely combined humus and the ratio of humic acid (HA) to fulvic acid (FA).

Land use Effects on Storage, Stability and Structure of Organic Carbon in Soil Density Fractions Revealed by 13C Natural Abundance and CPMAS 13C NMR

NASA Astrophysics Data System (ADS)

Flessa, H.; Helfrich, M.; John, B.; Yamashita, T.; Ludwig, B.

2004-12-01

The type of land use and soil cultivation are important factors controlling organic carbon storage (SOC) in soils and they can also influence the relative importance, the structure, and the stability of different SOC pools. The objectives of our study were: i) to quantify the SOC stocks in different density fractions (mineral-associated soil organic matter > 2 g cm-3 (Mineral-SOM), free particulate organic matter < 1.6 g cm-3 (free POM), light occluded particulate organic matter < 1.6 g cm-3 (occluded POM<1.6) and dense occluded particulate organic matter 1.6 to 2.0 g cm-3 (occluded POM1.6-2.0)) of silty soils under different land use (spruce forest, grassland, maize, wheat), ii) to determine the structure of these SOC fractions by CPMAS 13C NMR spectroscopy, and iii) to analyse the stability of these SOC fractions in the maize soil on the basis of the stable isotope composition of SOC. The SOC concentration in the A horizon increased in the order wheat (12.7 g kg-1) < maize (13.0 g kg-1) < grassland (24.5 g kg-1) < spruce (40.5 g kg-1). The major part (86-91%) of the SOC was associated with the heavy mineral fraction at the grassland, maize and wheat site. In the A horizon of the spruce soil, the particulate organic matter accounted for 52% of the total SOC content. The chemical structure of the soil organic matter (SOM) was influenced by litter quality, the intensity of litter decomposition and the related production and storage of microbially-derived substances. SOM of the acid forest soil was characterized by large amounts of POM with a high content of spruce litter-derived alkyl C. In the biologically more active grassland and maize soil, litter-derived POM was decomposed more rapidly and SOC stocks were dominated by mineral-associated SOM which contained greater proportions of aryl and carbonyl C. The cultivation of the grassland soil induced enhanced mineralization of POM and in particular of mineral-associated SOM. The faster SOC turnover was associated

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

Natural Isotope Abundance in Metabolites: Techniques and Kinetic Isotope Effect Measurement in Plant, Animal, and Human Tissues.

PubMed

Tea, Illa; Tcherkez, Guillaume

2017-01-01

The natural isotope abundance in bulk organic matter or tissues is not a sufficient base to investigate physiological properties, biosynthetic mechanisms, and nutrition sources of biological systems. In fact, isotope effects in metabolism lead to a heterogeneous distribution of 2 H, 18 O, 13 C, and 15 N isotopes in metabolites. Therefore, compound-specific isotopic analysis (CSIA) is crucial to biological and medical applications of stable isotopes. Here, we review methods to implement CSIA for 15 N and 13 C from plant, animal, and human samples and discuss technical solutions that have been used for the conversion to CO 2 and N 2 for IRMS analysis, derivatization and isotope effect measurements. It appears that despite the flexibility of instruments used for CSIA, there is no universal method simply because the chemical nature of metabolites of interest varies considerably. Also, CSIA methods are often limited by isotope effects in sample preparation or the addition of atoms from the derivatizing reagents, and this implies that corrections must be made to calculate a proper δ-value. Therefore, CSIA has an enormous potential for biomedical applications, but its utilization requires precautions for its successful application. © 2017 Elsevier Inc. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

High Resolution Spectrum of the 13C12C12C Lowest Bending Mode

NASA Astrophysics Data System (ADS)

Endres, C. P.; Lutter, V.; Kötting, J.; Krieg, J.; Thorwirth, S.; Schlemmer, S.; Giesen, T. F.; Harding, M. E.; Vazquez, J.

2012-06-01

Linear C_3 is a floppy molecule which possesses an extremely low lying bending mode, ν_2, at roughly 60 cm-1 or 1.9 THz. Based on highly accurate laboratory data C_3 has been detected in various astronomical sources most recently with the HIFI instrument aboard the Herschel satellite. Although C_3 turns out to be quite abundant in interstellar environments which makes a search for 13C substituted isotopologs feasible, other isotopologs could not be detected so far, because no accurate transition frequencies have been available for these species in this frequency range. Relative abundance ratios of C_3 isotopologs might give important hints on its building mechanism and further constraints for chemical networks. In this work, the spectrum of the ν_2 lowest bending mode of 13CCC has been investigated. We used laser ablation of 13C enriched carbon samples to record absorption spectra in a supersonic jet expansion. The radiation in our setup is generated by a synthesizer referenced to a Rubidium standard in combination with a frequency multiplier chain and detected by a liquid Helium cooled InSb bolometer. The laboratory search has been supported by high-level coupled-cluster calculations, which turns out to compare very favorably with obtained experimental molecular parameters. Schmuttenmaer, C. A., Cohen, R. C., Pugliano, N., Heath, et al., Science 249, 897-900 (1990) Giesen, T. F., van Orden, A. O., Cruzan, J. D., and Provencal, R. A., et al., Astrophys. J. 551, L181-L184 (2001) Gendriesch, R. and Pehl, K. and Giesen, T. and Winnewisser, G. and Lewen, F., Z. Naturforsch. 58a, 129-138 (2003) Van Orden, A., Cruzan, J. D., Provencal, R. A., et al. in Proc. Airborne Astronomy Symp., ASP Conf. Ser. 73, 67 (1995) ernicharo, J. and Goicoechea, J. R. and Caux, E., Astrophys. J. Lett. 534, L199-L202 (2000) Mookerjea, B., Giesen, T., Stutzki, J., Cernicharo, J., et al., Astron. Astrophys. 521, L13 (2010)

δ13C Analysis of Dissolved Organic Carbon in Eastern Canadian Coastal Waters

NASA Astrophysics Data System (ADS)

Gelinas, Y.; Barber, A.

2016-12-01

The application of carbon stable isotope analysis on dissolved organic carbon (δ13C-DOC) from natural seawater samples has been limited owing to the difficulty of such analysis, with order of magnitude differences between interfering ions and analyte concentrations. High temperature catalytic oxidation allows for the separation of interferences from the organic carbon by precipitation on quartz chips upstream from the oxidation catalyst. Unlike wet chemical oxidation, where salts inhibit the oxidation of organic matter to CO2 via side reactions between the salt anions and the persulfate oxidizing agent, high temperature combustion ensures complete organic matter oxidation in a stream of O2. Using a programmable chemical trap to switch carrier gasses from O2 to He, the OI 1030C combustion unit can be coupled to and IRMS, allowing for the analysis of low DOC content saline waters with relatively high throughput. The analytical limitations and large water volumes traditionally required for these types of analyses have prevented any large-scale δ13C-DOC studies. Here we present DOC concentrations and δ13C-DOC signatures for surface and bottom waters obtained along Canada's East Coast. Included in the study are samples from the Esquiman channel (between Newfoundland and Labrador), Lake Melville, the Saglek and Nachvak Fjords, the Hudson Strait and finally covering the salinity gradient across the Gulf of the St. Lawrence, the St. Lawrence Estuary and the Saguenay Fjord. Measured δ13C-DOC signatures ranged from predominantly marine values of -21.3 ± 0.6 ‰ (vs. VPDB) off the coast of Newfoundland to predominantly terrestrial signatures of -25.8 ± 0.1‰ in Lake Melville. Overall, proper blank subtraction using the isotope mass balance equation and four replicate injections are crucial for the collection of meaningful high quality δ13C-DOC signatures on natural abundance, seawater samples.

Natural Abundance 15 N and 13 C Solid-State NMR Chemical Shifts: High Sensitivity Probes of the Halogen Bond Geometry.

PubMed

Cerreia Vioglio, Paolo; Catalano, Luca; Vasylyeva, Vera; Nervi, Carlo; Chierotti, Michele R; Resnati, Giuseppe; Gobetto, Roberto; Metrangolo, Pierangelo

2016-11-14

Solid-state nuclear magnetic resonance (SSNMR) spectroscopy is a versatile characterization technique that can provide a plethora of information complementary to single crystal X-ray diffraction (SCXRD) analysis. Herein, we present an experimental and computational investigation of the relationship between the geometry of a halogen bond (XB) and the SSNMR chemical shifts of the non-quadrupolar nuclei either directly involved in the interaction ( 15 N) or covalently bonded to the halogen atom ( 13 C). We have prepared two series of X-bonded co-crystals based upon two different dipyridyl modules, and several halobenzenes and diiodoalkanes, as XB-donors. SCXRD structures of three novel co-crystals between 1,2-bis(4-pyridyl)ethane, and 1,4-diiodobenzene, 1,6-diiodododecafluorohexane, and 1,8-diiodohexadecafluorooctane were obtained. For the first time, the change in the 15 N SSNMR chemical shifts upon XB formation is shown to experimentally correlate with the normalized distance parameter of the XB. The same overall trend is confirmed by density functional theory (DFT) calculations of the chemical shifts. 13 C NQS experiments show a positive, linear correlation between the chemical shifts and the C-I elongation, which is an indirect probe of the strength of the XB. These correlations can be of general utility to estimate the strength of the XB occurring in diverse adducts by using affordable SSNMR analysis. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Two new organic reference materials for δ13C and δ15N measurements and a new value for the δ13C of NBS 22 oil

USGS Publications Warehouse

Qi, Haiping; Coplen, Tyler B.; Geilmann, Heike; Brand, Willi A.; Böhlke, J.K.

2003-01-01

Analytical grade L-glutamic acid is chemically stable and has a C/N mole ratio of 5, which is close to that of many of natural biological materials, such as blood and animal tissue. Two L-glutamic acid reference materials with substantially different 13C and 15N abundances have been prepared for use as organic reference materials for C and N isotopic measurements. USGS40 is analytical grade L-glutamic acid and has a δ13C value of −26.24‰ relative to VPDB and a δ15N value of −4.52‰ relative to N2 in air. USGS41 was prepared by dissolving analytical grade L-glutamic acid with L-glutamic acid enriched in 13C and 15N. USGS41 has a δ13C value of +37.76‰ and a δ15N value of +47.57‰. The δ13C and δ15N values of both materials were measured against the international reference materials NBS 19 calcium carbonate (δ13C = +1.95‰), L-SVEC lithium carbonate (δ13C = −46.48‰), IAEA-N-1 ammonium sulfate (δ15N = 0.43‰), and USGS32 potassium nitrate (δ15N = 180‰) by on-line combustion continuous-flow and off-line dual-inlet isotope-ratio mass spectrometry. Both USGS40 and USGS41 are isotopically homogeneous; reproducibility of δ13C is better than 0.13‰, and that of δ15N is better than 0.13‰ in 100-μg amounts. These two isotopic reference materials can be used for (i) calibrating local laboratory reference materials, and (ii) quantifying drift with time, mass-dependent fractionations, and isotope-ratio-scale contraction in the isotopic analysis of various biological materials. Isotopic results presented in this paper yield a δ13C value for NBS 22 oil of −29.91‰, in contrast to the commonly accepted value of −29.78‰ for which off-line blank corrections probably have not been quantified satisfactorily.

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

NASA Astrophysics Data System (ADS)

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

2007-12-01

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

Measuring 13 C-enriched CO2 in air with a cavity ring-down spectroscopy gas analyser: Evaluation and calibration.

PubMed

Dickinson, Dane; Bodé, Samuel; Boeckx, Pascal

2017-11-30

Cavity ring-down spectroscopy (CRDS) is becoming increasingly popular for δ 13 C-CO 2 analysis of air. However, little is known about the effect of high 13 C abundances on the performance of CRDS. Overlap between 12 CO 2 and 13 CO 2 spectral lines may adversely affect isotopic-CO 2 CRDS measurements of 13 C-enriched samples. Resolving this issue is important so that CRDS analysers can be used in CO 2 flux studies involving 13 C-labelled tracers. We tested a Picarro G2131-i CRDS isotopic-CO 2 gas analyser with specialty gravimetric standards of widely varying 13 C abundance (from natural to 20.1 atom%) and CO 2 mole fraction (xCO 2 : <0.1 to 2116 ppm) in synthetic air. The presence of spectroscopic interference between 12 CO 2 and 13 CO 2 bands was assessed by analysing errors in measurements of the standards. A multi-component calibration strategy was adopted, incorporating isotope ratio and mole fraction data to ensure accuracy and consistency in corrected values of δ 13 C-CO 2 , x 12 CO 2 , and x 13 CO 2 . CRDS measurements of x 13 CO 2 were found to be accurate throughout the tested range (<0.005 to 100 ppm). On the other hand, spectral cross-talk in x 12 CO 2 measurements of standards containing elevated levels of 13 CO 2 led to inaccuracy in x 12 CO 2 , total-xCO 2 (x 12 CO 2  + x 13 CO 2 ), and δ 13 C-CO 2 data. An empirical relationship for x 12 CO 2 measurements that incorporated the 13 C/ 12 C isotope ratio (i.e. 13 CO 2 / 12 CO 2 , RCO2) as a secondary (non-linear) variable was found to compensate for the perturbations, and enabled accurate instrument calibration for all CO 2 compositions covered by our standard gases. 13 C-enrichement in CO 2 leads to minor errors in CRDS measurements of x 12 CO 2 . We propose an empirical correction for measurements of 13 C-enriched CO 2 in air by CRDS instruments such as the Picarro G2131-i. Copyright © 2017 John Wiley & Sons, Ltd.

Directly detected 55Mn MRI: Application to phantoms for human hyperpolarized 13C MRI development

PubMed Central

von Morze, Cornelius; Carvajal, Lucas; Reed, Galen D.; Swisher, Christine Leon; Tropp, James; Vigneron, Daniel B.

2014-01-01

In this work we demonstrate for the first time directly detected manganese-55 (55Mn) MRI using a clinical 3T MRI scanner designed for human hyperpolarized 13C clinical studies with no additional hardware modifications. Due to the similar frequency of the 55Mn and 13C resonances, the use of aqueous permanganate for large, signal-dense, and cost-effective “13C” MRI phantoms was investigated, addressing the clear need for new phantoms for these studies. Due to 100% natural abundance, higher intrinsic sensitivity, and favorable relaxation properties, 55Mn MRI of aqueous permanganate demonstrates dramatically increased sensitivity over typical 13C phantom MRI, at greatly reduced cost as compared with large 13C-enriched phantoms. A large sensitivity advantage (22-fold) was demonstrated. A cylindrical phantom (d= 8 cm) containing concentrated aqueous sodium permanganate (2.7M) was scanned rapidly by 55Mn MRI in a human head coil tuned for 13C, using a balanced SSFP acquisition. The requisite penetration of RF magnetic fields into concentrated permanganate was investigated by experiments and high frequency electromagnetic simulations, and found to be sufficient for 55Mn MRI with reasonably sized phantoms. A sub-second slice-selective acquisition yielded mean image SNR of ~60 at 0.5cm3 spatial resolution, distributed with minimum central signal ~40% of the maximum edge signal. We anticipate that permanganate phantoms will be very useful for testing HP 13C coils and methods designed for human studies. PMID:25179135

Determining the Local Abundance of Martian Methane and its 13-C/l2-C and D/H Isotopic Ratios for Comparison with Related Gas and Soil Analysis on the 2011 Mars Science Laboratory (MSL) Mission

NASA Technical Reports Server (NTRS)

Webster, Christopher R.; Mahaffy, Paul R.

2011-01-01

Understanding the origin of Martian methane will require numerous complementary measurements from both in situ and remote sensing investigations and laboratory work to correlate planetary surface geophysics with atmospheric dynamics and chemistry. Three instruments (Quadrupole Mass Spectrometer (QMS), Gas Chromatograph (GC) and Tunable Laser Spectrometer (TLS)) with sophisticated sample handling and processing capability make up the Sample Analysis at Mars (SAM) analytical chemistry suite on NASA s 2011 Mars Science Laboratory (MSL) Mission. Leveraging off the SAM sample and gas processing capability that includes methane enrichment, TLS has unprecedented sensitivity for measuring absolute methane (parts-per-trillion), water, and carbon dioxide abundances in both the Martian atmosphere and evolved from heated soil samples. In concert with a wide variety of associated trace gases (e.g. SO2, H2S, NH3, higher hydrocarbons, organics, etc.) and other isotope ratios measured by SAM, TLS will focus on determining the absolute abundances of methane, water and carbon dioxide, and their isotope ratios: 13C/12C and D/H in methane; 13C/12C and 18O/17O/16O in carbon dioxide; and 18O/17O/16O and D/H in water. Measurements near the MSL landing site will be correlated with satellite (Mars Express, Mars 2016) and ground-based observations.

C3 Hydrocarbon Abundance in Titan's Atmosphere with Cassini Infrared Spectra

NASA Astrophysics Data System (ADS)

Lombardo, Nicholas; Nixon, Conor; Achterberg, Richard; Jolly, Antoine; Sung, Keeyoon; Irwin, Patrick; Flasar, F. M.

2018-01-01

Titan, the largest moon of the Saturn system, has an astrobiologically important atmosphere. The anoxic nature and high N2 abundance make it a strong analog to the early Earth. The secondary species, CH4, is easily photodissociated, and reactions between its dissociated products give rise to highly complex hydrocarbons and nitriles. The Voyager flyby and 14 year Cassini campaign allowed for the intense study of several of these molecules, enabling scientists to increase our understanding of the chemical pathways present above Titan. In this work, we report abundance profiles of four major C3 gasses expected to occur in Titan’s atmosphere, derived from Cassini/Composite Infrared Spectrometer (CIRS) data, allowing us to fill the gaps in the photochemical zoo that is Titan’s atmosphere.Using the NEMESIS iterative radiative transfer module, we retrieved vertical abundance profiles for propane (C3H8) and propyne (CHCCH3) both initially detected by the Voyager IRIS instrument. Using newly available line data, we were also able to determine the first vertical abundance profiles for propene (C3H6), initially detected in 2013. We present profiles for several latitudes and times and compare to photochemical model predictions and previous observations. We also discuss our ongoing search for allene (CH2CCH2), an isomer of propyne, which has yet to be definitively detected. The abundances we determined will help to further our understanding of the chemical pathways that occur in Titan's atmosphere.

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).

Quantifying Microbial Utilization of Petroleum Hydrocarbons in Salt Marsh Sediments by Using the 13C Content of Bacterial rRNA▿

PubMed Central

Pearson, Ann; Kraunz, Kimberly S.; Sessions, Alex L.; Dekas, Anne E.; Leavitt, William D.; Edwards, Katrina J.

2008-01-01

Natural remediation of oil spills is catalyzed by complex microbial consortia. Here we took a whole-community approach to investigate bacterial incorporation of petroleum hydrocarbons from a simulated oil spill. We utilized the natural difference in carbon isotopic abundance between a salt marsh ecosystem supported by the 13C-enriched C4 grass Spartina alterniflora and 13C-depleted petroleum to monitor changes in the 13C content of biomass. Magnetic bead capture methods for selective recovery of bacterial RNA were used to monitor the 13C content of bacterial biomass during a 2-week experiment. The data show that by the end of the experiment, up to 26% of bacterial biomass was derived from consumption of the freshly spilled oil. The results contrast with the inertness of a nearby relict spill, which occurred in 1969 in West Falmouth, MA. Sequences of 16S rRNA genes from our experimental samples also were consistent with previous reports suggesting the importance of Gamma- and Deltaproteobacteria and Firmicutes in the remineralization of hydrocarbons. The magnetic bead capture approach makes it possible to quantify uptake of petroleum hydrocarbons by microbes in situ. Although employed here at the domain level, RNA capture procedures can be highly specific. The same strategy could be used with genus-level specificity, something which is not currently possible using the 13C content of biomarker lipids. PMID:18083852

13C and (15)N chemical shift tensors in adenosine, guanosine dihydrate, 2'-deoxythymidine, and cytidine.

PubMed

Stueber, Dirk; Grant, David M

2002-09-04

The (13)C and (15)N chemical shift tensor principal values for adenosine, guanosine dihydrate, 2'-deoxythymidine, and cytidine are measured on natural abundance samples. Additionally, the (13)C and (15)N chemical shielding tensor principal values in these four nucleosides are calculated utilizing various theoretical approaches. Embedded ion method (EIM) calculations improve significantly the precision with which the experimental principal values are reproduced over calculations on the corresponding isolated molecules with proton-optimized geometries. The (13)C and (15)N chemical shift tensor orientations are reliably assigned in the molecular frames of the nucleosides based upon chemical shielding tensor calculations employing the EIM. The differences between principal values obtained in EIM calculations and in calculations on isolated molecules with proton positions optimized inside a point charge array are used to estimate the contributions to chemical shielding arising from intermolecular interactions. Moreover, the (13)C and (15)N chemical shift tensor orientations and principal values correlate with the molecular structure and the crystallographic environment for the nucleosides and agree with data obtained previously for related compounds. The effects of variations in certain EIM parameters on the accuracy of the shielding tensor calculations are investigated.

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).

{sup 13}C chemical shift anisotropies for carbonate ions in cement minerals and the use of {sup 13}C, {sup 27}Al and {sup 29}Si MAS NMR in studies of Portland cement including limestone additions

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

Sevelsted, Tine F.; Herfort, Duncan; Skibsted, Jørgen, E-mail: jskib@chem.au.dk

2013-10-15

{sup 13}C isotropic chemical shifts and chemical shift anisotropy parameters have been determined for a number of inorganic carbonates relevant in cement chemistry from slow-speed {sup 13}C MAS or {sup 13}C({sup 1}H) CP/MAS NMR spectra (9.4 T or 14.1 T) for {sup 13}C in natural abundance. The variation in the {sup 13}C chemical shift parameters is relatively small, raising some doubts that different carbonate species in Portland cement-based materials may not be sufficiently resolved in {sup 13}C MAS NMR spectra. However, it is shown that by combining {sup 13}C MAS and {sup 13}C({sup 1}H) CP/MAS NMR carbonate anions in anhydrousmore » and hydrated phases can be distinguished, thereby providing valuable information about the reactivity of limestone in cement blends. This is illustrated for three cement pastes prepared from an ordinary Portland cement, including 0, 16, and 25 wt.% limestone, and following the hydration for up to one year. For these blends {sup 29}Si MAS NMR reveals that the limestone filler accelerates the hydration for alite and also results in a smaller fraction of tetrahedrally coordinated Al incorporated in the C-S-H phase. The latter result is more clearly observed in {sup 27}Al MAS NMR spectra of the cement–limestone blends and suggests that dissolved aluminate species in the cement–limestone blends readily react with carbonate ions from the limestone filler, forming calcium monocarboaluminate hydrate. -- Highlights: •{sup 13}C chemical shift anisotropies for inorganic carbonates from {sup 13}C MAS NMR. •Narrow {sup 13}C NMR chemical shift range (163–171 ppm) for inorganic carbonates. •Anhydrous and hydrated carbonate species by {sup 13}C MAS and {sup 13}C({sup 1}H) CP/MAS NMR. •Limestone accelerates the hydration for alite in Portland – limestone cements. •Limestone reduces the amount of aluminium incorporated in the C-S-H phase.« less

Monthly Atmospheric 13C/12C Isotopic Ratios for 11 SIO Stations (1977-2008)

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

Keeling, R. F.; Piper, S. C.; Bollenbacher, A. F.

Stable isotopic measurements for atmospheric 13C/12C and 18O/16O at global sampling sites were initiated by Dr. C.D. Keeling and co-workers at Scripps Institution of Oceanography (SIO) in 1977. These isotopic measurements complement the continuing global atmospheric and oceanic CO2 measurements initiated by Keeling in 1957. This work is currently being continued under the direction of R.F. Keeling, who also runs a parallel program at SIO to measure changes in atmospheric O2 and Ar abundances (Scripps O2 Program). A more complete set of 13CO2 data is found online at http://scrippsco2.ucsd.edu/data/atmospheric_co2.html

Variability of 13C-labeling in plant leaves.

PubMed

Nguyen Tu, Thanh Thuy; Biron, Philippe; Maseyk, Kadmiel; Richard, Patricia; Zeller, Bernd; Quénéa, Katell; Alexis, Marie; Bardoux, Gérard; Vaury, Véronique; Girardin, Cyril; Pouteau, Valérie; Billiou, Daniel; Bariac, Thierry

2013-09-15

Plant tissues artificially labeled with (13)C are increasingly used in environmental studies to unravel biogeochemical and ecophysiological processes. However, the variability of (13)C-content in labeled tissues has never been carefully investigated. Hence, this study aimed at documenting the variability of (13)C-content in artificially labeled leaves. European beech and Italian ryegrass were subjected to long-term (13)C-labeling in a controlled-environment growth chamber. The (13)C-content of the leaves obtained after several months labeling was determined by isotope ratio mass spectrometry. The (13)C-content of the labeled leaves exhibited inter- and intra-leaf variability much higher than those naturally occurring in unlabeled plants, which do not exceed a few per mil. This variability was correlated with labeling intensity: the isotope composition of leaves varied in ranges of ca 60‰ and 90‰ for experiments that led to average leaf (13)C-content of ca +15‰ and +450‰, respectively. The reported variability of isotope composition in (13)C-enriched leaves is critical, and should be taken into account in subsequent experimental investigations of environmental processes using (13)C-labeled plant tissues. Copyright © 2013 John Wiley & Sons, Ltd.

13C cell wall enrichment and ionic liquid NMR analysis: progress towards a high-throughput detailed chemical analysis of the whole plant cell wall.

PubMed

Foston, Marcus; Samuel, Reichel; Ragauskas, Arthur J

2012-09-07

The ability to accurately and rapidly measure plant cell wall composition, relative monolignol content and lignin-hemicellulose inter-unit linkage distributions has become essential to efforts centered on reducing the recalcitrance of biomass by genetic engineering. Growing (13)C enriched transgenic plants is a viable route to achieve the high-throughput, detailed chemical analysis of whole plant cell wall before and after pretreatment and microbial or enzymatic utilization by (13)C nuclear magnetic resonance (NMR) in a perdeuterated ionic liquid solvent system not requiring component isolation. 1D (13)C whole cell wall ionic liquid NMR of natural abundant and (13)C enriched corn stover stem samples suggest that a high level of uniform labeling (>97%) can significantly reduce the total NMR experiment times up to ~220 times. Similarly, significant reduction in total NMR experiment time (~39 times) of the (13)C enriched corn stover stem samples for 2D (13)C-(1)H heteronuclear single quantum coherence NMR was found.

C-12/C-13 Ratio in Ethane on Titan and Implications for Methane's Replenishment

NASA Technical Reports Server (NTRS)

Jennings, Donald E.; Romani, Paul N.; Bjoraker, Gordon L.; Sada, Pedro V.; Nixon, Conor A.; Lunsford, Allen W.; Boyle, Robert J.; Hesman, Brigette E.; McCabe, George H.

2009-01-01

The C-12/C-13 abundance ratio in ethane in the atmosphere of Titan has been measured at 822 cm(sup -1) from high spectral resolution ground-based observations. The value 89(8), coincides with the telluric standard and also agrees with the ratio seen in the outer planets. It is almost identical to the result for ethane on Titan found by the composite infrared spectrometer (CIRS) on Cassini. The C-12/C-13 ratio for ethane is higher than the ratio measured in atmospheric methane by Cassini/Huygens GCMS, 82.3(l), representing an enrichment of C-12 in the ethane that might be explained by a kinetic isotope effect of approximately 1.1 in the formation of methyl radicals. If methane is being continuously resupplied to balance photochemical destruction, then we expect the isotopic composition in the ethane product to equilibrate at close to the same C-12/C-13 ratio as that in the supply. The telluric value of the ratio in ethane then implies that the methane reservoir is primordial.

Modelling aspects regarding the control in 13C isotope separation column

NASA Astrophysics Data System (ADS)

Boca, M. L.

2016-08-01

Carbon represents the fourth most abundant chemical element in the world, having two stable and one radioactive isotope. The 13Carbon isotopes, with a natural abundance of 1.1%, plays an important role in numerous applications, such as the study of human metabolism changes, molecular structure studies, non-invasive respiratory tests, Alzheimer tests, air pollution and global warming effects on plants [9] A manufacturing control system manages the internal logistics in a production system and determines the routings of product instances, the assignment of workers and components, the starting of the processes on not-yet-finished product instances. Manufacturing control does not control the manufacturing processes themselves, but has to cope with the consequences of the processing results (e.g. the routing of products to a repair station). In this research it was fulfilled some UML (Unified Modelling Language) diagrams for modelling the C13 Isotope Separation column, implement in STARUML program. Being a critical process and needing a good control and supervising, the critical parameters in the column, temperature and pressure was control using some PLC (Programmable logic controller) and it was made some graphic analyze for this to observe some critical situation than can affect the separation process. The main parameters that need to be control are: -The liquid nitrogen (N2) level in the condenser. -The electrical power supplied to the boiler. -The vacuum pressure.

12C/13C isotopic ratios in red-giant stars of the open cluster NGC 6791

NASA Astrophysics Data System (ADS)

Szigeti, László; Mészáros, Szabolcs; Smith, Verne V.; Cunha, Katia; Lagarde, Nadège; Charbonnel, Corinne; García-Hernández, D. A.; Shetrone, Matthew; Pinsonneault, Marc; Allende Prieto, Carlos; Fernández-Trincado, J. G.; Kovács, József; Villanova, Sandro

2018-03-01

Carbon isotope ratios, along with carbon and nitrogen abundances, are derived in a sample of 11 red-giant members of one of the most metal-rich clusters in the Milky Way, NGC 6791. The selected red-giants have a mean metallicity and standard deviation of [Fe/H] = +0.39 ± 0.06 (Cunha et al. 2015). We used high-resolution H-band spectra obtained by the SDSS-IV Apache Point Observatory Galactic Evolution Experiment. The advantage of using high-resolution spectra in the H band is that lines of CO are well represented and their line profiles are sensitive to the variation of 12C/13C. Values of the 12C/13C ratio were obtained from a spectrum synthesis analysis. The derived 12C/13C ratios varied between 6.3 and 10.6 in NGC 6791, in agreement with the final isotopic ratios from thermohaline-induced mixing models. The ratios derived here are combined with those obtained for more metal poor red-giants from the literature to examine the correlation between 12C/13C, mass, metallicity, and evolutionary status.

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.

{sup 13}CO/C{sup 18}O Gradients across the Disks of Nearby Spiral Galaxies

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

Jiménez-Donaire, María J.; Cormier, Diane; Bigiel, Frank

We use the IRAM Large Program EMPIRE and new high-resolution ALMA data to measure {sup 13}CO(1-0)/C{sup 18}O(1-0) intensity ratios across nine nearby spiral galaxies. These isotopologues of {sup 12}CO are typically optically thin across most of the area in galaxy disks, and this ratio allows us to gauge their relative abundance due to chemistry or stellar nucleosynthesis effects. Resolved {sup 13}CO/C{sup 18}O gradients across normal galaxies have been rare due to the faintness of these lines. We find a mean {sup 13}CO/C{sup 18}O ratio of 6.0 ± 0.9 for the central regions of our galaxies. This agrees well with resultsmore » in the Milky Way, but differs from results for starburst galaxies (3.4 ± 0.9) and ultraluminous infrared galaxies (1.1 ± 0.4). In our sample, the {sup 13}CO/C{sup 18}O ratio consistently increases with increasing galactocentric radius and decreases with increasing star formation rate surface density. These trends could be explained if the isotopic abundances are altered by fractionation; the sense of the trends also agrees with those expected for carbon and oxygen isotopic abundance variations due to selective enrichment by massive stars.« less

Spatiotemporal Variation in the Environmental Controls of C4-Grass Origin and Ecology: Insights from Grass-Pollen δ13C Data

NASA Astrophysics Data System (ADS)

Nelson, D. M.; Urban, M.; Hu, F.

2014-12-01

Understanding the environmental factors controlling the origin and shifting abundance of C4 grasses in Earth's history is useful for projecting the response of C4-grass dominated grasslands to future environmental change. Unfortunately, grass pollen is typically morphologically indistinct, making palynological analysis a blunt tool for studying C4-grasses in the paleorecord. δ13C of individual grass-pollen grains using a spooling wire microcombustion device interfaced with an isotope ratio mass spectrometer (Single Pollen Isotope Ratio AnaLysis, SPIRAL) overcomes this challenge and the potential biases of δ13C data from other substrates (e.g. leaf waxes). To assess the presence and relative abundance of C3- and C4-grass pollen in samples of unknown composition, we developed a hierarchical Bayesian model, trained with ~1,900 δ13C values from pollen grains of 31 grass species. Surface-sediment data from Africa, Australia, and North America demonstrate the reliability of this technique for quantifying C4-grass abundance on the landscape. To investigate the timing and control of the origin of C4-grasses we analyzed samples from the Oligocene-Miocene from Europe and from the Eocene from North America. Results indicate that C4 grasses appeared on the landscape of southwest Europe no later than the early Oligocene, implying that low atmospheric pCO2 may not have been the main driver and/or precondition for the development of C4 photosynthesis in the grass family. In contrast, we found no evidence for C4 grasses in the southeast United States before pCO2 fell. In application of SPIRAL to the late Quaternary, we found that shifts in pCO2 and moisture balance exerted key controls on the relative abundance of C3 and C4 grasses in Africa and Australia. Overall, our results imply that as in the past, future changes in the C3/C4 composition of grass-dominated ecosystems will likely exhibit striking spatiotemporal variability as a result of differing combinations of

Comparison of IRMS and NMR spectrometry for the determination of intramolecular 13C isotope composition: application to ethanol.

