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Sample records for 13c stable isotope

  1. Process Model for Studying Regional 13C Stable Isotope Exchange between Vegetation and Atmosphere

    NASA Astrophysics Data System (ADS)

    Chen, J. M.; Chen, B.; Huang, L.; Tans, P.; Worthy, D.; Ishizawa, M.; Chan, D.

    2007-12-01

    The variation of the stable isotope 13CO2 in the air in exchange with land ecosystems results from fractionation processes in both plants and soil during photosynthesis and respiration. Its diurnal and seasonal variations therefore contain information on the carbon cycle. We developed a model (BEPS-iso) to simulate its exchange between vegetation and the atmosphere. To be useful for regional carbon cycle studies, the model has the following characteristics: (i) it considers the turbulent mixing in the vertical profile from the soil surface to the top of the planetary boundary layer (PBL); (ii) it scales individual leaf photosynthetic discrimination to the whole canopy through the separation of sunlit and shaded leaf groups; (iii) through simulating leaf-level photosynthetic processes, it has the capacity to mechanistically examine isotope discrimination resulting from meteorological forcings, such as radiation, precipitation and humidity; and (iv) through complete modeling of radiation, energy and water fluxes, it also simulates soil moisture and temperature needed for estimating ecosystem respiration and the 13C signal from the soil. After validation using flask data acquired at 20 m level on a tower near Fraserdale, Ontario, Canada, during intensive campaigns (1998-2000), the model has been used for several purposes: (i) to investigate the diurnal and seasonal variations in the disequilibrium in 13C fractionation between ecosystem respiration and photosynthesis, which is an important step in using 13C measurements to separate these carbon cycle components; (ii) to quantify the 13C rectification in the PBL, which differs significantly from CO2 rectification because of the diurnal and seasonal disequilibriums; and (iii) to model the 13C spatial and temporal variations over the global land surface for the purpose of CO2 inversion using 13C as an additional constraint.

  2. Quinone-based stable isotope probing for assessment of 13C substrate-utilizing bacteria

    NASA Astrophysics Data System (ADS)

    Kunihiro, Tadao; Katayama, Arata; Demachi, Toyoko; Veuger, Bart; Boschker, Henricus T. S.; van Oevelen, Dick

    2015-04-01

    13C abundance in the quinone. In this study, we verified carbon stable isotope of quinone compared with bulk carbon stable isotope of bacterial culture. Results indicated a good correlation between carbon stable isotope of quinone compared with bulk carbon stable isotope. However, our measurement conditions for detection of quinone isotope-ions incurred underestimation of 13C abundance in the quinone. The quinone-SIP technique needs further optimization for measurement conditions of LC-MS/MS.

  3. On the status of IAEA delta-13C stable isotope reference materials.

    NASA Astrophysics Data System (ADS)

    Assonov, Sergey; Groening, Manfred; Fajgelj, Ales

    2016-04-01

    For practical reasons all isotope measurements are performed on relative scales realized through the use of international, scale-defining primary standards. In fact these standards were materials (artefacts, similar to prototypes of meter and kg) selected based on their properties. The VPDB delta-13C scale is realised via two highest-level reference materials NBS19 and LSVEC, the first defining the scale and the second aimed to normalise lab-to-lab calibrations. These two reference materials (RMs) have been maintained and distributed by IAEA and NIST. The priority task is to maintain these primary RMs at the required uncertainty level, thus ensuring the long-term scale consistency. The second task is to introduce replacements when needed (currently for exhausted NBS19, work in progress). The next is to produce a family of lower level RMs (secondary, tertiary) addressing needs of various applications (with different delta values, in different physical-chemical forms) and their needs for the uncertainty; these RMs should be traceable to the highest level RMs. Presently three is a need for a range of RMs addressing existing and newly emerging analytical techniques (e.g. optical isotopic analysers) in form of calibrated CO2 gases with different delta-13C values. All that implies creating a family of delta-13C stable isotope reference materials. Presently IAEA works on replacement for NBS19 and planning new RMs. Besides, we found that LSVEC (introduced as second anchor for the VPDB scale in 2006) demonstrate a considerable scatter of its delta-13C value which implies a potential bias of the property value and increased value uncertainty which may conflict with uncertainty requirements for atmospheric monitoring. That is not compatible with the status of LSVEC, and therefore it should be replaced as soon as possible. The presentation will give an overview of the current status, the strategic plan of developments and the near future steps.

  4. Tracing the diet of the monitor lizard Varanus mabitang by stable isotope analyses (δ15N, δ13C)

    NASA Astrophysics Data System (ADS)

    Struck, Ulrich; Altenbach, Alexander; Gaulke, Maren; Glaw, Frank

    2002-09-01

    In this study, we used analyses of stable isotopes of nitrogen (δ15N) and carbon (δ13C) to determine the trophic ecology of the monitor lizard Varanus mabitang. Stable isotopes from claws, gut contents, and soft tissues were measured from the type specimen. Samples from Varanus olivaceus, Varanus prasinus, Varanus salvator, the herbivorous agamid lizard Hydrosaurus pustulatus, and some plant matter were included for comparison. Our data show a rapid decrease in δ13C (about10‰) from food plants towards gut contents and soft tissues of herbivorous species. For the varanids, we found a significant linear correlation of decreasing δ13C and increasing δ15N from herbivorous towards carnivorous species. In terms of trophic isotope ecology, the type specimen of V. mabitang is a strict herbivore. Thus it differs significantly in its isotopic composition from the morphologically next closest related species V. olivaceus. The most highly carnivorous species is V. salvator, while δ15N values for V. prasinus and V. olivaceus are intermediate. Claws provide very valuable samples for such measurements, because they can be sampled from living animals without harm. Additionally, their range of variability is relatively small in comparison with measurements from soft tissues.

  5. Evaluating North Sea carbon sources using radiogenic (224Ra and 228Ra) and stable carbon isotope (DI13C) tracers

    NASA Astrophysics Data System (ADS)

    Burt, William; Thomas, Helmuth; Hagens, Mathilde; Brenner, Heiko; Paetsch, Johannes; Clargo, Nikki

    2015-04-01

    In the North Sea, much uncertainty still exists regarding the role of boundary fluxes (e.g. benthic input from sediments or lateral inputs from the coastline) in the overall biogeochemical cycling of the system. The stable carbon isotope signature of dissolved inorganic carbon (δ13C-DIC) is a common tool for following transformations of carbon in the water column and identifying carbon sources and sinks. Here, analyses of the first basin-wide observations of δ13C-DIC reveal that a balance between biological production and respiration, as well as a freshwater input near the European continental coast, predominantly control surface distributions in the North Sea. A strong relationship between the biological component of DIC (DICbio) and δ13C-DIC is then used to quantify the metabolic DIC flux associated with changes in the carbon isotopic signature. Correlations are also found between δ13C-DIC and naturally-occurring Radium isotopes (224Ra and 228Ra), which have well-identified sources from the seafloor and coastal boundaries. The relationship between δ13C-DIC and the longer-lived 228Ra isotope (half-life = 5.8 years) is used to derive a metabolic DIC flux from the European continental coastline. 228Ra is also shown to be a highly effective tracer of North Sea total alkalinity (TA) compared to the more conventional use of salinity as a tracer. Coastal alkalinity inputs are calculated using relationships with 228Ra, and ratios of DIC and TA suggest denitrification as the main metabolic pathway for the formation of these coastal inputs. Finally, coastal TA inputs are translated into inputs of protons to quantify their impact on the buffering capacity of the Southern North Sea.

  6. Continuous flow stable isotope methods for study of δ13C fractionation during halomethane production and degradation

    USGS Publications Warehouse

    Kalin, Robert M.; Hamilton, John T.G.; Harper, David B.; Miller, Laurence G.; Lamb, Clare; Kennedy, James T.; Downey, Angela; McCauley, Sean; Goldstein, Allen H.

    2001-01-01

    Gas chromatography/mass spectrometry/isotope ratio mass spectrometry (GC/MS/IRMS) methods for δ13C measurement of the halomethanes CH3Cl, CH3Br, CH3I and methanethiol (CH3SH) during studies of their biological production, biological degradation, and abiotic reactions are presented. Optimisation of gas chromatographic parameters allowed the identification and quantification of CO2, O2, CH3Cl, CH3Br, CH3I and CH3SH from a single sample, and also the concurrent measurement of δ13C for each of the halomethanes and methanethiol. Precision of δ13C measurements for halomethane standards decreased (±0.3, ±0.5 and ±1.3‰) with increasing mass (CH3Cl, CH3Br, CH3I, respectively). Given that carbon isotope effects during biological production, biological degradation and some chemical (abiotic) reactions can be as much as 100‰, stable isotope analysis offers a precise method to study the global sources and sinks of these halogenated compounds that are of considerable importance to our understanding of stratospheric ozone destruction. 

  7. Stable isotope analysis (δ (13)C and δ (15)N) of soil nematodes from four feeding groups.

    PubMed

    Melody, Carol; Griffiths, Bryan; Dyckmans, Jens; Schmidt, Olaf

    2016-01-01

    Soil nematode feeding groups are a long-established trophic categorisation largely based on morphology and are used in ecological indices to monitor and analyse the biological state of soils. Stable isotope ratio analysis ((13)C/(12)C and (15)N/(14)N, expressed as δ (13)C and δ (15)N) has provided verification of, and novel insights into, the feeding ecology of soil animals such as earthworms and mites. However, isotopic studies of soil nematodes have been limited to date as conventional stable isotope ratio analysis needs impractically large numbers of nematodes (up to 1,000) to achieve required minimum sample weights (typically >100 µg C and N). Here, micro-sample near-conventional elemental analysis-isotopic ratio mass spectrometry (μEA-IRMS) of C and N using microgram samples (typically 20 µg dry weight), was employed to compare the trophic position of selected soil nematode taxa from four feeding groups: predators (Anatonchus and Mononchus), bacterial feeders (Plectus and Rhabditis), omnivores (Aporcelaimidae and Qudsianematidae) and plant feeder (Rotylenchus). Free-living nematodes were collected from conventionally and organically managed arable soils. As few as 15 nematodes, for omnivores and predators, were sufficient to reach the 20 µg dry weight target. There was no significant difference in δ (15)N (p = 0.290) or δ (13)C (p = 0.706) between conventional and organic agronomic treatments but, within treatments, there was a significant difference in N and C stable isotope ratios between the plant feeder, Rotylenchus (δ (15)N = 1.08 to 3.22 mUr‰, δ (13)C = -29.58 to -27.87 mUr) and all other groups. There was an average difference of 9.62 mUr in δ (15)N between the plant feeder and the predator group (δ (15)N = 9.89 to 12.79 mUr, δ (13)C = -27.04 to -25.51 mUr). Isotopic niche widths were calculated as Bayesian derived standard ellipse areas and were smallest for the plant feeder (1.37 mUr(2)) and the predators (1.73 mUr(2)), but largest for

  8. Stable isotope analysis (δ13C and δ15N) of soil nematodes from four feeding groups

    PubMed Central

    Griffiths, Bryan; Dyckmans, Jens; Schmidt, Olaf

    2016-01-01

    Soil nematode feeding groups are a long-established trophic categorisation largely based on morphology and are used in ecological indices to monitor and analyse the biological state of soils. Stable isotope ratio analysis (13C/12C and 15N/14N, expressed as δ13C and δ15N) has provided verification of, and novel insights into, the feeding ecology of soil animals such as earthworms and mites. However, isotopic studies of soil nematodes have been limited to date as conventional stable isotope ratio analysis needs impractically large numbers of nematodes (up to 1,000) to achieve required minimum sample weights (typically >100 µg C and N). Here, micro-sample near-conventional elemental analysis–isotopic ratio mass spectrometry (μEA–IRMS) of C and N using microgram samples (typically 20 µg dry weight), was employed to compare the trophic position of selected soil nematode taxa from four feeding groups: predators (Anatonchus and Mononchus), bacterial feeders (Plectus and Rhabditis), omnivores (Aporcelaimidae and Qudsianematidae) and plant feeder (Rotylenchus). Free-living nematodes were collected from conventionally and organically managed arable soils. As few as 15 nematodes, for omnivores and predators, were sufficient to reach the 20 µg dry weight target. There was no significant difference in δ15N (p = 0.290) or δ13C (p = 0.706) between conventional and organic agronomic treatments but, within treatments, there was a significant difference in N and C stable isotope ratios between the plant feeder, Rotylenchus (δ15N = 1.08 to 3.22 mUr‰, δ13C = –29.58 to –27.87 mUr) and all other groups. There was an average difference of 9.62 mUr in δ15N between the plant feeder and the predator group (δ15N = 9.89 to 12.79 mUr, δ13C = –27.04 to –25.51 mUr). Isotopic niche widths were calculated as Bayesian derived standard ellipse areas and were smallest for the plant feeder (1.37 mUr2) and the predators (1.73 mUr2), but largest for omnivores (3.83 mUr2

  9. Characterising ontogenetic niche shifts in Nile crocodile using stable isotope13C, δ15N) analyses of scute keratin.

    PubMed

    Radloff, Frans G T; Hobson, Keith A; Leslie, Alison J

    2012-09-01

    Nile crocodiles undergo a three to five order of magnitude increase in body size during their lifespan. This shift coincides with a change in resource and habitat use which influences the strength, type and symmetry of interactions with other species. Identifying size-specific crocodile groups displaying similar traits is important for conservation planning. Here, we illustrate how stable carbon (δ(13) C) and nitrogen (δ(15) N) isotope analysis of scute keratin, together with breakpoint modelling analysis can be used to characterise ontogenetic niche shifts. Using a sample set of 238 crocodiles from the Okavango Delta, Botswana (35-463 cm total length), we found prominent size-related changes in the scute keratin δ(13) C and δ(15) N profiles close to 40 and 119 cm snout-vent length. The first shift corroborated the findings of a traditional stomach-content study conducted on the same population at the same time, and the second conformed to known crocodile ecology. This approach can be used as a first approximation to identify size-specific groups within crocodile populations, and these can then be investigated further using isotopic or other methods.

  10. Positional Enrichment by Proton Analysis (PEPA): A One-Dimensional (1) H-NMR Approach for (13) C Stable Isotope Tracer Studies in Metabolomics.

    PubMed

    Vinaixa, Maria; Rodríguez, Miguel A; Aivio, Suvi; Capellades, Jordi; Gómez, Josep; Canyellas, Nicolau; Stracker, Travis H; Yanes, Oscar

    2017-03-20

    A novel metabolomics approach for NMR-based stable isotope tracer studies called PEPA is presented, and its performance validated using human cancer cells. PEPA detects the position of carbon label in isotopically enriched metabolites and quantifies fractional enrichment by indirect determination of (13) C-satellite peaks using 1D-(1) H-NMR spectra. In comparison with (13) C-NMR, TOCSY and HSQC, PEPA improves sensitivity, accelerates the elucidation of (13) C positions in labeled metabolites and the quantification of the percentage of stable isotope enrichment. Altogether, PEPA provides a novel framework for extending the high-throughput of (1) H-NMR metabolic profiling to stable isotope tracing in metabolomics, facilitating and complementing the information derived from 2D-NMR experiments and expanding the range of isotopically enriched metabolites detected in cellular extracts.

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

    NASA Astrophysics Data System (ADS)

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

    2010-07-01

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

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

    USGS Publications Warehouse

    Piper, D.Z.; Kolodny, Y.

    1987-01-01

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

  13. Congener-specific concentrations and carbon stable isotope ratios (delta13C) of two technical toxaphene products (Toxaphene and Melipax).

    PubMed

    Vetter, Walter; Gleixner, Gerd; Armbruster, Wolfgang; Ruppe, Steffen; Stern, Gary A; Braekevelt, Eric

    2005-01-01

    In this study we compared the contribution of individual congeners and the ratios of stable carbon isotopes of two technical toxaphene products. The former US-American product Toxaphene was from 1978 and the East-German product Melipax from 1979. Both technical products showed the known complexity in GC/ECD measurements. Contributions of 24 peaks to each of the technical products were determined by gas chromatography in combination high resolution electron capture negative ion mass spectrometry (GC/ECNI-HRMS). The percentages of the compounds studied in the technical mixtures ranged from approximately 0.05% to approximately 2.5% but showed some individual differences. 2,2,5,5,8,9,9,10,10-nonachlorobornane (B9-1025 or P-62) was identified as a major congener in both mixtures. 2-Endo,3-exo,5-endo,6-exo,8,8,10,10-octachlorobornane (B8-1413 or P26) and 2-endo,3-exo,5-endo,6-exo,8,8,9,10,10-nonachlorobornane (B9-1679 or P-50) were found at similar concentration in both technical products. Identical amounts of Melipax or Toxaphene were combusted to CO2 in an element analyzer and their delta13C values were determined relative to the international standard Vienna PeeDee belemnite (VPDB). The mean delta13C values of both products varied by 2.8% (determined at two different locations) which is roughly one order of magnitude more than the precision obtained in repetitive analyses of the individual products. Thus, both investigated products could be unequivocally distinguished by stable isotope ratio mass spectrometry (IRMS). IRMS analyses may thus be a suitable tool for tracing back toxaphene residues in environmental and food samples to the one or both of the products.

  14. Food partitioning of leaf-eating mangrove crabs ( Sesarminae): Experimental and stable isotope ( 13C and 15N) evidence

    NASA Astrophysics Data System (ADS)

    Kristensen, Ditte K.; Kristensen, Erik; Mangion, Perrine

    2010-05-01

    The feasibility of mangrove leaves as a full diet for sesarmid crabs has been questioned for decades. Since these leaves are nitrogen-poor, sesarmids probably obtain nitrogen from other sources to sustain growth. The aim of this study was to assess the food partitioning of the sesarmid species Neoepisesarma versicolor with emphasis on nitrogen allocation. The preference for animal tissue when crabs were pre-fed diets of different nitrogen content was determined in the laboratory. Furthermore, the possible in situ diet composition of N. versicolor was established from carbon and nitrogen stable isotope signature ( δ13C and δ15N) of freshly caught individuals and their potential food sources, using a concentration-dependent mixing model. N. versicolor showed significantly higher feeding preferences for fish meat when pre-fed leaf material without than with access to meat, indicating that this crab species can meet its nitrogen demand by ingesting animal tissue. The stable isotope mixing model based on in situ materials suggests that the diet of N. versicolor consists of ˜60% leaves in terms of biomass, leaving ˜40% for other sources such as animal tissue and benthic microorganisms. The biomass contribution from animal tissues, in form of e.g. other crustaceans and fish carcasses, was found to account for ˜15%. Despite the relative low biomass fraction, animal food sources may contribute with up to half of the nitrogen in the diet of N. versicolor. The quantity of ingested sediment most likely exceeds that of animal tissues. However, due to the low concentration of assimilable microalgae and other microorganism, we propose that sediment associated sources are less important as a nitrogen source for N. versicolor than hitherto presumed.

  15. 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.

  16. A capillary absorption spectrometer for stable carbon isotope ratio (13C/12C) analysis in very small samples

    NASA Astrophysics Data System (ADS)

    Kelly, J. F.; Sams, R. L.; Blake, T. A.; Newburn, M.; Moran, J.; Alexander, M. L.; Kreuzer, H.

    2012-02-01

    A capillary absorption spectrometer (CAS) suitable for IR laser isotope analysis of small CO2 samples is presented. The system employs a continuous-wave (cw) quantum cascade laser to study nearly adjacent rovibrational transitions of different isotopologues of CO2 near 2307 cm-1 (4.34 μm). This initial CAS system can achieve relative isotopic precision of about 10 ppm 13C, or ˜1‰ (per mil in delta notation relative to Vienna Pee Dee Belemnite) with 20-100 picomoles of entrained sample within the hollow waveguide for CO2 concentrations ˜400-750 ppm. Isotopic analyses of such gas fills in a 1-mm ID hollow waveguide of 0.8 m overall physical path length can be carried out down to ˜2 Torr. Overall 13C/12C ratios can be calibrated to ˜2‰ accuracy with diluted CO2 standards. A novel, low-cost method to reduce cw-fringing noise resulting from multipath distortions in the hollow waveguide is presented, which allows weak absorbance features to be studied at the few ppm level (peak-to-rms) after 1000 scans are co-added in ˜10 s. The CAS is meant to work directly with converted CO2 samples from a laser ablation-catalytic combustion micro-sampler to provide 13C/12C ratios of small biological isolates currently operating with spatial resolutions ˜50 μm.

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  18. Positional Enrichment by Proton Analysis (PEPA): A One‐Dimensional 1H‐NMR Approach for 13C Stable Isotope Tracer Studies in Metabolomics

    PubMed Central

    Rodríguez, Miguel A.; Aivio, Suvi; Capellades, Jordi; Gómez, Josep; Canyellas, Nicolau; Stracker, Travis H.

    2017-01-01

    Abstract A novel metabolomics approach for NMR‐based stable isotope tracer studies called PEPA is presented, and its performance validated using human cancer cells. PEPA detects the position of carbon label in isotopically enriched metabolites and quantifies fractional enrichment by indirect determination of 13C‐satellite peaks using 1D‐1H‐NMR spectra. In comparison with 13C‐NMR, TOCSY and HSQC, PEPA improves sensitivity, accelerates the elucidation of 13C positions in labeled metabolites and the quantification of the percentage of stable isotope enrichment. Altogether, PEPA provides a novel framework for extending the high‐throughput of 1H‐NMR metabolic profiling to stable isotope tracing in metabolomics, facilitating and complementing the information derived from 2D‐NMR experiments and expanding the range of isotopically enriched metabolites detected in cellular extracts. PMID:28220994

  19. The effects of sex, tissue type, and dietary components on stable isotope discrimination factors (Δ13C and Δ15N) in mammalian omnivores.

    PubMed

    Kurle, Carolyn M; Koch, Paul L; Tershy, Bernie R; Croll, Donald A

    2014-01-01

    We tested the effects of sex, tissue, and diet on stable isotope discrimination factors (Δ(13)C and Δ(15)N) for six tissues from rats fed four diets with varied C and N sources, but comparable protein quality and quantity. The Δ(13)C and Δ(15)N values ranged from 1.7-4.1‰ and 0.4-4.3‰, respectively. Females had higher Δ(15)N values than males because males grew larger, whereas Δ(13)C values did not differ between sexes. Differences in Δ(13)C values among tissue types increased with increasing variability in dietary carbon sources. The Δ(15)N values increased with increasing dietary δ(15)N values for all tissues except liver and serum, which have fast stable isotope turnover times, and differences in Δ(15)N values among tissue types decreased with increasing dietary animal protein. Our results demonstrate that variability in dietary sources can affect Δ(13)C values, protein source affects Δ(15)N values even when protein quality and quantity are controlled, and the isotope turnover rate of a tissue can influence the degree to which diet affects Δ(15)N values.

  20. Isotopic discrimination of stable isotopes of nitrogen (δ15N) and carbon (δ13C) in a host-specific holocephalan tapeworm.

    PubMed

    Navarro, J; Albo-Puigserver, M; Coll, M; Saez, R; Forero, M G; Kutcha, R

    2014-09-01

    During the past decade, parasites have been considered important components of their ecosystems since they can modify food-web structures and functioning. One constraint to the inclusion of parasites in food-web models is the scarcity of available information on their feeding habits and host-parasite relationships. The stable isotope approach is suggested as a useful methodology to determine the trophic position and feeding habits of parasites. However, the isotopic approach is limited by the lack of information on the isotopic discrimination (ID) values of parasites, which is pivotal to avoiding the biased interpretation of isotopic results. In the present study we aimed to provide the first ID values of δ(15)N and δ(13)C between the gyrocotylidean tapeworm Gyrocotyle urna and its definitive host, the holocephalan Chimaera monstrosa. We also test the effect of host body size (body length and body mass) and sex of the host on the ID values. Finally, we illustrate how the trophic relationships of the fish host C. monstrosa and the tapeworm G. urna could vary relative to ID values. Similar to other studies with parasites, the ID values of the parasite-host system were negative for both isotopic values of N (Δδ(15)N = - 3.33 ± 0.63‰) and C (Δδ(13)C = - 1.32 ± 0.65‰), independent of the sex and size of the host. By comparing the specific ID obtained here with ID from other studies, we illustrate the importance of using specific ID in parasite-host systems to avoid potential errors in the interpretation of the results when surrogate values from similar systems or organisms are used.

  1. Stable isotopes (δD and δ(13)C) are geographic indicators of natal origins of monarch butterflies in eastern North America.

    PubMed

    Hobson, Keith A; Wassenaar, Leonard I; Taylor, Orley R

    1999-08-01

    Wing membranes of laboratory and field-reared monarch butterflies (Danaus plexippus) were analyzed for their stable-hydrogen (δD) and carbon (δ(13)C) isotope ratios to determine whether this technique could be used to identify their natal origins. We hypothesized that the hydrogen isotopic composition of monarch butterfly wing keratin would reflect the hydrogen isotope patterns of rainfall in areas of natal origin where wings were formed. Monarchs were reared in the laboratory on milkweed plants (Asclepias sp.) grown with water of known deuterium content, and, with the assistance of volunteers, on native milkweeds throughout eastern North America. The results show that the stable hydrogen isotopic composition of monarch butterflies is highly correlated with the isotopic composition of the milkweed host plants, which in turn corresponds closely with the long-term geographic patterns of deuterium in rainfall. Stable-carbon isotope values in milkweed host plants were similarly correlated with those values in monarch butterflies and showed a general pattern of enrichment along a southwest to northeast gradient bisecting the Great Lakes. These findings indicate that natal origins of migratory and wintering monarchs in Mexico can be inferred from the combined δD and δ(13)C isotopic signatures in their wings. This relationship establishes that analysis of hydrogen and carbon isotopes can be used to answer questions concerning the biology of migratory monarch butterflies and provides a new approach to tracking similar migratory movements of other organisms.

  2. Effects of roasting conditions on the changes of stable carbon isotope ratios (δ13 C) in sesame oil and usefulness of δ13 c to differentiate blended sesame oil from corn oil.

    PubMed

    Seol, Nam Gyu; Jang, Eun Yeong; Kim, Mi-Ja; Lee, Jaehwan

    2012-12-01

    Differentiating blended sesame oils from authentic sesame oil (SO) is a critical step in protecting consumer rights. Stable carbon isotope ratios (δ(13) C), color, fluorescence intensity, and fatty acid profiles were analyzed in SO prepared from sesame seeds with different roasting conditions and in corn oil blended with SO. Sesame seeds were roasted at 175, 200, 225, or 250 °C for 15 or 30 min at each temperature. SO was mixed with corn oil at varying ratios. Roasting conditions ranging from175 to 250 °C at the 30 min time point did not result in significant changes in δ(13) C (P > 0.05). Values of δ(13) C in corn oil and SO from sesame seeds roasted at 250 °C for 15 min were -17.55 and -32.13 ‰, respectively. Fatty acid ratios, including (O + L)/(P × Ln) and (L × L)/O, where O, L, P, and Ln were oleic, linoleic, palmitic, and linolenic acids, respectively, showed good discriminating abilities among the SO blended with corn oil. Therefore, using different combinations of stable carbon isotope ratios and some fatty acid ratios can allow successful differentiation of authentic SO from SO blended with corn oil.

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  4. Regional patterns of δ13C and δ15N stable isotopes of size-fractionated zooplankton in the western tropical North Pacific Ocean

    NASA Astrophysics Data System (ADS)

    Yang, Guang; Li, Chaolun; Guilini, Katja; Wang, Xiaocheng; Wang, Yanqing

    2017-02-01

    Zooplankton play a prominent role in the biogeochemical cycles of marine ecosystems. Little is known about the trophodynamics of zooplankton in response to geographic patterns in isotopic baselines and physical processes in the western tropical North Pacific. In this study, stable isotope ratios of five size fractions of zooplankton (100 to >2000 μm) from different current regions in the western tropical North Pacific Ocean were analyzed. Both δ13C and δ15N isotopic values increased with zooplankton size class. The largest zooplankton group (>2000 μm), with a diverse composition, showed relatively higher stable isotope signatures, covering a wider range. Regional variations in the zooplankton stable isotope signatures were similar across all size classes, with generally higher values in the North Equatorial Counter Current (NECC) and the North Equatorial Current (NEC) and lower values in the Subtropical Counter Current (STCC). These regional patterns of zooplankton isotope signatures were consistent with the variation of oceanographic features (temperature, salinity, nutrients, chlorophyll a) and were also related to the isotopic baselines of particulate organic matter (POM) in the different current regions. Moreover, the nitrogen-fixing cyanobacteria Trichodesmium spp. may be the main contributor to low δ15N values in the STCC. The results of this study demonstrate the influence of physical processes on the stable isotopic signatures of zooplankton. This baseline information is crucial for future food web studies in the western tropical North Pacific Ocean.

  5. Correlation between the synthetic origin of methamphetamine samples and their 15N and 13C stable isotope ratios.

    PubMed

    Billault, Isabelle; Courant, Frédérique; Pasquereau, Léo; Derrien, Solène; Robins, Richard J; Naulet, Norbert

    2007-06-12

    The active ingredient of ecstasy, N-methyl-3,4-methyldioxyphenylisopropylamine (MDMA) can be manufactured by a number of easy routes from simple precursors. We have synthesised 45 samples of MDMA following the five most common routes using N-precursors from 12 different origins and three different precursors for the aromatic moiety. The 13C and 15N contents of both the precursors and the MDMA samples derived therefrom were measured by isotope ratio mass spectrometry coupled to an elemental analyser (EA-IRMS). We show that within-pathway correlation between the 15N content of the precursor and that of the derived MDMA can be strong but that no general pattern of correlation can be defined. Rather, it is evident that the delta15N values of MDMA are strongly influenced by a combination of the delta15N values of the source of nitrogen used, the route by which the MDMA is synthesised, and the experimental conditions employed. Multivariate analysis (PCA) based on the delta15N values of the synthetic MDMA and of the delta15N and delta13C values of the N-precursors leads to good discrimination between the majority of the reaction conditions tested.

  6. Methylamphetamine synthesis: does an alteration in synthesis conditions affect the δ(13) C, δ(15) N and δ(2) H stable isotope ratio values of the product?

    PubMed

    Salouros, Helen; Collins, Michael; Cawley, Adam; Longworth, Mitchell

    2012-05-01

    Conventional chemical profiling of methylamphetamine has long been employed by national forensic laboratories to determine the synthetic route and where possible the precursor chemicals used in its manufacture. This laboratory has been studying the use of stable isotope ratio mass spectrometry (IRMS) analysis as a complementary technique to conventional chemical profiling of fully synthetic illicit drugs such as methylamphetamine. As part of these investigations the stable carbon (δ(13) C), nitrogen (δ(15) N), and hydrogen (δ(2) H) isotope values in the precursor chemicals of ephedrine and pseudoephedrine and the resulting methylamphetamine end-products have been measured to determine the synthetic origins of methylamphetamine. In this study, results are presented for δ(13) C, δ(15) N, and δ(2) H values in methylamphetamine synthesized from ephedrine and pseudoephedrine by two synthetic routes with varying experimental parameters. It was demonstrated that varying parameters, such as stoichiometry, reaction temperature, reaction time, and reaction pressure, had no effect on the δ(13) C, δ(15) N, and δ(2) H isotope values of the final methylamphetamine product, within measurement uncertainty. Therefore the value of the IRMS technique in identifying the synthetic origin of precursors, such as ephedrine and pseudoephedrine, is not compromised by the potential variation in synthetic method that is expected from one batch to the next, especially in clandestine laboratories where manufacture can occur without stringent quality control of reactions.

  7. Application of nitrogen and carbon stable isotopes (δ(15)N and δ(13)C) to quantify food chain length and trophic structure.

    PubMed

    Perkins, Matthew J; McDonald, Robbie A; van Veen, F J Frank; Kelly, Simon D; Rees, Gareth; Bearhop, Stuart

    2014-01-01

    Increasingly, stable isotope ratios of nitrogen (δ(15)N) and carbon (δ(13)C) are used to quantify trophic structure, though relatively few studies have tested accuracy of isotopic structural measures. For laboratory-raised and wild-collected plant-invertebrate food chains spanning four trophic levels we estimated nitrogen range (NR) using δ(15)N, and carbon range (CR) using δ(13)C, which are used to quantify food chain length and breadth of trophic resources respectively. Across a range of known food chain lengths we examined how NR and CR changed within and between food chains. Our isotopic estimates of structure are robust because they were calculated using resampling procedures that propagate variance in sample means through to quantified uncertainty in final estimates. To identify origins of uncertainty in estimates of NR and CR, we additionally examined variation in discrimination (which is change in δ(15)N or δ(13)C from source to consumer) between trophic levels and among food chains. δ(15)N discrimination showed significant enrichment, while variation in enrichment was species and system specific, ranged broadly (1.4‰ to 3.3‰), and importantly, propagated variation to subsequent estimates of NR. However, NR proved robust to such variation and distinguished food chain length well, though some overlap between longer food chains infers a need for awareness of such limitations. δ(13)C discrimination was inconsistent; generally no change or small significant enrichment was observed. Consequently, estimates of CR changed little with increasing food chain length, showing the potential utility of δ(13)C as a tracer of energy pathways. This study serves as a robust test of isotopic quantification of food chain structure, and given global estimates of aquatic food chains approximate four trophic levels while many food chains include invertebrates, our use of four trophic level plant-invertebrate food chains makes our findings relevant for a majority of

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

    NASA Astrophysics Data System (ADS)

    Horton, T. W.; Oze, C.

    2012-12-01

    Stable isotope-based proxy methods enhance our ability to interpret paleohydrology, paleoelevation, climate change, and biogeochemical cycles. In ancient carbonate lakes, these methods often require that the unmodified isotopic composition of meteoric water, or local carbon reservoirs, or both, are recorded by authigenic minerals. Surprisingly, these critical assumptions have not been tested across wide-ranging environmental contexts. Here, we show that globally distributed Quaternary lake carbonate oxygen isotope compositions are not strongly, nor significantly, correlated with local meteoric-derived water compositions due to the modification of in-flow waters following entry into the lake environment. These modifications are largely caused by surface water evaporation, and can result in dubious reconstructions of ancient hydrological conditions and water source effects such as the strength of prevailing air-mass trajectory, >3km errors in paleoelevation estimates, unrealistic shifts in lake water temperature, and misleading interpretations of local carbon cycle conditions if not accounted for. However, our analysis suggests that positive shifts in surface water δ18O are accompanied by similar magnitude shifts in δ13C-DIC during lake residence. This positive co-variation in δ18O and δ13C may be used to detrend lake carbonate compositions for the effects of surface water evaporation using a parameter we define here as the '13C-excess'. This approach uses the isotopic covariant trend between in-flow waters and lake waters, rather than lacustrine covariation alone, to better constrain ancient meteoric-derived water compositions. To demonstrate the potential strength of the 13C-excess approach over single element methods, we compare the paleoelevation estimates derived from lake carbonate compositions using both approaches. When Tibetan lakes are excluded from the dataset, 13C-excess values are significantly correlated with mean up-slope hypsometric altitude with

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

    NASA Astrophysics Data System (ADS)

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

    2010-04-01

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

  10. Effects of preservation methods of muscle tissue from upper-trophic level reef fishes on stable isotope values (δ (13)C and δ (15)N).

    PubMed

    Stallings, Christopher D; Nelson, James A; Rozar, Katherine L; Adams, Charles S; Wall, Kara R; Switzer, Theodore S; Winner, Brent L; Hollander, David J

    2015-01-01

    Research that uses stable isotope analysis often involves a delay between sample collection in the field and laboratory processing, therefore requiring preservation to prevent or reduce tissue degradation and associated isotopic compositions. Although there is a growing literature describing the effects of various preservation techniques, the results are often contextual, unpredictable and vary among taxa, suggesting the need to treat each species individually. We conducted a controlled experiment to test the effects of four preservation methods of muscle tissue from four species of upper trophic-level reef fish collected from the eastern Gulf of Mexico (Red Grouper Epinephelus morio, Gag Mycteroperca microlepis, Scamp Mycteroperca phenax, and Red Snapper Lutjanus campechanus). We used a paired design to measure the effects on isotopic values for carbon and nitrogen after storage using ice, 95% ethanol, and sodium chloride (table salt), against that in a liquid nitrogen control. Mean offsets for both δ (13)C and δ (15)N values from controls were lowest for samples preserved on ice, intermediate for those preserved with salt, and highest with ethanol. Within species, both salt and ethanol significantly enriched the δ (15)N values in nearly all comparisons. Ethanol also had strong effects on the δ (13)C values in all three groupers. Conversely, for samples preserved on ice, we did not detect a significant offset in either isotopic ratio for any of the focal species. Previous studies have addressed preservation-induced offsets in isotope values using a mass balance correction that accounts for changes in the isotope value to that in the C/N ratio. We tested the application of standard mass balance corrections for isotope values that were significantly affected by the preservation methods and found generally poor agreement between corrected and control values. The poor performance by the correction may have been due to preferential loss of lighter isotopes and

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

    NASA Astrophysics Data System (ADS)

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

    2004-12-01

    Coral skeletal stable oxygen isotopes (δ 18O) reflect changes in seawater temperature and salinity, while stable carbon isotopes13C) reflect a combination of both metabolic (photosynthesis and feeding) and kinetic fractionation. Together, the two isotopic signatures may be used as a proxy for past bleaching events. During bleaching, increased seawater temperatures often contribute to a decline in zooxanthellae and/or chlorophyll concentrations, resulting in a decrease in photosynthesis. We experimentally investigated the effect of bleaching and subsequent recovery on the δ 13C and δ 18O values of coral skeleton. Fragments from two coral species (Montipora capitata and Porites compressa) from Kaneohe Bay, Hawaii were bleached in outdoor tanks by raising the seawater temperature to 30° C. Additional fragments from the same parent colonies were maintained at ambient seawater temperatures (27° C) in separate tanks as controls. After one month in the tanks, a subset of the fragments was frozen and all remaining fragments were placed back on the reef to recover. All coral fragments were analyzed for their skeletal δ 13C and δ 18O compositions at five time intervals: before, immediately after, 1.5, 4, and 8 months after bleaching. In addition, rates of photosynthesis, calcification, and heterotrophy were also measured. Immediately after bleaching, δ 18O decreased in bleached M. capitata relative to controls, reflecting their exposure to increased seawater temperatures. During recovery, δ 18O values in the treatment M. capitata were not different from the controls. In P. compressa, δ 18O did not significantly differ in bleached and control corals at any time during the experiment. Immediately after bleaching, δ 13C decreased in the bleached fragments of both species relative to controls reflecting decreased photosynthetic rates. However, during recovery δ 13C in both species was greater in bleached than control fragments despite photosynthesis remaining

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

    NASA Astrophysics Data System (ADS)

    Horton, T. W.; Oze, C.

    2013-12-01

    Stable isotope based proxy methods enhance our ability to interpret paleohydrology, paleoelevation, climate change, and biogeochemical cycles. In ancient carbonate lakes, these methods often require that the unmodified isotopic composition of meteoric water or local carbon reservoirs, or both, are recorded by authigenic minerals. Surprisingly, these critical assumptions have not been tested across wide-ranging environmental contexts. A review of globally distributed Quaternary records reveals that lake carbonate oxygen isotope compositions are not strongly, nor significantly, correlated with local meteoric-derived water compositions due to the modification of in-flow waters following entry into the lake environment. These modifications are largely caused by surface water evaporation, and can result in dubious reconstructions of ancient environmental conditions if not accounted for. However, our analysis suggests that positive shifts in surface water δ18O are accompanied by similar magnitude shifts in δ13C-DIC during lake residence. This positive co-variation in δ18O and δ13C may be used to de-trend lake carbonate compositions for the effects of surface water evaporation using a parameter we define as the ';13C-excess'. This approach uses the isotopic covariant trend between in-flow waters and lake waters, rather than lacustrine covariation alone, to better constrain ancient meteoric-derived water compositions. In Quaternary lake systems, 13C-excess values are significantly correlated with modern mean up-slope hypsometric altitude with an error of ×500m. Application of the 13C-excess approach to Cenozoic lake carbonate records from the western U.S. Cordillera both challenges and reinforces previous paleoelevational interpretations based on δ18O alone, while application of the 13C-excess approach to Middle Miocene laminated lacustrine carbonates from California and New Zealand provides important insights into the paleohydrologies of these two highly debated

  13. Spatial and temporal variations in stable carbon (δ(13)C) and nitrogen (δ(15)N) isotopic composition of symbiotic scleractinian corals.

    PubMed

    Nahon, Sarah; Richoux, Nicole B; Kolasinski, Joanna; Desmalades, Martin; Ferrier Pages, Christine; Lecellier, Gael; Planes, Serge; Berteaux Lecellier, Véronique

    2013-01-01

    Tropical scleractinian corals are considered autotrophic as they rely mainly on photosynthesis-derived nutrients transferred from their photosymbionts. Corals are also able to capture and ingest suspended particulate organic matter, so heterotrophy can be an important supplementary trophic pathway to optimize coral fitness. The aim of this in situ study was to elucidate the trophic status of 10 coral species under contrasted environmental conditions in a French Polynesian lagoon. Carbon (δ(13)C) and nitrogen (δ(15)N) isotopic compositions of coral host tissues and photosymbionts were determined at 3 different fringing reefs during wet and dry seasons. Our results highlighted spatial variability in stable isotopic compositions of both coral host tissues and photosymbionts. Samples from the site with higher level of suspended particulate matter were (13)C-depleted and (15)N-enriched relative to corals and photosymbionts from less turbid sites. However, differences in both δ(13)C and δ(15)N between coral host tissues and their photosymbionts (Δ(host-photosymbionts 13)C and Δ(host-photosymbionts 15)N) were small (0.27 ± 0.76‰ and 1.40 ± 0.90‰, respectively) and similar at all sites, thus indicating no general increases in the heterotrophic pathway. Depleted δ(13)C and enriched δ(15)N values of coral host tissues measured at the most turbid site were explained by changes in isotopic composition of the inorganic nutrients taken up by photosymbionts and also by changes in rate of isotopic fractionation with environmental conditions. Our results also highlighted a lack of significant temporal variations in δ(13)C and δ(15)N values of coral host and photosymbiont tissues and in Δ(host-photosymbionts 13)C and Δ(host-photosymbionts 15)N values. This temporal stability indicated that corals remained principally autotrophic even during the wet season when photosymbiont densities were lower and the concentrations of phytoplankton were higher. Increased coral

  14. Sensitive, Efficient Quantitation of 13C-Enriched Nucleic Acids via Ultrahigh-Performance Liquid Chromatography-Tandem Mass Spectrometry for Applications in Stable Isotope Probing.

    PubMed

    Wilhelm, Roland; Szeitz, András; Klassen, Tara L; Mohn, William W

    2014-12-01

    Stable isotope probing (SIP) of nucleic acids is a powerful tool for studying the functional traits of microbial populations within complex communities, but SIP involves a number of technical challenges. Many of the difficulties in DNA-SIP and RNA-SIP experiments can be effectively overcome with an efficient, sensitive method for quantitating the isotopic enrichment of nucleic acids. Here, we present a sensitive method for quantitating (13)C enrichment of nucleic acids, requiring a few nanograms of sample, and we demonstrate its utility in typical DNA-SIP and RNA-SIP experiments. All five nucleobases (adenine, guanine, cytosine, thymine, and uracil) were separated and detected by using ultrahigh-performance liquid chromatography-tandem mass spectrometry. We detected all isotopic species in samples with as low as 1.5 atom% (13)C above natural abundance, using 1-ng loadings. Quantitation was used to characterize the isotopic enrichment kinetics of cellulose- and lignin-based microcosm experiments and to optimize the recovery of enriched nucleic acids. Application of our method will minimize the quantity of expensive isotopically labeled substrates required and reduce the risk of failed experiments due to insufficient recovery of labeled nucleic acids for sequencing library preparation.

  15. Sensitive, Efficient Quantitation of 13C-Enriched Nucleic Acids via Ultrahigh-Performance Liquid Chromatography–Tandem Mass Spectrometry for Applications in Stable Isotope Probing

    PubMed Central

    Wilhelm, Roland; Szeitz, András; Klassen, Tara L.

    2014-01-01

    Stable isotope probing (SIP) of nucleic acids is a powerful tool for studying the functional traits of microbial populations within complex communities, but SIP involves a number of technical challenges. Many of the difficulties in DNA-SIP and RNA-SIP experiments can be effectively overcome with an efficient, sensitive method for quantitating the isotopic enrichment of nucleic acids. Here, we present a sensitive method for quantitating 13C enrichment of nucleic acids, requiring a few nanograms of sample, and we demonstrate its utility in typical DNA-SIP and RNA-SIP experiments. All five nucleobases (adenine, guanine, cytosine, thymine, and uracil) were separated and detected by using ultrahigh-performance liquid chromatography–tandem mass spectrometry. We detected all isotopic species in samples with as low as 1.5 atom% 13C above natural abundance, using 1-ng loadings. Quantitation was used to characterize the isotopic enrichment kinetics of cellulose- and lignin-based microcosm experiments and to optimize the recovery of enriched nucleic acids. Application of our method will minimize the quantity of expensive isotopically labeled substrates required and reduce the risk of failed experiments due to insufficient recovery of labeled nucleic acids for sequencing library preparation. PMID:25217022

  16. UV-laser microdissection system - A novel approach for the preparation of high-resolution stable isotope records (δ13C/δ18O) from tree rings

    NASA Astrophysics Data System (ADS)

    Schollaen, Karina; Helle, Gerhard

    2013-04-01

    Intra-annual stable isotope13C and δ18O) studies of tree rings at various incremental resolutions have been attempting to extract valuable seasonal climatic and environmental information or assessing plant ecophysiological processes. For preparing high-resolution isotope samples normally wood segments or cores are mechanically divided in radial direction or cut in tangential direction. After mechanical dissection, wood samples are ground to a fine powder and either cellulose is extracted or bulk wood samples are analyzed. Here, we present a novel approach for the preparation of high-resolution stable isotope records from tree rings using an UV-laser microdissection system. Firstly, tree-ring cellulose is directly extracted from wholewood cross-sections largely leaving the wood anatomical structure intact and saving time as compared to the classical procedure. Secondly, micro-samples from cellulose cross-sections are dissected with an UV-Laser dissection microscope. Tissues of interest from cellulose cross-sections are identified and marked precisely with a screen-pen and dissected via an UV-laser beam. Dissected cellulose segments were automatically collected in capsules and are prepared for stable isotope13C and δ18O) analysis. The new techniques facilitate inter- and intra-annual isotope analysis on tree-ring and open various possibilities for comparisons with wood anatomy in plant eco-physiological studies. We describe the design and the handling of this novel methodology and discuss advantages and constraints given by the example of intra-annual oxygen isotope analysis on tropical trees.

  17. Provenancing Archaeological Wool Textiles from Medieval Northern Europe by Light Stable Isotope Analysis (δ13C, δ15N, δ2H)

    PubMed Central

    von Holstein, Isabella C. C.; Walton Rogers, Penelope; Craig, Oliver E.; Penkman, Kirsty E. H.; Newton, Jason; Collins, Matthew J.

    2016-01-01

    We investigate the origin of archaeological wool textiles preserved by anoxic waterlogging from seven medieval archaeological deposits in north-western Europe (c. 700–1600 AD), using geospatial patterning in carbon (δ13C), nitrogen (δ15N) and non-exchangeable hydrogen (δ2H) composition of modern and ancient sheep proteins. δ13C, δ15N and δ2H values from archaeological wool keratin (n = 83) and bone collagen (n = 59) from four sites were interpreted with reference to the composition of modern sheep wool from the same regions. The isotopic composition of wool and bone collagen samples clustered strongly by settlement; inter-regional relationships were largely parallel in modern and ancient samples, though landscape change was also significant. Degradation in archaeological wool samples, examined by elemental and amino acid composition, was greater in samples from Iceland (Reykholt) than in samples from north-east England (York, Newcastle) or northern Germany (Hessens). A nominal assignment approach was used to classify textiles into local/non-local at each site, based on maximal estimates of isotopic variability in modern sheep wool. Light element stable isotope analysis provided new insights into the origins of wool textiles, and demonstrates that isotopic provenancing of keratin preserved in anoxic waterlogged contexts is feasible. We also demonstrate the utility of δ2H analysis to understand the location of origin of archaeological protein samples. PMID:27764106

  18. Provenancing Archaeological Wool Textiles from Medieval Northern Europe by Light Stable Isotope Analysis (δ13C, δ15N, δ2H).

    PubMed

    von Holstein, Isabella C C; Walton Rogers, Penelope; Craig, Oliver E; Penkman, Kirsty E H; Newton, Jason; Collins, Matthew J

    2016-01-01

    We investigate the origin of archaeological wool textiles preserved by anoxic waterlogging from seven medieval archaeological deposits in north-western Europe (c. 700-1600 AD), using geospatial patterning in carbon (δ13C), nitrogen (δ15N) and non-exchangeable hydrogen (δ2H) composition of modern and ancient sheep proteins. δ13C, δ15N and δ2H values from archaeological wool keratin (n = 83) and bone collagen (n = 59) from four sites were interpreted with reference to the composition of modern sheep wool from the same regions. The isotopic composition of wool and bone collagen samples clustered strongly by settlement; inter-regional relationships were largely parallel in modern and ancient samples, though landscape change was also significant. Degradation in archaeological wool samples, examined by elemental and amino acid composition, was greater in samples from Iceland (Reykholt) than in samples from north-east England (York, Newcastle) or northern Germany (Hessens). A nominal assignment approach was used to classify textiles into local/non-local at each site, based on maximal estimates of isotopic variability in modern sheep wool. Light element stable isotope analysis provided new insights into the origins of wool textiles, and demonstrates that isotopic provenancing of keratin preserved in anoxic waterlogged contexts is feasible. We also demonstrate the utility of δ2H analysis to understand the location of origin of archaeological protein samples.

  19. [Carbon stable isotope composition (delta 13C) of lichen thalli in the forests in the vicinity of the Chernobyl atomic power station].

    PubMed

    Biazrov, L G; Gongal'skiĭ, K B; Pel'gunova, L A; Tiunov, A V

    2010-01-01

    The stable isotope abundance of carbon in the lichens Cladina mitis, Cladonia crispata Hypogymnia physodes, Parmelia sulcata has been investigated in a study relating these values with known levels of 106Ru, 134Cs, 137Cs and 144Ce defined activity in their thalli in the pine forests of region within a 30-km radius of the Chernobyl atomic power station and beyond it (37 km). All 63 samples of the lichens were obtained from 7 different sites. Small effects on delta 13C values in the lichens Cladina mitis, Hypogymnia physodes were found to be associated with distance from CNPP, activity level of radionuclides in them thalli whereas at Cladonia crispata is observed weighting of carbon with increase in values of 134Cs and 137Cs activity in thalli. Values of delta 13C the investigated lichen species more depends on habitat conditions rather than from levels of thalli radioactivity. In our study we didn't reveal the isotope specificity of any one species as it was not possible to establish a correlation between values of delta 13C and a particular species.

  20. Trophic ecology of the supralittoral rocky shore (Roscoff, France): A dual stable isotope13C, δ 15N) and experimental approach

    NASA Astrophysics Data System (ADS)

    Laurand, Sandrine; Riera, Pascal

    2006-07-01

    The present study investigates the trophic transfers on the upper littoral rocky shore (i.e. the supralittoral zone together with the upper midlittoral and adlittoral) of northern Brittany. The population mainly consists of four invertebrate species: the littorinids Littorina saxatilis and Melarhaphe neritoides, the isopod Ligia oceanica and the insect Petrobius maritimus. The utilisation of food sources available to these grazers was examined in a laboratory microcosm feeding experiment and a field study using stable isotopes13C, δ 15N). The results indicated that although Ligia oceanica preferentially occurs in the supralittoral zone, its trophic subsidies originate mostly from the adlittoral and lower intertidal zones. The stable isotope data also suggested that adlittoral terrestrial organic material may be the major food source of Petrobius maritimus. δ 15N of Littorina saxatilis indicated a highly variable diet consisting of supralittoral lichens, midlittoral macroalgae and other food sources (e.g. microalgae). Both feeding experiments and stable isotope data show that only Melarhaphe neritoides has a clearly identifiable diet based on a mixture of lichens, mostly Verrucaria maura and Caloplaca marina, as estimated by an isotopic mixing model. Hence, the food web of this intertidal zone appears largely based on trophic subsidies from other habitats (i.e. upper and lower intertidal zones).

  1. Experimental assessment of the purity of α-cellulose produced by variations of the Brendel method: Implications for stable isotope13C, δ18O) dendroclimatology

    NASA Astrophysics Data System (ADS)

    Brookman, Tom; Whittaker, Thomas

    2012-09-01

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

  2. A mantle origin for Paleoarchean peridotitic diamonds from the Panda kimberlite, Slave Craton: Evidence from 13C-, 15N- and 33,34S-stable isotope systematics

    NASA Astrophysics Data System (ADS)

    Cartigny, Pierre; Farquhar, James; Thomassot, Emilie; Harris, Jeffrey W.; Wing, Bozwell; Masterson, Andy; McKeegan, Kevin; Stachel, Thomas

    2009-11-01

    In order to address diamond formation and origin in the lithospheric mantle underlying the Central Slave Craton, we report N- and C-stable isotopic compositions and N-contents and aggregation states for 85 diamonds of known paragenesis (73 peridotitic, 8 eclogitic and 4 from lower mantle) from the Panda kimberlite (Ekati Mine, Lac de Gras Area, Canada). For 12 peridotitic and two eclogitic sulfide inclusion-bearing diamonds from this sample set, we also report multiple-sulfur isotope ratios. The 73 peridotitic diamonds have a mean δ13C-value of - 5.2‰ and range from - 6.9 to - 3.0‰, with one extreme value at - 14.1‰. The associated δ15N-values range from - 17.0 to + 8.5‰ with a mean value of - 4.0‰. N-contents range from 0 to 1280 ppm. The 8 eclogitic diamonds have δ13C-values ranging from - 11.2 to - 4.4‰ with one extreme value at - 19.4‰. Their δ15N ranges from - 2.1 to + 7.9‰ and N-contents fall between 0 and 3452 ppm. Four diamonds with an inferred lower mantle origin are all Type II (i.e. nitrogen-free) and have a narrow range of δ13C values, between - 4.5 and - 3.5‰. The δ34S of the 14 analyzed peridotitic and eclogitic sulfide inclusions ranges from - 3.5 to +5.7‰. None of them provide evidence for anomalous δ33S-values; observed variations in δ33S are from +0.19 to - 0.33‰, i.e. within the 2 sigma uncertainties of mantle sulfur ( δ33S = 0‰). At Panda, the N contents and the δ13C of sulfide-bearing peridotitic diamonds show narrower ranges than silicate-bearing peridotitic diamonds. This evidence supports the earlier suggestion established from eclogitic diamonds from the Kaapvaal that sulfide-(±silicate) bearing diamonds sample a more restricted portion of sublithospheric mantle than silicate-(no sulfide) bearing diamonds. Our findings at Panda suggest that sulfide-bearing diamonds should be considered as a specific diamond population on a global-scale. Based on our study of δ34S, Δ 33S, δ15N and δ13C, we find no

  3. Pan-Arctic concentrations of mercury and stable isotope ratios of carbon (δ(13)C) and nitrogen (δ(15)N) in marine zooplankton.

    PubMed

    Pomerleau, Corinne; Stern, Gary A; Pućko, Monika; Foster, Karen L; Macdonald, Robie W; Fortier, Louis

    2016-05-01

    Zooplankton play a central role in marine food webs, dictating the quantity and quality of energy available to upper trophic levels. They act as "keystone" species in transfer of mercury (Hg) up through the marine food chain. Here, we present the first Pan-Arctic overview of total and monomethylmercury concentrations (THg and MMHg) and stable isotope ratios of carbon (δ(13)C) and nitrogen (δ(15)N) in selected zooplankton species by assembling data collected between 1998 and 2012 from six arctic regions (Laptev Sea, Chukchi Sea, southeastern Beaufort Sea, Canadian Arctic Archipelago, Hudson Bay and northern Baffin Bay). MMHg concentrations in Calanus spp., Themisto spp. and Paraeuchaeta spp. were found to increase with higher δ(15)N and lower δ(13)C. The southern Beaufort Sea exhibited both the highest THg and MMHg concentrations. Biomagnification of MMHg between Calanus spp. and two of its known predators, Themisto spp. and Paraeuchaeta spp., was greatest in the southern Beaufort Sea. Our results show large geographical variations in Hg concentrations and isotopic signatures for individual species related to regional ecosystem features, such as varying water masses and freshwater inputs, and highlight the increased exposure to Hg in the marine food chain of the southern Beaufort Sea.

  4. Influence of diet on growth, condition and reproductive capacity in Newfoundland and Labrador cod ( Gadus morhua): Insights from stable carbon isotopes ( δ13C)

    NASA Astrophysics Data System (ADS)

    Sherwood, Graham D.; Rideout, Rick M.; Fudge, Susan B.; Rose, George A.

    2007-11-01

    Cod populations in Newfoundland and Labrador waters have shown differing growth, condition and recruitment since near-universal declines in these properties during the cold period of the late 1980s and early 1990s. To assess the influence of variable prey communities on these parameters, we compared cod energetics and diet in populations off Labrador and the northeast and south coasts of Newfoundland. Many properties were highest in the southern group(s) and lowest in the northern group(s), including growth, somatic condition, liver index and age-at-maturity. Most differences could be explained by variations in diet, as measured by stomach contents and stable carbon isotopes ( δ13C). The diet of Labrador cod consisted almost entirely of northern shrimp ( Pandalus borealis), and these cod displayed the most benthic δ13C signatures. Northeast cod had a more varied diet that included capelin and other fish, but still had mostly benthic δ13C signatures, suggesting the importance of benthic prey like shrimp in this population. South coast cod exhibited the most varied diet, including capelin ( Mallotus villosus), zooplankton, crabs and other fish, and had the most pelagic δ13C signatures. Among and within populations, the benefits of a more pelagic diet in medium-sized (30-69 cm) cod included higher somatic condition, higher liver index (lipid stores) and greater spawning potential (decreased incidence of atresia). It is hypothesized that major rebuilding of Newfoundland and Labrador cod stocks will require a return to a system that supports mostly pelagic feeding (i.e. capelin) in cod.

  5. Assessment of trace elements, POPs, (210)Po and stable isotopes ((15)N and (13)C) in a rare filter-feeding shark: The megamouth.

    PubMed

    Moura, Jailson Fulgencio de; Merico, Agostino; Montone, Rosalinda Carmela; Silva, Josilene; Seixas, Tércia Guedes; Godoy, José Marcus de Oliveira; Saint'Pierre, Tatiana Dillenburg; Hauser-Davis, Rachel Ann; Di Beneditto, Ana Paula Madeira; Reis, Estéfane Cardinot; Tavares, Davi Castro; Lemos, Leila Soledade; Siciliano, Salvatore

    2015-06-15

    With less than 60 records being reported worldwide, the megamouth (Megachasma pelagios) is today one of the least known shark species inhabiting our oceans. Therefore, information concerning the biology and ecology of this enigmatic organism is very scarce and limited to feeding behaviour and preferred habitat. The present work reports new data on the concentrations of trace elements, organic mercury, POPs and (210)Po in hepatic and muscular tissues of a specimen found stranded in the southeastern coast of Brazil. Additionally, we provide new evidence based on stable isotope analysis (δ(15)N and δ(13)C) confirming the preference for the pelagic habitat and the zooplanktivorous feeding behaviour of the megamouth. These results are consistent with the low concentrations of organic pollutant compounds and other elements measured in our samples.

  6. Spatial variation in the stable isotopes of 13C and 15N and trophic position of Leporinus friderici (Characiformes, Anostomidae) in Corumbá Reservoir, Brazil.

    PubMed

    Pereira, Alexandre L; Benedito, Evanilde; Sakuragui, Cássia M

    2007-03-01

    Stable isotopes of carbon (delta13C) and nitrogen (delta15N) were used to describe sources of energy and trophic position for adult Leporinus friderici in the area of the Corumbá Reservoir, Brazil. Samples were collected from April 1999 to March 2000. Spatial variations were not identified in the isotopic composition. The maximum and minimum contribution of C4 plants calculated integrating the variation of plants and fish were 47.7% and 2.4%, respectively. Among C3 plants, periphyton presented closer isotopic values to those observed for fishes, corresponding to an important carbon source. The proportion of ingested plant item is larger in rivers upstream from the reservoir (42.7%), which justifies the smaller trophic level among there. However, in the reservoir, the ingestion of fish was 81.4%, while ingested plants contributed with 18.6%. Downstream from the dam, participation of plant item was even smaller (14.4%). Although the trophic position calculated with diet data was proportional to the one calculated with delta15N values, the former elevated the trophic level of L. friderici in the food web, because estimated trophic positions were based on fish items belonging to the 2nd (a) and to the 3rd (b) trophic levels.

  7. Stable Isotope13C, δ15N, δ34S) Analysis and Satellite Telemetry Depict the Complexity of Gray Wolf (Canis lupus) Diets in Southwest Alaska

    NASA Astrophysics Data System (ADS)

    Stanek, A.; Watts, D. E.; Cohn, B. R.; Spencer, P.; Mangipane, B.; Welker, J. M.

    2010-12-01

    Throughout Alaska, gray wolves (Canis lupus) are a top predator of large ungulates. While they primarily rely on ungulates such as moose (Alces alces) and caribou (Rangifer tarandus) as food, they are opportunistic and use alternative resources. The variation and supplemental protein sources in wolf diet has not been studied extensively on live animals currently using the landscape. With large seasonal influxes of Pacific salmon (Oncorhynchus sp.) into Alaska, terrestrial carnivore use of marine species is of particular interest. Using stable isotope13C, δ15N, δ34S) analysis of wolf guard hair and blood, this study aims to determine the proportion of marine derived nutrients (MDN) in the diet of wolf packs within and surrounding Lake Clark National Park and Preserve and Alaska Peninsula and Becharof National Wildlife Refuges in Southwest Alaska. Satellite telemetry from the animals sampled facilitates quantification of landscape use patterns in correspondence with isotopic traits. Wolf pack territories within and surrounding the Lake Clark region appear to vary in spatial extent and in availability of MDN, such as salmon. Initial analysis shows that two packs with smaller home ranges, centrally located around areas with greater salmon availability, have enriched δ15N values compared to packs that have larger home ranges not centralized around salmon spawning waters. This pattern of isotopic enrichment is found in red blood cells, blood serum and hair, representing diets over different time scales. The enrichment in both blood and hair indicates a sustained use of MDN over the previous six to nine months. In the Lake Clark region, simple mixing model estimates suggest that up to 30% of wolf pack diets may be from marine sources. In contrast, packs with larger home ranges and less access to salmon have stable isotope values representative of a terrestrial diet.

  8. Spatial distribution of PAH concentrations and stable isotope signatures (δ13C, δ15N) in mosses from three European areas--characterization by multivariate analysis.