PubMed

Gilbert, Alexis; Hattori, Ryota; Silvestre, Virginie; Wasano, Nariaki; Akoka, Serge; Hirano, Satoshi; Yamada, Keita; Yoshida, Naohiro; Remaud, Gérald S

2012-09-15

Isotopic (13)C NMR is a relatively recent technique which allows the determination of intramolecular (13)C isotope composition at natural abundance. It has been used in various scientific fields such as authentication, counterfeiting or plant metabolism. Although its precision has already been evaluated, the determination of its trueness remains still challenging. To deal with that issue, a comparison with another normalized technique must be achieved. In this work, we compare the intramolecular (13)C isotope distribution of ethanol from different origins obtained using both Isotope Ratio Mass Spectrometry (IRMS) and Nuclear Magnetic Resonance (NMR) spectrometry techniques. The IRMS approach consists of the oxidation of ethanol to acetic acid followed by the degradation of the latter for the analysis of each fragments formed. We show here that the oxidation of ethanol to acetic acid does not bring any significant error on the determination of the site-specific δ(13)C (δ(13)C(i)) of ethanol using the IRMS approach. The difference between the data obtained for 16 samples from different origins using IRMS and NMR approaches is not statistically significant and remains below 0.3‰. These results are encouraging for the future studies using isotopic NMR, especially in combination with the IRMS approach. Copyright © 2012. Published by Elsevier B.V.

Liquid and gas chromatography coupled to isotope ratio mass spectrometry for the determination of 13C-valine isotopic ratios in complex biological samples.

PubMed

Godin, Jean-Philippe; Breuillé, Denis; Obled, Christiane; Papet, Isabelle; Schierbeek, Henk; Hopfgartner, Gérard; Fay, Laurent-Bernard

2008-10-01

On-line gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) is commonly used to measure isotopic ratios at natural abundance as well as for tracer studies in nutritional and medical research. However, high-precision (13)C isotopic enrichment can also be measured by liquid chromatography-isotope ratio mass spectrometry (LC-IRMS). Indeed, LC-IRMS can be used, as shown by the new method reported here, to obtain a baseline separation and to measure (13)C isotopic enrichment of underivatised amino acids (Asp, Thr-Ser, Glu, Pro, Gly, Ala, Cys and Val). In case of Val, at natural abundance, the SD(delta(13)C) reported with this method was found to be below 1 per thousand . Another key feature of the new LC-IRMS method reported in this paper is the comparison of the LC-IRMS approach with the conventional GC-C-IRMS determination. To perform this comparative study, isotopic enrichments were measured from underivatised Val and its N(O, S)-ethoxycarbonyl ethyl ester derivative. Between 0.0 and 1.0 molar percent excess (MPE) (delta(13)C= -12.3 to 150.8 per thousand), the calculated root-mean-square (rms) of SD was 0.38 and 0.46 per thousand and the calculated rms of accuracy was 0.023 and 0.005 MPE, respectively, for GC-C-IRMS and LC-IRMS. Both systems measured accurately low isotopic enrichments (0.002 atom percent excess (APE)) with an SD (APE) of 0.0004. To correlate the relative (delta(13)C) and absolute (atom%, APE and MPE) isotopic enrichment of Val measured by the GC-C-IRMS and LC-IRMS devices, mathematical equations showing the slope and intercept of the curves were established and validated with experimental data between 0.0 to 2.3 MPE. Finally, both GC-C-IRMS and LC-IRMS instruments were also used to assess isotopic enrichment of protein-bound (13)C-Val in tibial epiphysis in a tracer study performed in rats. Isotopic enrichments measured by LC-IRMS and GC-C-IRMS were not statistically different (p>0.05). The results of this work indicate that

A Computational Framework for High-Throughput Isotopic Natural Abundance Correction of Omics-Level Ultra-High Resolution FT-MS Datasets

PubMed Central

Carreer, William J.; Flight, Robert M.; Moseley, Hunter N. B.

2013-01-01

New metabolomics applications of ultra-high resolution and accuracy mass spectrometry can provide thousands of detectable isotopologues, with the number of potentially detectable isotopologues increasing exponentially with the number of stable isotopes used in newer isotope tracing methods like stable isotope-resolved metabolomics (SIRM) experiments. This huge increase in usable data requires software capable of correcting the large number of isotopologue peaks resulting from SIRM experiments in a timely manner. We describe the design of a new algorithm and software system capable of handling these high volumes of data, while including quality control methods for maintaining data quality. We validate this new algorithm against a previous single isotope correction algorithm in a two-step cross-validation. Next, we demonstrate the algorithm and correct for the effects of natural abundance for both 13C and 15N isotopes on a set of raw isotopologue intensities of UDP-N-acetyl-D-glucosamine derived from a 13C/15N-tracing experiment. Finally, we demonstrate the algorithm on a full omics-level dataset. PMID:24404440

Quantitative (13)C Solid-State NMR Spectra by Multiple-Contact Cross-polarization for Drug Delivery: From Active Principles to Excipients and Drug Carriers.

PubMed

Saïdi, Fadila; Taulelle, Francis; Martineau, Charlotte

2016-08-01

In this contribution, we present an analysis of the main parameters influencing the efficiency of the (1)H → (13)C multiple-contact cross-polarization nuclear magnetic resonance (NMR) experiment in the context of solid pharmaceutical materials. Using the optimum experimental conditions, quantitative (13)C NMR spectra are then obtained for porous metal-organic frameworks (potential drug carriers) and for components present in drug formulations (active principle ingredient and excipients, amorphous or crystalline). Finally, we show that mixtures of components can also be quantified with this method and, hence, that it represents an ideal tool for quantification of pharmaceutical formulations by (13)C cross-polarization under magic-angle spinning NMR in the industry as it is robust and easy to set up, much faster than direct (13)C polarization and is efficient for samples at natural abundance. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

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. © 2013 John Wiley & Sons Ltd.

[Determination of 13C enrichment in soil amino acid enantiomers by gas chromatogram/mass spectrometry].

PubMed

He, Hong-Bo; Zhang, Wei; Ding, Xue-Li; Bai, Zhen; Liu, Ning; Zhang, Xu-Dong

2008-06-01

The transformation and renewal of amino acid enantiomers is of significance in indicating the turnover mechanism of soil organic matter. In this paper, a method of gas chromatogram/mass spectrometry combined with U-13 C-glucose incubation was developed to determine the 13C enrichment in soil amino acid enantiomers, which could effectively differentiate the original and the newly synthesized amino acids in soil matrix. The added U-13 C-glucose was utilized rapidly to structure the amino acid carbon skeleton, and the change of relative abundance of isotope ions could be determined by mass spectrometry. The direct incorporation of U-13 C glucose was estimated by the intensity increase of m/z (F + n) to F (F was parent fragment, and n was the carbon number in the fragment), while the total isotope incorporation from the added 13C could be calculated according to the abundance ratio increment summation from m/z (Fa + 1) through (Fa + T) (Fa was the fragment containing all original skeleton carbons, and T was the carbon number in the amino acid molecule). The 13C enrichment in the target compound was expressed as atom percentage excess (APE), and that of D-amino acid needed to be corrected by the coefficient of hydrolysis-induced racemization. The 13C enrichment reflected the carbon turnover velocity of individual amino acid enantiomers, and was powerful to investigate the dynamics of soil amino acids.

13C-isotopic fingerprint of Pinus pinaster Ait. and Pinus sylvestris L. wood related to the quality of standing tree mass in forests from NW Spain.

PubMed

Fernandez, Irene; González-Prieto, Serafin J; Cabaneiro, Ana

2005-01-01

Pine forest plantations of Pinus pinaster Ait. and P. sylvestris L. located in Galicia, NW Spain, were selected to study the 13C/12C-isotopic fingerprint in wood core samples in order to find possible relationships between the delta(13)C at natural abundance levels and the quality of the standing tree mass. For each pine species, 24 forests growing on acidic soils were studied: half developed over granite and half over schists. Two dominant trees from each plot, corresponding to all possible combinations of forest stands with high or low site index and with adults or young trees, were drilled at the basal part of trunks using a Pressler drill to obtain tree ring samples. The C-isotopic compositions of the litter and the soil organic matter from different soil depths were also determined and statistically significant correlations between these values and the 13C content of the wood were observed. Despite internal variations due to the influence of site index, tree age and parent material, the isotopic fingerprint of P. pinaster wood (mean value delta13C=-26.2+/-0.8 per thousand) significantly differed (P<0.001) from that of P. sylvestris (mean value delta13C=-24.6+/-0.7 per thousand). Relationships between the quality of the stand and the C-isotopic composition of the wood were observed, high quality stands having trees more 13C-depleted than low quality ones. A high correlation between wood delta13C and site index values for P. pinaster stands (r=-0.667, P<0.001) was found, this correlation being even clearer when only P. pinaster growing over schists (r=-0.833, P<0.001) are considered. Again, the correlation between the site index and the wood delta13C of young P. pinaster trees is higher when plots over granite or schists are separately considered. A similar fact occurs for adult P. sylvestris trees from schists stands, high quality specimens being 13C-depleted compared with low quality ones. On the other hand, 13C natural abundance of wood from P. sylvestris

[Bioremediation of oil-polluted soils: using the [13C]/[12C] ratio to characterize microbial products of oil hydrocarbon biodegradation].

PubMed

Ziakun, A M; Brodskiĭ, E S; Baskunov, B P; Zakharchenko, V N; Peshenko, V P; Filonov, A E; Vetrova, A A; Ivanova, A A; Boronin, A M

2014-01-01

We compared data on the extent of bioremediation in soils polluted with oil. The data were obtained using conventional methods of hydrocarbon determination: extraction gas chromatography-mass spectrometry, extraction IR spectroscopy, and extraction gravimetry. Due to differences in the relative abundances of the stable carbon isotopes (13C/12C) in oil and in soil organic matter, these ratios could be used as natural isotopic labels of either substance. Extraction gravimetry in combination with characteristics of the carbon isotope composition of organic products in the soil before and after bioremediation was shown to be the most informative approach to an evaluation of soil bioremediation. At present, it is the only method enabling quantification of the total petroleum hydrocarbons in oil-polluted soil, as well as of the amounts of hydrocarbons remaining after bioremediation and those microbially transformed into organic products and biomass.

Application of Natural Isotopic Abundance ¹H-¹³C- and ¹H-¹⁵N-Correlated Two-Dimensional NMR for Evaluation of the Structure of Protein Therapeutics.

PubMed

Arbogast, Luke W; Brinson, Robert G; Marino, John P

2016-01-01

Methods for characterizing the higher-order structure of protein therapeutics are in great demand for establishing consistency in drug manufacturing, for detecting drug product variations resulting from modifications in the manufacturing process, and for comparing a biosimilar to an innovator reference product. In principle, solution NMR can provide a robust approach for characterization of the conformation(s) of protein therapeutics in formulation at atomic resolution. However, molecular weight limitations and the perceived need for stable isotope labeling have to date limited its practical applications in the biopharmaceutical industry. Advances in NMR magnet and console technologies, cryogenically cooled probes, and new rapid acquisition methodologies, particularly selective optimized flip-angle short transient pulse schemes and nonuniform sampling, have greatly ameliorated these limitations. Here, we describe experimental methods for the collection and analysis of 2D (1)H(N)-(15)N-amide- and (1)H-(13)C-methyl-correlated spectra applied to protein drug products at natural isotopic abundance, including representatives from the rapidly growing class of monoclonal antibody (mAb) therapeutics. Practical aspects of experimental setup and data acquisition for both standard and rapid acquisition NMR techniques are described. Furthermore, strategies for the statistical comparison of 2D (1)H(N)-(15)N-amide- and (1)H-(13)C-methyl-correlated spectra are detailed. 2016 Published by Elsevier Inc.

Rare earth element abundances in presolar SiC

NASA Astrophysics Data System (ADS)

Ireland, T. R.; Ávila, J. N.; Lugaro, M.; Cristallo, S.; Holden, P.; Lanc, P.; Nittler, L.; Alexander, C. M. O'D.; Gyngard, F.; Amari, S.

2018-01-01

Individual isotope abundances of Ba, lanthanides of the rare earth element (REE) group, and Hf have been determined in bulk samples of fine-grained silicon carbide (SiC) from the Murchison CM2 chondrite. The analytical protocol involved secondary ion mass spectrometry with combined high mass resolution and energy filtering to exclude REE oxide isobars and Si-C-O clusters from the peaks of interest. Relative sensitivity factors were determined through analysis of NIST SRM reference glasses (610 and 612) as well as a trace-element enriched SiC ceramic. When normalised to chondrite abundances, the presolar SiC REE pattern shows significant deficits at Eu and Yb, which are the most volatile of the REE. The pattern is very similar to that observed for Group III refractory inclusions. The SiC abundances were also normalised to s-process model predictions for the envelope compositions of low-mass (1.5-3 M⊙) AGB stars with close-to-solar metallicities (Z = 0.014 and 0.02). The overall trace element abundances (excluding Eu and Yb) appear consistent with the predicted s-process patterns. The depletions of Eu and Yb suggest that these elements remained in the gas phase during the condensation of SiC. The lack of depletion in some other moderately refractory elements (like Ba), and the presence of volatile elements (e.g. Xe) indicates that these elements were incorporated into SiC by other mechanisms, most likely ion implantation.

Regional origin assignment of red wines from Valencia (Spain) by (2)H NMR and (13)C IRMS stable isotope analysis of fermentative ethanol.

PubMed

Giménez-Miralles, J E; Salazar, D M; Solana, I

1999-07-01

The use of the stable hydrogen and carbon isotope ratios of fermentative ethanol as suitable environmental fingerprints for the regional origin identification of red wines from Valencia (Spain) has been explored. Monovarietal Vitis vinifera L. cvs. Bobal, Tempranillo, and Monastrell wines have been investigated by (2)H NMR and (13)C IRMS for the natural ranges of site-specific (2)H/(1)H ratios and global delta(13)C values of ethanol over three vintage years. Statistically significant interregional and interannual (2)H and (13)C abundance differences have been noticed, which are interpreted in terms of environmental and ecophysiological factors of isotope content variation. Multivariate discriminant analysis is shown to provide a convenient means for integration of the classifying information, high discriminating abilities being demonstrated for the (2)H and (13)C fingerprints of ethanol. Reasonable differentiation results are achieved at a microregional scale in terms of geographic provenance and even grapevine genotypic features.

Contribution of Anthropogenic and Natural Emissions to Global CH4 Balances by Utilizing δ13C-CH4 Observations in CarbonTracker Data Assimilation System (CTDAS)

NASA Astrophysics Data System (ADS)

Kangasaho, V. E.; Tsuruta, A.; Aalto, T.; Backman, L. B.; Houweling, S.; Krol, M. C.; Peters, W.; van der Laan-Luijkx, I. T.; Lienert, S.; Joos, F.; Dlugokencky, E. J.; Michael, S.; White, J. W. C.

2017-12-01

The atmospheric burden of CH4 has more than doubled since preindustrial time. Evaluating the contribution from anthropogenic and natural emissions to the global methane budget is of great importance to better understand the significance of different sources at the global scale, and their contribution to changes in growth rate of atmospheric CH4 before and after 2006. In addition, observations of δ13C-CH4 suggest an increase in natural sources after 2006, which matches the observed increase and variation of CH4 abudance. Methane emission sources can be identified using δ13C-CH4, because different sources produce methane with process-specific isotopic signatures. This study focuses on inversion model based estimates of global anthropogenic and natural methane emission rates to evaluate the existing methane emission estimates with a new δ13C-CH4 inversion system. In situ measurements of atmospheric methane and δ13C-CH4 isotopic signature, provided by the NOAA Global Monitoring Division and the Institute of Arctic and Alpine Research, will be assimilated into the CTDAS-13C-CH4. The system uses the TM5 atmospheric transport model as an observation operator, constrained by ECMWF ERA Interim meteorological fields, and off-line TM5 chemistry fields to account for the atmospheric methane sink. LPX-Bern DYPTOP ecosystem model is used for prior natural methane emissions from wetlands, peatlands and mineral soils, GFED v4 for prior fire emissions and EDGAR v4.2 FT2010 inventory for prior anthropogenic emissions. The EDGAR antropogenic emissions are re-divided into enteric fermentation and manure management, landfills and waste water, rice, coal, oil and gas, and residential emissions, and the trend of total emissions is scaled to match optimized anthropogenic emissions from CTE-CH4. In addition to these categories, emissions from termites and oceans are included. Process specific δ13C-CH4 isotopic signatures are assigned to each emission source to estimate 13CH4 fraction

Contribution of deep sourced carbon from hydrocarbon seeps to sedimentary organic carbon: Evidence from Δ14C and δ13C isotopes

NASA Astrophysics Data System (ADS)

Feng, D.; Peckmann, J.; Peng, Y.; Liang, Q.; Roberts, H. H.; Chen, D.

2017-12-01

Sulfate-driven anaerobic oxidation of methane (AOM) limits the release of methane from marine sediments and promotes the formation of carbonates close to the seafloor along continental margins. It has been established that hydrocarbon seeps are a source of dissolved inorganic and organic carbon to marine environments. However, questions remain about the contribution of deep sourced carbon from hydrocarbon seeps to the sedimentary organic carbon pool. For a number of hydrocarbon seeps from the South China Sea and the Gulf of Mexico, the portion of modern carbon was determined based on natural radiocarbon abundances (Δ14C) and stable carbon isotope (δ13Corganic carbon) compositions of the non-carbonate fractions extracted from authigenic carbonates. Samples from both areas show a mixing trend between ideal planktonic organic carbon (δ13C = -22‰ VPDB and 90% modern carbon) and the ambient methane. The δ13Corganic carbon values of non-carbonate fractions from three ancient seep deposits (northern Italy, Miocene; western Washington State, USA, Eocene to Oligocene) confirm that the proxy can be used to constrain the record of sulfate-driven AOM through most of Earth history by measuring the δ13C values of organic carbon. This study reveals the potential of using δ13C values of organic carbon to discern seep and non-seep environments. This new approach is particularly promising when authigenic carbonate is not present in ancient sedimentary environments. Acknowledgments: The authors thank BOEM and NOAA for their years' support of the deep-sea dives. Funding was provided by the NSF of China (Grants: 41422602 and 41373085).

The Chemical Composition Contrast between M3 and M13 Revisited: New Abundances for 28 Giant Stars in M3

NASA Astrophysics Data System (ADS)

Sneden, Christopher; Kraft, Robert P.; Guhathakurta, Puragra; Peterson, Ruth C.; Fulbright, Jon P.

2004-04-01

We report new chemical abundances of 23 bright red giant members of the globular cluster M3, based on high-resolution (R~45,000) spectra obtained with the Keck I telescope. The observations, which involve the use of multislits in the HIRES Keck I spectrograph, are described in detail. Combining these data with a previously reported small sample of M3 giants obtained with the Lick 3 m telescope, we compare metallicities and [X/Fe] ratios for 28 M3 giants with a 35-star sample in the similar-metallicity cluster M13, and with Galactic halo field stars having [Fe/H]<-1. For elements having atomic number A>=A(Si), we derive little difference in [X/Fe] ratios in the M3, M13, or halo field samples. All three groups exhibit C depletion with advancing evolutionary state beginning at the level of the red giant branch ``bump,'' but the overall depletion of about 0.7-0.9 dex seen in the clusters is larger than that associated with the field stars. The behaviors of O, Na, Mg, and Al are distinctively different among the three stellar samples. Field halo giants and subdwarfs have a positive correlation of Na with Mg, as predicted from explosive or hydrostatic carbon burning in Type II supernova sites. Both M3 and M13 show evidence of high-temperature proton-capture synthesis from the ON, NeNa, and MgAl cycles, while there is no evidence for such synthesis among halo field stars. But the degree of such extreme proton-capture synthesis in M3 is smaller than it is in M13: the M3 giants exhibit only modest deficiencies of O and corresponding enhancements of Na, less extreme overabundances of Al, fewer stars with low Mg and correspondingly high Na, and no indication that O depletions are a function of advancing evolutionary state, as has been claimed for M13. We have also considered NGC 6752, for which Mg isotopic abundances have been reported by Yong et al. Giants in NGC 6752 and M13 satisfy the same anticorrelation of O abundances with the ratio (25Mg+26Mg)/24Mg, which measures the

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.

Soil Fertilization Leads to a Decline in Between-Samples Variability of Microbial Community δ13C Profiles in a Grassland Fertilization Experiment

PubMed Central

Veresoglou, Stavros D.; Thornton, Barry; Menexes, George; Mamolos, Andreas P.; Veresoglou, Demetrios S.

2012-01-01

Gas chromatography combustion isotope ratio mass spectrometry (GC-C-IRMS) was used to measure the 13C/12C ratios of PLFAs at natural abundance levels from a temperate grassland nitrogen (N) and phosphorus (P) factorial fertilization experiment in northern Greece. In each plot two rhizosphere samples were derived centred around individual Agrostis capillaris and Prunella vulgaris plants. It was hypothesized that the isotopic signal of microbes that preferentially feed on recalcitrant litter such as fungi would be modified by fertilization more strongly than that of opportunistic microbes using labile C. Microbial community δ13C was affected by both P and N fertilization regime and plant species identity. However, we have been unable to detect significant nutrient effects on individual groups of microbes when analyzed separately in contrast to our original hypothesis. Intra-treatment variability, as evaluated from Hartley’s F max tests in the five first PCA components axes as well as the size of the convex hulls in PCA scoreplots and Mahalanobis distances, was considerably higher in the non-fertilized controls. Moreover, a significant relationship was established between the change in PLFA abundances and their respective changes in δ13C for the aggregate of samples and those simultaneously fertilized with N and P. We conclude that use of compound specific isotope analysis in the absence of labelling represents a valuable and overlooked tool in obtaining an insight of microbial community functioning. PMID:22962602

Differences in delta13C and diameter growth among remnant Scots pine populations in Scotland.

PubMed

Brendel, Oliver; Handley, Linda; Griffiths, Howard

2002-10-01

Published data suggest that differences in wood cellulose carbon isotope composition (delta13C) and xylem ring width among natural populations of Scots pine in Scotland (Pinus sylvestris L.) are attributable to the persistence of palaeotypes of various post-glacial migratory origins. We assessed differences in wood cellulose delta13C and ring width among Scottish Scots pine populations grown in a clone bank and in natural stands at various locations in northern and central Scotland. Ring width and wood cellulose delta13C varied significantly among natural stands. Potential water deficit was positively correlated with wood cellulose delta13C and xylem ring width in the natural stands. Neither wood cellulose delta13C nor xylem ring width of clone bank trees correlated with any climate variables at the sites from which the trees originated, indicating little adaptation to climate for these traits. Xylem ring width showed a site x population interaction for the growth sites (i.e., natural stands versus clone bank), but wood cellulose delta13C did not. These results suggest that climate variation in Scotland has not resulted in significant genetic variation in wood cellulose delta13C or xylem ring width in post-glacial populations.

Assessing the stability of soil organic matter by fractionation and 13C isotope techniques

NASA Astrophysics Data System (ADS)

Larionova, A. A.; Zolotareva, B. N.; Kvitkina, A. K.; Evdokimov, I. V.; Bykhovets, S. S.; Stulin, A. F.; Kuzyakov, Ya. V.; Kudeyarov, V. N.

2015-02-01

Carbon pools of different stabilities have been separated from the soil organic matter of agrochernozem and agrogray soil samples. The work has been based on the studies of the natural abundance of the carbon isotope composition by C3-C4 transition using the biokinetic, size-density, and chemical fractionation (6 M HCl hydrolysis) methods. The most stable pools with the minimum content of new carbon have been identified by particle-size and chemical fractionation. The content of carbon in the fine fractions has been found to be close to that in the nonhydrolyzable residue. This pool makes up 65 and 48% of Corg in the agrochernozems and agrogray soils, respectively. The combination of the biokinetic approach with particle-size fractionation or 6 M HCl hydrolysis has allowed assessing the size of the medium-stable organic carbon pool with a turnover time of several years to several decades. The organic matter pool with this turnover rate is usually identified from the variation in the 13C abundance by C3-C4 transition. In the agrochernozems and agrogray soils, the medium-stable carbon pool makes up 35 and 46% of Corg, respectively. The isotope indication may be replaced by a nonisotope method to significantly expand the study of the inert and mediumstable organic matter pools in the geographical aspect, but this requires a comparative analysis of particle-size and chemical fractionation data for all Russian soils.

Backbone dynamics of a model membrane protein: assignment of the carbonyl carbon /sup 13/C NMR resonances in detergent-solubilized M13 coat protein

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

Henry, G.D.; Weiner, J.H.; Sykes, B.D.

The major coat protein of the filamentous bacteriophage M13 is a 50-residue amphiphilic polypeptide which is inserted, as an integral membrane-spanning protein, in the inner membrane of the Escherichia coli host during infection. /sup 13/C was incorporated biosynthetically into a total of 23 of the peptide carbonyls using labeled amino acids (alanine, glycine, lysine, phenylalanine, and proline). The structure and dynamics of carbonyl-labeled M13 coat protein were monitored by /sup 13/C nuclear magnetic resonance (NMR) spectroscopy. Assignment of many resonances was achieved by using protease digestion, pH titration, or labeling of the peptide bond with both /sup 13/C and /supmore » 15/N. The carbonyl region of the natural-abundance /sup 13/C NMR spectrum of M13 coat protein in sodium dodecyl sulfate solution shows approximately eight backbone carbonyl resonances with line widths much narrower than the rest. Three of these more mobile residues correspond to assigned peaks (glycine-3, lysine-48, and alanine-49) in the individual amino acid spectra, and another almost certainly arises from glutamic acid-2. A ninth residue, alanine-1, also gives rise to a very narrow carbonyl resonance if the pH is well above or below the pK/sub a/ of the terminal amino group. These data suggest that only about four residues at either end of the protein experience large-amplitude spatial fluctuations; the rest of the molecule is essentially rigid on the time scale of the overall rotational tumbling of the protein-detergent complex. The relative exposure of different regions of detergent-bound protein was monitored by limited digestion with proteinase K. Comparable spectra and digestion patterns were obtained when the protein was solubilized in sodium deoxycholate, suggesting that the coat protein binds both amphiphiles in a similar fashion.« less

Rubidium and Lead Abundances in Giant Stars of the Globular Clusters M13 and NGC 6752

NASA Astrophysics Data System (ADS)

Yong, David; Aoki, Wako; Lambert, David L.; Paulson, Diane B.

2006-03-01

We present measurements of the neutron-capture elements Rb and Pb in five giant stars of the globular cluster NGC 6752 and Pb measurements in four giants of the globular cluster M13. The abundances were derived by comparing synthetic spectra with high-resolution, high signal-to-noise ratio spectra obtained using HDS on the Subaru telescope and MIKE on the Magellan telescope. The program stars span the range of the O-Al abundance variation. In NGC 6752, the mean abundances are [Rb/Fe]=-0.17+/-0.06 (σ=0.14), [Rb/Zr]=-0.12+/-0.06 (σ=0.13), and [Pb/Fe]=-0.17+/-0.04 (σ=0.08). In M13 the mean abundance is [Pb/Fe]=-0.28+/-0.03 (σ=0.06). Within the measurement uncertainties, we find no evidence for star-to-star variation for either Rb or Pb within these clusters. None of the abundance ratios [Rb/Fe], [Rb/Zr], or [Pb/Fe] are correlated with the Al abundance. NGC 6752 may have slightly lower abundances of [Rb/Fe] and [Rb/Zr] compared to the small sample of field stars at the same metallicity. For M13 and NGC 6752 the Pb abundances are in accord with predictions from a Galactic chemical evolution model. If metal-poor intermediate-mass asymptotic giant branch stars did produce the globular cluster abundance anomalies, then such stars do not synthesize significant quantities of Rb or Pb. Alternatively, if such stars do synthesize large amounts of Rb or Pb, then they are not responsible for the abundance anomalies seen in globular clusters. Based in part on data collected at the Subaru Telescope, which is operated by the National Astronomical Observatory of Japan, and on observations made with the Magellan Clay Telescope at Las Campanas Observatory.

Identifying guanosine self assembly at natural isotopic abundance by high-resolution 1H and 13C solid-state NMR spectroscopy.

PubMed

Webber, Amy L; Masiero, Stefano; Pieraccini, Silvia; Burley, Jonathan C; Tatton, Andrew S; Iuga, Dinu; Pham, Tran N; Spada, Gian Piero; Brown, Steven P

2011-12-14

By means of the (1)H chemical shifts and the proton-proton proximities as identified in (1)H double-quantum (DQ) combined rotation and multiple-pulse spectroscopy (CRAMPS) solid-state NMR correlation spectra, ribbon-like and quartet-like self-assembly can be identified for guanosine derivatives without isotopic labeling for which it was not possible to obtain single crystals suitable for diffraction. Specifically, characteristic spectral fingerprints are observed for dG(C10)(2) and dG(C3)(2) derivatives, for which quartet-like and ribbon-like self-assembly has been unambiguously identified by (15)N refocused INADEQUATE spectra in a previous study of (15)N-labeled derivatives (Pham, T. N.; et al. J. Am. Chem. Soc.2005, 127, 16018). The NH (1)H chemical shift is observed to be higher (13-15 ppm) for ribbon-like self-assembly as compared to 10-11 ppm for a quartet-like arrangement, corresponding to a change from NH···N to NH···O intermolecular hydrogen bonding. The order of the two NH(2)(1)H chemical shifts is also inverted, with the NH(2) proton closest in space to the NH proton having a higher or lower (1)H chemical shift than that of the other NH(2) proton for ribbon-like as opposed to quartet-like self-assembly. For the dG(C3)(2) derivative for which a single-crystal diffraction structure is available, the distinct resonances and DQ peaks are assigned by means of gauge-including projector-augmented wave (GIPAW) chemical shift calculations. In addition, (14)N-(1)H correlation spectra obtained at 850 MHz under fast (60 kHz) magic-angle spinning (MAS) confirm the assignment of the NH and NH(2) chemical shifts for the dG(C3)(2) derivative and allow longer range through-space N···H proximities to be identified, notably to the N7 nitrogens on the opposite hydrogen-bonding face. © 2011 American Chemical Society

Facultative methanotrophs are abundant at terrestrial natural gas seeps.

PubMed

Farhan Ul Haque, Muhammad; Crombie, Andrew T; Ensminger, Scott A; Baciu, Calin; Murrell, J Colin

2018-06-28

Natural gas contains methane and the gaseous alkanes ethane, propane and butane, which collectively influence atmospheric chemistry and cause global warming. Methane-oxidising bacteria, methanotrophs, are crucial in mitigating emissions of methane as they oxidise most of the methane produced in soils and the subsurface before it reaches the atmosphere. Methanotrophs are usually obligate, i.e. grow only on methane and not on longer chain alkanes. Bacteria that grow on the other gaseous alkanes in natural gas such as propane have also been characterised, but they do not grow on methane. Recently, it was shown that the facultative methanotroph Methylocella silvestris grew on ethane and propane, other components of natural gas, in addition to methane. Therefore, we hypothesised that Methylocella may be prevalent at natural gas seeps and might play a major role in consuming all components of this potent greenhouse gas mixture before it is released to the atmosphere. Environments known to be exposed to biogenic methane emissions or thermogenic natural gas seeps were surveyed for methanotrophs. 16S rRNA gene amplicon sequencing revealed that Methylocella were the most abundant methanotrophs in natural gas seep environments. New Methylocella-specific molecular tools targeting mmoX (encoding the soluble methane monooxygenase) by PCR and Illumina amplicon sequencing were designed and used to investigate various sites. Functional gene-based assays confirmed that Methylocella were present in all of the natural gas seep sites tested here. This might be due to its ability to use methane and other short chain alkane components of natural gas. We also observed the abundance of Methylocella in other environments exposed to biogenic methane, suggesting that Methylocella has been overlooked in the past as previous ecological studies of methanotrophs often used pmoA (encoding the alpha subunit of particulate methane monooxygenase) as a marker gene. New biomolecular tools designed in

Development of new method of δ13C measurement for trace hydrocarbons in natural gas using solid phase micro-extraction coupled to gas chromatography isotope ratio mass spectrometry.