    PubMed

    Foan, L; Leblond, S; Thöni, L; Raynaud, C; Santamaría, J M; Sebilo, M; Simon, V

    2014-01-01

    Polycyclic aromatic hydrocarbon (PAH) concentrations and N, C stable isotope signatures were determined in mosses Hypnum cupressiforme Hedw. from 61 sites of 3 European regions: Île-de-France (France); Navarra (Spain); the Swiss Plateau and Basel area (Switzerland). Total PAH concentrations of 100-700 ng g(-1), as well as δ(13)C values of -32 to -29‰ and δ(15)N values of -11 to -3‰ were measured. Pearson correlation tests revealed opposite trends between high molecular weight PAH (4-6 aromatic rings) content and δ(13)C values. Partial Least Square regressions explained the very significant correlations (r > 0.91, p < 0.001) between high molecular weight PAH concentrations by local urban land use (<10 km) and environmental factors such as elevation and pluviometry. Finally, specific correlations between heavy metal and PAH concentrations were attributed to industrial emissions in Switzerland and road traffic emissions in Spain.

  9. Quantitative twoplex glycan analysis using (12)C6 and (13)C6 stable isotope 2-aminobenzoic acid labelling and capillary electrophoresis mass spectrometry.

    PubMed

    Váradi, Csaba; Mittermayr, Stefan; Millán-Martín, Silvia; Bones, Jonathan

    2016-12-01

    Capillary electrophoresis (CE) offers excellent efficiency and orthogonality to liquid chromatographic (LC) separations for oligosaccharide structural analysis. Combination of CE with high resolution mass spectrometry (MS) for glycan analysis remains a challenging task due to the MS incompatibility of background electrolyte buffers and additives commonly used in offline CE separations. Here, a novel method is presented for the analysis of 2-aminobenzoic acid (2-AA) labelled glycans by capillary electrophoresis coupled to mass spectrometry (CE-MS). To ensure maximum resolution and excellent precision without the requirement for excessive analysis times, CE separation conditions including the concentration and pH of the background electrolyte, the effect of applied pressure on the capillary inlet and the capillary length were evaluated. Using readily available (12/13)C6 stable isotopologues of 2-AA, the developed method can be applied for quantitative glycan profiling in a twoplex manner based on the generation of extracted ion electropherograms (EIE) for (12)C6 'light' and (13)C6 'heavy' 2-AA labelled glycan isotope clusters. The twoplex quantitative CE-MS glycan analysis platform is ideally suited for comparability assessment of biopharmaceuticals, such as monoclonal antibodies, for differential glycomic analysis of clinical material for potential biomarker discovery or for quantitative microheterogeneity analysis of different glycosylation sites within a glycoprotein. Additionally, due to the low injection volume requirements of CE, subsequent LC-MS analysis of the same sample can be performed facilitating the use of orthogonal separation techniques for structural elucidation or verification of quantitative performance.

  10. Identification of biomass utilizing bacteria in a carbon-depleted glacier forefield soil by the use of 13C DNA stable isotope probing.

    PubMed

    Zumsteg, Anita; Schmutz, Stefan; Frey, Beat

    2013-06-01

    As Alpine glaciers are retreating rapidly, bare soils with low organic C and N contents are becoming exposed. Carbon availability is a key factor regulating microbial diversity and ecosystem functioning in these soils. The aim of this study was to investigate how bacterial activity, community structure and composition are influenced by organic carbon availability. Bare soils were supplied with (13)C-labelled fungal (Penicillium sp.) and green algal (Chlorella sp.) biomass and the CO2 evolution and its δ(13)C signature were monitored up to 60 days. These organisms have previously been isolated near the glacier terminus. DNA stable isotope probing followed by T-RFLP profiling and sequencing of 16S rRNA genes was employed to identify consumers able to assimilate carbon from these biomass amendments. Higher respiration and higher bacterial activity indicated a more efficient utilization of algal cells than fungal cells. Flavobacterium sp. predominantly incorporated fungal-derived C, whereas the algal-derived C was mainly incorporated by Acidobacteria and Proteobacteria. This study emphasizes the important role of both fungal and algal biomass in increasing the carbon pool in recently deglaciated bare soils, as only 20% of the added C was respired as CO2, and the rest, we presume, remained in the soil.

  11. Diet analysis of Alaska Arctic snow crabs (Chionoecetes opilio) using stomach contents and δ13C and δ15N stable isotopes

    NASA Astrophysics Data System (ADS)

    Divine, Lauren M.; Bluhm, Bodil A.; Mueter, Franz J.; Iken, Katrin

    2017-01-01

    We used stomach content and stable δ13C and δ15N isotope analyses to investigate male and female snow crab diets over a range of body sizes (30-130 mm carapace width) in five regions of the Pacific Arctic (southern and northern Chukchi Sea, western, central, and Canadian Beaufort Sea). Snow crab stomach contents from the southern Chukchi Sea were also compared to available prey biomass and abundance. Snow crabs consumed four main prey taxa: polychaetes, decapod crustaceans (crabs, amphipods), echinoderms (mainly ophiuroids), and mollusks (bivalves, gastropods). Both approaches revealed regional differences. Crab diets in the two Chukchi regions were similar to those in the western Beaufort (highest bivalve, amphipod, and crustacean consumption). The Canadian Beaufort region was most unique in prey composition and in stable isotope values. We also observed a trend of decreasing carbon stable isotopes in crabs from the Chukchi to those in the Canadian Beaufort, likely reflecting the increasing use of terrestrial carbon sources towards the eastern regions of the Beaufort Sea from Mackenzie River influx. Cannibalism on snow crabs was higher in the Chukchi regions relative to the Beaufort regions. We suggest that cannibalism may have an impact on recruitment in the Chukchi Sea via reduction of cohort strength after settlement to the benthos, as known from the Canadian Atlantic. Prey composition varied with crab size only in some size classes in the southern Chukchi and central Beaufort, while stable isotope results showed no size-dependent differences. Slightly although significantly higher mean carbon isotope values for males in the southern Chukchi may not be reflective of a gender-specific pattern but rather be driven by low sample size. Finally, the lack of prey selection relative to availability in crabs in the southern Chukchi suggests that crabs consume individual prey taxa in relative proportions to prey field abundances. The present study is the first to

  12. Carbon (δ13C) and Nitrogen (δ15N) Stable Isotope Signatures in Bat Fur Indicate Swarming Sites Have Catchment Areas for Bats from Different Summering Areas

    PubMed Central

    Segers, Jordi L.; Broders, Hugh G.

    2015-01-01

    Migratory patterns of bats are not well understood and traditional methods to study this, like capture-mark-recapture, may not provide enough detail unless there are many records. Stable isotope profiles of many animal species have been used to make inferences about migration. Each year Myotis lucifugus and M. septentrionalis migrate from summering roosts to swarming caves and mines in the fall, but the pattern of movement between them is not well understood. In this study, fur δ13C and δ15N values of 305 M. lucifugus and 200 M. septentrionalis were analyzed to make inferences about migration patterns between summering areas and swarming sites in Nova Scotia, Canada. We expected that there would be greater variability in δ13C and δ15N among individuals at swarming sites because it was believed that these sites are used by individuals originating from many summering areas. There was extensive overlap in the standard ellipse area, corrected for small sample sizes (SEAc), of bats at swarming sites and much less overlap in SEAc among groups sampled at summering areas. Meaningful inference could not be made on M. septentrionalis because their low variation in SEAc may have been the result of sampling only 3 summering areas. However, for M. lucifugus, swarming sites had larger SEAc than summering areas and predictive discriminant analysis assigned swarming bats to multiple summering areas, supporting the contention that swarming bats are mixed aggregations of bats from several summering areas. Together, these data support the contention that swarming sites have catchment areas for bats from multiple summering areas and it is likely that the catchment areas for swarming sites overlap. These data suggest that δ13C and δ15N profiling of bat fur offer some potential to make inferences about regional migration in bats. PMID:25923696

  13. Carbon (δ13C) and Nitrogen (δ15N) Stable Isotope Signatures in Bat Fur Indicate Swarming Sites Have Catchment Areas for Bats from Different Summering Areas.

    PubMed

    Segers, Jordi L; Broders, Hugh G

    2015-01-01

    Migratory patterns of bats are not well understood and traditional methods to study this, like capture-mark-recapture, may not provide enough detail unless there are many records. Stable isotope profiles of many animal species have been used to make inferences about migration. Each year Myotis lucifugus and M. septentrionalis migrate from summering roosts to swarming caves and mines in the fall, but the pattern of movement between them is not well understood. In this study, fur δ13C and δ15N values of 305 M. lucifugus and 200 M. septentrionalis were analyzed to make inferences about migration patterns between summering areas and swarming sites in Nova Scotia, Canada. We expected that there would be greater variability in δ13C and δ15N among individuals at swarming sites because it was believed that these sites are used by individuals originating from many summering areas. There was extensive overlap in the standard ellipse area, corrected for small sample sizes (SEAc), of bats at swarming sites and much less overlap in SEAc among groups sampled at summering areas. Meaningful inference could not be made on M. septentrionalis because their low variation in SEAc may have been the result of sampling only 3 summering areas. However, for M. lucifugus, swarming sites had larger SEAc than summering areas and predictive discriminant analysis assigned swarming bats to multiple summering areas, supporting the contention that swarming bats are mixed aggregations of bats from several summering areas. Together, these data support the contention that swarming sites have catchment areas for bats from multiple summering areas and it is likely that the catchment areas for swarming sites overlap. These data suggest that δ13C and δ15N profiling of bat fur offer some potential to make inferences about regional migration in bats.

  14. Benthic macroinvertebrates and the use of stable isotopes13C and δ15N) in the impact assessment of peatland use on boreal stream ecosystems

    NASA Astrophysics Data System (ADS)

    Nieminen, Mika L.; Daza Secco, Emmanuela; Nykänen, Hannu; Meissner, Kristian

    2013-04-01

    Stable isotope analysis (SIA) can provide insights into carbon flow dynamics and trophic positions of consumers in food webs. SIA is used in this study, where we assess the possible changes in the basal resources of Finnish boreal stream ecosystems and differences in the impact of two forms of peatland use, forestry and peat mining. About 30% of the total land area of Finland is classified as peatland, of which about 55% has been drained for forestry and about 0.6% is in peat production. Unlike forestry, peat production is regionally less scattered and can thus have measurable local impacts although the total area of peat production is small. Three watersheds were used as study areas. Within each watershed, one stream drains a subcatchment affected only by peat mining, whereas the other stream flows through a subcatchment affected by forestry. The two subcatchment streams merge to form a single stream flowing into a lake. Studied watersheds were subject to no other forms of land use. In addition to the impacted sites, we used two pristine natural mire and two natural forest catchments as controls. We analysed the stable isotopes of carbon (δ13C) and nitrogen (δ15N) from benthic macroinvertebrates, stream bank soil, stream sediment, and dissolved organic carbon (DOC) in stream water. Samples for stable isotope analyses were collected in the summer of 2011 and samples for invertebrate community analyses in the autumn of 2011. Upon sampling we measured several physical parameters at each sampling site. In addition, stream water samples collected in summer and autumn 2012 were analysed for CH4 and CO2 gas concentrations and autumn gas samples also for their δ13C values. Our initial SIA results of invertebrates suggest some degree of discrimination between different sources of OM and possible effects on feeding habits, presumably due to the quality of the basal resources. We will explore this result further by examining not only taxonomical structure, but also the

  15. Establishing spatial trends in water chemistry and stable isotopes (δ15N and δ13C) in the Elwha River prior to dam removal and salmon recolonization

    USGS Publications Warehouse

    Duda, J.J.; Coe, H.J.; Morley, S.A.; Kloehn, K.K.

    2011-01-01

    Two high-head dams on the Elwha River in Washington State (USA) have changed the migratory patterns of resident and anadromous fish, limiting Pacific salmon to the lower 7.9 km of a river that historically supported large Pacific salmon runs. To document the effects of the dams prior to their removal, we measured carbon and nitrogen stable isotope ratios of primary producers, benthic macroinvertebrates, and fish, and water chemistry above, between and below the dams. We found that δ15N was significantly higher in fish, stoneflies, black flies, periphyton and macroalgae where salmon still have access. Fish and chloroperlid stoneflies were enriched in δ13C, but the values were more variable than in δ15N. For some taxa, there were also differences between the two river sections that lack salmon, suggesting that factors other than marine-derived nutrients are structuring longitudinal isotopic profiles. Consistent with trophic theory, macroalgae had the lowest δ15N, followed by periphyton, macroinvertebrates and fish, with a range of 6.9, 6.2 and 7.7‰ below, between, and above the dams, respectively. Water chemistry analyses confirmed earlier reports that the river is oligotrophic. Phosphorous levels in the Elwha were lower than those found in other regional rivers, with significant differences among regulated, unregulated and reference sections. The removal of these dams, among the largest of such projects ever attempted, is expected to facilitate the return of salmon and their marine-derived nutrients (MDN) throughout the watershed, possibly altering the food web structure, nutrient levels and stable isotope values that we documented.

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  17. Assessing waterbird habitat use in coastal evaporative systems using stable isotopes13C, δ 15N and δD) as environmental tracers

    NASA Astrophysics Data System (ADS)

    Ramírez, Francisco; Abdennadher, Aida; Sanpera, Carola; Jover, Lluís; Wassenaar, Leonard I.; Hobson, Keith A.

    2011-04-01

    Isotopic patterns of biota across salinity gradients in man-made evaporative systems could assist in determining the use of these habitats by animals. Here we report δ 13C, δ 15N and δD measurements of a euryhaline fish, the Mediterranean toothcarp ( Aphanius fasciatus), inhabiting a range of salinities in the Thyna saltworks near Sfax (Tunisia). The contribution of these salinity niches to egg formation of two typically piscivorous bird species breeding in the area and feeding within saltworks, Little Tern ( Sternula albifrons) and Little Egret ( Egretta garzetta), was inferred trough a triple-isotope13C, δ 15N and δD) Bayesian mixing model. Isotopic trends for fish δ 15N and δD across the salinity gradient followed the equations: δ 15N = e (1.1 + 47.68/Salinity) and δD = -175.74 + Salinity + Salinity 2; whereas fish δ 13C increased as salinity rose (δ 13C = -10.83 + 0.02·Salinity), after a sudden drop in fish isotopic values for salinities >60 (Practical Salinity Scale) (average fish δ 13C for salinities <60 = -5.92‰). Both bird species fed largely on low hypersalinity ponds (salinity = 43; average contribution = 37% and 22% for Little Egrets and Little Terns, respectively), although the use of intermediate hypersalinities (salinities 63 and 70) by Little Terns also occurred (16% and 21%, respectively). Isotopic patterns across salinity gradients allow the use of isotopic measurements to inform studies of habitat occupancy within evaporative systems and provide further insights into how wildlife communities interact with them.

  18. A stable isotope ( δ13C, δ15N) model for the North Water food web: implications for evaluating trophodynamics and the flow of energy and contaminants

    NASA Astrophysics Data System (ADS)

    Hobson, Keith A.; Fisk, Aaron; Karnovsky, Nina; Holst, Meike; Gagnon, Jean-Marc; Fortier, Martin

    fundamentally in transferring energy and carbon flux to higher trophic-level seabirds and marine mammals. We measured PCB 153 among selected organisms to investigate the behavior of bioaccumulating contaminants within the food web. Our isotopic model confirmed the trophic magnification of PCB 153 in this high-Arctic food web due to a strong correlation between contaminant concentration and organism δ15N values, demonstrating the utility of combining isotopic and contaminant approaches to food-web studies. Stable-carbon isotope analysis confirmed an enrichment in 13C between POM and ice algae (-22.3 vs. -17.7‰). Benthic organisms were generally enriched in 13C compared to pelagic species. We discuss individual species isotopic data and the general utility of our stable isotope model for defining carbon flux and contaminant flow through the North Water food web.

  19. Similarities and differences in 13C and 15N stable isotope ratios in two non-lethal tissue types from shovelnose sturgeon Scaphirhynchus platorynchus (Rafinesque, 1820)

    USGS Publications Warehouse

    DeVries, R. J.; Schramm, Harold L.

    2015-01-01

    We tested the hypothesis that δ13C and δ15N signatures of pectoral spines would provide measures of δ13C and δ15N similar to those obtained from fin clips for adult shovelnose sturgeon Scaphirhynchus platorynchus. Thirty-two shovelnose sturgeon (fork length [FL] = 500–724 mm) were sampled from the lower Mississippi River, USA on 23 February 2013. Isotopic relationships between the two tissue types were analyzed using mixed model analysis of covariance. Tissue types differed significantly for both δ13C (P < 0.01; spine: mean = −23.83, SD = 0.62; fin clip: mean = −25.74, SD = 0.97) and δ15N (P = 0.01; spine: mean = 17.01, SD = 0.51; fin clip: mean = 17.19, SD = 0.62). Neither FL nor the FL × tissue type interaction had significant (P > 0.05) effects on δ13C. Fin clip δ13C values were highly variable and weakly correlated (r = 0.16, P = 0.40) with those from pectoral spines. We found a significant FL-tissue type interaction for δ15N, reflecting increasing δ15N with FL for spines and decreasing δ15N with FL for fin clips. These results indicate that spines are not a substitute for fin clip tissue for measuring δ13C and δ15N for shovelnose sturgeon in the lower Mississippi River, but the two tissues have different turnover rates they may provide complementary information for assessing trophic position at different time scales.

  20. Study and validity of 13C stable carbon isotopic ratio analysis by mass spectrometry and 2H site-specific natural isotopic fractionation by nuclear magnetic resonance isotopic measurements to characterize and control the authenticity of honey.

    PubMed

    Cotte, J F; Casabianca, H; Lhéritier, J; Perrucchietti, C; Sanglar, C; Waton, H; Grenier-Loustalot, M F

    2007-01-16

    Honey samples were analyzed by stable carbon isotopic ratio analysis by mass spectrometry (SCIRA-MS) and site-specific natural isotopic fractionation measured by nuclear magnetic resonance (SNIF-NMR) to first determine their potentials for characterizing the substance and then to combat adulteration. Honey samples from several geographic and botanical origins were analyzed. The delta(13)C parameter was not significant for characterizing an origin, while the (D/H)(I) ratio could be used to differentiate certain single-flower varieties. Application of the official control method of adding a C(4) syrup (AOAC official method 998.12) to our authentic samples revealed anomalies resulting from SCIRA indices that were more negative than -1 per thousand (permil). A filtration step was added to the experimental procedure and provided results that were compliant with the natural origin of our honey samples. In addition, spiking with a C(4) syrup could be detected starting at 9-10%. The use of SNIF-NMR is limited by the detection of a syrup spike starting only at 20%, which is far from satisfying.

  1. The signatures of stable isotopes δ 15N and δ 13C in anadromous and non-anadromous Coilia nasus living in the Yangtze River, and the adjacent sea waters

    NASA Astrophysics Data System (ADS)

    Wang, Lei; Tang, Wenqiao; Dong, Wenxia

    2015-12-01

    Stable isotopes are increasingly used to investigate seasonal migrations of aquatic organisms. This study employed stable isotopes ( δ 13C and δ 15N) for Coilia nasus from the lower Yangtze River and the adjacent East China Sea to distinguish different ecotypic groups, ascertain trophic nutrition positions, and reflect environmental influences on C. nasus. δ 13C signatures of C. nasus sampled from Zhoushan (ZS), Chongming (CM), and Jingjiang (JJ) waters were significantly higher than those from the Poyang Lake (PYL) ( P < 0.05). By contrast, δ 15N signatures of C. nasus in ZS, CM, and JJ groups were significantly lower than those in PYL group ( P < 0.05). Basing on δ 13C and δ 15N signatures, we could distinguish anadromous (ZS, CM, and JJ) and non-anadromous (PYL) groups. The trophic level (TL) of anadromous C. nasus ranged from 2.90 to 3.04, whereas that of non-anadromous C. nasus was 4.38. C. nasus occupied the middle and top nutrition positions in the marine and Poyang Lake food webs, respectively. C. nasus in Poyang Lake were significantly more enriched in δ 15N but depleted in δ 13C, suggesting that anthropogenic nutrient inputs and terrigenous organic carbon are important to the Poyang Lake food web. This study is the first to apply δ 15N and δ 13C to population assignment studies of C. nasus in the Yangtze River and its affiliated waters. Analysis of stable isotopes ( δ 15N and δ 13C) is shown to be a useful tool for discriminating anadromous and non-anadromous C. nasus.

  2. The Effect of Parasite Infection on Stable Isotope Turnover Rates of δ15N, δ13C and δ34S in Multiple Tissues of Eurasian Perch Perca fluviatilis

    PubMed Central

    Yohannes, Elizabeth; Grimm, Claudia; Rothhaupt, Karl-Otto; Behrmann-Godel, Jasminca

    2017-01-01

    Stable isotope analysis of commercially and ecologically important fish can improve understanding of life-history and trophic ecology. However, accurate interpretation of stable isotope values requires knowledge of tissue-specific isotopic turnover that will help to describe differences in the isotopic composition of tissues and diet. We performed a diet-switch experiment using captive-reared parasite-free Eurasian perch (Perca fluviatilis) and wild caught specimens of the same species, infected with the pike tapeworm Triaenophorus nodulosus living in host liver tissue. We hypothesize that metabolic processes related to infection status play a major role in isotopic turnover and examined the influence of parasite infection on isotopic turn-over rate of carbon (δ13C), nitrogen (δ15N) and sulphur (δ34S) in liver, blood and muscle. The δ15N and δ13C turnovers were fastest in liver tissues, followed by blood and muscle. In infected fish, liver and blood δ15N and δ13C turnover rates were similar. However, in infected fish, liver and blood δ13C turnover was faster than that of δ15N. Moreover, in infected subjects, liver δ15N and δ13C turnover rates were three to five times faster than in livers of uninfected subjects (isotopic half-life of ca.3-4 days compared to 16 and 10 days, respectively). Blood δ34S turnover rate were about twice faster in non-infected individuals implying that parasite infection could retard the turnover rate of δ34S and sulphur containing amino acids. Slower turnover rate of essential amino acid could probably decrease individual immune function. These indicate potential hidden costs of chronic and persistent infections that may have accumulated adverse effects and might eventually impair life-history fitness. For the first time, we were able to shift the isotope values of parasites encapsulated in the liver by changing the dietary source of the host. We also report variability in isotopic turnover rates between tissues, elements and

  3. The Effect of Parasite Infection on Stable Isotope Turnover Rates of δ15N, δ13C and δ34S in Multiple Tissues of Eurasian Perch Perca fluviatilis.

    PubMed

    Yohannes, Elizabeth; Grimm, Claudia; Rothhaupt, Karl-Otto; Behrmann-Godel, Jasminca

    2017-01-01

    Stable isotope analysis of commercially and ecologically important fish can improve understanding of life-history and trophic ecology. However, accurate interpretation of stable isotope values requires knowledge of tissue-specific isotopic turnover that will help to describe differences in the isotopic composition of tissues and diet. We performed a diet-switch experiment using captive-reared parasite-free Eurasian perch (Perca fluviatilis) and wild caught specimens of the same species, infected with the pike tapeworm Triaenophorus nodulosus living in host liver tissue. We hypothesize that metabolic processes related to infection status play a major role in isotopic turnover and examined the influence of parasite infection on isotopic turn-over rate of carbon (δ13C), nitrogen (δ15N) and sulphur (δ34S) in liver, blood and muscle. The δ15N and δ13C turnovers were fastest in liver tissues, followed by blood and muscle. In infected fish, liver and blood δ15N and δ13C turnover rates were similar. However, in infected fish, liver and blood δ13C turnover was faster than that of δ15N. Moreover, in infected subjects, liver δ15N and δ13C turnover rates were three to five times faster than in livers of uninfected subjects (isotopic half-life of ca.3-4 days compared to 16 and 10 days, respectively). Blood δ34S turnover rate were about twice faster in non-infected individuals implying that parasite infection could retard the turnover rate of δ34S and sulphur containing amino acids. Slower turnover rate of essential amino acid could probably decrease individual immune function. These indicate potential hidden costs of chronic and persistent infections that may have accumulated adverse effects and might eventually impair life-history fitness. For the first time, we were able to shift the isotope values of parasites encapsulated in the liver by changing the dietary source of the host. We also report variability in isotopic turnover rates between tissues, elements and

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

    NASA Astrophysics Data System (ADS)

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

    2010-03-01

    The aragonitic skeletons of bathyal cold-water corals have a high potential as geochemical in situ archives for paleoceanography. Oxygen isotopes and stable carbon isotopes (δ 18O and δ 13C) have been analyzed, as well as trace and minor element compositions (e.g. Mg/Ca, Sr/Ca, U/Ca, B/Ca and P/Ca) in Lophelia pertusa, one of the most important frame-builders at the Santa Maria di Leuca (SML) deep-water coral hotspot in the Central Mediterranean. The Apulian Bank is swept by strong currents of the Adriatic Deep Water Outflow. The temperature of 13.9 °C is the highest temperature recorded for L. pertusa and provides an important end-member of environmental conditions for geochemical analyses on living Atlantic and Mediterranean cold-water corals. Temperature and salinity (38.77 PSU) are stable throughout the year, and thus virtually no changes should be observed in the stable oxygen isotope signal—if the coral precipitates its skeleton in equilibrium with seawater. We measured various marine properties, such as the seawater oxygen isotope composition (δ 18O sw), stable carbon isotope composition (δ 13C DIC) of dissolved inorganic carbon (DIC), and dissolved inorganic nutrient concentrations (PO 4, NO 3, NO 2, NH 3 and SiO 2). Bottom water at the coral sites shows a mean oxygen isotope composition of 1.47‰ δ 18O sw-VSMOW, and δ 13C DIC showed a mean of 1.1‰ VPDB. A section of a living L. pertusa with a thick theca calcification was probed with a Merchantek MicroMill at a high spatial sampling resolution with 10 samples per 1 mm. This reduced the signal-smoothing inherent to conventional sampling. The δ 18O ag of coral aragonite ranges between -2.0‰ and +2.8‰ VPDB and the δ 13C ag ranges between -7.77‰ and +1.47‰ VPDB. The Gaussian data distribution for both parameters, including heavy equilibrium values, suggests the completeness of the captured isotopic variability. The strict linear correlation of δ 13C and δ 18O displays a strong 'kinetic

  5. Observations of atmospheric methane and its stable isotope ratio (δ13C) over the Arctic seas from ship cruises in the summer and autumn of 2015

    NASA Astrophysics Data System (ADS)

    Skorokhod, Andrey; Belikov, Igor; Pankratova, Natalia; Novigatsky, Alexander; Thompson, Rona

    2016-04-01

    Atmospheric methane (CH4) is the second most important long-lived greenhouse gas. The Arctic has significant sources of CH4, such as from wetlands and possibly also from methane hydrates, which may act as a positive feedback on the climate system. Despite significant efforts in establishing a network of ground-based CH4 observations in the Arctic zone, there is still a lack of measurements over the Arctic Ocean and sub-polar seas. From 21 July to 9 October 2015, concentrations of CH4 and CO2, as well as of the 13C:12C isotopic ratio in CH4, i.e., δ13C, were measured in the marine boundary layer from aboard the Research Vessel "Akademik Mstislav Keldysh" by the Shirshov Institute of Oceanology. Measurements were made using a Cavity Ring Down Spectroscopy instrument from Picarro™ (model G2132-i). The cruises covered a vast area including the North Atlantic up to 70°N, the Baltic, North, Norwegian, Greenland, Barents, White, Kara and Laptev Seas. To the best of our knowledge, these are the first measurements of their type made in these regions. Concentrations of CH4 typically had low variations (in the range of a few ppb) in the open sea but relatively large variations (of the order of 100 ppb) were recorded near and during stops in ports. High variability of atmospheric CH4 was also registered near the delta of the Lena River in the Laptev Sea, which has been suggested to be a large CH4 reservoir and where bubbles rising through the water column have been observed. The obtained set of δ13CCH4 is characterized by significant range of the measured values varying from open Atlantic to polluted regions near large sea ports. The Keeling plot analyses were implemented to study possible CH4 sources according to its isotopic signature. Footprint analyses are presented for the shipboard observations, as well as comparisons to simulated CH4 concentrations and δ13C using the Lagrangian transport model, FLEXPART. This work has been carried-out with the financial support of

  6. Combination of the (87)Sr/(86)Sr ratio and light stable isotopic values (δ(13)C, δ(15)N and δD) for identifying the geographical origin of winter wheat in China.

    PubMed

    Liu, Hongyan; Wei, Yimin; Lu, Hai; Wei, Shuai; Jiang, Tao; Zhang, Yingquan; Guo, Boli

    2016-12-01

    This study aims to investigate whether isotopic signatures can be used to develop reliable fingerprints for discriminating the geographical origin of Chinese winter wheat, and to evaluate the discrimination effects of δ(13)C, δ(15)N and δD, alone or with (87)Sr/(86)Sr. In this study, the values of δ(13)C, δ(15)N and δD, and the (87)Sr/(86)Sr ratios of wheat and provenance soils from three regions were determined. Significant differences were found in all parameters of wheat and (87)Sr/(86)Sr in soil extract (reflecting the bioavailable fraction of soil) among different regions. A significantly positive correlation was observed between the (87)Sr/(86)Sr ratios of wheat and soil extracts. An overall correct classification rate of 77.8% was obtained for discriminating wheat from three regions based on light stable isotopes (δ(13)C, δ(15)N, and δD). The correct classification rate of 98.1% could be obtained with the combination of the (87)Sr/(86)Sr ratio and the light stable isotopic values.

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

    NASA Astrophysics Data System (ADS)

    Fernandez, I.; Cabaneiro, A.

    2014-02-01

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

  8. Combining stable isotope13C) of trace gases and aerobiological data to monitor the entry and dispersion of microorganisms in caves.

    PubMed

    Garcia-Anton, E; Cuezva, S; Jurado, V; Porca, E; Miller, A Z; Fernandez-Cortes, A; Saiz-Jimenez, C; Sanchez-Moral, S

    2014-01-01

    Altamira Cave (north of Spain) contains one of the world's most prominent Paleolithic rock art paintings, which are threatened by a massive microbial colonization of ceiling and walls. Previous studies revealed that exchange rates between the cave and the external atmosphere through the entrance door play a decisive role in the entry and transport of microorganisms (bacteria and fungi) and nutrients to the interior of the cave. A spatial-distributed sampling and measurement of carrier (CO2) and trace (CH4) gases and isotopic signal of CO2 (δ(13)C) inside the cave supports the existence of a second connection (active gas exchange processes) with the external atmosphere at or near the Well Hall, the innermost and deepest area of the cave. A parallel aerobiological study also showed that, in addition to the entrance door, there is another connection with the external atmosphere, which favors the transport and increases microorganism concentrations in the Well Hall. This double approach provides a more complete knowledge on cave ventilation and revealed the existence of unknown passageways in the cave, a fact that should be taken into account in future cave management.

  9. Changing gull diet in a changing world: a 150-year stable isotope13C, δ15N) record from feathers collected in the Pacific Northwest of North America.

    PubMed

    Blight, Louise K; Hobson, Keith A; Kyser, T Kurt; Arcese, Peter

    2015-04-01

    The world's oceans have undergone significant ecological changes following European colonial expansion and associated industrialization. Seabirds are useful indicators of marine food web structure and can be used to track multidecadal environmental change, potentially reflecting long-term human impacts. We used stable isotope (δ(13)C, δ(15)N) analysis of feathers from glaucous-winged gulls (Larus glaucescens) in a heavily disturbed region of the northeast Pacific to ask whether diets of this generalist forager changed in response to shifts in food availability over 150 years, and whether any detected change might explain long-term trends in gull abundance. Sampled feathers came from birds collected between 1860 and 2009 at nesting colonies in the Salish Sea, a transboundary marine system adjacent to Washington, USA and British Columbia, Canada. To determine whether temporal trends in stable isotope ratios might simply reflect changes to baseline environmental values, we also analysed muscle tissue from forage fishes collected in the same region over a multidecadal timeframe. Values of δ(13)C and δ(15)N declined since 1860 in both subadult and adult gulls (δ(13)C, ~ 2-6‰; δ(15)N, ~4-5‰), indicating that their diet has become less marine over time, and that birds now feed at a lower trophic level than previously. Conversely, forage fish δ(13)C and δ(15)N values showed no trends, supporting our conclusion that gull feather values were indicative of declines in marine food availability rather than of baseline environmental change. Gradual declines in feather isotope values are consistent with trends predicted had gulls consumed less fish over time, but were equivocal with respect to whether gulls had switched to a more garbage-based diet, or one comprising marine invertebrates. Nevertheless, our results suggest a long-term decrease in diet quality linked to declining fish abundance or other anthropogenic influences, and may help to explain regional

  10. Leaf and root pectin methylesterase activity and 13C/12C stable isotopic ratio measurements of methanol emissions give insight into methanol production in Lycopersicon esculentum.

    PubMed

    Oikawa, Patricia Yoshino; Giebel, Brian M; Sternberg, Leonel da Silveira Lobo O'Reilly; Li, Lei; Timko, Michael P; Swart, Peter K; Riemer, Daniel D; Mak, John E; Lerdau, Manuel T

    2011-09-01

    Plant production of methanol (MeOH) is a poorly understood aspect of metabolism, and understanding MeOH production in plants is crucial for modeling MeOH emissions. Here, we have examined the source of MeOH emissions from mature and immature leaves and whether pectin methylesterase (PME) activity is a good predictor of MeOH emission. We also investigated the significance of below-ground MeOH production for mature leaf emissions. We present measurements of MeOH emission, PME activity, and MeOH concentration in mature and immature tissues of tomato (Lycopersicon esculentum). We also present stable carbon isotopic signatures of MeOH emission and the pectin methoxyl pool. Our results suggest that below-ground MeOH production was not the dominant contributor to daytime MeOH emissions from mature and immature leaves. Stable carbon isotopic signatures of mature and immature leaf MeOH were similar, suggesting that they were derived from the same pathway. Foliar PME activity was related to MeOH flux, but unexplained variance suggested PME activity could not predict emissions. The data show that MeOH production and emission are complex and cannot be predicted using PME activity alone. We hypothesize that substrate limitation of MeOH synthesis and MeOH catabolism may be important regulators of MeOH emission.

  11. Identifying carbon sources and trophic position of coral reef fishes using diet and stable isotope (δ15N and δ13C) analyses in two contrasted bays in Moorea, French Polynesia

    NASA Astrophysics Data System (ADS)

    Letourneur, Y.; Lison de Loma, T.; Richard, P.; Harmelin-Vivien, M. L.; Cresson, P.; Banaru, D.; Fontaine, M.-F.; Gref, T.; Planes, S.

    2013-12-01

    Stable isotope ratios (δ15N and δ13C) and diet of three fish species, Stegastes nigricans, Chaetodon citrinellus and Epinephelus merra, were analyzed on the fringing coral reefs of two bays that are differentially exposed to river runoff on Moorea Island, French Polynesia. S. nigricans and C. citrinellus relied mostly on turf algae and presented similar trophic levels and δ15N values, whereas E. merra fed on large invertebrates (crabs and shrimps) and had higher trophic levels and δ15N values. Discrepancies existed between stomach content and stable isotope analyses for the relative importance of food items. Bayesian mixing models indicated that sedimented organic matter was also an important additional food for S. nigricans and C. citrinellus, and fishes for E. merra. The main sources of organic matter involved in the food webs ending with these species were algal turfs and surface sediments, while water particulate organic matter was barely used. Significant spatial differences in C and N isotopic ratios for sources and fishes were found within and between bays. Lower 13C and higher 15N values were observed for various compartments of the studied trophic network at the end of each bay than at the entrance. Differences were observed between bays, with organic sources and consumers being, on average, slightly more 13C-depleted and 15N-enriched in Cook's Bay than in Opunohu Bay, linked with a higher mean annual flow of the river at Cook's Bay. Our results suggest that rivers bring continental material into these two bays, which is partly incorporated into the food webs of fringing coral reefs at least close to river mouths. Thus, continental inputs can influence the transfer of organic matter within coral reef food webs depending on the diet of organisms.

  12. Stable carbon ((12/13)C) and nitrogen ((14/15)N) isotopes as a tool for identifying the sources of cyanide in wastes and contaminated soils--a method development.

    PubMed

    Weihmann, Jenny; Mansfeldt, Tim; Schulte, Ulrike

    2007-01-23

    The occurrence of iron-cyanide complexes in the environment is of concern, since they are potentially hazardous. In order to determine the source of iron-cyanide complexes in contaminated soils and wastes, we developed a method based on the stable isotope ratios (13)C/(12)C and (15)N/(14)N of the complexed cyanide-ion (CN(-)). The method was tested on three pure chemicals and two industrials wastes: blast-furnace sludge (BFS) and gas-purifier waste (GPW). The iron-cyanide complexes were converted into the solid cupric ferrocyanide, Cu(2)[Fe(CN)(6)].7H(2)O, followed by combustion and determination of the isotope-ratios by continuous flow isotope ratio mass spectrometry. Cupric ferrocyanide was obtained from the materials by (i) an alkaline extraction with 1M NaOH and (ii) a distillate digestion. The [Fe(CN)(6)](4-) of the alkaline extraction was precipitated after adding Cu(2+). The CN(-) of the distillate digestion was at first complexed with Fe(2+) under inert conditions and then precipitated after adding Cu(2+). The delta(13)C-values obtained by the two methods differed slightly up to 1-3 per thousand for standards and BFS. The difference was larger for alkaline-extracted GPW (4-7 per thousand), since non-cyanide C was co-extracted and co-precipitated. Therefore the distillate digestion technique is recommended when determining the C isotope ratios in samples rich in organic carbon. Since the delta(13)C-values of BFS are in the range of -30 to -24 per thousand and of -17 to -5 per thousand for GPW, carbon seems to be a suitable tracer for identifying the source of cyanide in both wastes. However, the delta(15)N-values overlapped for BFS and GPW, making nitrogen unsuitable as a tracer.

  13. A stable isotope13C and δ15N) perspective on human diet on Rapa Nui (Easter Island) ca. AD 1400-1900.

    PubMed

    Commendador, Amy S; Dudgeon, John V; Finney, Bruce P; Fuller, Benjamin T; Esh, Kelley S

    2013-10-01

    Ecological and environmental evidence suggests that Rapa Nui was among the most marginally habitable islands in Eastern Polynesia, with only a fraction of the biotic diversity found on archipelagos to the west, and capable of sustaining many fewer cultigens traditionally transported by Polynesian colonizers. However, archaeological evidence for human dietary adaptations under such restrictions is limited. Little is known about the particulars of the subsistence base and dietary changes on Rapa Nui that may be associated with a hypothesized late prehistoric decline in the quality and diversity of food sources. To better understand prehistoric Rapa Nui diet we examined stable carbon and nitrogen isotope compositions of human teeth along with archaeological faunal material thought to comprise the Rapa Nui food web. Our results indicate that contrary to previous zooarchaeological studies diet was predominantly terrestrial throughout the entire sequence of occupation, with reliance on rats, chickens and C3 plants. While a few individuals may have had access to higher trophic level marine resources, this is evident only later in time (generally post-AD 1600). A decline in (15)N through time was observed, and may be attributed to declines in available terrestrial proteins; however, presently we cannot rule out the effect of changing soil and plant baseline δ(15)N. Our results also suggest differential access to higher trophic level marine resources among contemporaneous populations, but more research is required to clarify this observation.

  14. Latest Paleocene benthic extinction event on the southern Tethyan shelf (Egypt): Foraminiferal stable isotopic13C, δ18O) records

    NASA Astrophysics Data System (ADS)

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

    1996-04-01

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

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

    PubMed

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

    2013-06-01

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

  16. Study of Urban environmental quality through Isotopes δ13C

    NASA Astrophysics Data System (ADS)

    González-Sosa, E.; Mastachi-Loza, C.; Becerril-Piña, R.; Ramos-Salinas, N. M.

    2012-04-01

    Usually, trees with similar pH values on their bark develop epiphytes of similar species, the acidity to be a factor for growth. The aim of the study was evaluate the air quality through isotope δ13C in order to define the levels of environmental quality in the city of Queretaro, Mexico. In this work were collected at least 4 epiphytes positioned in trees of the species Prosopis Laevigata at 25 sites of Queretaro City. The samples were analyzed for trace elements with an inductively coupled plasma atomic emission spectroscopy (ICP). The collecting took place during dry period, in May and early rain June 2011 period, and on four sectors to identify the spatial distribution of pollution, using isotopic analysis of concentration of δ 13C. According with the results there are significant differences among the species in each of the sampled areas. The 5 February Avenue presented greater diversity and richness of δ13C, followed by those who were surveyed in the proximity of the UAQ and finally in the middle-east area. An average value of δ13C-17.92%, followed by those surveyed in the vicinity of the UAQ that correspond to sector I and II with an concentration of δ13C-17.55% and δ13C-17.22%, and finally the samples collected in trees scattered in the East-Sector II and IV with a value of δ13C-17.02% and δ13C-15.62%, respectively. Also were observed differences between the dry and wet period. It is likely that these results of δ 13C in moist period reflect the drag of the isotopes due to rain events that could mark a trend in the dilution of this element, however there is a trend in terms of abundance and composition of finding more impact in those species sampled in dry period, in May and early June 2011.

  17. Characterization of metabolic profile of honokiol in rat feces using liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry and (13)C stable isotope labeling.

    PubMed

    Dong, Yinfeng; Tang, Minghai; Song, Hang; Li, Rong; Wang, Chunyu; Ye, Haoyu; Qiu, Neng; Zhang, Yongkui; Chen, Lijuan; Wei, Yuquan

    2014-03-15

    As fecal excretion is one of important routes of elimination of drugs and their metabolites, it is indispensable to investigate the metabolites in feces for more comprehensive information on biotransformation in vivo. In this study, a sensitive and reliable approach based on ultra-performance liquid chromatography/quadrupole-time-of-flight-mass spectrometry (UHPLC-Q-TOF-MS) was applied to characterize the metabolic profile of honokiol in rat feces after the administration of an equimolar mixture of honokiol and [(13)C6]-labeled honokiol. Totally 42 metabolites were discovered and tentatively identified in rat feces samples, 26 metabolites were first reported, including two novel classes of metabolites, methylated and dimeric metabolites of honokiol. Moreover, this study provided basic comparative data on the metabolites in rat plasma, feces and urine, which gave better understanding of the metabolic fate of honokiol in vivo.

  18. Beneficial effects of sustained activity on the use of dietary protein and carbohydrate traced with stable isotopes 15N and 13C in gilthead sea bream (Sparus aurata).

    PubMed

    Felip, O; Blasco, J; Ibarz, A; Martin-Perez, M; Fernández-Borràs, J

    2013-02-01

    To determine the effects of sustained swimming on the use and fate of dietary nutrients in gilthead sea bream, a group of fish were forced to undertake moderate and sustained swimming (1.5 BL s(-1)) for 3 weeks and compared with a control group undertaking voluntary activity. The exercise group showed a significant increase in specific growth rate (C: 1.13 ± 0.05; E: 1.32 ± 0.06 % day(-1), P < 0.05) with no significant change in food intake (C: 3.56 ± 0.20; E: 3.84 ± 0.03 % of body weight). The addition of (13)C-starch and (15)N-protein to a single meal of 1 % ration allowed analysis of the fate of both nutrients in several tissues and in their components, 6 and 24 h after force-feeding. In exercised fish improved redistribution of dietary components increased the use of carbohydrates and lipid as fuels. Gilthead sea bream have a considerable capacity for carbohydrate absorption irrespective of swimming conditions, but in trained fish (13)C rose in all liver fractions with no changes in store contents. This implies higher nutrient turnover with exercise. Higher retention of dietary protein (higher (15)N uptake into white muscle during the entire post-prandial period) was found under sustained exercise, highlighting the protein-sparing effect. The combined effects of a carbohydrate-rich, low-protein diet plus sustained swimming enhanced amino acid retention and also prevented excessive lipid deposition in gilthead sea bream.

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

    NASA Astrophysics Data System (ADS)

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

    2010-12-01

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

  20. Automated determination of the stable carbon isotopic composition (δ13C) of total dissolved inorganic carbon (DIC) and total nonpurgeable dissolved organic carbon (DOC) in aqueous samples: RSIL lab codes 1851 and 1852

    USGS Publications Warehouse

    Révész, Kinga M.; Doctor, Daniel H.

    2014-01-01

    The purposes of the Reston Stable Isotope Laboratory (RSIL) lab codes 1851 and 1852 are to determine the total carbon mass and the ratio of the stable isotopes of carbon (δ13C) for total dissolved inorganic carbon (DIC, lab code 1851) and total nonpurgeable dissolved organic carbon (DOC, lab code 1852) in aqueous samples. The analysis procedure is automated according to a method that utilizes a total carbon analyzer as a peripheral sample preparation device for analysis of carbon dioxide (CO2) gas by a continuous-flow isotope ratio mass spectrometer (CF-IRMS). The carbon analyzer produces CO2 and determines the carbon mass in parts per million (ppm) of DIC and DOC in each sample separately, and the CF-IRMS determines the carbon isotope ratio of the produced CO2. This configuration provides a fully automated analysis of total carbon mass and δ13C with no operator intervention, additional sample preparation, or other manual analysis. To determine the DIC, the carbon analyzer transfers a specified sample volume to a heated (70 °C) reaction vessel with a preprogrammed volume of 10% phosphoric acid (H3PO4), which allows the carbonate and bicarbonate species in the sample to dissociate to CO2. The CO2 from the reacted sample is subsequently purged with a flow of helium gas that sweeps the CO2 through an infrared CO2 detector and quantifies the CO2. The CO2 is then carried through a high-temperature (650 °C) scrubber reactor, a series of water traps, and ultimately to the inlet of the mass spectrometer. For the analysis of total dissolved organic carbon, the carbon analyzer performs a second step on the sample in the heated reaction vessel during which a preprogrammed volume of sodium persulfate (Na2S2O8) is added, and the hydroxyl radicals oxidize the organics to CO2. Samples containing 2 ppm to 30,000 ppm of carbon are analyzed. The precision of the carbon isotope analysis is within 0.3 per mill for DIC, and within 0.5 per mill for DOC.

  1. Observations of atmospheric methane and its stable isotope ratio (δ13C) over the Russian Arctic seas from ship cruises in the summer and autumn of 2015

    NASA Astrophysics Data System (ADS)

    Skorokhod, A. I.; Pankratova, N. V.; Belikov, I. B.; Thompson, R. L.; Novigatsky, A. N.; Golitsyn, G. S.

    2016-10-01

    The results of experimental measurements of atmospheric methane concentrations and its isotopic composition in the Russian Arctic seas in the summer and autumn of 2015 are discussed. The Keeling plot method and inverse number simulation were used for revealing the factors responsible for elevated methane concentrations over the sea surface. Its maximum concentrations (up to 2050 ppb) were measured over the Kara and Laptev seas, as well as in the port area of Arkhangel'sk. It is shown that tundra and bog ecosystems of Siberia serve as the main sources of methane in the measurement zone (except for the area adjacent to large ports). As a whole, the share of methane from microbiological sources is as high as approximately 43% of the total methane concentrations along the ship route.

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

    PubMed

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

    2016-09-26

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

  3. Compound-specific stable carbon isotope ratios (delta13C values) of the halogenated natural product 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1).

    PubMed

    Vetter, Walter; Gleixner, Gerd

    2006-01-01

    Compound-specific isotope analysis using gas chromatography interfaced to isotope ratio mass spectrometry (GC/IRMS) was applied for the determination of delta13C values of the marine halogenated natural product 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1). The delta13C value of a lab-made Q1 standard (-34.20 +/- 0.27 per thousand) was depleted in 13C by more than 11 per thousand relative to the residues of Q1 in dolphin blubber from Australia and skua liver from Antarctica. This clarified that the synthesized Q1 was not the source for Q1 in the biota samples. However, two Australian marine mammals showed a large variation in the delta13C value, which, in our experience, was implausible. Since the GC/IRMS system was connected to a conventional ion trap mass spectrometer by a post-column splitter, we were able to closely inspect the peak purity of Q1 in the respective samples. While the mass spectra of Q1 did not indicate any impurity, a fronting peak of PCB 101 was identified in one sample. This interference falsified the delta13C value of the respective sample. Once this sample was excluded, we found that the delta13C values of the remaining samples, i.e. liver of Antarctic brown skua (-21.47 +/- 1.47 per thousand) and blubber of Australian melon-headed whale (-22.80 +/- 0.33 per thousand), were in the same order. The standard deviation for Q1 was larger in the skua samples than in the standard and the whale blubber sample. This was due to lower amounts of skua sample available. It remained unclear if the Q1 residues originate from the same producer and location.

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

    PubMed Central

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

    2008-01-01

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

  5. 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.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  7. Defining fish community structure in Lake Winnipeg using stable isotopes (δ(13)C, δ(15)N, δ(34)S): implications for monitoring ecological responses and trophodynamics of mercury & other trace elements.

    PubMed

    Ofukany, Amy F A; Wassenaar, Leonard I; Bond, Alexander L; Hobson, Keith A

    2014-11-01

    The ecological integrity of freshwater lakes is influenced by atmospheric and riverine deposition of contaminants, shoreline development, eutrophication, and the introduction of non-native species. Changes to the trophic structure of Lake Winnipeg, Canada, and consequently, the concentrations of contaminants and trace elements measured in tissues of native fishes, are likely attributed to agricultural runoff from the 977,800 km(2) watershed and the arrival of non-native zooplankters and fishes. We measured δ(13)C, δ(15)N, and δ(34)S along with concentrations of 15 trace elements in 17 native fishes from the north and south basins of Lake Winnipeg in 2009 and 2010. After adjusting for differences in isotopic baseline values between the two basins, fishes in the south basin had consistently higher δ(13)C and δ(34)S, and lower δ(15)N. We found little evidence of biomagnification of trace elements at the community level, but walleye (Sander vitreus) and freshwater drum (Aplodinotus grunniens) had higher mercury and selenium concentrations with increased trophic position, coincident with increased piscivory. There was evidence of growth dilution of cobalt, copper, manganese, molybdenum, thallium, and vanadium, and bioaccumulation of mercury, which could be explained by increases in algal (and consequently, lake and fish) productivity. We conclude that the north and south basins of Lake Winnipeg represent very different communities with different trophic structures and trace element concentrations.

  8. Paleoclimate record from Zidita Cave (Romania) using guano-derived δ13C isotopic data

    NASA Astrophysics Data System (ADS)

    Forray, Ferenc L.; Giurgiu, Alexandra; Onac, Bogdan P.; Tămaş, Tudor

    2014-05-01

    In this study, we measured the carbon isotopic composition of a core taken from a bat guano deposit in Zidita Cave (Metaliferi Mountains, Romania). The cave develops in Late Jurassic limestones, has a total length of 547 m, and its entrance was fortified during the XIV - XVIII centuries. The cave is a fossil maze with a filling represented by limestone blocks, clay sediments, and scarce calcite speleothems. The guano accumulation, 1.5 m thick, is located in a small room towards the end of the cave, under a Rhinolophus euryale roost site.The core was recovered with a Russian peat corer. 14C dating performed on the guano indicates a continuous deposition since ca. 500 years BP, but however, the upper first meter of the core has a modern age and high radiocarbon activity acquired from atmospheric radiocarbon bomb pulse. The core was sampled at 2 cm ± 2 mm intervals for δ13C analyses (76 samples) and at 5 cm for pollen. The investigations were carried out using a Picarro G2121-i δ13C analyzer (Combustion Module coupled with a Cavity Ring Down Spectroscopy technique) at the Stable Isotope Laboratory of the Department of Geology, Babes-Bolyai University (Cluj-Napoca, Romania). The result shows that guano δ13C range from -24.07 to -27.61 o‰The carbon isotopic profile indicates two major wet periods and 2 to 3 shorter periods characterized by drier climate.

  9. 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.

  10. 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.

  11. In vivo stable isotope studies in three patients affected with mitochondrial fatty acid oxidation disorders: limited diagnostic use of 1-13C fatty acid breath test using bolus technique.

    PubMed

    Jakobs, C; Kneer, J; Martin, D; Boulloche, J; Brivet, M; Poll-The, B T; Saudubray, J M

    1997-08-01

    The in vivo oxidation of fatty acids (FA) of different chain length was investigated in three patients with documented mitochondrial FA oxidation disorders: one patient with mild multiple acyl-CoA dehydrogenase deficiency (MADM), one with medium chain acyl-CoA dehydrogenase deficiency (MCAD), and one with carnitine palmitoyltransferase I deficiency (CPT I). Breath tests were performed after oral administration of 1-13C butyric. 1-13C octanoic, and 1-13C palmitic acids. 13C/12C ratio in the expired oxidative end product CO2 was measured. The cumulative 13C elimination was calculated and expressed as a percentage of the administered dose. In the MADM patient the influence of carnitine therapy (or deprivation) on the utilization of 1-13C palmitic acid was also examined. In the MCAD and CPT I patients, the 1-13C butyric, 1-13C octanoic and 1-13C palmitic acids in vivo oxidation were similar to five healthy controls. In the MADM patient, the oxidation of 1-13C butyric and 1-13C octanoic acids were normal, whereas the metabolism of 1-13C palmitic acid ranged from 33% of 66% of controls. In this patient the serum carnitine level decreased from 60 to 27 mumol/l without carnitine supplementation. Clinically there was mild hypotonia. 1-13C palmitic acid oxidation compared to controls was 50%. After 2 further weeks of carnitine deprivation the serum carnitine was 10-15 mumol/l. Clinically he was very hypotonic and had a large liver. 1-13C Palmitic acid oxidation was 33%. After 6 weeks of readministration of carnitine (L-carnitine 100 mg/kg/day p.o.) the serum carnitine was 60 mumol/l and the patient was in good clinical condition. 1-13C palmitic acid oxidation was 66% compared to controls. Our study implies that this simple fatty acid breath test is not of diagnostic use for detection of enzymatic defects in FA oxidation disorders. The carnitine dependent 1-13C palmitic acid oxidation indicates that this test might be of some value in cases with primary or secondary carnitine

  12. Embryotoxicity of stable isotopes and use of stable isotopes in studies of teratogenetic mechanisms

    SciTech Connect

    Spielmann, H.; Nau, H.

    1986-07-01

    Experiments on teratogenic effects of stable isotopes from our own and other laboratories are evaluated. In the first series of investigations, the enrichment of the stable isotope /sup 13/C derived from U-/sup 13/C-glucose was studied in mouse embryos at various stages of development, including limb buds in organ culture. Preimplantation mouse embryos incubated in vitro in /sup 13/C-enriched medium for 48 hours showed normal development during subsequent differentiation in vitro and also in vivo after embryo transfer to faster mothers. These embryos were 15% to 20% enriched in /sup 13/C. Administration of U-13-C-glucose to pregnant mice during organogenesis led to an increase of the absolute /sup 13/C content of the embryo for several days after the end of isotope administration, whereas the enrichment in maternal tissue decreased. No alterations of embryonic development were detected due to stable isotope enrichment. Development of cultured mouse limb buds was unaffected by incubation with 82 mol% U-/sup 13/C-glucose as judged from morphologic and biochemical criteria. The second part of the article describes the value of deuterium-labeled drugs as probes into the mechanism of activation of teratogenic metabolites. A comparison of the pharmacokinetics as well as the teratogenicity between cyclophosphamide and some specific deuterium-labeled analogues showed that the isotope effect observed can be related to a particular metabolic pathway crucial for teratogenic activation by this drug.

  13. Measurement of 13C/12C of chloroacetic acids by gas chromatography/combustion/isotope ratio mass spectrometry.

    PubMed

    Wong, Charles S; Muir, Derek C G; Mabury, Scott A

    2003-02-01

    This paper describes a novel analytical methodology using gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) to measure the 13C/12C ratios of chloroacetic acids (CAAs). CAAs are a major class of environmental pollutants that are widely distributed throughout the world, often at relatively high concentrations, and are of concern due to their toxic effects, particularly on plants. The 13C/12C of CAA reagents was measured by IRMS subsequent to offline combustion. Aqueous solutions of these CAAs were derivatized to the corresponding methyl chloroacetates (MCAAs) with acidic methanol with a known isotopic composition, extracted into pentane, and analyzed by GC/C/IRMS. Measured 13C/12C ratios of derivatized MCAAs were in agreement with calculated values within 1 per thousand for monochloroacetic acid and trichloroacetic acid and within 2 per thousand for dichloroacetic acid, suggesting that methylation and other analytical methodology steps do not isotopically fractionate derivatized MCAAs. 13C/12C ratios of reagent CAAs from different sources had varying isotopic signatures suggesting differences in source carbon and/or production methods. Our results underscore the potential of stable isotopes to serve as tracers of environmental sources of CAAs.

  14. 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.

  15. Analogy between mission critical detection in distributed systems and 13C isotope separation column

    NASA Astrophysics Data System (ADS)

    Boca, Maria L.; Secara, Mihai

    2015-02-01

    Carbon represents the fourth most abundant chemical element in the world, having two stable and one radioactive isotope. The 13 Carbon 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 [2]. Distributed systems are increasingly being applied in critical real-time applications and their complexity forces programmers to use design methods which guarantee correctness and increase the maintainability of the products. Objectoriented methodologies are widely used to cope with complexity in any kind of system, but most of them lack a formal foundation to allow the analysis and verification of designs, which is one of the main requirements for dealing with concurrent and reactive systems. This research is intended to make an analogy between two tips of industrial processes, one 13C Isotope Separation Column and other one distributed systems. We try to highlight detection of "mission critical "situations for this two processes and show with one is more critical and needs deeply supervisyon [1], [3].

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

    NASA Astrophysics Data System (ADS)

    Stepanov, E. V.

    2002-11-01

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

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

    SciTech Connect

    McConnaughey, T. )

    1989-01-01

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

  18. 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

  19. 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

  20. Stable isotopes in mineralogy

    USGS Publications Warehouse

    O'Neil, J.R.

    1977-01-01

    Stable isotope fractionations between minerals are functions of the fundamental vibrational frequencies of the minerals and therefore bear on several topics of mineralogical interest. Isotopic compositions of the elements H, C, O, Si, and S can now be determined routinely in almost any mineral. A summary has been made of both published and new results of laboratory investigations, analyses of natural materials, and theoretical considerations which bear on the importance of temperature, pressure, chemical composition and crystal structure to the isotopic properties of minerals. It is shown that stable isotope studies can sometimes provide evidence for elucidating details of crystal structure and can be a powerful tool for use in tracing the reaction paths of mineralogical reactions. ?? 1977 Springer-Verlag.

  1. Isotopic variability of cave bears (δ15N, δ13C) across Europe during MIS 3

    NASA Astrophysics Data System (ADS)

    Krajcarz, Magdalena; Pacher, Martina; Krajcarz, Maciej T.; Laughlan, Lana; Rabeder, Gernot; Sabol, Martin; Wojtal, Piotr; Bocherens, Hervé

    2016-01-01

    Collagen, the organic fraction of bone, records the isotopic parameters of consumed food for carbon (δ13C) and nitrogen (δ15N). This relationship of isotopic signature between diet and tissue is an important tool for the study of dietary preferences of modern and fossil animal species. Since the first information on the isotopic signature of cave bear was reported, numerous data from Europe have become available. The goal of this work is to track the geographical variation of cave bear collagen isotopic values in Europe during Marine Isotopic Stage 3 (about 60,000-25,000 yr BP). In this study the results of new δ13C and δ15N isotopic analyses of cave bear collagen from four Central-Eastern European sites are presented, as well as a review of all published isotopic data for cave bears of the same period. The main conclusion is a lack of geographical East-West pattern in the variations of δ13C and δ15N values of cave bear collagen. Moreover, no relationship was found between cave bear taxonomy and isotopic composition. The cave bears from Central-Eastern Europe exhibit δ13C and δ15N values near the average of the range of Central, Western and Southern European cave bears. Despite the fact that most cave bear sites follow an altitudinal gradient, separate groups of sites exhibit shift in absolute values of δ13C, what disturbs an altitude-related isotopic pattern. The most distinct groups are: high Alpine sites situated over 1500 m a.s.l. - in terms of δ13C; and two Romanian sites Peştera cu Oase and Urşilor - in case of δ15N. Although the cave bear isotopic signature is driven by altitude, the altitudinal adjustment of isotopic data is not enough to explain the isotopic dissimilarity of these cave bears. The unusually high δ15N signature of mentioned Romanian sites is an isolated case in Europe. Cave bears from relatively closely situated Central-Eastern European sites and other Romanian sites are more similar to Western European than to Romanian

  2. Methane concentration and isotopic composition (δ13C-CH4) in the Nerja Cave system (South Spain)

    NASA Astrophysics Data System (ADS)

    Vadillo, Iñaki; Etiope, Giuseppe; Benavente, José; Ojeda, Lucia; Liñán, Cristina; Carrasco, Francisco

    2016-04-01

    Air in underground caves often has methane (CH4) concentrations below the atmospheric level, due to methanotrophic or other unkown CH4 consuming processes. Caves are thus considered a potential sink for atmospheric methane. If globally important, this underground CH4 oxidation should be taken into account in the atmospheric methane budget, in addition to the known soil methanotrophy and tropospheric/stratospheric sinks. A large set of data is however necessary to understand how and how much methane from external atmospheric air is consumed in the caves. While methane concentration data are available for several caves worldwide, its isotopic composition and variations in space and time are poorly documented. We measured methane concentration and stable C isotope composition (δ13C) in the Nerja cave (Southern Spain) air during two surveys in March and April 2015. CH4 concentration decreases progressively from the more external cave rooms, with atmospheric levels of 1.9 ppmv, to the more internal and isolated rooms down to 0.5 ppmv. δ13C increases correspondingly from -47 ‰ to -41 ‰ (VPDB). CH4 is systematically 13C-enriched (δ13C > -45) in areas of the cave where the concentration is below 1.4 ppmv. This combination of concentration decrease and 13C-enrichment towards the more internal and isolated zones of the cave confirms the importance of CH4 oxidation, likely driven by methanotrophic bacteria. Further data, including stable H isotope composition of sub-atmospheric CH4 concentrations, CO2 and microbial analyses, shall be acquired over time to assess the actual role of methanotrophic bacteria and seasonal controls in the CH4 consumption process.

  3. Isotopic ((13)C) fractionation during plant residue decomposition and its implications for soil organic matter studies.

    PubMed

    Schweizer; Fear; Cadisch

    1999-07-01

    Carbon isotopic fractionations in plant materials and those occurring during decomposition have direct implications in studies of short-and longer-term soil organic matter dynamics. Thus the products of decomposition, the evolved CO(2) and the newly formed soil organic matter, may vary in their (13)C signature from that of the original plant material. To evaluate the importance of such fractionation processes, the variations in (13)C signatures between and within plant parts of a tropical grass (Brachiaria humidicola) and tropical legume (Desmodium ovalifolium) were measured and the changes in (13)C content (signatures) during decomposition were monitored over a period of four months. As expected the grass materials were less depleted in (13)C (-11.4 to -11.9 per thousand) than those of the legume (-27.3 to -25.8 per thousand). Root materials of the legume were less (1.5 per thousand) depleted in (13)C compared with the leaves. Plant lignin-C was strongly depleted in (13)C compared with the bulk material by up to 2.5 per thousand in the legume and up to 4.7 per thousand in the grass. Plant materials were subsequently incubated in a sand/nutrient-solution/microbial inoculum mixture. The respiration product CO(2) was trapped in NaOH and precipitated as CaCO(3), suitable for analysis using an automated C/N analyser coupled to an isotope ratio mass spectrometer. Significant depletion in (13)C of the evolved CO(2) was observed during the initial stages of decomposition probably as a result of microbial fractionation as it was not associated with the (13)C signatures of the measured more decomposable fractions (non-acid detergent fibre and cellulose). While the cumulative CO(2)-(13)C signatures of legume materials became slightly enriched with ongoing decomposition, the CO(2)-C of the grass materials remained depleted in (13)C. Associated isotopic fractionation correction factors for source identification of CO(2-)C varied with time and suggested errors of 2-19% in the

  4. BIODEGRADATION OF FLUORANTHENE AS MONITORED USING STABLE CARBON ISOTOPES

    EPA Science Inventory

    The measurement of stable isotope ratios of carbon (d13C values) was investigated as a viable technique to monitor the intrinsic bioremediation of polycyclic aromatic hydrocarbons (PAHs). Biometer-flask experiments were conducted in which the bacterium, Sphingomonas paucimobilis,...

  5. 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.

  6. (13) C dynamic nuclear polarization using isotopically enriched 4-oxo-TEMPO free radicals.

    PubMed

    Niedbalski, Peter; Parish, Christopher; Kiswandhi, Andhika; Lumata, Lloyd

    2016-12-01

    The nitroxide-based free radical 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) is a widely used polarizing agent in NMR signal amplification via dissolution dynamic nuclear polarization (DNP). In this study, we have thoroughly investigated the effects of (15) N and/or (2) H isotopic labeling of 4-oxo-TEMPO free radical on (13) C DNP of 3 M [1-(13) C] sodium acetate samples in 1 : 1 v/v glycerol : water at 3.35 T and 1.2 K. Four variants of this free radical were used for (13) C DNP: 4-oxo-TEMPO, 4-oxo-TEMPO-(15) N, 4-oxo-TEMPO-d16 and 4-oxo-TEMPO-(15) N,d16 . Our results indicate that, despite the striking differences seen in the electron spin resonance (ESR) spectral features, the (13) C DNP efficiency of these (15) N and/or (2) H-enriched 4-oxo-TEMPO free radicals are relatively the same compared with (13) C DNP performance of the regular 4-oxo-TEMPO. Furthermore, when fully deuterated glassing solvents were used, the (13) C DNP signals of these samples all doubled in the same manner, and the (13) C polarization buildup was faster by a factor of 2 for all samples. The data here suggest that the hyperfine coupling contributions of these isotopically enriched 4-oxo-TEMPO free radicals have negligible effects on the (13) C DNP efficiency at 3.35 T and 1.2 K. These results are discussed in light of the spin temperature model of DNP. Copyright © 2016 John Wiley & Sons, Ltd.

  7. Forensic Stable Isotope Biogeochemistry

    NASA Astrophysics Data System (ADS)

    Cerling, Thure E.; Barnette, Janet E.; Bowen, Gabriel J.; Chesson, Lesley A.; Ehleringer, James R.; Remien, Christopher H.; Shea, Patrick; Tipple, Brett J.; West, Jason B.

    2016-06-01

    Stable isotopes are being used for forensic science studies, with applications to both natural and manufactured products. In this review we discuss how scientific evidence can be used in the legal context and where the scientific progress of hypothesis revisions can be in tension with the legal expectations of widely used methods for measurements. Although this review is written in the context of US law, many of the considerations of scientific reproducibility and acceptance of relevant scientific data span other legal systems that might apply different legal principles and therefore reach different conclusions. Stable isotopes are used in legal situations for comparing samples for authenticity or evidentiary considerations, in understanding trade patterns of illegal materials, and in understanding the origins of unknown decedents. Isotope evidence is particularly useful when considered in the broad framework of physiochemical processes and in recognizing regional to global patterns found in many materials, including foods and food products, drugs, and humans. Stable isotopes considered in the larger spatial context add an important dimension to forensic science.

  8. Quantitative Microbial Ecology through Stable Isotope Probing

    PubMed Central

    Mau, Rebecca L.; Schwartz, Egbert; Caporaso, J. Gregory; Dijkstra, Paul; van Gestel, Natasja; Koch, Benjamin J.; Liu, Cindy M.; McHugh, Theresa A.; Marks, Jane C.; Morrissey, Ember M.; Price, Lance B.

    2015-01-01

    Bacteria grow and transform elements at different rates, and as yet, quantifying this variation in the environment is difficult. Determining isotope enrichment with fine taxonomic resolution after exposure to isotope tracers could help, but there are few suitable techniques. We propose a modification to stable isotope probing (SIP) that enables the isotopic composition of DNA from individual bacterial taxa after exposure to isotope tracers to be determined. In our modification, after isopycnic centrifugation, DNA is collected in multiple density fractions, and each fraction is sequenced separately. Taxon-specific density curves are produced for labeled and nonlabeled treatments, from which the shift in density for each individual taxon in response to isotope labeling is calculated. Expressing each taxon's density shift relative to that taxon's density measured without isotope enrichment accounts for the influence of nucleic acid composition on density and isolates the influence of isotope tracer assimilation. The shift in density translates quantitatively to isotopic enrichment. Because this revision to SIP allows quantitative measurements of isotope enrichment, we propose to call it quantitative stable isotope probing (qSIP). We demonstrated qSIP using soil incubations, in which soil bacteria exhibited strong taxonomic variations in 18O and 13C composition after exposure to [18O]water or [13C]glucose. The addition of glucose increased the assimilation of 18O into DNA from [18O]water. However, the increase in 18O assimilation was greater than expected based on utilization of glucose-derived carbon alone, because the addition of glucose indirectly stimulated bacteria to utilize other substrates for growth. This example illustrates the benefit of a quantitative approach to stable isotope probing. PMID:26296731

  9. The aspartate metabolism pathway is differentiable in human hepatocellular carcinoma: transcriptomics and (13) C-isotope based metabolomics.

    PubMed

    Darpolor, Moses M; Basu, Sankha S; Worth, Andrew; Nelson, David S; Clarke-Katzenberg, Regina H; Glickson, Jerry D; Kaplan, David E; Blair, Ian A

    2014-04-01

    Hepatocellular carcinoma (HCC), the primary form of human adult liver malignancy, is a highly aggressive tumor with average survival rates that are currently less than a year following diagnosis. Although bioinformatic analyses have indicated differentially expressed genes and cancer related mutations in HCC, integrated genetic and metabolic pathway analyses remain to be investigated. Herein, gene (i.e. messenger RNA, mRNA) enrichment analysis was performed to delineate significant alterations of metabolic pathways in HCC. The objective of this study was to investigate the pathway of aspartate metabolism in HCC of humans. Coupled with transcriptomic (i.e. mRNA) and NMR based metabolomics of human tissue extracts, we utilized liquid chromatography mass spectrometry based metabolomics analysis of stable [U-(13) C6 ]glucose metabolism or [U-(13) C5 ,(15) N2 ]glutamine metabolism of HCC cell culture. Our results indicated that aspartate metabolism is a significant and differentiable metabolic pathway of HCC compared with non-tumor liver (p value < 0.0001). In addition, branched-chain amino acid metabolism (p value < 0.0001) and tricarboxylic acid metabolism (p value < 0.0001) are significant and differentiable. Statistical analysis of measurable NMR metabolites indicated that at least two of the group means were significantly different for the metabolites alanine (p value = 0.0013), succinate (p value = 0.0001), lactate (p value = 0.0114), glycerophosphoethanolamine (p value = 0.015), and inorganic phosphate (p value = 0.0001). However, (13) C isotopic enrichment analysis of these metabolites revealed less than 50% isotopic enrichment with either stable [U-(13) C6 ]glucose metabolism or [U-(13) C5 ,(15) N2 ]glutamine. This may indicate the differential account of total metabolite pool versus de novo metabolites from a (13) C labeled substrate. The ultimate translation of these findings will be to determine putative enzyme activity via

  10. Validating the Incorporation of 13C and 15N in a Shorebird That Consumes an Isotopically Distinct Chemosymbiotic Bivalve

    PubMed Central

    van Gils, Jan A.; Ahmedou Salem, Mohamed Vall

    2015-01-01

    The wealth of field studies using stable isotopes to make inferences about animal diets require controlled validation experiments to make proper interpretations. Despite several pleas in the literature for such experiments, validation studies are still lagging behind, notably in consumers dwelling in chemosynthesis-based ecosystems. In this paper we present such a validation experiment for the incorporation of 13C and 15N in the blood plasma of a medium-sized shorebird, the red knot (Calidris canutus canutus), consuming a chemosymbiotic lucinid bivalve (Loripes lucinalis). Because this bivalve forms a symbiosis with chemoautotrophic sulphide-oxidizing bacteria living inside its gill, the bivalve is isotopically distinct from ‘normal’ bivalves whose food has a photosynthetic basis. Here we experimentally tested the hypothesis that isotope discrimination and incorporation dynamics are different when consuming such chemosynthesis-based prey. The experiment showed that neither the isotopic discrimination factor, nor isotopic turnover time, differed between birds consuming the chemosymbiotic lucinid and a control group consuming a photosynthesis-based bivalve. This was true for 13C as well as for 15N. However, in both groups the 15N discrimination factor was much higher than expected, which probably had to do with the birds losing body mass over the course of the experiment. PMID:26458005

  11. Deuterium isotope effects in 13C NMR spectra of trans-azobenzene

    NASA Astrophysics Data System (ADS)

    Vikić-Topić, Draz̆en; Novak, Predrag; Smrec̆ki, Vilko; Meić, Zlatko

    1997-06-01

    Deuterium isotope effects on 13C chemical shifts have been determined in a series of deuteriated trans-azobenzene isotopomers. The longest effect observed is the one over ten bonds ( 10Δ) in 4- 2H-isotopomer at C-4' atom amounting to 3.3 ppb. The magnitude and the extent of isotope effects in trans-azobenzene are related to those observed in isoelectronic and conformationally similar trans-stilbene. The sign alternation pattern of the long-range isotope effects in trans-azobenzene parallels that in isoelectronic trans-stilbene, cis-stilbene and trans-N-benzylideneaniline.

  12. 13C/12C isotope ratio MS analysis of testosterone, in chemicals and pharmaceutical preparations.

    PubMed

    de la Torre, X; González, J C; Pichini, S; Pascual, J A; Segura, J

    2001-02-01

    The 13C/12C ratio can be used to detect testosterone misuse in sport because (semi)-synthetic testosterone is supposed to have a 13C abundance different from that of endogenous natural human testosterone. In this study, gas chromatography/combustion isotope ratio mass spectrometry (GC/C/IRMS) analysis for the measurement of the delta 13C/1000 value of testosterone from esterified forms of 13 pharmaceutical preparations, six reagent grade chemicals and three bulk materials (raw materials used in pharmaceutical proarations) obtained world-wide was investigated after applying a strong acidic solvolytic procedure. Mean delta 13C/1000 values of non esterified (free) testosterone from chemicals and bulk materials of several testosterone esters were in the range: -25.91/-32.82/1000 while the value obtained for a (semi)-synthetic, reagent grade, free testosterone was -27.36/1000. The delta 13C/1000 results obtained for testosterone from the pharmaceuticals investigated containing testosterone esters were quite homogeneous (mean and S.D. of delta 13C/1000 values of free testosterone: 27.43 +/- 0.76/1000), being the range between -26.18 and -30.04/1000. Values described above were clearly different from those reported by several authors for endogenous natural human testosterone and its main metabolites excreted into the urine in non-consumers of testosterone (delta 13C/1000 range: from -21.3 to -24.4/1000), while they were similar to those of urinary testosterone and metabolites from individuals treated with testosterone esters and testosterone precursors. This finding justifies the fact that administration of these pharmaceutical formulations led to a statistical decrease of carbon isotope ratio of urinary testosterone and its main metabolites in treated subjects.

  13. OpenMebius: an open source software for isotopically nonstationary 13C-based metabolic flux analysis.

    PubMed

    Kajihata, Shuichi; Furusawa, Chikara; Matsuda, Fumio; Shimizu, Hiroshi

    2014-01-01

    The in vivo measurement of metabolic flux by (13)C-based metabolic flux analysis ((13)C-MFA) provides valuable information regarding cell physiology. Bioinformatics tools have been developed to estimate metabolic flux distributions from the results of tracer isotopic labeling experiments using a (13)C-labeled carbon source. Metabolic flux is determined by nonlinear fitting of a metabolic model to the isotopic labeling enrichment of intracellular metabolites measured by mass spectrometry. Whereas (13)C-MFA is conventionally performed under isotopically constant conditions, isotopically nonstationary (13)C metabolic flux analysis (INST-(13)C-MFA) has recently been developed for flux analysis of cells with photosynthetic activity and cells at a quasi-steady metabolic state (e.g., primary cells or microorganisms under stationary phase). Here, the development of a novel open source software for INST-(13)C-MFA on the Windows platform is reported. OpenMebius (Open source software for Metabolic flux analysis) provides the function of autogenerating metabolic models for simulating isotopic labeling enrichment from a user-defined configuration worksheet. Analysis using simulated data demonstrated the applicability of OpenMebius for INST-(13)C-MFA. Confidence intervals determined by INST-(13)C-MFA were less than those determined by conventional methods, indicating the potential of INST-(13)C-MFA for precise metabolic flux analysis. OpenMebius is the open source software for the general application of INST-(13)C-MFA.

  14. A twenty year record of the 13C isotopic composition of methane from Cape Meares, Oregon (1978-1998)

    NASA Astrophysics Data System (ADS)

    Teama, D.; Rice, A. L.

    2009-12-01

    Methane is an important greenhouse gas, second only to carbon dioxide in its radiative forcing since the industrial revolution. Over this time, the concentration of methane has increased by ~150% , primarily as a result of anthropogenic practices such as fossil fuel production, rice cultivation, biomass burning and waste management. In 1980s and through the 1990s, direct measurements of atmospheric methane from several global monitoring networks showed that the growth rate slowed from its previous ~1% per year climb. The year 2000 was the first year to record a negative annual growth. However, interannual variations are large and there remains considerable uncertainty regarding future trends in the global burden of methane due, in part, to poorly quantified trends of sources and sinks. One tool to better understand trends in sources and sinks of methane is through the use of stable isotopes. By comparing trends in the13C/12C and D/H content of atmospheric methane in time series to the isotopic signatures of sources, we can potentially disentangle trends in methane sources and sinks. Here we report preliminary measurements of 13C/12C ratios in atmospheric methane from a rare historic archive of whole air collected at Cape Meares, Oregon (45.5 °N, 124 °W) during the period 1978-1998 as part of the global monitoring program at the Oregon Graduate Institute. This unique dataset is the only direct time series of methane isotopic composition in the northern hemisphere prior to the late 1980s and early 1990s. The measurements reveal an increasing trend in the δ13C of methane consistent with more recent time series and firn air results (0.2-0.4‰ year-1). The increase in δ 13C over this time reflects an increase in fossil (~ -40‰) and pyrogenic (~ -25‰) sources of methane, which are enriched relative to biogenic sources (~ -60‰), and the relaxation of δ13C associated with isotopic disequilibrium. We discuss the long term trend in δ13C, its shorter term

  15. Comparing isotope signatures of prey fish: does gut removal affect δ13C or δ15N?

    USGS Publications Warehouse

    Chipps, Steven R.; Fincel, Mark J.; VanDeHey, Justin A.; Wuestewald, Andrew

    2011-01-01

    Stable isotope analysis is a quick and inexpensive method to monitor the effects of food web changes on aquatic communities. Traditionally, whole specimens have been used when determining isotope composition of prey fish or age-0 recreational fishes. However, gut contents of prey fish could potentially alter isotope composition of the specimen, especially when recent foraging has taken place or when the gut contains non-assimilated material that would normally pass through fishes undigested. To assess the impacts of gut content on prey fish isotope signatures, we examined the differences in isotopic variation of five prey fish species using whole fish, whole fish with the gut contents removed, and dorsal muscle only. We found significant differences in both δ15N and δ13C between the three tissue treatments. In most cases, muscle tissue was enriched compared to whole specimens or gut-removed specimens. Moreover, differences in mean δ15N within a species were up to 2‰ among treatments. This would result in a change of over half a trophic position (TP) based on a 3.4‰ increase per trophic level. However, there were no apparent relationships between tissue isotope values in fish with increased gut fullness (more prey tissue present). We suggest that muscle tissue should be used as the standard tissue for determining isotope composition of prey fish or age-0 recreational fishes, especially when determining enrichment for mixing models, calculating TP, or constructing aquatic food webs.

  16. Photobioreactor design for isotopic non-stationary 13C-metabolic flux analysis (INST 13C-MFA) under photoautotrophic conditions.

    PubMed

    Martzolff, Arnaud; Cahoreau, Edern; Cogne, Guillaume; Peyriga, Lindsay; Portais, Jean-Charles; Dechandol, Emmanuel; Le Grand, Fabienne; Massou, Stéphane; Gonçalves, Olivier; Pruvost, Jérémy; Legrand, Jack

    2012-12-01

    Adaptive metabolic behavior of photoautotrophic microorganisms toward genetic and environmental perturbations can be interpreted in a quantitative depiction of carbon flow through a biochemical reaction network using isotopic non-stationary (13) C-metabolic flux analysis (INST (13) C-MFA). To evaluate (13) C-metabolic flux maps for Chlamydomonas reinhardtii, an original experimental framework was designed allowing rapid, reliable collection of high-quality isotopomer data against time. It involved (i) a short-time (13) C labeling injection device based on mixing control in a torus-shaped photobioreactor with plug-flow hydrodynamics allowing a sudden step-change in the (13) C proportion in the substrate feed and (ii) a rapid sampling procedure using an automatic fast filtration method coupled to a manual rapid liquid nitrogen quenching step. (13) C-substrate labeling enrichment was controlled through the total dissolved inorganic carbon concentration in the pulsed solution. First results were obtained from steady-state continuous culture measurements allowing the characterization of the kinetics of label incorporation into light-limited growing cells cultivated in a photobioreactor operating at the maximal biomass productivity for an incident photon flux density of 200 µmol m(-2) s(-1). (13)C label incorporation was measured for 21 intracellular metabolites using IC-MS/MS in 58 samples collected across a labeling experiment duration of 7 min. The fastest labeling rate was observed for 2/3-phosphoglycerate with an apparent isotopic stationary state reached after 300 s. The labeling rate was consistent with the optimized mixing time of about 4.9 s inside the reactor and the shortest reliable sampling period assessed at 5 s.

  17. Quantitative analysis of deuterium using the isotopic effect on quaternary (13)C NMR chemical shifts.

    PubMed

    Darwish, Tamim A; Yepuri, Nageshwar Rao; Holden, Peter J; James, Michael

    2016-07-13

    Quantitative analysis of specifically deuterated compounds can be achieved by a number of conventional methods, such as mass spectroscopy, or by quantifying the residual (1)H NMR signals compared to signals from internal standards. However, site specific quantification using these methods becomes challenging when dealing with non-specifically or randomly deuterated compounds that are produced by metal catalyzed hydrothermal reactions in D2O, one of the most convenient deuteration methods. In this study, deuterium-induced NMR isotope shifts of quaternary (13)C resonances neighboring deuterated sites have been utilized to quantify the degree of isotope labeling of molecular sites in non-specifically deuterated molecules. By probing (13)C NMR signals while decoupling both proton and deuterium nuclei, it is possible to resolve (13)C resonances of the different isotopologues based on the isotopic shifts and the degree of deuteration of the carbon atoms. We demonstrate that in different isotopologues, the same quaternary carbon, neighboring partially deuterated carbon atoms, are affected to an equal extent by relaxation. Decoupling both nuclei ((1)H, (2)H) resolves closely separated quaternary (13)C signals of the different isotopologues, and allows their accurate integration and quantification under short relaxation delays (D1 = 1 s) and hence fast accumulative spectral acquisition. We have performed a number of approaches to quantify the deuterium content at different specific sites to demonstrate a convenient and generic analysis method for use in randomly deuterated molecules, or in cases of specifically deuterated molecules where back-exchange processes may take place during work up.

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

    PubMed

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

    2015-06-03

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

  19. Measurement of position-specific 13C isotopic composition of propane at the nanomole level

    NASA Astrophysics Data System (ADS)

    Gilbert, Alexis; Yamada, Keita; Suda, Konomi; Ueno, Yuichiro; Yoshida, Naohiro

    2016-03-01

    We have developed a novel method for analyzing intramolecular carbon isotopic distribution of propane as a potential new tracer of its origin. The method is based on on-line pyrolysis of propane followed by analysis of carbon isotope ratios of the pyrolytic products methane, ethylene and ethane. Using propane samples spiked with 13C at the terminal methyl carbon, we characterize the origin of the pyrolytic fragments. We show that the exchange between C-atoms during the pyrolytic process is negligible, and thus that relative intramolecular isotope composition can be calculated. Preliminary data from 3 samples show that site-preference (SP) values, defined as the difference of δ13C values between terminal and sub-terminal C-atom positions of propane, range from -1.8‰ to -12.9‰. In addition, SP value obtained using our method for a thermogenic natural gas sample is consistent with that expected from theoretical models of thermal cracking, suggesting that the isotope fractionation associated with propane pyrolysis is negligible. The method will provide novel insights into the characterization of the origin of propane and will help better understand the biogeochemistry of natural gas deposits.

  20. Understanding carbon isotope behaviour during combustion processes: a pre-requisite to using d13C in the field of air pollution.

    NASA Astrophysics Data System (ADS)

    Negrel, P.; Widory, D.

    2006-12-01

    Recent studies have demonstrated the effectiveness of stable isotopes in the field of air pollution research, especially their success in clearly discriminating the different sources of pollution in urban environments, and in tracing their respective impacts for a given sampling location. Among them, carbon isotopes have been used to track the origin of both gases (i.e. CO2; Widory &Javoy, 2003) and particulate matter (i.e. PM2 .5 and PM10; Widory et al., 2004). But understanding the carbon isotope behaviour that leads to this discrimination during combustion processes is a pre-requisite to using them as tracers of pollution sources in the atmosphere. d13C in fuels has been extensively used as an indicator of the processes leading to the generation of their parent crude-oil. Here, we isotopically characterise fuels and combustibles sold in Paris (France), and characterise the isotopic relations existing with their combustion by-products, i.e. gases (CO2) and particles (bulk carbon). Results show that d13C in fuels is clearly related to their physical state, with natural gas being strongly depleted in 13C while coal yields the highest d13C, and liquid fuels display intermediate values. This relation is also valid for exhaust gases, though d13C values of combustion particles form a homogeneous range within which no clear distinction is observed. Combustion processes are accompanied by carbon-isotope fractionation resulting from the combustion being incomplete. Carbon-isotope fractionation is strictly negative ( 1.3‰) during the formation of combustion gases, but generally positive in particle formation even if values close to zero are observed. This study helps understanding the processes leading to the d13C discrimination observed in pollution sources' exhausts, and definitely validates the use of carbon isotopes as tracers of atmospheric pollution.

  1. [Stable isotopes of carbon and nitrogen in soil ecological studies].

    PubMed

    Tiunov, A V

    2007-01-01

    The development of stable isotope techniques is one of the main methodological advances in ecology of the last decades of the 20th century. Many biogeochemical processes are accompanied by changes in the ratio between stable isotopes of carbon and nitrogen (12C/13C and 14N/15N), which allows different ecosystem components and different ecosystems to be distinguished by their isotopic composition. Analysis of isotopic composition makes it possible to trace matter and energy flows through biological systems and to evaluate the rate of many ecological processes. The main concepts and methods of stable isotope ecology and patterns of stable isotope fractionation during organic matter decomposition are considered with special emphasis on the fractionation of isotopes in food chains and the use of stable isotope studies of trophic relationships between soil animals in the field.

  2. Aspects regarding at 13C isotope separation column control using Petri nets system

    NASA Astrophysics Data System (ADS)

    Boca, M. L.; Ciortea, M. E.

    2015-11-01

    This paper is intended to show that Petri nets can be also applicable in the chemical industry. It used linear programming, modeling underlying Petri nets, especially discrete event systems for isotopic separation, the purpose of considering and control events in real-time through graphical representations. In this paper it is simulate the control of 13C Isotope Separation column using Petri nets. The major problem with 13C comes from the difficulty of obtaining it and raising its natural fraction. Carbon isotopes can be obtained using many methods, one of them being the cryogenic distillation of carbon monoxide. Some few aspects regarding operating conditions and the construction of such cryogenic plants are known today, and even less information are available as far as the separation process modeling and control are concerned. In fact, the efficient control of the carbon monoxide distillation process represents a necessity for large-scale 13C production. Referring to a classic distillation process, some models for carbon isotope separation have been proposed, some based on mass, component and energy balance equations, some on the nonlinear wave theory or the Cohen equations. For modeling the system it was used Petri nets because in this case it is deal with discrete event systems. In use of the non-timed and with auxiliary times Petri model, the transport stream was divided into sections and these sections will be analyzed successively. Because of the complexity of the system and the large amount of calculations required it was not possible to analyze the system as a unitary whole. A first attempt to model the system as a unitary whole led to the blocking of the model during simulation, because of the large processing times.

  3. Carbon isotope ratio (13C/12C) of pine honey and detection of HFCS adulteration.

    PubMed

    Çinar, Serap B; Ekşi, Aziz; Coşkun, İlknur

    2014-08-15

    Carbon isotope ratio ((13)C/(12)C=δ(13)C) of 100 pine honey samples collected from 9 different localities by Mugla region (Turkey) in years 2006, 2007 and 2008 were investigated. The δ(13)Cprotein value of honey samples ranged between -23.7 and -26.6‰, while the δ(13)Choney value varied between -22.7 and -27‰. For 90% of the samples, the difference in the C isotope ratio of protein and honey fraction (δ(13)Cpro-δ(13)Chon) was -1.0‰ and/or higher. Therefore, it can be said that the generally anticipated minimum value of C isotope difference (-1.0‰) for honey is also valid for pine honey. On the other hand, C4 sugar value (%), which was calculated from the δ(13)Cpro-δ(13)Chon difference, was found to be linearly correlated with the amount of adulterant (HFCS) in pine honey. These results indicate that C4 sugar value is a powerful criteria for detecting HFCS adulteration in pine honey. The δ(13)Choney and δ(13)Cprotein-δ(13)Choney values of the samples did not show any significant differences in terms of both year and locality (P>0.05), while the δ(13)Cprotein values showed significant differences due to year (P<0.05) but not due to locality (P>0.05).

  4. Affordable uniform isotope labeling with (2)H, (13)C and (15)N in insect cells.

    PubMed

    Sitarska, Agnieszka; Skora, Lukasz; Klopp, Julia; Roest, Susan; Fernández, César; Shrestha, Binesh; Gossert, Alvar D

    2015-06-01

    For a wide range of proteins of high interest, the major obstacle for NMR studies is the lack of an affordable eukaryotic expression system for isotope labeling. Here, a simple and affordable protocol is presented to produce uniform labeled proteins in the most prevalent eukaryotic expression system for structural biology, namely Spodoptera frugiperda insect cells. Incorporation levels of 80% can be achieved for (15)N and (13)C with yields comparable to expression in full media. For (2)H,(15)N and (2)H,(13)C,(15)N labeling, incorporation is only slightly lower with 75 and 73%, respectively, and yields are typically twofold reduced. The media were optimized for isotope incorporation, reproducibility, simplicity and cost. High isotope incorporation levels for all labeling patterns are achieved by using labeled algal amino acid extracts and exploiting well-known biochemical pathways. The final formulation consists of just five commercially available components, at costs 12-fold lower than labeling media from vendors. The approach was applied to several cytosolic and secreted target proteins.

  5. Deuterium isotope effect on 13C chemical shifts of tetrabutylammonium salts of Schiff bases amino acids.

    PubMed

    Rozwadowski, Z

    2006-09-01

    Deuterium isotope effects on 13C chemical shift of tetrabutylammonium salts of Schiff bases, derivatives of amino acids (glycine, L-alanine, L-phenylalanine, L-valine, L-leucine, L-isoleucine and L-methionine) and various ortho-hydroxyaldehydes in CDCl3 have been measured. The results have shown that the tetrabutylammonium salts of the Schiff bases amino acids, being derivatives of 2-hydroxynaphthaldehyde and 3,5-dibromosalicylaldehyde, exist in the NH-form, while in the derivatives of salicylaldehyde and 5-bromosalicylaldehyde a proton transfer takes place. The interactions between COO- and NH groups stabilize the proton-transferred form through a bifurcated intramolecular hydrogen bond.

  6. Stable Water Use Efficiency of Tibetan Alpine Meadows in Past Half Century: Evidence from Wool δ13C Values.

    PubMed

    Yang, Hao; He, Nianpeng; He, Yongtao; Li, Shenggong; Shi, Peili; Zhang, Xianzhou

    2015-01-01

    Understanding the influences of climatic changes on water use efficiency (WUE) of Tibetan alpine meadows is important for predicting their long-term net primary productivity (NPP) because they are considered very sensitive to climate change. Here, we collected wool materials produced from 1962 to 2010 and investigated the long-term WUE of an alpine meadow in Tibet on basis of the carbon isotope values of vegetation (δ13Cveg). The values of δ13Cveg decreased by 1.34‰ during 1962-2010, similar to changes in δ13C values of atmospheric CO2. Carbon isotope discrimination was highly variable and no trend was apparent in the past half century. Intrinsic water use efficiency (Wi) increased by 18 μmol·mol-1 (approximately 23.5%) during 1962-2010 because the increase in the intercellular CO2 concentration (46 μmol·mol-1) was less than that in the atmospheric CO2 concentration (Ca, 73 μmol·mol-1). In addition, Wi increased significantly with increasing growing season temperature and Ca. However, effective water use efficiency (We) remained relatively stable, because of increasing vapor pressure deficit. Ca, precipitation, and growing season temperature collectively explained 45% of the variation of We. Our findings indicate that the We of alpine meadows in the Tibetan Plateau remained relatively stable by physiological adjustment to elevated Ca and growing season temperature. These findings improve our understanding and the capacity to predict NPP of these ecosystems under global change scenarios.

  7. Stable isotope composition of human fingernails from Slovakia.

    PubMed

    Grolmusová, Zuzana; Rapčanová, Anna; Michalko, Juraj; Čech, Peter; Veis, Pavel

    2014-10-15

    Stable isotope composition of human fingernails has proven to be useful for documenting human dietary information and geographical patterns in archeological, forensic, anthropological and biological studies. Therefore, it is of interest to detect all factors influencing the stable isotopic composition in the certain regions in the world. Carbon and nitrogen isotope data of human fingernail keratin from 52 individuals from Slovakia were reported in this study. The online combustion and continuous flow isotope-ratio mass spectrometer Delta V Advantage was used for δ(13)C and δ(15)N analysis of fingernail keratin samples from 24 vegetarian and 28 omnivorous individuals. A group of people with frequent meat consumption showed enrichment in (13)C and (15)N isotopes in fingernails. A similar trend was observed with increasing seafood in an individual's diet. Moreover a significant difference was revealed between smokers and nonsmokers for both δ(13)C and δ(15)N values. These data were compared to previously published δ(13)C and δ(15)N fingernail values from across the globe. This study brings new information on the stable isotope signature of individuals from Slovakia and characterizes the Central European region for the first time. The stable isotope composition of fingernails is influenced by the frequency of meat and seafood consumption as well as smoking.

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

    SciTech Connect

    McConnaughey, T. )

    1989-01-01

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

  9. 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

  10. Optimization of automated gas sample collection and isotope ratio mass spectrometric analysis of delta(13)C of CO(2) in air.

    PubMed

    Zeeman, Matthias J; Werner, Roland A; Eugster, Werner; Siegwolf, Rolf T W; Wehrle, Günther; Mohn, Joachim; Buchmann, Nina

    2008-12-01

    The application of (13)C/(12)C in ecosystem-scale tracer models for CO(2) in air requires accurate measurements of the mixing ratios and stable isotope ratios of CO(2). To increase measurement reliability and data intercomparability, as well as to shorten analysis times, we have improved an existing field sampling setup with portable air sampling units and developed a laboratory setup for the analysis of the delta(13)C of CO(2) in air by isotope ratio mass spectrometry (IRMS). The changes consist of (a) optimization of sample and standard gas flow paths, (b) additional software configuration, and (c) automation of liquid nitrogen refilling for the cryogenic trap. We achieved a precision better than 0.1 per thousand and an accuracy of 0.11 +/- 0.04 per thousand for the measurement of delta(13)C of CO(2) in air and unattended operation of measurement sequences up to 12 h.

  11. 13C and 15N natural isotope abundance reflects breast cancer cell metabolism

    NASA Astrophysics Data System (ADS)

    Tea, Illa; Martineau, Estelle; Antheaume, Ingrid; Lalande, Julie; Mauve, Caroline; Gilard, Francoise; Barillé-Nion, Sophie; Blackburn, Anneke C.; Tcherkez, Guillaume

    2016-09-01

    Breast cancer is the most common cancer in women worldwide. Despite the information provided by anatomopathological assessment and molecular markers (such as receptor expression ER, PR, HER2), breast cancer therapies and prognostics depend on the metabolic properties of tumor cells. However, metabolomics have not provided a robust and congruent biomarker yet, likely because individual metabolite contents are insufficient to encapsulate all of the alterations in metabolic fluxes. Here, we took advantage of natural 13C and 15N isotope abundance to show there are isotopic differences between healthy and cancer biopsy tissues or between healthy and malignant cultured cell lines. Isotope mass balance further suggests that these differences are mostly related to lipid metabolism, anaplerosis and urea cycle, three pathways known to be impacted in malignant cells. Our results demonstrate that the isotope signature is a good descriptor of metabolism since it integrates modifications in C partitioning and N excretion altogether. Our present study is thus a starting point to possible clinical applications such as patient screening and biopsy characterization in every cancer that is associated with metabolic changes.

  12. 13C and 15N natural isotope abundance reflects breast cancer cell metabolism

    PubMed Central

    Tea, Illa; Martineau, Estelle; Antheaume, Ingrid; Lalande, Julie; Mauve, Caroline; Gilard, Francoise; Barillé-Nion, Sophie; Blackburn, Anneke C.; Tcherkez, Guillaume

    2016-01-01

    Breast cancer is the most common cancer in women worldwide. Despite the information provided by anatomopathological assessment and molecular markers (such as receptor expression ER, PR, HER2), breast cancer therapies and prognostics depend on the metabolic properties of tumor cells. However, metabolomics have not provided a robust and congruent biomarker yet, likely because individual metabolite contents are insufficient to encapsulate all of the alterations in metabolic fluxes. Here, we took advantage of natural 13C and 15N isotope abundance to show there are isotopic differences between healthy and cancer biopsy tissues or between healthy and malignant cultured cell lines. Isotope mass balance further suggests that these differences are mostly related to lipid metabolism, anaplerosis and urea cycle, three pathways known to be impacted in malignant cells. Our results demonstrate that the isotope signature is a good descriptor of metabolism since it integrates modifications in C partitioning and N excretion altogether. Our present study is thus a starting point to possible clinical applications such as patient screening and biopsy characterization in every cancer that is associated with metabolic changes. PMID:27678172

  13. Ca and Mg isotope constraints on the origin of Earth's deepest δ13 C excursion

    NASA Astrophysics Data System (ADS)

    Husson, Jon M.; Higgins, John A.; Maloof, Adam C.; Schoene, Blair

    2015-07-01

    Understanding the extreme carbon isotope excursions found in carbonate rocks of the Ediacaran Period (635-541 Ma), where δ13 C of marine carbonates (δ13 Ccarb) reach their minimum (- 12 ‰) for Earth history, is one of the most vexing problems in Precambrian geology. Known colloquially as the 'Shuram' excursion, the event has been interpreted by many as a product of a profoundly different Ediacaran carbon cycle. More recently, diagenetic processes have been invoked, with the very negative δ13 C values of Ediacaran carbonates explained via meteoric alteration, late-stage burial diagenesis or growth of authigenic carbonates in the sediment column, thus challenging models which rely upon a dramatically changing redox state of the Ediacaran oceans. Here we present 257 δ 44 / 40 Ca and 131 δ26 Mg measurements, along with [Mg], [Mn] and [Sr] data, from carbonates of the Ediacaran-aged Wonoka Formation (Fm.) of South Australia to bring new isotope systems to bear on understanding the 'Shuram' excursion. Data from four measured sections spanning the basin reveal stratigraphically coherent trends, with variability of ∼1.5‰ in δ26 Mg and ∼1.2‰ in δ 44 / 40 Ca. This Ca isotope variability dwarfs the 0.2-0.3 ‰ change seen coeval with the Permian-Triassic mass extinction, the largest recorded in the rock record, and is on par with putative changes in the δ 44 / 40 Ca value of seawater seen over the Phanerozoic Eon. Changes in both isotopic systems are too large to explain with changes in the isotopic composition of Ca and Mg in global seawater given modern budgets and residence times, and thus must be products of alternative processes. Relationships between δ 44 / 40 Ca and [Sr] and δ26 Mg and [Mg] are consistent with mineralogical control (e.g., aragonite vs. calcite, limestone vs. dolostone) on calcium and magnesium isotope variability. The most pristine samples in the Wonoka dataset, preserving Sr concentrations (in the 1000s of ppm range) and δ 44 / 40

  14. Metabolic Flux Elucidation for Large-Scale Models Using 13C Labeled Isotopes

    PubMed Central

    Suthers, Patrick F.; Burgard, Anthony P.; Dasika, Madhukar S.; Nowroozi, Farnaz; Van Dien, Stephen; Keasling, Jay D.; Maranas, Costas D.

    2007-01-01

    A key consideration in metabolic engineering is the determination of fluxes of the metabolites within the cell. This determination provides an unambiguous description of metabolism before and/or after engineering interventions. Here, we present a computational framework that combines a constraint-based modeling framework with isotopic label tracing on a large-scale. When cells are fed a growth substrate with certain carbon positions labeled with 13C, the distribution of this label in the intracellular metabolites can be calculated based on the known biochemistry of the participating pathways. Most labeling studies focus on skeletal representations of central metabolism and ignore many flux routes that could contribute to the observed isotopic labeling patterns. In contrast, our approach investigates the importance of carrying out isotopic labeling studies using a more comprehensive reaction network consisting of 350 fluxes and 184 metabolites in Escherichia coli including global metabolite balances on cofactors such as ATP, NADH, and NADPH. The proposed procedure is demonstrated on an E. coli strain engineered to produce amorphadiene, a precursor to the anti-malarial drug artemisinin. The cells were grown in continuous culture on glucose containing 20% [U-13C]glucose; the measurements are made using GC-MS performed on 13 amino acids extracted from the cells. We identify flux distributions for which the calculated labeling patterns agree well with the measurements alluding to the accuracy of the network reconstruction. Furthermore, we explore the robustness of the flux calculations to variability in the experimental MS measurements, as well as highlight the key experimental measurements necessary for flux determination. Finally, we discuss the effect of reducing the model, as well as shed light onto the customization of the developed computational framework to other systems. PMID:17632026

  15. Nicotine, acetanilide and urea multi-level 2H-, 13C- and 15N-abundance reference materials for continuous-flow isotope ratio mass spectrometry.

    PubMed

    Schimmelmann, Arndt; Albertino, Andrea; Sauer, Peter E; Qi, Haiping; Molinie, Roland; Mesnard, François

    2009-11-01

    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 delta values of these reference materials should bracket the isotopic range of samples with unknown delta 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 delta13C and delta15N, 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: delta2H(nicotine) -162 to -45 per thousand, delta13C(nicotine) -30.05 to +7.72 per thousand, delta15N(nicotine) -6.03 to +33.62 per thousand; delta15N(acetanilide) +1.18 to +40.57 per thousand; delta13C(urea) -34.13 to +11.71 per thousand, delta15N(urea) +0.26 to +40.61 per thousand (recommended delta values refer to calibration with NBS 19, L-SVEC, IAEA-N-1, and IAEA-N-2). Nicotines fill a gap as

  16. Stable light isotope biogeochemistry of hydrothermal systems.

    PubMed

    Des Marais, D J

    1996-01-01

    The stable isotopic composition of the elements O, H, S and C in minerals and other chemical species can indicate the existence, extent, conditions and the processes (including biological activity) of hydrothermal systems. Hydrothermal alteration of the 18O/16O and D/H values of minerals can be used to detect fossil systems and delineate their areal extent. Water-rock interactions create isotopic signatures which indicate fluid composition, temperature, water-rock ratios, etc. The 18O/16O values of silica and carbonate deposits tend to increase with declining temperature and thus help to map thermal gradients. Measurements of D/H values can help to decipher the origin(s) of hydrothermal fluids. The 34S/32S and 13C/12C values of fluids and minerals reflect the origin of the S and C as well as oxygen fugacities and key redox processes. For example, a wide range of 34S/32S values which are consistent with equilibration below 100 degrees C between sulfide and sulfate can be attributed to sulfur metabolizing bacteria. Depending on its magnitude, the difference in the 13C/12C value of CO2 and carbonates versus organic carbon might be attributed either to equilibrium at hydrothermal temperatures or, if the difference exceeds 1% (10/1000), to organic biosynthesis. Along the thermal gradients of thermal spring outflows, the 13C/12C value of carbonates and 13C-depleted microbial organic carbon increases, principally due to the outgassing of relatively 13C-depleted CO2.

  17. 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

  18. Measurement of insulin sensitivity indices using 13C-glucose and gas chromatography/combustion/isotope ratio mass spectrometry.

    PubMed

    Clapperton, Allan T; Coward, W Andrew; Bluck, Leslie J C

    2002-01-01

    Important aspects of glucose metabolism can be quantified by using the minimal model of glucose kinetics to interpret the results of intravenous glucose tolerance tests. The power of this methodology can be greatly increased by the addition of stable isotopically labelled tracer to the glucose bolus dose. This allows the separation of glucose disposal from endogenous glucose production and also increases the precision of the estimates of the physiological parameters measured. Until now the tracer of choice has been deuteriated glucose and the analytical technique has been gas chromatography/mass spectrometry (GC/MS). The consequence of this choice is that nearly 2 g of labelled material are needed and this makes the test expensive. We have investigated the use of (13)C-labelled glucose as the tracer in combination with gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) as the analytical technique. This methodology offers superior analytical precision when compared with the conventional method and so the amount of tracer used, and hence the cost, can be reduced considerably. Healthy non-obese male volunteers were recruited for a standard intravenous glucose tolerance test (IVGTT) protocol but 6,6-(2)H-glucose and 1-(13)C-glucose were administered simultaneously. Tracer/tracee ratios were derived from isotope ratio measurements of plasma glucose using both GC/MS and GC/C/IRMS. The results of these determinations indicated that the two tracers behaved identically under the test protocol. The combination of these results with plasma glucose and insulin concentration data allowed determination of the minimal model parameters S*g and S*i. The parameter relating to insulin-assisted glucose disposal, S*i, was found to be the same in the two techniques, but this was not the case for the non-insulin-dependent parameter S*g.

  19. Stable isotopes in obesity research.

    PubMed

    Dolnikowski, Gregory G; Marsh, Julian B; Das, Sai Krupa; Welty, Francine K

    2005-01-01

    Obesity is recognized as a major public health problem. Obesity is a multifactorial disease and is often associated with a wide range of comorbidities including hypertension, non-insulin dependent (Type II) diabetes mellitus, and cardiovascular disease, all of which contribute to morbidity and mortality. This review deals with stable isotope mass spectrometric methods and the application of stable isotopes to metabolic studies of obesity. Body composition and total energy expenditure (TEE) can be measured by mass spectrometry using stable isotope labeled water, and the metabolism of protein, lipid, and carbohydrate can be measured using appropriate labeled tracer molecules.

  20. Stable isotopic characterisation of francolite formation

    NASA Astrophysics Data System (ADS)

    McArthur, J. M.; Benmore, R. A.; Coleman, M. L.; Soldi, C.; Yeh, H.-W.; O'Brien, G. W.

    1986-02-01

    Stable isotopic data are presented for 112 samples of francolite from 18 separate phosphate deposits. Values of δ 13C and δ 34S in most offshore deposits suggest formation within oxic or suboxic environments either by carbonate replacement or direct precipitation of francolite from water of normal marine compositions. The exceptions are concretionary francolite from Namibia, which has an isotopic composition in keeping with its formation within organic-rich sediments, and that from offshore Morocco, which has an isotopic signature of the anoxic/suboxic interface. Onshore deposits from Jordan, Mexico, South Africa and, possibly, the Permian Phosphoria Formation in the western U.S.A., are substantially depleted in 18O: they appear to be too altered for deductions to be made about their environments of formation. In other onshore deposits which are unaltered, or minimally altered, the isotopic composition suggests that some formed within sulphate-reducing sediments (Sedhura, Morocco) whilst francolite from the Georgina Basin of Australia formed at the oxic/anoxic boundary, where oxidation of biogenic H 2S decreases the δ 34S of pore water. In general, pelletal samples show non-oxic isotopic signatures, whilst non-pelletal samples show oxic isotopic signatures, but samples from Namibia, Peru (Ica Plateau) and the Californian and Moroccan margins are exceptions to this rule. Morphology may therefore be a misleading indicator of francolite genesis as no definitive relation exists between phosphorite type and isotopic signature.

  1. Tellurium Stable Isotope Fractionation in Chondritic Meteorites

    NASA Astrophysics Data System (ADS)

    Fehr, M. A.; Hammond, S. J.; Parkinson, I. J.

    2014-09-01

    New Te double spike procedures were set up to obtain high-precision accurate Te stable isotope data. Tellurium stable isotope data for 16 chondrite falls are presented, providing evidence for significant Te stable isotope fractionation.

  2. Intrapopulation variation in gray wolf isotope (delta(15)N and delta(13)C) profiles: implications for the ecology of individuals.

    PubMed

    Urton, Erin J M; Hobson, Keith A

    2005-09-01

    Trophic relationships among organisms in terrestrial boreal ecosystems define ecological communities and are important in determining dynamics of energy flow and ecosystem function. We examined trophic relationships between the gray wolf (Canis lupus) and 18 mammalian species from the boreal forest of central Saskatchewan, Canada, using delta(13)C and delta(15)N stable isotope values measured in guard hair samples. Variance in isotope values for wolves and other carnivores was investigated as a proxy for variation in diet among individuals. Isosource, an isotopic source partitioning model, quantified the relative range in proportions of five most-likely prey items in the diets of wolves. The distribution of feasible contributions from each source was dominated by elk (Cervus elaphus; mean: 48%, range:11-75%), followed by white-tailed deer (Odocoileus virginianus; mean: 21%, range: 0-54%), moose (Alces alces; mean:14%, range: 0-41%), beaver (Castor canadensis; mean: 8%, range:0-25%) and snowshoe hare (Lepus americanus; mean: 8%, range: 0-24%). Despite social foraging, our results indicate highly variable diets among individuals and we discuss this in terms of individual versus group ecology of boreal wolves.

  3. Stable isotope analysis of breath using the optogalvanic effect

    NASA Astrophysics Data System (ADS)

    Murnick, Daniel E.; Colgan, M. J.; Lie, H. P.; Stoneback, D.

    1996-05-01

    A new technique based on the optogalvanic effect has been developed for the measurement of stable isotope ratios in the carbon dioxide of exhaled breath. Data obtained before and after ingestion of harmless stable isotope labeled compounds, metabolized to carbon dioxide, can be used for sensitive noninvasive diagnostics of various disease conditions. The technique uses the specificity of laser resonance spectroscopy and achieves sensitivity and accuracy typical of sophisticated isotope ratio mass spectrometers. Using fixed frequency carbon dioxide lasers, 13C/12C ratios can be determined with a precision of 2 ppm with 100 second averaging times. Multiple samples can be analyzed simultaneously providing real time continuous calibration. In a first application, analysis of 13C/12C ratios in exhaled human breath after ingestion of 13C labeled urea is being developed as a diagnostic for the bacterium H-pylori, known to be the causative agent for most peptic and duodenal ulcers.

  4. Evolution of E. coli on [U-13C]Glucose Reveals a Negligible Isotopic Influence on Metabolism and Physiology

    PubMed Central

    Sandberg, Troy E.; Long, Christopher P.; Gonzalez, Jacqueline E.; Feist, Adam M.; Antoniewicz, Maciek R.; Palsson, Bernhard O.

    2016-01-01

    13C-Metabolic flux analysis (13C-MFA) traditionally assumes that kinetic isotope effects from isotopically labeled compounds do not appreciably alter cellular growth or metabolism, despite indications that some biochemical reactions can be non-negligibly impacted. Here, populations of Escherichia coli were adaptively evolved for ~1000 generations on uniformly labeled 13C-glucose, a commonly used isotope for 13C-MFA. Phenotypic characterization of these evolved strains revealed ~40% increases in growth rate, with no significant difference in fitness when grown on either labeled (13C) or unlabeled (12C) glucose. The evolved strains displayed decreased biomass yields, increased glucose and oxygen uptake, and increased acetate production, mimicking what is observed after adaptive evolution on unlabeled glucose. Furthermore, full genome re-sequencing revealed that the key genetic changes underlying these phenotypic alterations were essentially the same as those acquired during adaptive evolution on unlabeled glucose. Additionally, glucose competition experiments demonstrated that the wild-type exhibits no isotopic preference for unlabeled glucose, and the evolved strains have no preference for labeled glucose. Overall, the results of this study indicate that there are no significant differences between 12C and 13C-glucose as a carbon source for E. coli growth. PMID:26964043

  5. Stable Water Use Efficiency of Tibetan Alpine Meadows in Past Half Century: Evidence from Wool δ13C Values

    PubMed Central

    Yang, Hao; He, Nianpeng; He, Yongtao; Li, Shenggong; Shi, Peili; Zhang, Xianzhou

    2015-01-01

    Understanding the influences of climatic changes on water use efficiency (WUE) of Tibetan alpine meadows is important for predicting their long-term net primary productivity (NPP) because they are considered very sensitive to climate change. Here, we collected wool materials produced from 1962 to 2010 and investigated the long-term WUE of an alpine meadow in Tibet on basis of the carbon isotope values of vegetation (δ13Cveg). The values of δ13Cveg decreased by 1.34‰ during 1962–2010, similar to changes in δ13C values of atmospheric CO2. Carbon isotope discrimination was highly variable and no trend was apparent in the past half century. Intrinsic water use efficiency (Wi) increased by 18 μmol·mol–1 (approximately 23.5%) during 1962–2010 because the increase in the intercellular CO2 concentration (46 μmol·mol–1) was less than that in the atmospheric CO2 concentration (Ca, 73 μmol·mol–1). In addition, Wi increased significantly with increasing growing season temperature and Ca. However, effective water use efficiency (We) remained relatively stable, because of increasing vapor pressure deficit. Ca, precipitation, and growing season temperature collectively explained 45% of the variation of We. Our findings indicate that the We of alpine meadows in the Tibetan Plateau remained relatively stable by physiological adjustment to elevated Ca and growing season temperature. These findings improve our understanding and the capacity to predict NPP of these ecosystems under global change scenarios. PMID:26660306

  6. Formation of nonextractable soil residues: A stable isotope approach

    SciTech Connect

    Richnow, H.H.; Eschenback, A.; Mahro, B.; Kaestner, M.; Annweiler, E.; Seifert, R.; Michaelis, W.

    1999-11-01

    Stable carbon isotopic measurements were employed to characterize the transformation of a {sup 13}C-labeled polycyclic aromatic hydrocarbon (PAH), anthracene, in a closed soil bioreactor system. The {sup 13}C-label was used to calculate a carbon mass balance including mineralization and the formation of nonextractable soil-bound residues. Similar results were obtained from {sup 13}C-labeled carbon and {sup 14}C-labeled carbon mass balance calculations for separate batch experiments with labeled anthracene. In concentration ranges typical for real PAH-contaminated sites, the sensitivity of the {sup 13}C tracer method meets the requirements of classical radiotracer experiments. Therefore, the authors balancing method based on stable isotope-labeled chemicals may supplement or substitute radiotracer experiments under many circumstances. One major advantage of using stable isotope-labeled tracers is the possible application in transformation studies where the use of radioactive substances is of environmental concern. The transformation of {sup 13}C-labeled PAH into nonextractable residues clearly depends on the metabolic activity of the soil microflora and occurs during an early phase of biodegradation. Successive contamination of the soil by anthracene leads to a progressive adaptation of the microflora to a complete mineralization of anthracene in the soil. The extent of residue formation is controlled by the capability of the microflora to degrade the contaminant. Results of long-term experiments indicate that nonextractable residues are relatively stable over time.

  7. Capillary Absorption Spectrometer for 13C Isotopic Composition of Pico to Subpico Molar Sample Quantities

    NASA Astrophysics Data System (ADS)

    Moran, J.; Kelly, J.; Sams, R.; Newburn, M.; Kreuzer, H.; Alexander, M.

    2011-12-01

    Quick incorporation of IR spectroscopy based isotope measurements into cutting edge research in biogeochemical cycling attests to the advantages of a spectroscopy versus mass spectrometry method for making some 13C measurements. The simple principles of optical spectroscopy allow field portability and provide a more robust general platform for isotope measurements. We present results with a new capillary absorption spectrometer (CAS) with the capability of reducing the sample size required for high precision isotopic measurements to the picomolar level and potentially the sub-picomolar level. This work was motivated by the minute sample size requirements for laser ablation isotopic studies of carbon cycling in microbial communities but has potential to be a valuable tool in other areas of biological and geological research. The CAS instrument utilizes a capillary waveguide as a sample chamber for interrogating CO2 via near IR laser absorption spectroscopy. The capillary's small volume (~ 0.5 mL) combined with propagation and interaction of the laser mode with the entire sample reduces sample size requirements to a fraction of that accessible with commercially available IR absorption including those with multi-pass or ring-down cavity systems. Using a continuous quantum cascade laser system to probe nearly adjacent rovibrational transitions of different isotopologues of CO2 near 2307 cm-1 permits sample measurement at low analyte pressures (as low as 2 Torr) for further sensitivity improvement. A novel method to reduce cw-fringing noise in the hollow waveguide is presented, which allows weak absorbance features to be studied at the few ppm level after averaging 1,000 scans in 10 seconds. Detection limits down to the 20 picomoles have been observed, a concentration of approximately 400 ppm at 2 Torr in the waveguide with precision and accuracy at or better than 1 %. Improvements in detection and signal averaging electronics and laser power and mode quality are

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

    PubMed

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

    2009-10-01

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

  9. Stable isotopic analysis of porcine, bovine, and ovine heparins.

    PubMed

    Jasper, John P; Zhang, Fuming; Poe, Russell B; Linhardt, Robert J

    2015-02-01

    The assessment of provenance of heparin is becoming a major concern for the pharmaceutical industry and its regulatory bodies. Batch-specific [carbon (δ(13) C), nitrogen (δ(15) N), oxygen (δ(18) O), sulfur (δ(34) S), and hydrogen (δD)] stable isotopic compositions of five different animal-derived heparins were performed. Measurements readily allowed their differentiation into groups and/or subgroups based on their isotopic provenance. Principle component analysis showed that a bivariate plot of δ(13) C and δ(18) O is the best single, bivariate plot that results in the maximum discrimination ability when only two stable isotopes are used to describe the variation in the data set. Stable isotopic analyses revealed that (1) stable isotope measurements on these highly sulfated polysaccharide (molecular weight ∼15 kDa) natural products ("biologics") were feasible; (2) in bivariate plots, the δ(13) C versus δ(18) O plot reveals a well-defined relationship for source differentiation of hogs raised in the United States from hogs raised in Europe and China; (3) the δD versus δ(18) O plot revealed the most well-defined relationship for source differentiation based on the hydrologic environmental isotopes of water (D/H and (18) O/(16) O); and (4) the δ(15) N versus δ(18) O and δ(34) S versus δ(18) O relationships are both very similar, possibly reflecting the food sources used by the different heparin producers.

  10. The Late Devonian Frasnian-Famennian (F/F) biotic crisis: Insights from δ13C carb, δ13C org and 87Sr / 86Sr isotopic systematics

    NASA Astrophysics Data System (ADS)

    Chen, Daizhao; Qing, Hairuo; Li, Renwei

    2005-06-01

    A severe biotic crisis occurred during the Late Devonian Frasnian-Famennian (F/F) transition (± 367 Myr). Here we present δ13C carb, δ13C org and 87Sr / 86Sr isotopic systematics, from identical samples of two sections across F/F boundary in South China, which directly demonstrate large and frequent climatic fluctuations (˜200 kyr) from warming to cooling during the F/F transition. These climate fluctuations are interpreted to have been induced initially by increased volcanic outgassing, and subsequent enhanced chemical weathering linked to the rapid expansion of vascular plants on land, which would have increased riverine delivery to oceans and primary bioproductivity, and subsequent burial of organic matter, thereby resulting in climate cooling. Such large and frequent climatic fluctuations, together with volcanic-induced increases in nutrient (e.g., biolimiting Fe), toxin (sulfide) and anoxic water supply, and subsequent enhanced riverine fluxes and microbial bloom, were likely responsible for the stepwise faunal demise of F/F biotic crisis.

  11. Using stable isotopes to determine seabird trophic relationships

    USGS Publications Warehouse

    Hobson, Keith A.; Piatt, John F.; Pitocchelli, Jay

    1994-01-01

    1. The stable isotopes of nitrogen (δ15N) and carbon (δ13C) were analysed in 22 species of marine birds from coastal waters of the northeast Pacific Ocean. Analyses confirm that stable nitrogen isotopes can predict seabird trophic positions.2. Based on δ15N analyses, seabird trophic-level inferences generally agree with those of conventional dietary studies, but suggest that lower trophic-level organisms are more important to several seabirds than was recognized previously.3. Stable-carbon isotope analysis may be a good indicator of inshore vs. offshore feeding preference.4. In general, stable-isotope analysis to determine trophic level offers many advantages over conventional dietary approaches since trophic inferences are based on time-integrated estimates of assimilated and not just ingested foods, and isotopic abundance represents a continuous variable that is amenable to statistical analysis.

  12. Design and Operation of a Continuous 13C and 15N Labeling Chamber for Uniform or Differential, Metabolic and Structural, Plant Isotope Labeling

    PubMed Central

    Soong, Jennifer L; Reuss, Dan; Pinney, Colin; Boyack, Ty; Haddix, Michelle L; Stewart, Catherine E; Cotrufo, M. Francesca

    2014-01-01

    Tracing rare stable isotopes from plant material through the ecosystem provides the most sensitive information about ecosystem processes; from CO2 fluxes and soil organic matter formation to small-scale stable-isotope biomarker probing. Coupling multiple stable isotopes such as 13C with 15N, 18O or 2H has the potential to reveal even more information about complex stoichiometric relationships during biogeochemical transformations. Isotope labeled plant material has been used in various studies of litter decomposition and soil organic matter formation1-4. From these and other studies, however, it has become apparent that structural components of plant material behave differently than metabolic components (i.e. leachable low molecular weight compounds) in terms of microbial utilization and long-term carbon storage5-7. The ability to study structural and metabolic components separately provides a powerful new tool for advancing the forefront of ecosystem biogeochemical studies. Here we describe a method for producing 13C and 15N labeled plant material that is either uniformly labeled throughout the plant or differentially labeled in structural and metabolic plant components. Here, we present the construction and operation of a continuous 13C and 15N labeling chamber that can be modified to meet various research needs. Uniformly labeled plant material is produced by continuous labeling from seedling to harvest, while differential labeling is achieved by removing the growing plants from the chamber weeks prior to harvest. Representative results from growing Andropogon gerardii Kaw demonstrate the system's ability to efficiently label plant material at the targeted levels. Through this method we have produced plant material with a 4.4 atom%13C and 6.7 atom%15N uniform plant label, or material that is differentially labeled by up to 1.29 atom%13C and 0.56 atom%15N in its metabolic and structural components (hot water extractable and hot water residual components

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

    PubMed

    Soong, Jennifer L; Reuss, Dan; Pinney, Colin; Boyack, Ty; Haddix, Michelle L; Stewart, Catherine E; Cotrufo, M Francesca

    2014-01-16

    Tracing rare stable isotopes from plant material through the ecosystem provides the most sensitive information about ecosystem processes; from CO2 fluxes and soil organic matter formation to small-scale stable-isotope biomarker probing. Coupling multiple stable isotopes such as (13)C with (15)N, (18)O or (2)H has the potential to reveal even more information about complex stoichiometric relationships during biogeochemical transformations. Isotope labeled plant material has been used in various studies of litter decomposition and soil organic matter formation(1-4). From these and other studies, however, it has become apparent that structural components of plant material behave differently than metabolic components (i.e. leachable low molecular weight compounds) in terms of microbial utilization and long-term carbon storage(5-7). The ability to study structural and metabolic components separately provides a powerful new tool for advancing the forefront of ecosystem biogeochemical studies. Here we describe a method for producing (13)C and (15)N labeled plant material that is either uniformly labeled throughout the plant or differentially labeled in structural and metabolic plant components. Here, we present the construction and operation of a continuous (13)C and (15)N labeling chamber that can be modified to meet various research needs. Uniformly labeled plant material is produced by continuous labeling from seedling to harvest, while differential labeling is achieved by removing the growing plants from the chamber weeks prior to harvest. Representative results from growing Andropogon gerardii Kaw demonstrate the system's ability to efficiently label plant material at the targeted levels. Through this method we have produced plant material with a 4.4 atom%(13)C and 6.7 atom%(15)N uniform plant label, or material that is differentially labeled by up to 1.29 atom%(13)C and 0.56 atom%(15)N in its metabolic and structural components (hot water extractable and hot water

  14. Stable Isotope Spectroscopy for Diagnostic Medicine

    NASA Astrophysics Data System (ADS)

    Murnick, D. E.

    2000-06-01

    Isotopic tracers have been used in medical research for more than fifty years. Radioactive isotopes have been most used because of the high detection efficiencies possible. With increased awareness of the effects of low level radiation and radioactive waste management problems, the need for safe non radioactive tracers has become apparent. Rare stable isotopes of biologically active elements can be used for metabolic and pharmacokinetic studies provided that both sufficient detection sensitivity can be achieved and reliable cost effective instruments can be developed. High resolution optical spectroscopic methods which can determine isotopic ratios with high precision and accuracy are viable for research and clinical use. The study of 13C/12C ratios in CO2 for breath test diagnostics will be described in detail. Using the laser optogalvonic effect with isotopic lasers a specific medical diagnostic for h-pylori infection, has recently received FDA approval. Opportunities exist to study D/H ratios in water and 18O/16O ratios in CO2 and water for basic metabolism diagnostics and 15N/14N ratios in urine for liver function and related studies.