PubMed

Li, Zhongping; Wang, Xibin; Li, Liwu; Zhang, Mingjie; Tao, Mingxin; Xing, Lantian; Cao, Chunhui; Xia, Yanqing

2014-11-01

Compound specific isotope analysis (CSIA) of normal-level hydrocarbons (C 1 -C 4 ) in natural gas is often successfully used in natural gas origin identification and classification, but little progress so far has been made for trace level hydrocarbons (C 5 -C 14 ) in natural gas. In this study, we developed a method for rapid analysis of carbon isotopic ratios for trace hydrocarbons in natural gas samples. This method can be described as a combined approach characterized by solid phase micro-extraction (SPME) technique coupled to gas chromatography isotope ratio mass spectrometry (GC/IRMS). In this study, the CAR-PDMS fiber was chosen as the SPME adsorptive material after comparative experiments with other four fibers, and the parameters, including equilibration time, extraction temperature and desorption time, for efficient extraction of trace hydrocarbons were systematically optimized. The results showed the carbon isotopic fractionation was not observed as a function of equilibration time and extraction temperature. And the δ 13 C signatures determined by SPME-GC/IRMS were in good agreement with the known δ 13 C values of C 5 -C 14 measured by GC-IRMS, and the accuracy is generally within ±0.5‰. Five natural gas samples were analyzed using this method, and the δ 13 C values for C 5 -C 14 components were obtained with satisfied repeatability. The SPME-GC/IRMS approach fitted with CAR-PDMS fiber is well suited for the preconcentration of trace hydrocarbons and provides so far the most reliable carbon isotopic analysis for trace compounds in natural gas. Published by Elsevier B.V.

Comparative structural analysis of cytidine, ethenocytidine and their protonated salts III. 1H, 13C and 15N NMR studies at natural isotope abundance.

PubMed Central

Kozerski, L; Sierzputowska-Gracz, H; Krzyzosiak, W; Bratek-Wiewiórowska, M; Jaskólski, M; Wiewiórowski, M

1984-01-01

The 1H, 13C, 15N NMR spectra of cytidine /Cyd/, ethenocytidine /epsilon Cyd/ and their hydrochlorides /Cyd X HC1/ and /epsilon Cyd X HC1/ have been analysed to compare structural differences observed in solution with those existing in the crystalline state. The effects of ethenobridging and protonation of the hertero-aromatic base on the intramolecular stereochemistry, intermolecular interactions and electronic structure of the whole molecule are discussed on the basis of the NMR studies in DMSO solutions. Particular interest is devoted to the discussion of the conformation of the ribose ring, the presence of the intramolecular C-5'-0...H-6-C hydrogen bond, unambiguous assignment of the site of protonation, the mechanism of the 5C-H deuterium exchange in Cyd X HC1, and the intermolecular interactions in solution. PMID:6701098

Association of δ13C in Fingerstick Blood with Added Sugars and Sugar-sweetened Beverage Intake

PubMed Central

Davy, Brenda M.; Jahren, A. Hope; Hedrick, Valisa E.; Comber, Dana L.

2011-01-01

A reliance on self-reported dietary intake measures is a common research limitation, thus the need for dietary biomarkers. Added sugar intake may play a role in the development and progression of obesity and related co-morbidities; common sweeteners include corn and sugar cane derivatives. These plants contain a high amount of 13C, a naturally-occurring stable carbon isotope. Consumption of these sweeteners, of which sugar-sweetened beverages (SSB) are the primary dietary source, may be reflected in the δ13C value of blood. Fingerstick blood represents an ideal substrate for bioassay due to its ease of acquisition. The objective of this investigation was to determine if the δ13C value of fingerstick blood is a potential biomarker of added sugar and SSB intake. Individuals aged ≥21 years (n=60) were recruited to attend three laboratory visits; assessments completed at each visit depended upon a randomly assigned sequence (sequence one or two). The initial visit included assessment of height, weight, and dietary intake (sequence one: beverage intake questionnaire [BEVQ], sequence two: four-day food intake record [FIR]). Sequence one participants completed an FIR at visit two, and non-fasting blood samples were obtained via routine finger sticks at visits one and three. Sequence two participants completed a BEVQ at visit two, and provided fingerstick blood samples at visits two and three. Samples were analyzed for δ13C value using natural abundance stable isotope mass spectrometry. δ13C value was compared to dietary outcomes in all participants, as well as among those in the highest and lowest tertile of added sugar intake. Reported mean added sugar consumption was 66±5g/day, and SSB consumption was 330±53g/day and 134±25 kcal/day. Mean fingerstick δ13C value was −19.94±0.10‰, which differed by BMI status. δ13C value was associated (all p<0.05) with intake of total added sugars (g, r=0.37; kcal, r=0.37), soft drinks (g, r=0.26; kcal, r=0.27), and total

Increased seawater temperature increases the abundance and alters the structure of natural Vibrio populations associated with the coral Pocillopora damicornis

PubMed Central

Tout, Jessica; Siboni, Nachshon; Messer, Lauren F.; Garren, Melissa; Stocker, Roman; Webster, Nicole S.; Ralph, Peter J.; Seymour, Justin R.

2015-01-01

Rising seawater temperature associated with global climate change is a significant threat to coral health and is linked to increasing coral disease and pathogen-related bleaching events. We performed heat stress experiments with the coral Pocillopora damicornis, where temperature was increased to 31°C, consistent with the 2–3°C predicted increase in summer sea surface maxima. 16S rRNA amplicon sequencing revealed a large shift in the composition of the bacterial community at 31°C, with a notable increase in Vibrio, including known coral pathogens. To investigate the dynamics of the naturally occurring Vibrio community, we performed quantitative PCR targeting (i) the whole Vibrio community and (ii) the coral pathogen Vibrio coralliilyticus. At 31°C, Vibrio abundance increased by 2–3 orders of magnitude and V. coralliilyticus abundance increased by four orders of magnitude. Using a Vibrio-specific amplicon sequencing assay, we further demonstrated that the community composition shifted dramatically as a consequence of heat stress, with significant increases in the relative abundance of known coral pathogens. Our findings provide quantitative evidence that the abundance of potential coral pathogens increases within natural communities of coral-associated microbes as a consequence of rising seawater temperature and highlight the potential negative impacts of anthropogenic climate change on coral reef ecosystems. PMID:26042096

Estimation of vector static magnetic field by a nitrogen-vacancy center with a single first-shell 13C nuclear (NV–13C) spin in diamond

NASA Astrophysics Data System (ADS)

Jiang, Feng-Jian; Ye, Jian-Feng; Jiao, Zheng; Huang, Zhi-Yong; Lv, Hai-Jiang

2018-05-01

We suggest an experimental scheme that a single nitrogen-vacancy (NV) center coupled to a nearest neighbor 13C nucleus as a sensor in diamond can be used to detect a static vector magnetic field. By means of optical detection magnetic resonance (ODMR) technique, both the strength and the direction of the vector field could be determined by relevant resonance frequencies of continuous wave (CW) and Ramsey spectrums. In addition, we give a method that determines the unique one of eight possible hyperfine tensors for an (NV–13C) system. Finally, we propose an unambiguous method to exclude the symmetrical solution from eight possible vector fields, which correspond to nearly identical resonance frequencies due to their mirror symmetry about 14N–Vacancy–13C (14N–V–13C) plane. Protect supported by the National Natural Science Foundation of China (Grant Nos. 11305074, 11135002, and 11275083), the Key Program of the Education Department Outstanding Youth Foundation of Anhui Province, China (Grant No. gxyqZD2017080), and the Natural Science Foundation of Anhui Province, China (Grant No. KJHS2015B09).

s-Processing from MHD-induced mixing and isotopic abundances in presolar SiC grains

NASA Astrophysics Data System (ADS)

Palmerini, S.; Trippella, O.; Busso, M.; Vescovi, D.; Petrelli, M.; Zucchini, A.; Frondini, F.

2018-01-01

In the past years the observational evidence that s-process elements from Sr to Pb are produced by stars ascending the so-called Asymptotic Giant Branch (or "AGB") could not be explained by self-consistent models, forcing researchers to extensive parameterizations. The crucial point is to understand how protons can be injected from the envelope into the He-rich layers, yielding the formation of 13C and then the activation of the 13C (α,n)16O reaction. Only recently, attempts to solve this problem started to consider quantitatively physically-based mixing mechanisms. Among them, MHD processes in the plasma were suggested to yield mass transport through magnetic buoyancy. In this framework, we compare results of nucleosynthesis models for Low Mass AGB Stars (M≲ 3M⊙), developed from the MHD scenario, with the record of isotopic abundance ratios of s-elements in presolar SiC grains, which were shown to offer precise constraints on the 13C reservoir. We find that n-captures driven by magnetically-induced mixing can indeed account for the SiC data quite well and that this is due to the fact that our 13C distribution fulfils the above constraints rather accurately. We suggest that similar tests should be now performed using different physical models for mixing. Such comparisons would indeed improve decisively our understanding of the formation of the neutron source.

A Contextual Comparison of Native Ice Abundances in Comet C/2013 US10 (Catalina) based on Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

DiSanti, Michael A.; Gibb, Erika L.; Roth, Nathanial; Bonev, Boncho P.; Keane, Jacqueline; Meech, Karen Jean; Villanueva, Geronimo Luis; Paganini, Lucas; Mumma, Michael J.

2016-10-01

The primitive nature of comets makes them the best available carriers of information pertaining to conditions in the early solar system. High-resolution spectrometers operating at IR wavelengths (~ 1 - 5 µm) permit quantifying molecular species (aka "parent volatiles") released into the coma upon sublimation of ices contained in the cometary nucleus (i.e., native ices). Over the past 20 years we used first CSHELL at the IRTF, then NIRSPEC at Keck and CRIRES at the VLT, amassing production rates and abundance ratios in 30-plus comets.We present a summary of molecular abundances in long period Comet C/2013 US10 (Catalina), which passed perihelion on UT 2015 November 15.7 at heliocentric distance Rh = 0.822 AU. We used CSHELL on UT 2015 November 23 (Rh = 0.84 AU), December 15 - 17 (Rh = 1.0 AU) and 2016 February 28 (Rh = 1.95 AU), and NIRSPEC on 2016 January 24 (Rh = 1.49 AU). We targeted H2O, CO, H2CO, CH3OH, OCS, HCN, NH3, CH4, C2H2, and C2H6, and obtained production rates or stringent upper limits for all of these. This allowed testing for potential changes in relative abundances as a function of Rh. Such IR measurements spanning a range in Rh are still rare, but are very important for testing possible heterogeneous nucleus composition and/or heliocentric dependence of abundances, for example through release from grains heated in the coma. Our measurements will be inter-compared, and also placed in the context of our current (and continually evolving) compositional taxonomy of comets.We gratefully acknowledge support from the NASA Solar System Observations/Planetary Astronomy Program (SSO15-0028 to MAD, PAST11-0045 to MJM), Planetary Atmospheres Program (NNX12AG60G to BPB), NASA Astrobiology Institute (13-13NAI7-0032 to MJM, NN09DA77A to KJM), and NSF Astronomy and Astrophysics Research Grants (AST-1211362 to BPB and ELG, and AST-1413736 to KJM). The IRTF is operated by the University of Hawaii under contract NNH14CK55B with the National Aeronautics and Space

Proton-decoupled, Overhauser-enhanced, spatially localized carbon-13 spectroscopy in humans.

PubMed

Bottomley, P A; Hardy, C J; Roemer, P B; Mueller, O M

1989-12-01

Spatially localized, natural abundance, carbon (13C) NMR spectroscopy has been combined with proton (1H) decoupling and nuclear Overhauser enhancement to improve 13C sensitivity up to five-fold in the human leg, liver, and heart. Broadhand-decoupled 13C spectra were acquired in 1 s to 17 min with a conventional 1.5-T imaging/spectroscopy system, an auxiliary 1H decoupler, an air-cooled dual-coil coplanar surface probe, and both depth-resolved surface coil spectroscopy (DRESS) and one-dimensional phase-encoding gradient NMR pulse sequences. The surface coil probe comprised circular and figure-eight-shaped coils to eliminate problems with mutual coupling of coils at high decoupling power levels applied during 13C reception. Peak decoupler RF power deposition in tissue was computed numerically from electromagnetic theory assuming a semi-infinite plane of uniform biological conductor. Peak values at the surface were calculated at 4 to 6 W/kg in any gram of tissue for each watt of decoupler power input excluding all coil and cable losses, warning of potential local RF heating problems in these and related experiments. The average power deposition was about 9 mW/kg per watt input, which should present no systemic hazard. At 3 W input, human 13C spectra were decoupled to a depth of about 5 cm while some Overhauser enhancement was sustained up to about 3 cm depth, without ill effect. The observation of glycogen in localized natural abundance 13C spectra of heart and muscle suggests that metabolites in the citric acid cycle should be observable noninvasively using 13C-labeled substrates.

Accurate determination of the fine-structure intervals in the 3P ground states of C-13 and C-12 by far-infrared laser magnetic resonance

NASA Technical Reports Server (NTRS)

Cooksy, A. L.; Saykally, R. J.; Brown, J. M.; Evenson, K. M.

1986-01-01

Accurate values are presented for the fine-structure intervals in the 3P ground state of neutral atomic C-12 and C-13 as obtained from laser magnetic resonance spectroscopy. The rigorous analysis of C-13 hyperfine structure, the measurement of resonant fields for C-12 transitions at several additional far-infrared laser frequencies, and the increased precision of the C-12 measurements, permit significant improvement in the evaluation of these energies relative to earlier work. These results will expedite the direct and precise measurement of these transitions in interstellar sources and should assist in the determination of the interstellar C-12/C-13 abundance ratio.

FTIR and NDIR spectroscopies as valuable alternatives to IRMS spectrometry for the δ(13)C analysis of food.

PubMed

Pironti, Concetta; Proto, Antonio; Camin, Federica; Cucciniello, Raffaele; Zarrella, Ilaria; Motta, Oriana

2016-11-01

The (13)C/(12)C carbon isotope ratio is a chemical parameter with many important applications in several scientific area and the technique of choice currently used for the δ(13)C determination is the isotope ratio mass spectrometry (IRMS). This latter is highly accurate (0.1‰) and sensitive (up to 0.01‰), but at the same time expensive and complex. The objective of this work was to assess the reliability of FTIR and NDIRS techniques for the measurement of carbon stable isotope ratio of food sample, in comparison to IRMS. IRMS, NDIRS and FTIR were used to analyze samples of food, such as oil, durum, cocoa, pasta and sugar, in order to determine the natural abundance isotopic ratio of carbon in a parallel way. The results were comparable, showing a close relationship among the three techniques. The main advantage in using FTIR and NDIRS is related to their cheapness and easy-to-operate in comparison to IRMS. Copyright © 2016 Elsevier B.V. All rights reserved.

Acceleration of natural-abundance solid-state MAS NMR measurements on bone by paramagnetic relaxation from gadolinium-DTPA

NASA Astrophysics Data System (ADS)

Mroue, Kamal H.; Zhang, Rongchun; Zhu, Peizhi; McNerny, Erin; Kohn, David H.; Morris, Michael D.; Ramamoorthy, Ayyalusamy

2014-07-01

Reducing the data collection time without affecting the signal intensity and spectral resolution is one of the major challenges for the widespread application of multidimensional nuclear magnetic resonance (NMR) spectroscopy, especially in experiments conducted on complex heterogeneous biological systems such as bone. In most of these experiments, the NMR data collection time is ultimately governed by the proton spin-lattice relaxation times (T1). For over two decades, gadolinium(III)-DTPA (Gd-DTPA, DTPA = Diethylene triamine pentaacetic acid) has been one of the most widely used contrast-enhancement agents in magnetic resonance imaging (MRI). In this study, we demonstrate that Gd-DTPA can also be effectively used to enhance the longitudinal relaxation rates of protons in solid-state NMR experiments conducted on bone without significant line-broadening and chemical-shift-perturbation side effects. Using bovine cortical bone samples incubated in different concentrations of Gd-DTPA complex, the 1H T1 values were calculated from data collected by 1H spin-inversion recovery method detected in natural-abundance 13C cross-polarization magic angle spinning (CPMAS) NMR experiments. Our results reveal that the 1H T1 values can be successfully reduced by a factor of 3.5 using as low as 10 mM Gd-DTPA without reducing the spectral resolution and thus enabling faster data acquisition of the 13C CPMAS spectra. These results obtained from 13C-detected CPMAS experiments were further confirmed using 1H-detected ultrafast MAS experiments on Gd-DTPA doped bone samples. This approach considerably improves the signal-to-noise ratio per unit time of NMR experiments applied to bone samples by reducing the experimental time required to acquire the same number of scans.

Acceleration of natural-abundance solid-state MAS NMR measurements on bone by paramagnetic relaxation from gadolinium-DTPA.

PubMed

Mroue, Kamal H; Zhang, Rongchun; Zhu, Peizhi; McNerny, Erin; Kohn, David H; Morris, Michael D; Ramamoorthy, Ayyalusamy

2014-07-01

Reducing the data collection time without affecting the signal intensity and spectral resolution is one of the major challenges for the widespread application of multidimensional nuclear magnetic resonance (NMR) spectroscopy, especially in experiments conducted on complex heterogeneous biological systems such as bone. In most of these experiments, the NMR data collection time is ultimately governed by the proton spin-lattice relaxation times (T1). For over two decades, gadolinium(III)-DTPA (Gd-DTPA, DTPA=Diethylene triamine pentaacetic acid) has been one of the most widely used contrast-enhancement agents in magnetic resonance imaging (MRI). In this study, we demonstrate that Gd-DTPA can also be effectively used to enhance the longitudinal relaxation rates of protons in solid-state NMR experiments conducted on bone without significant line-broadening and chemical-shift-perturbation side effects. Using bovine cortical bone samples incubated in different concentrations of Gd-DTPA complex, the (1)H T1 values were calculated from data collected by (1)H spin-inversion recovery method detected in natural-abundance (13)C cross-polarization magic angle spinning (CPMAS) NMR experiments. Our results reveal that the (1)H T1 values can be successfully reduced by a factor of 3.5 using as low as 10mM Gd-DTPA without reducing the spectral resolution and thus enabling faster data acquisition of the (13)C CPMAS spectra. These results obtained from (13)C-detected CPMAS experiments were further confirmed using (1)H-detected ultrafast MAS experiments on Gd-DTPA doped bone samples. This approach considerably improves the signal-to-noise ratio per unit time of NMR experiments applied to bone samples by reducing the experimental time required to acquire the same number of scans. Copyright © 2014 Elsevier Inc. All rights reserved.

Chemical abundances in the globular clusters M3, M13, and NGC 6752

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

Bell, R.A.; Dickens, R.J.

The abundances of iron, carbon, nitrogen, and oxygen have been investigated in red giant stars in the globular clusters M3, M13, and NGC 6752. The results are based on application of spectrum synthesis and theoretical colors to observed spectra, DDO colors, and infrared CO measurements. Carbon is depleted by a factor of about 3 relative to other metals in most giants studied, with no evidence for the discontinuity along the giant branch at M/sub v/approx. =-0.7 found for more metal-poor clusters. This contrasts with the greater depletion of about a factor of 6 for the more metal-poor cluster stars, amore » difference which is expected if meridional mixing is responsible for the carbon depletion. The spectroscopic results for nitrogen are imprecise, but the colors suggest enhancements of a factor of 3. The iron abundances for M3 and M13 stars have been determined from published equivalent widths, yielding (Fe/H) close to -1.4 for both clusters. The uncertainties in M3 and M13 CO colors and (O I) equivalent widths make it impossible to derive accurate oxygen abundances, but the depletion of carbon is real and is not caused by an overabundance of oxygen.« less

Determinations of the {sup 12}C/{sup 13}C Ratio for the Secondary Stars of AE Aquarii, SS Cygni, and RU Pegasi

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

Harrison, Thomas E.; Marra, Rachel E., E-mail: tharriso@nmsu.edu, E-mail: rmarra@nmsu.edu

We present new moderate-resolution near-infrared spectroscopy of three CVs obtained using GNIRS on Gemini-North. These spectra covered three {sup 13}CO bandheads found in the K -band, allowing us to derive the isotopic abundance ratios for carbon. We find small {sup 12}C/{sup 13}C ratios for all three donor stars. In addition, these three objects show carbon deficits, with AE Aqr being the most extreme ([C/Fe] = −1.4). This result confirms the conjecture that the donor stars in some long-period CVs have undergone considerable nuclear evolution prior to becoming semi-contact binaries. In addition to the results for carbon, we find that themore » abundance of sodium is enhanced in these three objects, and the secondary stars in both RU Peg and SS Cyg suffer magnesium deficits. Explaining such anomalies appears to require higher mass progenitors than commonly assumed for the donor stars of CVs.« less

The Rotational Spectrum of Singly and Doubly 13C-SUBSTITUTED Dimethylether

NASA Astrophysics Data System (ADS)

Koerber, Monika; Endres, Christian P.; Lewen, Frank; Giesen, Thomas F.; Schlemmer, Stephan; Pohl, Roland; Klein, Axel

2010-06-01

Dimethylether (DME) is a nearly prolate asymmetric top with two internal rotors (methyl groups) which undergo periodic large amplitude motions and show a complicated torsional splitting of each rotational energy level. Due to its complex spectrum and its high abundance in hot cores such as Orion KL or Sagittarius B2 at temperatures exceeding 100 K, DME is very prominent in astronomical line surveys and contributes to spectral line confusion of such sources. The interpretation of astronomical observations therefore depends on the knowledge of accurate rest frequencies and reliable intensities. Precise predictions for the ground state of DME's main isotopologue are now available up to 2.1 THz In contrast, very little is known about 13C-substituted DME. Only a few data are available on singly 13C-substituted DME, 12CH_3O13CH_3. However, no data are available on doubly 13C-substituted DME, (13CH_3)_2O, yet. While in (13CH_3)_2O the two internal rotating methyl groups are equivalent and the splitting of rotational energy levels into four substates is comparable to the main isotopologue, singly 13C-substituted DME has two non-equivalent internal rotors resulting in torsional splitting of rotational energy levels into five substates. The purpose of our new laboratory measurements is to extend the knowledge on the astrophysically relevant species 12CH_3O13CH_3. To analyze the complicated spectrum resulting from a 13C-enriched sample of DME, containing all different 13C-substituted species as well as the main isotopologue, also precise data on doubly 13C-substituted DME are inevitable. We performed measurements in the frequency region 35-120 GHz using an all solid state spectrometer. Rotational as well as torsional parameters have been obtained for (13CH_3)_2O as well as 12CH_3O13CH_3 by fitting the assigned transitions to an effective rotational Hamiltonian introduced by Peter Groner. C. Comito et al., Astrophys. J. Suppl. Ser. 156, 127-167 (2005) C. P. Endres et al

The C-12/C-13 isotope ratio of the interstellar medium in the neighborhood of the sun

NASA Technical Reports Server (NTRS)

Hawkins, Isabel; Jura, Michael

1987-01-01

Data from observations of Xi Per, P Cyg, 20 Tau, and 23 Tau, obtained at 4232 and 3957 A using a coude spectrograph and a 1872-element reticon on the 3-m Shane telescope at Lick Observatory during 1984-1985, are combined with data on Zeta Oph (Hawkins et al., 1985) and used to estimate the C isotope ratio of the ISM near the sun. The results are presented in extensive tables and graphs and characterized in detail. The (C-12)H(+)/(C-13)H(+) abundance ratios toward the five stars are found to agree to within 12 percent and shown to be representative of the C-12/C-13 ratios in the gas, strongly indicating that the local ISM is homogeneous. The difference between the ISM ratio (43 + or - 4) and the solar-system value (89) is attributed to the chemical evolution of the ISM in the 4.9 Gyr since the formation of the sun.

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.

[Ozone effects on soil microbial community of rice investigated by 13C isotope labeling].

PubMed

Chen, Zhan; Wang, Xiao-Ke; Shang, He

2014-10-01

This study was initiated to explore the effects of dynamic ozone (O3) exposure on soil microbial biomass and phospholipid fatty acids (PLFAs) under potted rice. A pulse-chase labeling experiment was designed to expose potted rice with 13CO2 for 6 h after one and two months, the rice were fumigated by elevated O3 concentration with an 8 h mean of 110 nL · L(-1) (O3). The allocation of the assimilated 13C to soil microorganisms was estimated by analyzing the 13C profile of microbial phospholipid fatty acids (PLFAs). After one month O3 exposure, the soil microbial biomass carbon was not affected, while the 13C-microbial biomass was significantly decreased with elevated O3. Both the total and 13C microbial biomass carbon was remarkably lower than that of control treatment after two months O3 exposure. Principal components analysis of 13C-PLFA data showed that elevated O3 significantly changed soil microbial structure after two month exposures, while there was no difference of 13C-PLFA structure between control and elevated O3 treatments after one month exposure. Δδ13C per hundred thousand of individual PLFA was significantly affected by O3 after both one and two month exposures. Only did ozone change the relative abundance of individual 13C-PLFA (13C%) of bacterial fatty acids after one month exposure, while after two month exposures, the 13C% of fungal and actinomycetic fatty acids were markedly changed by elevated O3.

Development and evaluation of a high-performance liquid chromatography/isotope ratio mass spectrometry methodology for delta13C analyses of amino sugars in soil.

PubMed

Bodé, Samuel; Denef, Karolien; Boeckx, Pascal

2009-08-30

Amino sugars have been used as biomarkers to assess the relative contribution of dead microbial biomass of different functional groups of microorganisms to soil carbon pools. However, little is known about the dynamics of these compounds in soil. The isotopic composition of individual amino sugars can be used as a tool to determine the turnover of these compounds. Methods to determine the delta(13)C of amino sugars using gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) have been proposed in literature. However, due to derivatization, the uncertainty on the obtained delta(13)C is too high to be used for natural abundance studies. Therefore, a new high-performance liquid chromatography/isotope ratio mass spectrometry (HPLC/IRMS) methodology, with increased accuracy and precision, has been developed. The repeatability on the obtained delta(13)C values when pure amino sugars were analyzed were not significantly concentration-dependent as long as the injected amount was higher than 1.5 nmol. The delta(13)C value of the same amino sugar spiked to a soil deviated by only 0.3 per thousand from the theoretical value. 2009 John Wiley & Sons, Ltd.

Abundance of SiC2 in carbon star envelopes

NASA Astrophysics Data System (ADS)

Massalkhi, S.; Agúndez, M.; Cernicharo, J.; Velilla Prieto, L.; Goicoechea, J. R.; Quintana-Lacaci, G.; Fonfría, J. P.; Alcolea, J.; Bujarrabal, V.

2018-03-01

Context. Silicon carbide dust is ubiquitous in circumstellar envelopes around C-rich asymptotic giant branch (AGB) stars. However, the main gas-phase precursors leading to the formation of SiC dust have not yet been identified. The most obvious candidates among the molecules containing an Si-C bond detected in C-rich AGB stars are SiC2, SiC, and Si2C. To date, the ring molecule SiC2 has been observed in a handful of evolved stars, while SiC and Si2C have only been detected in the C-star envelope IRC +10216. Aim. We aim to study how widespread and abundant SiC2, SiC, and Si2C are in envelopes around C-rich AGB stars, and whether or not these species play an active role as gas-phase precursors of silicon carbide dust in the ejecta of carbon stars. Methods: We carried out sensitive observations with the IRAM 30 m telescope of a sample of 25 C-rich AGB stars to search for emission lines of SiC2, SiC, and Si2C in the λ 2 mm band. We performed non-LTE excitation and radiative transfer calculations based on the LVG method to model the observed lines of SiC2 and to derive SiC2 fractional abundances in the observed envelopes. Results: We detect SiC2 in most of the sources, SiC in about half of them, and do not detect Si2C in any source except IRC +10216. Most of these detections are reported for the first time in this work. We find a positive correlation between the SiC and SiC2 line emission, which suggests that both species are chemically linked; the SiC radical is probably the photodissociation product of SiC2 in the external layer of the envelope. We find a clear trend where the denser the envelope, the less abundant SiC2 is. The observed trend is interpreted as evidence of efficient incorporation of SiC2 onto dust grains, a process that is favored at high densities owing to the higher rate at which collisions between particles take place. Conclusions: The observed behavior of a decline in the SiC2 abundance with increasing density strongly suggests that SiC2 is an

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.

SABRE hyperpolarization enables high-sensitivity 1H and 13C benchtop NMR spectroscopy.

PubMed

Richardson, Peter M; Parrott, Andrew J; Semenova, Olga; Nordon, Alison; Duckett, Simon B; Halse, Meghan E

2018-06-19

Benchtop NMR spectrometers operating with low magnetic fields of 1-2 T at sub-ppm resolution show great promise as analytical platforms that can be used outside the traditional laboratory environment for industrial process monitoring. One current limitation that reduces the uptake of benchtop NMR is associated with the detection fields' reduced sensitivity. Here we demonstrate how para-hydrogen (p-H2) based signal amplification by reversible exchange (SABRE), a simple to achieve hyperpolarization technique, enhances agent detectability within the environment of a benchtop (1 T) NMR spectrometer so that informative 1H and 13C NMR spectra can be readily recorded for low-concentration analytes. SABRE-derived 1H NMR signal enhancements of up to 17 000-fold, corresponding to 1H polarization levels of P = 5.9%, were achieved for 26 mM pyridine in d4-methanol in a matter of seconds. Comparable enhancement levels can be achieved in both deuterated and protio solvents but now the SABRE-enhanced analyte signals dominate due to the comparatively weak thermally-polarized solvent response. The SABRE approach also enables the acquisition of 13C NMR spectra of analytes at natural isotopic abundance in a single scan as evidenced by hyperpolarized 13C NMR spectra of tens of millimolar concentrations of 4-methylpyridine. Now the associated signal enhancement factors are up to 45 500 fold (P = 4.0%) and achieved in just 15 s. Integration of an automated SABRE polarization system with the benchtop NMR spectrometer framework produces renewable and reproducible NMR signal enhancements that can be exploited for the collection of multi-dimensional NMR spectra, exemplified here by a SABRE-enhanced 2D COSY NMR spectrum.

Compressed Sensing for Resolution Enhancement of Hyperpolarized 13C Flyback 3D-MRSI

PubMed Central

Hu, Simon; Lustig, Michael; Chen, Albert P.; Crane, Jason; Kerr, Adam; Kelley, Douglas A.C.; Hurd, Ralph; Kurhanewicz, John; Nelson, Sarah J.; Pauly, John M.; Vigneron, Daniel B.

2008-01-01

High polarization of nuclear spins in liquid state through dynamic nuclear polarization has enabled the direct monitoring of 13C metabolites in vivo at very high signal to noise, allowing for rapid assessment of tissue metabolism. The abundant SNR afforded by this hyperpolarization technique makes high resolution 13C 3D-MRSI feasible. However, the number of phase encodes that can be fit into the short acquisition time for hyperpolarized imaging limits spatial coverage and resolution. To take advantage of the high SNR available from hyperpolarization, we have applied compressed sensing to achieve a factor of 2 enhancement in spatial resolution without increasing acquisition time or decreasing coverage. In this paper, the design and testing of compressed sensing suited for a flyback 13C 3D-MRSI sequence are presented. The key to this design was the undersampling of spectral k-space using a novel blipped scheme, thus taking advantage of the considerable sparsity in typical hyperpolarized 13C spectra. Phantom tests validated the accuracy of the compressed sensing approach and initial mouse experiments demonstrated in vivo feasibility. PMID:18367420

Contributions of root and shoot derived-C to soil organic matter throughout an agricultural soil profile assessed by compound-specific 13C analysis

NASA Astrophysics Data System (ADS)

Mendez-Millan, Mercedes; Dignac, Marie-France; Rumpel, Cornelia; Rasse, Daniel P.; Derenne, Sylvie

2010-05-01

The turnover of soil organic matter (SOM) is generally studied in the topsoil horizons, where the highest concentrations of organic carbon (OC) are found. Subsoils, although containing lower amounts of organic carbon compared to topsoils, greatly contribute to the total carbon stocks within a soil profile. An increase in SOM aliphaticity was observed during SOM degradation, and also down the soil profile, suggesting that the stable pool of SOM is enriched in aliphatic structures. These alkyl-C structures might mainly derive from cutins and suberins, two biomacromolecules, which contain biomarkers specific for shoot and root plant biomass. The aim of this study was to use cutin and suberin structural units to follow the incorporation of plant biomass originating from roots and shoots throughout an agricultural soil profile. We measured the 13C natural abundance of root and shoot biomarkers in samples taken from 15 to 105 cm depth in a C3/C4 chronosequence. After 9 years of maize (C4) cropping, the distribution of root biomarkers (diacids) significantly changed and their concentration increased compared to the wheat (CC3) soil. The largest increase was observed at 60-75 cm where diacids reached up to 134 ?g/gOC compared to 23 ?g/gOC in the wheat soil. Higher inputs from maize root biomass are also suggested by an average 13C enrichment of the root markers in the maize compared to the wheat soil.