  15. Isotopic (13C) response of ponderosa pine ecosystem respiration to atmospheric stress events

    NASA Astrophysics Data System (ADS)

    Bowling, D. R.; McDowell, N. G.; Anthoni, P. M.; Law, B. E.; Bond, B. J.; Ehleringer, J. R.

    2001-12-01

    The carbon isotopic composition of ecosystem respiration (\\delta13CR) reflects several biological and physical factors influencing ecosystem physiology. Recent experiments in several Oregon coniferous forests have shown a link between annual precipitation, short-term atmospheric moisture deficit, air temperature, and \\delta13CR. This link appears to be driven by changes in photosynthetic discrimination associated with changes in soil or atmospheric moisture deficit (or both), and suggests there can be substantial variation in \\delta13CRon a time scale of days. Our objective was to investigate the response of ecosystem respiration to the passage of synoptic-scale air masses and accompanying weather changes, to see if such short-term changes occur. We examined the carbon isotopic content of ecosystem respiration every night for 13 consecutive nights (summer 2001), at the Metolius AmeriFlux site, a 50-250 year old ponderosa pine forest in central Oregon, USA. Additionally, the 13C contents of the soil and branch components of the ecosystem respiration flux were measured with soil chambers and branch bags. Mean daytime atmospheric moisture deficit during this period ranged from minimal to very dry (0.36 to 3.3 kPa), and minimum nocturnal air temperature varied from 0.2 to 16.4 C. A single near-freezing event was followed by enriched \\delta13CR for several days afterwards, moderating the expected humidity response. \\delta13CR changed only marginally (-25.1 to -25.9 \\permil), but the soil and branch fluxes showed larger night-to-night variation (-23.8 to -25.3 and -23.5 to -26.4 \\permil, respectively). Based on preliminary analyses, both the soil flux and branch flux were more enriched in 13C than the whole-ecosystem flux, indicating an inconsistency in terms of mass conservation. Possible reasons for this contradiction will be discussed. These data will be further evaluated relative to meteorological and eddy flux data collected during the same time period.

  16. Stable Isotope Characterization of TICs/TIMs: Analytical Progress Report

    SciTech Connect

    Volpe, A M; Singleton, M J

    2009-06-05

    We measured twelve alkali cyanide samples that were also sent to ORNL and PNNL collaborators. While results indicate distinct {delta}{sup 13}C and {delta}{sup 15}N values that would be useful to signature studies, the alkali cyanides, especially NaCN, show chemical breakdown during storage that will influence forensic analysis. Carbon and nitrogen stable isotopic compositions of raw materials used to synthesis TETS were measured. Results indicate wide ranges in {delta}{sup 13}C and {delta}{sup 15}N values. Using these raw materials, LLNL scientists synthesized three batches of TETS following published procedures. Stable isotopic measurements of TETS synthesis products indicates nitrogen ({var_epsilon} {sup 15}N = -1.7 to -0.8) and carbon ({var_epsilon} {sup 13}C = -1.0 to -0.1) fractionation during production.

  17. Coral skeletal carbon isotopes13C and Δ14C) record the delivery of terrestrial carbon to the coastal waters of Puerto Rico

    USGS Publications Warehouse

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

    2011-01-01

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

  18. Coral skeletal carbon isotopes13C and Δ14C) record the delivery of terrestrial carbon to the coastal waters of Puerto Rico

    USGS Publications Warehouse

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

    2011-01-01

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

  19. Dissecting the mechanisms of a class of chemical glycosylation using primary 13C kinetic isotope effects

    NASA Astrophysics Data System (ADS)

    Huang, Min; Garrett, Graham E.; Birlirakis, Nicolas; Bohé, Luis; Pratt, Derek A.; Crich, David

    2012-08-01

    Although arguably the most important reaction in glycoscience, chemical glycosylations are among the least well understood of organic chemical reactions, resulting in an unnecessarily high degree of empiricism and a brake on rational development in this critical area. To address this problem, primary 13C kinetic isotope effects have now been determined for the formation of β- and α-manno- and glucopyranosides using a natural abundance NMR method. In contrast to the common current assumption, for three of the four cases studied the experimental and computed values are indicative of associative displacement of the intermediate covalent glycosyl trifluoromethanesulfonates. For the formation of the α-mannopyranosides, the experimentally determined KIE differs significantly from that computed for an associative displacement, which is strongly suggestive of a dissociative mechanism that approaches the intermediacy of a glycosyl oxocarbenium ion. The application of analogous experiments to other glycosylation systems should shed further light on their mechanisms and thus assist in the design of better reactions conditions with improved stereoselectivity.

  20. Dissecting the Mechanisms of a Class of Chemical Glycosylation Using Primary 13C Kinetic Isotope Effects

    PubMed Central

    Huang, Min; Garrett, Graham E.; Birlirakis, Nicolas; Bohé, Luis

    2012-01-01

    Although arguably the most important reaction in glycoscience, chemical glycosylations are among the least well understood of organic chemical reactions resulting in an unnecessarily high degree of empiricism and a brake on rational development in this critical area. To address this problem primary 13C kinetic isotope effects now have been determined for the formation of β- and α-manno- and glucopyranosides by a natural abundance NMR method. In contrast to the common current assumption, for three of the four cases studied the experimental values concur with those computed for associative displacement of the intermediate covalent glycosyl trifluoromethanesulfonates. For the formation of the α-mannopyranosides the experimentally determined KIE differs significantly from that computed for an associative displacement, which is strongly suggestive of a dissociative mechanism that approaches the intermediacy of a glycosyl oxocarbenium ion. The application of comparable experiments to other glycosylation systems should shed further light on their glycosylation mechanisms and thus assist in the design of better reactions conditions with improved stereoselectivity. PMID:22824899

  1. Use of isotope ratio mass spectrometry to detect doping with oral testosterone undecanoate: inter-individual variability of 13C/12C ratio.

    PubMed

    Baume, Norbert; Saudan, Christophe; Desmarchelier, Aurélien; Strahm, Emmanuel; Sottas, Pierre-Edouard; Bagutti, Carlo; Cauderay, Michel; Schumacher, Yorck Olaf; Mangin, Patrice; Saugy, Martial

    2006-05-01

    The metabolic effect of multiple oral testosterone undecanoate (TU) doses over 4 weeks was assessed in seven voluntary men. The protocol was designed to detect accumulation of the substance by choosing the appropriate spot urines collections time and to study the urinary clearance of the substance after weeks of treatment. Urines were analysed by a new GC/C/isotope ratio mass spectrometry (IRMS) method to establish the delta(13)C-values of testosterone metabolites (androsterone and etiocholanolone) together with an endogenous reference compound (16(5alpha)-androsten-3alpha-ol). The significant differences in inter-individual metabolism following TU intake was illustrated by large variations in delta(13)C-values of both T metabolites (maximum Deltadelta(13)C-values = 5.5 per thousand), as well as by very stable longitudinal T/E profiles and carbon isotopic ratios in the first hours following administration. According to T/E ratios and delta(13)C-values, the washout period after 80 mg TU intake was less than 48 h for all subjects and no accumulation phenomenon was observed upon chronic oral administration.

  2. Synthesis of isotopically labeled R- or S-[.sup.13C, .sup.2H] glycerols

    DOEpatents

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

    2008-01-22

    The present invention is directed to asymmetric chiral labeled glycerols including at least one chiral atom, from one to two .sup.13C atoms and from zero to four deuterium atoms bonded directly to a carbon atom, e.g., (2S) [1,2-.sup.13C.sub.2]glycerol and (2R) [1,2-.sup.13C.sub.2]glycerol, and to the use of such chiral glycerols in the preparation of labeled amino acids.

  3. 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

  4. 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.

  5. 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

  6. Stable isotopes in tree rings

    NASA Astrophysics Data System (ADS)

    McCarroll, Danny; Loader, Neil J.

    2004-04-01

    Stable isotopes in tree rings could provide palaeoclimate reconstructions with perfect annual resolution and statistically defined confidence limits. Recent advances make the approach viable for non-specialist laboratories. The relevant literature is, however, spread across several disciplines, with common problems approached in different ways. Here we provide the first overview of isotope dendroclimatology, explaining the underlying theory and describing the steps taken in building and interpreting isotope chronologies. Stable carbon isotopes record the balance between stomatal conductance and photosynthetic rate, dominated at dry sites by relative humidity and soil water status and at moist sites by summer irradiance and temperature. Stable oxygen and hydrogen isotopic ratios record source water, which contains a temperature signal, and leaf transpiration, controlled dominantly by vapour pressure deficit. Variable exchange with xylem (source) water during wood synthesis determines the relative strength of the source water and leaf enrichment signals. Producing long Holocene chronologies will require a change in emphasis towards processing very large numbers of samples efficiently, whilst retaining analytical precision. A variety of sample preparation and data treatment protocols have been used, some of which have a deleterious effect on the palaeoclimate signal. These are reviewed and suggestions made for a more standardised approach.

  7. Bayesian stable isotope mixing models

    EPA Science Inventory

    In this paper we review recent advances in Stable Isotope Mixing Models (SIMMs) and place them into an over-arching Bayesian statistical framework which allows for several useful extensions. SIMMs are used to quantify the proportional contributions of various sources to a mixtur...

  8. The stable isotope ecology of Pan in Uganda and beyond.

    PubMed

    Loudon, James E; Sandberg, Paul A; Wrangham, Richard W; Fahey, Babette; Sponheimer, Matt

    2016-10-01

    Stable isotope analysis has long been used to study the dietary ecology of living and fossil primates, and there has been increasing interest in using stable isotopes to study primate habitat use and anthropogenic impacts on non-human primates. Here, we examine the stable carbon and nitrogen isotope compositions of chimpanzees (Pan troglodytes) from seven communities in Uganda across a continuum of habitat structure (closed to more open) and access to anthropogenic resources (no reliance to heavy reliance). In general, the hair δ(13) C, but not δ(15) N, values of these communities vary depending on forest structure and degree of anthropogenic influence. When integrated with previously published hair δ(13) C and δ(15) N values for Pan, it is apparent that modern "savanna" and "forest" Pan form discrete clusters in carbon and nitrogen isotope space, although there are exceptions probably relating to microhabitat specialization. The combined dataset also reveals that Pan δ(13) C values (but not δ(15) N values) are inversely related to rainfall (r(2)  = 0.62). We converted Pan hair δ(13) C values to enamel equivalents and made comparisons to the fossil hominoids Sivapithecus sp., Gigantopithecus blacki, Ardipithecus ramidus, and Australopithecus anamensis. The δ(13) C values of the fossil hominins Ar. ramidus and Au. anamensis do not cluster with the δ(13) C values of modern Pan in "forest" habitats, or with fossil hominoids that are believed to have inhabited forests. Am. J. Primatol. 78:1070-1085, 2016. © 2016 Wiley Periodicals, Inc.

  9. Amino acid delta13C analysis of hair proteins and bone collagen using liquid chromatography/isotope ratio mass spectrometry: paleodietary implications from intra-individual comparisons.

    PubMed

    Raghavan, Maanasa; McCullagh, James S O; Lynnerup, Niels; Hedges, Robert E M

    2010-03-15

    We report a novel method for the chromatographic separation and measurement of stable carbon isotope ratios (delta(13)C) of individual amino acids in hair proteins and bone collagen using the LC-IsoLink system, which interfaces liquid chromatography (LC) with isotope ratio mass spectrometry (IRMS). This paper provides baseline separation of 15 and 13 of the 18 amino acids in bone collagen and hair proteins, respectively. We also describe an approach to analysing small hair samples for compound-specific analysis of segmental hair sections. The LC/IRMS method is applied in a historical context by the delta(13)C analysis of hair proteins and bone collagen recovered from six individuals from Uummannaq in Greenland. The analysis of hair and bone amino acids from the same individual, compared for the first time in this study, is of importance in palaeodietary reconstruction. If hair proteins can be used as a proxy for bone collagen at the amino acid level, this validates compound-specific isotope studies using hair as a model for palaeodietary reconstruction. Our results suggest that a small offset observed in the bulk delta(13)C values of the hair and bone samples may be attributed to two factors: (i) amino acid compositional differences between hair and bone proteins, and (ii) differential turnover rates of the tissues and the amino acid pools contributing to their synthesis. This application proposes that hair may be a useful complementary or alternative source of compound-specific paleodietary information.

  10. Stable isotopes may provide evidence for starvation in reptiles.

    PubMed

    McCue, Marshall D; Pollock, Erik D

    2008-08-01

    Previous studies have attempted to correlate stable isotope signatures of tissues with the nutritional condition of birds, mammals, fishes, and invertebrates. Unfortunately, very little is known about the relationship between food limitation and the isotopic composition of reptiles. We examined the effects that starvation has on delta13C and delta15N signatures in the tissues (excreta, carcass, scales, and claws) of six, distantly related squamate reptiles (gaboon vipers, Bitis gabonica; ball pythons, Python regius; ratsnakes, Elaphe obsoleta; boa constrictors, Boa constrictor; western diamondback rattlesnakes, Crotalus atrox, and savannah monitor lizards, Varanus exanthematicus). Analyses revealed that the isotopic composition of reptile carcasses did not change significantly in response to bouts of starvation lasting up to 168 days. In contrast, the isotopic signatures of reptile excreta became significantly enriched in 15N and depleted in 13C during starvation. The isotopic signatures of reptile scales and lizard claws were less indicative of starvation time than those of excreta. We discuss the physiological mechanisms that might be responsible for the starvation-induced changes in 13C and 15N signatures in the excreta, and present a mixing model to describe the shift in excreted nitrogen source pools (i.e. from a labile source pool to a nonlabile source pool) that apparently occurs during starvation in these animals. The results of this study suggest that naturally occurring stable isotopes might ultimately have some utility for characterizing nitrogen and carbon stress among free-living reptiles.

  11. 2H/(1)H and (13)C/(12)C isotope ratios of trans-anethole using gas chromatography-isotope ratio mass spectrometry.

    PubMed

    Bilke, Steffi; Mosandl, Armin

    2002-07-03

    Authenticity assessment of trans-anethole is deduced from (2)H/(1)H and (13)C/(12)C isotope ratios, determined by gas chromatography-isotope ratio mass spectrometry (GC-IRMS). For that purpose, self-prepared anise and fennel oils, and synthetic and "natural" samples of trans-anethole, as well as commercially available anise and fennel oils have been investigated. Authenticity ranges of (2)H/(1)H and (13)C/(12)C isotope ratios of trans-anethole were defined. Scope and limitations of the applied online GC-IRMS techniques are discussed.

  12. Stable isotope deltas: tiny, yet robust signatures in nature.

    PubMed

    Brand, Willi A; Coplen, Tyler B

    2012-09-01

    Although most of them are relatively small, stable isotope deltas of naturally occurring substances are robust and enable workers in anthropology, atmospheric sciences, biology, chemistry, environmental sciences, food and drug authentication, forensic science, geochemistry, geology, oceanography, and paleoclimatology to study a variety of topics. Two fundamental processes explain the stable isotope deltas measured in most terrestrial systems: isotopic fractionation and isotope mixing. Isotopic fractionation is the result of equilibrium or kinetic physicochemical processes that fractionate isotopes because of small differences in physical or chemical properties of molecular species having different isotopes. It is shown that the mixing of radioactive and stable isotope end members can be modelled to provide information on many natural processes, including (14)C abundances in the modern atmosphere and the stable hydrogen and oxygen isotopic compositions of the oceans during glacial and interglacial times. The calculation of mixing fractions using isotope balance equations with isotope deltas can be substantially in error when substances with high concentrations of heavy isotopes (e.g. (13)C, (2)H, and (18)O ) are mixed. In such cases, calculations using mole fractions are preferred as they produce accurate mixing fractions. Isotope deltas are dimensionless quantities. In the International System of Units (SI), these quantities have the unit 1 and the usual list of prefixes is not applicable. To overcome traditional limitations with expressing orders of magnitude differences in isotope deltas, we propose the term urey (symbol Ur), after Harold C. Urey, for the unit 1. In such a manner, an isotope delta value expressed traditionally as-25 per mil can be written as-25 mUr (or-2.5 cUr or-0.25 dUr; the use of any SI prefix is possible). Likewise, very small isotopic differences often expressed in per meg 'units' are easily included (e.g. either+0.015 ‰ or+15 per meg

  13. Stable isotope deltas: Tiny, yet robust signatures in nature

    USGS Publications Warehouse

    Brand, Willi A.; Coplen, Tyler B.

    2012-01-01

    Although most of them are relatively small, stable isotope deltas of naturally occurring substances are robust and enable workers in anthropology, atmospheric sciences, biology, chemistry, environmental sciences, food and drug authentication, forensic science, geochemistry, geology, oceanography, and paleoclimatology to study a variety of topics. Two fundamental processes explain the stable isotope deltas measured in most terrestrial systems: isotopic fractionation and isotope mixing. Isotopic fractionation is the result of equilibrium or kinetic physicochemical processes that fractionate isotopes because of small differences in physical or chemical properties of molecular species having different isotopes. It is shown that the mixing of radioactive and stable isotope end members can be modelled to provide information on many natural processes, including 14C abundances in the modern atmosphere and the stable hydrogen and oxygen isotopic compositions of the oceans during glacial and interglacial times. The calculation of mixing fractions using isotope balance equations with isotope deltas can be substantially in error when substances with high concentrations of heavy isotopes (e.g. 13C, 2H, and 18O ) are mixed. In such cases, calculations using mole fractions are preferred as they produce accurate mixing fractions. Isotope deltas are dimensionless quantities. In the International System of Units (SI), these quantities have the unit 1 and the usual list of prefixes is not applicable. To overcome traditional limitations with expressing orders of magnitude differences in isotope deltas, we propose the term urey (symbol Ur), after Harold C. Urey, for the unit 1. In such a manner, an isotope delta value expressed traditionally as−25 per mil can be written as−25 mUr (or−2.5 cUr or−0.25 dUr; the use of any SI prefix is possible). Likewise, very small isotopic differences often expressed in per meg ‘units’ are easily included (e.g. either+0.015 ‰ or+15 per meg

  14. Variations in growth, survival and carbon isotope composition (delta(13)C) among Pinus pinaster populations of different geographic origins.

    PubMed

    Correia, Isabel; Almeida, Maria Helena; Aguiar, Alexandre; Alía, Ricardo; David, Teresa Soares; Pereira, João Santos

    2008-10-01

    To evaluate differences in growth and adaptability of maritime pine (Pinus pinaster Ait.), we studied growth, polycyclism, needle tissue carbon isotope composition (delta(13)C) as an estimate of water-use efficiency (WUE) and survival of seven populations at 10 years of age growing in a performance trial at a provenance test site in Escaroupim, Portugal. Six populations were from relatively high rainfall sites in Portugal and southwestern France (Atlantic group), and one population was from a more arid Mediterranean site in Spain. There were significant differences between some populations in total height, diameter at breast height, delta(13)C of bulk needle tissue, polycyclism and survival. A population from central Portugal (Leiria, on the Atlantic coast) was the tallest and had the lowest delta(13)C. Overall, the variation in delta(13)C was better explained by the mean minimum temperatures of the coldest month than by annual precipitation at the place of origin. Analyses of the relationships between delta(13)C and growth or survival revealed a distinct pattern for the Mediterranean population, with low delta(13)C (and WUE) associated with the lowest growth potential and reduced survival. There were significant negative correlations between delta(13)C and height or survival in the Atlantic group. Variation in polycyclism was correlated with annual precipitation at the place of origin. Some Atlantic populations maintained a high growth potential while experiencing moderate water stress. A detailed knowledge of the relationships between growth, survival and delta(13)C in contrasting environments will enhance our ability to select populations for forestry or conservation.

  15. Controlling for anthropogenically induced atmospheric variation in stable carbon isotope studies

    USGS Publications Warehouse

    Long, E.S.; Sweitzer, R.A.; Diefenbach, D.R.; Ben-David, M.

    2005-01-01

    Increased use of stable isotope analysis to examine food-web dynamics, migration, transfer of nutrients, and behavior will likely result in expansion of stable isotope studies investigating human-induced global changes. Recent elevation of atmospheric CO2 concentration, related primarily to fossil fuel combustion, has reduced atmospheric CO2 ??13C (13C/12C), and this change in isotopic baseline has, in turn, reduced plant and animal tissue ??13C of terrestrial and aquatic organisms. Such depletion in CO2 ??13C and its effects on tissue ??13C may introduce bias into ??13C investigations, and if this variation is not controlled, may confound interpretation of results obtained from tissue samples collected over a temporal span. To control for this source of variation, we used a high-precision record of atmospheric CO2 ??13C from ice cores and direct atmospheric measurements to model modern change in CO2 ??13C. From this model, we estimated a correction factor that controls for atmospheric change; this correction reduces bias associated with changes in atmospheric isotopic baseline and facilitates comparison of tissue ??13C collected over multiple years. To exemplify the importance of accounting for atmospheric CO2 ??13C depletion, we applied the correction to a dataset of collagen ??13C obtained from mountain lion (Puma concolor) bone samples collected in California between 1893 and 1995. Before correction, in three of four ecoregions collagen ??13C decreased significantly concurrent with depletion of atmospheric CO2 ??13C (n ??? 32, P ??? 0.01). Application of the correction to collagen ??13C data removed trends from regions demonstrating significant declines, and measurement error associated with the correction did not add substantial variation to adjusted estimates. Controlling for long-term atmospheric variation and correcting tissue samples for changes in isotopic baseline facilitate analysis of samples that span a large temporal range. ?? Springer-Verlag 2005.

  16. Controlling for anthropogenically induced atmospheric variation in stable carbon isotope studies.

    PubMed

    Long, Eric S; Sweitzer, Richard A; Diefenbach, Duane R; Ben-David, Merav

    2005-11-01

    Increased use of stable isotope analysis to examine food-web dynamics, migration, transfer of nutrients, and behavior will likely result in expansion of stable isotope studies investigating human-induced global changes. Recent elevation of atmospheric CO2 concentration, related primarily to fossil fuel combustion, has reduced atmospheric CO2 delta13C (13C/12C), and this change in isotopic baseline has, in turn, reduced plant and animal tissue delta13C of terrestrial and aquatic organisms. Such depletion in CO2 delta13C and its effects on tissue delta13C may introduce bias into delta13C investigations, and if this variation is not controlled, may confound interpretation of results obtained from tissue samples collected over a temporal span. To control for this source of variation, we used a high-precision record of atmospheric CO2 delta13C from ice cores and direct atmospheric measurements to model modern change in CO2 delta13C. From this model, we estimated a correction factor that controls for atmospheric change; this correction reduces bias associated with changes in atmospheric isotopic baseline and facilitates comparison of tissue delta13C collected over multiple years. To exemplify the importance of accounting for atmospheric CO2 delta13C depletion, we applied the correction to a dataset of collagen delta13C obtained from mountain lion (Puma concolor) bone samples collected in California between 1893 and 1995. Before correction, in three of four ecoregions collagen delta13C decreased significantly concurrent with depletion of atmospheric CO2 delta13C (n > or = 32, P < or = 0.01). Application of the correction to collagen delta13C data removed trends from regions demonstrating significant declines, and measurement error associated with the correction did not add substantial variation to adjusted estimates. Controlling for long-term atmospheric variation and correcting tissue samples for changes in isotopic baseline facilitate analysis of samples that span a

  17. Identifying the African Wintering Grounds of Hybrid Flycatchers Using a Multi–Isotope (δ2H, δ13C, δ15N) Assignment Approach

    PubMed Central

    Van Wilgenburg, Steven L.; Hobson, Keith A.; Folmer, Eelke; Font, Laura; Klaassen, Marcel

    2014-01-01

    Migratory routes and wintering grounds can have important fitness consequences, which can lead to divergent selection on populations or taxa differing in their migratory itinerary. Collared (Ficedula albicollis) and pied (F. hypoleuca) flycatchers breeding in Europe and wintering in different sub-Saharan regions have distinct migratory routes on the eastern and western sides of the Sahara desert, respectively. In an earlier paper, we showed that hybrids of the two species did not incur reduced winter survival, which would be expected if their migration strategy had been a mix of the parent species' strategies potentially resulting in an intermediate route crossing the Sahara desert to different wintering grounds. Previously, we compared isotope ratios and found no significant difference in stable-nitrogen isotope ratios (δ15N) in winter-grown feathers between the parental species and hybrids, but stable-carbon isotope ratios (δ13C) in hybrids significantly clustered only with those of pied flycatchers. We followed up on these findings and additionally analyzed the same feathers for stable-hydrogen isotope ratios (δ2H) and conducted spatially explicit multi-isotope assignment analyses. The assignment results overlapped with presumed wintering ranges of the two species, highlighting the efficacy of the method. In contrast to earlier findings, hybrids clustered with both parental species, though most strongly with pied flycatcher. PMID:24847717

  18. Use of Stable Isotope Technologies to Accomplish In-Situ Biological Remediation of Explosives

    DTIC Science & Technology

    2011-03-30

    Use of Stable Isotope Technologies to Accomplish In-Situ Biological Remediation of Explosives Eleanor M. Jennings, Ph.D. Dennis Clark URS...30 MAR 2011 2. REPORT TYPE 3. DATES COVERED 00-00-2011 to 00-00-2011 4. TITLE AND SUBTITLE Use of Stable Isotope Technologies to Accomplish In...98) Prescribed by ANSI Std Z39-18 Introduction to Isotopic Carbon  Carbon comes in different weights  12C and 13C are most common isotopes

  19. Using Bayesian Stable Isotope Mixing Models to Enhance Marine Ecosystem Models

    EPA Science Inventory

    The use of stable isotopes in food web studies has proven to be a valuable tool for ecologists. We investigated the use of Bayesian stable isotope mixing models as constraints for an ecosystem model of a temperate seagrass system on the Atlantic coast of France. δ13C and δ15N i...

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

    EPA Science Inventory

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

  1. Effect of age and ration on diet-tissue isotopic13C, Δ15N) discrimination in striped skunks (Mephitis mephitis).

    PubMed

    Hobson, Keith A; Quirk, Travis W

    2014-01-01

    An important prerequisite for the effective use of stable isotopes in animal ecology is the accurate assessment of isotopic discrimination factors linking animals to their diets for a multitude of tissue types. Surprisingly, these values are poorly known in general and especially for mammalian carnivores and omnivores in particular. Also largely unknown are the factors that influence diet-tissue isotopic discrimination such as nutritional quality and age. We raised adult and juvenile striped skunks (Mephitis mephitis) in captivity on a constant omnivore diet (Mazuri Omnivore A 5635). Adults (n=6) and juveniles (n=3) were kept for 7 months and young (n=7) to the age of 50 days. We then examined individuals for stable carbon (δ(13)C) and nitrogen (δ(15)N) isotope values of hair, nails, lipid, liver, muscle, bone collagen and the plasma, and cellular fractions of blood. Discrimination values differed among age groups and were significantly higher for young compared with their mothers, likely due to the effects of weaning. Δ(15)N isotopic discrimination factors ranged from 3.14 (nails) to 5.6‰ (plasma) in adults and 4.3 (nails) to 5.8‰ (liver) for young. For Δ(13)C, values ranged from-3.3 (fat) to 3.0‰ (collagen) in adults and from-3.3 (fat) to 2.0‰ (collagen) in young. Our data provide an important tool for predicting diets and source of feeding for medium-sized mammalian omnivorous adults integrated over short (e.g. liver, plasma) through long (e.g. collagen) periods and underline the potential effects of age on isotopic values in omnivore diets.

  2. Lipid Extraction and the Fugacity of Stable Isotope Values

    NASA Astrophysics Data System (ADS)

    Padula, V.; Causey, D.; Wolf, N.; Welker, J. M.

    2013-12-01

    Stable isotope analysis of blood, feathers, and other tissues are often used to infer migration patterns, diet composition and trophic status of seabirds. Tissues contain variable amounts of lipids that are depleted in the heavy carbon isotope (13C) and may introduce a bias in these values. There is evidence that lipid extraction may affect other stable isotope ratios, such as δ15N. Consequently, correction factors need to be applied to appropriately interpret δ13C and δ15N values for individual species and tissue type. In this study, we collected seven species of seabirds from the Near Islands, the western most group of islands in the Aleutian Island archipelago. We sampled kidney, liver, heart and muscle samples from each bird and after freeze drying, individual tissue samples were divided into two subsamples. We left one subsample unaltered and extracted lipids from the other subsample using a 2:1 chloroform-methanol solution. We found that the change in δ13C values after lipid extraction (Δδ13C) varied widely among categories (eg., species, tissue type) from 0 - 4 ‰, while Δδ15N values ranged from 0 to 2‰. Notably, within category variation was nonsignificant and the Δδ values were linear against the covariant C:N ratio of the isotopic data, which allows us to use arithmetic corrections for categorical values. Our data strongly indicate that the effects of lipid extraction on stable isotopic values, while linear within category, vary widely by species, tissue, geographic area, year of collection, and isotope. Fugacity is usually employed as a thermodynamic quantity related to the chemical potential or activity that characterizes the escaping tendency from a phase (eg. Mackay & Paterson 1982). Here we use fugacity in the earlier, broader sense of fleeting, transitory, or instable states (eg., S. Johnson 1751), and its measure may be approximated by the higher order variance of Δδ13C and Δδ15N among data categories. Clearly, understanding the

  3. Stable isotope analyses of palaeo-pollen records

    NASA Astrophysics Data System (ADS)

    Hemming, D.; Loader, N.

    2002-12-01

    Pollen stratigraphy is one of the most widely used tools for studying climate and vegetation dynamics over global and multi-millennial scales. Since the isotopic compositions of photosynthates that are used to form the pollen structure reflect environmental conditions during the time of pollen formation, the stable carbon, oxygen and hydrogen isotopic compositions (δ13C, δ18O and δ{}D) of the pollen grains may reflect this environmental information. Although there are many preliminary tests and methodological problems to overcome before we can fully utilise palaeo-pollen records, it is the general goal of our research to use pollen isotope records together with conventional palynological analyses to provide additional, independent spatial and temporal palaeo-environmental information and to provide new data on terrestrial ecosystem dynamics, including the timing of environmental changes, phase relationships of vegetation responses and regional and temporal variations in δ13C, Δ13C, δ18O and δ{}D. These isotopic records will facilitate in the modelling of palaeo-environments. By separating and analysing different pollen species, including C3 and C4, we also aim to assess species-specific climatic responses. We present results describing some recent investigations concerning the nature of the isotopic signal contained within pollen, the methodological developments we have made to measure the pollen isotopic composition and the future challenges that must be overcome before this potentially powerful quantitative terrestrial palaeo-archive can be fully and correctly utilised.

  4. Stable carbon isotope biogeochemistry of lakes along a trophic gradient

    NASA Astrophysics Data System (ADS)

    de Kluijver, A.; Schoon, P. L.; Downing, J. A.; Schouten, S.; Middelburg, J. J.

    2014-05-01

    The stable carbon (C) isotope variability of dissolved inorganic and organic C (DIC and DOC), particulate organic carbon (POC), glucose and polar-lipid derived fatty acids (PLFA) were studied in a survey of 22 North American oligotrophic to eutrophic lakes. The δ13C of different PLFA were used as proxy for phytoplankton producers and bacterial consumers. Lake pCO2 was primarily determined by autochthonous production (phytoplankton biomass), especially in eutrophic lakes, and governed the δ13C of DIC. All organic-carbon pools showed larger isotopic variability in eutrophic lakes compared to oligo-mesotrophic lakes because of the high variability in δ13C at the base of the food web (both autochthonous and allochthonous carbon). Phytoplankton δ13C was negatively related to lake pCO2 over all lakes and positively related to phytoplankton biomass in eutrophic lakes, which was also reflected in a large range in photosynthetic isotope fractionation (ϵCO2-phyto, 8-25 ‰). The carbon isotope ratio of allochthonous carbon in oligo-mesotrophic lakes was rather constant, while it varied in eutrophic lakes because of maize cultivation in the watershed.

  5. Stable carbon isotope biogeochemistry of lakes along a trophic gradient

    NASA Astrophysics Data System (ADS)

    de Kluijver, A.; Schoon, P. L.; Downing, J. A.; Schouten, S.; Middelburg, J. J.

    2014-11-01

    The stable carbon (C) isotope variability of dissolved inorganic and organic C (DIC and DOC), particulate organic carbon (POC), glucose and polar-lipid derived fatty acids (PLFAs) was studied in a survey of 22 North American oligotrophic to eutrophic lakes. The δ13C of different PLFAs were used as proxy for phytoplankton producers and bacterial consumers. Lake pCO2 was primarily determined by autochthonous production (phytoplankton biomass), especially in eutrophic lakes, and governed the δ13C of DIC. All organic-carbon pools showed overall higher isotopic variability in eutrophic lakes (n = 11) compared to oligo-mesotrophic lakes (n = 11) because of the high variability in δ13C at the base of the food web (both autochthonous and allochthonous carbon). Phytoplankton δ13C was negatively related to lake pCO2 over all lakes and positively related to phytoplankton biomass in eutrophic lakes, which was also reflected in a large range in photosynthetic isotope fractionation (ϵCO2-phyto, 8-25‰). The carbon isotope ratio of allochthonous carbon in oligo-mesotrophic lakes was rather constant, while it varied in eutrophic lakes because of maize cultivation in the watershed.

  6. Enhanced forensic discrimination of pollutants by position-specific isotope analysis using isotope ratio monitoring by (13)C nuclear magnetic resonance spectrometry.

    PubMed

    Julien, Maxime; Nun, Pierrick; Höhener, Patrick; Parinet, Julien; Robins, Richard J; Remaud, Gérald S

    2016-01-15

    In forensic environmental investigations the main issue concerns the inference of the original source of the pollutant for determining the liable party. Isotope measurements in geochemistry, combined with complimentary techniques for contaminant identification, have contributed significantly to source determination at polluted sites. In this work we have determined the intramolecular (13)C profiles of several molecules well-known as pollutants. By giving additional analytical parameters, position-specific isotope analysis performed by isotope ratio monitoring by (13)C nuclear magnetic resonance (irm-(13)C NMR) spectrometry gives new information to help in answering the major question: what is the origin of the detected contaminant? We have shown that isotope profiling of the core of a molecule reveals both the raw materials and the process used in its manufacture. It also can reveal processes occurring between the contamination site 'source' and the sampling site. Thus, irm-(13)C NMR is shown to be a very good complement to compound-specific isotope analysis currently performed by mass spectrometry for assessing polluted sites involving substantial spills of pollutant.

  7. [Distribution of carbon isotopes ((13)C/(12)C) in cells and temporal organization of cellular processes].

    PubMed

    Ivlev, A A

    1991-01-01

    Recent studies on fractionation of carbon isotopes in biological systems are reviewed. It follows that direct experimental proofs have been obtained that 1) basic fractionation of carbon isotopes in the cell is related to isotope effect in pyruvate decarboxylation; 2) fractionation of carbon isotopes in the above reaction in vivo proceeds with exhausting substrate pool. The latter provides natural relationship between metabolites isotope distribution and sequence of their synthesis in the cell cycle, or with the temporal organization of cellular metabolism. The non-steady and periodic pattern of pyruvate decarboxylation due to the exhausting substrate pool well agrees with the existing notions on reciprocal oscillations in the cell glycolytic chain. Experimental data are presented corroborating indirectly the existence of oscillations in bacterial cells. Earlier proposed model of the mechanism of carbon isotope fractionation based on the above principles can be used for analysing changes in isotopic characteristics of the organisms and interpreting their relations with metabolic processes.

  8. Coupling a high-temperature catalytic oxidation total organic carbon analyzer to an isotope ratio mass spectrometer to measure natural-abundance delta13C-dissolved organic carbon in marine and freshwater samples.

    PubMed

    Panetta, Robert J; Ibrahim, Mina; Gélinas, Yves

    2008-07-01

    The stable isotope composition of dissolved organic carbon (delta(13)C-DOC) provides powerful information toward understanding carbon sources and cycling, but analytical limitations have precluded its routine measurement in natural samples. Recent interfacing of wet oxidation-based dissolved organic carbon analyzers and isotope ratio mass spectrometers has simplified the measurement of delta(13)C-DOC in freshwaters, but the analysis of salty estuarine/marine samples still proves difficult. Here we describe the coupling of the more widespread high-temperature catalytic oxidation-based total organic carbon analyzer to an isotope ratio mass spectrometer (HTC-IRMS) through cryogenic trapping of analyte gases exiting the HTC analyzer for routine analysis of delta(13)C-DOC in aquatic and marine samples. Targeted elimination of major sources of background CO2 originating from the HTC analyzer allows for the routine measurement of samples over the natural range of DOC concentrations (from 40 microM to over 2000 microM), and salinities (<0.1-36 g/kg). Because consensus reference natural samples for delta(13)C-DOC do not exist, method validation was carried out with water-soluble stable isotope standards as well as previously measured natural samples (IAEA sucrose, Suwannee River Fulvic Acids, Deep Sargasso Sea consensus reference material, and St. Lawrence River water) and result in excellent delta(13)C-DOC accuracy (+/-0.2 per thousand) and precision (+/-0.3 per thousand).

  9. Stable isotopes of captive cetaceans (killer whales and bottlenose dolphins).

    PubMed

    Caut, Stéphane; Laran, Sophie; Garcia-Hartmann, Emmanuel; Das, Krishna

    2011-02-15

    There is currently a great deal of interest in using stable isotope methods to investigate diet, trophic level and migration in wild cetaceans. In order to correctly interpret the results stemming from these methods, it is crucial to understand how diet isotopic values are reflected in consumer tissues. In this study, we investigated patterns of isotopic discrimination between diet and blood constituents of two species of cetaceans (killer whale, Orcinus orca, and bottlenose dolphin, Tursiops truncatus) fed controlled diets over 308 and 312 days, respectively. Diet discrimination factors (Δ; mean ± s.d.) for plasma were estimated to Δ(13)C=2.3±0.6‰ and Δ(15)N=1.8±0.3‰, respectively, for both species and to Δ(13)C=2.7±0.3‰ and Δ(15)N=0.5±0.1‰ for red blood cells. Delipidation did not have a significant effect on carbon and nitrogen isotopic values of blood constituents, confirming that cetacean blood does not serve as a reservoir of lipids. In contrast, carbon isotopic values were higher in delipidated samples of blubber, liver and muscle from killer whales. The potential for conflict between fisheries and cetaceans has heightened the need for trophic information about these taxa. These results provide the first published stable isotope incorporation data for cetaceans, which are essential if conclusions are to be drawn on issues concerning trophic structures, carbon sources and diet reconstruction.

  10. Relationships between stable isotopes and metal contaminants in feathers are spurious and biologically uninformative.

    PubMed

    Bond, Alexander L

    2010-05-01

    Stable isotopes of carbon (delta(13)C) and nitrogen (delta(15)N) are used frequently in ecotoxicological investigations of birds to relate contaminant levels to trophic position (delta(15)N) or foraging location (delta(13)C) and many researchers using avian feathers in such investigations use delta(13)C or delta(15)N as a predictor of contaminant concentrations. Contaminants, especially mercury, however, are integrated into feathers over different time periods than are stable isotopes, resulting in spurious relationships that have no biological meaning. I show the fundamental principles behind the conclusion that relating delta(13)C or delta(15)N to contaminant concentrations in feathers is not appropriate in light of the number of recent studies that have employed this approach, and make recommendations for those wishing to investigate the relationship between contaminants and stable isotope ratios.

  11. Biogeochemical Indicators in High- and Low-Arctic Marine and Terrestrial Avian Community Changes: Comparative Isotopic (13C, 15N, and 34S) Studies in Alaska and Greenland

    NASA Astrophysics Data System (ADS)

    Causey, D.; Bargmann, N. A.; Burnham, K. K.; Burnham, J. L.; Padula, V. M.; Johnson, J. A.; Welker, J. M.

    2011-12-01

    Understanding the complex dynamics of environmental change in northern latitudes is of paramount importance today, given documented rapid shifts in sea ice, plant phenology, temperatures, deglaciation, and habitat fidelity. This knowledge is particularly critical for Arctic avian communities, which are integral components by which biological teleconnections are maintained between the mid and northern latitudes. Furthermore, Arctic birds are fundamental to Native subsistence lifestyles and a focus for conservation activities. Avian communities of marine and terrestrial Arctic environments represent a broad spectrum of trophic levels, from herbivores (eg., geese Chen spp.), planktivores (eg., auklets Aethia spp.), and insectivores (eg., passerines: Wheatears Oenanthe spp., Longspurs Calcarius spp.), to predators of marine invertebrates (eg., eiders Somateria spp.), nearshore and offshore fish (eg., cormorants Phalacrocorax spp, puffins Fratercula spp.), even other bird species (eg., gulls Larus spp., falcons Peregrinus spp.). This diversity of trophic interconnections is an integral factor in the dynamics of Arctic ecosystem ecology, and they are key indicators for the strength and trajectories of change. We are especially interested in their feeding ecology, using stable isotope-diet relations to examine historical diets and to predict future feeding ecology by this range of species. Since 2009, we have been studying the foodweb ecology using stable isotopes13C, δ15N, δ34S) of contemporaneous coastal and marine bird communities in High Arctic (Northwest Greenland) and Low Arctic (western Aleutian Islands, AK). We are quantifying the isotopic values of blood, organ tissues, and feathers, and have carried out comparisons between native and lipid-extracted samples. Although geographically distant, these communities comprise similar taxonomic and ecological congeners, including several species common to both (eg., Common Eider, Black-legged Kittiwake, Northern

  12. 13C-isotope analyses reveal that chemolithoautotrophic Gamma- and Epsilonproteobacteria feed a microbial food web in a pelagic redoxcline of the central Baltic Sea.

    PubMed

    Glaubitz, Sabine; Lueders, Tillmann; Abraham, Wolf-Rainer; Jost, Günter; Jürgens, Klaus; Labrenz, Matthias

    2009-02-01

    Marine pelagic redoxclines are zones of high dark CO(2) fixation rates, which can correspond up to 30% of the surface primary production. However, despite this significant contribution to the pelagic carbon cycle, the identity of most chemolithoautotrophic organisms is still unknown. Therefore, the aim of this study was to directly link the dark CO(2) fixation capacity of a pelagic redoxcline in the central Baltic Sea (Landsort Deep) with the identity of the main chemolithoautotrophs involved. Our approach was based on the analysis of natural carbon isotope signatures in fatty acid methyl esters (FAMEs) and on measurements of CO(2) incorporation in (13)C-bicarbonate pulse experiments. The incorporation of (13)C into chemolithoautotrophic cells was investigated by rRNA-based stable isotope probing (RNA-SIP) and FAME analysis after incubation for 24 and 72 h under in situ conditions. Our results demonstrated that fatty acids indicative of Proteobacteria were significantly enriched in (13)C slightly below the chemocline. RNA-SIP analyses revealed that two different Gammaproteobacteria and three closely related Epsilonproteobacteria of the Sulfurimonas cluster were active dark CO(2)-fixing microorganisms, with a time-dependent community shift between these groups. Labelling of Archaea was not detectable, but after 72 h of incubation the (13)C-label had been transferred to a potentially bacterivorous ciliate related to Euplotes sp. Thus, RNA-SIP provided direct evidence for the contribution of chemolithoautotrophic production to the microbial food web in this marine pelagic redoxcline, emphasizing the importance of dark CO(2)-fixing Proteobacteria within this habitat.

  13. Stimulated Raman scattering-active isotopically pure 12C and 13C diamond crystals: A milestone in the development of diamond photonics

    NASA Astrophysics Data System (ADS)

    Kaminskii, A. A.; Ral'chenko, V. G.; Yoneda, H.; Bol'shakov, A. P.; Inyushkin, A. V.

    2016-09-01

    Isotopically pure 12C and 13C diamonds are synthesized by chemical vapor deposition and impulsive stimulated Raman scattering in these crystals is investigated. The thermal conductivity of 12C isotopically pure damond and natC diamond with natural isotopic composition is measured. Phonon-nondegenerate Stokes lasing based on the χ(3) nonlinearity in the 12C, 13C, and natC diamond "triad" is attained, which opens a new stage in the development of diamond photonics.

  14. Isotope dilution/mass spectrometry of serum cholesterol with (3,4-/sup 13/C)cholesterol: proposed definitive method

    SciTech Connect

    Pelletier, O.; Wright, L.A.; Breckenridge, W.C.

    1987-08-01

    We describe a new gas-chromatographic/mass-spectrometric (GC/MS) isotope-dilution method for determination of serum cholesterol. The method has been fully optimized and documented to provide the high accuracy and precision expected for a Definitive Method. In the presence of (3,4-/sup 13/C)cholesterol, cholesteryl esters in serum are hydrolyzed under optimum conditions and the entire cholesterol pool is extracted and derivatized to silyl ethers. The cholesterol derivatives are resolved from other sterols by gas-liquid chromatography on a fused silica column, and selected ions characteristic of cholesterol and the (3,4-/sup 13/C)cholesterol are monitored with a GC/MS quandrupole system. We estimated the cholesterol content of samples by bracketing each sample with standards of comparable cholesterol concentration that also contained the (3,4-/sup 13/C)cholesterol. The procedure was highly reproducible (CV less than 0.5%), better accuracy and precision being obtained with (3,4-/sup 13/C)cholesterol than with heptadeuterated cholesterol. Mean values per gram of dry serum for one serum pool assayed by this method and that of the National Bureau of Standards differed by 0.5%. We conclude that the method satisfies the criteria for a Definitive Method.

  15. Easy Extraction Method To Evaluate δ13C Vanillin by Liquid Chromatography-Isotopic Ratio Mass Spectrometry in Chocolate Bars and Chocolate Snack Foods.

    PubMed

    Bononi, Monica; Quaglia, Giancarlo; Tateo, Fernando

    2015-05-20

    An easy extraction method that permits the use of a liquid chromatography-isotopic ratio mass spectrometry (LC-IRMS) system to evaluate δ(13)C of vanillin in chocolate products and industrial flavorings is presented. The method applies the determination of stable isotopes of carbon to discriminate between natural vanillin from vanilla beans and vanillin from other sources (mixtures from beans, synthesis, or biotechnology). A series of 13 chocolate bars and chocolate snack foods available on the Italian market and 8 vanilla flavorings derived from industrial quality control processes were analyzed. Only 30% of products considered in this work that declared "vanilla" on the label showed data that permitted the declaration "vanilla" according to European Union (EU) Regulation 1334/2008. All samples not citing "vanilla" or "natural flavoring" on the label gave the correct declaration. The extraction method is presented with data useful for statistical evaluation.

  16. 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.

  17. Mangrove isotopic (δ15N and δ13C) fractionation across a nitrogen vs. phosphorus limitation gradient

    USGS Publications Warehouse

    Mckee, Karen L.; Feller, Ilka C.; Popp, Marianne; Wanek, Wolfgang

    2002-01-01

    Mangrove islands in Belize are characterized by a unique switching from nitrogen (N) to phosphorus (P) limitation to tree growth from shoreline to interior. Fertilization has previously shown that Rhizophora mangle (red mangrove) fringe trees (5–6 m tall) growing along the shoreline are N limited; dwarf trees (!1.5 m tall) in the forestinterior are P limited; and transition trees (2–4 m tall) are co-limited by both N and P.  Growth patterns paralleled a landward decrease in soil flushing by tides and an increase in bioavailable N, but P availability remained consistently low across the gradient. Stable isotopic composition was measured in R. mangle leaves to aid in explaining this nutrient switching pattern and growth variation. Along control transects, leaf !15N decreased from "0.10‰ (fringe) to #5.38‰ (dwarf). The !15N of N-fertilized trees also varied spatially, but the values were consistently more negative (by $3‰) compared to control trees. Spatial variation in !15N values disappeared when the trees were fertilized with P, and values averaged "0.12‰, similar to that in control fringe trees. Neither variation in source inputs nor microbial fractionation could fully account for the observed patterns in !15N. The results instead suggest that the lower !15N values in transition and dwarf control trees were due to plant fractionation as a consequence of slower growth and lower N demand. P fertilization increased N demand and decreased fractionation. Although leaf !13C was unaffected by fertilization, values increased from fringe (#28.6‰) to transition (#27.9‰) to dwarf (#26.4‰) zones, indicating spatial variation in environmental stresses affecting stomatal conductance or carboxylation. The results thus suggest an interaction of external supply, internal demand, and plant ability to acquire nutrients under different hydro-edaphic conditions that vary across this tree-height gradient. The findings not only aid in understanding

  18. Carbon stable isotopes as indicators of coastal eutrophication.

    PubMed

    Oczkowski, Autumn; Markham, Erin; Hanson, Alana; Wigand, Cathleen

    2014-04-01

    Coastal ecologists and managers have frequently used nitrogen stable isotopes (delta15N) to trace and monitor sources of anthropogenic nitrogen (N) in coastal ecosystems. However, the interpretation of delta15N data can often be challenging, as the isotope values fractionate substantially due to preferential retention and uptake by biota. There is a growing body of evidence that carbon isotopes may be a useful alternative indicator for eutrophication, as they may be sensitive to changes in primary production that result from anthropogenic nutrient inputs. We provide three examples of systems where delta13C values sensitively track phytoplankton production. First, earlier (1980s) mesocosm work established positive relationships between delta13C and dissolved inorganic nitrogen and dissolved silica concentrations. Consistent with these findings, a contemporary mesocosm experiment designed to replicate a temperate intertidal salt marsh environment also demonstrated that the system receiving supplementary nutrient additions had higher nutrient concentrations, higher chlorophyll concentrations, and higher delta13C values. This trend was particularly pronounced during the growing season, with differences less evident during senescence. And finally, these results were replicated in the open waters of Narragansett Bay, Rhode Island, USA, during a spring phytoplankton bloom. These three examples, taken together with the pre-existing body of literature, suggest that, at least in autotrophic, phytoplankton-dominated systems, delta13C values can be a useful and sensitive indicator of eutrophication.

  19. Optimization of 13C dynamic nuclear polarization: isotopic labeling of free radicals

    NASA Astrophysics Data System (ADS)

    Niedbalski, Peter; Parish, Christopher; Kiswandi, Andhika; Lumata, Lloyd

    Dynamic nuclear polarization (DNP) is a physics technique that amplifies the nuclear magnetic resonance (NMR) signals by transferring the high polarization of the electrons to the nuclear spins. Thus, the choice of free radical is crucial in DNP as it can directly affect the NMR signal enhancement levels, typically on the order of several thousand-fold in the liquid-state. In this study, we have investigated the efficiency of four variants of the well-known 4-oxo-TEMPO radical (normal 4-oxo-TEMPO plus its 15N-enriched and/or perdeuterated variants) for use in DNP of an important metabolic tracer [1-13C]acetate. Though the variants have significant differences in electron paramagnetic resonance (EPR) spectra, we have found that changing the composition of the TEMPO radical through deuteration or 15N doping yields no significant difference in 13C DNP efficiency at 3.35 T and 1.2 K. On the other hand, deuteration of the solvent causes a significant increase of 13C polarization that is consistent over all the 4-oxo-TEMPO variants. These findings are consistent with the thermal mixing model of DNP. This work is supported by US Dept of Defense Award No. W81XWH-14-1-0048 and the Robert A. Welch Foundation Grant No. AT-1877.

  20. Uncertainty in source partitioning using stable isotopes.

    PubMed

    Phillips, D L; Gregg, J W

    2001-04-01

    Stable isotope analyses are often used to quantify the contribution of multiple sources to a mixture, such as proportions of food sources in an animal's diet, or C3 and C4 plant inputs to soil organic carbon. Linear mixing models can be used to partition two sources with a single isotopic signature (e.g., δ(13)C) or three sources with a second isotopic signature (e.g., δ(15)N). Although variability of source and mixture signatures is often reported, confidence interval calculations for source proportions typically use only the mixture variability. We provide examples showing that omission of source variability can lead to underestimation of the variability of source proportion estimates. For both two- and three-source mixing models, we present formulas for calculating variances, standard errors (SE), and confidence intervals for source proportion estimates that account for the observed variability in the isotopic signatures for the sources as well as the mixture. We then performed sensitivity analyses to assess the relative importance of: (1) the isotopic signature difference between the sources, (2) isotopic signature standard deviations (SD) in the source and mixture populations, (3) sample size, (4) analytical SD, and (5) the evenness of the source proportions, for determining the variability (SE) of source proportion estimates. The proportion SEs varied inversely with the signature difference between sources, so doubling the source difference from 2‰ to 4‰ reduced the SEs by half. Source and mixture signature SDs had a substantial linear effect on source proportion SEs. However, the population variability of the sources and the mixture are fixed and the sampling error component can be changed only by increasing sample size. Source proportion SEs varied inversely with the square root of sample size, so an increase from 1 to 4 samples per population cut the SE in half. Analytical SD had little effect over the range examined since it was generally

  1. Uses of stable isotopes in fish ecology

    EPA Science Inventory

    Analyses of fish tissues (other than otoliths) for stable isotope ratios can provide substantial information on fish ecology, including physiological ecology. Stable isotopes of nitrogen and carbon frequently are used to determine the mix of diet sources for consumers. Stable i...

  2. Pyrolysis compound specific isotopic analysis (δ13C and δD Py-CSIA) of soil organic matter size fractions under four vegetation covers.

    NASA Astrophysics Data System (ADS)

    Jiménez-Morillo, Nicasio T.; González-Vila, Francisco J.; Almendros, Gonzalo; De la Rosa, José M.; González-Pérez, José A.

    2015-04-01

    A chemical characterization of soil organic matter (SOM) under different ground cover from a Mediterranean climate (Doñana National Park, Andalusia, Spain) is approached using bulk δ15N, δ13C, δ18O and δD isotopic analysis (C/TC-IRMS) and δ13C and δD pyrolysis compound specific isotopic analysis (Py-CSIA: Py-GC-C/TC-IRMS). Soil samples were collected in sandy soils, Arenosols (WRB 2006) from the Doñana National Park (SW Spain) under different vegetation cover: cork oak (Quercus suber, QS), eagle fern (Pteridium aquilinum, PA), pine (Pinus pinea, PP) and rockrose (Halimium halimifolium, HH). Two size fractions; coarse (C: 1-2 mm) and fine (F: <0.05 mm) were studied from each soil. A complete conventional analytical pyrolysis (Py-GC/MS) of these samples have been studied in detail (Jiménez-Morillo et al., 2015). Bulk isotopic analysis of stable light elements (δ15N, δ13C, δ18O and δD) revealed particular isotopic signatures showing differences related with the main vegetation cover and the different soil size fraction. All samples had a carbon isotopic signature between -26 and -29 ‰, which indicated that the organic matter in the two fractions of each soil sample derived from C3-type plants. The bulk δD isotopic signature in whole soil sample indicate a lower deuterium fractionation occurs in SOM under arboreal than under no-arboreal vegetation, this can be caused by the occurrence of a higher water evaporation rate under bush vegetation and/or to differences due to leaf morphology as previously described (Leaney et al., 1985). A δ15N vs. δ18O chart may provide some clues about N origin in the soil and particularly about the original source of nitrates (Kendall et al., 1996). In in all sample and size fractions our values are in the chart area corresponding to NO3 in precipitation, with lighter δ18O (c. 20 ‰) values compatible with fertilizers may be from adjacent crops. In addition we were able to assign δ13C and δD values for a number of

  3. Modeling δ 13C and δ D of Stratospheric Methane: Implications for Kinetic Isotope Effects and the Isotopic Composition of Tropospheric Methane

    NASA Astrophysics Data System (ADS)

    McCarthy, M. C.; Boering, K. A.; Boering, K. A.; Rice, A. L.; Tyler, S. C.; Connell, P.; Atlas, E.

    2001-12-01

    New measurements of δ D and δ 13C in stratospheric CH4 from 78 whole air samples collected aboard the NASA ER-2 aircraft during the STRAT, POLARIS, and SOLVE field campaigns are compared with model results from the Lawrence Livermore National Laboratory 2-D model. Although uncertainties in stratospheric transport are not small, the effect of these uncertainties on the isotopic compositions is likely small compared to the current range of experimental values for the kinetic isotope effects (KIEs) for the 13C and D isotopomers of CH4 and their associated experimental uncertainties. Thus, by comparing the new δ 13C and δ D observations from the stratosphere with various model scenarios that vary the KIEs for OH, Cl, and O(1D), the uncertainty in the laboratory KIEs may be reduced. Furthermore, latitudinal and seasonal trends in the observations are compared with modeled variability. In addition, model results predict the influence of the KIEs of stratospheric sinks on the δ 13C and δ D of CH4 in the free troposphere, which is of importance in inverse models that use isotopic compositions to derive the magnitude and distribution of methane sources to the atmosphere.

  4. Stable Isotope Laser Spectrometer for Exploration of Mars

    NASA Technical Reports Server (NTRS)

    Sauke, Todd B.; Becker, Joseph F.

    1998-01-01

    On Earth, measurements of the ratios of stable carbon isotopes have providet much information about geological and biological processes. For example, fractionation of carbon occur in biotic processes and the retention of a distinctive 2-4% contrast in C-13/C-12 between organic carbon and carbonates in rocks as old as 3.8 billion years constitutes some of the firmest evidence for the antiquity of life on the Earth. We have developed a prototype tunable diode laser spectrometer which demonstrates the feasibility of making accurate in situ isotopic ratio measurements on Mars. This miniaturized instrument, with an optical path length of 10 cm should be capable of making accurate C-13/C-12 and N-15/N-14 measurements. Gas samples for measurement are to be produced by pyrolysis using soil samples as small as 50 mg. Measurements of C-13/C-12, O-18/O-16 and N-15/N-14 have been made to a precision of better than 0.1%, and various other isotopes are feasible. This laser technique, which relies on the extremely narrow emission linewidth of tunable diode lasers (less than 0.001/ cm),has favorable features in comparison to mass spectrometry, the standard method of accurate isotopic ratio measurement. The miniature instrument could be ready to deploy c 2003 or other Mars lander missions.

  5. δD and δ13C analyses of atmospheric volatile organic compounds by thermal desorption gas chromatography isotope ratio mass spectrometry.

    PubMed

    von Eckstaedt, Christiane Vitzthum; Grice, Kliti; Ioppolo-Armanios, Marisa; Chidlow, Geoff; Jones, Mark

    2011-09-16

    This paper describes the establishment of a robust method to determine compound specific δD and δ(13)C values of volatile organic compounds (VOCs) in a standard mixture ranging between C(6) and C(10) and was applied to various complex emission samples, e.g. from biomass combustion and car exhaust. A thermal desorption (TD) unit was linked to a gas chromatography isotope ratio mass spectrometer (GC-irMS) to enable compound specific isotope analysis (CSIA) of gaseous samples. TenaxTA was used as an adsorbent material in stainless steel TD tubes. We determined instrument settings to achieve a minimal water background level for reliable δD analysis and investigated the impact of storage time on δD and δ(13)C values of collected VOCs (176 days and 40 days of storage, respectively). Most of the standard compounds investigated showed standard deviations (SD)<6‰ (δD) when stored for 148 days at 4 °C. However, benzene revealed occasionally D depleted values (21‰ SD) for unknown reasons. δ(13)C analysis demonstrated that storage of 40 days had no effect on VOCs investigated. We also showed that breakthrough (benzene and toluene, 37% and 7%, respectively) had only a negligible effect (0.7‰ and 0.4‰, respectively) on δ(13)C values of VOCs on the sample tube. We established that the sample portion collected at the split flow effluent of the TD unit can be used as a replicate sample for isotope analysis saving valuable sampling time and resources. We also applied TD-GC-irMS to different emission samples (biomass combustion, petrol and diesel car engines exhaust) and for the first time δD values of atmospheric VOCs in the above range are reported. Significant differences in δD of up to 130‰ were observed between VOCs in emissions from petrol car engine exhaust and biomass combustion (Karri tree). However, diesel car emissions showed a high content of highly complex unresolved mixtures thus a baseline separation of VOCs was not achieved for stable hydrogen

  6. The {sup 13}C-pocket structure in AGB models: constraints from zirconium isotope abundances in single mainstream SiC grains

    SciTech Connect

    Liu, Nan; Davis, Andrew M.; Pellin, Michael J.; Gallino, Roberto; Bisterzo, Sara; Savina, Michael R.

    2014-06-20

    We present postprocess asymptotic giant branch (AGB) nucleosynthesis models with different {sup 13}C-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 {sup 92}Zr/{sup 94}Zr ratios can be predicted by adopting a {sup 13}C-pocket with a flat {sup 13}C profile, instead of the previous decreasing-with-depth {sup 13}C profile. The improved agreement between grain data for zirconium isotopes and AGB models provides additional support for a recent proposal of a flat {sup 13}C profile based on barium isotopes in mainstream SiC grains by Liu et al.

  7. Highly enriched multiply-labeled stable isotopic compounds as atmospheric tracers

    DOEpatents

    Goldblatt, M.; McInteer, B.B.

    1974-01-29

    Compounds multiply-labeled with stable isotopes and highly enriched in these isotopes are readily capable of detection in tracer experiments involving high dilutions. Thus, for example, /sup 13/C/sup 18/O/sub 2/ provides a useful tracer for following atmospheric pol lution produced as a result of fossil fuel burning. (Official Gazette)

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

    PubMed

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

    2012-08-01

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

  9. [Carbon isotope (13C/12C) effect of photorespiration in photosynthetic organisms. Evidence for existence, probable mechanism].

    PubMed

    Ivlev, A A

    2002-01-01

    Experimental evidence in favor of the new phenomenon predicted for photosynthesizing organisms, the fractionation of carbon isotopes in photorespiration is presented. A possible mechanism of this process is discussed. The fractionation of carbon in isotopes photorespiration occurs in the oxygenase phase of the functioning of ribulosebisphosphate carboxylase/oxygenase (rubisco), the key enzyme of photosynthesis, which is capable to act as carboxylase and oxygenase. Which function of the enzyme is active depends on CO2/O2 concentration ratio, which periodically changes in a cell. The key reaction in the mechanism of carbon isotope fractionation in photorespiration is glycine decarboxylation, which results in the splitting and removal from the cell of CO2 enriched with 12C and the accumulation of 13C photorespiratory carbon flow. The coupling of photorespiration and CO2 photoassimilation gives rise to two isotopically different carbon flows, which fill up separate carbohydrate pools, which are the sources of carbon in the following syntheses in the dark phase of photosynthesis. This enables one to identify, from the carbon isotope ratio of metabolites, their involvement in the photorespiratory and assimilatory carbon flows, to investigate the pathways of carbon metabolism, and to estimate more thoroughly the biosynthetic role of photorespiration.

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

    NASA Astrophysics Data System (ADS)

    Siegwolf, Rolf; Saurer, Matthias

    2016-04-01

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

  11. Stable Carbon and Nitrogen isoscapes of the California Coast: integrated δ15N and δ13C of suspended particulate organic matter inferred from tissues of the California Mussel (mytilus californianus)

    NASA Astrophysics Data System (ADS)

    Vokhshoori, N. L.; McCarthy, M. D.

    2011-12-01

    Spatial maps of isotopic variability in a single species, or isoscapes, can characterize the natural variability in carbon (C) and nitrogen (N) isotope ratios across ecosystems on broad spatial scales, trace the signature of a source across a given area, as well as constrain animal migration patterns (Graham et al. 2002). In this study, isoscapes of stable carbon (13C) and nitrogen (15N) isotopes were constructed using intertidal mussels for northeast Pacific coastal waters of California. In this region biogeochemical cycling is primarily controlled by upwelling intensity and large-scale transport of the California Current System (CCS). We hypothesize that sampling specific tissues of filter-feeding organisms can provide an integrated measure of variation in 15N and 13C of the suspended particulate organic matter (POM) pool vs. latitude within the CCS, as well indicate main sources of both organic C and N to littoral food webs. California mussels (mytilus californianus) were collected from 28 sites between Coos Bay, OR and La Jolla, CA in the winter of 2009-2010 and summer of 2011, and adductor tissue was analyzed for δ13C and δ15N. Mussel size classes were chosen to provide ~ 1 yr integrated signal. Spatial trends in δ15N from the winter sampling show a strong linear trend in increasing δ15N values with latitude north to south (δ15N values range from 7 % to 12%) consistent with slowly attenuating northward transport of 15N-depleted nitrate via California Undercurrent (Altabet et al. 1999). The δ13C values have no strong north to south correlation, but exhibit strong location-specific variability. The δ13C values range between -13 % and -18%. We propose the site-specific signature of δ13C indicates relative source of primary productin to POM at a given region (i.e. kelp, phytoplankton, zooplankton). Overall, these results suggest that isoscapes for filter-feeding organisms may offer a more accurate integrated picture of 15N and 13C values of POM than is

  12. Substitution of stable isotopes in Chlorella

    NASA Technical Reports Server (NTRS)

    Flaumenhaft, E.; Katz, J. J.; Uphaus, R. A.

    1969-01-01

    Replacement of biologically important isotopes in the alga Chlorella by corresponding heavier stable isotopes produces increasingly greater deviations from the normal cell size and changes the quality and distribution of certain cellular components. The usefulness of isotopically altered organisms increases interest in the study of such permuted organisms.

  13. Stable Isotope Signatures for Microbial Forensics

    SciTech Connect

    Kreuzer, Helen W.

    2012-01-03

    The isotopic distribution of the atoms composing the molecules of microorganisms is a function of the substrates used by the organisms. The stable isotope content of an organism is fixed so long as no further substrate consumption and biosynthesis occurs, while the radioactive isotopic content decays over time. The distribution of stable isotopes of C, N, O and H in heterotrophic microorganisms is a direct function of the culture medium, and therefore the stable isotope composition can be used to associate samples with potential culture media and also with one another. The 14C content depends upon the 14C content, and therefore the age, of the organic components of the culture medium, as well as on the age of the culture itself. Stable isotope signatures can thus be used for sample matching, to associate cultures with specific growth media, and to predict characteristics of growth media.

  14. Stable isotopes differentiate bottlenose dolphins off west-central Florida

    USGS Publications Warehouse

    Barros, Nélio B.; Ostrom, P. H.; Stricker, Craig A.; Wells, R.S.

    2010-01-01

    Distinguishing discrete population units among continuously distributed coastal small cetaceans is challenging and crucial to conservation. We evaluated the utility of stable isotopes in assessing group membership in bottlenose dolphins (Tursiops truncatus) off west-central Florida by analyzing carbon, nitrogen, and sulfur isotope values (δ13C, δ15N, and δ34S) of tooth collagen from stranded dolphins. Individuals derived from three putative general population units: Sarasota Bay (SB), nearshore Gulf of Mexico (GULF), and offshore waters (OFF). Animals of known history (SB) served to ground truth the approach against animals of unknown history from the Gulf of Mexico (GULF, OFF). Dolphin groups differed significantly for each isotope. Average δ13C values from SB dolphins (−10.6‰) utilizing sea grass ecosystems differed from those of GULF (−11.9‰) and OFF (−11.9‰). Average δ15N values of GULF (12.7‰) and OFF (13.2‰) were higher than those of SB dolphins (11.9‰), consistent with differences in prey trophic levels. δ34S values showed definitive differences among SB (7.1‰), GULF (11.3‰), and OFF (16.5‰) dolphins. This is the first application of isotopes to population assignment of bottlenose dolphins in the Gulf of Mexico and results suggest that isotopes may provide a powerful tool in the conservation of small cetaceans.

  15. The effect of different cooking processes on stable C, N, and H isotopic compositions of beef.

    PubMed

    Zhou, Jiuqing; Guo, Boli; Wei, Yimin; Zhang, Guoquan; Wei, Shuai; Ma, Yiyan

    2015-09-01

    The variability in the stable C, N, and H isotopic composition caused by different beef processing operations (boiling, frying, and roasting) was studied. The aim was to evaluate the stability of stable isotopic fingerprint information during the beef cooking process. The δ(13)C, δ(15)N, and δ(2)H values for raw, boiled, fried and roasted beef were measured, and the differences in the stable isotopic composition between raw and processed beef products were assessed. The results indicated that the δ(13)C and δ(15)N values in raw beef were not significantly different compared with processed beef, but the δ(2)H values were significantly higher in processed beef than in raw beef. In general, boiling, frying, and roasting had no significant effect on δ(13)C and δ(15)N values, but the δ(2)H value of processed beef increased.

  16. Seasonal variation in stable carbon and nitrogen isotope values of bats reflect environmental baselines.

    PubMed

    Popa-Lisseanu, Ana G; Kramer-Schadt, Stephanie; Quetglas, Juan; Delgado-Huertas, Antonio; Kelm, Detlev H; Ibáñez, Carlos

    2015-01-01

    The stable carbon and nitrogen isotope composition of animal tissues is commonly used to trace wildlife diets and analyze food chains. Changes in an animal's isotopic values over time are generally assumed to indicate diet shifts or, less frequently, physiological changes. Although plant isotopic values are known to correlate with climatic seasonality, only a few studies restricted to aquatic environments have investigated whether temporal isotopic variation in consumers may also reflect environmental baselines through trophic propagation. We modeled the monthly variation in carbon and nitrogen isotope values in whole blood of four insectivorous bat species occupying different foraging niches in southern Spain. We found a common pattern of isotopic variation independent of feeding habits, with an overall change as large as or larger than one trophic step. Physiological changes related to reproduction or to fat deposition prior to hibernation had no effect on isotopic variation, but juvenile bats had higher δ13C and δ15N values than adults. Aridity was the factor that best explained isotopic variation: bat blood became enriched in both 13C and 15N after hotter and/or drier periods. Our study is the first to show that consumers in terrestrial ecosystems reflect seasonal environmental dynamics in their isotope values. We highlight the danger of misinterpreting stable isotope data when not accounting for seasonal isotopic baselines in food web studies. Understanding how environmental seasonality is integrated in animals' isotope values will be crucial for developing reliable methods to use stable isotopes as dietary tracers.

  17. Complementary constraints from carbon (13C) and nitrogen (15N) isotopes on the glacial ocean's soft-tissue biological pump

    NASA Astrophysics Data System (ADS)

    Schmittner, A.; Somes, C. J.

    2016-06-01

    A three-dimensional, process-based model of the ocean's carbon and nitrogen cycles, including 13C and 15N isotopes, is used to explore effects of idealized changes in the soft-tissue biological pump. Results are presented from one preindustrial control run (piCtrl) and six simulations of the Last Glacial Maximum (LGM) with increasing values of the spatially constant maximum phytoplankton growth rate μmax, which accelerates biological nutrient utilization mimicking iron fertilization. The default LGM simulation, without increasing μmax and with a shallower and weaker Atlantic Meridional Overturning Circulation and increased sea ice cover, leads to 280 Pg more respired organic carbon (Corg) storage in the deep ocean with respect to piCtrl. Dissolved oxygen concentrations in the colder glacial thermocline increase, which reduces water column denitrification and, with delay, nitrogen fixation, thus increasing the ocean's fixed nitrogen inventory and decreasing δ15NNO3 almost everywhere. This simulation already fits sediment reconstructions of carbon and nitrogen isotopes relatively well, but it overestimates deep ocean δ13CDIC and underestimates δ15NNO3 at high latitudes. Increasing μmax enhances Corg and lowers deep ocean δ13CDIC, improving the agreement with sediment data. In the model's Antarctic and North Pacific Oceans modest increases in μmax result in higher δ15NNO3 due to enhanced local nutrient utilization, improving the agreement with reconstructions there. Models with moderately increased μmax fit both isotope data best, whereas large increases in nutrient utilization are inconsistent with nitrogen isotopes although they still fit the carbon isotopes reasonably well. The best fitting models reproduce major features of the glacial δ13CDIC, δ15N, and oxygen reconstructions while simulating increased Corg by 510-670 Pg compared with the preindustrial ocean. These results are consistent with the idea that the soft-tissue pump was more efficient

  18. 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

  19. Isotopically nonstationary 13C flux analysis of changes in Arabidopsis thaliana leaf metabolism due to high light acclimation

    DOE PAGES

    Ma, Fangfang; Jazmin, Lara J.; Young, Jamey D.; ...

    2014-11-03

    Improving plant productivity is an important aim for metabolic engineering. There are few comprehensive methods that quantitatively describe leaf metabolism, although such information would be valuable for increasing photosynthetic capacity, enhancing biomass production, and rerouting carbon flux toward desirable end products. Isotopically nonstationary metabolic flux analysis (INST-MFA) has been previously applied to map carbon fluxes in photoautotrophic bacteria, which involves model-based regression of transient 13C-labeling patterns of intracellular metabolites. However, experimental and computational difficulties have hindered its application to terrestrial plant systems. Here, we performed in vivo isotopic labeling of Arabidopsis thaliana rosettes with 13CO2 and estimated fluxes throughout leafmore » photosynthetic metabolism by INST-MFA. Plants grown at 200 µmol m$-$2s$-$1 light were compared with plants acclimated for 9 d at an irradiance of 500 µmol∙m$-$2∙s$-$1. Approximately 1,400 independent mass isotopomer measurements obtained from analysis of 37 metabolite fragment ions were regressed to estimate 136 total fluxes (54 free fluxes) under each condition. The results provide a comprehensive description of changes in carbon partitioning and overall photosynthetic flux after long-term developmental acclimation of leaves to high light. Despite a doubling in the carboxylation rate, the photorespiratory flux increased from 17 to 28% of net CO2 assimilation with high-light acclimation (Vc/Vo: 3.5:1 vs. 2.3:1, respectively). In conclusion, this study highlights the potential of 13C INST-MFA to describe emergent flux phenotypes that respond to environmental conditions or plant physiology and cannot be obtained by other complementary approaches.« less

  20. Stable isotope ratio method for the characterisation of the poultry house environment.

    PubMed

    Skipitytė, Raminta; Mašalaitė, Agnė; Garbaras, Andrius; Mickienė, Rūta; Ragažinskienė, Ona; Baliukonienė, Violeta; Bakutis, Bronius; Šiugždaitė, Jūratė; Petkevičius, Saulius; Maruška, Audrius Sigitas; Remeikis, Vidmantas

    2017-06-01

    Stable isotope analysis was applied to describe the poultry house environment. The poultry house indoor environment was selected for this study due to the relevant health problems in animals and their caretakers. Air quality parameters including temperature, relative humidity, airflow rate, NH3, CO2 and total suspended particles, as well as mean levels of total airborne bacteria and fungi count, were measured. Carbon isotope ratios ((13)C/(12)C) were obtained in size-segregated aerosol particles. The carbon ((13)C/(12)C) and nitrogen ((15)N/(14)N) isotope ratios were measured in feed, litter, scrapings from the ventilation system, feathers and eggs. Additionally, the distribution of δ(13)C and δ(15)N values in different tissues of the chicken was examined. The airborne bacteria and fungi extracted from the air filters collected from poultry farms were grown in the laboratory in media with known isotope values and measured for stable isotope ratios. Analysis of isotope fractionation between microorganisms and their media indicated the applicability of stable isotope analysis in bulk samples for the identification of source material. The analysed examples imply that stable isotope analysis can be used to examine the indoor environment along with its biology and ecology, and serve as an informative bioanalytical tool.

  1. delta 13C analyses of vegetable oil fatty acid components, determined by gas chromatography--combustion--isotope ratio mass spectrometry, after saponification or regiospecific hydrolysis.

    PubMed

    Woodbury, S E; Evershed, R P; Rossell, J B

    1998-05-01

    The delta 13C values of the major fatty acids of several different commercially important vegetable oils were measured by gas chromatography--combustion--isotope ratio mass spectrometry. The delta 13C values obtained were found to fall into two distinct groups, representing the C3 and C4 plants classes from which the oils were derived. The delta 13C values of the oils were measured by continuous flow elemental isotope ratio mass spectrometry and were found to be similar to their fatty acids, with slight differences between individual fatty acids. Investigations were then made into the influence on the delta 13C values of fatty acids of the position occupied on the glycerol backbone. Pancreatic lipase was employed to selectively hydrolyse fatty acids from the 1- and 3-positions with the progress of the reaction being followed by high-temperature gas chromatography in order to determine the optimum incubation time. The 2-monoacylglycerols were then isolated by thin-layer chromatography and fatty acid methyl esters prepared. The delta 13C values obtained indicate that fatty acids from any position on the glycerol backbone are isotopically identical. Thus, whilst quantification of fatty acid composition at the 2-position and measurement of delta 13C values of oils and their major fatty acids are useful criteria in edible oil purity assessment, measurement of delta 13C values of fatty acids from the 2-position does not assist with oil purity assignments.

  2. The Titan 14N/ 15N and 12C/ 13C isotopic ratios in HCN from Cassini/CIRS

    NASA Astrophysics Data System (ADS)

    Vinatier, Sandrine; Bézard, Bruno; Nixon, Conor A.

    2007-11-01

    We report the detection of H 13CN and HC 15N in mid-infrared spectra recorded by the Composite Infrared Spectrometer (CIRS) aboard Cassini, along with the determination of the 12C/ 13C and 14N/ 15N isotopic ratios. We analyzed two sets of limb spectra recorded near 13-15° S (Tb flyby) and 83° N (T4 flyby) at 0.5 cm -1 resolution. The spectral range 1210-1310 cm -1 was used to retrieve the temperature profile in the range 145-490 km at 13° S and 165-300 km at 83° N. These two temperature profiles were then incorporated in the atmospheric model to retrieve the abundance profile of H 12C 14N, H 13CN and HC 15N from their bands at 713, 706 and 711 cm -1, respectively. The HCN abundance profile was retrieved in the range 90-460 km at 15° S and 165-305 km at 83° N. There is no evidence for vertical variations of the isotopic ratios. Constraining the isotopic abundance profiles to be proportional to the HCN one, we find C12/C13=89-18+22 at 15° S, and 68-12+16 at 83° N, two values that are statistically consistent. A combination of these results yields a 12C/ 13C value equal to 75±12. This global result, as well as the 15° S one, envelop the value in Titan's methane ( 82.3±1) [Niemann, H.B., and 17 colleagues, 2005. Nature 438, 779-784] measured at 10° S and is slightly lower than the terrestrial inorganic standard value (89). The 14N/ 15N isotopic ratio is found equal to 56-13+16 at 15° S and 56-9+10 at 83° N. Combining the two values yields 14N/ 15N = 56 ± 8, which corresponds to an enrichment in 15N of about 4.9 compared with the terrestrial ratio. These results agree with the values obtained from previous ground-based millimeter observations [Hidayat, T., Marten, A., Bézard, B., Gautier, D., Owen, T., Matthews, H.E., Paubert, G., 1997. Icarus 126, 170-182; Marten, A., Hidayat, T., Biraud, Y., Moreno, R., 2002. Icarus 158, 532-544]. The 15N/ 14N ratio found in HCN is ˜3 times higher than in N 2 [Niemann, H.B., and 17 colleagues, 2005. Nature 438, 779

  3. C4 plant isotopic composition (delta13C) evidence for urban CO2 pollution in the city of Cotonou, Benin (West Africa).

    PubMed

    Kèlomé, Nelly C; Lévêque, Jean; Andreux, Francis; Milloux, Marie-Jeanne; Oyédé, Lucien-Marc

    2006-08-01

    The carbon isotopic composition (delta13C) of plants can reveal the isotopic carbon content of the atmosphere in which they develop. The delta13C values of air and plants depend on the amount of atmospheric fossil fuel CO2, which is chiefly emitted in urban areas. A new indicator of CO2 pollution is tested using the delta13C variation in a C4 grass: Eleusine indica. A range of about 4 per thousand delta units was observed at different sites in Cotonou, the largest city in the Republic of Benin. The highest delta13C values, from -12 per thousand to -14 per thousand, were found in low traffic zones; low delta13C values, from -14 per thousand to -16 per thousand, were found in high traffic zones. The amount of fossil fuel carbon assimilated by plants represented about 20% of the total plant carbon content. An overall decrease in plant delta13C values was observed over a four-year monitoring period. This decrease was correlated with increasing vehicle traffic. The delta13C dataset and the corresponding geographical database were used to map and define zones of high and low 13C-depleted CO2 emissions in urban and sub-urban areas. The spatial distribution follows dominant wind directions, with the lowest emission zones found in the southwest of Cotonou. High CO2 emissions occurred in the north, the east and the center, providing evidence of intense anthropogenic activity related to industry and transportation.

  4. Characterization of Northern California petroleum by stable carbon isotopes

    USGS Publications Warehouse

    Lillis, Paul G.; Magoon, Leslie B.; Stanley, Richard G.; McLaughlin, Robert J.; Warden, Augusta

    2001-01-01

    The purpose of this study is to characterize natural occurrences of petroleum at the surface and in the subsurface within northern California in order to define and map petroleum systems for U.S. Geological Survey energy resource assessments. Furthermore, the chemical characterization and mapping of natural petroleum occurrences could also be used to discriminate natural occurrences from accidental oil spills during the activities of extraction or transportation of petroleum. Samples include petroleum from exploratory well tests, producing fields, natural seeps, and oil-stained rocks, and condensates from gas wells. Most of the sample localities are in northern California but a few samples from central and southern California are included for comparison (table 1). Even though other analyses were performed, only stable carbon isotope13C) data are presented here for brevity and because δ13C values are one of the most discriminating characteristics of California petroleum.

  5. Stable Isotopic Signatures of CO Uptake and Emission by Soil

    NASA Astrophysics Data System (ADS)

    Popa, E.; Röckmann, T.

    2015-12-01

    CO is important for atmospheric chemistry, is a pollutant, and it has been recognized as an important indirect greenhouse gas. Globally, soil uptake is one of main sinks of CO. On local scale, soil can be either a net sink or a net source of CO, due to the fact that both consumption and production of CO take place in soil concomitantly. These two phenomena are independent: while the uptake is microbial, the production is from abiotic oxidation of organic matter. In order to determine the isotopic signature of the exchange of CO between soil and atmosphere, soil chamber experiments were performed at a forest site in the Netherlands. Flaks samples were filled from the soil chamber, and analyzed for the stable isotopes 13C and 18O using the high precision measurement facility at IMAU. We found that the uptake of CO by soil is associated with a small positive fractionation, i.e. the lighter CO is taken up faster. Although the soil at this site was a strong sink for CO, the isotopic data show that a small emission flux was also present in all cases. The isotopic composition of the emitted CO is depleted in 13C compared to atmospheric CO, and compatible with a source from plant and soil organic matter oxidation.

  6. Combining position-specific 13C labeling with compound-specific isotope analysis: first steps towards soil fluxomics

    NASA Astrophysics Data System (ADS)

    Dippold, Michaela; Kuzyakov, Yakov

    2015-04-01

    Understanding the soil organic matter (SOM) dynamics is one of the most important challenges in soil science. Transformation of low molecular weight organic substances (LMWOS) is a key step in biogeochemical cycles because 1) all high molecular substances pass this stage during their decomposition and 2) only LMWOS will be taken up by microorganisms. Previous studies on LMWOS were focused on determining net fluxes through the LMWOS pool, but they rarely identified transformations. As LMWOS are the preferred C and energy source for microorganisms, the transformations of LMWOS are dominated by biochemical pathways of the soil microorganisms. Thus, understanding fluxes and transformations in soils requires a detailed knowledge on the biochemical pathways and its controlling factors. Tracing C fate in soil by isotopes became on of the most applied and promising biogeochemistry tools. Up to now, studies on LMWOS were nearly exclusively based on uniformly labeled organic substances i.e. all C atoms in the molecules were labeled with 13C or 14C. However, this classical approach did not allow the differentiation between use of intact initial substances in any process, or whether they were transformed to metabolites. The novel tool of position-specific labeling enables to trace molecule atoms separately and thus to determine the cleavage of molecules - a prerequisite for metabolic tracing. Position-specific labeling of LMWOS and quantification of 13CO2 and 13C in bulk soil enabled following the basic metabolic pathways of soil microorganisms. However, only the combination of position-specific 13C labeling with compound-specific isotope analysis of microbial biomarkers and metabolites allowed 1) tracing specific anabolic pathways in diverse microbial communities in soils and 2) identification of specific pathways of individual functional microbial groups. So, these are the prerequisites for soil fluxomics. Our studies combining position-specific labeled glucose with amino

  7. The Stable Isotopic Composition of Atmospheric CO2

    NASA Astrophysics Data System (ADS)

    Yakir, D.

    2003-12-01

    in nature ( Thiemens, 1999; see Chapter 4.06, and of triple stable isotopes in geochemistry (e.g., Blunier et al., 2002; Luz et al., 1999; Luz and Barkan, 2000) greatly extended the potential of stable isotope applications.The chemical and isotopic composition of the atmosphere has drawn particular attention in climate-related research both because it is the most accessible component in the tightly coupled land-ocean-atmosphere system, and because the chemical composition of the atmosphere influences climate, particularly via the concentrations of the radiatively active greenhouse gases, such as CO2, O3, CH4, N2O, and water vapor. Information obtained by measurements of the atmospheric concentration of these gases alone is limited; the additional measurements of the stable isotopic composition provide information that cannot be obtained otherwise. Isotopic fractionations during chemical, physical, and biological process in the ocean, land, and the atmosphere result in unique natural labels. Tracing these labels in time and space allows us both to identify specific fluxes of these gases, and to gain insights into the processes influencing the observed fluxes. Quantitative use of 18O and 13C in CO2 must rely on precise observations, on experimentation addressing the isotope effects underlying these observations, and on modeling that tests basic assumptions and extends applications beyond our measuring capabilities. Progress is still needed on all of these fronts. But the importance of this still developing science of stable isotopes in environmental research is indisputable.

  8. The stable isotope fingerprinting technique for agricultural pesticide

    NASA Astrophysics Data System (ADS)

    Suto, N.; Kawashima, H.

    2014-12-01

    The compound specific isotope analysis (CSIA) is nowadays an important and powerful tool in geochemical, environmental, and forensics field. In particular, the stable isotope ratio of pesticide is applied to biological process and reaction in the soil and distribution channel as forensics science. The aim of this study is to measure the stable isotope ratios of pesticide using various analytical methodologies, GC/IRMS, EA/IRMS, and LC/IRMS under high accuracy and precision. Therefore, these methods seemed to be important knowledge as geological field. In particular case, we present the method to measure carbon isotope ratio of nine malathion emulsion pesticides using GC/IRMS with cryo-focusing system to identify the source. In December 2013, food poisoning occurred after eating frozen dumplings (i.e., pizza and chicken nuggets) in Japan. There was a very high concentration, maximum value 15,000ppm, of malathion (diethyl (dimethoxythiophosphorylthio) succinate) in products. This incident was caused by an employee of process, and threatened the food safety. We analyzed the δ13C of malathion ranged from -30.63‰ to -29.54‰ (S.D. 0.10‰), the differences less than 1.0‰. All malathion emulsion sold in Japan are imported from Cheminova India Lat., Denmark to Sumitomo Chemical Co. Ltd., Japan. After that, Japanese each manufacture buy from Sumitomo Chemical Co. Ltd. And blended malathion and organic solvent (ethylbenzene and xylene). Therefore, ethylbenzene and xylene may be important tool as source identification. We measured the δ13C of ethylbenzene and m-,p-xylene, too. As the results, the δ13C of ethylbenzene and m-,p-xylene ranged from -28.20‰ to -20.84‰ (S.D. 0.16‰), -28.69‰ to -25.15‰ (S.D. 0.13‰), respectively. The δ13C of ethylbenzene and m-,p-xylene can be identified manufacture, although the δ13C of malathion indicated same value. In addition, we measured five pesticides (acephate, acetamiprid, glufosinate, glyphosate, and oxamyl) using

  9. Rapid Stable Isotope Turnover of Larval Fish in a Lake Superior Coastal Wetland: Implications for Diet and Life History Studies

    EPA Science Inventory

    Trophic linkages of larval fish in Lake Superior coastal wetlands, rivers and embayments can be identified using naturally occurring differences in the stable isotope ratios of nitrogen (15N:14N, ?15N) and carbon (13C:12C, ?13C). We sampled pelagic fish larvae weekly during sprin...

  10. Results from the stable isotope sampling network in Carboeuroflux

    NASA Astrophysics Data System (ADS)

    Yakir, D.; Hemming, D.

    2002-12-01

    Integrating stable isotopic measurements of canopy air and ecosystem organics with flux tower and ecophysiological data provides a powerful tool to differentiate between carbon sources and sinks, and scale-up processes from plant to ecosystem levels. During the 2001 and 2002 growing-seasons monthly flask samples of nocturnal canopy air and ecosystem organics were collected from selected forest flux sites within the Carboeuroflux network (13 sites in 2001 and 18 in 2002). Flask air was analysed for CO2 concentration ([CO2]), and the carbon and oxygen isotopic compositions (δ13C and δ18O) of this CO2. The δ18O of waters distilled from leaf, stem and soil samples, and the δ13C and δ18O of these dried, homogonised organic samples were also measured. Analytical precisions were ñ0.1ppmv for [CO2], ñ0.1 permil and ñ0.2 permil for the δ13C and δ18O of atmospheric CO2, ñ0.05 permil for water δ18O and ñ0.1 permil for both the δ13C and δ18O of organics. The δ13C of ecosystem respired CO2 (δ13CR) was determined for each sampling period and location using a Keeling plot approach. Ecosystem discrimination (Δ13CE) was estimated as the difference between the δ13Cs of background atmospheric CO2 and ecosystem respired CO2. The seasonal and spatial variation in these variables, and the δ13C and δ18O compositions of the organic samples are examined relative to meteorological and ecophysiological conditions. We assessed the potential for using the δ18O of ecosystem respired CO2 (δ18OR) together with that of soil and leaf waters to partition between the soil and above-ground respired CO2 sources. At sites where soil δ13C varied significantly from leaf δ13C, we also assessed the partitioning potential in using the δ13C data. More intensive sampling campaigns, including incubations in branch-bags, and leaf, trunk and soil chambers, were also conducted at specific sites to examine the partitioning and scale relationships between individual source CO2 contributions

  11. Applications of stable isotopes in clinical pharmacology

    PubMed Central

    Schellekens, Reinout C A; Stellaard, Frans; Woerdenbag, Herman J; Frijlink, Henderik W; Kosterink, Jos G W

    2011-01-01

    This review aims to present an overview of the application of stable isotope technology in clinical pharmacology. Three main categories of stable isotope technology can be distinguished in clinical pharmacology. Firstly, it is applied in the assessment of drug pharmacology to determine the pharmacokinetic profile or mode of action of a drug substance. Secondly, stable isotopes may be used for the assessment of drug products or drug delivery systems by determination of parameters such as the bioavailability or the release profile. Thirdly, patients may be assessed in relation to patient-specific drug treatment; this concept is often called personalized medicine. In this article, the application of stable isotope technology in the aforementioned three areas is reviewed, with emphasis on developments over the past 25 years. The applications are illustrated with examples from clinical studies in humans. PMID:21801197

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

    NASA Technical Reports Server (NTRS)

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

    2000-01-01

    The BOREAS TE-5 team collected measurements in the NSA and SSA on gas exchange, gas composition, and tree growth. This data set contains measurements of the concentration and stable carbon (C-13/C-12 and oxygen (O-18/O-16) isotope ratios of atmospheric CO2 in air samples collected at different heights within forest canopies. The data were collected to determine the influence of photosynthesis and respiration by the forest ecosystems on the concentration and stable isotope ratio of atmospheric CO2 These measurements were collected at the SSA during each 1994 IFC at OJP, OBS, and OA sites. Measurements were also collected at the NSA during each 1994 IFC at the OJP, T6R5S TE UBS, and T2Q6A TE OA sites. The stable isotope ratios are expressed using standard delta notation and in units of per mil. The isotope ratios are expressed relative to the international standard, PDB, for both carbon and oxygen samples. The data are stored in tabular ASCII files. The data files are available on a CD-ROM (see document number 20010000884), or from the Oak Ridge National Laboratory (ORNL) Distributed Activity Archive Center (DAAC).

  13. Magnesium stable isotope ecology using mammal tooth enamel

    NASA Astrophysics Data System (ADS)

    Martin, Jeremy E.; Vance, Derek; Balter, Vincent

    2015-01-01

    Geochemical inferences on ancient diet using bone and enamel apatite rely mainly on carbon isotope ratios (δ13C) and to a lesser extent on strontium/calcium (Sr/Ca) and barium/calcium (Ba/Ca) elemental ratios. Recent developments in nontraditional stable isotopes provide an unprecedented opportunity to use additional paleodietary proxies to disentangle complex diets such as omnivory. Of particular relevance for paleodietary reconstruction are metals present in large quantity in bone and enamel apatite, providing that biologically mediated fractionation processes are constrained. Calcium isotope ratios (δ44Ca) meet these criteria but exhibit complex ecological patterning. Stable magnesium isotope ratios (δ26Mg) also meet these criteria but a comprehensive understanding of its variability awaits new isotopic data. Here, 11 extant mammal species of known ecology from a single locality in equatorial Africa were sampled for tooth enamel and, together with vegetation and feces, analyzed for δ26Mg, δ13C, Sr/Ca, and Ba/Ca ratios. The results demonstrate that δ26Mg incorporated in tooth enamel becomes heavier from strict herbivores to omnivores/faunivores. Using data from experimentally raised sheep, we suggest that this 26Mg enrichment up the trophic chain is due to a 26Mg enrichment in muscle relative to bone. Notably, it is possible to distinguish omnivores from herbivores, using δ26Mg coupled to Ba/Ca ratios. The potential effects of metabolic and dietary changes on the enamel δ26Mg composition remain to be explored but, in the future, multiproxy approaches would permit a substantial refinement of dietary behaviors or enable accurate trophic reconstruction despite specimen-limited sampling, as is often the case for fossil assemblages.

  14. Magnesium stable isotope ecology using mammal tooth enamel.

    PubMed

    Martin, Jeremy E; Vance, Derek; Balter, Vincent

    2015-01-13

    Geochemical inferences on ancient diet using bone and enamel apatite rely mainly on carbon isotope ratios (δ(13)C) and to a lesser extent on strontium/calcium (Sr/Ca) and barium/calcium (Ba/Ca) elemental ratios. Recent developments in nontraditional stable isotopes provide an unprecedented opportunity to use additional paleodietary proxies to disentangle complex diets such as omnivory. Of particular relevance for paleodietary reconstruction are metals present in large quantity in bone and enamel apatite, providing that biologically mediated fractionation processes are constrained. Calcium isotope ratios (δ(44)Ca) meet these criteria but exhibit complex ecological patterning. Stable magnesium isotope ratios (δ(26)Mg) also meet these criteria but a comprehensive understanding of its variability awaits new isotopic data. Here, 11 extant mammal species of known ecology from a single locality in equatorial Africa were sampled for tooth enamel and, together with vegetation and feces, analyzed for δ(26)Mg, δ(13)C, Sr/Ca, and Ba/Ca ratios. The results demonstrate that δ(26)Mg incorporated in tooth enamel becomes heavier from strict herbivores to omnivores/faunivores. Using data from experimentally raised sheep, we suggest that this (26)Mg enrichment up the trophic chain is due to a (26)Mg enrichment in muscle relative to bone. Notably, it is possible to distinguish omnivores from herbivores, using δ(26)Mg coupled to Ba/Ca ratios. The potential effects of metabolic and dietary changes on the enamel δ(26)Mg composition remain to be explored but, in the future, multiproxy approaches would permit a substantial refinement of dietary behaviors or enable accurate trophic reconstruction despite specimen-limited sampling, as is often the case for fossil assemblages.

  15. Magnesium stable isotope ecology using mammal tooth enamel

    PubMed Central

    Martin, Jeremy E.; Vance, Derek; Balter, Vincent

    2015-01-01

    Geochemical inferences on ancient diet using bone and enamel apatite rely mainly on carbon isotope ratios (δ13C) and to a lesser extent on strontium/calcium (Sr/Ca) and barium/calcium (Ba/Ca) elemental ratios. Recent developments in nontraditional stable isotopes provide an unprecedented opportunity to use additional paleodietary proxies to disentangle complex diets such as omnivory. Of particular relevance for paleodietary reconstruction are metals present in large quantity in bone and enamel apatite, providing that biologically mediated fractionation processes are constrained. Calcium isotope ratios (δ44Ca) meet these criteria but exhibit complex ecological patterning. Stable magnesium isotope ratios (δ26Mg) also meet these criteria but a comprehensive understanding of its variability awaits new isotopic data. Here, 11 extant mammal species of known ecology from a single locality in equatorial Africa were sampled for tooth enamel and, together with vegetation and feces, analyzed for δ26Mg, δ13C, Sr/Ca, and Ba/Ca ratios. The results demonstrate that δ26Mg incorporated in tooth enamel becomes heavier from strict herbivores to omnivores/faunivores. Using data from experimentally raised sheep, we suggest that this 26Mg enrichment up the trophic chain is due to a 26Mg enrichment in muscle relative to bone. Notably, it is possible to distinguish omnivores from herbivores, using δ26Mg coupled to Ba/Ca ratios. The potential effects of metabolic and dietary changes on the enamel δ26Mg composition remain to be explored but, in the future, multiproxy approaches would permit a substantial refinement of dietary behaviors or enable accurate trophic reconstruction despite specimen-limited sampling, as is often the case for fossil assemblages. PMID:25535375

  16. Investigation of amino acid δ 13C signatures in bone collagen to reconstruct human palaeodiets using liquid chromatography-isotope ratio mass spectrometry

    NASA Astrophysics Data System (ADS)

    Choy, Kyungcheol; Smith, Colin I.; Fuller, Benjamin T.; Richards, Michael P.

    2010-11-01

    This research presents the individual amino acid δ 13C values in bone collagen of humans ( n = 9) and animals ( n = 27) from two prehistoric shell midden sites in Korea. We obtained complete baseline separation of 16 of the 18 amino acids found in bone collagen by using liquid chromatography-isotope ratio mass spectrometry (LC-IRMS). The isotopic results reveal that the humans and animals in the two sites had similar patterns in essential amino acids (EAAs) and non-essential amino acids (NEAAs). The EAA and NEAA δ 13C values in humans are intermediate between those in marine and terrestrial animals. However, the threonine δ 13C values in humans and animals measured in this study are more highly enriched than those of other amino acids. At both sites, all amino acids in marine animals are 13C-enriched relative to those of the terrestrial animals. The isotopic evidence suggests that the Tongsamdong human had EAAs and NEAAs from marine food resources, while the Nukdo humans mainly had EAAs from terrestrial food resources but obtained NEAAs from both terrestrial and marine resources. The δ 13C isotopic differences in amino acids between marine and terrestrial animals were the largest for glycine (NEAA) and histidine (EAA) and the smallest for tyrosine (NEAA) and phenylalanine (EAA). In addition, threonine among the EAAs also had a large difference (˜8‰) in δ 13C values between marine and terrestrial animals, and has the potential to be used as an isotopic marker in palaeodietary studies. Threonine δ 13C values were used in conjunction with the established Δ 13C Glycine-phenylalanine values and produced three distinct dietary groups (terrestrial, omnivorous, and marine). In addition, threonine δ 13C values and Δ 13C Serine-phenylalanine values were discovered to separate between two dietary groups (terrestrial vs. marine), and these δ 13C values may provide a potential new indicator for investigating the distinction between marine and terrestrial protein

  17. 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

  18. The effects of preservation methods, dyes and acidification on the isotopic values (δ15N and δ13C) of two zooplankton species from the KwaZulu-Natal Bight, South Africa.

    PubMed

    de Lecea, Ander M; Cooper, Rachel; Omarjee, Aadila; Smit, Albertus J

    2011-07-15

    Stable isotope measurements are an important tool for ecosystem trophic linkage studies. Ideally, fresh samples should be used for isotopic analysis, but in many cases organisms must be preserved and analysed later. In some cases dyes must be used to help distinguish organisms from detritus. Since preservatives and dyes are carbon-based, their addition could influence isotopic readings. This study aims to improve understanding of the effects of sample storage method, dye addition and acidification on the δ(15)N and δ(13)C values of zooplankton (Euphasia frigida and Undinula vulgaris). Zooplankton was collected and preserved by freezing, or by the addition of 5% formalin, 70% ethanol, or 5% formalin with added Phloxine B or Rose Bengal, and stored for 1 month before processing. Samples in 5% formalin and 70% ethanol were also kept and processed after 3 and 9 months to study changes over time. Formalin caused the largest enrichment for δ(13)C and a slight enrichment for δ(15)N, while ethanol produced a slight depletion for δ(13)C, and different effects on δ(15)N depending on the species. In formalin, dyes depleted the δ(13)C values, but had variable effects on δ(15)N, relative to formalin alone. Acidification had no significant effect on δ(15)N or δ(13)C for either species. Long-term storage showed that the effects of the preservatives were species-dependent. Although the effects on δ(15)N varied, a relative enrichment in (13)C of samples occurred with time. This can have important consequences for the understanding of the organic flow within a food web and for trophic studies. .

  19. Stable carbon isotope depth profiles and soil organic carbon dynamics in the lower Mississippi Basin

    USGS Publications Warehouse

    Wynn, J.G.; Harden, J.W.; Fries, T.L.

    2006-01-01

    Analysis of depth trends of 13C abundance in soil organic matter and of 13C abundance from soil-respired CO2 provides useful indications of the dynamics of the terrestrial carbon cycle and of paleoecological change. We measured depth trends of 13C abundance from cropland and control pairs of soils in the lower Mississippi Basin, as well as the 13C abundance of soil-respired CO2 produced during approximately 1-year soil incubation, to determine the role of several candidate processes on the 13C depth profile of soil organic matter. Depth profiles of 13C from uncultivated control soils show a strong relationship between the natural logarithm of soil organic carbon concentration and its isotopic composition, consistent with a model Rayleigh distillation of 13C in decomposing soil due to kinetic fractionation during decomposition. Laboratory incubations showed that initially respired CO 2 had a relatively constant 13C content, despite large differences in the 13C content of bulk soil organic matter. Initially respired CO2 was consistently 13C-depleted with respect to bulk soil and became increasingly 13C-depleted during 1-year, consistent with the hypothesis of accumulation of 13C in the products of microbial decomposition, but showing increasing decomposition of 13C-depleted stable organic components during decomposition without input of fresh biomass. We use the difference between 13C / 12C ratios (calculated as ??-values) between respired CO 2 and bulk soil organic carbon as an index of the degree of decomposition of soil, showing trends which are consistent with trends of 14C activity, and with results of a two-pooled kinetic decomposition rate model describing CO2 production data recorded during 1 year of incubation. We also observed inconsistencies with the Rayleigh distillation model in paired cropland soils and reasons for these inconsistencies are discussed. ?? 2005 Elsevier B.V. All rights reserved.

  20. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Winschel, R.A.; Lancet, M.S.; Burke, F.P.

    1991-04-01

    This is the final report which was a thirty-four month project conducted to develop and demonstrate stable carbon isotope analysis as a method to quantitatively distinguish the source of carbon in products of coal/petroleum coprocessing. The work included assessing precision, accuracy, the range of application and the significance of selective isotopic fractionation effects. A method was devised to correct for selective isotopic fractionation errors. The method was demonstrated through application with samples from twelve continuous-unit coprocessing tests. A data base of carbon isotope analyses is appended. 21 refs.

  1. Multi-Isotopic (δ2H, δ13C, δ15N) Tracing of Molt Origin for Red-Winged Blackbirds Associated with Agro-Ecosystems

    PubMed Central

    Werner, Scott J.; Hobson, Keith A.; Van Wilgenburg, Steven L.; Fischer, Justin W.

    2016-01-01

    We analyzed stable-hydrogen (δ2H), carbon (δ13C) and nitrogen (δ 15N) isotope ratios in feathers to better understand the molt origin and food habits of Red-winged Blackbirds (Agelaius phoeniceus) near sunflower production in the Upper Midwest and rice production in the Mid-South of the United States. Outer primary feathers were used from 661 after-second-year (ASY) male blackbirds collected in Minnesota, Montana, North Dakota and South Dakota (spring collection), and Arkansas, Louisiana, Mississippi, Missouri and Texas (winter collection). The best-fit model indicated that the combination of feather δ2H, δ13C and δ15N best predicted the state of sample collections and thus supported the use of this approach for tracing molt origins in Red-winged Blackbirds. When considering only birds collected in spring, 56% of birds were classified to their collection state on the basis of δ2H and δ13C alone. We then developed feather isoscapes for δ13C based upon these data and for δ2H based upon continental patterns of δ2H in precipitation. We used 81 birds collected at the ten independent sites for model validation. The spatially-explicit assignment of these 81 birds to the δ2H isoscape resulted in relatively high rates (~77%) of accurate assignment to collection states. We also modeled the spatial extent of C3 (e.g. rice, sunflower) and C4 (corn, millet, sorghum) agricultural crops grown throughout the Upper Midwest and Mid-South United States to predict the relative use of C3- versus C4-based foodwebs among sampled blackbirds. Estimates of C3 inputs to diet ranged from 50% in Arkansas to 27% in Minnesota. As a novel contribution to blackbird conservation and management, we demonstrate how such feather isoscapes can be used to predict the molt origin and interstate movements of migratory blackbirds for subsequent investigations of breeding biology (e.g. sex-specific philopatry), agricultural depredation, feeding ecology, physiology of migration and sensitivity to

  2. Multi-Isotopic (δ2H, δ13C, δ15N) Tracing of Molt Origin for Red-Winged Blackbirds Associated with Agro-Ecosystems.

    PubMed

    Werner, Scott J; Hobson, Keith A; Van Wilgenburg, Steven L; Fischer, Justin W

    2016-01-01

    We analyzed stable-hydrogen (δ2H), carbon (δ13C) and nitrogen (δ 15N) isotope ratios in feathers to better understand the molt origin and food habits of Red-winged Blackbirds (Agelaius phoeniceus) near sunflower production in the Upper Midwest and rice production in the Mid-South of the United States. Outer primary feathers were used from 661 after-second-year (ASY) male blackbirds collected in Minnesota, Montana, North Dakota and South Dakota (spring collection), and Arkansas, Louisiana, Mississippi, Missouri and Texas (winter collection). The best-fit model indicated that the combination of feather δ2H, δ13C and δ15N best predicted the state of sample collections and thus supported the use of this approach for tracing molt origins in Red-winged Blackbirds. When considering only birds collected in spring, 56% of birds were classified to their collection state on the basis of δ2H and δ13C alone. We then developed feather isoscapes for δ13C based upon these data and for δ2H based upon continental patterns of δ2H in precipitation. We used 81 birds collected at the ten independent sites for model validation. The spatially-explicit assignment of these 81 birds to the δ2H isoscape resulted in relatively high rates (~77%) of accurate assignment to collection states. We also modeled the spatial extent of C3 (e.g. rice, sunflower) and C4 (corn, millet, sorghum) agricultural crops grown throughout the Upper Midwest and Mid-South United States to predict the relative use of C3- versus C4-based foodwebs among sampled blackbirds. Estimates of C3 inputs to diet ranged from 50% in Arkansas to 27% in Minnesota. As a novel contribution to blackbird conservation and management, we demonstrate how such feather isoscapes can be used to predict the molt origin and interstate movements of migratory blackbirds for subsequent investigations of breeding biology (e.g. sex-specific philopatry), agricultural depredation, feeding ecology, physiology of migration and sensitivity to

  3. Stable Isotope Resolved Metabolomics Studies in Ex Vivo TIssue Slices

    PubMed Central

    Fan, Teresa W-M.; Lane, Andrew N.; Higashi, Richard M.

    2016-01-01

    An important component of this methodology is to assess the role of the tumor microenvironment on tumor growth and survival. To tackle this problem, we have adapted the original approach of Warburg 1, by combining thin tissue slices with Stable Isotope Resolved Metabolomics (SIRM) to determine detailed metabolic activity of human tissues. SIRM enables the tracing of metabolic transformations of source molecules such as glucose or glutamine over defined time periods, and is a requirement for detailed pathway tracing and flux analysis. In our approach, we maintain freshly resected tissue slices (both cancerous and non- cancerous from the same organ of the same subject) in cell culture media, and treat with appropriate stable isotope-enriched nutrients, e.g. 13C6-glucose or 13C5, 15N2 -glutamine. These slices are viable for at least 24 h, and make it possible to eliminate systemic influence on the target tissue metabolism while maintaining the original 3D cellular architecture. It is therefore an excellent pre-clinical platform for assessing the effect of therapeutic agents on target tissue metabolism and their therapeutic efficacy on individual patients 2,3. PMID:27158639

  4. Stable Isotope Mapping of Alaskan Grasses and Marijuana

    NASA Astrophysics Data System (ADS)

    Booth, A. L.; Wooller, M. J.

    2008-12-01

    The spatial variation of isotope signatures in organic material is a useful forensic tool, particularly when applied to the task of tracking the production and distribution of plant-derived illicit drugs. In order to identify the likely grow-locations of drugs such as marijuana from unknown locations (i.e., confiscated during trafficking), base isotope maps are needed that include measurements of plants from known grow-locations. This task is logistically challenging in remote, large regions such as Alaska. We are therefore investigating the potential of supplementing our base (marijuana) isotope maps with data derived from other plants from known locations and with greater spatial coverage in Alaska. These currently include >150 samples of modern C3 grasses (Poaceae) as well as marijuana samples (n = 18) from known grow-locations across the state. We conducted oxygen, carbon and nitrogen stable isotope analyses of marijuana and grasses (Poaceae). Poaceae samples were obtained from the University of Alaska Fairbanks (UAF) Museum of the North herbarium collection, originally collected by field botanists from around Alaska. Results indicate that the oxygen isotopic composition of these grasses range from 10‰ to 30‰, and broadly mirror the spatial pattern of water isotopes in Alaska. Our marijuana samples were confiscated around the state of Alaska and supplied to us by the UAF Police Department. δ13C, δ15N and δ18O values exhibit geographic patterns similar to the modern grasses, but carbon and nitrogen isotopes of some marijuana plants appear to be influenced by additional factors related to indoor growing conditions (supplementary CO2 sources and the application of organic fertilizer). As well as providing a potential forensic resource, our Poaceae isotope maps could serve additional value by providing resources for studying ecosystem nutrient cycling, for tracing natural ecological processes (i.e., animal migration and food web dynamics) and providing

  5. Assimilation of benzene carbon through multiple trophic levels traced by different stable isotope probing methodologies.

    PubMed

    Bastida, Felipe; Jechalke, Sven; Bombach, Petra; Franchini, Alessandro G; Seifert, Jana; von Bergen, Martin; Vogt, Carsten; Richnow, Hans H

    2011-08-01

    The flow of benzene carbon along a food chain consisting of bacteria and eukaryotes, including larvae (Diptera: Chironomidae), was evaluated by total lipid fatty acids (TLFAs)-, amino acid- and protein-stable isotope probing (SIP). A coconut-fibre textile, colonized by a benzene-degrading biofilm, was sampled in a system established for the remediation of benzene, toluene, ethylbenzene and xylenes (BTEX)-polluted groundwater and incubated with (12)C- and [(13)C(6)]-benzene (>99 at.%) in a batch-scale experiment for 2-8 days. After 8 days, Chironomus sp. larvae were added to study carbon flow to higher trophic levels. Gas chromatography-combustion-isotope ratio monitoring mass spectrometry of TLFA showed increased isotope ratios in the (13)C-benzene-incubated biofilm. A higher (13)C-enrichment was observed in TLFAs, indicative of Gram-negative bacteria than for Gram-positive. Fatty acid indicators of eukaryotes showed significant (13)C-incorporation, but to a lower extent than bacterial indicators. Fatty acids extracted from larvae feeding on (13)C-biofilm reached an isotopic ratio of 1.55 at.%, illustrating that the larvae feed, to some extent, on labelled biomass. No (13)C-incorporation was detectable in larval proteins after their separation by sodium-dodecyl sulphate-polyacrylamide gel electrophoresis and analysis by nano-liquid-chromatography-mass spectrometry. The flow of benzene-derived carbon could be traced in a food web consisting of bacteria and eukaryotes.

  6. Diet of spotted bats (Euderma maculatum) in Arizona as indicated by fecal analysis and stable isotopes

    EPA Science Inventory

    We assessed diet of spotted bats (Euderma maculatum (J.A. Allen, 1891)) by visual analysis of bat feces and stable carbon (δ13C) and nitrogen (δ15N) isotope analysis of bat feces, wing, hair, and insect prey. We collected 33 fecal samples from spotted bats and trapped 3755 insect...

  7. Experimental Evaluation of Stable Isotope Fractionation in Fish Muscle and Otoliths

    EPA Science Inventory

    We investigated an unresolved question in the use of stable isotopes to determine diet and trophic position of fish using both muscle and otoliths. We determined: i) the degree of fractionation of δ13C and δ15N between diet and muscle, and assessed if fractionation was consistent...

  8. Patterns in stable isotope ratios of particulate material from the eastern US continental shelf

    EPA Science Inventory

    Stable isotope measurements of nitrogen and carbon (δ15N, δ13C) in estuarine, nearshore, and open ocean ecosystems are often utilized in order to characterize human influences, elucidate food web dynamics, or better understand nitrogen cycling. Reliable information a...

  9. Analysis of stable isotopes in fish mucus during a controlled diet switch

    EPA Science Inventory

    We have used a controlled diet switch in steelhead trout (Oncorhynchus mykiss) at the Oregon Hatchery Research Center to study the time rates of changes in stable isotopes of carbon and nitrogen (13C and 15N) in epidermal mucus, a rapidly responding “tissue.” Because of the ra...

  10. RAPID AND PRECISE METHOD FOR MEASURING STABLE CARBON ISOTOPE RATIOS OF DISSOLVED INORGANIC CARBON

    EPA Science Inventory

    We describe a method for rapid preparation, concentration and stable isotopic analysis of dissolved inorganic carbon (d13C-DIC). Liberation of CO2 was accomplished by placing 100 ?l phosphoric acid and 0.9 ml water in an evacuated 1.7-ml gas chromatography (GC) injection vial. Fo...

  11. Stable Carbon and Oxygen Isotope Ratios of Otoliths Differentiate Winter Flounder (Pseudopleuonectes americanus) Habitats

    EPA Science Inventory

    Stable carbon (13C) and oxygen (18O) isotope ratios were measured in otoliths of juvenile winter flounder (Pseudopleuronectes americanus) collected from 18 nursery areas along the coast of Rhode Island, USA. Samples were obtained during June and July of 2002 from locations tha...

  12. Quantifying intra-population variability in stable isotope data for spotted seatrout (cynoscion nebulosus)

    EPA Science Inventory

    Stable isotope (SI) values of carbon (δ13C) and nitrogen (δ15N) are useful for determining the trophic connectivity between species within an ecosystem, but interpretation of these data involves important assumptions about sources of intrapopulation variability. We compared i...

  13. FATTY ACID STABLE ISOTOPE INDICATORS OF MICROBIAL CARBON SOURCE IN TROPICAL SOILS

    EPA Science Inventory

    The soil microbial community plays an important role in tropical ecosystem functioning because of its importance in the soil organic matter (SOM) cycle. We have measured the stable carbon isotopic ratio (delta13C) of individual phospholipid fatty acids (PLFAs) in a variety of tr...

  14. Stable isotope analysis of fish mucus during a controlled diet switch

    EPA Science Inventory

    We have used a controlled diet switch in steelhead trout (Oncorhynchus mykiss) at the Oregon Hatchery Research Center to study the time rates of changes in stable isotopes of carbon and nitrogen (13C and 15N) in epidermal mucus, a rapidly responding “tissue.” Because of the ra...

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  16. Detection of adulteration in honey samples added various sugar syrups with 13C/12C isotope ratio analysis method.

    PubMed

    Tosun, Murat

    2013-06-01

    Honey can be adulterated in various ways. One of the adulteration methods is the addition of different sugar syrups during or after honey production. Starch-based sugar syrups, high fructose corn syrup (HFCS), glucose syrup (GS) and saccharose syrups (SS), which are produced from beet or canes, can be used for adulterating honey. In this study, adulterated honey samples were prepared with the addition of HFCS, GS and SS (beet sugar) at a ratio of 0%, 10%, 20%, 40% and 50% by weight. (13)C/(12)C analysis was conducted on these adulterated honey samples using an isotope ratio mass spectrometer in combination with an elemental analyser (EA-IRMS). As a result, adulteration using C(4) sugar syrups (HFCS and GS) could be detected to a certain extent while adulteration of honey using C(3) sugar syrups (beet sugar) could not be detected. Adulteration by using SS (beet sugar) still has a serious detection problem, especially in countries in which beet is used in manufacturing sugar. For this reason, practice and analysis methods are needed to meet this deficit and to detect the adulterations precisely in the studies that will be conducted.

  17. Geometries and tautomerism of OHN hydrogen bonds in aprotic solution probed by H/D isotope effects on (13)C NMR chemical shifts.

    PubMed

    Tolstoy, Peter M; Guo, Jing; Koeppe, Benjamin; Golubev, Nikolai S; Denisov, Gleb S; Smirnov, Sergei N; Limbach, Hans-Heinrich

    2010-10-14

    The (1)H and (13)C NMR spectra of 17 OHN hydrogen-bonded complexes formed by CH(3)(13)COOH(D) with 14 substituted pyridines, 2 amines, and N-methylimidazole have been measured in the temperature region between 110 and 150 K using CDF(3)/CDF(2)Cl mixture as solvent. The slow proton and hydrogen bond exchange regime was reached, and the H/D isotope effects on the (13)C chemical shifts of the carboxyl group were measured. In combination with the analysis of the corresponding (1)H chemical shifts, it was possible to distinguish between OHN hydrogen bonds exhibiting a single proton position and those exhibiting a fast proton tautomerism between molecular and zwitterionic forms. Using H-bond correlations, we relate the H/D isotope effects on the (13)C chemical shifts of the carboxyl group with the OHN hydrogen bond geometries.

  18. Stable Isotope Composition of Fatty Acids in Organisms of Different Trophic Levels in the Yenisei River

    PubMed Central

    Gladyshev, Michail I.; Sushchik, Nadezhda N.; Kalachova, Galina S.; Makhutova, Olesia N.

    2012-01-01

    We studied four-link food chain, periphytic microalgae and water moss (producers), trichopteran larvae (consumers I), gammarids (omnivorous – consumers II) and Siberian grayling (consumers III) at a littoral site of the Yenisei River on the basis of three years monthly sampling. Analysis of bulk carbon stable isotopes and compound specific isotope analysis of fatty acids (FA) were done. As found, there was a gradual depletion in 13C contents of fatty acids, including essential FA upward the food chain. In all the trophic levels a parabolic dependence of δ13C values of fatty acids on their degree of unsaturation/chain length occurred, with 18:2n-6 and 18:3n-3 in its lowest point. The pattern in the δ13C differences between individual fatty acids was quite similar to that reported in literature for marine pelagic food webs. Hypotheses on isotope fractionation were suggested to explain the findings. PMID:22470513

  19. Stable isotopes in Lithuanian bioarcheological material

    NASA Astrophysics Data System (ADS)

    Skipityte, Raminta; Jankauskas, Rimantas; Remeikis, Vidmantas

    2015-04-01

    Investigation of bioarcheological material of ancient human populations allows us to understand the subsistence behavior associated with various adaptations to the environment. Feeding habits are essential to the survival and growth of ancient populations. Stable isotope analysis is accepted tool in paleodiet (Schutkowski et al, 1999) and paleoenvironmental (Zernitskaya et al, 2014) studies. However, stable isotopes can be useful not only in investigating human feeding habits but also in describing social and cultural structure of the past populations (Le Huray and Schutkowski, 2005). Only few stable isotope investigations have been performed before in Lithuanian region suggesting a quite uniform diet between males and females and protein intake from freshwater fish and animal protein. Previously, stable isotope analysis has only been used to study a Stone Age population however, more recently studies have been conducted on Iron Age and Late medieval samples (Jacobs et al, 2009). Anyway, there was a need for more precise examination. Stable isotope analysis were performed on human bone collagen and apatite samples in this study. Data represented various ages (from 5-7th cent. to 18th cent.). Stable carbon and nitrogen isotope analysis on medieval populations indicated that individuals in studied sites in Lithuania were almost exclusively consuming C3 plants, C3 fed terrestrial animals, and some freshwater resources. Current investigation demonstrated social differences between elites and country people and is promising in paleodietary and daily life reconstruction. Acknowledgement I thank prof. dr. G. Grupe, Director of the Anthropological and Palaeoanatomical State Collection in Munich for providing the opportunity to work in her laboratory. The part of this work was funded by DAAD. Antanaitis-Jacobs, Indre, et al. "Diet in early Lithuanian prehistory and the new stable isotope evidence." Archaeologia Baltica 12 (2009): 12-30. Le Huray, Jonathan D., and Holger

  20. 13C/12C and 15N/14N Isotope Analysis to Characterize Natural Degradation of Atrazine: Evidence from Parent and Daughter Compound Values

    NASA Astrophysics Data System (ADS)

    Elsner, Martin; Meyer, Armin

    2013-04-01

    The mobile and still herbicidal metabolites desethylatrazine (DEA) and desisopropylatrazine (DIA) are frequently detected together with its parent compound atrazine (Atz) in the aquatic environment. Interpretation of their transformation state is often difficult with current methods, which are mainly measuring concentrations. Alternatively, compound specific isotope analyses (CSIA) has become a novel tool to detect degradation processes of contaminants in groundwater. The aim of our study was to investigate on the lab scale 13C/12C and 15N/14N isotope trends in parent and daughter compounds associated with different degradation scenarios of atrazine likely to occur in the environment. Thus atrazine was dealkylated with (i) permanganate and (ii) the bacterium Rhodococcus sp. NI86/21. In both transformations, 13C/12C ratios of atrazine increased strongly (epsilon carbon/permanganate = -4.6 ± 0.6 ‰ and epsilon carbon/Rhodoccoccus = -3.8 ± 0.2 ‰) whereas nitrogen isotope fractionation was small. 13C/12C ratios of DEA showed the following trends. (i) When DEA was formed as only product (Atz + permanganate) 13C/12C remained constant, close to the initial value of Atz. (ii) When DEA was formed together with deisopropylatrazine (biodegradation of Atz) 13C/12C increased, but only within 2‰. (iii) When DEA and DIA was further biodegraded, 13C/12C increased for both metabolites up to 9‰. Thus strong enrichment of 13C/12C in the metabolites in comparison to Atz can give strong testimony for further breakdown of the metabolite.

  1. Development of a stable isotope dilution assay for tenuazonic acid.

    PubMed

    Asam, Stefan; Liu, Yang; Konitzer, Katharina; Rychlik, Michael

    2011-04-13

    A stable isotope dilution assay (SIDA) for the Alternaria mycotoxin tenuazonic acid was developed. Therefore, [(13)C(6),(15)N]-tenuazonic acid was synthesized from [(13)C(6),(15)N]-isoleucine by Dieckmann intramolecular cyclization after acetoacetylation with diketene. The synthesized [(13)C(6),(15)N]-tenuazonic acid was used as the internal standard for determination of tenuazonic acid in tomato products by liquid chromatography tandem mass spectrometry after derivatization with 2,4-dinitrophenylhydrazine. Method validation revealed a limit of detection of 0.1 μg/kg and a limit of quantitation of 0.3 μg/kg. Recovery was close to 100% in the range of 3-300 μg/kg. Determination of tenuazonic acid in two samples of different tomato ketchups (naturally contaminated) was achieved with a coefficient of variation of 2.3% and 4.7%. Different tomato products (n = 16) were analyzed for their content of tenuazonic acid using the developed SIDA. Values were between 15 and 195 μg/kg (tomato ketchup, n = 9), 363 and 909 μg/kg (tomato paste, n = 2), and 8 and 247 μg/kg (pureed tomatoes and comparable products, n = 5).

  2. Stable isotope dilution assays in mycotoxin analysis.

    PubMed

    Rychlik, Michael; Asam, Stefan

    2008-01-01

    The principle and applications of stable isotope dilution assays (SIDAs) in mycotoxin analysis are critically reviewed. The general section includes historical aspects of SIDAs, the prerequisites and limitations of the use of stable isotopically labelled internal standards, and possible calibration procedures. In the application section actual SIDAs for the analysis of trichothecenes, zearalenone, fumonisins, patulin, and ochratoxin A are presented. The syntheses and availability of labelled mycotoxins for use as internal standards is reviewed and specific advances in food analysis and toxicology are demonstrated. The review indicates that LC-MS applications, in particular, require the use of stable isotopically labelled standards to compensate for losses during clean-up and for discrimination due to ion suppression. As the commercial availability of these compounds continues to increase, SIDAs can be expected to find expanding use in mycotoxin analysis.

  3. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Lancet, M.S.; Winschel, R.A.; Burke, F.P.

    1991-01-01

    Consol R D is developing and demonstrating stable carbon isotope analysis as a method to quantitatively distinguish coal-derived and petroleum-derived carbon in products from coal/petroleum coprocessing. The approach taken is to develop the method, then demonstrate its application an authentic continuous-unit products. The experimental details used for stable carbon isotope analyses by the organization that performs most of those analyses under this contract are described. A method was developed previously under this contract to correct the carbon sourcing calculations performed from stable carbon isotope analyses for selective isotopic fractionation. The method relies on three assumptions. This quarter, a study was completed to define the sensitivity of the carbon sourcing results to errors in the assumptions. Carbon contents and carbon isotope ratios were determined for the available feeds and product fractions from HRI bench-scale coprocessing Run 238-10 (Texas lignite/Hondo vacuum still bottoms (VSB), Texas lignite/Cold Lake VSB and Westerholt coal/Cold Lake VSB). These data were used for carbon sourcing calculations and individual feedstock conversion calculations. A previously devised means for correcting for selective isotope fractionation was applied. 6 refs., 30 figs., 16 tabs.

  4. Stable isotopes of C and S as indicators of habitat use by fish in small oregon Coast range streams

    EPA Science Inventory

    We are using stable isotopes of C, N, O and S (H planned) to study the ecology of coho salmon in streams of the Oregon Coast Range. We have found isotopes of C and, surprisingly, S to be very useful in discriminating rearing habitats in our small streams. We found 13C values ...