Carbon-13 Isotopic Abundance and Concentration of Atmospheric Methane for Background Air in the Southern and Northern Hemispheres from 1978 to 1989 (NDP-049)

DOE Data Explorer

Stevens, C. M. [Chemical Technology Division, Argonne National Laboratory, Argonne, Illinois (USA)

2012-01-01

This data package presents atmospheric CH4 concentration and 13C isotopic abundance data derived from air samples collected over the period 1978-1989 at globally distributed clean-air sites. The data set comprises 201 records, 166 from the Northern Hemisphere and 35 from the Southern Hemisphere. The air samples were collected mostly in rural or marine locations remote from large sources of CH4 and are considered representative of tropospheric background conditions. The air samples were processed by isolation of CH4 from air and conversion to CO2 for isotopic analysis by isotope ratio mass spectrometry. These data represent one of the earliest records of 13C isotopic yy!measurements for atmospheric methane and have been used to refine estimates of CH4 emissions, calculate annual growth rates of emissions from changing sources, and provide evidence for changes in the rate of atmospheric removal of CH4. The data records consist of sample collection date; number of samples combined for analysis; sampling location; analysis date; CH4 concentration; 13C isotopic abundance; and flag codes to indicate outliers, repeated analyses, and other information.

13C Mannitol as a Novel Biomarker for Measurement of Intestinal Permeability

PubMed Central

Grover, Madhusudan; Camilleri, Michael; Hines, Jolaine; Burton, Duane; Ryks, Michael; Wadhwa, Akhilesh; Sundt, Wendy; Dyer, Roy; Singh, Ravinder J.

2016-01-01

Background Gastrointestinal (GI) and non-GI disorders are associated with altered intestinal permeability, which can be measured in vivo by urinary excretion after oral lactulose and mannitol ingestion. Inadvertent dietary consumption of 12Carbon (12C, regular) mannitol in food or from other sources may interfere with the test’s interpretation. 13Carbon (13C) constitutes 1% of carbon in nature and 13C mannitol is a stable isotope. Our aim was to determine performance of 13C mannitol for measurement of intestinal permeability. Methods Ten healthy volunteers underwent intestinal permeability assay using co-administered 12C mannitol, 13C mannitol and lactulose, followed by timed urine collections. Urinary sugar concentrations were measured using tandem high performance liquid chromatography-mass spectrometry. Key Results We found that 13C mannitol can be distinguishable from 12C mannitol on tandem mass spectrometry. Additionally, 13C mannitol had ~20-fold lower baseline contamination compared to 12C mannitol. We describe here the 13C mannitol assay method for measurement of intestinal permeability. Conclusions & Inferences In conclusion, 13C mannitol is superior to 12C mannitol for measurement of intestinal permeability. It avoids issues with baseline contamination and erratic excretions during the testing period. PMID:26914765

(13) C mannitol as a novel biomarker for measurement of intestinal permeability.

PubMed

Grover, M; Camilleri, M; Hines, J; Burton, D; Ryks, M; Wadhwa, A; Sundt, W; Dyer, R; Singh, R J

2016-07-01

Gastrointestinal (GI) and non-GI disorders are associated with altered intestinal permeability, which can be measured in vivo by urinary excretion after oral lactulose and mannitol ingestion. Inadvertent dietary consumption of (12) Carbon ((12) C, regular) mannitol in food or from other sources may interfere with the test's interpretation. (13) Carbon ((13) C) constitutes 1% of carbon in nature and (13) C mannitol is a stable isotope. Our aim was to determine the performance of (13) C mannitol for measurement of intestinal permeability. Ten healthy volunteers underwent intestinal permeability assay using coadministered (12) C mannitol, (13) C mannitol and lactulose, followed by timed urine collections. Urinary sugar concentrations were measured using tandem high performance liquid chromatography-mass spectrometry. We found that (13) C mannitol can be distinguishable from (12) C mannitol on tandem mass spectrometry. In addition, (13) C mannitol had ~20-fold lower baseline contamination compared to (12) C mannitol. We describe here the (13) C mannitol assay method for the measurement of intestinal permeability. In conclusion, (13) C mannitol is superior to (12) C mannitol for measurement of intestinal permeability. It avoids issues with baseline contamination and erratic excretions during the testing period. © 2016 John Wiley & Sons Ltd.

Direct analysis of δ13C and concentration of dissolved organic carbon (DOC) in environmental samples by TOC-IRMS

NASA Astrophysics Data System (ADS)

Kirkels, Frédérique; Cerli, Chiara; Federherr, Eugen; Kalbitz, Karsten

2014-05-01

Dissolved organic carbon (DOC) plays an important role in carbon cycling in terrestrial and aquatic systems. Stable isotope analysis (delta 13C) of DOC could provide valuable insights in its origin, fluxes and environmental fate. Precise and routine analysis of delta 13C and DOC concentration are therefore highly desirable. A promising, new system has been developed for this purpose, linking a high-temperature combustion TOC analyzer trough an interface with a continuous flow isotope ratio mass spectrometer (Elementar group, Hanau, Germany). This TOC-IRMS system enables simultaneous stable isotope (bulk delta 13C) and concentration analysis of DOC, with high oxidation efficiency by high-temperature combustion for complex mixtures as natural DOC. To give delta 13C analysis by TOC-IRMS the necessary impulse for broad-scale application, we present a detailed evaluation of its analytical performance for realistic and challenging conditions inclusive low DOC concentrations and environmental samples. High precision (standard deviation, SD predominantly < 0.15 permil) and accuracy (R2 = 0.9997, i.e. comparison TOC-IRMS and conventional EA-IRMS) were achieved by TOC-IRMS for a broad diversity of DOC solutions. This precision is comparable or even slightly better than that typically reported for EA-IRMS systems, and improves previous techniques for δ13C analysis of DOC. Simultaneously, very good precision was obtained for DOC concentration measurements. Assessment of natural abundance and slightly 13C enriched DOC, a wide range of concentrations (0.2-150 mgC/L) and injection volumes (0.05-3 ml), demonstrated good analytical performance with negligible memory effects, no concentration/volume effects and a wide linearity. Low DOC concentrations (< 2 mgC/L), were correctly analyzed without any pre-concentration. Moreover, TOC-IRMS was successfully applied to analyze DOC from diverse terrestrial, freshwater and marine environments (SD < 0.23 permil). In summary, the TOC

Natural abundance 17O DNP two-dimensional and surface-enhanced NMR spectroscopy

DOE PAGES

Perras, Frédéric A.; Kobayashi, Takeshi; Pruski, Marek

2015-06-22

Due to its extremely low natural abundance and quadrupolar nature, the 17O nuclide is very rarely used for spectroscopic investigation of solids by NMR without isotope enrichment. Additionally, the applicability of dynamic nuclear polarization (DNP), which leads to sensitivity enhancements of 2 orders of magnitude, to 17O is wrought with challenges due to the lack of spin diffusion and low polarization transfer efficiency from 1H. Here, we demonstrate new DNP-based measurements that extend 17O solid-state NMR beyond its current capabilities. The use of the PRESTO technique instead of conventional 1H– 17O cross-polarization greatly improves the sensitivity and enables the facilemore » measurement of undistorted line shapes and two-dimensional 1H– 17O HETCOR NMR spectra as well as accurate internuclear distance measurements at natural abundance. This was applied for distinguishing hydrogen-bonded and lone 17O sites on the surface of silica gel; the one-dimensional spectrum of which could not be used to extract such detail. As a result, this greatly enhanced sensitivity has enabled, for the first time, the detection of surface hydroxyl sites on mesoporous silica at natural abundance, thereby extending the concept of DNP surface-enhanced NMR spectroscopy to the 17O nuclide.« less

The 12C/ 13C isotopic ratio in Titan hydrocarbons from Cassini/CIRS infrared spectra

NASA Astrophysics Data System (ADS)

Nixon, C. A.; Achterberg, R. K.; Vinatier, S.; Bézard, B.; Coustenis, A.; Irwin, P. G. J.; Teanby, N. A.; de Kok, R.; Romani, P. N.; Jennings, D. E.; Bjoraker, G. L.; Flasar, F. M.

2008-06-01

We have analyzed infrared spectra of Titan recorded by the Cassini Composite Infrared Spectrometer (CIRS) to measure the isotopic ratio 12C/ 13C in each of three chemical species in Titan's stratosphere: CH 4, C 2H 2 and C 2H 6. This is the first measurement of 12C/ 13C in any C 2 molecule on Titan, and the first measurement of 12CH 4/ 13CH 4 (non-deuterated) on Titan by remote sensing. Our spectra cover five widely-spaced latitudes, 65° S to 71° N and we have searched for both latitude variability of 12C/ 13C within a given species, and also for differences between the 12C/ 13C in the three gases. For CH 4 alone, we find C12/C13=76.6±2.7 (1- σ), essentially in agreement with the 12CH 4/ 13CH 4 measured by the Huygens Gas Chromatograph/Mass Spectrometer instrument (GCMS) [Niemann, H.B., and 17 colleagues, 2005. Nature 438, 779-784]: 82.3±1.0, and also with measured values in H 13CN and 13CH 3D by CIRS at lower precision [Bézard, B., Nixon, C., Kleiner, I., Jennings, D., 2007. Icarus 191, 397-400; Vinatier, S., Bézard, B., Nixon, C., 2007. Icarus 191, 712-721]. For the C 2 species, we find C12/C13=84.8±3.2 in C 2H 2 and 89.8±7.3 in C 2H 6, a possible trend of increasingly value with molecular mass, although these values are both compatible with the Huygens GCMS value to within error bars. There are no convincing trends in latitude. Combining all fifteen measurements, we obtain a value of C12/C13=80.8±2.0, also compatible with GCMS. Therefore, the evidence is mounting that 12C/ 13C is some 8% lower on Titan than on the Earth (88.9, inorganic standard), and lower than typical for the outer planets ( 88±7 [Sada, P.V., McCabe, G.H., Bjoraker, G.L., Jennings, D.E., Reuter, D.C., 1996. Astrophys. J. 472, 903-907]). There is no current model for this enrichment, and we discuss several mechanisms that may be at work.

Natural and Anthropogenic Factors Controlling the Down Profile Increase in δ13C of Soil Organic Matter

NASA Astrophysics Data System (ADS)

Serach, L.; Breecker, D.

2016-12-01

The increases in the stable C isotope ratio (δ13C) of soil organic carbon (SOC) with depth common in well-drained soils are widely accepted as being due to the C isotope fractionation between CO2 and SOC during microbial respiration. However, results from previous studies that investigate C isotope fractionation during respiration are conflicting. Respired CO2 with 13C values lower, higher and not significantly different than the associated SOC have been reported in the literature. This project aims to quantify the contribution of isotopic fractionation during microbial respiration to the down-profile shift in δ13C values by means of a long-term (2 year) incubation of topsoil (0-2cm). The topsoil used in the incubations was collected from undisturbed temperate and tropical forests. At each location, soil profiles from 0-20 cm depth were also collected and the down profile trends in concentrations and δ13C values of bulk organic carbon were measured. The CO2-SOC carbon isotope enrichment factor ɛCO2-SOM required to explain each profile was then calculated. We compared these calculated ɛCO2-SOM values with empirical values determined from soil incubations. ɛCO2-SOM values were determined from incubations as the difference between δ13C values of headspace CO2 and bulk SOC. We have thus far measured these δ13C values at 1,4 and 7 months, allowing us to track if and when empirical ɛCO2-SOM values reach the magnitude required to explain the profiles. Thus far, all empirical ɛCO2-SOM values are either too small or of the wrong sign to explain the profiles, suggesting that a mechanism other than C isotope fractionation during microbial respiration may be responsible. Therefore, we are also investigating the possibility that the anthropogenic increase in concentrations of atmospheric CO2, through its influence on δ13C values of C3 plants, explains a substantial portion of the typical down profile increase in SOC δ13C values.

Evaluating microbial carbon sources in Athabasca oil sands tailings ponds using natural abundance stable and radiocarbon isotopes

NASA Astrophysics Data System (ADS)

Ahad, J. M.; Pakdel, H.

2013-12-01

Natural abundance stable (δ13C) and radiocarbon (Δ14C) isotopes of phospholipid fatty acids (PLFAs) were used to evaluate the carbon sources utilized by the active microbial populations in surface sediments from Athabasca oil sands tailings ponds. The absence of algal-specific PLFAs at three of the four sites investigated, in conjunction with δ13C signatures for PLFAs that were generally within ~3‰ of that reported for oil sands bitumen (~ -30‰), indicated that the microbial communities growing on petroleum constituents were dominated by aerobic heterotrophs. The Δ14C values of PLFAs ranged from -906 to -586‰ and pointed to a significant uptake of fossil carbon (up to ~90% of microbial carbon derived from petroleum), particularly in PLFAs (e.g., cy17:0 and cy19:0) often associated with petroleum hydrocarbon degrading bacteria. The comparatively higher levels of 14C in other, less specific PLFAs (e.g., 16:0) indicated the preferential uptake of younger organic matter by the general microbial population (~50-80% of microbial carbon derived from petroleum). Since the main carbon pools in tailings sediment were essentially 'radiocarbon dead' (i.e., no detectable 14C), the principal source for this modern carbon is considered to be the Athabasca River, which provides the bulk of the water used in the bitumen extraction process. The preferential uptake of the minor amount of young and presumably more biodegradable material present in systems otherwise dominated by recalcitrant petroleum constituents has important implications for remediation strategies. On the one hand, it implies that mining-related organic contaminants could persist in the environment long after tailings pond reclamation has begun. Alternatively, it may be that the young, labile organic matter provided by the Athabasca River plays an important role in stimulating or supporting the microbial utilization of petroleum carbon in oil sands tailings ponds via co-metabolism or priming processes

Meteorological factors associated with abundance of airborne fungal spores over natural vegetation

NASA Astrophysics Data System (ADS)

Crandall, Sharifa G.; Gilbert, Gregory S.

2017-08-01

The abundance of airborne fungal spores in agricultural and urban settings increases with greater air temperature, relative humidity, or precipitation. The same meteorological factors that affect temporal patterns in spore abundance in managed environments also vary spatially across natural habitats in association with differences in vegetation structure. Here we investigated how temporal and spatial variation in aerial spore abundance is affected by abiotic (weather) and biotic (vegetation) factors as a foundation for predicting how fungi may respond to changes in weather and land-use patterns. We measured the phenology of airborne fungal spores across a mosaic of naturally occurring vegetation types at different time scales to describe (1) how spore abundance changes over time, (2) which local meteorological variables are good predictors for airborne spore density, and (3) whether spore abundance differs across vegetation types. Using an air volumetric vacuum sampler, we collected spore samples at 3-h intervals over a 120-h period in a mixed-evergreen forest and coastal prairie to measure diurnal, nocturnal, and total airborne spore abundance across vegetation types. Spore samples were also collected at weekly and monthly intervals in mixed-evergreen forest, redwood forest, and maritime chaparral vegetation types from 12 field sites across two years. We found greater airborne spore densities during the wetter winter months compared to the drier summer months. Mean total spore abundance in the mixed-evergreen forest was twice than in the coastal prairie, but there were no significant differences in total airborne spore abundance among mixed-evergreen forest, redwood forest, and maritime chaparral vegetation types. Weekly and monthly peaks in airborne spore abundance corresponded with rain events and peaks in soil moisture. Overall, temporal patterns in meteorological factors were much more important in determining airborne fungal spore abundance than the

Organic vs. conventional grassland management: do (15)N and (13)C isotopic signatures of hay and soil samples differ?

PubMed

Klaus, Valentin H; Hölzel, Norbert; Prati, Daniel; Schmitt, Barbara; Schöning, Ingo; Schrumpf, Marion; Fischer, Markus; Kleinebecker, Till

2013-01-01

Distinguishing organic and conventional products is a major issue of food security and authenticity. Previous studies successfully used stable isotopes to separate organic and conventional products, but up to now, this approach was not tested for organic grassland hay and soil. Moreover, isotopic abundances could be a powerful tool to elucidate differences in ecosystem functioning and driving mechanisms of element cycling in organic and conventional management systems. Here, we studied the δ(15)N and δ(13)C isotopic composition of soil and hay samples of 21 organic and 34 conventional grasslands in two German regions. We also used Δδ(15)N (δ(15)N plant - δ(15)N soil) to characterize nitrogen dynamics. In order to detect temporal trends, isotopic abundances in organic grasslands were related to the time since certification. Furthermore, discriminant analysis was used to test whether the respective management type can be deduced from observed isotopic abundances. Isotopic analyses revealed no significant differences in δ(13)C in hay and δ(15)N in both soil and hay between management types, but showed that δ(13)C abundances were significantly lower in soil of organic compared to conventional grasslands. Δδ(15)N values implied that management types did not substantially differ in nitrogen cycling. Only δ(13)C in soil and hay showed significant negative relationships with the time since certification. Thus, our result suggest that organic grasslands suffered less from drought stress compared to conventional grasslands most likely due to a benefit of higher plant species richness, as previously shown by manipulative biodiversity experiments. Finally, it was possible to correctly classify about two third of the samples according to their management using isotopic abundances in soil and hay. However, as more than half of the organic samples were incorrectly classified, we infer that more research is needed to improve this approach before it can be efficiently

Organic vs. Conventional Grassland Management: Do 15N and 13C Isotopic Signatures of Hay and Soil Samples Differ?

PubMed Central

Klaus, Valentin H.; Hölzel, Norbert; Prati, Daniel; Schmitt, Barbara; Schöning, Ingo; Schrumpf, Marion; Fischer, Markus; Kleinebecker, Till

2013-01-01

Distinguishing organic and conventional products is a major issue of food security and authenticity. Previous studies successfully used stable isotopes to separate organic and conventional products, but up to now, this approach was not tested for organic grassland hay and soil. Moreover, isotopic abundances could be a powerful tool to elucidate differences in ecosystem functioning and driving mechanisms of element cycling in organic and conventional management systems. Here, we studied the δ15N and δ13C isotopic composition of soil and hay samples of 21 organic and 34 conventional grasslands in two German regions. We also used Δδ15N (δ15N plant - δ15N soil) to characterize nitrogen dynamics. In order to detect temporal trends, isotopic abundances in organic grasslands were related to the time since certification. Furthermore, discriminant analysis was used to test whether the respective management type can be deduced from observed isotopic abundances. Isotopic analyses revealed no significant differences in δ13C in hay and δ15N in both soil and hay between management types, but showed that δ13C abundances were significantly lower in soil of organic compared to conventional grasslands. Δδ15N values implied that management types did not substantially differ in nitrogen cycling. Only δ13C in soil and hay showed significant negative relationships with the time since certification. Thus, our result suggest that organic grasslands suffered less from drought stress compared to conventional grasslands most likely due to a benefit of higher plant species richness, as previously shown by manipulative biodiversity experiments. Finally, it was possible to correctly classify about two third of the samples according to their management using isotopic abundances in soil and hay. However, as more than half of the organic samples were incorrectly classified, we infer that more research is needed to improve this approach before it can be efficiently used in practice

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

Stronger warming effects on microbial abundances in colder regions

PubMed Central

Chen, Ji; Luo, Yiqi; Xia, Jianyang; Jiang, Lifen; Zhou, Xuhui; Lu, Meng; Liang, Junyi; Shi, Zheng; Shelton, Shelby; Cao, Junji

2015-01-01

Soil microbes play critical roles in regulating terrestrial carbon (C) cycle and its feedback to climate change. However, it is still unclear how the soil microbial community and abundance respond to future climate change scenarios. In this meta-analysis, we synthesized the responses of microbial community and abundance to experimental warming from 64 published field studies. Our results showed that warming significantly increased soil microbial abundance by 7.6% on average. When grouped by vegetation or soil types, tundras and histosols had the strongest microbial responses to warming with increased microbial, fungal, and bacterial abundances by 15.0%, 9.5% and 37.0% in tundra, and 16.5%, 13.2% and 13.3% in histosols, respectively. We found significant negative relationships of the response ratios of microbial, fungal and bacterial abundances with the mean annual temperature, indicating that warming had stronger effects in colder than warmer regions. Moreover, the response ratios of microbial abundance to warming were positively correlated with those of soil respiration. Our findings therefore indicate that the large quantities of C stored in colder regions are likely to be more vulnerable to climate warming than the soil C stored in other warmer regions. PMID:26658882

29 CFR 790.13 - General nature of defense.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 29 Labor 3 2011-07-01 2011-07-01 false General nature of defense. 790.13 Section 790.13 Labor... Administrative Regulations, Etc. § 790.13 General nature of defense. (a) Under the provisions of sections 9 and... recognition by Congress of the remedial nature of the Fair Labor Standards Act and of the need for...

29 CFR 790.13 - General nature of defense.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 29 Labor 3 2012-07-01 2012-07-01 false General nature of defense. 790.13 Section 790.13 Labor... Administrative Regulations, Etc. § 790.13 General nature of defense. (a) Under the provisions of sections 9 and... recognition by Congress of the remedial nature of the Fair Labor Standards Act and of the need for...

29 CFR 790.13 - General nature of defense.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 29 Labor 3 2010-07-01 2010-07-01 false General nature of defense. 790.13 Section 790.13 Labor... Administrative Regulations, Etc. § 790.13 General nature of defense. (a) Under the provisions of sections 9 and... recognition by Congress of the remedial nature of the Fair Labor Standards Act and of the need for...

29 CFR 790.13 - General nature of defense.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 29 Labor 3 2013-07-01 2013-07-01 false General nature of defense. 790.13 Section 790.13 Labor... Administrative Regulations, Etc. § 790.13 General nature of defense. (a) Under the provisions of sections 9 and... recognition by Congress of the remedial nature of the Fair Labor Standards Act and of the need for...

29 CFR 790.13 - General nature of defense.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 29 Labor 3 2014-07-01 2014-07-01 false General nature of defense. 790.13 Section 790.13 Labor... Administrative Regulations, Etc. § 790.13 General nature of defense. (a) Under the provisions of sections 9 and... recognition by Congress of the remedial nature of the Fair Labor Standards Act and of the need for...

C-13 dynamics in benthic algae: Effects of light, phosphorus, and biomass development

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

Hill, Walter; Fanta, S.E.; Roberts, Brian J

2008-07-01

We performed three experiments in indoor streams and one experiment in a natural stream to investigate the effects of growth factors on {delta}{sup 13}C levels in benthic microalgae. In the indoor streams, algae grown under conditions of high light and high phosphorus had {delta}{sup 13}C values that were 16% higher than those in algae grown under conditions of low light and low phosphorus. Light effects were much stronger than phosphorus effects. The effects of both factors increased in strength as algal biomass accrued, and by the end of the experiments, algal {delta}{sup 13}C and biomass were highly correlated. In themore » natural stream, algae exposed to direct sunlight were enriched 15% over shaded algae, corroborating the strong effect of light in the indoor streams. Growth factors such as light and nutrients probably reduce discrimination against {delta}{sup 13}C (raising {delta}{sup 13}C values) in benthic microalgae by causing CO{sub 2} depletion both within individual cells and within the assemblage matrix. However, because the most marked fractionation occurred in older and thicker assemblages, CO{sub 2} depletion within the assemblage matrix appeared to be more important than depletion within individual cells. In the absence of carbon-concentrating mechanisms, elevated {delta}{sup 13}C suggests that inorganic carbon may limit the growth of benthic algae. The extensive range of d13C values (-14{per_thousand} to -36{per_thousand}) created by light and nutrient manipulations in this study easily encompassed the mean {delta}{sup 13}C values of both C{sub 3} and C{sub 4} terrestrial plants, indicating the challenge aquatic ecologists face in identifying carbon sources for higher trophic levels when light and nutrient conditions vary.« less

Miocene weathering environments in Western Australia-Inferences from the abundance and 13C/12C of Fe(CO3)OH in CID goethite

NASA Astrophysics Data System (ADS)

Fritz, Tyler O.; Yapp, Crayton J.

2018-04-01

The channel iron deposits (CID) of the Hamersley Province in Western Australia are dominated by pedogenic goethite/hematite-rich ooids and pisoids that were transported to, and deposited in, the meandering channels of Miocene rivers. Information about the Miocene weathering environments that produced the Fe(III) oxides is archived in the mole fraction (X) and δ13C of the Fe(CO3)OH component in solid solution in oolitic CID goethite (α-FeOOH). Values of X and δ13C were measured for 12 oolitic goethite samples from different depths in two cores drilled in CID of the Robe Formation of Mesa J. The weighted-average plateau values of X ranged from 0.0098 to 0.0334, which suggest ambient CO2 concentrations that ranged from ∼50,000 ppm V to perhaps as much as ∼200,000 ppm V at the time of goethite crystallization. In a vadose zone characterized by in situ production of CO2 with steady-state Fickian diffusive transport of the gas, such concentrations would correspond to modeled soil respiration rates (Q) ranging from about 10 to 30 mmol/m2/h. Values for Q of about 10 mmol/m2/h are reported for soils in modern tropical forests with MAP ≥ ∼2000 mm. However, model-derived values of Q that exceed 15 mmol/m2/h are larger than observed in modern systems. This could indicate that some of the CID goethites crystallized in conditions that were phreatic or near phreatic rather than vadose. The δ13C values of the Fe(CO3)OH component in these 12 CID samples ranged from -24.0‰ to -22.3‰, which are among the most negative measured to date. If they reflect steady-state diffusive transport of CO2 in vadose environments, the soil CO2 would have been derived from a source with δ13C values that ranged from ∼-31‰ to -29‰. If, on the other hand, the goethites crystallized in a nearly phreatic environment that was moderately acidic, the inferred δ13C of the ancient CO2 source would have been about -27.6‰ to -25.8‰. In either case, the δ13C values point to in situ

Relative contribution of shoot and ear photosynthesis to grain filling in wheat under good agronomical conditions assessed by differential organ δ13C

PubMed Central

Sanchez-Bragado, Rut; Molero, Gemma; Reynolds, Matthew P.; Araus, Jose Luis

2014-01-01

During grain filling in C3 cereals, the shoot (particularly the flag leaf) and the ear are believed to play major roles as sources of assimilates. However, both the cost and the intrusive nature of most of the methodologies available to investigate this have prevented conclusive results being obtained. This study compared the carbon isotope composition (δ13C) in its natural abundance in mature kernels with the δ13C of the water-soluble fraction of the peduncle, glumes, and awns to assess the relative contribution of the shoot (understood as the whole set of photosynthetic organs below the peduncle) and ear to grain filling in a set of highly productive wheat lines from the International Maize and Wheat Improvement Center, Mexico, under good agronomic conditions. In overall terms, the contribution of the ear was greater in comparison with that of the shoot. The specific contribution of the flag leaf blade to grain filling was also assessed by comparing the δ13C of grains with the δ13C of the water-soluble fraction of the flag leaf and the awns. The contribution of the flag leaf was minor, ranging between 3 and 18%. Complementary analyses performed such as gas-exchange rates and the accumulated water-soluble carbohydrates in both organs and light intercepted by the canopy at different strata suggested that the ear has a photosynthetic capacity at least comparable to that of the flag leaf. In this sense, selection for a higher contribution of ear photosynthesis to grain yield in breeding programmes could be addressed with the use of stable isotopes. PMID:25053645

A global ocean climatology of preindustrial and modern ocean δ13C

NASA Astrophysics Data System (ADS)

Eide, Marie; Olsen, Are; Ninnemann, Ulysses S.; Johannessen, Truls

2017-03-01

We present a global ocean climatology of dissolved inorganic carbon δ13C (‰) corrected for the 13C-Suess effect, preindustrial δ13C. This was constructed by first using Olsen and Ninnemann's (2010) back-calculation method on data from 25 World Ocean Circulation Experiment cruises to reconstruct the preindustrial δ13C on sections spanning all major oceans. Next, we developed five multilinear regression equations, one for each major ocean basin, which were applied on the World Ocean Atlas data to construct the climatology. This reveals the natural δ13C distribution in the global ocean. Compared to the modern distribution, the preindustrial δ13C spans a larger range of values. The maxima, of up to 1.8‰, occurs in the subtropical gyres of all basins, in the upper and intermediate waters of the North Atlantic, as well as in mode waters with a Southern Ocean origin. Particularly strong gradients occur at intermediate depths, revealing a strong potential for using δ13C as a tracer for changes in water mass geometry at these levels. Further, we identify a much tighter relationship between δ13C and apparent oxygen utilization (AOU) than between δ13C and phosphate. This arises because, in contrast to phosphate, AOU and δ13C are both partly reset when waters are ventilated in the Southern Ocean and underscore that δ13C is a highly robust proxy for past changes in ocean oxygen content and ocean ventilation. Our global preindustrial δ13C climatology is openly accessible and can be used, for example, for improved model evaluation and interpretation of sediment δ13C records.

Uncertainties of fluxes and 13C / 12C ratios of atmospheric reactive-gas emissions

NASA Astrophysics Data System (ADS)

Gromov, Sergey; Brenninkmeijer, Carl A. M.; Jöckel, Patrick

2017-07-01

We provide a comprehensive review of the proxy data on the 13C / 12C ratios and uncertainties of emissions of reactive carbonaceous compounds into the atmosphere, with a focus on CO sources. Based on an evaluated set-up of the EMAC model, we derive the isotope-resolved data set of its emission inventory for the 1997-2005 period. Additionally, we revisit the calculus required for the correct derivation of uncertainties associated with isotope ratios of emission fluxes. The resulting δ13C of overall surface CO emission in 2000 of -(25. 2 ± 0. 7) ‰ is in line with previous bottom-up estimates and is less uncertain by a factor of 2. In contrast to this, we find that uncertainties of the respective inverse modelling estimates may be substantially larger due to the correlated nature of their derivation. We reckon the δ13C values of surface emissions of higher hydrocarbons to be within -24 to -27 ‰ (uncertainty typically below ±1 ‰), with an exception of isoprene and methanol emissions being close to -30 and -60 ‰, respectively. The isotope signature of ethane surface emission coincides with earlier estimates, but integrates very different source inputs. δ13C values are reported relative to V-PDB.

Obtaining molecular and structural information from 13C-14N systems with 13C FIREMAT experiments.

PubMed

Strohmeier, Mark; Alderman, D W; Grant, David M

2002-04-01

The effect of dipolar coupling to 14N on 13C FIREMAT (five pi replicated magic angle turning) experiments is investigated. A method is developed for fitting the 13C FIREMAT FID employing the full theory to extract the 13C-14N dipolar and 13C chemical shift tensor information. The analysis requires prior knowledge of the electric field gradient (EFG) tensor at the 14N nucleus. In order to validate the method the analysis is done for the amino acids alpha-glycine, gamma-glycine, l-alanine, l-asparagine, and l-histidine on FIREMAT FIDs recorded at 13C frequencies of 50 and 100 MHz. The dipolar and chemical shift data obtained with this analysis are in very good agreement with the previous single-crystal 13C NMR results and neutron diffraction data on alpha-glycine, l-alanine, and l-asparagine. The values for gamma-glycine and l-histidine obtained with this new method are reported for the first time. The uncertainties in the EFG tensor on the resultant 13C chemical shift and dipolar tensor values are assessed. (c) 2002 Elsevier Science (USA).

Light-induced yellowing of selectively 13C-enriched dehydrogenation polymers (DHPs). Part 1, Side-chain 13C-enriched DHP ([alpha], [beta], and [gamma]-13C)

Treesearch

Jim Parkas; Magnus Paulsson; Terashima Noritsugu; Ulla Westermark; Sally Ralph

2004-01-01

Light-induced yellowing has been studied using side-chain ([alpha], [beta], and [gamma]) 13C-enriched DHP (dehydrogenation polymer) and quantitative solution state 13C NMR spectroscopy. The DHP was formed from 13C-enriched coniferin using an enzymatic system consisting of [beta]-glucosidase, glucose oxidase, and peroxidase in a pH 6 buffer solution. The DHP was applied...

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

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.

Development of LC-13C NMR

NASA Technical Reports Server (NTRS)

Dorn, H. C.; Wang, J. S.; Glass, T. E.

1986-01-01

This study involves the development of C-13 nuclear resonance as an on-line detector for liquid chromatography (LC-C-13 NMR) for the chemical characterization of aviation fuels. The initial focus of this study was the development of a high sensitivity flow C-13 NMR probe. Since C-13 NMR sensitivity is of paramount concern, considerable effort during the first year was directed at new NMR probe designs. In particular, various toroid coil designs were examined. In addition, corresponding shim coils for correcting the main magnetic field (B sub 0) homogeneity were examined. Based on these initial probe design studies, an LC-C-13 NMR probe was built and flow C-13 NMR data was obtained for a limited number of samples.