  5. Digenean trematodes-marine mollusc relationships: a stable isotope study.

    PubMed

    Dubois, S Y; Savoye, N; Sauriau, P-G; Billy, I; Martinez, P; de Montaudouin, X

    2009-03-09

    The stable carbon and nitrogen isotopic composition of digenean trematode parasites and their marine mollusc hosts was investigated to describe the potential influence of parasites on their host and its different tissues, and to obtain further insight into their trophic relationships. Four parasite-host systems were studied: Labratrema minimus-Cerastoderma edule, Monorchis parvus-C. edule, Lepocreadiidae parasites-Nassarius reticulatus and Zoogonidae parasites-N. reticulatus. Among the 4 sampling occasions reported here and corresponding to the 4 parasite-host systems, isotopic shifts from pathologic (i.e. linked to disturbances in host metabolism) and mass-balance (i.e. linked to significant differences between host and parasite isotopic signatures) origins were observed only once. Both corresponded to delta 13C measurements of the L. minimus-C. edule system when the infestation load (percentage parasite dry weight compared to total flesh dry weight) was highest (9 to 25%, mean = 16%) over the sampling period. Overall, measurements indicate that digenean trematode parasitism induced low or no shifts in isotopic signatures of C. edule and N. reticulatus tissues. The 2 endoparasites L. minimus and M. parvus appeared to be slightly depleted in 13C compared to C. edule digestive gland and gonads, which were the most parasitized tissues. In contrast, no fractionation or low 15N trophic enrichments occurred in the parasites. These results highly contrast with the classical trophic enrichment reported in prey-predator systems but are in agreement with the scarce literature regarding other parasite-host systems. Our results indicate that (1) digenean trematodes mainly feed on digestive glands (the cockle tissue with which they are mainly associated) with a possible slight preference for lipids, and (2) fractionation due to parasite metabolism should be low due to abbreviated metabolic pathways and/or slight loss of materials through excretion, tegument diffusion and

  6. Stable Isotope Evidence for Planetary Differentiation

    NASA Astrophysics Data System (ADS)

    Shahar, A.; Mao, W. L.; Schauble, E. A.; Caracas, R.; Reagan, M. M.; Gleason, A. E.

    2015-12-01

    Planetary differentiation occurred at high temperature and varying oxygen fugacity, on bodies with varying compositions and internal pressures. The specific conditions at which bodies differentiated and the chemical fingerprints left by differentiation can be investigated by measuring stable isotope ratios in natural samples. Much can be learned by combining those data with experiments that systematically investigate the chemical and physical conditions within differentiating bodies. In this talk we focus on one variable in particular that has not been well defined with respect to stable isotope fractionation: pressure. We will present new iron isotope data on how pressure affects isotope fractionation factors for a number of iron compounds relative to silicate. The processes governing iron isotope fractionation in igneous rocks have been debated extensively over the past decade. Analyses of natural samples show that iron isotopes are fractionated at both the whole rock and mineral scales. This fractionation has been interpreted to be a result of several processes including a possible signature of high pressure core formation. We have collected new high pressure synchrotron nuclear resonant inelastic x-ray scattering data from Sector 16-ID-D at the Advanced Photon Source on 57Fe enriched Fe, FeO, FeHx and Fe3C. Our data show clear trends with pressure implying that not only does pressure have an effect on the iron isotope beta factors but also a fractionation amongst the alloys. This suggests that depending on the light element in the core, there will be a different resulting signature in the iron isotope record. We will discuss the likelihood of different light elements in the core based on these results, as well as the theoretical predictions for the same phases. Finally, we will present the fractionation expected between metal and silicate at high pressure and high temperature in order to determine if core formation would indeed leave an isotopic signature in

  7. Equatorial Pacific ``stable isotope reference curve'' for the Oligocene

    NASA Astrophysics Data System (ADS)

    Pälike, H.; Norris, R.; Herle, J. O.; Wilson, P. A.; Lear, C. H.; Coxall, H. K.; Tripati, A. K.

    2005-12-01

    We present an uninterrupted chronology of climate and ocean carbon chemistry from ODP Site 1218 recovered in the equatorial Pacific, from the Eocene / Oligocene to the Oligocene / Miocene boundary, ~34 to 23 Ma. Using astronomically age calibrated data we find a strong imprint of the 405, 127 and 96-thousand-year (kyr) Earth's eccentricity as well as a dominant influence of the 1.2 million year (Myr) obliquity amplitude modulation cycles on periodically re-occurring Oligocene glacial and carbon cycle events. In combination, these astronomical modulations act as the ``heartbeat'' of the Oligocene climate system. The response of the climate system to intricate orbital variations is striking and suggests a fundamental role of the carbon cycle in the interaction between solar forcing and climate. Our record provides a new high-resolution view of the Oligocene climate system, prompts a re-evaluation of the previously hypothesised late Oligocene deglaciation, and sheds new light on Oligocene inter-ocean isotope gradients. Salient observations include foraminiferal benthic stable oxygen and carbon isotopes that co-vary, a phase lag of δ13C w.r.t. δ18O for the 405 kyr cycle, preferential filtering of longer orbital periods in δ13C, presumably due to σCO2 reservoir buffering. We then use simple orbitally forced carbon cycle box models and manage to re-create the patterns observed in our data, including the overall strong amplitude of 405 kyr cycles in δ13C. Depending on ice-sheet presence and pCO2 concentrations, our model predicts re-occurring conditions favouring glaciations every 2.4 Myr, including the Eocene/Oligocene transition.

  8. Abundance Anomaly of the 13C Isotopic Species of c-C3H2 in the Low-mass Star Formation Region L1527

    NASA Astrophysics Data System (ADS)

    Yoshida, Kento; Sakai, Nami; Tokudome, Tomoya; López-Sepulcre, Ana; Watanabe, Yoshimasa; Takano, Shuro; Lefloch, Bertrand; Ceccarelli, Cecilia; Bachiller, Rafael; Caux, Emmanuel; Vastel, Charlotte; Yamamoto, Satoshi

    2015-07-01

    The rotational spectral lines of c-C3H2 and two kinds of the 13C isotopic species, c-{}13{{CCCH}}2 ({C}2v symmetry) and c-{{CC}}13{{CH}}2 (Cs symmetry), have been observed in the 1-3 mm band toward the low-mass star-forming region L1527. We have detected 7, 3, and 6 lines of c-C3H2, c-{}13{{CCCH}}2, and c-{{CC}}13{{CH}}2, respectively, with the Nobeyama 45 m telescope and 34, 6, and 13 lines, respectively, with the IRAM 30 m telescope, where seven, two, and two transitions, respectively, are observed with both telescopes. With these data, we have evaluated the column densities of the normal and 13C isotopic species. The [c-C3H2]/[c-{}13{{CCCH}}2] ratio is determined to be 310 ± 80, while the [c-C3H2]/[c-{{CC}}13{{CH}}2] ratio is determined to be 61 ± 11. The [c-C3H2]/[c-{}13{{CCCH}}2] and [c-C3H2]/[c-{{CC}}13{{CH}}2] ratios expected from the elemental 12C/13C ratio are 60-70 and 30-35, respectively, where the latter takes into account the statistical factor of 2 for the two equivalent carbon atoms in c-C3H2. Hence, this observation further confirms the dilution of the 13C species in carbon-chain molecules and their related molecules, which are thought to originate from the dilution of 13C+ in the gas-phase C+ due to the isotope exchange reaction: {}13{{{C}}}++{CO}\\to {}13{CO}+{{{C}}}+. Moreover, the abundances of the two 13C isotopic species are different from each other. The ratio of c-{}13{{CCCH}}2 species relative to c-{{CC}}13{{CH}}2 is determined to be 0.20 ± 0.05. If 13C were randomly substituted for the three carbon atoms, the [c-{}13{{CCCH}}2]/[c-{{CC}}13{{CH}}2] ratio would be 0.5. Hence, the observed ratio indicates that c-{{CC}}13{{CH}}2 exists more favorably. Possible origins of the different abundances are discussed. Based on observations carried out with the IRAM 30 m Telescope and the NRO 45 m Telescope. IRAM is supported by INSU/CNRS (France), MPG (Germany), and IGN (Spain). NRO is a branch of the National Astronomical Observatory of Japan

  9. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Lancet, M.S.; Winschel, R.A.; Burke, F.P.

    1991-01-01

    The purpose of obtaining stable carbon isotope analyses of coprocessing products is to determine the amount of coal (or petroleum) carbon that is present in any reaction product. This carbon-sourcing of distillate fractions, soluble resid, and insoluble organic matter, etc. is useful in modeling reactions, and evaluating synergistic effects if they exist.

  10. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Lancet, M.S.; Winschel, R.A.; Burke, F.P.

    1991-12-31

    The purpose of obtaining stable carbon isotope analyses of coprocessing products is to determine the amount of coal (or petroleum) carbon that is present in any reaction product. This carbon-sourcing of distillate fractions, soluble resid, and insoluble organic matter, etc. is useful in modeling reactions, and evaluating synergistic effects if they exist.

  11. Synthesis on evaporation partitioning using stable isotopes

    NASA Astrophysics Data System (ADS)

    Coenders-Gerrits, Miriam; Bogaard, Thom; Wenninger, Jochen; Jonson Sutanto, Samuel

    2015-04-01

    Partitioning of evaporation into productive (transpiration) and non-productive evaporation (interception, soil evaporation) is of highest importance for water management practices, irrigation scheme design, and climate modeling. Despite this urge, the magnitude of the ratio of transpiration over total evaporation is still under debate and poorly understood due to measuring difficulties. However, with the current development in isotope measuring devices, new opportunities arise to untangle the partitioning of evaporation. In this paper we synthesize the opportunities and limitations using stable water isotopes in evaporation partitioning. We will analyze a set of field as well as laboratory studies to demonstrate the different evaporation components for various climate and vegetation conditions using stable isotopes 18O/16O and 2H/1H. Experimental data on evaporation partitioning of crops, grass, shrubs and trees are presented and we will discuss the specific experimental set-ups and data collection methods. The paper will be a synthesis of these studies.

  12. Non-lethal sampling of walleye for stable isotope analysis: a comparison of three tissues

    USGS Publications Warehouse

    Chipps, Steven R.; VanDeHey, J.A.; Fincel, M.J.

    2012-01-01

    Stable isotope analysis of fishes is often performed using muscle or organ tissues that require sacrificing animals. Non-lethal sampling provides an alternative for evaluating isotopic composition for species of concern or individuals of exceptional value. Stable isotope values of white muscle (lethal) were compared with those from fins and scales (non-lethal) in walleye, Sander vitreus (Mitchill), from multiple systems, size classes and across a range of isotopic values. Isotopic variability was also compared among populations to determine the potential of non-lethal tissues for diet-variability analyses. Muscle-derived isotope values were enriched compared with fins and depleted relative to scales. A split-sample validation technique and linear regression found that isotopic composition of walleye fins and scales was significantly related to that in muscle tissue for both δ13C and δ15N (r2 = 0.79–0.93). However, isotopic variability was significantly different between tissue types in two of six populations for δ15N and three of six populations for δ13C. Although species and population specific, these findings indicate that isotopic measures obtained from non-lethal tissues are indicative of those obtained from muscle.

  13. Linking Isotopes and Panmixia: High Within-Colony Variation in Feather δ2H, δ13C, and δ15N across the Range of the American White Pelican

    PubMed Central

    Reudink, Matthew W.; Kyle, Christopher J.; McKellar, Ann E.; Somers, Christopher M.; Reudink, Robyn L. F.; Kyser, T. Kurt; Franks, Samantha E.; Nocera, Joseph J.

    2016-01-01

    Complete panmixia across the entire range of a species is a relatively rare phenomenon; however, this pattern may be found in species that have limited philopatry and frequent dispersal. American white pelicans (Pelecanus erythrorhyncos) provide a unique opportunity to examine the role of long-distance dispersal in facilitating gene flow in a species recently reported as panmictic across its broad breeding range. This species is also undergoing a range expansion, with new colonies arising hundreds of kilometers outside previous range boundaries. In this study, we use a multiple stable isotope (δ2H, δ13C, δ15N) approach to examine feather isotopic structuring at 19 pelican colonies across North America, with the goal of establishing an isotopic basemap that could be used for assigning individuals at newly established breeding sites to source colonies. Within-colony isotopic variation was extremely high, exceeding 100‰ in δ2H within some colonies (with relatively high variation also observed for δ13C and δ15N). The high degree of within-site variation greatly limited the utility of assignment-based approaches (42% cross-validation success rate; range: 0–90% success). Furthermore, clustering algorithms identified four likely isotopic clusters; however, those clusters were generally unrelated to geographic location. Taken together, the high degree of within-site isotopic variation and lack of geographically-defined isotopic clusters preclude the establishment of an isotopic basemap for American white pelicans, but may indicate that a high incidence of long-distance dispersal is facilitating gene flow, leading to genetic panmixia. PMID:26974163

  14. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Burke, F.P.; Winschel, R.A.; Lancet, M.S.

    1990-05-01

    Consol R D is developing and demonstrating stable carbon isotope analysis as a method quantitatively distinguish coal-derived and petroleum-derived carbon in products from coal/petroleum coprocessing. The approach taken is to develop the method, then demonstrate its application on authentic continuous-unit products. The significance of selective isotopic fractionation is being determined and, if necessary, corrections will be applied to account for it. Activities for this quarter include: method development -- investigation of selective fractionation. Three petroleum atmospheric still bottoms (ASBs) were separated by distillation and solubility fractionation to determine the homogeneity of the carbon isotope ratios of the separated fractions. These same three petroleum ASBs and three geographically distinct coals were pyrolyzed at 800{degree}F for 30 min and hydrogenated over a CoMo catalyst at 750{degree}F for 60 min to determine the effects of these treatments on the isotopic compositions of the produce fractions. Twelve coal liquefaction oils were analyzed for carbon isotope ratios. These oils were derived from subbituminous and bituminous coals from the first- and second-stage reactors in the thermal/catalytic and modes; validation and application, analysis. Carbon isotope analyses of samples from HRI bench unit coprocessing run 238-2 (Taiheiyo coal/Maya VSB) were analyzed. A method to correct for selective isotopic fractionation was developed and applied to the data. Five coprocessing samples were analyzed at the request of SRI International. 12 refs., 15 figs., 24 tabs.

  15. Trophic Structure in a Seabird Host-Parasite Food Web: Insights from Stable Isotope Analyses

    PubMed Central

    Gómez-Díaz, Elena; González-Solís, Jacob

    2010-01-01

    Ecological studies on food webs rarely include parasites, partly due to the complexity and dimensionality of host-parasite interaction networks. Multiple co-occurring parasites can show different feeding strategies and thus lead to complex and cryptic trophic relationships, which are often difficult to disentangle by traditional methods. We analyzed stable isotope ratios of C (13C/12C, δ13C) and N (15N/14N, δ15N) of host and ectoparasite tissues to investigate trophic structure in 4 co-occurring ectoparasites: three lice and one flea species, on two closely related and spatially segregated seabird hosts (Calonectris shearwaters). δ13C isotopic signatures confirmed feathers as the main food resource for the three lice species and blood for the flea species. All ectoparasite species showed a significant enrichment in δ15N relatively to the host tissue consumed (discrimination factors ranged from 2 to 5‰ depending on the species). Isotopic differences were consistent across multiple host-ectoparasite locations, despite of some geographic variability in baseline isotopic levels. Our findings illustrate the influence of both ectoparasite and host trophic ecology in the isotopic structuring of the Calonectris ectoparasite community. This study highlights the potential of stable isotope analyses in disentangling the nature and complexity of trophic relationships in symbiotic systems. PMID:20454612

  16. Stable isotopes confirm a coastal diet for critically endangered Mediterranean monk seals.

    PubMed

    Karamanlidis, Alexandros A; Curtis, P Jeff; Hirons, Amy C; Psaradellis, Marianna; Dendrinos, Panagiotis; Hopkins, John B

    2014-01-01

    Understanding the ecology and behaviour of endangered species is essential for developing effective management and conservation strategies. We used stable isotope analysis to investigate the foraging behaviour of critically endangered Mediterranean monk seals (Monachus monachus) in Greece. We measured carbon and nitrogen isotope ratios (expressed as δ(13)C and δ(15)N values, respectively) derived from the hair of deceased adult and juvenile seals and the muscle of their known prey to quantify their diets. We tested the hypothesis that monk seals primarily foraged for prey that occupy coastal habitats in Greece. We compared isotope values from seal hair to their coastal and pelagic prey (after correcting all prey for isotopic discrimination) and used these isotopic data and a stable isotope mixing model to estimate the proportion of coastal and pelagic resources consumed by seals. As predicted, we found that seals had similar δ(13)C values as many coastal prey species and higher δ(13)C values than pelagic species; these results, in conjunction with mean dietary estimates (coastal=61 % vs. pelagic=39 %), suggest that seals have a diverse diet comprising prey from multiple trophic levels that primarily occupy the coast. Marine resource managers should consider using the results from this study to inform the future management of coastal habitats in Greece to protect Mediterranean monk seals.

  17. Stable isotope investigation of insect and plant use in the diets of two Puerto Rican bat species

    EPA Science Inventory

    We used stable isotope13C, δ15N) analysis to estimate the importance of plants and insects to the diet of two nectar-feeding bats on Puerto Rico, the brown flower bat (Erophylla bombifrons) and the Greater Antillean long-tongued bat (Monophyllus redmani). Stable carbon and nit...

  18. Stable isotopes of carbon and nitrogen in the study of organochlorine contaminants in albatrosses and petrels.

    PubMed

    Colabuono, Fernanda I; Barquete, Viviane; Taniguchi, Satie; Ryan, Peter G; Montone, Rosalinda C

    2014-06-15

    Carbon and nitrogen stable isotopes in albatrosses and petrels collected off southern Brazil were compared with concentrations of organochlorine contaminants (OCs). δ(13)C and δ(15)N values, as well as OCs concentrations, exhibited a high degree of variability among individuals and overlap among species. δ(13)C values reflected latitudinal differences among species, with lower values found in Wandering and Tristan Albatrosses and higher values found in Black-browed and Atlantic Yellow-nosed Albatrosses and White-chinned Petrels. Some relationships were found between OCs and stable isotopes, but in general a partial 'uncoupling' was observed between OCs concentrations and stable isotopes ratios (especially for δ(15)N). δ(13)C and δ(15)N values in Procellariiformes tissues during the non-breeding season appear to be a better indicator of foraging habitats than of trophic relationships, which may partially explain the high degree of variability between concentrations of OCs and stable isotopes ratios in birds with a diversified diet and wide foraging range.

  19. The potential for application of ink stable isotope analysis in questioned document examination.

    PubMed

    Chesson, Lesley A; Tipple, Brett J; Barnette, Janet E; Cerling, Thure E; Ehleringer, James R

    2015-01-01

    We investigated a novel application of stable isotope abundance analysis of nitrogen (15N), carbon (13C), hydrogen (2H), and oxygen (18O) to characterize pen ink. We focused on both ballpoint and gel pen inks. We found that the isotope ratios of ink from pens purchased together in a package were similar and within-package stable isotope ratio variability was not significantly larger than the variability of isotope reference materials used during analysis. In contrast, the isotope ratios of ink from pens of the same brand purchased in three states of the continental USA were significantly different from each other and there was isotope ratio variation among pens of the same brand but different, unknown production periods. The stable isotope ratios of inked paper were statistically distinguishable using measured δ15N values. Paper inked with different gel pens was statistically distinguishable using measured δ2H values. The capacity of stable isotope ratios to differentiate among ballpoint inks as well as gel inks shows that stable isotope analysis may be a useful and quantifiable investigative technique for questioned document examination, although current sample size requirements limit its utility. Application of the technique in casework will require the development of micro-scale sampling and analysis methods.

  20. Stable carbon isotope analysis in a South Texas cave: Investigating sources of CO2 production

    NASA Astrophysics Data System (ADS)

    Thompson, Reece

    Studies of interactions between modern local climate, cave atmosphere, and ?13C ratios are needed to determine sources of CO2 in caves, and the cycles of seasonal variations that alter karst geochemistry. A seasonal study, focusing on the analysis of stable isotopes collected from a modern cave system, was conducted in Robber Baron Cave (RBC) in order to identify sources of CO2 in its atmosphere. Determining what conditions affect cave morphology and the transfer path of carbon through a cave system is necessary in order to assess the role of caves in the carbon cycle and correctly interpret past ecological changes. This study investigates the extent that stable isotopic values of carbon in CO2 are affected by CO2 sourced from soils, bedrock, atmospheric air, and vegetation, and how ?13C signals are transmitted in a modern cave system. This study also measures how ventilation affects CO2 concentration and ?13C on seasonal scales. In-cave air grab samples were collected monthly at various transects located in RBC in order to measure CO2 composition in addition to factors such as temperature, and barometric pressure. Soil gas and limestone bedrock were also collected and tested for ?13C composition. Air samples were analyzed using an Ambient Air-Model G2101-I Picarro Cavity Ring-Down Spectroscopy Analyzer for both the concentration and ?13C isotopic value of CO2. These values were then compared to isotopic values of known sources of CO2 in order to determine possible sources of CO2 that result in high CO2 concentrations found in RBC. The background stable isotopic value of carbon from CO2 measured in RBC is -19.1‰ VPDB.

  1. Quantifying uncertainty in stable isotope mixing models

    NASA Astrophysics Data System (ADS)

    Davis, Paul; Syme, James; Heikoop, Jeffrey; Fessenden-Rahn, Julianna; Perkins, George; Newman, Brent; Chrystal, Abbey E.; Hagerty, Shannon B.

    2015-05-01

    Mixing models are powerful tools for identifying biogeochemical sources and determining mixing fractions in a sample. However, identification of actual source contributors is often not simple, and source compositions typically vary or even overlap, significantly increasing model uncertainty in calculated mixing fractions. This study compares three probabilistic methods, Stable Isotope Analysis in R (SIAR), a pure Monte Carlo technique (PMC), and Stable Isotope Reference Source (SIRS) mixing model, a new technique that estimates mixing in systems with more than three sources and/or uncertain source compositions. In this paper, we use nitrate stable isotope examples (δ15N and δ18O) but all methods tested are applicable to other tracers. In Phase I of a three-phase blind test, we compared methods for a set of six-source nitrate problems. PMC was unable to find solutions for two of the target water samples. The Bayesian method, SIAR, experienced anchoring problems, and SIRS calculated mixing fractions that most closely approximated the known mixing fractions. For that reason, SIRS was the only approach used in the next phase of testing. In Phase II, the problem was broadened where any subset of the six sources could be a possible solution to the mixing problem. Results showed a high rate of Type I errors where solutions included sources that were not contributing to the sample. In Phase III some sources were eliminated based on assumed site knowledge and assumed nitrate concentrations, substantially reduced mixing fraction uncertainties and lowered the Type I error rate. These results demonstrate that valuable insights into stable isotope mixing problems result from probabilistic mixing model approaches like SIRS. The results also emphasize the importance of identifying a minimal set of potential sources and quantifying uncertainties in source isotopic composition as well as demonstrating the value of additional information in reducing the uncertainty in calculated

  2. 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.

  3. Carbon isotope compositions (δ(13) C) of leaf, wood and holocellulose differ among genotypes of poplar and between previous land uses in a short-rotation biomass plantation.

    PubMed

    Verlinden, M S; Fichot, R; Broeckx, L S; Vanholme, B; Boerjan, W; Ceulemans, R

    2015-01-01

    The efficiency of water use to produce biomass is a key trait in designing sustainable bioenergy-devoted systems. We characterized variations in the carbon isotope composition (δ(13) C) of leaves, current year wood and holocellulose (as proxies for water use efficiency, WUE) among six poplar genotypes in a short-rotation plantation. Values of δ(13) Cwood and δ(13) Cholocellulose were tightly and positively correlated, but the offset varied significantly among genotypes (0.79-1.01‰). Leaf phenology was strongly correlated with δ(13) C, and genotypes with a longer growing season showed a higher WUE. In contrast, traits related to growth and carbon uptake were poorly linked to δ(13) C. Trees growing on former pasture with higher N-availability displayed higher δ(13) C as compared with trees growing on former cropland. The positive relationships between δ(13) Cleaf and leaf N suggested that spatial variations in WUE over the plantation were mainly driven by an N-related effect on photosynthetic capacities. The very coherent genotype ranking obtained with δ(13) C in the different tree compartments has some practical outreach. Because WUE remains largely uncoupled from growth in poplar plantations, there is potential to identify genotypes with satisfactory growth and higher WUE.

  4. Trophic partitioning in tropical rain forest birds: insights from stable isotope analysis.

    PubMed

    Herrera, L Gerardo; Hobson, Keith A; Rodríguez, Malinalli; Hernandez, Patricia

    2003-08-01

    Bird communities reach their highest taxonomic and trophic diversity in tropical rain forest, but the use of different foraging strategies to meet food requirements in such competitive environments is poorly understood. Conventional dietary analyses are poorly suited to investigate dietary patterns in complex systems. We used stable carbon ((13)C/(12)C) and nitrogen ((15)N/(14)N) isotope analysis of whole blood to examine avian trophic patterns and sources of diet in the tropical rain forest of Los Tuxtlas, Veracruz, Mexico. We used stable nitrogen isotope analysis to delineate trophic levels, and stable carbon isotope analysis to distinguish the relative contribution of C-3 and CAM/C-4 ultimate sources of proteins to diets. There was large inter- and intraspecific variation in whole blood delta(13)C and delta(15)N values in 23 species of birds. Stable nitrogen isotope analysis separated birds into several trophic levels, including species that obtained their dietary protein mostly from plants, insects or a combination of both food sources. Stable carbon isotope analysis showed that most birds fed on C3-based foods but Stub-tailed Spadebills (Platyrinchus cancrominus) included C-3- and C-4/CAM-specialist individuals. Our analyses provided insights into the nutritional contribution of plant and animal sources of protein and distinguish their photosynthetic origin over relatively long average time periods.

  5. Protein Stable Isotope Fingerprinting (P-SIF): A New Tool to Understand Natural Isotopic Heterogeneity of Mixed Microbial Ecosystems

    NASA Astrophysics Data System (ADS)

    Pearson, A.; Mohr, W.; Tang, T.; Sattin, S.; Bovee, R.

    2014-12-01

    Protein stable isotope fingerprinting (P-SIF) is a method to measure the carbon isotope ratios of whole proteins separated from complex mixtures, including cultures and environmental samples. The goal of P-SIF is to expose the links between identity and function in microbial ecosystems by (i) determining the ratios of 13C/12C (values of δ13C) for different taxonomic divisions, and (ii) using those values as clues to the metabolic pathways employed by the respective organisms, while (iii) not perturbing the system, i.e., not adding exogenous substrates or isotope labels. To accomplish this, we employ two-dimensional HPLC to resolve a sample containing ca. 5-10 mg of mixed proteins into 960-1440 fractions. Each fraction then is split in two aliquots: The first is digested with trypsin for peptide sequencing, while the second is measured in triplicate using an isotope-ratio mass spectrometer interfaced with a spooling wire microcombustion device. Data from pure cultures show that bacteria have a narrow distribution of protein δ13C values within individual taxa (±0.7-1.2‰, 1σ). This is moderately larger than the mean precision of the triplicate isotope measurements (±0.5‰, 1σ) and may reflect heterogeneous distribution of 13C among the amino acids. When cells from different species are mixed together prior to protein extraction and separation, the results can predict accurately (to within ±1σ) the δ13C values of the original taxa. The number of data points required for this endmember prediction is ≥20/taxon, yielding a theoretical resolution of ca. 10 taxonomic units/sample. Initial tests on environmental samples suggest the approach will be useful to determine the overall trophic breadth of mixed microbial ecosystems.

  6. Atmospheric pCO2 control on speleothem stable carbon isotope compositions

    NASA Astrophysics Data System (ADS)

    Breecker, Daniel O.

    2017-01-01

    The stable carbon isotope compositions of C3 plants are controlled by the carbon isotope composition of atmospheric CO2 (δ13Ca) and by the stomatal response to water stress. These relationships permit the reconstruction of ancient environments and assessment of the water use efficiency of forests. It is currently debated whether the δ13C values of C3 plants are also controlled by atmospheric pCO2. Here I show that globally-averaged speleothem δ13C values closely track atmospheric pCO2 over the past 90 kyr. After accounting for other possible effects, this coupling is best explained by a C3 plant δ13C sensitivity of - 1.6 ± 0.3 ‰ / 100 ppmV CO2 during the Quaternary. This is consistent with 20th century European forest tree ring δ13C records, providing confidence in the result and suggesting that the modest pCO2-driven increase in water use efficiency determined for those ecosystems and simulated by land surface models accurately approximates the global average response. The δ13C signal from C3 plants is transferred to speleothems relatively rapidly. Thus, the effect of atmospheric pCO2 should be subtracted from new and existing speleothem δ13C records so that residual δ13C shifts can be interpreted in light of the other factors known to control spleleothem δ13C values. Furthermore, global average speleothem δ13C shifts may be used to develop a continuous radiometric chronology for Pleistocene atmospheric pCO2 fluctuations and, by correlation, ice core climate records.

  7. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Winschel, R.A.; Lancet, M.S.; Burke, F.P.

    1990-07-01

    Consol R D is developing and demonstrating stable carbon isotope analysis as a method to quantitatively distinguish coal-derived and petroleum-derived carbon in products from coal/petroleum coprocessing. The approach taken is to develop the method, then demonstrate its application on authentic continuous-unit products. The significance of selective isotopic fractionation is being determined and, if necessary, corrections will be applied to account for it. Precision, accuracy and range of applicability are being defined. The value of accessory analytical techniques also is being assessed. The program is designed to address a substantial, demonstrated need of coprocessing research (both exploratory and development) for a technique to quantitatively distinguish the contributions of the individual coprocessing feedstocks to the various products. The carbon isotope technique currently is in routine use for other applications. Progress is discussed. 7 refs., 7 figs., 12 tabs.

  8. Stable isotope ecology of a hyper-diverse community of scincid lizards from arid Australia.

    PubMed

    Grundler, Maggie R; Pianka, Eric R; Pelegrin, Nicolás; Cowan, Mark A; Rabosky, Daniel L

    2017-01-01

    We assessed the utility of stable isotope analysis as a tool for understanding community ecological structure in a species-rich clade of scincid lizards from one of the world's most diverse lizard communities. Using a phylogenetic comparative framework, we tested whether δ15N and δ13C isotopic composition from individual lizards was correlated with species-specific estimates of diet and habitat use. We find that species are highly divergent in isotopic composition with significant correlations to habitat use, but this relationship shows no phylogenetic signal. Isotopic composition corresponds to empirical observations of diet for some species but much variation remains unexplained. We demonstrate the importance of using a multianalytical approach to questions of long-term dietary preference, and suggest that the use of stable isotopes in combination with stomach content analysis and empirical data on habitat use can potentially reveal patterns in ecological traits at finer scales with important implications for community structuring.

  9. Stable isotope ecology of a hyper-diverse community of scincid lizards from arid Australia

    PubMed Central

    Pianka, Eric R.; Pelegrin, Nicolás; Cowan, Mark A.; Rabosky, Daniel L.

    2017-01-01

    We assessed the utility of stable isotope analysis as a tool for understanding community ecological structure in a species-rich clade of scincid lizards from one of the world's most diverse lizard communities. Using a phylogenetic comparative framework, we tested whether δ15N and δ13C isotopic composition from individual lizards was correlated with species-specific estimates of diet and habitat use. We find that species are highly divergent in isotopic composition with significant correlations to habitat use, but this relationship shows no phylogenetic signal. Isotopic composition corresponds to empirical observations of diet for some species but much variation remains unexplained. We demonstrate the importance of using a multianalytical approach to questions of long-term dietary preference, and suggest that the use of stable isotopes in combination with stomach content analysis and empirical data on habitat use can potentially reveal patterns in ecological traits at finer scales with important implications for community structuring. PMID:28245270

  10. Hydrogen bond geometries and proton tautomerism of homoconjugated anions of carboxylic acids studied via H/D isotope effects on 13C NMR chemical shifts.

    PubMed

    Guo, Jing; Tolstoy, Peter M; Koeppe, Benjamin; Golubev, Nikolai S; Denisov, Gleb S; Smirnov, Sergei N; Limbach, Hans-Heinrich

    2012-11-26

    Ten formally symmetric anionic OHO hydrogen bonded complexes, modeling Asp/Glu amino acid side chain interactions in nonaqueous environment (CDF(3)/CDF(2)Cl solution, 200-110 K) have been studied by (1)H, (2)H, and (13)C NMR spectroscopy, i.e. intermolecularly H-bonded homoconjugated anions of acetic, chloroacetic, dichloroacetic, trifluoroacetic, trimethylacetic, and isobutyric acids, and intramolecularly H-bonded hydrogen succinate, hydrogen rac-dimethylsuccinate, hydrogen maleate, and hydrogen phthalate. In particular, primary H/D isotope effects on the hydrogen bond proton signals as well as secondary H/D isotope effects on the (13)C signals of the carboxylic groups are reported and analyzed. We demonstrate that in most of the studied systems there is a degenerate proton tautomerism between O-H···O(-) and O(-)···H-O structures which is fast in the NMR time scale. The stronger is the proton donating ability of the acid, the shorter and more symmetric are the H-bonds in each tautomer of the homoconjugate. For the maleate and phthalate anions exhibiting intramolecular hydrogen bonds, evidence for symmetric single well potentials is obtained. We propose a correlation between H/D isotope effects on carboxylic carbon chemical shifts and the proton transfer coordinate, q(1) = ½(r(OH) - r(HO)), which allows us to estimate the desired OHO hydrogen bond geometries from the observed (13)C NMR parameters, taking into account the degenerate proton tautomerism.

  11. Using (13)C isotopes to explore denitrification-dependent anaerobic methane oxidation in a paddy-peatland.

    PubMed

    Shi, Yao; Wang, Zhongqiang; He, Chunguang; Zhang, Xinyu; Sheng, Lianxi; Ren, Xiaodong

    2017-01-18

    Peatlands are organic-matter-rich but nitrogen-limited natural systems, the carbon/nitrogen (C/N) status of which are subject to increasing exposure from long-term nitrate (NO3(-)) fertilizer inputs and atmospheric nitrogen (N) deposits. To manage and protect these unique environments, an improved understanding of denitrification-dependent anaerobic oxidation of methane (DAMO) in peatlands is needed. In this study, we used stable isotope measurements and incubation with NO3(-) additions to facilitate an investigation and comparison of the potential DAMO rates in a paddy-peatland that has been influenced by N fertilizer over 40 years and an undisturbed peatland in northeast China. Monitoring of (13)CO2 production confimed DAMO did occur in both the paddy-peatland and the undisturbed peatland, the rates of which increased with NO3(-) additions, but decreased logarithmically with time. When NO3(-) was added, there were no significant differences between the CH4 oxidation in the paddy-peatland and peatland samples after 36 hours of incubation (97.08 vs. 143.69 nmol g(-1) dry peat) and the potential DAMO rate after incubation for 1 hour (92.53 vs. 69.99 nmol g(-1 )h(-1)). These results indicate that the occurrence of DAMO in peatlands might be controlled by the amount of NO3(-) applied and the depth to which it penetrates into the anoxic layer.

  12. Using 13C isotopes to explore denitrification-dependent anaerobic methane oxidation in a paddy-peatland

    NASA Astrophysics Data System (ADS)

    Shi, Yao; Wang, Zhongqiang; He, Chunguang; Zhang, Xinyu; Sheng, Lianxi; Ren, Xiaodong

    2017-01-01

    Peatlands are organic-matter-rich but nitrogen-limited natural systems, the carbon/nitrogen (C/N) status of which are subject to increasing exposure from long-term nitrate (NO3‑) fertilizer inputs and atmospheric nitrogen (N) deposits. To manage and protect these unique environments, an improved understanding of denitrification-dependent anaerobic oxidation of methane (DAMO) in peatlands is needed. In this study, we used stable isotope measurements and incubation with NO3‑ additions to facilitate an investigation and comparison of the potential DAMO rates in a paddy-peatland that has been influenced by N fertilizer over 40 years and an undisturbed peatland in northeast China. Monitoring of 13CO2 production confimed DAMO did occur in both the paddy-peatland and the undisturbed peatland, the rates of which increased with NO3‑ additions, but decreased logarithmically with time. When NO3‑ was added, there were no significant differences between the CH4 oxidation in the paddy-peatland and peatland samples after 36 hours of incubation (97.08 vs. 143.69 nmol g‑1 dry peat) and the potential DAMO rate after incubation for 1 hour (92.53 vs. 69.99 nmol g‑1 h‑1). These results indicate that the occurrence of DAMO in peatlands might be controlled by the amount of NO3‑ applied and the depth to which it penetrates into the anoxic layer.

  13. Using 13C isotopes to explore denitrification-dependent anaerobic methane oxidation in a paddy-peatland

    PubMed Central

    Shi, Yao; Wang, Zhongqiang; He, Chunguang; Zhang, Xinyu; Sheng, Lianxi; Ren, Xiaodong

    2017-01-01

    Peatlands are organic-matter-rich but nitrogen-limited natural systems, the carbon/nitrogen (C/N) status of which are subject to increasing exposure from long-term nitrate (NO3−) fertilizer inputs and atmospheric nitrogen (N) deposits. To manage and protect these unique environments, an improved understanding of denitrification-dependent anaerobic oxidation of methane (DAMO) in peatlands is needed. In this study, we used stable isotope measurements and incubation with NO3− additions to facilitate an investigation and comparison of the potential DAMO rates in a paddy-peatland that has been influenced by N fertilizer over 40 years and an undisturbed peatland in northeast China. Monitoring of 13CO2 production confimed DAMO did occur in both the paddy-peatland and the undisturbed peatland, the rates of which increased with NO3− additions, but decreased logarithmically with time. When NO3− was added, there were no significant differences between the CH4 oxidation in the paddy-peatland and peatland samples after 36 hours of incubation (97.08 vs. 143.69 nmol g−1 dry peat) and the potential DAMO rate after incubation for 1 hour (92.53 vs. 69.99 nmol g−1 h−1). These results indicate that the occurrence of DAMO in peatlands might be controlled by the amount of NO3− applied and the depth to which it penetrates into the anoxic layer. PMID:28098207

  14. Fatty acid and stable carbon isotope characterization of Camelina sativa oil: implications for authentication.

    PubMed

    Hrastar, Robert; Petrisic, Marinka G; Ogrinc, Nives; Kosir, Iztok Joze

    2009-01-28

    The importance of authenticity characterization is an increasing and pressing requirement for all foods. Vegetable oil is one of the most studied foods because of its nutritional and medicinal properties in a correct diet. In this study, a total of 53 Camelina sativa samples, from all known growing areas, were chemically and isotopically characterized. The fatty acid content of camelina oil was determined by gas chromatography (GC), and the ratios of stable carbon isotopes ((13)C/(12)C) of individual fatty acids and seed/bulk oil were determined by gas chromatography-combustion-stable isotope ratio mass spectrometry (GC/C/IRMS) and elemental analysis-stable isotope ratio mass spectrometry (IRMS). A total of 17 different fatty acids were detected by GC, with omega3 R-linolenic acid (C(18:3n3)) being the most abundant (29.7-40.0 wt %). Oleic acid (C(18:1n9)), linoleic acid (C(18:2n6)) and eicosenoic acid (C(20:1n9)) all belong to the second group of major fatty acids. The stable carbon isotopic values (delta(13)C) fell into a range typical for C(3) plants. The use of delta(13)C(18:2n6) vs delta(13)C(18:3n3) correlation could show cases where impurity or adulteration is suspected, whereas principal component analysis clearly separates oil samples from different continents. Preliminary results on the camelina oil authentication procedure provide a basis for the investigation of geographical origin and the further distinction between camelina and camelina refined or other, less expensive oils.

  15. Stable carbon and oxygen isotope fractionation processes during speleothem growth: systematic investigation in novel laboratory experiments

    NASA Astrophysics Data System (ADS)

    Scholz, D.; Hansen, M.; Dreybrodt, W.

    2012-04-01

    The most widely applied climate proxies in speleothems are stable carbon and oxygen isotopes13C and δ18O). The interpretation of the stable isotope signals in terms of past temperature and/or precipitation variability is complex because both δ18O and δ13C depend on a complex interplay of various processes occurring in the atmosphere, the soil and karst above the cave and inside the cave. Quantitative reconstruction of climate parameters such as temperature and precipitation has, thus, remained impossible so far. Here we present several novel laboratory experiments aiming to understand the basic physical and chemical processes affecting the δ18O and δ13C signals during precipitation of calcium carbonate on the stalagmite surface. In particular, we aim to quantify the influence of kinetic isotope fractionation and verify recently published modelling studies (Dreybrodt, 2008; Scholz et al., 2009, Dreybrodt and Scholz, 2011). Several experiments are conducted: Degassing of CO2 from a thin film of water sparged with CO2 flowing down an inclined glass plate. pH and electric conductivity are systematically documented in order to monitor degassing of CO2. The results show that degassing of CO2 is fast, and the pCO2 of the solution is in equilibrium with the atmosphere after a short distance of flow. Carbon isotope exchange between atmospheric CO2 and dissolved bicarbonate. The results show that carbon isotope exchange may have a significant effect on the δ13C value of the dissolved bicarbonate and, thus, speleothem calcite, in particular for slow drip rates. Degassing of CO2 and calcite precipitation from a thin film of water supersaturated with respect to calcite flowing down an inclined calcium carbonate plate. Drip water is sampled after different lengths of flow path and, thus, different residence times on the plate, and pH, electrical conductivity and the stable isotope composition of the water are determined. Decreasing conductivity with increasing distance

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

    PubMed Central

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

    2014-01-01

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

  17. Trophic Relationships and Habitat Preferences of Delphinids from the Southeastern Brazilian Coast Determined by Carbon and Nitrogen Stable Isotope Composition

    PubMed Central

    Bisi, Tatiana Lemos; Dorneles, Paulo Renato; Lailson-Brito, José; Lepoint, Gilles; Azevedo, Alexandre de Freitas; Flach, Leonardo; Malm, Olaf; Das, Krishna

    2013-01-01

    To investigate the foraging habitats of delphinids in southeastern Brazil, we analyzed stable carbon (δ13C) and nitrogen (δ15N) isotopes in muscle samples of the following 10 delphinid species: Sotalia guianensis, Stenella frontalis, Tursiops truncatus, Steno bredanensis, Pseudorca crassidens, Delphinus sp., Lagenodelphis hosei, Stenella attenuata, Stenella longirostris and Grampus griseus. We also compared the δ13C and δ15N values among four populations of S. guianensis. Variation in carbon isotope results from coast to ocean indicated that there was a significant decrease in δ13C values from estuarine dolphins to oceanic species. S. guianensis from Guanabara Bay had the highest mean δ13C value, while oceanic species showed significantly lower δ13C values. The highest δ15N values were observed for P. crassidens and T. truncatus, suggesting that these species occupy the highest trophic position among the delphinids studied here. The oceanic species S. attenuata, G. griseus and L. hosei had the lowest δ15N values. Stable isotope analysis showed that the three populations of S. guianensis in coastal bays had different δ13C values, but similar δ15N results. Guiana dolphins from Sepetiba and Ilha Grande bays had different foraging habitat, with specimens from Ilha Grande showing more negative δ13C values. This study provides further information on the feeding ecology of delphinids occurring in southeastern Brazil, with evidence of distinctive foraging habitats and the occupation of different ecological niches by these species in the study area. PMID:24358155

  18. Carbon stable isotopes as a palaeoclimate proxy in vascular plant dominated peatlands

    NASA Astrophysics Data System (ADS)

    Amesbury, M. J.; Charman, D. J.; Newnham, R. M.; Loader, N. J.; Goodrich, J. P.; Royles, J.; Campbell, D. I.; Roland, T. P.; Gallego-Sala, A.

    2015-09-01

    Carbon stable isotope13C) records from vascular plant dominated peatlands have been used as a palaeoclimate proxy, but a better empirical understanding of fractionation processes in these ecosystems is required. Here, we test the potential of δ13C analysis of ombrotrophic restiad peatlands in New Zealand, dominated by the wire rush (Empodisma spp.), to provide a methodology for developing palaeoclimatic records. We took surface plant samples alongside measurements of water table depth and (micro)climate over spatial (six sites spanning > 10° latitude) and temporal (monthly measurements over 1 year) gradients and analysed the relationships between cellulose δ13C values and environmental parameters. We found strong, significant negative correlations between δ13C and temperature, photosynthetically active radiation and growing degree days above 0 °C. No significant relationships were observed between δ13C and precipitation, relative humidity, soil moisture or water table depth, suggesting no growing season water limitation and a decoupling of the expected link between δ13C in vascular plants and hydrological variables. δ13C of Empodisma spp. roots may therefore provide a valuable temperature proxy in a climatically sensitive region, but further physiological and sub-fossil calibration studies are required to fully understand the observed signal.

  19. Stable isotope resolved metabolomics of lung cancer in a SCID mouse model.

    PubMed

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

    2011-06-01

    We have determined the time course of [U-(13)C]-glucose utilization and transformations in SCID mice via bolus injection of the tracer in the tail vein. Incorporation of (13)C into metabolites extracted from mouse blood plasma and several tissues (lung, heart, brain, liver, kidney, and skeletal muscle) were profiled by NMR and GC-MS, which helped ascertain optimal sampling times for different target tissues. We found that the time for overall optimal (13)C incorporation into tissue was 15-20 min but with substantial differences in (13)C labeling patterns of various organs that reflected their specific metabolism. Using this stable isotope resolved metabolomics (SIRM) approach, we have compared the (13)C metabolite profile of the lungs in the same mouse with or without an orthotopic lung tumor xenograft established from human PC14PE6 lung adenocarcinoma cells. The (13)C metabolite profile shows considerable differences in [U-(13)C]-glucose transformations between the two lung tissues, demonstrating the feasibility of applying SIRM to investigate metabolic networks of human cancer xenograft in the mouse model.

  20. Enhanced understanding of ectoparasite: host trophic linkages on coral reefs through stable isotope analysis

    USGS Publications Warehouse

    Demopoulos, Amanda W. J.; Sikkel, Paul C.

    2015-01-01

    Parasitism, although the most common type of ecological interaction, is usually ignored in food web models and studies of trophic connectivity. Stable isotope analysis is widely used in assessing the flow of energy in ecological communities and thus is a potentially valuable tool in understanding the cryptic trophic relationships mediated by parasites. In an effort to assess the utility of stable isotope analysis in understanding the role of parasites in complex coral-reef trophic systems, we performed stable isotope analysis on three common Caribbean reef fish hosts and two kinds of ectoparasitic isopods: temporarily parasitic gnathiids (Gnathia marleyi) and permanently parasitic cymothoids (Anilocra). To further track the transfer of fish-derived carbon (energy) from parasites to parasite consumers, gnathiids from host fish were also fed to captive Pederson shrimp (Ancylomenes pedersoni) for at least 1 month. Parasitic isopods had δ13C and δ15N values similar to their host, comparable with results from the small number of other host–parasite studies that have employed stable isotopes. Adult gnathiids were enriched in 15N and depleted in13C relative to juvenile gnathiids, providing insights into the potential isotopic fractionation associated with blood-meal assimilation and subsequent metamorphosis. Gnathiid-fed Pedersen shrimp also had δ13C values consistent with their food source and enriched in 15N as predicted due to trophic fractionation. These results further indicate that stable isotopes can be an effective tool in deciphering cryptic feeding relationships involving parasites and their consumers, and the role of parasites and cleaners in carbon transfer in coral-reef ecosystems specifically.

  1. Enhanced understanding of ectoparasite–host trophic linkages on coral reefs through stable isotope analysis

    PubMed Central

    Demopoulos, Amanda W.J.; Sikkel, Paul C.

    2015-01-01

    Parasitism, although the most common type of ecological interaction, is usually ignored in food web models and studies of trophic connectivity. Stable isotope analysis is widely used in assessing the flow of energy in ecological communities and thus is a potentially valuable tool in understanding the cryptic trophic relationships mediated by parasites. In an effort to assess the utility of stable isotope analysis in understanding the role of parasites in complex coral-reef trophic systems, we performed stable isotope analysis on three common Caribbean reef fish hosts and two kinds of ectoparasitic isopods: temporarily parasitic gnathiids (Gnathia marleyi) and permanently parasitic cymothoids (Anilocra). To further track the transfer of fish-derived carbon (energy) from parasites to parasite consumers, gnathiids from host fish were also fed to captive Pederson shrimp (Ancylomenes pedersoni) for at least 1 month. Parasitic isopods had δ13C and δ15N values similar to their host, comparable with results from the small number of other host–parasite studies that have employed stable isotopes. Adult gnathiids were enriched in 15N and depleted in 13C relative to juvenile gnathiids, providing insights into the potential isotopic fractionation associated with blood-meal assimilation and subsequent metamorphosis. Gnathiid-fed Pedersen shrimp also had δ13C values consistent with their food source and enriched in 15N as predicted due to trophic fractionation. These results further indicate that stable isotopes can be an effective tool in deciphering cryptic feeding relationships involving parasites and their consumers, and the role of parasites and cleaners in carbon transfer in coral-reef ecosystems specifically. PMID:25830112

  2. Linking mercury, carbon, and nitrogen stable isotopes in Tibetan biota: Implications for using mercury stable isotopes as source tracers

    PubMed Central

    Xu, Xiaoyu; Zhang, Qianggong; Wang, Wen-Xiong

    2016-01-01

    Tibetan Plateau is located at a mountain region isolated from direct anthropogenic sources. Mercury concentrations and stable isotopes of carbon, nitrogen, and mercury were analyzed in sediment and biota for Nam Co and Yamdrok Lake. Biotic mercury concentrations and high food web magnification factors suggested that Tibetan Plateau is no longer a pristine site. The primary source of methylmercury was microbial production in local sediment despite the lack of direct methylmercury input. Strong ultraviolet intensity led to extensive photochemical reactions and up to 65% of methylmercury in water was photo-demethylated before entering the food webs. Biota displayed very high Δ199Hg signatures, with some highest value (8.6%) ever in living organisms. The δ202Hg and Δ199Hg in sediment and biotic samples increased with trophic positions (δ15N) and %methylmercury. Fish total length closely correlated to δ13C and Δ199Hg values due to dissimilar carbon sources and methylmercury pools in different living waters. This is the first mercury isotope study on high altitude lake ecosystems that demonstrated specific isotope fractionations of mercury under extreme environmental conditions. PMID:27151563

  3. Linking mercury, carbon, and nitrogen stable isotopes in Tibetan biota: Implications for using mercury stable isotopes as source tracers

    NASA Astrophysics Data System (ADS)

    Xu, Xiaoyu; Zhang, Qianggong; Wang, Wen-Xiong

    2016-05-01

    Tibetan Plateau is located at a mountain region isolated from direct anthropogenic sources. Mercury concentrations and stable isotopes of carbon, nitrogen, and mercury were analyzed in sediment and biota for Nam Co and Yamdrok Lake. Biotic mercury concentrations and high food web magnification factors suggested that Tibetan Plateau is no longer a pristine site. The primary source of methylmercury was microbial production in local sediment despite the lack of direct methylmercury input. Strong ultraviolet intensity led to extensive photochemical reactions and up to 65% of methylmercury in water was photo-demethylated before entering the food webs. Biota displayed very high Δ199Hg signatures, with some highest value (8.6%) ever in living organisms. The δ202Hg and Δ199Hg in sediment and biotic samples increased with trophic positions (δ15N) and %methylmercury. Fish total length closely correlated to δ13C and Δ199Hg values due to dissimilar carbon sources and methylmercury pools in different living waters. This is the first mercury isotope study on high altitude lake ecosystems that demonstrated specific isotope fractionations of mercury under extreme environmental conditions.

  4. Determination of stable carbon isotopes of organic acids and carbonaceous aerosols in the atmosphere.

    PubMed

    Fisseha, R; Saurer, M; Jäggi, M; Szidat, S; Siegwolf, R T W; Baltensperger, U

    2006-01-01

    A wet oxidation method for the compound-specific determination of stable carbon isotopes (delta(13)C) of organic acids in the gas and aerosol phase, as well as of water-soluble organic carbon (WSOC), is presented. Sampling of the organic acids was done using a wet effluent diffusion denuder/aerosol collector (WEDD/AC) coupled to an ion chromatography (IC) system. The method allows for compound-specific stable carbon isotope analysis by collecting different fractions of organic acids at the end of the IC system using a fraction collector. delta(13)C analyses of organic acids were conducted by oxidizing the organic acids with sodium persulfate at a temperature of 100 degrees C and determining the delta(13)C value of the resulting carbon dioxide (CO(2)) with an isotope ratio mass spectrometer. In addition, analysis of delta(13)C of the WSOC was performed for particulate carbon collected on aerosol filters. The WSOC was extracted from the filters using ultrapure water (MQ water), and the dissolved organic carbon was oxidized to CO(2) using the oxidation method. The wet oxidation method has an accuracy of 0.5 per thousand with a precision of +/-0.4 per thousand and provides a quantitative result for organic carbon with a detection limit of 150 ng of carbon.

  5. Modelling of stable isotope fractionation by methane oxidation and diffusion in landfill cover soils

    SciTech Connect

    Mahieu, Koenraad De Visscher, Alex; Vanrolleghem, Peter A.; Van Cleemput, Oswald

    2008-07-01

    A technique to measure biological methane oxidation in landfill cover soils that is gaining increased interest is the measurement of stable isotope fractionation in the methane. Usually to quantify methane oxidation, only fractionation by oxidation is taken into account. Recently it was shown that neglecting the isotope fractionation by diffusion results in underestimation of the methane oxidation. In this study a simulation model was developed that describes gas transport and methane oxidation in landfill cover soils. The model distinguishes between {sup 12}CH{sub 4}, {sup 13}CH{sub 4}, and {sup 12}CH{sub 3}D explicitly, and includes isotope fractionation by diffusion and oxidation. To evaluate the model, the simulations were compared with column experiments from previous studies. The predicted concentration profiles and isotopic profiles match the measured ones very well, with a root mean square deviation (RMSD) of 1.7 vol% in the concentration and a RMSD of 0.8 per mille in the {delta}{sup 13}C value, with {delta}{sup 13}C the relative {sup 13}C abundance as compared to an international standard. Overall, the comparison shows that a model-based isotope approach for the determination of methane oxidation efficiencies is feasible and superior to existing isotope methods.

  6. Stable carbon isotope measurements of atmospheric organic acids in Los Angeles, California

    SciTech Connect

    Sakugawa, H.; Kaplan, I.R.

    1995-06-15

    Atmospheric organic acids are ubiquitous constituents of urban smog and haze and are also present in the atmospheres of rural and largely uninhabited areas (e.g., the Amazon Rain Forest Basin). The authors report here source characterization of atmospheric organic acids in Los Angeles by measurements of their stable carbon isotopic ratios, e.g., {sup 13}C/{sup 12}C({delta}{sup 13}C). The study was performed by separating formic and acetic acids using ion chromatography exclusion (ICE) and isolating milligram quantities of individual organic acids from atmospheric rain samples. Authentic reference samples of formic and acetic acids were used to determine that only a negligible isotope fractionation of {delta}{sup 13}C value occurs after the ICE separation. During 1991-1992, rainwaters were collected in Los Angeles to isolate formic and acetic acids for the isotope measurements. Results presented in this paper demonstrate a significant isotopic difference between the mean {delta}{sup 13}C value for acetic acid ({minus}20.5{per_thousand}) and formic acid ({minus}30.1{per_thousand}). The authors conclude from these results that the formic acid is derived from mixing of formic acid from direct emissions with the acid formed by secondary oxidation processes in the atmosphere, most probably from aldehydes, whereas acetic acid originates only from direct source emissions. 26 refs., 1 fig., 2 tabs.

  7. Stable carbon isotope measurements of atmospheric organic acids in Los Angeles, California

    NASA Astrophysics Data System (ADS)

    Sakugawa, Hiroshi; Kaplan, Isaac R.

    Atmospheric organic acids are ubiquitous constituents of urban smog and haze and are also present in the atmospheres of rural and largely uninhabited areas (e.g., the Amazon Rain Forest Basin). We report here source characterization of atmospheric organic acids in Los Angeles by measurements of their stable carbon isotopic ratios, e.g., 13C/12C(δ13C). The study was performed by separating formic and acetic acids using ion chromatography exclusion (ICE) and isolating milligram quantities of individual organic acids from atmospheric rain samples. Authentic reference samples of formic and acetic acids were used to determine that only a negligible isotope fractionation of δ13C value occurs after the ICE separation. During 1991-1992, rainwaters were collected in Los Angeles to isolate formic and acetic acids for the isotope measurements. Results presented in this paper demonstrate a significant isotopic difference between the mean δ13C value for acetic acid (-20.5‰) and formic acid (-30.1‰). We conclude from these results that the formic acid is derived from mixing of formic acid from direct emissions with the acid formed by secondary oxidation processes in the atmosphere, most probably from aldehydes, whereas acetic acid originates only from direct source emissions.

  8. Measurements of the D/H and 13C/12C Isotope Ratios in Stratospheric CH4 from the POLARIS, STRAT, and SOLVE Campaigns

    NASA Astrophysics Data System (ADS)

    Rice, A. L.; Tyler, S. C.; McCarthy, M. C.; Boering, K. A.; Boering, K. A.; Atlas, E.

    2001-12-01

    We report δ D and δ 13C measurements of stratospheric CH4 from 78 air samples collected aboard the NASA ER-2 aircraft during the SOLVE (2000), POLARIS (1997), and STRAT (1996) campaigns. These measurements are the first to be reported using continuous flow gas chromatography isotope mass spectrometry, which provides for high precision of measurement on 63 ml of air. The δ D-CH4 data comprise the only high precision data set of this kind to date. Precision of measurement is +/-1.5‰ for δ D (vs. V-SMOW) and +/-0.07‰ for δ 13C (vs. V-PDB) on samples with as little as 700 ppb CH4. The samples cover latitudes ranging from 1° S to 89° N and altitudes ranging from 11 to 21 km. Values of δ D range from -89.8‰ for CH4 near the tropical tropopause to +26.4‰ for CH4 in the polar vortex. Similarly, values of δ 13C range from -47.3‰ to -34.0‰ . The isotopic enrichment in CH4 with decreasing mixing ratio is a result of kinetic isotope effects in CH4 loss processes, i.e. chemical reaction with OH, Cl, and O(1D), as the air mass ages. Our measurement data have been compared to calculated values using the LLNL 2-D chemical-radiative-transport model of the atmosphere. We discuss the observed trends in δ D and δ 13C of CH4 and their implications for stratospheric chemistry.

  9. Deciphering Ecohydrological Interactions Using Stable Isotopes

    NASA Astrophysics Data System (ADS)

    McDonnell, J.; Evaristo, J. A.; Jasechko, S.

    2014-12-01

    Deciphering the nature of ecohydrological interconnections and scaling that knowledge gained at single points to watersheds is challenging. One tool that that has proved useful in this regard is stable isotope tracing. Single isotope studies have been used recently to quantify landuse change effects on streamflow source apportionment and ecological effects on transit time distributions of water at the catchment scale. However, most work to date has assumed that plant transpiration, groundwater recharge and streamflow are all sourced or mediated by the same well mixed reservoir—the soil. Recent work in Oregon and Mexico has shown evidence of ecohydrological separation, whereby different subsurface compartmentalized pools of water supply either plant transpiration fluxes or the combined fluxes of groundwater recharge and streamflow. However, these findings have not yet been widely tested. Here we assemble the first dual isotope database for δ2H and δ18O extracted from 47 globally-distributed stable isotopic datasets. We use these data to test the ecohydrological separation hypothesis. We combine this dual isotope dataset with global precipitation, streamwater, groundwater and soil water datasets. Our results show that precipitation, streamwater and groundwater from the 47 sites plot approximately along the δ2H/δ18O slope of eight, suggesting that local precipitation inputs supply streamwater and groundwater. Soil waters extracted from the 47 studies plot below the regression of local streamwater and groundwater with a slope of 6.6±0.05 ‰. Local plant xylem waters from our matched dataset plot on a slope 6.6±0.07 ‰ consistent with local soil waters. The tight association of soil water slopes and not that of local groundwater or streamflow suggests that plants use soil water that does not itself contribute to groundwater recharge or stream water. This ubiquity of subsurface water compartmentalization is surprising and has important implications for how we

  10. Stable isotopic analyses in paleoclimatic reconstruction

    SciTech Connect

    Wigand, P.E.

    1995-09-01

    Most traditional paleoclimatic proxy data have inherent time lags between climatic input and system response that constrain their use in accurate reconstruction of paleoclimate chronology, scaling of its variability, and the elucidation of the processes that determine its impact on the biotic and abiotic environment. With the exception of dendroclimatology, and studies of short-lived organisms and pollen recovered from annually varved lacustrine sediments, significant periods of time ranging from years, to centuries, to millennia may intervene between climate change and its first manifestation in paleoclimatic proxy data records. Reconstruction of past climate through changes in plant community composition derived from pollen sequences and plant remains from ancient woodrat middens, wet environments and dry caves all suffer from these lags. However, stable isotopic analyses can provide more immediate indication of biotic response to climate change. Evidence of past physiological response of organisms to changes in effective precipitation as climate varies can be provided by analyses of the stable isotopic content of plant macrofossils from various contexts. These analyses consider variation in the stable isotopic (hydrogen, oxygen and carbon) content of plant tissues as it reflects (1) past global or local temperature through changes in meteoric (rainfall) water chemistry in the case of the first two isotopes, and (2) plant stress through changes in plant respiration/transpiration processes under differing water availability, and varying atmospheric CO, composition (which itself may actually be a net result of biotic response to climate change). Studies currently being conducted in the Intermountain West indicate both long- and short-term responses that when calibrated with modem analogue studies have the potential of revealing not only the timing of climate events, but their direction, magnitude and rapidity.

  11. Quantifying uncertainty in stable isotope mixing models

    SciTech Connect

    Davis, Paul; Syme, James; Heikoop, Jeffrey; Fessenden-Rahn, Julianna; Perkins, George; Newman, Brent; Chrystal, Abbey E.; Hagerty, Shannon B.

    2015-05-19

    Mixing models are powerful tools for identifying biogeochemical sources and determining mixing fractions in a sample. However, identification of actual source contributors is often not simple, and source compositions typically vary or even overlap, significantly increasing model uncertainty in calculated mixing fractions. This study compares three probabilistic methods, SIAR [Parnell et al., 2010] a pure Monte Carlo technique (PMC), and Stable Isotope Reference Source (SIRS) mixing model, a new technique that estimates mixing in systems with more than three sources and/or uncertain source compositions. In this paper, we use nitrate stable isotope examples (δ15N and δ18O) but all methods tested are applicable to other tracers. In Phase I of a three-phase blind test, we compared methods for a set of six-source nitrate problems. PMC was unable to find solutions for two of the target water samples. The Bayesian method, SIAR, experienced anchoring problems, and SIRS calculated mixing fractions that most closely approximated the known mixing fractions. For that reason, SIRS was the only approach used in the next phase of testing. In Phase II, the problem was broadened where any subset of the six sources could be a possible solution to the mixing problem. Results showed a high rate of Type I errors where solutions included sources that were not contributing to the sample. In Phase III some sources were eliminated based on assumed site knowledge and assumed nitrate concentrations, substantially reduced mixing fraction uncertainties and lowered the Type I error rate. These results demonstrate that valuable insights into stable isotope mixing problems result from probabilistic mixing model approaches like SIRS. The results also emphasize the importance of identifying a minimal set of potential sources and quantifying uncertainties in source isotopic composition as well as demonstrating the value of additional information in reducing the

  12. Quantifying uncertainty in stable isotope mixing models

    DOE PAGES

    Davis, Paul; Syme, James; Heikoop, Jeffrey; ...

    2015-05-19

    Mixing models are powerful tools for identifying biogeochemical sources and determining mixing fractions in a sample. However, identification of actual source contributors is often not simple, and source compositions typically vary or even overlap, significantly increasing model uncertainty in calculated mixing fractions. This study compares three probabilistic methods, SIAR [Parnell et al., 2010] a pure Monte Carlo technique (PMC), and Stable Isotope Reference Source (SIRS) mixing model, a new technique that estimates mixing in systems with more than three sources and/or uncertain source compositions. In this paper, we use nitrate stable isotope examples (δ15N and δ18O) but all methods testedmore » are applicable to other tracers. In Phase I of a three-phase blind test, we compared methods for a set of six-source nitrate problems. PMC was unable to find solutions for two of the target water samples. The Bayesian method, SIAR, experienced anchoring problems, and SIRS calculated mixing fractions that most closely approximated the known mixing fractions. For that reason, SIRS was the only approach used in the next phase of testing. In Phase II, the problem was broadened where any subset of the six sources could be a possible solution to the mixing problem. Results showed a high rate of Type I errors where solutions included sources that were not contributing to the sample. In Phase III some sources were eliminated based on assumed site knowledge and assumed nitrate concentrations, substantially reduced mixing fraction uncertainties and lowered the Type I error rate. These results demonstrate that valuable insights into stable isotope mixing problems result from probabilistic mixing model approaches like SIRS. The results also emphasize the importance of identifying a minimal set of potential sources and quantifying uncertainties in source isotopic composition as well as demonstrating the value of additional information in reducing the uncertainty in calculated

  13. Protein Stable Isotope Fingerprinting (P-SIF): Multidimensional Protein Chromatography Coupled to Stable Isotope-Ratio Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Pearson, A.; Bovee, R. J.; Mohr, W.; Tang, T.

    2012-12-01

    As metagenomics increases our insight into microbial community diversity and metabolic potential, new approaches are required to determine the biogeochemical expression of this potential within ecosystems. Because stable isotopic analysis of the major bioactive elements (C, N) has been used historically to map flows of substrates and energy among macroscopic food webs, similar principles may apply to microbes. To address this challenge, we have developed a new analytical approach called Protein Stable Isotope Fingerprinting (P-SIF). P-SIF generates natural stable isotopic fingerprints of microbial individual or community proteomes. The main advantage of P-SIF is the potential to bridge the gap between diversity and function, thereby providing a window into the "black box" of environmental microbiology and helping to decipher the roles of uncultivated species. Our method implements a three-way, orthogonal scheme to separate mixtures of whole proteins into subfractions dominated by single or closely-related proteins. Protein extracts first are isoelectrically focused in a gel-free technique that yields 12 fractions separated over a gradient of pH 3-10. Each fraction then is separated by size-exclusion chromatography into 20 pools, ranging from >100kD to ~10kD. Finally, each of these pools is subjected to HPLC and collected in 40 time-slices based on protein hydrophobicity. Theoretical calculation reveals that the true chromatographic resolution of the total scheme is 5000, somewhat less than the 9600 resulting fractions. High-yielding fractions are subjected to δ13C analysis by spooling-wire microcombustion irMS (SWiM-irMS) optimized for samples containing 1-5 nmol carbon. Here we will present the method, results for a variety of pure cultures, and preliminary data for a sample of mixed environmental proteins. The data show the promise of this method for unraveling the metabolic complexity hidden within microbial communities.

  14. A gas chromatography/combustion/isotope ratio mass spectrometry system for high-precision delta13C measurements of atmospheric methane extracted from ice core samples.

    PubMed

    Behrens, Melanie; Schmitt, Jochen; Richter, Klaus-Uwe; Bock, Michael; Richter, Ulrike C; Levin, Ingeborg; Fischer, Hubertus

    2008-10-01

    Past atmospheric composition can be reconstructed by the analysis of air enclosures in polar ice cores which archive ancient air in decadal to centennial resolution. Due to the different carbon isotopic signatures of different methane sources high-precision measurements of delta13CH4 in ice cores provide clues about the global methane cycle in the past. We developed a highly automated (continuous-flow) gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) technique for ice core samples of approximately 200 g. The methane is melt-extracted using a purge-and-trap method, then separated from the main air constituents, combusted and measured as CO2 by a conventional isotope ratio mass spectrometer. One CO2 working standard, one CH4 and two air reference gases are used to identify potential sources of isotope fractionation within the entire sample preparation process and to enhance the stability, reproducibility and accuracy of the measurement. After correction for gravitational fractionation, pre-industrial air samples from Greenland ice (1831 +/- 40 years) show a delta13C(VPDB) of -49.54 +/- 0.13 per thousand and Antarctic samples (1530 +/- 25 years) show a delta13C(VPDB) of -48.00 +/- 0.12 per thousand in good agreement with published data.

  15. The Stable Carbon Isotope Ratio Analysis of Atmospheric Non-Methane Hydrocarbons in Los Angeles, California

    NASA Astrophysics Data System (ADS)

    Gotoh, A. A.; Tyler, S. C.; Meinardi, S.; Gervais, K.; Blake, D. R.

    2003-12-01

    Los Angeles type photochemical air pollution is caused by non-methane hydrocarbons (NMHCs) reacting with hydroxyl radicals and nitrous oxides in the presence of light. To create more effective control strategies in reducing such air pollution, it is essential to have both a better understanding of the complex photochemical processes of NMHCs and the sources of these compounds. From the past successful studies of other atmospheric trace gases such as methane and carbon monoxide, we expect that the stable carbon ratio (13C/12C, reported as a δ 13C value) of each of these hydrocarbons will also reflect the δ 13C value of the source material and/or provide formation on chemical loss processes that fractionate C isotopes. We have developed a NMHC preconcentrator system which enables us to measure δ 13C values using a continuous-flow gas chromatography combustion isotope ratio mass spectrometer (cf-GC/C/IRMS). Our system is similar to the successful design pioneered in Rudolph et al. (1997), but is custom designed by our laboratory. Stable carbon isotope measurements of any of the C2-C5 NMHCs in field and/or lab studies are scarce to date. Our system allows us to report on δ 13C measurements of ethane, ethene, ethyne, propane, propene, n-butane, i-butane, 1-butene, n-pentane, i-pentane, and methyl chloride. To see if we can learn the specific sources contributing to the emissions of a given NMHC within a region by comparing isotopic signatures of its potential sources to δ 13C measurements of it within the local air mass, urban air samples were collected in 3 different cities of Los Angeles County, California, USA, during the summer of 2003 and analyzed for the concentrations and δ 13C values of NMHCs. To our knowledge, this is the first δ 13C analysis of ambient NMHCs conducted in the United States. We report the results of the δ 13C analyses and concentration measurements for selected NMHC species from the urban air samples, and their implications for the local

  16. Experimental assessment of environmental influences on the stable isotopic composition of Daphnia pulicaria and their ephippia

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

  17. Linking Biogeochemistry to Microbial Diversity Using New 13C Approaches

    NASA Astrophysics Data System (ADS)

    Baggs, E. M.

    2005-12-01

    The use of 13C enables us to overcome uncertainties associated with soil C processes and to assess the links between species diversity and ecosystem function. Recent advances in stable isotope techniques enable determination of process rates, for example CH4 oxidation by direct measurement of 13C-CH4 and 13C-CO2. This overcomes uncertainties associated with reliance on changes in net CH4 emission, which may have compromised some earlier studies as both methanogenesis and CH4 oxidation may occur simultaneously in soil, providing significant advances in our understanding of the process of CH4 oxidation. These stable isotope techniques can be combined with molecular techniques (analysis of gene expression, stable isotope probing (SIP)) to relate the measured process to the microbial populations responsible. Here we will give a synthesis of results from experiments in which we applied 13C-CH4 to accurately determine CH4 oxidation rates in soils, and also present results of 13C-SIP from which we can identify the key players in the microbial population that are using the applied 13C substrate. With the 13C-CH4 technique we were able to provide direct evidence of inhibition of CH4 oxidation following fertiliser application (50-300 kg N ha-1) that was less under elevated pCO2, and evidence for anaerobic CH4 oxidation occurring in soil at 75% soil water filled pore space that would not have been apparent from changes in net CH4 emissions. 13C-SIP both through plants (using 13C-CO2) and directly into soil (using 13C-methane and -organic substrates) has revealed how key players in C utilisation vary under different soil conditions, for example, under improved and unimproved grasslands.

  18. Isotopic discrimination during litter decomposition and delta13C and delta15N soil profiles in a young artificial stand and in an old floodplain forest.

    PubMed

    Gioacchini, Paola; Masia, Andrea; Canaccini, Francesca; Boldreghini, Pietro; Tonon, Giustino

    2006-06-01

    In the present study, rates of litter decomposition and microbial biomass nitrogen were monitored over an 8-month period in a young broadleaf plantation (18 y) and in an old floodplain forest. Moreover, delta13C and delta15N temporal variations within soil profiles were evaluated at both sites. Rates of litter decomposition were higher in spring and autumn than in summer, in both forests. At the end of the observation period the percentage of original litter remaining was not statistically different between the young and the old forest and accounted for 60-70% of the original amount. Microbial biomass nitrogen in the remaining litter and the percentage of litter mass lost during decomposition were positively correlated. The difference in litter quality affected the decomposition rate and also the changes in carbon isotopic composition during the decomposition process. In contrast, 15N isotopic signatures showed a similar trend in the litter of the two forests irrespective of the litter quality. Although delta13Csoil and delta15Nsoil showed considerable temporal variation they increased with depth in the soils of both sites but their seasonal changes did not reflect those of the decomposing litter. Within the same soil horizon, both delta13C and delta15N showed similar seasonal trends in the soils of the two forests, suggesting the involvement of environmental factors acting at regional level, such as soil temperature and rainfall variations, in regulating seasonal delta13C and delta15N soil variations.

  19. High-resolution direct infusion-based mass spectrometry in combination with whole 13C metabolome isotope labeling allows unambiguous assignment of chemical sum formulas.

    PubMed

    Giavalisco, Patrick; Hummel, Jan; Lisec, Jan; Inostroza, Alvaro Cuadros; Catchpole, Gareth; Willmitzer, Lothar

    2008-12-15

    A new strategy for direct infusion-based metabolite analysis employing a combination of high-resolution mass spectrometry and (13)C-isotope labeling of entire metabolomes is described. Differentially isotope labeled metabolite extracts from otherwise identically grown reference plants were prepared and infused into a Fourier transform ion cyclotron resonance mass spectrometer. The derived accurate mass lists from each extract were searched, using an in-house-developed database search tool, against a number of comprehensive metabolite databases. Comparison of the retrieved chemical formulas from both, the (12)C and (13)C samples, leads to two major advantages compared to nonisotope-based metabolite fingerprinting: first, removal of background contaminations from the result list, due to the (12)C/(13)C peak pairing principle and therefore positive identification of compounds of true biological origin; second, elimination of ambiguity in chemical formula assignment due to the same principle, leading to the clear association of one measured mass to only one chemical formula. Applying this combination of strategies to metabolite extracts of the model plant Arabidopsis thaliana therefore resulted in the reproducible identification of more than 1000 unambiguous chemical sum formulas of biological origin of which more than 80% have not been associated to Arabidopsis before.

  20. Isotopically-selective two-photon ionization of 12C- and 13C-benzene and hexadeuterobenzene in a time-of-flight mass spectrometer

    NASA Astrophysics Data System (ADS)

    de La Cruz, A.; Ortiz, M.; Cabrera, J. A.; Campos, J.

    1994-04-01

    In this work the 610 band spectra for 12C6H6, 12C6D6, 13C12C5H6 and 13C12C5D6 isotopically-substituted benzenes are reported. Spectra of deuterated species are given for the first time. These molecular spectra can be employed to test the technical performances of REMPI-TOFMS systems. The experimental method was laser-induced two-photon ionization of molecules cooled in a He supersonic beam followed by time-of-flight mass spectrometry. A splitting of the 610 band appears when a 13C atom is present in the benzene-ring, favoring the isotope selectivity. In the present experiment a complete mass discrimination has been accomplished by using appropriate electronic circuits. A proportional counter has been used to obtain the corresponding spectra of the molecules at 300 K. The device is very useful to tune the laser wavelength to resonance in this kind of mass spectrometry experiment.

  1. (13)C/(12)C isotope ratios of organic acids, glucose and fructose determined by HPLC-co-IRMS for lemon juices authenticity.

    PubMed

    Guyon, Francois; Auberger, Pauline; Gaillard, Laetita; Loublanches, Caroline; Viateau, Maryse; Sabathié, Nathalie; Salagoïty, Marie-Hélène; Médina, Bernard

    2014-03-01

    High performance liquid chromatography linked to isotope ratio mass spectrometry via an interface allowing the chemical oxidation of organic matter (HPLC-co-IRMS) was used to simultaneously determine carbon 13 isotope ratio (δ(13)C) of organic acids, glucose and fructose in lime and lemon juices. Because of the significant difference between organic acids and sugars concentrations, the experimental protocol was optimised by applying a "current jump" to the IRMS device. The filament current is increased of 300μA during elution in order to enhance IRMS sensitivity. Then, analysis were performed on 35 lemon and lime fruits from various geographical origins and squeezed in the laboratory. An overall average δ(13)C values of -25.40±1.62‰, -23.83±1.82‰ and -25.67±1.72‰ is found for organic acids mixture mainly made up of citric acid, glucose and fructose, respectively. These authentic samples allowed the definition of a confidence domain to which have been confronted 30 commercial juices (24 "pure juices" and 6 coming from concentrate). Among these 30 samples, 10 present δ(13)C values outside the defined range revealing an added "C4" type organic acids or sugars, addition not specified on the label that is not in agreement with EU regulation.

  2. Stable carbon isotope analysis of coprocessing materials

    SciTech Connect

    Lancet, M.S.; Winschel, R.A.; Burke, F.P.

    1991-02-01

    Consol R D is developing and demonstrating stable carbon isotope analysis as a method to quantitatively distinguish coal-derived and petroleum-derived carbon in products from coal/petroleum coprocessing. The approach taken is develop the method, then demonstrate its application on authentic continuous-unit products. The significance of selective isotopic fractionation is being determined and, when necessary, corrections are applied to account for it. Precision, accuracy and range of applicability are being defined. The value of accessory analytical techniques also is being assessed. Previously reported data on samples from HRI bench-scale coprocessing Runs 227-53 (Texas lignite/Maya ASB and Texas lignite/Maya VSB) and 238-1 (Westerholt coal/Cold Lake VSB) were corrected for selective isotopic fractionation. Carbon sourcing was performed on samples from HRI bench-scale coprocessing Run 227-60 (Texas lignite/Maya VSB) and samples from UOP bench-scale coprocessing Run 26 (Illinois 6 coal/Lloydminster vacuum resid); the latter data were corrected for isotopic fractionation, though the former could not be corrected. A paper presented at the 1990 DOE Direct Liquefaction Contractor's Review Meeting is appended. 15 refs., 21 figs., 22 tabs.

  3. Principles and limitations of stable isotopes in differentiating organic and conventional foodstuffs: 2. Animal products.

    PubMed

    Inácio, Caio T; Chalk, Phillip M

    2017-01-02

    In this review, we examine the variation in stable isotope signatures of the lighter elements (δ(2)H, δ(13)C, δ(15)N, δ(18)O, and δ(34)S) of tissues and excreta of domesticated animals, the factors affecting the isotopic composition of animal tissues, and whether stable isotopes may be used to differentiate organic and conventional modes of animal husbandry. The main factors affecting the δ(13)C signatures of livestock are the C3/C4 composition of the diet, the relative digestibility of the diet components, metabolic turnover, tissue and compound specificity, growth rate, and animal age. δ(15)N signatures of sheep and cattle products have been related mainly to diet signatures, which are quite variable among farms and between years. Although few data exist, a minor influence in δ(15)N signatures of animal products was attributed to N losses at the farm level, whereas stocking rate showed divergent findings. Correlations between mode of production and δ(2)H and δ(18)O have not been established, and only in one case of an animal product was δ(34)S a satisfactory marker for mode of production. While many data exist on diet-tissue isotopic discrimination values among domesticated animals, there is a paucity of data that allow a direct and statistically verifiable comparison of the differences in the isotopic signatures of organically and conventionally grown animal products. The few comparisons are confined to beef, milk, and egg yolk, with no data for swine or lamb products. δ(13)C appears to be the most promising isotopic marker to differentiate organic and conventional production systems when maize (C4) is present in the conventional animal diet. However, δ(13)C may be unsuitable under tropical conditions, where C4 grasses are abundant, and where grass-based husbandry is predominant in both conventional and organic systems. Presently, there is no universal analytical method that can be applied to differentiate organic and conventional animal products.

  4. The δ13C evolution of cave drip water along discreet flow paths in a central Texas cave: Quantifying kinetic isotope fractionation factors

    NASA Astrophysics Data System (ADS)

    Mickler, P. J.; Carlson, P. E.; Banner, J.; Breecker, D.; Stern, L. A.; Baseman, A.

    2015-12-01

    Gaps remain in our understanding of in-cave processes that influence cave water chemistry during speleothem formation. Quantifying environmental controls on the isotopic and chemical evolution of karst groundwater would improve the accuracy of speleothem-based paleoclimate reconstructions. In this study, drip water chemical evolution along flow paths was sampled monthly at two locations in Inner Space Cavern, Texas, over a period of 8 months. In each of the two locations, cave water drips off a stalactite, flows along a flowstone and subsequently drips off a lower stalactite, allowing cave water to be sampled at two points, 1-2 meters apart, along each flow path. The chemical and isotopic evolution of drip water along its flow path shows seasonality, where 1) summer months (high cave-air pCO2) have small variations in δ13C values along the flow paths, high and relatively invariant DIC and Ca values,; and 2) winter months (low cave-air pCO2) generally have large increases in DIC δ13C values along the flow paths, lower DIC and Ca values. The magnitude of the increase in DIC δ13C values along the flow paths, <~1‰ to ~4‰, is controlled by the extent of DIC loss to CO2 degassing and calcite precipitation which is controlled by the pCO2 gradient between drip water and cave air. If the DIC loss is less than 15%, then the evolution of the δ13C value of the DIC reservoir can be modelled using a Rayleigh distillation model and equilibrium fractionation factors between (CO2(g)-HCO3-(aq)) and (CaCO3-HCO3-(aq)). As the loss of the DIC reservoir increases above 15% the DIC δ13C values become progressively higher such that the ɛ (CO2(g)-HCO3-(aq)) values needed to model the observed results change from equilibrium values of ~8‰ to non-equilibrium values up to ~25‰. The variance in magnitude of carbon isotope fractionation during CO2 degassing cannot be attributed to changes in temperature, and thus we infer significant kinetic isotope effects at higher rates of DIC

  5. Stable isotope fractionation in speleothems as a proxy for subsurface environmental changes, Milchbach cave (Switzerland)

    NASA Astrophysics Data System (ADS)

    Luetscher, M.; Hoffmann, D. L.; Smart, P. L.; Spötl, C.

    2009-04-01

    Recent modelling work concluded that stable isotope fractionation along speleothem growth layers is largely controlled by cave temperature and drip interval (e.g., Mühlinghaus et al. 2007, Romanov et al. 2008). The magnitude of isotope fractionation could, therefore, be used as a proxy of the subsurface depositional environment. Here, we present evidence of changing isotopic fractionation in speleothems from a periglacial karst system, which experienced drastic changes in cave ventilation and hydrology during the Holocene. Three coeval stalagmites were sampled from Milchbach cave (Switzerland) and U/Th-dated to between 2 and 8.6 ka. 2D mapping of stable isotopes reveals major changes in δ13C and δ18O along individual growth layers. These changes correlate noticeably with changes in the calcite fabric and speleothem growth rate suggesting that changes in drip rate were the predominant control, possibly related to fluctuations of the mass balance of the Upper Grindelwald Glacier. References: Mühlinghaus C., Scholz D., Mangini A., 2007. Modelling stalagmite growth and δ13C as a function of drip interval and temperature. Geochimica et Cosmochimica Acta, 71(11), 2780-2790. Romanov, D., Kaufmann, G., Dreybrodt, W., 2008. δ13C profiles along growth layers of stalagmites: Comparing theoretical and experimental results. Geochimica et Cosmochimica Acta, 72(2), 438-448.

  6. Modeling the dynamics of stable isotope tissue-diet enrichment.

    PubMed

    Remien, Christopher H

    2015-02-21

    Reconstructions of dietary composition and trophic level from stable isotope measurements of animal tissue rely on predictable offsets of stable isotope ratios from diet to tissue. Physiological processes associated with metabolism shape tissue stable isotope ratios, and as such the spacing between stable isotope ratios of diet and tissue may be influenced by processes such as growth, nutritional stress, and disease. Here, we develop a model of incorporation stable isotopes in diet to tissues by coupling stable isotope dynamics to a model of macronutrient energy metabolism. We use the model to explore the effect of changes in dietary intake, both composition and amount, and in energy expenditure, on body mass and carbon and nitrogen stable isotope ratios of tissue.

  7. Correlation between multielement stable isotope ratio and geographical origin in Peretta cows' milk cheese.

    PubMed

    Manca, G; Franco, M A; Versini, G; Camin, F; Rossmann, A; Tola, A

    2006-03-01

    The aim of this study was to characterize the isotopic composition and protect "Peretta" cows' milk cheese, a typical product of Sardinia, against other cheeses of the same appearance sold under the same name, but made of raw materials from northern Europe. The study was concerned with 3 types of cheese: those produced in local dairies from milk from free-grazing or pasture-grazing cows in Sardinia (local dairy product), cheeses made on an industrial scale from milk produced by intensive farming in Sardinia (factory cheese), and cheeses made with raw materials imported from other countries (imported product). To distinguish the Sardinian cheeses from the imported product, the stable isotope ratios 13C/12C, 15N/14N, D/H, 34S/32S, and (18)O/(16)O were used. Determination of the isotopic data delta13C, delta15N, delta2H, and delta34S was performed in the casein fraction, whereas delta(18)O and delta13C were determined in the glycerol fraction. Measurements were performed by isotope ratio mass spectrometry. A comparison between mean values of the isotope ratios by statistical analysis (ANOVA and Tukey's test) showed that the greatest difference between the 3 types of cheese (local dairy, factory, and imported products) was in the 13C/12C, 34S/32S, and (18)O/(16)O isotope ratios. In the other parameters, either no differences (delta15N) or minimal differences (delta2H) were found. Evaluation of the data by multivariate statistical analysis (principal component analysis and hierarchical cluster analysis) revealed that the isotope characteristics of the factory products were similar to those of the cheeses produced from imported raw materials, whereas a difference was found between the local dairy-produced cheeses and the products in the other 2 categories.

  8. Stable isotope, site-specific mass tagging for protein identification

    DOEpatents

    Chen, Xian

    2006-10-24

    Proteolytic peptide mass mapping as measured by mass spectrometry provides an important method for the identification of proteins, which are usually identified by matching the measured and calculated m/z values of the proteolytic peptides. A unique identification is, however, heavily dependent upon the mass accuracy and sequence coverage of the fragment ions generated by peptide ionization. The present invention describes a method for increasing the specificity, accuracy and efficiency of the assignments of particular proteolytic peptides and consequent protein identification, by the incorporation of selected amino acid residue(s) enriched with stable isotope(s) into the protein sequence without the need for ultrahigh instrumental accuracy. Selected amino acid(s) are labeled with .sup.13C/.sup.15N/.sup.2H and incorporated into proteins in a sequence-specific manner during cell culturing. Each of these labeled amino acids carries a defined mass change encoded in its monoisotopic distribution pattern. Through their characteristic patterns, the peptides with mass tag(s) can then be readily distinguished from other peptides in mass spectra. The present method of identifying unique proteins can also be extended to protein complexes and will significantly increase data search specificity, efficiency and accuracy for protein identifications.

  9. Stalagmite stable isotope record of recent tropical cyclone events

    NASA Astrophysics Data System (ADS)

    Benoit Frappier, Amy; Sahagian, Dork; Carpenter, Scott J.; González, Luis A.; Frappier, Brian R.

    2007-02-01

    We present a 23 yr stalagmite record (1977 2000) of oxygen isotope variation, associated with 11 tropical cyclones (TCs), from Actun Tunichil Muknal cave in central Belize. High-resolution microsampling yielded a record of monthly to weekly temporal resolution that contains abrupt decreases (negative excursions) in calcite δ18O values that correspond with recent TC rain events nearby. A logistic discriminant model reliably identified TC proxy signals using the measurable parameters δ18O and δ13C values, and single point changes in δ18O value. The logistic model correctly identified 80% of excursions as TC events and incorrectly classified only 1 of nearly 1200 nonstorm sampling points. In addition to enabling high-resolution TC frequency reconstruction, this geologic proxy also provides information about the intensity of individual TCs. A multiple regression predicted TC intensity (R2 = 0.465, p = 0.034) using sampling frequency and excursion amplitude. Consistent with previous low-resolution studies, we found that the decadal average δ18O value was lower during the 1990s when several TCs produced rainfall in the area, but higher during the 1980s when only one TC struck. Longer, accurately dated, high-resolution speleothem stable isotope records may be a useful new tool for paleotempestology, to clarify associations between highly variable TC activity and the dynamic range of Quaternary climate.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  11. Application of Stable Isotope-Assisted Metabolomics for Cell Metabolism Studies

    PubMed Central

    You, Le; Zhang, Baichen; Tang, Yinjie J.

    2014-01-01

    The applications of stable isotopes in metabolomics have facilitated the study of cell metabolisms. Stable isotope-assisted metabolomics requires: (1) properly designed tracer experiments; (2) stringent sampling and quenching protocols to minimize isotopic alternations; (3) efficient metabolite separations; (4) high resolution mass spectrometry to resolve overlapping peaks and background noises; and (5) data analysis methods and databases to decipher isotopic clusters over a broad m/z range (mass-to-charge ratio). This paper overviews mass spectrometry based techniques for precise determination of metabolites and their isotopologues. It also discusses applications of isotopic approaches to track substrate utilization, identify unknown metabolites and their chemical formulas, measure metabolite concentrations, determine putative metabolic pathways, and investigate microbial community populations and their carbon assimilation patterns. In addition, 13C-metabolite fingerprinting and metabolic models can be integrated to quantify carbon fluxes (enzyme reaction rates). The fluxome, in combination with other “omics” analyses, may give systems-level insights into regulatory mechanisms underlying gene functions. More importantly, 13C-tracer experiments significantly improve the potential of low-resolution gas chromatography-mass spectrometry (GC-MS) for broad-scope metabolism studies. We foresee the isotope-assisted metabolomics to be an indispensable tool in industrial biotechnology, environmental microbiology, and medical research. PMID:24957020

  12. Determination of methanogenic pathways through carbon isotope13C) analysis for the two-stage anaerobic digestion of high-solids substrates.

    PubMed

    Gehring, Tito; Klang, Johanna; Niedermayr, Andrea; Berzio, Stephan; Immenhauser, Adrian; Klocke, Michael; Wichern, Marc; Lübken, Manfred

    2015-04-07

    This study used carbon isotope (δ(13)C)-based calculations to quantify the specific methanogenic pathways in a two-stage experimental biogas plant composed of three thermophilic leach bed reactors (51-56 °C) followed by a mesophilic (36.5 °C) anaerobic filter. Despite the continuous dominance of the acetoclastic Methanosaeta in the anaerobic filter, the methane (CH4) fraction derived from carbon dioxide reduction (CO2), fmc, varied significantly over the investigation period of 200 days. At organic loading rates (OLRs) below 6.0 gCOD L(-1) d(-1), the average fmc value was 33%, whereas at higher OLRs, with a maximum level of 17.0 gCOD L(-1) d(-1), the fmc values reached 47%. The experiments allowed for a clear differentiation of the isotope fractionation related to the formation and consumption of acetate in both stages of the plant. Our data indicate constant carbon isotope fractionation for acetate formation at different OLRs within the thermophilic leach bed reactors as well as a negligible contribution of homoacetogenesis. These results present the first quantification of methanogenic pathway (fmc values) dynamics for a continually operated mesophilic bioreactor and highlight the enormous potential of δ(13)C analysis for a more comprehensive understanding of the anaerobic degradation processes in CH4-producing biogas plants.

  13. Paleobiological Implications of the Isotopic Signatures ( 13C, 15N) of Fossil Mammal Collagen in Scladina Cave (Sclayn, Belgium)

    NASA Astrophysics Data System (ADS)

    Bocherens, Hervé; Billiou, Daniel; Patou-Mathis, Marylène; Bonjean, Dominique; Otte, Marcel; Mariotti, André

    1997-11-01

    An isotopic investigation of upper Pleistocene mammal bones and teeth from Scladina cave (Sclayn, Belgium) demonstrated the very good quality of collagen preservation. A preliminary screening of the samples used the amount of nitrogen in whole bone and dentine in order to estimate the preserved amount of collagen before starting the extraction process. The isotopic abundances of fossil specimens from still-extant species are consistent with their trophic position. Moreover, the 15N isotopic abundance is higher in dentine than in bone in bears and hyenas, a phenomenon already observed in modern specimens. These results demonstrate that the isotopic compositions of samples from Scladina cave can be interpreted in ecological terms. Mammoths exhibit a high 15N isotopic abundance relative to other herbivores, as was the case in Siberian and Alaskan samples. These results suggest distinctive dietary adaptations in herbivores living in the mammoth steppe. Cave bears are clearly isotopically different from coeval brown bears, suggesting an ecological separation between species, with a pure vegetarian diet for cave bear and an omnivorous diet for brown bear.

  14. Mother-egg stable isotope conversions and effects of lipid extraction and ethanol preservation on loggerhead eggs.

    PubMed

    Kaufman, Temma J; Pajuelo, Mariela; Bjorndal, Karen A; Bolten, Alan B; Pfaller, Joseph B; Williams, Kristina L; Vander Zanden, Hannah B

    2014-01-01

    Carbon and nitrogen stable isotope (δ(13)C and δ(15)N) analysis has been used to elucidate foraging and migration behaviours of endangered sea turtle populations. Isotopic analysis of tissue samples from nesting females can provide information about their foraging locations before reproduction. To determine whether loggerhead (Caretta caretta) eggs provide a good proxy for maternal isotope values, we addressed the following three objectives: (i) we evaluated isotopic effects of ethanol preservation and lipid extraction on yolk; (ii) we examined the isotopic offset between maternal epidermis and corresponding egg yolk and albumen tissue δ(13)C and δ(15)N values; and (iii) we assessed the accuracy of foraging ground assignment using egg yolk and albumen stable isotope values as a proxy for maternal epidermis. Epidermis (n = 61), albumen (n = 61) and yolk samples (n = 24) were collected in 2011 from nesting females at Wassaw Island, GA, USA. Subsamples from frozen and ethanol-preserved yolk samples were lipid extracted. Both lipid extraction and ethanol preservation significantly affected yolk δ(13)C, while δ(15)N values were not altered at a biologically relevant level. The mathematical corrections provided here allow for normalization of yolk δ(13)C values with these treatments. Significant tissue conversion equations were found between δ(13)C and δ(15)N values of maternal epidermis and corresponding yolk and albumen. Finally, the consistency in assignment to a foraging area was high (up to 84%), indicating that these conversion equations can be used in future studies where stable isotopes are measured to determine female foraging behaviour and trophic relationships by assessing egg components. Loggerhead eggs can thus provide reliable isotopic information when samples from nesting females cannot be obtained.

  15. Stable carbon isotopic compositions of organic acids in total suspended particles and dusts from Guangzhou, China

    NASA Astrophysics Data System (ADS)

    Ma, Shexia; Peng, Ping'an; Song, Jianzhong; Zhao, Jinping; He, Lulu; Sheng, Guoying; Fu, Jiamo

    2010-10-01

    Stable carbon isotopic compositions of individual organic acids were determined in total suspended particles and dusts from Guangzhou. The δ 13C values of high molecular weight n-alkanoic acids (C 20-C 28) varied from -34.1‰ to -32.4‰ and tended to be heavier in summer and lighter in winter. These δ 13C values indicate that high molecular weight n-alkanoic acids were derived mainly from emission by C 3 plants. Reduced biological synthesis of high molecular weight n-alkanoic acids in winter may be the reason for the light carbon isotopic composition. The δ 13C values of low molecular weight n-alkanoic acids (C 10-C 18) changed from -31.7‰ to -30.3‰ and exhibited a reverse seasonal trend, i.e., heavier in winter and lighter in summer. Slightly heavier δ 13C values of low molecular weight n-alkanoic acids than those of high molecular weight n-alkanoic acids suggested that they may be emitted from blended sources, e.g., anthropogenic sources and vegetation waxes. Lighter δ 13C values in summer may be attributed to relatively low anthropogenic sources and high botanic sources in summer. Dicarboxylic acids and aromatic acids have been proposed as secondary products from photochemical degradation. The average δ 13C values of dicarboxylic acids and aromatic acids were heavier, and ranged from -25.2‰ to -22.9‰ and from -30.0‰ to -27.6‰, respectively. Both dicarboxylic acids and aromatic acids displayed the same temporal variations in the δ 13C values, i.e., negative δ 13C in the summer samples and positive in the winter samples, which may be controlled by photochemical reactions; they are generally severe in winter in Guangzhou under the monsoon weather system. The heaviest δ 13C values were observed in dicarboxylic acids, indicating that dicarboxylic acids were formed by fast and more complete oxidation reactions. These results indicate that the stable carbon isotopic composition of organic acids may provide important information about sources and

  16. Variability in Carbon Stable Isotope Ratio of Heterotrophic Soil Respiration in a Deciduous Needle-leaf Forest

    NASA Astrophysics Data System (ADS)

    Takahashi, Y.; Liang, N.; Machida, T.; Fujinuma, Y.; Inoue, G.

    2005-12-01

    We investigated spatial and temporal variability in the carbon stable isotope ratio (δ13C) of heterotrophic soil respiration in a deciduous Japanese needle-leaf forest for 3 years. We used high-precision isotope measurement coupled with a sampling system optimized for soil respiration to capture this variability under natural conditions. The limitations of chamber-based measurements combined with spatial variation created a representation error that prevented precise estimates of flux-weighted mean δ13C, but we could nonetheless characterize the δ13C variations intrinsic to heterotrophic respiration. In the absence of root respiration, δ13C exhibited significant seasonal variation, with a greater range than in previous models. In a root-exclusion plot, δ13C was lowest at high temperatures but showed a different seasonal course from that of CO2 efflux. A simple model explained the seasonal variation in δ13C using interpool differences in δ13C of decomposed organic matter, in the temperature dependence of decomposition rates, and in the seasonal changes in pool size. The characteristic seasonality of δ13C appears to be associated with the properties of the forest, including litterfall patterns.

  17. Food sources of macro-invertebrates in an important mangrove ecosystem of Vietnam determined by dual stable isotope signatures

    NASA Astrophysics Data System (ADS)

    Tue, Nguyen Tai; Hamaoka, Hideki; Sogabe, Atsushi; Quy, Tran Dang; Nhuan, Mai Trong; Omori, Koji

    2012-08-01

    Dual stable isotope signatures (δ13C and δ15N) were applied to determine the contribution of mangrove materials and other organic carbon sources to the invertebrate community in an ecologically important mangrove ecosystem of Vietnam. We have analyzed 181 specimens of 30 invertebrate species and found δ13C and δ15N ranging from - 14.5 to - 26.8‰ and from 1.3 to 12.1‰, respectively. From taxa measured for stable isotopes, polychaete, gastropods, bivalves, and grapsid crabs living in mangrove forest showed relative low δ13C values, while fiddler crabs inhabiting in the land-water ecotone showed the highest δ13C values. The δ13C showed that just a few mangrove inhabitants directly relied on the mangrove materials. The wide ranges of δ13C and δ15N signatures indicated that the invertebrates utilized heterogeneous diets, comprising benthic microalgae, marine phytoplankton, particulate organic matter, sediment organic matter, mangrove detritus, and meiofauna and rotten animal tissues as the supplemental nutrient food sources. Moreover, the significant correlation between δ13C values and body sizes of invertebrates showed that snails Littoraria melanostoma and Terebralia sulcata, bivalve Glauconome virens, and portunid crab Scylla serrata exhibited ontogenetic shifts in diets. The present study showed that adjacent habitats such as tidal flat and mangrove creeks seem to contribute an important microalgal food resource for invertebrates and highlighted the need for conservations of mangrove forests and the adjacent habitats.

  18. Evaluation of on-line pyrolysis coupled to isotope ratio mass spectrometry for the determination of position-specific (13)C isotope composition of short chain n-alkanes (C6-C12).

    PubMed

    Gilbert, Alexis; Yamada, Keita; Yoshida, Naohiro

    2016-06-01

    We measured (13)C intramolecular isotopic composition of commercially available short-chain hydrocarbons (n-C6-n-C12) using (13)C-NMR. Results show that the main variation is between the terminal and the sub-terminal C-atom positions. Site-preference (difference in δ(13)C values between terminal and sub-terminal C-atom positions) among all the samples varies between -12.2‰ and +8.4‰. Comparison of these results with those obtained using on-line pyrolysis coupled with GC-C-IRMS show that the thermal cracking of hydrocarbons occurs with a good isotopic fidelity between terminal and sub-terminal C-atom positions of the starting material and the related pyrolysis products (methane and ethylene). On-line pyrolysis coupled with GC-C-IRMS can thus be used for tracing hydrocarbons biogeochemical processes.

  19. Stable isotope analysis of 1987-1991 zooplankton samples and bowhead whale tissues. Final report

    SciTech Connect

    Schell, D.M.

    1992-06-01

    Stable isotope analyses of bowhead whale tissue samples and bowhead whale prey organisms collected over the years 1987 to 1991 were used to provide detail on the isotope ratio gradients evident in the arctic Alaskan zooplankton and to verify previous findings regarding the growth rates and age determination techniques developed for bowhead whales. Zooplankton of the Bering and Chukchi seas are enriched in (13)C relative to the eastern Beaufort Sea. The analysis of baleen from bowhead whales taken between 1987 to 1990 indicate that the whales are slow-growing and the young animals between year one and about six to seven years of age, undergo a period of little or no linear growth. The authors estimate that bowheads require 16-18 years to reach the length of sexual maturity, i.e., 13-14 m. From baleen Delta(13C) cycles, a 20 year record of the isotope ratios in the phytoplankton of the northern Bering and Chukchi seas was constructed. The long-term record has been compared with the temperature anomalies in surface waters of the Bering Sea. The Delta(13C) of the zooplankton is inversely correlated with temperature and refutes current models attempting to relate ocean temperature, and atmospheric carbon dioxide levels with the Delta(13C) of ocean sediment organic matter.

  20. Tracing Carbon Sources through Aquatic and Terrestrial Food Webs Using Amino Acid Stable Isotope Fingerprinting

    PubMed Central

    Larsen, Thomas; Ventura, Marc; Andersen, Nils; O’Brien, Diane M.; Piatkowski, Uwe; McCarthy, Matthew D.

    2013-01-01

    Tracing the origin of nutrients is a fundamental goal of food web research but methodological issues associated with current research techniques such as using stable isotope ratios of bulk tissue can lead to confounding results. We investigated whether naturally occurring δ13C patterns among amino acids (δ13CAA) could distinguish between multiple aquatic and terrestrial primary production sources. We found that δ13CAA patterns in contrast to bulk δ13C values distinguished between carbon derived from algae, seagrass, terrestrial plants, bacteria and fungi. Furthermore, we showed for two aquatic producers that their δ13CAA patterns were largely unaffected by different environmental conditions despite substantial shifts in bulk δ13C values. The potential of assessing the major carbon sources at the base of the food web was demonstrated for freshwater, pelagic, and estuarine consumers; consumer δ13C patterns of essential amino acids largely matched those of the dominant primary producers in each system. Since amino acids make up about half of organismal carbon, source diagnostic isotope fingerprints can be used as a new complementary approach to overcome some of the limitations of variable source bulk isotope values commonly encountered in estuarine areas and other complex environments with mixed aquatic and terrestrial inputs. PMID:24069196

  1. Tracing carbon sources through aquatic and terrestrial food webs using amino acid stable isotope fingerprinting.

    PubMed

    Larsen, Thomas; Ventura, Marc; Andersen, Nils; O'Brien, Diane M; Piatkowski, Uwe; McCarthy, Matthew D

    2013-01-01

    Tracing the origin of nutrients is a fundamental goal of food web research but methodological issues associated with current research techniques such as using stable isotope ratios of bulk tissue can lead to confounding results. We investigated whether naturally occurring δ(13)C patterns among amino acids (δ(13)CAA) could distinguish between multiple aquatic and terrestrial primary production sources. We found that δ(13)CAA patterns in contrast to bulk δ(13)C values distinguished between carbon derived from algae, seagrass, terrestrial plants, bacteria and fungi. Furthermore, we showed for two aquatic producers that their δ(13)CAA patterns were largely unaffected by different environmental conditions despite substantial shifts in bulk δ(13)C values. The potential of assessing the major carbon sources at the base of the food web was demonstrated for freshwater, pelagic, and estuarine consumers; consumer δ(13)C patterns of essential amino acids largely matched those of the dominant primary producers in each system. Since amino acids make up about half of organismal carbon, source diagnostic isotope fingerprints can be used as a new complementary approach to overcome some of the limitations of variable source bulk isotope values commonly encountered in estuarine areas and other complex environments with mixed aquatic and terrestrial inputs.

  2. Stable isotopic compositions in Australian precipitation

    NASA Astrophysics Data System (ADS)

    Liu, Jianrong; Fu, Guobin; Song, Xianfang; Charles, Stephen P.; Zhang, Yinghua; Han, Dongmei; Wang, Shiqin

    2010-12-01

    Stable deuterium (δD) and oxygen-18 (δ18O) isotopes in 1962 to 2002 precipitation from the seven Australian stations of the Global Network of Isotopes in Precipitation (GNIP) were used to investigate isotope characteristics including temporal and spatial distributions across different regions of Australia. On the basis of 1534 samples, the local meteoric water line (LMWL) was established as δD = 7.10δ18O + 8.21. δ18O showed a depletion trend from north and south to central Australia (a continental effect) and from west to east. Precipitation amount effects were generally greater than temperature effects, with quadratic or logarithmic correlations describing δ/T and δ/P better than linear relationships. Nonlinear stepwise regression was used to determine the significant meteorological control factors for each station, explaining about 50% or more of the δ18O variations. Geographical control factors for δ18O were given by the relationship δ18O (‰) = -0.005 longitude (°) - 0.034 latitude (°)-0.003 altitude (m) - 4.753. Four different types of d-excess patterns demonstrated particular precipitation formation conditions for four major seasonal rainfall zones. Finally, wavelet coherence (WTC) between δ18O and SOI confirmed that the influence of ENSO decreased from east and north to west Australia.

  3. Stable isotopes in fish as indicators of habitat use

    EPA Science Inventory

    In our isotopic studies of fish in Oregon Coast Range streams we have found stable isotopes of carbon, oxygen and sulfur to be surprisingly useful in identifying and discriminating specific habitat or tributary use by a variety of fish species. Stable isotopes of carbon can be u...

  4. An estimation of Central Iberian Peninsula atmospheric δ13C and water δD in the Upper Cretaceous using pyrolysis compound specific isotopic analysis (Py-CSIA) of a fossil conifer.

    NASA Astrophysics Data System (ADS)

    González-Pérez, José A.; Jiménez-Morillo, Nicasio T.; De la Rosa, José M.; Almendros, Gonzalo; González-Vila, Francisco J.

    2015-04-01

    Frenelopsis is a frequently found genus of the Cretaceous floras adapted to dry, saline and in general to environmental conditions marked by severe water stress [1]. Stable isotope analysis of fossil organic materials can be used to infer palaeoenvironmental variables helpful to reconstruct plant paleohabitats [2]. In this study stable isotope analysis of organic fossil remains (FR) and humic fractions (FA, HA and humin) of Frenelopsis oligiostomata are studied in bulk (C, H, O, N IRMS) and in specific compounds released by pyrolysis (C, H, Py-CSIA). Well preserved F. oligiostomata fossils were handpicked from a limestone included in compacted marls from Upper Cretaceous (Senonian c. 72 Mya) in Guadalix de la Sierra (Madrid, Spain) [3]. The fossils were decarbonated with 6M HCl. Humic substances were extracted from finely ground fossil remains (FR) by successive treatments with 0.1M Na4P2O7 + NaOH [4]. The extract was acidified resulting into insoluble HA and soluble FA fractions. The HA and FA were purified as in [5] and [6] respectively. Bulk stable isotopic analysis (δ13C, δD, δ18O, δ15N IRMS) was done in an elemental micro-analyser coupled to a continuous flow Delta V Advantage isotope ratio mass spectrometer (IRMS). Pyrolysis compound specific isotopic analysis Py-CSIA (δ13C, δD): was done by coupling a double-shot pyrolyzer to a chromatograph connected to an IRMS. Structural features of specific peaks were inferred by comparing/matching mass spectra from conventional Py-GC/MS (data not shown) with Py-GC/IRMS chromatograms obtained using the same chromatographic conditions. Bulk C isotopic signature found for FR (-20.5±0.02 ‰) was in accordance with previous studies [2, 7-9]. This heavy isotopic δ13C signature indicates a depleted stomatal conductance and paleoenvironmental growth conditions of water and salt stress. This is in line with the morphological and depositional characteristics [3] confirming that F. oligostomata was adapted to highly xeric

  5. Microbial Utilization of Estuarine Dissolved Organic Carbon: a Stable Isotope Tracer Approach Tested by Mass Balance

    PubMed Central

    Hullar, M.; Fry, B.; Peterson, B. J.; Wright, R. T.

    1996-01-01

    The natural stable isotope values of different plants have been used to trace the fate of organic carbon that enters estuarine ecosystems. Experiments were designed to determine the magnitude of (delta) (sup13)C changes of dissolved organic carbon (DOC) derived from tidal marsh vegetation that occurred during bacterial decomposition. Bacteria were grown on DOC leached from estuarine Spartina alterniflora and Typhus angustifolia plants. In four experiments, 25 to 80% of the initial carbon (2.6 to 9.1 mM organic C) was converted to bacterial biomass and CO(inf2). Mass balance calculations showed good recovery of total C and (sup13)C at the end of these experiments (100% (plusmn) 14% total C; (plusmn) 1(permil) (delta) (sup13)C). The (delta) (sup13)C values of DOC, bacterial biomass, and respired CO(inf2) changed only slightly in the four experiments by average values of -0.6, +1.4, and +0.5(permil), respectively. These changes are small relative to the range of (delta) (sup13)C values represented by different organic carbon sources to estuaries. Thus, microbial (delta) (sup13)C values determined in the field helped to identify the source of the carbon assimilated by bacteria. PMID:16535358

  6. Compound-Specific Stable Carbon Isotope Analysis of Chlorofluorocarbons in Groundwater.

    PubMed

    Horst, Axel; Lacrampe-Couloume, Georges; Sherwood Lollar, Barbara

    2015-10-20

    Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), controlled substances due to their role in stratospheric ozone loss, also occur as dissolved contaminants in groundwaters. Stable carbon isotopic signatures may provide valuable new information on the fate of these compounds as has been seen for other priority hydrocarbon contaminants, but to date no method for extraction and isotopic analysis of dissolved CFCs from groundwaters has been developed. Here we describe a cryogenic purge and trap system coupled to continuous flow compound-specific stable carbon isotope analysis mass spectrometry for concentrations as low as 35 μg/L. The method is validated by comparing isotopic signatures from water extracted CFCs against a new suite of isotopic CFC standards. Fractionation of CFCs in volatilization experiments from pure-phase CFC-11 and CFC-113 resulted in enrichment factors (ε) of +1.7 ± 0.1‰ and +1.1 ± 0.1‰, respectively, indicating that such volatile loss, if significant, would produce a more (13)C depleted signature in the remaining CFCs. Importantly, no significant fractionation was observed during volatile extraction of dissolved CFCs from aqueous solutions. δ(13)C values for groundwaters from a CFC-contaminated site were, on average, more enriched than δ(13)C values for pure compounds. Such enriched δ(13)C values have been seen in other hydrocarbon contaminants such as chlorinated ethenes and ethanes due to in situ degradation, but definitive interpretation of such enriched signatures in field samples requires additional experiments to characterize fractionation of CFCs during biodegradation. The establishment of a robust and sensitive method of extraction and analysis, as described here, provides the foundation for such future directions.

  7. Biosynthesis, molecular structure, and domain architecture of potato suberin: a (13)C NMR study using isotopically labeled precursors.

    PubMed

    Yan, B; Stark, R E

    2000-08-01

    Although suberin in potato wound periderm is known to be a polyester containing long-chain fatty acids and phenolics embedded within the cell wall, many aspects of its molecular structure and polymer-polymer connectivities remain elusive. The present work combines biosynthetic incorporation of site-specifically (13)C-enriched acetates and phenylalanines with one- and two-dimensional solid-state (13)C NMR spectroscopic methods to monitor the developing suberin polymer. Exogenous acetate is found to be incorporated preferentially at the carboxyl end of the aliphatic carbon chains, suggesting addition during the later elongation steps of fatty acid synthesis. Carboxyl-labeled phenylalanine precursors provide evidence for the concurrent development of phenolic esters and of monolignols typical of lignin. Experiments with ring-labeled phenylalanine precursors demonstrate a predominance of sinapyl and guaiacyl structures among suberin's phenolic moieties. Finally, the analysis of spin-exchange (solid-state NOESY) NMR experiments in ring-labeled suberin indicates distances of no more than 0.5 nm between pairs of phenolic and oxymethine carbons, which are attributed to the aromatic-aliphatic polyester and the cell wall polysaccharide matrix, respectively. These results offer direct and detailed molecular information regarding the insoluble intermediates of suberin biosynthesis, indicate probable covalent linkages between moieties of its polyester and polysaccharide domains, and yield a clearer overall picture of this agriculturally important protective material.

  8. USE OF THE COMPOSITION AND STABLE CARBON ISOTOPE RATIO OF MICROBIAL FATTY ACIDS TO STUDY CARBON CYCLING

    EPA Science Inventory

    We use measurements of the concentration and stable carbon isotopic ratio (Gamma 13C) of individual microbial phospholipid fatty acids (PLFAS) in soils and sediments as indicators of live microbial biomass levels and microbial carbon source. For studies of soil organic matter (SO...

  9. STABLE CARBON ISOTOPE EVIDENCE FOR COUPLING BETWEEN SEDIMENTARY BACTERIA AND SEAGRASSES IN A SUB-TROPICAL LAGOON

    EPA Science Inventory

    We measured stable carbon isotope ratios (d13C) in phospholipid fatty acids (PLFAs) to identify the primary carbon source utilized by sedimentary bacteria in Lower Laguna Madre, Texas, which is a seagrass dominated lagoon. Comparisons were made between three differing habitat ty...

  10. Stable isotope analyses reveal the importance of seagrass beds as feeding areas for juvenile Myrophic punctatus in Florida

    EPA Science Inventory

    The feeding habits and habitats of the speckled worm eel Myrophis punctatus were studied on the mangrove edge of the Indian River Lagoon (Florida) using stomach contents and stable isotope analyses of carbon (δ13C) and nitrogen (δ15N). Stomach dietary analyses identified four tax...

  11. The effects of early diagenesis on the chemical and stable carbon isotopic composition of wood

    USGS Publications Warehouse

    Spiker, E. C.; Hatcher, P.G.

    1987-01-01

    Studies of modern and ancient buried wood show that there is a linear correlation between carbohydrate content and the stable carbon isotope composition as carbohydrates are preferentially degraded during early diagenesis. As the carbohydrate content decreases, the ??13C value of the degraded wood decreases 1 to 2 per mil, approaching the value of the residual lignin. These results indicate that carbohydrate degradation products are lost and not incorporated into the aromatic structure as lignin is selectively preserved during early diagenesis of wood. These results also indicate that attempts to quantify terrestrial inputs to modern sedimentary organic matter based on ??13C values should consider the possibility of a 1 to 2 per mil decrease in the ??13C value of degraded wood. ?? 1987.

  12. Use of stable isotope probing to assess the fate of emerging contaminants degraded by white-rot fungus.

    PubMed

    Badia-Fabregat, Marina; Rosell, Mònica; Caminal, Glòria; Vicent, Teresa; Marco-Urrea, Ernest

    2014-05-01

    The widespread of emerging contaminants in the environment and their potential impact on humans is a matter of concern. White-rot fungi are cosmopolitan organisms able to remove a wide range of pharmaceuticals and personal care products (PPCP) through cometabolism (i.e. laccases and peroxidases) or detoxification mechanisms (i.e. cytochrome P450 system). However, the use of PPCP as carbon source for these organisms is largely unexplored. Here, we used carbon stable isotope tracer experiments to assess the fate of anti-inflammatory diclofenac (DCF) and UV filter benzophenone-3 (BP3) during degradation by Trametes versicolor. The comparison between carbon isotopic composition of emitted carbon dioxide from 13C-labelled DCF ([acetophenyl ring-13C6]-DCF) and 13C-BP3 ([phenyl-13C6]-BP3) versus their 12C-homologue compounds showed mineralization of about 45% and 10% of the 13C contained in their respective molecules after 9 days of incubation. The carbon isotopic composition of the bulk biomass and the application of amino acid-stable isotope probing (SIP) allowed distinguishing between incorporation of 13C from BP3 into amino acids, which implies the use of this emerging contaminant as carbon source, and major intracellular accumulation of 13C from DCF without implying the transformation of its labelled phenyl ring into anabolic products. A mass balance of 13C in different compartments over time provided a comprehensive picture of the fate of DCF and BP3 across their different transformation processes. This is the first report assessing biodegradation of PPCP by SIP techniques and the use of emerging contaminants as carbon source for amino acid biosynthesis.

  13. Unusually high stable carbon isotopic values of methane from low organic carbon Mars analog hypersaline environments

    NASA Astrophysics Data System (ADS)

    Kelley, C. A.; Poole, J. A.; Tazaz, A.; Chanton, J.; Bebout, B.

    2010-12-01

    Motivated by the Mars rovers’ findings of past hypersaline environments and the discovery of methane in the atmosphere of Mars, we examined methanogenesis in hypersaline ponds in Baja California Sur and in the Don Edwards National Wildlife Refuge in northern California. Methane-rich bubbles were observed to be released from below gypsum/halite crusts in these environments. The stable carbon isotopic composition of these bubbles ranged from about -30 to -40 ‰. Methane with these relatively high isotopic values would typically be considered non-biogenic, however incubations of crust and sediments samples over time resulted in the production of methane. We therefore undertook a series of measurements aimed at understanding the isotopic composition of methane in these environments. The concentrations and isotopic composition of the particulate organic carbon (POC) in these environments were measured. POC content was low (relative to most methane-producing sedimentary environments), generally less than 1%, and always less than 2% of the total mass. The isotopic composition of the POC ranged from -13 to -22 ‰. To determine the substrates used by the methanogens, 13C-labeled trimethylamine (TMA), monomethylamine, methanol, acetate and bicarbonate were added to incubation vials and the methane produced was monitored for 13C content. The main substrates used by the methanogens in these hypersaline environments were the non-competitive substrates, the methylamines and methanol. When unlabeled, but isotopically known, TMA was added to incubation vials in varying concentrations, the isotopic composition of the methane produced also varied. Little, if any, difference in the isotopic composition between the TMA and methane occurred at the lowest TMA concentration (10 µM final concentration). The lowest methane δ13C values (and so greatest fractionation between methane and TMA) occurred when the most TMA was added (1000 µM final concentration). This change in the

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

    SciTech Connect

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

    1992-01-01

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

  15. The C-13/C-12 kinetic isotope effect for soil oxidation of methane at ambient atmospheric concentrations

    NASA Technical Reports Server (NTRS)

    King, Stagg L.; Quay, Paul D.; Lansdown, John M.

    1989-01-01

    During a survey of the Alaskan North Slope to estimate the isotopic composition and fluxes of methane (CH4) from the tundra, two sites were encountered that showed net methane consumption within flux chambers. Methane concentrations decreased from ambient (1.78 ppmv) by up to 50 percent, and the delta C-13 increased by up to 10 percent in the two chamber deployments showing CH4 consumption. CH4 consumption rates were measured to be 1.2 and 0.6 mg CH4/sq m per day; the corresponding carbon kinetic isotope effects (k13/k12) were 0.974 and 0.984, respectively.

  16. Stable-isotope comparisons between embryos and mothers of a placentatrophic shark species.

    PubMed

    McMeans, B C; Olin, J A; Benz, G W

    2009-12-01

    Stable nitrogen (delta(15)N) and carbon (delta(13)C) isotopes of Atlantic sharpnose shark Rhizoprionodon terraenovae embryos and mothers were analysed. Embryos were generally enriched in (15)N in all studied tissue relative to their mothers' tissue, with mean differences between mother and embryo delta(15)N (i.e. Deltadelta(15)N) being 1.4 per thousand for muscle, 1.7 per thousand for liver and 1.1 per thousand for cartilage. Embryo muscle and liver were enriched in (13)C (both Deltadelta(13)C means = 1.5 per thousand) and embryo cartilage was depleted (Deltadelta(13)C mean = -1.01 per thousand) relative to corresponding maternal tissues. While differences in delta(15)N and delta(13)C between mothers and their embryos were significant, muscle delta(15)N values indicated embryos to be within the range of values expected if they occupied a similar trophic position as their respective mothers. Positive linear relationships existed between embryo total length (L(T)) and Deltadelta(15)N for muscle and liver and embryo L(T) and Deltadelta(13)C for muscle, with those associations possibly resulting from physiological differences between smaller and larger embryos or differences associated with the known embryonic nutrition shift (yolk feeding to placental feeding) that occurs during the gestation of this placentatrophic species. Together these results suggest that at birth, the delta(15)N and delta(13)C values of R. terraenovae are likely higher than somewhat older neonates whose postpartum feeding habits have restructured their isotope profiles to reflect their postembryonic diet.

  17. Stable carbon isotopic evidence for differences in the dietary origin of bone cholesterol, collagen and apatite: implications for their use in palaeodietary reconstruction

    NASA Astrophysics Data System (ADS)

    Jim, Susan; Ambrose, Stanley H.; Evershed, Richard P.

    2004-01-01

    Rats were raised on a variety of isotopically controlled diets comprising 20% C 3, C 4 or marine protein and C 3 and/or C 4 non-protein or energy (i.e. sucrose, starch and oil) macronutrients. Compound specific stable carbon isotope13C) analysis was performed on the cholesterol isolated from the diet ( n=7 ) and bone ( n=15 ) of these animals and the values compared with bulk δ 13C measurements of bone collagen and apatite. The dietary signals reflected by these three bone biochemical components were investigated using linear regression analysis. δ 13C values of bone cholesterol were shown to reflect whole diet δ 13C values, collagen to reflect mainly dietary protein values and apatite to reflect whole diet values. Further correlations between dietary protein-to-energy spacings (Δ 13C prot-engy = δ 13C protein - δ 13C energy) and whole diet-to-bone component fractionations (Δ 13C bcomp- wdiet = δ 13C bone component - δ 13C whole diet) indicates that for hypothetical diets where protein δ 13C values are equal to energy values, fractionations between whole diet and bone biochemical fractions are -3.3‰ for cholesterol, +5.4‰ for collagen and +9.5‰ for apatite. Moreover, the narrow range of variation observed in apatite-to-cholesterol spacings (Δ 13C apat- bchol ) suggests that cholesterol δ 13C values can potentially also be used as an independent test for the isotopic integrity of apatite δ 13C values. These insights into bone cholesterol, collagen and apatite dietary signals, diet-to-bone fractionations and bone component-to-bone component spacings provide the basis for more accurate interpretations of the dietary behaviour of archaeological populations and food webs when the δ 13C analysis of bone is employed.

  18. Controls on the stable isotope compositions of travertine from hyperalkaline springs in Oman: Insights from clumped isotope measurements

    NASA Astrophysics Data System (ADS)

    Falk, E. S.; Guo, W.; Paukert, A. N.; Matter, J. M.; Mervine, E. M.; Kelemen, P. B.

    2016-11-01

    Carbonate formation at hyperalkaline springs is typical of serpentinization in peridotite massifs worldwide. These travertines have long been known to exhibit large variations in their carbon and oxygen isotope compositions, extending from apparent equilibrium values to highly depleted values. However, the exact causes of these variations are not well constrained. We analyzed a suite of well-characterized fresh carbonate precipitates and travertines associated with hyperalkaline springs in the peridotite section of the Samail ophiolite, Sultanate of Oman, and found their clumped isotope compositions vary systematically with formation environments. Based on these findings, we identified four main processes controlling the stable isotope compositions of these carbonates. These include hydroxylation of CO2, partial isotope equilibration of dissolved inorganic carbon, mixing between isotopically distinct carbonate end-members, and post-depositional recrystallization. Most notably, in fresh crystalline films on the surface of hyperalkaline springs and in some fresh carbonate precipitates from the bottom of hyperalkaline pools, we observed large enrichments in Δ47 (up to ∼0.2‰ above expected equilibrium values) which accompany depletions in δ18O and δ13C, yielding about 0.01‰ increase in Δ47 and 1.1‰ decrease in δ13C for every 1‰ decrease in δ18O, relative to expected equilibrium values. This disequilibrium trend, also reflected in preserved travertines ranging in age from modern to ∼40,000 years old, is interpreted to arise mainly from the isotope effects associated with the hydroxylation of CO2 in high-pH fluids and agrees with our first-order theoretical estimation. In addition, in some fresh carbonate precipitates from the bottom of hyperalkaline pools and in subsamples of one preserved travertine terrace, we observed additional enrichments in Δ47 at intermediate δ13C and δ18O, consistent with mixing between isotopically distinct carbonate end

  19. Methane flux from Peltandra virginica: Stable isotope tracing and chamber effects

    NASA Astrophysics Data System (ADS)

    Chanton, Jeffrey P.; Whiting, Gary J.; Showers, William J.; Crill, Patrick M.