13C NMR study of the generation of C2- and C3-deuterated lactic acid by tumoral pancreatic islet cells exposed to D-[1-13C]-, D-[2-13C]- and D-[6-13C]-glucose in 2H2O.

PubMed

Willem, R; Biesemans, M; Kayser, F; Malaisse, W J

1994-03-01

Tumoral pancreatic islet cells of the RIN5mF line were incubated for 120 min in media prepared in 2H2O and containing D-[1-13C]glucose, D-[2-13C]glucose, and D-[6-13C]glucose. The generation of C2- and C3-deuterated lactic acid was assessed by 13C NMR. The interpretation of experimental results suggests that a) the efficiency of deuteration on the C1 of D-fructose 6-phosphate does not exceed about 47% and 4% in the phosphoglucoisomerase and phosphomannoisomerase reactions, respectively; b) approximately 38% of the molecules of D-glyceraldehyde 3-phosphate generated from D-glucose escape deuteration in the sequence of reactions catalyzed by triose phosphate isomerase and aldolase; and c) about 41% of the molecules of pyruvate generated by glycolysis are immediately converted to lactate, the remaining 59% of pyruvate molecules undergoing first a single or double back-and-forth interconversion with L-alanine. It is proposed that this methodological approach, based on high resolution 13C NMR spectroscopy, may provide novel information on the regulation of back-and-forth interconversion of glycolytic intermediates in intact cells as modulated, for instance, by enzyme-to-enzyme tunneling.

Comparison of liquid chromatography-isotope ratio mass spectrometry (LC/IRMS) and gas chromatography-combustion-isotope ratio mass spectrometry (GC/C/IRMS) for the determination of collagen amino acid δ13C values for palaeodietary and palaeoecological reconstruction.

PubMed

Dunn, Philip J H; Honch, Noah V; Evershed, Richard P

2011-10-30

Results are presented of a comparison of the amino acid (AA) δ(13)C values obtained by gas chromatography-combustion-isotope ratio mass spectrometry (GC/C/IRMS) and liquid chromatography-isotope ratio mass spectrometry (LC/IRMS). Although the primary focus was the compound-specific stable carbon isotope analysis of bone collagen AAs, because of its growing application for palaeodietary and palaeoecological reconstruction, the results are relevant to any field where AA δ(13)C values are required. We compare LC/IRMS with the most up-to-date GC/C/IRMS method using N-acetyl methyl ester (NACME) AA derivatives. This comparison involves the analysis of standard AAs and hydrolysates of archaeological human bone collagen, which have been previously investigated as N-trifluoroacetyl isopropyl esters (TFA/IP). It was observed that, although GC/C/IRMS analyses required less sample, LC/IRMS permitted the analysis of a wider range of AAs, particularly those not amenable to GC analysis (e.g. arginine). Accordingly, reconstructed bulk δ(13)C values based on LC/IRMS-derived δ(13)C values were closer to the EA/IRMS-derived δ(13)C values than those based on GC/C/IRMS values. The analytical errors for LC/IRMS AA δ(13)C values were lower than GC/C/IRMS determinations. Inconsistencies in the δ(13)C values of the TFA/IP derivatives compared with the NACME- and LC/IRMS-derived δ(13)C values suggest inherent problems with the use of TFA/IP derivatives, resulting from: (i) inefficient sample combustion, and/or (ii) differences in the intra-molecular distribution of δ(13)C values between AAs, which are manifested by incomplete combustion. Close similarities between the NACME AA δ(13)C values and the LC/IRMS-derived δ(13)C values suggest that the TFA/IP derivatives should be abandoned for the natural abundance determinations of AA δ(13)C values. Copyright © 2011 John Wiley & Sons, Ltd.

High-resolution solid-state 13C NMR spectroscopy of the paramagnetic metal-organic frameworks, STAM-1 and HKUST-1.

PubMed

Dawson, Daniel M; Jamieson, Lauren E; Mohideen, M Infas H; McKinlay, Alistair C; Smellie, Iain A; Cadou, Romain; Keddie, Neil S; Morris, Russell E; Ashbrook, Sharon E

2013-01-21

Solid-state (13)C magic-angle spinning (MAS) NMR spectroscopy is used to investigate the structure of the Cu(II)-based metal-organic frameworks (MOFs), HKUST-1 and STAM-1, and the structural changes occurring within these MOFs upon activation (dehydration). NMR spectroscopy is an attractive technique for the investigation of these materials, owing to its high sensitivity to local structure, without any requirement for longer-range order. However, interactions between nuclei and unpaired electrons in paramagnetic systems (e.g., Cu(II)-based MOFs) pose a considerable challenge, not only for spectral acquisition, but also in the assignment and interpretation of the spectral resonances. Here, we exploit the rapid T(1) relaxation of these materials to obtain (13)C NMR spectra using a spin-echo pulse sequence at natural abundance levels, and employ frequency-stepped acquisition to ensure uniform excitation of resonances over a wide frequency range. We then utilise selective (13)C isotopic labelling of the organic linker molecules to enable an unambiguous assignment of NMR spectra of both MOFs for the first time. We show that the monomethylated linker can be recovered from STAM-1 intact, demonstrating not only the interesting use of this MOF as a protecting group, but also the ability (for both STAM-1 and HKUST-1) to recover isotopically-enriched linkers, thereby reducing significantly the overall cost of the approach.

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

Treesearch

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

2003-01-01

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

Temporal δ13C records from bottlenose dolphins (Tursiops truncatus) reflect variation in foraging location and global carbon cycling

NASA Astrophysics Data System (ADS)

Rossman, S. L.; Barros, N. B.; Ostrom, P. H.; Gandhi, H.; Wells, R. S.

2010-12-01

With four decades of data on a population of bottlenose dolphins (Tursiops truncatus) resident to Sarasota Bay (SB), The Sarasota Dolphin Research Program offers an unparalleled platform for ground-truthing stable isotope data and exploring bottlenose dolphin ecology in a natural setting. We explored carbon isotope value fidelity to habitat utilization by comparing δ13C data from whole teeth and muscle to the individual dolphin's proclivity towards foraging in seagrass beds based on observational data. We then examined variation in habitat use based on temporal isotope records. Whole tooth protein isotope values do not show a significant correlation with the observed percentage of foraging in seagrass habitat. In contrast, δ13C values from muscle showed a significant positive relationship with the observational data. Differences in the degree of tissue turn over may account for this distinction between tooth and muscle. Dolphin teeth consist of annually deposited layers that are inert once formed. Thus, the isotopic composition of protein in annuli reflect foraging at the time of deposition. In addition to incorporating variation associated with differences in foraging over the lifetime of the individual, whole tooth isotope values are confounded because a disproportionate amount of tooth protein derives from the first few years of life. Given the turnover time of muscle tissue, isotope values reflect diet over the past several months. From 1991 to 2008, muscle δ13C values showed a significant decline, -13.5‰ to -15.1‰.This time period encompasses a state wide net fishing ban (1995) however other factors such as a series of red tide harmful algal blooms, a decline in predators, increases in shallow water boat traffic and an increase in string ray abundance may also contribute to the temporal isotope trend. To examine changes in dolphin foraging habitat further back in time we analyzed the tip of crown of the tooth which records the isotopic signal from the

Stronger warming effects on microbial abundances in colder regions

DOE PAGES

Chen, Ji; Luo, Yiqi; Xia, Jianyang; ...

2015-12-10

Soil microbes play critical roles in regulating terrestrial carbon (C) cycle and its feedback to climate change. However, it is still unclear how the soil microbial community and abundance respond to future climate change scenarios. In this meta-analysis, we synthesized the responses of microbial community and abundance to experimental warming from 64 published field studies. Our results showed that warming significantly increased soil microbial abundance by 7.6% on average. When grouped by vegetation or soil types, tundras and histosols had the strongest microbial responses to warming with increased microbial, fungal, and bacterial abundances by 15.0%, 9.5% and 37.0% in tundra,more » and 16.5%, 13.2% and 13.3% in histosols, respectively. We found significant negative relationships of the response ratios of microbial, fungal and bacterial abundances with the mean annual temperature, indicating that warming had stronger effects in colder than warmer regions. Moreover, the response ratios of microbial abundance to warming were positively correlated with those of soil respiration. Our results therefore indicate that the large quantities of C stored in colder regions are likely to be more vulnerable to climate warming than the soil C stored in other warmer regions.« less

In vivo carbon-13 nuclear magnetic resonance studies of heart metabolism.

PubMed Central

Neurohr, K J; Barrett, E J; Shulman, R G

1983-01-01

Guinea pig heart metabolism was studied in vivo by 13C NMR at 20.18 MHz. High-quality proton-decoupled 13C NMR spectra with excellent signal-to-noise ratios and resolution could be obtained in 6 min. Natural-abundance spectra showed resonances that could be assigned to fatty acids, but glycogen was not seen. During intravenous infusion of D-[1-13C]glucose and insulin, the time course of myocardial glycogen synthesis was followed serially for up to 4 hr. Anoxia resulted in degradation of the labeled glycogen within 6 min and appearance of 13C label in lactic acid. Infusion of sodium [2-13C]acetate resulted in incorporation of label into the C-4, C-2, and C-3 positions of glutamate and glutamine, reflecting "scrambling" of the label expected from tricarboxylic acid cycle activity. Examination of the 31P NMR spectrum of the guinea pig heart in vivo demonstrated no change in the high-energy phosphates during the time periods of the 13C NMR experiments. Our studies indicate that 13C NMR is a unique non-destructive tool for the study of heart metabolism in vivo. PMID:6572924

Metabolism of uniformly labeled 13C-eicosapentaenoic acid and 13C-arachidonic acid in young and old men.

PubMed

Léveillé, Pauline; Chouinard-Watkins, Raphaël; Windust, Anthony; Lawrence, Peter; Cunnane, Stephen C; Brenna, J Thomas; Plourde, Mélanie

2017-08-01

Background: Plasma eicosapentaenoic acid (EPA) and arachidonic acid (AA) concentrations increase with age. Objective: The aim of this study was to evaluate EPA and AA metabolism in young and old men by using uniformly labeled carbon-13 ( 13 C) fatty acids. Design: Six young (∼25 y old) and 6 old (∼75 y old) healthy men were recruited. Each participant consumed a single oral dose of 35 mg 13 C-EPA and its metabolism was followed in the course of 14 d in the plasma and 28 d in the breath. After the washout period of ≥28 d, the same participants consumed a single oral dose of 50 mg 13 C-AA and its metabolism was followed for 28 d in plasma and breath. Results: There was a time × age interaction for 13 C-EPA ( P time × age = 0.008), and the shape of the postprandial curves was different between young and old men. The 13 C-EPA plasma half-life was ∼2 d for both young and old men ( P = 0.485). The percentage dose recovered of 13 C-EPA per hour as 13 CO 2 and the cumulative β-oxidation of 13 C-EPA did not differ between young and old men. At 7 d, however, old men had a >2.2-fold higher plasma 13 C-DHA concentration synthesized from 13 C-EPA compared with young men ( P age = 0.03). 13 C-AA metabolism was not different between young and old men. The 13 C-AA plasma half-life was ∼4.4 d in both young and old participants ( P = 0.589). Conclusions: The metabolism of 13 C-AA was not modified by age, whereas 13 C-EPA metabolism was slightly but significantly different in old compared with young men. The higher plasma 13 C-DHA seen in old men may be a result of slower plasma DHA clearance with age. This trial was registered at clinicaltrials.gov as NCT02957188. © 2017 American Society for Nutrition.

Pendrin protein abundance in the kidney is regulated by nitric oxide and cAMP.

PubMed

Thumova, Monika; Pech, Vladimir; Froehlich, Otto; Agazatian, Diana; Wang, Xiaonan; Verlander, Jill W; Kim, Young Hee; Wall, Susan M

2012-09-15

Pendrin is a Cl(-)/HCO(3)(-) exchanger, expressed in the apical regions of some intercalated cell subtypes, and is critical in the pressor response to angiotensin II. Since angiotensin type 1 receptor inhibitors reduce renal pendrin protein abundance in mice in vivo through a mechanism that is dependent on nitric oxide (NO), we asked if NO modulates renal pendrin expression in vitro and explored the mechanism by which it occurs. Thus we quantified pendrin protein abundance by confocal fluorescent microscopy in cultured mouse cortical collecting ducts (CCDs) and connecting tubules (CNTs). After overnight culture, CCDs maintain their tubular structure and maintain a solute gradient when perfused in vitro. Pendrin protein abundance increased 67% in CNT and 53% in CCD when NO synthase was inhibited (N(G)-nitro-L-arginine methyl ester, 100 μM), while NO donor (DETA NONOate, 200 μM) application reduced pendrin protein by ∼33% in the CCD and CNT. When CNTs were cultured in the presence of the guanylyl cyclase inhibitor 1H-[1,2,4] oxadiazolo[4,3-a]quinoxalin-1-one (10 μM), NO donors did not alter pendrin abundance. Conversely, pendrin protein abundance rose when cAMP content was increased by the application of an adenylyl cyclase agonist (forskolin, 10 μM), a cAMP analog (8-bromo-cAMP, 1 mM), or a phosphodiesterase inhibitor (BAY60-7550, 50 μM). Since NO reduces cellular cAMP in the CNT, we asked if NO reduces pendrin abundance by reducing cAMP. With blockade of cGMP-stimulated phosphodiesterase II, NO did not alter pendrin protein abundance. We conclude that NO acts through cAMP to reduce pendrin total protein abundance by enhancing cAMP degradation.

Pendrin protein abundance in the kidney is regulated by nitric oxide and cAMP

PubMed Central

Thumova, Monika; Pech, Vladimir; Froehlich, Otto; Agazatian, Diana; Wang, Xiaonan; Verlander, Jill W.; Kim, Young Hee

2012-01-01

Pendrin is a Cl−/HCO3− exchanger, expressed in the apical regions of some intercalated cell subtypes, and is critical in the pressor response to angiotensin II. Since angiotensin type 1 receptor inhibitors reduce renal pendrin protein abundance in mice in vivo through a mechanism that is dependent on nitric oxide (NO), we asked if NO modulates renal pendrin expression in vitro and explored the mechanism by which it occurs. Thus we quantified pendrin protein abundance by confocal fluorescent microscopy in cultured mouse cortical collecting ducts (CCDs) and connecting tubules (CNTs). After overnight culture, CCDs maintain their tubular structure and maintain a solute gradient when perfused in vitro. Pendrin protein abundance increased 67% in CNT and 53% in CCD when NO synthase was inhibited (NG-nitro-l-arginine methyl ester, 100 μM), while NO donor (DETA NONOate, 200 μM) application reduced pendrin protein by ∼33% in the CCD and CNT. When CNTs were cultured in the presence of the guanylyl cyclase inhibitor 1H-[1,2,4] oxadiazolo[4,3-a]quinoxalin-1-one (10 μM), NO donors did not alter pendrin abundance. Conversely, pendrin protein abundance rose when cAMP content was increased by the application of an adenylyl cyclase agonist (forskolin, 10 μM), a cAMP analog (8-bromo-cAMP, 1 mM), or a phosphodiesterase inhibitor (BAY60-7550, 50 μM). Since NO reduces cellular cAMP in the CNT, we asked if NO reduces pendrin abundance by reducing cAMP. With blockade of cGMP-stimulated phosphodiesterase II, NO did not alter pendrin protein abundance. We conclude that NO acts through cAMP to reduce pendrin total protein abundance by enhancing cAMP degradation. PMID:22811483

Microscale Variations in the 13C Content of the Murchison Meteorite

NASA Astrophysics Data System (ADS)

Romanek, C.; Gibson, E.; Socki, R.; Burkett, P. J.

1993-07-01

within the cores of chondrules and/or aggregates. Three typical cores were analyzed, with an average bulk composition of -21.0 +/- 0.5 per mil (n = 7). The bulk ^13C content of C-bearing phases increases monotonically outward in all directions within 100 to 200 micrometers of each core (i.e., within dust mantles) to a constant matrix value of -12.5 +/- 0.5 per mil (n = 40). The most isotopically enriched textural component found in Murchison is a regolith breccia clast without chondrules that has an average bulk delta ^13C value of -10 +/-0.5 per mil (n = 5). The clast was originally detectable only under cathodoluminescence, but with the aid of the laser microprobe it is now characterized by an unusually low volatile content and enriched ^13C composition. In general, the most isotopically enriched components also produce the lowest yield of gas (normalized to sampling volume). This trend of isotopic enrichment from chondrule to matrix has been documented previously for oxygen isotopes in carbonaceous chondrites [2]. Carbon isotopic gradients and heterogeneities within Murchison reflect fundamental changes in the chemical speciation and/or isotopic content of the main C-bearing components (i.e., acid-soluble and insoluble hydrocarbon fractions) within the meteorite. Perhaps core interiors and dust mantles are responding to environmental changes reflected in the speciation of C-bearing species distributed within the solar nebula or the parent body. Inverse correlations between hydrocarbon atomic mass number and ^13C abundance in the acid-soluble [3] and insoluble residues [4] of Murchison have been documented. Alternatively, micrometer-scale isotopic gradients may reflect fundamental changes in the isotopic composition of individual C-bearing species through time. Enrichments may represent kinetically controlled processes related to hydrocarbon formation. In contrast, assuming an equilibrium fractionation mechanism, isotopic enrichments may record a temperature

Les phénols de la lignine et le 13C, traceurs de l'origine des matières organiques du solLabelling the origin of soil organic matter by lignin phenols and 13C natural abundance

NASA Astrophysics Data System (ADS)

Jolivet, Claudy; Guillet, Bernard; Karroum, Michel; Andreux, Francis; Bernoux, Martial; Arrouays, Dominique

2001-11-01

In spodosols of Gascony (France), conversion of maritime pine stands into maize cropping leads to an incorporation of maize organic matter, which changed the isotopic ( δ13C) and phenolic signature in A and L horizons of soil. Hydrolysis of phenol lignin in forests and cultivated soils showed the predominance of vanillic units under forest and the early but moderate incorporation of cinnamic acids. Incorporation of syringic units appeared higher, related to a large maize production of stable syringic phenols. Syringic units represented a long-term marker of maize inputs in soils, whereas vanillic units revealed the degradation of forest organic matter.

Determinations of the 12C/13C Ratio for the Secondary Stars of AE Aquarii, SS Cygni, and RU Pegasi

NASA Astrophysics Data System (ADS)

Harrison, Thomas E.; Marra, Rachel E.

2017-07-01

We present new moderate-resolution near-infrared spectroscopy of three CVs obtained using GNIRS on Gemini-North. These spectra covered three 13CO bandheads found in the K-band, allowing us to derive the isotopic abundance ratios for carbon. We find small 12C/13C ratios for all three donor stars. In addition, these three objects show carbon deficits, with AE Aqr being the most extreme ([C/Fe] = -1.4). This result confirms the conjecture that the donor stars in some long-period CVs have undergone considerable nuclear evolution prior to becoming semi-contact binaries. In addition to the results for carbon, we find that the abundance of sodium is enhanced in these three objects, and the secondary stars in both RU Peg and SS Cyg suffer magnesium deficits. Explaining such anomalies appears to require higher mass progenitors than commonly assumed for the donor stars of CVs. Based on observations obtained at the Gemini Observatory, which is operated by the Association of Universities for Research in Astronomy, Inc., under a cooperative agreement with the NSF on behalf of the Gemini partnership: the National Science Foundation (United States), the National Research Council (Canada), CONICYT (Chile), Ministerio de Ciencia, Tecnología e Innovación Productiva (Argentina), and Ministério da Ciência, Tecnologia e Inovação (Brazil).

Natural gas and temperature structured a microbial community response to the Deepwater Horizon oil spill.

PubMed

Redmond, Molly C; Valentine, David L

2012-12-11

Microbial communities present in the Gulf of Mexico rapidly responded to the Deepwater Horizon oil spill. In deep water plumes, these communities were initially dominated by members of Oceanospirillales, Colwellia, and Cycloclasticus. None of these groups were abundant in surface oil slick samples, and Colwellia was much more abundant in oil-degrading enrichment cultures incubated at 4 °C than at room temperature, suggesting that the colder temperatures at plume depth favored the development of these communities. These groups decreased in abundance after the well was capped in July, but the addition of hydrocarbons in laboratory incubations of deep waters from the Gulf of Mexico stimulated Colwellia's growth. Colwellia was the primary organism that incorporated (13)C from ethane and propane in stable isotope probing experiments, and given its abundance in environmental samples at the time that ethane and propane oxidation rates were high, it is likely that Colwellia was active in ethane and propane oxidation in situ. Colwellia also incorporated (13)C benzene, and Colwellia's abundance in crude oil enrichments without natural gas suggests that it has the ability to consume a wide range of hydrocarbon compounds or their degradation products. However, the fact that ethane and propane alone were capable of stimulating the growth of Colwellia, and to a lesser extent, Oceanospirillales, suggests that high natural gas content of this spill may have provided an advantage to these organisms.

Cyanide and isocyanide abundances in the cold, dark cloud TMC-1

NASA Technical Reports Server (NTRS)

Irvine, W. M.; Schloerb, F. P.

1984-01-01

Cold, dark molecular clouds are particularly useful for the study of interstellar chemistry because their physical parameters are better understood than those of heterogeneous, complex giant molecular clouds. Another advantage is their relatively small distance from the solar system. The present investigaation has the objective to provide accurate abundance ratios for several cyanides and isocyanides in order to constrain models of dark cloud chemistry. The relative abundances of such related species can be particularly useful for the study of chemical processes. The cloud TMC-1 considered in the current study has a remarkably high abundance of acetylene and polyacetylene derivatives. Data at 3 mm, corresponding to the J = 1 to 0 transitions of HCN, H(C-13)N, HN(C-13), HC(N-15), and H(N-15)C were obtained.

Studies of minute quantities of natural abundance molecules using 2D heteronuclear correlation spectroscopy under 100kHz MAS

DOE PAGES

Nishiyama, Y.; Kobayashi, T.; Malon, M.; ...

2015-02-16

Two-dimensional 1H{ 13C} heteronuclear correlation solid-state NMR spectra of naturally abundant solid materials are presented, acquired using the 0.75-mm magic angle spinning (MAS) probe at spinning rates up to 100 kHz. In spite of the miniscule sample volume (290 nL), high-quality HSQC-type spectra of bulk samples as well as surface-bound molecules can be obtained within hours of experimental time. The experiments are compared with those carried out at 40 kHz MAS using a 1.6-mm probe, which offered higher overall sensitivity due to a larger rotor volume. The benefits of ultrafast MAS in such experiments include superior resolution in 1H dimensionmore » without resorting to 1H– 1H homonuclear RF decoupling, easy optimization, and applicability to mass-limited samples. As a result, the HMQC spectra of surface-bound species can be also acquired under 100 kHz MAS, although the dephasing of transverse magnetization has significant effect on the efficiency transfer under MAS alone.« less

A Large C+N+O Abundance Spread in Giant Stars of the Globular Cluster NGC 1851

NASA Astrophysics Data System (ADS)

Yong, David; Grundahl, Frank; D'Antona, Francesca; Karakas, Amanda I.; Lattanzio, John C.; Norris, John E.

2009-04-01

Abundances of C, N, and O are determined in four bright red giants that span the known abundance range for light (Na and Al) and s-process (Zr and La) elements in the globular cluster NGC 1851. The abundance sum C+N+O exhibits a range of 0.6 dex, a factor of 4, in contrast to other clusters in which no significant C+N+O spread is found. Such an abundance range offers support for the Cassisi et al. scenario in which the double subgiant branch populations are coeval but with different mixtures of C+N+O abundances. Further, the Na, Al, Zr, and La abundances are correlated with C+N+O, and therefore NGC 1851 is the first cluster to provide strong support for the scenario in which asymptotic giant branch stars are responsible for the globular cluster light element abundance variations. This paper includes data gathered with the 6.5 meter Magellan Telescopes located at Las Campanas Observatory, Chile.

Determination of 13C/12C-ratios in rumen produced methane and CO2 of cows, sheep and camels.

PubMed

Schulze, E; Lohmeyer, S; Giese, W

1998-01-01

Naturally produced methane shows different delta 13C-values with respect to its origin, e.g., geological or biological. Methane-production of ruminants is considered to be the dominant source from the animal kingdom. Isotopic values of rumen methane--given in literature--range between -80/1000 and -50/1000 and are related to feed composition and also sampling techniques. Keeping cows, camels and sheep under identical feed conditions and sampling rumen gases via implanted fistuale we compared delta PDB 13C-values of methane and CO2 between the species. Referring to mean values obtained from 4 or 5 samples at different times of 11 animals (n = 47) we calculated delta PDB 13C-medians resulting in small but not significant differences within and significant differences between the species for CO2 and methane. The delta PDB 13C-differences between methane and CO2 were statistically equal within and also between the species. Therefore a linear regression of methane values on CO2 is appropriate and leads to: delta PDB 13C(methane)/1000 = 1.57 * delta PDB 13C(CO2)/1000 - 47/1000 with a correlation coefficient of r = 0.87.

13C nuclear magnetic resonance and gas chromatography-mass spectrometry studies of carbon metabolism in the actinomycin D producer Streptomyces parvulus by use of 13C-labeled precursors.

PubMed Central

Inbar, L; Lapidot, A

1991-01-01

Fructose and glutamate metabolism was monitored in cell suspensions of streptomyces parvulus by 13C nuclear magnetic resonance. The experiments were performed for cells grown with various 13C sources in a growth medium containing D-[U-13C]fructose, L-[13C]glutamate, or L-[U-13C]aspartate and with nonlabeled precursors to compare intracellular pools in S. parvulus cells at different periods of the cell life cycle. The transport of fructose into the cells was biphasic in nature; during rapid transport, mannitol, fructose, and glucose 6-phosphate were accumulated intracellularly, whereas during the passive diffusion of fructose, the intracellular carbohydrate pool comprised mainly trehalose (1,1'-alpha-alpha-D-glucose). The regulation of fructokinase activity by the intracellular intermediates may play an important role in fructose catabolism in S. parvulus. Transaldolase activity in S. parvulus was determined from the 13C nuclear magnetic resonance labeling pattern of trehalose carbons obtained from cells grown in medium containing either L-[U-13C]aspartate or L-[U-13C]glutamate. Only carbons 4, 5, and 6 of the disaccharide were labeled. Isotopomer analysis of the trehalose carbons led us to conclude that the flux through the reverse glycolytic pathway, condensation of glyceraldehyde 3-phosphate with dihydroxyacetone phosphate, makes at best a minor contribution to the 13C-labeled glucose units observed in trehalose. The pentose pathway and transaldolase activity can explain the labeling pattern of 4,5,6-13C3 of trehalose. Moreover, the transfer of the 13C label of L-[U-13C]aspartate into the different isotopomers of trehalose C4, C5, and C6 by the transaldolase activity allowed us to calculate the relative fluxes from oxaloacetate via gluconeogenesis and through the tricarboxylic acid cycle. The ratio of the two fluxes is approximately 1. However, the main carbon source for trehalose synthesis in S. parvulus is fructose and not glutamate or aspartate. The 13C

Hyperpolarized [U-(2) H, U-(13) C]Glucose reports on glycolytic and pentose phosphate pathway activity in EL4 tumors and glycolytic activity in yeast cells.

PubMed

Timm, Kerstin N; Hartl, Johannes; Keller, Markus A; Hu, De-En; Kettunen, Mikko I; Rodrigues, Tiago B; Ralser, Markus; Brindle, Kevin M

2015-12-01

A resonance at ∼181 ppm in the (13) C spectra of tumors injected with hyperpolarized [U-(2) H, U-(13) C]glucose was assigned to 6-phosphogluconate (6PG), as in previous studies in yeast, whereas in breast cancer cells in vitro this resonance was assigned to 3-phosphoglycerate (3PG). These peak assignments were investigated here using measurements of 6PG and 3PG (13) C-labeling using liquid chromatography tandem mass spectrometry (LC-MS/MS) METHODS: Tumor-bearing mice were injected with (13) C6 glucose and the (13) C-labeled and total 6PG and 3PG concentrations measured. (13) C MR spectra of glucose-6-phosphate dehydrogenase deficient (zwf1Δ) and wild-type yeast were acquired following addition of hyperpolarized [U-(2) H, U-(13) C]glucose and again (13) C-labeled and total 6PG and 3PG were measured by LC-MS/MS RESULTS: Tumor (13) C-6PG was more abundant than (13) C-2PG/3PG and the resonance at ∼181 ppm matched more closely that of 6PG. (13) C MR spectra of wild-type and zwf1Δ yeast cells showed a resonance at ∼181 ppm after labeling with hyperpolarized [U-(2) H, U-(13) C]glucose, however, there was no 6PG in zwf1Δ cells. In the wild-type cells 3PG was approximately four-fold more abundant than 6PG CONCLUSION: The resonance at ∼181 ppm in (13) C MR spectra following injection of hyperpolarized [U-(2) H, U-(13) C]glucose originates predominantly from 6PG in EL4 tumors and 3PG in yeast cells. © 2014 Wiley Periodicals, Inc.

Noninvasive Measurement of Murine Hepatic Acetyl-CoA 13C-Enrichment Following Overnight Feeding with 13C-Enriched Fructose and Glucose

PubMed Central

Carvalho, Filipa; Duarte, Joao; Simoes, Ana Rita; Cruz, Pedro F.; Jones, John G.

2013-01-01

The 13C-isotopomer enrichment of hepatic cytosolic acetyl-CoA of overnight-fed mice whose drinking water was supplemented with [U-13C]fructose, and [1-13C]glucose and p-amino benzoic acid (PABA) was quantified by 13C NMR analysis of urinary N-acetyl-PABA. Four mice were given normal chow plus drinking water supplemented with 5% [1-13C]glucose, 2.5% [U-13C]fructose, and 2.5% fructose (Solution 1) overnight. Four were given chow and water containing 17.5% [1-13C]glucose, 8.75% [U-13C]fructose and 8.75% fructose (Solution 2). PABA (0.25%) was present in both studies. Urinary N-acetyl-PABA was analyzed by 13C NMR. In addition to [2-13C]- and [1,2-13C]acetyl isotopomers from catabolism of [U-13C]fructose and [1-13C]glucose to acetyl-CoA, [1-13C]acetyl was also found indicating pyruvate recycling activity. This precluded precise estimates of [1-13C]glucose contribution to acetyl-CoA while that of [U-13C]fructose was unaffected. The fructose contribution to acetyl-CoA from Solutions 1 and 2 was 4.0 ± 0.4% and 10.6 ± 0.6%, respectively, indicating that it contributed to a minor fraction of lipogenic acetyl-CoA under these conditions. PMID:23841082

The C-12/C-13 Ratio as a Chemistry Indicator

NASA Technical Reports Server (NTRS)

Wirstroem, Eva; Geppert, Wolf; Persson, Carina; Charnley, Steven

2011-01-01

Isotopic ratios of elements are considered powerful tools, e.g. in tracing the origin of solar system body materials, or the degree of nucleosynthesis processing throughout the Galaxy. In interstellar molecules, some isotopic ratios like H/D and C-12/C-13 can also be used as indicators of their chemical origin. Isotope fractionation in gas-phase chemical reactions and gas-dust interaction makes observations of the ratio between C-12 and C-13 isotopologues suitable to distinguish between different formation scenarios. We will present observations of the C-12/C-13 ratio in methanol and formaldehyde towards a sample of embedded, massive young stellar objects. In relation to this we also present results from theoretical modeling showing the usefulness of the C-12/C-13 ratio as a chemistry indicator.

Understanding the role of soil erosion on co2-c loss using (13)c isotopic signatures in abandoned Mediterranean agricultural land.

PubMed

Novara, Agata; Keesstra, Saskia; Cerdà, Artemio; Pereira, Paulo; Gristina, Luciano

2016-04-15

Understanding soil water erosion processes is essential to evaluate the redistribution of soil organic carbon (SOC) within a landscape and is fundamental to assess the role of soil erosion in the global carbon (C) budget. The main aim of this study was to estimate the C redistribution and losses using (13)C natural abundance. Carbon losses in soil sediment, dissolved organic carbon (DOC) and CO2 emission were determined. Four bounded parallel plots were installed on a 10% slope. In the upper part of the plots, C3soil was replaced with C4soil. The SOC and δ(13)C were measured after 145.2mm rainfall in the upper (2m far from C4strip), middle (4m far from C4strip) lower (6m far from C4strip) trams of the plot and in the sediments collected in the Gerlach collector at the lower part of the plot. A laboratory incubation experiment was performed to evaluate the CO2 emission rate of soils in each area. OC was mainly lost in the sediments as 2.08g(-)(2) of C was lost after 145.2mm rainfall. DOC losses were only 5.61% of off-site OC loss. Three months after the beginning of the experiment, 15.90% of SOC in the upper tram of the plot had a C4 origin. The C4-SOC content decreased along the 6m length of the plot, and in the sediments collected by the Gerlach collector. CO2 emission rate was high in the upper plot tram due to the high SOC content. The discrimination of CO2 in C3 and C4 portion permitted to increase our level of understanding on the stability of SOC and its resilience to decomposition. The transport of sediments along the plot increased SOC mineralization by 43%. Our study underlined the impact of rainfall in C losses in soil and water in abandoned Mediterranean agriculture fields and the consequent implications on the C balance. Copyright © 2016 Elsevier B.V. All rights reserved.