    1992-03-01

    Methane flux from plots of Peltandra virginica in a bottomland hardwood swamp in southeast Virginia varied from 270 to 670 mg CH4m-2d-1 from May to August and was 6 times greater than the flux from unvegetated adjacent open waters. Variations in chamber temperature, light, and CO2 levels failed to produce systematic changes in CH4 flux rate or its isotopic composition from vegetated plots, suggesting that CH4 flux from Peltandra is independent of stomatal aperture or hourly variations in photosynthetic rate. Comparisons of different chamber techniques for the collection of CH4 for isotopic analysis and for flux measurements from Peltandra suggest that the effect of using simple uncontrolled chambers is small relative to temporal and spatial variations in methane emission and its isotopic composition. These results may be extended to other aquatic macrophytes which also transport gas primarily by molecular diffusion such as Oryza, Carex, Pontederia, Sagittaria, and Cladium. The δ13C of CH4 released from Peltandra varied between -61 and -71 °/oo. Isotopic variations in CH4 associated with Peltandra appeared to be controlled by transport effects. Methane withdrawn from Peltandra stems was considerably 13C enriched relative to sedimentary CH4 and was not an indicator of the isotopic composition of CH4 emitted by these plants. Hence emergent aquatic macrophytes rooted in organic-rich sediments do not appear to be a source of 13C enriched methane to the atmosphere. Emitted CH4 was 13C depleted relative both to the CH4 within stems (-49 to -55 °/oo) and within sediments (-56 to -58 °/oo), suggesting isotopic fractionation associated with the release of CH4 by the plants. The preferential release of 12CH4 by the plants is partly compensated for by the enrichment of 13C in CH4 contained within the plant stem. Although the presence of methanotrophic bacteria within the rhizosphere of Peltandra was demonstrated, the stable isotopic composition of methane emitted from

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

    NASA Astrophysics Data System (ADS)

    Charisi, Stella D.; Schmitz, Birger

    1998-02-01

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

  1. Spatially tracking 13C labeled substrate (bicarbonate) accumulation in microbial communities using laser ablation isotope ratio mass spectrometry

    SciTech Connect

    Moran, James J.; Doll, Charles G.; Bernstein, Hans C.; Renslow, Ryan S.; Cory, Alexandra B.; Hutchison, Janine R.; Lindemann, Stephen R.; Fredrickson, Jim K.

    2014-08-25

    This is a manuscript we would like to submit for publication in Environmental Microbiology Reports. This manuscript contains a description of a laser ablation isotope ratio mass spectrometry methodology developed at PNNL and applied to a microbial system at a PNNL project location – Hot Lake, Washington. I will submit a word document containing the entire manuscript with this Erica input request form.

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

    NASA Astrophysics Data System (ADS)

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

    1992-09-01

    The carbon isotopic composition of methane produced in anoxic marine sediment is controlled by four factors: (1) the pathway of methane formation, (2) the isotopic composition of the methanogenic precursors, (3) the isotope fractionation factors for methane production, and (4) the isotope fractionation associated with methane oxidation. The importance of each factor was evaluated by monitoring stable carbon isotope ratios in methane produced by a sediment microcosm. Methane did not accumulate during the initial 42-day period when sediment contained sulfate, indicating little methane production from "noncompetitive" substrates. Following sulfate depletion, methane accumulation proceeded in three distinct phases. First, CO2 reduction was the dominant methanogenic pathway and the isotopic composition of the methane produced ranged from -80 to -94‰. The acetate concentration increased during this phase, suggesting that acetoclastic methanogenic bacteria were unable to keep pace with acetate production. Second, acetate fermentation became the dominant methanogenic pathway as bacteria responded to elevated acetate concentrations. The methane produced during this phase was progressively enriched in 13C, reaching a maximum δ13C value of -42‰. Third, the acetate pool experienced a precipitous decline from >5 mM to <20 μM and methane production was again dominated by CO2 reduction. The δ13C of methane produced during this final phase ranged from -46 to -58‰. Methane oxidation concurrent with methane production was detected throughout the period of methane accumulation, at rates equivalent to 1 to 8% of the gross methane production rate. Thus methane oxidation was too slow to have significantly modified the isotopic signature of methane. A comparison of microcosm and field data suggests that similar microbial interactions may control seasonal variability in the isotopic composition of methane emitted from undisturbed Cape Lookout Bight sediment.

  3. Micronutrient Cadmium in the Oceans, Distribution and Stable Isotope Fractionation

    NASA Astrophysics Data System (ADS)

    Abouchami, W.; Galer, S. J.; Feldmann, H.; Andreae, M. O.; de Baar, H.; Middag, R.; Klunder, M.; Laan, P.

    2012-12-01

    Recent breakthroughs in ultra-clean seawater sampling, analytical instrumentation and chemical separation of trace metals have led to significant improvement in both sensitivity and accuracy of concentration measurements of some key bio-limiting metals such as Zn, Cd and Fe. Stable isotope fractionations of these transition metal elements have added a further new dimension to our understanding of the marine biogeochemical cycling of trace nutrients. Improving our understanding of the latter is essential for assessing the impact of climate changes on the global carbon cycle, given the control of oceanic nutrient inventories on the efficiency of the "biological pump" and hence, its strength in regulating the sequestration of atmospheric CO2. The first reliable vertical distribution profiles of trace metal element cadmium (Cd) in the oceans [1, 2] showed a correlation with the major nutrient phosphate. This apparent involvement of Cd in the ocean biological cycle was unexpected, as Cd was known to be toxic, notably at high Cd abundance where it interferes with the true biological function of zinc (Zn), due to their similar chemistry. The novel ability to measure accurately the stable isotope fractionation of Cd in seawater may now help unravel the apparent role of Cd in the ocean biological cycle, akin to the classical breakthroughs and numerous applications of the ratio 13C/12C for understanding the ocean carbon cycle. We have examined the distribution of Cd concentration and isotope ratios in depth profiles from the High Nutrients Low Chlorophyll (HNLC) Southern Ocean, collected within the framework of the international GEOTRACES program. The first surface water transect along the Greenwich Meridian in the Southern Ocean revealed a strong meridional isotope gradient and two major biogeochemical provinces with distinctive Cd isotope fractionation factors, apparently related to phytoplankton community compositions and cellular uptake mechanisms [3]. Here we focus on

  4. Stable isotope signatures for characterising the biological stability of landfilled municipal solid waste

    SciTech Connect

    Wimmer, Bernhard; Hrad, Marlies; Huber-Humer, Marion; Watzinger, Andrea; Wyhlidal, Stefan; Reichenauer, Thomas G.

    2013-10-15

    Highlights: ► The isotopic signature of δ{sup 13}C-DIC of leachates is linked to the reactivity of MSW. ► Isotopic signatures of leachates depend on aerobic/anaerobic conditions in landfills. ► In situ aeration of landfills can be monitored by isotope analysis in leachate. ► The isotopic analysis of leachates can be used for assessing the stability of MSW. ► δ{sup 13}C-DIC of leachates helps to define the duration of landfill aftercare. - Abstract: Stable isotopic signatures of landfill leachates are influenced by processes within municipal solid waste (MSW) landfills mainly depending on the aerobic/anaerobic phase of the landfill. We investigated the isotopic signatures of δ{sup 13}C, δ{sup 2}H and δ{sup 18}O of different leachates from lab-scale experiments, lysimeter experiments and a landfill under in situ aeration. In the laboratory, columns filled with MSW of different age and reactivity were percolated under aerobic and anaerobic conditions. In landfill simulation reactors, waste of a 25 year old landfill was kept under aerobic and anaerobic conditions. The lysimeter facility was filled with mechanically shredded fresh waste. After starting of the methane production the waste in the lysimeter containments was aerated in situ. Leachate and gas composition were monitored continuously. In addition the seepage water of an old landfill was collected and analysed periodically before and during an in situ aeration. We found significant differences in the δ{sup 13}C-value of the dissolved inorganic carbon (δ{sup 13}C-DIC) of the leachate between aerobic and anaerobic waste material. During aerobic degradation, the signature of δ{sup 13}C-DIC was mainly dependent on the isotopic composition of the organic matter in the waste, resulting in a δ{sup 13}C-DIC of −20‰ to −25‰. The production of methane under anaerobic conditions caused an increase in δ{sup 13}C-DIC up to values of +10‰ and higher depending on the actual reactivity of the MSW

  5. [Fractionation of hydrogen stable isotopes in the human body].

    PubMed

    Siniak, Iu E; Grigor'ev, A I; Skuratov, V M; Ivanova, S M; Pokrovskiĭ, B G

    2006-01-01

    Fractionation of hydrogen stable isotopes was studied in 9 human subjects in a chamber with normal air pressure imitating a space cabin. Mass-spectrometry of isotopes in blood, urine, saliva, and potable water evidenced increases in the contents of heavy H isotope (deuterium) in the body liquids as compared with water. These results support one of the theories according to which the human organism eliminates heavy stable isotopes of biogenous chemical elements.

  6. Trophic discrimination factors of stable carbon and nitrogen isotopes in hair of corn fed wild boar.

    PubMed

    Holá, Michaela; Ježek, Miloš; Kušta, Tomáš; Košatová, Michaela

    2015-01-01

    Stable isotope measurements are increasingly being used to gain insights into the nutritional ecology of many wildlife species and their role in ecosystem structure and function. Such studies require estimations of trophic discrimination factors (i.e. differences in the isotopic ratio between the consumer and its diet). Although trophic discrimination factors are tissue- and species-specific, researchers often rely on generalized, and fixed trophic discrimination factors that have not been experimentally derived. In this experimental study, captive wild boar (Sus scrofa) were fed a controlled diet of corn (Zea mays), a popular and increasingly dominant food source for wild boar in the Czech Republic and elsewhere in Europe, and trophic discrimination factors for stable carbon (Δ13C) and nitrogen (Δ15N) isotopes were determined from hair samples. The mean Δ13C and Δ15N in wild boar hair were -2.3‰ and +3.5‰, respectively. Also, in order to facilitate future derivations of isotopic measurements along wild boar hair, we calculated the average hair growth rate to be 1.1 mm d(-1). Our results serve as a baseline for interpreting isotopic patterns of free-ranging wild boar in current European agricultural landscapes. However, future research is needed in order to provide a broader understanding of the processes underlying the variation in trophic discrimination factors of carbon and nitrogen across of variety of diet types.

  7. Trophic Discrimination Factors of Stable Carbon and Nitrogen Isotopes in Hair of Corn Fed Wild Boar

    PubMed Central

    Holá, Michaela; Ježek, Miloš; Kušta, Tomáš; Košatová, Michaela

    2015-01-01

    Stable isotope measurements are increasingly being used to gain insights into the nutritional ecology of many wildlife species and their role in ecosystem structure and function. Such studies require estimations of trophic discrimination factors (i.e. differences in the isotopic ratio between the consumer and its diet). Although trophic discrimination factors are tissue- and species- specific, researchers often rely on generalized, and fixed trophic discrimination factors that have not been experimentally derived. In this experimental study, captive wild boar (Sus scrofa) were fed a controlled diet of corn (Zea mays), a popular and increasingly dominant food source for wild boar in the Czech Republic and elsewhere in Europe, and trophic discrimination factors for stable carbon (Δ13C) and nitrogen (Δ15N) isotopes were determined from hair samples. The mean Δ13C and Δ15N in wild boar hair were –2.3 ‰ and +3.5 ‰, respectively. Also, in order to facilitate future derivations of isotopic measurements along wild boar hair, we calculated the average hair growth rate to be 1.1 mm d-1. Our results serve as a baseline for interpreting isotopic patterns of free-ranging wild boar in current European agricultural landscapes. However, future research is needed in order to provide a broader understanding of the processes underlying the variation in trophic discrimination factors of carbon and nitrogen across of variety of diet types. PMID:25915400

  8. Strong anion exchange liquid chromatographic separation of protein amino acids for natural 13C-abundance determination by isotope ratio mass spectrometry.

    PubMed

    Abaye, Daniel A; Morrison, Douglas J; Preston, Tom

    2011-02-15

    Amino acids are the building blocks of proteins and the analysis of their (13)C abundances is greatly simplified by the use of liquid chromatography (LC) systems coupled with isotope ratio mass spectrometry (IRMS) compared with gas chromatography (GC)-based methods. To date, various cation exchange chromatography columns have been employed for amino acid separation. Here, we report strong anion exchange chromatography (SAX) coupled to IRMS with a Liquiface interface for amino acid δ(13)C determination. Mixtures of underivatised amino acids (0.1-0.5 mM) and hydrolysates of representative proteins (prawns and bovine serum albumin) were resolved by LC/IRMS using a SAX column and inorganic eluents. Background inorganic carbon content was minimised through careful preparation of alkaline reagents and use of a pre-injector on-line carbonate removal device. SAX chromatography completely resolved 11 of the 16 expected protein amino acids following acid hydrolysis in underivatised form. Basic and neutral amino acids were resolved with 35 mM NaOH in isocratic mode. Elution of the aromatic and acidic amino acids required a higher hydroxide concentration (180 mM) and a counterion (NO 3-, 5-25 mM). The total run time was 70 min. The average δ(13)C precision of baseline-resolved peaks was 0.75‰ (range 0.04 to 1.06‰). SAX is a viable alternative to cation chromatography, especially where analysis of basic amino acids is important. The technology shows promise for (13)C amino acid analysis in ecology, archaeology, forensic science, nutrition and protein metabolism.

  9. CH4 sources estimated from atmospheric observations of CH4 and its 13C/12C isotopic ratios: 1. Inverse modeling of source processes

    NASA Astrophysics Data System (ADS)

    Mikaloff Fletcher, Sara E.; Tans, Pieter P.; Bruhwiler, Lori M.; Miller, John B.; Heimann, Martin

    2004-12-01

    A time-dependent inverse modeling approach that estimates the global magnitude of atmospheric methane sources from the observed spatiotemporal distribution of atmospheric CH4, 13C/12C isotopic ratios, and a priori estimates of the source strengths is presented. Relative to the a priori source estimates, the inverse model calls for increased CH4 flux from sources with strong spatial footprints in the tropics and Southern Hemisphere and decreases in sources in the Northern Hemisphere. The CH4 and 13C/12C isotopic ratio observations suggest an unusually high CH4 flux from swamps (˜200 ± 44 Tg CH4/yr) and biomass burning (88 ± 18 Tg CH4/yr) with relatively low estimates of emissions from bogs (˜20 ± 14 Tg CH4/yr), and landfills (35 ± 14 Tg CH4/yr). The model results support the hypothesis that the 1998 CH4 growth rate anomaly was caused in part by a large increase in CH4 production from wetlands, and indicate that wetland sources were about 40 Tg CH4/yr higher in 1998 than 1999.

  10. Origins of etioporphyrins in sediments: Evidence from stable carbon isotopes

    SciTech Connect

    Boreham, C.J. ); Fookes, C.J.R. ); Popp, B.N.; Hayes, J.M. )

    1989-09-01

    In samples of the Julia Creek and Condor oil shales (Australia, Albian, and early Tertiary, respectively) etioporphyrin III is significantly depleted in {sup 13}C (4{per thousand}) relative to porphyrins derived from chlorophylls. This isotopic difference suggest a large contribution from some independent source. The haem group found in cytochromes derived from microbial sources is the most likely candidate.

  11. Origins of etioporphyrins in sediments: evidence from stable carbon isotopes.

    PubMed

    Boreham, C J; Fookes, C J; Popp, B N; Hayes, J M

    1989-01-01

    In samples of the Julia Creek and Condor oil shales (Australia, Albian, and early Tertiary, respectively) etioporphyrin III is significantly depleted in 13C (4%) relative to porphyrins derived from chlorophylls. This isotopic difference suggests a large contribution from some independent source. The haem group found in cytochromes derived from microbial sources is the most likely candidate.

  12. Influence of Reproduction on Stable-Isotope Ratios: Nitrogen and Carbon Isotope Discrimination between Mothers, Fetuses, and Milk in the Fin Whale, a Capital Breeder.

    PubMed

    Borrell, A; Gómez-Campos, E; Aguilar, A

    2016-01-01

    In mammals, the influence of gestation and lactation on the tissue stable-isotope ratios of females, fetuses, and milk remains poorly understood. Here we investigate the incidence of these events on δ(13)C and δ(15)N values in fin whales sampled off northwestern Spain between 1983 and 1985. The effect of gestation on tissue stable-isotope ratios was examined in the muscle of pregnant females (n = 13) and their fetuses (n = 10) and that of lactation in the muscle of nursing females (n = 21) and their milk (n = 25). Results suggest that fetuses are enriched compared to their mothers in both (15)N (Δ(15)N = 1.5‰) and (13)C (Δ(13)C =1.1‰), while, compared to muscle, milk is enriched in (15)N (Δ(15)N = 0.3‰) but depleted in (13)C (Δ(13)C = -0.62‰). This pattern is consistent with that previously observed for other species that, like the fin whale, rely on endogenous energy during reproduction, and it substantiates a general difference in the physiological processing of nitrogen and carbon balances between income and capital breeders. These findings are relevant to the understanding of the energetic balance of mammals during gestation and lactation and are central when inferences on trophic ecology are drawn from isotopic values of reproductive females.

  13. Stable isotope ratios of atmospheric CO_{2} and CH_{4} over Siberia measured at ZOTTO

    NASA Astrophysics Data System (ADS)

    Timokhina, Anastasiya; Prokushkin, Anatily; Lavric, Jost; Heimann, Martin

    2016-04-01

    The boreal and arctic zones of Siberia housing the large amounts of carbon stored in the living biomass of forests and wetlands, as well as in soils and specifically permafrost, play a crucial role in earth's global carbon cycle. The long-term studies of greenhouse gases (GHG) concentrations are important instruments to analyze the response of these systems to climate warming. In parallel to GHG observations, the measurements of their stable isotopic composition can provide useful information for distinguishing contribution of individual GHG source to their atmospheric variations, since each source has its own isotopic signature. In this study we report first results of laboratory analyses of the CO2 and CH4 concentrations, the stable isotope ratio of δ13C-CO2, δ18O-CO2, δ13C-CH4, δD-CH4 measured in one-liter glass flasks which were obtained from 301 height of ZOTTO (Zotino Tall Tower Observatory, near 60° N, 90° E, about 20 km west of the Yenisei River) during 2008 - 2013 and 2010 - 2013 for stable isotope composition of CO2 and CH4. The magnitudes of δ13C-CO2 and δ18O-CO2 in a seasonal cycle are -1.4±0.1‰ (-7.6 - -9.0‰) and -2.2±0.2‰ (-0.1 - -2.3‰), respectively. The δ13C-CO2 seasonal pattern opposes the CO2 concentrations, with a gradual enrichment in heavy isotope occurring during May - July, reflecting its discrimination in photosynthesis, and further depletion in August - September as photosynthetic activity decreases comparatively to ecosystem respiration. Relationship between the CO2 concentrations and respective δ13C-CO2 (Keeling plot) reveals isotopic source signature for growing season (May - September) -27.3±1.4‰ and -30.4±2.5‰ for winter (January - March). The behavior of δ18O-CO2 associated with both high photosynthetic rate in the June (enrichment of atmospheric CO2 by 18O as consequence of CO2 equilibrium with "heavy" leaf water) and respiratory activity of forest floor in June - October (depletion of respired CO2 by 18O

  14. Stable Isotope Models Predict Foraging Habitat of Northern Fur Seals (Callorhinus ursinus) in Alaska.

    PubMed

    Zeppelin, T K; Johnson, D S; Kuhn, C E; Iverson, S J; Ream, R R

    2015-01-01

    We developed models to predict foraging habitat of adult female northern fur seals (Callorhinus ursinus) using stable carbon (δ13C) and nitrogen (δ15N) isotope values from plasma and red blood cells. Binomial generalized linear mixed models were developed using blood isotope samples collected from 35 adult female fur seals on three breeding colonies in Alaska during July-October 2006. Satellite location and dive data were used to define habitat use in terms of the proportion of time spent or dives made in different oceanographic/bathymetric domains. For both plasma and red blood cells, the models accurately predicted habitat use for animals that foraged exclusively off or on the continental shelf. The models did not perform as well in predicting habitat use for animals that foraged in both on- and off-shelf habitat; however, sample sizes for these animals were small. Concurrently collected scat, fatty acid, and dive data confirmed that the foraging differences predicted by isotopes were associated with diet differences. Stable isotope samples, dive data, and GPS location data collected from an additional 15 females during August-October 2008 validated the effective use of the models across years. Little within year variation in habitat use was indicated from the comparison between stable isotope values from plasma (representing 1-2 weeks) and red blood cells (representing the prior few months). Constructing predictive models using stable isotopes provides an effective means to assess habitat use at the population level, is inexpensive, and can be applied to other marine predators.

  15. Applications of stable isotope analysis in mammalian ecology.

    PubMed

    Walter, W David; Kurle, Carolyn M; Hopkins, John B

    2014-01-01

    In this editorial, we provide a brief introduction and summarize the 10 research articles included in this Special Issue on Applications of stable isotope analysis in mammalian ecology. The first three articles report correction and discrimination factors that can be used to more accurately estimate the diets of extinct and extant mammals using stable isotope analysis. The remaining seven applied research articles use stable isotope analysis to address a variety of wildlife conservation and management questions from the oceans to the mountains.

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

    PubMed Central

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

    2012-01-01

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

  17. Multivariate Stable Isotope Analysis to Determine Linkages between Benzocaine Seizures

    NASA Astrophysics Data System (ADS)

    Kemp, H. F.; Meier-Augenstein, W.; Collins, M.; Salouros, H.; Cunningham, A.; Harrison, M.

    2012-04-01

    In July 2010, a woman was jailed for nine years in the UK after the prosecution successfully argued that attempting to import a cutting agent was proof of involvement in a conspiracy to supply Cocaine. That landmark ruling provided law enforcement agencies with much greater scope to tackle those involved in this aspect of the drug trade, specifically targeting those importing the likes of benzocaine or lidocaine. Huge quantities of these compounds are imported into the UK and between May and August 2010, four shipments of Benzocaine amounting to more then 4 tons had been seized as part of Operation Kitley, a joint initiative between the UK Border Agency and the Serious Organised Crime Agency (SOCA). By diluting cocaine, traffickers can make it go a lot further for very little cost, leading to huge profits. In recent years, dealers have moved away from inert substances, like sugar and baby milk powder, in favour of active pharmaceutical ingredients (APIs), including anaesthetics like Benzocaine and Lidocaine. Both these mimic the numbing effect of cocaine, and resemble it closely in colour, texture and some chemical behaviours, making it easier to conceal the fact that the drug has been diluted. API cutting agents have helped traffickers to maintain steady supplies in the face of successful interdiction and even expand the market in the UK, particularly to young people aged from their mid teens to early twenties. From importation to street-level, the purity of the drug can be reduced up to a factor of 80 and street level cocaine can have a cocaine content as low as 1%. In view of the increasing use of Benzocaine as cutting agent for Cocaine, a study was carried out to investigate if 2H, 13C, 15N and 18O stable isotope signatures could be used in conjunction with multivariate chemometric data analysis to determine potential linkage between benzocaine exhibits seized from different locations or individuals to assist with investigation and prosecution of drug

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

    NASA Astrophysics Data System (ADS)

    Li, Cai; Ji, Hongbing

    2016-05-01

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

  19. The fractionation factors of stable carbon and hydrogen isotope ratios for VOCs

    NASA Astrophysics Data System (ADS)

    Kawashima, H.

    2014-12-01

    Volatile organic compounds (VOCs) are important precursors of ozone and secondary organic aerosols in the atmosphere, some of which are carcinogenic, teratogenic, or mutagenic. VOCs in ambient air originate from many sources, including vehicle exhausts, gasoline evaporation, solvent use, natural gas emissions, and industrial processes, and undergo intricate chemical reactions in the atmosphere. To develop efficient air pollution remediation strategies, it is important to clearly identify the emission sources and elucidate the reaction mechanisms in the atmosphere. Recently, stable carbon isotope ratios (δ13C) of VOCs in some sources and ambient air have been measured by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). In this study, we measured δ13C and stable hydrogen isotope ratios (δD) of atmospheric VOCs by using the gas chromatography/thermal conversion/isotope ratio mass spectrometry coupled with a thermal desorption instrument (TD-GC/TC/IRMS). The wider δD differences between sources were found in comparison with the δ13C studies. Therefore, determining δD values of VOCs in ambient air is potentially useful in identifying VOC sources and their reactive behavior in the atmosphere. However, to elucidate the sources and behavior of atmospheric VOCs more accurately, isotopic fractionation during atmospheric reaction must be considered. In this study, we determined isotopic fractionation of the δ13C and δD values for the atmospheric some VOCs under irradiation conditions. As the results, δ13C for target all VOCs and δD for most VOCs were increasing after irradiation. But, the δD values for both benzene and toluene tended to decrease as irradiation time increased. We also estimated the fractionation factors for benzene and toluene, 1.27 and 1.05, respectively, which differed from values determined in previous studies. In summary, we were able to identify an inverse isotope effect for the δD values of benzene and toluene

  20. Simulating stable carbon and chlorine isotope ratios in dissolved chlorinated groundwater pollutants with BIOCHLOR-ISO.

    PubMed

    Höhener, Patrick

    2016-12-01

    BIOCHLOR is a well-known simple tool for evaluating the transport of dissolved chlorinated solvents in groundwater, ideal for rapid screening and teaching. This work extends the BIOCHLOR model for the calculation of stable isotope ratios of carbon and chlorine isotopes in chloroethenes. An exact solution for the three-dimensional reactive transport of a chain of degrading compounds including sorption is provided in a spreadsheet and applied for modeling the transport of individual isotopes (12)C, (13)C, (35)Cl, (37)Cl from a constant source. The model can consider secondary isotope effects that can occur in the breaking of CCl bonds. The model is correctly reproducing results for δ(13)C and δ(37)Cl modeled by a previously published 1-D numerical model without secondary isotope effects, and is also reproducing results from a microcosm experiment with secondary chlorine isotope effects. Two applications of the model using field data from literature are further given and discussed. The new BIOCHLOR-ISO model is distributed as a spreadsheet (MS EXCEL) along with this publication.

  1. Simulating stable carbon and chlorine isotope ratios in dissolved chlorinated groundwater pollutants with BIOCHLOR-ISO

    NASA Astrophysics Data System (ADS)

    Höhener, Patrick

    2016-12-01

    BIOCHLOR is a well-known simple tool for evaluating the transport of dissolved chlorinated solvents in groundwater, ideal for rapid screening and teaching. This work extends the BIOCHLOR model for the calculation of stable isotope ratios of carbon and chlorine isotopes in chloroethenes. An exact solution for the three-dimensional reactive transport of a chain of degrading compounds including sorption is provided in a spreadsheet and applied for modeling the transport of individual isotopes 12C, 13C, 35Cl, 37Cl from a constant source. The model can consider secondary isotope effects that can occur in the breaking of Csbnd Cl bonds. The model is correctly reproducing results for δ13C and δ37Cl modeled by a previously published 1-D numerical model without secondary isotope effects, and is also reproducing results from a microcosm experiment with secondary chlorine isotope effects. Two applications of the model using field data from literature are further given and discussed. The new BIOCHLOR-ISO model is distributed as a spreadsheet (MS EXCEL) along with this publication.

  2. Mathematical modeling of stable carbon isotope ratios in natural gases^@?

    NASA Astrophysics Data System (ADS)

    Tang, Y.; Perry, J. K.; Jenden, P. D.; Schoell, M.

    2000-08-01

    A new approach is presented for mathematical modeling of stable carbon isotope ratios in hydrocarbon gases based on both theoretical and experimental data. The kinetic model uses a set of parallel first-order gas generation reactions in which the relative cracking rates of isotopically substituted (k∗) and unsubstituted (k) bonds are represented by the equation k∗/k=(Af∗/Af) exp(-ΔEa/RT), where R is the gas constant and T is temperature. Quantum chemistry calculations have been used to estimate the entropic (A f∗/A f) and enthalpic (ΔEa) terms for homolytic bond cleavage in a variety of simple molecules. For loss of a methyl group from a short-chain n-alkane (≤ C 6), for example, we obtain an average ΔEa of 42.0 cal/mol and an average A f∗/A f of 1.021. Expressed differently, 13C-methane generation is predicted to be 2.4% (24‰) slower than 12C-methane generation (from a short-chain n-alkane) in a sedimentary basin at 200°C but only 0.7% (7‰) slower in a laboratory heating experiment at 500°C. Similar calculations carried out for homolytic bond cleavage in other molecules show that with few exceptions, ΔEa varies between 0 and 60 cal/mol and A f∗/A f between 1.00 and 1.04. Examination of this larger data set reveals: (1) a weak sigmoid relationship between ΔEa and bond dissociation energy; and (2) a strong positive correlation between ΔEa and A f∗/A f. The significance of these findings is illustrated by fitting a kinetic model to chemical and isotopic data for the generation of methane from n-octadecane under isothermal closed-system conditions. For a specific temperature history, the fitted model provides quantitative relationships among methane carbon isotope composition, total methane yield and methane generation rate which may have relevance to the cracking of oil-prone kerogens and crude oil. The observed variability of the kinetic reactivity of various methane source rocks highlights the need to apply and adequately calibrate such

  3. Stable Chlorine Isotopes in Ocean Crust Processes

    NASA Astrophysics Data System (ADS)

    Bach, W.; Layne, G.; Kent, A.

    2003-12-01

    shallow subduction zone. The depleted MORB mantle is believed to have a δ 37Cl between 4 and 7 ‰ , similar to C1-chondrite (Magenheim et al., 1995, EPSL, 131, 427). MORB with high Cl and Cl/K tend to have δ 37Cl close to 0 ‰ , which has been explained by contamination of basaltic magmas with seawater-derived Cl. However, the most evolved ferrobasalts and andesites from oceanic spreading ridges have negative δ 37Cl values, down to -1.7 ‰ (Magenheim, unpublished data). Together with data for oceanic gabbros, the δ 37Cl-[Cl] data for these highly evolved rocks form a trend that could be explained by an AFC-like process, although the fact that the trend extends to negative δ 37Cl values cannot be reconciled with batch mixing of magma and salt or brine. Rather, it indicates that 35Cl is preferentially incorporated into the magma and may be related to diffusive exchange between Cl in brine pools above the melt lens of an axial magma system. A more comprehensive global dataset as well as spot analyses of Cl isotope ratios by IMP-SIMS (e.g., of melt inclusions) and the combination of δ 37Cl with other stable isotope systems (B, Li, O, H) are required before these tentative models for global chlorine cycling and crustal assimilation at spreading ridges can be rigorously evaluated.

  4. Seasonal variations in the stable carbon isotopic signature of biogenic methane in a coastal sediment

    SciTech Connect

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

    1986-09-19

    Systematic seasonal variations in the stable carbon isotopic signature of methane gas occur in the anoxic sediments of Cape Lookout Bight, a lagoonal basin on North Carolina's Outer Banks. Values for the carbon isotope ratio (delta /sup 13/C) of methane range from -57.3 per mil during summer to -68.5 per mil during winter in gas bubbles with an average methane content of 95%. The variations are hypothesized to result from changes in the pathways of microbial methane production and cycling of key substrates including acetate and hydrogen. The use of stable isotopic signatures to investigate the global methane cycle through mass balance calculations, involving various sediment and soil biogenic sources, appears to require seasonally averaged data from individual sites. 17 references, 2 figures, 2 tables.

  5. Stables isotopes in submarine explosive volcanism

    NASA Astrophysics Data System (ADS)

    Pineau, F.; Shilobreeva, S.; Hekinian, R.; Bideau, D.; Javoy, M.

    2003-04-01

    The carbon and water contents and the corresponding isotopic compositions have been measured on a set of glassy samples collected by dives on the Mid-Atlantic Ridge (MAR) near 34^o50'N where volcanoclastic deposits are present. The volatile phases have been extracted by crushing under vacuum and step heating up to fusion. The δ18O of the glasses have been measured and it is shown that N-MORB are depleted in 18O (down to 5.2 ppm) whereas all the other lavas fall in the mantle range, 5.4 to 5.8 ppm. These data preclude strong interaction between seawater and magmas before eruption. The post-eruptive contents of dissolved water and carbon measured on N, T, E MORB and alkalic rocks range from 1125 up to 5253 ppm and from 20 up to 119 ppm respectively. The vesicle gas is dominated by CO_2 in N- and T-MORB. Water is very scarce in E-MORB vesicles but represents up to 17 vol% of the total gas in alkali-basalt vesicles. The pre-eruptive water and carbon concentrations of these magmas have been.They range from 1130 up to 8497 for water and from 343 up to 15677 ppm for carbon. The isotopic data demonstrate that seawater contamination is significant only in samples where most vesicles have been disrupted during eruption and quenching. Otherwise, all the δ13C and δD values of the volatiles phases expressed in vesicles or dissolved in glasses, fall in a typical mantle range, -4 to -7 ppm and -60 to -88 ppm, respectively. Degassing conditions were close to chemical equilibrium in the vesicle-rich samples (E- MORB and alkali-basalt) but kinetic fractionation occured during the last eruptive event, indicating that the enriched magmas travelled very fast impeding the attainment of isotopic equilibrium. Taking into account the crystal fractionation of the magmas, the primitive magmas had initial concentrations of water ranging from 1100 to 8000 ppm. The water-enriched magmas reached water saturation at about 1.5 km below the seafloor. Because of the important CO_2 degassing (80

  6. New Organic Stable Isotope Reference Materials for Distribution through the USGS and the IAEA

    NASA Astrophysics Data System (ADS)

    Schimmelmann, Arndt; Qi, Haiping

    2014-05-01

    the 10 laboratories. Successfully calibrated organic RMs could become available as early as 2015. - n-Hexadecane (C16 n-alkane), three H, C-isotopic varieties; - Glycine (amino acid), three H, C, N-isotopic varieties; - L-valine (amino acid), three H, C, N-isotopic varieties; - Methyl n-heptadecanoate (methyl ester of C17 n-alkanoic fatty acid); - Methyl icosanoate (methyl ester of C20 n-alkanoic fatty acid), three H, C-isotopic varieties; - Caffeine, three H, C, N-isotopic varieties; - Hydrocarbon vacuum pump oils, two H-isotopic varieties; - Polyethylene powder, and possibly a 2H and 13C-enriched polyethylene string. [1] Qi H., Coplen T.B., Geilmann H., Brand W.A., Böhlke J.K. (2003) Two new organic reference materials for δ13C and δ15N measurements and a new value for the δ13C of NBS 22 oil. Rapid Communications in Mass Spectrometry 17, 2483-2487. [2] Coplen T.B. (1996) New guidelines for reporting stable hydrogen, carbon, and oxygen isotope-ratio data. Geochimica et Cosmochimica Acta 60, 3359-3360. [3] Coplen T.B., Brand W.A., Gehre M., Gröning M., Meijer H.A.J., Toman B., Verkouteren R.M. (2006) New guidelines for δ13C measurements. Analytical Chemistry 78 (7), 2439-2441. [4] Werner R.A., Brand W.A. (2001) Referencing strategies and techniques in stable isotope ratio analysis. Rapid Communications in Mass Spectrometry 15, 501-519.

  7. Using C stable isotopes to infer shifting metabolism in response to variable environmental conditions

    NASA Astrophysics Data System (ADS)

    Ballantyne, Ford; Billings, Sharon; Lehmeier, Christoph; Min, Kyungjin

    2014-05-01

    for such isotopic effects is critical for a better interpretation of δ13C of soil respiration. Finally, we emphasize that performing controlled experiments, such as in chemostats, is critical for identifying and interrogating mechanisms responsible for the genesis of patterns in stable isotopes.

  8. Effects of acid washing on stable isotope ratios of C and N in penaeid shrimp and seagrass: Implications for food-web studies using multiple stable isotopes

    SciTech Connect

    Bunn, S.E.; Kempster, M.A.; Loneragan, N.R.

    1995-05-01

    We investigated the effects of acid washing on the carbon and nitrogen composition and stable isotope ratios of C and N in shrimp (Metapenaeus spp.) and seagrass (Enhalus acoroides). Acid washing did not affect the mean {delta}{sup 13}C ratios for juvenile Metapenaeus moyebi and resulted in only an ecologically insignificant change (0.3%) in mean {delta}{sup 13}C ratios for larger metapenaeus bennettae. In contrast, acid washing increased the mean {delta}{sup 15}N signatures of shrimp tissue ({approximately}3%) and decreased that of seagrass ({approximately}1.8%) to a degree that may confound the interpretation of food webs. The increase in %C and %N in both shrimp and seagrass after acid washing suggests that the changes in isotope ratios are due to loss of molecules comparatively low in C and N. Treating samples by acid washing also resulted in an increase in the variation among individuals for both {delta}{sup 15}N and {delta}{sup 13}C, which would lead to a loss of statistical power for testing differences between species, sites, or seasons. 13 refs., 2 figs., 1 tab.

  9. Calcium isotope constraints on the marine carbon cycle and CaCO3 deposition during the late Silurian (Ludfordian) positive δ13C excursion

    NASA Astrophysics Data System (ADS)

    Farkaš, Juraj; Frýda, Jiří; Holmden, Chris

    2016-10-01

    This study investigates calcium isotope variations (δ 44 / 40 Ca) in late Silurian marine carbonates deposited in the Prague Basin (Czech Republic), which records one of the largest positive carbon isotope excursion (CIE) of the entire Phanerozoic, the mid-Ludfordian CIE, which is associated with major climatic changes (abrupt cooling) and global sea-level fluctuations. Our results show that during the onset of the CIE, when δ13 C increases rapidly from ∼0‰ to ∼8.5‰, δ 44 / 40Ca remains constant at about 0.3 ± 0.1 ‰ (relative to NIST 915a), while 87Sr/86Sr in well-preserved carbonates are consistent with a typical Ludfordian seawater composition (ranging from ∼0.70865 to ∼0.70875). Such decoupling between δ13 C and δ 44 / 40Ca trends during the onset of the CIE is consistent with the expected order-of-magnitude difference in the residence times of Ca (∼106yr) and C (∼105yr) in the open ocean, suggesting that the mid-Ludfordian CIE was caused by processes where the biogeochemical pathways of C and Ca in seawater were mechanistically decoupled. These processes may include: (i) near shore methanogenesis and photosynthesis, (ii) changes in oceanic circulation and stratification, and/or (iii) increased production and burial of organic C in the global ocean. The latter, however, is unlikely due to the lack of geological evidence for enhanced organic C burial, and also because of unrealistic parameterization of the ocean C cycle needed to generate the observed CIE over the relatively short time interval. In contrast, higher up in the section where δ13 C shifts back to pre-excursion baseline values, there is a correlated shift to higher δ 44 / 40Ca values. Such coupling of the records of Ca and C isotope changes in this part of the study section is inconsistent with the abovementioned differences in oceanic Ca and C residence times, indicating that the record of δ 44 / 40Ca changes does not faithfully reflect the evolution of the oceanic Ca

  10. A method for carbon stable isotope analysis of methyl halides and chlorofluorocarbons at pptv concentrations.

    PubMed

    Archbold, Marie E; Redeker, Kelly R; Davis, Simon; Elliot, Trevor; Kalin, Robert M

    2005-01-01

    A pre-concentration system has been validated for use with a gas chromatography/mass spectrometry/isotope ratio mass spectrometer (GC/MS/IRMS) to determine ambient air (13)C/(12)C ratios for methyl halides (MeCl and MeBr) and chlorofluorocarbons (CFCs). The isotopic composition of specific compounds can provide useful information on their atmospheric budgets and biogeochemistry that cannot be ascertained from abundance measurements alone. Although pre-concentration systems have been previously used with a GC/MS/IRMS for atmospheric trace gas analysis, this is the first study also to report system validation tests. Validation results indicate that the pre-concentration system and subsequent separation technologies do not significantly alter the stable isotopic ratios of the target methyl halides, CFC-12 (CCl(2)F(2)) and CFC-113 (C(2)Cl(3)F(3)). Significant, but consistent, isotopic shifts of -27.5 per thousand to -25.6 per thousand do occur within the system for CFC-11 (CCl(3)F), although the shift is correctible. The method presented has the capacity to separate these target halocarbons from more than 50 other compounds in ambient air samples. Separation allows for the determination of stable carbon isotope ratios of five of these six target trace atmospheric constituents within ambient air for large volume samples (isotope results similar to published values for (13)C/(12)C analysis of MeCl (-39.1 per thousand) and CFC-113 (-28.1 per thousand). However, this is the first paper reporting stable carbon isotope signatures for CFC-11 (-29.4 per thousand) and CFC-12 (-37.0 per thousand).

  11. Inferring Foraging Areas of Nesting Loggerhead Turtles Using Satellite Telemetry and Stable Isotopes

    PubMed Central

    Ceriani, Simona A.; Roth, James D.; Evans, Daniel R.; Weishampel, John F.; Ehrhart, Llewellyn M.

    2012-01-01

    In recent years, the use of intrinsic markers such as stable isotopes to link breeding and foraging grounds of migratory species has increased. Nevertheless, several assumptions still must be tested to interpret isotopic patterns found in the marine realm. We used a combination of satellite telemetry and stable isotope analysis to (i) identify key foraging grounds used by female loggerheads nesting in Florida and (ii) examine the relationship between stable isotope ratios and post-nesting migration destinations. We collected tissue samples for stable isotope analysis from 14 females equipped with satellite tags and an additional 57 untracked nesting females. Telemetry identified three post-nesting migratory pathways and associated non-breeding foraging grounds: (1) a seasonal continental shelf–constrained migratory pattern along the northeast U.S. coastline, (2) a non-breeding residency in southern foraging areas and (3) a residency in the waters adjacent to the breeding area. Isotopic variability in both δ13C and δ15N among individuals allowed identification of three distinct foraging aggregations. We used discriminant function analysis to examine how well δ13C and δ15N predict female post-nesting migration destination. The discriminant analysis classified correctly the foraging ground used for all but one individual and was used to predict putative feeding areas of untracked turtles. We provide the first documentation that the continental shelf of the Mid- and South Atlantic Bights are prime foraging areas for a large number (61%) of adult female loggerheads from the largest loggerhead nesting population in the western hemisphere and the second largest in the world. Our findings offer insights for future management efforts and suggest that this technique can be used to infer foraging strategies and residence areas in lieu of more expensive satellite telemetry, enabling sample sizes that are more representative at the population level. PMID:23028943

  12. Nekton migration and feeding location in a coastal area - A stable isotope approach

    NASA Astrophysics Data System (ADS)

    Vinagre, C.; Máguas, C.; Cabral, H. N.; Costa, M. J.

    2011-03-01

    Stable isotope analysis was used to investigate nekton movements and feeding location in a coastal area adjacent to a major European river, the Tagus, Portugal. Particulate organic matter isotopic signatures presented a gradient from the river towards the sea. Phytoplankton, zooplankton, polychaetes and the crab, Polybius henslowii, provided evidence of the incorporation of terrestrial organic matter into the lower levels of the food web, reflecting local isotopic signatures. Two fish species reflected the coastal isotopic gradient in δ13C, Diplodus vulgaris and Arnoglossus imperialis and the latter also presented isotopic differerences among the sites for δ15N. Alloteuthis subulata, Trisopterus luscus and Callionymus lyra were isotopicaly distinct among sites for δ15N. An increase of δ15N with length was detected for T. luscus and C. lyra, possibly showing ontogenic trophic level changes. Since A. subulata did not present differences in length and still showed isotopic distinction for δ15N, among areas, it was concluded that local biogeochemical factors may also have an influence. Diplodus bellottii and Dicologlossa cuneata did not reflect any isotopic signature reflecting their wide migration and feeding across the coastal area. Central isotopic ranges, defined as the site mean values for δ13C and δ15N ± 1‰ were determined for each species and site and those deviating from these were considered transient individuals. Central isotopic ranges accounted for 87% of A. imperialis, 80% of A. subulata, 77% of T. luscus, 67% of C. lyra and 50% of D. vulgaris. The number of individuals within each central isotopic range was surprisingly high for an open coastal area and comparable to those of more structured environments.

  13. Heterogeneity in stable isotope profiles predicts coexistence of populations of barn swallows Hirundo rustica differing in morphology and reproductive performance.

    PubMed Central

    Møller, Anders Pape; Hobson, Keith A.

    2004-01-01

    Population studies assume that individuals belonging to a study population are homogeneous for natal and breeding origin, although this assumption is rarely tested. We tested for heterogeneity in stable-isotope profiles (delta15N, delta13C, deltaD) of feathers grown in the African winter quarters from a Danish breeding population of adult barn swallows, Hirundo rustica. Deuterium isotope values did not provide useful information on population segregation of wintering swallows in Africa. However, both delta15N and delta13C values showed a clearly bimodal distribution with 6% belonging to one category and the remaining birds belonging to another category, resulting in this population comprising three categories of birds. Adults belonging to the two categories of delta13C isotope profiles differed weakly in morphology for several different characters. The frequency and the size of second broods differed between categories of delta13C isotope profiles. Phenotypes of nestlings from the first brood in terms of tarsus length, body mass and T-cell response differed significantly between the two delta15N isotope categories, suggesting that conditions during winter carried over to the breeding season at least as late as the first brood. Polymorphism can be maintained only if fitness is similar for birds from categories of isotope profiles. We suggest that fluctuating selection or migration-selection balance may maintain the observed polymorphism. PMID:15306333

  14. Geographical origin of cereal grains based on element analyser-stable isotope ratio mass spectrometry (EA-SIRMS).

    PubMed

    Wu, Yuluan; Luo, Donghui; Dong, Hao; Wan, Juan; Luo, Haiying; Xian, Yanping; Guo, Xindong; Qin, Fangfang; Han, Wanqing; Wang, Li; Wang, Bin

    2015-05-01

    The stable carbon and nitrogen isotopic compositions (δ(13)C and δ(13)N) of different cereal grains from different regions were determined, using element analyser-stable isotope ratio mass spectrometry (EA-SIRMS) as the key method. Systematically, δ(13)C and δ(13)N of 5 kinds of cereal grains of different origins, 30 wheat samples from different cultivation areas and 160 rice samples of different cultivars from Guangdong province of China were examined. The results indicated that the δ(13)C values of rice, soybean, millet, wheat and corn were significantly (P < 0.05) different within different origins (Heilongjiang, Shandong and Jiangsu province of China), respectively, while δ(13)N values were not. Interestingly, there exists discrimination between these 5 kinds of cereals grains, no matter C-3 or C-4 plants. Further study showed that the δ(13)C values of wheat from Australia, the USA, Canada, and Jiangsu and Shandong province of China were also significantly (P < 0.01) different. Furthermore, the P-value test for 160 rice samples of 5 cultivars was not significant (P > 0.05), which indicated that the cultivar of cereal grains was not significant based on δ(13)C value. Thus, the comparison of δ(13)C would be potentially useful for rapid and routine discrimination of geographical origin of cereal grains.

  15. Stable Isotope Probing of Peat and Forest Floor Amendments

    NASA Astrophysics Data System (ADS)

    Quideau, Sylvie; Béasse, Mark

    2013-04-01

    In Alberta, Canada, land reclamation efforts utilize peat as an organic amendment to help reclaim decommissioned oil sands mine sites to upland boreal forests. This study investigates the rhizosphere microbial communities of two pioneer species, aspen (Populus tremuloides Michx.), a species not known for strong associations with the soil microbial community, and alder (Alnus crispa Ait.), a species well known for mutualism with actinomycetes. Specifically, the objective was to determine how different organic amendments (peat versus forest floor) influenced the rhizosphere microbial communities and how this could be linked to plant growth. Seedlings were grown for 20 weeks in forest floor material, peat, and a combination of both. They were pulse labelled with 13CO2 (g) and subsequently harvested for plant growth measurements. While analysis of plant growth attributes did not indicate any effect of the organic amendment on aspen growth, alder reported significantly less growth in peat treatments. The rhizosphere soils were extracted for compound-specific analysis of δ13C in microbial phospholipid fatty acids. Stable isotope probing showed greater carbon flow between trees and their rhizosphere communities when seedlings were grown in forest floor material.

  16. Biomagnification profiles of polycyclic aromatic hydrocarbons, alkylphenols and polychlorinated biphenyls in Tokyo Bay elucidated by delta13C and delta15N isotope ratios as guides to trophic web structure.

    PubMed

    Takeuchi, Ichiro; Miyoshi, Noriko; Mizukawa, Kaoruko; Takada, Hideshige; Ikemoto, Tokutaka; Omori, Koji; Tsuchiya, Kotaro

    2009-05-01

    Biomagnification profiles of polycyclic aromatic hydrocarbons (PAHs), alkylphenols, and polychlorinated biphenyls (PCBs) from the innermost part of Tokyo Bay, Japan were analyzed using stable carbon (delta(13)C) and nitrogen (delta(15)N) isotope ratios as guides to trophic web structure. delta(15)N analysis indicated that all species of mollusks tested were primary consumers, while decapods and fish were secondary consumers. Higher concentrations of PCBs occurred in decapods and fish than in mollusks. In contrast, concentrations of PAHs and alkylphenols were lower in decapods and fish than in mollusks. Unlike PCBs, whose concentrations largely increased with increasing delta(15)N (i.e. increasing trophic level), all PAHs and alkylphenols analyzed followed a reverse trend. Molecular weights of PAHs are lower than those of PCBs, therefore low membrane permeability caused by large molecular size is an unlikely factor in the "biodilution" of PAHs. Organisms at higher trophic levels may rapidly metabolize PAHs or they may assimilate less of them.

  17. Plant Water Use and Environmental Stress on Two Opposite Slopes: from Water and Carbon Stable Isotopic Perspective

    NASA Astrophysics Data System (ADS)

    Guan, H.; Xu, X.; Skrzypek, G.; Simmons, C. T.

    2014-12-01

    Climate-soil-vegetation dynamics are among key research focuses in the emerging ecohydrology discipline. Topographic relieves on landscapes provide various hydroclimatic conditions to examine vegetation functions and its responses to climate variation and changes in a short distance. In this study, we investigate ecohydrologic processes on two slopes of contrasting orientation and soil conditions in a native vegetation catchment with mean annual precipitation of 716 mm in South Australia, using water and carbon stable isotopes. Throughfall, soil water, twig water, and groundwater stable isotopes were measured and integrated into an isotope incorporated soil-plant-atmosphere model to examine different plant water use patterns on two slopes with different environmental conditions. The focuses are on how ecosystems on the two slopes receive, store, and use soil moisture in different manners. On these two slopes, trees are under different water stresses. Both leaf and soil 13C/12C ratio were measured for the two slopes to examine if δ13C can be used as an water stress indicator in this small catchment, and if the potential difference in δ13C can be observed in the soil organic matter. We monitored one-year leaf δ13C of two tree species, Eucalyptus leucoxylon and Acacia pycnantha. Our results indicate that leaf δ13C reflects different water stress conditions between slopes, seasons, and different locations on the slopes.

  18. Stable carbon isotope as a signal index for monitoring grassland degradation

    PubMed Central

    Yao, Hongyun; Wilkes, Andreas; Zhu, Guodong; Zhang, Hongdan; Liu, Xiaojuan; Dan Ding; Zhai, Xiajie; Tang, Shiming; Chen, Qing; Zhang, Yujuan; Huang, Ding; Wang, Chengjie

    2016-01-01

    Grassland degradation due to overgrazing is common in many areas of the world. This study analyzed the potential of the stable carbon isotope13C) value as a structural microcosmic index to monitor processes of grassland degradation. The δ13C values of plant leaves, roots and soils in non-grazed (NG) and over-grazed (OG) grassland were measured from samples collected from the seven types of grassland in China. We found that the leaf δ13C values of palatable species (δ13Cleaf) and root δ13C values (δ13Croot) in OG grasslands were reduced compared with those from NG grasslands. Furthermore, the δ13Cleaf and δ13Csoil were positive correlation with elevation and latitude, δ13Croot was negative correlation with them at high altitude (3000~5000m), and δ13Croot and δ13Csoil were negative correlation with them at low altitude (0~2000m), respectively. Consequently, tracing of the δ13C variations in grassland ecosystem can provide a powerful tool to evaluate the degree of grassland degradation. PMID:27527910

  19. Probing the metabolic phenotype of breast cancer cells by multiple tracer stable isotope resolved metabolomics.

    PubMed

    Lane, Andrew N; Tan, Julie; Wang, Yali; Yan, Jun; Higashi, Richard M; Fan, Teresa W-M

    2017-02-02

    Breast cancers vary by their origin and specific set of genetic lesions, which gives rise to distinct phenotypes and differential response to targeted and untargeted chemotherapies. To explore the functional differences of different breast cell types, we performed Stable Isotope Resolved Metabolomics (SIRM) studies of one primary breast (HMEC) and three breast cancer cells (MCF-7, MDAMB-231, and ZR75-1) having distinct genotypes and growth characteristics, using (13)C6-glucose, (13)C-1+2-glucose, (13)C5,(15)N2-Gln, (13)C3-glycerol, and (13)C8-octanoate as tracers. These tracers were designed to probe the central energy producing and anabolic pathways (glycolysis, pentose phosphate pathway, Krebs Cycle, glutaminolysis, nucleotide synthesis and lipid turnover). We found that glycolysis was not associated with the rate of breast cancer cell proliferation, glutaminolysis did not support lipid synthesis in primary breast or breast cancer cells, but was a major contributor to pyrimidine ring synthesis in all cell types; anaplerotic pyruvate carboxylation was activated in breast cancer versus primary cells. We also found that glucose metabolism in individual breast cancer cell lines differed between in vitro cultures and tumor xenografts, but not the metabolic distinctions between cell lines, which may reflect the influence of tumor architecture/microenvironment.

  20. Stable carbon isotope as a signal index for monitoring grassland degradation

    NASA Astrophysics Data System (ADS)

    Yao, Hongyun; Wilkes, Andreas; Zhu, Guodong; Zhang, Hongdan; Liu, Xiaojuan; Dan Ding; Zhai, Xiajie; Tang, Shiming; Chen, Qing; Zhang, Yujuan; Huang, Ding; Wang, Chengjie

    2016-08-01

    Grassland degradation due to overgrazing is common in many areas of the world. This study analyzed the potential of the stable carbon isotope13C) value as a structural microcosmic index to monitor processes of grassland degradation. The δ13C values of plant leaves, roots and soils in non-grazed (NG) and over-grazed (OG) grassland were measured from samples collected from the seven types of grassland in China. We found that the leaf δ13C values of palatable species (δ13Cleaf) and root δ13C values (δ13Croot) in OG grasslands were reduced compared with those from NG grasslands. Furthermore, the δ13Cleaf and δ13Csoil were positive correlation with elevation and latitude, δ13Croot was negative correlation with them at high altitude (3000~5000m), and δ13Croot and δ13Csoil were negative correlation with them at low altitude (0~2000m), respectively. Consequently, tracing of the δ13C variations in grassland ecosystem can provide a powerful tool to evaluate the degree of grassland degradation.

  1. Molecular isotopic engineering (MIE): industrial manufacture of naproxen of predetermined stable carbon-isotopic compositions for authenticity and security protection and intellectual property considerations

    NASA Astrophysics Data System (ADS)

    Jasper, J. P.; Farina, P.; Pearson, A.; Mezes, P. S.; Sabatelli, A. D.

    2016-05-01

    Molecular Isotopic Engineering (MIE) is the directed stable-isotopic synthesis of chemical products for reasons of product identification and of product security, and also for intellectual property considerations. We report here a generally excellent correspondence between the observed and predicted stable carbon-isotopic13C) results for a successful directed synthesis of racemic mixture from its immediate precursors. The observed results are readily explained by the laws of mass balance and isotope mass balance. Oxygen- and hydrogen isotopic results which require an additional assessment of the effects of O and H exchange, presumably due to interaction with water in the reaction solution, are addressed elsewhere. A previous, cooperative study with the US FDA-DPA showed that individual manufacturers of naproxen could readily be differentiated by their stable-isotopic provenance (δ13C, δ18O, and δD ref. 1). We suggest that MIE can be readily employed in the bio/pharmaceutical industry without alteration of present manufacturing processes other than isotopically selecting and/or monitoring reactants and products.

  2. Monitoring the bio-stimulation of hydrocarbon-contaminated soils by measurements of soil electrical properties, and CO2 content and its 13C/12C isotopic signature

    NASA Astrophysics Data System (ADS)

    Noel, C.; Gourry, J.; Ignatiadis, I.; Colombano, S.; Dictor, M.; Guimbaud, C.; Chartier, M.; Dumestre, A.; Dehez, S.; Naudet, V.

    2013-12-01

    Hydrocarbon contaminated soils represent an environmental issue as it impacts on ecosystems and aquifers. Where significant subsurface heterogeneity exists, conventional intrusive investigations and groundwater sampling can be insufficient to obtain a robust monitoring of hydrocarbon contaminants, as the information they provide is restricted to vertical profiles at discrete locations, with no information between sampling points. In order to obtain wider information in space volume on subsurface modifications, complementary methods can be used like geophysics. Among geophysical methods, geoelectrical techniques such as electrical resistivity (ER) and induced polarization (IP) seem the more promising, especially to study the effects of biodegradation processes. Laboratory and field geoelectrical experiments to characterize soils contaminated by oil products have shown that mature hydrocarbon-contaminated soils are characterized by enhanced electrical conductivity although hydrocarbons are electrically resistive. This high bulk conductivity is due to bacterial impacts on geological media, resulting in changes in the chemical and physical properties and thus, to the geophysical properties of the ground. Moreover, microbial activity induced CO2 production and isotopic deviation of carbon. Indeed, produced CO2 will reflect the pollutant isotopic signature. Thus, the ratio δ13C(CO2) will come closer to δ13C(hydrocarbon). BIOPHY, project supported by the French National Research Agency (ANR), proposes to use electrical methods and gas analyses to develop an operational and non-destructive method for monitoring in situ biodegradation of hydrocarbons in order to optimize soil treatment. Demonstration field is located in the South of Paris (France), where liquid fuels (gasoline and diesel) leaked from some tanks in 1997. In order to stimulate biodegradation, a trench has been dug to supply oxygen to the water table and thus stimulate aerobic metabolic bioprocesses. ER and

  3. Stable carbon and oxygen isotopic analysis of atmospheric carbon monoxide using continuous-flow isotope ratio MS by isotope ratio monitoring of CO.

    PubMed

    Tsunogai, Urumu; Nakagawa, Fumiko; Komatsu, Daisuke D; Gamo, Toshitaka

    2002-11-15

    We have developed a rapid and simple measurement system for both content and stable isotopic compositions (13C and 18O) of atmospheric CO, using continuous-flow isotope ratio mass spectrometry by simultaneously monitoring the CO+ ion currents at masses 28, 29, and 30. The analytical system consisted sequentially of a sample trapping port (liquid nitrogen temperature silica gel and molecular sieve 5A), a gas dryer, a CO purification column (molecular sieve 5A), a cryofocusing unit, and a final purification column using a GC capillary. Analytical precision of 0.2 per thousand for 13C and 0.4 per thousand for 18O can be realized for samples that contain as little as 300 pmol of CO within 40 min for one sample analysis. Analytical blanks associated with the method are less than 1 pmol. The extent of analytical error in delta13C due to mass-independent fractionation of oxygen in natural CO is estimated to be less than 0.3 per thousand. Based on this system, we report herein a kinetic isotopic effect during CO consumption in soil.

  4. Helium isotopes in ocelandic geothermal systems: I. [sup 3]He, gas chemistry, and [sup 13]C relations

    SciTech Connect

    Poreda, R.J.; Craig, H.; Welhan, J.A. ); Arnorsson, S. )

    1992-12-01

    Gas samples from seventeen high-temperature and twenty-two low-temperature geothermal systems have been analyzed for chemistry and [sup 3]He/[sup 4]He ratios. Within the Neo-Volcanic Zone the [sup 3]He/[sup 4]He ratios show a consistent regional pattern: 14-19 times the atmospheric ratio (R[sub A]) in the southwest, 8-11 R[sub A] in the north, and 17-26 R[sub A] in central Iceland. Outside of the rift zones a mantle helium component also dominates with the highest [sup 3]He/[sup 4]He ratios found in waters circulating through 9-My-old crust in Northwest Iceland (up to 29 R[sub A]). The minimum Icelandic [sup 3]He/[sup 4]He ratio (excluding a methane seep east of the rift) is 8.5 R[sub A] at Kverkfjoll, in central Iceland at the southern end of the narrow Northern Rift Zone; throughout the NRZ the ratios vary only from 8.5 to 10.7 R[sub A]. The Kverkfjoll ratio is precisely the mean MORB ratio: (8 [+-] 1)R[sub A] R[sub A]. Thus, the mantle helium emerging at Iceland is a simple mixture of two components: MORB He (8 R[sub A]) and deep-mantle plume He with R/R[sub A] > 29. High-temperature systems have CO[sub 2]/[sup 3]He ratios of 10[sup 9] to 10[sup 10] that encompass the range found in MORB (1-3 [times] 10[sup 9]). However, the CO[sub 2]/[sup 3]He values have been subjected to postmagmatic effects that alter and obscure the original magmatic CO[sub 2]/[sup 3]He ratios. [delta]([sup 13]C) in the fluid-phase CO[sub 2] is well defined at -3.8[per thousand] in the high-CO[sub 2] fluids (up to 1 mol/kg fluid), very similar to MORB values. CH[sub 4]/[sup 3]He ratios vary widely, from 3 [times] 10[sup 4] to 10[sup 8]. Most high-temperature systems from southwestern and northern Iceland have CH[sub 4]/[sup 3]He ratios less than 10[sup 6], while those from central Iceland have consistently higher ratios of the order of 10[sup 7]. Local conditions and possible proximity to an organic source of methane can have a strong effect on this ratio.

  5. Stable isotope records of inland California megafauna - new insights into Pleistocene paleoecology and paleoenvironmental conditions

    NASA Astrophysics Data System (ADS)

    Trayler, R. B.; Dundas, R. G.; Van De Water, P. K.; Fox-Dobbs, K.

    2012-12-01

    Paleodietary studies of California megafauna have focused primarily on the coastal late Pleistocene Rancho La Brea tar seeps (RLB) in Los Angeles, while other sites remain understudied. We examined two Pleistocene fossil localities from inland California (San Joaquin Valley) and report δ13C and δ18O values measured from tooth enamel of mammalian megafauna at both sites. The late Pleistocene McKittrick tar seeps in Kern County has a similar fauna to RLB. The middle Irvingtonian (~700,000 year old) Fairmead Landfill site, near Chowchilla, contains a megafaunal assemblage dominated by Equus, Camelops and Mammuthus. We used stable isotope values measured in carnivore and herbivore tooth enamel to investigate paleodietary and paleoecological patterns at both sites. δ13C values of tooth enamel is controlled by diet and can be used to investigate resource usage and partitioning among and between taxa. In large mammals δ18O ratios are controlled by drinking water, and by proxy, climate. Ontogenetic serial tooth δ18O and δ13C reveal seasonal trends in resource usage, from which we can infer patterns of forage availability. We sampled 85 individuals from 16 ta