The 12C/13C Isotopic Ratio In Titan's Hydrocarbons

NASA Astrophysics Data System (ADS)

Nixon, Conor A.; Achterberg, R. K.; Vinatier, S.; Bezard, B.; Coustenis, A.; Teanby, N. A.; Irwin, P. G.; Cassini CIRS Team

2007-10-01

Isotopic ratios in planetary atmospheres are of considerable interest, yielding insights both about currently occurring processes, and also the formation and early evolution of the body. Before Cassini, ground-based measurements of Titan's 12C/13C in HCN showed no firm evidence of deviation from the terrestrial inorganic standard (88.9) - albeit with large error bars of 20% - contrasting the enrichment in nitrogen (15N/14N≈4.5 terrestrial). Since 2004, the Composite Infrared Spectrometer (CIRS) instrument on Cassini has recorded spectra of Titan's stratosphere globally, including the emissions of multiple isotopologues for certain hydrocarbons. We selected spectra for analysis from four flybys (T4, T12, T19, T22), covering five latitudes from 65°S to 71°N. By means of a radiative transfer code and inversion scheme, we have first modeled the ν4 band of 12CH4 at 1304 cm-1 to retrieve stratospheric temperatures, and subsequently the emissions of 13CH4, 12C2H2, 13C12CH2, 12C2H6 and 13C12CH6. Our results indicate 12C/13C = 81.2±2.0 for all three species combined over all five latitudes, in excellent agreement with the Huygens GCMS value of 12CH4/13CH4 = 82.3±1.0 (Niemann et al. 2005), some 9% lower than terrestrial inorganic, and lower than in ethane on Saturn (91 (-13) (+26)) and Jupiter (99 (-23) (+43)) (Sada et al. 1996). No latitude variation was detected, however the 12C/13C in the C2 species (83.9±3.1 in acetylene, 89.9±7.2 in ethane) were consistently higher than in methane (78.0±2.7) after considering random errors. Although it is possible that this is a real chemical or physical (condensation) effect, it is more likely due to systematic errors in our temperature profile, as our spectra do not yield independent temperature information at 10 mbar where the emissions of 13C12CH2 and 13C12CH6 originate, and we default to the Huygens probe temperatures. In future, this problem may be resolved by modeling CIRS limb spectra.

Agricultural management legacy affects microbial energetics, resource utilization and active bacterial community membership during 13C-glucose consumption

NASA Astrophysics Data System (ADS)

Helgason, B. L.; Levy-Booth, D.; Arcand, M. M.

2017-12-01

Over the long-term, differences in soil management can result in fundamental changes in biogeochemical cycling. The Alternative Cropping Systems (ACS) Study at Scott, SK, Canada (est. 1994) compares organic (ORG) vs. conventionally (CON) managed crop rotations in a loamy Typic Borall. Nitrogen (N) and phosphorus (P) deficiency in the ORG systems have limited crop growth and thus plant carbon (C) inputs for over two decades, ultimately resulting in a C deficiency which has further altered biogeochemical cycling. We conducted a short-term microcosm experiment using 13C-glucose stable isotope probing (SIP) of DNA to test whether ORG soils have greater microbial C use efficiency due to long term resource limitation. Glucose-utilizing populations were dominated by Proteobacteria and Actinobacteria, with differing species-level identities and physiological capacities between CON and ORG systems. Of the 13C-utilizing taxa, relative abundance of Proteobacteria was greater in CON while Actinobacteria (and notably Firmicutes) were more dominant in ORG soils. Using isothermal calorimetry, we measured a thermodynamic efficiency (ηeff) of 0.68, which was not significantly different between soils indicating that the metabolic cost of glucose utilization was similar in CON and ORG soils. In spite of this, differential abundance analysis of 13C-labelled OTUs revealed that ORG soils had distinct active bacterial populations that were positively correlated with ηeff, ηsoil (glucose energy retained in soil) and primed soil organic matter (pSOM). In contrast, differentially abundant OTUs in the CON soils were negatively correlated with measures of thermodynamic efficiency but positively correlated with glucose-derived heat and CO2 production as well as NO3- and PO4- availability. ORG bacterial communities may co-metabolize other resources (N and P) from SOM to meet their metabolic requirements during glucose utilization, while the active bacteria in the CON soils could access these

Drivers of inter-annual variability in C4 abundance in mixed C3-C4 grasslands

NASA Astrophysics Data System (ADS)

Griffith, D.; Ratajczak, Z.; Anderson, M.; Lind, E. M.; Still, C. J.

2016-12-01

Grassland communities tend to be dominated by either C3 or C4 grass species, as opposed to being evenly mixed. Globally, this pattern is a consequence of the crossover temperature threshold above which C4 grasses are climatically favored. However, C3-C4 distributions can also be distinctly bimodal at the landscape scale, reflecting variation in fire regime, herbivory, soils, and other factors that favor either C3 or C4 vegetation. As such, our aims were to first investigate the global controls on C3 and C4 species pools, and second to determine the magnitude of inter-annual variation in C4 grass relative abundance in mixed C3-C4 grasslands with different fire regimes, soil nitrogen, and grazing pressures. Our analyses used data from 74 globally distributed Nutrient Network sites, 30 of which are mixed C3-C4 grasslands. Each site has factorial fertilizer (NPK) and herbivore exclosure treatments in replicated blocks. To address our first goal we conducted a random forest analysis of site-level C4 relative abundances in relation to mean annual temperature and rainfall, growing season temperature (GST) and rainfall, rainfall seasonality, aridity, fire frequency and management, frost, soil fertility, and grass lineage. In order to address our second goal, we narrowed our focus to sites having mixed C3-C4 grass composition and at least five years of species composition data (16 sites). A GST of 15 °C was a good descriptor of C4 versus C3 grass dominance, although there were marked differences among specific C4 grass lineages in their distributions. For example, whether or not a site has an actively managed burn regime was a greater predictor of Andropogoneae (C4) than GST. Furthermore, in mixed C3-C4 grasslands fertilization favored C3 grasses. Our research delineates the climatic limits of mixed C3-C4 grasslands and highlights the influence of disturbance, soil, and phylogeny on C4 and C3 grass dominance.

IRMS detection of testosterone manipulated with 13C labeled standards in human urine by removing the labeled 13C.

PubMed

Wang, Jingzhu; Yang, Rui; Yang, Wenning; Liu, Xin; Xing, Yanyi; Xu, Youxuan

2014-12-10

Isotope ratio mass spectrometry (IRMS) is applied to confirm testosterone (T) abuse by determining the carbon isotope ratios (δ(13)C value). However, (13)C labeled standards can be used to control the δ(13)C value and produce manipulated T which cannot be detected by the current method. A method was explored to remove the (13)C labeled atom at C-3 from the molecule of androsterone (Andro), the metabolite of T in urine, to produce the resultant (A-nor-5α-androstane-2,17-dione, ANAD). The difference in δ(13)C values between Andro and ANAD (Δδ(13)CAndro-ANAD, ‰) would change significantly in case manipulated T is abused. Twenty-one volunteers administered T manipulated with different (13)C labeled standards. The collected urine samples were analyzed with the established method, and the maximum value of Δδ(13)CAndro-ANAD post ingestion ranged from 3.0‰ to 8.8‰. Based on the population reference, the cut-off value of Δδ(13)CAndro-ANAD for positive result was suggested as 1.2‰. The developed method could be used to detect T manipulated with 3-(13)C labeled standards. Copyright © 2014 Elsevier B.V. All rights reserved.

Multiband Spectral-Spatial RF Excitation for Hyperpolarized [2-13C]Dihydroxyacetone 13C-MR Metabolism Studies

PubMed Central

Marco-Rius, Irene; Cao, Peng; von Morze, Cornelius; Merrit, Matthew; Moreno, Karlos X; Chang, Gene-Yuan; Ohliger, Michael A.; Pearce, David; Kurhanewicz, John; Larson, Peder E. Z.; Vigneron, Daniel B.

2016-01-01

Purpose To develop a specialized multislice, single-acquisition approach to detect the metabolites of hyperpolarized [2-13C]dihydroxyacetone (DHAc) to probe gluconeogenesis in vivo, which have a broad 144 ppm spectral range (~4.6 KHz at 3T). A novel multiband RF excitation pulse was designed for independent flip angle control over 5-6 spectral-spatial (SPSP) excitation bands, each corrected for chemical shift misregistration effects. Methods Specialized multi-band SPSP RF pulses were designed, tested and applied to investigate hyperpolarized [2-13C]DHAc metabolism in kidney and liver of fasted rats with dynamic 13C-MRS and an optimal flip angle scheme. For comparison, experiments were also performed with narrow-band slice-selective RF pulses and a sequential change of the frequency offset to cover the five frequency bands of interest. Results The SPSP pulses provided a controllable spectral profile free of baseline distortion with improved signal to noise of the metabolite peaks, allowing for quantification of the metabolic products. We observed organ-specific differences in DHAc metabolism. There was 2-5 times more [2-13C]phosphoenolpyruvate and about 19 times more [2-13C]glycerol 3-phosphate in the liver than in the kidney. Conclusion A multiband SPSP RF pulse covering a spectral range over 144 ppm enabled in vivo characterization of HP [2-13C]dihydroxyacetone metabolism in rat liver and kidney. PMID:27017966

Natural Enemy Abundance in Southeastern Blueberry Agroecosystems: Distance to Edge and Impact of Management Practices.

PubMed

Whitehouse, T Seth; Sial, Ashfaq A; Schmidt, Jason M

2018-02-08

Natural enemies are valuable components of agroecosystems as they provide biological control services to help regulate pest populations. Promoting biocontrol services can improve sustainability by decreasing pesticide usage, which is a major challenge for the blueberry industry. Our research is the first to compare natural enemy populations in managed (conventional and organic) and unmanaged blueberry systems, in addition to the effects of non-crop habitat. We conducted our study in 10 blueberry orchards during the growing season across the major blueberry producing counties in Georgia, United States. To estimate the spatial distribution of natural enemies, we conducted suction sampling at three locations in each orchard: within the forested border, along the edge of blueberry orchard adjacent to forested border, and within the interior of the blueberry orchard. Natural enemies maintained higher abundance over the season in unmanaged areas when compared with organic or conventional production systems. In the conventional orchards, natural enemies were more abundant in the surrounding non-crop area compared with the interior of the orchard. Populations were more evenly distributed in less intensive systems (organic and unmanaged). Our results indicate spatial structure in natural enemy populations is related to management practice, and less intensive management can retain higher abundance of natural enemies in blueberry systems. Considerations must be made towards promoting ecologically based management practices to sustain natural enemy populations and potentially increase the delivery of biological control services. © The Author(s) 2017. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Preparative chromatography for specific δ13C isotopic analysis of individual carbohydrates in environmental samples

NASA Astrophysics Data System (ADS)

Nouara, Amel; Panagiotopoulos, Christos; Balesdent, Jérôme; Sempéré, Richard

2017-04-01

Carbohydrates are among the most abundant organic molecules on the Earth and are present in all geochemical systems. Despite their high abundance in the environment, very few studies assessed their origin using molecular carbohydrate isotopic analyses. In contrast with bulk stable isotope analysis (BSIA), which gives the isotopic signature of the entire sample without any specification about its chemical composition, compound specific 13C isotopic analysis of individual sugars (CSIA) offers valuable information about the origin of single molecules. Previous investigations used gas or liquid chromatography coupled with isotope ratio mass spectroscopy (GC-IRMS; HPLC-IRMS) for CSIA of sugars however the former requires δ13C corrections due to the carbon added to the sugar (derivatization) while the later does not provide always adequate separations among monosaccharides. Here we used cation preparative chromatography (Ca2+, Pb2+ and Na+) with refractive index detection in order to produce pure monosaccharide targets for subsequent EA-IRMS analyses. Milli-Q water was used as eluant at a flow rate 0.6 ml min-1. In general, three successive purifications (Ca2+, Pb2+, Ca2+) were sufficient to produce pure compounds. Pure monosaccharides were compared with authentic monosaccharide standards using 1H NMR and/or mass spectroscopy. The detection limit of our technique was about 1µM/sugar with a precision of 10% (n=6). Blanks run with Milli-Q water after three successive purifications resulted in carbon content of 0.13 to 2.77 µgC per collected sugar. These values are much lower than the minimum required amount (5 µgC) of the EA-IRSMS system with a precision of ± 0.35 ‰. Application of our method to environmental samples resulted in δ13C values of glucose, fructose, and levoglucosan in the range of -24 to -26 ‰ (PM10 atmospheric particles), and -15‰ to -22 ‰ for arabinose, glucose, and xylose (marine high molecular dissolved organic matter). These results fall in

Total synthesis of natural derivatives and artificial analogs of 13-oxyingenol and their biological evaluation.

PubMed

Ohyoshi, Takayuki; Tamura, Yuki; Hayakawa, Ichiro; Hirai, Go; Miyazawa, Yamato; Funakubo, Shota; Sodeoka, Mikiko; Kigoshi, Hideo

2016-12-28

We have established an efficient synthetic methodology for the 13-oxyingenol natural derivative (13-oxyingenol-13-dodecanoate-20-hexanoate), featuring a ring-closing olefin metathesis reaction for the "direct" construction of a highly strained inside-outside framework and a Mislow-Evans-type [2,3]-sigmatropic rearrangement for the stereoselective introduction of the hydroxy group at C5. We also synthesized artificial analogs of 13-oxyingenol and ingenol by using our synthetic strategy. In vitro activation assays of protein kinase C (PKC) α and δ revealed that the dodecanoyl group at O13 on 13-oxyingenol analogs had a significant role in PKCδ activation. The PKCα- or PKCδ-activating 13-oxyingenol and ingenol analogs induced both distinct morphological changes and increases of CD11b expression in HL-60 cells, which would be typical signs of HL-60 cell differentiation to macrophage-like cells, as expected by previous reports. Intriguingly, however, similar differentiation phenotypes were observed with the use of 13-oxyingenol natural derivatives and 13-oxyingenol-13-dodecanoate showing a remarkably less potent PKCα or PKCδ activation ability, which the PKC inhibitor Gö6983 diminished. This indicated the involvement of other PKC isozymes or related kinase activities. 13-Oxyingenol analogs, which induced HL-60 cell differentiation, also induced HL-60 cell death, similar to the action of a phorbol ester, a strong PKC activator.

[Detection of Helicobacter pylori by culture and the 13C-urea breath test using an automated breath 13C analyzer].

PubMed

Yamamoto, Y; Kouda, M; Abe, K; Sakurabayashi, S; Sezai, S; Hirano, M; Oka, H

1995-11-01

Up to now, the diagnosis of H. pylori infection has been made by the breath test using 13C-urea. In this study, 13C-urea breath samples were tested in 34 patients (peptic ulcer scar 17, chronic gastritis 17 cases) with an automated breath 13C analyzer (ABCA. Europa Scientific, Crewe, UK) and compared with the results of endoscopical diagnosis for H. pylori infection. Endoscopic and 13C-urea breath test (13C-UBT) were performed before eradicative medication. We described a modified protocol for the growth grade of H. pylori colonies in microbiology (H. pylori score), and for the delta 13C area under curve (AUC; permil*hr) obtained from each sample of expired breath. There was a significant correlation between delta 13C-AUC and the delta 13C level of each sample, but the correlation coefficient obtained at 10min (R2 = 0.582) was lower than that obtained at the other four time points (20min; 0.891, 30min; 0.949, 40min; 0.946, 50min; 0.946, 60min; 0.820). The delta 13C-AUC well correlated with H. pylori score (p < 0.01), none of 26 H. pylori positive patients detected by culture was 13C-UBT negative (delta 13C-AUC < 8.2 permil*hr in mean + 2SD of H. pylori negative group). In conclusion, 13C-UBT using ABCA has high sensitivity and specificity, and it provides a non-invasive method for the detection of H. pylori urease activity.

Stable Carbon Isotopes (δ 13C) in Coral Skeletons: Experimental Approach and Applications for Paleoceanography

NASA Astrophysics Data System (ADS)

Grottoli, A. G.

2004-12-01

Scleractinian corals obtain fixed carbon via photosynthesis by their endosymbiotic algae (zooxanthellae) and via hetertrophy (injestion of zooplankton, δ 13C ≈ -17 to -22‰ ). Carbon dioxide (CO2) used for photosynthesis is obtained from seawater (δ 13C ≈ 0%) or from respired CO2 within the coral host. The δ 13C of the carbon used in the formation of the underlying coral skeleton is fractionated as a result of both of these metabolic processes. Here I have pooled evidence from several field and tank experiments on the effect of photosynthesis and heterotrophy of coral skeletal δ 13C. In the experiments, decreases in light levels due to shading or depth resulted in a significant decrease in skeletal δ 13C in all species studied (Pavona gigantea, Pavona clavus, Porites compressa). Decreases in photosynthesis in bleached corals also resulted in a decrease in skeletal δ 13C compared to non-bleached corals growing under the same conditions and at the same location. Skeletal δ 13C also decreased at higher than normal light levels most likely due to photoinhibition. Thus, decreases in photosynthesis due to reduced light levels, due to bleaching-induced decreases in chlorophyll a concentrations, or due to photodamage-induced decreases in functional cholorphyll a, results in significant δ 13C decreases. Comprehensive interpretation of all of the data showed that changes in photosynthesis itself can drive the changes in δ 13C. In field experiments, the addition of natural concentrations of zooplankton to the diet resulted in decreases in skeletal δ 13C. Such a decrease was more pronounced with depth and in P. gigantea compared to P. clavus. In situ feeding experiments have since confirmed these findings. However under tank conditions with unaturally high feeding rates, enhanced nitrogen supply in the diet can disrupt the coral-algal symbiosis, stimlate zooxanthellae growth and photosynthesis, and cause an incrase in skeletal δ 13C. It is proposed that under

The CO2 Abundance in Comets C2012 K1 (PanSTARRS), C2012 K5 (LINEAR), and 290P Jager as Measured with Spitzer

NASA Technical Reports Server (NTRS)

McKay, Adam J.; Kelley, Michael S.P.; Cochran, Anita L.; Bodewits, Dennis; DiSanti, Michael A.; Dello Russo, Neil; Lisse, Carey M.

2015-01-01

Carbon dioxide is one of the most abundant ices present in comets and is therefore important for understanding cometary composition and activity. We present analysis of observations of CO2 and [O I] emission in three comets to measure the CO2 abundance and evaluate the possibility of employing observations of [O I] emission in comets as a proxy for CO2. We obtained NIR imaging sensitive to CO2 of comets C/2012 K1 (PanSTARRS), C/2012 K5 (LINEAR), and 290P/Jager with the IRAC instrument on Spitzer. We acquired observations of [O I] emission in these comets with the ARCES echelle spectrometer mounted on the 3.5-m telescope at Apache Point Observatory and observations of OH with the Swift observatory (PanSTARRS) and with Keck HIRES (Jager). The CO2/H2O ratios derived from the Spitzer images are 12.6 +/- 1.3% (PanSTARRS), 28.9 +/- 3.6% (LINEAR), and 31.3 +/- 4.2% (Jager). These abundances are derived under the assumption that contamination from CO emission is negligible. The CO2 abundance for PanSTARRS is close to the average abundance measured in comets at similar heliocentric distance to date, while the abundances measured for LINEAR and Jager are significantly larger than the average abundance. From the coma morphology observed in PanSTARRS and the assumed gas expansion velocity, we derive a rotation period for the nucleus of about 9.2 h. Comparison of H2O production rates derived from ARCES and Swift data, as well as other observations, suggest the possibility of sublimation from icy grains in the inner coma. We evaluate the possibility that the [O I] emission can be employed as a proxy for CO2 by comparing CO2/H2O ratios inferred from the [O I] lines to those measured directly by Spitzer. We find that for PanSTARRS we can reproduce the observed CO2 abundance to an accuracy of approximately 20%. For LINEAR and Jager, we were only able to obtain upper limits on the CO2 abundance inferred from the [O I] lines. These upper limits are consistent with the CO2 abundances

Structural comparison of Gilsonite and Trinidad Lake Asphalt using 13C-NMR technique

NASA Astrophysics Data System (ADS)

Nciri, Nader; Cho, Namjun

2017-04-01

The recent increased importance of natural asphalt as an alternative binder for sustainable road pavement has dictated that more knowledge should be acquired about its structure and properties. Earlier, Carbon-13 NMR spectroscopy has been applied to very few natural bituminous materials. In this work, two types of raw binders namely Gilsonite and Trinidad Lake asphalt (TLA) have been subjected to an extensive investigation by using 13C-NMR technique. Results have shown that valuable chemical data can be readily withdrawn on aromatic ring structures and ring substituents in natural asphalts derived from different sources. The chemical significance of these findings will be discussed.

The δ13C Value of Fingerstick Blood Is a Valid, Reliable, and Sensitive Biomarker of Sugar-Sweetened Beverage Intake in Children and Adolescents.

PubMed

MacDougall, Carly R; Hill, Catelyn E; Jahren, A Hope; Savla, Jyoti; Riebl, Shaun K; Hedrick, Valisa E; Raynor, Hollie A; Dunsmore, Julie C; Frisard, Madlyn I; Davy, Brenda M

2018-01-01

Reliance on self-reported dietary intake methods is a commonly cited research limitation, and dietary misreporting is a particular problem in children and adolescents. Objective indicators of dietary intake, such as dietary biomarkers, are needed to overcome this research limitation. The added sugar (AS) biomarker δ13C, which measures the relative abundance of 13C to 12C, has demonstrated preliminary validity in adults. The purpose of this investigation was to determine the comparative validity, test-retest reliability, and sensitivity of the δ13C biomarker to detect AS and sugar-sweetened beverage (SSB) intake using fingerstick blood samples in children and adolescents. Children (aged 6-11 y, n = 126, 56% male, mean ± SD age: 9 ± 2 y) and adolescents (aged 12-18 y, n = 200, 44% male, mean ± SD age: 15 ± 2 y) completed 4 testing sessions within a 3-wk period. Participants' height, weight, demographic characteristics, and health history were determined at the first session; 24-h recalls were obtained at each visit and fingerstick blood samples were collected at visits 1 and 3. Samples were analyzed for δ13C value using natural abundance stable isotope mass spectrometry. δ13C value was compared with dietary outcomes in the full sample, and in child and adolescent subgroups. t Tests and correlational analyses were used to assess biomarker validity and reliability, whereas logistic regression and area under the receiver-operator characteristic curve (AUC) were used to evaluate sensitivity. Reported mean ± SD AS consumption was 82.2 ± 35.8 g/d and 329 ± 143 kcal/d, and SSB consumption was 222 ± 243 mL/d and 98 ± 103 kcal/d. Mean δ13C value was -19.65 ± 0.69‰, and was lower in children than in adolescents (-19.80 ± 0.67‰ compared with -19.56 ± 0.67‰, P = 0.002). δ13C values were similar across sessions (visit 1: -19.66 ± 0.68‰; visit 3: -19.64 ± 0.68‰; r = 0.99, P < 0.001) and were associated (P < 0.001) with intake of total AS (grams

Differentiation of Pigment in Eggs Using Carbon ((13)C/(12)C) and Nitrogen ((15)N/(14)N) Stable Isotopes.

PubMed

Sun, Feng M; Shi, Guang Y; Wang, Hui W

2016-07-01

Consumers prefer natural and healthy food, but artificial pigments are often abused in egg products. The study aimed at differentiating the origin of pigments in eggs by applying the technique of carbon ((13)C/(12)C) and nitrogen ((15)N/(14)N) stable isotope analysis. Five hundred sixty laying hens were randomly distributed into 14 treatments, which were divided into four groups: maize, carophyll red pigment, carophyll yellow pigment, and a mixture of carophyll red and yellow pigments. Eggs were collected and pretreated to determe the values of the Roche Yolk Color Fan (RCF), δ(13)C, and δ(15)N. With increasing maize content, the RCF and δ(13)C values of yolks increased. Moreover, the RCF values in the three pigment groups were significantly influenced by the artificial colors, but δ(13)C values were not significantly different, regardless of the existence of pigment. The δ(15)N values in all treatments did not vary as regularly as the carbon stable isotope. A strong positive correlation was found between RCF and δ(13)C in the maize group, but no such correlation was be observed in the pigment groups. It is concluded that carbon stable isotope ratio analysis (δ(13)C) of the yolk can be used to differentiate the origin of the pigment added to eggs.

Sheep Wool δ13C Reveals No Effect of Grazing on the C3/C4 Ratio of Vegetation in the Inner Mongolia–Mongolia Border Region Grasslands

PubMed Central

Auerswald, Karl; Wittmer, Max H.O.M.; Tungalag, Radnaakhand; Bai, Yongfei; Schnyder, Hans

2012-01-01

We tested whether the abundance of C4 vegetation in grasslands of the Mongolian plateau is influenced by grazing conditions. The analysis exploited the politically originated contrast that exists between Mongolia (low stocking rate, transhumant system) and the district of Inner Mongolia, China (high stocking rate, sedentary system). We estimated the proportion of C4 carbon (PC4) in grazed vegetation from the relative carbon isotope ratio (δ13C) of sheep wool sampled from 298 annual shearings originating from 1996 to 2007. Annual stocking rates varying over time and between the districts of both countries were taken from regional statistics. The PC4 pattern within the 0.7 million km2 sampling area was geostatistically analyzed and related to stocking rates and temperature gradients. For similar climatic conditions, PC4 was the same in both countries. Further, a unique relationship was found between PC4 and July temperature on both sides of the border, which explained 71% of the pattern. Stocking rate and grazing system had no significant influences on present-day C3/C4 abundance ratio. This finding suggests that recent changes in the C3/C4 ratio of these grasslands are mainly a consequence of regional warming, not overgrazing. PMID:23029090

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%.

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.

Calibration of the carbon isotope composition (δ13C) of benthic foraminifera

NASA Astrophysics Data System (ADS)

Schmittner, Andreas; Bostock, Helen C.; Cartapanis, Olivier; Curry, William B.; Filipsson, Helena L.; Galbraith, Eric D.; Gottschalk, Julia; Herguera, Juan Carlos; Hoogakker, Babette; Jaccard, Samuel L.; Lisiecki, Lorraine E.; Lund, David C.; Martínez-Méndez, Gema; Lynch-Stieglitz, Jean; Mackensen, Andreas; Michel, Elisabeth; Mix, Alan C.; Oppo, Delia W.; Peterson, Carlye D.; Repschläger, Janne; Sikes, Elisabeth L.; Spero, Howard J.; Waelbroeck, Claire

2017-06-01

The carbon isotope composition (δ13C) of seawater provides valuable insight on ocean circulation, air-sea exchange, the biological pump, and the global carbon cycle and is reflected by the δ13C of foraminifera tests. Here more than 1700 δ13C observations of the benthic foraminifera genus Cibicides from late Holocene sediments (δ13CCibnat) are compiled and compared with newly updated estimates of the natural (preindustrial) water column δ13C of dissolved inorganic carbon (δ13CDICnat) as part of the international Ocean Circulation and Carbon Cycling (OC3) project. Using selection criteria based on the spatial distance between samples, we find high correlation between δ13CCibnat and δ13CDICnat, confirming earlier work. Regression analyses indicate significant carbonate ion (-2.6 ± 0.4) × 10-3‰/(μmol kg-1) [CO32-] and pressure (-4.9 ± 1.7) × 10-5‰ m-1 (depth) effects, which we use to propose a new global calibration for predicting δ13CDICnat from δ13CCibnat. This calibration is shown to remove some systematic regional biases and decrease errors compared with the one-to-one relationship (δ13CDICnat = δ13CCibnat). However, these effects and the error reductions are relatively small, which suggests that most conclusions from previous studies using a one-to-one relationship remain robust. The remaining standard error of the regression is generally σ ≅ 0.25‰, with larger values found in the southeast Atlantic and Antarctic (σ ≅ 0.4‰) and for species other than Cibicides wuellerstorfi. Discussion of species effects and possible sources of the remaining errors may aid future attempts to improve the use of the benthic δ13C record.

Atmospheric Oxygen Concentrations for the Past 350 Myr Modeled from the δ13C of C3 Land Plants

NASA Astrophysics Data System (ADS)

Nordt, L.; Breecker, D.

2016-12-01

predictions from charcoal abundance or the δ13C of amber where the former overestimates and the latter underestimates pO2, respectively, compared to GEOCARBSULF. Results of our new proxy are encouraging, but further experimental work is needed to better understand the dynamics of pO2 and pCO2 on the Δ13C of C3 plants for application to paleobarometers.

Meta-analysis reveals that seed-applied neonicotinoids and pyrethroids have similar negative effects on abundance of arthropod natural enemies

PubMed Central

Tooker, John F.

2016-01-01

Background Seed-applied neonicotinoids are widely used in agriculture, yet their effects on non-target species remain incompletely understood. One important group of non-target species is arthropod natural enemies (predators and parasitoids), which contribute considerably to suppression of crop pests. We hypothesized that seed-applied neonicotinoids reduce natural-enemy abundance, but not as strongly as alternative insecticide options such as soil- and foliar-applied pyrethroids. Furthermore we hypothesized that seed-applied neonicotinoids affect natural enemies through a combination of toxin exposure and prey scarcity. Methods To test our hypotheses, we compiled datasets comprising observations from randomized field studies in North America and Europe that compared natural-enemy abundance in plots that were planted with seed-applied neonicotinoids to control plots that were either (1) managed without insecticides (20 studies, 56 site-years, 607 observations) or (2) managed with pyrethroid insecticides (eight studies, 15 site-years, 384 observations). Using the effect size Hedge’s d as the response variable, we used meta-regression to estimate the overall effect of seed-applied neonicotinoids on natural-enemy abundance and to test the influence of potential moderating factors. Results Seed-applied neonicotinoids reduced the abundance of arthropod natural enemies compared to untreated controls (d = −0.30 ± 0.10 [95% confidence interval]), and as predicted under toxin exposure this effect was stronger for insect than for non-insect taxa (QM = 8.70, df = 1, P = 0.003). Moreover, seed-applied neonicotinoids affected the abundance of arthropod natural enemies similarly to soil- or foliar-applied pyrethroids (d = 0.16 ± 0.42 or −0.02 ± 0.12; with or without one outlying study). Effect sizes were surprisingly consistent across both datasets (I2 = 2.7% for no-insecticide controls; I2 = 0% for pyrethroid controls), suggesting little moderating influence of

Meta-analysis reveals that seed-applied neonicotinoids and pyrethroids have similar negative effects on abundance of arthropod natural enemies.

PubMed

Douglas, Margaret R; Tooker, John F

2016-01-01

Seed-applied neonicotinoids are widely used in agriculture, yet their effects on non-target species remain incompletely understood. One important group of non-target species is arthropod natural enemies (predators and parasitoids), which contribute considerably to suppression of crop pests. We hypothesized that seed-applied neonicotinoids reduce natural-enemy abundance, but not as strongly as alternative insecticide options such as soil- and foliar-applied pyrethroids. Furthermore we hypothesized that seed-applied neonicotinoids affect natural enemies through a combination of toxin exposure and prey scarcity. To test our hypotheses, we compiled datasets comprising observations from randomized field studies in North America and Europe that compared natural-enemy abundance in plots that were planted with seed-applied neonicotinoids to control plots that were either (1) managed without insecticides (20 studies, 56 site-years, 607 observations) or (2) managed with pyrethroid insecticides (eight studies, 15 site-years, 384 observations). Using the effect size Hedge's d as the response variable, we used meta-regression to estimate the overall effect of seed-applied neonicotinoids on natural-enemy abundance and to test the influence of potential moderating factors. Seed-applied neonicotinoids reduced the abundance of arthropod natural enemies compared to untreated controls ( d = -0.30 ± 0.10 [95% confidence interval]), and as predicted under toxin exposure this effect was stronger for insect than for non-insect taxa ( Q M = 8.70, df = 1, P = 0.003). Moreover, seed-applied neonicotinoids affected the abundance of arthropod natural enemies similarly to soil- or foliar-applied pyrethroids ( d = 0.16 ± 0.42 or -0.02 ± 0.12; with or without one outlying study). Effect sizes were surprisingly consistent across both datasets ( I 2  = 2.7% for no-insecticide controls; I 2  = 0% for pyrethroid controls), suggesting little moderating influence of crop species

Welcoming natural isotopic abundance in solid-state NMR: probing π-stacking and supramolecular structure of organic nanoassemblies using DNP† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc02709a Click here for additional data file.

PubMed Central

Märker, Katharina; Paul, Subhradip; Fernández-de-Alba, Carlos; Lee, Daniel; Mouesca, Jean-Marie; Hediger, Sabine

2017-01-01

The self-assembly of small organic molecules is an intriguing phenomenon, which provides nanoscale structures for applications in numerous fields from medicine to molecular electronics. Detailed knowledge of their structure, in particular on the supramolecular level, is a prerequisite for the rational design of improved self-assembled systems. In this work, we prove the feasibility of a novel concept of NMR-based 3D structure determination of such assemblies in the solid state. The key point of this concept is the deliberate use of samples that contain 13C at its natural isotopic abundance (NA, 1.1%), while exploiting magic-angle spinning dynamic nuclear polarization (MAS-DNP) to compensate for the reduced sensitivity. Since dipolar truncation effects are suppressed to a large extent in NA samples, unique and highly informative spectra can be recorded which are impossible to obtain on an isotopically labeled system. On the self-assembled cyclic diphenylalanine peptide, we demonstrate the detection of long-range internuclear distances up to ∼7 Å, allowing us to observe π-stacking through 13C–13C correlation spectra, providing a powerful tool for the analysis of one of the most important non-covalent interactions. Furthermore, experimental polarization transfer curves are in remarkable agreement with numerical simulations based on the crystallographic structure, and can be fully rationalized as the superposition of intra- and intermolecular contributions. This new approach to NMR crystallography provides access to rich and precise structural information, opening up a new avenue to de novo crystal structure determination by NMR. PMID:28451235

[13C] GC-C-IRMS analysis of methylboronic acid derivatives of glucose from liver glycogen after the ingestion of [13C] labeled tracers in rats.

PubMed

Luengo, Catherine; Azzout-Marniche, Dalila; Fromentin, Claire; Piedcoq, Julien; Lemosquet, Sophie; Tomé, Daniel; Gaudichon, Claire

2009-11-01

We developed a complete method to measure low [(13)C] enrichments in glycogen. Fourteen rats were fed a control diet. Six of them also ingested either [U-(13)C] glucose (n=2) or a mixture of 20 [U-(13)C] amino acids (n=4). Hepatic glycogen was extracted, digested to glucose and purified on anion-cation exchange resins. After the optimization of methylboronic acid derivatization using GC-MS, [(13)C] enrichment of extracted glucose was measured by GC-C-IRMS. The accuracy was addressed by measuring the enrichment excess of a calibration curve, which observed values were in good agreement with the expected values (R=0.9979). Corrected delta values were -15.6+/-1.6 delta(13)C (per thousand) for control rats (n=8) and increased to -5 to 8 delta(13)C (per thousand) per thousand and 12-14 delta(13)C (per thousand) per thousand after the ingestion of [U-(13)C] amino acids or [U-(13)C] glucose as oral tracers, respectively. The method enabled the determination of dietary substrate transfer into glycogen. The sequestration of dietary glucose in liver glycogen 4 h after the meal was 35% of the ingested dose whereas the transfer of carbon skeletons from amino acids was only 0.25 to 1%.

Soil organic matter stability in agricultural land: New insights using δ15N, δ13C and C:N ratio

NASA Astrophysics Data System (ADS)

Mao, Yanling; Heiling, Maria; De Clercq, Tim; Resch, Christian; Aigner, Martina; Mayr, Leo; Vanlauwe, Bernard; Thuita, Moses; Steier, Peter; Leifeld, Jens; Merckx, Roel; Spiegel, Heide; Cepuder, Peter; Nguyen, Minh-Long; Zaman, Mohammad; Dercon, Gerd

2014-05-01

Soil organic matter (SOM) contains three times more carbon than in the atmosphere or terrestrial vegetation. This major pool of organic carbon is sensitive to climate change, but the mechanisms for carbon stabilization in soils are still not well understood and the ultimate potential for carbon stabilization is unknown. For predicting SOM dynamics, it is necessary to gain information on the turnover rates or stability of different soil organic carbon pools. The common method to determine stability and age of SOM is the 14C radio carbon technique, which is very expensive and therefore limited in use. Conen et al. (2008) developed a model to estimate the SOM stability based on the isotopic discrimination of 15N natural abundance by soil micro-organisms, and the decreasing C:N ratio during organic matter decomposition. This model has been developed for permanent grasslands in the Swiss Alps under steady-state conditions. The objective of our study was to validate whether this model could be used or adapted, in combination with 13C isotope signatures of SOM, to predict the relative age and stability of SOM fractions in more disturbed agricultural ecosystems. The present study was carried out on soils collected from six long-term experimental trials (from 12 to 50 years) under different agricultural management practices (e.g. no tillage vs conventional tillage, and mulch, fertilizer, green or animal manure application), located in Austria, Belgium, Kenya and China. Top and subsoil were sampled until 80-100 cm depth. Particulate organic matter (POM) fraction was obtained by wet sieving (> 63μm) after sonification and density separation (<1.8 g cm-3). Carbon and nitrogen contents and their stable isotopic ratios (i.e. 15N and 13C) were measured in POM and bulk soils. The mineral associated matter fraction (mOM), as the protected carbon, was calculated by difference to the bulk soil organic carbon. The relative age of the SOM was calculated using the Conen model and

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##

δ 13C of free and macromolecular aromatic structures in the murchison meteorite

NASA Astrophysics Data System (ADS)

Sephton, M. A.; Pillinger, C. T.; Gilmour, I.

1998-05-01

Analyses of the organic compounds in the Murchison meteorite have led to a greater understanding of the nature of extraterrestrial organic materials. However, the relationship between low and high molecular weight material remains poorly understood. To investigate this relationship, untreated Murchison was subjected to supercritical fluid extraction (SFE) to obtain the free organic components in the meteorite. Toluene and other volatile aromatic hydrocarbons dominated the extract, and the carbon isotopic composition of these molecules was determined by gas chromatography-isotope ratio-mass spectrometry (GCIRMS). δ 13C values of the aromatic hydrocarbons ranged from -28.8 to -5.8‰. These compounds displayed a 13C-enrichment with increasing carbon number suggesting an origin by cracking. The high molecular weight organic material in the meteorite was isolated and subjected to hydrous pyrolysis. This procedure produced a number of aromatic products, the majority of which were volatile aromatic hydrocarbons, particularly toluene. SFE was used to extract and successfully retain them. This enabled the first carbon isotopic analysis of this poorly understood material to be performed at the molecular level by GCIRMS. δ 13C values for aromatic pyrolysis products occupied a range from -24.6 to -5.6‰. The trend of 13C-enrichment with increasing carbon number, observed in the free compounds, was also evident in the macromolecular fragments. Furthermore, the organic fragments of the macromolecular material were consistently 13C-enriched when compared to structurally identical free molecules. This suggested that the free aromatic hydrocarbons in Murchison were produced by the preterrestrial degradation of the organic macromolecular material. This natural degradation event was extended by the hydrous pyrolysis experiment.

Synthesis of 13 C-labeled 5-Aminoimidazole-4-carboxamide-1-β-D-[13 C5 ] ribofuranosyl 5'-monophosphate.

PubMed

Zarkin, Allison K; Elkins, Phyllis D; Gilbert, Amanda; Jester, Teresa L; Seltzman, Herbert H

2018-06-14

5-Aminoimidazole-4-carboxamide-1-β-D-[ 13 C 5 ] ribofuranosyl 5'-monophosphate ([ 13 C 5 ribose] AICAR-PO 3 H 2 ) (6) has been synthesized from [ 13 C 5 ]adenosine. Incorporation of the mass-label into [ 13 C 5 ribose] AICAR-PO 3 H 2 provides a useful standard to aid in metabolite identification and quantification in monitoring metabolic pathways. A synthetic route to the 13 C-labeled compound has not been previously reported. Our method employs a hybrid enzymatic and chemical synthesis approach that applies an enzymatic conversion from adenosine to inosine followed by a ring-cleavage of the protected inosine. A direct phosphorylation of the resulting 2',3'-isopropylidine acadesine (5) was developed to yield the title compound in 99% purity following ion exchange chromatography. This article is protected by copyright. All rights reserved.

Imaging eubacteria and archaean cell abundance and nitrification activity on marine snow particles collected from the South Pacific using microscopy and nanoSIMS

NASA Astrophysics Data System (ADS)

Foster, R.; Santoro, A. E.; Tienken, D.; Littman, S.; Berelson, W.; Kuypers, M. M. M.

2016-02-01

The abundance and nitrification activity by marine-snow associated eubacteria and archaea were measured on particles collected in the South Pacific. The particles were first collected from 24 hour floating sediment traps moored at 100 and 200 m and later amended and incubated with 13C-bicarbonate and 15NH4 for 48 hours. Enrichment for 13C and 15N in cells above natural abundance was quantified using a coupled halogenated in situ hybridization assay with nano-meter scale secondary ion mass spectrometry (HISH-SIMS). Approximately 82% ± 10 of the observed hybridized cells were Eubacterial, while 24% ± 5 were positively hybridized with the Archaean probe. There was high variability in 13C/12C and 15N/14N in both bacterial and archaeal cells. Complementary measurements of δ15NNO3 at the conclusion of the experiment indicated no detectible nitrification activity associated with the particles. Thin sections of the particles imaged with Transmission Electron Microscopy (TEM) showed that a higher abundance of degrading phytoplanktonic cells, including numerous empty radiolarian and diatom frustules were associated with the deeper moored tap, while the shallow trap collected intact bacterial cells, including small picocyanobacteria. Single cell imaging and observations such as those presented here can provide subtle insights and measurements of cellular activity that are often diluted by bulk approaches and that are directly applicable to modeling N and C cycling.

{sup 13}C ISOTOPIC FRACTIONATION OF HC{sub 3}N IN STAR-FORMING REGIONS: LOW-MASS STAR-FORMING REGION L1527 AND HIGH-MASS STAR-FORMING REGION G28.28-0.36

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

Taniguchi, Kotomi; Saito, Masao; Ozeki, Hiroyuki, E-mail: kotomi.taniguchi@nao.ac.jp

2016-10-20

We observed the J = 9–8 and 10–9 rotational lines of three {sup 13}C isotopologues of HC{sub 3}N in L1527 and G28.28-0.36, with the 45 m radio telescope of the Nobeyama Radio Observatory, in order to constrain the main formation mechanisms of HC{sub 3}N in each source. The abundance ratios of the three {sup 13}C isotopologues of HC{sub 3}N are found to be 0.9 (±0.2) : 1.00 : 1.29 (±0.19) (1 σ ), and 1.0 (±0.2) : 1.00 : 1.47 (±0.17) (1 σ ), for [H{sup 13}CCCN : HC{sup 13}CCN : HCC{sup 13}CN] in L1527 and G28.28-0.36, respectively. We recognize,more » from a similar {sup 13}C isotopic fractionation pattern, that the abundances of H{sup 13}CCCN and HC{sup 13}CCN are comparable, and HCC{sup 13}CN is more abundant than the others. Based on the results, we discuss the main formation pathway of HC{sub 3}N. The {sup 13}C isotopic fractionation pattern derived from our observations can be explained by the neutral-neutral reaction between C{sub 2}H{sub 2} and CN in both the low-mass (L1527) and high-mass (G28.28-0.36) star-forming regions.« less

Analysis of dissolved organic carbon concentration and 13C isotopic signature by TOC-IRMS - assessment of analytical performance

NASA Astrophysics Data System (ADS)

Kirkels, Frédérique; Cerli, Chiara; Federherr, Eugen; Kalbitz, Karsten

2013-04-01

samples did not affect the precision of the analysis of natural abundance and labeled samples. Natural DOM, derived from different soils and assessed at various concentrations, was measured with similar good analytical performance, and also tested for the effect of freezing and re-dissolving. We found good performance of TOC-IRMS in comparison with other systems capable of determining C concentration and isotopic signatures. We recognize the advantages of this system providing: - High sample throughput, short measurement time (15 minutes), flexible sample volume - Easy maintenance, handling, rapid sample preparation (no pretreatment) This preliminary assessment highlights wide-ranging opportunities for further research on concentrations and isotopic signatures by TOC-IRMS to elucidate the role of dissolved carbon in terrestrial and aquatic systems.

Biomarkers: d13C and d15N Distribution Tightly Coupled to Nutrient Dynamics and Viral Lysing in a Microbial Mat From Death Valley, California

NASA Astrophysics Data System (ADS)

Hewson, I.; Archer, R.; Mahaffey, C.; Scott, J.; Tsapin, A.

2002-12-01

Extrapolations into ancient biomes make many assumptions and inferences regarding life modes and environmental habitat. While definition of a stromatolite as an extinct microbial biome by petrographic analysis is promising, Life interacts with is environment, actively manipulating energy flow across chemical disequilibria gradients, harvesting energy crucial for physiological maintenance and reproduction. Such structuring of communities in turn, leaves specific chemical/isotopic imprints related to physiological processes of prokaryotic communities specific to each oxidation/redox horizon. We examine stable isotopic d13C signals (d13C and d15N) as potential biomarkers reflecting bacterial physiology and microbial community nutrient-energy dynamics. While isotopes may reveal ancient chemical structuring of microbial mats, we also turn to invoking viral lysing of bacterial hosts in nutrient cycling within modern extreme environments as well as ancient stromatic structures of early Earth. Our records of d13C indicate extreme enrichment(-12%) for Corg in our extant mat due to CO2 limitation across a hypersaline diffusive barrier at the mat's surface. d15N is lowest at the mat's surface (indicating N2- fixation) where nitrogen- fixing cyanobacteria Microcoleus sp. are present . Viruses are extremely abundant in the microbial mat, exceeding bacterial abundances by a factor of ten. The ratio of viruses to bacteria was very high (VBR = 39 ñ 10) compared with abundances in marine sediments. Distribution of viruses closely follows distribution of bacteria, suggesting bacteria as primary hosts. The ratio of viruses to bacteria is inversely correlated to the concentration of organic C suggesting virus abundance is responsive to host substrate availability. High ratios of viruses to bacteria in mid-mat horizons (2.5 - 3.7 cm) above increasing levels of d13C in deeper horizons, coupled with a lack of increase in bacteria, suggests that viral lysis contributes to significant

In vivo detection of 13C isotopomer turnover in the human brain by sequential infusion of 13C labeled substrates

NASA Astrophysics Data System (ADS)

Li, Shizhe; Zhang, Yan; Ferraris Araneta, Maria; Xiang, Yun; Johnson, Christopher; Innis, Robert B.; Shen, Jun

2012-05-01

This study demonstrates the feasibility of simultaneously detecting human brain metabolites labeled by two substrates infused in a sequential order. In vivo 13C spectra of carboxylic/amide carbons were acquired only during the infusion of the second substrate. This approach allowed dynamic detection of 13C labeling from two substrates with considerably different labeling patterns. [2-13C]glucose and [U-13C6]glucose were used to generate singlet and doublet signals of the same carboxylic/amide carbon atom, respectively. Because of the large one-bond 13C-13C homonuclear J coupling between a carboxylic/amide carbon and an aliphatic carbon (˜50 Hz), the singlet and doublet signals of the same carboxylic/amide carbon were well distinguished. The results demonstrated that different 13C isotopomer patterns could be simultaneously and distinctly measured in vivo in a clinical setting at 3 T.

Development of an LC-MS/MS method for the determination of endogenous cortisol in hair using (13)C3-labeled cortisol as surrogate analyte.

PubMed

Binz, Tina M; Braun, Ueli; Baumgartner, Markus R; Kraemer, Thomas

2016-10-15

Hair cortisol levels are increasingly applied as a measure for stress in humans and mammals. Cortisol is an endogenous compound and is always present within the hair matrix. Therefore, "cortisol-free hair matrix" is a critical point for any analytical method to accurately quantify especially low cortisol levels. The aim of this project was to modify current methods used for hair cortisol analysis to more accurately determine low endogenous cortisol concentrations in hair. For that purpose, (13)C3-labeled cortisol, which is not naturally present in hair (above 13C natural abundance levels), was used for calibration and comparative validation applying cortisol versus (13)C3-labeled cortisol. Cortisol was extracted from 20mg hair (standard sample amount) applying an optimized single step extraction protocol. An LC-MS/MS method was developed for the quantitative analysis of cortisol using either cortisol or (13)C3-cortisol as calibrators and D7-cortisone as internal standard (IS). The two methods (cortisol/(13)C3-labeled cortisol) were validated in a concentration range up to 500pg/mg and showed good linearity for both analytes (cortisol: R(2)=0.9995; (13)C3-cortisol R(2)=0.9992). Slight differences were observed for limit of detection (LOD) (0.2pg/mg/0.1pg/mg) and limit of quantification (LOQ) (1pg/mg/0.5pg/mg). Precision was good with a maximum deviation of 8.8% and 10% for cortisol and (13)C3-cortisol respectively. Accuracy and matrix effects were good for both analytes except for the quality control (QC) low cortisol. QC low (2.5pg/mg) showed matrix effects (126.5%, RSD 35.5%) and accuracy showed a deviation of 26% when using cortisol to spike. These effects are likely to be caused by the unknown amount of endogenous cortisol in the different hair samples used to determine validation parameters like matrix effect, LOQ and accuracy. No matrix effects were observed for the high QC (400pg/mg) samples. Recovery was good with 92.7%/87.3% (RSD 9.9%/6.2%) for QC low and

Two Techniques for Estimating Deglacial Mean-Ocean δ13 C Change from the Same Set of 493 Benthic δ13C Records

NASA Astrophysics Data System (ADS)

Peterson, C. D.; Lisiecki, L. E.; Gebbie, G.

2013-12-01

The crux of carbon redistribution over the deglaciation centers on the ocean, where the isotopic signature of terrestrial carbon (δ13C terrestrial carbon = -25‰) is observed as a 0.3-0.7‰ shift in benthic foraminiferal δ13C. Deglacial mean-ocean δ13C estimates vary due to different subsets of benthic δ13C data and different methods of weighting the mean δ13C by volume. Here, we present a detailed 1-to-1 comparison of two methods of calculating mean δ13C change and uncertainty estimates using the same set of 493 benthic Cibicidoides spp. δ13C measurements for the LGM and Late Holocene. The first method divides the ocean into 8 regions, and uses simple line fits to describe the distribution of δ13C data for each timeslice over 0.5-5 km depth. With these line fits, we estimate the δ13C value at 100-meter intervals and weight those estimates by the regional volume at each depth slice. The mean-ocean δ13C is the sum of these volume-weighted regional δ13C estimates and the uncertainty of these mean-ocean δ13C estimates is computed using Monte Carlo simulations. The whole-ocean δ13C change is estimated using extrapolated surface- and deep-ocean δ13C estimates, and an assumed δ13C value for the Southern Ocean. This method yields an estimated LGM-to-Holocene change of 0.38×0.07‰ for 0.5-5km and 0.35×0.16‰ for the whole ocean (Peterson et al., 2013, submitted to Paleoceanography). The second method reconstructs glacial and modern δ13C by combining the same data compilation as above with a steady-state ocean circulation model (Gebbie, 2013, submitted to Paleoceanography). The result is a tracer distribution on a 4-by-4 degree horizontal resolution grid with 23 vertical levels, and an estimate of the distribution's uncertainty that accounts for the distinct modern and glacial water-mass geometries. From both methods, we compare the regional δ13C estimates (0.5-5 km), surface δ13C estimates (0-0.5 km), deep δ13C estimates (>5 km), Southern Ocean �

Prospective Work for Alma: the Millimeterwave and Submillimeterwave Spectrum of 13C-GLYCOLALDEHYDE

NASA Astrophysics Data System (ADS)

Haykal, Imane; Margulès, Laurent; Huet, Therese R.; Motiyenko, Roman; Guillemin, J.-C.

2011-06-01

Glycolaldehyde has been identified in interstellar sources. The relative abundance ratios of the three isomers (acetic acid) : (glycolaldehyde) : (methylformate) were estimated . The detection of 13C_1 and 13C_2 isotopomers of methylformate has been recently reported in Orion, as a result of the detailled labororatory spectroscopic study. Therefore the spectroscopy of the 13C isotopomers of glycolaldehyde is investigated in laboratory in order to provide data for an astronomical search. The instrument ALMA will certainly be a good instrument to detect them. Up to now, only the microwave spectra of 13CH_2OH-CHO and of CH_2OH-13CHO have been observed several years ago in the 12-40 GHz range. Spectra of both species are presently recorded in Lille in the 150-950 GHz range with the new submillimetre-wave spectrometer based on harmonic generation of a microwave synthesizer source, using only solid-state devices, and coupled to a cell of 2.2 m length The absolute accuracy of the line positions is better than 30 KHz. The rotational structure of the ground state and of the three first excited vibrational states has been observed. Two 13C enriched samples were used. The analysis is in progress. This work is supported by the Programme National de Physico-Chimie du Milieu Interstellaire (PCMI-CNRS) and by the contract ANR-08-BLAN-0054 J. M. Hollis, S. N. Vogel, L. E. Snyder, et al., Astrophys. J. 554(2001) L81 R. A. H. Butler, F. C. De Lucia, D. T Petkie, et al., Astrophys. J. Supp. 134 (2001) 319 M. T. Beltran, C. Codella, S. Viti, R. Niri, R. Cesaroni, Astrophys. J. 690 (2009) L93. M. Carjaval, L. Margulès, B. Tercero et al., Astron. Astrophys. 500 (2009) 1109. K.-M. Marstokk and H. Møllendal, J. Mol. Struct. 16 (1973) 259. R. A. Motiyenko, L. Margulès, E. A. Alekseev et al., J. Mol. Spectrosc. 264 (2010) 94.

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 section...

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 section...

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 section...

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 section...

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 section...

Chemical vs. biotechnological synthesis of C13-apocarotenoids: current methods, applications and perspectives.

PubMed

Cataldo, Vicente F; López, Javiera; Cárcamo, Martín; Agosin, Eduardo

2016-07-01

Apocarotenoids are natural compounds derived from the oxidative cleavage of carotenoids. Particularly, C13-apocarotenoids are volatile compounds that contribute to the aromas of different flowers and fruits and are highly valued by the Flavor and Fragrance industry. So far, the chemical synthesis of these terpenoids has dominated the industry. Nonetheless, the increasing consumer demand for more natural and sustainable processes raises an interesting opportunity for bio-production alternatives. In this regard, enzymatic biocatalysis and metabolically engineered microorganisms emerge as attractive biotechnological options. The present review summarizes promising bioengineering approaches with regard to chemical production methods for the synthesis of two families of C13-apocarotenoids: ionones/dihydroionones and damascones/damascenone. We discuss each method and its applicability, with a thorough comparative analysis for ionones, focusing on the production process, regulatory aspects, and sustainability.

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.

Modeling 13C discrimination in Tree Rings

NASA Astrophysics Data System (ADS)

Berninger, Frank; Sonninen, Eloni; Aalto, Tuula; Lloyd, Jon

2000-03-01

Annual variations from 1877 to 1995 in tree-ring α-cellulose 13C/12C isotopic ratios for four subarctic Pinus sylvestris trees were determined, and, in conjunction with a recent record of atmospheric 13CO2/12CO2 ratios, the historical pattern of photosynthetic isotope discrimination, Δ13C, was evaluated. Year-to-year variability in Δ13C has been as much as 1.5‰ with the period 1900-1920 showing an extended period of unusually high photosynthetic discriminations. The summers during these years were, on average, unusually cold. Since 1920 a long term trend of increasing Δ13C of ˜0.016‰yr-1 is inferred. We compared measured Δ13C with those predicted on the basis of the theoretical relationship between Δ13C and the ratio of substomatal to ambient CO2 concentration, Ci/Ca using mechanistic equations for chloroplast biochemistry coupled with a stomatal conductance model. Two variations of a nonlinear optimal-regulation stomatal conductance model were compared. Although both models were based on the assumption that stomata serve to minimize the average transpiration rate for a given average rate of CO2 assimilation, one version of the model incorporated reductions in stomatal conductance in response to recent increases in atmospheric CO2 concentrations and the other did not. The CO2 sensitive stomatal model failed to describe the long-term increase in 13C discrimination, especially after 1950. The insensitive model gave good agreement, suggesting that an observed increase in subarctic Pinus sylvestris Δ13C since 1920 is attributable to recent increases in atmospheric CO2 concentrations with subsequent increases in the ratio of substomatal to ambient CO2 concentrations. The model was also capable of accounting for high frequency (year-to-year) variations in Δ13C, these differences being attributable to year-to-year fluctuations in the average leaf-to-air vapor pressure difference affecting stomatal conductance and hence Ci/Ca.

Determination of 15N/14N and 13C/12C in Solid and Aqueous Cyanides

USGS Publications Warehouse

Johnson, C.A.

1996-01-01

The stable isotopic compositions of nitrogen and carbon in cyanide compounds can be determined by combusting aliquots in sealed tubes to form N2 gas and CO2 gas and analyzing the gases by mass spectrometry. Free cyanide (CN-aq + HCNaq) in simple solutions can also be analyzed by first precipitating the cyanide as copper(II) ferrocyanide and then combusting the precipitate. Reproducibility is ??0.5??? or better for both ??15N and ??13C. If empirical corrections are made on the basis of carbon yields, the reproducibility of ??13C can be improved to ??0.2???. The analytical methods described herein are sufficiently accurate and precise to apply stable isotope techniques to problems of cyanide degradation in natural waters and industrial process solutions.

Natural variation in stomatal abundance of Arabidopsis thaliana includes cryptic diversity for different developmental processes

PubMed Central

Delgado, Dolores; Alonso-Blanco, Carlos; Fenoll, Carmen; Mena, Montaña

2011-01-01

Background and Aims Current understanding of stomatal development in Arabidopsis thaliana is based on mutations producing aberrant, often lethal phenotypes. The aim was to discover if naturally occurring viable phenotypes would be useful for studying stomatal development in a species that enables further molecular analysis. Methods Natural variation in stomatal abundance of A. thaliana was explored in two collections comprising 62 wild accessions by surveying adaxial epidermal cell-type proportion (stomatal index) and density (stomatal and pavement cell density) traits in cotyledons and first leaves. Organ size variation was studied in a subset of accessions. For all traits, maternal effects derived from different laboratory environments were evaluated. In four selected accessions, distinct stomatal initiation processes were quantitatively analysed. Key Results and Conclusions Substantial genetic variation was found for all six stomatal abundance-related traits, which were weakly or not affected by laboratory maternal environments. Correlation analyses revealed overall relationships among all traits. Within each organ, stomatal density highly correlated with the other traits, suggesting common genetic bases. Each trait correlated between organs, supporting supra-organ control of stomatal abundance. Clustering analyses identified accessions with uncommon phenotypic patterns, suggesting differences among genetic programmes controlling the various traits. Variation was also found in organ size, which negatively correlated with cell densities in both organs and with stomatal index in the cotyledon. Relative proportions of primary and satellite lineages varied among the accessions analysed, indicating that distinct developmental components contribute to natural diversity in stomatal abundance. Accessions with similar stomatal indices showed different lineage class ratios, revealing hidden developmental phenotypes and showing that genetic determinants of primary and

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

DOEpatents

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

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.

Generation of C3- and C2-deuterated L-lactic acid by human erythrocytes exposed to D-[1-13C]glucose, D-[2-13C]glucose and D-[6-13C]glucose in the presence of D2O.

PubMed

Malaisse, W J; Biesemans, M; Willem, R

1994-05-01

1. The generation of C2- and C3-deuterated L-lactate was monitored by 13C NMR in human erythrocytes exposed to D-[1-13C]glucose, D-[2-13C]glucose or D-[6-13C]glucose and incubated in a medium prepared in D2O. 2. The results suggested that the deuteration of the C1 of D-fructose 6-phosphate in the phosphoglucoisomerase reaction, the deuteration of the C1 of D-glyceraldehyde-3-phosphate in the sequence of reactions catalyzed by triose phosphate isomerase and aldolase and the deuteration of the C3 of pyruvate in the reaction catalyzed by pyruvate kinase were all lower than expected from equilibration with D2O. 3. Moreover, about 40% of the molecules of pyruvate generated by glycolysis apparently underwent deuteration on their C3 during interconversion of the 2-keto acid and L-alanine in the reaction catalyzed by glutamate-pyruvate transaminase. 4. The occurrence of the latter process was also documented in cells exposed to exogenous [3-13C]pyruvate. 5. This methodological approach is proposed to provide a new tool to assess in intact cells the extent of back-and-forth interconversion of selected metabolic intermediates.

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

High-resolution detection of adulteration of maize oil using multi-component compound-specific delta13C values of major and minor components and discriminant analysis.

PubMed

Mottram, Hazel R; Woodbury, Simon E; Rossell, J Barry; Evershed, Richard P

2003-01-01

Maize oil commands a premium price and is thus a target for adulteration with cheaper vegetable oils. Detection of this activity presents a particular challenge to the analyst because of the natural variability in the fatty acid composition of maize oils and because of their high sterol and tocopherol contents. This paper describes a method that allows detection of adulteration at concentrations of just 5% (m/m), based on the Mahalanobis distances of the principal component scores of the delta(13)C values of major and minor vegetable oil components. The method makes use of a database consisting of delta(13)C values and relative abundances of the major fatty acyl components of over 150 vegetable oils. The sterols and tocopherols of 16 maize oils and 6 potential adulterant oils were found to be depleted in (13)C by a constant amount relative to the bulk oil. Moreover, since maize oil contains particularly high levels of sterols and tocopherols, their delta(13)C values were not significantly altered when groundnut oil was added up to 20% (m/m) and it is possible to use the values for the minor components to predict the values that would be expected in a pure oil; therefore, comparison of the predicted values with those obtained experimentally allows adulteration to be detected. A refinement involved performing a discriminant analysis on the delta(13)C values of the bulk oil and the major fatty acids (16:0, 18:1 and 18:2) and using the Mahalanobis distances to determine the percentage of adulterant oil present. This approach may be refined further by including the delta(13)C values of the minor components in the discriminant analysis thereby increasing the sensitivity of the approach to concentrations at which adulteration would not be attractive economically. Copyright 2003 John Wiley & Sons, Ltd.

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.

Daughter Species Abundances in Comet C/2014 Q2 (Lovejoy)

NASA Astrophysics Data System (ADS)

McKay, Adam; Cochran, Anita; Dello Russo, Neil; Kelley, Michael

2015-11-01

We present analysis of high spectral resolution optical spectra of C/2014 Q2 (Lovejoy) acquired with the Tull Coude spectrometer on the 2.7-meter Harlan J. Smith Telescope at McDonald Observatory and the ARCES spectrometer mounted on the 3.5-meter Astrophysical Research Consortium Telescope at Apache Point Observatory. Both Tull Coude and ARCES provide high spectral resolution (R=30,000-60,000) and a large spectral range of approximately 3500-10000 Angstroms. We obtained two observation epochs, one in February 2015 at a heliocentric distance of 1.3 AU, and another in May 2015 at a heliocentric distance of 1.9 AU. Another epoch in late August 2015 at a heliocentric distance of 3.0 AU is scheduled. We will present production rates of the daughter species CN, C3, CH, C2, and NH2. We will also present H2O production rates derived from the [OI]6300 emission, as well as measurements of the flux ratio of the [OI]5577 Angstrom line to the sum of the [OI]6300 and [OI]6364 Angstrom lines (sometimes referred to as the oxygen line ratio). This ratio is indicative of the CO2 abundance of the comet. As we have observations at several heliocentric distances, we will examine how production rates and mixing ratios of the various species change with heliocentric distance. We will compare our oxygen line measurements to observations of CO2 made with Spitzer, as well as our other daughter species observations to those of candidate parent molecules made at IR wavelengths.

Towards hyperpolarized 13C-succinate imaging of brain cancer

PubMed Central

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

2009-01-01

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

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.

Rotational spectrum of 13C{2}-methyl formate (HCOO13CH{3}) and detection of the two 13C-methyl formate in Orion

NASA Astrophysics Data System (ADS)

Carvajal, M.; Margulès, L.; Tercero, B.; Demyk, K.; Kleiner, I.; Guillemin, J. C.; Lattanzi, V.; Walters, A.; Demaison, J.; Wlodarczak, G.; Huet, T. R.; Møllendal, H.; Ilyushin, V. V.; Cernicharo, J.

2009-06-01

Context: Laboratory measurements and analysis of the microwave and millimeter-wave spectra of potential interstellar molecules are a prerequisite for their subsequent identification by radioastronomical techniques. The spectral analysis provides spectroscopic parameters that are used in the assignment procedure of the laboratory spectra, and that also predict the frequencies of transitions not measured in the laboratory with a high degree of precision. Aims: An experimental laboratory study and its theoretical analysis is presented for 13C2-methyl formate (HCOO13CH3) allowing a search for this isotopologue in the Orion molecular cloud. The 13C1-methyl formate (H13COOCH3) molecule was also searched for in this interstellar cloud, using previously published spectroscopic data. Methods: The experimental spectra of 13C2-methyl formate were recorded in the microwave and sub-mm energy ranges (4-20 GHz, 8-80 GHz, 150-700 GHz). The spectra were analyzed using the Rho-Axis Method (RAM), which takes the CH3 internal rotation and the coupling between internal rotation and global rotation into account. Results: Twenty-seven spectroscopic constants of 13C2-methyl formate have been obtained from a fit of 936 transitions of the ground torsional state with a standard (unitless) deviation of 1.08. A prediction of line positions and intensities is also produced. This prediction allowed us to identify 230 13C2-methyl formate lines in the Orion interstellar molecular cloud. We refitted all previously published ground state transitions of the 13C1-methyl formate molecule in order to provide a prediction of its ground state spectrum. 234 lines of 13C1-methyl formate were detected in the Orion interstellar cloud using that prediction. Tables A.1-A.5 are only available in electronic form at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsweb.u-strasbg.fr/cgi-bin/qcat?J/A+A/500/1109

Thz Spectroscopy of 13C Isotopic Species of a "weed": Acetaldehyde

NASA Astrophysics Data System (ADS)

Margulès, L.; Motiyenko, R. A.; Guillemin, J.-C.

2011-06-01

Our studies of the isotopic species of 13C and D isotopologues of methyl formate (HCOOCH_3), have allowed the detection of more than 600 lines in Orion. This confirms that many observed U-lines are coming from isotopic species of one of the most abundant molecules in space. Since its first detection in 1976 in SgrB2 and in Orion A, acetaldehyde (CH_3CHO) was detected in many other numerous objects. If its deuterated species (CD_3CHO and CH_3CDO) have been previously studied in the millimeterwave range, the data concerning the 13C species are limited to few lines measured in 1957 up to 40 GHz. In this context we decided to study the 13C species of acetaldehyde. Acetaldehyde molecule displays a large amplitude motion: the hindered rotation of the methyl group with respect to the rest of the molecule. The analysis is performed with the Rho Axis Method. Recent versions of the codes include high orders term in order to reproduce the observed frequencies for large quantum numbers values as J-values as high as 70a,b,. Measurements and analysis of the rotational spectra of 13C isotopic species are in progress in Lille with a solid-state submillimetre-wave spectrometer (50-950 GHz), the first results will be presented. This work is supported by the contract ANR-08-BLAN-0054 and by the Programme National de Physico-Chimie du Milieu Interstellaire (PCMI-CNRS). Carvajal, M.; Margulès, L.; Tercero, B.; et al.A&A 500, (2009) 1109 Margulès, L.; Huet, T. R.; Demaison J.; et al.,ApJ 714, (2010) 1120. Ikeda, M.; Ohishi, M.; Nummelin, A.; et al., ApJ, 560, (2001) 792 Kleiner, I.; Lopez, J.-C.; Blanco, S.; et al.J. Mol. Spectrosc. 197, (1999) 275 Elkeurti M.; Coudert, L. H.; Medvedev, I. R.; et al.J. Mol. Spectrosc. 263, (2010) 145 Kilb, R.W.; Lin, C.C.; and Wilson, E.B.J. Chem. Phys. 26, (1957) 1695 Kleiner, I. J. Mol. Spectrosc. 260, (2010) 1 Ilyushin, V.V.; Kryvda, A; and Alekseev, E;J. Mol. Spectrosc. 255, (2009) 32

Coral 13C/12C records of vertical seafloor displacement during megathrust earthquakes west of Sumatra

NASA Astrophysics Data System (ADS)

Gagan, Michael K.; Sosdian, Sindia M.; Scott-Gagan, Heather; Sieh, Kerry; Hantoro, Wahyoe S.; Natawidjaja, Danny H.; Briggs, Richard W.; Suwargadi, Bambang W.; Rifai, Hamdi

2015-12-01

The recent surge of megathrust earthquakes and tsunami disasters has highlighted the need for a comprehensive understanding of earthquake cycles along convergent plate boundaries. Space geodesy has been used to document recent crustal deformation patterns with unprecedented precision, however the production of long paleogeodetic records of vertical seafloor motion is still a major challenge. Here we show that carbon isotope ratios (δ13C) in the skeletons of massive Porites corals from west Sumatra record abrupt changes in light exposure resulting from coseismic seafloor displacements. Validation of the method is based on the coral δ13C response to uplift (and subsidence) produced by the March 2005 Mw 8.6 Nias-Simeulue earthquake, and uplift further south around Sipora Island during a M ∼ 8.4 megathrust earthquake in February 1797. At Nias, the average step-change in coral δ13C was 0.6 ± 0.1 ‰ /m for coseismic displacements of +1.8 m and -0.4 m in 2005. At Sipora, a distinct change in Porites microatoll growth morphology marks coseismic uplift of 0.7 m in 1797. In this shallow water setting, with a steep light attenuation gradient, the step-change in microatoll δ13C is 2.3 ‰ /m, nearly four times greater than for the Nias Porites. Considering the natural variability in coral skeletal δ13C, we show that the lower detection limit of the method is around 0.2 m of vertical seafloor motion. Analysis of vertical displacement for well-documented earthquakes suggests this sensitivity equates to shallow events exceeding Mw ∼ 7.2 in central megathrust and back-arc thrust fault settings. Our findings indicate that the coral 13C /12C paleogeodesy technique could be applied to convergent tectonic margins throughout the tropical western Pacific and eastern Indian oceans, which host prolific coral reefs, and some of the world's greatest earthquake catastrophes. While our focus here is the link between coral δ13C, light exposure and coseismic crustal deformation, the

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.

Quality or quantity: is nutrient transfer driven more by symbiont identity and productivity than by symbiont abundance?

PubMed

Freeman, Christopher J; Thacker, Robert W; Baker, David M; Fogel, Marilyn L

2013-06-01

By forming symbiotic interactions with microbes, many animals and plants gain access to the products of novel metabolic pathways. We investigated the transfer of symbiont-derived carbon and nitrogen to the sponges Aplysina cauliformis, Aplysina fulva, Chondrilla caribensis, Neopetrosia subtriangularis and Xestospongia bocatorensis, all of which host abundant microbial populations, and Niphates erecta, which hosts a sparse symbiont community. We incubated sponges in light and dark bottles containing seawater spiked with (13)C- and (15)N-enriched inorganic compounds and then measured (13)C and (15)N enrichment in the microbial (nutrient assimilation) and sponge (nutrient transfer) fractions. Surprisingly, although most sponges hosting abundant microbial communities were more enriched in (13)C than N. erecta, only N. subtriangularis was more enriched in (15)N than N. erecta. Although photosymbiont abundance varied substantially across species, (13)C and (15)N enrichment was not significantly correlated with photosymbiont abundance. Enrichment was significantly correlated with the ratio of gross productivity to respiration (P:R), which varied across host species and symbiont phylotype. Because irradiance impacts P:R ratios, we also incubated A. cauliformis in (13)C-enriched seawater under different irradiances to determine whether symbiont carbon fixation and transfer are dependent on irradiance. Carbon fixation and transfer to the sponge host occurred in all treatments, but was greatest at higher irradiances and was significantly correlated with P:R ratios. Taken together, these results demonstrate that nutrient transfer from microbial symbionts to host sponges is influenced more by host-symbiont identities and P:R ratios than by symbiont abundance.

Sensitivity-enhanced IPAP experiments for measuring one-bond 13C '- 13C α and 13C α- 1H α residual dipolar couplings in proteins

NASA Astrophysics Data System (ADS)

Ding, Keyang; Gronenborn, Angela M.

2004-04-01

Sensitivity-enhanced 2D IPAP experiments using the accordion principle for measuring one-bond 13C '- 13C α and 1H α- 13C α dipolar couplings in proteins are presented. The resolution of the resulting spectra is identical to that of the decoupled HSQC spectra and the sensitivity of the corresponding 1D acquisitions are only slightly lower than those obtained with 3D HNCO and 3D HN(COCA)HA pulse sequences due to an additional delay 2 Δ. For cases of limited resolution in the 2D 15N- 1H N HSQC spectrum the current pulse sequences can easily be modified into 3D versions by introducing a poorly digitized third dimension, if so desired. The experiments described here are a valuable addition to the suites available for determination of residual dipolar couplings in biological systems.

Non-stationary (13)C-metabolic flux ratio analysis.

PubMed

Hörl, Manuel; Schnidder, Julian; Sauer, Uwe; Zamboni, Nicola

2013-12-01

(13)C-metabolic flux analysis ((13)C-MFA) has become a key method for metabolic engineering and systems biology. In the most common methodology, fluxes are calculated by global isotopomer balancing and iterative fitting to stationary (13)C-labeling data. This approach requires a closed carbon balance, long-lasting metabolic steady state, and the detection of (13)C-patterns in a large number of metabolites. These restrictions mostly reduced the application of (13)C-MFA to the central carbon metabolism of well-studied model organisms grown in minimal media with a single carbon source. Here we introduce non-stationary (13)C-metabolic flux ratio analysis as a novel method for (13)C-MFA to allow estimating local, relative fluxes from ultra-short (13)C-labeling experiments and without the need for global isotopomer balancing. The approach relies on the acquisition of non-stationary (13)C-labeling data exclusively for metabolites in the proximity of a node of converging fluxes and a local parameter estimation with a system of ordinary differential equations. We developed a generalized workflow that takes into account reaction types and the availability of mass spectrometric data on molecular ions or fragments for data processing, modeling, parameter and error estimation. We demonstrated the approach by analyzing three key nodes of converging fluxes in central metabolism of Bacillus subtilis. We obtained flux estimates that are in agreement with published results obtained from steady state experiments, but reduced the duration of the necessary (13)C-labeling experiment to less than a minute. These results show that our strategy enables to formally estimate relative pathway fluxes on extremely short time scale, neglecting cellular carbon balancing. Hence this approach paves the road to targeted (13)C-MFA in dynamic systems with multiple carbon sources and towards rich media. © 2013 Wiley Periodicals, Inc.

Stellar Origins of C-13 and N-15-Enriched Presolar SiC Grains

NASA Technical Reports Server (NTRS)

Liu, Nan; Nittler, Larry R.; Alexander, Conel M. O’D.; Wang, Jianhua; Pignatari, Marco; Jose, Jordi; Nguyen, Ann

2016-01-01

Extreme excesses of 13 C ( C (12 C/ 13 C<10) and 15 N ( N (14 N/ 15 N< 20) in rare presolar SiC 20) in rare presolar SiClar SiC grains have been considered diagnostic of an origin in classical novae [1], though an origin in core-collapse supernovae (CCSNe) has also been proposed [2]. We report multi-element isotopic data for 19 13 C- and 15 N-enriched presolar SiC grains(12 C/13 C<16 and 14 N/ 15 N<150) from an acid resistant residue of the Murchison meteorite. These grains are enriched in 13 C and15 N, but with quite diverse Si isotopic signatures. Four grains with isotopic signatures. Four grains with isotopic signatures. Four grains with isotopic signatures. Four grains with isotopic signatures.

Determination of 13C/12C Isotope Ratio in Alcohols of Different Origin by 1н Nuclei NMR-Spectroscopy

NASA Astrophysics Data System (ADS)

Dzhimak, S. S.; Basov, A. A.; Buzko, V. Yu.; Kopytov, G. F.; Kashaev, D. V.; Shashkov, D. I.; Shlapakov, M. S.; Baryshev, M. G.

2017-02-01

A new express method of indirect assessment of 13C/12C isotope ratio on 1H nuclei is developed to verify the authenticity of ethanol origin in alcohol-water-based fluids and assess the facts of various alcoholic beverages falsification. It is established that in water-based alcohol-containing systems, side satellites for the signals of ethanol methyl and methylene protons in the NMR spectra on 1H nuclei, correspond to the protons associated with 13C nuclei. There is a direct correlation between the intensities of the signals of ethanol methyl and methylene protons' 1H- NMR and their side satellites, therefore, the data obtained can be used to assess 13C/12C isotope ratio in water-based alcohol-containing systems. The analysis of integrated intensities of main and satellite signals of methyl and methylene protons of ethanol obtained by NMR on 1H nuclei makes it possible to differentiate between ethanol of synthetic and natural origin. Furthermore, the method proposed made it possible to differentiate between wheat and corn ethanol.

Timing and Nature of Appearance of C4 Plants in the Indian Subcontinent: Clue from Isotopic Ratios of Biomarker

NASA Astrophysics Data System (ADS)

Sanyal, P.

2014-12-01

Appearance and expansion of C4 plants during the late Miocene was first documented from Siwalik Group of sediments using carbon isotope ratio of soil carbonates. It was proposed that C4 plants appeared drastically in response to change in hydrological cycle. Subsequently, various workers documented evolution and expansion of C4 plants from different Siwalik sections of India, Nepal and Pakistan. Although evolution and expansion of C4 plants was documented in all these studies but nature and timing of expansion of C4 plants showed variations from section to sections. Even from same section, the results varied with change in proxies. The hydrological changes also differ regionally. One of the reasons of differences in results was lack of modern data set from the Indian subcontinent. For example, in many cases δ18O values of New Delhi rainwater has been considered as reference data set and applied to site of investigation with some corrections. The average δ13C values of C3 and C4 plants was considered as -27‰ and -12.5‰ respectively, but modern C3 plants in the Gangetic plain is almost 2.5‰ lower than the value used in those studies. Additional problem raised as preservation of pristine isotopic character of soil organic matter is also apprehensive. To resolve all these issues, the δ13C value of long chain alkane have been used to reconstruct C3-C4 plants after isotopic characterization of modern plants and their biomarker from the Gangetic plain which is equivalent to the past Siwalik flood plain. Additionally, δD values of long chain alkane were also measured. Variations of d13C values of long chain alkane with time show presence of C4 plants in Siwalik from 11 Ma ago and since then gradual increase in C4 plants till 6 Ma followed by a sharp increase. The statistically significant correlation between δD and δ13C values of long chain alkane show that positive impact of hydrological change on abundance of C3-C4 plants.

The 13Carbon footprint of B[e] supergiants

NASA Astrophysics Data System (ADS)

Liermann, A.; Kraus, M.; Schnurr, O.; Fernandes, M. Borges

2010-10-01

We report on the first detection of 13C enhancement in two B[e] supergiants (B[e]SGs) in the Large Magellanic Cloud. Stellar evolution models predict the surface abundance in 13C to strongly increase during main-sequence and post-main-sequence evolution of massive stars. However, direct identification of chemically processed material on the surface of B[e]SGs is hampered by their dense, disc-forming winds, hiding the stars. Recent theoretical computations predict the detectability of enhanced 13C via the molecular emission in 13CO arising in the circumstellar discs of B[e]SGs. To test this potential method and to unambiguously identify a post-main-sequence B[e] SG by its 13CO emission, we have obtained high-quality K-band spectra of two known B[e] SGs in the Large Magellanic Cloud, using the Very Large Telescope's Spectrograph for INtegral Field Observation in the Near-Infrared (VLT/SINFONI). Both stars clearly show the 13CO band emission, whose strength implies a strong enhancement of 13C, in agreement with theoretical predictions. This first ever direct confirmation of the evolved nature of B[e]SGs thus paves the way to the first identification of a Galactic B[e]SG. Based on observations collected with the ESO VLT Paranal Observatory under programme 384.D-1078(A). E-mail: liermann@mpifr-bonn.mpg.de (AL); kraus@sunstel.asu.cas.cz (MK); oschnurr@aip.de (OS); borges@on.br (MBF)

Nicotine, acetanilide and urea multi-level2H-,13C- and15N-abundance reference materials for continuous-flow isotope ratio mass spectrometry

USGS Publications Warehouse

Schimmelmann, A.; Albertino, A.; Sauer, P.E.; Qi, H.; Molinie, R.; Mesnard, F.

2009-01-01

Accurate determinations of stable isotope ratios require a calibration using at least two reference materials with different isotopic compositions to anchor the isotopic scale and compensate for differences in machine slope. Ideally, the S values of these reference materials should bracket the isotopic range of samples with unknown S values. While the practice of analyzing two isotopically distinct reference materials is common for water (VSMOW-SLAP) and carbonates (NBS 19 and L-SVEC), the lack of widely available organic reference materials with distinct isotopic composition has hindered the practice when analyzing organic materials by elemental analysis/isotope ratio mass spectrometry (EA-IRMS). At present only L-glutamic acids USGS40 and USGS41 satisfy these requirements for ??13C and ??13N, with the limitation that L-glutamic acid is not suitable for analysis by gas chromatography (GC). We describe the development and quality testing of (i) four nicotine laboratory reference materials for on-line (i.e. continuous flow) hydrogen reductive gas chromatography-isotope ratio mass-spectrometry (GC-IRMS), (ii) five nicotines for oxidative C, N gas chromatography-combustion-isotope ratio mass-spectrometry (GC-C-IRMS, or GC-IRMS), and (iii) also three acetanilide and three urea reference materials for on-line oxidative EA-IRMS for C and N. Isotopic off-line calibration against international stable isotope measurement standards at Indiana University adhered to the 'principle of identical treatment'. The new reference materials cover the following isotopic ranges: ??2Hnicotine -162 to -45%o, ??13Cnicotine -30.05 to +7.72%, ?? 15Nnicotine -6.03 to +33.62%; ??15N acetanilide +1-18 to +40.57%; ??13Curea -34.13 to +11.71%, ??15Nurea +0.26 to +40.61% (recommended ?? values refer to calibration with NBS 19, L-SVEC, IAEA-N-1, and IAEA-N-2). Nicotines fill a gap as the first organic nitrogen stable isotope reference materials for GC-IRMS that are available with different ??13N

Carbon and nitrogen abundances in the giant stars of the globular clusters M3 and M13

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

Suntzeff, N.B.

Carbon and nitrogen abundances, as well as the strengths of calcium II H and K and the ..delta..v = 0 cyanogen band, have been measured in red giant stars in the globular clusters M3 and M13. The data consist of spectrophotometric scans of low resolution (10 A) of 29 giants in M3 and 35 giants in M13 in the wavelength region 3000--5000 A.

Methanogenic calcite, 13C-depleted bivalve shells, and gas hydrate from a mud volcano offshore southern California

USGS Publications Warehouse

Hein, J.R.; Normark, W.R.; McIntyre, B.R.; Lorenson, T.D.; Powell, C.L.

2006-01-01

Methane and hydrogen sulfide vent from a cold seep above a shallowly buried methane hydrate in a mud volcano located 24 km offshore southern California in?? 800 m of water. Bivalves, authigenic calcite, and methane hydrate were recovered in a 2.1 m piston core. Aragonite shells of two bivalve species are unusually depleted in 13C (to -91??? ??13C), the most 13C-depleted shells of marine macrofauna yet discovered. Carbon isotopes for both living and dead specimens indicate that they used, in part, carbon derived from anaerobically oxidized methane to construct their shells. The ??13C values are highly variable, but most are within the range -12??? to -91???. This variability may be diagnostic for identifying cold-seep-hydrate systems in the geologic record. Authigenic calcite is abundant in the cores down to ???1.5 m subbottom, the top of the methane hydrate. The calcite is depleted in 13C (??13C = -46??? to -58???), indicating that carbon produced by anaerobically oxidized methane is the main source of the calcite. Methane sources include a geologic hydrocarbon reservoir from Miocene source rocks, and biogenic and thermogenic degradation of organic matter in basin sediments. Oxygen isotopes indicate that most calcite formed out of isotopic equilibrium with ambient bottom water, under the influence of gas hydrate dissociation and strong methane flux. High metal content in the mud volcano sediment indicates leaching of basement rocks by fluid circulating along an underlying fault, which also allows for a high flux of fossil methane. ?? 2006 Geological Society of America.

Calcium abundances in giant stars of the globular clusters M3, M13, M15, and M92

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

Suntzeff, N.B.

The average calcium II H and K line strengths of giant stars in M3, M13, M15, and M92 are found to be closely correlated with the (Fe/H) of the cluster. Simple physical arguments are provided to show the observed average line strengths reproduce the difference in (Fe/H) between the clusters. The observed dispersion in H and K line strengths yields an upper limit of 0.15 dex for M15 and M92, and 0.11 dex for M3+M13 for the average intracluster variation of (Ca/H), provided (Ca/H)=Fe/H). The dispersions drop to half these values if the calcium abundance varies independently of the ironmore » peak abundances.« less

Abundances of presolar graphite and SiC from supernovae and AGB stars in the Murchison meteorite

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

Amari, Sachiko; Zinner, Ernst; Gallino, Roberto

2014-05-02

Pesolar graphite grains exhibit a range of densities (1.65 – 2.20 g/cm{sup 3}). We investigated abundances of presolar graphite grains formed in supernovae and in asymptotic giant branch (AGB) stars in the four density fractions KE3, KFA1, KFB1 and KFC1 extracted from the Murchison meteorite to probe dust productions in these stellar sources. Seventy-six and 50% of the grains in the low-density fractions KE3 and KFA1, respectively, are supernova grains, while only 7.2% and 0.9% of the grains in the high-density fractions KFB1 and KFC1 have a supernova origin. Grains of AGB star origin are concentrated in the high-density fractionsmore » KFB1 and KFC1. From the C isotopic distributions of these fractions and the presence of s-process Kr with {sup 86}Kr/{sup 82}Kr = 4.43±0.46 in KFC1, we estimate that 76% and 80% of the grains in KFB1 and KFC1, respectively, formed in AGB stars. From the abundance of graphite grains in the Murchison meteorite, 0.88 ppm, the abundances of graphite from supernovae and AGB stars are 0.24 ppm and 0.44 ppm, respectively: the abundances of graphite in supernovae and AGB stars are comparable. In contrast, it has been known that 1% of SiC grains formed in supernovae and 95% formed in AGB stars in meteorites. Since the abundance of SiC grains is 5.85 ppm in the Murchison meteorite, the abundances of SiC from supernovae and AGB stars are 0.063 ppm and 5.6 ppm, respectively: the dominant source of SiC grains is AGB stars. Since SiC grains are harder and likely to survive better in space than graphite grains, the abundance of supernova graphite grains, which is higher than that of supernova SiC grains, indicates that supernovae proficiently produce graphite grains. Graphite grains from AGB stars are, in contrast, less abundant that SiC grains from AGB stars (0.44 ppm vs. 5.6 ppm). It is difficult to derive firm conclusions for graphite and SiC formation in AGB stars due to the difference in susceptibility to grain destruction

Seasonal variation in natural abundance of 2H and 18O in urine samples from rural Nigeria

PubMed Central

Dugas, Lara R.; Brieger, William; Tayo, Bamidele O.; Alabi, Tunrayo; Schoeller, Dale A.; Luke, Amy

2015-01-01

The doubly labeled water (DLW) method is used to measure free-living energy expenditure in humans. Inherent to this technique is the assumption that natural abundances of stable isotopes 2H and 18O in body water remain constant over the course of the measurement period and after elimination of the loading dose of DLW will return to the same predose level. To determine variability in the natural abundances of 2H and 18O in humans living in a region with seasonal shifts in rain patterns and sources of drinking water, over the course of 12 mo we collected weekly urine samples from four individuals living in southwest Nigeria as well as samples of their drinking water. From ongoing regional studies of hypertension, obesity, and energy expenditure, we estimated average water turnover rate, urine volumes, and sodium and potassium excretion. Results suggest that 2H and 18O in urine, mean concentrations of urinary sodium and potassium, urine volume, and total body turnover differed significantly from dry to rainy season. Additionally, seasonal weather variables (mean monthly maximum temperatures, total monthly rainfall, and minimum relative humidity) were all significantly associated with natural abundances in urine. No seasonal difference was observed in drinking water samples. Findings suggest that natural abundances in urine may not remain constant as assumed, and studies incorporating DLW measurements across the transition of seasons should interpret results with caution unless appropriate doses of the tracers are used. PMID:25977450

Seasonal variation in natural abundance of 2H and 18O in urine samples from rural Nigeria.

PubMed

Harbison, Justin E; Dugas, Lara R; Brieger, William; Tayo, Bamidele O; Alabi, Tunrayo; Schoeller, Dale A; Luke, Amy

2015-07-01

The doubly labeled water (DLW) method is used to measure free-living energy expenditure in humans. Inherent to this technique is the assumption that natural abundances of stable isotopes (2)H and (18)O in body water remain constant over the course of the measurement period and after elimination of the loading dose of DLW will return to the same predose level. To determine variability in the natural abundances of (2)H and (18)O in humans living in a region with seasonal shifts in rain patterns and sources of drinking water, over the course of 12 mo we collected weekly urine samples from four individuals living in southwest Nigeria as well as samples of their drinking water. From ongoing regional studies of hypertension, obesity, and energy expenditure, we estimated average water turnover rate, urine volumes, and sodium and potassium excretion. Results suggest that (2)H and (18)O in urine, mean concentrations of urinary sodium and potassium, urine volume, and total body turnover differed significantly from dry to rainy season. Additionally, seasonal weather variables (mean monthly maximum temperatures, total monthly rainfall, and minimum relative humidity) were all significantly associated with natural abundances in urine. No seasonal difference was observed in drinking water samples. Findings suggest that natural abundances in urine may not remain constant as assumed, and studies incorporating DLW measurements across the transition of seasons should interpret results with caution unless appropriate doses of the tracers are used. Copyright © 2015 the American Physiological Society.

Thermal maturity of type II kerogen from the New Albany Shale assessed by13C CP/MAS NMR

USGS Publications Warehouse

Werner-Zwanziger, U.; Lis, G.; Mastalerz, Maria; Schimmelmann, A.

2005-01-01

Thermal maturity of oil and gas source rocks is typically quantified in terms of vitrinite reflectance, which is based on optical properties of terrestrial woody remains. This study evaluates 13C CP/MAS NMR parameters in kerogen (i.e., the insoluble fraction of organic matter in sediments and sedimentary rocks) as proxies for thermal maturity in marine-derived source rocks where terrestrially derived vitrinite is often absent or sparse. In a suite of samples from the New Albany Shale (Middle Devonian to the Early Mississippian, Illinois Basin) the abundance of aromatic carbon in kerogen determined by 13C CP/MAS NMR correlates linearly well with vitrinite reflectance. ?? 2004 Elsevier Inc. All rights reserved.

Application of capillary gas chromatography-reaction interface/mass spectrometry to the selective detection of sup 13 C-, sup 15 N-, sup 2 H-, and sup 14 C-labeled drugs and their metabolites

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

Chace, D.H.

1989-01-01

A novel reaction interface/mass spectrometer (RIMS) technique has been applied to the selective detection of {sup 13}C-, {sup 15}N-, {sup 2}H-, and {sup 14}C-labeled phenytoin and its metabolites in urine following separation by capillary gas chromatography. The microwave-powered reaction interface converts materials from their original forms into small molecules whose mass spectra serve to identify and quantify the nuclides. The presence of each element is followed by monitoring the isotopic variants of CO{sub 2}, NO, H{sub 2}, or CH{sub 4} that are produced by the reaction interface. Chromatograms showing only enriched {sup 13}C and {sup 15}N were produced using themore » net {sup 13}CO{sub 2} or {sup 15}NO signal derived by subtracting the abundance of naturally occurring isotopes from the observed M + 1 signal. When hydrogen was used as a reactant gas, a selective chromatogram of {sup 2}H (D) was obtained by measuring HD at m/Z 3.0219, and a chromatogram showing {sup 14}C was obtained by measuring {sup 14}CH{sub 4} at m/Z 18.034 with a high resolution. For a stable isotope detection, metabolites representing less than 1.5% of the total labeled compounds could be detected in the chromatogram. Detection limits of 170 pCi/mL (34 pCi on column that is equivalent to 187 pg) of a {sup 14}C- labeled metabolite was detected. To identify many of these labeled peaks (metabolites), the chromatographic analysis was repeated with the reaction interface turned off and mass spectra obtained at the retention times found in the RIMS experiment. In addition to the ability of GC-RIMS to detect the presence of {sup 13}C-, {sup 15}N-, and {sup 2}H- (D), it can also quantify the level of enrichment. Enrichment of {sup 13}C and {sup 15}N is quantified by measuring the ratio of excess {sup 13}CO{sub 2} to total {sup 12}CO{sub 2} or excess {sup 15}NO to total {sup 14}NO.« less

The Abundance of SiC2 in Carbon Star Envelopes: Evidence that SiC2 is a gas-phase precursor of SiC dust.

PubMed

Massalkhi, Sarah; Agúndez, M; Cernicharo, J; Velilla Prieto, L; Goicoechea, J R; Quintana-Lacaci, G; Fonfría, J P; Alcolea, J; Bujarrabal, V

2018-03-01

Silicon carbide dust is ubiquitous in circumstellar envelopes around C-rich AGB stars. However, the main gas-phase precursors leading to the formation of SiC dust have not yet been identified. The most obvious candidates among the molecules containing an Si-C bond detected in C-rich AGB stars are SiC 2 , SiC, and Si 2 C. To date, the ring molecule SiC 2 has been observed in a handful of evolved stars, while SiC and Si 2 C have only been detected in the C-star envelope IRC +10216. We aim to study how widespread and abundant SiC 2 , SiC, and Si 2 C are in envelopes around C-rich AGB stars and whether or not these species play an active role as gas-phase precursors of silicon carbide dust in the ejecta of carbon stars. We carried out sensitive observations with the IRAM 30m telescope of a sample of 25 C-rich AGB stars to search for emission lines of SiC 2 , SiC, and Si 2 C in the λ 2 mm band. We performed non-LTE excitation and radiative transfer calculations based on the LVG method to model the observed lines of SiC 2 and to derive SiC 2 fractional abundances in the observed envelopes. We detect SiC 2 in most of the sources, SiC in about half of them, and do not detect Si 2 C in any source, at the exception of IRC +10216. Most of these detections are reported for the first time in this work. We find a positive correlation between the SiC and SiC 2 line emission, which suggests that both species are chemically linked, the SiC radical probably being the photodissociation product of SiC 2 in the external layer of the envelope. We find a clear trend in which the denser the envelope, the less abundant SiC 2 is. The observed trend is interpreted as an evidence of efficient incorporation of SiC 2 onto dust grains, a process which is favored at high densities owing to the higher rate at which collisions between particles take place. The observed behavior of a decline in the SiC 2 abundance with increasing density strongly suggests that SiC 2 is an important gas

Tree-ring cellulose exhibits several distinct intramolecular 13C signals

NASA Astrophysics Data System (ADS)

Wieloch, Thomas; Ehlers, Ina; Frank, David; Gessler, Arthur; Grabner, Michael; Yu, Jun; Schleucher, Jürgen

2017-04-01

Stable carbon isotopes are a key tool in biogeosciences. Present applications including compound-specific isotope analysis measure 13C/12C ratios (δ13C) of bulk material or of whole molecules. However, it is well known that primary metabolites also show large intramolecular 13C variation - also called isotopomer variation. This variation reflects 13C fractionation by enzyme reactions and therefore encodes metabolic information. Furthermore, δ13C must be considered an average of the intramolecular 13C distribution. Here we will present (1) methodology to analyse intramolecular 13C distributions of tree-ring cellulose by quantitative 13C NMR (Chaintreau et al., 2013, Anal Chim Acta, 788, 108-113); (2) intramolecular 13C distributions of an annually-resolved tree ring chronology (Pinus nigra, 1961-1995); (3) isotope parameters and terminology for analysis of intramolecular isotope time series; (4) a method for correcting for heterotrophic C redistribution. We will show that the intramolecular 13C distribution of tree-ring cellulose shows large variation, with differences between isotopomers exceeding 10‰Ṫhus, individual 13C isotopomers of cellulose constitute distinct 13C inputs into major global C pools such as wood and soil organic matter. When glucose units with the observed intramolecular 13C pattern are broken down along alternative catabolic pathways, it must be expected that respired CO2 with strongly differing δ13C will be released; indicating that intramolecular 13C variation affects isotope signals of atmosphere-biosphere C exchange fluxes. taking this variation into account will improve modelling of the global C cycle. Furthermore, cluster analysis shows that tree-ring glucose exhibits several independent intramolecular 13C signals, which constitute distinct ecophysiological information channels. Thus, whole-molecule 13C analysis likely misses a large part of the isotope information stored in tree rings. As we have shown for deuterium (Ehlers et al